JP4283642B2 - Epoxy paint composition - Google Patents

Epoxy paint composition Download PDF

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JP4283642B2
JP4283642B2 JP2003381790A JP2003381790A JP4283642B2 JP 4283642 B2 JP4283642 B2 JP 4283642B2 JP 2003381790 A JP2003381790 A JP 2003381790A JP 2003381790 A JP2003381790 A JP 2003381790A JP 4283642 B2 JP4283642 B2 JP 4283642B2
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resin
epoxy
hydrocarbon resin
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unsaturated
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JP2005113103A (en
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正喜 千葉
和也 阪
範雄 田方
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Toho Chemical Industry Co Ltd
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Description

本発明は、ノンタール型エポキシ塗料組成物に関するものであり、さらに詳しくは顔料との濡れ性を改善し、耐水性、重ね塗り性、及び密着性に優れ、特に船舶の塗装に適したエポキシ塗料組成物に関するものである。  The present invention relates to a non-tar type epoxy coating composition, and more specifically, improves the wettability with a pigment, has excellent water resistance, overcoatability, and adhesion, and is particularly suitable for marine coating. It is about things.

従来のタール系エポキシ塗料は、防食性、耐水性、耐薬品性に優れていることから、船舶用、一般構造物用など広い範囲で使用されている。
しかしながら、タールを含有することから、環境安全面での問題が懸念されるのみならず、黒色であるため、カラー化の選択がむずかしく、使用範囲も限定されるなどの不具合がある。
Conventional tar-based epoxy paints have excellent corrosion resistance, water resistance, and chemical resistance, and are therefore used in a wide range of applications such as for ships and general structures.
However, since it contains tar, there is a concern that not only environmental safety problems are concerned, but since it is black, selection of coloration is difficult and the range of use is limited.

そこで、石油系炭化水素樹脂を用いたノンタール型エポキシ塗料が開発されたが、石油系炭化水素樹脂は極性基を含まないので、エポキシ樹脂及び硬化剤との相溶性に劣り、硬化物が白濁するなど、塗料としては不適である。
近年、相溶性を改善するため、石油の分解で得られる不飽和留分をフェノール類共存下で重合した水酸基含有の炭化水素樹脂について、特許文献1、特許文献2、特許文献3、特許文献4、特許文献5などに開示されている。又、特許文献6によると石油分解で得られる140〜220℃の芳香族留分を蒸留して得た、高純度のインデン留分60〜90%をフェノール類共存下で重合して製造された、水酸基含有炭化水素樹脂を使用した例なども挙げられている。
しかし、昨今の塗料の高機能化に伴い、顔料との濡れ、防食性、耐水性のほか、接着性、重ね塗り性など、高度の性能が要求されるに至り、上記の開示資料の範囲では、これらの性能要求を満足するまでには至っていない。
特開昭53−141361 特開昭54−43259 特開昭54−46258 特開昭61−203111 特開平9−263713 特開平11−323247
Therefore, a non-tar type epoxy paint using a petroleum hydrocarbon resin was developed, but since the petroleum hydrocarbon resin does not contain a polar group, the compatibility with the epoxy resin and the curing agent is inferior, and the cured product becomes cloudy. It is unsuitable as a paint.
In recent years, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4 describe hydroxyl group-containing hydrocarbon resins obtained by polymerizing unsaturated fractions obtained by cracking petroleum in the presence of phenols in order to improve compatibility. Patent Document 5 and the like. Further, according to Patent Document 6, it was produced by polymerizing 60 to 90% of a high-purity indene fraction obtained by distillation of an aromatic fraction at 140 to 220 ° C. obtained by petroleum cracking in the presence of phenols. Examples using a hydroxyl group-containing hydrocarbon resin are also mentioned.
However, with the recent enhancement of paint functions, advanced performance such as wettability with pigments, corrosion resistance, water resistance, adhesiveness, and overcoatability has been required. However, these performance requirements have not been met.
JP 53-141361 JP 54-43259 A JP 54-46258 JP-A-61-203111 JP-A-9-263713 JP-A-11-323247

本発明が解決しようとする課題は、前述の通り、環境安全性、エポキシ樹脂等との相溶性に優れ、また顔料との濡れ性、防食性、重ね塗り性等に優れたエポキシ塗料組成物を提供することである。  The problem to be solved by the present invention is, as described above, an epoxy coating composition excellent in environmental safety, compatibility with epoxy resin, etc., and excellent in wettability with pigment, anticorrosion, overcoatability, etc. Is to provide.

本発明者は、上記課題を解決すべく鋭意検討した結果、分子内に水酸基およびカルボキシル基を含んだ変性炭化水素樹脂が、エポキシ樹脂、および硬化剤との相溶性に優れていることを見出した。
その結果、環境安全上の問題もなく、色調が淡色で、顔料との濡れ性、防食性、耐水性および、塗膜の重ね塗り、密着性において、優れたエポキシ塗料組成物の発明を完成するに至った。
As a result of intensive studies to solve the above problems, the present inventors have found that a modified hydrocarbon resin containing a hydroxyl group and a carboxyl group in the molecule is excellent in compatibility with an epoxy resin and a curing agent. .
As a result, the invention of an epoxy coating composition excellent in terms of wettability with pigments, anticorrosion, water resistance, and overcoating and adhesion of a coating film is completed without any environmental safety problems. It came to.

すなわち、本発明はエポキシ樹脂(A)と硬化剤(B)及び分子中に水酸基およびカルボキシル基を有する変性炭化水素樹脂(C)を含有するエポキシ塗料組成物であって、該変性炭化水素樹脂(C)の配合量が、エポキシ樹脂(A)固形分100重量部に対して10〜500重量部であるエポキシ塗料組成物を提供するものである。
また、本発明の好ましい態様として、変性炭化水素樹脂(C)は、(1)第一段反応で、石油の熱分解で得られる沸点が140〜200℃の芳香族を含む、モノオレフィン留分(C9留分)に、沸点20〜80℃の脂肪族系共役二重結合を含む留分(C5留分)を重量比で1〜50%混合し、さらにフェノール類を加え、フリーデルクラフト型触媒の存在下で重合し、分子内に不飽和基と水酸基(0.1〜2.0個)を含有する不飽和炭化水素樹脂を得る。(2)第二段反応で、第一段反応で得られた不飽和炭化水素樹脂の不飽和基に、有機不飽和酸を加熱反応で付加することにより製造でき、酸価が2〜50で、軟化点が40〜150℃である。
That is, the present invention is an epoxy coating composition containing an epoxy resin (A), a curing agent (B), and a modified hydrocarbon resin (C) having a hydroxyl group and a carboxyl group in the molecule, the modified hydrocarbon resin ( An epoxy coating composition in which the blending amount of C) is 10 to 500 parts by weight with respect to 100 parts by weight of the solid content of the epoxy resin (A) is provided.
Further, as a preferred embodiment of the present invention, the modified hydrocarbon resin (C) is (1) a monoolefin fraction containing an aromatic having a boiling point of 140 to 200 ° C. obtained by pyrolysis of petroleum in the first stage reaction. (C9 fraction) is mixed with a fraction containing an aliphatic conjugated double bond having a boiling point of 20 to 80 ° C. (C5 fraction) in a weight ratio of 1 to 50%, and further added with phenols, Friedel Kraft type Polymerization is carried out in the presence of a catalyst to obtain an unsaturated hydrocarbon resin containing unsaturated groups and hydroxyl groups (0.1 to 2.0) in the molecule. (2) In the second stage reaction, it can be produced by adding an organic unsaturated acid to the unsaturated group of the unsaturated hydrocarbon resin obtained by the first stage reaction by heating reaction, and the acid value is 2-50. The softening point is 40 to 150 ° C.

また、本発明のエポキシ塗料組成物は、防食性、耐水性等に優れるため、船舶用、一般構造物用の塗料として使用することができる。  Moreover, since the epoxy coating composition of the present invention is excellent in corrosion resistance, water resistance, etc., it can be used as a coating for ships and general structures.

分子中に水酸基とカルボキシル基を有する変性炭化水素樹脂(C)は、エポキシ樹脂や硬化剤との相溶性に優れ、該変性炭化水素樹脂を配合したエポキシ塗料組成物は塗布時の作業性、耐水性、防食性、付着性にも優れた効果が見られる。また、タールを一切含有しないため、環境上の問題もなく、しかも淡色の塗膜を形成できることから、主に船舶や一般構造物の防食塗料としても有用である。  The modified hydrocarbon resin (C) having a hydroxyl group and a carboxyl group in the molecule is excellent in compatibility with an epoxy resin and a curing agent, and an epoxy coating composition containing the modified hydrocarbon resin is excellent in workability during application and water resistance. The effect which was excellent also in the property, corrosion resistance, and adhesiveness is seen. Moreover, since tar is not contained at all, there is no environmental problem and a light-colored coating film can be formed. Therefore, it is useful mainly as an anticorrosion paint for ships and general structures.

本発明に係るエポキシ塗料組成物の諸性能は、分子中に水酸基とカルボキシル基の双方を有する変性炭化水素樹脂(C)を使用することにより得られるが、これは主に、水酸基とカルボキシル基が適度な割合で存在することによりエポキシ樹脂および硬化剤との相溶性を改善するためであると考えられる。特に水酸基が多いと、親水性が増し、塗料の耐水性、防食性に悪い影響をおよぼし、さらには密着性の低下につながる。そこで、適量のカルボキシル基を導入することで親水性と疎水性のバランスをとることができ、その結果耐水性、防食性、密着性、および、顔料の濡れ性を改善するものと思われる。  Various performances of the epoxy coating composition according to the present invention can be obtained by using a modified hydrocarbon resin (C) having both a hydroxyl group and a carboxyl group in the molecule. This is considered to be due to the presence of an appropriate ratio to improve the compatibility with the epoxy resin and the curing agent. In particular, when the number of hydroxyl groups is large, the hydrophilicity increases, which adversely affects the water resistance and anticorrosion properties of the paint, and further leads to a decrease in adhesion. Therefore, by introducing an appropriate amount of carboxyl group, it is possible to balance hydrophilicity and hydrophobicity, and as a result, it seems to improve water resistance, corrosion resistance, adhesion, and pigment wettability.

以下本発明について詳細に説明する。
本発明で説明するエポキシ樹脂(A)は、1分子に少なくとも2個以上のエポキシ基を有するものであり、エポキシ当量150〜600のものが適当であり、さらに好ましくは180〜500である。この様な樹脂としては、例えば、ビスフェノールA型エポキシ樹脂、脂肪族型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン系エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾール型エポキシ樹脂、ダイマー酸変性エポキシ樹脂など、従来公知のものが挙げられ、これは1種のみ又は2種以上混合して使用することができる。
The present invention will be described in detail below.
The epoxy resin (A) described in the present invention has at least two epoxy groups per molecule, and those having an epoxy equivalent of 150 to 600 are suitable, more preferably 180 to 500. Examples of such resins include bisphenol A type epoxy resins, aliphatic type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, cresol type epoxy resins, dimer acid-modified epoxy resins, and the like. Conventionally known ones can be mentioned, and these can be used alone or in combination of two or more.

本発明の重合用原料として使用される、フェノール類としてはフェノール、o−クレゾール、m−クレゾール、p−クレゾール、ブチルフェノール、キシレノールなどの一価フェノール、ノニルフェノール、ジノニルフェノール等のアルキル置換フェノールを例示することができる。またこれらを混合して使用することも出来る。  Examples of phenols used as a raw material for polymerization of the present invention include monovalent phenols such as phenol, o-cresol, m-cresol, p-cresol, butylphenol and xylenol, and alkyl-substituted phenols such as nonylphenol and dinonylphenol. be able to. Moreover, these can also be mixed and used.

本発明で使用される硬化剤(B)は、エポキシ樹脂の硬化剤として公知のものを用いることができる。例えば各種脂肪族、又は芳香族アミン類、ポリアミド樹脂、酸無水物類、フェノール樹脂、ポリイソシアネート等が例示される。これらは1種又は2種以上混合して使用する事ができる。
特に好ましくは、アミン系硬化剤であり、例えばメタキシレンジアミン、イソホロンジアミン、ジエチレントリアミン、トリエチレンテトラアミン、ジアミノジフェニルメタンなどの脂肪族ポリアミン類、芳香族ポリアミン類、これらポリアミン類のエポキシ樹脂アダクト物、ポリアミドアミン類、ポリアミド樹脂などが挙げられる。これら1種のみ又は2種以上混合して使用することができる。
As the curing agent (B) used in the present invention, a known curing agent for epoxy resins can be used. Examples include various aliphatic or aromatic amines, polyamide resins, acid anhydrides, phenol resins, polyisocyanates, and the like. These can be used alone or in combination.
Particularly preferred are amine-based curing agents such as metaxylenediamine, isophoronediamine, diethylenetriamine, triethylenetetraamine, diaminodiphenylmethane and other aliphatic polyamines, aromatic polyamines, epoxy resin adducts of these polyamines, polyamides Examples include amines and polyamide resins. These can be used alone or in combination of two or more.

上記エポキシ樹脂(A)及び硬化剤(B)の割合は、両成分の種類により適宣選択できる。一般には、エポキシ樹脂100重量部当り硬化剤10〜500重量部の範囲から選択することが出来る。硬化剤(B)として好ましいアミン系硬化剤を用いる場合は、通常((B)の活性水素当量)/((A)中のエポキシ当量)で示される当量比が0.5〜1.0の範囲になるように選択することが適当である。  The proportions of the epoxy resin (A) and the curing agent (B) can be appropriately selected depending on the types of both components. Generally, it can be selected from the range of 10 to 500 parts by weight of the curing agent per 100 parts by weight of the epoxy resin. When using a preferable amine-based curing agent as the curing agent (B), the equivalent ratio usually expressed by (active hydrogen equivalent of (B)) / (epoxy equivalent in (A)) is 0.5 to 1.0. It is appropriate to select the range.

本発明における変性炭化水素樹脂(C)は、まず第一段反応で、予めフェノール類を、石油分解で得られるC9留分に混合し、更に、共役二重結合を含むC5留分を重量比で1〜50%範囲で混ぜたものを、フリーデルクラフト型触媒下で重合することにより得ることができる、分子中に不飽和基を持った水酸基含有不飽和炭化水素樹脂である。
次に第二段反応で、第一段反応で得られた水酸基含有不飽和炭化水素樹脂の不飽和基に、有機不飽和酸を常法で加熱反応させて、酸価が2〜50の範囲となるようにカルボキシル基を導入し、軟化点40〜150℃を有する水酸基とカルボキシル基含有の変性炭化水素樹脂(C)を得る。
In the modified hydrocarbon resin (C) in the present invention, phenols are first mixed in advance with the C9 fraction obtained by petroleum cracking in the first stage reaction, and the C5 fraction containing a conjugated double bond is further mixed by weight ratio. It is a hydroxyl group-containing unsaturated hydrocarbon resin having an unsaturated group in the molecule, which can be obtained by polymerizing the mixture in the range of 1 to 50% under a Friedel-Craft type catalyst.
Next, in the second stage reaction, the unsaturated group of the hydroxyl group-containing unsaturated hydrocarbon resin obtained by the first stage reaction is heated and reacted with an organic unsaturated acid in a conventional manner, and the acid value is in the range of 2-50. A carboxyl group is introduced so that a modified hydrocarbon resin (C) containing a hydroxyl group and a carboxyl group having a softening point of 40 to 150 ° C. is obtained.

ここで、例えばC9留分のみで重合した重合物は、第二段反応を進めるに足りる不飽和結合を分子内に有していないため、有機不飽和酸の付加によるカルボキシル基の導入は難しいと言うことができる。  Here, for example, a polymer obtained by polymerizing only the C9 fraction does not have an unsaturated bond in the molecule sufficient for proceeding with the second stage reaction, so that it is difficult to introduce a carboxyl group by addition of an organic unsaturated acid. I can say that.

有機不飽和酸の付加は、無水マレイン酸、フマル酸などのα・β不飽和酸の他、有機不飽和酸を加熱し、常法で付加する方法が挙げられる。  Examples of the addition of the organic unsaturated acid include a method of heating an organic unsaturated acid in addition to α / β unsaturated acids such as maleic anhydride and fumaric acid, and adding in a conventional manner.

変性炭化水素樹脂(C)の原料となる反応成分を更に詳しく説明すると、石油の熱分解で、エチレン、プロピレンを製造する際、副生物として得られるC9留分には、反応成分として、スチレン、α・βメチルスチレン、ビニルトルエン、インデン、メチルインデンなどのモノオレフィンが含まれている。また、C5留分の反応成分には、イソプレン、ピペリレン、シクロペンタジエンなどの共役二重結合のモノマーが含まれている。  The reaction components used as raw materials for the modified hydrocarbon resin (C) will be described in more detail. When ethylene and propylene are produced by pyrolysis of petroleum, the C9 fraction obtained as a by-product contains styrene, Mono-olefins such as α and β methylstyrene, vinyltoluene, indene and methylindene are included. The reaction component of the C5 fraction contains a conjugated double bond monomer such as isoprene, piperylene, or cyclopentadiene.

本発明のエポキシ塗料組成物に用いられる変性炭化水素樹脂(C)は、1分子中にフェノール性水酸基を0.1〜2.0個、好ましくは0.2〜1.0個含有する。これは重合に際して各原料の仕込み量、重合条件等により適宣調整することができる。フェノール性水酸基が2.0個を超えて存在すると親水性が増し、防食塗料としての耐水性、防食性が劣り、好ましくない。また、0.1個未満では、エポキシ樹脂、およびアミン類等の硬化剤との相溶性が低下し、同様に好ましくない。また、変性炭化水素樹脂(C)の酸価は2〜50である。酸価が2未満の場合は塗料の顔料の濡れ性、密着性において好ましくなく、酸価が50を超えれば耐水性、防食性において好ましくない。変性炭化水素樹脂(C)が最も塗料の特徴を引き出すためには、分子中に水酸基を0.1〜2.0個有し、かつ酸価が2〜50範囲であることが好ましい。  The modified hydrocarbon resin (C) used in the epoxy coating composition of the present invention contains 0.1 to 2.0, preferably 0.2 to 1.0, phenolic hydroxyl groups in one molecule. This can be appropriately adjusted depending on the amount of each raw material charged, the polymerization conditions, and the like. If there are more than 2.0 phenolic hydroxyl groups, the hydrophilicity increases, and the water resistance and anticorrosion properties as an anticorrosion paint are inferior, which is not preferable. On the other hand, when the number is less than 0.1, compatibility with a curing agent such as an epoxy resin and amines is lowered, which is also not preferable. The modified hydrocarbon resin (C) has an acid value of 2-50. When the acid value is less than 2, it is not preferable in terms of wettability and adhesion of the pigment of the paint, and when the acid value exceeds 50, it is not preferable in terms of water resistance and corrosion resistance. In order for the modified hydrocarbon resin (C) to bring out the characteristics of the paint most, it is preferable that the molecule has 0.1 to 2.0 hydroxyl groups and the acid value is in the range of 2 to 50.

また、変性炭化水素樹脂(C)の軟化点が40℃未満の場合は塗膜の表面に樹脂がブリードして粘着性が残存する場合がある。一方、150℃を超える場合は塗料の粘度が高く、塗膜の物性が低下するので好ましくない。なお、本発明による変性炭化水素樹脂(C)の好ましい数平均分子量の範囲は400〜2500である。  Further, when the softening point of the modified hydrocarbon resin (C) is less than 40 ° C., the resin may bleed on the surface of the coating film and stickiness may remain. On the other hand, when the temperature exceeds 150 ° C., the viscosity of the paint is high, and the physical properties of the coating film are deteriorated. In addition, the range of the preferable number average molecular weight of the modified hydrocarbon resin (C) by this invention is 400-2500.

本発明のエポキシ塗料組成物を得るため、エポキシ樹脂(A)100重量部に対して、変性炭化水素樹脂(C)を10〜500重量部配合する。配合量が10重量部未満では、得られた塗膜の硬度が硬く、耐衝撃性が劣る。一方500重量部を越えると、塗膜の柔らかさは増すが、耐水性が劣るなど、何れも好ましくない。  In order to obtain the epoxy coating composition of the present invention, 10 to 500 parts by weight of the modified hydrocarbon resin (C) is blended with 100 parts by weight of the epoxy resin (A). When the blending amount is less than 10 parts by weight, the resulting coating film has a high hardness and inferior impact resistance. On the other hand, when the amount exceeds 500 parts by weight, the softness of the coating film increases, but the water resistance is inferior.

本発明のエポキシ塗料組成物には、可撓性を付与するため等の目的で、液状の改質剤、例えばキシレン樹脂、トルエン樹脂、ブチルグリシジルエーテルなどの反応性樹脂を、エポキシ樹脂100重量部に対して、50重量部以下の範囲で添加してもよい、これらの添加物は、耐水性維持の面から芳香族系のものが好適に使用される。  For the purpose of imparting flexibility to the epoxy coating composition of the present invention, a liquid modifier, for example, a reactive resin such as xylene resin, toluene resin, butyl glycidyl ether, etc., is added to 100 parts by weight of the epoxy resin. On the other hand, these additives, which may be added in the range of 50 parts by weight or less, are preferably aromatic ones from the viewpoint of maintaining water resistance.

本発明のエポキシ塗料組成物には、更に必要に応じて、体質顔料、着色顔料等の顔料類、反応性希釈剤、有機溶剤、沈降防止剤、タレ止め剤、湿潤剤、反応促進剤、付着性付与剤、脱水剤等、通常の塗料用添加剤などを、適宜配合してもよい。  If necessary, the epoxy coating composition of the present invention further includes extenders, pigments such as color pigments, reactive diluents, organic solvents, anti-settling agents, sagging inhibitors, wetting agents, reaction accelerators, and adhesion. Ordinary paint additives such as a property-imparting agent and a dehydrating agent may be appropriately blended.

また、本発明の組成物は、エポキシ樹脂を含む主剤と硬化剤、好ましくはアミン系硬化剤からなる、二液型塗料であり、通常、ジンクプライマーなどの防錆塗膜に塗装される。すなわち、まず鋼板にショットブラストをかけてミルスケールを除き、エチルシリケート系などの無機ジンクショッププライマーを塗布し、その後本発明の塗料組成物の塗布を行う。プライマーはジンクシリケート等に限らず、各種のプライマーを使用することができる。
また、プライマーなしの鋼板等であっても、塗装が可能であり、充分な防食効果が得られる。塗装方法としては、エアースプレー、エアレススプレー、刷毛塗り、ローラーなど従来公知の方法を採用することができ、上記塗料組成物を乾燥膜厚で、150〜500μmになるように塗布することができる。
The composition of the present invention is a two-component paint comprising an epoxy resin-containing main agent and a curing agent, preferably an amine curing agent, and is usually applied to a rust-preventing coating such as a zinc primer. That is, first, shot blasting is applied to the steel plate to remove the mill scale, and an inorganic zinc shop primer such as ethyl silicate is applied, and then the coating composition of the present invention is applied. Primers are not limited to zinc silicate and the like, and various primers can be used.
Further, even a steel plate without a primer can be painted, and a sufficient anticorrosive effect can be obtained. As a coating method, conventionally known methods such as air spray, airless spray, brush coating, and roller can be adopted, and the coating composition can be applied to a dry film thickness of 150 to 500 μm.

以下、実施例と比較例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例により限定されるものではない。
なお、部および%は、それぞれ重量部および重量%を示す
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited by these Examples.
Parts and% indicate parts by weight and% by weight, respectively.

実施例1
1)変性炭化水素樹脂(C)の製造
まず第一段反応で、石油の熱分解により得られた沸点140〜200℃の芳香族C9留分(モノオレフィン55%含有)100部に、沸点20〜80℃の脂肪族系C5留分(共役二重結合30%含有)5部を加え、更に、フェノール8部を添加して反応温度20℃に保ちながら、触媒の三フッ化ホウ素フェノール錯体1.0部を1時間で滴下した。その後同じ温度で、4時間熟成し反応を終了した。その後、苛性ソーダ溶液で触媒を分解し、水洗した後に、減圧蒸留により未反応油および低重合物を除去し、分子中に水酸基0.6個含有した水酸基含有不飽和炭化水素樹脂60部を得た。
次に第二段反応として、第一段反応で得られた樹脂40部に、無水マレイン酸0.4部を添加し、200℃で3時間反応させた後、減圧処理を行い、未反応の無水マレイン酸を除去した。この樹脂の酸価は6であり、分子中に水酸基およびカルボキシル基を含有する変性炭化水素樹脂(C)が得られた。また、得られた変性炭化水素樹脂(C)の軟化点は98℃であった。
得られた樹脂の性状については表1に示す。
2)塗料化
容器にエポキシ樹脂100部、チタン白50部、タルク100部、変性炭化水素樹脂(C)120部、タレ止め5部ならびに可塑剤15部、混合溶剤(MIBK/キシレン;25/25)50部を添加し、攪拌機で均一に混合して、主剤とした。これに硬化剤として、ポリアミド樹脂80部(固形換算)を添加して、混合攪拌してエポキシ塗料組成物を得た。組成および塗料評価結果については表2、表3に示す。
Example 1
1) Production of Modified Hydrocarbon Resin (C) First, in the first stage reaction, 100 parts of an aromatic C9 fraction (containing 55% monoolefin) having a boiling point of 140 to 200 ° C. obtained by pyrolysis of petroleum had a boiling point of 20 Add 5 parts of aliphatic C5 fraction (containing 30% conjugated double bond) at -80 ° C., and further add 8 parts of phenol and keep the reaction temperature at 20 ° C. 0.0 part was added dropwise over 1 hour. Thereafter, the reaction was terminated by aging for 4 hours at the same temperature. Thereafter, the catalyst was decomposed with a caustic soda solution, washed with water, and then unreacted oil and low polymer were removed by distillation under reduced pressure to obtain 60 parts of a hydroxyl group-containing unsaturated hydrocarbon resin containing 0.6 hydroxyl groups in the molecule. .
Next, as the second-stage reaction, 0.4 part of maleic anhydride is added to 40 parts of the resin obtained in the first-stage reaction and reacted at 200 ° C. for 3 hours. Maleic anhydride was removed. The acid value of this resin was 6, and a modified hydrocarbon resin (C) containing a hydroxyl group and a carboxyl group in the molecule was obtained. The resulting modified hydrocarbon resin (C) had a softening point of 98 ° C.
The properties of the obtained resin are shown in Table 1.
2) Preparation of paint 100 parts of epoxy resin, 50 parts of titanium white, 100 parts of talc, 120 parts of modified hydrocarbon resin (C), 5 parts of sagging stopper and 15 parts of plasticizer, mixed solvent (MIBK / xylene; 25/25 ) 50 parts was added and mixed uniformly with a stirrer to obtain the main agent. As a curing agent, 80 parts of polyamide resin (in terms of solid) was added thereto, and mixed and stirred to obtain an epoxy coating composition. The compositions and paint evaluation results are shown in Tables 2 and 3.

実施例2、3
表1に示した処方により、実施例1と同じ条件で変性炭化水素樹脂(C)を製造した。その性状は表1に示す。
塗料化については、実施例1において示したものと同じ方法で塗料化した。組成、および塗料評価結果については表2、表3に示す。
Examples 2 and 3
A modified hydrocarbon resin (C) was produced under the same conditions as in Example 1 according to the formulation shown in Table 1. The properties are shown in Table 1.
The paint was made in the same manner as shown in Example 1. Tables 2 and 3 show the compositions and paint evaluation results.

比較製造例1
1)樹脂の製造
第一段反応をC9留分100部を(C5留分は処方せずに)、フェノール8部の共存下で重合した以外は、実施例1と同じ条件で行い、水酸基含有炭化水素樹脂を得た。次の第二段反応による無水マレイン酸の付加反応は行わなかった。得られた樹脂の性状については表1に示す。
2)塗料化
塗料化については、実施例1において示したものと同じ方法で塗料化した。組成、および塗料評価結果については表2、表3に示す。
Comparative production example 1
1) Production of resin The first stage reaction was carried out under the same conditions as in Example 1, except that 100 parts of C9 fraction (without prescribing C5 fraction) was polymerized in the presence of 8 parts of phenol, and contained hydroxyl groups. A hydrocarbon resin was obtained. The addition reaction of maleic anhydride by the next second stage reaction was not performed. The properties of the obtained resin are shown in Table 1.
2) Coating The coating was made by the same method as shown in Example 1. Tables 2 and 3 show the compositions and paint evaluation results.

比較製造例2
1)樹脂の製造
第一段反応をC9留分100部のみ(C5留分、フェノールの非共存下)で重合した以外は、実施例1と同じ条件で行い、水酸基を含有していない炭化水素樹脂を得た。
次の第二段反応で、この樹脂40部に、無水マレイン酸0.4部を添加し、実施例1と同様に無水マレイン酸の付加反応を試みた。しかしながら、実施例1とは異なり、得られた樹脂の酸価は1.6と低い値であった。これは、第一段反応で得られた樹脂が、付加反応を進めるに足りる不飽和結合を有していないため、反応性が劣ったものと推察される。
得られた樹脂の性状については表1に示す。
2)塗料化
塗料化については、実施例1において示したものと同じ方法で塗料化した。組成、および塗料評価結果については表2、表3に示す。
Comparative production example 2
1) Production of resin Hydrocarbons containing no hydroxyl group were carried out under the same conditions as in Example 1 except that the first stage reaction was polymerized only with 100 parts of C9 fraction (C5 fraction, in the absence of phenol). A resin was obtained.
In the next second stage reaction, 0.4 part of maleic anhydride was added to 40 parts of this resin, and an addition reaction of maleic anhydride was attempted in the same manner as in Example 1. However, unlike Example 1, the acid value of the obtained resin was as low as 1.6. This is presumably because the resin obtained in the first-stage reaction does not have an unsaturated bond sufficient to advance the addition reaction, and therefore the reactivity is inferior.
The properties of the obtained resin are shown in Table 1.
2) Coating The coating was made by the same method as shown in Example 1. Tables 2 and 3 show the compositions and paint evaluation results.

比較製造例3
1)樹脂の製造
比較例1で得られた水酸基含有炭化水素樹脂40部に無水マレイン酸0.4部を添加し、第二段反応を試みたが、比較例2と同様に反応性が劣り、得られた樹脂の酸価は1.7と低い値であった。
得られた樹脂の性状については表1に示す。
2)塗料化
塗料化については、実施例1において示したものと同じ方法で塗料化した。組成、および、塗料評価結果については、表2、表3に示す。
Comparative production example 3
1) Production of Resin 0.4 parts of maleic anhydride was added to 40 parts of the hydroxyl group-containing hydrocarbon resin obtained in Comparative Example 1 and a second-stage reaction was attempted. Similar to Comparative Example 2, the reactivity was poor. The acid value of the obtained resin was as low as 1.7.
The properties of the obtained resin are shown in Table 1.
2) Coating The coating was made by the same method as shown in Example 1. The compositions and paint evaluation results are shown in Tables 2 and 3.

Figure 0004283642
Figure 0004283642

Figure 0004283642
Figure 0004283642

Figure 0004283642
Figure 0004283642

表3の実施例1〜3に示したように、本発明のエポキシ塗料組成物は、耐久性、防食性、塗布時の作業性等に優れていることがわかる。また、タールを一切含有しないため環境上の問題もなく、しかも淡色の塗膜を形成できることから、船舶や一般構造物の防食塗料としても有用である。  As shown in Examples 1 to 3 in Table 3, it can be seen that the epoxy coating composition of the present invention is excellent in durability, corrosion resistance, workability during application, and the like. Moreover, since tar is not contained at all, there is no environmental problem and a light-colored coating film can be formed. Therefore, it is useful as an anticorrosion paint for ships and general structures.

Claims (2)

エポキシ樹脂(A)と、硬化剤(B)および、
(1)第一段反応で、石油の熱分解で得られる沸点が140〜200℃の芳香族を含む、モノオレフィン留分(C9留分)に、沸点20〜80℃の脂肪族系共役二重結合を含む留分(C5留分)を重量比で1〜50%混合し、さらにフェノール類を加え、フリーデルクラフト型触媒の存在下で重合することにより、分子内に不飽和基と水酸基(0.1〜2.0個)を含有する不飽和炭化水素樹脂を得る。
(2)第二段反応で、第一段反応で得られた不飽和炭化水素樹脂の不飽和基に、有機不飽和酸を加熱反応で付加することにより製造できるものであって、
酸価が2〜50で、軟化点が40〜150℃である、分子中に水酸基とカルボキシル基を有する変性炭化水素樹脂(C)を含有するエポキシ塗料組成物であって、該変性炭化水素樹脂(C)の配合量が、エポキシ樹脂(A)固形分100重量部に対し、10〜500重量部であるエポキシ塗料組成物。
Epoxy resin (A), curing agent (B), and
(1) In the first-stage reaction, a monoolefin fraction (C9 fraction) containing an aromatic having a boiling point of 140 to 200 ° C. obtained by pyrolysis of petroleum is added to an aliphatic conjugate 2 having a boiling point of 20 to 80 ° C. A fraction containing a heavy bond (C5 fraction) is mixed in a weight ratio of 1 to 50%, further phenols are added, and polymerization is carried out in the presence of a Friedel-Craft type catalyst. An unsaturated hydrocarbon resin containing (0.1 to 2.0) is obtained.
(2) In the second stage reaction, it can be produced by adding an organic unsaturated acid to the unsaturated group of the unsaturated hydrocarbon resin obtained in the first stage reaction by a heating reaction,
An epoxy coating composition containing a modified hydrocarbon resin (C) having a hydroxyl group and a carboxyl group in the molecule, having an acid value of 2 to 50 and a softening point of 40 to 150 ° C., wherein the modified hydrocarbon resin The epoxy coating composition whose compounding quantity of (C) is 10-500 weight part with respect to 100 weight part of epoxy resin (A) solid content.
請求項1に記載のエポキシ塗料組成物を含有する船舶用塗料。 A marine paint containing the epoxy paint composition according to claim 1 .
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