JP4061631B2 - Non-aqueous primer composition - Google Patents

Description

【００３０】
【化２】

【００３１】
式１に該当する化合物としては、Ｎ−メチルジエタノールアミン、Ｎ−メチルジプロパノールアミン、Ｎ−エチルジエタノールアミン等のＮ−アルキルジアルカノールアミン類、Ｎ−フェニルジエタノールアミン、Ｎ−フェニルジプロパノールアミン等のＮ−アリールジアルカノールアミン類等が挙げられる。
【００３２】
式２に該当する化合物としては、ジメチルアミノメタノール、ジメチルアミノプロパノール等のジアルキルアミノアルコール等が挙げられる。
【００３３】
本発明で用いられる第三級アミノ基含有活性水素化合物（Ｃ）は、式１に該当するＮ−メチルジエタノールアミンである。これは、式２のタイプでは、ポリウレタン系樹脂の末端に第三級アミノ基が導入されることになるため、ポリウレタン系樹脂の分子量によって導入量が影響される。しかし、式１のタイプでは、ポリウレタン系樹脂の中に第三級アミノ基が導入されるため、導入量はポリウレタン系樹脂の分子量に影響されることがないからである。
【００３４】
本発明で用いられる有機ジイソシアネート（Ｄ）は、耐候性や密着性を考慮して、イソホロンジイソシアネートである。
【００３５】
【００３６】
なお、必要に応じて反応停止剤を用いてもよい。反応停止剤としては、メタノール、エタノール等のようなモノアルコール、エチルアミン、プロピルアミン、ジブチルアミン等のようなモノアミン、モノエタノールアミン、ジエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−フェニルジプロパノールアミン等のアミノアルコールがある。また、場合によっては、前述のポリエステルポリオールやポリエステル−アミドポリオールに用いられる低分子ポリオールや低分子ポリアミンも使用できる。
【００３７】
本発明に用いられるポリウレタン系樹脂を合成する際の反応触媒としては、公知のいわゆるウレタン化触媒を用いることができる。具体的には、ジブチルチンジラウレート、ジオクチルチンジラウレート等の有機金属化合物や、トリエチレンジアミンやトリエチルアミン等の有機アミンやその塩等が挙げられる。
【００３８】
本発明に用いられるポリウレタン系樹脂の合成方法は、公知の方法が用いられる。すなわち、（１）活性水素基成分と有機ジイソシアネートを、活性水素基過剰の条件で所定分子量に達するまで反応させる方法（ワンショット法）、（２）ポリオール成分と有機ジイソシアネートを、イソシアネート基過剰の条件で反応させ、イソシアネート基含有のプレポリマーを得て、次にこのプレポリマーを低分子グリコールや低分子ジアミンで鎖延長させて所定分子量に達するまで反応させる方法（プレポリマー法）等がある。
【００３９】
また、必要に応じて有機溶剤を用いることができる。この有機溶剤は、トルエン、キシレン等の芳香族炭化水素系溶剤、ペンタン、ヘキサン、オクタン等の脂肪族炭化水素系溶剤、シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素系溶剤、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン等のケトン系溶剤、ジエチルエーテル、１，４−ジオキサン、テトラヒドロフラン等のエーテル系溶剤、エチレングリコールジメチルエーテル、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のセロソルブ系溶剤、酢酸エチル、酢酸ブチル等の一塩基酸エステル系溶剤、アジピン酸ジメチル、コハク酸ジメチル、フタル酸ジオクチル等の二塩基酸エステル類、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等のイソシアネート基に不活性なものであれば特に制限はない。また、条件によっては、イソプロパノールのようなアルコール系溶剤も用いることができる。
【００４０】
本発明に用いられるポリウレタン系樹脂を得るための反応装置としては、上記の反応が達成できればいかなる装置でもよく、例えば、攪拌装置の付いた反応釜やニーダー、一軸又は多軸押出し反応装置等の混合混練装置が挙げられる。本発明に用いられるポリウレタン系樹脂の好ましい合成方法は、溶液中でのプレポリマー法である。
【００４１】
溶液中でのプレポリマー法について、更に詳しく述べる。
ポリウレタン系樹脂を製造するに当たって、まず、活性水素基を有する原料を混合し、必要により活性水素基を持たないケトンやエステル、炭化水素系の溶剤等で適宜希釈する。
【００４２】
この活性水素基成分の混合物に有機ジイソシアネートを加え、必要に応じてウレタン化触媒を添加した後、反応温度を３０〜１００℃、好ましくは５０〜８０℃にて、数時間反応させ、イソシアネート基含有ウレタンプレポリマー溶液を合成する。このときのイソシアネート基／水酸基のモル比（Ｒ値）は１．１〜２．５が好ましく、特に１．１〜２が好ましい。
【００４３】
Ｒ値が１．１未満の場合は、最終的に得られるポリウレタン系樹脂の耐久性や耐ブロッキング性が低下する。また、Ｒ値が２．５を越える場合は、最終的に得られるポリウレタン系樹脂の溶剤への溶解性や密着性が低下する。
【００４４】
このようにして得られるイソシアネート基含有ウレタンプレポリマー溶液に、低分子グリコールや低分子ジアミンのような鎖延長剤及び必要に応じて反応停止剤を加えて、反応温度を３０〜８０℃、好ましくは３０〜５０℃にて、イソシアネート基が消失するまで鎖延長反応させることにより、目的とするポリウレタン系樹脂が得られる。
【００４５】
本発明の非水系プライマー組成物は、上述のポリウレタン系樹脂に、必要に応じて、顔料、染料、溶剤、揺変剤、酸化防止剤、紫外線吸収剤、消泡剤、増粘剤、分散剤、界面活性剤、防かび剤、抗菌剤、防腐剤、触媒、充填剤等のような添加剤や硝化綿等の副バインダーを添加し、混練、分散して製造されたものにポリイソシアネート硬化剤を配合したものである。なお、塩化ビニル樹脂、塩化ビニル−酢酸ビニル樹脂等の含ハロゲン樹脂を使用しても、特に不都合はないが、昨今の流れからすると、使用は好ましくない。
【００４６】
ポリイソシアネート硬化剤の添加量は、ポリウレタン系樹脂１００質量部に対して、１〜２０質量部である（各固形分換算）。ポリイソシアネート硬化剤としては、例えば、日本ポリウレタン工業（株）の商品で、ヘキサメチレンジイソシアネート変性タイプのコロネート（登録商標）ＨＸ、コロネートＨＬ、トリレンジイソシアネート変性タイプのコロネートＬ、コロネート２０３０、コロネート２０３１等が挙げられ、これらは単独あるいは混合して用いてもよい。
本発明においては、耐候性等を考慮すると、コロネートＨＸ、コロネートＨＬ等のような無黄変タイプのポリイソシアネート硬化剤が好ましい。
【００４７】
【実施例】
以下に実施例により本発明を説明するが、本発明はこれら実施例に限定されるものではない。なお、例中における「部」とは質量部、「％」は質量％をそれぞれ示す。
【００４８】
〔ポリウレタン系樹脂の製造〕
実施例１
攪拌機、温度計、アリーン冷却管、窒素ガス導入管を組んだ反応装置に、ポリオールＡを１２５．８部、ポリオールＥを５３．９部、ＣＨＤＭを２５．９部、ＭＤＥＡを６．４部、ＭＥＫを３００部仕込み、均一に攪拌した。このポリオール溶液にＩＰＤＩを８１．８部仕込み、ＤＢＴＤＬを０．０６部仕込み、７０℃にて４時間反応させて、イソシアネート基含有ウレタンプレポリマー溶液を得た。このプレポリマー溶液に、ＭＥＫを３００部加え均一にした後、ＭＥＫ１００部とＩＰＤＡ２．３部とＭＥＡ３．８部を混合したアミン液を一気に加え、４０℃で、ＦＴ−ＩＲによるイソシアネート基のピークが消失するまで反応させ、ポリウレタン系樹脂ＰＵ−１を得た。ＰＵ−１の固形分は３０％、粘度は４００ｍＰａ・ｓ（２５℃）、色数は３０ＡＰＨＡ、数平均分子量は２８，０００、ガラス転移温度は−９℃であった。また、ＰＵ−１を容器に充填して、窒素パージしてからこれを５０℃にて３０日保管したが、分子量低下はほとんど認められなかった。
【００４９】
実施例２〜４、比較例１〜４
実施例１と同様な装置と反応方法で、表１、２に記載した原料、量を使用してポリウレタン系樹脂ＰＵ−２〜４、７〜１０を得た。
【００５０】
【００５１】
実施例１〜４、比較例１〜４、及び表１、２における原料を以下に示す。
ポリオールＡ：テレフタル酸／アジピン酸＝１／１（モル比）と３−メチル−１
５−ペンタンジオールからなるポリエステルジオール
数平均分子量＝２，０００
芳香環含有量＝１．９８ｍｍｏｌ／ｇ
ポリオールＢ：テレフタル酸／アジピン酸＝２／１（モル比）と３−メチル−１
，５−ペンタンジオールからなるポリエステルジオール
数平均分子量＝３，０００
芳香環含有量＝２．６５ｍｍｏｌ／ｇ
ポリオールＣ：テレフタル酸／アジピン酸＝１／２（モル比）と３−メチル−１
，５−ペンタンジオールからなるポリエステルジオール
数平均分子量＝１，０００
芳香環含有量＝１．２５ｍｍｏｌ／ｇ
ポリオールＤ：２，６−ナフタレンジカルボン酸／アジピン酸＝３／７（モル比
）と３−メチル−１，５−ペンタンジオールからなるポリエステ ルジオール
数平均分子量＝２，０００
芳香環含有量＝１．１３ｍｍｏｌ／ｇ
ポリオールＥ：１，３−ブタンジオールとアジピン酸からなるポリエステルジオ
ール
数平均分子量＝２，０００
ポリオールＦ：ネオペンチルグリコールとアジピン酸からなるポリエステルジオ
ール
数平均分子量＝１，０００
ポリオールＧ：３，３−ジメチロールヘプタンとアジピン酸からなるポリエステ
ルジオール
数平均分子量＝３，０００
ポリオールＨ：テレフタル酸／イソフタル酸＝１／１（モル比）とエチレングリ
コール／ネオペンチルグリコール＝１／１（モル比）からなるポ リエステルジオール
数平均分子量＝２，０００
芳香環含有量＝４．５０ｍｍｏｌ／ｇ
ＣＨＤＭ ：シクロヘキサン−１，４−ジメタノール
ＭＤＥＡ ：Ｎ−メチルジエタノールアミン
ＩＰＤＩ ：イソホロンジイソシアネート
ＩＰＤＡ ：イソホロンジアミン
ＭＥＡ ：モノエタノールアミン
ＤＢＴＤＬ ：ジブチルチンジラウレート
ＭＥＫ ：メチルエチルケトン
数平均分子量測定方法：ポリスチレン検量線によるゲルパーミエーションクロマ
トグラフィー（ＧＰＣ）法
ガラス転移温度測定法：動的粘弾性におけるＥ″が極大となった時の温度
測定条件 周波数：３５Ｈｚ 昇温速度：２℃／分
経時安定性測定法 ：５０℃にて３０日保管し、数平均分子量を測定した。
評価 ○：分子量低下がほとんど認められない。
×：分子量低下が認められる。
芳香環含有量及び第三級アミノ基含有量は、仕込みから算出した。
【００５２】
【表１】

【００５３】
【表２】

【００５４】
〔プライマーの製造及び評価〕
実施例７
ＰＵ−１を以下に示す割合で混合し、プライマーＡを得た。このプライマーの密着性、耐ブロッキング性、耐久性、接着性を評価した。
プライマー配合処方 ＰＵ−１ ５８．８部
ＭＥＫ ３５．３部
コロネートＨＸ ５．９部
コロネートＨＸ：日本ポリウレタン工業（株）製品
ヘキサメチレンジイソシアネートのイソシアヌレート変性
ポリイソシアネート
【００５５】
プライマー塗布方法
配合したプライマーを乾燥炉を備えたグラビア印刷機にて、印刷速度２０ｍ／分、プライマー厚１μｍ（Ｄｒｙ）になるように各種フィルムに塗布し、８０℃の乾燥炉に２秒通した。
プライマー塗布材料
ａ）厚さ１５μｍのコロナ放電処理延伸ポリプロピレンフィルム
ｂ）厚さ１５μｍのコロナ放電処理ポリエチレンテレフタレートフィルム
ｃ）厚さ１５μｍのコロナ放電処理ナイロンフィルム
【００５６】
（１）密着性
ａ）〜ｃ）のフィルムにプライマーＡを塗布し、その上にウレタン系白インキを印刷した。その後、４０℃で７日間エージングした後、印刷面にセロハンテープを貼り付け、これを急速に剥がした。
評価 ◎：印刷面の破損が全く見られなかった。
○：印刷面が８０％〜１００％残存した。
△：印刷面が５０％〜８０％残存した。
×：印刷面が５０％以下しか残存しなかった。
【００５７】
（２）耐ブロッキング性
ａ）のフィルムにプライマーＡを塗布し、４０℃で７日間エージングした後、面−裏に重ね、ブロッキングテスターで０．５ＭＰａの荷重をかけて、２４時間、５０℃・８０ＲＨ％の条件下に置き、耐ブロッキング性を評価した。
評価 ○：剥がすときに全く抵抗なく剥がれ、プライマーの脱落がない。
△：剥がすときの抵抗がやや大きく、プライマーの脱落が多少見られる。
×：剥がすときの抵抗が大きく、プライマー面の脱落が見られる。
【００５８】
（３）耐久性
ａ）のフィルムにプライマーＡを塗布し、４０℃で７日間エージングした後、６０℃で９５％ＲＨの条件下で１ヶ月保存した。その後、塗布面にセロテープを貼り付け、これを急速に剥がした。
評価 ○：プライマーが８０％〜１００％残存した。
△：プライマーが５０％〜８０％残存した。
×：プライマーが５０％以下しか残存しなかった。
【００５９】
（４）接着性
ａ）のフィルムにプライマーＡを塗布し、その上にウレタン系接着剤を５ｇ／ｍ² 塗布して乾燥させ、接着剤塗布面同士を貼り合わせた。貼り合わせ後、４０℃で７日間エージングし、手による剥離試験を行った。
ウレタン系接着剤：
ニッポラン（登録商標）３０２２／コロネートＬ＝１００／２（質量比）
評価 ＣＦ：接着剤層の凝集破壊
ＡＦ：プライマー層−ａ）フィルム間の界面破壊
ＰＳ：プライマー層−接着剤層間の界面破壊
【００６０】
実施例８〜１０、比較例５〜８
実施例７におけるＰＵ−１をＰＵ−２〜４、７〜１０に置き換えること以外は、実施例７と同様の方法でプライマー液を調製し、同様に評価した。
密着性、耐ブロッキング性、耐久性、接着性の評価結果を表３、４に示す。
【００６１】
【表３】

【００６２】
【表４】

【００６３】
表３、４において
ＯＰＰ：厚さ１５μｍのコロナ放電処理延伸ポリプロピレン
ＰＥＴ：厚さ１５μｍのコロナ放電処理ポリエチレンテレフタレート
ＮＹ ：厚さ１５μｍのコロナ放電処理ナイロン
【００６４】
【発明の効果】
以上説明してきた通り、本発明に用いられるポリウレタン系樹脂は、経時安定性に優れ、これを用いたプライマー組成物は、特にポリオレフィンを含めたあらゆる種類のプラスチックに良好な密着性を示し、耐ブロッキング性、耐久性、接着性等に優れていることが判明した。また、本発明の非水系プライマー組成物は、耐久性に優れることから、特に建装材用プライマーに適している。[0001]
BACKGROUND OF THE INVENTION
  The present invention can be applied to various materialsNon-aqueous primer compositionIt is about. More specifically, plastic substrates used for various containers and building materials due to environmental problems such as acid rain and global warming are in line with the current trend in which polyvinyl chloride is being converted from polyvinyl chloride to polyolefins such as polypropylene and polyethylene. In other words, environmentally friendly for PVCNon-aqueous primer compositionIt is about.
[0002]
[Prior art]
  There is a great demand for expanding the field of use such as bonding different materials such as wood and metal to polyolefin such as polypropylene and polyethylene, and printing ink. However, since polyolefin is nonpolar and has poor adhesion and adhesion, it is not easy to make a composite. For this reason, various methods have been proposed. For example, a method for modifying the polyolefin itself, a polyolefin surface such as corona discharge treatment, etc. The method of processing, the method of using a primer, the method of using an adhesive, and the like are used depending on the purpose. Among them, a method of treating the polyolefin surface such as corona discharge treatment has a problem that wettability decreases with time. For this reason, a method using a coating-type primer or adhesive is particularly attracting attention because it is simple and has a wide range of applications.
[0003]
  Examples of the primer or adhesive used for such purposes include chlorine as disclosed in, for example, Japanese Patent Publication No. 50-10916, Japanese Patent Publication No. 55-149304, Japanese Patent Publication No. 6-23361. For example, the technology disclosed in Japanese Patent Application Laid-Open No. 9-20817 is used, in which the technology of a chemically modified polyolefin is used, or a chlorinated polyolefin is introduced into a urethane resin. With these techniques, the blocking resistance and the adhesion including the polyolefin film can be satisfactorily satisfied, but since the dechlorination reaction occurs with time, the stability over time such as corrosion of the filled container is poor. In addition, since chlorine is contained during recycling and combustion, chlorine gas and hydrogen chloride gas are generated, and there is a risk of adverse effects on the environment such as acid rain, and it does not contain chlorine from the standpoint of environmental protection. The development of environmentally friendly polyolefin primers and adhesives is desired.
[0004]
  Japanese Patent Laid-Open No. 1-60678 discloses a technique in which a polyurethane resin into which hydrogenated polybutadiene is introduced is applied to an adhesive. By introducing hydrogenated polybutadiene into the polyurethane resin, the adhesion to the polyolefin is improved. However, since this hydrogenated polybutadiene generally has a large number of functional groups, gelation occurs when it is polymerized in the production of a polyurethane resin, and the intended binder itself is difficult to obtain. For this reason, the molecular weight had to be reduced, and the durability was unsatisfactory.
[0005]
[Problems to be solved by the invention]
  In consideration of recent environmental problems, the present invention does not use a halogen-based raw material, and adheres to any substrate including a polyolefin-based substrate, processability after coating, stability over time, durability, and resistance. Excellent physical properties such as blocking propertiesNon-aqueous primer compositionThe purpose is to provide.
[0006]
[Means for Solving the Problems]
  In view of the above circumstances, the present inventors sufficiently satisfy the adhesiveness to all plastic films including general-purpose polyolefin films, and are suitable for processing after application, adhesiveness, durability, and blocking resistance. Environmentally friendly with excellent physical properties such asNon-aqueous primerAs a result of earnest examination aboutPolyurethane resin usedThe concept of glass transition temperature was introduced to complete the present invention.
[0007]
  That is, the present invention
  In a non-aqueous primer composition using 100 parts by weight of a polyurethane resin and 1 to 20 parts by weight of a polyisocyanate curing agent, the polyurethane resin is obtained by reacting the following (A) to (D), and Non-aqueous primer having a glass transition temperature of −35 to + 20 ° C., an aromatic ring content of 0.1 to 2 mmol / g, and a tertiary amino group content of 0.1 to 0.5 mmol / g It is a composition.
  (A) Number average molecular weight of 500 to 10,000, and (A1) and (A
        2) The mass ratio of (A1) :( A2) = 50: 50 to 90:10
        A long-chain polyol made of terpolyol.
      (A1): One or more isomers of phthalic acid and aliphatic dicar
                It is a mixture with a molar ratio of boronic acid of 1/4 to 4/1, and the alcohol component is charcoal.
                An aliphatic diol having a side chain with a prime number of 10 or less, wherein the aromatic ring content is
                Polyester polyol which is 0.5-5 mmol / g.
      (A2): Is it a low molecular diol having a side chain having 10 or less carbon atoms and an aliphatic dicarboxylic acid?
                Polyester diol obtained from the above.
  (B) Chain extension consisting of cyclohexane-1,4-dimethanol and isophoronediamine
        Agent.
  (C) A tertiary amino group-containing active hydrogen compound comprising N-methyldiethanolamine.
  (D) Organic diisocyanate comprising isophorone diisocyanate.
[0008]
[0009]
[0010]
DETAILED DESCRIPTION OF THE INVENTION
  The present inventionUsed forPolyurethane resinIt is obtained by reacting the following (A) to (D), and the glass transition temperature is −35 to + 20 ° C.
  (A) Number average molecular weight of 500 to 10,000, and (A1) and (A
        2) The mass ratio of (A1) :( A2) = 50: 50 to 90:10
        A long-chain polyol made of terpolyol.
      (A1): One or more isomers of phthalic acid and aliphatic dicar
                It is a mixture with a molar ratio of boronic acid of 1/4 to 4/1, and the alcohol component is charcoal.
                An aliphatic diol having a side chain with a prime number of 10 or less, wherein the aromatic ring content is
                Polyester polyol which is 0.5-5 mmol / g.
      (A2): Is it a low molecular diol having a side chain having 10 or less carbon atoms and an aliphatic dicarboxylic acid?
                Polyester diol obtained from the above.
  (B) Chain extension consisting of cyclohexane-1,4-dimethanol and isophoronediamine
        Agent.
  (C) A tertiary amino group-containing active hydrogen compound comprising N-methyldiethanolamine.
  (D) Organic diisocyanate comprising isophorone diisocyanate.
  When the glass transition temperature is less than the lower limit, the blocking resistance when used as a primer is insufficient. Moreover, when exceeding an upper limit, adhesiveness is insufficient. In the coating process, since the primer may be wound after being applied to a long original fabric, blocking resistance is one of the important performances of the primer resin.
[0011]
  Used in the present inventionThe aromatic ring content of the polyurethane resin is 0.1 to 2 mmol / g.AndFurthermore, 0.15-1.8 mmol / g is preferable. When the aromatic ring content is less than the lower limit, blocking resistance, durability and the like are likely to be insufficient. Moreover, when exceeding an upper limit, adhesiveness tends to be insufficient. In addition, the aromatic ring in this invention shows a benzene ring, a naphthalene ring, an anthracene ring, etc. The aromatic ring contained in the polyurethane-based resin is derived from any one of a long-chain polyol, a chain extender, a tertiary amino group-containing active hydrogen compound, and an organic diisocyanate.
[0012]
  Also,Used in the present inventionThe content of tertiary amino groups in the polyurethane resin is 0.1 to 0.5 mmol / g.AndFurthermore, it is preferable that it is 0.12-0.48 mmol / g. When the tertiary amino group content is less than the lower limit, adhesion and dispersibility are insufficient. On the other hand, if the upper limit is exceeded, the stability over time, durability, etc. of the resin tends to deteriorate.
[0013]
  In addition,Used in the present inventionThe glass transition temperature of the polyurethane-based resin is a temperature at which E ″ (loss elastic modulus) in the dynamic viscoelasticity becomes a maximum, and the measurement conditions are a frequency: 35 Hz and a heating rate: 2 ° C. per minute. It is.
[0014]
  Used in the present inventionThe viscosity of the polyurethane resin is preferably 500 to 10,000 mPa · s at 25 ° C. in a methyl ethyl ketone solution having a solid content of 30%. When the viscosity exceeds the upper limit, workability at the time of coating tends to deteriorate.
[0015]
  Used in the present inventionThe number of colors of the polyurethane-based resin is 150 APHA or less, preferably 100 APHA or less in a methyl ethyl ketone solution having a solid content of 30%. When the number of colors exceeds the upper limit, the appearance of the application site may be deteriorated.
[0016]
  Used in the present inventionThe number average molecular weight of the polyurethane-based resin is measured by a gel permeation chromatography (GPC) method using a polystyrene calibration curve, preferably 8,000 to 100,000, and particularly preferably 10,000 to 50,000. . When the number average molecular weight is less than the lower limit, durability and blocking resistance tend to be lowered. When the number average molecular weight exceeds the upper limit, the fluidity is deteriorated and the workability at the time of coating tends to be deteriorated.
[0017]
  continue,Used in the present inventionThe raw materials (A) to (D) used for the polyurethane resin will be described.
  The (A) long-chain polyol used in the present invention is a polyester polyol having a number average molecular weight of 500 to 10,000, preferably 1,000 to 5,000.Is mentioned.
[0018]
  As this polyester polyol, known phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, kurtaconic acid, azelaic acid, Sebacic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethyl One or more kinds of dicarboxylic acids, anhydrides, dialkyl esters and the like such as succinic acid, maleic acid and fumaric acid, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, , 3-butanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, Diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A, bis (β-hydroxyethyl) benzene, xylylene glycol , Glycerin, trimethylolpropane, pentaerythritol and other low-molecular polyols such as polycondensation reaction. Furthermore, there are lactone polyester polyols obtained from ring-opening polymerization of cyclic ester (so-called lactone) monomers such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone. Further, a low molecular polyol such as hexamethylene diamine, isophorone diamine, monoethanol amine or the like may be used as a part of the low molecular polyol. In this case, a polyester-amide polyol is obtained.
[0019]
[0020]
[0021]
[0022]
[0023]
[0024]
[0025]
  The present inventionUsed inThe long-chain polyol contains (A1) shown below in an amount of 50 to 90% by mass in the long-chain polyol.AndMore preferably, it is a mixed polyester polyol in which the mass ratio of (A1) and (A2) shown below is (A1) :( A2) = 50: 50 to 90:10. By introducing (A1) (and (A2)) into the polyurethane-based resin in an appropriate balance, it is possible to satisfy both stability over time and durability, and to achieve both contradictory performances of blocking resistance and adhesion. Become.
(A1): Polyester polyol having an aromatic ring content of 0.5 to 5 mmol / g
(A2): A polyester diol obtained from a low-molecular diol having a side chain of 10 or less carbon atoms and an aliphatic dicarboxylic acid
[0026]
  Further, (A1) is a polyester diol shown below.
  Acid component: One or more phthalic acid isomers and aliphatic dica
          A mixture having a rubonic acid molar ratio of 1/4 to 4/1.
  Alcohol component: aliphatic diol having a side chain of 10 or less carbon atoms
[0027]
  The chain extender (B) used in the present invention is:Cyclohexane-1,4-dimethanol and isophoronediamine.
[0028]
  The tertiary amino group-containing active hydrogen compound (C) used in the present invention is:
What is shown by the following formula 1 or formula 2.Of these, N-methyldiethanolamine.
[0029]
[Chemical 1]

[0030]
[Chemical formula 2]

[0031]
  Examples of the compound corresponding to Formula 1 include N-alkyldialkanolamines such as N-methyldiethanolamine, N-methyldipropanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine and the like N- Examples include aryl dialkanolamines.
[0032]
  Examples of the compound corresponding to Formula 2 include dialkylamino alcohols such as dimethylaminomethanol and dimethylaminopropanol.
[0033]
  In the present inventionUsedThe tertiary amino group-containing active hydrogen compound (C) corresponds to Formula 1.N-methyldiethanolamine.This is because, in the type of Formula 2, a tertiary amino group is introduced at the terminal of the polyurethane resin, and therefore the introduction amount is affected by the molecular weight of the polyurethane resin. However, in the type of the formula 1, since the tertiary amino group is introduced into the polyurethane resin, the introduction amount is not affected by the molecular weight of the polyurethane resin.
[0034]
  The organic diisocyanate (D) used in the present invention isConsidering weather resistance and adhesion, it is isophorone diisocyanate.
[0035]
[0036]
  A reaction terminator may be used as necessary. Reaction terminators include monoalcohols such as methanol and ethanol, monoamines such as ethylamine, propylamine and dibutylamine, aminoalcohols such as monoethanolamine, diethanolamine, N-methyldiethanolamine and N-phenyldipropanolamine. There is. Moreover, depending on the case, the low molecular polyol and low molecular polyamine which are used for the above-mentioned polyester polyol and polyester-amide polyol can also be used.
[0037]
  Used in the present inventionAs the reaction catalyst for synthesizing the polyurethane resin, a known so-called urethanization catalyst can be used. Specific examples thereof include organic metal compounds such as dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof.
[0038]
  Used in the present inventionA known method is used as a method for synthesizing the polyurethane-based resin. That is, (1) a method in which an active hydrogen group component and an organic diisocyanate are reacted until reaching a predetermined molecular weight under conditions of excess of active hydrogen groups (one-shot method), and (2) a condition of excess of isocyanate groups in the polyol component and organic diisocyanate. There is a method in which an isocyanate group-containing prepolymer is obtained, and then this prepolymer is chain-extended with a low molecular glycol or low molecular diamine and reacted until a predetermined molecular weight is reached (prepolymer method).
[0039]
  Moreover, an organic solvent can be used as needed. This organic solvent includes aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane and octane, alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane and methylcyclohexane, acetone, Ketone solvents such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, ether solvents such as diethyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, propylene Cellosolve solvents such as glycol dimethyl ether and propylene glycol monomethyl ether acetate; monobasic acid ester solvents such as ethyl acetate and butyl acetate; Phosphate, dimethyl succinate, dibasic esters such as dioctyl phthalate, dimethyl formamide, dimethyl acetamide, not particularly limited as long as it is inactive to the isocyanate group, such as N- methylpyrrolidone. Depending on the conditions, an alcohol solvent such as isopropanol may be used.
[0040]
  Used in the present inventionThe reaction apparatus for obtaining the polyurethane-based resin may be any apparatus as long as the above reaction can be achieved, and examples thereof include a mixing and kneading apparatus such as a reaction kettle or kneader equipped with a stirrer, a uniaxial or multiaxial extrusion reaction apparatus. .Used in the present inventionA preferred synthesis method of the polyurethane resin is a prepolymer method in a solution.
[0041]
  The prepolymer method in solution will be described in more detail.
  Polyurethane resinIn manufacturing, first, raw materials having an active hydrogen group are mixed and, if necessary, appropriately diluted with a ketone or ester having no active hydrogen group, a hydrocarbon solvent, or the like.
[0042]
  After adding an organic diisocyanate to the mixture of active hydrogen group components and adding a urethanization catalyst as necessary, the reaction temperature is 30 to 100 ° C., preferably 50 to 80 ° C., and reacted for several hours to contain isocyanate groups. A urethane prepolymer solution is synthesized. At this time, the isocyanate group / hydroxyl molar ratio (R value) is preferably 1.1 to 2.5, and more preferably 1.1 to 2.
[0043]
  When the R value is less than 1.1, the durability and blocking resistance of the polyurethane resin finally obtained are lowered. Moreover, when R value exceeds 2.5, the solubility and adhesiveness to the solvent of the polyurethane resin finally obtained fall.
[0044]
  The isocyanate group-containing urethane prepolymer solution thus obtained is added with a chain extender such as a low molecular glycol or low molecular diamine and a reaction terminator if necessary, and the reaction temperature is 30 to 80 ° C., preferably The target is obtained by chain extension reaction at 30 to 50 ° C. until the isocyanate group disappears.Polyurethane resinIs obtained.
[0045]
  Of the present inventionNon-aqueousThe primer composition isPolyurethane resinIf necessary, pigments, dyes, solvents, thixotropic agents, antioxidants, UV absorbers, antifoaming agents, thickeners, dispersants, surfactants, fungicides, antibacterial agents, preservatives, A polyisocyanate curing agent is blended with a product produced by adding an additive such as a catalyst or filler or a secondary binder such as nitrified cotton, kneading and dispersing. Although there is no particular inconvenience even when a halogen-containing resin such as vinyl chloride resin or vinyl chloride-vinyl acetate resin is used, the use is not preferred from the current trend.
[0046]
  The addition amount of the polyisocyanate curing agent is 1 to 20 parts by mass with respect to 100 parts by mass of the polyurethane resin (in terms of each solid content). Examples of the polyisocyanate curing agent include products of Nippon Polyurethane Industry Co., Ltd., hexamethylene diisocyanate-modified coronate (registered trademark) HX, coronate HL, tolylene diisocyanate-modified coronate L, coronate 2030, coronate 2031 and the like These may be used alone or in combination.
  In the present invention, a non-yellowing type polyisocyanate curing agent such as Coronate HX, Coronate HL or the like is preferable in consideration of weather resistance and the like.
[0047]
【Example】
  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means mass part, and “%” means mass%.
[0048]
[Production of polyurethane resin]
Example 1
  In a reaction apparatus including a stirrer, a thermometer, an Allen cooling pipe, and a nitrogen gas introduction pipe, 125.8 parts of polyol A, 53.9 parts of polyol E, 25.9 parts of CHDM, 6.4 parts of MDEA, 300 parts of MEK was charged and stirred uniformly. This polyol solution was charged with 81.8 parts of IPDI and 0.06 part of DBTDL and reacted at 70 ° C. for 4 hours to obtain an isocyanate group-containing urethane prepolymer solution. After adding 300 parts of MEK to this prepolymer solution and homogenizing it, an amine solution in which 100 parts of MEK, 2.3 parts of IPDA and 3.8 parts of MEA were mixed was added all at once. At 40 ° C., the peak of the isocyanate group by FT-IR was observed. It was made to react until it lose | disappeared and polyurethane-type resin PU-1 was obtained. PU-1 had a solid content of 30%, a viscosity of 400 mPa · s (25 ° C.), a color number of 30 APHA, a number average molecular weight of 28,000, and a glass transition temperature of −9 ° C. Moreover, although PU-1 was filled into a container and purged with nitrogen, it was stored at 50 ° C. for 30 days, but almost no decrease in molecular weight was observed.
[0049]
Example 24Comparative Examples 1 to 4
  In the same apparatus and reaction method as in Example 1, using the raw materials and amounts described in Tables 1 and 2.Polyurethane resinPU-2 ~47-10 were obtained.
[0050]
[0051]
  Example 14The raw materials in Comparative Examples 1 to 4 and Tables 1 and 2 are shown below.
Polyol A: terephthalic acid / adipic acid = 1/1 (molar ratio) and 3-methyl-1
       Polyester diol consisting of 5-pentanediol
              Number average molecular weight = 2,000
              Aromatic ring content = 1.98 mmol / g
Polyol B: terephthalic acid / adipic acid = 2/1 (molar ratio) and 3-methyl-1
      Polyester diol consisting of 1,5-pentanediol
              Number average molecular weight = 3,000
              Aromatic ring content = 2.65 mmol / g
Polyol C: terephthalic acid / adipic acid = 1/2 (molar ratio) and 3-methyl-1
      Polyester diol consisting of 1,5-pentanediol
              Number average molecular weight = 1,000
              Aromatic ring content = 1.25 mmol / g
Polyol D: 2,6-naphthalenedicarboxylic acid / adipic acid = 3/7 (molar ratio
      ) And 3-methyl-1,5-pentanediol
              Number average molecular weight = 2,000
              Aromatic ring content = 1.13 mmol / g
Polyol E: Polyester Geo consisting of 1,3-butanediol and adipic acid
      The
              Number average molecular weight = 2,000
Polyol F: Polyester Geo consisting of neopentyl glycol and adipic acid
      The
              Number average molecular weight = 1,000
Polyol G: Polyester composed of 3,3-dimethylolheptane and adipic acid
      Ludiol
              Number average molecular weight = 3,000
Polyol H: terephthalic acid / isophthalic acid = 1/1 (molar ratio) and ethylene glycol
      Polyester diol consisting of coal / neopentyl glycol = 1/1 (molar ratio)
              Number average molecular weight = 2,000
              Aromatic ring content = 4.50 mmol / g
CHDM: cyclohexane-1,4-dimethanol
MDEA: N-methyldiethanolamine
IPDI: Isophorone diisocyanate
IPDA: Isophoronediamine
MEA: Monoethanolamine
DBTDL: Dibutyltin dilaurate
MEK: methyl ethyl ketone
Number average molecular weight measurement method: Gel permeation chroma with polystyrene calibration curve
              Togography (GPC) method
Glass transition temperature measurement method: Temperature at which E ″ in dynamic viscoelasticity becomes maximum
      Measurement conditions Frequency: 35Hz Temperature increase rate: 2 ° C / min
Time stability measurement method: Stored at 50 ° C. for 30 days, and the number average molecular weight was measured.
    Evaluation ○: Almost no decrease in molecular weight is observed.
          X: A decrease in molecular weight is observed.
The aromatic ring content and the tertiary amino group content were calculated from the preparation.
[0052]
[Table 1]

[0053]
[Table 2]

[0054]
[Production and evaluation of primers]
Example 7
  PU-1 was mixed at the ratio shown below to obtain Primer A. The adhesion, blocking resistance, durability and adhesion of this primer were evaluated.
  Primer formulation PU-1 58.8 parts
                      MEK 35.3 parts
                      Coronate HX 5.9 parts
    Coronate HX: Nippon Polyurethane Industry Co., Ltd. product
                    Isocyanurate modification of hexamethylene diisocyanate.
            Polyisocyanate
[0055]
  Primer application method
  The blended primer was applied to various films with a gravure printing machine equipped with a drying oven so that the printing speed was 20 m / min and the primer thickness was 1 μm (Dry), and passed through a drying oven at 80 ° C. for 2 seconds.
  Primer application material
  a) 15 μm thick corona discharge-treated stretched polypropylene film
  b) 15 μm thick corona discharge treated polyethylene terephthalate film
  c) 15 μm thick corona discharge treated nylon film
[0056]
(1) Adhesion
  Primer A was applied to the films a) to c), and urethane-based white ink was printed thereon. Then, after aging at 40 ° C. for 7 days, a cellophane tape was attached to the printed surface, and this was quickly peeled off.
  Evaluation A: The printed surface was not damaged at all.
        A: The printed surface remained 80% to 100%.
        Δ: 50% to 80% of the printed surface remained.
        X: Only 50% or less of the printed surface remained.
[0057]
(2) Blocking resistance
  After applying Primer A to the film of a) and aging at 40 ° C. for 7 days, it is layered on the front and back, and a load of 0.5 MPa is applied with a blocking tester for 24 hours at 50 ° C. and 80 RH%. The blocking resistance was evaluated.
Evaluation (circle): It peels without resistance at the time of peeling, and a primer does not fall off.
      Δ: Slightly large resistance when peeled off and some dropping of primer is observed.
      X: The resistance when peeling off is large, and the primer surface is observed to fall off.
[0058]
(3) Durability
  Primer A was applied to the film a), aged at 40 ° C. for 7 days, and then stored at 60 ° C. under 95% RH for 1 month. Then, a cellophane tape was affixed to the coated surface, and this was rapidly peeled off.
Evaluation ○: 80% to 100% of the primer remained.
      Δ: 50% to 80% of the primer remained.
      X: Only 50% or less of the primer remained.
[0059]
(4) Adhesiveness
  Primer A is applied to the film of a), and a urethane adhesive is applied thereon at 5 g / m.² It applied and dried, and the adhesive application surfaces were bonded together. After bonding, the film was aged at 40 ° C. for 7 days, and a manual peeling test was performed.
  Urethane adhesive:
    Nipponran (registered trademark) 3022 / Coronate L = 100/2 (mass ratio)
Evaluation CF: Cohesive failure of adhesive layer
      AF: Primer layer-a) Interfacial fracture between films
      PS: Interfacial fracture between primer layer and adhesive layer
[0060]
Example 810Comparative Examples 5-8
  PU-1 in Example 7 is changed to PU-2-4, 7-10A primer solution was prepared in the same manner as in Example 7 except that it was replaced with and evaluated in the same manner.
  Tables 3 and 4 show the evaluation results of adhesion, blocking resistance, durability, and adhesiveness.
[0061]
[Table 3]

[0062]
[Table 4]

[0063]
  In Tables 3 and 4
  OPP: 15 μm-thick corona discharge-treated stretched polypropylene
  PET: 15 μm thick corona discharge-treated polyethylene terephthalate
  NY: Corona discharge-treated nylon with a thickness of 15 μm
[0064]
【The invention's effect】
  As explained above,Used in the present inventionPolyurethane resin is excellent in stability over time, and primer using thisCompositionShows good adhesion to all kinds of plastics including polyolefin, and has been found to be excellent in blocking resistance, durability, adhesion and the like. In addition, the present inventionNon-aqueousSince the primer composition is excellent in durability, it is particularly suitable as a primer for building materials.

Claims (1)

In a non-aqueous primer composition using 100 parts by weight of a polyurethane resin and 1 to 20 parts by weight of a polyisocyanate curing agent, the polyurethane resin is obtained by reacting the following (A) to (D), and Non-aqueous primer having a glass transition temperature of −35 to + 20 ° C., an aromatic ring content of 0.1 to 2 mmol / g, and a tertiary amino group content of 0.1 to 0.5 mmol / g Composition.
(A) Number average molecular weight of 500 to 10,000, and (A1) and (A
2) Mixed polyester having a mass ratio of (A1) :( A2) = 50: 50 to 90:10
A long-chain polyol made of terpolyol.
(A1): One or two or more isomers of phthalic acid and aliphatic dicar
It is a mixture with a molar ratio of boronic acid of 1/4 to 4/1, and the alcohol component is charcoal.
An aliphatic diol having a side chain with a prime number of 10 or less, wherein the aromatic ring content is
Polyester polyol which is 0.5-5 mmol / g.
(A2): Is it a low molecular diol having a side chain having 10 or less carbon atoms and an aliphatic dicarboxylic acid?
Polyester diol obtained from the above.
(B) Chain extension consisting of cyclohexane-1,4-dimethanol and isophoronediamine
Agent.
(C) A tertiary amino group-containing active hydrogen compound comprising N-methyldiethanolamine.
(D) Organic diisocyanate comprising isophorone diisocyanate.