JPWO2016098336A1 - 水系コーティング剤組成物、それからなる水系潤滑被膜用塗料組成物および部材 - Google Patents
水系コーティング剤組成物、それからなる水系潤滑被膜用塗料組成物および部材 Download PDFInfo
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- JPWO2016098336A1 JPWO2016098336A1 JP2016564682A JP2016564682A JPWO2016098336A1 JP WO2016098336 A1 JPWO2016098336 A1 JP WO2016098336A1 JP 2016564682 A JP2016564682 A JP 2016564682A JP 2016564682 A JP2016564682 A JP 2016564682A JP WO2016098336 A1 JPWO2016098336 A1 JP WO2016098336A1
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Classifications
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/38—Boron-containing compounds
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- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
Description
(A)水系エマルジョン形態の硬化性樹脂、
(B)界面活性剤、
(C)固体粒子、
(D)1種類以上の窒素含有複素環化合物、および
(E)水
を含む、水系コーティング剤組成物によって達成される。
(A)水系エマルジョン形態の硬化性樹脂、
(B)界面活性剤、
(C)固体粒子、
(D)1種類以上の窒素含有複素環化合物、および
(E)水
を含む。以下、各成分について説明する。
成分(A)は水系エマルジョン形態の硬化性樹脂であり、本発明に係る水系コーティング剤組成物の主剤であり、硬化によりコーティング被膜を形成し、固体粒子等のバインダー樹脂として機能する。特に、水系エマルジョン形態の硬化性樹脂は、乳化重合、ソープフリー乳化重合などにより合成される、連続相である水中に硬化性樹脂成分が分散されてなる硬化性樹脂組成物であり、ポリアクリル樹脂、ポリウレタン樹脂、ポリオレフィン樹脂、エポキシ樹脂、シリコーン樹脂、ポリアミドイミド樹脂またはその変性物およびこれらの混合物が例示される。
成分(B)は界面活性剤であり、成分(C)である固体粒子を水系コーティング剤組成物に均一分散するための成分である。固体粒子、特に固体潤滑剤である固体粒子は、例え表面に親水化処理等が施されていても、一般に水分散性に乏しく、成分(B)を用いない場合には、水系コーティング剤組成物から成分(C)である固体粒子が分離あるいは沈降して均一な水系コーティング剤を得ることが困難になる。
成分(C)は固体粒子であり、本発明の水系コーティング剤に所望の機能を付与する成分である。固体粒子の種類は特に制限されるものではないが、固体潤滑剤;補強性充填剤;増稠剤;耐摩耗剤;顔料;色材;紫外線吸収剤;熱伝導性充填剤;導電性充填剤;絶縁材等の機能性粒子が例示される。なお、一部の粒子は、複数の機能性粒子として配合することができる。
成分(D)は、本発明の特徴的成分である1種類以上の窒素含有複素環化合物であり、(E)水と混和する親水性溶媒であり、同時に、水系コーティング剤組成物の製膜助剤として機能する。
成分(E)は水であり、本発明の水系コーティング剤組成物の分散媒である。水は、上記の成分(A)である水系エマルジョン形態の硬化性樹脂の分散媒として系中に持ち込まれてもよく、成分(B)である界面活性剤の水溶液として系中に持ち込まれたものであってもよい。また、上記の成分(D)のほか、本発明の目的を損なわない限り、後述する他の水溶性の任意成分やアルコール等の他の親水性溶媒と予め混和されていてもよい。
本発明の水系コーティング剤は、上記の成分(A)〜(E)を含有するものであり、好適には、前記成分(A)の固形分100重量物に対し、
成分(B):0.1〜50重量部とすることができ、0.5〜50重量部、1〜50重量部とすることができ、2〜40重量部が好ましく、5〜35重量部がさらに好ましい。
成分(C):5〜200重量部とすることができ、20〜180重量部が好ましく、40〜150重量部がさらに好ましい。
成分(D):1〜20重量部とすることができ、2〜15重量部が好ましく、5〜10重量部がさらに好ましい。
成分(E):50〜1000重量部とすることができ、100〜800重量部が好ましく、300〜600重量部がさらに好ましい。なお、ここで、「成分(A)の固形分」とは、成分(A)から水あるいはその他の揮発性成分を、乾燥又は加熱により除去した場合の不揮発性の成分であり、主として硬化性樹脂の主剤あるいは不揮発性の硬化性樹脂それ自体からなる。
本発明の水系コーティング剤組成物は、上記の水系エマルジョン形態の硬化性樹脂の安定性、取り扱い作業性および得られるコーティング被膜の機能といった本発明の技術的効果を損なわない限り、ラメ剤、パール剤、防腐剤、香料、可塑剤、消泡剤、充填剤、酸化防止剤、紫外線吸収剤、硬化剤、触媒、溶剤、水溶性高分子、難燃剤、帯電防止剤、熱安定剤、pH調整剤、凍結防止、湿潤、顔料分散、乳化、皮張り防止、レベリング、乾燥促進等の目的で添加される添加剤を含むものであって良い。
本発明組成物の調製方法は、特に制限されるものではなく、上記の成分(A)〜(E)およびその他の水溶性任意成分を機械力を用いて均一に混合・分散することにより得ることができ、必要であれば、濃度調整用の水、その他の任意の添加物を混合・分散することにより製造される。その混合方法と混合順序には制約はない。
成分(C)である固体粒子の少なくとも一部が、固体潤滑剤を含む場合、本発明の水系コーティング剤組成物は基材表面に潤滑被膜を形成することが可能となり、水系潤滑被膜用塗料に用いることができる。本発明にかかる水系潤滑被膜用塗料は、水系塗料・コーティング剤として取り扱い作業性に優れ、かつ、当該潤滑被膜は優れた摺動特性を長時間維持することができる。したがって、本発明の組成物は、潤滑被膜用塗料組成物として、高い密着性と優れた摺動耐久性を備える潤滑被膜を与えることができる。
本発明の水系コーティング剤組成物、好適には水系潤滑被膜用塗料組成物は、加熱乾燥または高エネルギー線照射等により硬化して、コーティング被膜、好適には潤滑被膜形成に使用することができ、任意の基材の表面に高い密着性を有するコーティング被膜あるいは潤滑被膜を形成することができる。
本発明にかかるコーティング被膜、特に、潤滑被膜を備えた部材は、摺動部材として有用である。摺動部材の種類は特に限定されるものではないが、例えば、ゴム、プラスチック又は金属製のものが挙げられる。
各成分を表1及び表2に示す割合で混合して実施例1〜7及び比較例1〜8の水系コーティング剤(水系潤滑被膜用塗料組成物)を得た。
なお、表1及び表2に示す数値は質量部を表す。さらに、表中の水系ポリウレタン樹脂/水系ポリオレフィン樹脂は、本発明の(A)成分であるバインダーとして、固形分の質量部(100質量部)として記載し、水系エマルジョン形態の水は(E)水成分に含めて記載した。
[流動安定性]
コーティング剤の流動安定性については、以下の基準で判定し、表1(実施例1〜7)および表2(比較例1〜8)にあわせて示した。
◎:非常に安定
○:安定であるが増粘
△:増粘し24時間後にゲル化
×:瞬時にゲル化
××:固体潤滑剤が分散できず、浮上分離もしくは沈殿する
また、表中で使用した各成分および用語は、以下の通りである。なお、表中、「水」の質量部は、他の原料成分に由来する成分の和である。
水系ポリウレタン樹脂:脂肪族系ポリウレタン樹脂の水系エマルジョン(固形分40重量%)
水系ポリオレフィン樹脂:無水マレイン酸変性1-プロペン-1-ブテン共重合体の水系エマルジョン(固形分30重量%)
ドデシルベンゼンスルホン酸ナトリウム:固形分50重量%、日油(株)製
PTFE(ポリテトラフルオロエチレン)パウダー:レーザー回折散乱式粒度分布測定によるメジアン径が3〜5μmである球状ポリテトラフルオロエチレン樹脂微粒子(固形分100重量%)
PTFE(ポリテトラフルオロエチレン)ディスパージョン:レーザー回折散乱式粒度分布測定によるメジアン径が0.10〜1.00μmである球状ポリテトラフルオロエチレン樹脂微粒子(固形分50重量%)
Agitan295:MUNZING CHEMIE GMBH製消泡剤
1,3−ジメチル−2−イミダゾリジノン:川研ファインケミカル(株)製、DMEU
N−メチル−2−ピロリドン:BASFジャパン(株)製、N-メチル-2-ピロリドン
N−エチル−2−ピロリドン:BASFジャパン(株)製、N-エチル-2-ピロリドン
トリエタノールアミン:和光純薬工業(株)製、シグマアルドリッチジャパン(株)製、トリエタノールアミン,>=98.0%
ジエタノールアミン:和光純薬工業(株)製、ジエタノールアミン,99%
γ−ブチロラクトン:三菱化学(株)製、ガンマーブチロラクトン,99.5%以上
安息香酸ベンジル:和光純薬工業(株)製、安息香酸ベンジル 和光特級
メチルエチルケトン:和光純薬工業(株)製、メチルエチルケトン
アクリロニトリル−ブタジエン−スチレン共重合体(ABS)樹脂板:住友ベークライト1(
株)製、タフエースEAR-003
SPCC-SB鋼板:日新製鋼(株)製、SPCC-SB
表1に示す配合比で、水系ポリウレタン樹脂エマルジョン(樹脂固形分40%)に溶媒として1,3−ジメチル−2−イミダゾリジノンを添加し攪拌混合して溶解した。その後、アニオン性界面活性剤であるドデシルベンゼンスルホン酸ナトリウムを攪拌しながら加え溶解させた後、固体潤滑剤としてPTFEパウダーを分散した。消泡剤を添加した後、得られた混合物を600rpmで30分間混合攪拌して水系コーティング剤組成物を得た。
表1に示す配合比で、水系ポリオレフィン樹脂エマルジョン(樹脂固形分30%)を使用した以外は、実施例1と同様の方法で水系コーティング剤組成物を得た。
表1に示す配合比で、固体潤滑剤としてPTFEディスパージョンを使用し、溶媒として1,3−ジメチル−2−イミダゾリジノン単独、もしくはそれと安息香酸ベンジルを併用した以外は、実施例1と同様の方法で水系コーティング剤組成物を得た。
表1に示す配合比で、溶媒としてN−メチル−2−ピロリドン、もしくはN−エチル−2−ピロリドンを使用した以外は、実施例1と同様の方法で水系コーティング剤組成物を得た。
表2に示す配合比で、溶媒としてトリエタノールアミン、もしくはジエタノールアミンを使用した以外は、実施例1と同様の方法で水系コーティング剤組成物を得た。得られた混合物を室温で放置していたところ、経時で増粘し24時間後に流動しないゲル化状態となった。
表2に示す配合比で、溶媒としてγ−ブチロラクトン、もしくは安息香酸ベンジルを使用した以外は、実施例1と同様の方法で得られた混合物を600rpmで攪拌混合していたところ、急激に増粘し流動しないゲル化状態となった。
表2に示す配合比で、水系ポリウレタン樹脂エマルジョン(樹脂固形分40%)に溶媒としてメチルエチルケトンを添加し攪拌混合したところ、樹脂エマルジョンの凝集物が発生し沈殿した。
表2に示す配合比で、固体潤滑剤としてPTFEディスパージョン、溶媒として安息香酸ベンジルを使用した以外は、実施例1と同様の方法で得られた混合物を600rpmで攪拌混合していたところ、樹脂エマルジョンの凝集物が発生し沈殿した。
表2に示す配合比で、溶媒は何も使用しない状態で実施例1と同様の方法で得られた混合物を600rpmで攪拌混合していたところ、急激に増粘し流動しないゲル化状態となった。
表2に示す配合比で、界面活性剤を使用しない状態で実施例1と同様の方法で得られた混合物を600rpmで攪拌混合していたところ、固体潤滑剤のPTFEが十分に分散できず、浮上分離物と沈殿物が発生した。
表1の実施例で得られた水系コーティング剤組成物を、前記のアクリロニトリル−ブタジエン−スチレン共重合体(ABS)樹脂板または前記のSPCC-SB鋼板(SPCC鋼板)に乾燥後の膜厚が10〜20μmとなるようにスプレー塗装した。溶媒および水を蒸発させるため25℃×60分放置し乾燥硬化させ、潤滑被膜を作成した。なお、比較例においては、ゲル化等により、潤滑被膜を形成させることができなかったため、「測定不可能」と表2に記載した。
[摩擦係数測定]
潤滑被膜を形成した各試験片(ABS)に対し、垂直荷重をかけたローラーを回転移動させることによって往復させる往復動摩擦摩耗試験機を用いて、滑り速度0.2m/s、荷重100g、滑り距離(ストローク)40mmの条件で、SUJ2鋼ローラーに対する摺動時の動摩擦係数(単位:μ)を測定し、以下の基準で判定した。
◎:0.10〜0.19
○:0.20〜0.29
△:0.30〜0.39
×:0.40〜0.49
潤滑被膜を形成した各試験片(ABS樹脂板、SPCC鋼板)の当該被膜を100マスの碁盤目にカットし、セロテープ(登録商標)剥離試験を行った。碁盤目100マスのうち被膜の残った格子数を確認し、以下の基準で判定した。
◎(100)
○(90〜99)
△(50〜89)
×(0〜49)
Claims (15)
- (A)水系エマルジョン形態の硬化性樹脂、
(B)界面活性剤、
(C)固体粒子、
(D)1種類以上の窒素含有複素環化合物、および
(E)水
を含む、水系コーティング剤組成物。 - 前記成分(D)が、1,3−ジメチル−2−イミダゾリジノン、N−メチル−2−ピロリドン、N−エチル−2−ピロリドン、N−メチル−3−メチル−2−ピロリドン、シクロヘキシルピロリドン、2−オキサゾリドン、および3−メチル−2−オキサゾリドンから選ばれる1種類以上の窒素含有複素環化合物である、請求項1または請求項2の水系コーティング剤組成物。
- 前記成分(B)が前記成分(A)のエマルジョン形成に用いられる界面活性剤と異なるアニオン性界面活性剤を含み、かつ、前記成分(D)が、1,3−ジメチル−2−イミダゾリジノンである、請求項1〜請求項3のいずれかの水系コーティング剤組成物。
- 前記成分(A)の固形分 100質量物に対し、前記成分(B)0.1〜50質量部、前記成分(C)5〜200質量部、前記成分(D)1〜20質量部、前記成分(E)50〜1000質量部を含有する、請求項1〜請求項4のいずれかの水系コーティング剤組成物。
- 前記成分(A)が、水系エマルジョン形態のポリアクリル樹脂、ポリウレタン樹脂、ポリオレフィン樹脂、エポキシ樹脂、シリコーン樹脂、ポリアミドイミド樹脂またはその変性物およびこれらの混合物である、請求項1〜請求項5のいずれかの水系コーティング剤組成物。
- 前記成分(C)の少なくとも一部が固体潤滑剤である、請求項1〜請求項6のいずれかの水系コーティング剤組成物。
- 前記成分(C)が、フッ素樹脂、ポリエチレン樹脂、ポリアミド樹脂、二硫化モリブデン、グラファイト、酸化アルミニウム、窒化ホウ素、酸化亜鉛及びこれらの混合物から選ばれる固体潤滑剤を含む、請求項1〜請求項7のいずれかの水系コーティング剤組成物。
- 請求項1〜請求項8のいずれかの水系コーティング剤組成物からなる、水系潤滑被膜用塗料組成物。
- 請求項1〜請求項8のいずれかの水系コーティング剤組成物の、水系潤滑被膜用塗料組成物としての使用。
- 請求項1〜請求項8のいずれかの水系コーティング剤組成物を硬化させてなるコーティング被膜。
- 請求項1〜請求項8のいずれかの水系コーティング剤組成物を硬化させてなるコーティング被膜を備えた部材。
- 請求項11のコーティング被膜の潤滑被膜としての使用。
- 摺動部材である、請求項12の部材。
- 請求項1〜請求項8のいずれかの水系コーティング剤組成物を基材表面に塗布し、乾燥及び/又は高エネルギー線照射により、基材表面にコーティング被膜を形成する方法。
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EP3235887A4 (en) | 2018-07-25 |
WO2016098336A1 (ja) | 2016-06-23 |
EP3235887B1 (en) | 2019-07-31 |
CN107429116B (zh) | 2020-07-07 |
CN107429116A (zh) | 2017-12-01 |
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