JPH10286926A - Flame retardant phenol resin laminate - Google Patents
Flame retardant phenol resin laminateInfo
- Publication number
- JPH10286926A JPH10286926A JP9620697A JP9620697A JPH10286926A JP H10286926 A JPH10286926 A JP H10286926A JP 9620697 A JP9620697 A JP 9620697A JP 9620697 A JP9620697 A JP 9620697A JP H10286926 A JPH10286926 A JP H10286926A
- Authority
- JP
- Japan
- Prior art keywords
- phenol resin
- resin
- phenolic resin
- parts
- weight
- 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
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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、耐水性、打抜き加
工性の良好な難燃性フェノール樹脂積層板に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant phenol resin laminate having good water resistance and good punching workability.
【0002】[0002]
【従来の技術】電子機器などに搭載される印刷回路用基
板として紙基材フェノール樹脂積層板が多用されてい
る。この紙基材フェノール樹脂積層板において、紙基材
に含浸されるフェノール樹脂としては、打抜き加工性向
上のために乾性油又は半乾性油で変性したフェノール樹
脂が用いられている。更に、紙基材フェノール樹脂積層
板に難燃性を付与するために、フェノール樹脂にリン系
難燃剤、ハロゲン系難燃剤を添加する方法が知られてい
る。しかし、ハロゲン系難燃剤は公害上の問題からその
使用量の削減または不使用が求められている。一方、リ
ン系難燃剤は添加量を多くすると難燃性は向上するが、
打ち抜き加工性及び半田耐熱性が低下するという問題が
生じてくる。2. Description of the Related Art Paper-based phenolic resin laminates are frequently used as substrates for printed circuits mounted on electronic equipment and the like. In this paper-based phenolic resin laminate, as the phenolic resin impregnated in the paper-based material, a phenolic resin modified with a drying oil or a semi-drying oil is used to improve punching workability. Further, a method of adding a phosphorus-based flame retardant and a halogen-based flame retardant to a phenol resin in order to impart flame retardancy to a paper base phenol resin laminate is known. However, the use of halogen-based flame retardants is required to be reduced or not used due to pollution problems. On the other hand, as the phosphorus-based flame retardant increases, the flame retardancy improves,
A problem arises in that the punching workability and solder heat resistance are reduced.
【0003】[0003]
【発明が解決しようとする課題】本発明は上記の事実に
鑑みてなされたもので、その目的とするところは、ハロ
ゲン系難燃剤を使用せず、難燃性、半田耐熱性及び打抜
き加工性が良好な難燃性紙基材フェノール樹脂積層板を
提供することである。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above facts, and has as its object to eliminate the use of halogen-based flame retardants, to provide flame retardancy, solder heat resistance and punching workability. Is to provide a good flame-retardant paper-based phenolic resin laminate.
【0004】[0004]
【課題を解決するための手段】本発明は、紙基材にフェ
ノール樹脂組成物を含浸せしめたプリプレグを積層成形
して得られる難燃性フェノール樹脂積層板において、フ
ェノール樹脂組成物が未変性レゾール型フェノール樹
脂、ノボラック型フェノール樹脂、リン酸エステル、ア
ミノ樹脂及び無機フィラーからなる難燃性フェノール樹
脂積層板、を要旨とするものである。SUMMARY OF THE INVENTION The present invention relates to a flame-retardant phenolic resin laminate obtained by laminating a prepreg impregnated with a phenolic resin composition on a paper base, wherein the phenolic resin composition comprises an unmodified resol. And a flame-retardant phenolic resin laminate comprising a phenolic resin, a novolak phenolic resin, a phosphoric ester, an amino resin and an inorganic filler.
【0005】本発明のフェノール樹脂積層板において
は、ハロゲン系難燃剤を使用せずに難燃性が優れたもの
とするために、難燃性であり使いやすさ及び入手の容易
さの点で有利なリン酸エステル及びアミノ樹脂を使用
し、一方燃えやすい成分である乾性油を使用することな
く難燃性を維持向上させている。この場合打ち抜き加工
性の低下が起こるが、これを防止するために、ノボラッ
ク型フェノール樹脂を用いることとした。このことによ
り難燃性を良好に維持したまま打ち抜き加工性の良好な
紙基材フェノール樹脂積層板を得ることができたもので
ある。[0005] The phenolic resin laminate of the present invention is flame-retardant, easy to use, and easily available in order to provide excellent flame retardancy without using a halogen-based flame retardant. Advantageous phosphate ester and amino resin are used, and flame retardancy is maintained and improved without using a drying oil which is a flammable component. In this case, a drop in punching workability occurs, but in order to prevent this, a novolak type phenol resin is used. As a result, a paper-based phenolic resin laminate having good punching workability was obtained while maintaining good flame retardancy.
【0006】更に、本発明においては無機フィラーを配
合する。無機フィラーは不燃成分及び又は難燃助剤とし
て作用するものであり、このことにより一層難燃性を向
上させるものである。Further, in the present invention, an inorganic filler is blended. The inorganic filler functions as a non-combustible component and / or a flame retardant auxiliary agent, thereby further improving the flame retardancy.
【0007】更に詳しく本発明を説明すれば、レゾール
型フェノール樹脂としては、フェノール、クレゾール等
のフェノール類とパラホルムアルデヒド、ホルマリン水
溶液等のホルムアルデヒドと反応させたものであり、通
常はアミン類、アンモニア等の塩基性触媒によって得ら
れるレゾール型フェノール樹脂が用いられる。In more detail, the present invention is a resol type phenol resin obtained by reacting a phenol such as phenol or cresol with formaldehyde such as an aqueous solution of paraformaldehyde or formalin. The resol type phenol resin obtained by the basic catalyst is used.
【0008】本発明で用いられるノボラック型フェノー
ル樹脂は、フェノール、クレゾール等のフェノール類と
パラホルムアルデヒド、ホルマリン水溶液等のホルムア
ルデヒドと反応させたものであり、通常は塩酸またはシ
ュウ酸などの無機酸や有機酸などを触媒にして得られる
ノボラック型フェノール樹脂が用いられる。The novolak type phenol resin used in the present invention is obtained by reacting a phenol such as phenol or cresol with a formaldehyde such as aqueous paraformaldehyde or formalin, and usually an inorganic acid such as hydrochloric acid or oxalic acid or an organic acid. A novolak-type phenol resin obtained using an acid or the like as a catalyst is used.
【0009】本発明で用いられるリン酸エステルは、ト
リエチルホスフェイト、トリブチルホスフェイト、トリ
フェニルホスフェイト、トリクレジルホスフェイト、ク
レジルジフェニルホスフェイト、レゾルシルジフェニル
ホスフェイト、トリイソプロピルフェニルホスフェイト
等が挙げられ、これらは1種または2種以上の混合系と
して使用される。この中で、トリフェニルホスフェイ
ト、トリクレジルホスフェイト、クレジルジフェニルホ
スフェイトが入手のしやすさから好ましいものである。The phosphate ester used in the present invention includes triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcil diphenyl phosphate, triisopropyl phenyl phosphate and the like. These are used as one kind or a mixture of two or more kinds. Among these, triphenyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate are preferred from the viewpoint of availability.
【0010】本発明に用いられるアミノ樹脂は、メラミ
ン樹脂、グアナミン樹脂などであるが、難燃化の効果を
高めるためにはメラミン樹脂が好ましい。アミノ樹脂
は、メラミンやグアナミンなどのアミノ化合物とホルム
アルデヒド等のアルデヒド類との初期反応物であり、そ
れらのメチロール基の一部または全部をメタノール、ブ
タノール等の低級アルコールでエーテル化したものも含
まれる。The amino resin used in the present invention is a melamine resin, a guanamine resin or the like, but a melamine resin is preferable in order to enhance the flame-retardant effect. Amino resin is an initial reaction product of an amino compound such as melamine or guanamine and an aldehyde such as formaldehyde, and includes those obtained by etherifying some or all of the methylol groups with a lower alcohol such as methanol or butanol. .
【0011】本発明で使用される無機フィラーは、水酸
化アルミニウム、水酸化マグネシウム、炭酸カルシウ
ム、アルミン酸カルシウム、ほう素化合物、水酸化カル
シウムなどが挙げられる。この中で水酸化アルミニウ
ム、水酸化マグネシウムは難燃助剤としての作用を有す
ることから難燃効果が大きく、さらには入手のしやすさ
から好ましいものである。The inorganic filler used in the present invention includes aluminum hydroxide, magnesium hydroxide, calcium carbonate, calcium aluminate, boron compounds, calcium hydroxide and the like. Among them, aluminum hydroxide and magnesium hydroxide have a large flame-retardant effect because they have a function as a flame-retardant aid, and are preferable because they are easily available.
【0012】本発明の難燃性フェノール樹脂積層板にお
いて、フェノール樹脂組成物の配合割合は、未変性レゾ
ール型フェノール樹脂100重量部に対して、ノボラッ
ク型フェノール樹脂50〜180重量部、リン酸エステ
ル40〜130重量部、アミノ樹脂20〜100重量
部、及び無機フィラー10〜200重量部が好ましい。In the flame-retardant phenolic resin laminate of the present invention, the mixing ratio of the phenolic resin composition is 50 to 180 parts by weight of a novolak type phenolic resin, 100 parts by weight of an unmodified resol type phenolic resin, and Preferred are 40 to 130 parts by weight, 20 to 100 parts by weight of amino resin, and 10 to 200 parts by weight of inorganic filler.
【0013】ノボラック型フェノール樹脂が50重量部
未満では打ち抜き加工性の低下が生じ好ましくない。1
80重量部を越えても打ち抜き加工性の低下が生じ好ま
しくない。リン酸エステル類が40重量部未満では難燃
性に十分な効果が得られず、また130重量部を越える
と打ち抜き加工性の低下が生じ好ましくない。アミノ樹
脂が20重量部未満では難燃性向上に十分な効果が得ら
れず、また100重量部を越えると打ち抜き加工性の低
下が起こり好ましくない。無機フィラーが10重量部未
満では打ち抜き加工性の低下が生じ好ましくなく、20
0重量部を越えると加工性の問題が生じ好ましくない。If the novolak-type phenolic resin is less than 50 parts by weight, the punching processability is undesirably reduced. 1
If the amount exceeds 80 parts by weight, the punching workability is undesirably reduced. If the amount of the phosphoric acid ester is less than 40 parts by weight, a sufficient effect on the flame retardancy cannot be obtained. When the amount of the amino resin is less than 20 parts by weight, a sufficient effect for improving the flame retardancy cannot be obtained. If the amount of the inorganic filler is less than 10 parts by weight, the punching processability is deteriorated, which is not preferable.
Exceeding 0 parts by weight undesirably causes a problem of workability.
【0014】本発明に使用する紙基材としては、クラフ
ト紙、リンター紙などがあげられる。また、紙基材とし
て水溶性フェノール樹脂、メチロールメラミン樹脂等で
前もって処理したものも本発明に含まれる。The paper base material used in the present invention includes kraft paper, linter paper and the like. Further, a paper base material previously treated with a water-soluble phenol resin, a methylol melamine resin or the like is also included in the present invention.
【0015】[0015]
【実施例】以下、本発明を実施例に基づいて詳細に説明
するが、本発明はこれに限定されるものではない。The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
【0016】[未変性レゾール型フェノール樹脂(ワニ
スa)の合成]フェノール1000g、37%ホルムア
ルデヒド水溶液980g、トリエチルアミン20gから
なる混合物を60℃で2時間反応させ、次に減圧下で濃
縮し、これをメタノールで希釈して樹脂分50%のレゾ
ール型フェノール樹脂ワニスを得た。[Synthesis of unmodified resol type phenol resin (varnish a)] A mixture of 1000 g of phenol, 980 g of 37% aqueous formaldehyde solution and 20 g of triethylamine was reacted at 60 ° C. for 2 hours, and then concentrated under reduced pressure. After dilution with methanol, a resol-type phenol resin varnish having a resin content of 50% was obtained.
【0017】[ノボラック型フェノール樹脂(ワニス
b)の合成]フェノール1000gとホルマリン112
0gをシュウ酸の存在下、還流温度で1時間反応し、次
に塩酸を加えて更に35分間縮合させる。水を130g
添加して反応を停止させ30分間放置後水を蒸留した
後、更に樹脂温度115℃で脱水する。脱水終了後、樹
脂を冷却し、メタノールに溶解させて樹脂分50%のノ
ボラック型フェノール樹脂ワニスを得た。[Synthesis of novolak type phenol resin (varnish b)] 1000 g of phenol and formalin 112
0 g is reacted for 1 hour at reflux temperature in the presence of oxalic acid, then hydrochloric acid is added and condensation is carried out for a further 35 minutes. 130 g of water
After the addition, the reaction was stopped, the mixture was left for 30 minutes, and then water was distilled off. After the dehydration was completed, the resin was cooled and dissolved in methanol to obtain a novolak-type phenol resin varnish having a resin content of 50%.
【0018】《実施例1》ワニスa200重量部、ワニ
スb140重量部、クレジルジフェニルホスフェイト1
00重量部、メチロール化メラミン樹脂(樹脂分50
%)50重量部、及び水酸化アルミニウム80重量部を
配合したワニスを樹脂含浸率55%(紙基材に対する割
合)となるように紙基材を含浸させてプリプレグを得
た。このプリプレグ8枚とその表裏両面に接着剤つき銅
箔を重ね合わせ、加熱加圧成形して厚さ1.6mmの積
層板Aを得た。Example 1 200 parts by weight of varnish a, 140 parts by weight of varnish b, cresyl diphenyl phosphate 1
00 parts by weight, methylolated melamine resin (resin content 50
%) And a varnish containing 50 parts by weight of aluminum hydroxide and 80 parts by weight of aluminum hydroxide was impregnated with a paper base material so as to have a resin impregnation rate of 55% (ratio to the paper base material) to obtain a prepreg. Eight prepregs and a copper foil with an adhesive were superimposed on both front and back surfaces thereof, and heated and pressed to obtain a laminate A having a thickness of 1.6 mm.
【0019】《実施例2》ワニスa200重量部、ワニ
スb100重量部、クレジルジフェニルホスフェイト8
0重量部、メチロール化メラミン樹脂(樹脂分50%)
50重量部、及び水酸化アルミニウム180重量部を配
合したワニスを樹脂含浸率55%(紙基材に対する割
合)となるように紙基材を含浸させてプリプレグを得
た。このプリプレグ8枚とその表裏両面に接着剤つき銅
箔を重ね合わせ、加熱加圧成形して厚さ1.6mmの積
層板Bを得た。Example 2 200 parts by weight of varnish a, 100 parts by weight of varnish b, cresyl diphenyl phosphate 8
0 parts by weight, methylolated melamine resin (resin content 50%)
A varnish containing 50 parts by weight of aluminum hydroxide and 180 parts by weight of aluminum hydroxide was impregnated into a paper base so as to have a resin impregnation rate of 55% (ratio to the paper base) to obtain a prepreg. Eight prepregs and copper foil with an adhesive were superimposed on the front and back surfaces of the prepregs, and heated and pressed to obtain a laminate B having a thickness of 1.6 mm.
【0020】《比較例1》実施例2において、ワニスb
をワニスaに変更した以外は実施例2と同様の方法にて
厚さ1.6mmの積層板Cを得た。<< Comparative Example 1 >> In Example 2, varnish b
Was changed to varnish a, and a laminate C having a thickness of 1.6 mm was obtained in the same manner as in Example 2.
【0021】以上の方法により得られたそれぞれの積層
板の特性を測定し、表1に示す結果を得た。The characteristics of each laminate obtained by the above method were measured, and the results shown in Table 1 were obtained.
【0022】[0022]
【表1】 [Table 1]
【0023】(測定方法) 1.難燃性 UL規格による 2.半田耐熱性 JIS C 6481による 3.打抜き加工性 ASTM D617−44による 4.曲げ強度 JIC C 6481による(Measurement method) 1. Flame retardant according to UL standard 2. Solder heat resistance According to JIS C6481. 3. Punching workability According to ASTM D617-44. Flexural strength According to JIC C6481
【0024】[0024]
【発明の効果】本発明に従うと、ハロゲン系難燃剤を用
いることなく難燃性(UL規格、V−0)を達成し、か
つ半田耐熱性及び打ち抜き加工性の良好な紙基材フェノ
ール樹脂積層板を得ることができる。According to the present invention, a paper-based phenol resin laminate which achieves flame retardancy (UL standard, V-0) without using a halogen-based flame retardant, and has good solder heat resistance and punching workability. You can get a board.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C08K 3/22 C08K 3/22 5/521 5/521 C08L 61/06 C08L 61/06 61/20 61/20 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08K 3/22 C08K 3/22 5/521 5/521 C08L 61/06 C08L 61/06 61/20 61/20
Claims (2)
しめたプリプレグを積層成形して得られる難燃性フェノ
ール樹脂積層板において、フェノール樹脂組成物が未変
性レゾール型フェノール樹脂、ノボラック型フェノール
樹脂、リン酸エステル、アミノ樹脂及び無機フィラーか
らなることを特徴とする難燃性フェノール樹脂積層板。1. A flame-retardant phenolic resin laminate obtained by laminating a prepreg impregnated with a phenolic resin composition on a paper substrate, wherein the phenolic resin composition is an unmodified resol-type phenolic resin or a novolak-type phenolic resin. A flame-retardant phenolic resin laminate, comprising: a phosphoric acid ester, an amino resin and an inorganic filler.
しめたプリプレグを積層成形して得られる難燃性フェノ
ール樹脂積層板において、フェノール樹脂組成物が未変
性レゾール型フェノール樹脂100重量部に対して、ノ
ボラック型フェノール樹脂50〜180重量部、リン酸
エステル40〜130重量部、アミノ樹脂20〜100
重量部及び無機フィラー10〜200重量部からなるこ
とを特徴とする難燃性フェノール樹脂積層板。2. A flame-retardant phenolic resin laminate obtained by laminating a prepreg impregnated with a phenolic resin composition on a paper substrate, wherein the phenolic resin composition is based on 100 parts by weight of an unmodified resol type phenolic resin. Novolak type phenol resin 50 to 180 parts by weight, phosphate ester 40 to 130 parts by weight, amino resin 20 to 100 parts
A flame-retardant phenolic resin laminate comprising 10 parts by weight and 10 to 200 parts by weight of an inorganic filler.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9620697A JPH10286926A (en) | 1997-04-14 | 1997-04-14 | Flame retardant phenol resin laminate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9620697A JPH10286926A (en) | 1997-04-14 | 1997-04-14 | Flame retardant phenol resin laminate |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10286926A true JPH10286926A (en) | 1998-10-27 |
Family
ID=14158802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9620697A Pending JPH10286926A (en) | 1997-04-14 | 1997-04-14 | Flame retardant phenol resin laminate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH10286926A (en) |
-
1997
- 1997-04-14 JP JP9620697A patent/JPH10286926A/en active Pending
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