JPS60212435A - Flame-retardant plasticizer - Google Patents
Flame-retardant plasticizerInfo
- Publication number
- JPS60212435A JPS60212435A JP6981684A JP6981684A JPS60212435A JP S60212435 A JPS60212435 A JP S60212435A JP 6981684 A JP6981684 A JP 6981684A JP 6981684 A JP6981684 A JP 6981684A JP S60212435 A JPS60212435 A JP S60212435A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- ethylene oxide
- formula
- plasticizer
- halogen
- 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
- 239000004014 plasticizer Substances 0.000 title claims abstract description 18
- 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 title claims description 16
- 239000003063 flame retardant Substances 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 125000005907 alkyl ester group Chemical group 0.000 abstract description 7
- 150000002367 halogens Chemical class 0.000 abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- DTRGDWOPRCXRET-UHFFFAOYSA-N (9Z,11E,13E)-4-Oxo-9,11,13-octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCC(=O)CCC(O)=O DTRGDWOPRCXRET-UHFFFAOYSA-N 0.000 abstract 2
- DTRGDWOPRCXRET-SUTYWZMXSA-N (9e,11e,13e)-4-oxooctadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCC(=O)CCC(O)=O DTRGDWOPRCXRET-SUTYWZMXSA-N 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- -1 Phosphate ester Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はプラスチックを難燃化すると同時に可塑性を付
与するために使用される難燃性可塑剤に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to flame-retardant plasticizers used to make plastics flame-retardant and at the same time impart plasticity.
フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹
脂等のプラスチックは各種の用途に使用され、特に電気
、電子部品用途においては、電気的特性、耐温性もさる
ことながら、難燃性。Plastics such as phenolic resins, epoxy resins, and unsaturated polyester resins are used for a variety of purposes, especially in electrical and electronic component applications, where they are not only good at electrical properties and temperature resistance, but also flame retardant.
可塑性を同時に要求する領域が多い０例えば積層板（プ
リント配線基板を含む）にこれらの樹脂を使用する場合
、積層板の加工工程の自動化、低温加工性１曲面加工性
等の要求に対応するため可塑剤としてリン酸エステル、
長鎖アルキルフェニルグリシジルエーテル、桐油等が使
用されており、最近低温パンチング、スルーホールのホ
ール間短縮等の要求に対応するためこれらの可塑剤の使
用量の増大が見られる。For example, when using these resins for laminates (including printed wiring boards), there are many areas that require plasticity at the same time.In order to meet the requirements such as automation of the processing process of laminates, low temperature processability, and single curved surface processability. Phosphate ester as a plasticizer,
Long-chain alkyl phenyl glycidyl ethers, tung oil, etc. are used, and recently, the amount of these plasticizers used has been increasing to meet the demands for low-temperature punching, shortening the distance between through holes, etc.
一方、積層板のうち、高電圧部に使用するものについて
は難燃化が必須要件となっている。そのため樹脂に難燃
剤を添加しなければならないが、可塑剤量の増大は難燃
化を困難にし、また難燃剤の多量の使用は物性面での劣
化が大きい。On the other hand, flame retardancy is an essential requirement for laminates used in high voltage parts. Therefore, it is necessary to add a flame retardant to the resin, but increasing the amount of plasticizer makes flame retardation difficult, and using a large amount of flame retardant significantly deteriorates the physical properties.
本発明者らは、均一成分をもって樹脂にバランスの取れ
たＪｌ燃性と可塑性とを同時に付与することができる難
燃性可塑剤を開発し、上記の欠点を解消することに成功
した。すなわち、下記一般式（Ｉ）で示される化合物（
以下一般式（Ｉ）の化合物という）を主成分とすること
を特徴とする難燃性可塑剤である。The present inventors have succeeded in solving the above-mentioned drawbacks by developing a flame-retardant plasticizer that can simultaneously impart well-balanced Jl flammability and plasticity to resins using homogeneous components. That is, a compound represented by the following general formula (I) (
This is a flame-retardant plasticizer characterized by containing as a main component a compound of general formula (I).
■
物としては、含ハロゲンフェノール類のエチレンオキシ
ド付加物とりカン酸の低級アルキルエステルをエステル
交換反応させることによって得られる化合物があげられ
る。Examples of the compound include compounds obtained by transesterifying an ethylene oxide adduct of a halogen-containing phenol with a lower alkyl ester of canonic acid.
含ハロゲンフェノール類のエチレンオキシド付加物とし
ては、
等があげれる。。Examples of ethylene oxide adducts of halogen-containing phenols include the following. .
含ハロゲンフェノール類のエチレンオキシド付ｂｙ物に
おいて、エチレンオキシドの付加モル数が５モルを超え
た場合、含ハロゲンフェノールＩの軟化点、融点等降下
による可塑性の向上、管らびにエステル化反応時の反応
性の向上等の同点が得られるものの耐熱性の低下および
分子獣増加に伴う相対的な臭素含量の低下による難熱性
の低下等が起り、好ましくない。When the number of moles of ethylene oxide added exceeds 5 moles in a by-product of halogen-containing phenols with ethylene oxide, the softening point, melting point, etc. of halogen-containing phenol I will decrease, resulting in improved plasticity, and reactivity during pipe and esterification reactions. Although the same points, such as an improvement in the molecular weight, can be obtained, there is a decrease in heat resistance, and a decrease in heat retardancy due to a decrease in relative bromine content due to an increase in molecular weight, which is not preferable.
また、１モル未満の場合、フェノール性基が残学するこ
ととなり、リカン酸の低級アルキルエステルとのエステ
ル化坂応が不完全となるためｑましくない。If the amount is less than 1 mole, the phenolic group will remain and the esterification reaction with the lower alkyl ester of ricanic acid will be incomplete, which is undesirable.
ノカン酸の低級アルキルエステルとしては、例（ばリカ
ン酸メチルエステル、リカン酸エチルＬステル等があげ
られる。Examples of lower alkyl esters of nocanoic acid include methyl ricanate, ethyl ricanate L ester, and the like.
１ハロゲンフエノール類のエチレンオキシド付；■物と
りカン酸の低級アルキルエステルを区スチル交換反応さ
せる場合、公知の方法に従う。1. Attachment of halogen phenols with ethylene oxide; (2) When lower alkyl esters of monocaroic acid are subjected to a still exchange reaction, a known method is followed.
本発明は、上記のような一般式（１）の化合物を難燃性
可塑剤とするものである。The present invention uses the compound of general formula (1) as described above as a flame-retardant plasticizer.
本発明の難燃性可塑剤を適用する樹脂は、特に限定され
るものではないが１例えば熱硬化性樹脂、具体的には不
飽和ポリエステル樹脂、エポキシ雫脂、フェノール樹脂
、メラミン樹脂等の積層板製造用樹脂に有用である。The resin to which the flame retardant plasticizer of the present invention is applied is not particularly limited; for example, a thermosetting resin, specifically a lamination of unsaturated polyester resin, epoxy resin, phenol resin, melamine resin, etc. Useful as a resin for plate manufacturing.
本発明の難燃性可塑剤は、樹脂１００重量部に対し１０
〜５０重量部の割合で使用するのが好ましい。The flame retardant plasticizer of the present invention is 10 parts by weight per 100 parts by weight of the resin.
It is preferable to use it in a proportion of 50 parts by weight.
本発明に従って得られる難燃性可塑剤を、とりわけ積層
板の製造に用いた場合、難燃性および可塑性に優れた積
層板が得られる。When the flame-retardant plasticizer obtained according to the invention is used in particular for the production of laminates, laminates with excellent flame retardancy and plasticity are obtained.
以下に本発明の実施例を記載する。Examples of the present invention are described below.
実施例１
含ハロゲンフェノール類のエチレンオキシド付加物にリ
カン酸の低級アルキルエステルおよび触媒ジブチルチン
ジラウレートを加え、Ｎ２ガスを通しつつ、＠度１５０
〜１７０℃で留出する低級アルコールを採取しながら５
時間反応させ、さらに２時間減圧で反応させる。Example 1 A lower alkyl ester of licanoic acid and a catalyst dibutyltin dilaurate were added to an ethylene oxide adduct of a halogen-containing phenol, and the mixture was heated at 150°C while passing N2 gas.
5 while collecting lower alcohol distilled at ~170℃
The mixture was allowed to react for an additional 2 hours under reduced pressure.
反応終了後、難燃性可塑剤を得た。After the reaction was completed, a flame retardant plasticizer was obtained.
同様にして各種難燃性可塑剤を得た。それらを第１表に
示す。Various flame retardant plasticizers were obtained in the same manner. They are shown in Table 1.
実施例２ フェノール類２００ｇ、メタクレゾール２２８ｇ。Example 2 200g of phenols, 228g of metacresol.
３７％ポルマリン８００ｇ、トリエチルアミン８ｇを６
０〜７０℃で６時間反応させ、減圧下で脱水した後、こ
の脱水物に実施例！で得たＭ燃性可塑剤を４００ｇ加え
、メタノールで希釈して樹脂分５０％のワニスを得た。37% Polmarin 800g, triethylamine 8g 6
After reacting at 0 to 70°C for 6 hours and dehydrating under reduced pressure, this dehydrated product was used in Examples! 400 g of the M flammable plasticizer obtained above was added and diluted with methanol to obtain a varnish with a resin content of 50%.
比較例として難燃性可塑剤無添加の樹脂分５０％のワニ
スを同様にして得た。それらを、それぞれクラフト紙に
含浸させ、樹脂含量５０％のプリプレグを製造した。こ
のようにして得たプリプレグをそれぞれ８枚ずつ重ね、
プレス１（１６０℃±５℃、１５０ｋｇ／ｄ３０分）厚
さ１．６ａｍの積層板を得た。それらの積層板の諸特性
を第２表に示す。As a comparative example, a varnish containing no flame retardant plasticizer and having a resin content of 50% was similarly obtained. Each of them was impregnated into kraft paper to produce a prepreg with a resin content of 50%. Layer 8 sheets of each prepreg obtained in this way,
Press 1 (160° C.±5° C., 150 kg/d for 30 minutes) A laminate having a thickness of 1.6 am was obtained. Table 2 shows the properties of those laminates.
Claims (1)
を特徴とする難燃性可塑剤。 閤[Scope of Claims] A flame-retardant plasticizer characterized by containing a compound represented by the following general formula (I) as a main component.閤
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6981684A JPS60212435A (en) | 1984-04-06 | 1984-04-06 | Flame-retardant plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6981684A JPS60212435A (en) | 1984-04-06 | 1984-04-06 | Flame-retardant plasticizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60212435A true JPS60212435A (en) | 1985-10-24 |
Family
ID=13413659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6981684A Pending JPS60212435A (en) | 1984-04-06 | 1984-04-06 | Flame-retardant plasticizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60212435A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208145B2 (en) | 2002-12-31 | 2007-04-24 | Nektar Therapeutics Al, Corporation | Polymeric reagents comprising a ketone or a related functional group |
-
1984
- 1984-04-06 JP JP6981684A patent/JPS60212435A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7208145B2 (en) | 2002-12-31 | 2007-04-24 | Nektar Therapeutics Al, Corporation | Polymeric reagents comprising a ketone or a related functional group |
| US8865149B2 (en) | 2002-12-31 | 2014-10-21 | Nektar Therapeutics | Polymeric reagents comprising a ketone or a related functional group |
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