JP6297795B2 - 潤滑被膜用塗料組成物 - Google Patents
潤滑被膜用塗料組成物 Download PDFInfo
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- JP6297795B2 JP6297795B2 JP2013131903A JP2013131903A JP6297795B2 JP 6297795 B2 JP6297795 B2 JP 6297795B2 JP 2013131903 A JP2013131903 A JP 2013131903A JP 2013131903 A JP2013131903 A JP 2013131903A JP 6297795 B2 JP6297795 B2 JP 6297795B2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
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Description
(A) (メタ)アクリル当量が100以下の(メタ)アクリル酸化合物、
(B) (メタ)アクリル当量が120〜300の範囲にある(メタ)アクリル酸化合物、
(C) 熱硬化性樹脂及び/又は高エネルギー線硬化性樹脂
(D) 少なくとも1種の固体潤滑剤
を含む、潤滑被膜用塗料組成物によって達成される。
(A) (メタ)アクリル当量が100以下の(メタ)アクリル酸化合物、
(B) (メタ)アクリル当量が120〜300の範囲にある(メタ)アクリル酸化合物、
(C) 熱硬化性樹脂及び/又は高エネルギー線硬化性樹脂
(D) 少なくとも1種の固体潤滑剤
を含む。なお、本発明において「高エネルギー線」とは、赤外線、可視光線、紫外線、X線、電子線、放射線等の電磁波及び粒子線を意味しており、180〜500nm、好ましくは200〜450nm、の波長を有する紫外線が好ましい。
本発明の組成物は、硬化物のハードセグメントを構成する成分として、(A)(メタ)アクリル当量が100以下、好ましくは95以下、より好ましくは90以下の(メタ)アクリル酸化合物、及び、硬化物のソフトセグメントを構成する成分として、(B)(メタ)アクリル当量が120〜300、好ましくは130〜270、より好ましくは150〜250である(メタ)アクリル酸化合物を共に含む。前記(A)成分及び前記(B)成分を併用することで、本発明の組成物の硬化物(重合物)は各種の基材に対して高い密着性を備えることができる。
本発明の組成物は、熱硬化性樹脂及び/又は高エネルギー線硬化性樹脂を含む。熱硬化性樹脂及び/又は高エネルギー線硬化性樹脂は、熱及び/又は高エネルギー線照射により硬化可能な有機樹脂又はそれらの混合物であり、特に、ラジカル重合性であることが好ましい。
本発明の組成物は、更に(D)少なくとも1種の固体潤滑剤を含む。このように固体潤滑剤を含むことで、本発明の組成物は基材表面に潤滑被膜を形成することが可能であり、また、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。
撹拌機及び加熱器を備えた反応装置に、ポリカーボネートポリオール(数平均分子量:1,000)0.1molと、ジメチロールプロピオン酸0.2molと、4,4'-ジシクロヘキシルメタンジイソシアネート0.3molと、ジブチル錫ジラウリレート0.1gと、N−エチル−2−ピロリドン(NEP)50gとを導入し、撹拌して反応させた。ウレタン化反応終了後、トリエチルアミン0.2molと、メチルアクリレート(アクリル当量=86)30g(0.300mol)と、ヒドロキシブチルアクリレート(アクリル当量=144)30g(0.208mol)とを添加して撹拌した。これを水300gと1,6-ヘキサンジアミン0.1molとの混合溶液に加え、ラジカル重合性樹脂組成物(紫外線硬化性ポリウレタン樹脂分散物)を得た。
撹拌機及び加熱器を備えた反応装置に、ポリカーボネートポリオール(数平均分子量:1,000)0.1molと、ジメチロールプロピオン酸0.2molと、4,4'-ジシクロヘキシルメタンジイソシアネート0.3molと、ジブチル錫ジラウリレート0.1gと、NEP50gとを導入し、撹拌して反応させた。ウレタン化反応終了後、トリエチルアミン0.2molと、ヒドロキシブチルアクリレート(アクリル当量=144)60gとを添加して撹拌した。これを水300gと1,6-ヘキサンジアミン 0.1molとの混合溶液に加え、ラジカル重合性樹脂組成物(紫外線硬化性ポリウレタン樹脂分散物)を得た。
撹拌機及び加熱器を備えた反応装置に、ポリカーボネートポリオール(数平均分子量:1,000)0.1molと、ジメチロールプロピオン酸0.2molと、4,4'-ジシクロヘキシルメタンジイソシアネート0.3molと、ジブチル錫ジラウリレート0.1gと、NEP50gとを導入し、撹拌して反応させた。ウレタン化反応終了後、トリエチルアミン0.2molと、ヒドロキシブチルアクリレート(アクリル当量=144)30gと、ラウリルメタアクリレート(アクリル当量=240)30gとを添加して撹拌した。これを水300gと1,6-ヘキサンジアミン0.1molとの混合溶液に加え、ラジカル重合性樹脂組成物(紫外線硬化性ポリウレタン樹脂分散物)を得た。
合成例1並びに比較合成例1及び2で得られたラジカル重合性樹脂組成物100重量部に対してラジカル型光重合開始剤(IRGACURE 907)を2重量部の配合比で添加し、撹拌して溶解した。得られた混合物をエチレン−プロピレン−ジエンゴム板(厚さ1mm)の表面に、バーコーターで乾燥被膜厚が5μmとなるように塗布し、250WハンディタイプUV照射機((株)あすみ技研製)により積算光量1000mJ/cm2で硬化させた。硬化後の試験片の塗膜面同士を図1のように貼り合わせ瞬間接着剤にて先端から70mmまでを接着し常温にて10分間放置後、島津オートグラフAGSシリーズ((株)島津製作所製)を用いて引張ったときの剥離強度を測定した。結果を表1に示す。なお、表1において■は、該当成分が存在することを示す。また、評価結果は以下の基準による。
剥離強度 ○:>10N/10mm、△:5〜10N/10mm、×:1〜5N/10mm
合成例1で得られたラジカル重合性樹脂組成物にラジカル型光重合開始剤(IRGACURE 907)を表2に示す配合比で撹拌混合して溶解した。その後、固体潤滑剤及びその他の添加剤を攪拌しながら加え、得られた混合物を1000rpmで30分間混合攪拌して潤滑被膜用塗料組成物を得た。
合成例1で得られたラジカル重合性樹脂組成物にラジカル型熱重合開始剤(OTAZO-15)を表3に示す配合比で撹拌混合して溶解した。その後、固体潤滑剤及びその他の添加剤を攪拌しながら加え、得られた混合物を1000rpmで30分間混合攪拌して潤滑被膜用塗料組成物を得た。
比較合成例1及び2で得られたラジカル重合性樹脂組成物にラジカル型光重合開始剤(IRGACURE 907)を表2に示す配合比で撹拌混合して溶解した。その後、固体潤滑剤及びその他の添加剤を攪拌しながら加え、得られた混合物を1000rpmで30分間混合攪拌して潤滑被膜用塗料組成物を得た。
比較合成例1及び2で得られたラジカル重合性樹脂組成物にラジカル型熱重合開始剤(OTAZO-15)を表3に示す配合比で撹拌混合して溶解した。その後、固体潤滑剤及びその他の添加剤を攪拌しながら加え、得られた混合物を1000rpmで30分間混合攪拌して潤滑被膜用塗料組成物を得た。
潤滑被膜用塗料組成物を表2及び表3に示す各種基材に膜厚5〜100μmとなるようにスプレー塗装した。溶媒を蒸発させるため25℃×1分間放置した後、実施例1〜5並びに比較例1〜6(表2)については250WハンディタイプUV照射機((株)あすみ技研製)により2000mJ/cm2〜3000mJ/cm2の積算光量で照射し、硬化被膜を作成した。実施例6及び比較例7〜8(表3)については、180℃、15分間加熱し、硬化被膜を作成した。
[摩擦係数測定]
潤滑被膜を形成した各試験片に対し、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1kg、滑り距離(ストローク)100mm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)を測定した。
潤滑被膜を形成した各試験片の当該被膜を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た。
◎(100),○(90〜99),△(50〜89),×(0〜49)
リングオンプレート試験機を用いて、回転数0.5m/s、ステップアップ荷重(98N/cm2/分)の条件で、摺動により基材表面の潤滑被膜が摩耗により消失し、潤滑被膜と相手材(鋼リング)との摩擦が生じる状態になった際の荷重を評価した。
JIS K 5400に準拠し、潤滑被膜を形成した試験片に対して、荷重1000g、移動速度0.5mm/sの条件で引っ掻いたときの潤滑被膜が界面破壊したときの鉛筆濃度の一段階下位の濃度番号を記録した。
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(固形分30重量%)東洋紡(株)製
IRGACURE 907: 2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン(固形分100重量%)BASFジャパン(株)製
ポリエチレン微粒子:レーザー回折散乱式粒度分布測定によるメジアン径が5〜30μmである球状ポリエチレン樹脂微粒子(固形分100重量%)
ナイロン微粒子:レーザー回折散乱式粒度分布測定によるメジアン径が3〜10μmである球状ナイロン12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)微粒子:レーザー回折散乱式粒度分布測定によるメジアン径が0.15〜0.3μm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%)
アルミナ微粒子:レーザー回折散乱式粒度分布測定によるメジアン径が0.03〜0.06μmである球状アルミナ微粒子(固形分55重量%)
二硫化モリブデン:レーザー回折散乱式粒度分布測定によるメジアン径が1〜6μmである二硫化モリブデン粉末(固形分100重量%)
グラファイト: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であるグラファイト粉末(固形分100重量%)
Dow Corning 52 Additive:重量平均分子量50万〜100万のポリジメチルシロキサン水中油型エマルジョン(固形分65重量%)東レ・ダウコーニング(株)製
Agitan295:MUNZING CHEMIE GMBH製消泡剤
Rheolate 255:Elementis Specialty製増粘剤
エチレンプロピレンジエン(EPDM)ゴム:入間川ゴム(株)製EP-5065
ニトリル(NR)ゴム:入間川ゴム(株)製IN-80
ナイロン繊維:東レ(株)製、プロミランからなるナイロン66繊維
ポリエステル繊維:東レ(株)製、テトロン(セミダル糸)からなるポリエステル繊維
SPCC-SB鋼板:日新製鋼(株)製SPCC-SB
OTAZO-15: OTAZO-15 [1,1'-Azobis(1-acetoxy-1-phenylethane)] (大塚化学(株)製)
Claims (9)
- (A)(メタ)アクリル当量が100以下の(メタ)アクリル酸化合物、
(B)(メタ)アクリル当量が120〜300の範囲にある(メタ)アクリル酸化合物、
(C)熱硬化性樹脂及び/又は高エネルギー線硬化性樹脂、
(D)少なくとも1種の固体潤滑剤
を含み、
前記成分(A):前記成分(B)のモル比が1:9〜9:1の範囲にある潤滑被膜用塗料組成物。 - 前記成分(C)が、(c1)少なくとも1種のポリオールと(c2)少なくとも1種のイソシアネートを反応させてなるウレタン樹脂である、請求項1に記載の潤滑被膜用塗料組成物。
- 前記成分(C)が、(c1−1)ポリカーボネートポリオールと(c2−1)ジイソシアネートを反応させてなる、ポリカーボネート系ウレタン樹脂である、請求項1又は2に記載の潤滑被膜用塗料組成物。
- 前記成分(A)である(メタ)アクリル酸化合物が、(メタ)アクリル酸エステルであり、及び/又は、
前記成分(B)である(メタ)アクリル酸化合物が、(メタ)アクリル酸エステルである、請求項1〜3のいずれかに記載の潤滑被膜用塗料組成物。 - 前記成分(D)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、請求項1〜4のいずれかに記載の潤滑被膜用塗料組成物。
- 前記成分(A)〜前記成分(C)の和 100質量部に対し、前記成分(D)1〜200質量部含むことを特徴とする、請求項1〜5のいずれかに記載の潤滑被膜用塗料組成物。
- 請求項1〜6のいずれかに記載の潤滑被膜用塗料組成物を硬化させてなる潤滑被膜。
- 請求項7記載の潤滑被膜を備える摺動部材。
- 請求項1〜6のいずれかに記載の潤滑被膜用塗料組成物を基材表面に塗布し、加熱及び/又は高エネルギー線照射により、基材表面に潤滑被膜を形成する方法。
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| KR1020157036102A KR102221926B1 (ko) | 2013-06-24 | 2014-04-21 | 윤활 피막용 코팅 조성물 |
| US14/896,211 US20160115421A1 (en) | 2013-06-24 | 2014-04-21 | Coating composition for lubrication film |
| CN201480035626.4A CN105324448B (zh) | 2013-06-24 | 2014-04-21 | 用于润滑膜的涂料组合物 |
| EP14725781.0A EP3013911B1 (en) | 2013-06-24 | 2014-04-21 | Coating composition for lubrication film |
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| JP6361636B2 (ja) * | 2015-11-18 | 2018-07-25 | コニカミノルタ株式会社 | 摺動部材の製造方法 |
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| EP3013911A1 (en) | 2016-05-04 |
| CN105324448A (zh) | 2016-02-10 |
| EP3013911B1 (en) | 2017-05-17 |
| KR20160022828A (ko) | 2016-03-02 |
| WO2014208191A1 (en) | 2014-12-31 |
| KR102221926B1 (ko) | 2021-03-04 |
| CN105324448B (zh) | 2017-12-19 |
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