JP2000280432A - Phenol resin laminate - Google Patents
Phenol resin laminateInfo
- Publication number
- JP2000280432A JP2000280432A JP11089879A JP8987999A JP2000280432A JP 2000280432 A JP2000280432 A JP 2000280432A JP 11089879 A JP11089879 A JP 11089879A JP 8987999 A JP8987999 A JP 8987999A JP 2000280432 A JP2000280432 A JP 2000280432A
- Authority
- JP
- Japan
- Prior art keywords
- phenol resin
- type phenol
- resol type
- starch
- drying oil
- 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
Landscapes
- 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、フェノール積層板
特有のホルムアルデヒド臭が少なく、打抜加工性の良好
な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 phenol resin laminate having a low formaldehyde odor peculiar to a phenol laminate and having 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。しかし、フェノール樹脂を合成す
る際に未反応のホルムアルデヒドが残存する。この為、
紙基材フェノール樹脂積層板においては、特有の臭気が
あり、特に米国等では臭気面からその使用が敬遠されて
いる。また、電子機器等を長時間使用した場合、機器の
温度が上昇し、よりホルムアルデヒドを放出しやすくな
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. However, unreacted formaldehyde remains when synthesizing the phenol resin. Because of this,
Paper-based phenolic resin laminates have a peculiar odor, and their use is avoided in the United States and the like in view of odor. In addition, when an electronic device or the like is used for a long time, the temperature of the device increases, and formaldehyde is easily released.
【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、未反
応のホルムアルデヒドが少なく、低臭気で打抜き加工性
が良好な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 reduce the amount of unreacted formaldehyde, to have a low odor, and to provide a paper-based phenol having good punching workability. It is to provide a 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
ル樹脂組成物が乾性油変性レゾール型フェノール樹脂及
び未変性レゾール型フェノール樹脂、デンプンからなる
ことを要旨とするものである。The present invention relates to a phenolic resin laminate obtained by laminating a prepreg impregnated with a phenolic resin composition on a paper base, wherein the phenolic resin composition is a dry oil-modified resol type phenol. The gist consists of a resin, an unmodified resol-type phenol resin, and starch.
【０００５】本発明のフェノール樹脂積層板において
は、未反応のホルムアルデヒドの発生を抑制するため、
使いやすさ及び入手の容易さの点で有利なデンプンを使
用する。デンプンは、ホルムアルデヒドを吸着する性質
を有しており、この為、ホルムアルデヒド臭の小さい積
層板が得られる。また、デンプンの可塑性効果の為、打
抜き加工性の向上した紙基材フェノール樹脂積層板を得
ることができた。[0005] In the phenolic resin laminate of the present invention, in order to suppress the generation of unreacted formaldehyde,
Use starch which is advantageous in terms of ease of use and availability. Starch has the property of adsorbing formaldehyde, so that a laminate with a small formaldehyde odor can be obtained. Also, due to the plasticity of starch, a paper-based phenolic resin laminate having improved punching workability was obtained.
【０００６】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。そして、
レゾール型フェノール樹脂として乾性油又は半乾性油
（以下、油という）で変性したフェノール樹脂を用いる
ことができる。このような油としては、桐油、カシュー
ナッツ油などである。In more detail, the resole type phenol resin is obtained by reacting phenols such as phenol and cresol with formaldehyde such as paraformaldehyde and aqueous solution of formalin, usually amines, ammonia and the like. The resol type phenol resin obtained by the basic catalyst is used. And
As the resol-type phenol resin, a phenol resin modified with a drying oil or a semi-dry oil (hereinafter referred to as oil) can be used. Such oils include tung oil, cashew nut oil and the like.
【０００７】また難燃性が必要な場合には、ハロゲン化
合物、リン酸エステル、アミノ樹脂等を添加する。[0007] When flame retardancy is required, a halogen compound, a phosphoric acid ester, an amino resin and the like are added.
【０００８】ハロゲン化合物は、テトラブロモビスフェ
ノールＡ（ＴＢＢＡ）、ＴＢＢＡ−エポキシオリゴマー
等が挙げられる。Examples of the halogen compound include tetrabromobisphenol A (TBBA) and TBBA-epoxy oligomer.
【０００９】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 includes triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcil diphenyl phosphate, triisopropyl phenyl phosphate and the like. 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】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 is, for example, a melamine resin or a guanamine resin, and is preferably a melamine resin 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 in which some or all of their methylol groups are etherified with a lower alcohol such as methanol or butanol. .
【００１１】本発明において難燃性フェノール樹脂積層
板を得るためには、フェノール樹脂組成物の配合割合
は、乾性油変性レゾール型フェノール樹脂１００重量部
に対して、未変性レゾール型フェノール樹脂２０〜１０
０重量部、ハロゲン化合物０〜１００重量部、リン酸エ
ステル５０〜２５０重量部、及びアミノ樹脂５０〜２５
０重量部が好ましい。In order to obtain a flame-retardant phenolic resin laminate in the present invention, the mixing ratio of the phenolic resin composition is from 20 parts by weight of the non-modified resolable phenolic resin to 100 parts by weight of the dry oil-modified resolable phenolic resin. 10
0 parts by weight, 0 to 100 parts by weight of a halogen compound, 50 to 250 parts by weight of a phosphoric ester, and 50 to 25 parts of an amino resin
0 parts by weight is preferred.
【００１２】配合するデンプンは、入手しやすさの面か
らコーンスターチが好ましい。また配合量としては、乾
性油変性レゾール型フェノール樹脂及び又は未変性レゾ
ール型フェノール樹脂の合計量、ハロゲン化合物、リン
酸エステル又はアミノ樹脂が配合される場合は、これら
との合計量に対して２〜２０重量％の割合で配合するこ
とが望ましい。２重量％未満では、ホルムアルデヒドの
吸着効果が十分発揮されない。また、２０重量％を越え
ると、耐水性・電気絶縁性が低下する。より好ましく
は、５〜１０重量％である。[0012] The starch to be blended is preferably corn starch from the viewpoint of availability. In addition, the compounding amount is 2 parts based on the total amount of the drying oil-modified resol type phenol resin and / or the unmodified resol type phenol resin, and when a halogen compound, a phosphate ester or an amino resin is mixed, the total amount thereof is 2 parts. It is desirable to mix at a ratio of ２０20% by weight. If it is less than 2% by weight, the effect of adsorbing formaldehyde is not sufficiently exhibited. On the other hand, if it exceeds 20% by weight, the water resistance and the electrical insulation are reduced. More preferably, it is 5 to 10% by weight.
【００１３】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.
【００１４】[0014]
【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。説明
中、「％」は「重量％」を示す。The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In the description, “%” indicates “% by weight”.
【００１５】［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 consisting 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.
【００１６】［油変性レゾール型フェノール樹脂（ワニ
スｂ）の合成］フェノール１６００ｇと桐油１０００ｇ
をパラトルエンスルホン酸の存在下、９５℃で２時間反
応させ、更にパラホルムアルデヒド６５０ｇ、ヘキサメ
チレンテトラミン３０ｇ、トルエン２０００ｇを加えて
９０℃で２時間反応後、減圧下で濃縮し、これをトルエ
ンとメタノールの混合溶媒で希釈して樹脂分５０％の油
変性フェノール樹脂ワニスを得た。[Synthesis of oil-modified resol type phenol resin (varnish b)] 1600 g of phenol and 1000 g of tung oil
Was reacted at 95 ° C. for 2 hours in the presence of p-toluenesulfonic acid, 650 g of paraformaldehyde, 30 g of hexamethylenetetramine and 2,000 g of toluene were added. After reacting at 90 ° C. for 2 hours, the mixture was concentrated under reduced pressure. It was diluted with a mixed solvent of methanol to obtain an oil-modified phenol resin varnish having a resin content of 50%.
【００１７】《実施例１》ワニスａ８０重量部、ワニス
ｂ１００重量部、ＴＢＢＡ−エポキシオリゴマー２０重
量部、クレジルジフェニルホスフェイト１００重量部、
メチロール化メラミン樹脂（樹脂分５０％）１００重量
部及びコーンスターチ２５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 80 parts by weight of varnish a, 100 parts by weight of varnish b, 20 parts by weight of TBBA-epoxy oligomer, 100 parts by weight of cresyl diphenyl phosphate,
A varnish prepared by mixing 100 parts by weight of a methylolated melamine resin (resin content: 50%) and 25 parts by weight of corn starch was impregnated into a paper base so as to have a resin impregnation rate of 55% (relative to the paper base) to obtain a prepreg. . This prepreg 8
A copper foil with an adhesive was superimposed on both sides of the sheet and the front and back surfaces thereof, and the resultant was heated and pressed to obtain a laminate A having a thickness of 1.6 mm.
【００１８】《実施例２》実施例１において、コーンス
ターチの配合量を１０重量部とした以外は実施例１と同
様の方法にて厚さ１．６ｍｍの積層板Ｂを得た。Example 2 A laminated board B having a thickness of 1.6 mm was obtained in the same manner as in Example 1 except that the amount of corn starch was changed to 10 parts by weight.
【００１９】《比較例１》実施例１において、コーンス
ターチを配合しない以外は実施例１と同様の方法にて厚
さ１．６ｍｍの積層板Ｃを得た。Comparative Example 1 A laminated board C having a thickness of 1.6 mm was obtained in the same manner as in Example 1 except that corn starch was not used.
【００２０】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 properties of each laminate obtained by the above method were measured, and the results shown in Table 1 were obtained.
【００２１】[0021]
【表１】 [Table 1]
【００２２】（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 ＪＩＳ Ｃ ６４８１による ５．ホルムアルデヒド放出量 ＪＡＳデシケータ法によ
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. 4. Bending strength According to JIS C6481 Formaldehyde emission Amount by JAS desiccator method
【００２３】[0023]
【発明の効果】本発明に従うと、ホルムアルデヒド放出
量が少なく低臭気で、かつ打抜き加工性の向上した紙基
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, it is possible to obtain a paper-based phenolic resin laminate having a small amount of formaldehyde emission, a low odor, and improved punching workability.
Claims (1)
しめたプリプレグを積層成形して得られるフェノール樹
脂積層板において、フェノール樹脂組成物にデンプンを
配合することを特徴とするフェノール樹脂積層板。1. A phenolic resin laminate obtained by laminating a prepreg impregnated with a phenolic resin composition on a paper substrate, wherein starch is blended into the phenolic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08987999A JP4141578B2 (en) | 1999-03-30 | 1999-03-30 | Phenolic resin laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08987999A JP4141578B2 (en) | 1999-03-30 | 1999-03-30 | Phenolic resin laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000280432A true JP2000280432A (en) | 2000-10-10 |
| JP4141578B2 JP4141578B2 (en) | 2008-08-27 |
Family
ID=13983067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08987999A Expired - Fee Related JP4141578B2 (en) | 1999-03-30 | 1999-03-30 | Phenolic resin laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4141578B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110183564A1 (en) * | 2008-10-03 | 2011-07-28 | Masao Uesaka | Metal-clad phenolic resin laminate |
-
1999
- 1999-03-30 JP JP08987999A patent/JP4141578B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110183564A1 (en) * | 2008-10-03 | 2011-07-28 | Masao Uesaka | Metal-clad phenolic resin laminate |
| US8999510B2 (en) * | 2008-10-03 | 2015-04-07 | Sumitomo Bakelite Company, Ltd. | Metal-clad phenolic resin laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4141578B2 (en) | 2008-08-27 |
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