JP2020152830A - Epoxy resin composition and its cured product - Google Patents
Epoxy resin composition and its cured product Download PDFInfo
- Publication number
- JP2020152830A JP2020152830A JP2019053063A JP2019053063A JP2020152830A JP 2020152830 A JP2020152830 A JP 2020152830A JP 2019053063 A JP2019053063 A JP 2019053063A JP 2019053063 A JP2019053063 A JP 2019053063A JP 2020152830 A JP2020152830 A JP 2020152830A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- cured product
- epoxy
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 136
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 136
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 28
- CXENHBSYCFFKJS-UHFFFAOYSA-N (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene Natural products CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 24
- 229930009668 farnesene Natural products 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000002009 diols Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 239000000047 product Substances 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000008065 acid anhydrides Chemical class 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 150000002460 imidazoles Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- -1 diene compound Chemical class 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- JXBSHSBNOVLGHF-UHFFFAOYSA-N 10-cis-Dihydrofarnesen Natural products CC=C(C)CCC=C(C)CCC=C(C)C JXBSHSBNOVLGHF-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- NSYRAUUZGRPOHS-UHFFFAOYSA-N 2-methylocta-1,3-diene Chemical compound CCCCC=CC(C)=C NSYRAUUZGRPOHS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FKBMTBAXDISZGN-UHFFFAOYSA-N 5-methyl-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1C(C)CCC2C(=O)OC(=O)C12 FKBMTBAXDISZGN-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical group N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004886 head movement Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JFNWATIZEGZGSY-UHFFFAOYSA-N n,n-diethylethanamine;trifluoroborane Chemical compound FB(F)F.CCN(CC)CC JFNWATIZEGZGSY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、エポキシ樹脂組成物及びその硬化物に関する。 The present invention relates to an epoxy resin composition and a cured product thereof.
一般的にエポキシ樹脂は種々の硬化剤で硬化させることにより、機械的性質、耐水性、耐薬品性、耐熱性、及び電気的性質等に優れた硬化物を形成する。そのため、電気及び／又は電子材料、構造用材料、並びに塗料等の幅広い分野で利用されている。特に、半導体用封止剤、積層板、ＦＲＰ（複合材料）、接着剤等の電気及び／又は電子材料用分野では、耐熱性及び機械強度のバランスの良さから、ビスフェノールＡ型エポキシ樹脂等のエポキシ樹脂が多用されている。 Generally, an epoxy resin is cured with various curing agents to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, it is used in a wide range of fields such as electrical and / or electronic materials, structural materials, and paints. In particular, in the field of electrical and / or electronic materials such as semiconductor encapsulants, laminates, FRP (composite materials), and adhesives, epoxy such as bisphenol A type epoxy resin has a good balance of heat resistance and mechanical strength. Resin is often used.
特許文献１には、ファルネセン由来の単量体単位を有する重合体に対して重合可能な官能基を導入した重合体が、強度、柔軟性、低透湿性及び透明性に優れる硬化物を与えることができ、更に重合体として粘度が低く、硬化速度が速く、更に硬化収縮性に優れることが記載されている。 According to Patent Document 1, a polymer in which a polymerizable functional group is introduced into a polymer having a monomer unit derived from farnesene provides a cured product having excellent strength, flexibility, low moisture permeability and transparency. It is described that the polymer has a low viscosity, a high curing rate, and an excellent curing shrinkage.
国際公開第２０１４／１５７６２４号 International Publication No. 2014/157624
しかしながら、従来の樹脂組成物は、絶縁性及び耐熱性が不十分であり、改善の余地がある。 However, the conventional resin composition has insufficient insulating properties and heat resistance, and there is room for improvement.
本開示は、低い誘電率及び高い耐熱性を有する硬化物を与えることができるエポキシ樹脂組成物を提供することを目的とする。 It is an object of the present disclosure to provide an epoxy resin composition capable of providing a cured product having a low dielectric constant and high heat resistance.
本開示の第一は、ファルネセン由来の単量体単位を含む重合体骨格（ａ）及びエポキシ基を有するエポキシ樹脂（Ａ）、並びに前記エポキシ樹脂（Ａ）以外のエポキシ樹脂（Ｂ）を含む、エポキシ樹脂組成物に関する。 The first of the present disclosure includes a polymer skeleton (a) containing a monomer unit derived from farnesene, an epoxy resin (A) having an epoxy group, and an epoxy resin (B) other than the epoxy resin (A). Regarding epoxy resin compositions.
前記エポキシ樹脂組成物において、前記エポキシ基がグリシジル基であってよい。 In the epoxy resin composition, the epoxy group may be a glycidyl group.
前記エポキシ樹脂組成物において、前記重合体骨格（ａ）がファルネセン由来の単量体のホモポリマー骨格であってよい。 In the epoxy resin composition, the polymer skeleton (a) may be a homopolymer skeleton of a monomer derived from farnesene.
前記エポキシ樹脂組成物において、前記エポキシ樹脂（Ａ）が下記一般式（１）で表されるポリファルネセンジオールのエポキシ化物であってよい。 In the epoxy resin composition, the epoxy resin (A) may be an epoxidized product of a polyfarnesene diol represented by the following general formula (1).
（上記一般式（１）中、ｍ及びｎは、それぞれ０又は１以上の整数であり、かつ、ｍ＋ｎは３以上の整数である。） (In the above general formula (1), m and n are integers of 0 or 1 or more, respectively, and m + n is an integer of 3 or more.)
前記エポキシ樹脂組成物において、前記エポキシ樹脂（Ｂ）が芳香族エポキシ樹脂であってよい。 In the epoxy resin composition, the epoxy resin (B) may be an aromatic epoxy resin.
前記エポキシ樹脂組成物において、さらに硬化剤及び／又は硬化促進剤を含んでよい。 The epoxy resin composition may further contain a curing agent and / or a curing accelerator.
前記エポキシ樹脂組成物は、イミダゾール硬化系であってよい。 The epoxy resin composition may be an imidazole curing system.
本開示の第二は、前記エポキシ樹脂組成物の硬化物に関する。 The second aspect of the present disclosure relates to a cured product of the epoxy resin composition.
本開示によれば、低い誘電率及び高い耐熱性を有する硬化物を与えることができるエポキシ樹脂組成物を提供することができる。 According to the present disclosure, it is possible to provide an epoxy resin composition capable of giving a cured product having a low dielectric constant and high heat resistance.
［エポキシ樹脂組成物］
本開示のエポキシ樹脂組成物は、ファルネセン由来の単量体単位を含む重合体骨格（ａ）及びエポキシ基を有するエポキシ樹脂（Ａ）、並びに前記エポキシ樹脂（Ａ）以外のエポキシ樹脂（Ｂ）を含む。
[Epoxy resin composition]
The epoxy resin composition of the present disclosure comprises a polymer skeleton (a) containing a monomer unit derived from farnesene, an epoxy resin (A) having an epoxy group, and an epoxy resin (B) other than the epoxy resin (A). Including.
（エポキシ樹脂（Ａ））
エポキシ樹脂（Ａ）における、ファルネセン由来の単量体単位を含む重合体骨格（ａ）について詳述する。重合体骨格（ａ）は、ファルネセン由来の単量体単位を含むものであれば、特に限定されず、ファルネセン由来の単量体単位のみからなるものでよく、ファルネセン由来の単量体単位以外の単量体単位を含んでもよい。誘電率を効率的に低下出来るため、重合体骨格（ａ）は、ファルネセン由来の単量体のホモポリマー骨格であることが好ましい。
(Epoxy resin (A))
The polymer skeleton (a) containing the farnesene-derived monomer unit in the epoxy resin (A) will be described in detail. The polymer skeleton (a) is not particularly limited as long as it contains a monomer unit derived from farnesene, and may consist only of a monomer unit derived from farnesene, other than the monomer unit derived from farnesene. It may contain monomeric units. Since the dielectric constant can be reduced efficiently, the polymer skeleton (a) is preferably a homopolymer skeleton of a monomer derived from farnesene.
ファルネセン由来の単量体単位としては、下記式（２）に示すようなα−ファルネセン由来の単量体単位であってよく、下記式（３）に示すようなβ−ファルネセン由来の単量体単位であってよい。また、重合体骨格（ａ）は、α−ファルネセン由来の単量体単位及びβ−ファルネセン由来の単量体単位を両方有してよい。 The farnesene-derived monomer unit may be an α-farnesene-derived monomer unit as shown in the following formula (2), and a β-farnesene-derived monomer as shown in the following formula (3). It may be a unit. Further, the polymer skeleton (a) may have both a monomer unit derived from α-farnesene and a monomer unit derived from β-farnesene.
なお、β−ファルネセンは、サトウキビ等の植物から製造することができる。 In addition, β-farnesene can be produced from plants such as sugar cane.
ファルネセン由来の単量体単位以外の単量体単位としては、共役ジエン化合物由来の単量体単位を挙げることができる。 Examples of the monomer unit other than the monomer unit derived from farnesene include a monomer unit derived from a conjugated diene compound.
共役ジエン化合物としては、例えば、イソプレン、ブタジエン、２−フェニル−ブタジエン、２，３−ジメチル−ブタジエン、１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、１，３−ヘキサジエン、１，３−オクタジエン、１，３−シクロヘキサジエン、及び２−メチル−１，３−オクタジエン等が挙げられる。これらのうちイソプレン、及びブタジエンが好ましい。これらの共役ジエン化合物は、１種が単独で含まれてよく、２種以上が併用して含まれてよい。 Examples of the conjugated diene compound include isoprene, butadiene, 2-phenyl-butadiene, 2,3-dimethyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1, Examples thereof include 3-octadien, 1,3-cyclohexadiene, and 2-methyl-1,3-octadien. Of these, isoprene and butadiene are preferable. One of these conjugated diene compounds may be contained alone, and two or more thereof may be contained in combination.
ファルネセン由来の単量体単位を含む重合体骨格（ａ）におけるファルネセン由来の単量体単位の含有量としては、６０モル％以上、７０モル％以上、８０モル％以上、９０モルモル％以上、９５モル％以上、又は１００モル％であってよい。 The content of the farnesene-derived monomer unit in the polymer skeleton (a) containing the farnesene-derived monomer unit is 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol mol% or more, 95. It may be 100 mol% or more, or 100 mol%.
エポキシ樹脂（Ａ）におけるエポキシ基について詳述する。ここで、エポキシ基とは、脂環を構成する隣接する２つの炭素原子と酸素原子とで構成される三員環のエーテルであるオキシラン骨格をいう。 The epoxy group in the epoxy resin (A) will be described in detail. Here, the epoxy group refers to an oxylan skeleton which is a three-membered ring ether composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic.
エポキシ基は、ファルネセン由来の単量体単位を含む重合体骨格（ａ）の末端に位置するエポキシ基であってよく、ファルネセン由来の単量体単位を含む重合体骨格（ａ）の内部に位置する内部エポキシ基であってよい。 The epoxy group may be an epoxy group located at the end of the polymer skeleton (a) containing a phenolicene-derived monomer unit, and may be located inside the polymer skeleton (a) containing a farnesen-derived monomer unit. It may be an internal epoxy group.
エポキシ樹脂組成物がより高い耐熱性を有する硬化物を与えることができる観点からは、エポキシ樹脂（Ａ）が内部エポキシ基を有する方が好ましい。 From the viewpoint that the epoxy resin composition can provide a cured product having higher heat resistance, it is preferable that the epoxy resin (A) has an internal epoxy group.
前記末端に位置するエポキシ基としては、例えば、グリシジル基、及びグリシジルエーテル基等が挙げられる。 Examples of the epoxy group located at the terminal include a glycidyl group and a glycidyl ether group.
前記内部エポキシ基は、ファルネセン由来の単量体単位を含む重合体骨格（ａ）の主鎖に位置してよく、側鎖に結合してよい。また、ファルネセンに由来する炭素−炭素二重結合をエポキシ化したものであってよい。 The internal epoxy group may be located in the main chain of the polymer skeleton (a) containing a monomer unit derived from farnesene, and may be bonded to the side chain. Further, the carbon-carbon double bond derived from farnesene may be epoxidized.
エポキシ樹脂（Ａ）のエポキシ当量は、２００ｇ／ｅｑ以上８０００ｇ／ｅｑ以下が好ましく、３００ｇ／ｅｑ以上７０００ｇ／ｅｑ以下がより好ましく、４００ｇ／ｅｑ以上６０００ｇ／ｅｑ以下がさらに好ましい。２００ｇ／ｅｑ未満であると、得られる硬化物の架橋密度が高くなりすぎ、機械強度が著しく悪化する恐れがあり、８０００ｇ／ｅｑを超えると架橋密度が不十分（低すぎること）となり、硬化不良が起きる恐れがある。 The epoxy equivalent of the epoxy resin (A) is preferably 200 g / eq or more and 8000 g / eq or less, more preferably 300 g / eq or more and 7000 g / eq or less, and further preferably 400 g / eq or more and 6000 g / eq or less. If it is less than 200 g / eq, the crosslink density of the obtained cured product becomes too high and the mechanical strength may be significantly deteriorated. If it exceeds 8000 g / eq, the crosslink density becomes insufficient (too low) and curing is poor. May occur.
エポキシ樹脂（Ａ）のエポキシ当量は、ＪＩＳ Ｋ ７２３６に基づき測定することができる。 The epoxy equivalent of the epoxy resin (A) can be measured based on JIS K 7236.
エポキシ樹脂（Ａ）の重量平均分子量Ｍｗは１０００以上８０００以下が好ましく、２０００以上６０００以下がより好ましい。１０００未満であると、得られる硬化物の機械強度が低下する原因となり、８０００を超えるとそのエポキシ樹脂（Ａ）及びエポキシ樹脂組成物の粘度が著しく高くなり、作業性が悪化する恐れがある。 The weight average molecular weight Mw of the epoxy resin (A) is preferably 1000 or more and 8000 or less, and more preferably 2000 or more and 6000 or less. If it is less than 1000, it causes a decrease in the mechanical strength of the obtained cured product, and if it exceeds 8000, the viscosity of the epoxy resin (A) and the epoxy resin composition becomes remarkably high, and workability may be deteriorated.
エポキシ樹脂（Ａ）の数平均分子量Ｍｎは１０００以上８０００以下が好ましく、２０００以上６０００以下がより好ましい。１０００未満であると、得られる硬化物の機械強度が低下する原因となり、８０００を超えるとそのエポキシ樹脂（Ａ）及びエポキシ樹脂組成物の粘度が著しく高くなり、作業性が悪化する恐れがある。 The number average molecular weight Mn of the epoxy resin (A) is preferably 1000 or more and 8000 or less, and more preferably 2000 or more and 6000 or less. If it is less than 1000, it causes a decrease in the mechanical strength of the obtained cured product, and if it exceeds 8000, the viscosity of the epoxy resin (A) and the epoxy resin composition becomes remarkably high, and workability may be deteriorated.
重量平均分子量Ｍｗ及び数平均分子量Ｍｎはポリスチレン換算ゲル透過クロマトグラフィー（ＧＰＣ）にて測定することができる。 The weight average molecular weight Mw and the number average molecular weight Mn can be measured by polystyrene conversion gel permeation chromatography (GPC).
エポキシ樹脂（Ａ）の粘度は、２５℃における粘度として、１００ｍＰａ・ｓ以上３００００ｍＰａ・ｓ以下が好ましく、５００ｍＰａ・ｓ以上１００００ｍＰａ・ｓ以下がより好ましく、１０００ｍＰａ・ｓ以上８０００ｍＰａ・ｓ以下がさらに好ましい。作業性に優れるためである。１００ｍＰａ・ｓ未満であると、エポキシ樹脂組成物の粘度が著しく低くなり、３００００を超えると配合時（言い換えれば、エポキシ樹脂組成物の調製時）の作業が困難となる。 The viscosity of the epoxy resin (A) at 25 ° C. is preferably 100 mPa · s or more and 30,000 mPa · s or less, more preferably 500 mPa · s or more and 10000 mPa · s or less, and further preferably 1000 mPa · s or more and 8000 mPa · s or less. This is because it is excellent in workability. If it is less than 100 mPa · s, the viscosity of the epoxy resin composition becomes remarkably low, and if it exceeds 30,000, the work at the time of blending (in other words, at the time of preparing the epoxy resin composition) becomes difficult.
エポキシ樹脂（Ａ）の２５℃における粘度は、Ｅ型粘度計により測定することができる。 The viscosity of the epoxy resin (A) at 25 ° C. can be measured with an E-type viscometer.
前記エポキシ樹脂（Ａ）が下記一般式（１）で表されるポリファルネセンジオールのエポキシ化物であることが好ましい。下記一般式（１）で表されるポリファルネセンジオールは、ランダム共重合体、交互共重合体、及びブロック共重合体のいずれであってもよい。
上記一般式（１）中、ｍ及びｎは、それぞれ０又は１以上の整数であり、かつ、ｍ＋ｎは３以上の整数である。 In the general formula (1), m and n are integers of 0 or 1 or more, respectively, and m + n is an integer of 3 or more.
上記一般式（１）で表されるポリファルネセンジオールのエポキシ化物としては、ｉ）上記一般式（１）で表されるポリファルネセンジオールの水酸基をエピクロルヒドリン等のエピハロヒドリンと反応させてエポキシ化することにより得られるエポキシ化物、ｉｉ）上記一般式（１）で表されるポリファルネセンジオールの炭素−炭素二重結合を過酸化水素等の過酸化物と反応させてエポキシ化することにより得られるエポキシ化物、及びｉｉｉ）上記一般式（１）で表されるポリファルネセンジオールの水酸基及び炭素−炭素二重結合の両方をエポキシ化することにより得られるエポキシ化物のいずれであってもよい。 Examples of the epoxy compound of the polyfarnesenediol represented by the general formula (1) include i) an epoxy obtained by reacting the hydroxyl group of the polyfarnesenediol represented by the general formula (1) with an epihalohydrin such as epichlorohydrin. Epoxy product obtained by epoxiation, ii) Epoxy by reacting the carbon-carbon double bond of the polyfarnesene diol represented by the above general formula (1) with a peroxide such as hydrogen peroxide. And iii) Any of the epoxidized products obtained by epoxidizing both the hydroxyl group and the carbon-carbon double bond of the polyfarnesene diol represented by the above general formula (1). May be good.
より高い耐熱性を有する硬化物を与えることができる観点からは、ｉｉ）上記一般式（１）で表されるポリファルネセンジオールの炭素−炭素二重結合を過酸化水素等の過酸化物と反応させてエポキシ化することにより得られるエポキシ化物が好ましい。 From the viewpoint of being able to provide a cured product having higher heat resistance, ii) the carbon-carbon double bond of the polyfarnesene diol represented by the above general formula (1) is a peroxide such as hydrogen peroxide. An epoxidized product obtained by reacting with and epoxidizing is preferable.
後述するように、硬化剤として酸無水物を用いる場合、機械強度、特に曲げ強度に優れる硬化物を与えることができる観点からは、ｉ）上記一般式（１）で表されるポリファルネセンジオールの水酸基をエピクロルヒドリン等のエピハロヒドリンと反応させてエポキシ化することにより得られるエポキシ化物が好ましい。 As will be described later, when an acid anhydride is used as the curing agent, from the viewpoint of being able to provide a cured product having excellent mechanical strength, particularly bending strength, i) polyfarnesene represented by the above general formula (1). An epoxidized product obtained by reacting the hydroxyl group of the diol with epichlorohydrin such as epichlorohydrin to epoxidize it is preferable.
エポキシ樹脂組成物におけるエポキシ樹脂（Ａ）の配合量は適宜調整すればよく、特に限定されないが、エポキシ樹脂（Ａ）及びエポキシ樹脂（Ｂ）の合計１００重量部に対し、エポキシ樹脂（Ａ）が１重量部以上５０重量部以下が好ましく、３重量部以上１５重量部以下がより好ましく、５重量部以上２５重量部以下がさらに好ましい。特に低い誘電率を有する、より誘電特性に優れる硬化物が得られるためである。５０重量部を超えると機械強度が低下する。 The blending amount of the epoxy resin (A) in the epoxy resin composition may be appropriately adjusted and is not particularly limited, but the epoxy resin (A) is used with respect to a total of 100 parts by weight of the epoxy resin (A) and the epoxy resin (B). It is preferably 1 part by weight or more and 50 parts by weight or less, more preferably 3 parts by weight or more and 15 parts by weight or less, and further preferably 5 parts by weight or more and 25 parts by weight or less. This is because a cured product having a particularly low dielectric constant and having more excellent dielectric properties can be obtained. If it exceeds 50 parts by weight, the mechanical strength decreases.
（エポキシ樹脂（Ｂ））
前記エポキシ樹脂（Ａ）以外のエポキシ樹脂（Ｂ）について詳述する。エポキシ樹脂（Ｂ）は、前記エポキシ樹脂（Ａ）以外であって、１分子あたり２以上のエポキシ基を有する樹脂であれば、特に限定されない。エポキシ樹脂（Ｂ）としては、脂肪族エポキシ樹脂及び芳香族エポキシ樹脂が挙げられる。これらの中では、特に低い誘電率を有し、より誘電特性に優れ、さらに、耐熱性にも優れる硬化物が得られるため、芳香族エポキシ樹脂が好ましい。
(Epoxy resin (B))
The epoxy resin (B) other than the epoxy resin (A) will be described in detail. The epoxy resin (B) is not particularly limited as long as it is a resin other than the epoxy resin (A) and has two or more epoxy groups per molecule. Examples of the epoxy resin (B) include an aliphatic epoxy resin and an aromatic epoxy resin. Among these, an aromatic epoxy resin is preferable because a cured product having a particularly low dielectric constant, more excellent dielectric properties, and excellent heat resistance can be obtained.
脂肪族エポキシ樹脂としては、ポリブタジエン骨格を有するエポキシ樹脂、及び水素化ポリブタジエン骨格を有するエポキシ樹脂、ポリエチレングリコール骨格を有するエポキシ樹脂、及びポリプロピレングリコール骨格を有するエポキシ樹脂等が挙げられる。 Examples of the aliphatic epoxy resin include an epoxy resin having a polybutadiene skeleton, an epoxy resin having a hydride polybutadiene skeleton, an epoxy resin having a polyethylene glycol skeleton, and an epoxy resin having a polypropylene glycol skeleton.
芳香族エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂及びビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂、並びにフェノールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂等が挙げられる。これらの中でも、ビスフェノールＡ型エポキシ樹脂が好ましい。より耐熱性に優れる硬化物を与えられるためである。 Examples of the aromatic epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, and novolac type epoxy resins such as phenol novolac type epoxy resin. Among these, bisphenol A type epoxy resin is preferable. This is because a cured product having more excellent heat resistance can be provided.
（任意成分）
エポキシ樹脂組成物は、任意成分として、硬化剤、硬化促進剤、及び無機フィラー等を適宜含んでよい。各任意成分は１種を単独で用いてよく、２種以上を併用してよい。
(Optional ingredient)
The epoxy resin composition may appropriately contain a curing agent, a curing accelerator, an inorganic filler and the like as optional components. As each optional component, one kind may be used alone, and two or more kinds may be used in combination.
硬化剤とは、エポキシ樹脂組成物に含まれるエポキシ樹脂の種類を問わず、エポキシ樹脂のエポキシ基間の架橋及び／又は鎖延長反応に寄与して、エポキシ樹脂組成物を硬化する化合物をいう。硬化剤としては、一般的なエポキシ樹脂の硬化剤として従来公知のものを採用できる。例えば、２−エチル−４−メチルイミダゾール、及び２−フェニル−４−メチルイミダゾール等のイミダゾール誘導体；無水フタル酸、テトラヒドロ無水フタル酸、無水トリメリット酸等の酸無水物；三フッ化ホウ素トリエチルアミン錯体等の三フッ化ホウ素のアミン錯体；並びにジシアンジアミド等が挙げられる。これらは１種単独で、又は２種以上を併用してもよい。 The curing agent refers to a compound that cures the epoxy resin composition by contributing to the cross-linking and / or chain extension reaction between the epoxy groups of the epoxy resin, regardless of the type of epoxy resin contained in the epoxy resin composition. As the curing agent, conventionally known curing agents for general epoxy resins can be adopted. For example, imidazole derivatives such as 2-ethyl-4-methylimidazole and 2-phenyl-4-methylimidazole; acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride; boron trifluoride triethylamine complex. Amine complex of boron trifluoride; and dicyandiamide. These may be used alone or in combination of two or more.
これらの中でも、硬化剤としては、イミダゾール誘導体又は酸無水物が好ましい。 Among these, as the curing agent, an imidazole derivative or an acid anhydride is preferable.
さらに、エポキシ樹脂組成物の硬化は、イミダゾール硬化系で行うことが好ましい。イミダゾール硬化系とは、イミダゾール誘導体がエポキシ樹脂のエポキシ基間の架橋及び／又は鎖延長反応に寄与する系である。イミダゾール硬化系とすることで、より誘電率を下げ、耐熱性を向上した硬化物を与えることができる。 Further, the epoxy resin composition is preferably cured by an imidazole curing system. The imidazole curing system is a system in which an imidazole derivative contributes to cross-linking and / or chain extension reaction between epoxy groups of an epoxy resin. By adopting an imidazole curing system, it is possible to provide a cured product having a lower dielectric constant and improved heat resistance.
なお、酸無水物硬化系とは、酸無水物がエポキシ樹脂のエポキシ基間の架橋及び／又は鎖延長反応に寄与する系である。酸無水物硬化系とすることで、機械強度に優れる硬化物を与えることができる。 The acid anhydride curing system is a system in which the acid anhydride contributes to the cross-linking and / or chain extension reaction between the epoxy groups of the epoxy resin. By adopting an acid anhydride curing system, a cured product having excellent mechanical strength can be provided.
エポキシ樹脂組成物が硬化剤を含む場合、その硬化剤の配合量は適宜調整すればよく、特に限定されないが、エポキシ樹脂（Ａ）及びエポキシ樹脂（Ｂ）の合計１００重量部に対し、０．１重量部以上１５０重量部以下が好ましく、０．５重量部以上１００重量部以下がさらに好ましい。得られる硬化物の耐熱性に特に優れるためである。０．１重量部未満であると硬化反応後も未反応のエポキシが多く残存する。 When the epoxy resin composition contains a curing agent, the blending amount of the curing agent may be appropriately adjusted, and is not particularly limited. However, the amount of the epoxy resin (A) and the epoxy resin (B) is 0. It is preferably 1 part by weight or more and 150 parts by weight or less, and more preferably 0.5 parts by weight or more and 100 parts by weight or less. This is because the obtained cured product has particularly excellent heat resistance. If it is less than 0.1 part by weight, a large amount of unreacted epoxy remains even after the curing reaction.
硬化剤として、イミダゾール誘導体を用いる場合、そのイミダゾール誘導体の配合量は、エポキシ樹脂（Ａ）及びエポキシ樹脂（Ｂ）の合計１００重量部に対し、０．１重量部以上１０重量部以下が好ましく、０．５重量部以上５重量部以下がより好ましい。 When an imidazole derivative is used as the curing agent, the blending amount of the imidazole derivative is preferably 0.1 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight in total of the epoxy resin (A) and the epoxy resin (B). More preferably, it is 0.5 parts by weight or more and 5 parts by weight or less.
硬化剤として、酸無水物を用いる場合、その酸無水物の配合量は、エポキシ樹脂（Ａ）及びエポキシ樹脂（Ｂ）の合計１００重量部に対し、５０重量部以上１５０重量部以下が好ましく、７０重量部以上１００重量部以下がより好ましい。 When an acid anhydride is used as the curing agent, the blending amount of the acid anhydride is preferably 50 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the total of the epoxy resin (A) and the epoxy resin (B). More preferably, it is 70 parts by weight or more and 100 parts by weight or less.
硬化促進剤とは、エポキシ樹脂組成物が硬化する際に、それ自体が架橋及び／又は鎖延長反応をしないが、これらの反応を促進するものをいう。硬化促進剤としては、一般的なエポキシ樹脂の硬化促進剤として従来公知のものを採用できる。例えば、２−エチル−４−メチルイミダゾール、２−フェニル−４−メチルイミダゾール等のイミダゾール誘導体（イミダゾール誘導体とは、イミダゾール基を有する化合物をいう）；第３級アミン類；及び有機ホスフィン類等が挙げられる。これらは１種単独で、又は２種以上を併用してもよい。 The curing accelerator means one that does not carry out a cross-linking and / or chain extension reaction by itself when the epoxy resin composition is cured, but promotes these reactions. As the curing accelerator, conventionally known curing accelerators for general epoxy resins can be adopted. For example, imidazole derivatives such as 2-ethyl-4-methylimidazole and 2-phenyl-4-methylimidazole (imidazole derivatives refer to compounds having an imidazole group); tertiary amines; and organic phosphines and the like. Can be mentioned. These may be used alone or in combination of two or more.
硬化促進剤は、硬化剤と併用することが好ましい。硬化剤として酸無水物を用いる場合、硬化促進剤としてイミダゾール誘導体を用いることが好ましい。室温で液状であるため配合が容易であり、硬化反応を効率良く促進出来るためである。 The curing accelerator is preferably used in combination with the curing agent. When an acid anhydride is used as a curing agent, it is preferable to use an imidazole derivative as a curing accelerator. This is because it is liquid at room temperature, so it is easy to mix, and the curing reaction can be efficiently promoted.
エポキシ樹脂組成物が硬化促進剤を含む場合、その硬化促進剤の配合量は適宜調整すればよく、特に限定されないが、エポキシ樹脂（Ａ）及びエポキシ樹脂（Ｂ）の合計１００重量部に対し、０．０１重量部以上１０重量部以下が好ましく、０．０５重量部以上５重量部以下がより好ましく、０．１重量部以上２重量部以下がさらに好ましい。０．０１重量部未満であると硬化不良が起きる可能性があり、１０重量部を超えると得られる硬化物が著しく着色するためである。 When the epoxy resin composition contains a curing accelerator, the blending amount of the curing accelerator may be appropriately adjusted and is not particularly limited, but with respect to a total of 100 parts by weight of the epoxy resin (A) and the epoxy resin (B). It is preferably 0.01 part by weight or more and 10 parts by weight or less, more preferably 0.05 part by weight or more and 5 parts by weight or less, and further preferably 0.1 part by weight or more and 2 parts by weight or less. This is because if it is less than 0.01 parts by weight, curing failure may occur, and if it exceeds 10 parts by weight, the obtained cured product is significantly colored.
本開示のエポキシ樹脂組成物は、目的を損なわない限り、無機フィラーを含有しても良い。無機フィラーとしては、シリカ、アルミナ、窒化珪素、及び窒化アルミニウムの各粉末等が挙げられる。 The epoxy resin composition of the present disclosure may contain an inorganic filler as long as the purpose is not impaired. Examples of the inorganic filler include powders of silica, alumina, silicon nitride, and aluminum nitride.
エポキシ樹脂組成物が無機フィラーを含む場合、その無機フィラーの配合量は適宜調整すればよく、特に限定されないが、エポキシ樹脂（Ａ）及びエポキシ樹脂（Ｂ）の合計１００重量部に対し、１０〜２５０重量部の範囲が好ましい。 When the epoxy resin composition contains an inorganic filler, the blending amount of the inorganic filler may be appropriately adjusted and is not particularly limited, but is 10 to 10 based on 100 parts by weight of the total of the epoxy resin (A) and the epoxy resin (B). The range of 250 parts by weight is preferable.
本開示のエポキシ樹脂組成物は、低い誘電率及び高い耐熱性を有する硬化物を与えることができるため、プリント基板、半導体封止材、電子材料用接着剤、及び層間絶縁材等の絶縁材料として好適である。また、重合体骨格（ａ）として、植物中に存在するファルネセンに由来する単量体単位を含む重合体骨格を用いることで、エポキシ樹脂組成物及びその硬化物のバイオマス化が期待できる。 Since the epoxy resin composition of the present disclosure can provide a cured product having a low dielectric constant and high heat resistance, it can be used as an insulating material such as a printed circuit board, a semiconductor encapsulant, an adhesive for an electronic material, and an interlayer insulating material. Suitable. Further, by using a polymer skeleton containing a monomer unit derived from farnesene existing in a plant as the polymer skeleton (a), it can be expected that the epoxy resin composition and its cured product will be converted into biomass.
［硬化物］
本開示の硬化物は、上記エポキシ樹脂組成物の硬化物である。上記エポキシ樹脂の硬化条件としては、硬化反応が十分に進行すれば、特に限定されず、成分及び組成等に応じて適宜調整すればよい。
[Cured product]
The cured product of the present disclosure is a cured product of the epoxy resin composition. The curing conditions of the epoxy resin are not particularly limited as long as the curing reaction proceeds sufficiently, and may be appropriately adjusted according to the components, composition, and the like.
イミダゾール硬化系の場合、熱硬化のための温度条件としては、例えば、１５０℃以上２５０℃以下が好ましく、１７０℃以上２００℃以下がさらに好ましい。熱硬化のための時間としては、１時間以上２４時間以下が好ましく、３時間以上１０時間以下がさらに好ましい。 In the case of an imidazole curing system, the temperature condition for thermosetting is, for example, preferably 150 ° C. or higher and 250 ° C. or lower, and more preferably 170 ° C. or higher and 200 ° C. or lower. The time for thermosetting is preferably 1 hour or more and 24 hours or less, and more preferably 3 hours or more and 10 hours or less.
酸無水物硬化系の場合、熱硬化のための温度条件としては、例えば、６０℃以上２００℃以下が好ましく、８０℃以上１８０℃以下がより好ましく、１００℃以上１５０℃以下がさらに好ましい。熱硬化のための時間としては、１時間以上２４時間以下が好ましく、３時間以上１０時間以下がさらに好ましい。 In the case of an acid anhydride curing system, the temperature conditions for thermosetting are, for example, preferably 60 ° C. or higher and 200 ° C. or lower, more preferably 80 ° C. or higher and 180 ° C. or lower, and further preferably 100 ° C. or higher and 150 ° C. or lower. The time for thermosetting is preferably 1 hour or more and 24 hours or less, and more preferably 3 hours or more and 10 hours or less.
本開示のエポキシ樹脂組成物の硬化物は、低い誘電率を有する。その誘電率はより小さい方が好ましい。周波数１ＭＨｚにおける比誘電率として、３．４以下が好ましく、３．２以下がより好ましく、３．０以下がさらに好ましく、２．８以下が最も好ましい。また、実使用上の観点からは、２．７以上であってよい。 The cured product of the epoxy resin composition of the present disclosure has a low dielectric constant. It is preferable that the dielectric constant is smaller. The relative permittivity at a frequency of 1 MHz is preferably 3.4 or less, more preferably 3.2 or less, further preferably 3.0 or less, and most preferably 2.8 or less. Further, from the viewpoint of actual use, it may be 2.7 or more.
本開示のエポキシ樹脂組成物の硬化物の誘電正接はより小さい方が好ましい。０．０３５以下が好ましく、０．０３０以下がより好ましく、０．０２５以下がさらに好ましい。また、実使用上の観点からは、０．０１０以上であってよい。 The dielectric loss tangent of the cured product of the epoxy resin composition of the present disclosure is preferably smaller. It is preferably 0.035 or less, more preferably 0.030 or less, and even more preferably 0.025 or less. Further, from the viewpoint of actual use, it may be 0.010 or more.
前記誘電率及び誘電正接は、平行板コンデンサ法を用いて導くことができる。 The permittivity and the dielectric loss tangent can be derived by using the parallel plate capacitor method.
本開示のエポキシ樹脂組成物の硬化物は、高い耐熱性を有する。ガラス転移温度Ｔｇは、１５０℃以下が好ましく、１５４℃以上がより好ましく、１６０℃以上がさらに好ましく、１７０℃以上が最も好ましい。また、１８０℃以下であってよい。 The cured product of the epoxy resin composition of the present disclosure has high heat resistance. The glass transition temperature Tg is preferably 150 ° C. or lower, more preferably 154 ° C. or higher, further preferably 160 ° C. or higher, and most preferably 170 ° C. or higher. Further, the temperature may be 180 ° C. or lower.
硬化物の曲げ強度は、８０ＭＰａ以上、８５ＭＰａ以上、８８ＭＰａ以上、９５ＭＰａ以上、１００ＭＰａ以上、１１０ＭＰａ以上の順により好ましい。曲げ強度はより高い方が好ましく、上限値は特に限定されないが、例えば、実用上の使用の観点から１１５ＭＰａ以下であってもよい。 The bending strength of the cured product is more preferably 80 MPa or more, 85 MPa or more, 88 MPa or more, 95 MPa or more, 100 MPa or more, and 110 MPa or more in that order. It is preferable that the bending strength is higher, and the upper limit value is not particularly limited, but for example, it may be 115 MPa or less from the viewpoint of practical use.
なお、硬化物の曲げ強度は、ＪＩＳ Ｋ７１７１に準じて測定することができる。ストログラフＶＧ２０−Ｅ（東洋精機製作所社製）を用いて、測定温度２５℃、測定湿度５０％ＲＨ、ロードセル１．０ｋＮ、ヘッド移動速度５ｍｍ／ｍｉｎの条件で測定すればよい。 The bending strength of the cured product can be measured according to JIS K7171. The measurement may be performed using a stromagraph VG20-E (manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the conditions of a measurement temperature of 25 ° C., a measurement humidity of 50% RH, a load cell of 1.0 kN, and a head movement speed of 5 mm / min.
（合成例１：エポキシ樹脂１）
ポリファルネセンジオール（Krasol F 3000；CRAY VALLEY社製）と過剰量のエピクロルヒドリンを混合し、水酸化ナトリウムを用いて３０℃で２４時間反応を行った。得られた樹脂液から副生した塩化ナトリウムを除去し、過剰のエピクロルヒドリンを濃縮除去することで目的化合物であるポリファルネセンポリグリシジルエーテル（エポキシ樹脂１）を得た。得られたエポキシ樹脂１は、エポキシ基が、グリシジルエーテル基として、ファルネセン由来の単量体単位を含む重合体骨格（ａ）の末端に位置するものである。エポキシ樹脂１の各物性を表１に示す。
(Synthesis Example 1: Epoxy Resin 1)
Polyfarnesene diol (Krasol F 3000; manufactured by CRAY VALLEY) and an excess amount of epichlorohydrin were mixed, and a reaction was carried out at 30 ° C. for 24 hours using sodium hydroxide. Sodium chloride produced as a by-product was removed from the obtained resin solution, and excess epichlorohydrin was concentrated and removed to obtain a target compound, polyfarnesene polyglycidyl ether (epoxy resin 1). In the obtained epoxy resin 1, the epoxy group is located at the end of the polymer skeleton (a) containing a monomer unit derived from farnesene as a glycidyl ether group. Table 1 shows the physical properties of the epoxy resin 1.
（合成例２：エポキシ樹脂２）
ポリファルネセンジオール（Krasol F 3000；CRAY VALLEY社製）と過剰量の過酸化水素とギ酸をトルエン中で混合し、４０℃で２０時間反応を行った。室温まで放冷後、５％炭酸ナトリウム水溶液で中和処理した。続いて水洗した後に分液し、得られた樹脂溶液を濃縮することで目的化合物（エポキシ樹脂２）を得た。得られたエポキシ樹脂２は、ファルネセン由来の単量体単位を含む重合体骨格（ａ）の内部に位置するエポキシ基、つまり内部エポキシ基を有する。エポキシ樹脂２の各物性を表１に示す。
(Synthesis Example 2: Epoxy Resin 2)
Polyfarnesene diol (Krasol F 3000; manufactured by CRAY VALLEY), an excess amount of hydrogen peroxide and formic acid were mixed in toluene, and the reaction was carried out at 40 ° C. for 20 hours. After allowing to cool to room temperature, it was neutralized with a 5% aqueous sodium carbonate solution. Subsequently, the solution was washed with water and then separated, and the obtained resin solution was concentrated to obtain the target compound (epoxy resin 2). The obtained epoxy resin 2 has an epoxy group located inside the polymer skeleton (a) containing a monomer unit derived from farnesene, that is, an internal epoxy group. Table 1 shows the physical properties of the epoxy resin 2.
（エポキシ樹脂３）
エポキシ化ポリブタジエン（ＰＢ３６００、株式会社ダイセル製）をエポキシ樹脂３として用いた。エポキシ樹脂３の各物性を表１に示す。
(Epoxy resin 3)
Epoxyized polybutadiene (PB3600, manufactured by Daicel Corporation) was used as the epoxy resin 3. Table 1 shows the physical properties of the epoxy resin 3.
表１の各物性は、次の方法で評価した。
＜粘度＞
２５℃及び４５℃における粘度は、Ｅ型粘度計により測定した。
Each physical property in Table 1 was evaluated by the following method.
<Viscosity>
The viscosities at 25 ° C. and 45 ° C. were measured with an E-type viscometer.
＜エポキシ当量＞
エポキシ当量は、ＪＩＳ Ｋ ７２３６に基づいて測定した。
<Epoxy equivalent>
Epoxy equivalents were measured based on JIS K 7236.
＜重量平均分子量Ｍｗ、数平均分子量Ｍｎ＞
重量平均分子量Ｍｗ及び数平均分子量Ｍｎは、ポリスチレン換算ゲル透過クロマトグラフィー（ＧＰＣ）にて測定した。
<Weight average molecular weight Mw, number average molecular weight Mn>
The weight average molecular weight Mw and the number average molecular weight Mn were measured by polystyrene conversion gel permeation chromatography (GPC).
表１に示すように、エポキシ樹脂１及び２は、いずれもエポキシ樹脂３に比べて低粘度であり、流動性があるため、作業性及びハンドリング性に優れる。 As shown in Table 1, both the epoxy resins 1 and 2 have a lower viscosity than the epoxy resin 3 and have fluidity, so that they are excellent in workability and handleability.
（実施例１〜４、比較例１〜２）
表２に示す配合（重量比）により各成分を混合し、目的の組成物を得た。得られた各組成物を５分間脱泡撹拌した後、１５０℃で３時間、その後さらに２００℃で３時間の条件で硬化させて、厚み２ｍｍの硬化物を得た。この硬化物の各物性を評価した結果を表２に示す。
(Examples 1 to 4, Comparative Examples 1 to 2)
Each component was mixed according to the formulation (weight ratio) shown in Table 2 to obtain the desired composition. Each of the obtained compositions was defoamed and stirred for 5 minutes and then cured at 150 ° C. for 3 hours and then at 200 ° C. for 3 hours to obtain a cured product having a thickness of 2 mm. Table 2 shows the results of evaluating each physical property of this cured product.
（実施例５〜６、比較例３〜４）
表３に示す配合（重量比）により各成分を混合し、目的の組成物を得た。得られた各組成物を５分間脱泡撹拌した後、８０℃で１時間、その後さらに１５０℃で３時間の条件で硬化させて、厚み２ｍｍの硬化物を得た。この硬化物の各物性を評価した結果を表３に示す。
(Examples 5 to 6, Comparative Examples 3 to 4)
Each component was mixed according to the formulation (weight ratio) shown in Table 3 to obtain the desired composition. Each of the obtained compositions was defoamed and stirred for 5 minutes and then cured at 80 ° C. for 1 hour and then at 150 ° C. for 3 hours to obtain a cured product having a thickness of 2 mm. Table 3 shows the results of evaluating each physical property of this cured product.
表２及び３に示す各成分の詳細は次のとおりである。
ＪＥＲ８２８：ビスフェノールＡ型エポキシ樹脂（三菱ケミカル）
２Ｅ４ＭＺ：２−エチル−４メチルイミダゾール（四国化成）
ＭＨ−７００Ｇ：４−メチルヘキサヒドロ無水フタル酸／ヘキサヒドロ無水フタル酸＝７０／３０（新日本理化）
Details of each component shown in Tables 2 and 3 are as follows.
JER828: Bisphenol A type epoxy resin (Mitsubishi Chemical)
2E4MZ: 2-Ethyl-4methylimidazole (Shikoku Kasei)
MH-700G: 4-Methylhexahydrophthalic anhydride / Hexahydrophthalic anhydride = 70/30 (New Japan Chemical Co., Ltd.)
ガラス転移温度Ｔｇ（℃）、誘電率（周波数１ＭＨｚにおける比誘電率）、及び誘電正接の測定方法は以下のとおりである。 The methods for measuring the glass transition temperature Tg (° C.), the permittivity (relative permittivity at a frequency of 1 MHz), and the dielectric loss tangent are as follows.
＜ガラス転移温度Ｔｇ＞
厚み２ｍｍの硬化物を１０ｍｍ×５０ｍｍの大きさに切り出して試験片とした。当該試験片について、示差走査熱量測定（ＤＳＣ）装置ＤＭＳ６１００（セイコーインスツル社製）を用いて、温度範囲３０〜２５０℃、昇温速度２℃／分、周波数１ＭＨｚの条件で、ガラス転移温度Ｔｇ（℃）を測定した。
<Glass transition temperature Tg>
A cured product having a thickness of 2 mm was cut into a size of 10 mm × 50 mm to obtain a test piece. The test piece was subjected to a glass transition temperature Tg using a differential scanning calorimetry (DSC) device DMS6100 (manufactured by Seiko Instruments Inc.) under the conditions of a temperature range of 30 to 250 ° C., a heating rate of 2 ° C./min, and a frequency of 1 MHz. (° C.) was measured.
＜誘電率及び誘電正接＞
厚み２ｍｍの硬化物を５０ｍｍ×５０ｍｍの大きさに切り出して試験片とした。当該試験片について、以下のとおり誘電率及び誘電正接を求めた。
<Permittivity and dielectric loss tangent>
A cured product having a thickness of 2 mm was cut into a size of 50 mm × 50 mm to obtain a test piece. The permittivity and dielectric loss tangent of the test piece were determined as follows.
アジレント・テクノロジー株式会社製 ＰＲＥＣＩＳＩＯＮ ＬＣＲ ＭＥＴＥＲ ４２８４Ａ型にＤＩＥＬＥＣＴＲＩＣ ＴＥＳＴ ＦＩＸＴＵＲＥ １６４５１Ｂを取り付け、１ＭＨｚの周波数にて、平行板コンデンサ法により測定し、下記式により誘電率及び誘電正接を算出した。 DIELECTRIC TEST FIXTURE 16451B was attached to PRECISION LCR METER 4284A manufactured by Azilent Technology Co., Ltd., and measured by the parallel plate capacitor method at a frequency of 1 MHz, and the dielectric constant and dielectric loss tangent were calculated by the following formulas.
εｒ＝（ｔａ×Ｃｐ）／（Ａ×ε０）
＝（ｔａ×Ｃｐ）／（π×（ｄ／２）２×ε０）
Ｄｔ＝Ｄ
εｒ：試料の誘電率
ｔａ：試料の平均の厚さ［ｍ］
Ｃｐ：等価の並列容量［Ｆ］
Ａ：主電極の面積［ｍ２］
ε０：真空の誘電率（＝８．８５４×１０−１２）
ｄ：主電極の直径［ｍ］
Ｄｔ：試料の誘電正接
Ｄ：誘電正接
εr = (ta × Cp) / (A × ε0)
= (Ta × Cp) / (π × (d / 2) 2 × ε0)
Dt = D
εr: Permittivity of the sample ta: Average thickness of the sample [m]
Cp: Equivalent parallel capacitance [F]
A: Area of main electrode [m 2 ]
ε0: Permittivity of vacuum (= 8.854 × 10-12 )
d: Diameter of main electrode [m]
Dt: Dissipation factor of sample D: Dissipation factor
表２は、硬化剤としてイミダゾール誘導体を用いたイミダゾール硬化系のエポキシ樹脂の硬化物の物性を示す。エポキシ樹脂３を配合した比較例２の硬化物は、比較例１の硬化物に比べて、誘電率が若干低いが、ガラス転移温度Ｔｇが低く、耐熱性に劣る。 Table 2 shows the physical properties of a cured product of an imidazole-curing epoxy resin using an imidazole derivative as a curing agent. The cured product of Comparative Example 2 containing the epoxy resin 3 has a slightly lower dielectric constant than the cured product of Comparative Example 1, but has a lower glass transition temperature Tg and is inferior in heat resistance.
一方、実施例１〜６の硬化物は、いずれも比較例１及び２の硬化物に比べ、低い誘電率及び誘電正接、並びに高いガラス転移温度Ｔｇを有する。そのため、実施例１〜６の硬化物は、低い誘電率及び高い耐熱性を有することが分かる。内部エポキシ基を有する実施例３〜６は、特に高い耐熱性を有する。 On the other hand, the cured products of Examples 1 to 6 all have a lower dielectric constant, a dielectric loss tangent, and a higher glass transition temperature Tg than the cured products of Comparative Examples 1 and 2. Therefore, it can be seen that the cured products of Examples 1 to 6 have a low dielectric constant and high heat resistance. Examples 3 to 6 having an internal epoxy group have particularly high heat resistance.
表３は、硬化剤として酸無水物を用いた酸無水物硬化系のエポキシ樹脂の硬化物の物性を示す。エポキシ樹脂３を配合した比較例４の硬化物は、比較例３の硬化物に比べて、誘電率及び誘電正接が低いが、ガラス転移温度Ｔｇも低く、耐熱性に劣る。 Table 3 shows the physical properties of the cured product of an acid anhydride-curing epoxy resin using an acid anhydride as a curing agent. The cured product of Comparative Example 4 containing the epoxy resin 3 has a lower dielectric constant and dielectric loss tangent than the cured product of Comparative Example 3, but also has a lower glass transition temperature Tg and is inferior in heat resistance.
一方、実施例７〜８の硬化物は、いずれも比較例３の硬化物に比べ、低い誘電率及び誘電正接、並びに同等以上のガラス転移温度Ｔｇを有する。そのため、実施例７〜８の硬化物は、低い誘電率及び高い耐熱性を有することが分かる。特に、内部エポキシ基を有する実施例８は、エポキシ基が末端に位置する実施例７と同様以上の誘電特性及び耐熱性を有する。
On the other hand, the cured products of Examples 7 to 8 have a lower dielectric constant, a dielectric loss tangent, and a glass transition temperature Tg equal to or higher than that of the cured product of Comparative Example 3. Therefore, it can be seen that the cured products of Examples 7 to 8 have a low dielectric constant and high heat resistance. In particular, Example 8 having an internal epoxy group has the same or higher dielectric properties and heat resistance as Example 7 in which the epoxy group is located at the end.
Claims (8)
（上記一般式（１）中、ｍ及びｎは、それぞれ０又は１以上の整数であり、かつ、ｍ＋ｎは３以上の整数である。） The epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin (A) is an epoxidized product of a polyfarnesene diol represented by the following general formula (1).
(In the above general formula (1), m and n are integers of 0 or 1 or more, respectively, and m + n is an integer of 3 or more.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019053063A JP2020152830A (en) | 2019-03-20 | 2019-03-20 | Epoxy resin composition and its cured product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019053063A JP2020152830A (en) | 2019-03-20 | 2019-03-20 | Epoxy resin composition and its cured product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2020152830A true JP2020152830A (en) | 2020-09-24 |
Family
ID=72557848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019053063A Pending JP2020152830A (en) | 2019-03-20 | 2019-03-20 | Epoxy resin composition and its cured product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2020152830A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008214599A (en) * | 2007-02-05 | 2008-09-18 | Asahi Kasei Corp | Liquid crystalline epoxy resin and composition thereof |
| JP2014189613A (en) * | 2013-03-27 | 2014-10-06 | Nippon Steel & Sumikin Chemical Co Ltd | Epoxy resin composition, resin sheet, and epoxy resin cured product |
| JP2018100320A (en) * | 2016-12-19 | 2018-06-28 | Dic株式会社 | Epoxy resin, curable resin composition and cured product thereof |
| JP2019501265A (en) * | 2016-01-06 | 2019-01-17 | フィナ テクノロジー，インコーポレイティド | Curable polyfarnesene-based composition |
| US20190055336A1 (en) * | 2017-08-18 | 2019-02-21 | Fina Technology, Inc. | Epoxidized polyfarnesene and methods for producing the same |
-
2019
- 2019-03-20 JP JP2019053063A patent/JP2020152830A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008214599A (en) * | 2007-02-05 | 2008-09-18 | Asahi Kasei Corp | Liquid crystalline epoxy resin and composition thereof |
| JP2014189613A (en) * | 2013-03-27 | 2014-10-06 | Nippon Steel & Sumikin Chemical Co Ltd | Epoxy resin composition, resin sheet, and epoxy resin cured product |
| JP2019501265A (en) * | 2016-01-06 | 2019-01-17 | フィナ テクノロジー，インコーポレイティド | Curable polyfarnesene-based composition |
| JP2018100320A (en) * | 2016-12-19 | 2018-06-28 | Dic株式会社 | Epoxy resin, curable resin composition and cured product thereof |
| US20190055336A1 (en) * | 2017-08-18 | 2019-02-21 | Fina Technology, Inc. | Epoxidized polyfarnesene and methods for producing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4632077B2 (en) | Epoxy resin composition, method for producing epoxy resin, novel epoxy resin, and novel phenol resin | |
| US7569654B2 (en) | Epoxy resin composition, process for producing epoxy resin, novel epoxy resin, novel phenol resin | |
| EP2421907B1 (en) | Thermosettable composition containing a half ester of a cycloaliphatic diol and a thermoset product therefrom | |
| KR20180130111A (en) | Epoxy resin composition comprising eco-friendly curing agent and cured product thereof | |
| JP6429793B2 (en) | Liquid epoxy resin composition | |
| JP5135951B2 (en) | Epoxy resin composition, cured product thereof, and novel epoxy resin | |
| KR20160061323A (en) | A curable epoxy resin composition | |
| JP2013108011A (en) | Epoxy resin solution, epoxy resin composition, hardened material and adhesive | |
| KR20180127273A (en) | Epoxy resin composition comprising eco-friendly curing agent and cured product thereof | |
| JP4883842B2 (en) | Additive for epoxy resin composition and epoxy resin composition thereof | |
| JP2004231787A (en) | Epoxy resin diluent, epoxy resin composition and epoxy resin cured product | |
| JPS62201923A (en) | Epoxy resin composition | |
| JP2015081306A (en) | Epoxy resin composition | |
| JP2020152830A (en) | Epoxy resin composition and its cured product | |
| JP5744010B2 (en) | Epoxy resin composition and cured product thereof | |
| EP3916034A1 (en) | Composition, cured product, method for producing cured product, method for producing coating film, and method for producing composition | |
| JPS60170620A (en) | Novel epoxy resin composition | |
| KR102377780B1 (en) | Toughened epoxy adhesive composition | |
| JP2014162854A (en) | Resin composition and cured product | |
| JPH0641395A (en) | Epoxy resin composition | |
| JPH06128352A (en) | Epoxy resin composition | |
| JP2008255367A (en) | Epoxy resin composition and molded and cured form thereof | |
| JP2004256580A (en) | Epoxy resin composition and cured epoxy resin product | |
| JPH02296821A (en) | Cold-setting resin composition | |
| JPH0741543A (en) | Flame-retardant epoxy resin composition for laminated board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220303 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20221205 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20221220 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20230613 |