JPS6096643A - Improvement of storage stability of phenolic resin - Google Patents
Improvement of storage stability of phenolic resinInfo
- Publication number
- JPS6096643A JPS6096643A JP20650883A JP20650883A JPS6096643A JP S6096643 A JPS6096643 A JP S6096643A JP 20650883 A JP20650883 A JP 20650883A JP 20650883 A JP20650883 A JP 20650883A JP S6096643 A JPS6096643 A JP S6096643A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- solvent
- tung oil
- phenolic resin
- viscosity
- 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
- 238000003860 storage Methods 0.000 title claims abstract description 11
- 239000005011 phenolic resin Substances 0.000 title claims description 8
- 229920001568 phenolic resin Polymers 0.000 title claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 235000010678 Paulownia tomentosa Nutrition 0.000 claims abstract description 7
- 240000002834 Paulownia tomentosa Species 0.000 claims abstract description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 210000003323 beak Anatomy 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002383 tung oil Substances 0.000 abstract description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001879 gelation Methods 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000002966 varnish Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- -1 Glycerin ester Chemical class 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CUXYLFPMQMFGPL-FWSDQLJQSA-N alpha-Eleostearic acid Natural products CCCCC=CC=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-FWSDQLJQSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- IXLCRBHDOFCYRY-UHFFFAOYSA-N dioxido(dioxo)chromium;mercury(2+) Chemical compound [Hg+2].[O-][Cr]([O-])(=O)=O IXLCRBHDOFCYRY-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
フェノール樹脂積層板の製造技術に関し、％に使用樹脂
の貯ｇ技術に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] This invention relates to a technology for manufacturing phenolic resin laminates, and relates to a technology for storing grams of resin used in %.
印刷回路用フェノール積層板において打抜性を付与する
為、桐油を反応性可塑剤として用いることはよく行わｎ
る。桐油とはアブラギリの種子から得られる油であり、
α−エレオステアリン酸のグリセリンエステルを通常８
０チ程度含有する不飽和脂肪酸エステルである。フェノ
ールか桐油の共役２１結合して付加することにより、反
応性可塑剤として作用する。したがって比較的電気特性
を低下させることなく、打抜性が改良される可塑剤とし
てよく使用される。Tung oil is often used as a reactive plasticizer to impart punchability in phenolic laminates for printed circuits.
Ru. Tung oil is oil obtained from the seeds of Aburagiri.
Glycerin ester of α-eleostearic acid is usually 8
It is an unsaturated fatty acid ester containing about 0%. The addition of conjugated 21 bonds of phenol or tung oil acts as a reactive plasticizer. Therefore, it is often used as a plasticizer that improves punchability without comparably reducing electrical properties.
一般的にハ４［油とフェノール全ｐ−１ルエンスルホ／
酸等の酸等の酸性触媒下で反応させ、中和後ホルマリン
及び塩基性触媒を添加し、レゾール化反応を行ない桐油
変性フェノール樹脂を得る。Generally Ha 4 [oil and phenol total p-1 luene sulfo/
The reaction is carried out under an acidic catalyst such as an acid, and after neutralization formalin and a basic catalyst are added to carry out a resolization reaction to obtain a tung oil modified phenolic resin.
しかる後メタノールに希釈し含浸用フェスとして貯蔵す
る。Thereafter, it is diluted with methanol and stored as an impregnating face.
ところがフェスの保存性が不安定である。つまり、時間
の経過と共に粘度が低下１−１かつゲル化時間が長くな
る。１週間程度で粘度は半分になりゲル化時間は２倍と
なる。However, the preservation of festivals is unstable. That is, as time passes, the viscosity decreases 1-1 and the gelation time increases. In about a week, the viscosity will be halved and the gelation time will be doubled.
フェス作成後直ちに含浸乾燥成形を行なえば問題はない
が、実際上は生産計画上、１週間程度の保存は必要であ
る。その為、粘度調整用に溶媒量をｖ４整したり、レシ
ンペーパーの流れ調整（成形性）の為、乾燥時間を調整
する必要があり、工程管理上非常に手間がかかり、保存
安定性の改善が強く望まれていた。There is no problem if impregnating and drying molding is performed immediately after creating the face, but in practice, it is necessary to store it for about a week due to production planning. Therefore, it is necessary to adjust the amount of solvent to v4 to adjust the viscosity, and to adjust the drying time to adjust the flow (formability) of the resin paper, which is extremely time-consuming in terms of process control, and improves storage stability. was strongly desired.
保存安定性（粘度、ゲル化時＋Ｎｊ等）の良好な桐油変
性フェノール樹脂ワニスを提供することを目的とする。The purpose of the present invention is to provide a tung oil-modified phenolic resin varnish with good storage stability (viscosity, gelling +Nj, etc.).
本発明者らは桐油変性フェノール樹脂ワニスの保存安定
性金種々検討した結果、フェノール樹脂を希釈する溶媒
がアルコール系溶媒と非アルコール系溶媒の混合溶媒か
ら成り、アルコール系溶媒が桐油変性フェノール樹脂に
対して２〜１０％ｖｔ％とすることＶこより保存安定性
の艮好なワニスを得ることかできた。The present inventors investigated various storage stability properties of tung oil-modified phenolic resin varnish, and found that the solvent for diluting the phenolic resin was a mixed solvent of an alcoholic solvent and a non-alcoholic solvent, and the alcoholic solvent was mixed with the tung oil-modified phenolic resin. On the other hand, by setting the Vt% to 2 to 10% Vt%, it was possible to obtain a varnish with excellent storage stability.
ここでアルコール系溶媒とはメタノール、エタノール、
イソプロピルアルコール ｎ−フｏヒルアルコールは希
釈効果あるいは揮発性の点から好ましくない。非アルコ
ール系溶媒はアルコール系溶媒訃よびフェノール樹脂と
相容性かあるもの、例えばアセトン、メチルエチルケト
ン、ベンゼン、トルエン、キシレン、テトラヒドロフラ
ン、ジオキサン、クロロホルム、四塩化炭素等がある。Here, alcoholic solvents include methanol, ethanol,
Isopropyl alcohol n-propyl alcohol is not preferred from the viewpoint of dilution effect or volatility. Non-alcoholic solvents include those that are compatible with alcoholic solvents and phenolic resins, such as acetone, methyl ethyl ketone, benzene, toluene, xylene, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, and the like.
通常セルロース糸基材に含浸させる為にはワニスの粘度
はｌ０ＬＩ〜５００センチボイズが好ましい。粘度が上
記範囲内に入るように混合溶媒１ｔを調整する。Generally, in order to impregnate a cellulose yarn base material, the viscosity of the varnish is preferably 10LI to 500 centivoise. One ton of mixed solvent is adjusted so that the viscosity falls within the above range.
ここで、非アルコール系溶媒のみで希釈すると逆に時間
の経過と共に粘度が上昇し、ゲル化時間は短くなる。保
存中ＶＣレゾール化反応が進行する為と考えられるうア
ルコール系溶媒を桐油変性フェノール樹脂の２〜ｌＱｗ
ｔ％とすることによって初めて経時変化のない安定なワ
ニスが得られる、アルコール系溶媒単独でワニス粘度ｅ
ｌＯＵ〜５００センチボイズにした場合（通常溶媒量は
１ＯＰＨＲ以上必要である）時間の経過と共に粘度が低
下し、ゲル化時間が短くなる理由は明らかでないが分子
量分布の測定等から、アルコールにより桐油のエステル
基が分解される九めと考えられる。Here, if diluted with only a non-alcoholic solvent, the viscosity will increase over time and the gelation time will become shorter. This is thought to be due to the progress of the VC resolization reaction during storage.
t%, a stable varnish that does not change over time can be obtained for the first time.With alcohol solvent alone, the varnish viscosity e
The reason why the viscosity decreases over time and the gelation time shortens when the viscosity is set to 1OU to 500 centiboise (normally, the amount of solvent is required to be 1OPHR or more) is not clear, but from measurements of molecular weight distribution, etc., the ester of tung oil is reduced by alcohol. This is considered to be the ninth point in which the group is decomposed.
アルコール系容媒が２〜１ ｇ ）））ＩＲで保存安定
性が良好となるのはレゾール化反応の進行とエステル結
合の分解のバランスがとれているからであると推定され
る。It is presumed that the reason why the storage stability of the alcoholic medium is 2 to 1 g))) IR is good is that the progress of the resolization reaction and the decomposition of the ester bond are well balanced.
実施例１
桐油４２部（爪址部を意味する、以下同じ）、フェノー
ル５８．１７Ｂ、ハラトルエンスルホン酸０．３部、水
３部をフラスコに仕込み、８０℃で３時間反応させた。Example 1 A flask was charged with 42 parts of tung oil (meaning the nail part, the same applies hereinafter), phenol 58.17B, halatoluenesulfonic acid 0.3 part, and 3 parts of water, and reacted at 80°C for 3 hours.
仄いで３７チ閾度のホルマリン４３部、トリエチルアミ
ン５部を添加し、８０℃で３時間反１１１、さ…た１菱
、１５０ｍａ）層減圧丁脱水を行ない桐油変性フェノー
ル圏脂に得た。43 parts of 37-threshold formalin and 5 parts of triethylamine were added, and dehydration was carried out under reduced pressure at 80° C. for 3 hours to obtain a tung oil-modified phenol resin.
得られ、を洞油変１生フェノール樹脂１１）０部を表１
に示す溶Ｉ＆に希釈し、粘度、ゲル化時間、分子盪分４
Ｈの経時変化を測ｚｕした。粘度はＢ型粘度計を用い３
０ ’Ｃで抑ｊ定した。ゲル化時間は一１興−＃にワニ
スを入れ、１３５℃の恒諷遭中ν０受潰し、ワニスの粘
度が２００ボイズに達するまでの時間とした。分子量分
布はＧＰＣＫより測定しｌ賓東殖モ均分子量と数平均分
子瀘の比（Ｍ ｗ ／ Ｍ ｎ ）で表わした。Table 1: Obtained, Dong Yuhen 1 raw phenolic resin 11) 0 parts
Dilute the solution I & viscosity, gel time, molecular weight as shown in 4
Changes in H over time were measured. The viscosity was measured using a B-type viscometer.
It was suppressed at 0'C. The gelation time was defined as the time required for the varnish to reach 200 voids during constant heating at 135° C. and for the viscosity of the varnish to reach 200 voids. The molecular weight distribution was measured by GPCK and expressed as the ratio of the average molecular weight to the number average molecular weight (Mw/Mn).
この発明は桐油変性のフェノール樹脂を貯蔵する場合に
おいて、アルコール系溶媒と非アルコール系尋媒の混合
温媒を使用し希釈することとし。In the case of storing phenolic resin modified with tung oil, this invention uses a mixed heating medium of an alcoholic solvent and a non-alcoholic solvent to dilute it.
かつアルコール系溶媒が前記樹脂の２〜ｌＯ重量係使用
するので貯蔵安定性が改良された。Moreover, since the alcoholic solvent is used in an amount of 2 to 10% by weight of the resin, storage stability is improved.
特許出願人 松下電工株式会社 代理人弁理士 竹 元 敏 丸 （ほか２名）patent applicant Matsushita Electric Works Co., Ltd. Representative Patent Attorney Toshimaru Takemoto (2 others)
Claims (1)
いて、アルコール系溶媒と非アルコール系溶媒の混合溶
媒を、使用して希釈することとし、かつアルコール系溶
媒が前記樹脂の２〜１０重ｔチ使用されていることを％
徴とするフェノール系樹脂の貯蔵安定性の改良法。(1) When storing tung oil-modified phenol beak fat, a mixed solvent of an alcoholic solvent and a non-alcoholic solvent should be used for dilution, and the alcoholic solvent should contain 2 to 10% of the resin. % that is used
A method for improving the storage stability of phenolic resins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20650883A JPS6096643A (en) | 1983-10-31 | 1983-10-31 | Improvement of storage stability of phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20650883A JPS6096643A (en) | 1983-10-31 | 1983-10-31 | Improvement of storage stability of phenolic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6096643A true JPS6096643A (en) | 1985-05-30 |
Family
ID=16524526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20650883A Pending JPS6096643A (en) | 1983-10-31 | 1983-10-31 | Improvement of storage stability of phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6096643A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62151471A (en) * | 1985-12-26 | 1987-07-06 | Sumitomo Bakelite Co Ltd | Phenolic resin varnish for lamination |
| JPS62151472A (en) * | 1985-12-26 | 1987-07-06 | Sumitomo Bakelite Co Ltd | Phenolic resin varnish for lamination |
-
1983
- 1983-10-31 JP JP20650883A patent/JPS6096643A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62151471A (en) * | 1985-12-26 | 1987-07-06 | Sumitomo Bakelite Co Ltd | Phenolic resin varnish for lamination |
| JPS62151472A (en) * | 1985-12-26 | 1987-07-06 | Sumitomo Bakelite Co Ltd | Phenolic resin varnish for lamination |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3001967A (en) | Method of copolymerizing polyester, ethylenically unsaturated monomer and metal salt of acid half ester of alpha, beta-ethylenically unsaturated dicarboxylic acid and a monohydric alcohol and copolymers thereof | |
| ES8202801A1 (en) | Process for producing water-dilutable epoxy resin esters containing oxazolidine groups, coating compositions produced therefrom, and their use as cathodic-deposition lacquers. | |
| US3001961A (en) | Water dispersible oil modified alkyd resins containing oxyalkylated glycols and method of manufacture of the same | |
| JPS6096643A (en) | Improvement of storage stability of phenolic resin | |
| Matsuda et al. | Preparation and crosslinking of oligoesterified woods based on maleic anhydride and allyl glycidyl ether | |
| US3223681A (en) | Polymer compositions from an alkylenimine derivative, a dicarboxylic acid anhydride and water | |
| DE1067220B (en) | ||
| US2323334A (en) | Enamel composition | |
| US3483152A (en) | Paint vehicles prepared by treating adducts of fatty acid esters with peroxide and/or polybutadiene | |
| AT217040B (en) | Process for the preparation of new, unsaturated ethers of aminotriazine-formaldehyde condensation products | |
| US4043954A (en) | Compositions and laminates made therefrom | |
| GB942472A (en) | Polyester-amide resins and conductors insulated therewith | |
| US2151975A (en) | Varnish | |
| US1898709A (en) | Aldehyde amino resinous compounds and processes | |
| US2323706A (en) | Interpolymers of an unsaturated alkyd resin and a 3-hydroxy alkene-1 polyester of a polycarboxylic acid | |
| DE2402039C2 (en) | ||
| US2582704A (en) | Reaction products of a polyethylene melamine and an alkyd resin | |
| US2911316A (en) | Glyceride oil gel paints | |
| JPS63453B2 (en) | ||
| US2382213A (en) | Copolymerization of drying oils and vinyl compounds | |
| RU2084483C1 (en) | Composition for production of pigment paste | |
| SU1599412A1 (en) | Method of producing varnish for impregnating mica-containing materials | |
| US4323412A (en) | Process of impregnating paper laminate plies with oil modified phenolic resole varnish | |
| JPS5575421A (en) | Epoxy resin composition | |
| JPH02222456A (en) | Dimension stabilizer and resin composition using same |