Composition for Film Formation and Material for Forming Insulation Film

专利摘要:
PURPOSE: To obtain a composition for forming a film, as a material for the interlayer insulating film in semiconductor devices, which can make a coating film that has low dielectric property and excels in crack resistance, elastic modulus of film, and adhesiveness to a substrate. CONSTITUTION: A composition for forming a film containing an aromatic polyarylene and/or an aromatic polyarylene ether (A), a polyvinylsiloxane (B), and an organic solvent (C).
公开号:KR20020076126A
申请号:KR1020020015835
申请日:2002-03-23
公开日:2002-10-09
发明作者:노리야스 시노하라；가오리 시라또；다께시 오까다；미찌노리 니시까와；긴지 야마다
申请人:제이에스알 가부시끼가이샤；
IPC主号:

专利说明:

[0001] The present invention relates to a composition for forming a film,
[1] More particularly, the present invention relates to a film forming composition capable of forming a coating film having excellent low dielectric constant, crack resistance, coating film elastic modulus, and adhesion to a substrate as an interlayer insulating film material in a semiconductor device or the like will be.
[2] In recent years, in the use of electronic materials, circuit resistance and capacitance between wirings have increased due to high integration, multifunctionalization, and high performance, resulting in not only an increase in power consumption but also an increase in delay time, ) Is a big factor. Therefore, it is required to lower the parasitic resistance and the parasitic capacitance. One of the solutions is to reduce the parasitic capacitance and to cope with the high-speed operation of the device by covering the periphery of the wiring with the low dielectric interlayer insulating film. In addition, in applications related to LCD, besides low dielectric properties, there is a growing demand for transparency.
[3] Although polyimide is widely known as a heat-resistant organic material meeting this demand, since it contains an imide group having a high polarity, there is a problem of low dielectric constant, low absorbability and coloring, and satisfactory results can not be obtained.
[4] On the other hand, polyphenylene is known as a highly heat-resistant organic material that does not contain a polar group. This polyphenylene is excellent in heat resistance, but since the polyphenylene has low solubility in an organic solvent, a soluble group is generally introduced into the side chain. Examples of such polyphenylene include polymers described in United States Patent No. 5,214,044, International Patent Application Publication No. WO96 / 28491, European Patent Publication No. 629217, and the like.
[5] These polymers mainly comprise polyparaphenylene structures and partially copolymerize the flexible monomers. However, since they are soluble only in a specific organic solvent and have a problem of a high-viscosity solution caused by rigid molecules, the processability is never satisfactory .
[6] Bridges of polyphenylene polymers have also been studied for the purpose of imparting solvent resistance, physical heat resistance, and mechanical properties, and conventionally known bridge reactions using acetylene bonds have been known. However, polyphenylene (Polyarylene) structure and reaction are limited, and a special acetylene compound is also used as a raw material, and the curing temperature is also high, so that there is a problem in processing versatility.
[7] Further, in order to increase the workability and solubility of the polyarylene, the introduction of an ether element into the polymer has also been studied, but there is a problem in the heat resistance of the resulting polymer.
[8] As described above, there is a very small number of techniques for imparting curability to a simple process for improving low dielectric constant, crack resistance, coating film elastic modulus, and adhesiveness to a substrate.
[9] The present invention has been made in view of the above problems, and an object of the present invention is to provide a composition for forming a film which is excellent in low dielectric constant, crack resistance, coating film elastic modulus and adhesion to a substrate as an interlayer insulating film in a semiconductor device or the like.
[10] The present invention relates to a polyolefin resin composition comprising (A) either one of an aromatic polyarylene and an aromatic polyarylene ether,
[11] (B) a polymer having a repeating unit structure represented by the following formula (1), and
[12] (C) an organic solvent
[13] , Wherein the film forming composition is a film-forming composition.
[14]
[15] Wherein R ¹ is a hydrocarbon group of 1 to 5 carbon atoms, and a is an integer of 2 to 1000.
[16] The component (A) is preferably a polymer having at least one kind selected from the group consisting of repeating structural units represented by the following general formulas (2) to (5).
[17]
[18]
[19]
[20]
[21] In the formulas, R ² to R ⁸ each independently represent 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, X is -CQQ ' , Q 'is the same or may be different, a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group denotes) at least one member selected from the group, and a fluorenyl alkenylene group consisting of groups represented by, Y, R ⁹ to R ¹² are each independently at least one member selected from the group consisting of -O-, -CH ₂ -, -CO-, -COO-, -CONH-, -S-, -SO ₂ - and phenylene groups, J represents an integer of 0 to 4, k represents 0 to 95 mol%, and 1 represents 0 to 95 mol (provided that j + k + 1 M is 0 to 100 mol%, n is 0 to 100 mol% (m + n = 100 mol%), o is an integer of 0 to 3, p is an integer of 0 to 3, q Is 0 to 10 0 mol%, and r is 0 to 100 mol% (provided that q + r = 100 mol%).
[22] The component (A) preferably contains at least one member selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a reactive double bond, and a reactive triple bond in the polymer.
[23] As the polymer constituting the component (B), a polymer represented by the above formula (1) is preferable.
[24] The proportion of the components (A) and (B) is 0.001 to 10 parts by weight based on 100 parts by weight of the component (A).
[25] Next, the present invention relates to a material for forming an insulating film, which comprises the film-forming composition.
[26] ( A) Component
[27] The component (A) of the present invention is either an aromatic polyarylene and / or an aromatic polyarylene ether.
[28] (Hereinafter referred to as "polymer (1)"), a polymer having a repeating structural unit represented by the above formula (3) (hereinafter referred to as "polymer (2)") (Hereinafter referred to as "polymer (3)"), repeating structural units represented by the general formula (4) and repeating structural units represented by the general formula (5) Polymers having structural units are preferred.
[29] It is preferable that the component (A) contains at least one member selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a reactive double bond, and a reactive triple bond in the polymer in order to improve the heat resistance of the coating film.
[30] Polymer (1);
[31] Polymer (1) can be prepared, for example, by polymerizing a monomer containing a compound represented by the following formula (6) in the presence of a catalyst system containing a transition metal compound.
[32]
[33] Wherein R ² to R ³ are each independently 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, X is -CQQ ' Q and Q 'may be the same or different and are a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group, and a fluorenylene group, and c to d are Each independently represents an integer of 0 to 4, and Z represents an alkyl group, a halogenated alkyl group or an aryl group.
[34] Among the Q and Q 'constituting X in the above formula (6), examples of the alkyl group include methyl, ethyl, i-propyl, n-propyl, butyl, pentyl and hexyl; Examples of the halogenated alkyl group include a trifluoromethyl group, a pentafluoroethyl group and the like; Examples of the arylalkyl group include a benzyl group and a diphenylmethyl group, and the aryl group includes a phenyl group, a biphenyl group, a tolyl group, and a pentafluorophenyl group.
[35] As Z constituting -OSO ₂ Z in the formula (6), examples of the alkyl group include a methyl group and an ethyl group; Examples of the halogenated alkyl group include a trifluoromethyl group, a pentafluoroethyl group and the like; Examples of the aryl group include a phenyl group, a biphenyl group, a p-tolyl group, and a p-pentafluorophenyl group.
[36] The X in the formula (6) is preferably a divalent group represented by the following formulas (7) to (12). Of these, a fluorenylene group is more preferable.
[37]
[38]
[39]
[40]
[41]
[42]
[43] Specific examples of the compound (monomer) represented by Formula 6 include, for example,
[44] 2,2-bis (4-methylsulfonyloxyphenyl) hexafluoropropane,
[45] Bis (4-methylsulfonyloxyphenyl) methane,
[46] Bis (4-methylsulfonyloxyphenyl) diphenylmethane,
[47] 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) hexafluoropropane,
[48] 2,2-bis (4-methylsulfonyloxy-3-propenylphenyl) hexafluoropropane,
[49] 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane,
[50] 2,2-bis (4-methylsulfonyloxyphenyl) propane,
[51] 2,2-bis (4-methylsulfonyloxy-3-methylphenyl) propane,
[52] 2,2-bis (4-methylsulfonyloxy-3-propenylphenyl) propane,
[53] 2,2-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) propane,
[54] 2,2-bis (4-methylsulfonyloxy-3-fluorophenyl) propane,
[55] 2,2-bis (4-methylsulfonyloxy-3,5-difluorophenyl) propane,
[56] 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) propane,
[57] 2,2-bis (4-trifluoromethylsulfonyloxy) -3-propenylphenyl) propane,
[58] 2,2-bis (4-phenylsulfonyloxyphenyl) propane,
[59] 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) propane,
[60] 2,2-bis (4-phenylsulfonyloxy-3-propenylphenyl) propane,
[61] 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) propane,
[62] 2,2-bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[63] 2,2-bis (p-tolylsulfonyloxyphenyl) propane,
[64] 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane,
[65] 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane,
[66] 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane,
[67] 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) propane,
[68] 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) propane,
[69] 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) propane,
[70] Bis (p-tolylsulfonyloxy-3-fluorophenyl) propane,
[71] Bis (p-tolylsulfonyloxy-3,5-difluorophenyl) propane,
[72] 9,9-bis (4-methylsulfonyloxyphenyl) fluorene,
[73] 9,9-bis (4-methylsulfonyloxy-3-methylphenyl) fluorene,
[74] 9,9-bis (4-methylsulfonyloxy-3,5-dimethylphenyl) fluorene,
[75] 9,9-bis (4-methylsulfonyloxy-3-propenylphenyl) fluorene,
[76] 9,9-bis (4-methylsulfonyloxy-3-phenylphenyl) fluorene,
[77] Bis (4-methylsulfonyloxy-3-methylphenyl) diphenylmethane,
[78] Bis (4-methylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane,
[79] Bis (4-methylsulfonyloxy-3-propenylphenyl) diphenylmethane,
[80] Bis (4-methylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[81] Bis (4-methylsulfonyloxy-3,5-difluorophenyl) diphenylmethane,
[82] 9,9-bis (4-methylsulfonyloxy-3-fluorophenyl) fluorene,
[83] 9,9-bis (4-methylsulfonyloxy-3,5-difluorophenyl) fluorene,
[84] Bis (4-methylsulfonyloxyphenyl) methane,
[85] Bis (4-methylsulfonyloxy-3-methylphenyl) methane,
[86] Bis (4-methylsulfonyloxy-3,5-dimethylphenyl) methane,
[87] Bis (4-methylsulfonyloxy-3-propenylphenyl) methane,
[88] Bis (4-methylsulfonyloxyphenyl) trifluoromethylphenylmethane,
[89] Bis (4-methylsulfonyloxyphenyl) phenylmethane,
[90] 2,2-bis (4-trifluoromethylsulfonyloxyphenyl) hexafluoropropane,
[91] Bis (4-trifluoromethylsulfonyloxyphenyl) methane,
[92] Bis (4-trifluoromethylsulfonyloxyphenyl) diphenylmethane,
[93] 2,2-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) hexafluoropropane,
[94] 2,2-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) hexafluoropropane,
[95] 2,2-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane,
[96] 9,9-bis (4-trifluoromethylsulfonyloxyphenyl) fluorene,
[97] 9,9-bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) fluorene,
[98] 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) fluorene,
[99] 9,9-bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) fluorene,
[100] 9,9-bis (4-trifluoromethylsulfonyloxy-3-phenylphenyl) fluorene,
[101] Bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) diphenylmethane,
[102] Bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane,
[103] Bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) diphenylmethane,
[104] Bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[105] Bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) diphenylmethane,
[106] 9,9-bis (4-trifluoromethylsulfonyloxy-3-fluorophenyl) fluorene,
[107] 9,9-bis (4-trifluoromethylsulfonyloxy-3,5-difluorophenyl) fluorene,
[108] Bis (4-trifluoromethylsulfonyloxyphenyl) methane,
[109] Bis (4-trifluoromethylsulfonyloxy-3-methylphenyl) methane,
[110] Bis (4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl) methane,
[111] Bis (4-trifluoromethylsulfonyloxy-3-propenylphenyl) methane,
[112] Bis (4-trifluoromethylsulfonyloxyphenyl) trifluoromethylphenyl methane,
[113] Bis (4-trifluoromethylsulfonyloxyphenyl),
[114] 2,2-bis (4-phenylsulfonyloxyphenyl) hexafluoropropane,
[115] Bis (4-phenylsulfonyloxyphenyl) methane,
[116] Bis (4-phenylsulfonyloxyphenyl) diphenylmethane,
[117] 2,2-bis (4-phenylsulfonyloxy-3-methylphenyl) hexafluoropropane,
[118] 2,2-bis (4-phenylsulfonyloxy-3-propenylphenyl) hexafluoropropane,
[119] 2,2-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane,
[120] 9,9-bis (4-phenylsulfonyloxyphenyl) fluorene,
[121] 9,9-bis (4-phenylsulfonyloxy-3-methylphenyl) fluorene,
[122] 9,9-bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) fluorene,
[123] 9,9-bis (4-phenylsulfonyloxy-3-propenylphenyl) fluorene,
[124] 9,9-bis (4-phenylsulfonyloxy-3-phenylphenyl) fluorene,
[125] Bis (4-phenylsulfonyloxy-3-methylphenyl) diphenylmethane,
[126] Bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane,
[127] Bis (4-phenylsulfonyloxy-3-propenylphenyl) diphenylmethane,
[128] Bis (4-phenylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[129] Bis (4-phenylsulfonyloxy-3,5-difluorophenyl) diphenylmethane,
[130] 9,9-bis (4-phenylsulfonyloxy-3-fluorophenyl) fluorene,
[131] 9,9-bis (4-phenylsulfonyloxy-3,5-difluorophenyl) fluorene,
[132] Bis (4-phenylsulfonyloxyphenyl) methane,
[133] Bis (4-phenylsulfonyloxy-3-methylphenyl) methane,
[134] Bis (4-phenylsulfonyloxy-3,5-dimethylphenyl) methane,
[135] Bis (4-phenylsulfonyloxy-3-propenylphenyl) methane,
[136] Bis (4-phenylsulfonyloxyphenyl) trifluoromethylphenylmethane,
[137] Bis (4-phenylsulfonyloxyphenyl) phenylmethane,
[138] 2,2-bis (p-tolylsulfonyloxyphenyl) hexafluoropropane,
[139] Bis (p-tolylsulfonyloxyphenyl) methane,
[140] Bis (p-tolylsulfonyloxyphenyl) diphenylmethane,
[141] 2,2-bis (p-tolylsulfonyloxy-3-methylphenyl) hexafluoropropane,
[142] 2,2-bis (p-tolylsulfonyloxy-3-propenylphenyl) hexafluoropropane,
[143] 2,2-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) hexafluoropropane,
[144] 9,9-bis (p-tolylsulfonyloxyphenyl) fluorene,
[145] 9,9-bis (p-tolylsulfonyloxy-3-methylphenyl) fluorene,
[146] 9,9-bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) fluorene,
[147] 9,9-bis (p-tolylsulfonyloxy-3-propenylphenyl) fluorene,
[148] 9,9-bis (p-tolylsulfonyloxy-3-phenylphenyl) fluorene,
[149] Bis (p-tolylsulfonyloxy-3-methylphenyl) diphenylmethane,
[150] Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) diphenylmethane,
[151] Bis (p-tolylsulfonyloxy-3-propenylphenyl) diphenylmethane,
[152] Bis (p-tolylsulfonyloxy-3-fluorophenyl) diphenylmethane,
[153] Bis (p-tolylsulfonyloxy-3,5-difluorophenyl) diphenylmethane,
[154] 9,9-bis (p-tolylsulfonyloxy-3-fluorophenyl) fluorene,
[155] 9,9-bis (p-tolylsulfonyloxy-3,5-difluorophenyl) fluorene,
[156] Bis (p-tolylsulfonyloxyphenyl) methane,
[157] Bis (p-tolylsulfonyloxy-3-methylphenyl) methane,
[158] Bis (p-tolylsulfonyloxy-3,5-dimethylphenyl) methane,
[159] Bis (p-tolylsulfonyloxy-3-propenylphenyl) methane,
[160] Bis (p-tolylsulfonyloxyphenyl) trifluoromethylphenylmethane,
[161] Bis (p-tolylsulfonyloxyphenyl) phenylmethane and the like.
[162] The compound represented by the above formula (6) can be synthesized, for example, by the following production process.
[163] That is, when two or more equivalent amounts of a dihydroxy compound having two hydroxyl groups, for example, 2,2-bis (4-hydroxyphenyl) hexafluoropropane and dihydroxy compound are dissolved in a solvent, pyridine and the like are dissolved in a solvent , It can be used both as a solvent and as a base. If necessary, a catalyst such as 4-dimethylaminopyridine may be added.
[164] Then, sulfonic acid chloride or an anhydride thereof, for example, methanesulfonic acid chloride, is added dropwise over 5 to 60 minutes under a dry nitrogen stream while maintaining the temperature at 15 ° C or less, and then stirred at that temperature for 0 to 60 minutes. For 24 hours to prepare a suspension. The obtained suspension is reprecipitated in 3 to 20 times as much ice water, the precipitation is recovered, and the operation such as recrystallization is repeated to obtain a crystalline bis-sulfonate compound.
[165] Alternatively, first, a dihydroxy compound such as 2,2-bis (4-hydroxyphenyl) hexafluoropropane is dissolved in two equivalents of an alkali aqueous solution such as an aqueous solution of sodium hydroxide. On the other hand, the sulfonic acid chloride or an anhydride thereof, for example, methanesulfonic acid chloride is dissolved in an organic solvent such as toluene or chloroform, and if necessary, an interphase-transfer catalyst such as acetyltrimethylammonium chloride is added and stirred vigorously. The organic layer obtained by the reaction is purified to obtain the intended bis-sulfonate compound.
[166] In the present invention, at least one compound selected from the group consisting of the compounds represented by the general formulas (6) and (13) to (14) may be copolymerized.
[167]
[168] In the formulas, R ⁴ to R ⁵ each independently represent 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 ¹³ to R ¹⁴ are -OSO ₂ Z (where, Z represents an alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a denotes a bromine atom or an iodine atom, Y is _{-O-, -CH 2 -, -CO-,} -C00-, -CONH-, -S-, -SO ₂ - and phenylene group, b represents 0 or 1, and e to f represent an integer of 0 to 4.
[169] And such R ⁴ to R ⁵ in the halogen atom include fluorine atom, organic group-valent 1 is a methyl group as the alkyl group, an ethyl group, etc., and the like as a methyl group, pentafluoroethyl trifluoromethyl as a halogenated alkyl group, and the like propenyl group as an allyl group, an aryl Examples of the group include a phenyl group and a pentafluorophenyl group. Examples of Z constituting -OSO ₂ Z include a methyl group and an ethyl group as an alkyl group, a trifluoromethyl group as a halogenated alkyl group, and a phenyl group, a p-tolyl group and a p-fluorophenyl group as an aryl group.
[170] As the compound represented by the above formula (13), for example,
[171] 4,4'-dimethylsulfonyloxybiphenyl,
[172] 4,4'-dimethylsulfonyloxy-3,3'-diprophenylbiphenyl,
[173] 4,4'-dibromobiphenyl, 4,4'-diiodobiphenyl,
[174] 4,4'-dimethylsulfonyloxy-3,3'-dimethylbiphenyl,
[175] 4,4'-dimethylsulfonyloxy-3,3'-difluorobiphenyl,
[176] 4,4'-dimethylsulfonyloxy-3,3 ', 5,5'-tetrafluorobiphenyl,
[177] 4,4'-dibromoctafluorobiphenyl, 4,4'-
[178] 4,4-methylsulfonyloxy octafluorobiphenyl,
[179] 3,3'-diallyl-4,4'-bis (4-fluorobenzenesulfonyloxy) biphenyl,
[180] 4,4'-dichloro-2,2'-trifluoromethylbiphenyl,
[181] 4,4'-dibromo-2,2'-trifluoromethylbiphenyl,
[182] 4,4'-diiodo-2,2'-trifluoromethylbiphenyl,
[183] Bis (4-chlorophenyl) sulfone,
[184] 4,4'-dichlorobenzophenone,
[185] 2,4-dichlorobenzophenone, and the like.
[186] The compounds represented by the above formula (13) may be used singly or in combination of two or more.
[187]
[188] Wherein R ⁶ 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 ¹⁵ to R ¹⁶ are -OSO ₂ Z, An alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom, and g represents an integer of 0 to 4.
[189] And such as R ⁶ in a halogen atom include a fluorine atom, an organic group valency 1, such as a methyl group, pentafluoro as, halogenated alkyl group, or the like group as the alkyl group trifluoromethyl group, or the like propenyl group as an allyl group, a phenyl group as the aryl group, And a pentafluorophenyl group. Examples of the Z constituting -OSO ₂ Z include a methyl group, an ethyl group and the like as the alkyl group, a trifluoromethyl group and the like as the halogenated alkyl group, and a phenyl group, a p-tolyl group and a p-fluorophenyl group as the aryl group.
[190] Examples of the compound represented by the formula (14) include o-dichlorobenzene, o-dibromobenzene, o-diiodobenzene, o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene, 2,3 -Dibromotoluene, 2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene, 3,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene, Dibromobenzene, m-diiodobenzene, m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2,4-dibromoethane, But are not limited to, toluene, m-toluene, 2,4-diiodotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6- But are not limited to, toluene, toluene, 2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride, 2,4-diiodobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodobenzotrifluoride, 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, Bromobenzoic acid, 3,5-dibromobenzoic acid, methyl 2,4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, methyl 3,5-dibromobenzoate, methyl 2,4-dibromobenzoate, 2 T-butyl dibromobenzoate, t-butyl dibromobenzoate, t-butyl dibromobenzoate, t-butyl dibromobenzoate, t-butyl dibromobenzoate, And preferably, m-dichlorobenzene, 2,4-dichlorotoluene, 3,5-dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoro De, such as a 2, 4-dichloro-benzophenone, 4-dichloro-phenoxy benzene.
[191] The compounds represented by the above formula (13) may be used singly or in combination of two or more.
[192] The ratio of repeating structural units in the polymer (1) is 5 to 100% by mole, k is 0 to 95% by mole, and 0 to 95% by mole in the formula 1, provided that j + k + %)to be.
[193] The catalyst used in the production of the polymer (1) used in the present invention is preferably a catalyst system containing a transition metal compound,
[194] (1) a transition metal salt and a ligand, or a transition metal (salt) in which a ligand is coordinated and
[195] (2) In order to increase the polymerization rate, a "salt"
[196] Examples of the transition metal salt include nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate, palladium compounds such as palladium chloride, palladium bromide and palladium iodide, iron compounds such as iron chloride, iron bromide and iron iodide, Cobalt compounds such as cobalt, cobalt bromide, and cobalt iodide. Of these, nickel chloride and nickel bromide are particularly preferable.
[197] Examples of the ligand include triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene, 1,3-bis (diphenylphosphino) , 2'-bipyridine are preferable. The ligands may be used singly or in combination of two or more.
[198] The transition metal (salt) in which the ligand is coordinated in advance includes, for example, nickel chloride 2-triphenylphosphine, nickel bromide 2-triphenylphosphine, nickel iodide 2-triphenylphosphine, nickel nitrate 2-triphenylphosphine , Nickel chloride 2,2'piperidine, nickel bromide 2,2'bipyridine, nickel iodide 2,2'bipyridine, nickel nitrate 2,2'bipyridine, bis (1,5-cyclooctadiene) nickel, tetra (Triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like, but nickel chloride 2 triphenylphosphine, nickel chloride 2, 2 'bipyridine .
[199] Examples of the reducing agent usable in this catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium and the like, but zinc and manganese are preferable. These reducing agents can be activated by contacting them with an acid and an organic acid.
[200] Examples of the "salt" which can be used in these catalyst systems include 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, And ammonium compounds such as ethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide and ammonium tetraethylammonium sulfate. Of these, sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide, tetraethylammonium iodide .
[201] In the catalyst system, the proportion of each component is such that the transition metal salt or the transition metal (salt) in which the ligand is coordinated is 1 mole of the total amount of the compound represented by Formula 5, the compound represented by Formula 13 and the compound represented by Formula 14 Is generally from 0.0001 to 10 mol, preferably from 0.01 to 0.5 mol. When the amount is less than 0.0001 mol, the polymerization reaction does not proceed sufficiently, and when it exceeds 10 mol, the molecular weight decreases.
[202] When a transition metal salt and a ligand are used in such a catalyst system, the ratio of the ligand is usually 0.1 to 100 mol, preferably 1 to 10 mol, per mol of the transition metal salt. When the amount is less than 0.1 mol, the catalytic activity becomes insufficient, while when it exceeds 100 mol, the molecular weight is decreased.
[203] The ratio of the reducing agent in the catalyst system is generally 0.1 to 100 moles, preferably 1 to 100 moles per 1 mole of the total amount of the compound represented by the formula (5), the compound represented by the formula (13) and the compound represented by the formula 10 moles. When the amount is less than 0.1 mole, the polymerization does not proceed sufficiently, while when it exceeds 100 moles, purification of the resulting polymer sometimes becomes difficult.
[204] When the "salt" is used in the catalyst system, the ratio is generally 0.001 to 100 moles per mole of the total amount of the compound represented by the formula (5), the compound represented by the formula (13) , Preferably 0.01 to 1 mol. If the amount is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient. On the other hand, if it exceeds 100 mol, the purification of the obtained polymer sometimes becomes difficult.
[205] Examples of the polymerization solvent that can be used in the present invention include tetrahydrofuran, cyclohexanone, dimethylsulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, , γ-butyrolactone, γ-butyrolactam and the like, and tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone are preferable. These polymerization solvents are preferably used after being sufficiently dried.
[206] The concentration of the total amount of the compound represented by the formula (5), the compound represented by the formula (13) and the compound represented by the formula (13) in the polymerization solvent is usually 1 to 100% by weight, preferably 5 to 40% by weight.
[207] The polymerization temperature for polymerizing the polymer (1) is usually from 0 to 200 캜, preferably from 50 to 80 캜. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.
[208] The weight average molecular weight of the polymer (1) in terms of polystyrene is usually 1,000 to 1,000,000.
[209] Polymer (2);
[210] The polymer (2) represented by the general formula (3) can be prepared, for example, by polymerizing a monomer containing a compound represented by the following general formulas (15) to (17) in the presence of a catalyst system.
[211]
[212] Wherein R ² to R ³ are each independently 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, X is -CQQ ' , Q 'may be the same or different and are a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group, and a fluorenylene group, and c to d are 0 And R ¹⁷ to R ¹⁸ represent at least one member selected from the group consisting of a hydroxyl group, a halogen atom and a -OM group (M is an alkali metal).
[213] Specific examples of the compound (monomer) represented by the formula (15) include, for example,
[214] 2,2-bis (4-hydroxyphenyl) hexafluoropropane,
[215] Bis (4-hydroxyphenyl) methane,
[216] Bis (4-hydroxyphenyl) diphenylmethane,
[217] 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane,
[218] 2,2-bis (4-hydroxy-3-propenylphenyl) hexafluoropropane,
[219] 2,2-bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane,
[220] 2,2-bis (4-hydroxyphenyl) propane,
[221] 2,2-bis (4-hydroxy-3-methylphenyl) propane,
[222] 2,2-bis (4-hydroxy-3-propenylphenyl) propane,
[223] 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane,
[224] 2,2-bis (4-hydroxy-3-fluorophenyl) propane,
[225] 2,2-bis (4-hydroxy-3,5-difluorophenyl) propane,
[226] 2,2-bis (4-chlorophenyl) hexafluoropropane,
[227] Bis (4-chlorophenyl) methane,
[228] Bis (4-chlorophenyl) diphenylmethane,
[229] 2,2-bis (4-chloro-3-methylphenyl) hexafluoropropane,
[230] 2,2-bis (4-chloro-3-propenylphenyl) hexafluoropropane,
[231] 2,2-bis (4-chloro-3,5-dimethylphenyl) hexafluoropropane,
[232] 2,2-bis (4-chlorophenyl) propane,
[233] 2,2-bis (4-chloro-3-methylphenyl) propane,
[234] 2,2-bis (4-chloro-3-propenylphenyl) propane,
[235] 2,2-bis (4-chloro-3,5-dimethylphenyl) propane,
[236] 2,2-bis (4-chloro-3-fluorophenyl) propane,
[237] 2,2-bis (4-chloro-3,5-difluorophenyl) propane,
[238] 2,2-bis (4-chlorophenyl) hexafluoropropane,
[239] Bis (4-bromophenyl) methane,
[240] Bis (4-bromophenyl) diphenylmethane,
[241] 2,2-bis (4-bromo-3-methylphenyl) hexafluoropropane,
[242] 2,2-bis (4-bromo-3-propenylphenyl) hexafluoropropane,
[243] 2,2-bis (4-bromo-3,5-dimethylphenyl) hexafluoropropane,
[244] 2,2-bis (4-bromophenyl) propane,
[245] 2,2-bis (4-bromo-3-methylphenyl) propane,
[246] 2,2-bis (4-bromo-3-propenylphenyl) propane,
[247] 2,2-bis (4-bromo-3,5-dimethylphenyl) propane,
[248] 2,2-bis (4-bromo-3-fluorophenyl) propane,
[249] 2,2-bis (4-bromo-3,5-difluorophenyl) propane,
[250] Bis (4-fluorophenyl) methane,
[251] Bis (4-fluorophenyl) diphenylmethane,
[252] 2,2-bis (4-fluoro-3-methylphenyl) hexafluoropropane
[253] 2,2-bis (4-fluoro-3-propenylphenyl) hexafluoropropane,
[254] 2,2-bis (4-fluoro-3,5-dimethylphenyl) hexafluoropropane,
[255] 2,2-bis (4-fluorophenyl) propane,
[256] 2,2-bis (4-fluoro-3-methylphenyl) propane,
[257] 2,2-bis (4-fluoro-3-propenylphenyl) propane,
[258] 2,2-bis (4-fluoro-3,5-dimethylphenyl) propane,
[259] 2,2-bis (4-fluoro-3-fluorophenyl) propane,
[260] 2,2-bis (4-fluoro-3,5-difluorophenyl) propane, and the like.
[261] Of the above compounds, the compound having a hydroxyl group can be substituted with a -OM group (M is an alkali metal) by a basic compound containing sodium, potassium or the like.
[262] In the present invention, two or more compounds represented by the above formula (15) may be copolymerized.
[263]
[264] Wherein R ⁴ to R ⁵ each independently represent 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 ¹⁹ to R ²⁰ each independently represent a hydroxyl group, a halogen -OM group (wherein M is an alkali metal), Y represents -O-, -CH ₂ -, -CO-, -COO-, -CONH-, -S- , -SO ₂ - and a phenylene group, b represents 0 or 1, and e to f represent an integer of 0 to 4.
[265] As the compound represented by the above formula (16), for example,
[266] 4,4'-dichlorobiphenyl, 4,4'-dibromobiphenyl,
[267] 4,4'-difluorobiphenyl, 4,4'-diiodobiphenyl, 4,4'-
[268] 4,4'-dihydroxybiphenyl,
[269] 4,4'-dihydroxy-3,3'-diprophenylbiphenyl,
[270] 4,4'-dihydroxy-3,3'-dimethylbiphenyl,
[271] 4,4'-dihydroxy-3,3'-diethylbiphenyl,
[272] 4,4'-dimethylhydroxy-3,3 ', 5,5'-tetrafluorobiphenyl,
[273] 4,4'-dibromoctafluorobiphenyl, 4,4'-
[274] 4,4'-dihydroxyoctafluorobiphenyl, 4,4'-
[275] 3,3'-diallyl-4,4'-bis (4-hydroxy) biphenyl,
[276] 4,4'-dichloro-2,2'-trifluoromethylbiphenyl,
[277] 4,4'-dibromo-2,2'-trifluoromethylbiphenyl,
[278] 4,4'-diiodo-2,2'-trifluoromethylbiphenyl,
[279] Bis (4-chlorophenyl) sulfone, bis (4-hydroxyphenyl) sulfone,
[280] Bis (4-chlorophenyl) ether, bis (4-hydroxyphenyl) ether,
[281] 4,4'-dichlorobenzophenone, 4,4'-dihydroxybenzophenone,
[282] 2,4-dichlorobenzophenone, 2,4-dihydroxybenzophenone, and the like.
[283] Among the above compounds, the compound having a hydroxyl group can be substituted with a -OM group (M is an alkali metal) by a basic compound containing sodium, potassium or the like.
[284] The compounds represented by the above formula (16) may be used singly or in combination of two or more.
[285]
[286] Wherein R ⁶ 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 ²¹ to R ²² are -OSO ₂ Z, An alkyl group, a halogenated alkyl group or an aryl group), a chlorine atom, a bromine atom or an iodine atom, and g represents an integer of 0 to 4.
[287] As the compound represented by the above formula (17), for example,
[288] 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 2,3-dihydroxytoluene, 2,5-dihydroxytoluene, 2,6-di Dihydroxytoluene, 3,5-dihydroxytoluene, o-dichlorobenzene, o-dibromobenzene, o-diiodobenzene, o-dimethylsulfonyloxybenzene, 2 , 3-dichlorotoluene, 2,3-dibromotoluene, 2,3-diiodotoluene, 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-diiodotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6- Dichlorotoluene, 2,6-dibromotoluene, 2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene, 2,6-dimethylsulfonyloxytoluene, 2,4- Benzotrifluoride, 2,4-dibromobenzotrifluoride, 2,4-diiodobenzotrifluoride, 3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 2,4-dichloropentyl alcohol, 3,5-dichlorobenzyl alcohol, 2, 3-dichlorobenzyl alcohol, 3-dibromo-2,4,5,6-tetrafluorobenzene, Dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-dichloro-t-butoxycarbonyloxyphenyl, Dichlorobenzoic acid, 3,5-dibromobenzoic acid, 3,5-dibromobenzoic acid, 2-dibromobenzoic acid, 2, , Methyl 4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, methyl 3,5-dibromobenzoate, methyl 2,4-dibromobenzoate, 2,4-dichlorobenzoate- Dibromobenzoic acid-t-butyl, 2,4-dibromobenzoic acid-t-butyl, 3,5-dibromobenzoic acid- .
[289] The compound having a hydroxyl group in the compound can be substituted with a -OM group (M is an alkali metal) by a basic compound containing sodium, potassium or the like.
[290] The compounds represented by the above formula (17) may be used alone or in combination of two or more.
[291] The proportion of repeating structural units in the polymer (2) represented by the general formula (3) is 0 to 100 mol% and 0 to 100 mol% (provided that m + n = 100 mol%) in the above formula (3).
[292] As a synthesis method of the polymer (2), for example, a dihydroxy compound having two hydroxyl groups and a dihalogenated compound are heated in a solvent in the presence of an alkali metal compound.
[293] The dihydroxy compound and the dihalogenated compound are used in an amount of 45 to 55 mol%, preferably 48 to 52 mol%, and 55 to 45 mol%, preferably 52 to 48 mol%, of the dihydroxy compound, %to be. When the proportion of the dihydroxy compound used is less than 45 mol%, or when it exceeds 55 mol%, the molecular weight of the polymer is hardly increased and the coating property of the coating film may be poor.
[294] Examples of the alkali metal compound to be used in this case include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium hydride, , Metal sodium, metal potassium, metal lithium and the like.
[295] These may be used alone or in combination of two or more.
[296] The amount of the alkali metal compound to be used is usually 100 to 400 mol%, preferably 100 to 250 mol%, based on the dihydroxy compound.
[297] In order to accelerate the reaction, it is also possible to use a metal salt such as metal copper, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cuprous sulfate, cupric sulfate, A promoter such as cuprous acetate, cupric acetate, cuprous formate, cupric formate, or the like may be used.
[298] The amount of this promoter to be used is usually 1 to 50 mol%, preferably 1 to 30 mol%, based on the dihydroxy compound.
[299] Examples of the solvent to be used in the reaction include pyridine, quinoline, benzophenone, diphenyl ether, dialkoxybenzene (the number of carbon atoms of the alkoxyl group is 1 to 4), trialkoxybenzene (the number of carbon atoms of the alkoxyl group is 1 to 4) Examples of the organic solvent include dimethyl sulfoxide, dimethyl sulfoxide, diethyl sulfoxide, diethyl sulfone, diisopropyl sulfone, tetrahydrofuran, tetrahydrothiophene, sulfolane, N-methyl- Pyrrolidone, dimethylimidazolidinone, -Butyrolactone, dimethylformamide, dimethylacetamide and the like can be used.
[300] These may be used alone or in combination of two or more.
[301] The reaction concentration in the synthesis of the polymer (2) is 2 to 50% by weight based on the weight of the monomer, and the reaction temperature is 50 to 250 캜.
[302] Further, in order to remove the metal salt and the unreacted monomers generated during the synthesis of the polymer, it is preferable to filter the reaction solution or to re-precipitate the reaction solution with a solvent which is a poor solvent for the polymer and to clean it with an acidic, alkaline aqueous solution.
[303] The weight average molecular weight of the polymer (2) obtained by the GPC method is usually 500 to 500,000, preferably 800 to 100,000.
[304] Polymer (3);
[305] Polymer (3) can be prepared, for example, by polymerizing a monomer containing a compound represented by the following general formulas (18) to (20) in the presence of a catalyst system.
[306]
[307] In the formulas, R ² to R ⁴ each independently represent 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 ⁹ to R ¹⁰ each independently -O-, -CH ₂ -, -CO-, -COO-, -CONH-, -S-, -SO ₂ - and phenylene groups, and R ²³ to R ²⁴ each independently Each of c to e independently represents an integer of 0 to 4, and o represents an integer of 0 to 3.
[308] Examples of the compound represented by the formula (18) include 4,4'-dibromodiphenyl ether, 4,4'-diiododiphenyl ether, 3,4'-dibromodiphenyl ether, 3,4 '-Diiododiphenyl ether, 2,4'-dibromodiphenyl ether, 2,4'-diiododiphenyl ether, 3,3'-dibromodiphenyl ether, 3,3'-diiodo Dodiphenyl ether, 2,2'-dibromodiphenyl ether, 2,2'-diiododiphenyl ether, 4,4'-dibromodiphenyl ketone, 4,4'-dibromodiphenyl ketone , 3,4'-dibromodiphenylketone, 3,4'-diiododiphenylketone, 2,4'-dibromodiphenylketone, 2,4'-diiododiphenylketone, 3,3 Dibromodiphenyl ketone, 3,3'-diiododiphenyl ketone, 2,2'-dibromodiphenyl ketone, 2,2'-diiododiphenyl ketone, 1,2-bis (2 Bis (3-bromophenoxy) benzene, 1,2-bis (2-iodophenoxy) benzene, ) Benzene, 1,2-bis (4-bromophenoxy) benzene, 1,2-bis Benzene, 1,3-bis (2-bromophenoxy) benzene, 1,3-bis (2-iodophenoxy) , 3-bis (3-iodophenoxy) benzene, 1,3-bis (4-bromophenoxy) benzene, Bis (2-bromophenoxy) benzene, 1,4-bis (3-iodophenoxy) benzene, Benzene, 1,4-bis (4-bromophenoxy) benzene, 1,4-bis (4-iodophenoxy) benzene, 1- (3-bromophenoxy) benzene, 1- (2-iodobenzoyl) -3- (2-iodophenoxy) benzene, 1- Benzene, 1- (3-iodobenzoyl) -3- (3-iodophenoxy) benzene, 1- (4- bromobenzoyl) -3- 4- (3-bromophenoxy) benzene, 1- (3-iodobenzoyl) -4- (3-iodophenoxy) benzene, 1- (4-bromobenzoyl) -4- (4-bromophenoxy ) Benzene, 1- (4-iodobenzoyl) -4- (4-iodophenoxy) benzene, 2,2'-bis (2-bromophenoxy) benzophenone, 2,2'-bis Benzophenone, 2,4'-bis (2-bromophenoxy) benzophenone, 2,4'-bis (2-iodophenoxy) benzophenone, 4,4'-bis 2-bromophenoxy) benzophenone, 4,4'-bis (2-iodophenoxy) benzophenone, 2,2'-bis (3-bromophenoxy) benzophenone, 2,2'-bis (3-iodophenoxy) benzophenone, 2,4'-bis (3-bromophenoxy) benzophenone, 2,4'-bis Bis (4-bromophenoxy) benzophenone, 2,2 '-bis (3-bromophenoxy) benzophenone, Bis (4-iodophenoxy) benzophenone, 2,4'-bis (4-bromophenoxy) benzophenone, 2,4'-bis Bis (4-bromophenoxy) benzophenone, 4, 4'-bis (4-iodophenoxy) benzophenone, 2,2'- '- bis (2-iodobenzoyl) benzo Benzophenone, 2,4'-bis (2-bromobenzoyl) benzophenone, 2,4'-bis (2-iodobenzoyl) benzophenone, Benzophenone, 2,2'-bis (3-bromobenzoyl) benzophenone, 2,2'-bis (3-iodobenzoyl) benzophenone, Bis (3-bromobenzoyl) benzophenone, 2,4'-bis (3-iodobenzoyl) benzophenone, 4,4'- Bis (4-bromobenzoyl) benzophenone, 2,2'-bis (4-iodobenzoyl) benzophenone, 2,2'- (4-bromobenzoyl) benzophenone, 2,4'-bis (4-iodobenzoyl) benzophenone, 4,4'-bis Bis (2-bromophenoxy) diphenyl ether, 3,4'-bis (2-iodophenoxy) diphenyl ether, 3,4'-bis (3-bromophenoxy) diphenyl ether, 3,4'-bis (3-iodophenoxy) diphenyl ether, 3,4'-bis Bis (4-iodophenoxy) diphenyl ether, 4,4'-bis (2-bromophenoxy) diphenyl ether, 4,4'-bis 4,4'-bis (3-bromophenoxy) diphenyl ether, 4,4'-bis (3-iodophenoxy) diphenyl ether, Bis (4-bromophenoxy) diphenyl ether, 3,4'-bis (4-bromophenoxy) diphenyl ether, 3,4'- (3-bromobenzoyl) diphenyl ether, 3,4'-bis (3-iodobenzoyl) diphenyl ether, 3,4'- Bis (4-bromobenzoyl) diphenyl ether, 4,4'-bis (4-bromobenzoyl) diphenyl ether, 3,4'- , 4,4'-bis (2-iodobenzoyl) diphenyl ether, 4,4'-bis (3-bromobenzoyl) Ether, 4,4'-bis (4-bromobenzoyl) diphenyl ether, 4,4'-bis And the like can be mentioned benzoyl) diphenyl ether.
[309] The compounds represented by the above formula (18) may be used singly or in combination of two or more.
[310]
[311] Wherein R ⁵ to R ⁷ are each independently 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 ¹¹ to R ¹² each independently -O-, -CH ₂ -, -CO-, -COO-, -CONH-, -S-, -SO ₂ - and phenylene groups, f to h are each independently 0 And p represents an integer of 0 to 3;
[312] Examples of the compound represented by Formula 19 include 4,4'-diethynylbiphenyl, 3,3'-diethynylbiphenyl, 3,4'-diethynylbiphenyl, 4,4'-di Diethynyldiphenyl ether, 3,4'-diethynylbenzophenone, 3,3'-diethynylbenzophenone, 3,4'-diethynyldiphenyl ether, 3,4'- Diethynylbenzophenone, 4,4'-diethynyldiphenylmethane, 3,3'-diethynyldiphenylmethane, 3,4'-diethynyldiphenylmethane, 4,4'-diethynylbenzoic acid phenyl ester, 3'-diethynylbenzoic acid phenyl ester, 3,4'-diethynylbenzoic acid phenyl ester, 4,4'-diethynylbenzanilide, 3,3'-diethynylbenzanilide, 3,4'-diethynylbenzene Anilide, 4,4'-diethynyldiphenyl sulfide, 3,3'-diethynyldiphenyl sulfide, 3,4'-diethynyldiphenyl sulfide, 4,4'-diethynyldiphenyl sulfone, 3 , 3'-diethynyldiphenyl sulfone, 3,4'diethynyldiphenyl sulfone, 2,4,4'-triethynyldiphenyl ether, 9,9-bis (4-ethynylphenyl) fluoro And the like diethoxy ethynyl -o- terphenyl -, 4,4 '- diethoxy-ethynyl -p- terphenyl, 4,4' - diethoxy-ethynyl -m- terphenyl, 4,4 ".
[313] The compounds represented by the above formula (19) may be used alone or in combination of two or more.
[314]
[315] R ⁸ represents 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 i represents an integer of 0 to 4.
[316] Examples of the compound represented by Formula 20 include 1,2-diethynylbenzene, 1,3-diethynylbenzene, 1,4-diethynylbenzene, 2,5-diethynyltoluene, And toluyl toluene.
[317] The compounds represented by the above formula (20) may be used singly or in combination of two or more.
[318] The polymer (3) is synthesized by, for example, polymerizing the compound represented by the formula (18), the compound represented by the formula (19) and the compound represented by the formula (20) or any one of them in the presence of a catalyst.
[319] The ratio of the compound represented by the general formula (18) to the compound represented by the general formula (19) and the compound represented by the general formula (20) or the ratio of any one of them to the compound represented by the general formula Is 0.8 to 1.2 moles, preferably 0.9 to 1.1 moles, and particularly preferably 0.95 to 1.05. When the total amount of the compound represented by the general formula (19) and the compound represented by the general formula (20) is less than 0.8 mol or exceeds 1.2 mol, the molecular weight of the obtained polymer (3) is hardly increased.
[320] In the production of the polymer (3), it is preferable to carry out polymerization in the presence of a catalyst system comprising a transition metal compound, preferably a catalyst system comprising a palladium catalyst and a basic compound containing a palladium compound described below.
[321] The catalyst that can be used at this time is preferably a catalyst system containing a transition metal compound and a basic compound. This catalyst is preferably composed of the following components.
[322] 1) a palladium salt and a ligand, or palladium coordinated with a ligand and a salt thereof, and optionally a compound in which a ligand is added,
[323] 2) monovalent copper compound.
[324] Examples of the palladium salt include palladium chloride, palladium bromide, and palladium iodide. Examples of the ligand include triphenylphosphine, tri-o-tolylphosphine, tricyanophenylphosphine, and tricyanomethylphosphine. Among them, triphenylphosphine is preferable.
[325] These compounds may be used alone or in combination of two or more.
[326] Examples of the palladium (salt) in which the ligand is coordinated in advance include palladium (triphenylphosphine) palladium, dibromobis (triphenylphosphine) palladium, diiodobis (triphenylphosphine) palladium, dichloro Palladium of dibromobis (tri-o-tolylphosphine), dibromobis (tri-o-tolylphosphine) palladium, dibromobis (tricyanophenylphosphine) palladium, Palladium, dibromobis (tricyanomethylphosphine) palladium, diiodobis (tri-o-tolylphosphine) palladium, diiodobis (tricyanophenylphosphine) palladium, (Tri-o-tolylphosphine) palladium, tetrakis (tricyanomethylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tetrakis Tricyanomethylphosphine) palladium and the like. Among them, dichlorobis (triphenylphosphine) palladium and tetrakis (triphenylphosphine) palladium are preferable.
[327] These compounds may be used alone or in combination of two or more.
[328] Examples of the monovalent copper compound include copper (I) chloride, copper (I) bromide and copper (I) iodide.
[329] These compounds may be used alone or in combination of two or more.
[330] The use ratio of the above catalyst is as follows.
[331] The use ratio of the palladium salt is preferably 0.0001 to 10 mol, more preferably 0.001 to 1 mol, per 1 mol of the total amount of the compounds represented by the general formulas (18) to (20). When the amount is less than 0.0001 mol, polymerization does not proceed sufficiently, and when it exceeds 10 mol, purification sometimes becomes difficult.
[332] The ratio of the ligand used is preferably 0.0004 to 50 mol, more preferably 0.004 to 5 mol, per mol of the total amount of the compounds represented by the general formulas (18) to (20). When the amount is less than 0.0004 mol, the polymerization does not proceed sufficiently, while when it exceeds 50 mol, purification sometimes becomes difficult.
[333] The ratio of the palladium (salt) to which the ligand is pre-coordinated is preferably 0.0001 to 10 mol, more preferably 0.001 to 1 mol, per 1 mol of the total amount of the compounds represented by the general formulas (18) to (20). When the amount is less than 0.0001 mol, polymerization does not proceed sufficiently, and when it exceeds 10 mol, purification sometimes becomes difficult.
[334] The amount of the monovalent copper compound used is preferably 0.0001 to 10 mol, more preferably 0.001 to 1 mol, per mol of the total amount of the compounds represented by the formulas (18) to (20). When the amount is less than 0.0001 mol, polymerization does not proceed sufficiently, and when it exceeds 10 mol, purification sometimes becomes difficult.
[335] Examples of the basic compound include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, Diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicyclo-undecene, tetramethylammonium hydroxide, diethylamine, ammonia, n-butylamine, imidazole and the like. Among them, diethylamine, piperidine and n-butylamine are preferable.
[336] These compounds may be used alone or in combination of two or more.
[337] The ratio of the base to be used is preferably 1 to 1000 moles, more preferably 1 to 100 moles, per 1 mole of the total amount of the compounds represented by the general formulas (18) to (20). When the amount is less than 1 mole, polymerization does not proceed sufficiently, and when it exceeds 100 moles, it is not economical.
[338] In the production of the polymer (3), a solvent may be used if necessary. The polymerization solvent is not particularly limited, and examples thereof include halogenated solvents such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene and dichlorobenzene;
[339] Aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene and diethylbenzene;
[340] Ether solvents such as diethyl ether, tetrahydrofuran, dioxane, jig lime, anisole, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether;
[341] Ketone solvents such as acetone, methyl ethyl ketone, 2-heptanone, cyclohexanone, and cyclopentanone;
[342] Ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate and -Butyrolactone;
[343] Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone. These solvents are preferably sufficiently dried and deoxygenated to be used.
[344] These compounds may be used alone or in combination of two or more.
[345] The concentration of the monomer (polymerization component) in the polymerization solvent is preferably 1 to 80% by weight, more preferably 5 to 60% by weight.
[346] Component (B)
[347] (B) is a polymer having a repeating unit structure represented by the above formula (1).
[348] Examples of the compound represented by the formula (1) include, for example,
[349] Polyvinyl butoxy siloxane, polyvinyl isobutoxysiloxane, polyvinyl isopropoxy siloxane, polyvinyl-n-propoxysiloxane, polyvinyl-n-butoxysiloxane, polyvinylisobutoxysiloxane, polyvinyl- Siloxane, and the like.
[350] The repeating unit of a is 2 to 1000, preferably 3 to 500, particularly preferably 5 to 500.
[351] The compounds represented by the formula (1) may be used alone or in combination of two or more.
[352] (C) an organic solvent
[353] The film forming composition of the present invention is obtained by dissolving or dispersing the component (A) and the component (B) in an organic solvent (C).
[354] Examples of the organic solvent (C) used in the present invention include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, Aliphatic hydrocarbon solvents such as octane, i-octane, cyclohexane, and methylcyclohexane; Examples of the organic solvent include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, , An aromatic hydrocarbon solvent such as trimethylbenzene; Propanol, n-butanol, i-butanol, sec-butanol, t-butanol, Butanol, 2-ethylhexanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol n-decanol, sec-undecyl alcohol, trimethyl nonyl 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- Polyhydric alcohol solvents such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and glycerin; acetone, methyl ethyl ketone, methyl- Butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, Ketone-based solvents such as 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone and fenchone; Ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, Ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 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- , Diethylene glycol mono-n-hexyl ether, ethoxy triglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Call monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyl-solvent include ether solvents such as tetrahydrofuran; Diethyl carbonate, methyl acetate, ethyl acetate, -Butyrolactone, -Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec- propyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, Methyl ethyl ketone, methyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, Glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate , Di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, diethyl lactate, dimethyl malonate, dimethyl phthalate and diethyl phthalate; N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, Nitrogen-containing type solvents such as pyrrolidone; Sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesultone.
[355] These solvents may be used alone or in combination of two or more.
[356] Other additives
[357] The film-forming composition obtained in the present invention may further contain components such as colloidal silica, colloidal alumina, an organic polymer, a surfactant, a triazine compound, a radical generator, a reactive double bond-containing compound and a reactive triple bond- You may.
[358] The colloidal silica is, for example, a dispersion in which a high-purity silicic anhydride is dispersed in the above-mentioned hydrophilic organic solvent, and usually has an average particle diameter of 5 to 30 nm, preferably 10 to 20 nm, and a solid content concentration of about 10 to 40% will be. Examples of such colloidal silica include, for example, methanol silica sol and isopropanol silica sol manufactured by Nissan Chemical Industries, Ltd.; Ltd., Oskar, manufactured by Showa Kagaku Kogyo Co., Ltd., and the like.
[359] As the colloidal alumina, alumina sol 520, 100, copper 200 manufactured by Nissan Chemical Industries, Ltd.; Alumina clear sol, alumina sol 10, and copper 132 manufactured by Kawaken Fine Chemicals Co., Ltd., and the like.
[360] Examples of the organic polymer include organic polymers such as compounds having a sugar chain structure, vinylamide polymers, (meth) acrylic polymers, aromatic vinyl compounds, dendrimers, polyimides, polyamic acids, polyamides, polyquinoxaline, polyoxadiazoles, Polymers, compounds having a polyalkylene oxide structure, and the like.
[361] Examples of the compound having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure.
[362] Specific examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene sterol ethers, polyoxyethylene lanolin derivatives, ethylene oxide derivatives of alkylphenol formalin condensates, polyoxyethylene polyoxypropylene block An ether type compound such as a polyoxyethylene polyoxypropylene alkyl ether, an ether such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyoxyethylene fatty acid alkanolamide sulfates Ester type compounds, polyethylene glycol fatty acid esters, ethylene glycol fatty acid esters, fatty acid monoglycerides, polyglycerin fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, And the like ether ester type compounds such as LE.
[363] Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structure.
[364] - (X ') p- (Y') q-
[365] - (X ') p- (Y') q- (X ') r-
[366] In the formulas, X 'is a group represented by -CH ₂ CH ₂ O-,
[367] Y 'is a group represented by -CH ₂ CH (CH ₃ ) O-,
[368] p represents 1 to 90, q represents 10 to 99, and r represents a number of 0 to 90. [
[369] Of these, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters Are more preferable examples.
[370] These may be used alone or in combination of two or more.
[371] Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and further include fluorine surfactants, silicone surfactants, polyalkylene oxide surfactants, poly (Meth) acrylate type surfactants, and the like. Of these, fluorine type surfactants and silicone type surfactants are preferable.
[372] Examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl Ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di 1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,1,2,2- , 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (perfluorooctanesulfone Amide) propyl] -N, N'-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidepropyltrimethylammonium salt, perfluoroalkyl-N- ethylsulfonylglycine salt, bis Ethyloctylsulfonyl-N-ethylaminoethyl), monoperfluoroalkylethylphosphoric acid esters and the like, Fluoro at least any one portion of the chain and a side chain there may be mentioned a fluorine-based surface active agent containing a compound having an alkylene group with an alkyl or fluoro.
[373] (Commercially available from Dainippon Ink and Chemicals, Inc.), F-top EF301, B-303, B-352 (manufactured by Shin-Aichi Kasei K.K.), F- SC-101, SC-102, SC-103, SC-104 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surfron S-382, (Available from Asahi Glass Co., Ltd.), BM-1000, BM-1100 (manufactured by Yusoh Corp.) and NBX-15 (manufactured by Neos Corporation) And a fluorine-based surfactant. Of these, Megapac F172, BM-1000, BM-1100 and NBX-15 are particularly preferable.
[374] As the silicone surfactant, for example, SH7PA, SH21PA, SH30PA, ST94PA (both manufactured by Toray Dow Corning Silicone Co., Ltd.) can be used. Of these, SH28PA and SH30PA are particularly preferable.
[375] The amount of the surfactant to be used is usually 0.00001 to 1 part by weight based on 100 parts by weight of the component (A).
[376] These may be used alone or in combination of two or more.
[377] Examples of the triazine compound include 1,2-bis (3,3-dimethyltriazinyl) benzene, 1,3-bis (3,3-dimethyltriazinyl) benzene, 1,4- Bis (3,3-dimethyltriazenylphenyl) methane, bis (3,3-dimethyltriazenylphenyl) sulfone, bis (3,3- Bis [4- (3,3-dimethyltriazinylphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2 , 2-bis [4- (3,3-dimethyltrienylphenoxy) phenyl] propane, 1,3,5-tris (3,3-dimethyltriazinyl) benzene, 2,7- Bis (3,3-dimethyltriazinyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazinyl) -9,9-bis [3- (3,3-dimethyltriazinyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazenyl) -9,9- Dimethyltriazenyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazinyl) -9,9-bis (3,3-dimethyltriazinyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazinyl) -9,9-bis [3-fluoro- (3,3-dimethyltriazinyl) phenyl] fluorene, 2,7-bis (3,3-dimethyltriazinyl) -9,9-bis [3,5- difluoro-4- Phenyl) fluorene, 2,7-bis (3,3-dimethyltriazinyl) -9,9-bis [3-trifluoromethyl- 4- (3,3- dimethyltriazenyl) phenyl ] Fluorene.
[378] These may be used alone or in combination of two or more.
[379] Examples of the radical generator include isobutyryl peroxide, , 'Bis (neodecanoylperoxy) diisopropylbenzene, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, di Isopropyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methyl Ethyl peroxyneodecanoate, di-2-ethoxyethyl peroxydicarbonate, di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxy neodecanoate, dimethoxybutyl peroxydicar T-butyl peroxyneodecanoate, 2,4-dichlorobenzoyl peroxide, t-hexyl peroxy pivalate, t-butyl peroxyneodecanoate, t-butyl peroxyneodecanoate, Butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1- (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, Ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, m-toluoyl and benzoyl peroxide, benzoyl peroxide Butyl peroxyisobutyrate, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1 , T-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclodecane, t-hexylperoxyisopropyl monocarbonate butylperoxymaleic acid, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxylureate, 2,5-dimethyl-2,5-di (m- Butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5- Butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) butane, t-butylperoxyacetate, Di-t-butylperoxy isophthalate, , '- bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl- (t-butylperoxy) hexane, t-butylcumylperoxide, di-t-butylperoxide, p- menthydroperoxide, 2,5- -3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyldihydroperoxide, t-butyl Hydroperoxide, dibenzyl, 2,3-dimethyl-2,3-diphenylbutane, , '- dimethoxy- , Non-benzyl, , '- diphenyl- -Methoxybibenzyl, , ' - diphenyl- , '- dimethoxybibenzyl, , ' - dimethoxy- , '- dimethyl Benzyl, , '- dimethoxybibenzyl, 3,4-dimethyl-3,4-diphenyl-n-hexane and 2,2,3,3-tetraphenylsuccinate nitrile.
[380] These may be used alone or in combination of two or more.
[381] Examples of the reactive double bond-containing compound include allylbenzene, diallylbenzene, triallylbenzene, allyloxybenzene, diallyloxybenzene, triallyloxybenzene, , - diallyloxyalkanes, , There may be mentioned diallylalkene, , - diallylalkene, allylamine, diallylamine, triallyl amine, N-arylphthalimide, N-allyl pyromellitimide, N, N'- Allyl isocyanurate, and 2,2'-diallyl bisphenol A;
[382] There may be mentioned styrene, divinylbenzene, trivinylbenzene, stilbene, propenylbenzene, diprophenylbenzene, triprophenylbenzene, phenylvinylketone, methylstyrylketone, α, Vinyl esters, vinyl esters, vinyl esters, vinyl esters, vinyl esters, vinyl esters, vinyl esters, vinyl esters, vinyl esters, vinyl esters, vinyl esters, vinyl esters, , , - diacryl alkenes, , - diacrylalkenes, , - dimethacryloxyalkanes, , - dimethacryloalkenes, , - dimethacryloalkenes, Vinyl compounds such as bisacryloxybenzene, trisacryloxybenzene, bismethacryloxybenzene, trismethacryloxybenzene, N-vinylphthalimide and N-vinyl pyromellitimide;
[383] Polyarylene ethers including 2,2'-diallyl-4,4'-biphenol,
[384] And polyarylenes including 2,2'-diallyl-4,4'-biphenol.
[385] These may be used alone or in combination of two or more.
[386] Examples of the reactive triple bond-containing compound include ethynylbenzene, diethynylbenzene, triethynylbenzene, trantrimethylsilylethynylbenzene, trimethylsilylethynylbenzene, bis (trimethylsilylethynyl) benzene, tris (trimethylsilyl (Phenylethynyl) benzene, bis (ethynylphenyl) ether, bis (trimethylsilylethynylphenyl) ether, bis (phenylethynyl) benzene, bis ) Ether, and the like.
[387] These may be used alone or in combination of two or more.
[388] The amount of at least one member selected from the group consisting of the radical generator, the reactive double bond-containing compound and the reactive triple bond-containing compound is 0.2 to 30 parts by weight, preferably 0.5 to 30 parts by weight, per 100 parts by weight of the component (A) To 25 parts by weight. When the amount is less than 0.2 part by weight, the heat resistance of the coating film may be poor. When the amount is more than 30 parts by weight, uniformity of application of the coating film is deteriorated.
[389] When the composition of the present invention contains at least one member selected from the group consisting of a radical generator, a reactive double bond-containing compound and a reactive triple bond-containing compound, the heat resistance of the coating film can be improved by the bridge.
[390] The total solid concentration of the film-forming composition of the present invention is preferably 2 to 30% by weight, and is appropriately adjusted according to the purpose of use. When the total solid concentration of the composition is from 2 to 30% by weight, the film thickness of the coating film becomes a suitable range, and storage stability is further improved.
[391] When the composition of the present invention is applied to a substrate such as a silicon wafer, a SiO ₂ wafer, or an SiN wafer, a coating means such as a spin coating method, a dipping method, a roll coating method, or a spraying method is used.
[392] The film thickness at this time is a dry film thickness, and it is possible to form a coating film having a thickness of 0.02 to 1.5 占 퐉 in one application and a thickness of 0.04 to 3 占 퐉 in two applications. Thereafter, it can be dried by drying at room temperature or by heating at a temperature of about 80 to 600 ° C for about 5 to 240 minutes.
[393] As the heating method at this time, a hot plate, an oven, a furnace or the like can be used. In the heating atmosphere, the heating can be performed under an atmosphere, under a nitrogen atmosphere, under an argon atmosphere, under vacuum, .
[394] In addition, a coating film can be formed by irradiating electron beams and ultraviolet rays.
[395] Since the coating film (interlayer insulating film) thus obtained is excellent in heat resistance, low dielectric constant, crack resistance, and adhesion to the substrate, it can be used as an interlayer insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM and D- A stopper film, a CMP stopper film, a diffusion barrier film of copper, a protective film such as a surface coating film of a semiconductor element, an intermediate layer and an antireflection film of a semiconductor manufacturing process using a multilayer resist, an interlayer insulating film of a multilayer wiring substrate, Lt; / RTI >
[396] <Examples>
[397] Hereinafter, the present invention will be described more specifically by way of examples.
[398] "Parts" and "%" in the examples and comparative examples represent "parts by weight" and "% by weight", respectively.
[399] The evaluation of the film-forming composition in the examples was carried out as follows.
[400] Weight average molecular weight (Mw)
[401] Was measured by Gel Permeation Chromatography (GPC) under the following conditions.
[402] Sample: Prepared by dissolving 1 g of a polymer (hydrolysis condensate) in 100 cc of tetrahydrofuran using tetrahydrofuran as a solvent.
[403] Standard polystyrene: Standard polystyrene manufactured by Freescale Chemical Co., USA was used.
[404] Apparatus: High-temperature high-speed gel permeation chromatogram (Model 150-C ALC / GPC) manufactured by Waters,
[405] Column: SHODEX A-80M (length 50 cm) manufactured by Showa Denko K.K.
[406] Measuring temperature: 40 ° C
[407] Flow rate: 1 cc / min
[408] Relative dielectric constant of coating film
[409] The composition sample was applied on a 20.32 cm (8 inch) silicon wafer by spin coating, and the substrate was baked on a hot plate for 1 minute at 100 占 폚 and for 9 minutes in a hot plate at 430 占 폚 in a nitrogen atmosphere. Aluminum was vapor-deposited on the obtained substrate to prepare a substrate for evaluation of relative dielectric constant. The relative dielectric constant was calculated from the capacitance value at 10 kHz using an HP16451B electrode manufactured by Yokogawa Hewlett-Packard Co., Ltd. and an HP4284A Precision LCR meter.
[410] Coating film crack resistance
[411] A sample of the composition was coated on a 20.32 cm (8 inch) silicon wafer by spin coating, and the substrate was baked on a hot plate for 1 minute at 100 占 폚 and for 9 minutes in a hot plate at 430 占 폚 in a nitrogen atmosphere. The film thickness of the final coating film at this time was 6 탆. The obtained substrate with a coating film was immersed in hot water at 60 DEG C for 2 hours, and the appearance of the coated film was observed with a surface observation lamp of 350,000 lux and evaluated according to the following criteria.
[412] ○; No cracks were observed on the surface of the coating film.
[413] ×; A crack was observed on the surface of the coating film.
[414] Coating film elasticity
[415] A sample of the composition was coated on a 20.32 cm (8 inch) silicon wafer by spin coating, and the substrate was baked on a hot plate for 1 minute at 100 占 폚 and for 9 minutes in a hot plate at 430 占 폚 in a nitrogen atmosphere. The film thus obtained was measured for elastic modulus by a continuous stiffness measurement method using an ultra-minute altimeter (Nanoindentator XP-manufactured by Nano Instruments).
[416] Coating film adhesion
[417] The composition sample was applied on a 20.32 cm (8 inch) silicon wafer with a SiC of 1,000 ANGSTROM by spin coating and the substrate was heated on a hot plate for 1 minute at 100 DEG C and in a hot plate at 430 DEG C for 12 minutes Lt; / RTI &gt; The substrate with the coated film was immersed in hot water at 60 DEG C for 2 hours, then ten stud pins were fixed on the obtained substrate using an epoxy resin and dried at 150 DEG C for 1 hour. This stud pin was subjected to a draw test using the Sebastian method, and the adhesion was evaluated according to the following criteria.
[418] ○; All 10 stud pins No peeling at the interface between the silicon wafer and the coating film
[419] X: Peeling occurred at the interface between the silicon wafer and the coating film
[420] &Lt; Synthesis Example 1 &
[421] 7.5 g of sodium iodide, 1.3 g of anhydrous nickel chloride, 15.7 g of triphenylphosphine, 19.6 g of zinc powder activated with acetic acid, and 16.7 g of 9,9-bis (methylsulfonyloxy) fluorene were added to a three-necked flask After drying for 24 hours under vacuum, the interior of the three-necked flask was filled with argon gas. Subsequently, 50 ml of anhydrous N, N-dimethylacetamide, 50 ml of anhydrous tetrahydrofuran and 10.8 g of 2,4-dichlorotoluene were added, and the mixture was stirred under an argon atmosphere at 70 ° C to give a brownish reaction liquid. The mixture was allowed to react at 70 ° C for 20 hours. The reaction mixture was poured into a mixture of 36% hydrochloric acid (400 ml) and methanol (1600 ml) to recover the precipitate.
[422] The obtained precipitate was added to chloroform to suspend, and the mixture was extracted with a 2N hydrochloric acid aqueous solution. The chloroform layer was poured into methanol to recover the precipitate and dried to obtain polymer 1 in the form of a white powder having a weight average molecular weight of 10,300.
[423] &Lt; Synthesis Example 2 &
[424] In a 1 L three-necked flask equipped with a nitrogen inlet tube, a Dean Stark and a cooling tube, 26.48 g of 9,9-bis (4-hydroxyphenyl) fluorene, Phenyl) fluorene, 45.60 g of anhydrous potassium carbonate, 500 ml of dimethylacetamide and 150 ml of toluene, and the mixture was heated at 140 占 폚 for 3 hours under a nitrogen atmosphere. After the water and excess toluene formed during the formation of the salt were removed, the reaction solution was cooled to room temperature. Then, 32.73 g of 4,4'-difluorobenzophenone was added to the reaction solution, and the mixture was reacted at 165 ° C for 10 hours. After cooling, the reaction solution was poured into 5 L of methanol containing 10% HCl to reprecipitate. The precipitate was filtered, sufficiently washed with ion-exchanged water, and pre-dried in a vacuum oven. This precipitate was redissolved in tetrahydrofuran to remove the insoluble portion, and then reprecipitated in methanol. This reprecipitation operation was repeated another time to purify the polymer, and the drying was carried out in a vacuum oven at 80 DEG C for 12 hours to obtain a polymer (2) in the form of a white powder having a weight average molecular weight of 150,000.
[425] &Lt; Synthesis Example 3 &
[426] To a 1000 ml three-necked flask equipped with a thermometer, an argon gas introducing tube and a stirrer, 150 ml of diethylamine, 2.1 g of dichlorobistriphenylphosphinepalladium, 0.286 g of copper iodide, 600 ml of 1,2-dichloroethane, 185.72 g of 4'-bis (2-iodophenoxy) benzophenone was added. Then, 65.48 g of 4,4'-diethynyldiphenyl ether was added, and the mixture was reacted at 50 ° C for 20 hours. This reaction solution was reprecipitated twice with 5 liters of acetic acid, dissolved in chloroform, washed twice with ultrapure water, and reprecipitated with 5 liters of cyclohexane. The precipitate was filtered and dried to obtain a polymer ③ having a weight average molecular weight of 35,000 .
[427] &Lt; Reference Example 1 &
[428] In a quartz separable flask, 77.04 g of methyltrimethoxysilane, 24.05 g of tetramethoxysilane and 0.48 g of acetic acid were dissolved in 290 g of propylene glycol monopropyl ether, stirred with a three-one motor, and the solution temperature was adjusted to 60 DEG C Stabilized. Next, 84 g of ion-exchanged water was added to the solution over one hour. Thereafter, the reaction was carried out at 60 DEG C for 2 hours, then 25 g of acetylacetone was added, and the reaction was continued for 30 minutes to cool the reaction solution to room temperature. 149 g of a solution containing methanol and water was evaporated from the reaction solution at 50 DEG C to obtain a reaction solution (1).
[429] The weight average molecular weight of the hydrolyzed condensate thus obtained was 1,900.
[430] &Lt; Example 1 >
[431] 2 g of the polymer (1) obtained in Synthesis Example 1 and 0.05 g of polyvinylmethoxysiloxane having a weight average molecular weight of 500 were dissolved in 18 g of cyclohexanone, and 0.5 g of polytetrafluoroethylene (manufactured by DuPont) Followed by filtration through a filter to obtain a film-forming composition of the present invention.
[432] The obtained composition was applied on a silicon wafer by spin coating.
[433] The relative dielectric constant of the coating film was measured to be 2.87, and the relative dielectric constant was 3 or less. The modulus of elasticity of the coating film was 6.3 GPa and excellent mechanical strength was exhibited. In addition, cracking did not occur even when the coating film was dipped in water, and peeling from the substrate did not occur in the evaluation of adhesion.
[434] &Lt; Examples 2 to 8 &
[435] The evaluation was made with the composition shown in Table 1 in the same manner as in Example 1.
[436] Example(A) ComponentComponent (B)(C) ComponentRelative dielectric constantCrack resistanceModulus of Elasticity (GPa)Adhesiveness OnePolymer 1 2 g0.05 g of polyvinylmethoxysiloxane (weight average molecular weight 500)18 g of cyclohexanone2.87○6.3○ 2Polymer 1 2 g0.05 g of polyvinylethoxysiloxane (weight average molecular weight 500)18 g of cyclohexanone2.88○6.4○ 3Polymer 2 2 g0.04 g of polyvinylethoxysiloxane (weight average molecular weight 500)18 g of cyclohexanone2.92○7.3○ 4Polymer 2 2 g0.04 g of polyvinylethoxysiloxane (weight average molecular weight 1000)18 g of cyclohexanone2.93○7.2○ 5Polymer ③ 2 g0.05 g of polyvinylmethoxysiloxane (weight average molecular weight 500)18 g of cyclohexanone2.97○5.8○ 6Polymer ③ 2 g0.01 g of polyvinylmethoxysiloxane (weight average molecular weight 500)18 g of cyclohexanone2.95○5.7○
[437] &Lt; Example 7 >
[438] Except that 0.04 g of a polyvinylmethoxysiloxane having a weight average molecular weight of 500 was added to 100 g of a commercially available polyarylene ether solution (trade name: SiLK I (manufactured by Dow Chemical Co., Ltd.)) The solution and the coating film were evaluated.
[439] The relative dielectric constant of the coated film was measured to be 2.67, and the relative dielectric constant was 3 or less. The elastic modulus of the coated film was 5.0 GPa and the mechanical strength was excellent. In addition, cracking did not occur even if the coating film was immersed in water, and peeling from the substrate did not occur in the evaluation of adhesion.
[440] &Lt; Example 8 >
[441] Except that 0.04 g of polyvinylethoxysiloxane having a weight average molecular weight of 1,500 was added to 100 g of a commercially available polyarylene ether solution (trade name FLARE 2.0 (Honeywell)) in Example 1, The solution and the coating film were evaluated in the same manner.
[442] The relative dielectric constant of the coated film was measured to be 2.87, and the relative dielectric constant was 3 or less. The elastic modulus of the coated film was 5.0 GPa and the mechanical strength was excellent. In addition, cracking did not occur even when the coating film was dipped in water, and peeling from the substrate did not occur in the evaluation of adhesion.
[443] &Lt; Reference Example 1 &
[444] Evaluation was made in the same manner as in Example 1 except that only 2 g of polymer (1) obtained in Synthesis Example 1 was dissolved in 18 g of cyclohexanone.
[445] The coated film exhibited a relative dielectric constant of 2.88, but in the evaluation of the coating film adhesion, interfacial peeling with the substrate was confirmed with six stud pull pins.
[446] <Reference Example 2>
[447] Evaluation was made in the same manner as in Example 1 except that only 2 g of the polymer (2) obtained in Synthesis Example 2 was dissolved in 18 g of cyclohexanone.
[448] The coated film showed a relative dielectric constant of 2.93, but in the evaluation of the coating film adhesion, the interface peeling between the substrate and the substrate was confirmed with five stud pull pins.
[449] <Reference Example 3>
[450] Evaluation was made in the same manner as in Example 1 except that only 2 g of the polymer (3) obtained in Synthesis Example 3 was dissolved in 18 g of cyclohexanone.
[451] The coated film exhibited a relative dielectric constant of 2.98, but the interface peeling between the substrate and the substrate was confirmed by the use of eight stud pull pins in the coating film adhesion evaluation.
[452] <Reference Example 4>
[453] The evaluation was carried out in the same manner as in Example 1 except that only a commercially available polyarylene ether solution (trade name: SiLK I (manufactured by Dow Chemical)) was used.
[454] The coated film exhibited a relative dielectric constant of 2.66, but in the evaluation of the coating film adhesion, the interface peeling between the substrate and the two stud pull pins was confirmed.
[455] <Reference Example 5>
[456] The evaluation was carried out in the same manner as in Example 1 except that only a commercially available polyarylene ether solution (trade name FLARE 2.0 (manufactured by Honeywell)) was used.
[457] The coating film exhibited a relative dielectric constant of 2.84, but in the evaluation of coating film adhesion, interfacial peeling with the silicon wafer was recognized with three stud pull pins.
[458] <Reference Example 6>
[459] Evaluation was conducted in the same manner as in Example 1 except that the reaction solution (1) obtained in Comparative Synthesis Example 1 was used.
[460] The relative dielectric constant of the coating film was 3.23, and a large number of cracks were generated in the coating film in the evaluation of crack resistance.
[461] According to the present invention,
[462] (A) an aromatic polyarylene and an aromatic polyarylene ether,
[463] (B) a siloxane polymer having a specific structure, and
[464] It is possible to provide a film forming composition (material for an interlayer insulating film) excellent in balance of low dielectric constant, crack resistance, coating film elastic modulus, adhesion with a substrate and the like by using a composition containing (C) an organic solvent.

权利要求:
Claims (5)
[1" claim-type="Currently amended] (A) an aromatic polyarylene and an aromatic polyarylene ether,
(B) a polymer having a repeating unit structure represented by the following formula (1), and
(C) an organic solvent
&Lt; / RTI &gt; based on the total weight of the composition.
&Lt; Formula 1 >

R ¹ is a hydrocarbon group of 1 to 5 carbon atoms, and a is an integer of 2 to 1000.
[2" claim-type="Currently amended] The film-forming composition according to claim 1, wherein the component (A) contains at least one member selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a reactive double bond, and a reactive triple bond.
[3" claim-type="Currently amended] The film-forming composition according to claim 1 or 2, wherein the component (A) is a polymer having at least one member selected from the group consisting of repeating structural units represented by the following general formulas (2) to (5).
(2)

(3)

&Lt; Formula 4 >

&Lt; Formula 5 >

In the formulas, R ² to R ⁸ each independently represent 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, X is -CQQ ' , Q 'is the same or may be different, a halogenated alkyl group, an alkyl group, a hydrogen atom, a halogen atom or an aryl group denotes) at least one member selected from the group, and a fluorenyl alkenylene group consisting of groups represented by, Y, R ⁹ to R ¹² are each independently at least one member selected from the group consisting of -O-, -CH ₂ -, -CO-, -COO-, -CONH-, -S-, -SO ₂ - and phenylene groups, J represents an integer of 0 to 4, k represents 0 to 95 mol%, and 1 represents 0 to 95 mol (provided that j + k + 1 M is 0 to 100 mol%, n is 0 to 100 mol% (m + n = 100 mol%), o is an integer of 0 to 3, p is an integer of 0 to 3, q Is 0 to 10 0 mol%, and r is 0 to 100 mol% (provided that q + r = 100 mol%).
[4" claim-type="Currently amended] The film-forming composition according to claim 1, wherein the ratio of the component (A) to the component (B) is 0.001 to 10 parts by weight based on 100 parts by weight of the component (A).
[5" claim-type="Currently amended] An insulating film forming material comprising the film forming composition according to any one of claims 1 to 4.

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同族专利:

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公开号 | 公开日

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JP2002285080A|2002-10-03|

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JP5320653B2|2013-10-23|

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TW583262B|2004-04-11|

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US6852370B2|2005-02-08|

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KR100885368B1|2009-02-26|

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EP1245638A1|2002-10-02|

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EP1245638B1|2009-01-14|

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US20020172652A1|2002-11-21|

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DE60230830D1|2009-03-05|

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:
2001-03-26|Priority to JPJP-P-2001-00088033

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2001-03-26|Priority to JP2001088033A

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2002-03-23|Application filed by 제이에스알 가부시끼가이샤

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2002-10-09|Publication of KR20020076126A

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2009-02-26|Application granted

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2009-02-26|Publication of KR100885368B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2001-00088033|2001-03-26|

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JP2001088033A|JP5320653B2|2001-03-26|2001-03-26|Film forming composition and insulating film forming material|