JPH08113704A - Production of aqueous polyurethane composition having discoloration resistance - Google Patents
Production of aqueous polyurethane composition having discoloration resistanceInfo
- Publication number
- JPH08113704A JPH08113704A JP6275559A JP27555994A JPH08113704A JP H08113704 A JPH08113704 A JP H08113704A JP 6275559 A JP6275559 A JP 6275559A JP 27555994 A JP27555994 A JP 27555994A JP H08113704 A JPH08113704 A JP H08113704A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- solid content
- aqueous dispersion
- component
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐変色性水系ウレタン
組成物の製造方法に関し、詳しくは、良好な透明性を有
しかつ熱および光に対する耐変色性にすぐれたフィルム
を形成し得る水系ウレタン組成物を得る方法に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a discoloration-resistant water-based urethane composition, and more specifically, an aqueous system capable of forming a film having good transparency and excellent discoloration resistance to heat and light. The present invention relates to a method for obtaining a urethane composition.
【０００２】[0002]
【従来の技術】従来からウレタン樹脂は耐衝撃性、耐薬
品性、耐磨耗性、耐寒性に優れた樹脂であり、接着、塗
料、コーティング材など種々の分野、用途に用いられて
いる。しかし、ウレタン樹脂は熱、光等の外的要因で黄
変するという欠点があった。2. Description of the Related Art Urethane resins have hitherto been excellent in impact resistance, chemical resistance, abrasion resistance and cold resistance, and have been used in various fields and applications such as adhesion, paints and coating materials. However, the urethane resin has a drawback that it turns yellow due to external factors such as heat and light.
【０００３】このような欠点を解消する試みとして、特
開昭６１−１２６１２２号公報記載の改良技術ではベン
ゾトリアゾール系紫外線吸収剤、ヒンダードフェノール
系酸化防止剤、亜リン酸エステル等を添加している。
又、特開平２−２４０１７０号公報では酸化防止剤、架
橋剤を選択することで繊維強化プラスチック（ＦＲＰ）
を安定化することが開示されている。In an attempt to eliminate such a drawback, in the improved technique described in JP-A-61-126122, a benzotriazole type ultraviolet absorber, a hindered phenol type antioxidant, a phosphite ester, etc. are added. There is.
Further, in JP-A-2-240170, a fiber reinforced plastic (FRP) is prepared by selecting an antioxidant and a cross-linking agent.
Is disclosed to be stabilized.
【０００４】[0004]
【本発明が解決しようとする課題】しかし、これら従来
の黄変防止技術では、良好な透明性を与えると同時に充
分に黄変を防止することのできる水系ウレタン組成物を
得ることはできなかった。However, with these conventional techniques for preventing yellowing, it has not been possible to obtain a water-based urethane composition which can impart good transparency and at the same time sufficiently prevent yellowing. .
【０００５】従って、本発明の目的は上記問題点を解消
し、良好な透明性を有すると共に熱や光に対する耐変色
性にすぐれたフィルムを形成し得る水系ウレタン組成物
の製造方法を提供することにある。Therefore, an object of the present invention is to solve the above problems and to provide a method for producing an aqueous urethane composition capable of forming a film having excellent transparency and excellent color fastness to heat and light. It is in.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上記問題を
解決すべく鋭意研究した結果、特定成分の水分散液を夫
々所定の割合で混合することにより上記目的を達成し得
ることを見出し、本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 the above objects can be achieved by mixing respective aqueous dispersions of specific components in predetermined proportions. The present invention has been completed.
【０００７】即ち、本発明は、以下の（ａ）〜（ｅ）の
成分を混合することを特徴とする耐変色性水系ウレタン
組成物の製造方法である。 （ａ）アニオン基を有する末端イソシアネートプレポリ
マー水分散液 （ｂ）チオエーテル系酸化防止剤水分散液 （ｃ）ベンゾトリアゾール系紫外線吸収剤水分散液 （ｄ）ビスフェノールＡ型エポキシ樹脂水分散液 （ｅ）メラミン系架橋剤水分散液 （但し、それぞれ固形分重量として（ａ）１００重量部
に対して（ｂ）が０．０１〜１重量部、（ｃ）が０．０
１〜５重量部、（ｄ）が１〜５０重量部、（ｅ）が０．
０１〜２０重量部であり、（ａ）〜（ｅ）の各成分の濃
度は、これら成分の混合後における全固形分含量が１０
〜７０重量％となるように調整する。）That is, the present invention is a method for producing a discoloration-resistant water-based urethane composition, which comprises mixing the following components (a) to (e). (A) Aqueous dispersion of terminal isocyanate prepolymer having anion group (b) Aqueous dispersion of thioether antioxidant (c) Aqueous dispersion of benzotriazole ultraviolet absorber (d) Aqueous dispersion of bisphenol A type epoxy resin (e) ) Aqueous dispersion of melamine-based cross-linking agent (however, with respect to 100 parts by weight of (a), 0.01 to 1 part by weight of (b) and 0.0 of (c) are used as solid content weight, respectively)
1-5 parts by weight, (d) 1-50 parts by weight, (e) 0.
01 to 20 parts by weight, and the concentration of each of the components (a) to (e) is such that the total solid content after mixing these components is 10
Adjust to be ~ 70% by weight. )
【０００８】また、本発明は、上記方法により得られる
耐変色性水系ウレタン組成物に関するものである。The present invention also relates to a discoloration-resistant water-based urethane composition obtained by the above method.
【０００９】本発明に使用する（ａ）アニオン基を有す
る末端イソシアネートプレポリマー水分散液は、分子中
にアニオン基を有する末端イソシアネートプレポリマー
単独若しくはこれと分子中にアニオン基を有しない末端
イソシアネートプレポリマーとの混合物を水に分散させ
たものであり、好ましくは樹脂分（分子中にアニオン基
を有する末端イソシアネートプレポリマーと分子中にア
ニオン基を有しない末端イソシアネートプレポリマーと
の合計量）１００グラム当たり０．００１〜０．５当量
のアニオン基を有するものであると（ａ）成分の水分散
性がよく、乳化剤乃至分散剤を使用しなくとも水分散液
を得ることができるので好ましい。The (a) aqueous dispersion of a terminal isocyanate prepolymer having an anionic group used in the present invention is a terminal isocyanate prepolymer having an anionic group in the molecule alone or a terminal isocyanate prepolymer having no anionic group in the molecule. A mixture of a polymer and water is dispersed, and preferably 100 g of a resin component (the total amount of a terminal isocyanate prepolymer having an anion group in the molecule and a terminal isocyanate prepolymer having no anion group in the molecule). It is preferable to have 0.001 to 0.5 equivalents of anionic groups per component because the component (a) has good water dispersibility and an aqueous dispersion can be obtained without using an emulsifier or dispersant.
【００１０】上記分子中にアニオン基を有する末端イソ
シアネートプレポリマーのアニオン基としてはカルボキ
シル基、スルホン基及びこれらの併用が挙げられるが、
好ましくはカルボキシル基が好ましい。Examples of the anionic group of the terminal isocyanate prepolymer having an anionic group in the molecule include a carboxyl group, a sulfone group and a combination thereof.
A carboxyl group is preferred.
【００１１】上記分子中にアニオン基を有する末端イソ
シアネートプレポリマーは、従来公知の方法で得ること
ができ、例えばカルボキシル基の導入を例にとると、
２，２−ジメチロールプロピオン酸、２，２−ジメチロ
ール酪酸、２，２−ジメチロール吉草酸等のカルボキシ
ル基含有ジオール単位を有するポリエーテルポリオール
及び／又はポリエステルポリオールをポリオール成分と
してポリイソシアネートと反応させて得ることができ
る。The terminal isocyanate prepolymer having an anion group in the molecule can be obtained by a conventionally known method. For example, when introducing a carboxyl group,
2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylol valeric acid, etc. Polyether polyol and / or polyester polyol having a carboxyl group-containing diol unit such as valeric acid is reacted with polyisocyanate as a polyol component. Obtainable.
【００１２】上記分子中にアニオン基を有する末端イソ
シアネートプレポリマー及び分子中にアニオン基を有し
ない末端イソシアネートプレポリマーに使用されるポリ
エーテルポリオール及び／又はポリエステルポリオール
のポリオール成分は平均分子量が５００〜４０００のも
のが望ましく、又、ポリイソシアネート成分としては特
に限定されず、例えば、テトラメチレンジイソシアネー
ト、ヘキサメチレンジイソシアネート、リジンジイソシ
アネート等の脂肪族ポリイソシアネート、１，４−シク
ロヘキシレンジイソシアネート、イソホロンジイソシア
ネート、４，４’−ジシシクロヘキシルジイソシアネー
ト等の脂環族ポリイソシアネート、トリレンジイソシア
ネート、４，４’−ジフェニルメタンジイソシアネート
等の芳香族ポリイソシアネート等が挙げられ、中でも脂
肪族又は脂環族ポリイソシアネートが好ましい。The polyol component of the polyether polyol and / or polyester polyol used in the terminal isocyanate prepolymer having an anion group in the molecule and the terminal isocyanate prepolymer having no anion group in the molecule has an average molecular weight of 500 to 4000. The polyisocyanate component is not particularly limited, and examples thereof include aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate and 4,4. Alicyclic polyisocyanates such as'-disycyclohexyl diisocyanate, tolylene diisocyanate, aromatic polyisols such as 4,4'-diphenylmethane diisocyanate Aneto, and among them aliphatic or alicyclic polyisocyanate is preferred.
【００１３】また、この末端イソシアネートプレポリマ
ーはジアルキルアミン、ジアルキルヒドラジド等で鎖伸
長させた末端イソシアネートプレポリマーであってもよ
く、水分散が可能な範囲内で用途により任意に選択でき
る。The terminal isocyanate prepolymer may be a terminal isocyanate prepolymer which is chain-extended with dialkylamine, dialkylhydrazide or the like, and can be arbitrarily selected depending on the application within a range in which water dispersion is possible.
【００１４】本発明に使用する（ｂ）チオエーテル系酸
化防止剤水分散液は、合成樹脂用酸化防止剤として公知
のチオエーテル系酸化防止剤を、必要に応じて乳化剤乃
至分散剤を用いて、若しくは用いることなく水に分散さ
せたものである。かかるチオエーテル系抗酸化剤として
は、例えば、ジラウリルチオジプロピオネート、ジトリ
デシルチオジプロピオネート、ジミリスチルチオジプロ
ピオネート、ジステアリルチオジプロピオネート等のチ
オジプロピオネート類、テトラキス（メチレン−３−ド
デシルメルカプトプロピオネート）メタン、４，４’−
チオビス（２−第三ブチル−５−メチルフェニル）−ビ
ス（３−ドデシルメルカプトプロピオネート）等の３−
アルキルメルカプトプロピオン酸エステル類が挙げられ
る。The (b) thioether-based antioxidant aqueous dispersion used in the present invention comprises a thioether-based antioxidant known as an antioxidant for synthetic resins, optionally using an emulsifier or dispersant, or It was dispersed in water without using it. Examples of such thioether antioxidants include thiodipropionates such as dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, tetrakis (methylene- 3-dodecyl mercaptopropionate) methane, 4,4'-
3- such as thiobis (2-tert-butyl-5-methylphenyl) -bis (3-dodecylmercaptopropionate)
Examples thereof include alkyl mercaptopropionic acid esters.
【００１５】これらのチオエーテル系抗酸化剤は、固形
分重量として（ａ）１００重量部に対して（ｂ）を０．
０１〜１重量部の割合で使用する。These thioether type antioxidants have a solid content of (a) of 100 parts by weight and (b) of 0.
It is used in a proportion of 01 to 1 part by weight.
【００１６】上記量未満であると耐変色性に劣り、上記
量を超えるとフィルム形成の用途に使用した場合透明性
に欠ける。When the amount is less than the above amount, the color fastness is poor, and when the amount is more than the above amount, the transparency is insufficient when used for film forming.
【００１７】本発明に使用する（ｃ）ベンゾトリアゾー
ル系紫外線吸収剤水分散液は、合成樹脂用紫外線吸収剤
として公知のベンゾトリアゾール系紫外線吸収剤を、必
要に応じて乳化剤乃至分散剤を用いて、若しくは用いる
ことなく水に分散させたものである。かかるベンゾトリ
アゾール系紫外線吸収剤としては、例えば、２−（２−
ヒドロキシ−５−メチルフェニル）ベンゾトリアゾー
ル、２−（２−ヒドロキシ−５−第三オクチルフェニ
ル）ベンゾトリアゾール、２−（２−ヒドロキシ−３，
５−ジ第三ブチルフェニル）−５−クロロベンゾトリア
ゾール、２−（２−ヒドロキシ−３−第三ブチル−５−
メチルフェニル）−５−クロロベンゾトリアゾール、２
−（２−ヒドロキシ−３，５−ジクミルフェニル）ベン
ゾトリアゾール、２，２’−メチレンビス（４−第三オ
クチル−６−ベンゾトリアゾリル）フェノール、２−
（２−ヒドロキシ−３−第三ブチル−５−カルボキシフ
ェニル）ベンゾトリアゾールのポリエチレングリコール
エステル等が挙げられる。The (c) benzotriazole-based UV absorber aqueous dispersion used in the present invention comprises a benzotriazole-based UV absorber known as a UV absorber for synthetic resins and, if necessary, an emulsifier or dispersant. Or, it is dispersed in water without using. Examples of the benzotriazole-based ultraviolet absorber include 2- (2-
Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,
5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-
Methylphenyl) -5-chlorobenzotriazole, 2
-(2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiaryoctyl-6-benzotriazolyl) phenol, 2-
Examples thereof include polyethylene glycol ester of (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole.
【００１８】これらのベンゾトリアゾール系紫外線吸収
剤は、固形分重量として（ａ）１００重量部に対して
（ｃ）を０．０１〜５重量部の割合で使用する。These benzotriazole type ultraviolet absorbers are used in a proportion of 0.01 to 5 parts by weight of (c) with respect to 100 parts by weight of (a) as a solid content weight.
【００１９】上記量未満であると耐変色性に劣り、上記
量を超えるとフィルム形成の用途に使用した場合透明性
に欠ける。If the amount is less than the above amount, the discoloration resistance is poor, and if the amount is more than the above amount, the transparency is insufficient when used for film forming.
【００２０】本発明に使用する（ｄ）ビスフェノールＡ
型エポキシ樹脂水分散液は、従来公知のエポシキ樹脂、
好ましくはエポキシ当量１００〜４００のエポキシ樹脂
を、必要に応じて乳化剤乃至分散剤を用いて、若しくは
用いることなく水に分散させたものであり、特に水溶性
乃至自己乳化性のエポキシ樹脂を使用するとエポキシ樹
脂単独で水分散液とすることができるので好ましく、例
えば、ビスフェノールＡにエチレンオキサイドを付加し
て親水性を付与し両末端をエポキシ化させたものなどを
水溶性乃至自己乳化性のビスフェノールＡ型エポキシ樹
脂として例示することができる。(D) Bisphenol A used in the present invention
Type epoxy resin aqueous dispersion is a conventionally known epoxy resin,
Preferably, an epoxy resin having an epoxy equivalent of 100 to 400 is dispersed in water with or without an emulsifier or dispersant as necessary, and particularly when a water-soluble or self-emulsifying epoxy resin is used. Epoxy resin alone is preferable because it can be made into an aqueous dispersion, and for example, bisphenol A, which is water-soluble or self-emulsifying, is obtained by adding ethylene oxide to bisphenol A to impart hydrophilicity and epoxidizing both terminals. The epoxy resin can be exemplified.
【００２１】これらの（ｄ）ビスフェノールＡ型エポキ
シ樹脂水分散液は、固形分重量として（ａ）１００重量
部に対して（ｄ）を１〜５０重量部の割合で使用する。These (d) bisphenol A type epoxy resin aqueous dispersions contain 1 to 50 parts by weight of (d) per 100 parts by weight of solid content (a).
【００２２】ビスフェノールＡ型エポキシ樹脂は架橋剤
として作用するので、上記量未満であると硬化物が安定
性に劣り、長時間の屋外曝露に対し割れや膨れが生じる
ようになり、上記量を超えるとフィルム形成の用途に使
用した場合透明性に欠ける。Since the bisphenol A type epoxy resin acts as a cross-linking agent, if the amount is less than the above amount, the cured product is inferior in stability and cracks or swelling will occur after long-term outdoor exposure, and the amount exceeds the above amount. And lacks transparency when used for film forming applications.
【００２３】本発明に使用する（ｅ）メラミン系架橋剤
水分散液は、合成樹脂用架橋剤として公知のメラミン系
架橋剤を、必要に応じて乳化剤乃至分散剤を用いて、若
しくは用いることなく水に分散させたものであり、メラ
ミン系架橋剤としては特に限定されないが、例えば、ホ
ルムアルデヒド単位を含む３級メチロールメラミン系架
橋剤が好ましく、昭和高分子（株）製のミルベンレジン
ＳＭ−８５０等を使用することができる。The (e) melamine-based crosslinking agent aqueous dispersion used in the present invention contains a melamine-based crosslinking agent known as a crosslinking agent for synthetic resins, optionally with or without an emulsifier or dispersant. The melamine-based cross-linking agent dispersed in water is not particularly limited, but, for example, a tertiary methylol melamine-based cross-linking agent containing a formaldehyde unit is preferable, and Milben resin SM-850 manufactured by Showa High Polymer Co., Ltd. Can be used.
【００２４】これらの（ｅ）メラミン系架橋剤水分散液
は、固形分重量として（ａ）１００重量部に対して
（ｅ）を０．０１〜２０重量部の割合で使用する。These (e) melamine-based crosslinking agent aqueous dispersions are used in a proportion of 0.01 to 20 parts by weight of (e) per 100 parts by weight of the solid content (a).
【００２５】上記量未満であると硬化物が安定性に劣
り、長時間の屋外曝露に対し割れや膨れが生じるように
なり、上記量を超えるとフィルム形成の用途に使用した
場合透明性に欠ける。When the amount is less than the above amount, the cured product is inferior in stability and may be cracked or swelled after long-term outdoor exposure, and when the amount is more than the above amount, transparency is insufficient when used for film formation. .
【００２６】本発明に使用する上記（ａ）〜（ｅ）の各
成分の濃度は、これらが混合された後において、全固形
分含量が１０〜７０重量％、好ましくは２０〜４０重量
％となるように調整する。The concentration of each of the components (a) to (e) used in the present invention is such that the total solid content is 10 to 70% by weight, preferably 20 to 40% by weight after they are mixed. Adjust so that
【００２７】固形分含量が上記量未満であると硬化性が
悪く、フィルム形成などの用途に使用することができ
ず、又、上記量を超えると相溶性が悪化し、沈殿、ゲル
化が起こりやすく、フィルム形成などの用途に使用した
場合、透明性に欠けるようになる。If the solid content is less than the above amount, the curability is poor and it cannot be used for applications such as film formation. If it exceeds the above amount, the compatibility deteriorates and precipitation and gelation occur. It is easy to use and lacks transparency when used for applications such as film formation.
【００２８】（ａ）〜（ｅ）の各成分の濃度の下限は特
になく、各成分の固形分重量が上記規定量の範囲内であ
り、かつ、得られた耐変色性水系ウレタン組成物の全固
形分含量が上記範囲内であれば希薄な液でも差し支えな
い。There is no particular lower limit to the concentration of each of the components (a) to (e), the solid content weight of each component is within the specified amount range, and the obtained discoloration-resistant water-based urethane composition is If the total solid content is within the above range, a dilute liquid may be used.
【００２９】また、（ａ）〜（ｅ）の各成分の濃度の上
限も特になく、各成分の固形分重量が上記規定量の範囲
内であり、かつ、得られた耐変色性水系ウレタン組成物
の全固形分含量が上記範囲内であり、実質的に分散液と
なっていれば濃厚な液でも差し支えない。Also, there is no particular upper limit to the concentration of each of the components (a) to (e), the solid content weight of each component is within the above-specified range, and the obtained discoloration-resistant water-based urethane composition. If the total solid content of the substance is within the above range and the substance is substantially a dispersion liquid, a concentrated liquid may be used.
【００３０】本発明においては、（ａ）〜（ｅ）の各成
分を混合するが、混合の順序は特に制限されず、すべて
を同時に混合してもよいし、予め混合しておいた複数の
成分を他の成分と混合してもよいし、あるいはまた予め
混合しておいた複数の成分同士をさらに混合してもよい
が、（ｄ）成分及び（ｅ）成分は硬化剤として作用する
ので、予め混合した成分を使用する場合には、（ａ）成
分と、（ｄ）成分及び／又は（ｅ）成分は別の系として
おくと使用上便宜である。In the present invention, the components (a) to (e) are mixed, but the order of mixing is not particularly limited, and all of them may be mixed at the same time, or a plurality of premixed components may be mixed. The components may be mixed with other components, or a plurality of components that have been mixed in advance may be further mixed, but the components (d) and (e) act as a curing agent. When using components that have been mixed in advance, it is convenient to use if the components (a) and (d) and / or (e) are separate systems.
【００３１】なお、混合後直ち（概ね８時間程度以内）
に使用するのであれば、（ａ）成分と、（ｄ）成分及び
／又は（ｅ）成分が同一系であっても何等問題となるこ
とはないことは勿論のことである。Immediately after mixing (approximately within 8 hours)
If it is used for the above, it goes without saying that there is no problem even if the component (a) and the component (d) and / or the component (e) are in the same system.
【００３２】[0032]
【実施例】次に、実施例により本発明を具体的に説明す
る。 実施例１ ポリエステルポリオールを基本骨格にもちカルボキシル
基を含有する末端イソシアネートプレポリマー水分散液
（旭電化工業（株）製アデカボンタイターＨＵＸ−２３
２：樹脂分１００グラム当たりカルボキシル基０．０７
当量：固形分含量３０重量％：粘度２０ｃｐｓ：ｐＨ
７．５）１００重量部に、チオエーテル系酸化防止剤
（旭電化工業（株）製アデカスタブＡＯ−２３）水分散
液（固形分含量３０重量％）０．１２５重量部、ベンゾ
トリアゾール系紫外線吸収剤（旭電化工業（株）製アデ
カスタブＬＡ−３６）水分散液（固形分含量３０重量
％）１．２５重量部、ビスフェノールＡ型エポキシ樹脂
水分散液（旭電化工業（株）製：アデカボンタイターＨ
ＵＸ−ＸＷ：固形分含量５５重量％）を７重量部、メラ
ミン系架橋剤水分散液（昭和高分子（株）製：ミルベン
レジンＳＭ−８５０：固形分含量７０重量％）を３重量
部混合し、耐変色性水系ウレタン組成物を得た。EXAMPLES Next, the present invention will be described in detail with reference to examples. Example 1 Aqueous dispersion of a terminal isocyanate prepolymer having a polyester polyol as a basic skeleton and containing a carboxyl group (Adekabon Titer HUX-23 manufactured by Asahi Denka Co., Ltd.)
2: Carboxyl group 0.07 per 100 grams of resin content
Equivalent: Solid content 30% by weight: Viscosity 20 cps: pH
7.5) To 100 parts by weight, 0.125 parts by weight of a thioether antioxidant (Adeka Stab AO-23 manufactured by Asahi Denka Kogyo Co., Ltd.) aqueous dispersion (solid content 30% by weight), a benzotriazole ultraviolet absorber (Adeka Stab LA-36 manufactured by Asahi Denka Kogyo Co., Ltd.) 1.25 parts by weight of aqueous dispersion (solid content 30% by weight), bisphenol A type epoxy resin aqueous dispersion (Asahi Denka Kogyo KK: ADEKA BON TITER) H
7 parts by weight of UX-XW: solid content 55% by weight, and 3 parts by weight of melamine-based crosslinking agent aqueous dispersion (manufactured by Showa Polymer Co., Ltd .: Milven Resin SM-850: solid content 70% by weight). A discoloration-resistant water-based urethane composition was obtained.
【００３３】この水系ウレタン組成物をガラス板上に流
し、室温にて１８時間乾燥させた後、１２０℃で３０分
間乾燥させて膜厚８０ミクロンのポリウレタンフィルム
を作製した。The aqueous urethane composition was poured onto a glass plate, dried at room temperature for 18 hours, and then dried at 120 ° C. for 30 minutes to prepare a polyurethane film having a thickness of 80 μm.
【００３４】実施例２、比較例１〜８ それぞれ下記の表１に示す配合内容で実施例１と同様に
してポリウレタンフィルムを作製した。上記実施例１〜
２、比較例１〜８で得られたポリウレタンフィルムに対
して以下の試験を行った。Example 2 and Comparative Examples 1 to 8 Polyurethane films were prepared in the same manner as in Example 1 with the formulation contents shown in Table 1 below. Examples 1 to 1 above
2. The following tests were performed on the polyurethane films obtained in Comparative Examples 1 to 8.
【００３５】透明性試験 １２０℃の定温恒温器にフィルムを７日間入れ、目視に
より、透明で濁りのないものを◎、透明ではあるがやや
曇りのあるものを○、曇っているがやや透明性を有する
ものを△、不透明なものを×として評価した。Transparency test The film was placed in a thermostat of 120 ° C. for 7 days, and when visually observed, the transparent and non-turbid film was ⊚, the transparent but slightly clouded film was ○, and the cloudy but slightly transparent film was observed. The evaluation was evaluated as Δ for those having “A” and as × for those having an opacity.
【００３６】耐熱変色性試験 １３０℃、１４０℃、１５０℃の定温恒温器にそれぞれ
フィルムを７日間入れた後、分光光度計にて４００ナノ
メーターの光透過率を測定し、透過率９０％以上を◎、
８０％以上９０％未満を○、５０％以上８０％未満を
△、５０％未満を×として評価した。Heat-resistant discoloration test After the films were placed in constant-temperature thermostats of 130 ° C., 140 ° C. and 150 ° C. for 7 days, the light transmittance of 400 nanometer was measured with a spectrophotometer, and the transmittance was 90% or more. ◎,
80% or more and less than 90% was evaluated as ◯, 50% or more and less than 80% was evaluated as Δ, and less than 50% was evaluated as x.
【００３７】耐候性試験 ウェザーメーター（サンシャインカーボンアーク型）に
て試験し、５００時間後、１０００時間後、１５００時
間後、２０００時間後の外観を、目視により、平面性に
変化のないものを◎、やや変形しているものの実用上問
題の無いものを○、クラックや膨れは無いが変形してお
り実用上支障のあるものを△、クラックや膨れがあるも
のを×として評価した。また、光沢保持率をグロスメー
ターで測定した。得られた結果を下記の表１に併記す
る。Weather resistance test A weather meter (sunshine carbon arc type) was tested, and after 500 hours, 1000 hours, 1500 hours, and 2000 hours, the appearance was visually confirmed to have no change in flatness. A sample that was slightly deformed but had no problem in practical use was evaluated as ◯, a sample that was not cracked or swollen but had a problem in practical use was evaluated as Δ, and a sample that was cracked or swollen was evaluated as x. Further, the gloss retention rate was measured with a gloss meter. The results obtained are also shown in Table 1 below.
【００３８】[0038]
【表１】 [Table 1]
【００３９】１）旭電化工業（株）製ポリエステルポリ
オールを基本骨格にもちカルボキシル基を含有する末端
イソシアネートポレポリマー水分散液アデカボンタイタ
ーＨＵＸ−２３２：樹脂分１００グラム当たりカルボキ
シル基０．０７当量：固形分含量３０重量％：粘度２０
ｃｐｓ：ｐＨ７．５ ２）旭電化工業（株）製ポリエーテルポリオールを基本
骨格にもちカルボキシル基を含有する末端イソシアネー
トポレポリマー水分散液アデカボンタイターＨＵＸ−１
６０：樹脂分１００グラム当たりカルボキシル基０．１
当量：固形分含量３５重量％：粘度３０ｃｐｓ：ｐＨ
７．５ ３）旭電化工業（株）製チオエーテル系酸化防止剤アデ
カスタブＡＯ−２３（水に分散せず粉体で使用） ４）旭電化工業（株）製チオエーテル系酸化防止剤アデ
カスタブＡＯ−２３水分散液（固形分含量３０重量％） ５）旭電化工業（株）製ヒンダードフェノール系酸化防
止剤アデカスタブＡＯ−８８水分散液（固形分含量３０
重量％） ６）旭電化工業（株）製ベンゾトリアゾール系紫外線吸
収剤アデカスタブＬＡ−３６水分散液（固形分含量３０
重量％） ７）旭電化工業（株）製自己乳化性ビスフェノールＡ型
エポキシ樹脂水分散物アデカボンタイターＨＵＸ−ＸＷ
（固形分含量５５重量％） ８）昭和高分子（株）製メラミン系架橋剤水分散液ミル
ベンレジンＳＭ−８５０（固形分含量７５重量％）1) Adicapone titer HUX-232 water dispersion of terminal isocyanate pole polymer having a carboxyl group and having a polyester skeleton manufactured by Asahi Denka Co., Ltd. as a basic skeleton: HUX-232: 0.07 equivalent of carboxyl group per 100 g of resin content: Solid content 30% by weight: viscosity 20
cps: pH 7.5 2) Aqueous terminal isocyanate polymer dispersion containing carboxyl group and polyether polyol manufactured by Asahi Denka Kogyo Co., Ltd. Adecabon Titer HUX-1
60: 0.1 carboxyl group per 100 grams of resin content
Equivalent: Solid content 35% by weight: Viscosity 30 cps: pH
7.5 3) Asahi Denka Kogyo Co., Ltd. thioether antioxidant ADEKA STAB AO-23 (used as a powder without being dispersed in water) 4) Asahi Denka Co., Ltd. thioether antioxidant ADEKA STAB AO-23 Aqueous dispersion (solid content 30% by weight) 5) Asahi Denka Kogyo Co., Ltd. hindered phenolic antioxidant ADEKA STAB AO-88 aqueous dispersion (solid content 30)
%) 6) Asahi Denka Kogyo Co., Ltd. benzotriazole-based UV absorber ADEKA STAB LA-36 aqueous dispersion (solid content 30
% By weight) 7) Self-emulsifying bisphenol A type epoxy resin water dispersion made by Asahi Denka Co., Ltd. ADEKA BON TITER HUX-XW
(Solid content 55% by weight) 8) Showa High Polymer Co., Ltd. melamine-based cross-linking agent aqueous dispersion milbenresin SM-850 (solid content 75% by weight)
【００４０】[0040]
【発明の効果】以上説明してきたように、本発明の耐変
色性水系ウレタン組成物の製造方法においては、得られ
る水系ウレタン組成物によって形成させるフィルムが良
好な透明性を有すると共に、熱や光等に対する耐変色性
に優れているという効果を有している。As described above, in the method for producing a discoloration-resistant water-based urethane composition of the present invention, the film formed from the obtained water-based urethane composition has good transparency and heat and light. It has an effect that it is excellent in discoloration resistance to the like.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 175/04 ＰＨＴ ＰＨＶ ＰＨＷ (72)発明者 松岡 勉 東京都荒川区東尾久七丁目２番35号 旭電 化工業株式会社内Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI Technical indication location C09D 175/04 PHT PHV PHW (72) Inventor Tsutomu Matsuoka 7-2 35 Higashiohisa, Arakawa-ku, Tokyo Asahi Denka Industry Co., Ltd.
Claims (2)
ことを特徴とする耐変色性水系ウレタン組成物の製造方
法。 （ａ）アニオン基を有する末端イソシアネートプレポリ
マー水分散液 （ｂ）チオエーテル系酸化防止剤水分散液 （ｃ）ベンゾトリアゾール系紫外線吸収剤水分散液 （ｄ）ビスフェノールＡ型エポキシ樹脂水分散液 （ｅ）メラミン系架橋剤水分散液 （但し、それぞれ固形分重量として（ａ）１００重量部
に対して（ｂ）が０．０１〜１重量部、（ｃ）が０．０
１〜５重量部、（ｄ）が１〜５０重量部、（ｅ）が０．
０１〜２０重量部であり、（ａ）〜（ｅ）の各成分の濃
度は、これら成分の混合後における全固形分含量が１０
〜７０重量％となるように調整する。）1. A method for producing a discoloration-resistant water-based urethane composition, which comprises mixing the following components (a) to (e). (A) Aqueous dispersion of terminal isocyanate prepolymer having anion group (b) Aqueous dispersion of thioether antioxidant (c) Aqueous dispersion of benzotriazole ultraviolet absorber (d) Aqueous dispersion of bisphenol A type epoxy resin (e) ) Aqueous dispersion of melamine-based cross-linking agent (however, with respect to 100 parts by weight of (a), 0.01 to 1 part by weight of (b) and 0.0 of (c) are used as solid content weight, respectively)
1-5 parts by weight, (d) 1-50 parts by weight, (e) 0.
01 to 20 parts by weight, and the concentration of each of the components (a) to (e) is such that the total solid content after mixing these components is 10
Adjust to be ~ 70% by weight. )
変色性水系ウレタン組成物。2. A discoloration-resistant water-based urethane composition produced by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27555994A JP3588375B2 (en) | 1994-10-17 | 1994-10-17 | Method for producing discoloration-resistant aqueous urethane composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27555994A JP3588375B2 (en) | 1994-10-17 | 1994-10-17 | Method for producing discoloration-resistant aqueous urethane composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08113704A true JPH08113704A (en) | 1996-05-07 |
| JP3588375B2 JP3588375B2 (en) | 2004-11-10 |
Family
ID=17557140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27555994A Expired - Fee Related JP3588375B2 (en) | 1994-10-17 | 1994-10-17 | Method for producing discoloration-resistant aqueous urethane composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3588375B2 (en) |
Cited By (6)
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|---|---|---|---|---|
| WO2005049683A1 (en) * | 2003-11-18 | 2005-06-02 | Basf Aktiengesellschaft | Laminating adhesives containing polyurethane and epoxide resin |
| KR100842411B1 (en) * | 2006-12-08 | 2008-07-01 | 전북대학교산학협력단 | Composition of Water-soluble Polyurethane/Epoxy Hybrid and Method of Producing the Same |
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| KR20190020287A (en) | 2016-06-17 | 2019-02-28 | 도레이 카부시키가이샤 | Resin composition, cured film, method of manufacturing cured film and display device |
| CN110540743A (en) * | 2019-07-30 | 2019-12-06 | 燕京理工学院 | Zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005049683A1 (en) * | 2003-11-18 | 2005-06-02 | Basf Aktiengesellschaft | Laminating adhesives containing polyurethane and epoxide resin |
| US7749604B2 (en) * | 2003-11-18 | 2010-07-06 | Basf Aktiengesellschaft | Laminating adhesives containing polyurethane and epoxide resin |
| KR100842411B1 (en) * | 2006-12-08 | 2008-07-01 | 전북대학교산학협력단 | Composition of Water-soluble Polyurethane/Epoxy Hybrid and Method of Producing the Same |
| KR20190020287A (en) | 2016-06-17 | 2019-02-28 | 도레이 카부시키가이샤 | Resin composition, cured film, method of manufacturing cured film and display device |
| US10858509B2 (en) | 2016-06-17 | 2020-12-08 | Toray Industries, Inc. | Resin composition, cured film, method for producing cured film, and display device |
| JP2018051435A (en) * | 2016-09-26 | 2018-04-05 | 日本ペイント株式会社 | Multilayer coating film forming method |
| CN110540743A (en) * | 2019-07-30 | 2019-12-06 | 燕京理工学院 | Zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and preparation method thereof |
| CN110540743B (en) * | 2019-07-30 | 2021-09-28 | 燕京理工学院 | Zinc oxide-DOPO functionalized benzotriazole composite modified polyurethane material and preparation method thereof |
| JP2021050292A (en) * | 2019-09-26 | 2021-04-01 | 株式会社タムラ製作所 | Composition that gives cured article having elasticity and ultraviolet laser processability, and thermosetting sheet of the composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3588375B2 (en) | 2004-11-10 |
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