JP4425788B2 - (メタ)アクリル系共重合体樹脂及びそれからなる塗膜 - Google Patents
(メタ)アクリル系共重合体樹脂及びそれからなる塗膜 Download PDFInfo
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- JP4425788B2 JP4425788B2 JP2004524170A JP2004524170A JP4425788B2 JP 4425788 B2 JP4425788 B2 JP 4425788B2 JP 2004524170 A JP2004524170 A JP 2004524170A JP 2004524170 A JP2004524170 A JP 2004524170A JP 4425788 B2 JP4425788 B2 JP 4425788B2
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Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
1.(A)(メタ)アクリル系共重合体樹脂からなる塗膜であって、剛体振り子型粘弾性測定装置で測定したガラス転移温度(Tg1)および示差走査型熱量計(DSC)で測定したガラス転移温度(Tg2)が110℃以上、テーパー摩耗試験法で測定した耐磨粍性が80回以上である耐磨耗性塗膜。
2.剛体振り子型粘弾性測定装置で測定したガラス転移温度(Tg1)および示差走査型熱量計(DSC)で測定したガラス転移温度(Tg2)と、塗膜を構成するモノマー組成から計算されるガラス転移温度(Tg3)の差が30℃以上である上記1記載の塗膜。
3.計算上のガラス転移温度(Tg3)が50〜150℃である(A)(メタ)アクリル系共重合体。
4.(a−1)(メタ)アクリル酸4〜50質量%、(a−2)(メタ)アクリル酸アミド0.5〜17質量%、(b)(a−1)(a−2)以外の反応性不飽和結合を含有する化合物35〜95.5質量%をラジカル重合し、重量平均分子量(Mw)が2万以上である(A)(メタ)アクリル系共重合体樹脂。
5.上記4記載の樹脂を(B)有機溶剤に溶解してなる塗液。
である。
、Tg2)が110℃以上であればテーパー摩耗試験法で測定した耐磨耗性が80回以上である耐磨耗性塗膜が得られることを見出しさらに、剛体振り子型粘弾性測定装置および示差走査型熱量計(DSC)で測定したガラス転移温度(Tg1、Tg2)と、塗膜を構成するモノマー組成から計算されるガラス転移温度(Tg3)の差が30℃以上である(メタ)アクリル系の共重合体樹脂は、外観、耐溶剤性、密着性が良好であり耐摩耗性に優れた塗膜であることを見いだし本発明に到達した。
塗膜
本発明において塗膜の剛体振り子型粘弾性測定装置および示差走査型熱量計(DSC)で測定したガラス転移温度(Tg1、Tg2)は、110〜250℃であるが、好ましくは120〜250℃の範囲であり、更に好ましくは130〜250℃の範囲である。110℃未満では塗膜形成後の硬度、耐摩耗性が不十分となり、250℃を超えると硬く脆くなり硬度摩耗性が不十分となる。
)(ISO 7784−2:1997)に従って測定した。その測定方法は、摩耗輪法(
CS10F,荷重500g)にて摩耗試験を行い目視で塗膜が削り取られたり、塗膜が基材から脱落する等変化が起こるまでの回転数を読み取った。
American Physical Society、Series 2)1巻・3号・123項(1956年)に記載されている。フォックスの式による共重合体のTgを算出するための基礎となる各種反応性不飽和結合を有する化合物についてのTgは、例えば、新高分子文庫・第7巻・塗料用合成樹脂入門(北岡協三著、高分子刊行会、京都、1974年)168〜169項の表10−2(塗料用アクリル樹脂の主な原料単量体)に記載されている数値を用いることができる。
(A)(メタ)アクリル系共重合体樹脂
ここで、(A)(メタ)アクリル系共重合体樹脂について説明をする。
溶剤と塗液
本発明の(A)(メタ)アクリル系共重合体樹脂を溶解・分散させるために用いる溶剤は、重合体を完全に溶解し、蒸発除去できる限り特に制限はないが塗液として利用するに際しての好ましい粘度、蒸発速度、塗膜の白化の程度を改善するため2種以上の溶剤を混合することができる。
じて連鎖移動剤として、ドデシルメルカプタン、メルカプトエタノール、α−メチルスチレンダイマー等を用いることができる。
塗膜作成方法
本発明の(A)アクリル系共重合樹脂は、基材等に各方法により塗装され室温から110℃で20秒程度の加熱乾燥により塗膜を形成する事ができる。また基材としては、例えば鉄、アルミ、亜鉛、ステンレス及びこれらに表面処理をされたもの等の金属素材、塩化ビニル,ポリエチレンテレフタレート、ポリエチレン、ポリプロピレン、ポリカーボネート及びこれらに表面処理をされたもの等のプラスチック素材等があげられる。また、これらの基材に必要に応じてプライマー、中塗り、上塗り塗料が塗装された基材も使用することができる。
塗膜の評価方法
前記で希釈調整された各塗料組成物をポリ塩化ビニルのシート状(厚さ1mm×縦100mm×横100mm)の基材にバーコーターにて、乾燥膜厚で2〜3μmとなるように塗装し、熱風乾燥機にて雰囲気110℃で20秒程度乾燥し各試験片を作成した。得られた試験片を下記の各項目について観察、及び評価を行った。その結果を表−2に示す。
塗膜状態
(1)外観
(i)透明性;作成された試験片塗膜を目視観察し、下記の方法により評価した。
△:若干曇り
×:不透明(白濁)
(ii)ワレ・クラック性;作成された試験片塗膜を顕微鏡観察し、下記の方法により評価した。
△:わずかなワレ・クラック
×:ワレ・クラックあり
(2)密着性(碁盤目付着性);作成された試験片塗膜を碁盤目法(K5400−8−5)に従い密着試験を行い観察し、下記の方法により評価した。
(3)耐溶剤性;作成された試験片塗膜に、各溶剤(アセトン/トルエン)に浸したガーゼを用いラビング50回(往復)目視観察し、下記の方法により評価した。
△:若干痕跡あり
×:明らかな痕跡もしくは傷付き
塗膜物性
(4)耐摩耗性;作成された試験片塗膜をテーパー摩耗試験法(JIS K5600−5
−9)の摩耗輪法(CS10F,荷重500g)にて、摩耗試験を行い目視で塗膜が削り取られたり、塗膜が基材から脱落する等の変化が起こるまでの回転数を読み取った。
(5)塗膜Tg1,Tg2;試験片作成に用いた塗料化品を下記測定機器に応じた条件で乾燥し、測定値を記載した。
(i)剛体振り子型粘弾性測定装置:(DDV−OPAIII;エーアンドデー社製)
(ii)DSC(示差走査型熱量計):(DSC−60A;島津社製)
〔参考例1〕
撹拌機、温度計、窒素導入管、還流コンデンサーを備えた5リッタ4ツ口フラスコにイソプロピルアルコール750g、トルエン250g、メチルエチルケトン500gを仕込み、窒素パージを行ないながら80℃まで昇温した。次に昇温後ただちにメタアクリル酸100g、メタアクリル酸アミド40g、メチルメタアクリレート502g、イソブチル
メタアクリレート358g及び重合開始剤を定量ポンプにて5時間かけて連続滴下し、その後80℃にて重合開始剤を更に加え3時間保ちメタアクリル系共重合樹脂(A)を得た。
〔実施例1〜5、参考例1、2及び比較例1〜5〕
参考例1と同様に表1−1,2に示す(メタ)アクリル酸、(メタ)アクリル酸アミド、反応性不飽和結合を有する化合物、溶剤組成等を変更して製造した。その結果を表1−1,2に示す。
ここで計算に使用した各種反応性不飽和結合を有する化合物のTgは新高分子文庫・第7巻・塗料用合成樹脂入門(北岡協三著、高分子刊行会、京都、1974年)168〜169項の表10−2(塗料用アクリル樹脂の主な原料単量体)を用いた。
Claims (3)
- (a−1)(メタ)アクリル酸20〜50質量%、(a−2)(メタ)アクリル酸アミド0.5〜17質量%、(b)(a−1)(a−2)以外の反応性不飽和結合を含有する化合物35〜95.5質量%をラジカル重合し、重量平均分子量(Mw)が2万〜6.6万の(A)(メタ)アクリル系共重合体樹脂であって、剛体振り子型粘弾性測定装置で測定したガラス転移温度(Tg1)および示差走査型熱量計(DSC)で測定したガラス転移温度(Tg2)が115℃〜250℃の範囲であることを特徴とする(メタ)アクリル系共重合体樹脂。
- 請求項1に記載の(メタ)アクリル系共重合体樹脂を(B)有機溶剤に溶解してなる塗液。
- 請求項1に記載の(A)(メタ)アクリル系共重合体樹脂からなる塗膜であって、剛体振り子型粘弾性測定装置で測定したガラス転移温度(Tg1)および示差走査型熱量計(DSC)で測定したガラス転移温度(Tg2)が115℃〜250℃の範囲であり、摩耗試験法(JIS K5600−5−9)の摩耗輪法(CS10F,荷重500g)に従い、テーパー摩耗試験法で測定した塗膜が削り取られたり、塗膜が基材から脱落するまでの耐磨耗性が80回以上である耐磨耗性塗膜。
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JP2002222343 | 2002-07-31 | ||
PCT/JP2003/009526 WO2004011564A1 (ja) | 2002-07-31 | 2003-07-28 | (メタ)アクリル系共重合体樹脂及びそれからなる塗膜 |
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US3048501A (en) * | 1959-06-23 | 1962-08-07 | Rohm & Haas | Paper products having a coating of mineral pigment in a binder of ammonium or amine salt of a copolymer of acrylic acid or methacrylic acid, acrylamide or methacrylamide, and a (c1-c4)-alkyl acrylate or methacrylate, and production thereof |
JPH0642073B2 (ja) * | 1984-04-10 | 1994-06-01 | 三菱レイヨン株式会社 | 光重合性樹脂組成物 |
JPS61251844A (ja) * | 1985-04-30 | 1986-11-08 | Fuji Photo Film Co Ltd | ハロゲン化銀写真感光材料 |
JPS61268731A (ja) * | 1985-05-23 | 1986-11-28 | Mitsubishi Rayon Co Ltd | 表面被覆用組成物 |
JP2542813B2 (ja) * | 1985-12-05 | 1996-10-09 | 大日本インキ化学工業株式会社 | 塗料用樹脂組成物 |
JP2517965B2 (ja) | 1987-05-19 | 1996-07-24 | 日本合成ゴム株式会社 | 床用光沢組成物用共重合体エマルジョン |
US4770795A (en) * | 1987-08-24 | 1988-09-13 | Nalco Chemical Company | Calcium tolerant deflocculant for drilling fluids |
JPH07156567A (ja) | 1993-12-10 | 1995-06-20 | Dainippon Printing Co Ltd | 保護層転写フィルム及び印画物 |
US5536627A (en) * | 1995-03-21 | 1996-07-16 | Eastman Kodak Company | Photographic elements with improved cinch scratch resistance |
JP3642635B2 (ja) | 1996-07-08 | 2005-04-27 | 旭電化工業株式会社 | 熱可塑性樹脂フィルム |
JP3640037B2 (ja) | 1996-10-31 | 2005-04-20 | 東レ・ファインケミカル株式会社 | 塗料用アクリル樹脂の製造方法 |
KR19980079940A (ko) * | 1997-03-05 | 1998-11-25 | 후지이 히로시 | 빗물오염방지성 도막, 도료 조성물, 도막 형성방법 및 도장물 |
JPH11181334A (ja) | 1997-12-24 | 1999-07-06 | Nippon Paint Co Ltd | 塗料組成物、塗膜形成方法及び塗装物 |
JP2000144049A (ja) | 1998-11-12 | 2000-05-26 | Kansai Paint Co Ltd | 塗料組成物 |
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- 2003-07-28 WO PCT/JP2003/009526 patent/WO2004011564A1/ja active Application Filing
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WO2004011564A1 (ja) | 2004-02-05 |
DE60334552D1 (de) | 2010-11-25 |
EP1544266A4 (en) | 2006-08-02 |
CN1671812A (zh) | 2005-09-21 |
JPWO2004011564A1 (ja) | 2005-11-24 |
CN100387665C (zh) | 2008-05-14 |
EP1544266A1 (en) | 2005-06-22 |
US7186788B2 (en) | 2007-03-06 |
US20050222321A1 (en) | 2005-10-06 |
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