JPH02180921A - Curable resin - Google Patents
Curable resinInfo
- Publication number
- JPH02180921A JPH02180921A JP33527688A JP33527688A JPH02180921A JP H02180921 A JPH02180921 A JP H02180921A JP 33527688 A JP33527688 A JP 33527688A JP 33527688 A JP33527688 A JP 33527688A JP H02180921 A JPH02180921 A JP H02180921A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- curable resin
- parts
- storage stability
- meth
- 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
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 18
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 9
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 229920000570 polyether Polymers 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- -1 2-ethylhexyl Chemical group 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、比較的低温で硬化できる硬化性樹脂に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a curable resin that can be cured at a relatively low temperature.
（従来の技術およびその問題点）
従来、カルボキシル基を有するポリマーと多官能エポキ
シ化合物との混合物や、エポキシ基を有するポリマーと
多官能カルボキシル化合物との混合物が加熱により硬化
することが知られている。(Prior art and its problems) It has been known that mixtures of polymers having carboxyl groups and polyfunctional epoxy compounds, and mixtures of polymers having epoxy groups and polyfunctional carboxyl compounds are cured by heating. .
し
しか・ながら、これらの混合物は、混合後の貯蔵安定性
が悪く、また硬化に比較的高温を要すると（式中、Ｒ＋
は水素原子又はメチル基を表わす。）で示される化合物
を単量体の一成分とした共重合体である請求項２記載の
硬化性樹脂。However, these mixtures have poor storage stability after mixing and require relatively high temperatures for curing (in the formula, R+
represents a hydrogen atom or a methyl group. 3. The curable resin according to claim 2, which is a copolymer containing a compound represented by the following formula as one monomer component.
悪（、塗膜を形成させた場合、硬化塗膜の平滑性が十分
でないという問題もあった。When a coating film was formed, there was also the problem that the smoothness of the cured coating film was insufficient.
（問題点を解決するための手段・作用）本発明者らは、
カルボキシル基とエポキシ基との硬化反応を利用でき、
上記の問題点のない樹脂を得るべく、鋭意研究を重ねた
結果、１分子中に２個以上のカルボキシル基と２個以上
のエボキシ基とを有する数平均分子量１０００以上の樹
脂が比較的低温で架橋硬化でき、しかも驚くべきことに
、この樹脂溶液は貯蔵安定性が良好であることを見出し
、本発明に到達した。(Means/effects for solving the problem) The present inventors
Can utilize the curing reaction between carboxyl groups and epoxy groups,
As a result of extensive research in order to obtain a resin that does not have the above problems, we have found that a resin with a number average molecular weight of 1000 or more and having two or more carboxyl groups and two or more epoxy groups in one molecule can be produced at relatively low temperatures. It was discovered that this resin solution can be crosslinked and cured, and surprisingly, has good storage stability, leading to the present invention.
本発明の硬化性樹脂としては、１分子中に２個以上のカ
ルボキシル基と２個以上のエポキシ基とを有する数平均
分子量１０００以上の樹脂であれば良く、例えばビニル
共重合体、ポリエステル、ポリウレタン、ポリエーテル
等が挙げられ、なかでもビニル共重合体が貯蔵安定性の
点から好ましく、さらには下記式（Ｉ）
Ｒ，０
（式中、Ｒ１は水素原子またはメチル基を表わす。）で
示される化合物を単量体の一成分とした共重合体である
ことが貯蔵安定性および硬化性の点から特に好ましい。The curable resin of the present invention may be any resin having a number average molecular weight of 1000 or more and having two or more carboxyl groups and two or more epoxy groups in one molecule, such as vinyl copolymers, polyesters, and polyurethanes. , polyether, etc. Among them, vinyl copolymers are preferred from the viewpoint of storage stability, and furthermore, vinyl copolymers represented by the following formula (I) R,0 (wherein R1 represents a hydrogen atom or a methyl group) In view of storage stability and curability, it is particularly preferable to use a copolymer containing a compound as a monomer component.
ビニル共重合体とする場合に、カルボキシル基導入のた
めに使用するカルボキシル基含有モノマーとしては、メ
タアクリル酸、アクリル酸が一般的であるが、その他、
マレイン酸、イタコン酸、クロトン酸、（メタ）アクリ
ル酸とε−カプロラクトンとの付加物等も使用できる。When making a vinyl copolymer, methacrylic acid and acrylic acid are generally used as carboxyl group-containing monomers to introduce carboxyl groups, but other
Adducts of maleic acid, itaconic acid, crotonic acid, (meth)acrylic acid and ε-caprolactone can also be used.
ビニル共重合体にエポキシ基導入のために使用するエポ
キシ基含有モノマーとしては、（Ｉ）式の化合物以外に
グリシジルアクリレート、グリシジルメタクリレート、
アリルグリシジルエーテルなどが使用できる。また、カ
ルボキシル基含有モノマーやエポキシ基含有モノマー以
外の、ビニル共重合体形成に使用できるその他の七ツマ
ー成分としては、例えばメチル（メタ）アクリレート、
エチル（メタ）アクリレート、ｎ−ブチル（メタ）アク
リレート、イソブチル（メタ）アクリレート、ヘキシル
（メタ）アクリレート、２−エチルヘキシル（メタ）ア
クリレート、ラウリルメタアクリレートなどの炭素数１
〜１８のアルキル（メタ）アクリレート：２−ヒドロキ
シエチル（メタ）アクリレート、ヒドロキシプロピル（
メタ）アクリレート、アリルアルコールなどの水酸基含
有不飽和単量体：スチレン、α−メチルスチレン、ビニ
ルトルエン、酢酸ビニル、（メタ）アクリルアミド、（
メタ）アクリロニトリル、Ｎ−メチロール（メタ）アク
リルアミドブチルエーテルなどの、その他の共重合可能
な七ツマ−を挙げることができる。In addition to the compound of formula (I), the epoxy group-containing monomers used for introducing epoxy groups into the vinyl copolymer include glycidyl acrylate, glycidyl methacrylate,
Allyl glycidyl ether etc. can be used. In addition, other seven-mer components other than carboxyl group-containing monomers and epoxy group-containing monomers that can be used to form vinyl copolymers include, for example, methyl (meth)acrylate,
1 carbon number such as ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl methacrylate, etc.
~18 alkyl (meth)acrylates: 2-hydroxyethyl (meth)acrylate, hydroxypropyl (
Hydroxyl group-containing unsaturated monomers such as meth)acrylate and allyl alcohol: styrene, α-methylstyrene, vinyltoluene, vinyl acetate, (meth)acrylamide, (
Mention may be made of other copolymerizable hexamers such as meth)acrylonitrile and N-methylol(meth)acrylamide butyl ether.
本発明において、ビニル共重合体は、上記カルボキシル
基含有モノマー エポキシ基含有モノマーおよび必要に
応じてその他のモノマー成分を配合して、重合触媒およ
び好ましくは有機溶剤の存在下で共重合することによっ
て得られる。この際の重合温度は１００℃以下、さらに
好ましくは８０℃以下の温度であることが望ましい。In the present invention, the vinyl copolymer is obtained by blending the above carboxyl group-containing monomer, epoxy group-containing monomer, and other monomer components as necessary, and copolymerizing the mixture in the presence of a polymerization catalyst and preferably an organic solvent. It will be done. The polymerization temperature at this time is preferably 100°C or lower, more preferably 80°C or lower.
本発明の硬化性樹脂の数平均分子量は１０００以上であ
れば使用可能であるが３０００〜しい。数平均分子量が
１０００未満の場合には貯蔵安定性が悪いという問題点
がある。The number average molecular weight of the curable resin of the present invention can be used as long as it is 1000 or more, but it is preferably 3000 or more. When the number average molecular weight is less than 1000, there is a problem that storage stability is poor.
また樹脂中に導入されるカルボキシル基の数は、１分子
中に２個以上あれば十分なネットワークを形成するが、
特に５〜ｌＯ個の範囲内であることが好ましい。樹脂中
に導入されるエポキシ基の数は１分子中に２個以上あれ
ば十分なネットワークを形成するが特に５〜ｌＯ個の範
囲にあることが好ましい。In addition, the number of carboxyl groups introduced into the resin is two or more in one molecule to form a sufficient network.
It is particularly preferable that the number is in the range of 5 to 10. The number of epoxy groups introduced into the resin is preferably in the range of 5 to 10, although a sufficient network can be formed if the number is 2 or more in one molecule.
本発明の硬化性樹脂は、貯蔵安定性を向上させるため、
アルコール系、脂肪族炭化水素系、芳香族炭化水素系、
ケトン系、エステル系等の有機溶剤で固形分８０重量％
以下となるよう希釈されることが好ましい。In order to improve the storage stability of the curable resin of the present invention,
Alcohol-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based,
Solid content 80% by weight with organic solvents such as ketones and esters
It is preferable that the dilution is as follows.
本発明の硬化性樹脂は被塗物に塗布後、例えば８０℃〜
１６０℃の温度でｌＯ〜３０分程度焼付けることにより
架橋硬化する。また、３級アミンや４級アンモニウム塩
等の触媒を添加することによって常温でも硬化できるよ
うになる。After applying the curable resin of the present invention to the object to be coated, for example, from 80°C to
It is crosslinked and hardened by baking at a temperature of 160° C. for about 30 minutes. Further, by adding a catalyst such as a tertiary amine or a quaternary ammonium salt, it becomes possible to cure the resin at room temperature.
本発明の硬化性樹脂が貯蔵安定性が良好である理由は明
らかではないが、樹脂の分子量の大きいものほど優れて
いる傾向があることから、立体障害による効果であると
考えられる。The reason why the curable resin of the present invention has good storage stability is not clear, but since resins with larger molecular weights tend to have better storage stability, it is thought that this is due to the effect of steric hindrance.
（実施例） 本発明を実施例にて、さらに詳細に説明する。(Example) The present invention will be explained in more detail with reference to Examples.
なお以下１部」および１％」は「重量部」および「重量
％」を意味する。Hereinafter, "1 part" and "1%" mean "part by weight" and "% by weight."
実施例１
アクリル酸 ７２部Ｃ８，０
で示される化合物 ２３５部ｎ−ブチ
ルメタクリレート ６９３部アゾビスジメチル
バレロニトリル ３０部４つロフラスコ中にキシレ
ン１０００部を配合し、８０℃に保持した中に、上記モ
ノマーおよび重合開始剤の混合物を３時間かけて滴下し
、滴下終了後、８０℃にて２時間熟成して固形分約５０
％、ガードナー粘度Ｐ（２５℃）の硬化性樹脂溶液を得
た。得られた樹脂の数平均分子量は約２５０００であっ
た。また、この樹脂はエポキシ基を約１．１モル／にｇ
、カルボキシル基を約１．０モル／にｇ有していた。Example 1 Acrylic acid 72 parts Compound represented by C8.0 235 parts A mixture of monomer and polymerization initiator was added dropwise over 3 hours, and after the addition was completed, the mixture was aged at 80°C for 2 hours until the solid content was approximately 50.
%, and a curable resin solution having a Gardner viscosity P (25° C.) was obtained. The number average molecular weight of the obtained resin was about 25,000. In addition, this resin has an epoxy group of approximately 1.1 mol/g.
, it had about 1.0 mol/g of carboxyl groups.
実施例２
トリメリット酸 １０５部エチレン
グリコール ５６部アジピン酸
７３部４つロフラスコ中にて上記
混合物を２２０℃で脱水縮合し、樹脂酸価が１９６にな
った点を終点とした。この縮合物にエチレングリコール
モノブチルエーテル６００部およびエピコート＃８２８
（注１）４００部を添加し１５０℃にて、樹脂酸価が１
９になるまで反応させ、冷却して固形分約５０％、ガー
ドナー粘度Ｘ（２５°Ｃ）の硬化性樹脂溶液を得た。Example 2 Trimellitic acid 105 parts Ethylene glycol 56 parts Adipic acid
The above mixture was subjected to dehydration condensation at 220° C. in 73 parts (4 parts) of a Lof flask, and the point at which the resin acid value reached 196 was defined as the end point. This condensate was added with 600 parts of ethylene glycol monobutyl ether and Epicoat #828.
(Note 1) When 400 parts were added and the resin acid value was 1 at 150°C.
9, and was cooled to obtain a curable resin solution having a solid content of about 50% and a Gardner viscosity of X (25°C).
得られた樹脂の数平均分子量は約８０００であった。ま
た、この樹脂はエポキシ基を約０．８３モル／にｇ、カ
ルボキシル基を約０．３３モル／Ｋｇ有していた。The number average molecular weight of the obtained resin was about 8,000. Further, this resin had an epoxy group of about 0.83 mol/g and a carboxyl group of about 0.33 mol/Kg.
（注１）エビコー１−８８２８・・・・・シェル化学社
製、エポキシ樹脂、分子量的３５０゜
実施例３
メタクリル酸 ８６部グリシジ
ルメタアクリレート １４２部スチレン
２００部ｎ−ブチルアクリレート
５７２部アゾビスジメチルバレロニトリル
５０部４つロフラスコ中にｎ−ブタノール１０００
部を配合し、８０℃に保持した中に、上記モノマーおよ
び重合開始剤の混合物を３時間かけて滴下し、滴下終了
後、８０℃にて２時間熟成して固形分約５０％、ガード
ナー粘度Ｈ（２５℃）の硬化性樹脂溶液を得た。得られ
た樹脂の数平均分子量は約１８０００であった。また、
この樹脂は、エポキシ基を約１．０モル／ Ｋｇ、カル
ボキシル基を約１．０モル／Ｋｇ有していた。(Note 1) Ebicor 1-8828... Shell Chemical Co., Ltd., epoxy resin, molecular weight 350° Example 3 Methacrylic acid 86 parts Glycidyl methacrylate 142 parts Styrene
200 parts n-butyl acrylate
572 parts Azobisdimethylvaleronitrile
50 parts n-butanol 1000 in 4 flasks
The mixture of monomers and polymerization initiator was added dropwise over 3 hours to the mixture kept at 80°C, and after the addition was completed, the mixture was aged at 80°C for 2 hours until the solid content was approximately 50% and the Gardner viscosity was A curable resin solution of H (25° C.) was obtained. The number average molecular weight of the obtained resin was about 18,000. Also,
This resin had about 1.0 mol/Kg of epoxy groups and about 1.0 mol/Kg of carboxyl groups.
実施例４
メタクリル酸 １７２部で示され
る化合物 １９０部メチルメタクリレ
ート ６３８部アゾビスジメチルバレロニ
トリル ５０部４つロフラスコにキシレン１０００
部を配合し、８０℃に保持した中に、上記モノマーおよ
び重合開始剤の混合物を３時間かけて滴下し、滴下終了
後、８０℃にて２時間熟成して固形分約５０％、ガード
ナー粘度Ｄ（２５℃）の硬化性樹脂溶液を得た。Example 4 Methacrylic acid 172 parts Compound 190 parts Methyl methacrylate 638 parts Azobisdimethylvaleronitrile 50 parts
The mixture of monomers and polymerization initiator was added dropwise over 3 hours to the mixture kept at 80°C, and after the addition was completed, the mixture was aged at 80°C for 2 hours to achieve a solid content of about 50% and a Gardner viscosity. A curable resin solution of D (25°C) was obtained.
得られた樹脂の数平均分子量は約１２０００であった。The number average molecular weight of the obtained resin was about 12,000.
また、この樹脂はエポキシ基を約１．０モル／Ｋｇ、カ
ルボキシル基を約２．０モル／Ｋｇ有していた。Further, this resin had about 1.0 mol/Kg of epoxy groups and about 2.0 mol/Kg of carboxyl groups.
比較例１
アクリル酸 ７２部ｎ−ブチ
ルメタアクリレート ９２８部アゾビスジメチル
バレロニトリル ３０部４つロフラスコ中にキシレ
ン１０００部を配合し、８０℃に保持した中に上記モノ
マーおよび重合開始剤の混合物を３時間かけて滴下し、
滴下終７後、８０℃にて２時間熟成して固形公約５０％
、ガードナー粘度Ｍ（２５℃）のアクリル樹脂溶液を得
た。得られた樹脂の数平均分子量は約２５０００であっ
た。この樹脂はカルボキシル基を約１．０モル／Ｋｇ有
していた。Comparative Example 1 Acrylic acid 72 parts Drip over time,
After 7 hours of dropping, mature at 80℃ for 2 hours until the solidity is approximately 50%.
, an acrylic resin solution having a Gardner viscosity M (25° C.) was obtained. The number average molecular weight of the obtained resin was about 25,000. This resin had about 1.0 mol/Kg of carboxyl groups.
得られたアクリル樹脂溶液にエピコート＃８２８を４０
０部とキシレンを４００部配合して硬化性樹脂溶液を得
た。40 minutes of Epicoat #828 was added to the obtained acrylic resin solution.
0 parts and 400 parts of xylene were blended to obtain a curable resin solution.
［試験方法］
実施例１〜３および比較例１で得た硬化性樹脂溶液を、
それぞれ２枚のガラス板に、乾燥膜厚が約５０ミクロシ
となるよう塗布し、そのうち各１枚を１００℃で３０分
間焼付け、残りの各１枚は１４０℃で３０分間焼付けた
。[Test method] The curable resin solutions obtained in Examples 1 to 3 and Comparative Example 1 were
The coating was applied to two glass plates each to a dry film thickness of about 50 microns, one of each was baked at 100°C for 30 minutes, and the remaining one was baked at 140°C for 30 minutes.
得られた焼付塗膜について、塗面状態の評価およびゲル
分率の測定を行なった。Regarding the obtained baked coating film, the coating surface condition was evaluated and the gel fraction was measured.
塗面状態二目視で評価し、異常のないものは○とした。The condition of the painted surface was evaluated with a second glance, and those with no abnormalities were rated ○.
ゲル分率ニガラス板より焼付塗膜を剥離し、その遊離塗
膜をアセトン中で、約５７
℃の還流条件下に４時間浸漬して下
記式より求めた。Gel fraction The baked paint film was peeled off from the glass plate, and the free paint film was immersed in acetone under reflux conditions at about 57°C for 4 hours, and was determined from the following formula.
浸漬後の塗膜重量
ゲル分率（％）＝ Ｘ１００浸漬前の
塗膜重量
また、実施例１〜３および比較例１で得た硬化性樹脂溶
液の貯蔵安定性を下記方法にて調べた。Weight of coating film after immersion Gel fraction (%) = X100 Weight of coating film before immersion In addition, the storage stability of the curable resin solutions obtained in Examples 1 to 3 and Comparative Example 1 was investigated by the following method.
貯蔵安定性：硬化性樹脂溶液を各々、内容積２５０ＣＧ
の密閉容器に１５０ｇずつ
入れ、４０℃で３ケ月間貯蔵を行な
った。著しい増粘、ゲル化などの異
常の認められないものを○とした。Storage stability: each curable resin solution has an internal volume of 250CG
150 g each was placed in a sealed container and stored at 40°C for 3 months. Those in which abnormalities such as significant thickening and gelation were not observed were rated as ○.
なお、これらの試験結果を第１表に 示す。The test results are shown in Table 1. show.
Claims (1)
エポキシ基とを有する数平均分子量１０００以上の硬化
性樹脂。 ２、硬化性樹脂がビニル共重合体である請求項１記載の
硬化性樹脂。 ３、ビニル共重合体が下記式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１は水素原子又はメチル基を表わす。）で
示される化合物を単量体の一成分とした共重合体である
請求項２記載の硬化性樹脂。[Claims] 1. A curable resin having a number average molecular weight of 1000 or more and having two or more carboxyl groups and two or more epoxy groups in one molecule. 2. The curable resin according to claim 1, wherein the curable resin is a vinyl copolymer. 3. The vinyl copolymer is a compound represented by the following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a hydrogen atom or a methyl group) as a monomer. The curable resin according to claim 2, which is a copolymer as a component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63335276A JPH082939B2 (en) | 1988-12-29 | 1988-12-29 | Curable resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63335276A JPH082939B2 (en) | 1988-12-29 | 1988-12-29 | Curable resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02180921A true JPH02180921A (en) | 1990-07-13 |
| JPH082939B2 JPH082939B2 (en) | 1996-01-17 |
Family
ID=18286709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63335276A Expired - Lifetime JPH082939B2 (en) | 1988-12-29 | 1988-12-29 | Curable resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082939B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994021737A1 (en) * | 1993-03-19 | 1994-09-29 | Mazda Motor Corporation | Low-solvent resin composition, low-solvent coating composition, and method of coating therewith |
| WO1998051718A1 (en) * | 1997-05-15 | 1998-11-19 | Nippon Steel Chemical Co., Ltd. | Alkali-soluble resins and image-forming material prepared by using the same |
| EP1138731A1 (en) * | 1998-08-26 | 2001-10-04 | Clariant International Ltd. | Coating composition |
| KR100642446B1 (en) * | 2004-10-15 | 2006-11-02 | 제일모직주식회사 | Thermosetting One-Solution Type Composition For Protective Film Of Color Filter And Color Filter By Using The Same |
| KR100805688B1 (en) * | 2005-09-15 | 2008-02-21 | 제일모직주식회사 | Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same |
| KR100845692B1 (en) * | 2004-12-29 | 2008-07-11 | 제일모직주식회사 | Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same |
| JP2009506153A (en) * | 2005-08-25 | 2009-02-12 | アルタナ エレクトリカル インシュレイション ゲゼルシャフト ミット ベシュレンクテル ハフツング | Coating material |
| KR100907092B1 (en) * | 2007-09-07 | 2009-07-09 | 제일모직주식회사 | Ink composition for color filter, method for manufacturing picture element of color filter, and color filter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5747365A (en) * | 1980-09-05 | 1982-03-18 | Daicel Chem Ind Ltd | Thermosetting resin composition |
| JPS61127726A (en) * | 1984-11-26 | 1986-06-16 | Mitsubishi Rayon Co Ltd | Thermosetting preform |
| JPS61130330A (en) * | 1984-11-28 | 1986-06-18 | Mitsubishi Rayon Co Ltd | Production of resin molding excellent in heat and chemical resistance |
-
1988
- 1988-12-29 JP JP63335276A patent/JPH082939B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5747365A (en) * | 1980-09-05 | 1982-03-18 | Daicel Chem Ind Ltd | Thermosetting resin composition |
| JPS61127726A (en) * | 1984-11-26 | 1986-06-16 | Mitsubishi Rayon Co Ltd | Thermosetting preform |
| JPS61130330A (en) * | 1984-11-28 | 1986-06-18 | Mitsubishi Rayon Co Ltd | Production of resin molding excellent in heat and chemical resistance |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994021737A1 (en) * | 1993-03-19 | 1994-09-29 | Mazda Motor Corporation | Low-solvent resin composition, low-solvent coating composition, and method of coating therewith |
| US5786435A (en) * | 1993-03-19 | 1998-07-28 | Mazda Motor Corporation | Low solvent composition of alicyclic epoxy oligomer |
| WO1998051718A1 (en) * | 1997-05-15 | 1998-11-19 | Nippon Steel Chemical Co., Ltd. | Alkali-soluble resins and image-forming material prepared by using the same |
| EP1138731A1 (en) * | 1998-08-26 | 2001-10-04 | Clariant International Ltd. | Coating composition |
| EP1138731A4 (en) * | 1998-08-26 | 2002-01-02 | Clariant Int Ltd | Coating composition |
| KR100642446B1 (en) * | 2004-10-15 | 2006-11-02 | 제일모직주식회사 | Thermosetting One-Solution Type Composition For Protective Film Of Color Filter And Color Filter By Using The Same |
| KR100845692B1 (en) * | 2004-12-29 | 2008-07-11 | 제일모직주식회사 | Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same |
| JP2009506153A (en) * | 2005-08-25 | 2009-02-12 | アルタナ エレクトリカル インシュレイション ゲゼルシャフト ミット ベシュレンクテル ハフツング | Coating material |
| KR100805688B1 (en) * | 2005-09-15 | 2008-02-21 | 제일모직주식회사 | Thermosetting One-Solution type Composition for Protective Film of Color Filter and Color Filter by using the Same |
| KR100907092B1 (en) * | 2007-09-07 | 2009-07-09 | 제일모직주식회사 | Ink composition for color filter, method for manufacturing picture element of color filter, and color filter |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH082939B2 (en) | 1996-01-17 |
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