JPH0680747A - Production of phenol resin - Google Patents
Production of phenol resinInfo
- Publication number
- JPH0680747A JPH0680747A JP15505293A JP15505293A JPH0680747A JP H0680747 A JPH0680747 A JP H0680747A JP 15505293 A JP15505293 A JP 15505293A JP 15505293 A JP15505293 A JP 15505293A JP H0680747 A JPH0680747 A JP H0680747A
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- phenols
- formaldehyde
- phenol
- catalyst
- 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
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、レゾール型フェノール
樹脂の製造法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a resol type phenol resin.
【０００２】[0002]
【従来の技術】フェノール樹脂積層板等に用いられるレ
ゾール型フェノール樹脂は、通常フェノール類とホルム
アルデヒドを塩基性触媒下において反応させた樹脂であ
り、難燃性、耐熱性等様々な特性の付与が行なわれる。
中でも触媒によるものは多く、一般的にアンモニア、ア
ミンなどが用いられる。2. Description of the Related Art Resole type phenolic resins used for phenolic resin laminates are resins obtained by reacting phenols and formaldehyde under a basic catalyst, and have various properties such as flame retardancy and heat resistance. Done.
Of these, many are due to catalysts, and ammonia, amine, etc. are generally used.
【０００３】触媒量はフェノールに対してモル比で０．
１倍程度である。製造したレゾール型フェノール樹脂を
紙基材等に含浸し乾燥させプリプレグを作り、プリプレ
グを重ねて加熱加圧し積層板としている。The amount of catalyst is 0.1 in molar ratio with respect to phenol.
It is about 1 time. A paper base material or the like is impregnated with the produced resol-type phenol resin and dried to prepare a prepreg, and the prepreg is stacked and heated and pressed to form a laminated plate.
【０００４】[0004]
【発明が解決しようとする課題】しかし、従来の方法で
はフェノール類とホルムアルデヒドとの反応は、完全に
進行せず、樹脂ワニス中には未反応フェノール類、未反
応ホルムアルデヒドが残りこれらは積層板中にもそのま
ま存在する。However, in the conventional method, the reaction between phenols and formaldehyde does not proceed completely, and unreacted phenols and unreacted formaldehyde remain in the resin varnish, which remain in the laminate. Exists as it is.
【０００５】このような積層板を使用すると、プリント
配線板に加工しても低分子物ガスのために、ホルムアル
デヒド、フェノール類等の臭気を発生する。そしてその
臭気は、搭載部品が発熱したり、使用環境が高温である
場合はガスの発生が促進されより強い臭気となる。その
ために機器周囲の環境を悪化させ人体へ悪影響を及ぼ
す。When such a laminated board is used, even if it is processed into a printed wiring board, odors such as formaldehyde and phenols are generated due to the low molecular weight gas. Then, the odor becomes a stronger odor when the mounted parts generate heat or the use environment is high temperature and the generation of gas is promoted. Therefore, the environment around the device is deteriorated and the human body is adversely affected.
【０００６】本発明は、未反応フェノール類とホルムア
ルデヒドとを低減するフェノール樹脂の製造法を提供す
ることを目的とする。An object of the present invention is to provide a method for producing a phenol resin which reduces unreacted phenols and formaldehyde.
【０００７】[0007]
【課題を解決するための手段】本発明は、フェノール類
とホルムアルデヒドとを、フェノール類１モルに対して
アンモニアと３級アミンの混合触媒０．１２〜０．２０
モルの存在下に反応させることを特徴とするフェノール
樹脂の製造法である。According to the present invention, a mixed catalyst of ammonia and a tertiary amine of 0.12 to 0.20 is used in which phenols and formaldehyde are mixed with 1 mol of phenols.
It is a method for producing a phenol resin, which comprises reacting in the presence of a mole.
【０００８】未反応物を低減するために、レゾール化反
応触媒としてアンモニアと３級アミンを併用する。触媒
量はフェノール類に対してモル比で０．１２倍以上０．
２０倍以下用いる。０．１２倍未満だとフェノール類と
ホルムアルデヒドとの反応が充分に進まず、未反応物が
残存する。また、０．２０倍より多いと反応が進みす
ぎ、高分子量化しすぎるため積層板の基材等への含浸性
等が悪化する。ここで用いる３級アミンは、例えばトリ
エチルアミン、トリメチルアミン、トリ−ｎ−プロピル
アミン、ベンジルジメチルアミンである。触媒併用比
は、モル比でアンモニア：３級アミン＝２：８〜８：２
の範囲が望ましい。In order to reduce unreacted substances, ammonia and a tertiary amine are used together as a resolization reaction catalyst. The amount of catalyst is 0.12 times or more in molar ratio with respect to phenols.
Use 20 times or less. If it is less than 0.12 times, the reaction between phenols and formaldehyde does not proceed sufficiently and unreacted substances remain. On the other hand, if it is more than 0.20 times, the reaction proceeds excessively and the molecular weight becomes too high, so that the impregnating property of the laminated plate into the substrate and the like deteriorates. The tertiary amine used here is, for example, triethylamine, trimethylamine, tri-n-propylamine, or benzyldimethylamine. The catalyst combination ratio is ammonia: tertiary amine = 2: 8 to 8: 2 in molar ratio.
The range of is desirable.
【０００９】また同様の目的は、フェノール類とホルム
アルデヒドとを塩基性触媒の存在下において反応させて
得られるレゾール型フェノール樹脂の製造法において、
３級アミンを触媒としてフェノール類を反応させた後、
アンモニアを加えてさらに反応させることによっても達
成される。A similar object is to provide a method for producing a resol type phenol resin obtained by reacting phenols with formaldehyde in the presence of a basic catalyst,
After reacting phenols with a tertiary amine as a catalyst,
It is also achieved by adding ammonia and further reacting.
【００１０】[0010]
【作用】レゾール化反応機構は、アンモニアと３級アミ
ンでは異なる。アンモニアは、樹脂系に入って高分子化
を進め、３級アミンは、フェノール類のメチロール化を
進める傾向がある。高分子化のみ促進されると未反応フ
ェノール類が多く残り、メチロール化のみ促進されると
低分子量のメチロール化物が多くできることとなり、い
ずれも低分子物の割合が多くなる。そこで、アンモニア
と３級アミンを併用することにより、メチロール化を促
進して未反応物を低減し、かつ高分子化を促進すること
により、低分子量物を低減できる。[Action] The mechanism of resolization reaction differs between ammonia and tertiary amines. Ammonia tends to enter the resin system to promote polymerization, and tertiary amines tend to promote the methylation of phenols. If only the high molecular weight is promoted, a large amount of unreacted phenols remain, and if only the methylolation is promoted, a large amount of low molecular weight methylol compound can be produced, and the proportion of low molecular weight substances increases in both cases. Therefore, by using ammonia and a tertiary amine in combination, low molecular weight substances can be reduced by promoting methylolation and reducing unreacted substances, and by promoting high molecular weight.
【００１１】上記のように、高分子化のみ促進されると
未反応フェノール類が多く残り、メチロール化のみ促進
されると低分子量のメチロール化物が多くできるため、
まず３級アミンを触媒として反応させ、未反応フェノー
ルを少なくし、その後アンモニアを加え反応させること
によってメチロールフェノール類どうしを反応させて高
分子化させる。こうすることによって系全体の低分子物
は少なくなる。As described above, when only the high molecular weight is promoted, a large amount of unreacted phenols remain, and when only the methylolation is promoted, a low molecular weight methylol compound can be increased.
First, a tertiary amine is used as a catalyst for reaction to reduce unreacted phenol, and then ammonia is added for reaction to cause methylolphenols to react with each other and polymerize. By doing so, the amount of low molecular weight substances in the entire system is reduced.
【００１２】[0012]
実施例１ 桐脂で変性したメタパラクレゾールに、レゾール化触媒
としてアンモニアとトリエチルアミンを６：４になるよ
うに配合しフェノールに対してモル比で０．１６倍加え
て７０℃、４時間反応後濃縮を行ないワニスとした。こ
のワニスをクラフト紙に含浸後、乾燥してプリプレグと
した。このプリプレグ８枚と接着剤付き銅はくを組合せ
て加熱、加圧し厚さ１．６ｍｍの片面銅張積層板を得
た。Example 1 Tung fat-modified metaparacresol was mixed with ammonia and triethylamine as a resolization catalyst in a ratio of 6: 4, and the mixture was added at a molar ratio of 0.16 times that of phenol and reacted at 70 ° C. for 4 hours. A varnish was prepared by concentration. Kraft paper was impregnated with this varnish and dried to obtain a prepreg. Eight pieces of this prepreg and a copper foil with an adhesive were combined and heated and pressed to obtain a single-sided copper-clad laminate having a thickness of 1.6 mm.
【００１３】比較例１ 桐脂で変性したメタパラクレゾールに、レゾール化触媒
としてアンモニアをフェノールに対してモル比で０．１
６倍加えて、実施例と同様の方法で厚さ１．６ｍｍの片
面銅張積層板を得た。COMPARATIVE EXAMPLE 1 Metaparacresol modified with tung oil was mixed with 0.1 mol of ammonia as a resole-forming catalyst in a molar ratio to phenol.
Six times the amount was added, and a single-sided copper-clad laminate having a thickness of 1.6 mm was obtained in the same manner as in the example.
【００１４】比較例２ 桐脂で変性したメタパラクレゾールに、レゾール化触媒
としてアンモニアをフェノールに対してモル比で０．１
倍加えて、実施例と同様の方法で厚さ１．６ｍｍの片面
銅張積層板を得た。Comparative Example 2 Tung-fat-modified metapara-cresol was mixed with ammonia as a resolelation catalyst in a molar ratio of 0.1 to phenol.
Double addition and a single-sided copper-clad laminate having a thickness of 1.6 mm was obtained in the same manner as in the example.
【００１５】実施例２ 桐脂で変性したメタパラクレゾールに、トリエチルアミ
ンをメタパラクレゾールに対してモル比で０．０６倍加
えて７０℃２時間反応させた。次ぎにアンモニアをメタ
パラクレゾールに対してアンモニアのモル比が０．０９
倍になるように加えてさらに７０℃２時間反応させた
後、濃縮を行ないワニスとしたこのワニスをクラフト紙
に含浸後、乾燥してプリプレグとした。このプリプレグ
８枚と接着剤付き銅はくを組合せて加熱、加圧し厚さ
１．６ｍｍの片面銅張積層板を得た。Example 2 To a metaparacresol modified with tung oil, triethylamine was added in a molar ratio of 0.06 times that of metaparacresol, and the mixture was reacted at 70 ° C. for 2 hours. Next, the molar ratio of ammonia to metaparacresol is 0.09.
After doubling it, the mixture was further reacted at 70 ° C. for 2 hours, then concentrated to impregnate kraft paper with this varnish and dried to obtain a prepreg. Eight pieces of this prepreg and a copper foil with an adhesive were combined and heated and pressed to obtain a single-sided copper-clad laminate having a thickness of 1.6 mm.
【００１６】比較例３ 桐脂で変性したメタパラクレゾールに、トリエチルアミ
ンとアンモニアをメタパラクレゾールに対するモル比
で、０．０６：０．０９になるように加えて実施例２と
同様の方法で厚さ１．６ｍｍの片面銅張積層板を得た。Comparative Example 3 To the metaparacresol modified with tung oil, triethylamine and ammonia were added in a molar ratio of 0.06: 0.09 to metaparacresol, and the thickness was increased in the same manner as in Example 2. A single-sided copper-clad laminate having a thickness of 1.6 mm was obtained.
【００１７】比較例４ 桐脂で変性したメタパラクレゾールに、アンモニアをメ
タパラクレゾールに対して０．１５倍加えて実施例実施
例２と同様の方法で厚さ１．６ｍｍの片面銅張積層板を
得た。Comparative Example 4 To a metaparacresol modified with tung oil, ammonia was added 0.15 times as much as metaparacresol, and a 1.6 mm thick single-sided copper clad laminate was prepared in the same manner as in Example 2. I got a plate.
【００１８】実施例、比較例でそれぞれ得られた片面銅
張積層板からの発生ガス量の測定結果を表１、表２に示
す。なお発生ガス量は、試験片（５０×２０ｍｍ）を５
００ｍｌヘッドスペーサーボトル中で、１００℃６０分
加熱後、ガスクロマトグラフィー用シリンジでボトル内
の気体を捕集し、ガスクロマトグラフィーにより定量し
た。Tables 1 and 2 show the measurement results of the amount of gas generated from the single-sided copper-clad laminates obtained in Examples and Comparative Examples, respectively. In addition, the amount of generated gas is 5 for the test piece (50 x 20 mm).
After heating at 100 ° C. for 60 minutes in a 00 ml head spacer bottle, the gas in the bottle was collected by a gas chromatography syringe and quantified by gas chromatography.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【表２】 [Table 2]
【００２１】[0021]
【発明の効果】本発明によれば、レゾール化反応触媒を
通常より多く使用したり、加える順番を指定することに
より未反応物が低減し成形後の臭気発生を少なくでき
る。EFFECTS OF THE INVENTION According to the present invention, unreacted substances can be reduced and generation of odor after molding can be reduced by using more resolization reaction catalyst than usual or by designating the order of addition.
Claims (2)
ェノール類１モルに対してアンモニアと３級アミンの混
合触媒０．１２〜０．２０モルの存在下に反応させるこ
とを特徴とするフェノール樹脂の製造法。1. A method for producing a phenol resin, which comprises reacting phenols and formaldehyde in the presence of 0.12 to 0.20 mol of a mixed catalyst of ammonia and a tertiary amine with respect to 1 mol of phenols. Law.
性触媒の存在下において反応させて得られるレゾール型
フェノール樹脂の製造法において、３級アミンを触媒と
してフェノール類を反応させた後、アンモニアを加えて
さらに反応させることを特徴とするレゾール型フェノー
ル樹脂の製造法。2. A method for producing a resol-type phenolic resin obtained by reacting phenols with formaldehyde in the presence of a basic catalyst, wherein phenols are reacted with a tertiary amine as a catalyst, and then ammonia is added. A method for producing a resol-type phenol resin, which is characterized by further reacting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15505293A JPH0680747A (en) | 1992-07-15 | 1993-06-25 | Production of phenol resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18795492 | 1992-07-15 | ||
| JP4-187954 | 1992-07-15 | ||
| JP15505293A JPH0680747A (en) | 1992-07-15 | 1993-06-25 | Production of phenol resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0680747A true JPH0680747A (en) | 1994-03-22 |
Family
ID=26483159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15505293A Pending JPH0680747A (en) | 1992-07-15 | 1993-06-25 | Production of phenol resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680747A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517124A (en) * | 2018-11-08 | 2019-03-26 | 天津市盛世德新材料科技有限公司 | Impregnated paper environment-friendly resin glue and preparation method thereof |
-
1993
- 1993-06-25 JP JP15505293A patent/JPH0680747A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517124A (en) * | 2018-11-08 | 2019-03-26 | 天津市盛世德新材料科技有限公司 | Impregnated paper environment-friendly resin glue and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0680747A (en) | Production of phenol resin | |
| JPH07309921A (en) | Production of phenol resin | |
| JPH10251380A (en) | Thermoset resin composition | |
| JPH06271634A (en) | Production of modified phenol resin for laminated product | |
| JP4036050B2 (en) | Phenol resin for laminate plate formation, method for producing phenol resin for laminate plate formation, and phenol resin laminate plate | |
| JP4821064B2 (en) | Paper base phenolic resin copper clad laminate | |
| JPS5952905B2 (en) | Flame retardant phenolic resin composition | |
| JP3252730B2 (en) | Method for producing phenolic resin composition | |
| JPH11279514A (en) | Resin varnish, resin paper and laminate | |
| JPS63122725A (en) | Epoxy resin composition, prepreg and laminated board | |
| JPH09157414A (en) | Production of phenol resin | |
| JP2003221424A (en) | Phenolic resin copper-clad laminated board using drying oil-modified phenolic resin | |
| JPH0686511B2 (en) | Method for producing oil-modified phenolic resin | |
| JPS6245607A (en) | Production of improved phenolic resin | |
| JPH02311550A (en) | Resin composition for laminate | |
| JP2000280432A (en) | Phenol resin laminate | |
| JPH0912686A (en) | Phenolic resin composition, prepreg using the phenolic resin composition, and laminated board wherein that prepreg is used | |
| JPS59176328A (en) | Production of laminated sheet | |
| JPH07157576A (en) | Resin composition for laminated board and laminated board | |
| JPH10279716A (en) | Flame-resistant phenolic resin laminate | |
| JPH02283753A (en) | Laminate resin composition | |
| JPH03197550A (en) | Flame-retardant phenolic resin composition | |
| JPS58164613A (en) | Production of oil-modified phenolic resin for laminate | |
| JPH08208857A (en) | Production of laminate | |
| JPH02311515A (en) | Laminating resin composition |