JPH04145106A - Propargyl ether compound and composition containing the same - Google Patents
Propargyl ether compound and composition containing the sameInfo
- Publication number
- JPH04145106A JPH04145106A JP2266446A JP26644690A JPH04145106A JP H04145106 A JPH04145106 A JP H04145106A JP 2266446 A JP2266446 A JP 2266446A JP 26644690 A JP26644690 A JP 26644690A JP H04145106 A JPH04145106 A JP H04145106A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxystyrene
- propargyl
- ether compound
- propargyl ether
- resin
- 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.)
- Granted
Links
- -1 Propargyl ether compound Chemical class 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims description 16
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 12
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 2
- 239000003063 flame retardant Substances 0.000 abstract description 6
- 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 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000011342 resin composition Substances 0.000 abstract description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 abstract description 2
- 238000006266 etherification reaction Methods 0.000 abstract description 2
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 9
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 7
- 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 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 3
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- IHMXVSZXHFTOFN-UHFFFAOYSA-N 2-ethyloxolane Chemical compound CCC1CCCO1 IHMXVSZXHFTOFN-UHFFFAOYSA-N 0.000 description 1
- 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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 1
- HRDCVMSNCBAMAM-UHFFFAOYSA-N 3-prop-2-ynoxyprop-1-yne Chemical compound C#CCOCC#C HRDCVMSNCBAMAM-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- AUYQDAWLRQFANO-UHFFFAOYSA-N [4-[(4-cyanatophenyl)methyl]phenyl] cyanate Chemical compound C1=CC(OC#N)=CC=C1CC1=CC=C(OC#N)C=C1 AUYQDAWLRQFANO-UHFFFAOYSA-N 0.000 description 1
- INHGSGHLQLYYND-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(OC#N)C=C1 INHGSGHLQLYYND-UHFFFAOYSA-N 0.000 description 1
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、臭化ボッ（ｐ−ヒドロキシスチレン）のプロ
パルギルエーテル化合物及びこれを含有する、作業性、
硬化性が良好で、耐熱性と耐湿性に優れた難燃性の低誘
電率積層板用に特に有用な熱硬化性樹脂組成物に関する
ものである。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a propargyl ether compound of boron bromide (p-hydroxystyrene) and a compound containing the same, which has excellent workability and
The present invention relates to a thermosetting resin composition that has good curability, excellent heat resistance and moisture resistance, and is particularly useful for flame-retardant low dielectric constant laminates.
（従来技術）
近年、高周波領域で用いられるプリント配′線板に、耐
熱性かっ難燃性で、低誘ｉｉＥ率、低誘電正接の積層板
用樹脂が望まれている。(Prior Art) In recent years, resins for laminates that are heat resistant, flame retardant, have a low dielectric constant, and have a low dielectric loss tangent have been desired for printed wiring boards used in the high frequency range.
これに対し、誘電率の小さいフッ素樹脂やポリフェニレ
ンオキシドなどの熱可塑性樹脂が提案されているが、耐
熱性が低く信頼性に欠けるなどの問題点がある。In response, thermoplastic resins such as fluororesins and polyphenylene oxides with low dielectric constants have been proposed, but they have problems such as low heat resistance and lack of reliability.
また、誘電率が低く耐熱性の良好な樹脂として、ゴム変
性ポリマレイミド（特開昭６２−１２７３１０号公報）
やトリアジン樹脂（特公昭４５−１１７１２号公報など
）も提案されている。In addition, as a resin with a low dielectric constant and good heat resistance, rubber-modified polymaleimide (Japanese Patent Application Laid-open No. 127310/1982)
and triazine resins (Japanese Patent Publication No. 45-11712, etc.) have also been proposed.
しかし前者はゴムとポリマレイミドとの相溶性が悪く、
硬化樹脂は脆く、可撓性に欠け、スルポール加工時にク
ラックが発生し易い。後者は吸湿性が大きく製品が不安
定で、耐湿性、信頼性に欠けている。However, the former has poor compatibility between rubber and polymaleimide,
Cured resin is brittle, lacks flexibility, and is prone to cracking during Surpol processing. The latter has high hygroscopicity and is unstable, lacking moisture resistance and reliability.
（発明が解決しようとする課題）
本発明の目的とするところは、臭化ポリ（ｐ−ヒドロキ
シスチレン）のプロパルギルエーテル化合物及びこれを
含有する、作業性、硬化性が良好で、耐熱性、耐湿性、
靭性に優れた難燃性の低誘電率積層板用熱硬化性樹脂組
成物を提供するにある。(Problems to be Solved by the Invention) The object of the present invention is to provide a propargyl ether compound of poly(p-hydroxystyrene) bromide and a product containing the same, which has good workability and curability, and has good heat resistance and moisture resistance. sex,
An object of the present invention is to provide a flame-retardant thermosetting resin composition for a low dielectric constant laminate having excellent toughness.
（課題を解決するための手段）
第一の発明は、下記式〔Ｉ〕で示される臭化ポリ（ｐ−
ヒドロキシスチレン）のプロパルギルエーテル化合物で
あり、
（Ｒ：Ｈ又は−ＣＨ２−Ｃ＝ＣＨ
但しＨ／−Ｃｌ（２−ＣＥ ＣＨが０〜３．０ｍは、ベ
ンゼン環に結合する臭素個数の平均値を示し、Ｏ＜ｍ＜
４である。(Means for Solving the Problems) The first invention is a brominated poly(p-
Hydroxystyrene) is a propargyl ether compound of (R:H or -CH2-C=CH, where H/-Cl(2-CE CH is 0 to 3.0m, which means the average number of bromines bonded to the benzene ring. and O<m<
It is 4.
ｎは、ρ−ヒドロキシスチレンの重合度を示し、５≦ｎ
≦１００である。）
第二の発明は、下記式〔Ｉ〕で示される臭化ポリ（ｐ−
ヒドロキシスチレン）のプロパルギルエーテル化合物と
（Ｒ： Ｈ又は−ＣＨ２−ＣミＣＨ
但しＨ／−ＣＬ−Ｃ＝ＣＨが０〜３．０ｍは、ベンゼン
環に結合する臭素個数の平均値を示し、Ｏ＜ｍ＜４であ
る。n indicates the degree of polymerization of ρ-hydroxystyrene, and 5≦n
≦100. ) The second invention is a brominated poly(p-
Hydroxystyrene) propargyl ether compound and (R: H or -CH2-CmiCH, where H/-CL-C=CH is 0 to 3.0m indicates the average number of bromines bonded to the benzene ring, and O <m<4.
ｎは、ｐ−ヒドロキシスチレンの重合度を示し、５≦ｎ
≦１００である。）
熱硬化性樹脂とを含有又は反応させてなることを特徴と
する組成物である。n indicates the degree of polymerization of p-hydroxystyrene, and 5≦n
≦100. ) A composition characterized by containing or reacting with a thermosetting resin.
（作用）
本発明において用いられる臭化ポリ（ｐ−ヒドロキシス
チレン）のプロパルギルエーテル化合物は、式（Ｉ）で
示される臭化ポリ（ｐ−ヒドロキシスチレン）を、塩化
プロパルギル又は臭化プロパルギルと反応させ、プロパ
ルギルエーテル化したものである。(Function) The propargyl ether compound of poly(p-hydroxystyrene) bromide used in the present invention is produced by reacting poly(p-hydroxystyrene) bromide represented by formula (I) with propargyl chloride or propargyl bromide. , propargyl ether.
ｎは、ｐ−ヒドロキシスチレンの重合度を示し、５≦ｎ
≦１００である。分子量が大き過ぎると、溶解性が悪く
なり、ワニス粘度も高くなって作業が困難になる。逆に
小さ過ぎるのは、ポリマー収率が下がって好ましくない
。n indicates the degree of polymerization of p-hydroxystyrene, and 5≦n
≦100. If the molecular weight is too large, the solubility will be poor and the varnish will have a high viscosity, making it difficult to work with. On the other hand, if it is too small, the polymer yield will decrease, which is undesirable.
ｍは、ベンゼン環に結合する臭素個数の平均値を示し、
Ｏ＜ｍ＜４である。好ましくは、０．５≦ｍ≦２が良い
。臭素個数が少な過ぎると、難燃性が向上しない。また
多過ぎると、溶解性、硬化性、作業性が悪化する。m indicates the average number of bromines bonded to the benzene ring,
O<m<4. Preferably, 0.5≦m≦2. If the number of bromines is too small, flame retardancy will not improve. On the other hand, if the amount is too large, solubility, hardenability, and workability will deteriorate.
プロパルギルエーテル化率は、フェノール性ＯＨ基に対
し、５０％以上１００％以下が好ましい。５０％未満で
はフェノール性ＯＨ基が多量に残存するため、吸水率が
大きくなり、耐湿性、低誘電特性が向上しない。The propargyl etherification rate is preferably 50% or more and 100% or less based on the phenolic OH group. If it is less than 50%, a large amount of phenolic OH groups remain, resulting in a high water absorption rate and no improvement in moisture resistance or low dielectric properties.
本発明のプロパルギルエーテル化合物は、下記式（ＩＩ
）のポリ（ｐ−ヒドロキシスチレン）のプロパルギル
エーテル化合物と併用して差し支えない。The propargyl ether compound of the present invention has the following formula (II
) may be used in combination with the propargyl ether compound of poly(p-hydroxystyrene).
（ｎは、ｐ−ヒドロキシスチレンの重合度を示し、５≦
ｎ≦ｉｏｏである。）
本発明において用いられる熱硬化性樹脂としては、エポ
キシ樹脂、シアネート樹脂、マレイミド樹脂又はこれら
の２種以上の併用などを挙げることができる。(n indicates the degree of polymerization of p-hydroxystyrene, 5≦
n≦ioo. ) Examples of the thermosetting resin used in the present invention include epoxy resins, cyanate resins, maleimide resins, and combinations of two or more of these resins.
エポキシ樹脂としては、分子内に少なくとも２個以上の
エポキシ基を有するもので、例えば、ビスフェノールＡ
系エポキシ樹脂、ビスフェノールＦ系エポキシ樹脂、臭
素化エポキシ樹脂、フェノール・ノボラック系エポキシ
樹脂、クレゾールノボラック系エポキシ樹脂、その他の
多官能エポキシ樹脂を用いることができる。Epoxy resins have at least two or more epoxy groups in their molecules, such as bisphenol A
epoxy resins, bisphenol F-based epoxy resins, brominated epoxy resins, phenol-novolac-based epoxy resins, cresol novolac-based epoxy resins, and other polyfunctional epoxy resins can be used.
シアネート樹脂としては、分子内に少なくとも２個以上
のシアネート基（−００＝Ｎ）を有するもので、例えば
、ジシアネートヘンゼン、ビス（４−シアネートフェニ
ル）メタン、ビス（３，５−ジメチル。The cyanate resin has at least two or more cyanate groups (-00=N) in its molecule, such as dicyanate henzhen, bis(4-cyanatophenyl)methane, and bis(3,5-dimethyl).
４−シアネートフェニル）メタン、２，２−ビス（４−
シアネートフェニル）プロパン、２，２−ビス（４−シ
アネートフェニル） −１，１，１，３，３，３−へキ
サフロロプロパン、トリシアネートベンゼン、フェノー
ル。4-cyanatophenyl)methane, 2,2-bis(4-
cyanatophenyl)propane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, tricyanatebenzene, phenol.
ノボラックのポリシアネートなどを用いることができる
。Novolac polycyanate and the like can be used.
エポキシ樹脂、シアネート樹脂又はこの両者を配合する
ことによって、より好ましくは予め反応させることによ
って、後硬化を必要とせず、作業性、硬化性、接着性が
より向上する。しかし、多過ぎると耐熱性、難燃性、誘
電率、誘電正接が悪化する。By blending an epoxy resin, a cyanate resin, or both, and more preferably reacting them in advance, workability, curability, and adhesiveness are further improved without requiring post-curing. However, if the amount is too high, heat resistance, flame retardance, dielectric constant, and dielectric loss tangent will deteriorate.
マレイミド樹脂は、分子内に少なくとも２個以上のマレ
イミド基を有する化合物、例えば、Ｎ、Ｎ′−Ｉ−フェ
ニレンビスマレイミド、Ｎ、Ｎ’−ｐ−フェニレンビス
マレイミド、Ｎ、Ｎ′−ｍ−トルイレンビスマレイミド
、Ｎ、Ｎ′−４，４’−ビフェニレンビスマレイミド、
Ｎ、Ｎ’−４，４’−（３，３’−ジメチル−ビフェニ
レンビスマレイミド、Ｎ、Ｎ’−４，４’−（３，３′
−ジメチルジフェニルメタン〕ビスマレイミド、Ｎ、Ｎ
’−４，４’−（３，３’−ジエチルジフェニルメタン
〕ビスマレイミド、Ｎ。Maleimide resin is a compound having at least two or more maleimide groups in the molecule, such as N,N'-I-phenylenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-m-tolu Ilene bismaleimide, N,N'-4,4'-biphenylene bismaleimide,
N, N'-4,4'-(3,3'-dimethyl-biphenylene bismaleimide, N, N'-4,4'-(3,3'
-dimethyldiphenylmethane] bismaleimide, N, N
'-4,4'-(3,3'-diethyldiphenylmethane)bismaleimide, N.
Ｎ’−４，４′−ジフェニルメタンビスマレイミド、Ｎ
、Ｎ’−４，４′−ジフェニルプロパンビスマレイミド
、Ｎ、Ｎ’−４，４′−ジフェニルエーテルビスマレイ
ミド、Ｎ、Ｎ’−３，３′−ジフェニルスルホンビスマ
レイミド、Ｎ、Ｎ’−４，４′−ジフェニルスルホンビ
スマレイミド、一般式（ｍ）又は（ＩＶ）で示されるポ
リマレイミドな（Ｒ３ニーＨ、アルキル基又はフェニル
基 ｏ＜ ｉ ＜１０）または、これらの化合物と
芳香族アミン類、芳香族シアネート類、あるいはアワル
エーテル化フェノール類とを反応させて得られる変性マ
レイミド樹脂などを挙げることができる。これらは２種
以上含まれていても何ら差し支えない。N'-4,4'-diphenylmethane bismaleimide, N
, N'-4,4'-diphenylpropane bismaleimide, N, N'-4,4'-diphenyl ether bismaleimide, N, N'-3,3'-diphenylsulfone bismaleimide, N, N'-4, 4'-diphenylsulfone bismaleimide, a polymaleimide represented by the general formula (m) or (IV) (R3nieH, alkyl group or phenyl group o < i < 10), or these compounds and aromatic amines, Examples include modified maleimide resins obtained by reacting aromatic cyanates or awal-etherified phenols. There is no problem even if two or more of these are included.
マレイミド樹脂を配合することによって、より好ましく
は予め反応させることによって、硬化性、作業性がより
向上する。しかし多過ぎると吸水率が大きくなり、低誘
電特性、難燃性が悪化する。By blending a maleimide resin, more preferably by reacting it in advance, curability and workability are further improved. However, if the amount is too large, the water absorption rate will increase, resulting in poor dielectric properties and flame retardancy.
この他に、熱硬化性樹脂としては、不飽和ポリエステル
樹脂やジアリルフタレート樹脂なども使用することがで
きる。In addition, as the thermosetting resin, unsaturated polyester resin, diallyl phthalate resin, etc. can also be used.
これらの熱硬化性樹脂の量は、臭化ポリ（ｐ−ヒドロキ
シスチレン）のプロパルギルエーテル化合物１００重量
部に対し、２０〜５００重量部が良い。The amount of these thermosetting resins is preferably 20 to 500 parts by weight based on 100 parts by weight of the propargyl ether compound of poly(p-hydroxystyrene) bromide.
本発明のプロパルギルエーテル化合物を含む組成物は、
必要に応じて、三酸化アンチモンなどの他の難燃剤、３
級アミン類、イミダゾール類、ホスフィン類、有機過酸
化物などの硬化促進剤を併用することもできる。The composition containing the propargyl ether compound of the present invention is
If necessary, other flame retardants such as antimony trioxide, 3
Curing accelerators such as grade amines, imidazoles, phosphines, and organic peroxides can also be used in combination.
ワニス溶剤としては、特に限定されるものではないが、
例えば、ジメチルホルムアミド、ジメチルアセトアミド
、Ｎ−メチルピロリドンなどの高沸点極性溶剤も使用で
きるが、低温、短時間で溶剤の除去が可能な作業性の良
い、アセトン、メチルエチルケトン、メチルブチルケト
ンなどのケトン類、テトラヒドロフラン、２−メチルテ
トラヒドロフラン、３−メチルテトラヒドロフラン、２
，５−ジメチルテトラヒドロフラン、２−エチルテトラ
ヒドロフラン、１．４−ジオキサン、１，３−ジオキサ
ンなどの環状エーテル類、ベンゼン、トルエン、キシレ
ンなどの芳香族炭化水素類がより好ましい。これらの溶
剤は、２種以上を併用しても構わない。Varnish solvents are not particularly limited, but include:
For example, high-boiling polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone can be used, but ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone have good workability and can remove the solvent in a short time at low temperatures. , tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2
, 5-dimethyltetrahydrofuran, 2-ethyltetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and other cyclic ethers; and benzene, toluene, xylene, and other aromatic hydrocarbons. Two or more of these solvents may be used in combination.
（実施例）
実施例１
撹拌装置、還流冷却器、温度計及び滴下ロートを付けた
反応容器に、第１表の処方に従って、水酸化カリウムと
、水／アセトン（１／１）の混合溶媒を入れて溶解させ
、これに莫化ポリ（ｐ−ヒドロキシスチレン）を添加し
、溶解させた。この溶液を加熱し、塩化プロパルギルを
滴下して、還流下３時間反応させた。その後、アセトン
と未反応の塩化プロパルギルを留去し、トルエン１ ￥
Ｍを添加した。分液ロートに移し、水洗を３回行い、エ
バポレーターで溶媒を除去した。得られたプロパルギル
エーテル化合物の反応率（フェノール性水酸基の反応率
）を第１表に示した。(Example) Example 1 A mixed solvent of potassium hydroxide and water/acetone (1/1) was added to a reaction vessel equipped with a stirring device, a reflux condenser, a thermometer, and a dropping funnel according to the recipe in Table 1. Poly(p-hydroxystyrene) was added thereto and dissolved. This solution was heated, propargyl chloride was added dropwise, and the mixture was reacted under reflux for 3 hours. Then, acetone and unreacted propargyl chloride were distilled off, and toluene 1 ￥
M was added. The mixture was transferred to a separating funnel, washed with water three times, and the solvent was removed using an evaporator. Table 1 shows the reaction rate (reaction rate of phenolic hydroxyl group) of the obtained propargyl ether compound.
実施例２〜４
撹拌装置、減圧蒸留装置及び温度計を付けた反応容器に
、第２表の処方に従って、プロパルギルエーテル化合物
とエポキシ樹脂、シアネート樹脂又はマレイミド樹脂と
を入れた。なお実施例２は、更に反応促進剤として、２
−エチル−４−メチルイミダゾールを添加した。これを
１７０°Ｃに加熱し、減圧下（約２０ａ＋ｍＨｇ ）で
反応させた。生成樹脂の融点は、第２表に示した。Examples 2 to 4 A propargyl ether compound and an epoxy resin, a cyanate resin, or a maleimide resin were placed in a reaction vessel equipped with a stirring device, a vacuum distillation device, and a thermometer according to the formulation in Table 2. In addition, in Example 2, 2 was further added as a reaction accelerator.
-Ethyl-4-methylimidazole was added. This was heated to 170°C and reacted under reduced pressure (approximately 20a+mHg). The melting points of the resulting resins are shown in Table 2.
実施例５
実施例１のプロパルギルエーテル化合物を、粘度が５±
３ポイズ（２５°Ｃ）になるように、１．４−ジオキサ
ンに溶かした。このワニスを、表面処理を行ったガラス
クロス（Ｅガラス）に含浸させ、乾燥機中で、１３０°
Ｃ３分間加熱して溶剤を除去し、プリプレグを作成した
。このプリプレグを８枚重ね、その両側に片面粗化銅箔
（３５μｍ）を重ねて、加熱加圧して銅張り積層板を得
た。硬化が遅いため、プレス時間は１５時間であった。Example 5 The propargyl ether compound of Example 1 was prepared with a viscosity of 5±
It was dissolved in 1,4-dioxane to a concentration of 3 poise (25°C). A surface-treated glass cloth (E glass) was impregnated with this varnish and heated at 130° in a dryer.
C was heated for 3 minutes to remove the solvent and prepare a prepreg. Eight sheets of this prepreg were stacked, one-sided roughened copper foil (35 μm) was stacked on both sides, and heated and pressed to obtain a copper-clad laminate. Due to slow curing, pressing time was 15 hours.
更に２００°Ｃ８時間後硬化させたものの積層板特性を
第３表に示した。Table 3 shows the properties of the laminate which was further cured at 200°C for 8 hours.
実施例６
実施例１のプロパルギルエーテル化合物、マレイミド樹
脂及び２−エチル−４−メチルイミダゾールを用い、第
３表の配合に従って、粘度が５±３ボイス（２５°Ｃ）
になるように、１，４−ジオキサンに溶かした。このワ
ニスを、表面処理を行ったガラスクロス（Ｅガラス）に
含浸させ、乾燥機中で、１３０’Ｃ３分間加熱して溶剤
を除去し、プリプレグを作成した。このプリプレグを８
枚重ね、その両側に片面粗化銅箔（３５μｍ）を重ねて
、加熱加圧して銅張り積層板を得た。更に２００°Ｃ３
時間後硬化させたものの積層板特性を第３表に示した。Example 6 Using the propargyl ether compound of Example 1, maleimide resin, and 2-ethyl-4-methylimidazole, the viscosity was 5 ± 3 voices (25°C) according to the formulation in Table 3.
It was dissolved in 1,4-dioxane so that A surface-treated glass cloth (E glass) was impregnated with this varnish and heated in a dryer at 130'C for 3 minutes to remove the solvent, thereby producing a prepreg. This prepreg is 8
The sheets were stacked, one-sided roughened copper foil (35 μm) was placed on both sides, and heated and pressed to obtain a copper-clad laminate. Further 200°C3
Table 3 shows the properties of the laminates after curing.
実施例７〜８
実施例２．３の樹脂を用い、第３表の配合に従って、実
施例６と同様に行って銅張り積層板を得た。２００°Ｃ
の後処理をしていないものの積層板特性を第３表に示し
た。Examples 7 to 8 A copper-clad laminate was obtained in the same manner as in Example 6 using the resins of Examples 2.3 and according to the formulations in Table 3. 200°C
Table 3 shows the properties of the laminate without any post-treatment.
実施例９
実施例４の樹脂を用い、第３表の配合に従って、実施例
６と同様に行った。Example 9 Using the resin of Example 4, the same procedure as Example 6 was carried out according to the formulation shown in Table 3.
比較例１
シアネート樹脂を用い、第３表の配合に従って実施例８
と同様に行った。吸水率が大きく、ドリル加工時に小さ
なりラックが発生しやすい。難燃性はＨＢであった。Comparative Example 1 Using cyanate resin, Example 8 according to the formulation in Table 3
I did the same thing. It has a high water absorption rate and tends to cause small racks during drilling. Flame retardancy was HB.
比較例２
マレイミド樹層を用い、第３表の配合に従って実施例９
と同様に行った。ガラス転移温度は高くて良好であるが
、誘電率と吸水率が大きく、銅箔引き剥がし強さが弱く
、ド「ノル加工時クラックが発生した。難燃性はＶ−１
であった。Comparative Example 2 Using maleimide tree layer, Example 9 according to the formulation in Table 3.
I did the same thing. The glass transition temperature is high and good, but the dielectric constant and water absorption are large, the copper foil peel strength is weak, and cracks occurred during dowel processing.Flame retardancy is V-1.
Met.
（発明の効果）
本発明のプロパルギルエーテル化合物を含む組成物は、
作業性、硬化性が良好で、これを用いた積層板は、高Ｔ
ｇでかつ難燃性であり、吸水率が小さく耐湿性に優れ、
ドリル加工時にクラックの発生もなく、かつ誘電率、誘
電正接の値も小さい。(Effect of the invention) The composition containing the propargyl ether compound of the present invention is
It has good workability and hardenability, and laminates using it have high T.
g, flame retardant, low water absorption and excellent moisture resistance.
No cracks occur during drilling, and the dielectric constant and dielectric loss tangent values are small.
低誘電率積層板、低誘電率多層プリント板用熱硬化性樹
脂として、非常に信頼性の高い優れたものである。It is an extremely reliable and excellent thermosetting resin for low dielectric constant laminates and low dielectric constant multilayer printed boards.
プ
１愚
第３表
寧１：ハイテクポリマーＷＡｒｏＣｙＢ−３０電２：日
本ポリイミド■製 ケルイミド６０１＄３ ： ＪＩＳ
−Ｃ−６４８１に従って測定＄４ ： Ａ−９４に準じ
て測定1: High-tech polymer WAroCyB-30 2: Made by Japan Polyimide Kelimide 601 $3: JIS
- Measured according to C-6481 $4: Measured according to A-94
Claims (5)
キシスチレン）のプロパルギルエーテル化合物。 ▲数式、化学式、表等があります▼ （Ｒ：Ｈ又は−ＣＨ＿２−Ｃ≡ＣＨ 但しＨ／−ＣＨ＿２−Ｃ≡ＣＨが０〜３．０ｍは、ベン
ゼン環に結合する臭素個数の平均値を示し、０＜ｍ＜４
である。 ｎは、ｐ−ヒドロキシスチレンの重合度を示し、５≦ｎ
≦１００である。）(1) A propargyl ether compound of bromated poly(p-hydroxystyrene) represented by the following formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R: H or -CH_2-C≡CH However, H/-CH_2-C≡CH is 0 to 3.0m, which indicates the average number of bromines bonded to the benzene ring. ,0<m<4
It is. n indicates the degree of polymerization of p-hydroxystyrene, and 5≦n
≦100. )
キシスチレン）のプロパルギルエーテル化合物と▲数式
、化学式、表等があります▼ （Ｒ：Ｈ又は−ＣＨ＿２−Ｃ≡ＣＨ 但しＨ／−ＣＨ＿２−Ｃ≡ＣＨが０〜３．０ｍは、ベン
ゼン環に結合する臭素個数の平均値を示し、０＜ｍ＜４
である。 ｎは、ｐ−ヒドロキシスチレンの重合度を示し、５≦ｎ
≦１００である。） 熱硬化性樹脂とを含有又は反応させてなることを特徴と
する組成物。(2) Propargyl ether compound of poly(p-hydroxystyrene) bromide represented by the following formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R: H or -CH_2-C≡CH However, H/- CH_2-C≡CH from 0 to 3.0m indicates the average number of bromines bonded to the benzene ring, and 0<m<4
It is. n indicates the degree of polymerization of p-hydroxystyrene, and 5≦n
≦100. ) A composition characterized by containing or reacting with a thermosetting resin.
する特許請求の範囲第２項記載の組成物。(3) The composition according to claim 2, wherein the thermosetting resin is an epoxy resin.
とする特許請求の範囲第２項記載の組成物。(4) The composition according to claim 2, wherein the thermosetting resin is a cyanate resin.
とする特許請求の範囲第２項記載の組成物。(5) The composition according to claim 2, wherein the thermosetting resin is a maleimide resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2266446A JP2859413B2 (en) | 1990-10-05 | 1990-10-05 | Propargyl ether compound and composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2266446A JP2859413B2 (en) | 1990-10-05 | 1990-10-05 | Propargyl ether compound and composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04145106A true JPH04145106A (en) | 1992-05-19 |
| JP2859413B2 JP2859413B2 (en) | 1999-02-17 |
Family
ID=17431050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2266446A Expired - Fee Related JP2859413B2 (en) | 1990-10-05 | 1990-10-05 | Propargyl ether compound and composition containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2859413B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2650544C2 (en) * | 2016-02-29 | 2018-04-16 | Федеральное государственное бюджетное учреждение науки Иркутский институт химии им. А.Е. Фаворского Сибирского отделения Российской академии наук (ИрИХ СО РАН) | Process for preparing water-soluble propargyl esters of arabinogalactan polysaccharide |
-
1990
- 1990-10-05 JP JP2266446A patent/JP2859413B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2650544C2 (en) * | 2016-02-29 | 2018-04-16 | Федеральное государственное бюджетное учреждение науки Иркутский институт химии им. А.Е. Фаворского Сибирского отделения Российской академии наук (ИрИХ СО РАН) | Process for preparing water-soluble propargyl esters of arabinogalactan polysaccharide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2859413B2 (en) | 1999-02-17 |
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