JP2802798B2 - Flame retardant thermosetting resin composition - Google Patents
Flame retardant thermosetting resin compositionInfo
- Publication number
- JP2802798B2 JP2802798B2 JP2032235A JP3223590A JP2802798B2 JP 2802798 B2 JP2802798 B2 JP 2802798B2 JP 2032235 A JP2032235 A JP 2032235A JP 3223590 A JP3223590 A JP 3223590A JP 2802798 B2 JP2802798 B2 JP 2802798B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- thermosetting resin
- resin
- flame
- resin composition
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Description
〔産業上の利用分野〕 本発明は、耐熱性及び相溶性が改善された難燃性の熱
硬化性樹脂組成物に関するものである。 〔従来の技術〕 （１）背景 熱硬化性樹脂に難燃性を付与する方法としては従来、
例えば樹脂に難燃剤を添加配合することが行われてい
る。こうした難燃剤としては、ハロゲン系難燃剤、リン
系難燃剤などが使用されている。これらの難燃剤には、
例えば樹脂を成形加工する間、或は成形品使用時におけ
る熱履歴に耐え得る耐熱性が要求される。かつ、一般
に、熱硬化性樹脂は比較的粘度の低い液状又は溶液状の
低重合物を重合させて成形する場合が多いが、比重の大
きい難燃剤を重合前のプレポリマー中に均一状態に分散
又は溶解させ、長時間保存することは困難である。この
ため、樹脂のプレポリマー又はその溶液と相溶性に優れ
た難燃剤が要求されるが、リン系難燃剤は、樹脂との相
溶性及び耐熱性が充分でない。またハロゲン系難燃剤
も、樹脂との相溶性、耐熱性及び被添加物の成形性等に
問題がある。 〔発明が解決しようとする課題〕 そこで本発明が解決しようとする課題は、樹脂との相
溶性、耐熱性及び被添加物の成形性等に優れた難燃性の
熱硬化性樹脂組成物を開発し、提供することである。[Industrial Application Field] The present invention relates to a flame-retardant thermosetting resin composition having improved heat resistance and compatibility. [Prior art] (1) Background As a method of imparting flame retardancy to a thermosetting resin, a conventional method has
For example, a flame retardant is added to and blended with a resin. As such flame retardants, halogen-based flame retardants, phosphorus-based flame retardants, and the like are used. These flame retardants include:
For example, heat resistance is required to withstand the heat history during molding of a resin or during use of a molded product. In general, thermosetting resins are often formed by polymerizing a liquid or solution-like low polymer having a relatively low viscosity, but a flame retardant having a large specific gravity is dispersed in a uniform state in a prepolymer before polymerization. Or it is difficult to dissolve and store for a long time. For this reason, a flame retardant excellent in compatibility with the prepolymer of the resin or its solution is required, but the phosphorus-based flame retardant has insufficient compatibility with the resin and heat resistance. Further, halogen-based flame retardants also have problems in compatibility with resins, heat resistance, moldability of additives, and the like. [Problems to be Solved by the Invention] Accordingly, the problem to be solved by the present invention is to provide a flame-retardant thermosetting resin composition having excellent compatibility with resins, heat resistance and moldability of additives. Develop and deliver.
〔課題を解決するための手段〕 （１）概要 以上の課題を解決するため、本発明に係る難燃性の熱
硬化性樹脂組成物は、（Ａ）臭素化エポキシ化合物及び
／又はその変性化合物（以下、化合物（Ａ）という）と
（Ｂ）臭素化フェノールアルキレンオキサイド付加物
（以下、化合物（Ｂ）という）とを配合してなることを
特徴とする。 以下、発明を構成する諸要素につき項分けして説明す
る。 （２）化合物（Ａ） 化合物（Ａ）としては、下記一般式（Ｉ）の化合物、 具体的には、テトラブロモビスフェノールＡジグリシジ
ルエーテル、テトラブロモビスフェノールＳジグリシジ
ルエーテル、テトラブロモビスフェノールＦジグリシジ
ルエーテル； 下記一般式（II）の化合物、 具体的にはトリブロモフェニルグリシジルエーテル、ジ
ブロモクレジルグリシジルエーテル； 及び 前記一般式（Ｉ）及び／又は一般式（II）に、下記一
般式（III）の化合物、 例えば、トリブロモフェノール、ジブロモクレゾール、
フェノール、クレゾール、ノニルフェノール、スチレン
化フェノール等を反応させた反応物等が夫々例示され
る。 （３）化合物（Ｂ） 本発明組成物における化合物（Ｂ）としては、下記一
般式（IV）の化合物、 具体的には、トリブロモフェノールエチレンオキサイ
ド１〜５モル付加物、トリブロモフェノールプロピレン
オキサイド１〜５モル付加物、トリブロモフェノールブ
チレンオキサイド１〜５モル付加物、ジブロモクレゾー
ルエチレンオキサイド１〜５モル付加物、ジブロモクレ
ゾールプロピレンオキサイド１〜５モル付加物、ジブロ
モクレゾールブチレノキサイド１〜５モル付加物等が挙
げられる。 化合物（Ｂ）におけるアルキレンオキサイドの付加モ
ル数は、１〜５であることが望ましい。付加モル数が５
モルを超える場合は、熱硬化性樹脂の耐熱性を低下させ
る。 （４）対象熱硬化性樹脂 本発明において、対象となる熱硬化性樹脂としては、
例えば、不飽和ポリエステル樹脂、メラミン樹脂、エポ
キシ化合物樹脂、フェノール樹脂、フラン樹脂、ケイ素
樹脂、尿素樹脂、ジアリルフタレート樹脂、ブタジエン
系樹脂、ポリウレタン樹脂等が挙げられる。 （５）二成分の配合比率及び添加量等 化合物（Ａ）と（Ｂ）との配合比率は、1:9〜9:1が望
ましく、特に、4:6〜8:2の範囲が好ましい。 化合物（Ｂ）の配合比率が９を超える場合は、難燃性
熱硬化樹脂の耐熱性を低下させる。逆に１より少ない場
合は、熱硬化性樹脂との相溶性が悪くなる。 更に化合物（Ａ）と（Ｂ）とを熱硬化性樹脂に添加す
る場合、前記樹脂100重量部に対して前記二成分の合計
量で５〜50重量部である。 （６）他の添加物 本発明の難燃性の熱硬化性樹脂組成物に添加、他の添
加物としては、他の臭素系難燃剤、塩素系難燃剤、リン
系難燃剤、酸化防止剤、可塑剤、安定剤、染料、顔料、
溶媒等が挙げられる。更に所望により、水酸化アルミニ
ウムの如き無機系難燃剤、三酸化アンチモン、硼酸亜鉛
等をも添加することができる。 〔作用〕 本発明に従って得られる難燃性の熱硬化性樹脂組成物
は、化合物（Ａ）と（Ｂ）を含有することから、ワニス
の安定性、樹脂との相溶性、耐熱性及び被添加物の成形
性等に優れた特性を有する。 〔実施例〕 以下実施例及び比較例により発明実施の態様及び効果
につき述べるが、例示は単に説明用のものであって、発
明思想の限定又は制限を意図したものではない。 また、実施例中、部及び％は、重量基準である。 実施例１〜４及び比較例１〜２ フェノール樹脂ワニスに、化合物（Ａ）と化合物
（Ｂ）を前記樹脂液の固形分換算100部に対して、合計
量で12重量部及びクレジルジフェニルホスフェート３重
量部を加え（但比較例ではＡ又はＢの一方を省略）、目
付量125g/m2のクラフト紙に樹脂含量が50重量％となる
ように含浸・乾燥して樹脂含浸紙を得た。 得られた樹脂含浸紙を８枚積層し、圧力150kg/cm2、1
50℃の条件下に60分間加圧成形し、厚さ1.6mmの難燃性
フェノール樹脂積層板を得た。 上記難燃剤配合ワニスの保存安定性及び成形積層板の
難燃性、半田耐熱性、絶縁抵抗、打抜加工性を下表−１
に示す。 同表から明らかなように、化合物（Ａ）と化合物
（Ｂ）を含む実施例の難燃化剤を含む樹脂積層体は、前
記化合物（Ａ）又は（Ｂ）を欠く比較例のものに比べて
難燃性及び打抜性に優れるのみでなく、ワニス自体も安
定である。 [Means for Solving the Problems] (1) Outline In order to solve the above problems, the flame-retardant thermosetting resin composition according to the present invention comprises (A) a brominated epoxy compound and / or a modified compound thereof. (Hereinafter referred to as compound (A)) and (B) a brominated phenol alkylene oxide adduct (hereinafter referred to as compound (B)). Hereinafter, the various elements constituting the present invention will be described separately. (2) Compound (A) As the compound (A), a compound represented by the following general formula (I): Specifically, tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol S diglycidyl ether, tetrabromobisphenol F diglycidyl ether; a compound of the following general formula (II): Specifically, tribromophenyl glycidyl ether, dibromocresyl glycidyl ether; and a compound of the following general formula (III) in the general formula (I) and / or general formula (II): For example, tribromophenol, dibromocresol,
Reactants obtained by reacting phenol, cresol, nonylphenol, styrenated phenol, and the like are each exemplified. (3) Compound (B) As the compound (B) in the composition of the present invention, a compound represented by the following general formula (IV): Specifically, 1-5 mol adduct of tribromophenol ethylene oxide, 1-5 mol adduct of tribromophenol propylene oxide, 1-5 mol adduct of tribromophenol butylene oxide, 1-5 mol addition of dibromocresol ethylene oxide Product, dibromocresol propylene oxide 1 to 5 mol adduct, dibromocresol butyrenoxide 1 to 5 mol adduct, and the like. The addition mole number of the alkylene oxide in the compound (B) is desirably 1 to 5. 5 moles added
When the amount exceeds mol, the heat resistance of the thermosetting resin is reduced. (4) Target thermosetting resin In the present invention, the target thermosetting resin includes:
For example, unsaturated polyester resin, melamine resin, epoxy compound resin, phenol resin, furan resin, silicon resin, urea resin, diallyl phthalate resin, butadiene resin, polyurethane resin and the like can be mentioned. (5) Mixing ratio and addition amount of two components The compounding ratio of compounds (A) and (B) is desirably 1: 9 to 9: 1, and particularly preferably is in the range of 4: 6 to 8: 2. When the compounding ratio of the compound (B) exceeds 9, the heat resistance of the flame-retardant thermosetting resin is reduced. Conversely, if it is less than 1, the compatibility with the thermosetting resin will be poor. When the compounds (A) and (B) are further added to the thermosetting resin, the total amount of the two components is 5 to 50 parts by weight based on 100 parts by weight of the resin. (6) Other additives The flame-retardant thermosetting resin composition of the present invention is added to the composition. Other additives include other bromine-based flame retardants, chlorine-based flame retardants, phosphorus-based flame retardants, and antioxidants. , Plasticizers, stabilizers, dyes, pigments,
And the like. If desired, an inorganic flame retardant such as aluminum hydroxide, antimony trioxide, zinc borate and the like can be added. [Action] Since the flame-retardant thermosetting resin composition obtained according to the present invention contains the compounds (A) and (B), the stability of the varnish, the compatibility with the resin, the heat resistance and the addition of the varnish. It has excellent properties such as moldability of the product. [Examples] Hereinafter, embodiments and effects of the invention will be described with reference to examples and comparative examples. However, the exemplification is merely for explanation, and is not intended to limit or limit the inventive idea. In Examples, parts and% are based on weight. Examples 1-4 and Comparative Examples 1-2 Compound (A) and compound (B) were added to a phenolic resin varnish in a total amount of 12 parts by weight and cresyl diphenyl phosphate based on 100 parts in terms of solid content of the resin solution. 3 parts by weight were added (however, one of A and B was omitted in Comparative Examples), and kraft paper having a basis weight of 125 g / m 2 was impregnated and dried so that the resin content was 50% by weight, to obtain a resin-impregnated paper. . Eight pieces of the obtained resin-impregnated paper were laminated, and the pressure was 150 kg / cm 2 , 1
Pressure molding was performed at 50 ° C. for 60 minutes to obtain a flame-retardant phenol resin laminate having a thickness of 1.6 mm. Table 1 below shows the storage stability of the varnish containing the flame retardant and the flame retardancy, solder heat resistance, insulation resistance, and punching workability of the molded laminate.
Shown in As is evident from the table, the resin laminate containing the flame retardant of the example containing the compound (A) and the compound (B) has a smaller thickness than that of the comparative example lacking the compound (A) or (B). In addition to excellent flame retardancy and punching properties, the varnish itself is stable.
以上説明し、かつ実証した通り、本発明は、ワニスの
安定性、樹脂との相溶性、耐熱性及び被添加物の成形性
等に優れた難燃性の熱硬化性樹脂組成物を提供できたこ
とにより、それらから、各種の成形品、フィルム、樹脂
含浸紙積層品、塗料、接着剤等を製造することが可能で
ある。As described and demonstrated above, the present invention can provide a flame-retardant thermosetting resin composition excellent in varnish stability, compatibility with resin, heat resistance, moldability of additives, and the like. Accordingly, it is possible to produce various molded products, films, resin-impregnated paper laminates, paints, adhesives, and the like from them.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ０８Ｇ 59/14 Ｃ０８Ｇ 59/14 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI // C08G 59/14 C08G 59/14
Claims (3)
の変性化合物（以下、化合物（Ａ）という）と（Ｂ）下
記一般式（IV）で表わされる化合物からなる臭素化フェ
ノールアルキレンオキサイド付加物（以下、化合物
（Ｂ）という）とを配合してなる難燃性の熱硬化樹脂組
成物。 1. A brominated phenol alkylene oxide adduct comprising (A) a brominated epoxy compound and / or a modified compound thereof (hereinafter referred to as compound (A)) and (B) a compound represented by the following general formula (IV): (Hereinafter, referred to as compound (B)) and a flame-retardant thermosetting resin composition.
前者1:後者９〜前者9:後者１の範囲である請求項１記載
の難燃性の熱硬化性樹脂組成物。2. The compounding ratio of the compound (A) and the compound (B) is as follows:
The flame-retardant thermosetting resin composition according to claim 1, wherein the former is in the range of the former 1: the latter 9 to the former 9: the latter 1.
ド付加モル数が、１〜５モルの範囲である請求項１記載
の難燃性の熱硬化性樹脂組成物。3. The flame-retardant thermosetting resin composition according to claim 1, wherein the addition mole number of the alkylene oxide in the compound (B) is in the range of 1 to 5 mol.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2032235A JP2802798B2 (en) | 1990-02-13 | 1990-02-13 | Flame retardant thermosetting resin composition |
| KR1019910000612A KR940010940B1 (en) | 1990-02-13 | 1991-01-16 | Flame-retarding thermosetting resin composition |
| TW080100389A TW224980B (en) | 1990-02-13 | 1991-01-17 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2032235A JP2802798B2 (en) | 1990-02-13 | 1990-02-13 | Flame retardant thermosetting resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03234726A JPH03234726A (en) | 1991-10-18 |
| JP2802798B2 true JP2802798B2 (en) | 1998-09-24 |
Family
ID=12353323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2032235A Expired - Fee Related JP2802798B2 (en) | 1990-02-13 | 1990-02-13 | Flame retardant thermosetting resin composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2802798B2 (en) |
| KR (1) | KR940010940B1 (en) |
| TW (1) | TW224980B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007132463A1 (en) * | 2006-05-15 | 2007-11-22 | Bromine Compounds Ltd. | Flame retardant composition |
| US11560448B2 (en) * | 2016-12-14 | 2023-01-24 | Bromine Compounds Ltd. | Antimony free flame-retarded epoxy compositions |
-
1990
- 1990-02-13 JP JP2032235A patent/JP2802798B2/en not_active Expired - Fee Related
-
1991
- 1991-01-16 KR KR1019910000612A patent/KR940010940B1/en not_active IP Right Cessation
- 1991-01-17 TW TW080100389A patent/TW224980B/zh active
Also Published As
| Publication number | Publication date |
|---|---|
| KR940010940B1 (en) | 1994-11-19 |
| KR910021449A (en) | 1991-12-20 |
| TW224980B (en) | 1994-06-11 |
| JPH03234726A (en) | 1991-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20100233486A1 (en) | Flame-retardant resin composition, and prepreg, resin sheet and molded article using the same | |
| JP2000080251A (en) | Phosphorus-modified flame-retardant epoxy resin composition and its production and molded product and laminate using the phosphorus-modified flame-retardant epoxy resin composition | |
| JP4530187B2 (en) | Curable resin composition containing thermoplastic polyhydroxypolyether resin | |
| JP2802798B2 (en) | Flame retardant thermosetting resin composition | |
| US5116670A (en) | Allyl ester resin composition and laminated sheet using the same | |
| JP2000290490A (en) | Flame retardant curable resin composition | |
| JPS6253342A (en) | Production of epoxy resin laminate sheet | |
| JPS5845947A (en) | Manufacture of flame-retarded laminated board | |
| CN104892906A (en) | Single aromatic ring phenol based phosphorus-nitrogen compound containing hardener, and epoxy composition | |
| JP3261596B2 (en) | Flame retardant thermosetting resin composition | |
| JPH0649797B2 (en) | Flame retardant for thermosetting resin and method for producing the same | |
| JP2001253951A (en) | Laminate sheet formed by using flame-retardant resin composition | |
| CN109306149B (en) | Halogen-containing antimony-free resin composition, prepreg using same, laminated board and printed circuit board | |
| CN104945601A (en) | Curing agent and epoxy composition containing bisphenol-A-base phosphorus nitrogen compounds | |
| JPS60181163A (en) | Flame-retardant thermosetting resin composition | |
| JP3331774B2 (en) | Phenolic resin composition, laminate using this phenolic resin composition | |
| JPS5952907B2 (en) | Resin composition for flame-retardant laminates | |
| JPH0564966B2 (en) | ||
| JPH02283753A (en) | Laminate resin composition | |
| JPH0393849A (en) | Flame-retardant phenol resin composition | |
| JPS5831746A (en) | Copper lined laminated board | |
| WO1992005206A1 (en) | Flame-retardant thermosetting resin composition | |
| JPS5831747A (en) | Copper lined laminated board | |
| JPS63283938A (en) | Metal foil-clad laminated plate | |
| JPS59106960A (en) | Manufacture of flame-retarded laminated board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |