JP2019206637A - Vinyl benzyl ether resin, method of producing that vinyl benzyl ether resin, curable resin composition, cured product of that curable resin composition, and shield member - Google Patents
Vinyl benzyl ether resin, method of producing that vinyl benzyl ether resin, curable resin composition, cured product of that curable resin composition, and shield member Download PDFInfo
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- JP2019206637A JP2019206637A JP2018102235A JP2018102235A JP2019206637A JP 2019206637 A JP2019206637 A JP 2019206637A JP 2018102235 A JP2018102235 A JP 2018102235A JP 2018102235 A JP2018102235 A JP 2018102235A JP 2019206637 A JP2019206637 A JP 2019206637A
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- vinyl benzyl
- benzyl ether
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- 229920005989 resin Polymers 0.000 title claims abstract description 69
- 239000011347 resin Substances 0.000 title claims abstract description 69
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title description 7
- -1 alkylene diol Chemical class 0.000 claims abstract description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 6
- 230000001588 bifunctional effect Effects 0.000 claims description 20
- 150000002989 phenols Chemical class 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 239000005011 phenolic resin Substances 0.000 abstract 1
- 229920001568 phenolic resin Polymers 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000047 product Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920001955 polyphenylene ether Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RCOVTJVRTZGSBP-UHFFFAOYSA-N 4-(chloromethyl)benzoyl chloride Chemical compound ClCC1=CC=C(C(Cl)=O)C=C1 RCOVTJVRTZGSBP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 5
- 235000019799 monosodium phosphate Nutrition 0.000 description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004727 Noryl Substances 0.000 description 4
- 229920001207 Noryl Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229920006270 hydrocarbon resin Polymers 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 2
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- YCAIYRWHKSJKEB-UHFFFAOYSA-N 3-(chloromethyl)benzoyl chloride Chemical compound ClCC1=CC=CC(C(Cl)=O)=C1 YCAIYRWHKSJKEB-UHFFFAOYSA-N 0.000 description 1
- SIDYFHJPUCRHJY-UHFFFAOYSA-N 4-[2-[4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]phenyl]propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=CC(=CC=2)C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 SIDYFHJPUCRHJY-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WHTKZGCDQCGCFG-UHFFFAOYSA-N [diphenyl-(2-trimethylsilylphenyl)silyl]peroxy-diphenyl-(2-trimethylsilylphenyl)silane Chemical compound C[Si](C)(C)C1=CC=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)OO[Si](C=1C(=CC=CC=1)[Si](C)(C)C)(C=1C=CC=CC=1)C1=CC=CC=C1 WHTKZGCDQCGCFG-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Polyethers (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、硬化性樹脂組成物の成分として有用なビニルベンジルエーテル樹脂、そのビニルベンジルエーテル樹脂の製造方法、上記のビニルベンジルエーテル樹脂を含有する硬化性樹脂組成物、当該硬化性樹脂組成物の硬化物、およびシールド部材に関する。 The present invention relates to a vinyl benzyl ether resin useful as a component of a curable resin composition, a method for producing the vinyl benzyl ether resin, a curable resin composition containing the vinyl benzyl ether resin, and the curable resin composition. The present invention relates to a cured product and a shield member.
近年の情報通信機器の高機能化、高密度化などの性能向上に従い、機器に実装される複数の電子部品がそれぞれ小型化し、互いに近接配置されるようになってきている。このため、各電子部品が放出する電磁波が他の電子部品に影響を及ぼしやすくなっている。また、通信用無線や放送用電波、さらには雷などの外部からの電磁波に対する耐性も高いレベルで有することが求められている。こうした電気的ストレスに耐えうる能力（イミュニティ）を機器として有するための手段の一例として、電子機器内に電磁波を遮蔽することができる部材（シールド部材）を設けることが挙げられる。 In accordance with recent performance improvements such as higher functionality and higher density of information communication devices, a plurality of electronic components mounted on the devices have been downsized and placed close to each other. For this reason, the electromagnetic waves emitted from each electronic component are likely to affect other electronic components. In addition, it is required to have a high level of resistance to communication radio waves, broadcast radio waves, and external electromagnetic waves such as lightning. As an example of means for having an ability (immunity) that can withstand such an electrical stress as a device, a member (shield member) capable of shielding electromagnetic waves may be provided in the electronic device.
上記のとおり情報通信機器は高機能化、高密度化が進んでいるため、シールド部材を例えばシート状にして設ける場合には、そのシートが小型化した電子部品群に追随して配置できるようにシールド部材は優れた柔軟性（変形容易性）を有することが好ましい。そこで、シールド部材を構成する材料として、樹脂系材料からなるマトリックスに導電性材料の粉体を分散させた複合材料が用いられる場合がある。この複合材料におけるマトリックスとなる樹脂系材料は、柔軟性を有するとともに、誘電率および誘電損失が低い（本明細書において「誘電特性に優れる」という。）ことが好ましい。また、機器内において電子部品が高密度実装されるため、熱分解温度が高いことなど耐熱性に優れることも当該樹脂系材料には求められる。 As described above, since information communication devices have advanced functions and high density, when the shield member is provided in a sheet shape, for example, the sheet can be arranged following the downsized electronic component group. The shield member preferably has excellent flexibility (easiness of deformation). Therefore, a composite material in which a conductive material powder is dispersed in a matrix made of a resin material may be used as a material constituting the shield member. The resin-based material that is a matrix in the composite material preferably has flexibility and low dielectric constant and dielectric loss (referred to as “excellent in dielectric properties” in this specification). In addition, since the electronic components are densely mounted in the device, the resin-based material is also required to have excellent heat resistance such as a high thermal decomposition temperature.
誘電特性に優れる観点、特に低い誘電正接を有する観点から、例えば特許文献１に記載されるようなビニルベンジルエーテル樹脂を含有する硬化性組成物が提案されている。ビニルベンジルエーテル樹脂は、ナフトールザイロック樹脂のようなナフトールアラルキル樹脂の水酸基にビニルベンジルハライドを反応させることにより得られる。 From the viewpoint of excellent dielectric properties, particularly from the viewpoint of having a low dielectric loss tangent, for example, a curable composition containing a vinyl benzyl ether resin as described in Patent Document 1 has been proposed. The vinyl benzyl ether resin is obtained by reacting a vinyl benzyl halide with a hydroxyl group of a naphthol aralkyl resin such as a naphthol zylock resin.
樹脂系材料の誘電特性を高める観点からは、樹脂系材料が分子量の大きい脂肪族炭化水素骨格を有することが有利である。分子量の大きい脂肪族炭化水素骨格を導入するための手法として、特許文献２から特許文献４に記載されるように、水酸基末端の炭化水素樹脂とポリイソシアネート化合物とを反応させて、ウレタン結合を骨格内に有することで分子量を高める方法が知られている。 From the viewpoint of enhancing the dielectric properties of the resin material, it is advantageous that the resin material has an aliphatic hydrocarbon skeleton having a large molecular weight. As a technique for introducing an aliphatic hydrocarbon skeleton having a large molecular weight, a hydroxyl group-terminated hydrocarbon resin and a polyisocyanate compound are reacted to form a urethane bond as described in Patent Document 2 to Patent Document 4. There are known methods for increasing the molecular weight by having them inside.
特許文献１に記載されるようなナフトールザイロックベースのビニルベンジルエーテル樹脂は熱分解温度が非常に高いが、このような樹脂は硬くて脆いため、柔軟性を有することが求められるシート状の電磁シールド部材のマトリックスを構成する樹脂系材料としては適切ではない。また、上記ビニルベンジルエーテル樹脂の欠点を補いつつ、誘電特性を向上させるために炭化水素系の熱可塑性樹脂を配合する手法が取られているが、熱可塑性の炭化水素樹脂は熱分解温度が低く、熱硬化後でも耐熱性が高い熱硬化性樹脂との間で結合が形成されるわけではないため、硬化物の熱分解温度が著しく低下する懸念がある。 The naphthol sylock-based vinyl benzyl ether resin described in Patent Document 1 has a very high thermal decomposition temperature. However, since such a resin is hard and brittle, it is a sheet-like electromagnetic that is required to have flexibility. It is not suitable as a resin material constituting the matrix of the shield member. In addition, in order to improve the dielectric properties while compensating for the drawbacks of the vinyl benzyl ether resin, a technique of blending a hydrocarbon-based thermoplastic resin has been taken, but the thermoplastic hydrocarbon resin has a low thermal decomposition temperature. Since a bond is not formed with a thermosetting resin having high heat resistance even after thermosetting, there is a concern that the thermal decomposition temperature of the cured product is remarkably lowered.
特許文献２から特許文献４に記載されるような水酸基末端の炭化水素樹脂とポリイソシアネート化合物を反応させる技術によれば、誘電特性、柔軟性に優れる樹脂が得られるが、上記のとおりウレタン結合を形成して分子量を増やす構成のため、耐熱性に乏しいものとなってしまう。また、硬化物の誘電特性を特に高める観点から、分極の程度が大きいウレタン結合を骨格構造に有することは有利とは言えない。 According to the technique of reacting a hydroxyl-terminated hydrocarbon resin and a polyisocyanate compound as described in Patent Document 2 to Patent Document 4, a resin having excellent dielectric properties and flexibility can be obtained. Due to the structure of forming and increasing the molecular weight, the heat resistance is poor. From the viewpoint of particularly improving the dielectric properties of the cured product, it is not advantageous to have a urethane bond having a large degree of polarization in the skeleton structure.
本発明は、優れた誘電特性（誘電率、誘電正接）および優れた機械特性（柔軟性）を備え、さらに耐熱性（耐熱分解性）も優れる硬化物を形成可能な硬化性樹脂組成物の成分として有用なビニルベンジルエーテル樹脂、そのビニルベンジルエーテル樹脂の製造方法、上記のビニルベンジルエーテル樹脂を含有する硬化性樹脂組成物、当該硬化性樹脂組成物の硬化物、および当該硬化性樹脂組成物を用いてなるシールド部材を提供することを課題とする。 The present invention is a component of a curable resin composition capable of forming a cured product having excellent dielectric properties (dielectric constant, dielectric loss tangent), excellent mechanical properties (flexibility), and excellent heat resistance (heat decomposability). Useful vinyl benzyl ether resin, method for producing the vinyl benzyl ether resin, curable resin composition containing the above vinyl benzyl ether resin, cured product of the curable resin composition, and the curable resin composition It is an object to provide a shield member to be used.
上記の課題を解決するために提供される本発明は次のとおりである。
［１］下記一般式（１）に示されるビニルベンジルエーテル樹脂。
（上記一般式（１）中、Ａは下記一般式（２）で示されるビニルベンジル基であり、Ｚは下記一般式（３）で示される２官能フェノール類の残基であり、Ｙは下記一般式（４）で示されるアルキレン基であり、平均繰り返し数ｎは０．３以上２．０以下である。）
（上記一般式（２）中、Ｒ１からＲ５は同一または異なってもよく、水素またはメチル基である。）
（上記一般式（３）中、Ｒ６は直接結合、−ＣＨ２−、−ＣＨ（ＣＨ３）−、−Ｃ（ＣＨ３）２−、または下記式（５）であり、ｍおよびｌはそれぞれ０以上の整数であり、ｍ＋ｌは２以上３０以下である。）
（上記一般式（４）中、Ｒ７およびＲ１１はいずれも−ＣＨ２−ＣＨ２−であり、Ｒ８は−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−であり、Ｒ９は−ＣＨ２−ＣＨ（Ｃ２Ｈ５）−であり、Ｒ１０は−ＣＨ２−ＣＨ（ＣＨ３）−ＣＨ２−ＣＨ２−であり、ａおよびｅはそれぞれ０または１であり、ｂ，ｃ，およびｄはそれぞれ０以上１００以下の整数であり、ａ＋ｂ＋ｃ＋ｄ＋ｅは１以上である。）
［２］数平均分子量が２０００以上１００００以下である、上記［１］に記載のビニルベンジルエーテル樹脂。
［３］前記一般式（４）で示されるアルキル基の数平均分子量が１０００以上４０００以下である、上記［２］に記載のビニルベンジルエーテル樹脂。
［４］前記一般式（３）で示される２官能フェノール類の残基の数平均分子量が５００以上２５００以下である、上記［２］および［３］に記載のビニルベンジルエーテル樹脂。
［５］上記［１］から［４］のいずれかに記載されるビニルベンジルエーテル樹脂と、ラジカル重合開始剤とを含有する硬化性樹脂組成物。
［６］上記［５］に記載される硬化性樹脂組成物の硬化物。
［７］上記［６］に記載される硬化物を含むシールド部材。
［８］下記一般式（６）に示されるアルキレンジオールと、ハロメチル芳香族酸ハライドとを反応させて、下記一般式（７）に示されるエステル化合物を得る第１ステップと、前記第１ステップで得られた前記エステル化合物と、下記一般式（８）に示される２官能フェノール類と、下記一般式（９）に示されるビニルベンジルハライド化合物とを反応させて、上記［１］に記載されるビニルベンジルエーテル樹脂を得る第２ステップとを備えることを特徴とするビニルベンジルエーテル樹脂の製造方法。
（上記一般式（６）におけるＹは上記［１］に定義されるとおりである。）
（上記一般式（７）におけるＸ１はハロゲン元素であり、Ｙは上記［１］に定義されるとおりである。）
（上記一般式（８）におけるＲ６ならびにｍおよびｌは上記［１］に定義されるとおりである。）
（上記一般式（９）におけるＲ１からＲ５は上記［１］に定義されるとおりであり、Ｘ２はハロゲン元素である。）
The present invention provided to solve the above-described problems is as follows.
[1] A vinyl benzyl ether resin represented by the following general formula (1).
(In the above general formula (1), A is a vinylbenzyl group represented by the following general formula (2), Z is a residue of a bifunctional phenol represented by the following general formula (3), and Y is (It is an alkylene group represented by the general formula (4), and the average repeating number n is 0.3 or more and 2.0 or less.)
(In the general formula (2), R 1 to R 5 may be the same or different, and are hydrogen or a methyl group.)
(In the general formula (3), R 6 is a direct bond, —CH 2 —, —CH (CH 3 ) —, —C (CH 3 ) 2 —, or the following formula (5), and m and l are Each is an integer of 0 or more, and m + 1 is 2 or more and 30 or less.)
(In the general formula (4), R 7 and R 11 are both —CH 2 —CH 2 —, R 8 is —CH 2 —CH 2 —CH 2 —CH 2 —, and R 9 is — CH 2 —CH (C 2 H 5 ) —, R 10 is —CH 2 —CH (CH 3 ) —CH 2 —CH 2 —, a and e are each 0 or 1, b, c , And d are each an integer of 0 or more and 100 or less, and a + b + c + d + e is 1 or more.)
[2] The vinyl benzyl ether resin according to the above [1], wherein the number average molecular weight is 2000 or more and 10,000 or less.
[3] The vinyl benzyl ether resin according to the above [2], wherein the number average molecular weight of the alkyl group represented by the general formula (4) is 1000 or more and 4000 or less.
[4] The vinyl benzyl ether resin according to the above [2] and [3], wherein the number average molecular weight of the residue of the bifunctional phenol represented by the general formula (3) is 500 or more and 2500 or less.
[5] A curable resin composition containing the vinyl benzyl ether resin described in any one of [1] to [4] above and a radical polymerization initiator.
[6] A cured product of the curable resin composition described in [5] above.
[7] A shield member containing the cured product described in [6].
[8] A first step in which an alkylene diol represented by the following general formula (6) is reacted with a halomethyl aromatic acid halide to obtain an ester compound represented by the following general formula (7); The obtained ester compound is reacted with a bifunctional phenol represented by the following general formula (8) and a vinylbenzyl halide compound represented by the following general formula (9), and is described in the above [1]. And a second step of obtaining a vinyl benzyl ether resin.
(Y in the general formula (6) is as defined in [1] above.)
(X 1 in the general formula (7) is a halogen element, and Y is as defined in [1] above.)
(R 6 and m and l in the general formula (8) are as defined in [1] above.)
(R 1 to R 5 in the general formula (9) are as defined in [1] above, and X 2 is a halogen element.)
本発明によれば、優れた誘電特性（誘電率、誘電正接）および優れた機械特性（柔軟性）を備え、さらに耐熱性（耐熱分解性）も優れる硬化物を形成可能な硬化性樹脂組成物の成分として有用なビニルベンジルエーテル樹脂、そのビニルベンジルエーテル樹脂の製造方法、上記のビニルベンジルエーテル樹脂を含有する硬化性樹脂組成物、当該硬化性樹脂組成物の硬化物、および当該硬化性樹脂組成物を用いてなるシールド部材が提供される。 According to the present invention, a curable resin composition capable of forming a cured product having excellent dielectric properties (dielectric constant, dielectric loss tangent) and excellent mechanical properties (flexibility), and also having excellent heat resistance (thermal decomposition resistance). Vinyl benzyl ether resin useful as a component of the above, a method for producing the vinyl benzyl ether resin, a curable resin composition containing the vinyl benzyl ether resin, a cured product of the curable resin composition, and the curable resin composition There is provided a shield member using an object.
以下、本発明の実施形態を説明する。本発明の一実施形態に係るビニルベンジルエーテル樹脂（ａ）は、下記一般式（１）で示される。
上記一般式（１）中、Ａは下記一般式（２）で示されるビニルベンジル基であり、Ｚは下記一般式（３）で示される２官能フェノール類の残基であり、Ｙは下記一般式（４）で示されるアルキレン基（２価の炭化水素基）であり、平均繰り返し数ｎは０．３以上２．０以下である。なお、平均繰り返し数ｎが非整数となるのは、ビニルベンジルエーテル樹脂（ａ）は、上記一般式（１）のカッコ内に示される構造部位の連結数が異なる複数種類の化合物を含む組成物からなるためである。
上記一般式（２）中、Ｒ１からＲ５は同一または異なってもよく、水素またはメチル基である。
上記一般式（３）中、Ｒ６は直接結合、−ＣＨ２−、−ＣＨ（ＣＨ３）−、−Ｃ（ＣＨ３）２−、または下記式（５）であり、ｍおよびｌはそれぞれ０以上の整数であり、ｍ＋ｌは２以上３０以下である。
上記一般式（４）中、Ｒ７およびＲ１１はいずれも−ＣＨ２−ＣＨ２−であり、Ｒ８は−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−であり、Ｒ９は−ＣＨ２−ＣＨ（Ｃ２Ｈ５）−であり、Ｒ１０は−ＣＨ２−ＣＨ（ＣＨ３）−ＣＨ２−ＣＨ２−であり、ａおよびｅはそれぞれ０または１であり、ｂ，ｃ，およびｄはそれぞれ０以上１００以下の整数であり、ａ＋ｂ＋ｃ＋ｄ＋ｅは１以上である。ビニルベンジルエーテル樹脂（ａ）を含む硬化性樹脂組成物の硬化物の柔軟性を高める観点から、上記一般式（４）で示されるアルキレン基（−ＣｒＨ２ｒ−）の炭素数ｒ（＝２ａ＋４ｂ＋４ｃ＋５ｄ＋２ｅ）は、５０以上であることが好ましく、７０以上であることがより好ましい。上記の炭素数の上限は設定されないが、原料の取り扱い性や入手容易性を考慮すると、４００以下である。
ビニルベンジルエーテル樹脂（ａ）は、エステル結合やエーテル結合を有し、相対的に分子内分極が大きいアミド結合やウレタン結合を有しないため、ビニルベンジルエーテル樹脂（ａ）を含む硬化性樹脂組成物の硬化物は誘電特性に優れる。具体的には、誘電率が２．５以下となることが容易であり、しかも誘電正接が０．００４以下となることが容易である。また、上記一般式（４）で示されるアルキレン基を有するため、樹脂全体における炭化水素の割合が高くなりやすいことも、上記の硬化物の誘電特性が優れる一因である。上記のアルキレン基を有することは、ビニルベンジルエーテル樹脂（ａ）の分子運動を容易にし、上記の硬化物の柔軟性を高めることにも寄与する。さらに、上記一般式（３）で示される２官能フェノール類に基づく構造部位を有することや、骨格内にウレタン結合有しないことから、ビニルベンジルエーテル樹脂（ａ）を含む硬化性樹脂組成物の硬化物は耐熱性（耐熱分解性）に優れる。 The vinyl benzyl ether resin (a) has an ester bond and an ether bond, and does not have an amide bond or a urethane bond having a relatively large intramolecular polarization, and therefore includes a vinyl benzyl ether resin (a). The cured product is excellent in dielectric properties. Specifically, the dielectric constant is easily 2.5 or less, and the dielectric loss tangent is easily 0.004 or less. Moreover, since it has an alkylene group represented by the general formula (4), the ratio of hydrocarbons in the entire resin tends to be high, which is one of the reasons why the dielectric properties of the cured product are excellent. Having the above alkylene group facilitates the molecular motion of the vinyl benzyl ether resin (a) and contributes to increasing the flexibility of the cured product. Furthermore, since it has a structural site based on the bifunctional phenols represented by the general formula (3) and does not have a urethane bond in the skeleton, curing of the curable resin composition containing the vinylbenzyl ether resin (a) The product is excellent in heat resistance (heat decomposition resistance).
ビニルベンジルエーテル樹脂（ａ）を含む硬化性樹脂組成物の硬化物が優れた誘電特性、優れた機械特性、および優れた耐熱性を適切に兼ね備えることを容易にする観点から、ビニルベンジルエーテル樹脂（ａ）の数平均分子量は、２０００以上１００００以下であることが好ましく、２５００以上８０００以下であることがより好ましい。同様の観点から、上記一般式（４）で示されるアルキレン基の数平均分子量は１０００以上４０００以下であることが好ましく、上記一般式（３）で示される２官能フェノール類の残基の数平均分子量は５００以上２５００以下であることが好ましい。なお、ビニルベンジルエーテル樹脂（ａ）などの数平均分子量は、ＧＰＣ（ゲル浸透クロマトグラフィ）などの測定方法により測定することができる。 From the viewpoint of facilitating that the cured product of the curable resin composition containing the vinyl benzyl ether resin (a) appropriately has excellent dielectric properties, excellent mechanical properties, and excellent heat resistance, the vinyl benzyl ether resin ( The number average molecular weight of a) is preferably 2000 or more and 10,000 or less, and more preferably 2500 or more and 8000 or less. From the same viewpoint, the number average molecular weight of the alkylene group represented by the general formula (4) is preferably 1000 or more and 4000 or less, and the number average of the residues of the bifunctional phenols represented by the general formula (3). The molecular weight is preferably 500 or more and 2500 or less. In addition, number average molecular weights, such as vinyl benzyl ether resin (a), can be measured by measuring methods, such as GPC (gel permeation chromatography).
次に、ビニルベンジルエーテル樹脂（ａ）の製造方法について説明する。本実施形態に係るビニルベンジルエーテル樹脂（ａ）は、例えば次のような、第１ステップおよび第２ステップを有する方法により製造することができる。 Next, the manufacturing method of vinyl benzyl ether resin (a) is demonstrated. The vinyl benzyl ether resin (a) according to the present embodiment can be produced, for example, by a method having the first step and the second step as follows.
まず、第１ステップでは、下記一般式（６）に示されるアルキレンジオール（α）と、ハロメチル芳香族酸ハライド（β）とを反応させて、下記一般式（７）に示されるエステル化合物（Ａ）を得る。
上記一般式（６）および上記一般式（７）におけるＹならびにＹにおいて用いられるａ，ｂ，ｃ，ｄ，およびｅは上記一般式（１）に定義されるとおりである。上記一般式（７）におけるＸ１はハロゲン元素である。 Y in the general formula (6) and the general formula (7) and a, b, c, d, and e used in Y are as defined in the general formula (1). X 1 in the general formula (7) is a halogen element.
アルキレンジオール（α）の例として末端に水酸基を有するポリオレフィンが挙げられ、具体例として、末端水酸基水添ポリブタジエン「ＧＩ−１０００」（数平均分子量：約１５００）、「ＧＩ−２０００」（数平均分子量：約２０００）、「ＧＩ−３０００」（数平均分子量：約３０００）（以上日本曹達社製）、「ポリテールＨ」（三菱ケミカル社製、数平均分子量：約２０００）；末端水酸基水添ポリイソプレン（出光興産社製、数平均分子量：約２０００〜２５００）などが挙げられる。 Examples of the alkylene diol (α) include a polyolefin having a hydroxyl group at the terminal. Specific examples include hydrogenated terminal hydroxylated polybutadiene “GI-1000” (number average molecular weight: about 1500), “GI-2000” (number average molecular weight). : About 2000), "GI-3000" (number average molecular weight: about 3000) (manufactured by Nippon Soda Co., Ltd.), "Polytail H" (manufactured by Mitsubishi Chemical, number average molecular weight: about 2000); terminal hydroxylated hydrogenated polyisoprene (Idemitsu Kosan Co., Ltd., number average molecular weight: about 2000 to 2500).
ハロメチル芳香族酸ハライド（β）の具体例として、４−(クロロメチル)ベンゾイルクロリド、３−(クロロメチル)ベンゾイルクロリドなどが挙げられる。 Specific examples of the halomethyl aromatic acid halide (β) include 4- (chloromethyl) benzoyl chloride, 3- (chloromethyl) benzoyl chloride and the like.
原料物質であるアルキレンジオール（α）およびハロメチル芳香族酸ハライド（β）を、トルエンなどの双方を溶解可能な溶媒に溶解して、反応液を撹拌しながら７０℃から１３０℃の範囲で加熱保持することにより、原料物質の脱塩化水素反応を進行させることができる。双方の原料物質の当量比（α／β）は０．８／１から１．２／１の範囲で設定することが好ましく、１／１に近いことがより好ましい。加熱保持時間は反応が適切に終了するように設定すればよく、限定されない例示として、５時間から２０時間が挙げられる。 The raw materials, alkylene diol (α) and halomethyl aromatic acid halide (β), are dissolved in a solvent that can dissolve both toluene and the like, and the reaction solution is stirred and heated in the range of 70 ° C to 130 ° C. By doing so, the dehydrochlorination reaction of the raw material can be advanced. The equivalent ratio (α / β) of both raw materials is preferably set in the range of 0.8 / 1 to 1.2 / 1, and more preferably close to 1/1. What is necessary is just to set the heat holding time so that reaction may complete | finish appropriately, and 5 to 20 hours is mentioned as a non-limiting example.
反応の際に、塩基性化合物を添加しなくてもよいが、必要に応じて、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウムなどのアルカリ化合物を塩基として用いることもできる。 In the reaction, it is not necessary to add a basic compound, but an alkali compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or the like can be used as a base as necessary.
第２ステップでは、第１ステップで得られた上記一般式（７）に示されるエステル化合物（Ａ）と、下記一般式（８）に示される２官能フェノール類（Ｂ）と、下記一般式（９）に示されるビニルベンジルハライド化合物（Ｃ）とを反応させて、ビニルベンジルエーテル樹脂（ａ）を得る。
上記一般式（８）におけるＲ６ならびにｍおよびｌは上記一般式（１）に定義されるとおりである。２官能フェノール類（Ｂ）の具体例として、下記一般式（８−１）に示されるポリフェニレンエーテルオリゴマー（ＳＡＢＩＣイノベーティブプラスチックス社製「ＮＯＲＹＬ ＰＰＯ ＳＡ９０」、数平均分子量：約１７００）、下記一般式（８−２）に示されるポリフェニレンエーテルオリゴマー（三菱ガス化学社製「ＯＰＥ１０００」、数平均分子量：約９００〜約１０００）などが挙げられる。
上記一般式（８−１）におけるｍおよびｌはそれぞれ０以上の整数であり、ｍ＋ｌは２以上３０以下である。上記一般式（８−２）におけるｐおよびｑはそれぞれ１以上の整数であり、ｐ＋ｑは１５以下である。上記のようにポリフェニレンエーテルオリゴマーの主鎖を構成するフェニル基に複数のメチル基が設けられていることにより、２官能フェノール類（Ｂ）は主鎖方向を回転軸とする回転が生じにくい。それゆえ、２官能フェノール類（Ｂ）のフェノール残基を骨格内に有するビニルベンジルエーテル樹脂（ａ）を含む硬化性樹脂組成物の硬化物は耐熱性（耐熱分解性）に優れる。
上記一般式（９）におけるＲ１からＲ５は上記一般式（１）に定義されるとおりであり、Ｘ２はハロゲン元素である。ビニルベンジルハライド化合物（Ｃ）は、芳香核にビニル基およびハロゲン化メチル基が結合していればよく、ビニル基とハロゲン化メチル基との位置関係は限定されない。ビニルベンジルハライド化合物（Ｃ）の具体例として、ｐ−ビニルベンジルクロライドとｍ−ビニルベンジルクロライドの約５０／５０の混合体（ＡＧＣセイミケミカル社製「ＣＭＳ−Ｐ」）、ｐ−ビニルベンジルクロライドとｍ−ビニルベンジルクロライドの約９５／５の混合体（ＡＧＣセイミケミカル社製「ＣＭＳ−１４」）などが挙げられる。 R 1 to R 5 in the general formula (9) are as defined in the general formula (1), and X 2 is a halogen element. In the vinylbenzyl halide compound (C), the vinyl group and the halogenated methyl group may be bonded to the aromatic nucleus, and the positional relationship between the vinyl group and the halogenated methyl group is not limited. Specific examples of the vinylbenzyl halide compound (C) include a mixture of about 50/50 of p-vinylbenzyl chloride and m-vinylbenzyl chloride (“CMS-P” manufactured by AGC Seimi Chemical Co.), p-vinylbenzyl chloride, Examples include a mixture of about 95/5 of m-vinylbenzyl chloride (“CMS-14” manufactured by AGC Seimi Chemical Co., Ltd.).
エステル化合物（Ａ）と２官能フェノール類（Ｂ）とビニルベンジルハライド化合物（Ｃ）との反応条件は例えば次のように設定することが好ましい。エステル化合物（Ａ）は前述のとおり、アルキレンジオール（α）とハロメチル芳香族酸ハライド（β）との脱ハロゲン化水素反応により得られる。反応生成物に対して原料のハロメチル芳香族酸ハライド（β）と当量程度のアルカリを用いて中和し、中和後の反応液（エステル化合物（Ａ）を含む。）と２官能フェノール類（Ｂ）とビニルベンジルハライド化合物（Ｃ）とを、アルカリ条件で、トルエンなどを溶媒として撹拌しながら加熱保持する。 The reaction conditions for the ester compound (A), the bifunctional phenols (B), and the vinylbenzyl halide compound (C) are preferably set as follows, for example. As described above, the ester compound (A) can be obtained by a dehydrohalogenation reaction between an alkylene diol (α) and a halomethyl aromatic acid halide (β). The reaction product is neutralized with the raw material halomethyl aromatic acid halide (β) and an equivalent amount of alkali, and the neutralized reaction solution (including the ester compound (A)) and bifunctional phenols ( B) and the vinylbenzyl halide compound (C) are heated and held under alkaline conditions while stirring with toluene or the like as a solvent.
２官能フェノール類（Ｂ）の仕込み量は、エステル化合物（Ａ）の原料物質であるアルキレンジオール（α）に対する当量比（Ｂ／α）で、１．５／１〜３／１の範囲とすることが好ましい場合があり、１．７／１〜２．５／１の範囲とすることがより好ましい場合がある。また、ビニルベンジルハライド化合物（Ｃ）の仕込み量は、２官能フェノール（Ｂ）の当量からアルキレンジオール（α）の当量を引いた当量の０．９５倍から１．１０倍が好ましい。 The charged amount of the bifunctional phenols (B) is an equivalent ratio (B / α) to the alkylene diol (α) that is the raw material of the ester compound (A), and is in the range of 1.5 / 1 to 3/1. It may be preferable, and it may be more preferable to set it as the range of 1.7 / 1-2.5 / 1. The amount of the vinylbenzyl halide compound (C) charged is preferably 0.95 to 1.10 times the equivalent of the bifunctional phenol (B) minus the equivalent of the alkylene diol (α).
反応温度は５０℃から１２０℃の範囲が例示され、反応温度を６０℃から９５℃の範囲で適切に撹拌することが、ビニルベンジルエーテル樹脂（ａ）を含む硬化性樹脂組成物の硬化物の柔軟性を高める観点から好ましい。加熱保持時間は反応が適切に終了するように設定すればよく、限定されない例示として、５時間から４０時間が挙げられる。所定の時間の加熱保持が終了したら、冷却・静置して、分液された水分を除去し、アルカリで中和して、再び冷却・静置して、水分を除去し、濃縮して溶媒を除去することにより、ビニルベンジルエーテル樹脂（ａ）が得られる。 The reaction temperature is exemplified by a range of 50 ° C. to 120 ° C., and appropriately stirring the reaction temperature within the range of 60 ° C. to 95 ° C. It is preferable from the viewpoint of increasing flexibility. What is necessary is just to set the heat holding time so that reaction may complete | finish appropriately, and 5 to 40 hours are mentioned as a non-limiting example. After heating and holding for a predetermined time, cool and let stand to remove the separated water, neutralize with alkali, cool and let to stand again, remove the water, concentrate and solvent Is removed to obtain the vinylbenzyl ether resin (a).
本発明の一実施形態に係る硬化性樹脂組成物は、本発明の一実施形態に係るビニルベンジルエーテル樹脂（ａ）およびラジカル重合開始剤（ｂ）を含有する。 The curable resin composition which concerns on one Embodiment of this invention contains the vinyl benzyl ether resin (a) and radical polymerization initiator (b) which concern on one Embodiment of this invention.
ラジカル重合開始剤（ｂ）は公知のものを使用することができる。具体例として、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、２，５−ジメチルヘキサン−２，５−ジハイドロパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルクミルパーオキサイド、α，α’−ビス（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、ジクミルパーオキサイド、ジ−ｔ−ブチルパーオキシイソフタレート、ｔ−ブチルパーオキシベンゾエート、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、２，２−ビス（ｔ−ブチルパーオキシ）オクタン、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ジ（トリメチルシリル）パーオキサイド、トリメチルシリルトリフェニルシリルパーオキサイド等の過酸化物が挙げることができる。これらの物質は単独でも２種類以上を併用してもよい。 A well-known thing can be used for a radical polymerization initiator (b). Specific examples include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3. , Di-t-butyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butyl) Peroxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxa And peroxides such as trimethylsilyltriphenylsilyl peroxide. These substances may be used alone or in combination of two or more.
硬化性樹脂組成物におけるラジカル重合開始剤（ｂ）の含有量は、硬化性樹脂組成物全体に対して、０．１質量％以上１０質量％以下であることが、硬化性樹脂組成物の硬化反応を適切に進行させる観点や硬化物の物性、特に誘電特性および耐熱性を適切に確保する観点から好ましい。 The content of the radical polymerization initiator (b) in the curable resin composition is 0.1% by mass or more and 10% by mass or less based on the entire curable resin composition. This is preferable from the viewpoint of appropriately proceeding the reaction and from the viewpoint of appropriately ensuring the physical properties of the cured product, particularly the dielectric properties and heat resistance.
本発明の一実施形態に係る熱硬化性樹脂組成物には、さらに必要に応じて、溶剤、カップリング剤、離型剤、着色剤、難燃剤、低応力剤、増粘剤などを添加、あるいは予め反応させて用いることができる。 To the thermosetting resin composition according to an embodiment of the present invention, a solvent, a coupling agent, a release agent, a colorant, a flame retardant, a low stress agent, a thickener, and the like are further added as necessary. Or it can be made to react beforehand and can be used.
本発明の一実施形態に係る硬化性樹脂組成物を例えば加熱することにより、硬化物を得ることができる。かかる本発明の一実施形態に係る硬化物は、ビニルベンジルエーテル樹脂（ａ）に由来するアルキル基やエステル基に基づく構造部位を有するため、本実施形態に係る硬化物は、誘電率が低い、誘電正接が低い、など誘電特性に優れる。また、ビニルベンジルエーテル樹脂（ａ）に由来するに基づく構造部位を有することは、硬化物が優れた柔軟性を有することにも寄与する。さらに、２官能フェノール類（Ｂ）に由来する芳香環に基づく構造部位を有するため、硬化物は耐熱分解性に優れる。 A cured product can be obtained by, for example, heating the curable resin composition according to one embodiment of the present invention. Since the cured product according to one embodiment of the present invention has a structural portion based on an alkyl group or an ester group derived from the vinyl benzyl ether resin (a), the cured product according to the present embodiment has a low dielectric constant. Excellent dielectric properties such as low dielectric loss tangent. In addition, having a structural portion based on the vinyl benzyl ether resin (a) contributes to the excellent flexibility of the cured product. Furthermore, since it has a structural site based on an aromatic ring derived from the bifunctional phenols (B), the cured product is excellent in thermal decomposition resistance.
本発明の一実施形態に係る硬化性樹脂組成物を加熱により硬化させる場合には、その加熱温度は、その硬化物の組成に応じて適宜設定される。限定されない例示として、１００〜２５０℃の温度範囲で加熱することが挙げられる。 When the curable resin composition according to one embodiment of the present invention is cured by heating, the heating temperature is appropriately set according to the composition of the cured product. A non-limiting example is heating in a temperature range of 100 to 250 ° C.
硬化のための具体的な作業は限定されない。例えば、本発明の一実施形態に係る熱硬化性樹脂組成物を必要に応じて溶媒で希釈し、得られた希釈溶液を基材に塗工して、加熱により乾燥、硬化させる。得られた硬化塗膜を基材から剥すことにより、本発明の一実施形態に係る硬化物（硬化物フィルム）を得ることができる。 The specific operation for curing is not limited. For example, the thermosetting resin composition according to one embodiment of the present invention is diluted with a solvent as necessary, the obtained diluted solution is applied to a substrate, and dried and cured by heating. By removing the obtained cured coating film from the substrate, a cured product (cured product film) according to one embodiment of the present invention can be obtained.
本発明の一実施形態に係るシールド部材は、上記の本実施形態に係る硬化性樹脂組成物からなるマトリックスと、導電性材料からなる部材（導電部材）とを含有し、導電部材からなる粉体がマトリックス内に分散する複合構造が具体例となる。導電性材料は、アルミニウムなどの金属系材料であってもよいし、グラファイトなどの無機系導電性材料であってもよい。 A shield member according to an embodiment of the present invention includes a matrix made of the curable resin composition according to the above embodiment and a member (conductive member) made of a conductive material, and a powder made of the conductive member. A composite structure in which is dispersed in a matrix is a specific example. The conductive material may be a metal material such as aluminum, or may be an inorganic conductive material such as graphite.
本発明の一実施形態に係るシールド部材が含有する導電部材の含有量は適宜設定される。限定されない例として、導電部材の配合量を硬化性樹脂組成物全体の６０質量％〜９０質量％とすることが挙げられる。 Content of the electrically-conductive member which the shield member which concerns on one Embodiment of this invention contains is set suitably. As an example which is not limited, it is mentioned that the compounding quantity of a conductive member shall be 60 mass%-90 mass% of the whole curable resin composition.
以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。 The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.
以下、実施例等により本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.
＜ＧＰＣ分析条件＞
（１）使用機器：東ソー社製「ＨＬＣ−８３２０ ＧＰＣ」
（２）カラム：いずれも東ソー社製、「ＴＳＫｇｅｌ ｓｕｐｅｒＨＺ４０００」（１本）＋「ＴＳＫｇｅｌ ｓｕｐｅｒＨＺ３０００」（１本）＋「ＴＳＫｇｅｌ ｓｕｐｅｒＨＺ２０００」（２本）＋「ＴＳＫｇｅｌ ｓｕｐｅｒＨＺ１０００」（１本）（各々６．０ｍｍ×１５ｃｍのカラムを接続）
（３）溶媒：テトラヒドロフラン
（４）流量：０．６ｍｌ／ｍｉｎ
（５）温度：４０℃
（６）検出器：示唆屈折率（ＲＩ）計（測定装置「ＨＬＣ−８３２０ ＧＰＣ」内蔵ＲＩ検出器）
（７）検量線用標準物質：東ソー社製 ポリスチレン
分子量 １．９０×Ｅ５、９．６４×Ｅ４、３．７９×Ｅ４、１．８１×Ｅ４、１．０２×Ｅ４、２．６３×Ｅ３、５．０×Ｅ２
<GPC analysis conditions>
(1) Equipment used: “HLC-8320 GPC” manufactured by Tosoh Corporation
(2) Column: All manufactured by Tosoh Corporation, “TSKgel superHZ4000” (1) + “TSKgel superHZ3000” (1) + “TSKgel superHZ2000” (2) + “TSKgel superHZ1000” (1) (each 6.) (Connect a column of 0mm x 15cm)
(3) Solvent: Tetrahydrofuran (4) Flow rate: 0.6 ml / min
(5) Temperature: 40 ° C
(6) Detector: Suggested refractive index (RI) meter (RI detector with built-in measuring device “HLC-8320 GPC”)
(7) Standard material for calibration curve: polystyrene manufactured by Tosoh Corporation
Molecular weight 1.90 × E5, 9.64 × E4, 3.79 × E4, 1.81 × E4, 1.02 × E4, 2.63 × E3, 5.0 × E2
（実施例１）
窒素ガス導入管、温度計、撹拌機を備えた四口の５００ｍＬフラスコに、末端水酸基含有水添ポリブタジエン（日本曹達社製「ＧＩ−３０００」、水酸基価２９．３ｍｇＫＯＨ／ｇ）５７．４ｇ、トルエン２８．７ｇを仕込み、室温で溶解した。次いで、４−クロロメチルベンゾイルクロライド５．７ｇ、トルエン６．１ｇを仕込み、１００〜１１０℃まで昇温して１０時間反応させ、室温まで冷却した。反応の際に生成する塩化水素ガスは系外に追い出して、水酸化ナトリウム水溶液のトラップに吸収させた。さらに、ポリフェニレンエーテルオリゴマー（ＳＡＢＩＣイノベーティブプラスチックス社製「ＮＯＲＹＬ ＳＡ９０」、水酸基当量７９２ｇ／ｅｑ）５３．５ｇ、クロロメチルスチレン（ＡＧＣセイミケミカル社製「ＣＭＳ−Ｐ」）５．９ｇ、テトラｎ−ブチルアンモニウムブロマイド０．５２ｇ、トルエン１８６．８ｇを仕込み、室温で溶解させた。次いで、１５％水酸化ナトリウム水溶液２３．８ｇを仕込み、７５℃に昇温して、その温度で２０時間反応させ、室温まで冷却した。さらに２０％リン酸二水素ナトリウム水溶液１２．５ｇを仕込み中和した。次いで、純水でトルエン層を洗浄し、減圧下でトルエンを留去し濃縮した。固形分５３．０％のビニルベンジルエーテル樹脂溶液（Ａ−１）を１７９．６ｇ得た。数平均分子量は６３００であった。
Example 1
In a four-necked 500 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 57.4 g of a hydroxyl group-containing hydrogenated polybutadiene (“GI-3000” manufactured by Nippon Soda Co., Ltd., hydroxyl value 29.3 mg KOH / g), toluene 28.7 g was charged and dissolved at room temperature. Next, 5.7 g of 4-chloromethylbenzoyl chloride and 6.1 g of toluene were charged, the temperature was raised to 100 to 110 ° C., the reaction was performed for 10 hours, and the mixture was cooled to room temperature. The hydrogen chloride gas produced during the reaction was driven out of the system and absorbed in a sodium hydroxide aqueous solution trap. Furthermore, 53.5 g of polyphenylene ether oligomer (“NORYL SA90” manufactured by SABIC Innovative Plastics, hydroxyl equivalent 792 g / eq), 5.9 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co.), tetra n-butyl 0.52 g of ammonium bromide and 186.8 g of toluene were charged and dissolved at room temperature. Next, 23.8 g of a 15% aqueous sodium hydroxide solution was added, the temperature was raised to 75 ° C., the reaction was carried out at that temperature for 20 hours, and the mixture was cooled to room temperature. Further, 12.5 g of a 20% aqueous sodium dihydrogen phosphate solution was charged and neutralized. Subsequently, the toluene layer was washed with pure water, and the toluene was distilled off under reduced pressure and concentrated. 179.6 g of vinylbenzyl ether resin solution (A-1) having a solid content of 53.0% was obtained. The number average molecular weight was 6300.
（実施例２）
窒素ガス導入管、温度計、撹拌機を備えた四口の５００ｍＬフラスコに、末端水酸基含有水添ポリイソプレン（出光興産社製「エポール」、水酸基価５２．２ｇＫＯＨ／ｇ）４３．０ｇ、トルエン２１．６ｇを仕込み、室温で溶解した。次いで、４−クロロメチルベンゾイルクロライド７．６ｇ、トルエン８．３ｇを仕込み、１００〜１１０℃まで昇温して１０時間反応させ、室温まで冷却した。反応の際に生成する塩化水素ガスは系外に追い出して、水酸化ナトリウム水溶液のトラップに吸収させた。さらに、ポリフェニレンエーテルオリゴマー（ＳＡＢＩＣイノベーティブプラスチックス社製「ＮＯＲＹＬ ＳＡ９０」、水酸基当量７９２ｇ／ｅｑ）６３．４ｇ、クロロメチルスチレン（ＡＧＣセイミケミカル社製「ＣＭＳ−Ｐ」）６．３ｇ、テトラｎ−ブチルアンモニウムブロマイド０．５２ｇ、トルエン１８６．６ｇを仕込み、室温で溶解させた。次いで、１５％水酸化ナトリウム水溶液２８．３ｇを仕込み、７５℃に昇温して、その温度で２０時間反応させ、室温まで冷却した。さらに２０％リン酸二水素ナトリウム水溶液１４．７ｇを仕込み中和した。次いで、純水でトルエン層を洗浄し、減圧下でトルエンを留去し濃縮した。固形分３５．２％のビニルベンジルエーテル樹脂溶液（Ａ−２）を２５８．８ｇ得た。数平均分子量は７４００であった。
(Example 2)
In a four-necked 500 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 43.0 g of a hydroxyl group-containing hydrogenated polyisoprene (“Epol” manufactured by Idemitsu Kosan Co., Ltd., hydroxyl value 52.2 gKOH / g), toluene 21 .6 g was charged and dissolved at room temperature. Next, 7.6 g of 4-chloromethylbenzoyl chloride and 8.3 g of toluene were charged, the temperature was raised to 100 to 110 ° C., the mixture was reacted for 10 hours, and cooled to room temperature. The hydrogen chloride gas produced during the reaction was driven out of the system and absorbed in a sodium hydroxide aqueous solution trap. Further, polyphenylene ether oligomer (“NORYL SA90” manufactured by SABIC Innovative Plastics, hydroxyl group equivalent 792 g / eq) 63.4 g, chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co.) 6.3 g, tetra n-butyl 0.52 g of ammonium bromide and 186.6 g of toluene were charged and dissolved at room temperature. Next, 28.3 g of a 15% aqueous sodium hydroxide solution was charged, the temperature was raised to 75 ° C., the reaction was carried out at that temperature for 20 hours, and the mixture was cooled to room temperature. Further, 14.7 g of a 20% aqueous sodium dihydrogen phosphate solution was added and neutralized. Subsequently, the toluene layer was washed with pure water, and the toluene was distilled off under reduced pressure and concentrated. 258.8 g of vinyl benzyl ether resin solution (A-2) having a solid content of 35.2% was obtained. The number average molecular weight was 7400.
（実施例３）
窒素ガス導入管、温度計、撹拌機を備えた四口の５００ｍＬフラスコに、末端水酸基含有水添ポリブタジエン（日本曹達社製「ＧＩ−２０００」、水酸基価４９．１ｇＫＯＨ／ｇ）４０．１ｇ、トルエン２０．０ｇを仕込み、室温で溶解した。次いで、４−クロロメチルベンゾイルクロライド６．７ｇ、トルエン７．２ｇを仕込み、１００〜１１０℃まで昇温して１０時間反応させ、室温まで冷却した。反応の際に生成する塩化水素ガスは系外に追い出して、水酸化ナトリウム水溶液のトラップに吸収させた。さらに、ポリフェニレンエーテルオリゴマー（三菱ガス化学社製「ＯＰＥ１０００」、水酸基当量４３５ｇ／ｅｑ、固形分４９．２％のトルエン溶液）６９．６ｇ、クロロメチルスチレン（ＡＧＣセイミケミカル社製「ＣＭＳ−Ｐ」）６．９ｇ、テトラｎ−ブチルアンモニウムブロマイド０．３８ｇ、トルエン９３．４ｇを仕込み、室温で溶解させた。次いで、１５％水酸化ナトリウム水溶液２７．７ｇを仕込み、７５℃に昇温して、その温度で２０時間反応させ、室温まで冷却した。さらに２０％リン酸二水素ナトリウム水溶液１４．４ｇを仕込み中和した。次いで、純水でトルエン層を洗浄し、減圧下でトルエンを留去し濃縮した。固形分６５．７％のビニルベンジルエーテル樹脂溶液（Ａ−３）を１１８．７ｇ得た。数平均分子量は２８００であった。
(Example 3)
In a four-necked 500 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 40.1 g of a hydroxyl group-containing hydrogenated polybutadiene (“GI-2000” manufactured by Nippon Soda Co., Ltd., hydroxyl value 49.1 gKOH / g), toluene 20.0 g was charged and dissolved at room temperature. Next, 6.7 g of 4-chloromethylbenzoyl chloride and 7.2 g of toluene were charged, the temperature was raised to 100 to 110 ° C., the mixture was reacted for 10 hours, and cooled to room temperature. The hydrogen chloride gas produced during the reaction was driven out of the system and absorbed in a sodium hydroxide aqueous solution trap. Furthermore, polyphenylene ether oligomer (Mitsubishi Gas Chemical Co., Ltd. “OPE1000”, hydroxyl group equivalent 435 g / eq, solid solution 49.2% toluene solution) 69.6 g, chloromethylstyrene (AGC Seimi Chemical Co., Ltd. “CMS-P”) 6.9 g, tetra n-butylammonium bromide 0.38 g, and toluene 93.4 g were charged and dissolved at room temperature. Next, 27.7 g of a 15% aqueous sodium hydroxide solution was charged, the temperature was raised to 75 ° C., the reaction was carried out at that temperature for 20 hours, and the mixture was cooled to room temperature. Furthermore, 14.4 g of a 20% aqueous sodium dihydrogen phosphate solution was charged and neutralized. Subsequently, the toluene layer was washed with pure water, and the toluene was distilled off under reduced pressure and concentrated. 118.7 g of a vinylbenzyl ether resin solution (A-3) having a solid content of 65.7% was obtained. The number average molecular weight was 2800.
（比較例１）
窒素ガス導入管、温度計、撹拌機を備えた四口の１Ｌフラスコに、ダイマージオール（クローダジャパン社製「プリポール２０３３」、水酸基価２１１ｍｇＫＯＨ／ｇ）５３．２ｇ、トルエン９１．４ｇを仕込み、室温で溶解した。次いで、４−クロロメチルベンゾイルクロライド３８．２ｇを仕込み、１００〜１１０℃まで昇温して１０時間反応させ、室温まで冷却した。反応の際に生成する塩化水素ガスは系外に追い出して、水酸化ナトリウム水溶液のトラップに吸収させた。さらに、α,α'−ビス(４−ヒドロキシ−３，５−ジメチルフェニル)−１，４−ジイソプロピルベンゼン（水酸基当量２０１ｇ／ｅｑ）８０．５ｇ、クロロメチルスチレン（ＡＧＣセイミケミカル社製「ＣＭＳ−Ｐ」）３０．５ｇ、テトラｎ−ブチルアンモニウムブロマイド０．５９ｇ、トルエン１１１．０ｇを仕込み、室温で溶解させた。次いで、１５％水酸化ナトリウム水溶液１３９．４ｇを仕込み、７５℃に昇温して、その温度で２０時間反応させ、室温まで冷却した。さらに２０％リン酸二水素ナトリウム水溶液７２．４ｇを仕込み中和した。次いで、純水でトルエン層を洗浄し、減圧下でトルエンを留去し濃縮した。固形分６３．６％のビニルベンジルエーテル樹脂溶液（Ａ−４）を２３４．０ｇ得た。数平均分子量は１９００であった。
(Comparative Example 1)
A four-neck 1 L flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer was charged with 53.2 g of dimer diol (Cropa Japan “Prepol 2033”, hydroxyl value 211 mg KOH / g) and 91.4 g of toluene at room temperature. And dissolved. Next, 48.2 g of 4-chloromethylbenzoyl chloride was charged, the temperature was raised to 100 to 110 ° C., the reaction was performed for 10 hours, and the mixture was cooled to room temperature. The hydrogen chloride gas produced during the reaction was driven out of the system and absorbed in a sodium hydroxide aqueous solution trap. Furthermore, α, α′-bis (4-hydroxy-3,5-dimethylphenyl) -1,4-diisopropylbenzene (hydroxyl equivalent 201 g / eq) 80.5 g, chloromethylstyrene (AGC Seimi Chemical Co., Ltd. “CMS- P ") 30.5 g, tetra n-butylammonium bromide 0.59 g, and toluene 111.0 g were charged and dissolved at room temperature. Next, 139.4 g of a 15% aqueous sodium hydroxide solution was charged, the temperature was raised to 75 ° C., the reaction was carried out at that temperature for 20 hours, and the mixture was cooled to room temperature. Further, 72.4 g of a 20% aqueous sodium dihydrogen phosphate solution was added and neutralized. Subsequently, the toluene layer was washed with pure water, and the toluene was distilled off under reduced pressure and concentrated. 234.0g of vinyl benzyl ether resin solution (A-4) with a solid content of 63.6% was obtained. The number average molecular weight was 1900.
(比較例２)
窒素ガス導入管、温度計、撹拌機を備えた四口の５００ｍＬフラスコに、ポリフェニレンエーテルオリゴマー（ＳＡＢＩＣイノベーティブプラスチックス社製「ＮＯＲＹＬ ＳＡ９０」、水酸基当量７９２ｇ／ｅｑ）７９．２ｇ、クロロメチルスチレン（ＡＧＣセイミケミカル社製「ＣＭＳ−Ｐ」）１５．４ｇ、テトラｎ−ブチルアンモニウムブロマイド０．３９ｇ、トルエン２１２．４ｇを仕込み、室温で溶解させた。次いで、１５％水酸化ナトリウム水溶液３５．２ｇを仕込み、７５℃に昇温して、その温度で２０時間反応させ、室温まで冷却した。さらに２０％リン酸二水素ナトリウム水溶液１８．３ｇを仕込み中和した。次いで、純水でトルエン層を洗浄し、減圧下でトルエンを留去し濃縮した。固形分５１．２％のビニルベンジルエーテル樹脂溶液（Ａ−５）を１７５．８ｇ得た。数平均分子量は１８００であった。
(Comparative Example 2)
In a four-necked 500 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, polyphenylene ether oligomer (“NORYL SA90” manufactured by SABIC Innovative Plastics, hydroxyl equivalent 792 g / eq) 79.2 g, chloromethylstyrene (AGC) 15.4 g of “CMS-P” manufactured by Seimi Chemical Co., Ltd., 0.39 g of tetra-n-butylammonium bromide and 212.4 g of toluene were charged and dissolved at room temperature. Next, 35.2 g of a 15% aqueous sodium hydroxide solution was charged, the temperature was raised to 75 ° C., the reaction was carried out at that temperature for 20 hours, and the mixture was cooled to room temperature. Further, 18.3 g of a 20% aqueous sodium dihydrogen phosphate solution was charged and neutralized. Subsequently, the toluene layer was washed with pure water, and the toluene was distilled off under reduced pressure and concentrated. 175.8 g of vinyl benzyl ether resin solution (A-5) having a solid content of 51.2% was obtained. The number average molecular weight was 1800.
（実施例４〜６、比較例３、４）
実施例１〜３および比較例１および２において作製した各ビニルベンジルエーテル樹脂溶液（Ａ−１〜Ａ−５）を固形分として１５質量部に対しジクミルパーオキサイド（ＤＣＰ）０．１５質量部を混合・溶解し、樹脂組成物ワニスを作製した。さらに、銅箔光沢面に樹脂組成物ワニスを塗工し、８０℃で５分間乾燥し、実施例４〜６および比較例３は１７０℃にて１時間真空下で硬化させた。比較例４は２３０℃にて２時間真空化で硬化させた。硬化後、銅箔から引き剥がして膜厚約１００μｍの硬化物フィルム（硬化物）を得た。
(Examples 4 to 6, Comparative Examples 3 and 4)
Each vinyl benzyl ether resin solution (A-1 to A-5) prepared in Examples 1 to 3 and Comparative Examples 1 and 2 is 0.15 parts by mass of dicumyl peroxide (DCP) with respect to 15 parts by mass as a solid content. Were mixed and dissolved to prepare a resin composition varnish. Further, the resin composition varnish was applied to the glossy surface of the copper foil and dried at 80 ° C. for 5 minutes, and Examples 4 to 6 and Comparative Example 3 were cured at 170 ° C. for 1 hour under vacuum. Comparative Example 4 was cured by vacuuming at 230 ° C. for 2 hours. After curing, it was peeled off from the copper foil to obtain a cured film (cured product) having a film thickness of about 100 μm.
（耐熱分解性の測定）
実施例４〜６および比較例３、４で得られた硬化物フィルムを、測定容器に入る大きさにカット（切り出）して耐熱分解性のサンプルとした。以下の条件にてサンプルの重量が１％したときの温度（１％重量減少温度）および５％減少したときの温度（５％重量減少温度）を測定し、この温度により耐熱分解性を評価した。
測定機器：日立ハイテクサイエンス社製 熱機械分析装置「ＴＧ／ＤＴＡ７２２０」
雰囲気：空気中
測定温度：２５〜４５０℃
昇温速度：１０℃／分
(Measurement of thermal decomposition resistance)
The cured product films obtained in Examples 4 to 6 and Comparative Examples 3 and 4 were cut (cut out) into a size that could fit into a measurement container to obtain a heat-resistant decomposable sample. Under the following conditions, the temperature when the weight of the sample was 1% (1% weight reduction temperature) and the temperature when the sample was reduced by 5% (5% weight reduction temperature) were measured, and the thermal decomposition resistance was evaluated based on this temperature. .
Measuring instrument: Thermomechanical analyzer “TG / DTA7220” manufactured by Hitachi High-Tech Science Co., Ltd.
Atmosphere: In air Measurement temperature: 25-450 ° C
Temperature increase rate: 10 ° C / min
（機械特性の評価）
実施例４〜６および比較例３，４で得られた硬化物フィルムを、所定の大きさにカット（切り出）して柔軟性評価のサンプルとした。以下の条件にてサンプルの機械特性を測定した。
測定機器：島津製作所社製万能試験機「オートグラフＡＧ−Ｘｐｌｕｓ」
サンプル寸法：幅１０ｍｍ×長さ（掴み具間距離）１００ｍｍ×厚さ０．１ｍｍ（１００μｍ）
測定項目：引張弾性率（単位：ＧＰａ）、引張強度（単位：ＭＰａ）、伸び率（単位：％）いずれも５回の測定の平均値
(Evaluation of mechanical properties)
The cured film obtained in Examples 4 to 6 and Comparative Examples 3 and 4 was cut (cut out) into a predetermined size to obtain a sample for flexibility evaluation. The mechanical properties of the sample were measured under the following conditions.
Measuring instrument: Universal test machine "Autograph AG-Xplus" manufactured by Shimadzu Corporation
Sample dimensions: width 10 mm x length (distance between grippers) 100 mm x thickness 0.1 mm (100 μm)
Measurement items: Tensile modulus (unit: GPa), tensile strength (unit: MPa), elongation (unit:%) are all average values of five measurements.
（誘電特性の評価）
実施例４〜６および比較例３、４で得られた硬化物フィルムで得られた硬化物フィルムを所定の大きさに切り出して、測定用のサンプルとした。下記の測定機器を用いて、以下の条件にてサンプルの誘電特性を測定した。
測定機器：キーサイトテクノロジー社製ネットワークアナライザー「Ｅ５０７１Ｃ」
関東電子応用開発社製摂動法空洞共振器「ＣＰ−５２１」
周波数：５．８ＧＨｚ
サンプル寸法：幅２ｍｍ×長さ７０ｍｍ×厚さ０．１ｍｍ（１００μｍ）
(Evaluation of dielectric properties)
The cured product films obtained from the cured product films obtained in Examples 4 to 6 and Comparative Examples 3 and 4 were cut into a predetermined size and used as measurement samples. The dielectric properties of the samples were measured using the following measuring equipment under the following conditions.
Measuring equipment: Network analyzer “E5071C” manufactured by Keysight Technology
Perturbation cavity resonator “CP-521” manufactured by Kanto Electronics Application Development Co., Ltd.
Frequency: 5.8GHz
Sample dimensions: width 2 mm x length 70 mm x thickness 0.1 mm (100 μm)
評価結果を表１に示す。
表１に示されるように、分子量１０００以上のアルキレン基と分子量５００以上の２官能フェノールで構成させるビニルベンジルエーテル樹脂を硬化させた実施例４〜６において、誘電特性および柔軟性に優れることが判る。分子量１０００未満の脂肪族構造および分子量５００未満の２官能フェノールで構成される比較例３は誘電特性および柔軟性に劣ることが判る。アルキレン基で変性されていない比較例４は、耐熱性（５％重量減少温度）は高いものの、柔軟性が全くなく誘電特性も劣る。 As shown in Table 1, in Examples 4 to 6 in which a vinylbenzyl ether resin composed of an alkylene group having a molecular weight of 1000 or more and a bifunctional phenol having a molecular weight of 500 or more was cured, it was found that the dielectric properties and flexibility were excellent. . It can be seen that Comparative Example 3 composed of an aliphatic structure having a molecular weight of less than 1000 and a bifunctional phenol having a molecular weight of less than 500 is inferior in dielectric properties and flexibility. Comparative Example 4 that is not modified with an alkylene group has high heat resistance (5% weight loss temperature), but has no flexibility and poor dielectric properties.
Claims (8)
（上記一般式（１）中、Ａは下記一般式（２）で示されるビニルベンジル基であり、Ｚは下記一般式（３）で示される２官能フェノール類の残基であり、Ｙは下記一般式（４）で示されるアルキレン基であり、平均繰り返し数ｎは０．３以上２．０以下である。）
（上記一般式（２）中、Ｒ１からＲ５は同一または異なってもよく、水素またはメチル基である。）
（上記一般式（３）中、Ｒ６は直接結合、−ＣＨ２−、−ＣＨ（ＣＨ３）−、−Ｃ（ＣＨ３）２−、または下記式（５）であり、ｍおよびｌはそれぞれ０以上の整数であり、ｍ＋ｌは２以上３０以下である。）
（上記一般式（４）中、Ｒ７およびＲ１１はいずれも−ＣＨ２−ＣＨ２−であり、Ｒ８は−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−であり、Ｒ９は−ＣＨ２−ＣＨ（Ｃ２Ｈ５）−であり、Ｒ１０は−ＣＨ２−ＣＨ（ＣＨ３）−ＣＨ２−ＣＨ２−であり、ａおよびｅはそれぞれ０または１であり、ｂ，ｃ，およびｄはそれぞれ０以上１００以下の整数であり、ａ＋ｂ＋ｃ＋ｄ＋ｅは１以上である。）
(In the above general formula (1), A is a vinylbenzyl group represented by the following general formula (2), Z is a residue of a bifunctional phenol represented by the following general formula (3), and Y is (It is an alkylene group represented by the general formula (4), and the average repeating number n is 0.3 or more and 2.0 or less.)
(In the general formula (2), R 1 to R 5 may be the same or different, and are hydrogen or a methyl group.)
(In the general formula (3), R 6 is a direct bond, —CH 2 —, —CH (CH 3 ) —, —C (CH 3 ) 2 —, or the following formula (5), and m and l are Each is an integer of 0 or more, and m + 1 is 2 or more and 30 or less.)
(In the general formula (4), R 7 and R 11 are both —CH 2 —CH 2 —, R 8 is —CH 2 —CH 2 —CH 2 —CH 2 —, and R 9 is — CH 2 —CH (C 2 H 5 ) —, R 10 is —CH 2 —CH (CH 3 ) —CH 2 —CH 2 —, a and e are each 0 or 1, b, c , And d are each an integer of 0 or more and 100 or less, and a + b + c + d + e is 1 or more.)
前記第１ステップで得られた前記エステル化合物と、下記一般式（８）に示される２官能フェノール類と、下記一般式（９）に示されるビニルベンジルハライド化合物とを反応させて、請求項１に記載されるビニルベンジルエーテル樹脂を得る第２ステップと
を備えることを特徴とするビニルベンジルエーテル樹脂の製造方法。
（上記一般式（６）におけるＹは請求項１に定義されるとおりである。）
（上記一般式（７）におけるＸ１はハロゲン元素であり、Ｙは請求項１に定義されるとおりである。）
（上記一般式（８）におけるＲ６ならびにｍおよびｌは請求項１に定義されるとおりである。）
（上記一般式（９）におけるＲ１からＲ５は請求項１に定義されるとおりであり、Ｘ２はハロゲン元素である。）
A first step of reacting an alkylene diol represented by the following general formula (6) with a halomethyl aromatic acid halide to obtain an ester compound represented by the following general formula (7);
The ester compound obtained in the first step, a bifunctional phenol represented by the following general formula (8), and a vinylbenzyl halide compound represented by the following general formula (9) are reacted with each other. And a second step of obtaining a vinyl benzyl ether resin described in 1. above.
(Y in the general formula (6) is as defined in claim 1)
(X 1 in the general formula (7) is a halogen element, and Y is as defined in claim 1.)
(In the general formula (8), R 6 and m and l are as defined in claim 1).
(R 1 to R 5 in the general formula (9) are as defined in claim 1 and X 2 is a halogen element.)
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