JPH03185073A - Curable resin composition - Google Patents

Curable resin composition

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Publication number
JPH03185073A
JPH03185073A JP32249189A JP32249189A JPH03185073A JP H03185073 A JPH03185073 A JP H03185073A JP 32249189 A JP32249189 A JP 32249189A JP 32249189 A JP32249189 A JP 32249189A JP H03185073 A JPH03185073 A JP H03185073A
Authority
JP
Japan
Prior art keywords
group
amino group
parts
grafted
curable resin
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
Application number
JP32249189A
Other languages
Japanese (ja)
Inventor
Koichiro Saeki
康一郎 佐伯
Koji Nagaoka
長岡 宏司
Kazumoto Akasaki
赤崎 一元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Priority to JP32249189A priority Critical patent/JPH03185073A/en
Publication of JPH03185073A publication Critical patent/JPH03185073A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To obtain the subject curable resin composition free from influences of humidity and water, excellent in workability, reactivity, weather resistance, chemical resistance, etc., and suitable for a coating material, an adhesive, etc., by blending a polymer having a grafted primary (secondary) amino group with a specified compound. CONSTITUTION:(A) A polymer having a grafted primary or secondary amino group is blended with (B) a compound, e.g. an alkylacrylamide glycolate alkyl ether represented by formula I (R1 is H or 1-2C alkyl; R2 and R3 are 1-4C alkyl) and having an unsaturated bond capable of Michael addition with an amino group and an active ester group capable of interchange reaction with an amino group or a compound expressed by formula II (R4 is same as R1; R5 is alcohol, phenol, amine or hydroxylamine residue capable of interchange with amino group at ordinary temperature) and having an unsaturated bond capable of Michael addition with an amino group and an active ester group capable of interchange reaction with an amino group or an amide group, e.g. N-(meth) acryloxysuccinamide, thus obtaining the objective curable resin composition.

Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は(a)グラフト一級アミノ基又はグラフト二級
アミノ基を持ったポリマーと、(b)−分子内に少なく
とも、アミノ基とマイゲル付加する不飽和結合と、アミ
ノ基と交換反応する活性エステル基又は、アミド基を有
する化合物よりなる硬化性樹脂組成物に関するものであ
る。
Detailed Description of the Invention [Industrial Application Field] The present invention relates to (a) a polymer having a grafted primary amino group or a grafted secondary amino group, and (b) a polymer having at least an amino group and a Migel addition in the molecule The present invention relates to a curable resin composition comprising a compound having an unsaturated bond, and an active ester group or amide group that undergoes an exchange reaction with an amino group.

[従来の技術] 従来より、硬化性樹脂組成物としては、ポリエステルポ
リオールやアクリルポリオール等の多価アルコール化合
物と多価インシアネート化合物との硬化性樹脂組成物や
、ポリアミンやポリアミドアミン等の多価アミン化合物
とエポキシ樹脂との硬化性樹脂組成物が、塗料、接着剤
、表面処理剤、成型物、発泡樹脂等多岐用途に利用され
ている。
[Prior Art] Conventionally, curable resin compositions include curable resin compositions of polyhydric alcohol compounds such as polyester polyols and acrylic polyols and polyvalent incyanate compounds, and curable resin compositions of polyhydric incyanate compounds such as polyamines and polyamide amines. Curable resin compositions of amine compounds and epoxy resins are used in a wide variety of applications, including paints, adhesives, surface treatment agents, molded products, and foamed resins.

[発明が解決しようとする問題点] しかし、多価アルコール化合物と多価インシアネート化
合物との硬化性樹脂組成物においては、その反応性、耐
候性、汎用性等の特徴はめるものの、イソシアネート化
合物の毒性の問題、水ε反応するため基本的には水系で
使用できないという問題及び、溶剤系又は無溶剤系で使
用する場合でも、水、湿気等によるイソシアネート化合
物の副反応をおさえるための管理上の問題があり、これ
らの問題点は未だ解決されていない、多価アミン化合物
とエポキシ樹脂との硬化性樹脂組成物においては、その
反応性、耐薬品性、汎用性等の特徴はあるものの耐候性
、低温硬化性等に問題があった。
[Problems to be Solved by the Invention] However, although the curable resin composition of a polyhydric alcohol compound and a polyhydric incyanate compound has characteristics such as its reactivity, weather resistance, and versatility, Problems of toxicity, the problem that it cannot be used in aqueous systems because it reacts with water, and management issues to suppress side reactions of isocyanate compounds due to water, moisture, etc. even when used in solvent or non-solvent systems. Although there are some problems in curable resin compositions of polyvalent amine compounds and epoxy resins that have not yet been resolved, they have characteristics such as reactivity, chemical resistance, and versatility, but they do not have good weather resistance. , there were problems with low-temperature curability, etc.

c問題点を解決するための手段〕 本発明者らは、多価アルコール化合物と多価イソシアネ
ート化合物との硬化性樹脂組成物や、多価アミン化合物
とエポキシ樹脂との硬化性樹脂組成物に見られるような
上記問題点が無い硬化性樹脂組成物について鋭意検討し
た結果、本発明に到達した。
c. Means for Solving Problems] The present inventors have discovered a curable resin composition of a polyhydric alcohol compound and a polyvalent isocyanate compound, and a curable resin composition of a polyvalent amine compound and an epoxy resin. As a result of intensive research into curable resin compositions that do not have the above-mentioned problems, the present invention was achieved.

すなわち、本発明は、(a)グラフト一級アミノ基又は
、グラフト二級アミノ基を持ったポリマーおよび、 (b)−数式(I) 0  0R2 II CH2= C−C−NH−C−C−0−R31 R10 ・・・ (I) (式中、R1は水素および炭素原子1〜2の低級アルキ
ル基より成る群より選らばれ、R2およびR3は各々独
立に炭素原子1〜4の低級アルキル基より戒る群より選
らばれる。)で表示されるアミン基とマイケル付加する
不飽和結合と、アミノ基と交換反応する活性エステル基
を有する金物又は 一般式(II) CI+2 = C−C−R5 ・・・ (II) (式中、R4は水素および炭素原子1〜2の低級アルキ
ル基より成る群より選らばれ、R5は常温でアミノ基と
交換反応を起こし得るアルコール、フェノール、アミン
、ヒドロキシルアミン残基より成る群より選らばれる。
That is, the present invention provides (a) a polymer having a grafted primary amino group or a grafted secondary amino group, and (b) - Formula (I) 0 0R2 II CH2= C-C-NH-C-C-0 -R31 R10 ... (I) (wherein R1 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R2 and R3 are each independently selected from the group consisting of a lower alkyl group having 1 to 4 carbon atoms) A metal product having an unsaturated bond that undergoes Michael addition with an amine group and an active ester group that undergoes an exchange reaction with an amino group represented by the formula (II) CI+2 = C-C-R5... - (II) (wherein R4 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R5 is an alcohol, phenol, amine, or hydroxylamine residue that can undergo an exchange reaction with an amino group at room temperature) selected from the group consisting of.

) で表示されるアミノ基とマイケル付加する不飽和結合と
、アミノ基と交換反応する活性エステル基又は、アミド
基を有する化合物よりなることを特徴とする硬化性樹脂
組成物に関するものである。
The present invention relates to a curable resin composition characterized by comprising a compound having an unsaturated bond that undergoes a Michael addition with an amino group represented by the following formula, and an active ester group or amide group that undergoes an exchange reaction with the amino group.

更に詳しくは、本発明に用いる(a)グラフト一級アミ
ノ基または、二級アミノ基を持ったポリマーとは、例え
ば、米国特許第3228823号、米国特許第3467
611号、米国特許第4104230号、特開昭63−
56549号等に記載されているカルボキシル基を含有
する不飽和単量体と、その他共重合性不飽和単量体を共
重合して得られるポリマーのカルボキシル基をアルキレ
ンイミンと反応して得られるグラフト一級アミノ基又は
、グラフト二級アミノ基を持ったポリマー又は特開昭6
1−136515号等に記載されている側鎖にエポキシ
基を持ったポリマーにアンモニアを反応して得られるグ
ラフト一級アミン基又は、グラフト二級アミノ基を持っ
たポリマー、又は米国特許第3037969号、米国特
許第3497485号等に記載されているアクリロキシ
アルキルーゲチミン又は、アクリロキシアルキロキシア
ルキルーゲチミン等の重合性不飽和単量体のホモポリマ
ー又は、これらケチミン含有重合性不飽和単量体と、そ
の他共重合性不飽和単量体とのコポリマーを加水分解し
て得られるグラフト一級アミノ基を持ったポリマー、又
は特公昭62−17601号、特公昭63−61321
号等に記載されているカルボキシル基を含有する不飽和
単量体と、その他共重合性不飽和単量体を共重合して得
られるポリマーのカルボキシル基を、脂肪族アミノ基を
有するポリアミン又は、脂肪族アミノ基を有し及び少な
くとも一つのエーテル基を有するポリアミンを反応させ
て得られるグラフト一級アミノ基を持ったポリマー、又
は特開昭54−110248号、特開昭54−1444
32号、特開昭57−3850号、特開昭62−727
42号等に記載されているアルド基またはケト基に限定
されるカルボニル基を含有するポリマーに、ビドラジン
ヒドラートに代表される少なくとも2個のビドラジン残
基を有するビドラジン誘@体を反応させて得られるグラ
フト一級アミノ基を持ったポリマー、または特公昭62
−4047号に記載されているアミド基またはエステル
基を含有するポリマーに、ビドラジンヒドラートを反応
させて得られるグラフト一級アミノ基を持ったポリマー
米国特許第4414250号に記載されているアンハイ
ドライド基を含有したポリマーにポリアミンを反応させ
て得られるグラフト一級アミノ基又は、グラフト二級ア
ミノ基を持ったポリマー、その他ポリアリルアミンや、
特開昭61−51006号等に記載されている種々合成
方法で得られるビニルアミン等のグラフト一級アミノ基
を持ったポリマーである。
More specifically, the (a) polymer having a grafted primary amino group or secondary amino group used in the present invention includes, for example, US Pat. No. 3,228,823 and US Pat. No. 3,467.
No. 611, U.S. Patent No. 4,104,230, JP-A-63-
Graft obtained by reacting the carboxyl group of a polymer obtained by copolymerizing an unsaturated monomer containing a carboxyl group described in No. 56549 etc. with other copolymerizable unsaturated monomers with an alkylene imine. A polymer having a primary amino group or a grafted secondary amino group or JP-A No. 6
A polymer having a grafted primary amine group or a grafted secondary amino group obtained by reacting a polymer having an epoxy group in a side chain with ammonia as described in No. 1-136515, etc., or a polymer having a grafted secondary amino group, or US Pat. Homopolymers of polymerizable unsaturated monomers such as acryloxyalkylugetimine or acryloxyalkyloxyalkylugetimine described in U.S. Patent No. 3,497,485, etc., or these ketimine-containing polymerizable unsaturated monomers , a polymer having a grafted primary amino group obtained by hydrolyzing a copolymer with other copolymerizable unsaturated monomers, or Japanese Patent Publication No. 62-17601, Japanese Patent Publication No. 63-61321
The carboxyl group of the polymer obtained by copolymerizing the unsaturated monomer containing a carboxyl group described in the above, and other copolymerizable unsaturated monomers, or the polyamine having an aliphatic amino group, A polymer having a grafted primary amino group obtained by reacting a polyamine having an aliphatic amino group and at least one ether group, or JP-A-54-110248, JP-A-54-1444
No. 32, JP-A-57-3850, JP-A-62-727
A hydrazine derivative having at least two hydrazine residues represented by hydrazine hydrate is reacted with a polymer containing a carbonyl group limited to an aldo group or a keto group as described in No. 42 etc. Polymers with grafted primary amino groups obtained or Japanese Patent Publication No. 1983
A polymer having a grafted primary amino group obtained by reacting a polymer containing an amide group or an ester group with hydrazine hydrate as described in US Pat. No. 4,414,250. A polymer having a grafted primary amino group or a grafted secondary amino group obtained by reacting a polyamine with a polymer containing
It is a polymer having a grafted primary amino group such as vinylamine obtained by various synthesis methods described in JP-A No. 61-51006 and the like.

本発明で使用する(b)−分子内に少なくとも、アミノ
基とマイゲル付加する不飽和結合と、アミン基と交換反
応する活性エステル基を有する化合物とは、 一般式(I) 0  0R2 II CI+2=C−C−NH−C−C−0−R31 R20 ・・・ (I> (式中、R1は水素および炭素原子1〜2の低級アルキ
ル基より成る群より選らばれ、R2およびR3は各々独
立に炭素原子1〜4の低級アルキル基より成る群より選
ばれる。) で表示されるアミノ基とマイゲル付加する不飽和結合と
、アミノ基と交換反応する活性エステル基を有する化合
物又は 一般式(II) ・・・ (n) (式中、R4は水素および炭素原子1〜2の低級アルキ
ル基より成る群より選らばれ、R5は常温で一級アミノ
基と交換反応を起こし得るアルコール、フェノール、ア
ミン、ヒドロキシルアミン残基より成る群より選らばれ
る。) で表示されるアミノ基とマイケル付加する不飽和結合と
、アミノ基と交換反応する活性エステル基又は、アミド
基を有する化合物であり、−数式(I)で示される化合
物としては、具体的には米国特許第4443623号等
に製造方法が記載されているアルキルアクリルアミドグ
リコレートアルキルエーテル類であり、例えばメチルア
クリルアミドグリコレートメチルエーテル、エチルアク
リルアミドグリコレートエチルエーテル、ブチルアクリ
ルアミドグリコレートブチルエーテル等が挙げられる。
The compound (b) used in the present invention that has at least an unsaturated bond that undergoes a migel addition with an amino group and an active ester group that exchanges with an amine group in its molecule has the following general formula (I) 0 0R2 II CI+2= C-C-NH-C-C-0-R31 R20... (I> (wherein, R1 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R2 and R3 are each independently is selected from the group consisting of lower alkyl groups having 1 to 4 carbon atoms in ) ... (n) (wherein R4 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R5 is an alcohol, phenol, amine, which can undergo an exchange reaction with a primary amino group at room temperature, (I ) Examples of the compound include alkyl acrylamide glycolate alkyl ethers whose manufacturing method is described in U.S. Pat. , butylacrylamide glycolate butyl ether, and the like.

−数式(II)で示される化合物としては、Po ] 
yme r、13.462〜464(1972)に記載
されているN−(メタ)アクリロキシスクシノアミドや
、J、PolymerSci、、12,553〜559
 (1974)に記載されている1−(メタ)アクリロ
イルベンゾトリアゾールや、J、Polmer  Sc
i。
- As a compound represented by formula (II), Po ]
ymer, 13.462-464 (1972), and N-(meth)acryloxysuccinoamide described in J. Polymer Sci., 12,553-559.
(1974) and 1-(meth)acryloylbenzotriazole described in J. Polmer Sc.
i.

12.2453〜2452 (1974)1− (メタ
)アクリロイルイミダゾールや、Makromof  
Chem、172.27〜45(1973に記載されて
いる2、4.5−トリクロロフェノール(メタ〉アクリ
レート、4−ニトロフェニル(メタ)アクリレート等の
電子吸引基を持ったフェノールの(メタ)アクリル酸エ
ステル類が挙げられる。
12.2453-2452 (1974) 1-(meth)acryloyl imidazole and Makromof
Chem, 172.27-45 (1973; Examples include esters.

本発明の硬化機構は、例えば、メチルアクリルアミドグ
リコレートメチルエーテルを使用した場合は以下の一般
式で表わされる。
The curing mechanism of the present invention is expressed by the following general formula when, for example, methyl acrylamide glycolate methyl ether is used.

0C■3 1 OCH3 すなわち、メチルアクリルアミドグリコレートメチルエ
ーテルの不飽和結合部は、グラフト一級アミノ基又は、
グラフト二級アミノ基の活性水素とマイケル付加的に反
応し、活性エステル部は、交換反応にてアミド結合が生
じ三次元的に架橋する硬化81椙を有する。−数的にア
ミノ基の活性水素と不飽和結合部とのマイゲル付加反応
速度は速く、低温でも進行し、この反応により生じた結
合は、硬化物の耐薬品性向上にはあまり寄与できないも
のの優れた耐候性、フレキシビリティを与える。アミノ
基の活性水素と活性エステル部の交換反応はマイケル付
加程の反応速度は速くないものの、生じたアミド結合は
その凝集力より硬化物に優れた耐薬品性、強靭性を与え
る0本発明の硬化性樹脂組成物は以上のような硬化機構
より二種類の反応が関与しており、それぞれの特徴が生
かされた硬化物を提供できる。
0C■3 1 OCH3 That is, the unsaturated bond of methyl acrylamide glycolate methyl ether is a grafted primary amino group or
The active ester part reacts in a Michael addition manner with the active hydrogen of the grafted secondary amino group, and the active ester part has a hardening time of 81 cm, which is three-dimensionally crosslinked by forming an amide bond in the exchange reaction. - The Migel addition reaction rate between the active hydrogen of the amino group and the unsaturated bond is numerically fast and proceeds even at low temperatures, and the bonds formed by this reaction are excellent although they do not contribute much to improving the chemical resistance of the cured product. Provides weather resistance and flexibility. Although the reaction rate of the exchange reaction between the active hydrogen of the amino group and the active ester moiety is not as fast as that of Michael addition, the resulting amide bond gives the cured product excellent chemical resistance and toughness due to its cohesive force. In the curable resin composition, two types of reactions are involved in the curing mechanism as described above, and a cured product that takes advantage of the characteristics of each can be provided.

本発明の硬化性樹脂組成物の硬化物物性の特徴を発現す
るためには、上記硬化機構から明らかなようにアミノ基
の活性水素2個につき、−数式(I)又は、−数式(n
)であられされるアミノ基の活性水素とマイゲル付加す
る不飽和結合部と、アミノ基の活性水素と交換反応する
活性エステル又は、活性アミド部を持った化合物−分子
とが理論当量であり、ごれを基準に、以下のモル比で使
用できる。
In order to express the characteristics of the physical properties of the cured product of the curable resin composition of the present invention, as is clear from the above-mentioned curing mechanism, for each two active hydrogens of the amino group, - formula (I) or - formula (n
) is the theoretical equivalent of the unsaturated bond that undergoes Migel addition with the active hydrogen of the amino group, and the compound-molecule having an active ester or active amide moiety that exchange-reacts with the active hydrogen of the amino group. Based on this, the following molar ratios can be used.

(−数式(I)又は−数式(n)のモル数)/(活性ア
ミン水素モル数)=0.1〜2.0であり、更に好まし
くは、062〜1.0のモル比の範囲である。
(-number of moles of formula (I) or -formula (n))/(number of moles of active amine hydrogen) = 0.1 to 2.0, more preferably a molar ratio of 062 to 1.0. be.

[作 用] 本発明は、(a)グラフト一級アミノ基又は、グラフト
二級アミノ基を持ったポリマーおよび、(b)−数式(
I) 0  0R2 1 0H2= C−C−NH−C−C−0−R31 R40 ・・・<I) (式中、R1は水素および炭素原子1〜2の低級アルキ
ル基より成る群より選らばれ、R2およびR3は各々独
立に炭素原子1〜4の低級アルキル基より成る群より選
らばれる。〉で表示されるアミノ基とマイケル付加する
不飽和結合と、アミノ基と交換反応する活性エステル基
をを有する化合物又は 一般式(n) 1 CH2= C−C−R5 ・・・ (n) (式中、R4は水素および炭素原子1〜2の低級アルキ
ル基より成る群より選らばれ、R5は常温で一級アミノ
基と交換反応を起こし得るアルコール、フェノール、ア
ミン、ヒドロキシルアミン残基より成る群より選らばれ
る。) で表示されるアミノ基とマイケル付加する不飽和結合と
、アミノ基と交換反応する活性エステル基又は、アミド
基を有する化合物よりなることを特徴とする硬化性樹脂
組成物を提供することにより、湿度等の影響を受けず、
優れた作業性、反応性を有し、耐薬品性、耐候性、汎用
性等に特徴を有する硬化性樹脂組成物を提供できる。更
にこの硬化性樹脂組成物は、塗料、接着剤、表面処理剤
、成型物、発泡樹脂等多岐用途に利用され得る。
[Function] The present invention provides (a) a polymer having a grafted primary amino group or a grafted secondary amino group, and (b) a polymer having the formula (
I) 0 0R2 1 0H2 = C-C-NH-C-C-0-R31 R40...<I) (wherein R1 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms) , R2 and R3 are each independently selected from the group consisting of lower alkyl groups having 1 to 4 carbon atoms. or a compound having the general formula (n) 1 CH2= C-C-R5... (n) (wherein R4 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R5 is (selected from the group consisting of alcohol, phenol, amine, and hydroxylamine residues that can undergo an exchange reaction with a primary amino group.) An unsaturated bond that forms a Michael addition with an amino group represented by By providing a curable resin composition characterized by comprising a compound having an ester group or an amide group, it is not affected by humidity etc.
It is possible to provide a curable resin composition that has excellent workability and reactivity, and has characteristics such as chemical resistance, weather resistance, and versatility. Furthermore, this curable resin composition can be used in a wide variety of applications such as paints, adhesives, surface treatment agents, molded products, and foamed resins.

[実 施 例] 以下、実施例をあげて本発明の実施の態様を具体的に例
示して説明する9本発明はこれらの実施例になんら限定
されるものではない。
[Examples] Hereinafter, nine embodiments of the present invention will be specifically illustrated and explained using Examples.The present invention is not limited to these Examples in any way.

なお、実施例において部は、重量部を示し、百分率(%
)は重量%を示す。
In the examples, parts indicate parts by weight, and percentages (%
) indicates weight %.

参考例1 撹拌器、還流冷却器、温度計、窒素導入管および滴下ロ
ートを備えたIJのフラスコにイソプロピルアルコール
336部とトルエン224部を仕込んだ後、窒素を導入
しつつ80℃に昇温した。
Reference Example 1 After charging 336 parts of isopropyl alcohol and 224 parts of toluene into an IJ flask equipped with a stirrer, reflux condenser, thermometer, nitrogen introduction tube, and dropping funnel, the temperature was raised to 80°C while introducing nitrogen. .

メタクリル酸72部、ブチルアクリレート120部、ス
チレン48部およびアゾビスイソブチロニトリル9.6
部からなる重合性単量体混合物を2時間にわたって滴下
した0滴下終了後、更に80℃で6時間熟成を行い冷却
し、不揮発分30%のアクリル共重合体を得た0次いで
、この共重合体に25℃でエチレンイミン36部を添加
し、1時間撹拌後75℃に昇温し、5時間反応させた0
反応終了後、フラスコに蒸留装置を装着し、減圧下に加
熱しながら流出分をトルエンで補充しつつ、イングロビ
ルアルコールを未反応のエチレンイミンと共に系外に流
出させた。残存のエチレンイミンを完全に除去した後、
メチルイソブチルゲトンを添加し不揮発分を30%に調
製しグラフトアミン含有アクリル共重合体を得た。
72 parts of methacrylic acid, 120 parts of butyl acrylate, 48 parts of styrene, and 9.6 parts of azobisisobutyronitrile.
After dropping a polymerizable monomer mixture consisting of 30% and 50% over 2 hours, the copolymer was further aged at 80°C for 6 hours and cooled to obtain an acrylic copolymer with a non-volatile content of 30%. 36 parts of ethyleneimine was added to the mixture at 25°C, and after stirring for 1 hour, the temperature was raised to 75°C and reacted for 5 hours.
After the reaction was completed, the flask was equipped with a distillation device, and while heating under reduced pressure, the effluent was replenished with toluene, and Inglovil alcohol was flowed out of the system together with unreacted ethyleneimine. After completely removing the remaining ethyleneimine,
Methyl isobutyl getone was added to adjust the nonvolatile content to 30% to obtain a grafted amine-containing acrylic copolymer.

参考例2 参考例1と同様なフラスコにイソプロピルアルコール2
80部とn−ブトキシェタノール124゜6部を仕込ん
だ後、窒素を導入しつつ80℃に昇温した。メタクリル
980.5部、メチルメタクリレート63部、ブチルア
クリレート136.5部、スチレン70部およびアゾビ
スイソブチロニトリル9部からなる重合性単量体混合物
を2時間にわたって滴下した0滴下終了後、更に80℃
で6時間熟成を行ない冷却し、不揮発分46.4%の重
合物を得た。この重合物にトリエチルアミン33部を添
加し均一に混合後、エチレンイミン37%水溶液61.
6部を滴下し80℃で4時間反応後、更にトリエチルア
ミン8.4部と脱イオン水75部を添加して、不揮発分
401%のグラフトアミン含有水溶性アクリル共重合体
を得た。
Reference Example 2 In a flask similar to Reference Example 1, add 2 isopropyl alcohol.
After charging 80 parts and 124.6 parts of n-butoxyshetanol, the temperature was raised to 80°C while nitrogen was introduced. A polymerizable monomer mixture consisting of 980.5 parts of methacrylate, 63 parts of methyl methacrylate, 136.5 parts of butyl acrylate, 70 parts of styrene and 9 parts of azobisisobutyronitrile was added dropwise over 2 hours. 80℃
The mixture was aged for 6 hours and cooled to obtain a polymer with a non-volatile content of 46.4%. After adding 33 parts of triethylamine to this polymer and mixing uniformly, 61 parts of a 37% ethyleneimine aqueous solution was added.
After dropping 6 parts of the mixture and reacting at 80° C. for 4 hours, 8.4 parts of triethylamine and 75 parts of deionized water were further added to obtain a grafted amine-containing water-soluble acrylic copolymer with a nonvolatile content of 401%.

参考例3 参考例1と同様なフラスコに、脱イオン水400部とア
ニオン系活性剤(25%水溶液)40部を仕込んだ後、
窒素を導入しつつ68℃に昇温した。アクリル酸48部
、2−エチルへキシルアクリレート160部、スチレン
192部からなる重合性単量体混合物40部をフラスコ
内に添加し15分撹拌を行なった後、1.75%の過酸
化水素水4.6部と3%L−アスコルビン’fllyk
J液4゜2部を添加し重合を開始した0重合開始15分
後から残りの重合性単量体混合物を90分にわたって均
一に滴下した。この間1.75%の過酸化水素水41部
と3%L−アスコルビン酸水溶液37部を10分毎に重
合性混合物の滴下終了まで分割してフラスコ内に滴下し
た0滴下終了後、1時間熟成を行ない冷却し、不揮発分
44.5%のエマルジョンを得た0次にこのエマルジョ
ン150部に、脱イオン水40.6部を加え均一に混合
した。
Reference Example 3 After charging 400 parts of deionized water and 40 parts of an anionic activator (25% aqueous solution) into a flask similar to Reference Example 1,
The temperature was raised to 68° C. while introducing nitrogen. After adding 40 parts of a polymerizable monomer mixture consisting of 48 parts of acrylic acid, 160 parts of 2-ethylhexyl acrylate, and 192 parts of styrene into a flask and stirring for 15 minutes, 1.75% hydrogen peroxide solution was added. 4.6 parts and 3% L-ascorbine'fllyk
15 minutes after the start of polymerization by adding 4.2 parts of Solution J, the remaining polymerizable monomer mixture was uniformly added dropwise over 90 minutes. During this time, 41 parts of 1.75% hydrogen peroxide solution and 37 parts of 3% L-ascorbic acid aqueous solution were added dropwise into the flask every 10 minutes until the dropwise addition of the polymerizable mixture was completed. 40.6 parts of deionized water was added to 150 parts of this emulsion and uniformly mixed.

10%エチレンイミン水溶液47.8部を添加し50℃
で2時間反応して、不揮発分30%のグラフトアミン含
有エマルジョンを得た。
Add 47.8 parts of 10% ethyleneimine aqueous solution and heat to 50°C.
The mixture was reacted for 2 hours to obtain a grafted amine-containing emulsion with a non-volatile content of 30%.

参考例4 実施例1と同様なフラスコに、イソプロピルアルコール
520部を仕込んだ後、窒素を導入しつつ80℃に昇温
した。2−((1,3−ジメチルブチル)イミノ)エチ
ルメタクリレート50部、2−エチルへキシルアクリレ
ート108部、スチレン147部およびアゾビスイソブ
チロニトリル12.2部からなる重合性単量体混合物を
2時間にわたって滴下した0滴下終了後、更に80℃で
6時間熟成を行い冷却し、水を4.3部加え不揮発分3
4%のグラフトアミン含有アクリル共重合体を得た。
Reference Example 4 After 520 parts of isopropyl alcohol was charged into the same flask as in Example 1, the temperature was raised to 80° C. while introducing nitrogen. A polymerizable monomer mixture consisting of 50 parts of 2-((1,3-dimethylbutyl)imino)ethyl methacrylate, 108 parts of 2-ethylhexyl acrylate, 147 parts of styrene, and 12.2 parts of azobisisobutyronitrile was prepared. After 0 drops of water were added over 2 hours, it was further aged at 80°C for 6 hours, cooled, and 4.3 parts of water was added to reduce the non-volatile content to 3.
An acrylic copolymer containing 4% grafted amine was obtained.

実施例1 参考例1で得られたグラフトアミン含有アクリル共重合
体を主剤として、主剤100部にMAGME(商品名:
米国アメリカンサイアナミツド社製、メチルアクリルア
ミドグリコレートメチルエーテル)の30%ブタノール
溶液30.2部を添加し均一に混合した。この混合物を
用いて以下に示す試験を行った。結果を表−1に示す。
Example 1 Using the grafted amine-containing acrylic copolymer obtained in Reference Example 1 as a main ingredient, MAGME (trade name:
30.2 parts of a 30% butanol solution of methyl acrylamide glycolate methyl ether (manufactured by American Cyanamid, Inc.) was added and mixed uniformly. The following tests were conducted using this mixture. The results are shown in Table-1.

[塗膜の硬化性試験および評価基準] (1)乾燥性: 上記混合物をガラス板上に75μmア
プリゲータ−を用い塗布 し、25℃、相対湿度60%に おいてRCCトドライングメー タにて指触乾燥および硬化乾燥 時間で評価した。
[Coating film curing test and evaluation criteria] (1) Drying property: The above mixture was applied onto a glass plate using a 75 μm applicator, and dried to the touch using an RCC drying meter at 25°C and 60% relative humidity. Evaluation was made based on curing and drying time.

(2)鉛筆硬度:(1)と同様に上記混合物を塗布して
7日間養生後の塗膜の2 50gr荷重における鉛筆の傷 付硬度を、JIS  K−540 0に準じて鉛筆引っかき試験機 を用いて測定した。
(2) Pencil hardness: After applying the above mixture and curing it for 7 days in the same manner as in (1), the pencil scratch hardness at a load of 250 gr was measured using a pencil scratch tester according to JIS K-540 0. It was measured using

(3)ゲル分率二上記混合物をテフロン板上に適当量塗
布して7日間養生後塗膜 をはがし取り、ソックスレー抽 出器をもちいてアセトンで4時 間抽出を行いゲル分率を測定し た。
(3) Gel Fraction 2 An appropriate amount of the above mixture was applied onto a Teflon plate, and after 7 days of aging, the coating was peeled off and extracted with acetone using a Soxhlet extractor for 4 hours to measure the gel fraction.

また、上記主剤100部に酸化チタン14部とガラスピ
ーズを適当量添加して、ペイントシェーカーを用いて2
時間分散混合を行った後、700cpsになる様に希釈
した。これに上記混合物と同様にMAGMEを添加し、
均一に混合して塗料配合物を得た。この配合物を用いて
以下に示す試験を行った。結果を表−1に示す。
In addition, 14 parts of titanium oxide and appropriate amounts of glass beads were added to 100 parts of the above base material, and 2 parts were added using a paint shaker.
After time-dispersed mixing, the mixture was diluted to 700 cps. Add MAGME to this in the same way as the above mixture,
A paint formulation was obtained by uniformly mixing. The following tests were conducted using this formulation. The results are shown in Table-1.

[塗膜の性能試験および評価基準] (4)耐候性 :上記配合物をステンレス鋼板上に75
μmアプリケータにて塗 布し、25℃、相対湿度60% で7日間養生後JIS  K−5 400に準じてサンシャイン型 ウェザオメターで240時間照 射した後の塗膜の状態を観測し た。
[Performance test and evaluation criteria for coating film] (4) Weather resistance: The above formulation was applied to a stainless steel plate at 75%
The coating was applied with a μm applicator, cured for 7 days at 25° C. and 60% relative humidity, and then irradiated for 240 hours with a sunshine weather meter according to JIS K-5 400. The state of the coating film was then observed.

[色差] ◎;変化無し ○:僅かに変色 Δ;少し変色 ×:変色 [光沢保持率] 初期光沢からの光沢度の保持率 で表示する。[Color difference] ◎;No change ○: Slight discoloration Δ: Slight discoloration ×: Discoloration [Gloss retention rate] Gloss retention rate from initial gloss Display in .

(5)耐溶剤性:(1)と同様に塗布しに塗膜をメチル
エチルゲトンを用いてラ ピングを行い、塗膜が変質する までのラビング回数を測定した。
(5) Solvent resistance: After coating in the same manner as in (1), the coating film was lapped using methyl ethyl getone, and the number of times of rubbing until the coating film deteriorated was measured.

実施例2 参考例2で得られたグラフトアミン含有水溶性アクリル
共重合体を主剤として、主剤100部にMAGMEの3
0%水溶液17.4部を添加し均一に混合した。この混
合物を用いた以外は実施例1と同様に試験を行った。結
果を表−1に示す。
Example 2 Using the grafted amine-containing water-soluble acrylic copolymer obtained in Reference Example 2 as a main ingredient, 3 parts of MAGME were added to 100 parts of the main ingredient.
17.4 parts of a 0% aqueous solution was added and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used. The results are shown in Table-1.

また、上記主剤100部に酸化チタン16部とガラスピ
ーズを適当量添加して、実施例1と同様な操作にて塗料
配合物を得た。この配合物を用いた以外は実施例1と同
様に試験を行った。結果を表−1に示す。
Further, a coating composition was obtained in the same manner as in Example 1 by adding 16 parts of titanium oxide and appropriate amounts of glass beads to 100 parts of the above base resin. The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

実施例3 参考例3で得られたグラフトアミン含有エマルジョンを
主剤として、主剤100部に、MAGMEの30%水溶
液14.4部を添加し均一に混合した。この混合物を用
いた以外は実施例1と同様に試験を行った。結果を表−
1に示す。
Example 3 Using the grafted amine-containing emulsion obtained in Reference Example 3 as a main ingredient, 14.4 parts of a 30% aqueous solution of MAGME was added to 100 parts of the main ingredient and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used. Display the results -
Shown in 1.

また、上記主剤100部と酸化チタン18部を混合し、
さらにMAGMEの30%水溶液14゜4部を添加し均
一に混合して塗料配合物を得た。
In addition, 100 parts of the above base agent and 18 parts of titanium oxide were mixed,
Further, 14.4 parts of a 30% aqueous solution of MAGME was added and mixed uniformly to obtain a paint formulation.

この配合物を用いた以外は、実施例1と同様に試験を行
った。結果を表−1に示す。
The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

実施例4 参考例1で得られたグラフトアミン含有アクリル共重合
体100部に対して1−メタクリロイルオキシベンゾト
リアゾールの30%酢酸エチル溶液35.4部を添加す
る以外は、実施例1と同様に混合物および塗料配合物を
調製し試験を行った。
Example 4 Same as Example 1 except that 35.4 parts of a 30% ethyl acetate solution of 1-methacryloyloxybenzotriazole was added to 100 parts of the grafted amine-containing acrylic copolymer obtained in Reference Example 1. Mixtures and paint formulations were prepared and tested.

結果を表−1に゛示す。The results are shown in Table-1.

実施例5 参考例4で得られたグラフトアミン含有アクリル共重合
体を主剤として、主剤100部にMAGMEの30%イ
ソプロピルアルコール溶液8.4部を添加し均一に混合
した。この混合物を用いた以外は実施例1と同様に試験
を行った。結果を表−1に示す。
Example 5 Using the grafted amine-containing acrylic copolymer obtained in Reference Example 4 as a main ingredient, 8.4 parts of a 30% isopropyl alcohol solution of MAGME was added to 100 parts of the main ingredient and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used. The results are shown in Table-1.

また、上記主剤100部に酸化チタン16部とガラスピ
ーズを適当量添加して、実施例1と同様な操作にて、塗
料配合物を得た。この配合物を用いた以外は実施例1と
同様に試験を行った。結果を表−1に示す。
Further, a coating composition was obtained in the same manner as in Example 1 by adding 16 parts of titanium oxide and appropriate amounts of glass beads to 100 parts of the above base resin. The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

実施例6 ヒドラジン誘導体変成グラフトアミン含有アクリル系共
重合体(アクロナールYJ−2715D;油化バディッ
シュ)を主剤として、主剤100部にMAGMEの30
%水溶液11.9部を添加し均一に混合した。この混合
物を用いた以外は実施例1と同様に試験を行った。結果
を表−1に示す。
Example 6 A hydrazine derivative-modified graft amine-containing acrylic copolymer (Acronal YJ-2715D; Yuka Badish) was used as the main ingredient, and 30 parts of MAGME was added to 100 parts of the main ingredient.
% aqueous solution was added and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used. The results are shown in Table-1.

また、上記主剤100部と酸化チタン18部を混合し、
さらにMAGMEの30%水溶液11゜9部を添加し均
一に混合して塗料配合物を得た。
In addition, 100 parts of the above base agent and 18 parts of titanium oxide were mixed,
Furthermore, 11.9 parts of a 30% aqueous solution of MAGME was added and mixed uniformly to obtain a coating composition.

この配合物を用いた以外は実施例1と同様に試験を行っ
た。結果を表−1に示す。
The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

比較例1 参考例1で得られたグラフトアミン含有アクリル共重合
体100部に対してビスフェノールA型ジグリシジルエ
ーテル、エピコート828(商品名:油化シェル(株)
製エポキシ化合物)を19゜9部添加する以外は実施例
1と同様に混合物および塗料配合物を調製し試験を行っ
た。結果を表−1に示す。
Comparative Example 1 Bisphenol A diglycidyl ether, Epicoat 828 (trade name: Yuka Shell Co., Ltd.) was added to 100 parts of the grafted amine-containing acrylic copolymer obtained in Reference Example 1.
Mixtures and coating formulations were prepared and tested in the same manner as in Example 1, except that 19.9 parts of epoxy compound) was added. The results are shown in Table-1.

比較例2 市販ポリアミドアミンを主剤として、主剤100部にエ
ピコート828を122部添加し均一に混合した。この
混合物を用いた以外は実施例1と同様に試験を行った。
Comparative Example 2 Using commercially available polyamide amine as the main ingredient, 122 parts of Epikote 828 was added to 100 parts of the main ingredient and mixed uniformly. The test was conducted in the same manner as in Example 1 except that this mixture was used.

結果を表−1に示す。The results are shown in Table-1.

また、上記主剤100部に酸化チタン18部とガラスピ
ーズを適当量添加して、実施例1と同様な操作にて塗料
配合物を得た。この配合物を用いた以外は実施例1と同
様に試験を行なった。結果を表−1に示す。
Further, a coating composition was obtained in the same manner as in Example 1 by adding 18 parts of titanium oxide and appropriate amounts of glass beads to 100 parts of the above base resin. The test was conducted in the same manner as in Example 1 except that this formulation was used. The results are shown in Table-1.

比較例3 市販アクリルポリオール(水酸基価80mgKOH/g
r、5olid、不揮発分50%、トルエン、酢酸n−
ブチル溶?lり100部を主剤として1.6−へキサメ
チレンジイソシアネートの3量体(NGO含量16.5
%、不揮発分75%、酢酸エチル溶液)18部を添加し
、均一に混合してトルエンにて希釈した。この混合物を
用いた以外は実施例1と同様に試験を行った。結果を表
1に示す。
Comparative Example 3 Commercially available acrylic polyol (hydroxyl value 80 mgKOH/g
r, 5solid, non-volatile content 50%, toluene, acetic acid n-
Butyl solution? Trimer of 1,6-hexamethylene diisocyanate (NGO content 16.5
%, nonvolatile content 75%, ethyl acetate solution) were added thereto, mixed uniformly, and diluted with toluene. The test was conducted in the same manner as in Example 1 except that this mixture was used. The results are shown in Table 1.

また、上記アクリルポリオールをトルエンにて不揮発分
40%としたもの100部に酸化チタン30部とガラス
ピーズを適当量添加して、実施例1と同様な操作にて混
合した。これに1.6−へキサメチレンジイソシアネー
トの3量体(NGO含量16.5%、不揮発分75%、
酢酸エチル溶液)9.6部を添加し、均一に混合して塗
料配合物を得た。
Further, 30 parts of titanium oxide and appropriate amounts of glass beads were added to 100 parts of the above acrylic polyol with a non-volatile content of 40% in toluene, and mixed in the same manner as in Example 1. This was added to a trimer of 1.6-hexamethylene diisocyanate (NGO content 16.5%, non-volatile content 75%,
9.6 parts of ethyl acetate solution) were added and mixed uniformly to obtain a paint formulation.

この配合物を用いた以外は実施例1と 同様に試験を行なった。Same as Example 1 except that this formulation was used. A similar test was conducted.

結果を表−1に示す。The results are shown in Table-1.

実施例7 実施例3で得られたグラフトアミン含有エマルジョン1
00部に25℃、1%水溶液の粘度が10.0OOcp
sであるCMC(セルロースグリコール酸ナトリウム)
の2%水溶液20部、MAGMHの30%水溶液14.
4部を添加し均一に混合して接着剤を得た。この接着剤
を塗布量150 g / aJになる様にカバ材からな
る被着体へ塗布し貼り合わせ、25℃、圧締め圧10に
g/cd、圧締め時間1時間条件下で接着した。更に、
25℃、相対湿度60%で3日間養生を行った後に、J
IS  K−6852に準じて常態接着力および煮沸繰
り返し処理後の耐煮沸接着力を圧縮剪断接着力(ktr
 f / d )として測定した。結果を表−2に示す
Example 7 Grafted amine-containing emulsion 1 obtained in Example 3
00 parts at 25℃, the viscosity of a 1% aqueous solution is 10.0OOcp
CMC (sodium cellulose glycolate)
20 parts of a 2% aqueous solution of MAGMH, 14 parts of a 30% aqueous solution of MAGMH.
4 parts were added and mixed uniformly to obtain an adhesive. This adhesive was applied to an adherend made of birch material in a coating amount of 150 g/aJ and bonded together under conditions of 25° C., a pressing pressure of 10 g/cd, and a pressing time of 1 hour. Furthermore,
After curing for 3 days at 25°C and 60% relative humidity, J
In accordance with IS K-6852, the normal state adhesive strength and the boiling resistant adhesive strength after repeated boiling treatment are calculated as compressive shear adhesive strength (ktr
f/d). The results are shown in Table-2.

比較例4 参考例3で得られたグラフトアミン含有エマルジョン1
00部に実施例7と同様にCMCを添加し、これにエチ
レングリコールジグリシジルエーチル5.8部を添加し
均一に混合して接−着剤を得た。
Comparative Example 4 Grafted amine-containing emulsion 1 obtained in Reference Example 3
CMC was added to 00 parts in the same manner as in Example 7, and 5.8 parts of ethylene glycol diglycidyl ethyl was added thereto and mixed uniformly to obtain an adhesive.

この接着剤を用いる以外は実施例7と同様に行った。結
果を表−2に示す。
The same procedure as in Example 7 was carried out except that this adhesive was used. The results are shown in Table-2.

比較例5 2液型で調製後の不揮発分46.8%の水性ビニルウレ
タン系接着剤を比較例5とし、この接着剤を用いる以外
は実施例7と同様に行った。結果を表−2に示す。
Comparative Example 5 Comparative Example 5 was a water-based vinyl urethane adhesive with a non-volatile content of 46.8% prepared in a two-component type, and the same procedure as in Example 7 was conducted except that this adhesive was used. The results are shown in Table-2.

[発明の効果] 本発明の硬化性樹脂組成物は、実施例よりも明らかなよ
うに、湿度、水等の影響を受けず、優れた作業性、反応
性を有し、耐薬品性、耐候性、汎用性等に特徴を有し、
これらの特徴を生かした塗料、接着剤、表面処理剤、成
型物、発泡樹脂等多岐用途に利用され得る効果を有する
ものである。
[Effects of the Invention] As is clear from the examples, the curable resin composition of the present invention is not affected by humidity, water, etc., has excellent workability and reactivity, and has excellent chemical resistance and weather resistance. Characterized by its versatility and versatility,
Taking advantage of these characteristics, it can be used in a wide variety of applications such as paints, adhesives, surface treatment agents, molded products, and foamed resins.

Claims (1)

【特許請求の範囲】[Claims] (1)(a)グラフト一級アミノ基又は、グラフト二級
アミノ基を持ったポリマーおよび、 (b)一般式( I ) ▲数式、化学式、表等があります▼ ・・・( I ) (式中、R_1は水素および炭素原子1〜2の低級アル
キル基より成る群より選らばれ、R_2およびR_3は
各々独立に炭素原子1〜4の低級アルキル基より成る群
より選らばれる。)で表示されるアミノ基とマイケル付
加する不飽和結合と、アミノ基と交換反応する活性エス
テル基を有する化合物又は 一般式(II) ▲数式、化学式、表等があります▼ ・・・(II) (式中、R_4は水素および炭素原子1〜2の低級アル
キル基より成る群より選らばれ、R_5は常温でアミノ
基と交換反応を起こし得るアルコール、フェノール、ア
ミン、ヒドロキシルアミン残基より成る群より選らばれ
る。) で表示されるアミノ基とマイケル付加する不飽和結合と
、アミノ基と交換反応する活性エステル基又は、アミド
基を有する化合物よりなることを特徴とする硬化性樹脂
組成物。
(1) (a) A polymer with a grafted primary amino group or a grafted secondary amino group, and (b) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ...(I) (in the formula , R_1 is selected from the group consisting of hydrogen and a lower alkyl group having 1 to 2 carbon atoms, and R_2 and R_3 are each independently selected from the group consisting of lower alkyl groups having 1 to 4 carbon atoms.) A compound or general formula (II) that has an unsaturated bond that undergoes a Michael addition with a group and an active ester group that exchanges with an amino group ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ...(II) (R_5 is selected from the group consisting of hydrogen and lower alkyl groups having 1 to 2 carbon atoms, and R_5 is selected from the group consisting of alcohol, phenol, amine, and hydroxylamine residues that can undergo exchange reactions with amino groups at room temperature.) 1. A curable resin composition comprising a compound having an unsaturated bond that undergoes a Michael addition with an amino group, and an active ester group or amide group that undergoes an exchange reaction with the amino group.
JP32249189A 1989-12-14 1989-12-14 Curable resin composition Pending JPH03185073A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP32249189A JPH03185073A (en) 1989-12-14 1989-12-14 Curable resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP32249189A JPH03185073A (en) 1989-12-14 1989-12-14 Curable resin composition

Publications (1)

Publication Number Publication Date
JPH03185073A true JPH03185073A (en) 1991-08-13

Family

ID=18144237

Family Applications (1)

Application Number Title Priority Date Filing Date
JP32249189A Pending JPH03185073A (en) 1989-12-14 1989-12-14 Curable resin composition

Country Status (1)

Country Link
JP (1) JPH03185073A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2995921A1 (en) 2014-09-15 2016-03-16 Wen-San Chou Pen-type pressure indicator for air compressor
EP2998583A1 (en) 2014-09-15 2016-03-23 Wen-San Chou Pressure indicator for air compressor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2995921A1 (en) 2014-09-15 2016-03-16 Wen-San Chou Pen-type pressure indicator for air compressor
EP2998583A1 (en) 2014-09-15 2016-03-23 Wen-San Chou Pressure indicator for air compressor

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