JPH01223158A - Flame-retardant phenolic resin composition - Google Patents
Flame-retardant phenolic resin compositionInfo
- Publication number
- JPH01223158A JPH01223158A JP63049244A JP4924488A JPH01223158A JP H01223158 A JPH01223158 A JP H01223158A JP 63049244 A JP63049244 A JP 63049244A JP 4924488 A JP4924488 A JP 4924488A JP H01223158 A JPH01223158 A JP H01223158A
- Authority
- JP
- Japan
- Prior art keywords
- group
- phosphoric acid
- acid ester
- cresyl
- phenolic 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
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 18
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 15
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 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 7
- 239000003063 flame retardant Substances 0.000 title claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 claims abstract description 10
- 125000002256 xylenyl group Chemical group C1(C(C=CC=C1)C)(C)* 0.000 claims abstract description 10
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims abstract description 3
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims abstract 3
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims abstract 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 38
- -1 ethylphenyl group Chemical group 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims 3
- 150000002148 esters Chemical class 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 description 18
- 239000010452 phosphate Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229960001755 resorcinol Drugs 0.000 description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の技術分野）
本発明は耐熱性、耐溶剤性、加工性に優れた難燃性フェ
ノール樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a flame-retardant phenolic resin composition having excellent heat resistance, solvent resistance, and processability.
（従来の技術）
フェノール樹脂は電気部品、電子部品の絶縁材料として
現在美景に使用されている。一方において電気火災防止
の立場から、こうした部品に対する難燃化の要求は益々
高まっている方向にある。(Prior Art) Phenol resin is currently used aesthetically as an insulating material for electrical and electronic parts. On the other hand, from the standpoint of preventing electrical fires, there is an increasing demand for flame retardant properties for these parts.
こうしたことから現在のフェノール樹脂は、難燃性をも
たせるために含りん化合物や含ハロゲン化合物が添加さ
れて用いられている。含りん化合物としては、りん酸エ
ステル類が最も一般的である。For these reasons, current phenolic resins are used with phosphorus-containing compounds and halogen-containing compounds added to impart flame retardancy. As phosphorus-containing compounds, phosphoric acid esters are the most common.
りん酸エステル類は樹脂に難燃性を与えると共に、可塑
剤として働いて板の加工性を向上させる効果がある。近
年の電子部品の小型化、高密度化にともない、板の加工
性を向上させることは重要である。現在、この分野で使
用されているりん酸エステルとしては、トリフェニルホ
スフェート、クレジルジフェニルホスフェ−１、イソプ
ロピル化されたトリフェニルホスフェート等が代表的で
ある。Phosphate esters not only impart flame retardancy to the resin, but also act as plasticizers and have the effect of improving the workability of the plate. As electronic components have become smaller and more dense in recent years, it has become important to improve the workability of plates. Typical phosphoric acid esters currently used in this field include triphenyl phosphate, cresyl diphenyl phosphate-1, and isopropylated triphenyl phosphate.
これらのりん酸エステルはいずれも添加型と呼ばれる種
類の難燃剤であって、フェノール樹脂を硬化させるとき
に樹脂とは反応し得ないために、樹脂の物性に様々な悪
影響を及ぼすことが知られている。一方Ｊ反応性のりん
酸エステルを用いる方法、すなわちりん酸エステルに適
当な官能基を導入して、フェノール樹脂を硬化させると
きにポリマー中に取り込まれるようにする方法がある０
例えば特開昭６０−２４８７６８では、反応性のりん酸
エステルとしてジフェニルレゾルシニルホスフェートを
用いる積層板樹脂組成物が提案されている。この反応性
の難燃剤を用いる方法では、りん酸エステルのもう一つ
の機能である板の加工性の向上という効果は失われてし
まう、この改善のため、特開昭６０−２４８７６８では
石油樹脂を添加して、板に可塑性を与えている。All of these phosphate esters are a type of flame retardant called an additive type, and because they cannot react with the phenolic resin when it is cured, they are known to have various negative effects on the physical properties of the resin. ing. On the other hand, there is a method using a J-reactive phosphate ester, that is, a method in which an appropriate functional group is introduced into the phosphate ester so that it is incorporated into the polymer when curing the phenolic resin.
For example, JP-A-60-248768 proposes a laminate resin composition using diphenylresorcinyl phosphate as a reactive phosphate ester. In the method of using this reactive flame retardant, the effect of improving the processability of the plate, which is another function of phosphoric acid ester, is lost.To improve this, Japanese Patent Application Laid-Open No. 60-248768 uses petroleum resin. It is added to give the board plasticity.
（発明が解決しようとする問題点）
りん酸エステルのうち添加型のものは樹脂からのしみだ
しによる電気特性の低下、耐熱性や、耐溶剤性の低下が
起こる。一方１反応型では添加型の欠点は補われるが、
成型された樹脂の加工性が失われる。しかしこの場合石
油樹脂を添加すると難燃性が低下するという問題がある
。(Problems to be Solved by the Invention) Among the phosphoric acid esters, those of the additive type seep out from the resin, resulting in a decrease in electrical properties, heat resistance, and solvent resistance. On the other hand, the one-reaction type compensates for the disadvantages of the additive type, but
Processability of molded resin is lost. However, in this case, there is a problem in that adding petroleum resin reduces flame retardancy.
フェノール樹脂はエポキシ樹脂に比べ安価ではあるが、
樹脂の耐熱性や、電気特性において劣っているために用
途が限られていた。フェノール樹脂の難燃性と加工性を
落とさずに、電気特性、耐熱性等を向上させることがで
きれば、電子産業に貢献するところは大きいと思われる
が、このような方法は実用化に至っていない。Although phenolic resin is cheaper than epoxy resin,
Its uses have been limited due to the resin's poor heat resistance and electrical properties. If it were possible to improve the electrical properties and heat resistance of phenolic resin without compromising its flame retardancy and processability, it would make a significant contribution to the electronics industry, but such a method has not yet been put into practical use. .
（問題を解決するための手段）
発明者らは上記の問題を解決するために鋭意検討を重ね
た結果、以下に示すようなりん酸エステル混合物をフェ
ノール樹脂に添加することにより目的を達成することが
できた。すなわち次の３或分からなるりん酸エステル混
合物である。(Means for Solving the Problem) As a result of intensive studies in order to solve the above problem, the inventors found that the purpose was achieved by adding the following phosphoric acid ester mixture to the phenolic resin. was completed. That is, it is a phosphoric acid ester mixture consisting of the following three parts.
■ −数式
（ただしＸはフェニル基、クレジル基、キシレニル基、
エチルフェニル基、イソプロピルフェニル基、またはブ
チルフェニル基を表し、Ｙはオルト、メタ、ま・たはバ
ラの）ユニレン基を表す、また、ｋは０〜２の整数を表
し、ｋ−２のとき２つのＸは互いに同じでも異なってい
てもよい）で表されるりん酸エステルの少なくとも１種
。- Numerical formula (where X is a phenyl group, cresyl group, xylenyl group,
It represents an ethylphenyl group, an isopropylphenyl group, or a butylphenyl group, and Y represents an ortho, meta, or rose) unilene group, and k represents an integer from 0 to 2, and when k-2 At least one type of phosphoric acid ester represented by (two X's may be the same or different).
■ −数式
％式％）
（ただしＸはフェニル基、クレジル基、キシレニル基、
エチルフェニル基、イソプロピルフェニル基、またはブ
チルフェニル基を表し、３つのＸは互いに同じでも異な
っていてもよい）
で表されるりん酸エステルの少なくとも１種。■ -Formula %Formula %) (However, X is a phenyl group, cresyl group, xylenyl group,
At least one type of phosphoric acid ester represented by: an ethylphenyl group, an isopropylphenyl group, or a butylphenyl group, and the three X's may be the same or different from each other.
■ −数式
（ただしＸはフェニル基、クレジル基、キシレニル基、
エチルフェニル基、イソプロピルフェニル基、またはブ
チルフェニル基を表し、Ｙはオルト、メタ、またはパラ
の）ユニレン基を表し、２はフェニル基、クレジル基、
キシレニル基、エチルフェニル基、イソプロピルフェニ
ル基、ブチルフェニル基、またはヒドロキシフェニル基
を表す、また、ｋおよびｊはＯ〜３の整数を表し、Ｘが
２つ以上ある時はＸは互いに同じでも興なっていてもよ
い、またｎはＯ〜３の整数を表す、）で表されるりん酸
エステルの少なくとも１種。- Numerical formula (where X is a phenyl group, cresyl group, xylenyl group,
represents an ethylphenyl group, isopropylphenyl group, or butylphenyl group, Y represents an ortho, meta, or para) unilene group, 2 represents a phenyl group, a cresyl group,
Represents a xylenyl group, ethylphenyl group, isopropylphenyl group, butylphenyl group, or hydroxyphenyl group, and k and j represent integers of O to 3, and when there are two or more X, X may be the same or different. and n represents an integer of O to 3.
ただし、それぞれの成分の含有量は■が２２〜６５重量
％、■が１５〜３０重量％、■が５〜６８重量％の範囲
でなくてはならない。However, the content of each component must be in the range of 22 to 65% by weight for (1), 15 to 30% by weight for (2), and 5 to 68% by weight for (2).
■に該当するりん酸エステルの一例を示すと、（以下ｐ
ｈはフェニル基を示す）
また■に該当するりん酸エステルの一例を示すと、
等が挙げられる。An example of a phosphoric acid ester corresponding to ■ is (below p
(h represents a phenyl group) Examples of phosphoric acid esters corresponding to (■) include the following.
本発明のりん酸エステル混合物の製造例を次に示す、ま
ず２僅のフェノ−ル類と１価のフェノール類を混合し、
この混合物にエステル化の触媒を加え、さらにオキシ塩
化りんを反応させる。別の反応の工程としては、さきに
オキシ塩化りんと１価のフェノール類を反応させた後に
２価のフェノール類を加えて反応させてもよいし、また
オキシ塩化りんと２価のフェノールを先に反応させた後
に１価のフェノールを反応させてもよい、いずれの反応
にも、塩化アルミニウム、ふり化はう素、塩化チタンな
どのルイス酸を触媒として用いることができる０反応の
手順によって生成物の組成は変化するが、その組成が特
許請求範囲の第（２）項を満たす限りどの順序で反応さ
せてもかまわないるように、別途合成したりん酸エステ
ルを混合して用いてもよい０反応生成物は必要に応じて
、これまでに知られている適当な方法で後処理して触媒
や塩素分を取り除いて用いられる。An example of producing the phosphoric acid ester mixture of the present invention is shown below. First, a few phenols and a monohydric phenol are mixed,
An esterification catalyst is added to this mixture, and phosphorus oxychloride is further reacted. As another reaction step, phosphorus oxychloride and monovalent phenols may be reacted first, and then divalent phenols may be added and reacted, or phosphorus oxychloride and divalent phenol may be reacted first. After the reaction, a monohydric phenol may be reacted. In either reaction, a Lewis acid such as aluminum chloride, borofluoride, or titanium chloride can be used as a catalyst. The composition may vary, but the reaction may be carried out in any order as long as the composition satisfies item (2) of the claims. If necessary, the product is used after being post-treated to remove the catalyst and chlorine content by an appropriate method known so far.
本発明の特徴は、特許請求範囲第（１）項の■に示され
た反応性のりん酸エステルと、■に示された非反応性の
りん酸エステル、および■に示されたオリゴマー状のり
ん酸エステルを特定の範囲の割合で含んでいることによ
りフェノール樹脂に良好な物性を与えることができると
いう点である。The feature of the present invention is that the reactive phosphoric ester shown in (1) of claim 1, the non-reactive phosphoric ester shown in (2), and the oligomeric ester shown in (2) The point is that good physical properties can be imparted to the phenol resin by containing the phosphoric acid ester in a specific range of proportions.
反応性のりん酸エステルは、フェノール樹脂を硬化させ
るときに樹脂に取り込まれ、製品の耐熱性や耐溶剤性を
向上させるのに効果がある。この効果を発揮させるには
、りん酸エステル混合物中に反応性のりん酸エステルが
、少なくとも２２１ｉ量％以上なくてはならない、しか
し、反応性のりん酸エステルが、６５重量％以上になる
と、樹脂の加工性が損なわれてしまう、非反応性のりん
酸エステルの働きは樹脂の加工性を維持することである
。ただしこれが余り多くなると、樹脂の耐熱性やｌ１ｒ
ｓ剤性が損なわれるので、この一部をオリゴマー状のり
ん酸エステルで置き換えることにより、樹脂の物性の低
下を抑えることができる。オリゴマー状のりん酸エステ
ルの中には、フェノール性水駿基を有する反応性の化合
物と、非反応性の化合物があるが、通常はりん酸エステ
ルを合成するときに両方が生成し混合物となる。オリゴ
マー状のりん酸エステルの混合物は、樹脂に耐熱性を与
える効果と可塑性を与える効果において、単量体の反応
性りん酸エステルと、単量体の非反応性りん酸エステル
の中間の性質を示す０以上のように性質の異なったりん
酸エステルが同時に配合されることにより、各種の物性
のバランスの取れた優れた樹脂を得ることができる。Reactive phosphoric acid esters are incorporated into the phenolic resin when it is cured, and are effective in improving the heat resistance and solvent resistance of the product. In order to exhibit this effect, the amount of reactive phosphate ester in the phosphate ester mixture must be at least 221% by weight. However, if the amount of reactive phosphate ester exceeds 65% by weight, the resin The function of the non-reactive phosphate ester is to maintain the processability of the resin. However, if this amount increases too much, the heat resistance of the resin
Since the s-agent properties are impaired, by replacing a part of this with an oligomeric phosphoric acid ester, it is possible to suppress the deterioration of the physical properties of the resin. Among oligomeric phosphoric acid esters, there are reactive compounds with phenolic hydrogen groups and non-reactive compounds, but both are usually produced when synthesizing phosphoric acid esters, resulting in a mixture. . A mixture of oligomeric phosphate esters has properties intermediate between monomeric reactive phosphoric esters and monomeric non-reactive phosphoric esters in the effect of imparting heat resistance and plasticity to the resin. By simultaneously blending phosphoric acid esters having different properties as shown in 0 or more, it is possible to obtain an excellent resin with well-balanced various physical properties.
本発明にはフェノール類とホルムアルデヒド類を原料と
する一般のフェノール樹脂が用いられるのが基本である
が、各種の変性樹脂であってもかまわない、フェノール
類としては、フェノール、クレゾール、キシレノール、
ブチルフェノール、ノニルフェノール、キシレン樹脂−
フェノール混合物、桐油のフェノール付加物等が挙げら
れ、これらの１種または２種以上の混合系として使用さ
れる。また樹脂の性質を向上させる効果のある各種の添
加剤を加えて使用できる０例えば製品の耐アーク性、耐
トラツキング性のような電気的な性質を向上させるため
、各種の窒素化合物を添加して用いることができる。こ
のような添加剤としては、メラミン、ベンゾグアナミン
、アセトグアナミン、ホルムグアナミンなどが挙げられ
る。さらに樹脂の難燃性を向上させるために、含ハロゲ
ン化合物を添加して用いることができる。The present invention basically uses general phenolic resins made from phenols and formaldehydes, but various modified resins may also be used. Examples of phenols include phenol, cresol, xylenol,
Butylphenol, nonylphenol, xylene resin
Examples include phenol mixtures and phenol adducts of tung oil, and these are used alone or as a mixture of two or more. In addition, various additives can be added that have the effect of improving the properties of the resin.For example, various nitrogen compounds can be added to improve the electrical properties of the product, such as arc resistance and tracking resistance. Can be used. Such additives include melamine, benzoguanamine, acetoguanamine, formguanamine, and the like. Furthermore, in order to improve the flame retardancy of the resin, a halogen-containing compound can be added.
以下の実施例において、特に電子部品用フェノール積層
板を例にとり、本発明を具体的に説明する。In the following examples, the present invention will be specifically explained by taking a phenol laminate for electronic parts as an example.
（実施例１） 以下に述べる方法でりん酸エステルを合成した。(Example 1) A phosphoric acid ester was synthesized by the method described below.
フェノール９４．１ｇ、レゾルシン５５．０ｇ、塩化ア
ルミニウム０．７５ｇをフラスコにとり、８０〜９０℃
に加熱した。この混合液に、オキシ塩化りん７６．７ｇ
を１時間かけて滴下した。Place 94.1 g of phenol, 55.0 g of resorcinol, and 0.75 g of aluminum chloride in a flask and heat at 80 to 90°C.
heated to. Add 76.7 g of phosphorus oxychloride to this mixture.
was added dropwise over 1 hour.
滴下終了後２時間かけて徐々に１９０℃まで昇温しエス
テル化を完了させた０反応生成物を冷却し、水洗して触
媒及び塩素分を取り除き製品とした。After completion of the dropwise addition, the temperature was gradually raised to 190° C. over 2 hours to complete esterification, and the reaction product was cooled and washed with water to remove the catalyst and chlorine content to obtain a product.
このりん酸エステル混合物中には、ジフェニルレゾルシ
ニルホスフエートとフェニルジレゾルシニルホスフェー
トが３２％、トリフェニルホスフェートが１９％、オリ
ゴマー状のりん酸エステルが４９％含有されていた。This phosphate ester mixture contained 32% diphenylresorcinyl phosphate and phenyl diresorcinyl phosphate, 19% triphenyl phosphate, and 49% oligomeric phosphoric ester.
このようにして合成されたりん酸エステルを用いてフェ
ノール積層板を作成した。まず下記の配合でワニスを調
製した。A phenol laminate was produced using the phosphoric acid ester synthesized in this way. First, a varnish was prepared with the following formulation.
配合：
積層板用フェノール樹＠ ８５部りん
酸エステル １５部アセトン
１５部メタノール
１５郁このワニスをクラフト紙
に含浸させ、樹脂含有量５０％のプリプレグとした。プ
リプレグ８枚と接着剤付き鋼箔１枚を重ね合わせ、１６
０℃、 １００ｋｇ／ｃｍ’の条件で６０分間加熱加圧
して厚さ１．６ｍｍの銅張積層板を作製した。Composition: Phenolic tree for laminates @ 85 parts phosphoric acid ester 15 parts acetone
15 parts methanol
15 Ikuko's varnish was impregnated into kraft paper to form a prepreg with a resin content of 50%. Layer 8 sheets of prepreg and 1 sheet of steel foil with adhesive, 16
A copper-clad laminate with a thickness of 1.6 mm was produced by heating and pressing at 0° C. and 100 kg/cm' for 60 minutes.
（実施例２）
フェノール９４．１ｇ、塩化アルミニウム０゜７５ｇを
フラスコに取り９０℃でオキシ塩化りんを滴下した。生
成した中間体にレゾルシン５５゜０ｇを加えさらに反応
させた。゛反応を完結させるために、徐々に昇温し最終
的には１８０℃まで温度を上げた。このりん酸エステル
混合物中には、ジフェニルレゾルシニルホスフェートと
フェニルジレゾルシニルホスフェートが５９％、トリフ
ェニルホスフェートが２７％、オリゴマー状のりん酸エ
ステルが１４％含有されていた。(Example 2) 94.1 g of phenol and 0.75 g of aluminum chloride were placed in a flask, and phosphorus oxychloride was added dropwise at 90°C. 55.0 g of resorcinol was added to the produced intermediate and further reacted. ``In order to complete the reaction, the temperature was gradually raised to 180°C. This phosphate ester mixture contained 59% diphenylresorcinyl phosphate and phenyl diresorcinyl phosphate, 27% triphenyl phosphate, and 14% oligomeric phosphoric ester.
このりん酸エステルを用いて実施例１と同様にフェノー
ル積層板を作製した。A phenol laminate was produced in the same manner as in Example 1 using this phosphoric acid ester.
（実施例３）
実施例２と同じ方法で、フェノールの代わりににハイド
ロキノン５５．０ｇを用いてりん酸エステルを合成した
。このりん酸エステル混合物中には、りん原子１つと水
酸基１以上を持つりん酸エステルが６２％、トリクレジ
ルホスフェートが２０％、オリゴマー状のりん酸エステ
ルが１８％が含有されていた。(Example 3) A phosphoric acid ester was synthesized in the same manner as in Example 2, using 55.0 g of hydroquinone instead of phenol. This phosphoric acid ester mixture contained 62% phosphoric acid ester having one phosphorus atom and one or more hydroxyl groups, 20% tricresyl phosphate, and 18% oligomeric phosphoric acid ester.
このりん酸エステルを用いて実施例１と同様にフェノー
ル積層板を作製した。A phenol laminate was produced in the same manner as in Example 1 using this phosphoric acid ester.
（比較例１） レゾルシン７０ｇ、塩化アルミニウム０．５ｇ。(Comparative example 1) 70 g of resorcinol, 0.5 g of aluminum chloride.
の混合物を１３０℃に加熱し、そこにジフェニルホスホ
クロリド１３４．３ｇを滴下し反応させた。The mixture was heated to 130° C., and 134.3 g of diphenylphosphochloride was added dropwise thereto to react.
反応終了後余分なレゾルシンを水洗して除いた。After the reaction was completed, excess resorcin was removed by washing with water.
得られたりん酸エステル混合物中には、ジフェニルレゾ
ルシニルホスフェートが６９％、オリゴマー状のりん酸
エステルが３１％含まれていた。The resulting phosphoric acid ester mixture contained 69% diphenylresorcinyl phosphate and 31% oligomeric phosphoric acid ester.
このりん酸エステルを用いて実施例１と同様にフェノー
ル積層板を作製した。A phenol laminate was produced in the same manner as in Example 1 using this phosphoric acid ester.
（比較例２）
レゾルシン５５．０ｇ、塩化アルミニウム０゜５ｇの混
合物を１３０℃に加熱し、そこにジフェニルホスホクロ
リド２６８．６ｇを滴下し反応させた。得られたりん酸
エステル混合物に比較例１で合成したりん酸エステルを
混合し、ジフェニルレゾルシニルホスフェートを１８％
、オリゴマー状のりん酸エステルを６２％含むりん酸エ
ステル混合物を調製した。(Comparative Example 2) A mixture of 55.0 g of resorcinol and 0.5 g of aluminum chloride was heated to 130° C., and 268.6 g of diphenylphosphochloride was added dropwise thereto to react. The phosphoric ester synthesized in Comparative Example 1 was mixed with the obtained phosphoric ester mixture, and 18% of diphenylresorcinyl phosphate was added.
, a phosphate ester mixture containing 62% oligomeric phosphate ester was prepared.
このりん酸エステルを用いて実施ＩＮ１と同様にフェノ
ール積層板を作製した。Using this phosphoric acid ester, a phenol laminate was produced in the same manner as in Example IN1.
（比較例３）
実施例１のりん酸エステル混合物の代わりに、トリフェ
ニルホスフェートを用いてフェノール積層板を作製した
。(Comparative Example 3) Instead of the phosphoric acid ester mixture of Example 1, triphenyl phosphate was used to produce a phenol laminate.
以上のように作製した積層板について各種の特性をＪＩ
Ｓ Ｃ６４８１に準じて試験し、その結果を表に示し
た。Various properties of the laminates produced as described above were determined by JI.
It was tested according to SC6481 and the results are shown in the table.
（発明の効果）
表からも明かな通り、本発明のフェノール樹脂を用いた
積層板は、全ての項目についてバランスの取れた優れた
性能を示す。(Effects of the Invention) As is clear from the table, the laminate using the phenolic resin of the present invention exhibits well-balanced and excellent performance in all items.
Claims (2)
エチルフェニル基、イソプロピルフェニル基、またはブ
チルフェニル基を表し、Ｙはオルト、メタ、またはパラ
のフェニレン基を表す。また、Ｋは０〜２の整数を表し
、Ｋ＝２のとき２つのＸは互いに同じでも異なっていて
もよい）で表されるりん酸エステルの少なくとも一種 ［２］一般式 ▲数式、化学式、表等があります▼ （ただしＸはフェニル基、クレジル基、キシレニル基、
エチルフェニル基、イソプロピルフェニル基、またはブ
チルフェニル基を表し、３つのＸは互いに同じでも異な
っていてもよい）で表されるりん酸エステルの少なくと
も一種 ［３］一般式 ▲数式、化学式、表等があります▼ （ただしＸはフェニル基、クレジル基、キシレニル基、
エチルフェニル基、イソプロピルフェニル基、またはブ
チルフェニル基を表し、Ｙはオルト、メタ、またはパラ
のフェニレン基を表し、Ｚはフェニル基、クレジル基、
キシレニル基、エチルフェニル基、イソプロピルフェニ
ル基、ブチルフェニル基、またはヒドロキシフェニル基
を表す。 また、ｋおよびｊは０〜３の整数を表し、Ｘが２つ以上
ある時はＸは互いに同じでも異なっていてもよい。また
ｎは０〜３の整数を表す。） で表されるりん酸エステルの少なくとも一種で構成され
るりん酸エステル混合物を、フェノール樹脂に対し５〜
５０重量％含有させることを特徴とする難燃性フェノー
ル樹脂組成物。(1) A mixture of the following three types of phosphoric acid esters, namely [1] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, X is a phenyl group, cresyl group, xylenyl group,
It represents an ethylphenyl group, an isopropylphenyl group, or a butylphenyl group, and Y represents an ortho, meta, or para phenylene group. In addition, K represents an integer of 0 to 2, and when K = 2, the two X may be the same or different from each other) [2] General formula ▲ Numerical formula, chemical formula, There are tables, etc.▼ (However, X is a phenyl group, cresyl group, xylenyl group,
[3] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, X is a phenyl group, cresyl group, xylenyl group,
represents an ethylphenyl group, isopropylphenyl group, or butylphenyl group, Y represents an ortho, meta, or para phenylene group, Z represents a phenyl group, a cresyl group,
Represents a xylenyl group, ethylphenyl group, isopropylphenyl group, butylphenyl group, or hydroxyphenyl group. Moreover, k and j represent integers of 0 to 3, and when there are two or more X's, the X's may be the same or different. Moreover, n represents an integer of 0 to 3. ) A phosphoric acid ester mixture composed of at least one type of phosphoric acid ester represented by
A flame-retardant phenol resin composition characterized by containing 50% by weight.
記載の難燃性フェノール樹脂組成物。(2) The phosphoric acid ester mixture is characterized in that it contains 22 to 65% by weight of [1], 15 to 30% by weight of [2], and 5 to 63% by weight of [3]. A flame-retardant phenolic resin composition according to claim (1).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63049244A JP2661109B2 (en) | 1988-03-02 | 1988-03-02 | Flame retardant phenolic resin composition |
| KR1019890002389A KR960002527B1 (en) | 1988-03-02 | 1989-02-28 | Flame-retardant phenol resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63049244A JP2661109B2 (en) | 1988-03-02 | 1988-03-02 | Flame retardant phenolic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01223158A true JPH01223158A (en) | 1989-09-06 |
| JP2661109B2 JP2661109B2 (en) | 1997-10-08 |
Family
ID=12825448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63049244A Expired - Lifetime JP2661109B2 (en) | 1988-03-02 | 1988-03-02 | Flame retardant phenolic resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2661109B2 (en) |
| KR (1) | KR960002527B1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5508462A (en) * | 1994-12-07 | 1996-04-16 | Akzo Nobel Nv | Process for making hydroxy-terminated aromatic oligomeric phosphates |
| US5618867A (en) * | 1994-12-07 | 1997-04-08 | Akzo Nobel Nv | Hydroxy-terminated aromatic oligomeric phosphate as additive flame retardant in polycarbonate resin composition |
| US5728859A (en) * | 1996-10-31 | 1998-03-17 | Akzo Nobel N.V. | Process for making monohydroxy-terminated phosphate compositions |
| WO1999014289A1 (en) * | 1997-09-17 | 1999-03-25 | Akzo Nobel N.V. | Thermostability enhancement of polyphosphate flame retardants |
| US6403819B1 (en) | 1997-05-21 | 2002-06-11 | Akzo Nobel, Nv | Process for making di(hydroxyalkylaryl) aryl phosphate compounds |
| WO2003089442A1 (en) * | 2002-04-22 | 2003-10-30 | Songwon Industrial Co., Ltd. | A method of preparing phosphoric ester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5665041A (en) * | 1979-11-01 | 1981-06-02 | Toshiba Chem Corp | Flame-retardant phenolic resin precondensate |
| JPS6063251A (en) * | 1983-09-16 | 1985-04-11 | Adeka Argus Chem Co Ltd | Flame-retardant phenolic resin composition |
| JPS60248768A (en) * | 1984-05-24 | 1985-12-09 | Toshiba Chem Corp | Resin composition for laminated board |
-
1988
- 1988-03-02 JP JP63049244A patent/JP2661109B2/en not_active Expired - Lifetime
-
1989
- 1989-02-28 KR KR1019890002389A patent/KR960002527B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5665041A (en) * | 1979-11-01 | 1981-06-02 | Toshiba Chem Corp | Flame-retardant phenolic resin precondensate |
| JPS6063251A (en) * | 1983-09-16 | 1985-04-11 | Adeka Argus Chem Co Ltd | Flame-retardant phenolic resin composition |
| JPS60248768A (en) * | 1984-05-24 | 1985-12-09 | Toshiba Chem Corp | Resin composition for laminated board |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5508462A (en) * | 1994-12-07 | 1996-04-16 | Akzo Nobel Nv | Process for making hydroxy-terminated aromatic oligomeric phosphates |
| US5618867A (en) * | 1994-12-07 | 1997-04-08 | Akzo Nobel Nv | Hydroxy-terminated aromatic oligomeric phosphate as additive flame retardant in polycarbonate resin composition |
| EP0796265A1 (en) * | 1994-12-07 | 1997-09-24 | Akzo Nobel N.V. | Process for making hydroxy-terminated aromatic oligomeric phosphates |
| EP0796265A4 (en) * | 1994-12-07 | 1998-05-06 | Akzo Nobel Nv | Process for making hydroxy-terminated aromatic oligomeric phosphates |
| US5728859A (en) * | 1996-10-31 | 1998-03-17 | Akzo Nobel N.V. | Process for making monohydroxy-terminated phosphate compositions |
| EP0937087B1 (en) * | 1996-10-31 | 2003-09-10 | Akzo Nobel N.V. | Monohydroxy-terminated phosphates and their use as flame retardants |
| US6403819B1 (en) | 1997-05-21 | 2002-06-11 | Akzo Nobel, Nv | Process for making di(hydroxyalkylaryl) aryl phosphate compounds |
| WO1999014289A1 (en) * | 1997-09-17 | 1999-03-25 | Akzo Nobel N.V. | Thermostability enhancement of polyphosphate flame retardants |
| WO2003089442A1 (en) * | 2002-04-22 | 2003-10-30 | Songwon Industrial Co., Ltd. | A method of preparing phosphoric ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2661109B2 (en) | 1997-10-08 |
| KR890014672A (en) | 1989-10-25 |
| KR960002527B1 (en) | 1996-02-22 |
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