JP2008106087A - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- JP2008106087A JP2008106087A JP2006287577A JP2006287577A JP2008106087A JP 2008106087 A JP2008106087 A JP 2008106087A JP 2006287577 A JP2006287577 A JP 2006287577A JP 2006287577 A JP2006287577 A JP 2006287577A JP 2008106087 A JP2008106087 A JP 2008106087A
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- epoxy resin
- magnesium hydroxide
- resin composition
- inorganic
- acid resistance
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 62
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 35
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 35
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000011256 inorganic filler Substances 0.000 claims abstract description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 11
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000011147 inorganic material Substances 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 229920003986 novolac Polymers 0.000 description 12
- 239000005011 phenolic resin Substances 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 238000002156 mixing Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 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 class 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- -1 terpene modified phenol Chemical class 0.000 description 4
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、エポキシ樹脂組成物に関するものである。 The present invention relates to an epoxy resin composition.
従来、電子部品や半導体装置等に使用する封止剤用のエポキシ樹脂には、難燃性を付与するために、ハロゲン系難燃化合物及びアンチモン化合物が用いられている。具体的には、臭素化エポキシ樹脂と三酸化アンチモンを使用するのが一般的である。しかし、臭素化エポキシ樹脂は半導体装置の信頼性・高温放置特性を低下させるという問題点を有しており、また、近年では、環境負荷を低減するために、臭素化合物やアンチモン化合物を含まない封止樹脂とすることへの要望は強くなってきている。そこで、代替難燃材料が検討されてきており、難燃性に優れる水酸化マグネシウムが注目されている。ただ、水酸化マグネシウムは耐酸性が劣るため、樹脂バリ取り、半田メッキなどの工程における酸性薬品によって表面が変色してしまう問題点を有していた。 Conventionally, halogen-based flame retardant compounds and antimony compounds have been used for epoxy resins for sealants used in electronic components, semiconductor devices, and the like, in order to impart flame retardancy. Specifically, it is common to use brominated epoxy resin and antimony trioxide. However, brominated epoxy resins have the problem of reducing the reliability and high-temperature storage characteristics of semiconductor devices, and in recent years, in order to reduce the environmental burden, they do not contain bromine compounds or antimony compounds. There is a growing demand for a stop resin. Therefore, alternative flame retardant materials have been studied, and magnesium hydroxide, which is excellent in flame retardancy, has attracted attention. However, since magnesium hydroxide is inferior in acid resistance, it has a problem that the surface is discolored by acidic chemicals in processes such as resin deburring and solder plating.
このような耐酸性の欠点を解決するために、水酸化マグネシウムを無機物で被覆し、さらにシランカップリング剤で表面処理することで耐酸性を向上させることが提案されている（特許文献１）。 In order to solve such disadvantages of acid resistance, it has been proposed to improve acid resistance by coating magnesium hydroxide with an inorganic substance and further surface-treating with a silane coupling agent (Patent Document 1).
しかしながら、特許文献１記載のような方法では、エポキシ樹脂組成物の流動性が低下して、取り扱いが困難である問題点を有していた。
本発明は、以上の通りの事情に鑑みてなされたものであり、水酸化マグネシウムを使用するエポキシ樹脂組成物において、従来の問題点を解消し、優れた耐酸性及び流動性を有し、さらに高温放置特性、難燃性が良好なエポキシ樹脂組成物を提供することを課題としている。 The present invention has been made in view of the circumstances as described above, and in an epoxy resin composition using magnesium hydroxide, it has solved the conventional problems, has excellent acid resistance and fluidity, and An object of the present invention is to provide an epoxy resin composition having good high-temperature storage characteristics and flame retardancy.
本発明のエポキシ樹脂組成物は、上記の課題を解決するために、以下のことを特徴としている。 The epoxy resin composition of the present invention is characterized by the following in order to solve the above problems.
第１には、エポキシ樹脂と、硬化剤と、無機質充填材並びに水酸化マグネシウムと、無機物で被覆した水酸化マグネシウムとを含み、水酸化マグネシウムと無機物で被覆した水酸化マグネシウムは、その重量比が２：８〜８：２の範囲内であり、また、いずれもシランカップリング剤としてのトリメトキシシランの少なくとも一種で表面処理されている。 First, an epoxy resin, a curing agent, an inorganic filler and magnesium hydroxide, and magnesium hydroxide coated with an inorganic substance, the magnesium hydroxide and the magnesium hydroxide coated with an inorganic substance have a weight ratio of It is in the range of 2: 8 to 8: 2, and all are surface-treated with at least one kind of trimethoxysilane as a silane coupling agent.
第２には、硬化剤は、１分子中に２個以上のフェノール水酸基を有する。 Secondly, the curing agent has two or more phenolic hydroxyl groups in one molecule.
第３には、エポキシ樹脂中のエポキシ基数に対する硬化剤中のフェノール水酸基数の当量比（エポキシ基／フェノール水酸基）が、０．５〜２である。 Third, the equivalent ratio of the number of phenolic hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (epoxy group / phenolic hydroxyl group) is 0.5-2.
第４には、無機質充填材の配合量が、エポキシ樹脂組成物に対して６０〜９５重量％である。 4thly, the compounding quantity of an inorganic filler is 60 to 95 weight% with respect to an epoxy resin composition.
上記第１の発明のよれば、水酸化マグネシウムと無機物被覆された水酸化マグネシウムとの特定の重量比範囲内での併用をもって、特定のシランカップリング剤、つまりはトリメトキシシランを用いることで、優れた耐酸性及び流動性を有し、さらに高温放置特性、難燃性が良好なエポキシ樹脂組成物を得ることができる。 According to the first aspect of the present invention, by using a specific silane coupling agent, that is, trimethoxysilane, in combination with a specific weight ratio range of magnesium hydroxide and inorganic-coated magnesium hydroxide, It is possible to obtain an epoxy resin composition having excellent acid resistance and fluidity, and having excellent high-temperature storage characteristics and flame retardancy.
上記第２〜４の発明のよれば、上記の効果は確実に安定して実現される。 According to the second to fourth aspects of the present invention, the above-described effects are reliably and stably realized.
なお、本発明においては、後述の実施例にも説明しているように、耐酸性の効果は、０．１Ｎ塩酸溶液に２４ｈ成形品を浸漬させた後の成形品表面の外観を目視にて評価している。難燃性の効果は、１７５℃で厚さ０．８ｍｍに成形した成形品をＵＬ耐炎性規格に基づき燃焼性の試験を実施して評価し、高温放置特性の効果は、３μｍのアルミ配線ＴＥＧ：試験用半導体素子を、２００℃においてＴＥＧのアルミ配線の低効率変化を測定し、変化率が５０％を超えたものを不良として、不良数が５０％を超えた時間をもって、その優劣を評価することとしている。流動性の効果は、実際の射出成形における流動性を判断するために、電気機能材料工業規格に基づきスパイラルフローを測定する際に、スパイラルフロー金型を用いて、金型温度１７５℃、トランスファ圧力１０ＭＰａ、プランジャ速度３０ｍｍ／ｓ、プランジャ直径４０ｍｍとして測定している。 In addition, in this invention, as also demonstrated in the below-mentioned Example, the acid-resistant effect is the visual appearance of the surface of the molded product after immersing the molded product in a 0.1N hydrochloric acid solution for 24 hours. Evaluating. The flame retardant effect is evaluated by conducting a flammability test on a molded product molded at 175 ° C. to a thickness of 0.8 mm based on the UL flame resistance standard. The effect of the high temperature storage property is 3 μm aluminum wiring TEG : Measure the low efficiency change of TEG aluminum wiring at 200 ° C, and evaluate the superiority or inferiority when the rate of change exceeds 50% and the number of defects exceeds 50%. To do. In order to determine the fluidity in actual injection molding, the effect of fluidity is that when measuring spiral flow based on the electrical functional material industry standard, a spiral flow mold is used, the mold temperature is 175 ° C., the transfer pressure is The measurement is performed at 10 MPa, the plunger speed is 30 mm / s, and the plunger diameter is 40 mm.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
本発明は、（１）エポキシ樹脂、（２）硬化剤、（３）無機質充填材、並びに、（４）水酸化マグネシウム、（５）無機物で被覆した水酸化マグネシウムを含み、さらに、（４）水酸化マグネシウムと（５）無機物で被覆した水酸化マグネシウムは、その重量比が２：８〜８：２の範囲内であって、かつ、いずれも（６）シランカップリング剤としてのトリメトキシシランの少なくとも一種で表面処理されていることを必須の要件としている。 The present invention includes (1) an epoxy resin, (2) a curing agent, (3) an inorganic filler, and (4) magnesium hydroxide, (5) magnesium hydroxide coated with an inorganic substance, and (4) Magnesium hydroxide and (5) magnesium hydroxide coated with an inorganic substance have a weight ratio in the range of 2: 8 to 8: 2, and (6) trimethoxysilane as a silane coupling agent. It is an essential requirement that it is surface-treated with at least one kind.
本発明における（１）エポキシ樹脂は、封止用エポキシ樹脂材料として一般に使用されているものであればその種類に特に制限はないが、例えば、ノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニレン型エポキシ樹脂、ナフトール・アラルキル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、スチルベン型エポキシ樹脂、硫黄原子含有エポキシ樹脂等が挙げられ、これらを単独で用いても２種以上を組み合わせて用いてもよい。 The type of (1) epoxy resin in the present invention is not particularly limited as long as it is generally used as an epoxy resin material for sealing. For example, novolac type epoxy resin, biphenyl type epoxy resin, bisphenol F type Epoxy resin, naphthalene type epoxy resin, biphenylene type epoxy resin, naphthol / aralkyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, etc. May be used alone or in combination of two or more.
上記のような（１）エポキシ樹脂の中でも、耐リフロー性の観点からはビフェニル型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、スチルベン型エポキシ樹脂及び硫黄原子含有エポキシ樹脂が好ましく、硬化性の観点からはノボラック型エポキシ樹脂が好ましく、低吸湿性の観点からはジシクロペンタジエン型エポキシ樹脂が好ましく、耐熱性及び低反り性の観点からはナフタレン型エポキシ樹脂及びトリフェニルメタン型エポキシ樹脂が好ましく、難燃性の観点からはビフェニレン型エポキシ樹脂及びナフトール・アラルキル型エポキシ樹脂が好ましい。これらのエポキシ樹脂の少なくとも１種を含有し、適宜選択することが好ましい。 Among the above (1) epoxy resins, biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin are preferable from the viewpoint of reflow resistance, and novolak from the viewpoint of curability. Type epoxy resin is preferred, dicyclopentadiene type epoxy resin is preferred from the viewpoint of low moisture absorption, naphthalene type epoxy resin and triphenylmethane type epoxy resin are preferred from the viewpoint of heat resistance and low warpage, and flame retardant From the viewpoint, biphenylene type epoxy resins and naphthol / aralkyl type epoxy resins are preferable. It is preferable that at least one of these epoxy resins is contained and appropriately selected.
さらに、上記ノボラック型エポキシ樹脂の中でも、オルトクレゾールノボラック型エポキシ樹脂が好ましく、その性能を発揮するためにエポキシ樹脂全量に対して２０重量％以上とすることが好ましく、３０重量％以上がより好ましい。 Furthermore, among the novolak type epoxy resins, orthocresol novolak type epoxy resins are preferable, and in order to exhibit the performance, the amount is preferably 20% by weight or more, more preferably 30% by weight or more based on the total amount of the epoxy resin.
本発明における（２）硬化剤は、エポキシ樹脂組成物に一般に使用されているものであればその種類は特に制限されないが、例えば、ノボラック型フェノール樹脂、ビフェニル型フェノール樹脂、アラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、テルペン変性フェノール樹脂、トリフェニルメタン型フェノール樹脂などが挙げられ、これらを単独で用いても２種以上を組み合わせて用いてもよい。 The type of (2) curing agent in the present invention is not particularly limited as long as it is generally used in epoxy resin compositions. For example, novolak type phenol resins, biphenyl type phenol resins, aralkyl type phenol resins, dialkyl resins, A cyclopentadiene type phenol resin, a terpene modified phenol resin, a triphenylmethane type phenol resin, etc. are mentioned, These may be used independently or may be used in combination of 2 or more types.
上記のような（２）硬化剤の中でも、難燃性の観点からはビフェニル型フェノール樹脂が好ましく、耐リフロー性及び硬化性の観点からはアラルキル型フェノール樹脂が好ましく、低吸湿性の観点からはジシクロペンタジエン型フェノール樹脂が好ましく、耐熱性、低膨張率及び低そり性の観点からはトリフェニルメタン型フェノール樹脂が好ましく、硬化性の観点からはノボラック型フェノール樹脂が好ましく、これらのフェノール樹脂の少なくとも１種を含有していることが好ましい。 Among the above (2) curing agents, biphenyl type phenol resins are preferable from the viewpoint of flame retardancy, aralkyl type phenol resins are preferable from the viewpoint of reflow resistance and curability, and from the viewpoint of low hygroscopicity. Dicyclopentadiene type phenol resins are preferred, triphenylmethane type phenol resins are preferred from the viewpoint of heat resistance, low expansion rate and low warpage, and novolac type phenol resins are preferred from the viewpoint of curability. It is preferable to contain at least one kind.
さらに、上記ノボラック型フェノール樹脂としては、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、ナフトールノボラック樹脂等が挙げられ、中でも汎用性の高いフェノールノボラック樹脂が好ましい。さらには、架橋の高密度化を図るために、１分子中に２個以上のフェノール水酸基を有することが好ましい。 Furthermore, examples of the novolak type phenol resin include phenol novolak resin, cresol novolak resin, naphthol novolak resin, and the like, and phenol novolak resin having high versatility is preferable. Furthermore, in order to increase the density of crosslinking, it is preferable to have two or more phenolic hydroxyl groups in one molecule.
これらの硬化剤の配合割合は、特に制限されないが、（１）エポキシ樹脂中のエポキシ基数に対する（２）硬化剤中のフェノール水酸基数の当量比（エポキシ基／フェノール水酸基）について、それぞれの未反応分を少なく抑えるために０．５〜２とすることが好ましく、さらには耐熱性，耐湿性を考慮した場合、０．６〜１．３とすることがより好ましい。 The mixing ratio of these curing agents is not particularly limited, but (1) the equivalent ratio of the number of phenolic hydroxyl groups in the curing agent to the number of epoxy groups in the epoxy resin (epoxy group / phenolic hydroxyl group) is unreacted. In order to suppress the minute amount, it is preferably 0.5 to 2, and more preferably 0.6 to 1.3 when considering heat resistance and moisture resistance.
また、（２）硬化剤を効率的に硬化させるために、硬化触媒を添加してもよく、アミン系硬化触媒、イミダゾール系硬化触媒、リン系硬化触媒、有機酸塩系硬化触媒等、特に制限されるところはなく、適宜選択することが好ましい。 (2) In order to cure the curing agent efficiently, a curing catalyst may be added, and amine-based curing catalyst, imidazole-based curing catalyst, phosphorus-based curing catalyst, organic acid salt-based curing catalyst, etc. are particularly limited. However, it is preferable to select appropriately.
本発明における（３）無機質充填材は、溶融シリカ、結晶シリカ、アルミナ、珪酸カルシウム、炭酸カルシウム、炭化珪素、窒化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコニア、チタニア等の粉体、ビーズ、繊維等が挙げられ、これらの無機質充填材は単独で用いても２種以上を組み合わせて用いてもよい。 (3) Inorganic filler in the present invention is fused silica, crystalline silica, alumina, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, titania, etc., beads, fibers These inorganic fillers may be used alone or in combination of two or more.
上記のような（３）無機質充填材の中でも、充填性、線膨張係数の低減の観点からは溶融シリカが好ましく、また、無機質充填材の形状は充填性及び金型摩耗性の点から球形が好ましい。 Among the above (3) inorganic fillers, fused silica is preferable from the viewpoint of reducing the filling property and linear expansion coefficient, and the shape of the inorganic filler is spherical from the viewpoint of filling properties and mold wear. preferable.
ここで、（３）無機質充填材の配合量は、難燃性、成形性、吸湿性、線膨張係数低減、強度向上及び耐リフロー性の観点から、エポキシ樹脂組成物に対して６０〜９５重量％が好ましい。６０重量％未満では難燃性、耐リフロー性が低下し、９５重量％を超えると流動性、難燃性が低下してしまう。 Here, the blending amount of (3) the inorganic filler is 60 to 95 weight with respect to the epoxy resin composition from the viewpoints of flame retardancy, moldability, hygroscopicity, reduction of linear expansion coefficient, strength improvement and reflow resistance. % Is preferred. If it is less than 60% by weight, the flame retardancy and reflow resistance are lowered, and if it exceeds 95% by weight, the fluidity and flame retardancy are lowered.
本発明において用いられる水酸化マグネシウムは、天然物でも合成物でもよく、特に限定されるものではない。そして、耐酸性の観点から、（４）水酸化マグネシウム及び（５）無機物で被覆した水酸化マグネシウムとはどちらも、平均粒径２０μｍ以下であることが好ましい。 Magnesium hydroxide used in the present invention may be a natural product or a synthetic product, and is not particularly limited. From the viewpoint of acid resistance, it is preferable that both (4) magnesium hydroxide and (5) magnesium hydroxide coated with an inorganic substance have an average particle size of 20 μm or less.
水酸化マグネシウムを被覆した無機物としては、シリカ、アルミナ、ジルコニア、チタニア等の無機物が例示され、被覆する方法は特に限定されない。これら無機物被覆層は、耐酸性、流動性、成形性及び難燃性の観点から水酸化マグネシウム１００重量％に対して０.０５〜３０重量％とすることが好ましい。０.０５重量％未満であると耐酸性が低下し、３０重量％を超えると難燃性が低下してしまう。 Examples of the inorganic substance coated with magnesium hydroxide include inorganic substances such as silica, alumina, zirconia, and titania, and the coating method is not particularly limited. These inorganic coating layers are preferably 0.05 to 30% by weight with respect to 100% by weight of magnesium hydroxide from the viewpoints of acid resistance, fluidity, moldability and flame retardancy. If it is less than 0.05% by weight, the acid resistance is lowered, and if it exceeds 30% by weight, the flame retardancy is lowered.
本発明においては、上記のとおりの（４）水酸化マグネシウムと（５）無機物で被覆した水酸化マグネシウムを併用することを必須としている。その重量比は、前記のとおり、２：８〜８：２である。この範囲外の場合には、本発明の効果である耐酸性および流動性は得られない。 In the present invention, it is essential to use (4) magnesium hydroxide as described above and (5) magnesium hydroxide coated with an inorganic substance in combination. The weight ratio is 2: 8 to 8: 2, as described above. If it is outside this range, the acid resistance and fluidity that are the effects of the present invention cannot be obtained.
このような併用とともに、これら成分（４）（５）はいずれも（６）シランカップリング剤としてのトリメトキシシランの少なくとも一種で表面処理されていることが欠かせない。一方だけの表面処理では所定の効果を得ることは難しい。 Along with such a combination, it is essential that these components (4) and (5) are surface-treated with at least one of (6) trimethoxysilane as a silane coupling agent. It is difficult to obtain a predetermined effect with only one surface treatment.
本発明における（６）シランカップリング剤は、一分子中に有機官能基と加水分解基を持っていて、一般式、Ｒ−Ｓｉ（ＯＲ’）３で表されるものである。官能基Ｒは、樹脂成分と化学結合又は架橋して強固に結合することによって、無機物とエポキシ樹脂との接着性を向上させることができ、例えば、アミノ基、エポキシ基、ビニル基、アクリロイル基、メタクリロイル基、メルカプト基等が例示される。 The (6) silane coupling agent in the present invention has an organic functional group and a hydrolyzable group in one molecule, and is represented by the general formula, R—Si (OR ′) 3 . The functional group R can improve the adhesiveness between the inorganic substance and the epoxy resin by chemically bonding or cross-linking with the resin component and, for example, an amino group, an epoxy group, a vinyl group, an acryloyl group, A methacryloyl group, a mercapto group, etc. are illustrated.
ここで、本発明において特徴とするところは、上記のＲ’がメチル基に限定（すなわち、トリメトキシシランに限定）されることである。これは、従来の知見にはない、全く新しい知見に基づくものであり、エチル基では十分な耐酸性は得られないが、メチル基とした場合、無機物で水酸化マグネシウムを被覆しなくても、ある程度の耐酸性を得ることができる。さらに、アミノ基含有トリメトキシシランは、特に耐酸性の向上に有効であり、好適に用いることができる。 Here, a feature of the present invention is that the above R ′ is limited to a methyl group (that is, limited to trimethoxysilane). This is based on a completely new knowledge that is not found in the conventional knowledge, and sufficient acid resistance cannot be obtained with an ethyl group, but when a methyl group is used, even if magnesium hydroxide is not coated with an inorganic substance, A certain degree of acid resistance can be obtained. Furthermore, amino group-containing trimethoxysilane is particularly effective for improving acid resistance and can be suitably used.
上記（６）シランカップリング剤（トリメトキシシラン）によって、（４）水酸化マグネシウム及び（５）無機物を被覆した水酸化マグネシウムを表面処理する方法は、一般的な噴霧、浸漬等が例示され、特に制限されない。 The method of surface-treating magnesium hydroxide coated with (4) magnesium hydroxide and (5) inorganic substance with the above (6) silane coupling agent (trimethoxysilane) is exemplified by general spraying, immersion, etc. There is no particular limitation.
ここで、耐酸性の観点から、トリメトキシシランの少なくとも一種により、水酸化マグネシウム１００重量％に対して１〜５０重量％の割合で表面処理されていることが、好ましい。 Here, from the viewpoint of acid resistance, it is preferable that the surface treatment is performed with at least one kind of trimethoxysilane at a ratio of 1 to 50% by weight with respect to 100% by weight of magnesium hydroxide.
本発明においてはその他に、離型ワックスを添加してもよく、通常封止材料に用いるものであれば制限はなく、ステアリン酸、モンタン酸、モンタン酸エステル、リン酸エステル等が例示される。 In the present invention, a release wax may be added, and there is no limitation as long as it is normally used for a sealing material, and examples thereof include stearic acid, montanic acid, montanic acid ester, and phosphoric acid ester.
本発明のエポキシ樹脂組成物は、各種原材料を均一に分散混合できるのであれば、いかなる手法を用いても調製でき、一般的な手法としては、所定の配合量の原材料をミキサー等によって十分混合した後、ミキシングロール、押出機、らいかい機、プラネタリミキサ等によって混合又は溶融混練した後、冷却して得ることができる。 The epoxy resin composition of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, raw materials of a predetermined blending amount are sufficiently mixed by a mixer or the like. Then, after mixing or melt-kneading with a mixing roll, an extruder, a raking machine, a planetary mixer, etc., it can cool and obtain.
そこで以下に実施例を説明する。もちろん以下の例によって発明が限定されることはない。 Accordingly, examples will be described below. Of course, the invention is not limited by the following examples.
表１〜３に、実施例及び比較例の各種材料の配合比（エポキシ樹脂（オルトクレゾールノボラック型エポキシ樹脂）を１００とした際の重量比で記載）、及び耐酸性、難燃性、高温放置特性、流動性の評価試験結果を示す。 In Tables 1 to 3, the blending ratio of various materials in Examples and Comparative Examples (described in terms of weight ratio when the epoxy resin (ortho-cresol novolak type epoxy resin) is 100), and acid resistance, flame resistance, and high temperature storage The evaluation results of characteristics and fluidity are shown.
表１〜３に記載されるような配合比で、原材料をミキサーで十分混合した後、ミキシングロールによって加熱混練して、成形した後、冷却して、本発明によるエポキシ樹脂組成物の成形品を得た。また、表１〜３には、同様に作製した比較例を示す。そして、実施例１〜１１及び、比較例１〜９について耐酸性、難燃性、高温放置性を評価した。 After mixing the raw materials sufficiently with a mixer at a compounding ratio as shown in Tables 1 to 3, the mixture is heated and kneaded with a mixing roll, molded, cooled, and molded with the epoxy resin composition according to the present invention. Obtained. Tables 1 to 3 show comparative examples produced in the same manner. Then, Examples 1 to 11 and Comparative Examples 1 to 9 were evaluated for acid resistance, flame retardancy, and high temperature storage property.
耐酸性の評価は、０．１Ｎ塩酸溶液に２４ｈ成形品を浸漬させた後の成形品表面の外観を目視にて確認し、変色のないものを○、軽度の変色については△、白色化したものを■として三段階で評価した。 The acid resistance was evaluated by visually observing the appearance of the molded product surface after immersing the molded product in a 0.1N hydrochloric acid solution for 24 hours, ○ for those with no discoloration, and Δ for mild discoloration, and whitening. Items were evaluated in three stages as ■.
難燃性の評価は、１７５℃で厚さ０．８ｍｍに成形した成形品をＵＬ耐炎性規格に基づき燃焼性の試験を実施した。 For the evaluation of flame retardancy, a flammability test was conducted on a molded product molded at 175 ° C. to a thickness of 0.8 mm based on the UL flame resistance standard.
高温放置特性の評価は、３μｍのアルミ配線ＴＥＧ：試験用半導体素子を、２００℃においてＴＥＧのアルミ配線の低効率変化を測定し、変化率が５０％を超えたものを不良として、不良数が５０％を超えた時間を測定した。 Evaluation of high temperature storage characteristics is 3μm aluminum wiring TEG: Test semiconductor element is measured for low efficiency change of TEG aluminum wiring at 200 ° C, and the rate of change exceeds 50%. The time exceeding 50% was measured.
流動性の評価は、実際の射出成形における材料の流動性を判断するために、電気機能材料工業規格に基づきスパイラルフローを測定する際に、スパイラルフロー金型を用いて、金型温度１７５℃、トランスファ圧力１０ＭＰａ、プランジャ速度３０ｍｍ／ｓ、プランジャ直径４０ｍｍとして測定し、６０ｃｍ以下のエポキシ樹脂組成物については実際の使用に困難をきたすため本願発明からは除外するものとする。 In order to evaluate the fluidity of the material in actual injection molding, the fluidity is evaluated using a spiral flow mold when measuring the spiral flow based on the electrical functional material industry standard, The epoxy resin composition measured at a transfer pressure of 10 MPa, a plunger speed of 30 mm / s, and a plunger diameter of 40 mm is difficult to actually use, and is excluded from the present invention.
もちろん本発明は以上の例に限定されるものではなく、細部については様々な態様が可能であることは言うまでもない。 Of course, the present invention is not limited to the above examples, and it goes without saying that various aspects are possible in detail.
以上のように、本発明によれば、無機物被覆の有無に関わらず、優れた耐酸性を有し、さらに高温放置特性に優れ、難燃性が良好なエポキシ樹脂組成物を得ることができる。 As described above, according to the present invention, it is possible to obtain an epoxy resin composition having excellent acid resistance, excellent high-temperature storage characteristics, and good flame retardancy regardless of the presence or absence of inorganic coating.
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| US9206308B2 (en) | 2010-03-26 | 2015-12-08 | Panasonic Intellectual Property Management Co., Ltd. | Epoxy resin composition for prepreg, prepreg, and multilayer printed circuit board |
| EP2554561A4 (en) * | 2010-03-26 | 2017-02-22 | Panasonic Intellectual Property Management Co., Ltd. | Epoxy resin composition for prepreg, prepreg, and multilayer printed circuit board |
| KR101242570B1 (en) | 2011-06-17 | 2013-03-19 | 한국화학연구원 | Abrasion-resistant coating composition with self-cooling characteristics |
| KR20210052808A (en) * | 2019-10-31 | 2021-05-11 | 주식회사 엘지화학 | Thermal curable adhesive composition, composite structure having adhesive layer and its preparation method |
| KR20210052811A (en) * | 2019-10-31 | 2021-05-11 | 주식회사 엘지화학 | Thermal curable adhesive composition, composite structure having adhesive layer and its preparation method |
| KR102445300B1 (en) | 2019-10-31 | 2022-09-20 | 주식회사 엘지화학 | Heat curable adhesive composition, structure including adhesive layer, and method for manufacturing the same |
| KR102445303B1 (en) | 2019-10-31 | 2022-09-20 | 주식회사 엘지화학 | Thermal curable adhesive composition, composite structure having adhesive layer and its preparation method |
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