JPS62181305A - Production of heat-resistant resin - Google Patents
Production of heat-resistant resinInfo
- Publication number
- JPS62181305A JPS62181305A JP2340286A JP2340286A JPS62181305A JP S62181305 A JPS62181305 A JP S62181305A JP 2340286 A JP2340286 A JP 2340286A JP 2340286 A JP2340286 A JP 2340286A JP S62181305 A JPS62181305 A JP S62181305A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyvinyl acetal
- acetal resin
- heat
- 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
- 229920006015 heat resistant resin Polymers 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 39
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011354 acetal resin Substances 0.000 claims abstract description 29
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 organosilane compound Chemical class 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 29
- 239000011347 resin Substances 0.000 abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012948 isocyanate Substances 0.000 abstract description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000915 polyvinyl chloride Polymers 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 31
- 239000000853 adhesive Substances 0.000 description 30
- 150000001241 acetals Chemical class 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- 241000270298 Boidae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000001672 ovary Anatomy 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
３、 Ｈの量 なｆＥ＋
（産業上の利用分野）
本発明は、耐熱性および接着強度、特に、高温時におけ
る接着強度に優れた耐熱性樹脂の製造方・法に関する。[Detailed description of the invention] 3. Amount of H fE+ (Field of industrial application) The present invention relates to a method for producing a heat-resistant resin that has excellent heat resistance and adhesive strength, particularly adhesive strength at high temperatures. .
（従来の技術）
ポリビニルアセタール、特に、ポリビニルブチラールは
接着性が良くかつ物理的強度に優れていることから安全
合せガラスの中間膜として多用されている。他方、ポリ
ビニルアセタールは、多くの有機溶剤に可溶であり、ま
た金属に対する密着性や接着性に優れているため、ウォ
ソシュプライマーなどの金属用塗料や金属用接着剤にも
広く使用されている。(Prior Art) Polyvinyl acetal, particularly polyvinyl butyral, has good adhesive properties and excellent physical strength, and is therefore frequently used as an interlayer film for safety laminated glass. On the other hand, polyvinyl acetal is soluble in many organic solvents and has excellent adhesion and adhesion to metals, so it is widely used in metal paints such as wash primer and metal adhesives. .
金属用接着剤としてポリビニルアセタールを用いる場合
１通常ポリビニルアセタールのみをアルコール＋ｉ、ケ
トン頚、芳香族炭化水素などの有機溶剤に溶解して使用
に供される。しかし、この接着剤は、特に高温時におけ
る接着強度が低い。When polyvinyl acetal is used as an adhesive for metals 1. Usually, only polyvinyl acetal is dissolved in an organic solvent such as alcohol, ketone, or aromatic hydrocarbon. However, this adhesive has low adhesive strength, especially at high temperatures.
このような欠点を解決するために、フェノール樹脂、エ
ポキシ樹脂などの熱硬化性樹脂をポリビニルアセタール
に加え、これを有機溶剤に溶解した接着剤が用いられて
いる。これにより、高温時における接着強度は改善され
るものの、必ずしも充分ではない。接着強度をさらに向
上させることが要求されている。In order to solve these drawbacks, adhesives have been used in which thermosetting resins such as phenol resins and epoxy resins are added to polyvinyl acetal and this is dissolved in an organic solvent. Although this improves the adhesive strength at high temperatures, it is not necessarily sufficient. There is a need to further improve adhesive strength.
（発明が解決しようとする問題点）
本発明は上記従来の問題点を解決するものであり、その
目的とするところは、耐熱性および接着強度、特に高温
時における接着強度に優れた耐熱性樹脂の製造方法を提
供することにある０本発明の他の目的は、粘度の経時安
定性に優れた耐熱性樹脂の製造方法を提供することにあ
る。(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its purpose is to provide a heat-resistant resin with excellent heat resistance and adhesive strength, especially adhesive strength at high temperatures. Another object of the present invention is to provide a method for producing a heat-resistant resin having excellent viscosity stability over time.
（問題点養屑決するための手段）
本発明は、ポリビニルアセタール樹脂の側鎖にケイ素を
４人することにより、樹脂の耐熱性および高温時におけ
る接着性が著しく向上しうる。しかも、得られたケイ素
変性ポリビニルアセタール樹脂に低級アルコールを作用
させることにより。(Means for solving problems) In the present invention, by adding four silicon atoms to the side chains of polyvinyl acetal resin, the heat resistance and adhesiveness of the resin at high temperatures can be significantly improved. Moreover, by allowing a lower alcohol to act on the obtained silicon-modified polyvinyl acetal resin.
樹脂粘度の経時安定性が改善されうる。との発明者の知
見にもとづいて完成された。The stability of resin viscosity over time can be improved. It was completed based on the inventor's knowledge.
本発明の耐熱性樹脂の製造方法は、（１）ポリビニルア
セタール樹脂の有機溶剤溶液に、ｖ！擢ｍ酉履低級アル
コキシ基を有する有機シラン化合物を加えて反応させる
ことにより、側鎖にケイ素が導入された変性ポリビニル
アセタール樹脂を合成する工程、および（２）該変性ポ
リビニルアセタール樹脂に低級アルコールを加える工程
、を包含し、そのことにより上記目的が達成される。The method for producing a heat-resistant resin of the present invention includes (1) adding v! to an organic solvent solution of polyvinyl acetal resin; A step of synthesizing a modified polyvinyl acetal resin in which silicon is introduced into the side chain by adding and reacting an organic silane compound having a lower alkoxy group, and (2) adding a lower alcohol to the modified polyvinyl acetal resin. The above object is thereby achieved.
本発明における有機シラン化合物としては、いわゆるシ
ランカップリング剤と称される化合物が広く用いられ１
例えば、Ｓｉに少なくとも１個の低級アルコキシ基と、
少なくとも１個の−Ｒ基とが結合した化合物がある。た
だし上記−Ｒ基は、ポリビニルアセタール樹脂の官能基
と反応し得る官能基（アミノ基、エポキシ基、イソシア
ネート基。As the organic silane compound in the present invention, compounds called so-called silane coupling agents are widely used.
For example, at least one lower alkoxy group on Si,
There are compounds to which at least one -R group is bonded. However, the above-mentioned -R group is a functional group (amino group, epoxy group, isocyanate group) that can react with the functional group of the polyvinyl acetal resin.
メルカプト基など）を含む炭化水素基を表す。また、こ
の有機シラン化合物には、塩素などのハロゲン原子が結
合していてもよい。低級アルコキシ基には９例えば、メ
トキシ基、エトキシ基がある。represents a hydrocarbon group containing a mercapto group, etc. Further, a halogen atom such as chlorine may be bonded to this organic silane compound. Examples of lower alkoxy groups include methoxy and ethoxy groups.
これらの有機シラン化合物は、一般に、 Ｓｉｎ、で表
されるシランから誘導して得られる。These organic silane compounds are generally derived from a silane represented by Sin.
上記有機シラン化合物の好ましい例としては。Preferred examples of the above organic silane compounds include:
３−イソシアネートプロピルトリエトキシシランのよう
なイソシアネート基を有する化合物、３−アミノプロピ
ルトリエトキシシランのようなアミノ基を有する化合物
、３−グリシドキシプロピルメチルジメトキシシランの
ようなエポキシ基を有する化合物などがある。Compounds having an isocyanate group such as 3-isocyanatepropyltriethoxysilane, compounds having an amino group such as 3-aminopropyltriethoxysilane, compounds having an epoxy group such as 3-glycidoxypropylmethyldimethoxysilane, etc. There is.
ポリビニルアセタール樹脂としては、アセタール環、残
存水酸基および残存アセチル基を有する通常のポリビニ
ルアセタール樹脂が多用される。゛しかし、これに限定
されず、あらかじめカルボキシル基やアミノ基などの特
定の官能基が導入されたポリビニルアセタール樹脂も使
用可能である。As the polyvinyl acetal resin, a common polyvinyl acetal resin having an acetal ring, a residual hydroxyl group, and a residual acetyl group is often used. However, the present invention is not limited to this, and polyvinyl acetal resins into which specific functional groups such as carboxyl groups and amino groups have been introduced in advance can also be used.
カルボキシル基が導入されたポリビニルアセタール樹脂
を得るに番よ、カルボキシル基を有するアルデヒドを用
いてポリビニルアセタールをアセタール化する方法、ポ
リビニルアセタールの残存水酸基にジカルボン酸を反応
させて半エステル化する方法などを採用し得る。また、
ポリビニルアセタールの原料として用いられるポリビニ
ルアルコールの平均重合度は、一般に１００〜３０００
．好ましくは３００〜３０００とされる。To obtain a polyvinyl acetal resin into which a carboxyl group has been introduced, there are methods such as acetalization of polyvinyl acetal using an aldehyde having a carboxyl group, and a method of half-esterifying polyvinyl acetal by reacting a dicarboxylic acid with the remaining hydroxyl group. Can be adopted. Also,
The average degree of polymerization of polyvinyl alcohol used as a raw material for polyvinyl acetal is generally 100 to 3000.
．． Preferably it is 300-3000.
有機シラン化合物は、ポリビニルアセタール樹脂１００
重量部に対し、０．１〜２０重量部、好ましくは、０．
２〜６重量部の範囲で加えられる。０．１重量部を下ま
わると、得られた耐熱性樹脂が充分な耐熱性および接着
強度を有しない。２０重量部を上まわると、得られた耐
熱性樹脂の特性が損なわれる。The organic silane compound is polyvinyl acetal resin 100
0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight.
It is added in a range of 2 to 6 parts by weight. If it is less than 0.1 part by weight, the resulting heat-resistant resin will not have sufficient heat resistance and adhesive strength. If it exceeds 20 parts by weight, the properties of the resulting heat-resistant resin will be impaired.
上記ポリビニルアセタールに上記有機シラン化合物を反
応させるには９例えば、有機溶剤に溶解したポリビニル
アセタール溶液にシラン化合物を添加し、必要に応じて
、ジブチル錫ジアセテート。To react the polyvinyl acetal with the organic silane compound, for example, a silane compound is added to a polyvinyl acetal solution dissolved in an organic solvent, and if necessary, dibutyltin diacetate is added.
ジブチル錫ジラウレート、酢酸第一錫、ナフテン酸鉛な
どのシラノール縮合触媒の存在下に、上記溶液を一定時
間、常温〜８０℃程度、好ましくは５０〜６０℃程度に
保持する。In the presence of a silanol condensation catalyst such as dibutyltin dilaurate, stannous acetate, or lead naphthenate, the solution is maintained at room temperature to about 80°C, preferably about 50 to 60°C, for a certain period of time.
このようにして得られた変性ポリビニルアセタール樹脂
は、有機シラン化合物のケイ素が樹脂の側鎖部分に位置
するように導入されており、場合によってはケイ素を介
して分子内もしくは分子間架橋が行われていると推定さ
れる。そのことにより、優れた耐熱性および接着強度が
得られる。In the modified polyvinyl acetal resin obtained in this way, the silicon of the organosilane compound is introduced so that it is located in the side chain part of the resin, and in some cases, intramolecular or intermolecular crosslinking is performed via the silicon. It is estimated that This provides excellent heat resistance and adhesive strength.
この変性ポリビニルアセタール樹脂には、さらに低級ア
ルコールが添加される。低級アルコールを添加すること
により、樹脂の粘度の経時安定性が著しく改善される。A lower alcohol is further added to this modified polyvinyl acetal resin. By adding a lower alcohol, the stability of the viscosity of the resin over time is significantly improved.
従って、樹脂が、変性直後から短時間でゲル化して、接
着性を喪失することはない。低級アルコールは、変性反
応後直ちに投入される。Therefore, the resin will not gel in a short period of time immediately after modification and will not lose its adhesive properties. The lower alcohol is added immediately after the denaturation reaction.
低級アルコールには２例えば、メタノール、エタノール
がある。低級アルコールは、５重量％以上、好ましくは
、 １０〜３０重量％の範囲で添加される。５重量％を
下まわると、樹脂の粘度の経時安定性が充分に改善され
ない。低級アルコールの添加量は多いほど効果があるも
のの、多量の添加によれば、樹脂の流動性が増し、その
ために接着剤としての使用が困難となる。Examples of lower alcohols include methanol and ethanol. The lower alcohol is added in an amount of 5% by weight or more, preferably in the range of 10 to 30% by weight. If it is less than 5% by weight, the stability of the resin's viscosity over time will not be sufficiently improved. Although the greater the amount of lower alcohol added, the greater the effect, the addition of a large amount increases the fluidity of the resin, making it difficult to use it as an adhesive.
低級アルコールの添加効果は、ポリビニルアセタール樹
脂の側鎖に導入された有機シラン化合物中のアルコキシ
基と低級アルコールとのエステル交換によると推定され
る。The effect of adding lower alcohol is estimated to be due to transesterification between the lower alcohol and the alkoxy group in the organic silane compound introduced into the side chain of the polyvinyl acetal resin.
（実施例） 以下に本発明を実施例について述べる。(Example) The present invention will be described below with reference to examples.
災施■土
１、ポリビニルアセク−ル樹脂の合成
５１セパラブルフラスコに純水３２００ｇおよびポリビ
ニルアルコール（重合度１７００．ケン化度９９モル％
）を３２０ｇ入れ、 ９０℃で２時間加温して溶解後２
次のようにしてアセタール化反応を行なった。Disaster soil 1. Synthesis of polyvinyl acetate resin 51 In a separable flask, add 3200 g of pure water and polyvinyl alcohol (degree of polymerization 1700, degree of saponification 99 mol%).
) was added and heated at 90°C for 2 hours to dissolve.
The acetalization reaction was carried out as follows.
溶液を冷却しながら、４０〜５０℃で触媒として塩酸（
３５％）を２３ｇ投入し、１５〜２０℃でブチルアルデ
ヒドを４８ｇ投入し、さらに１０〜１５℃でブチルアル
デヒドを１２６ｇを追加投入して白色粉末を得た。While cooling the solution, add hydrochloric acid (
35%) was added, 48g of butyraldehyde was added at 15 to 20°C, and 126g of butyraldehyde was further added at 10 to 15°C to obtain a white powder.
この白色粉末に塩酸を２００ｇ追加投入した後、液温を
３０〜３５℃に昇温し３〜５時間熟成した。得′られた
樹脂を精製するため、常法に従って水洗・中和をし、触
媒および残存アルデヒドを除去した後。After adding 200 g of hydrochloric acid to this white powder, the liquid temperature was raised to 30 to 35°C and aged for 3 to 5 hours. In order to purify the obtained resin, it is washed with water and neutralized according to a conventional method to remove the catalyst and residual aldehyde.
乾燥し約３５０ｇの白色粉末状のポリビニルアセタール
樹脂Ａを得た。After drying, about 350 g of white powdery polyvinyl acetal resin A was obtained.
得られた樹脂のブチラール化度は、６５モル％であった
。The degree of butyralization of the obtained resin was 65 mol%.
２、ポリビニルアセタール樹脂の変性
得られた樹脂Ａ ６０ｇをメチルエチルケトンとトルエ
ンとの混合溶剤（混合比１ ： １） ３１５ｇに溶
解した。溶液の温度を５０〜６０℃に保持し、シラノー
ル縮合触媒としてジブチル錫ジアセテート０．０５ｇを
添加した後、３−イソシアネートブロピルトリエトギシ
シラン０．６５ｇを加え１時間反応させた。2. Modification of polyvinyl acetal resin 60 g of the obtained resin A was dissolved in 315 g of a mixed solvent of methyl ethyl ketone and toluene (mixing ratio 1:1). The temperature of the solution was maintained at 50 to 60° C., and 0.05 g of dibutyltin diacetate was added as a silanol condensation catalyst, and then 0.65 g of 3-isocyanate propyltriethoxysilane was added and reacted for 1 hour.
その後、メタノールを１２４ｇ加え、変性ポリビニルア
セタール樹脂Ｂの溶液を得た。Thereafter, 124 g of methanol was added to obtain a solution of modified polyvinyl acetal resin B.
得られた溶液の粘度は、２０℃で３０ボイズであった。The resulting solution had a viscosity of 30 voids at 20°C.
３、接着剤の調製 変性樹脂Ｂを用い１次の要領で、接着剤を調製した。3. Preparation of adhesive An adhesive was prepared using modified resin B in the following manner.
変性樹脂Ｂの溶液にレゾール型フェノール樹脂（卵巣化
学社製Ｐ Ｌ −２２０５固形分６５％）１８ｇおよび
エポキシ樹脂（シェル化学社製エピコート８２８）０．
６ｇを添加、混合して接着剤Ｃを得た。To a solution of modified resin B, 18 g of resol type phenol resin (PL-2205, solid content 65%, manufactured by Ovary Kagaku Co., Ltd.) and 0.0 g of epoxy resin (Epicoat 828, manufactured by Shell Chemical Co., Ltd.) were added.
Adhesive C was obtained by adding and mixing 6 g.
４、耐熱性および接着強度の評価
変性樹脂Ｂの軟化温度、ゲル分率、および接着、剤Ｃの
半田耐熱性を下記の方法で測定した。4. Evaluation of heat resistance and adhesive strength The softening temperature and gel fraction of modified resin B, and the soldering heat resistance of adhesive agent C were measured by the following method.
＋１１軟化温度
樹脂の耐熱性の評価法として軟化温度を測定することが
広く行われている。本発明においても高化式フローテス
ター（島津製作所社製ＣＦＴ−５００型）を用いて軟化
温度を測定した。+11 Softening Temperature Measuring the softening temperature is widely used as a method for evaluating the heat resistance of resins. In the present invention, the softening temperature was also measured using a Koka type flow tester (CFT-500 model manufactured by Shimadzu Corporation).
変性樹脂Ｂ溶液からキャスティング法にてフィルムを作
成したのち、粉砕品１．５ｇをサンプルとした。After creating a film from the modified resin B solution by a casting method, 1.5 g of the pulverized product was used as a sample.
サンプルをノズル径１ｍｍ、ノズルの長さ１０１■の金
型に入れ１００ｋｇ／ｃｊの荷重をかけ、１４０℃で３
分間予備加熱後、１分間に６℃の割金で昇温し。The sample was placed in a mold with a nozzle diameter of 1 mm and a nozzle length of 101 cm, and a load of 100 kg/cj was applied, and the sample was heated at 140°C for 3
After preheating for a minute, the temperature was raised at a rate of 6°C per minute.
樹脂の流量が１秒間に１０−’ｃｃとなる温度を軟化温
度とした。その結果、樹脂Ｂの軟化温度は３３０℃であ
った。The temperature at which the resin flow rate was 10-'cc per second was defined as the softening temperature. As a result, the softening temperature of resin B was 330°C.
（２）ゲル分率
上記（１）で得たフィルム粉砕品をサンプルとした。溶
媒としてアセトンを用いソックスレー抽出器を用いてゲ
ル分率を測定した。その結果、ゲル分率は６５％であっ
た。(2) Gel fraction The film pulverized product obtained in (1) above was used as a sample. The gel fraction was measured using a Soxhlet extractor using acetone as a solvent. As a result, the gel fraction was 65%.
口）半田耐熱性
接着剤を３５μ−厚の銅箔に、乾燥厚が約３０μ−にな
るように塗布して１４０〜１５０℃で２〜５分間乾燥し
た。この銅箔をフェノール含浸紙に貼り合せ１５０〜１
６０℃で３０分間、 １００ｋｇ／ｃｄの条件で加圧
成型し銅箔積層板を得た。(1) Solder A heat-resistant adhesive was applied to a 35μ-thick copper foil to a dry thickness of about 30μ, and dried at 140 to 150°C for 2 to 5 minutes. This copper foil was pasted on phenol-impregnated paper.
A copper foil laminate was obtained by pressure molding at 60° C. for 30 minutes at 100 kg/cd.
得られた銅箔積層板をＪ Ｉ Ｓ Ｃ−６４８１の方法
に従って半田耐熱性を測定した。その結果、半田耐熱性
は２３秒であった。The solder heat resistance of the obtained copper foil laminate was measured according to the method of JIS C-6481. As a result, the soldering heat resistance was 23 seconds.
５、溶液粘度の経時安定性測定
２、により得られた変性ポリビニルアセタール樹脂Ｂの
溶液を２００ｍ Ｉｔのサンプルびんに入れ、密栓番し
、４０℃のギアオーブン内に１ケ月間放置した。放置後
の溶液の粘度をＢ型回転粘度計により測定したところ、
２０℃で３１ボイズでありゲル化もなかった。5. Measurement of stability over time of solution viscosity The solution of modified polyvinyl acetal resin B obtained in step 2 was placed in a 200 m It sample bottle, sealed tightly, and left in a gear oven at 40° C. for one month. The viscosity of the solution after standing was measured using a B-type rotational viscometer.
There were 31 voids at 20°C and no gelation occurred.
スｍ
メチルエチルケトンとトルエンとの混合溶剤を３９０ｇ
とし、メタノールを５０ｇとしたこと以外は。Sum 390g of mixed solvent of methyl ethyl ketone and toluene
except that methanol was 50g.
実施例１と同様にして、変性ポリビニルアセタール樹脂
の溶液を得た。得られた溶液の粘度は、 ２０℃で３３
ポイズであった。この溶液について、実施例１と同様の
方法により、粘度の経時安定性を測定したところ、４０
℃で１ケ月間放置後の粘度は３８ボイズであった。A solution of modified polyvinyl acetal resin was obtained in the same manner as in Example 1. The viscosity of the resulting solution was 33 at 20°C.
It was Poise. Regarding this solution, the stability of the viscosity over time was measured using the same method as in Example 1.
The viscosity after standing at ℃ for 1 month was 38 boids.
スｍ
メタノールに代えてエタノールを用いたこと以外は、実
施例１と同様にして、変性ポリビニルアセタール樹脂の
溶液を得た。得られた溶液の粘度は、 ２０″Ｃで３８
ポイズであった。この溶液について。A solution of modified polyvinyl acetal resin was obtained in the same manner as in Example 1 except that ethanol was used instead of methanol. The viscosity of the solution obtained was 38 at 20"C.
It was Poise. About this solution.
実施例１と同様の方法により、粘度の経時安定性を測定
したところ、３０℃で１ケ月間放置後の粘度は１００ボ
イズであった。The stability of viscosity over time was measured by the same method as in Example 1, and the viscosity after being left at 30° C. for one month was 100 voids.
此１Ｕ」１
実施例１と同様にしてポリビニルアセタール樹脂Ａを得
た。この樹脂Ａについて、実施例１と同様の方法により
接着剤Ｃ゛を５ＩＲ１！ｊした。樹脂Ａの軟化温度、ゲ
ル分率、および接着剤Ｃ゛の半田耐熱性を、実施例１と
同様の方法により測定したところ、軟化温度は１９４℃
、ゲル分率は０．１％、そして半田耐熱性は８秒であっ
た。1U''1 Polyvinyl acetal resin A was obtained in the same manner as in Example 1. For this resin A, adhesive C was applied with 5IR1! in the same manner as in Example 1. I did it. When the softening temperature and gel fraction of resin A and the soldering heat resistance of adhesive C were measured in the same manner as in Example 1, the softening temperature was 194°C.
The gel fraction was 0.1%, and the soldering heat resistance was 8 seconds.
止較皿又
メチルエチルケトンとトルエンとの混合溶剤を４４０ｇ
とし、メタノールを加えなかったこと以外は。440g of mixed solvent of methyl ethyl ketone and toluene
except that no methanol was added.
実施例１と同様にして、変性ポリビニルアセタール樹脂
の溶液を得た。得られた溶液の粘度は、 ２０℃で５０
ボイズであった。この溶液について、実施例１と同様の
方法により、粘度の経時安定性の測定を試みたところ、
４０℃で１ケ月間放置後は完全にゲル化状態であり、粘
度の測定は不可能であった。A solution of modified polyvinyl acetal resin was obtained in the same manner as in Example 1. The viscosity of the obtained solution was 50 at 20°C.
It was Boyz. Regarding this solution, we attempted to measure the stability of viscosity over time using the same method as in Example 1.
After being left at 40° C. for one month, it was completely gelled and the viscosity could not be measured.
実施例および比較例から明らかなように１本発明により
″得られた・耐熱性樹脂は、耐熱性および接着強度、特
に高温時における接着強度に優れている。しかも、溶液
粘度の経時安定性が良好である。As is clear from the examples and comparative examples, the heat-resistant resin obtained according to the present invention has excellent heat resistance and adhesive strength, especially adhesive strength at high temperatures.Moreover, the stability of solution viscosity over time is excellent. In good condition.
有機シラン化合物を加えなかった樹脂は、耐熱性に欠け
、高温時における接着強度も低い。メタノールを加えな
かった樹脂は、溶液粘度の経時安定性に欠ける。A resin to which no organic silane compound is added lacks heat resistance and has low adhesive strength at high temperatures. A resin without methanol added lacks stability in solution viscosity over time.
（発明の効果）
本発明によれば、このように、耐熱性および接着強度、
特に高温時における接着強度に優れた耐熱性樹脂が得ら
れる。しかも、この樹脂は、粘度の経時安定性も良好で
ある。従って１例えば、金属用接着剤、特に印刷回路用
接着剤、ブレーキシュー用接着剤や金属用塗料などの耐
熱性が要求される用途に用いられて優れた性能を発揮し
うる。(Effects of the Invention) According to the present invention, heat resistance, adhesive strength,
A heat-resistant resin with excellent adhesive strength especially at high temperatures can be obtained. Furthermore, this resin also has good viscosity stability over time. Therefore, it can be used, for example, in applications requiring heat resistance, such as adhesives for metals, particularly adhesives for printed circuits, adhesives for brake shoes, and paints for metals, and exhibits excellent performance.
Claims (1)
、低級アルコキシ基を有する有機シラン化合物を加えて
反応させることにより、側鎖にケイ素が導入された変性
ポリビニルアセタール樹脂を合成する工程、および （２）該変性ポリビニルアセタール樹脂に低級アルコー
ルを加える工程、 を包含する耐熱性樹脂の製造方法。 ２、前記有機シラン化合物が、３−イソシアネートプロ
ピルトリエトキシシラン、３−アミノプロピルトリエト
キシシランおよび３−グリシドキシプロピルメチルジメ
トキシシランのうちの少なくとも一種である特許請求の
範囲第１項に記載の耐熱性樹脂の製造方法。 ３、前記ポリビニルアセタール樹脂１００重量部に対し
、前記有機シラン化合物が０．１〜２０重量部の範囲で
加えられた特許請求の範囲第１項に記載の耐熱性樹脂の
製造方法。 ４、前記低級アルコールが、メタノールおよびエタノー
ルのうちの少なくとも一種である特許請求の範囲第１項
に記載の耐熱性樹脂の製造方法。 ５、前記低級アルコールが５重量％以上の割合で加えら
れた特許請求の範囲第１項に記載の耐熱性樹脂の製造方
法。[Claims] 1. (1) Synthesis of modified polyvinyl acetal resin in which silicon is introduced into the side chain by adding and reacting an organic silane compound having a lower alkoxy group to an organic solvent solution of polyvinyl acetal resin. and (2) adding a lower alcohol to the modified polyvinyl acetal resin. 2. The organic silane compound according to claim 1, wherein the organic silane compound is at least one of 3-isocyanatepropyltriethoxysilane, 3-aminopropyltriethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. Method for producing heat-resistant resin. 3. The method for producing a heat-resistant resin according to claim 1, wherein the organic silane compound is added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the polyvinyl acetal resin. 4. The method for producing a heat-resistant resin according to claim 1, wherein the lower alcohol is at least one of methanol and ethanol. 5. The method for producing a heat-resistant resin according to claim 1, wherein the lower alcohol is added in a proportion of 5% by weight or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2340286A JPS62181305A (en) | 1986-02-05 | 1986-02-05 | Production of heat-resistant resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2340286A JPS62181305A (en) | 1986-02-05 | 1986-02-05 | Production of heat-resistant resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62181305A true JPS62181305A (en) | 1987-08-08 |
Family
ID=12109509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2340286A Pending JPS62181305A (en) | 1986-02-05 | 1986-02-05 | Production of heat-resistant resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62181305A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6756442B2 (en) | 2001-08-16 | 2004-06-29 | Wacker Polymer Systems Gmbh & Co. Kg | Silane-modified polyvinyl acetals |
| US7368515B2 (en) | 2002-07-25 | 2008-05-06 | Wacker Polymer Systems Gmbh & Co. Kg | Polyvinyl alcohols and polyvinyl acetals containing silane |
| WO2013184479A1 (en) * | 2012-06-05 | 2013-12-12 | Ticona Llc | Low emission polyoxymethylene |
-
1986
- 1986-02-05 JP JP2340286A patent/JPS62181305A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6756442B2 (en) | 2001-08-16 | 2004-06-29 | Wacker Polymer Systems Gmbh & Co. Kg | Silane-modified polyvinyl acetals |
| US7368515B2 (en) | 2002-07-25 | 2008-05-06 | Wacker Polymer Systems Gmbh & Co. Kg | Polyvinyl alcohols and polyvinyl acetals containing silane |
| WO2013184479A1 (en) * | 2012-06-05 | 2013-12-12 | Ticona Llc | Low emission polyoxymethylene |
| US8816015B2 (en) | 2012-06-05 | 2014-08-26 | Ticona, Llc | Low emission polyoxymethylene |
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