JP4910682B2 - Epoxy resin curing agent and epoxy resin composition - Google Patents
Epoxy resin curing agent and epoxy resin composition Download PDFInfo
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本発明は、特定の構造を有するポリアミン化合物とジグリシジル化合物との反応生成物を含むエポキシ樹脂硬化剤、該エポキシ樹脂硬化剤を含むエポキシ樹脂組成物、該エポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物に関する。 The present invention relates to an epoxy resin curing agent including a reaction product of a polyamine compound having a specific structure and a diglycidyl compound, an epoxy resin composition including the epoxy resin curing agent, and an epoxy resin curing obtained by curing the epoxy resin composition. Related to things.
各種ポリアミン化合物がエポキシ樹脂硬化剤及びその原料として広く用いられていることは良く知られている。これらのエポキシ樹脂硬化剤を利用した常温硬化用エポキシ樹脂組成物は、特に船舶・橋梁・陸海上鉄構築物用防食塗料等の塗料分野、コンクリート構造物のライニング・補強・補修、建築物の床材、上下水道設備のライニング、舗装材、接着剤等の土木・建築分野に広く利用されている。 It is well known that various polyamine compounds are widely used as epoxy resin curing agents and their raw materials. Epoxy resin compositions for room temperature curing using these epoxy resin curing agents are used in coatings such as anticorrosion paints for ships, bridges, land and sea iron structures, lining, reinforcement and repair of concrete structures, and flooring for buildings. Widely used in civil engineering and construction fields such as lining of water and sewage facilities, paving materials, and adhesives.
ポリアミン化合物のうち、下記(I)式で示される互いに側鎖基の構成が異なる各付加物を含むポリアミン化合物からなるエポキシ樹脂硬化剤は、良好なエポキシ樹脂硬化塗膜物性、良好なエポキシ樹脂硬化物物性を与える(特許文献1参照)。
(R)2N−H2C−A−CH2−NHR ・・・(I)
(Aはフェニレン基またはシクロヘキシレン基であり、Rは水素原子またはフェネチル基である。複数のRは同一でも異なっていてもよく、Rの少なくとも1つはフェネチル基である。)
Among the polyamine compounds, an epoxy resin curing agent comprising a polyamine compound containing adducts having different side chain groups represented by the following formula (I) has good epoxy resin cured coating film properties and good epoxy resin curing. Provides physical properties (see Patent Document 1).
(R) 2 N-H 2 C-A-CH 2 -NHR ··· (I)
(A is a phenylene group or a cyclohexylene group, R is a hydrogen atom or a phenethyl group. A plurality of R may be the same or different, and at least one of R is a phenethyl group.)
しかしながら、(I)式で示されるポリアミン化合物を含むエポキシ樹脂硬化剤を用いたエポキシ樹脂組成物を硬化させてなるエポキシ樹脂硬化物は、可撓性が必要とされる分野においては必ずしも十分な性能を有してはいなかった。
本発明の目的は、ポリアミン化合物を用いたエポキシ樹脂硬化剤であって、良好な硬化性、及び可撓性の点で良好なエポキシ樹脂硬化塗膜性能並びに硬化物物性を与え得るエポキシ樹脂硬化剤、ならびに該エポキシ樹脂硬化剤を含むエポキシ樹脂組成物、該エポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物を提供することである。 An object of the present invention is an epoxy resin curing agent using a polyamine compound, which can provide good epoxy resin cured coating film performance and cured physical properties in terms of good curability and flexibility. And an epoxy resin composition containing the epoxy resin curing agent, and an epoxy resin cured product obtained by curing the epoxy resin composition.
本発明者らは、鋭意検討した結果、(I)式で示される化合物からなるポリアミン化合物と、特定の構造を有するジグリシジル化合物とを反応させてなるポリアミン化合物からなるエポキシ樹脂硬化剤を含むエポキシ樹脂組成物が可撓性に優れることを見出した。
即ち本発明は、(I)式で示されるポリアミン化合物と、グリシジル基間の炭素数が3以上である直鎖状ジグリシジル化合物との反応生成物を含む、エポキシ樹脂硬化剤、および該エポキシ樹脂硬化剤を含むエポキシ樹脂組成物、ならびに該エポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物に関する。
(R)2N−H2C−A−CH2−NHR ・・・(I)
(Aはフェニレン基またはシクロヘキシレン基であり、Rは水素原子またはフェネチル基である。複数のRは同一でも異なっていてもよく、Rの少なくとも1つはフェネチル基である。)
As a result of intensive studies, the present inventors have determined that an epoxy resin containing an epoxy resin curing agent comprising a polyamine compound obtained by reacting a polyamine compound comprising a compound represented by formula (I) with a diglycidyl compound having a specific structure. It has been found that the composition is excellent in flexibility.
That is, the present invention provides an epoxy resin curing agent containing a reaction product of a polyamine compound represented by the formula (I) and a linear diglycidyl compound having 3 or more carbon atoms between glycidyl groups, and the epoxy resin curing The present invention relates to an epoxy resin composition containing an agent and a cured epoxy resin obtained by curing the epoxy resin composition.
(R) 2 N-H 2 C-A-CH 2 -NHR ··· (I)
(A is a phenylene group or a cyclohexylene group, R is a hydrogen atom or a phenethyl group. A plurality of R may be the same or different, and at least one of R is a phenethyl group.)
本発明のエポキシ樹脂硬化剤は、良好な硬化性(具体的には指触乾燥性)、及び良好なエポキシ樹脂硬化塗膜性能並びに硬化物物性(特に、優れた可撓性)を有するエポキシ樹脂組成物を与えることができる。 The epoxy resin curing agent of the present invention is an epoxy resin having good curability (specifically, dryness to touch), good epoxy resin cured coating film performance and cured material properties (particularly excellent flexibility). A composition can be provided.
本発明は、(I)式で示されるポリアミン化合物とジグリシジル化合物との反応生成物を含むエポキシ樹脂硬化剤に関する。
(R)2N−H2C−A−CH2−NHR ・・・(I)
(Aはフェニレン基またはシクロヘキシレン基であり、Rは水素原子またはフェネチル基である。複数のRは同一でも異なっていてもよく、Rの少なくとも1つはフェネチル基である。)
The present invention relates to an epoxy resin curing agent containing a reaction product of a polyamine compound represented by the formula (I) and a diglycidyl compound.
(R) 2 N-H 2 C-A-CH 2 -NHR ··· (I)
(A is a phenylene group or a cyclohexylene group, R is a hydrogen atom or a phenethyl group. A plurality of R may be the same or different, and at least one of R is a phenethyl group.)
本発明で使用される(I)式で示されるポリアミン化合物は、下記(III)式で示されるジアミン化合物とスチレンとの反応によって得られる反応生成物である。
H2N−CH2−A−CH2−NH2 ・・・(III)
(Aはフェニレン基またはシクロヘキシレン基である。)
(III)式で示されるジアミン化合物としてはオルソキシリレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、1,2−ビス(アミノメチル)シクロヘキサン、1,3−ビス(アミノメチル)シクロヘキサン、1,4−ビス(アミノメチル)シクロヘキサンが挙げられる。中でも好ましいのはメタキシリレンジアミン、1,3−ビス(アミノメチル)シクロヘキサンである。特に好ましいのはメタキシリレンジアミンである。
The polyamine compound represented by the formula (I) used in the present invention is a reaction product obtained by reacting a diamine compound represented by the following formula (III) with styrene.
H 2 N—CH 2 —A—CH 2 —NH 2 (III)
(A is a phenylene group or a cyclohexylene group.)
Examples of the diamine compound represented by the formula (III) include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane is mentioned. Among these, metaxylylenediamine and 1,3-bis (aminomethyl) cyclohexane are preferable. Particularly preferred is metaxylylenediamine.
(I)式で示されるポリアミン化合物は、(III)式で表されるジアミン化合物のアミノ基とスチレンのアルケニル基との付加反応によって得られる付加物であり、スチレンの付加数により、以下に示す種々の1付加物、2付加物及び3付加物が生成する可能性がある。ここで、Phはフェネチル基を表す。
(a):(Ph)HN−H2C−A−CH2−NH2
(b):(Ph)HN−H2C−A−CH2−NH(Ph)
(c):(Ph)2N−H2C−A−CH2−NH2
(d):(Ph)2N−H2C−A−CH2−NH(Ph)
本発明の(I)式で示されるポリアミン化合物は、1付加物、2付加物及び3付加物の各々単独からなるものであっても、これらの任意の混合物であってもよい。
The polyamine compound represented by the formula (I) is an adduct obtained by the addition reaction between the amino group of the diamine compound represented by the formula (III) and the alkenyl group of styrene. Various 1-, 2- and 3-adducts can be formed. Here, Ph represents a phenethyl group.
(A): (Ph) HN—H 2 C—A—CH 2 —NH 2
(B): (Ph) HN—H 2 C—A—CH 2 —NH (Ph)
(C): (Ph) 2 N—H 2 C—A—CH 2 —NH 2
(D) :( Ph) 2 N -H 2 C-A-CH 2 -NH (Ph)
The polyamine compound represented by the formula (I) of the present invention may be composed of a monoadduct, a biadduct, and a triadduct, respectively, or any mixture thereof.
このうち、本発明で使用される(I)式で示されるポリアミン化合物中に、下記(II)式で示されるポリアミン化合物が80重量%以上含まれることが好ましく、さらには90重量%以上含まれることが好ましい。
RHN−H2C−A−CH2−NHR ・・・(II)
(Aはフェニレン基またはシクロヘキシレン基であり、Rは水素原子またはフェネチル基である。複数のRは同一でも異なっていてもよく、Rの少なくとも1つはフェネチル基である。)
Of these, the polyamine compound represented by the formula (I) used in the present invention preferably contains 80% by weight or more of the polyamine compound represented by the following formula (II), and more preferably 90% by weight or more. It is preferable.
RHN—H 2 C—A—CH 2 —NHR (II)
(A is a phenylene group or a cyclohexylene group, R is a hydrogen atom or a phenethyl group. A plurality of R may be the same or different, and at least one of R is a phenethyl group.)
(II)式で示されるポリアミン化合物は、上述した付加物(a)〜(d)のうちの1付加物(a)及び2付加物(b)に相当する。したがって、本発明で使用される(I)式で示されるポリアミン化合物中に含まれる1付加物(a)と2付加物(b)の合計が80重量%以上、さらには90重量%以上であることが好ましい。
(I)式で示されるポリアミン化合物中に含まれる(II)式で示されるポリアミン化合物が80重量%未満であると、エポキシ樹脂硬化塗膜及びエポキシ樹脂硬化物の疎水性及び架橋密度が低下する場合がある。その結果、エポキシ樹脂硬化塗膜及びエポキシ樹脂硬化物の耐水性、耐有機溶剤性が低下するため好ましくない。
The polyamine compound represented by the formula (II) corresponds to the 1-adduct (a) and 2-adduct (b) among the adducts (a) to (d) described above. Therefore, the total of 1-adduct (a) and 2-adduct (b) contained in the polyamine compound represented by the formula (I) used in the present invention is 80% by weight or more, and further 90% by weight or more. It is preferable.
When the polyamine compound represented by the formula (II) contained in the polyamine compound represented by the formula (I) is less than 80% by weight, the hydrophobicity and crosslinking density of the cured epoxy resin coating and the cured epoxy resin are lowered. There is a case. As a result, the water resistance and organic solvent resistance of the epoxy resin cured coating and the cured epoxy resin are lowered, which is not preferable.
このような特定の組成を有する(I)式で示されるポリアミン化合物を得るためには、(III)式で表されるジアミン化合物とスチレンとの反応比(スチレン/ジアミン化合物)が1.5以下、より好ましくは1.2以下(モル比)で反応させることが好ましい。 In order to obtain the polyamine compound represented by the formula (I) having such a specific composition, the reaction ratio of the diamine compound represented by the formula (III) and styrene (styrene / diamine compound) is 1.5 or less. More preferably, the reaction is performed at a ratio of 1.2 or less (molar ratio).
本発明で使用されるジグリシジル化合物(2つのグリシジル基を有する化合物;以下、単に「ジグリシジル化合物」と称する)は、グリシジル基間の炭素数が3以上、好ましくは4以上の、直鎖状ジグリシジル化合物である。直鎖状ジグリシジル化合物は、グリシジル基間の炭素鎖(主鎖)の側鎖に2つ以上の原子よりなる原子団が結合していない化合物のことであり、エポキシ樹脂硬化塗膜及び硬化物へ可撓性を付与する。グリシジル基間の炭素数が3未満であるとエポキシ樹脂硬化塗膜及びエポキシ樹脂硬化物への可撓性付与効果が小さい。 The diglycidyl compound used in the present invention (compound having two glycidyl groups; hereinafter simply referred to as “diglycidyl compound”) is a linear diglycidyl compound having 3 or more, preferably 4 or more carbon atoms between glycidyl groups. It is. A linear diglycidyl compound is a compound in which an atomic group composed of two or more atoms is not bonded to a side chain of a carbon chain (main chain) between glycidyl groups. Gives flexibility. When the number of carbon atoms between the glycidyl groups is less than 3, the effect of imparting flexibility to the cured epoxy resin coating and the cured epoxy resin is small.
グリシジル基間の炭素数の上限に制限はないが、好ましくは12以下である。具体例としては、1,3−プロパンジオールジグリシジルエーテル、1,4−ブタンジオールジグリシジルエーテル、1,5−ペンタンジオールジグリシジルエーテル、1,6−ヘキサンジオールジグリシジルエーテル、1,7−ヘプタンジオールジグルシジルエーテル、1,8−オクタンジオールジグリシジルエーテル、1,9−ノナンジオールジグリシジルエーテル、1,10−デカンジオールジグリシジルエーテル、1,11−ウンデカンジオールジグリシジルエーテル、1,12−ドデカンジオールジグリシジルエーテルが挙げられる。グリシジル基間の炭素数が12を超えると有機溶剤に対する親和性が高くなり、エポキシ樹脂硬化塗膜及びエポキシ樹脂硬化物の耐有機溶剤性が低下するため好ましくない。
グリシジル基間の炭素数は、より好ましくは8以下、さらに好ましくは6以下である。中でも特に好ましい直鎖状ジグリシジル化合物は1,4−ブタンジオールジグリシジルエーテルと1,6−ヘキサンジオールジグリシジルエーテルである。
Although there is no restriction | limiting in the upper limit of the carbon number between glycidyl groups, Preferably it is 12 or less. Specific examples include 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,7-heptane. Diol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,11-undecanediol diglycidyl ether, 1,12-dodecane Diol diglycidyl ether is mentioned. When the number of carbon atoms between glycidyl groups exceeds 12, the affinity for an organic solvent is increased, and the organic solvent resistance of the cured epoxy resin coating and the cured epoxy resin is reduced, such being undesirable.
The number of carbon atoms between glycidyl groups is more preferably 8 or less, and even more preferably 6 or less. Among these, particularly preferred linear diglycidyl compounds are 1,4-butanediol diglycidyl ether and 1,6-hexanediol diglycidyl ether.
本発明のエポキシ樹脂硬化剤は、(I)式で示されるポリアミン化合物とジグリシジル化合物との反応によって得られる反応生成物を含む。この反応生成物は、(I)式で示されるポリアミン化合物のアミノ基とジグリシジル化合物のグリシジル基との反応により生成する。
反応に使用されるジグリシジル化合物は単独でも良いし、2種以上のジグリシジル化合物を使用しても良い。2種以上のジグリシジル化合物を使用する場合、2種以上を混合して(I)式で示されるポリアミン化合物と反応させても良いし、1種類ずつ逐次反応させても良い。
The epoxy resin curing agent of the present invention contains a reaction product obtained by a reaction between a polyamine compound represented by the formula (I) and a diglycidyl compound. This reaction product is generated by a reaction between the amino group of the polyamine compound represented by the formula (I) and the glycidyl group of the diglycidyl compound.
The diglycidyl compound used in the reaction may be used alone or in combination of two or more diglycidyl compounds. When two or more types of diglycidyl compounds are used, two or more types may be mixed and reacted with the polyamine compound represented by the formula (I), or may be sequentially reacted one by one.
前記反応における(I)式で示されるポリアミン化合物とジグリシジル化合物の仕込み比(ポリアミン化合物の活性水素数/ジグリシジル化合物のエポキシ基数)は好ましくは3〜10、さらに好ましくは4〜8である。反応比が10を超えると可撓性の付与効果が不十分であり、3未満であると著しく粘度が高くなるため好ましくない。 The charging ratio of the polyamine compound represented by the formula (I) and the diglycidyl compound in the reaction (the number of active hydrogens in the polyamine compound / the number of epoxy groups in the diglycidyl compound) is preferably 3 to 10, and more preferably 4 to 8. When the reaction ratio exceeds 10, the effect of imparting flexibility is insufficient, and when it is less than 3, the viscosity is remarkably increased, which is not preferable.
ジグリシジル化合物と(I)式で示されるポリアミン化合物とを反応させる方法としては従来公知の方法が使用できる。例えば、反応装置にジグリシジル化合物のエポキシ基数に対して過剰の活性水素数となる量のポリアミン化合物を仕込み、ジグリシジル化合物を滴下し、加熱、反応させる方法が挙げられる。この場合の反応温度、反応時間は特に限定されないが、1例としてポリアミン化合物を80℃まで昇温した後、液温を80〜90℃に保持してジグリシジル化合物の滴下を行い、滴下終了後100℃まで昇温して2時間反応を行い、IRスペクトルによりグリシジル基の消失を確認して反応終了とする方法がある。 As a method of reacting the diglycidyl compound with the polyamine compound represented by the formula (I), a conventionally known method can be used. For example, there is a method in which a polyamine compound in an amount that gives an excessive number of active hydrogens relative to the number of epoxy groups in the diglycidyl compound is charged in a reaction apparatus, and the diglycidyl compound is dropped, heated, and reacted. In this case, the reaction temperature and reaction time are not particularly limited, but as an example, the polyamine compound is heated to 80 ° C., then the diglycidyl compound is dropped while maintaining the liquid temperature at 80 to 90 ° C. There is a method of raising the temperature to 0 ° C., performing a reaction for 2 hours, and confirming the disappearance of the glycidyl group by IR spectrum to complete the reaction.
本発明のエポキシ樹脂硬化剤は、(1)式で示されるポリアミン化合物とジグリシジル化合物の反応によって得られる上記反応生成物を含むものであり、該反応生成物単独からなるものであっても良いし、他のポリアミン化合物との混合物であっても良い。混合しうる他のポリアミン化合物としては、脂肪族ポリアミン化合物、例えばエチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサメチレンジアミン等;芳香環をもった脂肪族ポリアミン化合物、例えばキシリレンジアミン等;脂環族ポリアミン化合物、例えばメンセンジアミン、イソホロンジアミン、ビス(アミノメチル)シクロヘキサン、N−アミノメチルピペラジン等;芳香族ポリアミン化合物、例えばフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等;その他ポリエーテル骨格のポリアミノ化合物、ノルボルナン骨格のポリアミン化合物等が挙げられる。これら他のポリアミン化合物は変性せずに混合しても良いし、カルボキシル基を有する化合物との反応によるアミド変性、エポキシ化合物との付加反応によるアダクト変性、ホルムアルデヒドとフェノール類との反応によるマンニッヒ変性などの変性を行った後に混合しても良い。この場合の混合比は、本発明のエポキシ樹脂硬化剤の特徴が損なわれない範囲であれば特に限定されるものではないが、本発明の反応混合物100重量部に対し、他のポリアミン化合物を100重量部以下程度とするのが好ましい。 The epoxy resin curing agent of the present invention includes the reaction product obtained by the reaction of the polyamine compound represented by the formula (1) and the diglycidyl compound, and may consist of the reaction product alone. It may be a mixture with other polyamine compounds. Other polyamine compounds that can be mixed include aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine and the like; aliphatic polyamine compounds having an aromatic ring such as xylylene Range amines, etc .; Alicyclic polyamine compounds such as mensendiamine, isophoronediamine, bis (aminomethyl) cyclohexane, N-aminomethylpiperazine, etc .; Aromatic polyamine compounds such as phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc. Examples thereof include a polyamino compound having a polyether skeleton and a polyamine compound having a norbornane skeleton. These other polyamine compounds may be mixed without modification, amide modification by reaction with a compound having a carboxyl group, adduct modification by addition reaction with an epoxy compound, Mannich modification by reaction of formaldehyde and phenols, etc. It may be mixed after the modification. The mixing ratio in this case is not particularly limited as long as the characteristics of the epoxy resin curing agent of the present invention are not impaired, but other polyamine compounds are added to 100 parts by weight of the reaction mixture of the present invention. It is preferable that the amount is about parts by weight or less.
本発明のエポキシ樹脂組成物は、主剤であるエポキシ樹脂とエポキシ樹脂硬化剤を含むものである。本発明のエポキシ樹脂組成物に使用されるエポキシ樹脂は、本発明のエポキシ樹脂硬化剤に含まれるアミノ基由来の活性水素と反応するグリシジル基を有するエポキシ樹脂であれば特に限定されない。このようなエポキシ樹脂としては、多官能のエポキシ樹脂及び単官能のエポキシ樹脂が挙げられる。多官能のエポキシ樹脂としては、レソルシノール、ヒドロキノン等の単核二価フェノール化合物のジグリシジルエーテル化合物;4,4’−イソプロピリデンジフェノール(ビスフェノールA)、4,4’−メチレンジフェノール(ビスフェノールF)等の多核二価フェノールのジグリシジルエーテル化合物;エチレングリコール、プロピレングリコール、ブタンジオール、ヘキサンジオール等のジオール類のジグリシジルエーテル化合物;マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、スベリン酸、アジピン酸、アゼライン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸、シクロヘキサンジカルボン酸等の脂肪族、芳香族または脂環族二塩基酸のジグリシジルエステル化合物;1,3−ビス(N,N−ジグリシジルアミノメチル)ベンゼン、 1,3−ビス(N,N−ジグリシジルアミノメチル)シクロヘキサン等のグリシジルアミン化合物等が挙げられる。また、単官能のエポキシ樹脂としては例えばブチルアルコール、高級アルコール等のアルコールのグリシジルエーテル化合物、フェノール、メタクレゾール、パラクレゾール、オルトクレゾール等の単核一価フェノール化合物のグリシジルエーテル化合物、ネオデカン酸等の一価カルボン酸のグリシジルエステル化合物等が挙げられる。
中でも4,4’−イソプロピリデンジフェノールジグリシジルエーテル(ビスフェノールA型エポキシ樹脂)及び4,4’−メチレンジフェノールジグリシジルエーテル(ビスフェノールF型エポキシ樹脂)、ならびにこれらの混合物を主成分とするのが好ましい。
The epoxy resin composition of this invention contains the epoxy resin which is a main ingredient, and an epoxy resin hardening | curing agent. The epoxy resin used in the epoxy resin composition of the present invention is not particularly limited as long as it is an epoxy resin having a glycidyl group that reacts with an active hydrogen derived from an amino group contained in the epoxy resin curing agent of the present invention. Examples of such epoxy resins include polyfunctional epoxy resins and monofunctional epoxy resins. Examples of the polyfunctional epoxy resin include diglycidyl ether compounds of mononuclear dihydric phenol compounds such as resorcinol and hydroquinone; 4,4′-isopropylidenediphenol (bisphenol A), 4,4′-methylenediphenol (bisphenol F) ) Diglycidyl ether compounds of polynuclear dihydric phenols; diglycidyl ether compounds of diols such as ethylene glycol, propylene glycol, butanediol, hexanediol; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberin Diglycidyl ester compounds of aliphatic, aromatic or alicyclic dibasic acids such as acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid; 1,3-bis (N , N-Diglycidyl Minomechiru) benzene, 1,3-bis (N, glycidyl amine compounds such as N- diglycidyl aminomethyl) cyclohexane. Examples of monofunctional epoxy resins include glycidyl ether compounds of alcohols such as butyl alcohol and higher alcohols, glycidyl ether compounds of mononuclear monohydric phenol compounds such as phenol, metacresol, paracresol, and orthocresol, neodecanoic acid, etc. Examples thereof include glycidyl ester compounds of monovalent carboxylic acids.
Of these, 4,4′-isopropylidene diphenol diglycidyl ether (bisphenol A type epoxy resin), 4,4′-methylene diphenol diglycidyl ether (bisphenol F type epoxy resin), and mixtures thereof are the main components. Is preferred.
さらに、ビスフェノールA型エポキシ樹脂及び/又はビスフェノールF型エポキシ樹脂を主成分とする場合に、ビスフェノールA型エポキシ樹脂及び/又はビスフェノールF型エポキシ樹脂以外のグリシジル基を有するエポキシ樹脂、例えばジオール類のジグリシジルエーテル化合物や単官能のグリシジル化合物などを、反応性希釈剤として少量併用することもできる。 Furthermore, when bisphenol A type epoxy resin and / or bisphenol F type epoxy resin is the main component, epoxy resin having a glycidyl group other than bisphenol A type epoxy resin and / or bisphenol F type epoxy resin, A small amount of a glycidyl ether compound or a monofunctional glycidyl compound may be used in combination as a reactive diluent.
さらに本発明のエポキシ樹脂組成物には、用途に応じて本発明の上記エポキシ樹脂硬化剤以外のエポキシ樹脂硬化剤、あるいは充填材、可塑剤などの改質成分、非反応性希釈剤、揺変性付与剤などの流動調整成分、顔料、粘着付与剤などの成分やハジキ防止剤、流展剤、消泡剤、紫外線吸収剤、光安定剤、硬化促進剤などの添加剤を本発明の効果を損なわない範囲で用いることができる。 Furthermore, the epoxy resin composition of the present invention includes an epoxy resin curing agent other than the above epoxy resin curing agent of the present invention, or a modifying component such as a filler and a plasticizer, a non-reactive diluent, a thixotropic agent, depending on the application. Additives such as flow control components such as imparting agents, pigments and tackifiers, and additives such as anti-repelling agents, spreading agents, antifoaming agents, ultraviolet absorbers, light stabilizers, curing accelerators, etc. It can be used as long as it is not impaired.
本発明のエポキシ樹脂組成物の、エポキシ樹脂とエポキシ樹脂硬化剤の配合比は、エポキシ樹脂のエポキシ基数に対する本発明のエポキシ樹脂硬化剤の活性水素数の比が0.7〜1.2の範囲となることが好ましい。この範囲であると、硬化物の架橋度および耐水性の点で好ましい。 The compounding ratio of the epoxy resin and the epoxy resin curing agent of the epoxy resin composition of the present invention is such that the ratio of the active hydrogen number of the epoxy resin curing agent of the present invention to the number of epoxy groups of the epoxy resin is in the range of 0.7 to 1.2. It is preferable that Within this range, the degree of crosslinking of the cured product and the water resistance are preferred.
本発明のエポキシ樹脂組成物は、公知の方法で硬化させ、エポキシ樹脂硬化物とすることができる。硬化条件は用途に応じて本発明の効果を損なわない範囲で適時選択することができる。 The epoxy resin composition of the present invention can be cured by a known method to obtain a cured epoxy resin. Curing conditions can be selected in a timely manner within a range that does not impair the effects of the present invention depending on the application.
以下に実施例を挙げて本発明を具体的に説明する。但し本発明はこれらの実施例により何ら制限されるものではない。なお、(I)式で示されるポリアミン化合物の含有率の測定、(II)式で示されるポリアミン化合物の含有率の測定およびエポキシ樹脂硬化塗膜性能(エポキシ樹脂硬化物性能)の評価は、以下の方法にて行った。 The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. In addition, the measurement of the content rate of the polyamine compound shown by Formula (I), the measurement of the content rate of the polyamine compound shown by Formula (II), and evaluation of epoxy resin cured coating film performance (epoxy resin cured product performance) are as follows. It went by the method of.
<(1)式及び(2)式で示される化合物の含有率の測定>
ガスクロマトグラフィーGC−14A(株式会社島津製作所製)により下記の条件で測定した。
カラム:フロンティアラボ株式会社製UltraAlloy-1
(長さ15m、Film厚1.5μm、内径0.5mm)
キャリアーガス:ヘリウム 流速:5.3ml/min
内部標準物質:α,α’-Bis(4-aminophenyl)-1,4-diisopropylbenzene
溶媒:メタノール
試料注入量:0.5μl
温度条件;INJ,DET:300℃ COL:250℃/10min→20℃/min昇温→300℃/18.7min
<Measurement of content ratio of compounds represented by formulas (1) and (2)>
It measured on condition of the following by gas chromatography GC-14A (made by Shimadzu Corporation).
Column: UltraAlloy-1 from Frontier Lab
(Length 15m, Film thickness 1.5μm, Inner diameter 0.5mm)
Carrier gas: helium Flow rate: 5.3 ml / min
Internal standard substance: α, α'-Bis (4-aminophenyl) -1,4-diisopropylbenzene
Solvent: Methanol sample injection volume: 0.5 μl
Temperature conditions: INJ, DET: 300 ° C. COL: 250 ° C./10 min → 20 ° C./min temperature increase → 300 ° C./18.7 min
<エポキシ樹脂硬化塗膜性能評価>
エポキシ樹脂組成物を23℃、50%RHの条件下で、#240サンドペーパ処理を行い、キシレン脱脂した冷間圧延鋼板(SPCC−SB)(JIS−G−3141)に200μmの厚さで塗装した。
外観:塗装7日後の塗膜外観(光沢、透明性、平滑性)を目視で評価し、乾燥性(硬化16時間後、1、4、7日後)は指触により4段階(◎:優秀 ○:良好 △:やや不良 ×:不良)で評価した。
耐水性:塗装16時間後、1、4、7日後の塗膜上に水滴を滴下し、1日放置後の塗膜の変化を目視により4段階(◎:優秀 ○:良好 △:やや不良 ×:不良)で評価した。
耐薬品性:塗装7日後の塗装鋼板を各薬品に23℃で4週間浸漬し、1、4週間後の塗膜の変化を目視により4段階(◎:優秀 ○:良好 △:やや不良 ×:不良)で評価した。なお、塩水噴霧試験はJIS K 5600準拠。
可撓性(耐カッピング性試験):塗装7日後の塗膜を耐カッピング性試験(JIS−K−5600準拠)により評価した。
<Epoxy resin cured coating film performance evaluation>
The epoxy resin composition was subjected to # 240 sandpaper treatment under conditions of 23 ° C. and 50% RH, and coated on a cold rolled steel sheet (SPCC-SB) (JIS-G-3141) degreased with xylene at a thickness of 200 μm. .
Appearance: Appearance of coating film (gloss, transparency, smoothness) 7 days after coating is visually evaluated, and dryness (16 hours after curing, 1, 4, 7 days later) has four levels by touch (◎: Excellent ○ : Good △: Somewhat bad ×: Bad)
Water resistance: Water droplets were dropped on the coating film 16 hours after coating, 1, 4, 7 days later, and the change in the coating film after standing for 1 day was visually observed in 4 stages (◎: Excellent ○: Good △: Slightly poor × : Bad).
Chemical resistance: The coated steel sheet 7 days after coating is immersed in each chemical for 4 weeks at 23 ° C, and the coating changes after 1 and 4 weeks are visually observed in 4 stages (◎: Excellent ○: Good △: Slightly poor ×: Bad). The salt spray test is based on JIS K 5600.
Flexibility (Copping Resistance Test): The coating film 7 days after coating was evaluated by a cupping resistance test (based on JIS-K-5600).
<合成例1>
攪拌装置、温度計、窒素導入管、滴下漏斗及び冷却管を備えた内容積0.5リットルのセパラブルフラスコに、メタキシリレンジアミンとスチレンとの付加反応物であるポリアミン化合物(商品名「G−240」;三菱ガス化学株式会社製、活性水素当量(AHEW):103g/eq、(I)式で示される化合物の含有率:99.8重量%、(II)式で示される化合物の含有率:88.8重量%)206.0gを仕込み、窒素気流下、攪拌しながら80℃に昇温した。80℃に保ちながら1,4−ブタンジオールジグリシジルエーテル(メルク株式会社製、エポキシ当量:156g/eq、以下1,4−BDと称する。)62.4gを1時間かけて滴下した。滴下終了後、100℃に昇温して2時間反応を行い、G−240の1,4−BD付加物(反応生成物A)267.6gを得た。
<Synthesis Example 1>
To a separable flask having an internal volume of 0.5 liter equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dropping funnel and a cooling tube, a polyamine compound (trade name “G”) is an addition reaction product of metaxylylenediamine and styrene. -240 "; manufactured by Mitsubishi Gas Chemical Industries, Inc., active hydrogen equivalent (AHEW): 103 g / eq, content of compound represented by formula (I): 99.8% by weight, content of compound represented by formula (II) (Rate: 88.8 wt%) was charged with 206.0 g, and the temperature was raised to 80 ° C. with stirring under a nitrogen stream. While maintaining at 80 ° C., 62.4 g of 1,4-butanediol diglycidyl ether (manufactured by Merck & Co., Inc., epoxy equivalent: 156 g / eq, hereinafter referred to as 1,4-BD) was added dropwise over 1 hour. After completion of the dropwise addition, the temperature was raised to 100 ° C. and the reaction was performed for 2 hours to obtain 267.6 g of a 1,4-BD adduct (reaction product A) of G-240.
<合成例2>
合成例1と同様のフラスコにG−240(三菱ガス化学株式会社製、活性水素当量:103g/eq)206.0gを仕込み、窒素気流下、攪拌しながら80℃に昇温した。80℃に保ちながら1,6−ヘキサンジオールジグリシジルエーテル(阪本薬品工業株式会社製、エポキシ当量:156g/eq、以下1,6−HDと称する。)62.4gを1時間かけて滴下した。滴下終了後、100℃に昇温して2時間反応を行い、G−240の1,6−HD付加物(反応生成物B)267.7gを得た。
<Synthesis Example 2>
206.0 g of G-240 (Mitsubishi Gas Chemical Co., Ltd., active hydrogen equivalent: 103 g / eq) was charged into the same flask as in Synthesis Example 1, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining the temperature at 80 ° C., 62.4 g of 1,6-hexanediol diglycidyl ether (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent: 156 g / eq, hereinafter referred to as 1,6-HD) was added dropwise over 1 hour. After completion of the dropwise addition, the temperature was raised to 100 ° C. and the reaction was performed for 2 hours to obtain 267.7 g of a 1,6-HD adduct (reaction product B) of G-240.
<合成例3>
合成例1と同様のフラスコにG−240(三菱ガス化学株式会社製、AHEW:103g/eq)206.0gを仕込み、窒素気流下、攪拌しながら80℃に昇温した。80℃に保ちながら1,2−プロパンジオールジグリシジルエーテル(阪本薬品工業株式会社製、エポキシ当量:134g/eq、以下1,2−PDと称する。)53.6gを1時間かけて滴下した。滴下終了後、100℃に昇温して2時間反応を行い、G−240の1,2−PD付加物(反応生成物C)258.8gを得た。
<Synthesis Example 3>
206.0 g of G-240 (manufactured by Mitsubishi Gas Chemical Company, AHEW: 103 g / eq) was charged into the same flask as in Synthesis Example 1, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining at 80 ° C., 53.6 g of 1,2-propanediol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd., epoxy equivalent: 134 g / eq, hereinafter referred to as 1,2-PD) was added dropwise over 1 hour. After completion of the dropwise addition, the temperature was raised to 100 ° C. and the reaction was performed for 2 hours to obtain 258.8 g of a 1,2-PD adduct (reaction product C) of G-240.
<実施例1>
反応生成物AをビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製、商品名エピコート828、エポキシ当量:186g/eq)と表1に示す割合で配合し、23℃50%RHの条件下で硬化させてエポキシ樹脂硬化塗膜を作製し、性能評価を行った。結果を表1に示す。
<Example 1>
Reaction product A was blended with bisphenol A type epoxy resin (trade name Epicoat 828, epoxy equivalent: 186 g / eq) manufactured by Japan Epoxy Resin Co., Ltd. in the proportions shown in Table 1, and cured under conditions of 23 ° C. and 50% RH. An epoxy resin cured coating film was prepared and performance evaluation was performed. The results are shown in Table 1.
<実施例2>
反応生成物BをビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製、商品名エピコート828、エポキシ当量:186g/eq)と表1に示す割合で配合し、23℃50%RHの条件下で硬化させてエポキシ樹脂硬化塗膜を作製し、性能評価を行った。結果を表1に示す。
<Example 2>
Reaction product B was blended with bisphenol A type epoxy resin (trade name Epicoat 828, epoxy equivalent: 186 g / eq) manufactured by Japan Epoxy Resin Co., Ltd. in the proportions shown in Table 1, and cured under conditions of 23 ° C. and 50% RH. An epoxy resin cured coating film was prepared and performance evaluation was performed. The results are shown in Table 1.
<実施例3>
反応生成物BをビスフェノールF型エポキシ樹脂(ジャパンエポキシレジン株式会社製、商品名:エピコート807、エポキシ当量:168g/eq)と表2に示す割合で配合し、23℃50%RHの条件下で硬化させてエポキシ樹脂硬化塗膜を作製し、性能評価を行った。結果を表1に示す。
<Example 3>
Reaction product B was blended with bisphenol F-type epoxy resin (Japan Epoxy Resin Co., Ltd., trade name: Epicoat 807, epoxy equivalent: 168 g / eq) in the proportions shown in Table 2, and at 23 ° C. and 50% RH. The cured epoxy resin cured coating film was prepared and performance evaluation was performed. The results are shown in Table 1.
<比較例1>
反応生成物CをビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製、商品名エピコート828、エポキシ当量:186g/eq)と表3に示す割合で配合し、23℃50%RHの条件下で硬化させてエポキシ樹脂硬化塗膜を作製し、性能評価を行った。結果を表2に示す。
<Comparative Example 1>
Reaction product C was blended with bisphenol A type epoxy resin (trade name Epicoat 828, epoxy equivalent: 186 g / eq) manufactured by Japan Epoxy Resin Co., Ltd. in the proportions shown in Table 3, and cured under conditions of 23 ° C. and 50% RH. An epoxy resin cured coating film was prepared and performance evaluation was performed. The results are shown in Table 2.
<比較例2>
G−240(三菱ガス化学株式会社製、活性水素当量103g/eq)をビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製、商品名:エピコート828、エポキシ当量:186g/eq)及び1,6−ヘキサンジオールジグリシジルエーテル(阪本薬品工業株式会社製、エポキシ当量:156g/eq、以下1,6−HDと称する。)と表3に示す割合で配合し、23℃50%RHの条件下で硬化させてエポキシ樹脂硬化塗膜を作製し、性能評価を行った。結果を表2に示す。
<Comparative example 2>
G-240 (Mitsubishi Gas Chemical Co., Ltd., active hydrogen equivalent 103 g / eq) was replaced with bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., trade name: Epicoat 828, epoxy equivalent: 186 g / eq) and 1,6- Hexanediol diglycidyl ether (Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent: 156 g / eq, hereinafter referred to as 1,6-HD) was blended in the proportions shown in Table 3, and cured under conditions of 23 ° C. and 50% RH. An epoxy resin cured coating film was prepared and performance evaluation was performed. The results are shown in Table 2.
<比較例3>
G−240(三菱ガス化学株式会社製、活性水素当量103g/eq)をビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン株式会社製、商品名:エピコート828、エポキシ当量:186g/eq)と表3に示す割合で配合し、23℃50%RHの条件下で硬化させてエポキシ樹脂硬化塗膜を作製し、性能評価を行った。結果を表2に示す。
<Comparative Example 3>
Table 3 shows G-240 (Mitsubishi Gas Chemical Co., Ltd., active hydrogen equivalent 103 g / eq) and bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., trade name: Epicoat 828, epoxy equivalent: 186 g / eq). It mix | blended in the ratio, it was made to harden | cure on the conditions of 23 degreeC50% RH, the epoxy resin cured coating film was produced, and performance evaluation was performed. The results are shown in Table 2.
Claims (7)
(R)2N−H2C−A−CH2−NHR ・・・ (I)
(Aはフェニレン基またはシクロヘキシレン基であり、Rは水素原子またはフェネチル基である。複数のRは同一でも異なっていてもよく、Rの少なくとも1つはフェネチル基である。) (I) An epoxy resin curing agent comprising a reaction product of a polyamine compound represented by the formula and a linear diglycidyl compound having 3 or more carbon atoms between glycidyl groups , and the polyamine compound and the diglycidyl compound in the reaction An epoxy resin curing agent having a charging ratio (number of active hydrogens of polyamine compound / number of epoxy groups of diglycidyl compound) of 3 to 10 .
(R) 2 N—H 2 C—A—CH 2 —NHR (I)
(A is a phenylene group or a cyclohexylene group, R is a hydrogen atom or a phenethyl group. A plurality of R may be the same or different, and at least one of R is a phenethyl group.)
RHN−H2C−A−CH2−NHR ・・・ (II)
(Aはフェニレン基またはシクロヘキシレン基であり、Rは水素原子またはフェネチル基である。複数のRは同一でも異なっていてもよく、Rの少なくとも1つはフェネチル基である。) The epoxy resin curing agent according to claim 1, wherein the polyamine compound contains a polyamine compound represented by the formula (II) in an amount of 80% by weight or more.
RHN—H 2 C—A—CH 2 —NHR (II)
(A is a phenylene group or a cyclohexylene group, R is a hydrogen atom or a phenethyl group. A plurality of R may be the same or different, and at least one of R is a phenethyl group.)
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