JPH0742396B2 - Internally added release agent for phenolic resin and method of releasing phenolic resin using the same - Google Patents
Internally added release agent for phenolic resin and method of releasing phenolic resin using the sameInfo
- Publication number
- JPH0742396B2 JPH0742396B2 JP1137674A JP13767489A JPH0742396B2 JP H0742396 B2 JPH0742396 B2 JP H0742396B2 JP 1137674 A JP1137674 A JP 1137674A JP 13767489 A JP13767489 A JP 13767489A JP H0742396 B2 JPH0742396 B2 JP H0742396B2
- Authority
- JP
- Japan
- Prior art keywords
- alcohol
- phenolic resin
- amine
- release agent
- releasing
- 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 - Lifetime
Links
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
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Description
〔産業上の利用分野〕 本発明は、フェノール樹脂自体に添加して使用されるた
めの内部離型剤及びそれを使用したフェノール樹脂の離
型方法に関するものである。 〔従来の技術〕 フェノール樹脂用の内部離型剤としては、従来からステ
アリン酸等の高級飽和脂肪酸又は特公昭46−28648号公
報記載の中鎖又は長鎖アルキルリン酸エステル又はその
アミン塩が知られている。 しかしながら、このような従来の離型剤において、前者
の高級飽和脂肪酸は、成形体の耐熱性を低下させる。ま
た、後者の特公昭46−28648号の離型剤では、アルキル
基がC12以上の飽和アルキル基の場合、溶剤及びフェノ
ール樹脂との相溶性が悪く、離型性にむらが生じる他、
型を反復使用すると型離れが悪くなるので頻繁な洗浄が
必要となり、しかも離型性能が不十分であるという問題
点がある。[Field of Industrial Application] The present invention relates to an internal mold release agent to be used by adding it to a phenol resin itself and a method for releasing a phenol resin using the same. [Prior Art] As an internal mold release agent for phenolic resins, higher saturated fatty acids such as stearic acid or medium- or long-chain alkyl phosphates described in JP-B-46-28648 or amine salts thereof have been known. Has been. However, in such a conventional mold release agent, the former higher saturated fatty acid reduces the heat resistance of the molded body. Further, in the latter release agent of Japanese Patent Publication No. 46-28648, when the alkyl group is a saturated alkyl group having a carbon number of 12 or more, the compatibility with the solvent and the phenol resin is poor, and uneven release characteristics occur.
When the mold is used repeatedly, the mold release becomes worse, so frequent cleaning is required, and the mold release performance is insufficient.
よって本発明が解決しようとする課題は、成形物の耐熱
性、型の反復使用性及び離型性の諸点を満足するフェノ
ール樹脂用の内部離型剤を開発、提供することである。Therefore, the problem to be solved by the present invention is to develop and provide an internal mold release agent for a phenol resin that satisfies various points of heat resistance of a molded product, reusability of a mold, and mold releasability.
〔課題を解決するための手段〕 （１）概要 以上の課題を解決せんがため、本発明に係る要旨は、ア
ルコール類と無水リン酸との反応物をアミンで中和して
なるアルキルリン酸エステルのアミン塩を主とする剤で
あって、該エステルを構成するアルコール類が沃素価30
から150の範囲内の炭素数C6からC24のアルコールであ
り、かつ該アミンが第三級アミンであることを特徴とす
るフェノール樹脂用内部添加型離型剤並びにそれをフェ
ノール樹脂に添加することを特徴とするフェノール樹脂
の離型方法である。 以下、上記発明の構成に関連する主要事項につき項分け
して説明する。 （２）アルコール 本発明のリン酸エステルを構成するアルコールとして
は、例えば不飽和アルコールと飽和アルコールとの混合
物として天然に存在する天然アルコール、合成不飽和ア
ルコール、さらに前記合成不飽和アルコールと合成飽和
アルコールを混合したアルコール等であって、沃素価30
〜150の範囲の炭素数C6〜C24のものが例示される。 かかる炭素数６〜24の不飽和アルコールとしては、例え
ばドデセノール（C12）、フィセテリルアルコール
（C14）、ゾーマリルアルコール（C16）、ヘキサデセノ
ール（C16）、オレイルアルコール（C18）、リノレイル
アルコール（C18）、リノレニルアルコール（C18）、エ
イコセノール（C20）、エルシルアルコール（C22）等が
例示される。 また炭素数６〜24の飽和アルコールとしては、例えばｎ
−ヘキシルアルコール（C6）、２−エチルヘキシルアル
コール（C8）、ヘプチルアルコール（C7）、オクチルア
ルコール（C8）、デシルアルコール（C10）、ラウリル
アルコール（C12）、ミリスチルアルコール（C14）、セ
チルアルコール（C16）、ステアリルアルコール
（C18）、エイコサノール（C20）、ベヘニルアルコール
（C22）、テトラコサノール（C24）等が例示される。 なお、（ ）内は炭素数を示し、かつ不飽和アルコール
は平均炭素数を示す。 （３）アミン 本発明において、アルコール類と無水リン酸との反応物
を中和するためのアミンとしては、殊に第三級アミンが
望ましい。ここに“第三級アミン”としては、トリエチ
ルアミン、トリエタノールアミン、トリイソプロパノー
ルアミン、トリブチルアミン、ジエタノールラウリルア
ミン、ジエタノールステアリルアミン、モノエタノール
ブチルアミン等が例示される。 （４）合成 本発明のアルキルリン酸エステルのアミン塩は、常法に
より合成される。すなわち、所望の該アルコール（３モ
ル）中に無水リン酸（１モル）を徐々に添加し、そのま
ま又は溶剤で希釈した後、アミンを徐々に添加してpH6
からpH8に中和する。 使用したアルコール類の炭素数がC6未満の場合は、目的
の離型性能が十分に発揮されない。逆に炭素数がC24を
越える場合又は沃素価30未満の場合は、樹脂及び溶剤と
の相溶性が悪くなり、離型性能にバラツキが生じる。一
方、沃素価が150を越える場合は、成形体の耐熱性が低
下する。特に、炭素数C14からC22及び沃素価が60から12
0の範囲のものは、フェノール樹脂及び溶剤との相溶性
及び成形品の耐熱性の両面で好適である。 更に、アミンが第一級又は第二級アミンである場合は、
成形品の耐熱性を低下させるので目的上好ましくない。
なお、第三級アミンの中でも、アルカノールアミンが離
型性の点で優れている。 （５）使用量 本発明離型剤は、フェノール樹脂に対し固形分として0.
1重量％から５重量％の添加で十分な効果を発揮する。
0.1％未満の場合、目的とする離型性能が十分には発揮
されない。他方、５％を越えて添加した場合は、フェノ
ール積層板の場合、成形基板の耐熱性、印刷特性等に悪
影響を与える。好適な配合量は、0.1〜２％の範囲であ
る。 〔作用〕 本発明の対象物である。沃素価30から150の範囲内の、
炭素数C6からC24のアルコールと無水リン酸との反応物
を、第三級アミンで中和してなるアルキルリン酸エステ
ルのアミン塩を主とする剤は、フェノール樹脂用内部添
加離型剤として、成形物の耐熱性、型の反復使用性及び
離型性の諸点を満足するので、本樹脂の圧縮成形、トラ
ンスファー成形等の目的に使用して、作業性の向上に多
大の効果を奏する。 〔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
につき説明するが、例示は、説明用のもので、発明思想
の限定を意図したものではない。 実施例１ フェノールワニス（スミライトレジン：住友ベークライ
ト（株）製品）100重量部に、オレイルアルコール（沃
素価90）リン酸エステルのエタノールアミン塩0.5重量
部を添加混合した後、クラフト紙（目付量135g/m2）に
含浸させ、樹脂量50％のプリプレグを得た。このプリプ
レグを８枚重ねにし、両面に鏡板を当てて、温度160
℃、圧力100kg/cm2で60分間加熱加圧し、厚さ1.6m/mの
積層板を成型した。 離型剤混合時のワニスとの相溶性、成型時の鏡板と積層
板との離型性、成型後の外観、半田耐熱性、煮沸後絶縁
抵抗を評価した。結果を添加第１表に示す。 実施例２〜５ アルコール及びアミンについて第１表のごとく添加量を
変え実施例１と同様にして積層板を成型し評価した。結
果を第１表に示す。 比較例１ 実施例１のリン酸エステルアミン塩に替え、ステアリン
酸を樹脂に対し3.0重量部添加し、同様に成型、評価し
た。結果を第１表に示す。 比較例２〜７ 該アルコールについて実施例１と同様にして積層板を成
型、評価した。結果を第１表に示す。 以上実施例１〜５と比較例１〜７との対比から明らかな
ように、本発明に係る実施例のものは、ワニスとの相溶
性、離型力（離型性）、成形物の外観、半田耐熱性及び
煮沸後の絶縁性のいずれにおいても優れた成績を示して
いる。 これに反し、アルコールの沃素価が低い比較例２、アル
コールの沃素価が高すぎる比較例３、アルコールの平均
炭素数の少ない比較例４、アルコールの平均炭素数の大
きすぎる比較例５、アミンが第一級アミンである比較例
６、及びアミンで中和されていない比較例７のものは、
上記いずれかの点で不満足な結果を示していることが知
られる。[Means for Solving the Problems] (1) Outline In order to solve the above problems, the gist of the present invention is to provide an alkylphosphoric acid obtained by neutralizing a reaction product of an alcohol and phosphoric anhydride with an amine. An agent mainly composed of an amine salt of an ester, in which alcohols constituting the ester have an iodine value of 30
To an alcohol having a carbon number of C 6 to C 24 in the range from 1 to 150, and the amine is a tertiary amine; It is a method for releasing a phenol resin from the above. Hereinafter, the main items related to the configuration of the invention will be described by dividing them into items. (2) Alcohol As the alcohol constituting the phosphoric acid ester of the present invention, for example, natural alcohol naturally present as a mixture of unsaturated alcohol and saturated alcohol, synthetic unsaturated alcohol, and further synthetic unsaturated alcohol and synthetic saturated alcohol. Alcohol, etc., with an iodine value of 30
Examples are those having carbon numbers C 6 to C 24 in the range of to 150. Examples of the unsaturated alcohol having 6 to 24 carbon atoms include dodecenol (C 12 ), fiseteryl alcohol (C 14 ), zomalyl alcohol (C 16 ), hexadecenol (C 16 ), oleyl alcohol (C 18 ), linoleyl alcohol (C 18), linolenyl alcohol (C 18), Eikosenoru (C 20), erucyl alcohol (C 22), and the like. Examples of the saturated alcohol having 6 to 24 carbon atoms include n
- hexyl alcohol (C 6), 2- ethylhexyl alcohol (C 8), heptyl alcohol (C 7), octyl alcohol (C 8), decyl alcohol (C 10), lauryl alcohol (C 12), myristyl alcohol (C 14 ), Cetyl alcohol (C 16 ), stearyl alcohol (C 18 ), eicosanol (C 20 ), behenyl alcohol (C 22 ), tetracosanol (C 24 ), and the like. In addition, () shows carbon number, and unsaturated alcohol shows average carbon number. (3) Amine In the present invention, as the amine for neutralizing the reaction product of the alcohol and phosphoric anhydride, a tertiary amine is particularly desirable. Examples of the "tertiary amine" include triethylamine, triethanolamine, triisopropanolamine, tributylamine, diethanollaurylamine, diethanolstearylamine, monoethanolbutylamine and the like. (4) Synthesis The amine salt of the alkyl phosphate of the present invention is synthesized by a conventional method. That is, phosphoric anhydride (1 mol) was gradually added to the desired alcohol (3 mol), and the pH was adjusted to 6 by adding amine slowly after diluting as it is or with a solvent.
Neutralize to pH8. If the alcohol used has a carbon number of less than C 6 , the desired release performance will not be sufficiently exhibited. On the other hand, when the carbon number exceeds C 24 or the iodine value is less than 30, the compatibility with the resin and the solvent is deteriorated and the releasing performance varies. On the other hand, when the iodine value exceeds 150, the heat resistance of the molded product decreases. In particular, carbon numbers C 14 to C 22 and iodine values 60 to 12
Those in the range of 0 are suitable in terms of both compatibility with the phenol resin and the solvent and heat resistance of the molded product. Further, when the amine is a primary or secondary amine,
It is not preferable for the purpose because it lowers the heat resistance of the molded product.
Among the tertiary amines, alkanolamines are excellent in mold releasability. (5) Amount of use The release agent of the present invention has a solid content of 0.
Addition of 1 to 5% by weight exerts a sufficient effect.
If it is less than 0.1%, the target release performance is not sufficiently exhibited. On the other hand, if it is added in excess of 5%, in the case of a phenol laminate, the heat resistance and printing characteristics of the molded substrate are adversely affected. A suitable blending amount is in the range of 0.1 to 2%. [Operation] The object of the present invention. Iodine value in the range of 30 to 150,
An agent mainly composed of an amine salt of an alkyl phosphoric acid ester obtained by neutralizing a reaction product of an alcohol having C 6 to C 24 with phosphoric anhydride with a tertiary amine is an internally added release agent for phenol resin. As an agent, it satisfies various points of heat resistance of molded products, reusability of molds, and mold releasability, so it is used for the purpose of compression molding, transfer molding, etc. of this resin, and greatly improves workability. Play. [Examples] Hereinafter, embodiments and effects of the invention will be described with reference to Examples and Comparative Examples, but the examples are for the purpose of explanation, and are not intended to limit the idea of the invention. Example 1 100 parts by weight of phenol varnish (Sumilite resin: Sumitomo Bakelite Co., Ltd. product) was added and mixed with 0.5 part by weight of ethanolamine salt of oleyl alcohol (iodine value 90) phosphate ester, and then kraft paper (weight per unit area) It was impregnated with 135 g / m 2 ) to obtain a prepreg with a resin amount of 50%. 8 sheets of this prepreg are piled up, and the end plates are applied to both sides, and the temperature is set to 160
The mixture was heated and pressed at 100 ° C. and a pressure of 100 kg / cm 2 for 60 minutes to form a laminated board having a thickness of 1.6 m / m. The compatibility with the varnish at the time of mixing the release agent, the releasability between the end plate and the laminated plate at the time of molding, the appearance after molding, the solder heat resistance, and the insulation resistance after boiling were evaluated. The results are shown in Table 1 of addition. Examples 2 to 5 Laminates were molded and evaluated in the same manner as in Example 1 except that the addition amounts of alcohol and amine were changed as shown in Table 1. The results are shown in Table 1. Comparative Example 1 In place of the phosphate ester amine salt of Example 1, 3.0 parts by weight of stearic acid was added to the resin, and molding and evaluation were carried out in the same manner. The results are shown in Table 1. Comparative Examples 2 to 7 Laminates were molded and evaluated in the same manner as in Example 1 with respect to the alcohol. The results are shown in Table 1. As is clear from the comparison between Examples 1 to 5 and Comparative Examples 1 to 7, the examples according to the present invention have compatibility with varnish, releasing force (releasing property), and appearance of molded articles. In addition, excellent results are shown in both solder heat resistance and insulation after boiling. On the contrary, Comparative Example 2 in which the iodine value of alcohol is low, Comparative Example 3 in which the iodine value of alcohol is too high, Comparative Example 4 in which the average carbon number of alcohol is small, Comparative Example 5 in which the average carbon number of alcohol is too large, and amine is Comparative Example 6, which is a primary amine, and Comparative Example 7, which is not neutralized with an amine,
It is known that unsatisfactory results are shown in any of the above points.
本発明のフェノール樹脂用内部添加離型剤は、以上説明
し、かつ実証した通り、成形物の耐熱性、型の反復使用
性及び離型性の諸点を満足するので、フェノール樹脂成
形産業に対し、大きな便益を与える。 As described above and demonstrated, the internally added release agent for phenolic resin of the present invention satisfies the heat resistance of the molded product, the reusability of the mold, and the releasability of the molded product. , Give great benefits.
Claims (2)
ミンで中和してなるアルキルリン酸エステルのアミン塩
を主とする剤であって、該エステルを構成するアルコー
ル類が沃素価30から150の範囲内の炭素数C6からC24のア
ルコールであり、かつ該アミンが第三級アミンであるこ
とを特徴とするフェノール樹脂用内部添加離型剤。1. An agent mainly comprising an amine salt of an alkyl phosphoric acid ester obtained by neutralizing a reaction product of an alcohol and phosphoric anhydride with an amine, wherein the alcohol constituting the ester has an iodine value of 30. An internally added release agent for a phenol resin, which is an alcohol having a carbon number of C 6 to C 24 in the range of 1 to 150, and the amine is a tertiary amine.
離型剤を添加することを特徴とするフェノール樹脂の離
型方法。2. A method for releasing a phenol resin, comprising adding the internally added release agent according to claim 1 to the phenol resin.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1137674A JPH0742396B2 (en) | 1989-05-31 | 1989-05-31 | Internally added release agent for phenolic resin and method of releasing phenolic resin using the same |
| KR1019900008012A KR960003426B1 (en) | 1989-05-31 | 1990-05-31 | Mold release agent for phenolic resin and the method of releasing thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1137674A JPH0742396B2 (en) | 1989-05-31 | 1989-05-31 | Internally added release agent for phenolic resin and method of releasing phenolic resin using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH032256A JPH032256A (en) | 1991-01-08 |
| JPH0742396B2 true JPH0742396B2 (en) | 1995-05-10 |
Family
ID=15204170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1137674A Expired - Lifetime JPH0742396B2 (en) | 1989-05-31 | 1989-05-31 | Internally added release agent for phenolic resin and method of releasing phenolic resin using the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0742396B2 (en) |
| KR (1) | KR960003426B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5490376B2 (en) * | 2007-05-31 | 2014-05-14 | 三洋化成工業株式会社 | Active energy ray-curable resin composition |
-
1989
- 1989-05-31 JP JP1137674A patent/JPH0742396B2/en not_active Expired - Lifetime
-
1990
- 1990-05-31 KR KR1019900008012A patent/KR960003426B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR960003426B1 (en) | 1996-03-13 |
| KR900017745A (en) | 1990-12-19 |
| JPH032256A (en) | 1991-01-08 |
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