HK1069407B - Curable resin composition and cured product thereof - Google Patents
Curable resin composition and cured product thereof Download PDFInfo
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Description
Technical Field
The present invention relates to a curable resin composition comprising a combination of a bifunctional phenylene ether oligomer having a specific structure and a polyfunctional cyanate ester resin, and a cured product thereof. The polymer material excellent in heat resistance and having low dielectric characteristics can be prepared by curing the curable resin composition of the present invention. Such a curable resin composition has wide applications such as semiconductor encapsulating materials, electrical insulating materials, resins for copper-clad laminates, resists, encapsulating resins for electronic parts, resins for liquid crystal color filters, coating compositions, various coating agents, adhesives, raw materials for build-up laminates, and FRPs.
Background
Conventionally, cyanate ester resins have been used as a raw material of functional polymer materials. In recent years, as higher performance raw materials are required in the field of application, improvement of physical properties required as a functional polymer material has become more urgent. These physical properties, such as heat resistance, weather resistance, chemical resistance, low moisture absorption, high fracture toughness, low dielectric constant, and low dielectric loss tangent, are desirable.
In the field of printed circuit boards, for example, substrates having low dielectric characteristics are required in view of the signal attenuation problem accompanying the increase in signal frequency. Among thermosetting resins, cyanate ester resins are excellent in heat resistance and low dielectric characteristics, and thus there have been many patent applications in this respect, for example, a composition containing a cyanate ester resin and an epoxy resin (JP-B-46-41112), a method of using a composition containing a bismaleimide, a cyanate ester resin and an epoxy resin (JP-B-52-31279), a method of combining a polyfunctional phenol compound with a cyanate ester resin (JP-B-7-47637), and a method of combining a monofunctional phenol compound with a cyanate ester resin (patent No. 3261061).
However, the method of combining a polyfunctional phenol compound with a cyanate ester resin disclosed in JP-B-7-47637 is insufficient for high frequency applications because deterioration of dielectric characteristics occurs in the GHz zone. In addition, although the mixture of monofunctional phenol and cyanate ester resin of patent 3261061 is excellent in high-frequency properties, there is a problem in that its heat resistance is lowered due to a decrease in crosslinking density due to the use of monofunctional phenol compound.
Disclosure of Invention
An object of the present invention is to provide a curable resin composition and a cured product thereof, with which a cured product having excellent heat resistance and a low dielectric constant and a low dielectric loss tangent can be prepared.
According to the present invention, there is provided a curable resin composition comprising a polyfunctional cyanate ester resin and a bifunctional phenylene ether oligomer having a number average molecular weight of 500-3,000 and having a specific structure represented by the formula (1).
Wherein- (O-X-O) -has a structure shown in formula (2), wherein R1、R2、R7And R8May be the same or different halogen atoms, or alkyl groups containing 6 or less than 6 carbon atoms, R3、R4、R5And R6Which may be the same or different, hydrogen atoms, halogen atoms, or alkyl groups containing 6 or less than 6 carbon atoms, and A is a linear, branched, or cyclic hydrocarbon containing 20 or less than 20 carbon atoms, or is a direct bond, - (Y-O) -is an arrangement of structures as defined by formula (3), wherein R is9And R10May be the same or different halogen atoms, or alkyl groups containing 6 or less than 6 carbon atoms, R11And R12May be the same or different hydrogen atom, halogen atom, or alkyl group having 6 or less than 6 carbon atoms, and both a and b are an integer of 0 to 30, provided that at least one of a or b is not 0.
The present invention also provides a cured product of the above curable resin composition.
Detailed Description
The present inventors have conducted extensive and intensive studies and, as a result, have found that, when a bifunctional phenylene ether oligomer having a polyphenylene ether structure (hereinafter, sometimes referred to as "PRE") excellent in dielectric characteristics and heat resistance has a number average molecular weight of 500-3,000 and a specific structure, it is mixed with a polyfunctional cyanate ester resin and cured, and a cured product having excellent heat resistance and low dielectric characteristics can be prepared. On the basis of the above findings, the present inventors have completed the present invention. That is, the present invention relates to a curable resin composition containing a bifunctional phenylene ether oligomer having a specific structure represented by the formula (1) and a polyfunctional cyanate ester resin, and to a cured product obtained by curing the composition.
Wherein- (O-X-O) -has a structure shown in formula (2) (wherein R is1、R2、R7And R8May be the same or different halogen atoms, alkyl groups containing 6 or less than 6 carbon atoms or phenyl groups, R3、R4、R5And R6Which may be identical or different, hydrogen atoms, halogen atoms, alkyl groups having 6 or less than 6 carbon atoms or phenyl groups, and A is a linear, branched or cyclic hydrocarbon having 20 or less than 20 carbon atoms, or a direct bond, - (Y-O) -is an arrangement of structures defined by formula (3) or a random arrangement of at least two structures defined by formula (3) (wherein R is9And R10May be the same or different halogen atoms, alkyl groups containing 6 or less than 6 carbon atoms or phenyl groups, R11And R12May be the same or different hydrogen atom, halogen atom, alkyl group having 6 or less than 6 carbon atoms or phenyl group), and both a and b are an integer of 0 to 30, provided that at least one of a or b is not 0.
Hereinafter, the present invention will be explained in detail. Among the compounds represented by the formula (1), when A in the formula (2) is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms, it is preferable to be a compound in which R is1、R2、R7And R8Is an alkyl group having 3 or less than 3 carbon atoms, R3、R4、R5And R6Is a hydrogen atom or an alkyl group having 3 or less than 3 carbon atoms, R in the formula (3)9And R10Is an alkyl group having 3 or less than 3 carbon atoms, R11And R12Is a hydrogen atom or an alkyl group having 3 or less than 3 carbon atoms. More preferred are compounds wherein R is1、R2、R7And R8Is a methyl group and the- (Y-O) -structure of formula (3) is an arrangement of the structure of formula (4) or the structure of formula (5) or a random arrangement of the structure of formula (4) and the structure of formula (5),
more preferred are compounds wherein R in formula (2)1、R2、R7And R8Is methyl, R3、R4、R5And R6Is a hydrogen atom, and the- (Y-O) -structure of the formula (3) is an arrangement of the structure of the formula (4) or the structure of the formula (5) or a random arrangement of the structure of the formula (4) and the structure of the formula (5).
When A in formula (2) is a direct bond, preferred are compounds wherein R is1、R2、R4、R5、R7And R8Is an alkyl group having 3 or less than 3 carbon atoms, R3And R6Is a hydrogen atom or an alkyl group having 3 or less than 3 carbon atoms, R in the formula (3)9And R10Is an alkyl group having 3 or less than 3 carbon atoms, R11And R12Is a hydrogen atom or an alkyl group having 3 or less than 3 carbon atoms. More preferred are compounds wherein R is1、R2、R4、R5、R7And R8Is a methyl group, and the- (Y-O) -structure of formula (3) is an arrangement of the structure of formula (4) or the structure of formula (5) or a random arrangement of the structure of formula (4) and the structure of formula (5).
More preferred are compounds wherein R in formula (2)1、R2、R4、R5、R7And R8Is a methyl group, R3And R6Is a hydrogen atom, and the- (Y-O) -structure of the formula (3) is an arrangement of the structure of the formula (4) or the structure of the formula (5) or a random arrangement of the structure of the formula (4) and the structure of the formula (5).
When the molecular weight is too small, the heat resistance and electrical characteristics possessed by the phenylene ether structure cannot be obtained. When the molecular weight is too large, the solubility in a conventional solvent is lowered. The number average molecular weight is preferably between 500 and 3,000.
The process for producing the bifunctional phenylene ether oligomer represented by the formula (1) is not particularly limited. The above bifunctional phenylene ether oligomer can be prepared by any process. For example, such ｃA bifunctional phenylene ether oligomer can be prepared by oxidatively coupling ｃA bifunctional phenol compound and ｃA monofunctional phenol compound in the presence of copper and an amine according to the method disclosed in JP-A-2003-212990.
The polyfunctional cyanate ester compound (b) used in the present invention is represented by the formula (7),
R-(O-CN)m (7)
(wherein m is an integer of from 2 or more to generally 5 or less, R is an organic group having aromaticity, and the above cyanate group is directly attached to the aromatic ring of the above organic group R).
Specific examples of the polyfunctional cyanate ester compound include 1, 3-or 1, 4-dicyanobenzene, 1, 3, 5-tricyanobenzene, 1, 3-, 1, 4-, 1, 6-, 1, 8-, 2, 6-or 2, 7-dicyanobenzene, 1, 3, 6-tricyanobenzene, 4' -dicyanobenzene, bis (4-cyanatophenyl) methane, bis (3, 5-dimethyl-4-cyanatophenyl) methane, 2-bis (4-cyanatophenyl) propane, 2-bis (3, 5-dibromo-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) sulfide, bis (4-cyanatophenyl) sulfone, and the like, Tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, cyanate esters obtained by reacting ｃA novolak resin with ｃA cyanogen halide, and cyanate ester resins having PPE structures disclosed in JP-A-2003-238676 and JP-A-2003-238677.
In addition, prepolymers having triazine rings formed by trimerization of cyanate groups in these polyfunctional cyanate ester resins may also be used. The prepolymer is obtained by polymerizing the above polyfunctional cyanate ester monomer in the presence of an acid such as an inorganic acid or a Lewis acid, a base such as sodium ethoxide or a tertiary amine, or a salt such as sodium carbonate as a catalyst.
These polyfunctional cyanate ester resin and polyfunctional cyanate ester resin prepolymer may be used alone or in combination. As for the mixing ratio of the bifunctional polyphenylene ether oligomer and the cyanate ester resin, it is preferable to mix the bifunctional polyphenylene ether oligomer and the cyanate ester resin in such a ratio that the molar ratio (B/A) of the hydroxyl group (A) in the bifunctional polyphenylene ether oligomer to the cyanate ester group (B) in the cyanate ester resin is 2 to 100.
The curable resin composition of the present invention may contain a curing accelerator, an epoxy resin, an oxetane resin and a compound containing a polymerizable unsaturated group, as required.
The curing accelerator for the polyfunctional cyanate ester resin may be selected from known accelerators. Examples thereof include: organic metal complexes such as zinc octoate, tin octoate, cobalt naphthenate, zinc naphthenate, and iron acetylacetonate; metal salts such as aluminum chloride, tin chloride and zinc chloride; and amines such as triethylamine and dimethylbenzylamine. The curing accelerator is not limited to these examples. These curing accelerators may be used alone or in combination. The curing accelerator is preferably used in an amount of 0.001 to 0.5 wt%, more preferably 0.01 to 0.2 wt%, based on the total weight of the bifunctional phenylene ether oligomer and the polyfunctional cyanate ester resin.
The epoxy resin may be selected from generally known epoxy resins. Examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, xylene novolac epoxy resins, triglycidyl isocyanurate, alicyclic epoxy resins, dicyclopentadiene phenol novolac epoxy resins, diphenyl phenol novolac epoxy resins, and epoxy resins containing PPE structures disclosed in JP-A-2003-155340 and JP-A-2003-212990.
The oxetane resin can be selected from generally known oxetane resins. Examples thereof include: alkyl oxetanes such as oxetane, 2-methyl oxetane, 2-dimethyl oxetane, 3-methyl oxetane and 3, 3-dimethyl oxetane; 3-methyl-3-methoxymethyloxetane; 2-chloromethyloxetane; 3, 3-bis (chloromethyl) oxetane; OXT-101 (trade name, available from TOAGOSEI Co., Ltd.) and OXT-121 (trade name, available from TOAGOSEI Co., Ltd.). These oxetane resins may be used alone or in combination.
When the curable resin composition of the present invention contains an epoxy resin and/or an oxetane resin, an epoxy resin curing agent and/or an oxetane resin curing agent may be used. The epoxy resin curing agent is selected from generally known curing agents. Examples thereof include: derivatives of imidazole such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine and 4-methyl-N, N-dimethylbenzylamine; and phosphine compounds such as a phospho-acidic compound. The oxetane resin curing agent can be selected from a number of well-known cationic polymerization initiators. Examples of commercial uses include SAN-AID SI-60L, SAN-AID SI-80L, SAN-AID SI-100L (supplied by Sanshin chemical industries, Inc.), CI-2064 (supplied by Nippon soda, Inc.), IRGACURE 261 (supplied by Ciba specialty Chemicals), ADEKAOPTMER SP-170, ADEKAOPTMER SP-150 (supplied by Asahi Denka Kogyo K.K.), and CYRACURE UVI-6990 (supplied by Union Carbide, Inc.). These cationic polymerization initiators can be used as curing agents for epoxy resins. These curing agents may be used alone or in combination.
The compound containing a polymerizable unsaturated group is generally selected from a few well-known compounds containing a polymerizable unsaturated group. Examples include: vinyl compounds such as ethylene, propylene and styrene; (meth) acrylates of monohydric or polyhydric alcohols, such as methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate and epoxy (meth) acrylates containing PPE structures disclosed in JP-A-2003-183350 and JP-A-2003-238653; (meth) acrylates containing PPE structures disclosed in JP-A-2003-252983 and JP-A-2003-252833; vinyl compounds having PPE structures disclosed in Japanese patent application Nos. 2002-216724 and 2002-224937; and benzocyclobutene resins. These unsaturated group-containing compounds may be used alone or in combination.
When the unsaturated group-containing compound is used, a known photopolymerization initiator and/or a thermal polymerization initiator can be used as necessary.
In addition, when the cured resin composition of the present invention is prepared, a known additive such as a solvent, glass fiber, an organic raw material, an inorganic filler, a pigment, an antifoaming agent, a surface treatment agent, a flame retardant, an ultraviolet absorber, an antioxidant, a polymerization initiator, a flow regulator or a thermoplastic resin may be added as needed. Examples of the inorganic filler include silicon such as natural silicon, fused silica and amorphous silicon, white carbon, titanium white, fumed silica, alumina, talc, natural mica, synthetic mica, kaolin, clay, aluminum hydroxide, barium sulfate, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass, NE-glass and M-glass G20. The thus obtained curable resin composition is suitable for various uses such as semiconductor encapsulating materials, electrical insulating materials, resins for copper-clad laminates, resists, encapsulating resins for electronic parts, resins for liquid crystal color filters, coating compositions, various coating agents, adhesives, raw materials for build-up laminates and FRP.
The cured product of the present invention can be obtained by curing the curable resin composition of the present invention, according to the above-mentioned method, by a publicly known curing method such as using electron beam, ultraviolet light or heat.
Effects of the invention
A cured product having a high glass transition temperature, a low dielectric constant and a low dielectric loss tangent can be prepared by the cured resin composition of the present invention, and thus its use as a high-performance polymeric material is significantly increased. For example, the cured resin composition of the present invention has a very wide range of applications as excellent materials for heat or electricity, such as semiconductor encapsulating materials, electrical insulating materials, resins for copper-clad laminates, resists, encapsulating resins for electronic parts, resins for liquid crystal color filters, coating compositions, various coating agents, adhesives, raw materials for build-up laminates, and FRP.
Examples
The present invention will be explained more specifically by the following examples, but the present invention is not limited to these examples. The number average molecular weight and the weight average molecular weight were measured by a Gel Permeation Chromatography (GPC) method.
(Synthesis of bifunctional phenylene Ether oligomer)
(Synthesis example 1)
Into a longitudinally long reactor having a capacity of 12 liters and equipped with a stirrer, a thermometer, an air-introducing tube and baffleplates was charged 2.77g (12.5mmol) of CuBr20.54g (3.1mmol) of N, N' -di-tert-butylethylenediamine, 20.03g (198.3mmol) of N-butyldimethylamine and 2,600g of toluene. These components were stirred at a reaction temperature of 40 ℃. 129.32g (0.48mol) of 2, 2 ', 3, 3', 5, 5 '-hexamethyl- (1, 1' -diphenyl) -4, 4 '-diol (hereinafter referred to as "HMBP"), 175.31g (1.44mol) of 2, 6-dimethylphenol, 0.36g (2.1mmol) of N, N' -di-tert-butylethylenediamine and 7.79g (77.1mmol) of N-butyldimethylamine were dissolved in 2300g of methanol to give a mixed solution (the molar ratio of divalent phenol in formula (2) to monovalent phenol in formula (3) was equal to 1: 3). The mixed solution was added dropwise to the mixture in the reactor over 230 minutes while passing an oxygen gas at a rate of 5.2L/minA mixed gas of nitrogen and air having a degree of 8% was bubbled and stirred. After the completion of the addition, 1500g of an aqueous solution in which 14.20g (37.4mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to the stirred mixture to terminate the reaction. The aqueous and organic layers were separated. The organic layer was then washed with 1.0N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 295.6g of an oligomer a. The oligomer a had a number average molecular weight of 650, a weight average molecular weight of 1,040 and 325 equivalents of hydroxyl groups.
(Synthesis example 2)
Into a longitudinally long reactor having a capacity of 12 liters and equipped with a stirrer, a thermometer, an air-introducing tube and baffleplates was charged 6.64g (29.9mmol) of CuBr21.29g (7.5mmol) of N, N' -di-tert-butylethylenediamine, 48.07g (475.9mmol) of N-butyldimethylamine and 2,600g of toluene. These components were stirred at a reaction temperature of 40 ℃. 129.32g (0.48mol) of HMBP, 584.38g (4.79mol) of 2, 6-dimethylphenol, 0.87g (5.1mmol) of N, N' -di-tert-butylethylenediamine and 18.69g (185.1mmol) of N-butyldimethylamine were dissolved in 2300g of methanol to give a mixed solution (the molar ratio of the bivalent phenol of the formula (2) to the monovalent phenol of the formula (3) was equal to 1: 10). The mixed solution was added dropwise to the mixture in the reactor over 230 minutes while a mixed gas of nitrogen and air having an oxygen concentration of 8% was introduced at a rate of 5.2L/min to form a bubbling state, and stirring was performed. After the completion of the addition, 1500g of an aqueous solution in which 34.09g (89.7mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to the stirred mixture to terminate the reaction. The aqueous and organic layers were separated. The organic layer was then washed with 1.0N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 702.2g of an oligomer b. The oligomer b had a number average molecular weight of 1,490, a weight average molecular weight of 2,320 and 750 equivalents of hydroxyl groups.
(Synthesis example 3)
A stirrer, a thermometer, an air inlet pipe and a baffle plate are arranged in the longitudinal long shape with the capacity of 12 litersInto a reactor of (2) was charged 9.36g (42.1mmol) of CuBr21.81g (10.5mmol) of N, N' -di-tert-butylethylenediamine, 67.77g (671.0mmol) of N-butyldimethylamine and 2,600g of toluene. These components were stirred at a reaction temperature of 40 ℃. 129.32g (0.48mol) of HMBP, 878.4g (7.2mol) of 2, 6-dimethylphenol, 1.22g (7.2mmol) of N, N' -di-tert-butylethylenediamine and 26.35g (260.9mmol) of N-butyldimethylamine are dissolved in 2300g of methanol to give a mixed solution (the molar ratio of the bivalent phenol of formula (2) to the monovalent phenol of formula (3) is equal to 1: 15). The mixed solution was added dropwise to the mixture in the reactor over 230 minutes while bubbling a mixed gas of nitrogen and air having an oxygen concentration of 8% at a rate of 5.2L/min, and stirring was performed. After the completion of the addition, 1500g of an aqueous solution in which 48.06g (126.4mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to the stirred mixture to terminate the reaction. The aqueous and organic layers were separated. The organic layer was then washed with 1.0N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 990.1g of an oligomer c. The oligomer c had a number average molecular weight of 1,975, a weight average molecular weight of 3,514 and a hydroxyl group equivalent of 990.
(examples 1 to 5)
Each of the oligomer a, the oligomer b and the oligomer c was mixed with a cyanate ester resin and a curing accelerator, respectively, as shown in table 1, the mixture was melted by stirring at a temperature of 150 ℃ for 10 minutes, the melted mixture was degassed and molded, and then cured at a temperature of 230 ℃ for 10 hours to obtain a cured product.
(comparative examples 1 and 2)
A cyanate ester resin was mixed with a curing accelerator, and as shown in table 1, the mixture was melted by stirring at a temperature of 130 ℃ for 10 minutes, the molten mixture was degassed and molded, and then cured at a temperature of 230 ℃ for 10 hours to obtain a cured product.
TABLE 1
| Ex.1 | Ex.2 | Ex.3 | Ex.4 | Ex.5 | CEx.1 | CEx.2 | ||
| Oligomer a | 15 | 30 | 30 | - | - | - | - | |
| Oligomer b | - | - | - | 30 | - | - | - | |
| Oligomer c | - | - | - | - | 30 | - | - | |
| Cyanate ester resin | ArocyB-10 | 85 | 70 | - | 70 | 70 | 100 | - |
| ArocyM-10 | - | - | 70 | - | - | - | 100 | |
| Zinc naphthenate | 0.1 | 0.02 | 0.05 | 0.02 | 0.02 | 0.2 | 0.5 | |
Ex. ═ example, cex. ═ comparative example
Arocy B-10: 2, 2-bis (4-cyanatophenyl) propane
Arocy M-10: bis (3, 5-dimethyl-4-cyanatophenyl) methane
Table 2 shows the results of evaluation of the physical properties of the cured products.
TABLE 2
| Ex.1 | Ex.2 | Ex.3 | Ex.4 | Ex.5 | CEx.1 | CEx.2 | |
| Tg(℃) | 281 | 275 | 277 | 274 | 270 | 304 | 303 |
| Dielectric constant (1GHz) | 2.76 | 2.75 | 2.60 | 2.73 | 2.73 | 2.85 | 2.71 |
| Dielectric loss tangent (1GHz) | 0.006 | 0.006 | 0.005 | 0.006 | 0.005 | 0.011 | 0.010 |
Ex. ═ example, cex. ═ comparative example
(Synthesis of bifunctional phenylene Ether oligomer)
(Synthesis example 4)
A longitudinally long reactor having a capacity of 2 liters and equipped with a stirrer, a thermometer, an air-introducing tube and baffleplates was charged with 1.3g (0.012mol) of CuCl, 70.7g (0.55mol) of di-n-butylamine and 400g of methyl ethyl ketone. These components were stirred at a reaction temperature of 40 ℃ and 800g of a butanone solution containing 45.4g (0.16mol) of 4, 4' - (1-methylethylidene) bis (2, 6-dimethylphenol) as a divalent phenol and 58.6g (0.48mol) of 2, 6-dimethylphenol was added dropwise to the mixture in the reactor over 120 minutes while passing air at a rate of 2L/min in a bubbling state. After the completion of the addition, the mixture was stirred for 60 minutes under bubbling with air at a rate of 2L/min. The reaction was then terminated by adding an aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogendisodium salt to the stirred mixture. Subsequently, the organic layer was washed with 1N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 98.8g of an oligomer d represented by the formula (1). The oligomer d had a number average molecular weight of 845, a weight average molecular weight of 1,106 and 451 equivalents of hydroxyl groups.
(Synthesis example 5)
A longitudinally long reactor having a capacity of 2 liters and equipped with a stirrer, a thermometer, an air-introducing tube and baffleplates was charged with 1.3g (0.012mol) of CuCl, 70.7g (0.55mol) of di-n-butylamine and 400g of methyl ethyl ketone. These components were stirred at a reaction temperature of 40 ℃. A solution of 45.4g (0.16mol) of 4, 4' -cyclohexylidene-bis (2, 6-dimethylphenol) as a bivalent phenol and 58.6g (0.48mol) of 2, 6-dimethylphenol in 800g of butanone was added dropwise to the mixture in the reactor over 120 minutes while bubbling with 2L/min of air. After the completion of the addition, the mixture was stirred for 60 minutes while keeping bubbling with air at a rate of 2L/min. The reaction was then terminated by adding an aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogendisodium salt to the stirred mixture. Subsequently, the organic layer was washed with 1N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 102.6g of an oligomer e represented by the formula (1). The oligomer e had a number average molecular weight of 877, a weight average molecular weight of 1,183 and 477 equivalents of hydroxyl groups.
(Synthesis example 6)
A longitudinally long reactor having a capacity of 2 liters and equipped with a stirrer, a thermometer, an air-introducing tube and baffleplates was charged with 1.3g (0.012mol) of CuCl, 70.7g (0.55mol) of di-n-butylamine and 400g of methyl ethyl ketone. These components were stirred at a reaction temperature of 40 ℃. A solution of 800g of 4, 4 '-methine (which may be wrong in the original text, methylidenebis is found in the original page 19, line 1, the term "methylidyne" in the dictionary meaning methine "bis means" bis "so that the translation may be correct) as a bivalent phenol, 45.4g (0.16mol) of 4, 4' -methine as a bivalent phenol was added dropwise to the mixture in the reactor over 120 minutes while introducing air at a rate of 2L/min to form a bubble. After the completion of the addition, the mixture was stirred for 60 minutes while continuously introducing air at a rate of 2L/min in a bubbling state. The reaction was then terminated by adding an aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogendisodium salt to the stirred mixture. Subsequently, the organic layer was washed with 1N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 97.4g of an oligomer f represented by the formula (1). The oligomer f had a number average molecular weight of 852, a weight average molecular weight of 1,133 and 460 equivalents of hydroxyl groups.
(Synthesis example 7)
A longitudinally long reactor having a capacity of 2 liters and equipped with a stirrer, a thermometer, an air-introducing tube and baffleplates was charged with 1.3g (0.012mol) of CuCl, 70.7g (0.55mol) of di-n-butylamine and 400g of methyl ethyl ketone. These components were stirred at a reaction temperature of 40 ℃. A solution of 68.8g (0.16mol) of 4, 4' - [1, 4-phenylenebis (1-methylethylidene) ] -bis (2, 3, 6-trimethylphenol) as a bivalent phenol and 58.6g (0.48mol) of 2, 6-dimethylphenol in 800g of butanone was added dropwise to the mixture in the reactor over 120 minutes while bubbling with 2L/min of air. After the completion of the addition, the mixture was stirred for 60 minutes under conditions in which air was continuously introduced at a rate of 2L/min to form a bubbling state. The reaction was then terminated by adding an aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogendisodium salt to the stirred mixture. Subsequently, the organic layer was washed with 1N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 114.6g of an oligomer g represented by the formula (1). The oligomer g had a number average molecular weight of 934, a weight average molecular weight of 1,223 and 496 equivalents of hydroxyl groups.
(Synthesis example 8)
A longitudinally long reactor having a capacity of 2 liters and equipped with a stirrer, a thermometer, an air-introducing tube and baffleplates was charged with 1.3g (0.012mol) of CuCl, 70.7g (0.55mol) of di-n-butylamine and 400g of methyl ethyl ketone. These components were stirred at a reaction temperature of 40 ℃. A solution of 41.0g (0.16mol) of 4, 4' -methylenebis (2, 6-dimethylphenol) as a bivalent phenol and 58.6g (0.48mol) of 2, 6-dimethylphenol in 800g of butanone was added dropwise to the mixture in the reactor over 120 minutes while bubbling with 2L/min of air. After the completion of the addition, the mixture was stirred for 60 minutes under conditions in which air was continuously introduced at a rate of 2L/min to form a bubbling state. The reaction was then terminated by adding an aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogendisodium salt to the stirred mixture. Subsequently, the organic layer was washed with 1N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 94.6g of an oligomer h represented by the formula (1). The oligomer h had a number average molecular weight of 801, a weight average molecular weight of 1,081 and a hydroxyl group equivalent of 455.
(Synthesis example 9)
A longitudinally long reactor having a capacity of 5 liters and equipped with a stirrer, a thermometer, an air-introducing tube and baffleplates was charged with 2.8g (0.028mol) of CuCl, 169.7g (1.32mol) of di-n-butylamine and 1,000g of methyl ethyl ketone. These components were stirred at a reaction temperature of 40 ℃. 1900g of a butanone solution containing 41.0g (0.16mol) of 4, 4' -methylenebis (2.6-dimethylphenol) as a bivalent phenol and 195.3g (1.6mol) of 2, 6-dimethylphenol was added dropwise to the mixture in the reactor over 120 minutes while bubbling with air at a rate of 2L/min. After the completion of the addition, the mixture was stirred for 60 minutes under conditions in which air was continuously introduced at a rate of 2L/min to form a bubbling state. The reaction was then terminated by adding an aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogendisodium salt to the stirred mixture. Subsequently, the organic layer was washed with 1N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 212.5g of an oligomer i represented by the formula (1). The oligomer i had a number average molecular weight of 1,613, a weight average molecular weight of 2,420 and 834 equivalents of hydroxyl groups.
(Synthesis example 10)
A longitudinally long reactor having a capacity of 5 liters and equipped with a stirrer, a thermometer, an air-introducing tube and baffleplates was charged with 3.9g (0.039mol) of CuCl, 237.5g (1.84mol) of di-n-butylamine and 1300g of methyl ethyl ketone. These components were stirred at a reaction temperature of 40 ℃. 1700g of a butanone solution containing 41.0g (0.16mol) of 4, 4' -methylenebis (2, 6-dimethylphenol) as a bivalent phenol and 292.9g (2.4mol) of 2, 6-dimethylphenol was added dropwise to the mixture in the reactor over 120 minutes while bubbling with 2L/min of air. After the completion of the addition, the mixture was stirred for 60 minutes under conditions in which air was continuously introduced at a rate of 2L/min to form a bubbling state. The reaction was then terminated by adding an aqueous solution of ethylenediaminetetraacetic acid disodium dihydrogendisodium salt to the stirred mixture. Subsequently, the organic layer was washed with 1N hydrochloric acid aqueous solution and then with pure water. The thus-obtained solution was concentrated by an evaporator and dried under reduced pressure to obtain 305g of an oligomer j represented by the formula (1). The oligomer j had a number average molecular weight of 2,150, a weight average molecular weight of 3,256 and a hydroxyl group equivalent of 1,093.
(examples 6 to 14)
Each of the oligomers d to j obtained in Synthesis examples 4 to 10 was mixed with a cyanate ester resin and a curing accelerator, respectively, and as shown in Table 3, the mixture was melted by stirring at a temperature of 150 ℃ for 10 minutes, and the molten mixture was degassed and molded, followed by curing at a temperature of 230 ℃ for 10 hours to obtain cured products.
(comparative examples 3 and 4)
The cyanate ester resin was mixed with the curing accelerator, and as shown in table 3, the mixture was melted by stirring at a temperature of 130 ℃ for 10 minutes, and the molten mixture was degassed and molded, followed by curing at a temperature of 230 ℃ for 10 hours to obtain a cured product.
TABLE 3
| Ex.6 | Ex.7 | Ex.8 | Ex.9 | Ex.10 | ||
| Oligomer d | 15 | 30 | 30 | - | - | |
| Oligomers e | - | - | - | 30 | - | |
| Oligomer f | - | - | - | - | 30 | |
| Oligomer g | - | - | - | - | - | |
| Oligomers h | - | - | - | - | - | |
| Oligomer i | - | - | - | - | - | |
| Oligomer j | - | - | - | - | - | |
| Cyanate ester resin | ArocyB-10 | 85 | 70 | - | 70 | 70 |
| Acroy-M-10 | - | - | 70 | - | - | |
| Zinc naphthenate | 0.1 | 0.02 | 0.05 | 0.02 | 0.02 | |
Ex. ═ example
Table 3 (continuation)
| Ex.11 | Ex.12 | Ex.13 | Ex.14 | CEx.3 | Cex.4 | ||
| Oligomer d | - | - | - | - | - | - | |
| Oligomers e | - | - | - | - | - | - | |
| Oligomer f | - | - | - | - | - | - | |
| Oligomer g | 30 | - | - | - | - | - | |
| Oligomers h | - | 30 | - | - | - | - | |
| Oligomer i | - | - | 30 | - | - | - | |
| Oligomer j | - | - | - | 30 | - | - | |
| Cyanate ester resin | ArocyB-10 | 70 | 70 | 70 | 70 | 100 | - |
| AcroyM-10 | - | - | - | - | - | 100 | |
| Zinc naphthenate | 0.02 | 0.02 | 0.02 | 0.02 | 0.2 | 0.5 | |
Ex. ═ example, cex. ═ comparative example
Arocy B-10: 2, 2-bis (4-cyanatophenyl) propane
Arocy M-10: bis (3, 5-dimethyl-4-cyanatophenyl) methane
The properties of the cured products obtained in examples 6 to 14 and comparative examples 3 and 4 were measured by the following methods.
Glass transition temperature (Tg): determined according to the dynamic viscoelasticity measurement (DMA) method. The measurement was carried out at a vibration frequency of 10 Hz.
Dielectric constant and dielectric loss tangent: determined according to the resonant cavity method.
Table 4 shows the results of evaluation of the physical properties of the cured products.
TABLE 4
| Ex.6 | Ex.7 | Ex.8 | Ex.9 | Ex.10 | |
| Tg(℃) | 281 | 273 | 274 | 270 | 270 |
| Dielectric constant (1GHz) | 2.76 | 2.75 | 2.61 | 2.73 | 2.72 |
| Dielectric loss tangent (1GHz) | 0.007 | 0.006 | 0.005 | 0.006 | 0.005 |
Ex. ═ example
Table 4 (continuation)
| Ex.11 | Ex.12 | Ex.13 | Ex.14 | CEx.3 | Cex.4 | |
| Tg(℃) | 266 | 265 | 263 | 268 | 304 | 303 |
| Dielectric constant (1GHz) | 2.73 | 2.71 | 2.71 | 2.70 | 2.85 | 2.71 |
| Dielectric loss angle normal training value (1GHz) | 0.006 | 0.005 | 0.005 | 0.006 | 0.011 | 0.010 |
Ex. ═ example, cex. ═ comparative example
Claims (7)
1. A curable resin composition comprising a polyfunctional cyanate ester resin and a bifunctional phenylene ether oligomer having a number average molecular weight of 500-3,000 and having a specific structure represented by the formula (1),
wherein- (O-X-O) -has a structure shown in formula (2), wherein R1、R2、R7And R8May be the same or different halogen atoms,Or alkyl having 6 or less than 6 carbon atoms, R3、R4、R5And R6Which may be the same or different, hydrogen atoms, halogen atoms, or alkyl groups containing 6 or less than 6 carbon atoms, and A is a linear, branched, or cyclic hydrocarbon containing 20 or less than 20 carbon atoms, or is a direct bond, - (Y-O) -is an arrangement of structures as defined by formula (3), wherein R is9And R10May be the same or different halogen atoms, or alkyl groups containing 6 or less than 6 carbon atoms, R11And R12May be the same or different hydrogen atom, halogen atom, or alkyl group having 6 or less than 6 carbon atoms, and both a and b are an integer of 0 to 30, provided that at least one of a or b is not 0.
2. The curable resin composition according to claim 1, wherein A in the formula (2) — (O-X-O) -is a direct bond, and R in the formula (2) — (O-X-O) -1、R2、R4、R5、R7And R8Is methyl, - (Y-O) -has a structure as shown in formula (5).
3. The cured resin composition according to claim 2, wherein R3And R6Is a hydrogen atom.
4. The curable resin composition according to claim 1, wherein A of- (O-X-O) -in the formula (2) is a linear, branched or cyclic hydrocarbon having 20 or less carbon atoms, and R of- (O-X-O) -in the formula (2)1、R2、R7Or R8Is methyl, - (Y-O) -has a structure as shown in formula (5).
5. The cured resin composition according to claim 4, wherein R3、R4、R5And R6Is a hydrogen atom.
6. The curable resin composition according to claim 1, wherein the molar ratio of the cyanate group in the polyfunctional cyanate ester resin to the hydrogen atom group in the bifunctional phenylene ether oligomer is 2 to 100.
7. A cured product obtained by curing the curable resin composition of claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003-009422 | 2003-01-17 | ||
| JP2003009422A JP4359746B2 (en) | 2003-01-17 | 2003-01-17 | Curable resin composition and cured product thereof |
| JP2003-020150 | 2003-01-29 | ||
| JP2003020150A JP4300401B2 (en) | 2003-01-29 | 2003-01-29 | Curable resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1069407A1 HK1069407A1 (en) | 2005-05-20 |
| HK1069407B true HK1069407B (en) | 2007-06-15 |
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