JPH04153268A - Thermosetting resin composition - Google Patents
Thermosetting resin compositionInfo
- Publication number
- JPH04153268A JPH04153268A JP27727390A JP27727390A JPH04153268A JP H04153268 A JPH04153268 A JP H04153268A JP 27727390 A JP27727390 A JP 27727390A JP 27727390 A JP27727390 A JP 27727390A JP H04153268 A JPH04153268 A JP H04153268A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- acetal
- composition
- acid 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.)
- Granted
Links
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 15
- 239000011342 resin composition Substances 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 37
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000004010 onium ions Chemical class 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 150000003459 sulfonic acid esters Chemical class 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 abstract description 20
- 238000003860 storage Methods 0.000 abstract description 16
- 230000000704 physical effect Effects 0.000 abstract description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000000976 ink Substances 0.000 abstract description 4
- 125000002947 alkylene group Chemical group 0.000 abstract description 2
- 125000000732 arylene group Chemical group 0.000 abstract description 2
- 229940098779 methanesulfonic acid Drugs 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 150000001241 acetals Chemical group 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- -1 acetal compound Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000017788 Cydonia oblonga Nutrition 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000036314 physical performance Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- ONUJSMYYXFLULS-UHFFFAOYSA-N 2-nonylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(CCCCCCCCC)=CC=C21 ONUJSMYYXFLULS-UHFFFAOYSA-N 0.000 description 1
- DDPMQWOBGOWNKA-UHFFFAOYSA-N 4,4-dimethoxybutan-1-ol Chemical compound COC(OC)CCCO DDPMQWOBGOWNKA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- CWNKMHIETKEBCA-UHFFFAOYSA-N alpha-Ethylaminohexanophenone Chemical compound CCCCC(NCC)C(=O)C1=CC=CC=C1 CWNKMHIETKEBCA-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940072282 cardura Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- VJECBOKJABCYMF-UHFFFAOYSA-N doxazosin mesylate Chemical compound [H+].CS([O-])(=O)=O.C1OC2=CC=CC=C2OC1C(=O)N(CC1)CCN1C1=NC(N)=C(C=C(C(OC)=C2)OC)C2=N1 VJECBOKJABCYMF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は新規な熱硬化性組成物、さらに詳しくは、化学
性能、物理性能及び耐候性などに優れる硬化物を与える
上に、貯蔵安定性にも優れ、例えば塗料、インク、接着
剤、成形品などに好適に用いられる熱硬化性組成物に関
するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention provides a novel thermosetting composition, more specifically, a cured product having excellent chemical performance, physical performance, weather resistance, etc., as well as storage stability. The present invention relates to a thermosetting composition which is excellent in the composition and is suitable for use in, for example, paints, inks, adhesives, molded products, etc.
従来よりポリマーポリオールをアセタールアルコキシ基
又はケタールアルコキ７基のアセタール交換反応を利用
した熱硬化性組成物は知られており、例えばこの反応を
利用した被覆組成物が開示されている（米国特許第３，
２００，０９９明細書、ヨーロッパ特許第１４０，３５
７Ａ２明細書、同第２５５，６０８Ａ２明細書）。Thermosetting compositions that utilize acetal exchange reaction of polymer polyols with acetal alkoxy groups or ketal alkoxy 7 groups have been known, and for example, coating compositions that utilize this reaction have been disclosed (U.S. Patent No. 3,
200,099 specification, European Patent No. 140,35
7A2 specification, 255,608A2 specification).
このようなアセタール交換反応を利用した熱硬化性組成
物は、イソンア不−ト類やアルデヒド類などの人体に対
して有害な物質を含まず、また排出することもないため
安全である上、得られる硬化物の化学性能や物理性能が
優れるなどの特徴を有している。Thermosetting compositions that utilize such acetal exchange reactions are safe and advantageous because they do not contain or emit substances that are harmful to the human body, such as isonia inerts and aldehydes. The cured product has excellent chemical and physical properties.
前記アセタール交換反応は酸触媒の存在下において進行
するものであり、この反応を利用した熱硬化性組成物に
おいて酸触媒は必須の成分である。The acetal exchange reaction proceeds in the presence of an acid catalyst, and the acid catalyst is an essential component in a thermosetting composition that utilizes this reaction.
しかしながら、酸触媒の存在下におけるポリマーポリオ
ールとアセタールアルコキシ基又はケタールアルコキン
基の反応性は極めて高く、これら３成分が共存する組成
物においては、貯蔵中にゲル化が生じたり、可使時間が
短くなるなどの問題を生じる。However, the reactivity of polymer polyols and acetal alkoxy groups or ketal alkoxy groups in the presence of acid catalysts is extremely high, and compositions containing these three components may undergo gelation during storage or have a long pot life. Problems such as shortening occur.
したがって、このような問題を解決する手段として、例
えば酸触媒を揮発性のアミン類で中和したり、あるいは
低分子−級モノアルコール類ヲ添加し、アセタールアル
コキン基又はケタールアルコキノ基と該アルコール類と
のアセタール平衡を利用するなとの方法が提案されてい
る［「ファルベ・ランド・ラック（Ｆａｒｂｅ ｕｎ
ｄ Ｌａｃｋ）Ｊ第９４巻、第６号、第４２５ページ
（１９８８年）］。しかしなから、これらの方法は、い
ずれも室温付近の温度における貯蔵安定性の改善には効
果はあるものの、夏季の屋外での貯蔵を想定した５０°
Ｃ以上の温度における貯蔵安定性の改善については必ず
しも十分ではなく、１液型塗料として使用に耐えうる組
成物を与えることができないという問題を有している。Therefore, as a means to solve such problems, for example, the acid catalyst is neutralized with volatile amines, or low-molecular-weight monoalcohols are added to form an acetal alkoke group or a ketal alkokino group. A method has been proposed that does not utilize acetal equilibrium with alcohols [Farbe-Land-Lac (Farbe un.
d Lack) J Vol. 94, No. 6, Page 425 (1988)]. However, although these methods are effective in improving storage stability at temperatures around room temperature,
The improvement in storage stability at temperatures above C or higher is not necessarily sufficient, and there is a problem in that it is not possible to provide a composition that can withstand use as a one-component paint.
［発明が解決しようとする課題〕
本発明は、有害物質を含有若しくは排出することなく安
全性に優れる上、化学性能や物理性能に優れる硬化物を
与え、かつ良好な貯蔵安定性を有し、ｌ成型として利用
可能な熱硬化性組成物を提供することを目的としてなさ
れたものである。[Problems to be Solved by the Invention] The present invention provides a cured product that is not only safe without containing or emitting harmful substances, but also has excellent chemical and physical properties, and has good storage stability. The purpose of this invention is to provide a thermosetting composition that can be used for molding.
［課題を解決するだめの手段コ
本発明者らは、前記の好ましい性質を有する熱硬化性組
成物を開発すべく鋭意研究を重ねた結果、特定の水酸基
含有樹脂と、１分子中にアセタールアルコキン基又はケ
タールアルコキシ基少なくとも３個を有する化合物と、
加熱時にのみ熱的に解離して、活性な酸性基を発現する
特殊な熱潜在性酸触媒とを必須成分として含有する組成
物により、その目的を達成しうろことを見い出し、この
知見に基づいて本発明を完成するに至った。[Means to Solve the Problem] As a result of intensive research to develop a thermosetting composition having the above-mentioned preferable properties, the present inventors found that a specific hydroxyl group-containing resin and an acetal alcohol in one molecule. A compound having at least three quinone or ketal alkoxy groups;
Based on this knowledge, we discovered that this objective could be achieved by using a composition containing as an essential component a special thermally latent acid catalyst that thermally dissociates to reveal active acidic groups only when heated. The present invention has now been completed.
すなわち、本発明は、（Ａ）数平均分子量ｉ、ｏｏｏ〜
１００．０００及び水酸基価５０〜３００の水酸基含有
樹脂、（Ｂ）１分子中に、−数式
（式中のＲは炭素数１〜６のアルキル基である）で表さ
れるアセタールアルコキン基又はケタールアルコキン基
少なくとも３個を有する化合物、及び（Ｃ）加熱硬化時
に活性を示す熱潜在性酸触媒を必須成分として含有して
成る熱硬化性組成物を提供するものである。That is, the present invention provides (A) number average molecular weight i, ooo~
100.000 and a hydroxyl group-containing resin with a hydroxyl value of 50 to 300, (B) an acetal alkokyne group represented by the formula - (R in the formula is an alkyl group having 1 to 6 carbon atoms) in one molecule, or The object of the present invention is to provide a thermosetting composition comprising, as essential components, a compound having at least three ketal alkoke groups and (C) a thermally latent acid catalyst that is active during heat curing.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明組成物において、（Ａ）成分として用いられる水
酸基含有樹脂は、数平均分子量が１．０００〜ｌｏｏ、
ｏｏｏの範囲にあり、かつ水酸基価か５０〜３００の範
囲にあることが必要である。該数平均分子量が１ 、Ｏ
Ｏ０未満では硬化物の耐水性や耐溶剤性が劣り、本発明
の目的が十分に達せられないし、１００，０００を超え
ると得られる組成物の粘度が高くなりすぎて、作業性か
悪くなる傾向がみられる。一方、該水酸基価が５０未満
では架橋点が少ないため、十分な硬度を有する硬化物が
得られないおそれがあるし、３００を超えるとその樹脂
自体の粘度が高くなるとともに、有機溶媒に対する溶解
性が低下する傾向がみもれる。In the composition of the present invention, the hydroxyl group-containing resin used as component (A) has a number average molecular weight of 1.000 to loo,
ooo, and the hydroxyl value must be in the range of 50 to 300. The number average molecular weight is 1, O
If it is less than O0, the water resistance and solvent resistance of the cured product will be poor, and the object of the present invention cannot be fully achieved. If it is more than 100,000, the viscosity of the resulting composition will become too high, and the workability will tend to deteriorate. can be seen. On the other hand, if the hydroxyl value is less than 50, there are few crosslinking points, so there is a risk that a cured product with sufficient hardness cannot be obtained.If it exceeds 300, the viscosity of the resin itself becomes high and the solubility in organic solvents increases. There is a tendency for this to decline.
この水酸基含有樹脂については、数平均分子量及び水酸
基価が前記範囲にあればよく、特に制限はない。このよ
うな樹脂としては、例えばポリエステル樹脂、ポリアク
リル樹脂、ポリビニルアルコール樹脂、エポキン樹脂、
フェノール樹脂、ポリウレタン樹脂、フッソ樹脂などが
挙げられる。This hydroxyl group-containing resin is not particularly limited as long as its number average molecular weight and hydroxyl value are within the above ranges. Examples of such resins include polyester resin, polyacrylic resin, polyvinyl alcohol resin, Epoquin resin,
Examples include phenol resin, polyurethane resin, and fluorine resin.
前記（Ａ）成分の水酸基含有樹脂は、水酸基以外に、必
要に応じて貯蔵安定性を低下させない範囲で、カルボキ
シル基、メルカプト基、エポキン基などの官能基を有し
ていてもよい。また、本発明組成物においては、この（
Ａ）成分の水酸基含有樹脂は１種用いてもよいし、２種
以上を組み合わせて用いてもよい。In addition to the hydroxyl group, the hydroxyl group-containing resin of component (A) may have a functional group such as a carboxyl group, a mercapto group, or an epochine group, if necessary, within a range that does not reduce storage stability. Moreover, in the composition of the present invention, this (
One type of hydroxyl group-containing resin as component A) may be used, or two or more types may be used in combination.
本発明組成物においては、（Ｂ）成分として、１分子中
に、−数式
％式％（）
（Ｒは前記と同じ意味をもつ）
で表されるアセタールアルコキノ基又はケタールアルコ
キシ基少なくとも３個を有する化合物か用いられる。In the composition of the present invention, as component (B), at least three acetal alkokino groups or ketal alkoxy groups represented by the formula % (R has the same meaning as above) are present in one molecule. Compounds with
前記アセタールアルコキノ基又はケタールアルコキシ基
におけるアルキル基の炭素数が６を超えるとポリマーポ
リオールとのアセタール交換反応性に劣るし、また１分
子中の該アセタールアルコキン基又はケタールアルコキ
ン基の量が３個未満では十分な架橋密度が得られず、硬
化物の硬度、耐水性、耐溶剤性が劣り、本発明の目的が
十分に達せられない。If the number of carbon atoms in the alkyl group in the acetal alkokino group or ketal alkoxy group exceeds 6, the acetal exchange reactivity with the polymer polyol will be poor, and the amount of the acetal alkokyne group or ketal alkoxy group in one molecule will decrease. If there are less than three, sufficient crosslinking density cannot be obtained, and the hardness, water resistance, and solvent resistance of the cured product are poor, and the object of the present invention cannot be fully achieved.
このような
（Ｂ）
成分の化合物としては、
例え
は、−数式
％式％（）
（式中のＲＩ 、 Ｒ２、Ｒ３及びＲ４は、それぞれ炭
素数１〜６のアルキル基であり、それらは同一であって
もよいし、たがいに異なっていてもよく、Ｙは炭素数２
〜１５のアルキレン基、アリーレン基又はアルカリーレ
ン基である）
で表される化合物や、−数式
％式％（）
（式中のＲ５、Ｒ６、Ｒ７及びＲ８は、それぞれ炭素数
１〜６のアルキル基であり、それらは同一であってもよ
いし、たがいに異なっていてもよく、ｎは１〜１５の整
数である）
で表される化合物を挙げることかできる。Such a compound of component (B) is, for example, -Formula%Formula%() (In the formula, RI, R2, R3 and R4 are each an alkyl group having 1 to 6 carbon atoms, and they are the same or may be different from each other, and Y has 2 carbon atoms.
~15 alkylene group, arylene group, or alkaline group) or - formula % formula % () (in the formula, R5, R6, R7, and R8 are each an alkyl group having 1 to 6 carbon atoms) (where n is an integer of 1 to 15), which may be the same or different from each other.
前記−数式（ＩＩ）で表される化合物は、例えば炭素数
２〜１５の脂肪族ジアルデヒドや１個又は複数個の芳香
環を有するジアルデヒドを炭素数１〜６のｍ個アルコー
ルとから製造することができる。また、前記−数式（Ｉ
［Ｉ）で表される化合物は、例えばルイス酸触媒の存在
下、ビニルエーテル［１こオルツギ酸トリアルキルエス
テルを付加させることにより、製造することができる（
米国特許第２，５２７，５３３号明細書）。The compound represented by formula (II) is produced from, for example, an aliphatic dialdehyde having 2 to 15 carbon atoms or a dialdehyde having one or more aromatic rings and m alcohols having 1 to 6 carbon atoms. can do. Moreover, the above-mentioned formula (I
The compound represented by [I] can be produced, for example, by adding vinyl ether [1-orthoformic acid trialkyl ester] in the presence of a Lewis acid catalyst (
(U.S. Pat. No. 2,527,533).
さらに、該（Ｂ）成分として、４．４−ジメトキシブタ
ン−１−オールのような水酸基含有アセタール化合物と
多官能性イソンア不−ト化合物との付加体や、前記低分
子多価アセタール化合物とジオール類又はトリオール類
との縮合体も使用することができる。Furthermore, as the component (B), an adduct of a hydroxyl group-containing acetal compound such as 4,4-dimethoxybutan-1-ol and a polyfunctional isonic acid compound, or an adduct of the low-molecular polyvalent acetal compound and a diol or condensates with triols can also be used.
本発明組成物においては、該（Ｂ）成分の化合物は１種
用いてもよいし、２種以上を組み合わせて用いてもよく
、またその配合量は、前記（Ａ）成分の水酸基１当量当
たり、アルコキシ基か０５〜２．０当量になるように選
ぶのが望ましい。In the composition of the present invention, one type of compound as the component (B) may be used, or two or more types may be used in combination, and the compounding amount is determined per equivalent of hydroxyl group of the component (A). It is preferable that the amount of the alkoxy group is 0.5 to 2.0 equivalents.
本発明組成物において、（Ｃ）成分として用いられる熱
潜在性酸触媒は、該組成物の硬化時には硬化反応を促進
し、硬化物に良好な化学性能及び物理性能を付与すると
ともに、該組成物の貯蔵時には長期にわたる安定性を実
現するために不可欠な成分であり、６０°Ｃ以上の温度
において酸触媒活性を示す化合物か望ましい。この熱潜
在性酸触媒が６０°Ｃ未満の温度で酸触媒活性を示す場
合、得られる組成物は貯蔵中に増粘したり、ゲル化する
など、好ましくない事態を招来するおそれがある。In the composition of the present invention, the thermal latent acid catalyst used as component (C) accelerates the curing reaction during curing of the composition, imparts good chemical and physical properties to the cured product, and It is an essential component to achieve long-term stability during storage, and compounds that exhibit acid catalytic activity at temperatures of 60° C. or higher are desirable. If this thermally latent acid catalyst exhibits acid catalytic activity at a temperature below 60° C., the resulting composition may increase in viscosity or gel during storage, leading to undesirable situations.
この（Ｃ）成分の熱潜在性酸触媒としては、スルホン酸
エステル類、リン酸エステル類及びオニウム化合物が好
ましく用いられる。Sulfonic acid esters, phosphoric acid esters and onium compounds are preferably used as the thermally latent acid catalyst of component (C).
該スルホン酸エステル類としては、例えば一般式
Ｒ”Ｓ−０−Ｒ”
Ｉ
・・・ （ｒＶ）
（式中のＲ９はフェニル基、置換フェニル基、ナフチル
基、置換ナフチル基又はアルキル基、Ｒ１０１１−級炭
素又は二級炭素を介してスルボニルオキ７基と結合して
いる炭素数３〜１８のアルキル基、アルケニル基、アリ
ール基、アルカリール基、アルカノール基、飽和若しく
は不飽和の７クロアルキル又はヒドロキシンクロアルキ
ル基である）
で表される化合物、具体的にはメタンスルポン酸、エタ
ンスルホン酸、ベンゼンスルホン酸、トデンルベンゼン
スルホン酸、ナフタレンスルホン酸、ノニルナフタレン
スルホン酸などのスルポン酸類と、ｎ−プロパツール、
ｎ−ブタノール、ｎ−ヘキサノール、ｎ−オクタツール
などの一級アルコル類又はインプロパツール、２−ブタ
ノール、２−ヘキサノール、２−オクタツール呟 ンク
ロヘキサノールなどの二級アルコール類とのエステル化
物、さらには前記スルホン酸類とオキシラン基含有化合
物との反応により得られるβ−ヒドロキシアルキルスル
ホン酸エステル類などが挙げられる。The sulfonic acid esters include, for example, the general formula R"S-0-R" I ... (rV) (R9 in the formula is a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group or an alkyl group, R1011 An alkyl group, an alkenyl group, an aryl group, an alkaryl group, an alkanol group, a saturated or unsaturated 7-chloroalkyl group or a hydroxyl group having 3 to 18 carbon atoms, which is bonded to a sulfonylox7 group through a -class carbon or a secondary carbon. synchroalkyl group), specifically sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, todenlebenzenesulfonic acid, naphthalenesulfonic acid, nonylnaphthalenesulfonic acid, and n- property tools,
Esterified products with primary alcohols such as n-butanol, n-hexanol, n-octatool, or secondary alcohols such as impropanol, 2-butanol, 2-hexanol, 2-octatool, and nclohexanol; Examples include β-hydroxyalkyl sulfonic acid esters obtained by the reaction of the sulfonic acids and an oxirane group-containing compound.
該リン酸エステル類としては、例えば−数式％式％）
（式中のＲ”は炭素数３〜１０のアルキル基、シクロア
ルキル基又はアリール基、ｍは１又は２である）
で表される化合物、具体的にはｎ−プロパツール、ｎ−
ブタノール、ｎ−ヘキサノール、ｎ−オクタノール、２
−エチルヘキサ／−ルなどの一級アルコール類又はイン
プロパ／−ル、２−ブタノール、２−ヘキサノール、２
−オクタツール、ソクロヘキサノールなどの二級アルコ
ール類のリン酸モノエステル類やリン酸ジエステル類な
どが挙げられる。The phosphoric acid esters are, for example, represented by the following formula: compounds, specifically n-propatool, n-
Butanol, n-hexanol, n-octanol, 2
-Primary alcohols such as ethylhex/-ol or impropyl, 2-butanol, 2-hexanol, 2
- Examples include phosphoric acid monoesters and phosphoric diesters of secondary alcohols such as octatool and soclohexanol.
さらに、該オニウム化合物としては、例えば数式
％式％（）
（［）
（式中のＲ１２は炭素数１〜１２のアルキル基、アルケ
ニル基、アリール基、アルカリール基、アルカノール基
又はンクロアルキル基であって、２個のＲｌｊはたがい
に結合してＮ、Ｐ、０又はＳ。Further, as the onium compound, for example, R12 is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, an alkanol group, or an cycloalkyl group. Therefore, two Rlj are bonded to each other to form N, P, 0, or S.
をヘテロ原子とする複素環を形成していてもよく、Ｒｌ
ｊは水紫原子、炭素数１〜１２のアルキル基、アルケニ
ル基、アリール基、アルカリール基、Ｘ−はｓｂｐ、−
１ＡｓＦ、−５ＰＦ、−又はＢＰ、−である）
で表される化合物などが挙げられる。may form a heterocyclic ring having Rl as a heteroatom, and Rl
j is a water purple atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, X- is sbp, -
1AsF, -5PF, - or BP, -.
本発明組成物Ｉ：８いては、該（Ｃ）成分の熱潜在性酸
触媒は１種用いてもよいし、２種以上を組み合わせて用
いてもよく、またその配合量は（Ａ）成分と（Ｂ）成分
との総置形分量１００重量部当たり、通常０．０１〜１
０重量部の範囲で選ばれる。In Composition I:8 of the present invention, one type of thermally latent acid catalyst as component (C) may be used, or two or more types may be used in combination, and the blending amount is determined as component (A). Usually 0.01 to 1 per 100 parts by weight of the total amount of component (B).
It is selected within the range of 0 parts by weight.
本発明の熱硬化性組成物の硬化に要する温度及び時間に
ついては、使用する熱潜在性酸触媒の種類により異なる
が、通常６０〜２００ ’Ｃの範囲の温度で２分ないし
１時間程度加熱することにより硬化が完了する。The temperature and time required for curing the thermosetting composition of the present invention vary depending on the type of thermal latent acid catalyst used, but it is usually heated at a temperature in the range of 60 to 200'C for about 2 minutes to 1 hour. This completes the curing.
本発明の熱硬化性組成物はそのままで、あるいは必要Ｉ
コ応じ、着色顔料、フィラー、溶剤、紫外線吸収剤、酸
化防止剤などを配合して、塗料、インク、接着剤、成形
品などｔこ用いることができる。The thermosetting composition of the present invention can be used as is or as required.
Depending on the situation, coloring pigments, fillers, solvents, ultraviolet absorbers, antioxidants, etc. can be added to the composition to make it possible to use it in paints, inks, adhesives, molded products, etc.
Ｌ寅流側フ
次に、寅流側によって本発明をさらＪコ詳細に説明する
が、本発明はこれらの例によってなんら限定されるもの
ではなＣ゛。Next, the present invention will be explained in more detail based on the third direction, but the present invention is not limited to these examples in any way.
製造例１〜３
水酸基含有樹脂Ａ−１〜Ａ−３の製造
温度計、還流冷却器、滴下ロート、撹拌機を備工た４つ
ロフラスコに、それぞれ第１表に示した合成用溶剤を仕
込み、溶剤が還流状態になるまで加熱撹拌した。次に、
それぞれ第１表に示した七ツマー混合物を還流、撹拌を
維持しながら滴下ロートを用いて２時間かけてフラスコ
中に滴下した。滴下終了後、還流、撹拌状態を３０分続
けたのち、反応温度を１００°Ｃに下げ、第１表に示し
た追加触媒をそれぞれ加えて、さらに１００°Ｃの温度
を２時間保ったところで反応を終了し、それぞれ第１表
記載の特性値を宵する水酸基含有樹脂Ａ−１〜Ａ−３を
得た。Production Examples 1 to 3 Production of hydroxyl group-containing resins A-1 to A-3 Four loaf flasks equipped with a thermometer, reflux condenser, dropping funnel, and stirrer were charged with the synthesis solvents shown in Table 1, respectively. The mixture was heated and stirred until the solvent reached a reflux state. next,
Each of the seven-mer mixtures shown in Table 1 was added dropwise into the flask over 2 hours using a dropping funnel while maintaining reflux and stirring. After the dropwise addition was completed, the refluxing and stirring state was continued for 30 minutes, and then the reaction temperature was lowered to 100°C, each of the additional catalysts shown in Table 1 was added, and the temperature was maintained at 100°C for another 2 hours, after which the reaction started. After completing the above steps, hydroxyl group-containing resins A-1 to A-3 having the characteristic values listed in Table 1 were obtained.
（以下余白）
製造例４．５
アセタールアルコキン基含有化合物Ｂ−１、Ｂ−２の製
造
温度計、Ｄｅａｎ−５ｔａｒｋ分留管、還流冷却器、窒
素ガス導入管、撹拌機を備えた４つロフラスコに、それ
ぞれ第２表の組成の混合物を仕込み、窒素ガスを導入し
ながら１３０〜１４０°Ｃに加熱、撹拌した。反応はア
セタール交換によるメタノールの発生とともに進行し、
反応の終点は赤外吸収スペクトルによる３ ５００ｃｍ
−’付近の水酸基に由来する吸収の消失及び、発生した
メタノール量によって決定される。反応終了後トリエチ
ルアミンを用いて生成物をｐＨ値が７になるまで中和し
、それぞれ第２表記載の特性値を有するアセタールアル
コキン基含有化合物Ｂ−１及びＢ−２を 得 ｌ二 。(Left below) Production Example 4.5 Production of Acetal Alcoquine Group-Containing Compounds B-1 and B-2 Four units equipped with a thermometer, a Dean-5 tark distillation tube, a reflux condenser, a nitrogen gas introduction tube, and a stirrer. Each of the mixtures having the composition shown in Table 2 was placed in a flask, and heated to 130 to 140° C. and stirred while introducing nitrogen gas. The reaction proceeds with the generation of methanol by acetal exchange,
The end point of the reaction is 3,500 cm according to the infrared absorption spectrum.
It is determined by the disappearance of absorption derived from the hydroxyl group near -' and the amount of methanol generated. After the reaction was completed, the product was neutralized using triethylamine until the pH value reached 7, yielding acetal alkokene group-containing compounds B-1 and B-2, each having the characteristic values listed in Table 2.
（以下余白）
第
表
リン酸系酸触媒、Ｋ ｉ ｎ ｇ
ＩｎｄｕｓｔｒＹ社製、商品名
製造例６〜８
熱潜在性酸触媒Ｃ−１〜Ｃ−３の製造
温度計、冷却管、滴下ロート、撹拌機を装着した２Ｑ４
つロフラスコに、それぞれ第３表に示したアルコール類
３５０重量部を入れて氷冷し、そこへカリウム−【−ブ
トキ／ド４４．９重量部を加えて溶解したのち、ジエチ
ルエーテル３００重量部に溶かした第３表記載のスルホ
ニルクロリド５３．４重量部を３０分かけて滴下した。(Left below) Table Phosphoric Acid Catalyst, Manufactured by Kin Industry Co., Ltd., Product Name Production Examples 6 to 8 Production of Heat Latent Acid Catalysts C-1 to C-3 Thermometer, cooling tube, dropping funnel, 2Q4 equipped with a stirrer
350 parts by weight of each of the alcohols shown in Table 3 were placed in a two-glass flask, cooled on ice, and 44.9 parts by weight of potassium-[-butoxide] was added thereto and dissolved, followed by 300 parts by weight of diethyl ether. 53.4 parts by weight of the dissolved sulfonyl chloride shown in Table 3 was added dropwise over 30 minutes.
滴下後１時間で水浴をはずし、さらに１時間反応させた
。The water bath was removed 1 hour after the dropwise addition, and the reaction was continued for another 1 hour.
反応終了後、反応混合物を水３００重量部で３回洗浄し
たのち、モレキュラーンーブ４Ａ１／１６［和光紬薬（
株）製］を加えて脱水乾燥処理を施し、溶媒ヲロータリ
ー・エバポレーターにて留去することにより、それぞれ
第３表記載の化合物である熱潜在性酸触媒Ｃ−１〜Ｃ−
３を得た。After the reaction was completed, the reaction mixture was washed three times with 300 parts by weight of water, and then mixed with Molecular Lube 4A1/16 [Wako Tsumugi Pharmaceutical Co., Ltd.].
Co., Ltd.] and subjected to dehydration and drying treatment, and the solvent was distilled off using a rotary evaporator to obtain thermally latent acid catalysts C-1 to C-, which are the compounds listed in Table 3, respectively.
I got 3.
（以下余白）
製造例９
熱潜在性酸触媒Ｃ−４のアセトン溶液の製造温度計、冷
却管、滴下ロート、撹拌機を装着した２１４つロフラス
コに、アセトン３２２重を部を入れて、ｐ−トルエンス
ルホン酸１７２重量部を加えて溶解したのち、１０°Ｃ
まで冷却した。そこへ、アセトン１００重量部に溶かし
たカージュラＥ−１０（エボキン当量２５０、シェル化
学社製）２５０重量部を内温か１０°Ｃから１５°Ｃの
間になるように１時間３０分かけて滴下した。その後、
１０°Ｃ付近に温度を保ち３０分間撹拌し、さらに室温
で２時間撹拌を続けることにより、熱潜在性酸触媒Ｃ−
４の５０ｗｔ％アセトン溶液を得ｔこ 。(Leaving space below) Production Example 9 Production of an acetone solution of thermally latent acid catalyst C-4 Place 322 parts of acetone in a 214-bottle flask equipped with a thermometer, cooling tube, dropping funnel, and stirrer, and add p- After adding and dissolving 172 parts by weight of toluenesulfonic acid, the mixture was heated at 10°C.
Cooled to . 250 parts by weight of Cardura E-10 (Evokin equivalent: 250, manufactured by Shell Chemical Co., Ltd.) dissolved in 100 parts by weight of acetone was added dropwise over 1 hour and 30 minutes so that the internal temperature was between 10°C and 15°C. did. after that,
Thermal latent acid catalyst C-
Obtain a 50 wt% acetone solution of No. 4.
実施例１
製造例２で得た水酸基含有樹脂（Ａ−２）１００重量部
に、製造例４で得たアセタールアルコキシ樹脂（Ｂ−１
）１１．４重量部、製造例６で得た熱潜在性酸触媒（Ｃ
−１）をり−トルエンスルホン酸換算で１０ｗｔ％にな
るようにキシレンで希釈した溶液１２．５重量部及びキ
ンレン７．５重量部を加えて、均一になるまで撹拌しク
リヤー溶液を得た。次にンンナー（キ／レン／メチルイ
ソブチルケトン−９／１重量比）で塗装粘度（７オード
カツプＮｏ、４．２０℃で２２秒）に希釈したのち、ブ
リキ板に乾燥膜厚３０ｐｍとなるようにエアースプレー
塗装し、１４０°Ｃで３０分間硬化させた。Example 1 Acetal alkoxy resin (B-1) obtained in Production Example 4 was added to 100 parts by weight of hydroxyl group-containing resin (A-2) obtained in Production Example 2.
) 11.4 parts by weight, thermally latent acid catalyst (C
-1) - 12.5 parts by weight of a solution diluted with xylene to 10 wt % in terms of toluenesulfonic acid and 7.5 parts by weight of quince were added and stirred until homogeneous to obtain a clear solution. Next, after diluting the paint with a coating solution (xy/lene/methyl isobutyl ketone - 9/1 weight ratio) to a coating viscosity (7 ord cup number, 4.22 seconds at 20°C), apply it on a tin plate to a dry film thickness of 30 pm. Air spray painted and cured at 140°C for 30 minutes.
得られた硬化膜はＡＳＴＭ−１４７４に記載された方法
でヌープ硬度１１．４を示すとともに、キンレンを浸し
たネルを用いて該硬化膜をラビングしても膜の溶解、軟
化は認められず、前記硬化条件下で十分な硬化性を示し
た。The obtained cured film showed a Knoop hardness of 11.4 according to the method described in ASTM-1474, and no dissolution or softening of the film was observed even when the cured film was rubbed using a flannel soaked with quince. It showed sufficient curability under the above curing conditions.
一方、ンンナーで希釈する以前のクリヤー溶液を５０°
Ｃで１週間貯蔵後もゲル化することなく、良好な貯蔵安
定性を示した。On the other hand, the clear solution before being diluted with the
Even after storage for one week at C, it did not gel and showed good storage stability.
実施例２〜１１
第４表に記載した配合に基づいて、実施例１と同様な操
作でクリヤー溶液をそれぞれ作成した。Examples 2 to 11 Clear solutions were prepared in the same manner as in Example 1 based on the formulations listed in Table 4.
次いで、実施例１と同様な操作で塗装したのち、第４表
記載の硬化条件で硬化させｌ：。このようにして得られ
たそれぞれの硬化膜について実施例１と同様な手法で硬
化性及び貯蔵安定性の試験を行った。その結果を第４表
′に示す。Next, after coating in the same manner as in Example 1, it was cured under the curing conditions listed in Table 4. The cured films thus obtained were tested for curability and storage stability in the same manner as in Example 1. The results are shown in Table 4'.
いずれの実施例においても十分な硬化性及び良好な貯蔵
安定性が確認された。Sufficient curability and good storage stability were confirmed in all Examples.
比較例１
第４表に記載した配合に基づいて、実施例１と同様な操
作でクリヤー溶液及び硬化膜を作成し、実施例１と同様
な性能評価を行ったが、酸触媒を配合中に含まない本例
では１４０°Ｃ１３０分の硬化条件では硬化しないこと
が判明した。Comparative Example 1 Based on the formulation listed in Table 4, a clear solution and a cured film were prepared in the same manner as in Example 1, and the performance evaluation was conducted in the same manner as in Example 1. It has been found that in this example, which does not contain the resin, it does not cure under the curing conditions of 140° C. for 130 minutes.
比較例２
第４表に記載した配合に基づいて、実施例１と同様な操
作でクリヤー溶液及び硬化膜を作成し、実施例１と同様
な性能評価を行った。酸触媒を配合中に含む本例では１
４０°Ｃ１３０分の硬化条件では硬化するものの、ｐ−
トルエンスルホン酸基の水素がブロフクされている熱潜
在性酸触媒でないために５０℃の安定性試験１日後にゲ
ル化し、十分な貯蔵安定性を示さないことが判明した。Comparative Example 2 Based on the formulations listed in Table 4, a clear solution and a cured film were prepared in the same manner as in Example 1, and performance evaluations were performed in the same manner as in Example 1. In this example containing an acid catalyst in the formulation, 1
Although it hardens under the curing conditions of 40°C for 130 minutes, p-
It was found that because the catalyst was not a thermally latent acid catalyst in which the hydrogen of the toluenesulfonic acid group was blocked, it gelled after one day of the stability test at 50°C and did not exhibit sufficient storage stability.
［発明の効果］
本発明の熱硬化性組成物は、化学性能、物理性能及び耐
候性などに優れる上に、貯蔵安定性にも優れるので、多
種多様の塗料、インク、接着剤、プラスチック成形品な
どに好適に用いられる。[Effects of the Invention] The thermosetting composition of the present invention not only has excellent chemical performance, physical performance, and weather resistance, but also has excellent storage stability, so it can be used in a wide variety of paints, inks, adhesives, and plastic molded products. It is suitably used for such purposes.
特許出馴大 日本油脂株式会社Patent Jujudai Nippon Oil & Fats Co., Ltd.
Claims (1)
び水酸基価５０〜３００の水酸基含有樹脂、（Ｂ）１分
子中に、一般式 ▲数式、化学式、表等があります▼ （式中のＲは炭素数１〜６のアルキル基である）で表さ
れるアセタールアルコキシ基又はケタールアルコキシ基
少なくとも３個を有する化合物、及び（Ｃ）加熱硬化時
に活性を示す熱潜在性酸触媒を必須成分として含有して
成る熱硬化性組成物。 ２ （Ｃ）成分がスルホン酸エステル類、リン酸エステ
ル類及びオニウム化合物の中から選ばれた少なくとも１
種である請求項１記載の熱硬化性組成物。[Scope of Claims] 1 (A) a hydroxyl group-containing resin with a number average molecular weight of 1,000 to 100,000 and a hydroxyl value of 50 to 300; (B) one molecule contains a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ A compound having at least three acetal alkoxy groups or ketal alkoxy groups represented by the formula (R in the formula is an alkyl group having 1 to 6 carbon atoms), and (C) a thermally latent acid that exhibits activity during heat curing. A thermosetting composition containing a catalyst as an essential component. 2 Component (C) is at least one selected from sulfonic acid esters, phosphoric acid esters, and onium compounds
The thermosetting composition according to claim 1, which is a seed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27727390A JP2876771B2 (en) | 1990-10-16 | 1990-10-16 | Thermosetting composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27727390A JP2876771B2 (en) | 1990-10-16 | 1990-10-16 | Thermosetting composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04153268A true JPH04153268A (en) | 1992-05-26 |
| JP2876771B2 JP2876771B2 (en) | 1999-03-31 |
Family
ID=17581230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27727390A Expired - Fee Related JP2876771B2 (en) | 1990-10-16 | 1990-10-16 | Thermosetting composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2876771B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001214099A (en) * | 1999-11-29 | 2001-08-07 | Xerox Corp | Ink composition containing malonaldehyde bis (dimethylacetal) |
-
1990
- 1990-10-16 JP JP27727390A patent/JP2876771B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001214099A (en) * | 1999-11-29 | 2001-08-07 | Xerox Corp | Ink composition containing malonaldehyde bis (dimethylacetal) |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2876771B2 (en) | 1999-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6434566B2 (en) | Crosslinkable composition capable of being cross-linked by latent base catalyst | |
| JP2018516290A (en) | Method for curing RMA crosslinkable resin coating, RMA curable composition, and resin used therein | |
| JPS63221123A (en) | Low-temperature-curable resin composition | |
| CN110066371A (en) | A kind of polyhydroxy anacardol benzoxazine resin and preparation method thereof | |
| KR20210000138A (en) | Clear coat composition | |
| US4171423A (en) | Derivatives of ester diol alkoxylates and compositions thereof | |
| JPS5937308B2 (en) | Low energy curable coating composition | |
| JP3041945B2 (en) | Thermosetting composition | |
| JPH04153268A (en) | Thermosetting resin composition | |
| US4376844A (en) | Hydrocurable ambient curing polyepoxide coating and adhesive compositions and method of using them | |
| US4188477A (en) | Isocyanate derivatives of ester diol alkoxylates and compositions thereof | |
| EP0542220A1 (en) | Polyurethanes and processes for preparing same | |
| JP2893947B2 (en) | Thermosetting composition | |
| US4308356A (en) | Hydrocurable ambient curing polyepoxide coating and adhesive compositions and method of using same | |
| US4331793A (en) | Hydrocurable ambient curing polyepoxide coating and adhesive compositions and method of using them | |
| JP3041897B2 (en) | Heat latent acid catalyst and thermosetting composition containing the same | |
| JP2926825B2 (en) | New curing system and resin composition therefor | |
| JP3042033B2 (en) | Latent carboxyl compound and thermosetting composition containing the same | |
| JP4124106B2 (en) | Self-crosslinking resin, production method, resin composition and application | |
| JPH02232253A (en) | Thermosetting resin composition | |
| US4192789A (en) | Blends of acrylic latexes and derivatives of ester diol alkoxylates | |
| JPH01123817A (en) | Curable composition | |
| JP2787240B2 (en) | Thermosetting resin composition | |
| JPH0586297A (en) | Fluorine-containing thermosetting composition | |
| WO2023280809A1 (en) | Powder coating and crystalline donor and/or acceptor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |