Chemical Mechanical Polishing Stopper Film, Preparation Thereof, and Chemical Mechanical Polishing M

专利摘要:
PURPOSE: A chemical mechanical polishing(CMP) stopper film is provided to form a material for an interlayer dielectric which is little damaged by CMP treatment, by using the chemical mechanical polishing stopper film made of an organic polymer having a specific inductive capacity 4 or below. CONSTITUTION: A CMP stopper film whose specific inductive capacity is 4 or below is composed of an organic polymer. The organic polymer is aromatic polyarylene and aromatic polyarylene ether or either one of them. Embrocation composed of organic polymer and organic solvent is applied on a substrate and the substrate is heated.
公开号:KR20020018005A
申请号:KR1020010051539
申请日:2001-08-25
公开日:2002-03-07
发明作者:미찌노리 니시까와；다까시 오까다；긴지 야마다
申请人:마쯔모또 에이찌；제이에스알 가부시끼가이샤；
IPC主号:

专利说明:

Chemical Mechanical Polishing Stopper Film, Manufacturing Method thereof and Chemical Mechanical Polishing Method {Chemical Mechanical Polishing Stopper Film, Preparation Thereof, and Chemical Mechanical Polishing Method}
[2] The present invention relates to a chemical mechanical polishing stopper film. More specifically, the present invention relates to SiO ₂ , fluorine-doped SiO ₂ , organic / inorganic SOG (Spin-on glass) in chemical mechanical polishing (hereinafter also referred to as “CMP”) of a wafer provided with a wiring pattern in the manufacture of semiconductor devices. A stopper film for protecting an interlayer insulating film made of a material or the like from damage caused by a CMP process.
[3] Conventional Technology
[4] Background Art [0002] Aqueous dispersions containing inorganic particles such as colloidal silica and colloidal alumina have conventionally been used as abrasives for CMP such as metal wirings and barrier films in semiconductor devices. However, when the CMP process using such an aqueous dispersion is performed, there is a problem that scratches and peelings are likely to occur in the interlayer insulating film.
[5] This invention solves the above-mentioned conventional problem, and aims at reducing the damage of an interlayer insulation film by CMP by laminating | stacking a specific coating film on the upper layer of an interlayer insulation film.
[1] FIG. 1 (a) shows an application example of the present invention after metal film formation, and (b) shows a structure obtained after unnecessary metal is removed by CMP after metal film formation.
[6] The present invention relates to a chemical mechanical polishing stopper film.
[7] (A) organic polymer
[8] The chemical mechanical polishing stopper film of this invention contains the organic polymer whose dielectric constant is four or less.
[9] As such an organic polymer, a dielectric constant is 4 or less, Preferably it is 3.5 or less, Carbon content is 60 weight% or more, Preferably, 70 weight% or more of an aromatic polymer is mentioned.
[10] In particular, the organic polymer is an aromatic polyarylene or an aromatic polyarylene ether or any one thereof, and has a polymer having a repeating structural unit represented by the following general formula (1) (polymer (1)), a repeating structure represented by the following general formula (2) Preference is given to polymers having units (polymers (2)) and polymers having repeating structural units represented by the formula (36).
[11]
[12]
[13] In formula, R <^7> -R <^11> is respectively independently a C1-C20 hydrocarbon group, a cyano group, a nitro group, a C1-C20 alkoxyl group, an aryl group, or a halogen atom, X is -CQQ'- (here Q and Q 'may be the same or different and are at least one selected from the group consisting of a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group), and a fluorenylene group, and Y is -O-, -CO-, -COO-, -CONH-, -S-, -SO ₂ -and at least one selected from the group of phenylene groups, a represents 0 or 1, b to f are 0 to An integer of 4, g is from 5 to 100 mol%, h is from 0 to 95 mol%, i is from 0 to 95 mol% (wherein g + h + i = 100 mol%), j is from 0 to 100 mol% and k are 0-100 mol% (where j + k = 100 mol%).
[14] Moreover, in the polymer (1) and the polymer (2) which comprise (A) component, containing a C1-C20 hydrocarbon group is preferable at the point which improves the heat resistance of a coating film.
[15] In addition, it is preferable that the repeating structural units of the polymer (1) and the polymer (2) are linked at the para position with respect to X in terms of obtaining a high molecular weight polymer.
[16]
[17] In the formula, Y represents a divalent organic group represented by the following formula (37) or (38), Ar represents a divalent organic group, and n is 0 or 1.
[18]
[19] In the formula, R ³¹ and R ³² are the same or different and are in the cis position and represent a hydrogen atom, an alkyl group, an aryl group.
[20]
[21] In the formula, R ³³ to R ³⁶ are the same or different and represent a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group, or an aryl group.
[22] Polymer (1);
[23] The polymer represented by the formula (1) can be produced by polymerizing a monomer containing a compound represented by the following formula (3), for example, in the presence of a catalyst system containing a transition metal compound.
[24]
[25] In formula, R <^7> , R <^8> is respectively independently a C1-C20 hydrocarbon group, cyano group, a nitro group, a C1-C20 alkoxyl group, an aryl group, or a halogen atom, X is -CQQ'- (wherein Q, Q 'may be the same or different and is at least one selected from the group consisting of a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group), and a fluorenylene group, b, c represents an integer of 0 to 4, and Z represents an alkyl group, a halogenated alkyl group or an aryl group.
[26] As Q, Q 'which comprises X in the said Formula (3), as an alkyl group, a methyl group, an ethyl group, i-propyl group, n-propyl group, a butyl group, a pentyl group, a hexyl group, etc .; As a halogenated alkyl group, a trifluoromethyl group, pentafluoroethyl group, etc .; As an arylalkyl group, benzyl group, diphenylmethyl group, etc .; A phenyl group, biphenyl group, tolyl group, pentafluorophenyl group etc. are mentioned as an aryl group.
[27] Further, as the Z constituting -OSO ₂ Z in the above formula (3), a methyl group as the alkyl group, an ethyl group, and the like; As a halogenated alkyl group, a trifluoromethyl group, pentafluoroethyl group, etc .; A phenyl group, a biphenyl group, p-tolyl group, p-pentafluorophenyl group etc. are mentioned as an aryl group.
[28] As X in the said Formula (3), the bivalent group represented by following formula (4)-9 is preferable.
[29] Among these, the fluorenylene group represented by the formula (9) is more preferable.
[30]
[31]
[32]
[33]
[34]
[35]
[36] As a specific example of the compound (monomer) represented by the said General formula (3), for example
[37] 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane,
[38] Bis (4-methylsulfonyloxyphenyl) methane,
[39] Bis (4-methylsulfonyloxyphenyl) diphenylmethane,
[40] 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) hexafluoropropane,
[41] 2,2-bis (4-methylsulfonyloxy-3-propenylphenyl) hexafluoropropane,
[42] 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane,
[43] 2,2-bis (4-methylsulfonyloxyphenyl) propane,
[44] 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) propane,
[45] 2,2-bis (4-methylsulfonyloxy-3-propenylphenyl) propane,
[46] 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) propane,
[47] 2,2-bis (4-methylsulfonyloxy-3-fluorophenyl) propane,
[48] 2,2-bis (4-methylsulfonyloxy-3,5-difluorophenyl) propane,
[49] 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) propane,
[50] 2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) propane,
[51] 2,2-bis (4-phenylsulfonyloxyphenyl) propane,
[52] 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) propane,
[53] 2,2-bis (4-phenylsulfonyloxy-3-propenylphenyl) propane,
[54] 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) propane,
[55] 2,2-bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[56] 2,2-bis (p-tolylsulfonyloxyphenyl) propane,
[57] 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane,
[58] 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane,
[59] 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane,
[60] 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane,
[61] 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane,
[62] 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane,
[63] Bis (p-tolylsulfonyloxy-3-fluorophenyl) propane,
[64] Bis (p-tolylsulfonyloxy-3,5-difluorophenyl) propane,
[65] 9,9-bis (4-methylsulfonyloxyphenyl) fluorene,
[66] 9,9-bis (4-methylsulfonyloxy-3-methylphenyl) fluorene,
[67] 9,9-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) fluorene,
[68] 9,9-bis (4-methylsulfonyloxy-3-propenylphenyl) fluorene,
[69] 9,9-bis (4-methylsulfonyloxy-3-phenylphenyl) fluorene,
[70] Bis (4-methylsulfonyloxy-3-methylphenyl) diphenylmethane,
[71] Bis (4-methylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane,
[72] Bis (4-methylsulfonyloxy-3-propenylphenyl) diphenylmethane,
[73] Bis (4-methylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[74] Bis (4-methylsulfonyloxy-3,5-difluorophenyl) diphenylmethane,
[75] 9,9-bis (4-methylsulfonyloxy-3-fluorophenyl) fluorene,
[76] 9,9-bis (4-methylsulfonyloxy-3,5-difluorophenyl) fluorene,
[77] Bis (4-methylsulfonyloxyphenyl) methane,
[78] Bis (4-methylsulfonyloxy-3-methylphenyl) methane,
[79] Bis (4-methylsulfonyloxy-3,5-dimethylphenyl) methane,
[80] Bis (4-methylsulfonyloxy-3-propenylphenyl) methane,
[81] Bis (4-methylsulfonyloxyphenyl) trifluoromethylphenylmethane,
[82] Bis (4-methylsulfonyloxyphenyl) phenylmethane,
[83] 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane,
[84] Bis (4-trifluoromethylsulfonyloxyphenyl) methane,
[85] Bis (4-trifluoromethylsulfonyloxyphenyl) diphenylmethane,
[86] 2,2-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) hexafluoropropane,
[87] 2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) hexafluoropropane,
[88] 2,2-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane,
[89] 9,9-bis (4-trifluoromethylsulfonyloxyphenyl) fluorene,
[90] 9,9-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) fluorene,
[91] 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) fluorene,
[92] 9,9-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) fluorene,
[93] 9,9-bis (4-trifluoromethylsulfonyloxy-3-phenylphenyl) fluorene,
[94] Bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) diphenylmethane,
[95] Bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane,
[96] Bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) diphenylmethane,
[97] Bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[98] Bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) diphenylmethane,
[99] 9,9-bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) fluorene,
[100] 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) fluorene,
[101] Bis (4-trifluoromethylsulfonyloxyphenyl) methane,
[102] Bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) methane,
[103] Bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) methane,
[104] Bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) methane,
[105] Bis (4-trifluoromethylsulfonyloxyphenyl) trifluoromethylphenylmethane,
[106] Bis (4-trifluoromethylsulfonyloxyphenyl),
[107] 2,2-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane,
[108] Bis (4-phenylsulfonyloxyphenyl) methane,
[109] Bis (4-phenylsulfonyloxyphenyl) diphenylmethane,
[110] 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) hexafluoropropane,
[111] 2,2-bis (4-phenylsulfonyloxy-3-propenylphenyl) hexafluoropropane,
[112] 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane,
[113] 9,9-bis (4-phenylsulfonyloxyphenyl) fluorene,
[114] 9,9-bis (4-phenylsulfonyloxy-3-methylphenyl) fluorene,
[115] 9,9-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) fluorene,
[116] 9,9-bis (4-phenylsulfonyloxy-3-propenylphenyl) fluorene,
[117] 9,9-bis (4-phenylsulfonyloxy-3-phenylphenyl) fluorene,
[118] Bis (4-phenylsulfonyloxy-3-methylphenyl) diphenylmethane,
[119] Bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane,
[120] Bis (4-phenylsulfonyloxy-3-propenylphenyl) diphenylmethane,
[121] Bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[122] Bis (4-phenylsulfonyloxy-3,5-difluorophenyl) diphenylmethane,
[123] 9,9-bis (4-phenylsulfonyloxy-3-fluorophenyl) fluorene,
[124] 9,9-bis (4-phenylsulfonyloxy-3,5-difluorophenyl) fluorene,
[125] Bis (4-phenylsulfonyloxyphenyl) methane,
[126] Bis (4-phenylsulfonyloxy-3-methylphenyl) methane,
[127] Bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) methane,
[128] Bis (4-phenylsulfonyloxy-3-propenylphenyl) methane,
[129] Bis (4-phenylsulfonyloxyphenyl) trifluoromethylphenylmethane,
[130] Bis (4-phenylsulfonyloxyphenyl) phenylmethane,
[131] 2,2-bis (p-tolylsulfonyloxyphenyl) hexafluoropropane,
[132] Bis (p-tolylsulfonyloxyphenyl) methane,
[133] Bis (p-tolylsulfonyloxyphenyl) diphenylmethane,
[134] 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) hexafluoropropane,
[135] 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) hexafluoropropane,
[136] 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane,
[137] 9,9-bis (p-tolylsulfonyloxyphenyl) fluorene,
[138] 9,9-bis (p-tolylsulfonyloxy-3-methylphenyl) fluorene,
[139] 9,9-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) fluorene,
[140] 9,9-bis (p-tolylsulfonyloxy-3-propenylphenyl) fluorene,
[141] 9,9-bis (p-tolylsulfonyloxy-3-phenylphenyl) fluorene,
[142] Bis (p-tolylsulfonyloxy-3-methylphenyl) diphenylmethane,
[143] Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane,
[144] Bis (p-tolylsulfonyloxy-3-propenylphenyl) diphenylmethane,
[145] Bis (p-tolylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[146] Bis (p-tolylsulfonyloxy-3,5-difluorophenyl) diphenylmethane,
[147] 9,9-bis (p-tolylsulfonyloxy-3-fluorophenyl) fluorene,
[148] 9,9-bis (p-tolylsulfonyloxy-3,5-difluorophenyl) fluorene,
[149] Bis (p-tolylsulfonyloxyphenyl) methane,
[150] Bis (p-tolylsulfonyloxy-3-methylphenyl) methane,
[151] Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) methane,
[152] Bis (p-tolylsulfonyloxy-3-propenylphenyl) methane,
[153] Bis (p-tolylsulfonyloxyphenyl) trifluoromethylphenylmethane,
[154] Bis (p-tolylsulfonyloxyphenyl) phenylmethane
[155] Etc. can be mentioned.
[156] In the present invention, two or more kinds of compounds represented by the general formula (3) may be copolymerized.
[157] The compound represented by the said Formula (3) can be synthesized by the following manufacturing method, for example.
[158] In other words, two equivalents or more of a bisphenol compound [eg, 2,2-bis (4-hydroxyphenyl) hexafluoropropane] and a bisphenol compound are dissolved in a solvent. In this case, pyridine or the like may be used as a solvent to serve as both a solvent and a base. Moreover, you may add a catalyst, such as 4-dimethylaminopyridine, as needed.
[159] Subsequently, sulfonic acid chloride (anhydride) (for example, methanesulfonic acid chloride) is added dropwise under a dry nitrogen stream for 5 to 60 minutes while being kept at 15 ° C or lower. Thereafter, the mixture is stirred at the same temperature for 0 to 60 minutes, then returned to room temperature and stirred for 0 to 24 hours to prepare a suspension. The obtained suspension can be reprecipitated in 3 to 20 times of ice water to recover the precipitate, and operations such as recrystallization can be repeated to obtain a bissulfonate compound as crystals.
[160] Alternatively, a bisphenol compound [for example, 2,2-bis (4-hydroxyphenyl) hexafluoropropane] is dissolved in two equivalents of an aqueous alkali solution such as an aqueous sodium hydroxide solution. On the other hand, sulfonic acid chloride (anhydride) (for example, methanesulfonic acid chloride) is dissolved in organic solvents such as toluene and chloroform. Subsequently, after adding a phase transfer catalyst, such as acetyl trimethylammonium chloride here, as needed, it is stirred vigorously. Thereafter, the desired bissulfonate compound can also be obtained by purifying the organic layer obtained by reaction.
[161] In the present invention, one or more kinds of the compound represented by the formula (3) and one or more kinds selected from the group consisting of the compounds represented by the following formulas (10) to (11) may be copolymerized.
[162]
[163] Wherein, R ⁹ to R ¹⁰ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group, an aryl group or a halogen atom having 1 to 20 carbon atoms, R ¹² to R ¹³ is -OSO ₂ Z (Wherein Z represents an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom, and Y represents -0-, -CO-,-C0O-, -CONH-, -S-,- SO ₂ - is at least one selected from the group of a phenyl group, a is 0 or 1, d, e represents an integer of 0 to 4.
[164] As the halogen atom among R ⁹ to R ¹⁰ , a monovalent organic group such as a fluorine atom may be used as an aryl group such as a methyl group or an ethyl group as an alkyl group, a trifluoromethyl group as a halogenated alkyl group, a pentafluoroethyl group, or a propenyl group as an allyl group. A phenyl group, pentafluorophenyl group, etc. are mentioned. Further, as the Z constituting a -OSO ₂ Z, there may be mentioned methyl group, ethyl group or the like, such as a trifluoromethyl group as a halogenated alkyl group, a phenyl group, p- tolyl group, a phenyl group, such as p- fluorobenzyl an aryl group as an alkyl group.
[165] As a compound represented by the said Formula (10), for example
[166] 4,4'-dimethylsulfonyloxybiphenyl,
[167] 4,4'-dimethylsulfonyloxy-3,3'-dipropenylbiphenyl,
[168] 4,4'-dibromobiphenyl,
[169] 4,4'-diiodine biphenyl,
[170] 4,4'-dimethylsulfonyloxy-3,3'-dimethylbiphenyl,
[171] 4,4'-dimethylsulfonyloxy-3,3'-difluorobiphenyl,
[172] 4,4'-dimethylsulfonyloxy-3,3 ', 5,5'-tetrafluorobiphenyl,
[173] 4,4'-dibromooctafluorobiphenyl,
[174] 4,4-methylsulfonyloxyoctafluorobiphenyl,
[175] 3,3'-diallyl-4,4'-bis (4-fluorobenzenesulfonyloxy) biphenyl,
[176] 4,4'-dichloro-2,2'-trifluoromethylbiphenyl,
[177] 4,4'-dibromo-2,2'-trifluoromethylbiphenyl,
[178] 4,4'-diiodine-2,2'-trifluoromethylbiphenyl,
[179] Bis (4-chlorophenyl) sulfone,
[180] 4,4'-dichlorobenzophenone,
[181] 2,4-dichlorobenzophenone
[182] Etc. can be mentioned.
[183] The compound represented by the formula (10) may be used alone or in combination of two or more.
[184]
[185] Wherein R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group or a halogen atom, and R ¹⁴ to R ¹⁵ are each selected from -OSO ₂ Z (where Z is an alkyl group). , A halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom, and f represents an integer of 0 to 4.
[186] As the halogen atom in R ¹¹ , a monovalent organic group such as a fluorine atom, such as an alkyl group, a methyl group, an ethyl group, etc., a halogenated alkyl group, such as a trifluoromethyl group, a pentafluoroethyl group, an allyl group, such as a propenyl group, a phenyl group, a penta A fluorophenyl group etc. are mentioned. Further, as the Z constituting a -OSO ₂ Z, there may be mentioned methyl group, ethyl group or the like, such as a trifluoromethyl group as a halogenated alkyl group, a phenyl group, p- tolyl group, a phenyl group, such as p- fluorobenzyl an aryl group as an alkyl group.
[187] As the compound represented by the formula (11), for example
[188] o-dichlorobenzene, o-dibromobenzene, o-diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene, 2,3-dibromotoluene, 2,3-diiotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, 3,4-dimethylsulfonyloxybenzene, m-dichlorobenzene, m -Dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2,4-dibromotoluene, 2,4-diiotoluene, 3,5-dichlorotoluene , 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene, 2,6-diiodotoluene, 3,5-dimethylsulfonyloxy Toluene, 2,6-dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dibromobenzotrifluoride, 2,4-diiodinebenzotrifluoride, 3,5-dichloro Benzotrifluoride, 3,5-dibromotrifluoride, 3,5-diyo Debenzotrifluoride, 1,3-dibromo-2,4,5,6-tetrafluorobenzene, 2,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 2,4-dibromo Benzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-dichloro-t-butoxycarbonyloxyphenyl, 3,5-dibro Mother-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid, 2,4-dichlorobenzoic acid methyl Methyl 3,5-dichlorobenzoate, methyl 3,5-dibromobenzoate, methyl 2,4-dibromobenzoate, 2,4-dichlorobenzoic acid-t-butyl, 3,5-dichlorobenzoic acid-t-butyl , 2,4-dibromobenzoic acid-t-butyl, 3,5-dibromobenzoic acid-t-butyl, etc. are mentioned, Preferably m-dichlorobenzene, 2,4-dichlorotoluene, 3,5 -Dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-dichlorobenzophenone, 2,4-dichlorophenoxybenzene, etc. Can be mentioned.
[189] The compound represented by the formula (11) may be used alone or in combination of two or more.
[190] The ratio of the repeating structural unit in the polymer (1) is 5 to 100 mol%, preferably 5 to 95 mol%, h is 0 to 95 mol%, preferably 0 to 90 mol% in the formula (1). and i is 0 to 95 mol%, preferably 0 to 90 mol% (wherein g + h + i = 100 mol%).
[191] If g is less than 5 mol% (h or i is more than 95 mol%), the solubility with respect to the organic solvent of a polymer may be inferior.
[192] The catalyst used when preparing the polymer (1) is preferably a catalyst system containing a transition metal compound. The catalyst system includes (1) a transition metal salt and a ligand, or a transition metal (salt) having a ligand coordinated, and (2) a reducing agent as essential components. And a "salt" may be further added to increase the polymerization rate.
[193] Examples of the transition metal salts include nickel compounds such as nickel chloride, nickel bromide, nickel iodide, and nickel acetylacetonato, palladium compounds such as palladium chloride, palladium bromide, and palladium iodide, iron compounds such as iron chloride, iron bromide, and iron iodide, and chlorides. Cobalt compounds, such as cobalt, cobalt bromide, and cobalt iodide, etc. are mentioned. Among these, nickel chloride and nickel bromide are particularly preferable.
[194] As the ligand, triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene, 1,3-bis (diphenylphosphino) propane, etc. may be mentioned, but triphenylphosphine, 2, 2'-bipyridine is preferred. The ligands may be used alone or in combination of two or more.
[195] As the transition metal (salt) to which the ligand is coordinated in advance, for example, nickel chloride 2 triphenylphosphine, nickel bromide 2 triphenylphosphine, nickel iodide 2 triphenylphosphine, nickel nitrate 2-triphenylphosphine, Nickel chloride 2,2'-bipyridine, nickel bromide 2,2'-bipyridine, nickel iodide 2,2'-bipyridine, nickel nitrate 2,2'-bipyridine, bis (1,5-cyclooctadiene) Nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium, and the like. Nickel chloride 2 triphenylphosphine, nickel chloride 2,2 '-Bipyridine is preferred.
[196] Examples of the reducing agent that can be used in such a catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium and the like, but zinc and manganese are preferable. Such a reducing agent can be used by further activating by contact with an acid or an organic acid.
[197] Moreover, as "salt" which can be used in such a catalyst system, sodium compounds, such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, and sodium sulfate, potassium compounds, such as potassium fluoride, potassium chloride, potassium bromide, potassium iodide, and potassium sulfate, tetraethyl fluoride Ammonium compounds, such as ammonium, tetraethylammonium chloride, tetraethylammonium bromide, tetramethylammonium iodide, tetraethylammonium sulfate, etc. are mentioned, but sodium bromide, sodium iodide, potassium bromide, tetraethylammonium iodide, tetraethylammonium iodide, desirable.
[198] The use ratio of each component in such a catalyst system is that the transition metal salt or the transition metal (salt) to which the ligand is coordinated is usually 0.0001 to 10 moles, preferably 0.01 to 0.5 to 1 mole of the total amount of the compounds of Formulas 3 and 10 to 11. It's a mole. If it is less than 0.0001 mol, a polymerization reaction will not fully advance, whereas if it exceeds 10 mol, molecular weight may fall.
[199] In the case of using a transition metal salt and a ligand in such a catalyst system, the use ratio of the ligand is usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the transition metal salt. If it is less than 0.1 mol, the catalytic activity becomes insufficient, while if it exceeds 100 mol, there is a problem that the molecular weight is lowered.
[200] In addition, the rate of use of the reducing agent in the catalyst system is usually 0.1 to 100 moles, preferably 1 to 10 moles, based on 1 mole of the total amount of the compounds of Formulas 3 and 10 to 11. If it is less than 0.1 mol, superposition | polymerization will not fully advance, On the other hand, if it exceeds 100 mol, purification of the polymer obtained may become difficult.
[201] In addition, when "salt" is used in the catalyst system, the use ratio is usually 0.001 to 100 moles, preferably 0.01 to 1 mole, based on 1 mole of the total amount of the compounds of Formulas 3 and 10 to 11. When the amount is less than 0.001 mole, the effect of increasing the polymerization rate is insufficient. On the other hand, when the amount exceeds 100 mole, purification of the polymer obtained may be difficult.
[202] Examples of the polymerization solvent that can be used in the present invention include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and 1-methyl-2-pyrrolidone. , γ-butyrolactone, γ-butyrolactam and the like, among which tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone desirable. It is preferable to use such a polymerization solvent after fully drying.
[203] The concentration of the total amount of the above formulas (3), (10-11) compounds in the polymerization solvent is usually 1 to 100% by weight, preferably 5 to 40% by weight.
[204] In addition, the polymerization temperature at the time of superposing | polymerizing the said polymer is 0-200 degreeC normally, Preferably it is 50-80 degreeC. In addition, the polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.
[205] In addition, the weight average molecular weight of polystyrene conversion of the said polymer (1) is 1,000-1,000,000 normally.
[206] Polymer (2);
[207] The polymer represented by the formula (2) can be produced, for example, by polymerizing a monomer containing a compound represented by the following formulas (12) to (14) in the presence of a catalyst system.
[208]
[209] In formula, R <^7> , R <^8> is respectively independently a C1-C20 hydrocarbon group, a cyano group, a nitro group, a C1-C20 alkoxyl group, an aryl group, or a halogen atom, X is -CQQ'- (where Q is , Q 'may be the same or different and is at least one selected from the group consisting of a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group), and a fluorenylene group, b, c Represents an integer of 0 to 4, and R ¹⁶ and R ¹⁷ represent one or more selected from the group consisting of a hydroxyl group, a halogen atom and a -0M group (M is an alkali metal).
[210] As a specific example of the compound (monomer) represented by the said General formula (12), for example
[211] 2,2-bis (4-hydroxyphenyl) hexafluoropropane,
[212] Bis (4-hydroxyphenyl) methane,
[213] Bis (4-hydroxyphenyl) diphenylmethane,
[214] 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane,
[215] 2,2-bis (4-hydroxy-3-propenylphenyl) hexafluoropropane,
[216] 2,2-bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane,
[217] 2,2-bis (4-hydroxyphenyl) propane,
[218] 2,2-bis (4-hydroxy-3-methylphenyl) propane,
[219] 2,2-bis (4-hydroxy-3-propenylphenyl) propane,
[220] 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane,
[221] 2,2-bis (4-hydroxy-3-fluorophenyl) propane,
[222] 2,2-bis (4-hydroxy-3,5-difluorophenyl) propane,
[223] 2,2-bis (4-chlorophenyl) hexafluoropropane,
[224] Bis (4-chlorophenyl) methane,
[225] Bis (4-chlorophenyl) diphenylmethane,
[226] 2,2-bis (4-chloro-3-methylphenyl) hexafluoropropane,
[227] 2,2-bis (4-chloro-3-propenylphenyl) hexafluoropropane,
[228] 2,2-bis (4-chloro-3,5-dimethylphenyl) hexafluoropropane,
[229] 2,2-bis (4-chlorophenyl) propane,
[230] 2,2-bis (4-chloro-3-methylphenyl) propane,
[231] 2,2-bis (4-chloro-3-propenylphenyl) propane,
[232] 2,2-bis (4-chloro-3,5-dimethylphenyl) propane,
[233] 2,2-bis (4-chloro-3-fluorophenyl) propane,
[234] 2,2-bis (4-chloro-3,5-difluorophenyl) propane,
[235] 2,2-bis (4-chlorophenyl) hexafluoropropane,
[236] Bis (4-bromophenyl) methane,
[237] Bis (4-bromophenyl) diphenylmethane,
[238] 2,2-bis (4-bromo-3-methylphenyl) hexafluoropropane,
[239] 2,2-bis (4-bromo-3-propenylphenyl) hexafluoropropane,
[240] 2,2-bis (4-bromo-3,5-dimethylphenyl) hexafluoropropane,
[241] 2,2-bis (4-bromophenyl) propane,
[242] 2,2-bis (4-bromo-3-methylphenyl) propane,
[243] 2,2-bis (4-bromo-3-propenylphenyl) propane,
[244] 2,2-bis (4-bromo-3,5-dimethylphenyl) propane,
[245] 2,2-bis (4-bromo-3-fluorophenyl) propane,
[246] 2,2-bis (4-bromo-3,5-difluorophenyl) propane,
[247] Bis (4-fluorophenyl) methane,
[248] Bis (4-fluorophenyl) diphenylmethane,
[249] 2,2-bis (4-fluoro-3-methylphenyl) hexafluoropropane,
[250] 2,2-bis (4-fluoro-3-propenylphenyl) hexafluoropropane,
[251] 2,2-bis (4-fluoro-3,5-dimethylphenyl) hexafluoropropane,
[252] 2,2-bis (4-fluorophenyl) propane,
[253] 2,2-bis (4-fluoro-3-methylphenyl) propane,
[254] 2,2-bis (4-fluoro-3-propenylphenyl) propane,
[255] 2,2-bis (4-fluoro-3,5-dimethylphenyl) propane,
[256] 2,2-bis (4-fluoro-3-fluorophenyl) propane,
[257] 2, 2-bis (4-fluoro-3, 5-difluorophenyl) propane etc. are mentioned.
[258] The said bisphenol compound can also substitute a -0M group (M is an alkali metal) with a hydroxyl group with the basic compound containing sodium, potassium, etc.
[259] In the present invention, two or more kinds of compounds represented by the above formula (12) may be copolymerized.
[260]
[261] Wherein, R ^9, R ¹⁰ each independently represent a group having a carbon number of 1 to 20 hydrocarbon group, a cyano group, a nitro group, a C 1 -C 20 alkoxyl group, an aryl group or a halogen atom, R ^18, R ¹⁹ is a hydroxy group, a halogen atom , -0M group (M is an alkali metal) represents one or more selected from the group consisting of, Y is -O-, -CO-, -COO-, -CONH-, -S-, -SO ₂ -and phenyl It is at least 1 type selected from the group of a len group, a represents 0 or 1, d, e represents the integer of 0-4.
[262] As the compound represented by the formula (13), for example
[263] 4,4'-dichlorobiphenyl, 4,4'-dibromobiphenyl, 4,4'-difluorobiphenyl, 4,4'-diiobibiphenyl, 4,4'-dihydroxybiphenyl,
[264] 4,4'-dihydroxy-3,3'-dipropenylbiphenyl,
[265] 4,4'-dihydroxy-3,3'-dimethylbiphenyl,
[266] 4,4'-dihydroxy-3,3'-diethylbiphenyl,
[267] 4,4'-dimethylhydroxy-3,3 ', 5,5'-tetrafluorobiphenyl,
[268] 4,4'-dibromooctafluorobiphenyl,
[269] 4,4-dihydroxyoctafluorobiphenyl,
[270] 3,3'-diallyl-4,4'-bis (4-hydroxy) biphenyl,
[271] 4,4'-dichloro-2,2'-trifluoromethylbiphenyl,
[272] 4,4'-dibromo-2,2'-trifluoromethylbiphenyl,
[273] 4,4'-diiodine-2,2'-trifluoromethylbiphenyl,
[274] Bis (4-chlorophenyl) sulfone, bis (4-hydroxyphenyl) sulfone,
[275] Bis (4-chlorophenyl) ether, bis (4-hydroxyphenyl) ether, 4,4'-dichlorobenzophenone, 4,4'-dihydroxybenzophenone,
[276] 2,4-dichlorobenzophenone, 2,4-dihydroxybenzophenone
[277] Etc. can be mentioned.
[278] The said bisphenol compound can also substitute a -0M group (M is an alkali metal) with a hydroxyl group with the basic compound containing sodium, potassium, etc.
[279] The compound represented by the formula (13) may be used alone or in combination of two or more.
[280]
[281] Wherein R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, a cyano group, a nitro group, an alkoxyl group having 1 to 20 carbon atoms, an aryl group or a halogen atom, R ²⁰ , R ²¹ is -OSO ₂ Z (wherein Z is Alkyl group, halogenated alkyl group or aryl group), a chlorine atom, a bromine atom or an iodine atom, and f represents an integer of 0-4.
[282] As the compound represented by the formula (14), for example
[283] 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 2,3-dihydroxytoluene, 2,5-dihydroxytoluene, 2,6-di Hydroxytoluene, 3,4-dihydroxytoluene, 3,5-dihydroxytoluene, o-dichlorobenzene, o-dibromobenzene, o-diiobenzene, o-dimethylsulfonyloxybenzene, 2, 3-dichlorotoluene, 2,3-dibromotoluene, 2,3-diiotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3,4-diiotoluene, 2,3- Dimethylsulfonyloxybenzene, 3,4-dimethylsulfonyloxybenzene, m-dichlorobenzene, m-dibromobenzene, m-diiobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2 , 4-dibromotoluene, 2,4-diiotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiotoluene, 2,6-dichlorotoluene, 2,6 -Dibromotoluene, 2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 2,4-dichloro Benzotrifluoride, 2,4-dibromobenzotrifluoride, 2,4-diiodinebenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3 , 5-diiodinebenzotrifluoride, 1,3-dibromo-2,4,5,6-tetrafluorobenzene, 2,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol, 2,4 Dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-dichloro-t-butoxycarbonyloxyphenyl, 3, 5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoic acid, 2,4 Methyl dichlorobenzoate, methyl 3,5-dichlorobenzoate, methyl 3,5-dibromobenzoate, methyl 2,4-dibromobenzoate, 2,4-dichlorobenzoic acid-t-butyl, 3,5-dichlorobenzoic acid -t-butyl, 2,4-dibromobenzoic acid -t-butyl, 3,5-dibromobenzoic acid -t-butyl, etc. are mentioned. have.
[284] The bisphenol compound may be substituted with a -0 M group (M is an alkali metal) with a basic compound containing sodium, potassium or the like.
[285] The compound represented by the formula (14) can be used alone or in combination of two or more.
[286] The ratio of the repeating structural unit in the polymer represented by the general formula (2) is 0 to 100 mol% and k is 0 to 100 mol% (wherein j + k = 100 mol%) in the general formula (2).
[287] As a synthesis method of the polymer represented by General formula (2), it can obtain by heating a bisphenol compound and a dihalogenation compound in a solvent in presence of an alkali metal compound.
[288] The use ratio of the said bisphenol compound and the dihalogenated compound is 45-55 mol%, Preferably it is 48-52 mol%, The dihalogenated compound is 55-45 mol%, Preferably it is 52-48 mol% of a bisphenol compound. When the use ratio of a bisphenol compound exceeds 45 and 55, it is difficult to raise the molecular weight of a polymer, and the applicability | paintability of a coating film may be inferior.
[289] Examples of the alkali metal compound used at this time include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium hydrogen carbonate, lithium carbonate, sodium hydride, potassium hydride, lithium hydride, Sodium metal, potassium metal, lithium metal, and the like.
[290] These can also use 1 type (s) or 2 or more types simultaneously.
[291] The usage-amount of an alkali metal compound is 100-400 mol% normally with respect to a bisphenol compound, Preferably it is 100-250 mol%.
[292] Further, in order to promote the reaction, copper copper, cuprous chloride, cupric chloride, cuprous bromide, cuprous bromide, cuprous iodide, cuprous iodide, cuprous sulfate, cupric sulfate, Cocatalysts, such as cuprous acetate, cupric acetate, cuprous formate, and cupric formate, can also be used.
[293] The usage-amount of this cocatalyst is 1-50 mol% normally with respect to a bisphenol compound, Preferably it is 1-30 mol%.
[294] Examples of the solvent used for the reaction include pyridine, quinoline, benzophenone, diphenyl ether, dialkoxybenzene (carbon number of alkoxyl group is 1 to 4), trialkoxybenzene (carbon number of alkoxyl group is 1 to 4), di Phenyl sulfone, dimethyl sulfoxide, dimethyl sulfone, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrofuran, tetrahydrothiophene, sulfolane, N-methyl-2-pyrrolidone, N-ethyl- 2-pyrrolidone, dimethylimidazolidinone, gamma -butyrolactone, dimethylformamide, dimethylacetamide and the like can be used.
[295] These can also use 1 type (s) or 2 or more types simultaneously.
[296] As a reaction concentration at the time of synthesize | combining the polymer represented by General formula (2), it is 2-50 weight% based on the weight of a monomer, and reaction temperature is 50-250 degreeC.
[297] In addition, in order to remove metal salts or unreacted monomers generated during the synthesis of the polymer, filtering the reaction solution and reprecipitating the reaction solution with a poor solvent for the polymer, or washing with an acidic or alkaline aqueous solution desirable.
[298] Thus, the weight average molecular weight by the GPC method of the polymer represented by General formula (2) is 500-500,000 normally, Preferably it is 800-100,000.
[299] Polymer (3)
[300] I. Diyne-containing (co) polymers
[301] The diyne-containing (co) polymer of the present invention comprises 10 mol% or more of the repeating unit represented by the above formula (36), and has a weight average molecular weight of 500 to 1,000,000.
[302] Hereinafter, the diyne-containing (co) polymer of the present invention will be described in more detail for each component.
[303] 1. Repeating unit represented by formula (36)
[304] The diyne (co) polymer of this invention has 10 mol% or more of repeating units represented by following formula (36).
[305] <Formula 36>
[306]
[307] In the formula, Y represents a divalent organic group represented by the following formula (37) or (38), Ar represents a divalent organic group, and n is 0 or 1.
[308] <Formula 37>
[309]
[310] In the formula, R ³¹ and R ³² are the same or different and are in the cis position, and each represent a hydrogen atom, an alkyl group, or an aryl group.
[311] <Formula 38>
[312]
[313] In the formula, R ³³ to R ³⁶ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group or an aryl group.
[314] As an alkyl group represented by R <^31> and R <^32> in the said Chemical formula 37, a methyl group, an ethyl group, isopropyl group, n-propyl group, etc. are mentioned; A phenyl group etc. are mentioned as an aryl group.
[315] Examples of the alkyl group represented by R ³³ to R ³⁶ in Formula 38 include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, and the like; Examples of the halogenated alkyl group include trifluoromethyl group and pentafluoroethyl group; A phenyl group, pentafluorophenyl group, etc. are mentioned as an aryl group.
[316] As a divalent organic group represented by Y in the said General formula (36), a cis-vinylene group, a 1, 2- phenylene group, etc. are mentioned, for example.
[317] Examples of the divalent organic group represented by Ar in the above formula (36) include groups such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, and the following formulas (a) to (j).
[318] <Formula a>
[319]
[320] <Formula b>
[321]
[322] <Formula c>
[323]
[324] <Formula d>
[325]
[326] <Formula e>
[327]
[328] <Formula f>
[329]
[330] <Formula g>
[331]
[332] <Formula h>
[333]
[334] <Formula i>
[335]
[336] <Formula j>
[337]
[338] Among these, aromatic groups, such as a 1, 3- phenylene group, a 1, 4- phenylene group, and the said general formula a and d are preferable.
[339] The diyne (co) polymer used in the present invention is 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, particularly preferably 50 mol% or more of the repeating unit represented by the above formula (36). To have. If it is less than 10 mol%, solvent resistance is inadequate.
[340] 2. Weight average molecular weight
[341] The weight average molecular weight of the diyne (co) polymer of the present invention is 500 to 1,000,000, preferably 1,000 to 200,000. If it is less than 500, coating film property will become inadequate, and when it exceeds 1,00,0000, organic solvent solubility will become inadequate or a viscosity will become high, and the smoothness of a coating film (cured film) will become insufficient.
[342] II. Process for preparing diyne (co) polymer
[343] The method for producing a diyne-containing (co) polymer of the present invention is (Al) polymerizing at least one selected from the group consisting of a compound represented by the following formula (39) and a compound represented by the following formula (40) and a compound represented by the following formula (Bl) (Hereinafter, this method may be referred to as a "first manufacturing method.").
[344] Moreover, the manufacturing method of the diyne containing (co) polymer of this invention is represented by (A2) at least 1 sort (s) chosen from the group which consists of a compound shown by following formula (42) and a compound shown by following formula (43), and (B2) shown by following formula (44) It may be characterized by polymerizing the compound (hereinafter, this method may be referred to as a "second manufacturing method").
[345] 1. First manufacturing method
[346] The first production method polymerizes the polymerization component (A1) and the polymerization component (B1).
[347] (1) polymerization component (A1)
[348] A polymerization component (Al) is at least 1 sort (s) chosen from the group which consists of a compound shown by following formula (39) and a compound shown by Formula (40).
[349] ① Compound represented by the formula (39)
[350]
[351] In the formula, X ¹ and X ² are the same or different and represent a halogen atom in the cis configuration, and R ³⁷ and R ³⁸ are the same or different and each represent a hydrogen atom, an alkyl group or an aryl group.
[352] As a halogen atom of the cis arrangement represented by X <^1> and X <^2> in the said General formula (39), a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
[353] As an alkyl group represented by R <^37> and R <^38> in the said Chemical formula 39, a methyl group, an ethyl group, isopropyl group, n-propyl group, etc. are mentioned; A phenyl group etc. are mentioned as an aryl group.
[354] Examples of the compound represented by the above formula (39) include cis-1,2-dichloroethylene, cis-1,2-dibromoethylene, cis-diioethylene and the like.
[355] ② Compound represented by the formula (40)
[356]
[357] Wherein X ³ and X ⁴ are the same or different and represent a halogen atom or —SO ₃ R ³⁹ (R ³⁹ is an alkyl group, a fluoroalkyl group, an aryl group), and R ⁴⁰ to R ⁴³ are the same or different and are hydrogen Atom, a fluorine atom, an alkyl group, a halogenated alkyl group, and an aryl group are shown.
[358] As a halogen atom represented by X <^3> and X <^4> in the said General formula (40), a bromine atom and an iodine atom are mentioned, for example. In addition, -SO ₃ R ³⁹ (R ³⁹ the alkyl group represented by methyl group, ethyl group, isopropyl group, n- propyl group, etc.; a group such as a methyl group, pentafluoroethyl trifluoromethyl As the fluoroalkyl group represented by R ^39; R ³⁹ Examples of the aryl group include a phenyl group, pentafluorophenyl group, p-tolyl group, p-fluorophenyl group, and the like), for example, methyl sulfonyl group, trifluoromethyl sulfonyl group, and phenyl sulfony A hydroxy group, a p-tolyl sulfonyl oxy group, a p-fluorophenyl sulfonyl oxy group, etc. are mentioned.
[359] As a compound represented by the said General formula (40), 1, 2- dibromo benzene, 1, 2- diiodobenzene, 1, 2- di (trifluoromethyl sulfonyl oxy) benzene, etc. are mentioned, for example.
[360] The compounds represented by the formulas (39) and (40), which are specific examples of the polymerization component (A1), may be used alone or in combination of two or more thereof.
[361] (2) polymerization component (B1)
[362] A polymerization component (B1) is a compound represented by following formula (41).
[363] HC≡C-Ar'-C≡CH
[364] In the formula, Ar 'represents a divalent organic group.
[365] As a bivalent organic group represented by Ar 'in the said General formula (41), a 1, 2- phenylene group, a 1, 3- phenylene group, a 1, 4- phenylene group, said Formula (a)-j etc. are mentioned, for example.
[366] Especially, a 1, 3- phenylene group, a 1, 4- phenylene group, said Formula a and d are preferable.
[367] Examples of the compound represented by the formula (41) include 1,2-diethynylbenzene, 1,3-diethynylbenzene, 1,4-diethynylbenzene, 1,2,4-triethynylbenzene, 1,3,5 -Triethynylbenzene, 2,5-diethynyltoluene, 3,4-diethynyltoluene, 4,4'- dietinyl biphenyl, 3,3'- dietinyl biphenyl, 3,4'- dietinyl bi Phenyl, 4,4'- dietinyldiphenyl ether, 3,3'- dietinyl diphenyl ether, 3,4'- dietinyl diphenyl ether, 4,4'- dietinyl benzophenone, 3,3'- Dietinylbenzophenone, 3,4'- dietinylbenzophenone, 4,4'- dietinyldiphenylmethane, 3,3'- dietinyldiphenylmethane, 3,4'- dietinyldiphenylmethane, 4, 4'- dietinyl benzoic acid phenyl ester, 3,3'- dietinyl benzoic acid phenyl ester, 3,4'- dietinyl benzoic acid phenyl ester, 4,4'- dietinyl benzanilide, 3,3'- dietinyl benzanilide , 3,4'-diethynylbenzanilide, 4,4'-diethynyldiphenylsulfide, 3,3'-diethynyldiphenylsulfide, 3,4'-diethynyldiphenylsulfide, 4,4 ' -Diethynyldiphenylsulfone, 3,3'- dietinyldiphenylsulfone, 3,4'- dietinyldiphenylsulfone, 2,4,4'-triethynyldiphenyl ether, 9,9-bis (4 -Ethynylphenyl) fluorene, 4,4 "-diethynyl-p-terphenyl, 4,4" -diethynyl-m-terphenyl, 4,4 "-diethynyl-o-terphenyl, 2,2 -Bis (4-ethynylphenyl) propane, 2,2-bis (4-ethynylphenyl) hexafluoropropane, bis (4-ethynylphenyl) diphenyl methane, 9,9-bis [4- (4 -Ethynylphenoxy) phenyl] fluorene, 9,9-bis [4- (3-ethynylphenoxy) phenyl] fluorene, 4,4'-diethynylbibenzyl, 1,4-diethynylnaphthalene, 9,10-diethynylanthracene, 2,6-diethynylpyridine, 2,3-diethynylthiophene, 2,5-diethynylthiophene, 3,4-diethynylthiophene, 2,5-diethynyl And furan, 4,4'-diethynyldibenzofuran and the like, and 1,2-diethynylbenzene, 1,3-diethynylbenzene, 1,4-diethynylbenzene, 1,2,4-trier Tinylbenzene, 1,3,5-triethynylbenzene, 2,5-diethynyltoluene, 3,4-diethynyltoluene, 4,4'-di Tinylbiphenyl, 4,4'- dietinyl biphenyl, 3,3'- dietinyl biphenyl, 3,4'- dietinyl biphenyl, 4,4'- dietinyl diphenyl ether, 3,3'- Diethynyl diphenyl ether, 3,4'- dietinyl diphenyl ether, and 9, 9-bis (4-ethynylphenyl) fluorene are especially preferable from a heat resistant viewpoint.
[368] The compound shown by the said General formula (41) which is a specific example of a polymerization component (B1) can be used individually by 1 type or in combination of 2 or more types.
[369] In the first production method, the molar ratio of the polymerization component (A1) and the polymerization component (B1) is preferably (A1) / (B1), preferably 0.1 to 2.0, more preferably 0.5 to 1.5, and particularly preferably 0.9. To 1.1.
[370] In the first production method, the polymerization component (A1) and the polymerization component (B1) are used in the presence of a catalyst system containing a transition metal compound (preferably a catalyst system composed of a palladium catalyst and a basic compound containing a palladium compound described later). It is preferable to polymerize.
[371] As a catalyst used for a 1st manufacturing method, the catalyst system containing a transition metal compound and a basic compound is preferable. As this catalyst system, what is comprised from the following component is preferable.
[372] 1) a compound consisting of a palladium salt and a ligand, or a palladium (salt) to which the ligand is coordinated (a ligand may be added if necessary),
[373] 2) monovalent copper compound
[374] Examples of the palladium salt include palladium chloride, palladium bromide, palladium iodide and the like. Examples of the ligand include triphenylphosphine, tri-o-tolylphosphine, tricyanophenylphosphine, tricyanomethylphosphine, and the like. Especially, triphenyl phosphine is preferable.
[375] As palladium (salt) to which the ligand was previously coordinated, for example, dichlorobis (triphenylphosphine) palladium, dibromobis (triphenylphosphine) palladium, diiobisbis (triphenylphosphine) palladium, dichlorobis (tri-) o-tolylphosphine) palladium, dichlorobis (tricyanophenylphosphine) palladium, dichlorobis (tricyanomethylphosphine) palladium, dibromobis (tri-o-tolylphosphine) palladium, dibromobis (tricyano Phenylphosphine) palladium, dibromobis (tricyanomethylphosphine) palladium, diiobisbis (tri-o-tolylphosphine) palladium, diiobisbis (tricyanophenylphosphine) palladium, diiobisbis (tricyano Methylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tetrakis (tri-o-tolylphosphine) palladium, tetrakis (tricyanophenylphosphine) palladium, tetrakis (tricyanomethylphosphine) palladium Etc. can be mentioned. Especially, dichlorobis (triphenyl phosphine) palladium and tetrakis (triphenyl phosphine) palladium are preferable.
[376] As a monovalent copper compound, copper chloride (I), copper bromide (I), copper iodide (I), etc. are mentioned, for example.
[377] The use ratio of the above catalyst is as follows.
[378] The use ratio of the palladium salt is preferably 0.0001 to 10 mol, more preferably 0.001 to 1 mol, with respect to 1 mol of the total amount of the polymerization components. If it is less than 0.001 mole, the polymerization may not proceed sufficiently, while if it is more than 10 moles, purification may become difficult.
[379] In addition, the use ratio of the ligand is preferably 0.004 to 50 mol, more preferably 0.004 to 5 mol, with respect to 1 mol of the total amount of the polymerization components. If it is less than 0.0004 moles, the polymerization may not proceed sufficiently, while if it exceeds 50 moles, purification may be difficult.
[380] The use ratio of the palladium (salt) in which the ligand is previously coordinated is preferably 0.0001 to 10 mol, more preferably 0.001 to 1 mol, based on 1 mol of the total amount of the polymerized component. If it is less than 0.0001 mole, the polymerization may not proceed sufficiently, while if it exceeds 10 moles, purification may be difficult.
[381] The use ratio of the * monovalent copper compound is preferably 0.001 to 10 mol, more preferably 0.001 to 1 mol, based on 1 mol of the total amount of the polymerization components. If it is less than 0.0001 mole, the polymerization may not proceed sufficiently, while if it exceeds 10 moles, purification may be difficult.
[382] On the other hand, examples of the basic compound include pyridine, pyrrole, piperazine, pyrrolidin, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, and monomethyl diethanol. Amine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicyclo undecene, tetramethylammonium hydrooxide, diethylamine, ammonia, n-butylamine, imidazole and the like. Especially, diethylamine, piperidine, and n-butylamine are preferable.
[383] * The use ratio of base is preferably 1 to 1000 moles, more preferably 1 to 100 moles with respect to 1 mole of the total amount of the polymerization components. If it is less than 1 mol, the polymerization may not proceed sufficiently, while if it exceeds 100 mol, it is not economical.
[384] In the manufacturing method used by this invention, a solvent can be used as needed. Although there is no restriction | limiting in particular as a polymerization solvent, For example, aromatic hydrocarbons, such as halogen solvents, such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, xylene, mesitylene, diethylbenzene, System solvents; Ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane, diglyme, and anisole: ketone solvents such as acetone, methyl ethyl ketone, 2-heptanone, and cyclohexanone; Ester solvent, such as ethyl acetate, ethyl lactate, (gamma)-butyrolactone; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. It is preferable to use these solvents after fully drying and deoxidizing.
[385] The monomer (polymerization component) concentration in the polymerization solvent is preferably 1 to 80% by weight, more preferably 5 to 60% by weight.
[386] Moreover, the polymerization temperature in a 1st manufacturing method becomes like this. Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC. Further, the polymerization time is preferably 0.5 to 100 hours, more preferably 1 to 40 hours.
[387] 2. Second manufacturing method
[388] The second production method polymerizes the polymerization component (A2) and the polymerization component (B2).
[389] (1) polymerization component (A2)
[390] A polymerization component (A2) is at least 1 sort (s) chosen from the group which consists of a compound shown by following formula (42) and a compound shown by following formula (43).
[391] ① Compound represented by chemical formula 42
[392]
[393] In the formula, R ⁴⁴ and R ⁴⁵ are the same or different and are in the cis position and represent a hydrogen atom, an alkyl group and an aryl group.
[394] As an alkyl group represented by R <^44> and R <^45> in the said General formula (42), a methyl group, an ethyl group, isopropyl group, n-propyl group, etc. are mentioned; A phenyl group etc. are mentioned as an aryl group.
[395] As a compound represented by the said General formula (42), Z-hexa-3-ene-1, 5- diyne etc. are mentioned, for example.
[396] ② the compound represented by chemical formula 43
[397]
[398] In the formula, R ⁴⁶ to R ⁴⁹ are the same or different and represent a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group, or an aryl group.
[399] As an alkyl group represented by R <^46> -R <^49> in the said Chemical formula 43, a methyl group, an ethyl group, isopropyl group, n-propyl group, etc .; Examples of the halogenated alkyl group include trifluoromethyl group and pentafluoroethyl group; A phenyl group, pentafluorophenyl group, etc. are mentioned as an aryl group.
[400] As a compound represented by the said General formula (43), 1, 2-diethynyl benzene etc. are mentioned, for example.
[401] The compounds represented by the formulas (42) and (43), which are specific examples of the polymerization component (A2), may be used alone or in combination of two or more thereof.
[402] (2) polymerization component (B2)
[403] A polymerization component (B2) is a compound shown by following formula (44).
[404]
[405] In the formula, X ⁵ and X ⁶ are the same or different and represent a halogen atom or —SO ₃ R ⁵⁰ (R ⁵⁰ is an alkyl group, a fluoroalkyl group, an aryl group), and Ar ″ represents a divalent organic group.
[406] Examples of the halogen atoms represented by X ⁵ and X ⁶ in the general formula (44) include bromine and iodine. In addition, -SO ₃ R ⁵⁰ (R ⁵⁰ the alkyl group represented by methyl group, ethyl group, isopropyl group, n- propyl group, etc.; a a methyl group, pentafluoroethyl trifluoromethyl As the fluoroalkyl group represented by the R ⁵⁰ group and the like; R ⁵⁰ Examples of the aryl group include phenyl group, pentafluorophenyl group, p-tolyl group, p-fluorophenyl group, and the like), for example, methylsulfonyloxy group, trifluoromethylsulfonyloxy group, and phenylsulfony. A hydroxy group, a p-tolyl sulfonyl oxy group, a p-fluoro sulfonyl oxy group, etc. are mentioned.
[407] Examples of the divalent aromatic group represented by Ar ″ in the general formula (44) include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and the formulas (a) to (j).
[408] Especially, a 1, 3- phenylene group, a 1, 4- phenylene group, said Formula (a) and (d) are preferable.
[409] As a compound represented by the said General formula (44), for example, 1, 2- dibromo benzene, 1, 3- dibromo benzene, 1, 4- dibromo benzene, 1, 2- di-iodine benzene, 1, 3-di Iodinebenzene, 1,4-diiodinebenzene, 1,2-di (trifluoromethylsulfononioxy) benzene, 1,3-di (trifluoromethylsulfonyloxy) benzene, 1,4-di (tri Fluoromethylsulfonioxy) benzene, 9,9-bis (4-bromophenyl) fluorene, 9,9-bis (4-iodinephenyl) fluorene, 9,9-bis (4-trifluoromethyl Sulfonyxyphenyl) fluorene, 9,9-bis [4- (4-bromophenoxy) phenyl] fluorene, 9,9-bis [4- (4-iodinephenoxy) phenyl] fluorene, 3 , 3'-dibromodiphenyl ether, 3,3'-diiodi diphenyl ether, 3,3'-di (trifluoromethylsulfononioxy) diphenyl ether, 3,4'-dibromodiphenyl ether , 3,4'-diiodi diphenyl ether, 3,4'-di (trifluoromethylsulfonyloxy) diphenyl ether, 4,4'-dibromodiphenyl ether, 4,4'-diiodine dipe Ether, 4,4'-di (trifluoromethylsulfonyloxy) diphenylether, 2,2-bis (4-bromophenyl) hexafluoropropane, 2,2-bis (4-iodinephenyl) hexa Fluoropropane, 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane, 2,5-dibromobenzotrifluoride, 1,2-dibromotetrafluorobenzene, 1,3-dibromotetrafluorobenzene, 1,4-dibromotetrafluorobenzene, etc. are mentioned.
[410] The compound shown by the said General formula (44) which is a specific example of a polymerization component (B2) can be used individually by 1 type or in combination of 2 or more types.
[411] In the second production method, the molar ratio of the polymerization component (A2) and the polymerization component (B2) is preferably (A2) / (B2) of 0.5 to 2.0, more preferably 0.7 to 1.5.
[412] (3) polymerization method
[413] In a 2nd manufacturing method, the polymerization method similar to a 1st manufacturing method can be used.
[414] Third manufacturing method
[415] In the third production method, the compound represented by Chemical Formula 41 is oxidatively polymerized in the presence of a catalyst.
[416] As a catalyst for oxidatively polymerizing the compound represented by the formula (41), a catalyst containing copper is preferable. As such a catalyst, for example, metal copper, cuprous chloride, cuprous chloride, cuprous bromide, cuprous bromide, cuprous iodide, cuprous iodide, cuprous sulfate, cuprous sulfate, cuprous sulfate, acetic acid Cuprous oxide, cupric acetate, cuprous formate, cuprous formate, cuprous oxide, cuprous oxide, cuprous oxide, copper (I) triflate, copper (I) methoxide, copper (II) triflate, copper ( II) methoxide, copper (II) acetylacetate, copper (II) dipyvaloyl methane, etc. are mentioned. Among these, monovalent copper compounds are preferable, and particularly preferred are cuprous chloride, cuprous bromide, cuprous iodide, cuprous acetate, and cuprous formate.
[417] The copper compound can also be used as a catalyst supported on silica or alumina.
[418] In addition, when polymerizing the compound represented by the formula (41), a promoter may be used to increase the molecular weight of the polymer. Such cocatalysts include, for example, pyridine, quinoline, pyrrole, piperazine, pyrrolidine, piperizine, picoline, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, dimethyl Monoethanolamine, monomethyldiethanolamine, triethanolamine, bipyridine, NN, N ', N'-tetramethylethylenediamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide Seeds, diethylamine, ammonia, methylamine, ethylamine, propylamine, butylamine, imidazole and the like, and pyridine, bipyridine, quinoline, N, N, N ', N'-tetramethylethylenediamine Particularly preferred.
[419] In this production method, the catalyst amount is 0.0001 to 10 mol, preferably 0.001 to 1 mol, based on 1 mol of the total amount of the compound represented by the formula (41). If it is less than 0.0001 mole, the polymerization may not proceed sufficiently, while if it exceeds 10 moles, purification may be difficult. The amount of the promoter used is 0.0004 to 50 mol, preferably 0.004 to 5 mol, based on 1 mol of the total amount of the compound represented by the formula (41). If it is less than 0.0004 mol, superposition | polymerization may not fully advance, and if it exceeds 50 mol, a polymer may precipitate.
[420] As a polymerization solvent which can be used by this manufacturing method, For example, Halogen-type solvents, such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene; Aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene and diethylbenzene; Ether solvents such as diethyl ether, tetrahydrofuran, dioxane, diglyme, and anisole; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone and cyclopentane; Ester solvent, such as methyl acetate, ethyl acetate, methyl lactate, ethyl lactate, (gamma)-butyrolactone, and (gamma)-butyrolactam; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylimidazolidinone; And polar solvents such as nitrobenzene, carbon disulfide, nitromethane and dimethyl sulfoxide. Preferably, nitrobenzene, chloroform, dichloromethane, 1,2-dichloroethane having excellent solubility of the polymer is preferable.
[421] The concentration of the compound represented by the formula (41) in the polymerization solvent is preferably 1 to 80% by weight, more preferably 5 to 60% by weight. If the concentration of the compound A is less than 1% by weight, the molecular weight of the polymer is less likely to increase, and if it is more than 80% by weight, the polymer may precipitate.
[422] Moreover, the said polymerization temperature is 0-150 degreeC normally, Preferably it is 10-100 degreeC. Moreover, polymerization time is 0.5 to 100 hours normally, Preferably it is 1 to 80 hours.
[423] In addition, the weight average molecular weight of polystyrene conversion of the said polymer is 500-200,000 normally.
[424] In the present invention, in order to advance the oxidative polymerization of the compound represented by the chemical formula (41), oxygen needs to be present in the solution. For this reason, it is necessary to inject | pour air and / or oxygen in the method of putting oxygen in air into a reaction liquid, or a reaction liquid by stirring a solution in air.
[425] (B) organic solvent
[426] The film-forming composition of the present invention is obtained by dissolving or dispersing the component (A) in the organic solvent (B).
[427] Examples of the organic solvent (B) used in the present invention include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane and n- Aliphatic hydrocarbon solvents such as octane, i-octane, cyclohexane and methylcyclohexane; Benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene Aromatic hydrocarbon solvents such as trimethylbenzene; Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol , sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, Monoalcohol solvents such as cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol and cresol; Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2 Polyhydric alcohol solvents such as ethyl hexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl Ketones such as ketones, di-i-butyl ketones, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone and pentone menstruum; Ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldi Oxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2- Ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether Diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Ether solvents such as propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-acetic acid Pentyl, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate Ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol mono-n-butyl acetate, propylene glycol monoacetic acid Methyl ether, propylene acetate monoethyl ether, propylene acetate Col monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate Ester solvents such as diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonic acid, dimethyl phthalate and diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpy Nitrogen-containing solvents such as rolidone; And sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane and 1,3-propanesultone.
[428] These solvents can be used individually by 1 type or in combination of 2 or more type.
[429] OTHER ADDITIVES
[430] The film-forming composition of the present invention includes colloidal silica, colloidal alumina, organic polymers other than the component (A), surfactants, silane coupling agents, triazene compounds, radical generators, compounds containing polymerizable double bonds, and polymerization. You may further add components, such as a triple bond.
[431] Examples of the organic polymer include a polymer having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound polymer, a dendrimer, a polyimide, a polyamic acid, a polyamide, a polyquinoxaline, and a polyoxadia. A sol, a fluorine-type polymer, the polymer which has a polyalkylene oxide structure, etc. are mentioned.
[432] As a polymer which has a polyalkylene oxide structure, the polymer which has a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, a polybutylene oxide structure, etc. is mentioned.
[433] Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivatives, ethylene oxide derivatives of alkylphenol formalin condensation, polyoxyethylene polyoxypropylene block Ether type compounds, such as a copolymer and polyoxyethylene polyoxypropylene alkyl ether, ether, such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene fatty acid alkanolamide sulfate Ester compound, polyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid Ether ester type compounds, such as ester, etc. are mentioned.
[434] As a polyoxyethylene polyoxypropylene block copolymer, the compound which has the following block structure is mentioned.
[435] -(X ') p- (Y') q-
[436] -(X ') p- (Y') q- (X ') r-
[437] Wherein, X 'is a group Y, which is represented by -CH ₂ CH ₂ O-' represents a group represented by _{-CH 2 CH (CH 3) O-} , p is 1 to 90, q is from 10 to 99, r Represents a number from 0 to 90.
[438] Among these, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, etc. Ether type compounds are mentioned as a more preferable example.
[439] These can also use 1 type (s) or 2 or more types simultaneously.
[440] As surfactant, a nonionic surfactant, anionic surfactant, cationic surfactant, an amphoteric surfactant, etc. are mentioned, for example, A fluorine-type surfactant, silicone type surfactant, polyalkylene oxide type surfactant, poly (Meth) acrylate type surfactant etc. are mentioned, Preferably, a fluorine type surfactant and silicone type surfactant are mentioned.
[441] Examples of the silane coupling agent include 3-glycidyloxypropyl trimethoxysilane, 3-aminoglycidyloxypropyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, and 3-glycidyloxy. Propyl methyldimethoxysilane, 1-methacryloxypropyl methyldimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl trie Methoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, 3-ureidopropyl trimethoxysilane, 3 -Ureidopropyl triethoxysilane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyl triethylene Triamine, N-triethoxysilylpropyl triethylenetriamine, 10-tri Oxysilyl-1,4,7-triadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanyl acetate, 9-trie Oxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl triethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane , N-phenyl-3-aminopropyl triethoxysilane, N-bis (oxyethylene) -3-aminopropyl trimethoxysilane, N-bis (oxyethylene) -3-aminopropyl triethoxysilane, poly ( Vinyl methoxy siloxane), poly (vinyl ethoxy siloxane), etc. are mentioned.
[442] These can also use 1 type (s) or 2 or more types simultaneously.
[443] As a triazene compound, a 1, 2-bis (3, 3- dimethyl triazenyl) benzene, a 1, 3-bis (3, 3- dimethyl triazenyl) benzene, a 1, 4-bis (3, 3-, Dimethyltriazenyl) benzene, bis (3,3-dimethyltriazenylphenyl) ether, bis (3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, bis (3,3 -Dimethyltriazenylphenyl) sulfide, 2,2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2, 2-bis [4- (3,3-dimethyltriazenylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazenyl) benzene, 2,7-bis (3,3-dimethyl Triazenyl) -9,9-bis [4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-methyl -4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-phenyl-4- (3,3-dimethyl Triazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9 -Bis [3-propenyl-4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-fluoro- 4- (3,3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3,5-difluoro-4- (3, 3-dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9-bis [3-trifluoromethyl-4- (3,3-dimethyltriazenyl) Phenyl] fluorene, etc. are mentioned.
[444] These can also use 1 type (s) or 2 or more types simultaneously.
[445] Examples of the radical generator include isobutyryl peroxide, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate, di-n-propylperoxydicarbonate, di Isopropyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxy neo Decanoate, di-2-ethoxyethylperoxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxy neodecanoate, dimethoxybutylperoxydicarbonate, di (3-methyl- 3-methoxybutylperoxy) dicarbonate, t-butylperoxy neodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 3,5, 5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 1,1,3,3-te Tramethylbutylperoxy 2-ethylhexanoate, succinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2 -Ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluoyl and benzoyl peroxide, benzoyl peroxide, t-butylperoxy isobutyl Late, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy ) Cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4, 4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy maleic acid, t-butyl Peroxy-3,3,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoyl Peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy Hexane, t-butylperoxy acetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate , Di-t-butylperoxy isophthalate, α, α'-bis (t-butylperoxy) diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di (t-butylper Oxy) hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, p-mentane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3, diiso Propylbenzenehydroperoxide, t-butyltrimethylsilperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumene hydroperoxide, t-hexylhydroperoxide, t-butylhydroperoxide and the like Organic peroxides;
[446] Dibenzyl, 2,3-dimethyl-2,3-diphenylbutane, α, α'-dimethoxy-α, α'-diphenylbibenzyl, α, α'-diphenyl-α-methoxybibenzyl, α , α'-diphenyl-α, α'-dimethoxybibenzyl, α, α'-dimethoxy-α, α'-dimethylbibenzyl, α, α'-dimethoxybibenzyl, 3,4-dimethyl- Bibenzyl compounds, such as a 3, 4- diphenyl- n-hexane and a 2,2,3,3- tetraphenyl succinate nitrile, are mentioned.
[447] These can also use 1 type (s) or 2 or more types simultaneously.
[448] As the compound containing a polymerizable double bond, for example, allylbenzene, diallylbenzene, triallylbenzene, allyloxybenzene, diallyloxybenzene, triallyloxybenzene, α, ω-diallyloxyalkane, α, ω-diallylalkenes, α, ω-diallylalkenes, allylamine, diallylamine, triallylamine, N-allylphthalimide, N-allylpyromellilimide, N, N'-diallylurea Allyl compounds such as triallyl isocyanurate and 2,2'-diallyl bisphenol A;
[449] Styrene, divinylbenzene, trivinylbenzene, stilbene, propenylbenzene, dipropenylbenzene, tripropenylbenzene, phenylvinyl ketone, methyl styryl ketone, α, ω-divinyl alkanes, α, ω-di Vinyl alkenes, α, ω-divinyl alkynes, α, ω-divinyloxy alkanes, α, ω-divinyl alkenes, α, ω-divinyl alkynes, α, ω-diacryloxyalkanes , α, ω-diacrylic alkenes, α, ω-diacrylic alkenes, α, ω-dimethacryloxyalkanes, α, ω-dimethacrylic alkenes, α, ω-dimethacrylic alkenes, Vinyl compounds such as bisacryloxybenzene, trisacryloxybenzene, bismethacryloxybenzene, trismethacryloxybenzene, N-vinylphthalimide, and N-vinyl pyromellitimide;
[450] The polyarylene ether containing 2,2'- diallyl-4, 4'- biphenol, the polyarylene containing 2,2'- diallyl-4, 4'- biphenol, etc. are mentioned.
[451] These can also use 1 type (s) or 2 or more types simultaneously.
[452] As a compound containing a polymerizable triple bond, the compound represented by following formula (15) and formula (16), or any one thereof is mentioned, for example.
[453]
[454]
[455] In the formula, R ²³ represents a 2 to m valent aromatic group, R ²⁴ represents a 2 to n valent aromatic group, R ²² represents an alkyl group having 1 to 3 carbon atoms, l is an integer of 0 to 5, m and n are each Independently, an integer of 2 to 6;
[456] In said Formula (15), R <^22> is a C1-C3 alkyl group, and a methyl group, an ethyl group, n-propyl group, and i-propyl group are mentioned. In addition, R <^23> in General formula (15) and R <^24> in General formula (16) are 2-M and 2-N-valent aromatic groups, respectively, For example, group represented by following formula (17) is mentioned.
[457]
[458] In the formula, M represents at least one group selected from -O-, -S-, -CH _2- , -C (CH ₃ ) _2- , and fluorenyl group.
[459] As a specific example of the compound represented by such a formula (15), the compound of the following formulas (18)-(29) is mentioned, for example.
[460]
[461]
[462]
[463]
[464]
[465]
[466]
[467]
[468]
[469]
[470]
[471]
[472] Moreover, as a specific example of the compound represented by the said General formula (16), the compound of the following general formulas (30-35) is mentioned, for example.
[473]
[474]
[475]
[476]
[477]
[478]
[479] Examples of the compound containing a polymerizable triple bond include ethynylbenzene, bis (trimethylsilylethynyl) benzene, tris (trimethylsilylethynyl) benzene, tris (trimethylsilylethynyl) benzene, and bis (trimethylsilylethynylphenyl ) Ether, trimethylsilylethynylbenzene, etc. are mentioned.
[480] The compound containing these polymerizable triple bonds can also use 1 type (s) or 2 or more types simultaneously.
[481] As for the total solid content concentration of the solution used by this invention, 1-30 weight% is preferable, and is adjusted suitably according to a use purpose. When the total solid concentration of the composition is 1 to 30% by weight, the film thickness of the coating film is in a suitable range, and the storage stability is also excellent.
[482] The chemical mechanical polishing stopper film thus obtained is useful for semiconductor device applications such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM because of its excellent resistance to CMP processing.
[483] Examples of the polishing method using the chemical mechanical polishing stopper film of the present invention include the following examples. After the chemical mechanical polishing stopper film of the present invention is formed on an insulating film formed on a substrate such as a silicon wafer, a SiO ₂ wafer, a SiN wafer, a SiC wafer, a SiCO wafer, a SiCN wafer, or a SiCON wafer, an opening is formed and the chemical mechanical polishing is performed. The wiring metal is filled on the stopper film and in the opening, and an unnecessary portion of the wiring metal is removed using a chemical mechanical polishing liquid.
[484] As the insulating film, inorganic insulating films such as polysiloxane, polysilsesuccioxane, CVD-SiO ₂ film, and CVD-carbon doped SiO ₂ film can be given.
[485] In order to form a chemical mechanical polishing stopper film on the insulating film, a coating liquid made of an organic polymer and an organic solvent is first applied by coating means such as spin coating, dipping, roll coating, or spray.
[486] The film thickness at this time can form a coating film with a thickness of about 0.02 to 1.5 micrometers by one coating and a thickness of about 0.04 to 3 micrometers by two coatings as a dry film thickness. Thereafter, the chemical mechanical polishing stopper film can be formed by drying at room temperature or by heating at a temperature of about 80 to 600 ° C for 5 to 240 minutes. At this time, a hot plate, an oven, a furnace, etc. can be used as a heating method, As a heating atmosphere, it can carry out in air | atmosphere, nitrogen atmosphere, argon atmosphere, under vacuum, under reduced pressure which adjusted oxygen concentration.
[487] Moreover, a chemical mechanical polishing stopper film can also be formed by irradiating an electron beam and an ultraviolet-ray.
[488] Next, an opening is formed in a two-layer film made of an insulating film and a chemical mechanical polishing stopper film, and a metal layer is deposited on the chemical mechanical polishing stopper and in the opening.
[489] Here, as the metal layer, a first metal film made of a barrier metal such as a titanium nitride (TiN) film, a tantalum (Ta) film, or a tantalum nitride (TaN) film, and a second metal made of an alloy or Cu compound composed mainly of Cu or Cu Deposited membranes are commonly used.
[490] The application example of this invention after metal film formation is shown to FIG. 1 (a).
[491] After the metal film is formed, unnecessary metal is removed by CMP to obtain the structure shown in Fig. 1B.
[492] Here, the polishing liquid capable of removing the metal film may be any one of known polishing liquids, and the chemical mechanical polishing stopper film of the present invention can suppress the film decrease and scratch of the insulating film with respect to any polishing liquid.
[493] <Example>
[494] Hereinafter, an Example is given and this invention is demonstrated further more concretely.
[495] In addition, "part" and "%" in an Example and a comparative example represent "weight part" and "weight%", respectively, unless there is particular notice.
[496] In addition, evaluation of the film forming composition in an Example is measured as follows.
[497] Weight average molecular weight (Mw)
[498] It measured by the gel permeation chromatography (GPC) method by the following conditions.
[499] Sample: Using tetrahydrofuran as a solvent, 1 g of sample was prepared by dissolving in 100 cc of tetrahydrofuran.
[500] Standard polystyrene: Standard polystyrene manufactured by Pressure Chemical, USA was used.
[501] Apparatus: high temperature high speed gel permeation chromatogram (Model 150-C ALC / GPC), manufactured by Waters, USA
[502] Column: SHODEX A-80M (50 cm in length) produced by Showa Denko Co., Ltd.
[503] Measuring temperature: 4 ℃
[504] Flow rate: 1 cc / min
[505] Relative dielectric constant
[506] The composition was applied on an 8 inch silicon wafer using a spin coating method, and the substrate was baked for 30 minutes at 100 ° C. on a hot plate and in an oven at 420 ° C. for 30 minutes. Aluminum was vapor-deposited on the obtained board | substrate, and the board | substrate for dielectric constant evaluation was produced. The relative dielectric constant was calculated from a capacitance value at 10 kHz using an HP16451B electrode manufactured by Yokogawa Hewlett Packard Co., Ltd. and an HP4284A Freshzone LCR meter.
[507] CMP resistance
[508] The coating film was CMP polished under the following conditions.
[509] Slurry: Silica-hydrogen peroxide
[510] Polishing pressure: 400 g / ㎠
[511] Polishing time: 180 seconds
[512] The following reference | standard evaluated from the film thickness change of the coating film before and behind CMP, and the external appearance test in the 350,000 lux surface observation lamp.
[513] (Circle): A film thickness change is 2% or less, and a scratch and peeling are not recognized by a coating film.
[514] X: The film thickness change exceeds 2%, or a flaw and peeling are recognized by a coating film.
[515] Synthesis Example 1
[516] To a three-necked flask, 75 g of sodium iodide, 13 g of nickel chloride anhydride, 15.7 g of triphenylphosphine, 19.6 g of zinc powder activated by acetic acid and 16.7 g of 9,9-bis (methylsulfonyloxy) fluorene were added thereto. After drying under vacuum under time, the three-necked flask was filled with argon gas. Subsequently, 50 ml of dry N, N-dimethylacetamide, 50 ml of dry tetrahydrofuran, and 10.8 g of 2,4-dichlorotoluene were added thereto, and the mixture was stirred under an argon stream of 70 ° C, and the reaction solution turned brown. After reacting at 70 degreeC for 20 hours in that state, the reaction liquid was put into 400 ml of 36% hydrochloric acid and 1600 ml of methanol, and the precipitate was collect | recovered.
[517] The obtained precipitate was added to chloroform and suspended, followed by extraction with an aqueous solution of 2 hydrochloric acid. Then, the chloroform layer was placed in methanol, and the precipitate was recovered and dried to obtain a white powdery polymer ① having a weight average molecular weight of 10,300.
[518] Polymer ① Dissolve 0.2 g of 2 g, 2,3-dimethyl-2,3-diphenylbutane, 0.2 g of 1,3,5-triethynylbenzene in 18 g of cyclohexanone and use a 0.2 µm pore filter. It filtered and the dielectric constant of the coating film was measured. The relative dielectric constant was 3.12.
[519] Synthesis Example 2
[520] 26 L of 9,9-bis (4-hydroxyphenyl) fluorene 26.48 g, 9,9-bis (4-hydro-) in a 1 L three-necked flask equipped with a nitrogen inlet tube, Dean-Stark and cooling tube 28.35 g of 3-methyloxyphenyl) fluorene, 45.60 g of potassium carbonate anhydride, 500 mL of dimethylacetamide and 150 mL of toluene were added, and the mixture was heated at 140 ° C. for 3 hours under a nitrogen atmosphere. After removing water and excess toluene produced at the time of salt formation, the reaction solution was cooled to room temperature. Then, 32.73 g of 4,4'- difluoro benzophenone was added to this reaction liquid, and it was made to react at 165 degreeC for 10 hours. After cooling, the reaction solution was poured into 5 L of 10% HCl-containing methanol and reprecipitated. The precipitate was sufficiently washed with filtration and ion-exchanged water, and then dried in a vacuum oven. This precipitate was redissolved in tetrahydrofuran to remove insoluble portions and then reprecipitated in methanol. The polymer was refine | purified by repeating this reprecipitation operation once again, and drying was performed at 80 degreeC in the vacuum oven for 12 hours. As a result, a white powdery polymer ② having a weight average molecular weight of 150,000 was obtained.
[521] 2 g of polymer ②, 0.2 g of 2,3-dimethyl-2,3-diphenylbutane, 0.2 g of 1,3,5-triethynylbenzene were dissolved in 18 g of cyclohexanone, and a 0.2 µm pore filter was used. It filtered and the dielectric constant of the coating film was measured. The relative dielectric constant was 3.24.
[522] Synthesis Example 3
[523] In a 1000 ml three-necked flask equipped with a thermometer, an argon gas introduction tube and a stirring device, 120 ml of tetrahydrofuran, 3.46 g of tetrakistriphenylphosphine palladium, 2.1 g of dichlorobistriphenylphosphine palladium, 1.44 g of copper iodide, and piperi 20 ml of Dean, 185.72 g of 4,4'-bis (2-iodinephenoxy) benzophenone was added. Subsequently, 65.48 g of 4,4'- dietinyl diphenyl ether were added, and it reacted at 25 degreeC for 20 hours. The reaction solution was repeatedly reprecipitated with 5 L of acetic acid twice, dissolved in cyclohexane, washed twice with ultrapure water, reprecipitated with 5 L of methanol, filtered and dried to precipitate, white powder having a weight average molecular weight of 35,000. A type polymer ③ was obtained.
[524] 2 g of the polymer (3) was dissolved in 18 g of cyclohexanone, filtered through a filter made of a teflon having a 0.2 µm pore diameter, and the dielectric constant of the coating film was measured. The relative dielectric constant was 3.19.
[525] Synthesis Example 4
[526] In a separable flask made of quartz, 77.04 g of methyltrimethoxysilane, 24.05 g of tetramethoxysilane, and 0.48 g of tetrakis (acetylacetonato) titanium were dissolved in 290 g of propylene glycol monopropyl ether, followed by stirring with a three-one motor. The solution temperature was stabilized at 60 ° C. 84 g of ion-exchanged water was then added to the solution over 1 hour. Then, after making it react at 60 degreeC for 2 hours, 25 g of acetylacetone were added, it was made to react for 30 more minutes, and the reaction liquid was cooled to room temperature. The solution containing methanol and water was removed by 149 g evaporation from the reaction liquid at 50 degreeC, and reaction liquid (1) was obtained.
[527] The weight average molecular weight of the hydrolyzed condensate (hydrolyzate and its condensate or any one thereof) obtained in this manner was 8,900.
[528] <Example 1>
[529] The reaction solution 1 obtained in Synthesis Example 4 was applied onto an 8-inch silicon wafer by spin coating, and the substrate A was baked on a hot plate for 1 minute at 100 ° C. in a nitrogen atmosphere at 420 ° C. for 30 minutes, and then the substrate A Got. The film thickness of the coating film at this time was adjusted to 500 nm.
[530] 2 g of the polymer obtained in Synthesis Example 1, 0.2 g of 2,3-dimethyl-2,3-diphenylbutane, 0.2 g of 1,3,5-triethynylbenzene were dissolved in 18 g of cyclohexanone, and having a pore diameter of 0.2 µm. Filtration was performed using a Teflon filter. This solution was applied onto the substrate A so as to have a film thickness of 100 nm by using a spin coating method, and the substrate was calcined at 100 ° C. for 2 minutes on a hot plate for 30 minutes in an oven at 420 ° C. in a nitrogen atmosphere.
[531] When the CMP tolerance of this board | substrate was evaluated, the film thickness change of the coating film before and behind CMP was 0.5%. In addition, no scratches or peelings were observed on the substrate even after CMP.
[532] <Example 2>
[533] 2 g of the polymer 2 obtained in Synthesis Example 2, 0.2 g of 2,3-dimethyl-2,3-diphenylbutane, 0.2 g of 1,3,5-triethynylbenzene were dissolved in 18 g of cyclohexanone, and 0.2 µm in diameter. Filtration was performed using a Teflon filter. This solution was applied onto the substrate A obtained by the same operation as in Example 1 using a spin coating method so as to have a film thickness of 100 nm, 2 minutes at 100 ° C. on a hot plate, and 30 minutes in an oven at 420 ° C. in a nitrogen atmosphere. The substrate was fired.
[534] When the CMP tolerance of this board | substrate was evaluated, the film thickness change of the coating film before and behind CMP was 0.8%. In addition, no scratches or peelings were observed on the substrate even after CMP.
[535] <Example 3>
[536] Commercially available polyarylene ether solution trade name SiLK I (manufactured by Dow Chemica1) was applied on the substrate A obtained by the same operation as in Example 1 so as to have a thickness of 100 nm by spin coating, and then heated to 100 ° C. on a hot plate. The board | substrate was baked for 30 minutes in the oven of 420 degreeC nitrogen atmosphere for 2 minutes.
[537] When the CMP tolerance of this board | substrate was evaluated, the film thickness change of the coating film before and behind CMP was 0.6%. In addition, no scratches or peelings were observed on the substrate even after CMP.
[538] <Example 4>
[539] On the board | substrate A obtained by the same operation as Example 1, the commercially available polyarylene ether solution brand name FLARE 2.0 (made by Honeywell) was apply | coated so that it might be set to film thickness of 100 nm by the spin coating method, and it was carried out at 100 degreeC on a hotplate. The board | substrate was baked for 30 minutes in the oven of 420 degreeC nitrogen atmosphere.
[540] When the CMP tolerance of this board | substrate was evaluated, the film thickness change of the coating film before and behind CMP was 0.7%. In addition, no scratches or peelings were observed on the substrate even after CMP.
[541] Example 5
[542] In Example 1, it evaluated similarly to Example 1 except having used the board | substrate with a 500 nm-thick CVD-TEOS film instead of the board | substrate A.
[543] When the CMP tolerance of this board | substrate was evaluated, the film thickness change of the coating film before and behind CMP was 0.7%. In addition, no scratches or peelings were observed on the substrate even after CMP.
[544] <Example 6>
[545] In Example 2, except that there was used a joined substrate (a carbon-doped SiO ₂ film film-forming by CVD apparatus of the company Applied Materials Ltd.) substrate A instead of just the Black Diamond film thickness of 500 nm in the same manner as in Example 1 Evaluated.
[546] When the CMP tolerance of this board | substrate was evaluated, the film thickness change of the coating film before and behind CMP was 0.7%. In addition, no scratches or peelings were observed on the substrate even after CMP.
[547] <Example 7>
[548] 2 g of the polymer (3) obtained in Synthesis Example 3 was dissolved in 18 g of cyclohexanone and filtered through a teflon filter having a 0.2 µm pore size. This solution was applied onto the substrate A obtained by the same operation as in Example 1 using a spin coating method so as to have a film thickness of 100 nm, 2 minutes at 100 ° C. on a hot plate, and 30 minutes in an oven at 420 ° C. in a nitrogen atmosphere. The substrate was fired.
[549] When the CMP tolerance of this board | substrate was evaluated, the film thickness change of the coating film before and behind CMP was 0.2%. In addition, no scratches or peelings were observed on the substrate even after CMP.
[550] <Example 8>
[551] In Example 7, it replaced with the board | substrate A similarly to Example 1 except having used the board | substrate with a 500 nm-thick Black Diamond film | membrane (carbon doped Si0 ₂ film formed by the CVD apparatus by Applied Materials). Evaluated.
[552] When the CMP tolerance of this board | substrate was evaluated, the film thickness change of the coating film before and behind CMP was 0.2%. In addition, no scratches or peelings were observed on the substrate even after CMP.
[553] Comparative Example 1
[554] It evaluated similarly to Example 1 except having carried out the CMP process of the board | substrate A obtained in Example 1 directly.
[555] The film thickness change before and after CMP was 5%, and several scratches were observed in the coating film after CMP.
[556] Comparative Example 2
[557] The evaluation was carried out in the same manner as in Example 1, except that the substrate on which the Black Diamond film of Example 6 (a carbon doped SiO ₂ film formed by a CVD apparatus manufactured by Applied Materials) was directly subjected to CMP treatment.
[558] The film thickness change before and after CMP was 4%, and several scratches were observed in the coating film after CMP.
[559] According to the present invention, by using a chemical mechanical polishing stopper film made of an organic polymer having a relative dielectric constant of 4 or less, it is possible to provide a semiconductor coating film (material for an interlayer insulating film) with little damage due to CMP treatment.

权利要求:
Claims (9)
[1" claim-type="Currently amended] A chemical mechanical polishing stopper film made of an organic polymer, and having a relative dielectric constant of 4 or less.
[2" claim-type="Currently amended] The chemical mechanical polishing stopper film according to claim 1, wherein the organic polymer is an aromatic polyarylene or an aromatic polyarylene ether or any one of them.
[3" claim-type="Currently amended] The chemical mechanical polishing stopper film according to claim 1, wherein the organic polymer is at least one selected from polymers having a repeating structural unit represented by the following general formulas (1) to (2).
<Formula 1>

<Formula 2>

In formula, R <^7> -R <^11> is respectively independently a C1-C20 hydrocarbon group, a cyano group, a nitro group, a C1-C20 alkoxyl group, an aryl group, or a halogen atom, X is -CQQ'- (here Q and Q 'may be the same or different and are at least one selected from the group consisting of a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group), and a fluorenylene group, and Y is -O-, -CO-, -COO-, -CONH-, -S-, -SO ₂ -and at least one selected from the group of phenylene groups, a represents 0 or 1, b to f are 0 to An integer of 4, g is from 5 to 100 mol%, h is from 0 to 95 mol%, i is from 0 to 95 mol% (wherein g + h + i = 100 mol%), j is from 0 to 100 mol% and k are 0-100 mol% (where j + k = 100 mol%).
[4" claim-type="Currently amended] The chemical mechanical polishing stopper film according to claim 1, wherein the organic polymer has a structure represented by the following Chemical Formula 36.
<Formula 36>

In the formula, Y represents a divalent organic group represented by the following formula (37) or (38), Ar represents a divalent organic group, and n is 0 or 1.
<Formula 37>

In the formula, R ³¹ and R ³² are the same or different and are in the cis position and each represent a hydrogen atom, an alkyl group or an aryl group.
<Formula 38>

In the formula, R ³³ to R ³⁶ are the same or different and each represents a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group or an aryl group.
[5" claim-type="Currently amended] The coating liquid which consists of (A) organic polymer and (B) organic solvent is apply | coated to a board | substrate, and is heated, The manufacturing method of the chemical mechanical polishing stopper film characterized by the above-mentioned.
[6" claim-type="Currently amended] A chemical mechanical polishing stopper film comprising an organic polymer is provided between the insulating film and the metal film when the metal film formed on the insulating film is removed using a polishing liquid.
[7" claim-type="Currently amended] 7. The chemical mechanical polishing method according to claim 6, wherein the metal film is made of a first metal film made of a barrier metal and a second metal film made of an alloy or Cu compound composed mainly of Cu or Cu formed thereon.
[8" claim-type="Currently amended] 7. The chemical mechanical polishing method according to claim 6, wherein the chemical mechanical polishing stopper film is at least one selected from polyarylene and polyarylene ether.
[9" claim-type="Currently amended] A layer having an opening as a two layer comprising an insulating film and a chemical mechanical polishing stopper film provided on the insulating film is formed over the semiconductor region, and the first metal film made of a barrier metal and Cu or Cu in the chemical mechanical polishing stopper film and the opening. Depositing a second metal film made of an alloy or a Cu compound containing as a main component, filling the inside of the opening with a deposited metal film, and removing the second metal film on the chemical mechanical polishing stopper film with a chemical mechanical polishing liquid. Polishing method.

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同族专利:

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公开号 | 公开日

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DE60130953T2|2008-07-17|

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KR100738774B1|2007-07-12|

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EP1188807A3|2003-12-10|

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EP1188807A2|2002-03-20|

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DE60130953D1|2007-11-29|

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TWI299192B|2008-07-21|

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US20020064953A1|2002-05-30|

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US20050003218A1|2005-01-06|

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US7153767B2|2006-12-26|

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EP1188807B1|2007-10-17|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-08-28|Priority to JP2000257536

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2000-08-28|Priority to JPJP-P-2000-00257536

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2001-08-25|Application filed by 마쯔모또 에이찌, 제이에스알 가부시끼가이샤

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2002-03-07|Publication of KR20020018005A

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2007-07-12|Application granted

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2007-07-12|Publication of KR100738774B1

优先权:

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申请号 | 申请日 | 专利标题

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JP2000257536|2000-08-28|

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JPJP-P-2000-00257536|2000-08-28|