JP4269663B2 - Heat exchange device and refrigeration device - Google Patents

Description

【００４６】
（式中、Ｒｆは炭素数１〜２１のフルオロアルキル基、Ｒ¹は水素又は炭素数１〜１０のアルキル基、Ｒ²は炭素数１〜１０のアルキレン基、Ｒ³は水素又はメチル基、Ａｒは置換基を有することもあるアリーレン基、ｎは１〜１０の整数である。）
限定されないフルオロアルキル基含有（メタ）アクリレートの具体例を次に示す。
ＣＦ₃(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃ＣＦ₂(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃ＣＦ₂(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＨ₂)₃ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃ＣＦ₂(ＣＨ₂)₃ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃(ＣＨ₂)₃ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄(ＣＨ₂)₃ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅(ＣＨ₂)₃ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆(ＣＨ₂)₃ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)₃ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＨ₂)₆ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃ＣＦ₂(ＣＨ₂)₆ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃(ＣＨ₂)₆ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄(ＣＨ₂)₆ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅(ＣＨ₂)₆ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆(ＣＨ₂)₆ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)₆ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃ＣＨ＝ＣＨＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃ＣＦ₂ＣＨ＝ＣＨＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃ＣＨ＝ＣＨＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄ＣＨ＝ＣＨＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅ＣＨ＝ＣＨＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆ＣＨ＝ＣＨＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇ＣＨ＝ＣＨＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₂(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₃(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₄(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₅(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₆(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
Ｈ(ＣＦ₂)(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
Ｈ(ＣＦ₂)₂(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
Ｈ(ＣＦ₂)₄(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
Ｈ(ＣＦ₂)₆(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
Ｈ(ＣＦ₂)₈(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃ＣＨＦＣＦ₂(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃ＣＦ₂(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＨ₂)ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃ＣＦ₂(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＨ₂)₃ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃ＣＦ₂(ＣＨ₂)₃ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃(ＣＨ₂)₃ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄(ＣＨ₂)₃ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅(ＣＨ₂)₃ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆(ＣＨ₂)₃ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)₃ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＨ₂)₆ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃ＣＦ₂(ＣＨ₂)₆ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃(ＣＨ₂)₆ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄(ＣＨ₂)₆ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅(ＣＨ₂)₆ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆(ＣＨ₂)₆ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇(ＣＨ₂)₆ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃ＣＨ＝ＣＨＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃ＣＦ₂ＣＨ＝ＣＨＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃ＣＨ＝ＣＨＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄ＣＨ＝ＣＨＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅ＣＨ＝ＣＨＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆ＣＨ＝ＣＨＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇ＣＨ＝ＣＨＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₂(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₃(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₄(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₅(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₆(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
Ｈ(ＣＦ₂)(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
Ｈ(ＣＦ₂)₂(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
Ｈ(ＣＦ₂)₄(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
Ｈ(ＣＦ₂)₆(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
Ｈ(ＣＦ₂)₈(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃ＣＨＦＣＦ₂(ＣＨ₂)ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃ＳＯ₂Ｎ(ＣＨ₃)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)ＳＯ₂Ｎ(ＣＨ₃)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₂ＳＯ₂Ｎ(ＣＨ₃)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₃ＳＯ₂Ｎ(ＣＨ₃)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₄ＳＯ₂Ｎ(ＣＨ₃)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₅ＳＯ₂Ｎ(ＣＨ₃)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₆ＳＯ₂Ｎ(ＣＨ₃)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
ＣＦ₃(ＣＦ₂)₇ＳＯ₂Ｎ(Ｃ₂Ｈ₅)(ＣＨ₂)₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
ＣＦ₃Ｃ₆Ｆ₁₀(ＣＦ₂)₂ＳＯ₂Ｎ(ＣＨ₃)(ＣＨ₂)₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦＣＨ₂ＣＨ(ＯＣＯＣＨ₃)ＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)ＣＨ₂ＣＨ(ＯＣＯＣＨ₃)ＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₂ＣＨ₂ＣＨ(ＯＣＯＣＨ₃)ＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₃ＣＨ₂ＣＨ(ＯＣＯＣＨ₃)ＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₄ＣＨ₂ＣＨ(ＯＣＯＣＨ₃)ＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₅ＣＨ₂ＣＨ(ＯＣＯＣＨ₃)ＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₆ＣＨ₂ＣＨ(ＯＣＯＣＨ₃)ＣＨ₂ＯＣＯＣ(ＣＨ₃)＝ＣＨ₂、
(ＣＦ₃)₂ＣＦＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₂ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₃ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₄ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₅ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₆ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₇ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
(ＣＦ₃)₂ＣＦ(ＣＦ₂)₈ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂、
【００４７】
【化２】

【００４８】
上記のフルオロアルキル基含有（メタ）アクリレートは２種以上を混合して用いることももちろん可能である。
【００４９】
非フッ素系モノマーとしては、例えば、（メタ）アクリレートエステルが挙げられる。（メタ）アクリレートエステルは、（メタ）アクリル酸と、脂肪族アルコール、例えば、一価アルコール又は多価アルコール（例えば、２価アルコール）とのエステルであってもよい。
【００５０】
非フッ素系モノマーとしては、例えば以下のものを例示できる。
【００５１】
２−エチルヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ラウリル（メタ）アクリレート、ステアリル(メタ)アクリレート、ヒドロキシアルキル(メタ)アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ポリオキシアルキレン(メタ)アクリレート、アルコキシポリオキシアルキレン(メタ)アクリレート、３−クロロ−２−ヒドロキシプロピル(メタ)アクリレート、グリシジル(メタ)アクリレート、Ｎ,Ｎ−ジメチルアミノエチル(メタ)アクリレート、Ｎ,Ｎ−ジエチルアミノエチル(メタ)アクリレート、ベンジル（メタ）アクリレートグリシジルメタクリレート、ヒドロキシプロピルモノメタクリレート、２−ヒドロキシ−３−フェノキシプロピルアクリレート、２−ヒドロキシエチルアクリレート、グリセロールモノメタクリレート、β−アクリロイルオキシエチルハイドロジェンサクシネート、β−メタクリロイルオキシエチルハイドロジェンフタレート、２−アクリロイロキシエチルヘキサヒドロフタル酸、２−アクリロイロキシエチルフタル酸、２−アクリロイロキシエチル−２−ヒドロキシエチルフタル酸、メタクリル酸ヒドロキシプロピルトリメチルアンモニウムクロライド、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート、２−アクリロイロキシエチルアシッドホスフェート、グルコシルエチルメタクリレート、メタクリルアミド、２−ヒドロキシ−３−アクリロイロキシプロピルメタクリレート、２−メタクリロイロキシエチルアシッドホスフェート、ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート等の(メタ)アクリレート類；スチレン、ｐ−イソプロピルスチレン等のスチレン類；(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド、Ｎ−メチロール(メタ)アクリルアミド、Ｎ−ブトキシメチルアクリルアミド、２−アクリルアミド−２−メチルプロパンスルホン酸等の（メタ）アクリルアミド類；ビニルアルキルエーテル等のビニルエーテル類。
【００５２】
更に、エチレン、ブタジエン、酢酸ビニル、クロロプレン、塩化ビニルなどのハロゲン化ビニル、ハロゲン化ビニリデン、アクリロニトリル、ビニルアルキルケトン、無水マレイン酸、Ｎ−ビニルカルバゾール、ビニルピロリドン、(メタ）アクリル酸等が挙げられる。
【００５３】
また、非フッ素系モノマーは、ケイ素系モノマー（例えば、（メタ）アクリロイル基含有アルキルシラン、（メタ）アクリロイル基含有アルコキシシラン、（メタ）アクリロイル基含有ポリシロキサン）であってよい。
【００５４】
含フッ素重合体（ｃ（１））は、ラジカル重合法で製造できる。
【００５５】
重合体（ｃ（１））の重量平均分子量は比較的小さいものであり、３，０００以上、更には５，０００以上、特に７，０００以上であり、また３０，０００以下、更には２０，０００以下、特に１５，０００以下であるが好ましい。
【００５６】
低熱容量の無機粒子（ｄ）としては、多くの金属単体又は非金属単体、更には一部の金属化合物の粒子が該当する。具体例としては、例えば金、銀、アルミニウム、鉄、銅などの金属；炭素、ホウ素などの非金属；その他金属化合物などを掲げることができる。
また、低熱容量の無機粒子（ｄ）は、別の観点からは、導電性であることが望ましい。撥水性バインダーの多くは帯電性であり、塗膜表面に氷結の核となる塵を付着させやすいので、塗膜表面の帯電を防止することにより着氷（雪）を更に防止できる。
なお、耐候性を損なわないためには低熱容量の無機粒子も耐候性や耐食性、耐溶剤性に富むものが望ましい。
低熱容量の無機粒子（ｄ）の熱容量としては、モル熱容量で７ＪＫ^−１ｍｏｌ^−１以下が好ましい。下限は通常６ＪＫ^−１ｍｏｌ^−１である。
低熱容量の無機粒子（ｄ）の１次平均粒子径としては、分散性の点から２μｍ以上、１２μｍ以下が好ましい。
【００５７】
かかる低熱容量の無機粒子（ｄ）としては、特に炭素の単体であるカーボンブラック、とりわけ結晶性のカーボンブラックが好ましい。
【００５８】
なお、低熱容量の無機粒子（ｄ）を配合するときは、その理由は不明であるが、撥水性の有無にかかわらず、滑落性が更に向上する。また、着霜してしまった場合の除霜を容易にする作用も期待できる。
【００５９】
溶媒（ｅ）は、表面処理組成物の各成分の均一な混合を容易にし、塗膜の形成を容易にし、更に各種成分を撥水性バインダー樹脂（ａ）中に均一分散させる観点から有用である。したがって、溶媒（ｅ）は他の成分（ａ）、（ｂ）、（ｃ）及び（ｄ）を考慮して選択される。
【００６０】
溶媒（ｅ）としては水などの無機溶媒系でもよいが、上記観点から有機溶媒系が好ましい。有機溶媒系としては単一の溶媒でも２種以上の混合溶媒系でもよい。２種以上使用する場合は、極性有機溶媒と非極性有機溶媒を含むことが他の各成分をより一層均一に分散させ得る点から望ましい。
【００６１】
極性有機溶媒としては、例えば酢酸ブチル、酢酸エチル、アセトン、メチルイソブチルケトン、エタノール、イソプロパノール、ブタノール、エチレングリコールモノアルキルエーテルなどが揚げられる。
【００６２】
非極性有機溶媒としては、例えばトルエン、キシレン、ｎ−ヘキサン、シクロヘキサン、ヘプタンのほか、石油スピリッツであるターペンなどが揚げられる。
【００６３】
特に酢酸ブチルと石油系溶剤（トルエン、キシレン、ｎ−ヘキサン、シクロヘキサン、ヘプタン、ターペンなど）とを混合使用することにより、得られる塗膜の滑水性を調節できる。混合割合は組み合わせる溶剤の種類によって異なり任意であるが、同じ重量か酢酸ブチルの多いほうが滑水性が良好な点から好ましい。
【００６４】
本発明の表面処理組成物における好ましい配合割合は、撥水性のバインダー樹脂（ａ）１００重量部に対して（以下、特に断らない限り同じ）、ＰＴＦＥ粒子（ｂ）は１００重量部以上で２００重量部以下であり、分散剤（ｃ）は５重量部以上で３０重量部以下である。低熱容量の無機粒子（ｄ）は２５重量部以上で２００重量部以下、また溶媒（ｅ）は４００重量部以上で２０００重量部以下とすることが好ましい。
【００６５】
かかる表面処理組成物は、塗膜を形成できる形態であれば種々の形態に調製できるが、塗膜の形成が容易な点から溶媒型塗料に調製するのが好ましく、塗装性や分散性の点から固形分濃度を５〜４０重量％、特に１５〜３０重量％とするのが好ましい。また、本発明の目的を損なわない限り、顔料、他の樹脂類、流動調整剤、色分かれ防止剤、酸化防止剤、紫外線吸収剤などの各種添加剤を配合してもよい。
【００６６】
溶媒型塗料としての表面処理用組成物の調製は、溶剤（ｅ）に各成分を投入し、充分攪拌して行う。攪拌方法としては特に限定されないが、超音波攪拌法や強制攪拌法などがＰＴＦＥ粒子（ｂ）や低熱容量の無機粒子（ｄ）などの粒子成分を容易に均一に分散できる点から好ましい。
【００６７】
塗装方法としては特に限定されず、例えばディップコート法、バーコート法、ロールコート法、スプレー法などの方法が採用できる。塗布後、室温で乾燥するか、必要に応じて加熱乾燥させて硬化被膜を形成する。
【００６８】
塗膜の膜厚は適用部分によって適宜選定すればよいが、通常１０μｍ以上、更には３０μｍ以上、また０．２ｍｍ以下、更には０．１ｍｍ以下が好ましい。
【００６９】
塗布する基材は特に限定されず、着霜が問題となる熱交換器によって決まる。例えばアルミニウム、ステンレススチール、銅、各種合金、セラミックスなどが揚げられる。
【００７０】
かくして得られる塗膜（熱交換面を形成する表面構造）は、熱交換面に表面部分Ａと表面部分Ｂを与え、易霜氷剥離性を有するものである。
更にこの塗膜は、熱交換面の滑落角（４μリットル水滴）を１０度以下、更に好ましくは５度以下にすることができ、また、塗膜表面の対水接触角を１４０度以上、更には１４５度以上、特に１５０度以上にし、撥水性表面に形成された微小な水滴も容易に滑落し、着霜の核を形成させず、着霜を防止する効果を向上させるものである。
【００７１】
（試験例）
次に、上記塗膜により表面構造を形成した試験例について説明する。なお、本発明に係る塗膜形成方法は下記の試験例に用いた形成方法に限定されるものではない。
【００７２】
比較試験例１
撥水性バインダー樹脂（ａ）としてダイキン工業（株）製のゼッフルＧＫ−５１０、ＰＴＦＥ粒子（ｂ）としてセントラル硝子（株）製のセフラルルーブ（商品名。平均一次粒子径５〜１０μｍの変性ＰＴＦＥ。重量平均分子量１５００〜２００００）、分散剤（ｃ）としてダイキン工業（株）製のユニダインＴＧ−６５６を用い、表１に記載の量を表１に示す有機溶剤（ｅ）に投入し、超音波攪拌法により攪拌混合して表面処理用組成物を調製した。
【００７３】
得られた表面処理用組成物をアルミニウム板（ＪＩＳＨ４０００のＡ１２００系。１００ｍｍ×１００ｍｍ）上にスプレー法で塗装し、室温で１日間放置して硬化させた後、塗膜表面を洗浄せずに乾燥して試験用の塗板（塗膜の膜厚２０μｍ）を作製した。
【００７４】
この塗板について以下の方法により、対水接触角及び滑落角（４μリットル）を調べた。結果を表１に示す。
【００７５】
なお、対水接触角は次のようにして測定した。
ＪＩＳＲ３２５７に準じ、協和界面科学（株）製の接触角計（ＣＡ−ＶＰ、商品名）により、温度１５〜２０℃、相対湿度５０〜７０％で測定した。対水接触角の角度は大きいほうが撥水性が高い。
【００７６】
また、滑落角は次のようにして測定した。
塗板を協和界面科学（株）製の接触角計（ＣＡ−ＶＰ、商品名）に水平に固定し、温度１７±１℃で相対湿度６０±２％の環境下に水平に載置された試料板上に蒸留水を４μリットル滴下して水滴を形成し、次いで試料板を角度０．１度ずつ傾斜させていき、水滴が転がり始めたときの試料板の角度を測定した。表に示す測定値は初回の滑落角である。滑落角の角度は小さいほうが水滴滑落性（滑水性）がよい。
【００７７】
【表１】

【００７８】
試験例１
上記の比較試験例１において、成分（ａ）、（ｂ）、（ｃ）及び（ｅ）の配合割合を表２に示す割合とし、更に低熱容量の無機粒子（ｄ）として表２に示す粒子を同表に示す量加えたほかは試験例１と同様にして表面処理用組成物を調製し塗装して試験用の塗板を作製した。攪拌方法は超音波攪拌法を採用した。
【００７９】
この塗板について、対水接触角及び転落角を比較試験例１と同様にして調べた。結果を表２に示す。この結果から、低熱容量の無機粒子（ｄ）を加えることにより滑落性を改善し得ることが分かる。
【００８０】
なお、表２中の低熱容量の無機粒子（ｄ）は次のものである。
ＣＢ：カーボンブラック（シグマ・アルドリッチ製。一次平均粒子径２〜１２μｍ）
ＧＦ：天然黒鉛（一次平均粒子径約３μｍ）
【００８１】
【表２】

【００８２】
試験例２
試験例１の実験番号２−２（カーボンブラック粒子）及び実験番号２−８（天然黒鉛粒子）において、得られた塗膜を１２０℃で１０時間加熱硬化させ、試験用の塗板を作製した。
【００８３】
この加熱硬化塗板について、対水接触角及び転落角を比較試験例１と同様に調べた。その結果を表３に示す。この試験例２においても比較試験例１のものに比し滑落性を改善し得ることが分かる。
【００８４】
【表３】

【００８５】
試験例３
撥水性バインダー樹脂（ａ）としてダイキン工業（株）製のゼッフルＧＫ−５１０を４．０ｇ、ＰＴＦＥ粒子（ｂ）としてセントラル硝子（株）製のセフラルルーブ（商品名。平均一次粒子径５〜１０μｍの変性ＰＴＦＥ。重量平均分子量１５００〜２００００）を４．０ｇ、分散剤（ｃ）としてダイキン工業（株）製のユニダインＴＧ−６５６を４．０ｇ、低熱容量の無機粒子（ｄ）としてカーボンブラック（シグマ・アルドリッチ製。平均粒子径２〜１２μｍ）を２．０ｇ用い、酢酸ブチル２０ｇとヘプタン２０ｇの混合溶媒に投入し、超音波攪拌により攪拌混合して表面処理用組成物を調製した。
【００８６】
得られた表面処理用組成物をアルミニウム板（ＪＩＳ Ｈ４０００のＡ１２００系。１００ｍｍ×１００ｍｍ）上にスプレー法で塗装し、室温で１日間放置して硬化させた後、塗膜表面を洗浄しないで乾燥して試験用の塗板（塗膜の膜厚２０〜３０μｍ）を作製した。
【００８７】
この塗板をついて対水接触角及び滑落角（４μリットル）を前述の比較試験例１と同様の方法で測定したところ、対水接触角は１５２．１度であり、滑落角は４．６度であった。
【００８８】
次に、着霜（フロスト）−除霜（デフロスト）試験を次の要領で行った。
まず、風洞内に試料板を鉛直に固定し、試料板の表面温度を−７±２℃に維持する。この風洞内に相対湿度８７±３％の湿気を含んだ空気（温度７±０．２℃）を試料板の表面に平行に風速１ｍ／秒で流し、試料板表面に強制的に着霜させる。このフロスト運転は２０分間続ける。
フロスト運転後直ちに試料板表面温度を５℃に加熱しデフロスト運転を開始する。空気はフロスト運転時と同じものを同じ条件で流す。デフロスト運転は２分間続ける。
このようなフロスト運転−デフロスト運転を１サイクルとし、これを連続して２サイクル行う。
以上が着霜（フロスト）−除霜（デフロスト）試験の要領である。
【００８９】
上記着霜（フロスト）−除霜（デフロスト）試験により次の結果が得られた。
（１） 第１サイクルのフロスト運転開始１０分後に着霜が始まった。この着霜開始時の試料板表面の状態をＣＣＤカメラ（ＥＬＭＯ社製のＣＮ４０１。商品名）で撮影した写真を図１（全体）及び図２（拡大。倍率１．２倍。以下同様）に示す。
また、フロスト運転開始から２０分後の、フロスト運転終了時の試料板表面の着霜状態をＣＣＤカメラで撮影した写真を図３（全体）及び図４（拡大）に示す。この写真から分かるように、試料板表面に形成された霜又は氷は綿状（針状結晶の集合体）であった。
【００９０】
（２） 第１サイクルのデフロスト運転では、デフロスト運転開始後直後から着霜している霜又は氷が剥離し始めた。この霜又は氷の剥離開始時の試料板表面の状態をＣＣＤカメラで撮影した写真を図５（全体）及び図６（拡大）に示す。これら写真から分かるように、この試験例３では、氷は塊のままでずれ落ちている。なお、従来の熱交換器では、氷が略解けていた、また、氷が略解ける前に氷の塊がずれ落ちるようなことはなかった。
また、第１サイクルのデフロスト運転開始２分後のデフロスト運転終了時には完全に霜又は氷が試料板表面から剥がれ落ちてしまっていた。このデフロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した写真を図７（全体）及び図８（拡大）に示す。これら写真から分かるように、デフロスト運転終了時の試料板表面には肉眼で観察できる水滴は認められなかった。
【００９１】
（３） 引き続く第２サイクルでは、フロスト運転開始６分後に着霜が始まった。
そして、第２サイクルのフロスト運転開始２０分後の、フロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した写真を図９（全体）及び図１０（拡大）に示す。これら写真から分かるように、第１回目のフロスト運転の状態と比較し変化がない。
（４）次いで行った第２サイクルのデフロスト運転では、デフロスト運転開始直後から霜又は氷が剥離し始めた。この霜又は氷の剥離開始時の試料板表面の状態をＣＣＤカメラで撮影した写真を図１１（全体）に示す。
また、第２サイクルのデフロスト運転開始から３０秒後には、試料板表面に付着した霜又は氷が略完全に剥離した。この霜又は氷が略完全に剥離したときの試料板表面の状態をＣＣＤカメラで撮影した写真を図１２（全体）に示す。これら写真から分かるように、第２サイクルのデフロスト運転時においても、霜又は氷が塊のままでずれ落ちている。
また、第２サイクルのデフロスト運転開始から２分後の、デフロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した写真を図１３（全体）及び図１４（拡大）に示す。これら写真から分かるように、第２サイクルのデフロスト運転終了後にも試料板表面には肉眼で観察できる水滴は認められなかった。
【００９２】
比較試験例２
試験例３において、低熱容量の無機粒子（ｄ）を配合しなかったほかは同様にして調製した表面処理用組成物を用いて試料板を作製し、同様にして着霜（フロスト）−除霜（デフロスト）試験を行った。その結果は次のようであった。
【００９３】
（１） 第１サイクルのフロスト運転開始約５分後に着霜が始まり、第１サイクルのフロスト運転開始から約１０分後にはほぼ全面が氷結した。このフロスト運転開始約１０分後の、全面フロスト状態の試料板表面の状態をＣＣＤカメラで撮影した写真を図１５（全体）及び図１６（拡大）に示す。
また、第１サイクルのフロスト運転開始２０分後の、フロスト運転終了時の試料板表面における着霜状態をＣＣＤカメラで撮影した写真を図１７（全体）及び図１８（拡大）に示す。
前述の試験例３と比較すると、フロスト運転終了時において着霜量の多いことが分かる。これは試験例３のものでは、試料板表面で結露した水滴が風圧で川下に流されたり、容易に下方に落下したりするため、フロスト運転により氷結する水滴が試料板表面に少ないことを示しているものと解釈できる。
【００９４】
（２） 第１サイクルのデフロスト運転では、デフロスト運転開始直後から着霜している霜又は氷が融解し始めた。この霜又は氷の融解開始時の試料板表面の状態をＣＣＤカメラで撮影した写真を図１９（全体）及び図２０（拡大）に示す。これら写真から分かるように、氷が剥離しているところでは水玉模様の水滴が付着して霜又は氷が完全に融解した状態となっており、前述の試験例３のように氷の塊がずれ落ちる状況とは異なっている。
また、第１サイクルのデフロスト運転開始２分後のデフロスト運転終了時には完全に霜又は氷が融解した。このデフロスト運転終了時の試料板表面の状態を撮影した写真を図２１（全体）及び図２２（拡大）に示す。これら写真から分かるように、前述の試験例３とは異なり、デフロスト運転終了後の試料板表面には肉眼で観察できる大小の水滴が多数認められた。
【００９５】
（３） 引き続く第２サイクルでは、運転開始６分後に着霜が始まった。
第２サイクルのフロスト運転開始２０分後の、フロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した写真を図２３（全体）及び図２４（拡大）に示す。これら写真から大きな水滴が氷結した状態であることが分かる。この点で第１回目のフロスト運転時の状態と比較し大きな変化のあることが分かる。これは、第１回目のデフロスト運転終了後の試料板表面に付着していた大きな水滴が氷結したものと思われる。
（４）次いで行った第２サイクルのデフロスト運転では、デフロスト運転開始直後から霜又は氷が融解し始めた。デフロスト運転開始直後の霜又は氷が融解開始時の試料板表面の状態をＣＣＤカメラで撮影した写真を図２５（全体）に示す。また、デフロスト運転開始１分後には霜又は氷が略完全に融解した。このときの試料板表面の状態を撮影した写真を図２６（全体）に示す。これら写真から分かるように、付着した霜又は氷は塊のままでずれ落ちることなく融解している。
また、第２サイクルにおけるデフロスト運転開始２分後の、デフロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した写真を図２７（全体）及び図２８（拡大）に示す。これら写真から分かるように、前述の第１回目のデフロスト運転終了時より更に多くの大小の水滴が表面に残存していた。
【００９６】
上記のように、本発明に係る表面構造を熱交換面に施すと、熱交換面が撥水性、滑水性及び易霜氷剥離性に優れたものとなる。
【００９７】
（実施の形態１）
実施の形態１を図２９〜図３２に基づき説明する。図２９は実施の形態１に係る熱交換装置の構成図である。図３０は同熱交換装置の上部冷媒通路用の冷媒遮断機構が閉鎖された状態図である。図３１は同熱交換装置の中間部冷媒通路用の冷媒遮断機構が閉鎖された状態図である。図３２は同熱交換装置の下部冷媒通路用の冷媒遮断機構が閉鎖された状態図である。
【００９８】
実施の形態１に係る熱交換装置は、セパレート型ヒートポンプ式空気調和機の室外側熱交換器などに用いられるものである。また、同熱交換装置は、対空気用熱交換器１が使用され、平板型プレートフィン２に熱交換パイプ２ａが嵌挿されたものである。また、この平板型プレートフィン２の熱交換面には、前述の表面処理物を塗装して前述の表面構造が形成されている。さらに、この対空気用熱交換器１の入口側配管３には分流器４が配置され、この分流器４により三つの分流管５ａ、５ｂ、５ｃに分岐されている。また、分流器４に接続された分流管５ａ、５ｂ、５ｃにはそれぞれ冷媒遮断機構６ａ、６ｂ、６ｃが設けられている。対空気用熱交換器１は、各分流管５ａ、５ｂ、５ｃに接続された上部冷媒通路１１、中間部冷媒通路１２及び下部冷媒通路１３を備えている。また、上部冷媒通路１１、中間部冷媒通路１２及び下部冷媒通路１３は、出口側ヘッダー７により集合され、この出口側ヘッダー７を介して次の機器へ冷媒を移送するように構成されている。
【００９９】
なお、平板型プレートフィン２は三つの冷媒通路１１、1２、１３間で熱が移動しないように上中下に３分割されている。また、上部冷媒通路用の冷媒遮断機構６ａ、中間部冷媒通路用の冷媒遮断機構６ｂ、下部冷媒通路用の冷媒遮断機構６ｃとしては具体的には電磁開閉弁又は電動弁が用いられる。
【０１００】
この熱交換装置は、例えば、ヒートポンプ式空気調和機の室外側熱交換器として使用されている場合のように、暖房運転時に蒸発器として作用する場合には、熱を汲み上げる空気温度（通常、外気温度）が低下すると熱交換面に着霜が発生する。しかしながら、この熱交換装置の場合には、低熱容量の表面部分Ａと霜又は氷との結合性又は付着性が低い表面部分Ｂの２種類の表面部分が分散配置されていることにより、熱交換面が撥水性及び滑落性に優れたものとなる。このため、熱交換装置の熱交換面で凝縮した凝縮水は、球形状となってこの対空気用熱交換器１を通過する風圧で飛散されやすくなり、過冷却状態となり凍りにくくなる。したがって、熱交換面に付着した霜の成長速度が低下し除霜が必要となる着霜量までの冷凍運転（ヒートポンプ式空気調和機の場合は暖房運転）時間が延長される。
【０１０１】
また、対空気用熱交換器１が着霜した場合この熱交換装置では、まず上部冷媒通路１１用の冷媒遮断機構６ａを遮断して、上部冷媒通路１１への冷媒の流通を停止させる。これにより、上部冷媒通路１１は対空気用熱交換器１の周囲空気が流通することにより加熱され、上部冷媒通路１１部分の熱交換面では次のようにして除霜が行われる。
【０１０２】
すなわち、上部冷媒通路１１部分の熱交換面は、表面部分Ａと表面部分Ｂとが分散配置されているので、上記除霜運転時（上部冷媒通路１１用の冷媒遮断機構６ａを閉鎖する運転）においては、まず周囲空気空の熱を吸収して表面部分Ａと接触する界面部分の霜又は氷が融解し、表面部分Ａ上の霜又は氷が剥離する。そして、この剥離した霜又は氷と表面部分Ｂ上の霜又は氷とが少なくとも部分的に結合し、自重により表面部分Ｂ上の霜又は氷が剥離される。
したがって、この上部冷媒通路１１部分の除湿運転では、従来のように熱交換面に付着した霜又は氷を全面的に融解する必要がなくなり除霜運転時間が短縮される。また、周囲空気が保有する熱エネルギを利用して除霜されるので、エネルギー効率が良い。
【０１０３】
また、対空気用熱交換器１の熱交換面は易霜氷剥離性を有するので、除霜運転時、熱交換面の霜又は氷が自重により表面から塊のまま剥離（離脱）し、霜又は氷が融解又は剥離された後の熱交換面に水滴が残存しなくなる。このため、冷凍運転再開後の着霜量又は氷結量が減少し、冷凍運転時間の延長と除霜運転時間の短縮を継続して発揮させることができる。したがって、除霜に要する熱エネルギーが少なくて済むとともに、除霜運転時間が短縮される。
【０１０４】
上記した上部冷媒通路１１部分の除霜運転（冷媒遮断機構６ａを閉鎖する運転）は、所定時間継続することにより除霜が終了するようにタイマーにより時間設定されている。また、この所定時間が経過すると、冷媒遮断機構６ａを開放して上部冷媒通路１１部分を蒸発器として作用させ、次の中間部冷媒通路１２部分の除霜運転（冷媒遮断機構６ｂを閉鎖する運転）を所定時間継続する。そして、中間部冷媒通路１２部分の除霜運転が終了すると、冷媒遮断機構６ｂを開放して上部冷媒通路１１部分を蒸発器として作用させ、さらに下部冷媒通路１３部分の除霜運転（冷媒遮断機構６ｃを閉鎖する運転）を所定時間継続させる。対空気用熱交換器１の除霜運転は以上のようにして行われる。なお、上部冷媒通路１１部分の除霜運転、中間部冷媒通路１２部分の除霜運転及び下部冷媒通路１３部分の除霜運転間での順番は特に限定されるものではない。例えば、上部冷媒通路１１部分の除霜運転の次に下部冷媒通路１３部分の除霜運転を行ってもよい。
【０１０５】
このように、実施の形態１によれば、暖房運転時間が延長され、除霜運転時間が短くなるので、暖房快感度が向上し、エネルギー効率が向上する。
【０１０６】
（実施の形態２）
実施の形態２は、対空気用熱交換器１を多数の冷媒通路２１〜２９に形成する。そして、多数の冷媒通路２１〜２９を複数の冷媒通路群、この場合上部冷媒通路群３１、中間部冷媒通路群３２及び下部冷媒通路群３３に纏めたものである。なお、図３２に実施の形態２に係る熱交換装置の構成図を示す。
なお、これら冷媒通路群３１、３２、３３毎に１本の分流管５ａ、５ｂ、５ｃを接続するように構成している。また、分流器４に接続されている分流管５ａ、５ｂ、５ｃには実施の形態１の場合と同様に冷媒遮断機構６ａ、６ｂ、６ｃを設けている。
【０１０７】
上記実施の形態２における除霜運転は、上部冷媒通路群３１、中間部冷媒通路群３２、及び下部冷媒通路群３３を実施の形態１における上部冷媒通路１１、中間部冷媒通路１２、及び下部冷媒通路１３と同様に扱うことにより行われる。
【０１０８】
実施の形態２は、以上のように構成されているので、大型の対空気用熱交換器１の場合には分流管５ａ、５ｂ、５ｃの数が減少し、冷媒遮断機構６ａ、６ｂ、６ｃの数が減少するので、設備が簡略化されコストの上昇を抑制することができる。
【０１０９】
【発明の効果】
本発明の熱交換装置によれば、熱交換面に撥水性及び滑落性に優れた表面構造が形成されているので、着霜を遅延させ、除霜運転時間を短縮し、除霜に必要な熱エネルギーを低減することができる。また、熱交換装置の一部分毎に冷媒の流通を停止させて除霜運転を行うので、冷凍運転を連続運転させながら、しかも熱交換装置の周囲空気の熱エネルギーを利用しながら除霜運転するので、冷凍運転効果の低下（例えば、ヒートポンプ式空気調和機に応用した場合における暖房快感度の低下）を回避することができ、かつ、エネルギー効率の向上を図ることができる。
【図面の簡単な説明】
【図１】試験例３における第１サイクルのフロスト運転開始１０分後の、着霜開始時の試料板表面の状態をＣＣＤカメラで撮影した写真である。
【図２】図１の部分拡大写真である。
【図３】試験例３における第１サイクルのフロスト運転開始２０分後の、フロスト運転終了時の試料板表面の着霜状態をＣＣＤカメラで撮影した全体写真である。
【図４】図３の部分拡大写真である。
【図５】試験例３における第１サイクルのデフロスト運転開始直後の、霜又は氷の剥離開始時の試料板表面の剥離状態をＣＣＤカメラで撮影した全体写真である。
【図６】図５の部分拡大写真である。
【図７】試験例３における第１サイクルのデフロスト運転開始２分後の、デフロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図８】図７の部分拡大写真である。
【図９】試験例３における第２サイクルのフロスト運転開始２０分後の、フロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図１０】図９の部分拡大写真である。
【図１１】試験例３における第２サイクルのデフロスト運転開始直後の、霜又は氷の剥離開始時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図１２】試験例３における第２サイクルのデフロスト運転開始３０秒後の、剥離略完了時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図１３】試験例３における第２サイクルのデフロスト運転開始２分後の、デフロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図１４】図１３の部分拡大写真である。
【図１５】比較試験例２における第１サイクルのフロスト運転開始約１０分後の、全面フロスト状態の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図１６】図１５の部分拡大写真である。
【図１７】比較試験例２における第１サイクルのフロスト運転開始２０分後の、フロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図１８】図１７の部分拡大写真である。
【図１９】比較試験例２におけるで第１サイクルのデフロスト運転開始直後の、霜又は氷の融解開始時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図２０】図１９の部分拡大写真である。
【図２１】比較試験例２の第１サイクルにおけるデフロスト運転開始２分後の、デフロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図２２】図２１の部分拡大写真である。
【図２３】比較試験例２の第２サイクルにおけるフロスト運転開始２０分後の、フロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図２４】図２３の部分拡大写真である。
【図２５】比較試験例２の第２サイクルにおけるデフロスト運転開始直後の、霜又は氷の融解開始時の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図２６】比較試験例２の第２サイクルにおけるデフロスト運転開始１分後の試料板表面の状態をＣＣＤカメラで撮影した全体写真である。
【図２７】比較試験例２の第２サイクルにおけるデフロスト運転開始２分後の、デフロスト運転終了時の試料板表面の状態をＣＣＤカメラで撮影した全体写真
【図２８】図２７の部分拡大写真である。
【図２９】実施の形態１に係る熱交換装置の構成図である。
【図３０】同熱交換装置の上部冷媒通路用の冷媒遮断機構が閉鎖された状態図である。
【図３１】同熱交換装置の中間部冷媒通路用の冷媒遮断機構が閉鎖された状態図である。
【図３２】同熱交換装置の下部冷媒通路用の冷媒遮断機構が閉鎖された状態図である。
【図３３】実施の形態２に係る熱交換装置の構成図である。
【符号の説明】
１ 対空気用熱交換器
２ 平板型プレートフィン
４ 分流器
５ａ 分流管
５ｂ 分流管
５ｃ 分流管
６ａ 冷媒遮断機構
６ｂ 冷媒遮断機構
６ｃ 冷媒遮断機構
１１ 上部冷媒通路
１２ 中間部冷媒通路
１３ 下部冷媒通路
２１〜２９ 冷媒通路
３１ 上部冷媒通路群
３２ 中間部冷媒通路群
３３ 下部冷媒通路群[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a heat exchange device and a refrigeration device, and more particularly to an improvement in the surface structure of a heat exchanger.
[0002]
[Prior art]
Generally, in a refrigeration system using an air-to-air heat exchanger as an evaporator, this heat exchange surface is used when the air temperature for heat exchange with the air-to-air heat exchanger is low or when the evaporation temperature of the evaporator is low. Frost is generated. And when frost generate | occur | produces, the heat exchanger capacity | capacitance of this evaporator will fall and a refrigerating capacity will fall.
For example, in a heat pump type air conditioner that is a kind of refrigeration apparatus, when the outside air temperature is lowered during heating operation, the evaporation temperature is lowered, and frost is formed on the outdoor heat exchanger in which the air heat exchanger is used. In addition, when frosting occurs, the evaporation capacity of the outdoor heat exchanger decreases and the heating capacity decreases. For this reason, the defrosting operation for removing the adhering frost or ice frozen by frost (hereinafter simply referred to as frost or ice) is appropriately performed. However, when the defrosting operation is performed, it may differ depending on the defrosting operation method. However, since the heating operation is stopped or the heating capacity is reduced, there is a problem that the heating comfort sensitivity is lowered.
Further, the defrosting operation requires heat energy to remove frost or ice adhering to the evaporator, which causes a problem that the energy efficiency of the heating operation decreases.
Therefore, conventionally, the frost formation in the evaporator of the refrigeration apparatus is delayed to extend the refrigeration operation (particularly in the case of the heat pump type air conditioner that is a typical example of the refrigeration apparatus, the heating operation is targeted), the defrost operation. Shortening the time and reducing the heat energy required for the defrosting operation have been problems.
[0003]
As a solution to such a problem, a method of reducing the amount of frost formation on the evaporator by providing a frost prevention layer on a heat exchange surface with air can be considered. That is, the method of providing this frost prevention layer is a method of preventing frost formation mainly by increasing the water repellency of the heat exchange surface of the evaporator.
In addition, as a method for providing such a frost prevention layer, for example, a coating described in Patent Document 1, that is, a terminal fluorinated polytetrafluoroethylene (PTFE) powder having a molecular weight of 500 to 20000 is made of a non-fluorine type. A method of applying a water-repellent paint mixed in the resin to the heat exchange surface is conceivable. Similarly, the paint described in Patent Document 2, that is, a frost-preventing paint obtained by blending a terminal fluorinated PTFE powder having a molecular weight of 500 to 20000 in a liquid resin (for example, a fluororesin, a silicone resin, or a polyester resin). The method of apply | coating to the heat exchanger surface of an evaporator etc. can be considered.
[0004]
[Patent Document 1]
JP-A-8-3477
[Patent Document 2]
JP-A-8-3479
[Patent Document 3]
JP-A-57-34107
[Patent Document 4]
Japanese Patent Laid-Open No. 62-7767
[Patent Document 5]
Japanese Patent Laid-Open No. 62-174213
[Patent Document 6]
Japanese Patent Laid-Open No. 2-26579
[Patent Document 7]
JP-A-2-298645
[Patent Document 8]
JP-A-4-279612
[0005]
[Problems to be solved by the invention]
However, it has been found that it is difficult to uniformly disperse the PTFE powder in the resin with the above-mentioned conventional paint, and a portion having a small water repellency remains on the surface, which impairs the effect of preventing frost formation. Moreover, even if the anti-frost layer is formed on the heat exchange surface, it is difficult to completely avoid frost formation, so defrosting is required in the heat exchanger. However, the conventional paints described above do not take into consideration shortening the defrosting operation time or reducing the thermal energy required for defrosting.
As described above, the conventional method for providing the anti-frost layer on the surface has not been sufficient.
[0006]
In addition to applying the frost prevention method in which the frost prevention layer is provided on the surface, it is conceivable to use a defrost method in which heat energy is applied from the outside of the evaporator. However, in the method of applying this heat energy from the outside of the evaporator, frost and ice are rarely left on the heat exchange surface, but it is necessary to melt all the frost and ice on the interface portion in contact with the heat exchange surface. In addition to requiring energy, the temperature also rises, and there is a problem that it cannot be applied to devices sensitive to heat.
In addition, a method of spraying the anti-frosting agent on the surface is also conceivable, but there is a problem that frost formation may occur even with the anti-frosting agent.
In addition, it is conceivable to use a defrosting method that applies mechanical energy such as vibration or impact to the heat exchange device, but even if this method is used, the heat exchange surface of the conventional heat exchanger has water repellency and sliding properties (heat Since the property indicating the degree of drop of water droplets adhering to the replacement surface is small, frost or ice remains, and the problem of facilitating subsequent frost formation remains.
Thus, the defrost methods other than the anti-frost method that provides the anti-frost layer on the surface also reduce the defrost operation time of the defrosted heat exchanger and reduce the thermal energy necessary for defrost. It does not lead to anything.
[0007]
The present invention has been made paying attention to the problems existing in the above-described conventional technology, and delays frost formation, shortens the defrosting operation time, and reduces the heat energy required for defrosting. And it aims at providing a freezing apparatus.
[0008]
[Means for Solving the Problems]
Solve the above issuesThe present inventionThe heat exchange device according toMolar heat capacity is 6JK ^-1 mol ^-1 ~ 7JK ^-1 mol ^-1 A fin having a heat exchange surface with air having a surface portion A mainly composed of a substance having conductivity and a surface portion B mainly composed of a water repellent binder resin and polytetrafluoroethylene particles.And an evaporator comprising an air-to-air heat exchanger having a plurality of refrigerant passages, a flow divider for diverting refrigerant into the plurality of refrigerant passages, and a plurality of refrigerant flow passages and flow dividers formed in the evaporator And a refrigerant shut-off mechanism provided in each of the shunt pipes. When the evaporator is frosted, some refrigerant shut-off mechanisms are closed, and after a predetermined time, the shut-off mechanism is opened and another Switching the refrigerant shut-off mechanism to closeIt is characterized by performing defrosting.
[0009]
According to the heat exchange device configured as described above, the two types of surface portions, that is, the surface portion A having a low heat capacity surface portion A and the surface portion B having low binding or adhesion to frost or ice, are dispersedly arranged. The heat exchange surface has excellent water repellency and sliding properties. For this reason, the condensed water condensed on the heat exchange surface of the heat exchange device becomes sphere-shaped and easily scattered by the wind pressure passing through the evaporator, and becomes supercooled and hardly freezes. Therefore, the growth time of frost adhering to the heat exchange surface is reduced, and the refrigeration operation (heating operation in the case of a heat pump air conditioner) up to the amount of frost that requires defrosting is extended.
On the other hand, at the time of defrosting operation, defrosting is performed with the heat of the surrounding air by closing a part of the refrigerant shut-off mechanisms to prevent the refrigerant from flowing to a part of the heat exchange device. In this case, the frost or ice at the interface portion that contacts the surface portion A on the heat exchange surface of the heat exchange device is first melted, and the frost or ice on the surface portion A is peeled off. Then, the peeled frost or ice and the frost or ice attached to the surface portion B are at least partially combined, and the frost or ice attached to the surface portion B is peeled off by its own weight. Therefore, in this heat exchange device, it is not necessary to completely melt the frost or ice at the interface portion that contacts the heat exchange surface of the evaporator as in the conventional case, and only the frost or ice that contacts the surface portion A is melted. Therefore, the defrosting operation time is shortened.
In addition, the heat exchange surface in which the surface portion A and the surface portion B as described above are arranged in a distributed manner is provided with easy frost ice peelability. In addition, in this specification, when it says easy frost ice peelability, when defrosting a heat exchange device, the frost or ice adhering to the heat exchange surface of this heat exchange device peels (detaches) from the heat exchange surface by its own weight. And the property that the amount of water droplets or frost remaining on the heat exchange surface after frost or ice is melted or peeled is reduced. In addition, when the defrosting operation is repeated after the refrigerating operation is resumed, if water drops, frost or ice remains on the heat exchange surface of the heat exchange device after the defrosting, frost or icing is formed during the next freezing operation. The refrigeration operation time is shortened. However, in the heat exchange device according to the present invention, since the amount of water droplets or frost remaining on the heat exchange surface of the evaporator after defrosting is reduced, frost and freezing nuclei are reduced during the freezing operation, and the freezing operation time is reduced. Can be repeatedly demonstrated and the defrosting operation time can be shortened. Therefore, less heat energy is required for defrosting and the defrosting operation time is shortened.
Further, in the present invention, each part of the heat exchange device is defrosted sequentially using the thermal energy held by the air surrounding the heat exchange device, so that the energy efficiency is also improved from this point.
Further, since the defrosting operation is performed while continuing the refrigeration operation, it is possible to prevent a decrease in the refrigeration operation effect (for example, a decrease in heating comfort sensitivity when applied to a heat pump air conditioner).
in this way,The present inventionAccording to the heat exchange device according to the above, it is possible to prevent a decrease in the refrigeration operation effect and to suppress a decrease in energy efficiency.
[0010]
Also solve the above problemsThe present inventionThe heat exchange device according toMolar heat capacity is 6JK ^-1 mol ^-1 ~ 7JK ^-1 mol ^-1 It is preferable that the conductive material is carbon black..
[0012]
  Also solve the above problemsThe present inventionIn the heat exchange device according toThe water-repellent binder resin is a fluororesin, and the polytetrafluoroethylene particles preferably have a weight average molecular weight of 500 to 200,000 and an average particle diameter of 0.1 μm or more.
[0014]
Further, in the above heat exchange device, the number of the diversion pipes may be set to a number corresponding to the number of refrigerant passages so as to be connected to each refrigerant passage formed in the evaporator. .
If comprised in this way, since the heat exchange surface which stops an evaporation effect | action at the time of a defrost operation becomes small, the influence which it has on the fall of a freezing effect becomes smaller.
[0015]
Further, in the heat exchange device, the flow dividing pipe is configured by collecting a plurality of refrigerant passages formed in the evaporator into a plurality of refrigerant passage groups, and one branch pipe is connected to each refrigerant passage group. It can also be.
With this configuration, in the case of a large air-to-air heat exchanger, the number of branch pipes is reduced and the number of refrigerant shut-off mechanisms is reduced, so that the equipment is simplified and the increase in cost can be suppressed. it can.
[0016]
The refrigerant shut-off mechanism may be configured as an electromagnetic on-off valve or an electric valve.
If comprised in this way, a versatile automatic control apparatus can be used as a refrigerant | coolant interruption | blocking mechanism, and it becomes cheap.
[0017]
Moreover, the refrigerating apparatus according to the means for solving the problems uses the heat exchange apparatus.
If comprised in this way, the frost formation of an evaporator can be delayed, defrost operation time can be shortened, and the refrigeration apparatus which improved the thermal energy efficiency can be supplied.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments according to the present invention will be described below. First, the surface structure of the heat exchange surface applied to the heat exchange apparatus according to the present invention will be described.
In the present invention, the heat exchange surface of the evaporator has a surface structure in which two kinds of surface portions A and B satisfying the following characteristics 1 and 2 are distributed and excellent in easy frost ice releasability. It is formed.
[0019]
Here, the characteristics 1 and 2 refer to the characteristics defined above. This will be further described in connection with this. Characteristic 1 is a characteristic for facilitating the detachment of frost or ice as a whole by first solving the close bonding relationship between the surface portion A and ice. Conventionally, the frost or ice that is in contact with the heat exchange surface is simply melted at the interface portion of the heat exchange surface, so that the frost or ice adhering to the heat exchange surface is removed, so that the heat exchange surface is large. If the melting does not occur in the portion, the frost or ice separation phenomenon does not occur. However, according to the surface structure of the evaporator according to the present invention, the frost or the entire ice is detached only by melting the interface portion contacting the surface portion A. It becomes a state that occurs.
[0020]
Further, in order to further facilitate the detachment of frost or ice, it is preferable that the surface portion B has a property of low binding or adhesion to frost or ice, such as water repellency or a rough surface. In this case, if frost or ice melts at the interface portion of the surface portion A, the characteristic 2 can occur regardless of the presence or absence of melting of the interface portion with the surface portion B.
[0021]
Characteristic 2 is a characteristic indicating that the frost or ice adhering to the surface portion B is peeled off from the surface portion B without necessarily melting. The feature in this case is that the frost or ice crystals on the surface portion B are peeled off integrally with the frost or ice crystals previously detached from the surface portion A. Conventionally, the frost or ice at the interface part in contact with the surface part B had to be melted before peeling.
[0022]
When the surface structure is applied to the heat exchange surface, the frost or ice can be easily removed by applying a small amount of heat energy to the heat exchange surface to which frost or ice is attached.
[0023]
The heat exchange surface may have a surface portion other than the surface portion A and the surface portion B, but should not impair the above-described characteristics 1 and 2 of the surface portion A and the surface portion B.
[0024]
The area ratio, the planar shape, the arrangement, the three-dimensional shape of the surface portion, and the like of the surface portion A and the surface portion B are not limited as long as the above characteristics 1 and 2 are satisfied, but the following are preferable.
[0025]
The area ratio between the surface portion A and the surface portion B can be selected within a wide range of 1/99 to 99/1. However, in terms of energy efficiency, the surface portion A is within the range where the effect of the characteristic 2 can be exhibited. It is desirable to reduce the ratio.
[0026]
The planar shape and arrangement of the surface portion may be any shape or arrangement. As specific examples, the surface portion A and the surface portion B are arranged in stripes, the surface portion A and the surface portion B are arranged in a sea-island shape, and the surface portion A is dotted in the surface portion B Or it is dispersed in a polka dot shape (or vice versa), the surface portion A is arranged in a lattice pattern on the surface portion B (or vice versa), the surface portion A is in a ring shape on the surface portion B What is arranged (or vice versa) can be listed.
[0027]
The three-dimensional shape of the surface portion is not particularly limited, and may be planar, protruding, or irregular. Alternatively, one surface may have a terrace shape (such as a truncated cone shape or a frustum shape) higher than the other surface.
[0028]
Next, a method for forming a surface structure according to the present invention will be described.
The formation method is not particularly limited, and a known method can be applied. For example, (1) painting method, (2) various molding methods, (3) various chemical surface processing methods, (4) various physical surface processing methods, and (5) composites such as laminates. The method of making the body is fried.
[0029]
The method by painting will be described in detail below.
The following surface treatment composition is applied to the heat exchange surface to form the surface structure according to the present invention.
As the composition for surface treatment to be used, for example,
(A) a water-repellent binder resin,
(B) polytetrafluoroethylene (PTFE) particles,
(C) a dispersant,
(D) Low heat capacity inorganic particles
as well as
(E) Solvent
A composition for surface treatment comprising:
[0030]
In the surface structure of the coating film formed with this surface treatment composition, the surface portion A is formed of inorganic particles (d) having a low heat capacity, and the surface portion B is formed of a water repellent binder resin (a) and PTFE particles (b). Is presumed to have formed.
[0031]
The water-repellent binder resin (a) is not particularly limited as long as it is water-repellent and can hold the PTFE particles (b) and the low heat capacity inorganic particles (d) in a uniformly dispersed state. Further, as the degree of water repellency, it is desirable that the water contact angle is large, and it is preferable that the water contact angle of the surface portion B is 140 degrees or more. However, the water contact angle of the surface of the single coating film of the water repellent binder resin (a) is not necessarily 140 degrees or more, but it is 100 degrees or more to impart the desired water repellency to the treated surface. It is preferable from the point of being easy to do.
[0032]
Examples of such a water-repellent binder resin (a) include a fluororesin, a silicone resin, and a urethane resin, and a fluororesin is preferable from the viewpoint of excellent dispersibility of PTFE particles.
[0033]
The fluororesin can be selected from conventionally known fluororesins, but is advantageous for weather resistance, coating, solvent solubility, etc., so tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), hexafluoro A copolymer mainly composed of propylene (HFP) is preferable.
[0034]
As these fluororesins, for example, fluorine-containing copolymers described in Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6, Patent Document 7, Patent Document 8, and the like are preferably fried, and particularly described in Patent Document 8. of
(1) Fluoroolefin structural unit represented by the following formula I
-CF₂-CFX- (Formula I)
(Wherein X is a fluorine atom, a chlorine atom, a hydrogen atom or a trifluoromethyl group)
(2) β-methyl-substituted α-olefin structural unit represented by the following formula II
-CH₂-CR (CH_Three-(Formula II)
(Wherein R is an alkyl group having 1 to 8 carbon atoms)
(3) Structural units based on monomers having chemically curable reactive groups
(4) Structural units based on monomers having an ester group in the side chain
as well as
(5) Structural units based on other copolymerizable monomers
The structural unit (1) is 20 to 60 mol%, the structural unit (2) is 5 to 25 mol%, the structural unit (3) is 1 to 45 mol%, and the structural unit (4) is 1 to 45 mol%. And a fluorine-containing copolymer having a number average molecular weight of 1,000 to 500,000, comprising 0 to 45 mol% of the structural unit (5) (however, the total of the structural units (1) + (2) is 40 to 90 mol%) Coalescence is useful.
[0035]
Specific examples include CTFE / isobutylene (IB) / HBVE / vinyl propionate (VPi) copolymer, CTFE / IB / hydroxyethyl allyl ether (HEAE) / VAc copolymer, and TFE / IB / HBVE / VPi copolymer. Copolymer, CTFE / IB / HBVE / Beova 9 (manufactured by Shell Chemical Co., Ltd., trade name) copolymer, TFE / IB / HBVE / VBz copolymer, CTFE / IB / HBVE / diethyl maleate (DEM) copolymer, TFE / IB / HBVE / veova 9 / dibutyl maleate (DBM) copolymer, CTFE / IB / HBVE / diethyl fumarate (DEF) copolymer, CTFE / IB / HEVE / dibutyl fumarate (DBF) copolymer , HFP / IB / HBVE / VBz copolymer, TFE / 2-methyl-1-pentene (MP) / H VE / VPi copolymer, TFE / IB / HBVE / VPi / CH₂= CH (CF₂)_pCF_Three(P = 1-5) copolymer, TFE / IB / HBVE / VPi / VBz copolymer, CTFE / IB / HBVE / VAc copolymer, TFE / IB / HBVE / vinyl t-butylbenzoate (VtBz) Copolymer, TFE / IB / HBVE / VPi / DEM copolymer, CTFE / IB / HBVE / VBz / DEF copolymer, CTFE / IB / HBVE / VPi / CH₂= CH (CF₂)_pCF_Three(P = 1-5) copolymer, CTFE / MP / HEVE / VPi copolymer, TFE / IB / HBVE / VPi / vinyl acetic acid (VAA) copolymer, TFE / IB / HEVE / VAc / VAA copolymer Coalescence, TFE / IB / HBVE / VPi / VBz / crotonic acid (CA) copolymer, TFE / IB / HBVE / veova 9 / CA copolymer, TFE / IB / HBVE / veova 9 / VBz / CA copolymer TFE / IB / HBVE / Veoba 10 / VtBz / CA copolymer, TFE / IB / HBVE / VtBz / CA copolymer, TFE / IB / HBVE / DEMTFE / IB / HBVE / DFM / CA copolymer, CA copolymer, TFE / MP / HBVE / VPi / VAA copolymer, etc. are fried.
[0036]
Commercially available products of the above fluororesins include, for example, Zeffle (manufactured by Daikin Industries, Ltd., Lumiflon (manufactured by Asahi Glass Co., Ltd.), Fluonate (manufactured by Dainippon Ink Co., Ltd.), Cefral Coat (manufactured by Central Glass Co., Ltd.) Etc. are fried.
[0037]
The PTFE particles (b) preferably have a weight average molecular weight of 500 or more and 500,000 or less. Normally, PTFE has a weight average molecular weight of 1,000,000 to 10,000,000, but PTFE in this range fibrillates when shearing force is applied, so the PTFE used in the present invention should use PTFE having a molecular weight in the above range. Is preferred. A preferred weight average molecular weight is 600 or more, particularly 5,000 or more, and 500,000 or less, preferably 200,000 or less, and more preferably 12,000 or less.
[0038]
The average particle diameter is preferably in the range of 0.05 μm to 10 μm. The average particle diameter is preferably 0.1 μm or more, more preferably 0.2 μm or more, and preferably 7 μm or less, further 5 μm or less.
[0039]
Further, PTFE may be a tetrafluoroethylene (TFE) homopolymer or a modified PTFE modified with a known modifying agent.
[0040]
In addition, PTFE particles have unstable groups at the molecular ends due to polymerization initiators and the like, but PTFE particles in which such terminal groups are completely fluorinated and stabilized are preferred. Particularly preferred PTFE particles are those having a weight average molecular weight of 500 to 20,000 having a terminal group completely fluorinated and an average particle diameter of 2 to 10 μm.
[0041]
As a commercial item of PTFE particles (b), for example, Lubron manufactured by Daikin Industries, Ltd., cefral lube manufactured by Central Glass Co., Ltd. and the like are fried.
[0042]
The dispersant (c) has an action of uniformly dispersing the PTFE particles (b) in the water repellent binder (a). The dispersing agent used here is not only the function of dispersing the PTFE particles (b) in the solvent, for example, when using a solvent, but also the function of uniformly dispersing the PTFE particles (b) in the water-repellent binder resin in the coating film. It is necessary to have Therefore, a suitable dispersant is selected in consideration of the types of PTFE particles (b) and the water-repellent binder resin (a), and further the type of the solvent (e).
[0043]
When a fluororesin is selected as the water repellent binder (a) and an organic solvent is selected as the solvent (e) described later, a polymer containing a repeating unit derived from a vinyl monomer having a fluoroalkyl group (as a dispersant) C1) is preferred.
More preferably, a copolymer of a vinyl monomer having a fluoroalkyl group and a non-fluorinated vinyl monomer is fried.
[0044]
The vinyl monomer having a fluoroalkyl group may be a fluoroalkyl group-containing (meth) acrylate, and the fluoroalkyl group-containing (meth) acrylate may be represented by the following general formula.
Rf-A¹-OC (= O) CB¹= CH₂
(In the formula, Rf is a C1-C21 fluoroalkyl group, B¹Is hydrogen or methyl group, A¹Is a divalent organic group. )
Examples of the fluoroalkyl group-containing (meth) acrylate include the following.
[0045]
[Chemical 1]

[0046]
(Wherein Rf is a fluoroalkyl group having 1 to 21 carbon atoms, R¹Is hydrogen or an alkyl group having 1 to 10 carbon atoms, R²Is an alkylene group having 1 to 10 carbon atoms, R^ThreeIs hydrogen or a methyl group, Ar is an arylene group which may have a substituent, and n is an integer of 1 to 10. )
Specific examples of the non-limiting fluoroalkyl group-containing (meth) acrylate are shown below.
CF_Three(CH₂) OCOCH = CH₂,
CF_ThreeCF₂(CH₂) OCOCH = CH₂,
CF_Three(CF₂)_Three(CH₂) OCOCH = CH₂,
CF_Three(CF₂)_Four(CH₂) OCOCH = CH₂,
CF_Three(CF₂)_Five(CH₂) OCOCH = CH₂,
CF_Three(CF₂)₆(CH₂) OCOCH = CH₂,
CF_Three(CF₂)₇(CH₂) OCOCH = CH₂,
CF_Three(CH₂)₂OCOCH = CH₂,
CF_ThreeCF₂(CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)_Three(CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)_Four(CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)_Five(CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)₆(CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)₇(CH₂)₂OCOCH = CH₂,
CF_Three(CH₂)_ThreeOCOCH = CH₂,
CF_ThreeCF₂(CH₂)_ThreeOCOCH = CH₂,
CF_Three(CF₂)_Three(CH₂)_ThreeOCOCH = CH₂,
CF_Three(CF₂)_Four(CH₂)_ThreeOCOCH = CH₂,
CF_Three(CF₂)_Five(CH₂)_ThreeOCOCH = CH₂,
CF_Three(CF₂)₆(CH₂)_ThreeOCOCH = CH₂,
CF_Three(CF₂)₇(CH₂)_ThreeOCOCH = CH₂,
CF_Three(CH₂)₆OCOCH = CH₂,
CF_ThreeCF₂(CH₂)₆OCOCH = CH₂,
CF_Three(CF₂)_Three(CH₂)₆OCOCH = CH₂,
CF_Three(CF₂)_Four(CH₂)₆OCOCH = CH₂,
CF_Three(CF₂)_Five(CH₂)₆OCOCH = CH₂,
CF_Three(CF₂)₆(CH₂)₆OCOCH = CH₂,
CF_Three(CF₂)₇(CH₂)₆OCOCH = CH₂,
CF_ThreeCH = CHCH₂OCOCH = CH₂,
CF_ThreeCF₂CH = CHCH₂OCOCH = CH₂,
CF_Three(CF₂)_ThreeCH = CHCH₂OCOCH = CH₂,
CF_Three(CF₂)_FourCH = CHCH₂OCOCH = CH₂,
CF_Three(CF₂)_FiveCH = CHCH₂OCOCH = CH₂,
CF_Three(CF₂)₆CH = CHCH₂OCOCH = CH₂,
CF_Three(CF₂)₇CH = CHCH₂OCOCH = CH₂,
(CF_Three)₂CF (CH₂)₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂) (CH₂)₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)₂(CH₂)₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)_Three(CH₂)₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)_Four(CH₂)₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)_Five(CH₂)₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)₆(CH₂)₂OCOCH = CH₂,
H (CF₂) (CH₂) OCOCH = CH₂,
H (CF₂)₂(CH₂) OCOCH = CH₂,
H (CF₂)_Four(CH₂) OCOCH = CH₂,
H (CF₂)₆(CH₂) OCOCH = CH₂,
H (CF₂)₈(CH₂) OCOCH = CH₂,
CF_ThreeCHFCF₂(CH₂) OCOCH = CH₂,
CF_Three(CH₂) OCOC (CH_Three) = CH₂,
CF_ThreeCF₂(CH₂) OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Three(CH₂) OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Four(CH₂) OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Five(CH₂) OCOC (CH_Three) = CH₂,
CF_Three(CF₂)₆(CH₂) OCOC (CH_Three) = CH₂,
CF_Three(CF₂)₇(CH₂) OCOC (CH_Three) = CH₂,
CF_Three(CH₂) OCOCH = CH₂,
CF_Three(CH₂)₂OCOC (CH_Three) = CH₂,
CF_ThreeCF₂(CH₂)₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Three(CH₂)₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Four(CH₂)₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Five(CH₂)₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)₆(CH₂)₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)₇(CH₂)₂OCOC (CH_Three) = CH₂,
CF_Three(CH₂)_ThreeOCOC (CH_Three) = CH₂,
CF_ThreeCF₂(CH₂)_ThreeOCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Three(CH₂)_ThreeOCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Four(CH₂)_ThreeOCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Five(CH₂)_ThreeOCOC (CH_Three) = CH₂,
CF_Three(CF₂)₆(CH₂)_ThreeOCOC (CH_Three) = CH₂,
CF_Three(CF₂)₇(CH₂)_ThreeOCOC (CH_Three) = CH₂,
CF_Three(CH₂)₆OCOC (CH_Three) = CH₂,
CF_ThreeCF₂(CH₂)₆OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Three(CH₂)₆OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Four(CH₂)₆OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_Five(CH₂)₆OCOC (CH_Three) = CH₂,
CF_Three(CF₂)₆(CH₂)₆OCOC (CH_Three) = CH₂,
CF_Three(CF₂)₇(CH₂)₆OCOC (CH_Three) = CH₂,
CF_ThreeCH = CHCH₂OCOC (CH_Three) = CH₂,
CF_ThreeCF₂CH = CHCH₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_ThreeCH = CHCH₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_FourCH = CHCH₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)_FiveCH = CHCH₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)₆CH = CHCH₂OCOC (CH_Three) = CH₂,
CF_Three(CF₂)₇CH = CHCH₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CH₂)₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂) (CH₂)₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)₂(CH₂)₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)_Three(CH₂)₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)_Four(CH₂)₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)_Five(CH₂)₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)₆(CH₂)₂OCOC (CH_Three) = CH₂,
H (CF₂) (CH₂) OCOC (CH_Three) = CH₂,
H (CF₂)₂(CH₂) OCOC (CH_Three) = CH₂,
H (CF₂)_Four(CH₂) OCOC (CH_Three) = CH₂,
H (CF₂)₆(CH₂) OCOC (CH_Three) = CH₂,
H (CF₂)₈(CH₂) OCOC (CH_Three) = CH₂,
CF_ThreeCHFCF₂(CH₂) OCOC (CH_Three) = CH₂,
CF_ThreeSO₂N (CH_Three) (CH₂)₂OCOCH = CH₂,
CF_Three(CF₂) SO₂N (CH_Three) (CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)₂SO₂N (CH_Three) (CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)_ThreeSO₂N (CH_Three) (CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)_FourSO₂N (CH_Three) (CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)_FiveSO₂N (CH_Three) (CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)₆SO₂N (CH_Three) (CH₂)₂OCOCH = CH₂,
CF_Three(CF₂)₇SO₂N (C₂H_Five) (CH₂)₂OCOC (CH_Three) = CH₂,
CF_ThreeC₆F_Ten(CF₂)₂SO₂N (CH_Three) (CH₂)₂OCOCH = CH₂,
(CF_Three)₂CFCH₂CH (OCOCH_Three) CH₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂) CH₂CH (OCOCH_Three) CH₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)₂CH₂CH (OCOCH_Three) CH₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)_ThreeCH₂CH (OCOCH_Three) CH₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)_FourCH₂CH (OCOCH_Three) CH₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)_FiveCH₂CH (OCOCH_Three) CH₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CF (CF₂)₆CH₂CH (OCOCH_Three) CH₂OCOC (CH_Three) = CH₂,
(CF_Three)₂CFCH₂CH (OH) CH₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂) CH₂CH (OH) CH₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)₂CH₂CH (OH) CH₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)_ThreeCH₂CH (OH) CH₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)_FourCH₂CH (OH) CH₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)_FiveCH₂CH (OH) CH₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)₆CH₂CH (OH) CH₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)₇CH₂CH (OH) CH₂OCOCH = CH₂,
(CF_Three)₂CF (CF₂)₈CH₂CH (OH) CH₂OCOCH = CH₂,
[0047]
[Chemical formula 2]

[0048]
Of course, a mixture of two or more of the above-mentioned fluoroalkyl group-containing (meth) acrylates can be used.
[0049]
As a non-fluorine-type monomer, (meth) acrylate ester is mentioned, for example. The (meth) acrylate ester may be an ester of (meth) acrylic acid and an aliphatic alcohol, for example, a monohydric alcohol or a polyhydric alcohol (for example, a dihydric alcohol).
[0050]
Examples of non-fluorinated monomers include the following.
[0051]
2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxyalkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyoxyalkylene (meth) acrylate, alkoxy Polyoxyalkylene (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Benzyl (meth) acrylate glycidyl methacrylate, hydroxypropyl monomethacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxyethyl acrylate, glycerol Methacrylate, β-acryloyloxyethyl hydrogen succinate, β-methacryloyloxyethyl hydrogen phthalate, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2 -Hydroxyethylphthalic acid, hydroxypropyltrimethylammonium chloride methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-acryloyloxyethyl acid phosphate, glucosylethyl methacrylate, methacrylamide, 2-hydroxy-3-acryloyloxypropyl methacrylate 2-methacryloyloxyethyl acid phosphate, neopentyl glycol diacrylate of hydroxypivalate (Meth) acrylates such as styrene; styrenes such as styrene and p-isopropylstyrene; (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethylacrylamide, 2-acrylamide- (Meth) acrylamides such as 2-methylpropanesulfonic acid; vinyl ethers such as vinyl alkyl ether.
[0052]
Furthermore, vinyl halides such as ethylene, butadiene, vinyl acetate, chloroprene, vinyl chloride, vinylidene halides, acrylonitrile, vinyl alkyl ketone, maleic anhydride, N-vinyl carbazole, vinyl pyrrolidone, (meth) acrylic acid and the like can be mentioned. .
[0053]
Further, the non-fluorine-based monomer may be a silicon-based monomer (for example, (meth) acryloyl group-containing alkylsilane, (meth) acryloyl group-containing alkoxysilane, (meth) acryloyl group-containing polysiloxane).
[0054]
The fluorine-containing polymer (c (1)) can be produced by a radical polymerization method.
[0055]
The weight average molecular weight of the polymer (c (1)) is relatively small and is not less than 3,000, more preferably not less than 5,000, particularly not less than 7,000, and not more than 30,000, more preferably 20,000. 000 or less, and particularly preferably 15,000 or less.
[0056]
  As the inorganic particles (d) having a low heat capacity, many metal simple particles or non-metal simple particles, and particles of some metal compounds are applicable. Specific examples include metals such as gold, silver, aluminum, iron and copper; nonmetals such as carbon and boron; and other metal compounds.
Moreover, it is desirable that the low heat capacity inorganic particles (d) are conductive from another viewpoint. Many of the water-repellent binders are electrified, and dust that becomes the core of freezing tends to adhere to the surface of the coating film, so that it is possible to further prevent icing (snow) by preventing the coating surface from being charged.
  In order not to impair the weather resistance, it is desirable that the inorganic particles having a low heat capacity are rich in weather resistance, corrosion resistance and solvent resistance.
The heat capacity of the low heat capacity inorganic particles (d) is the molar heat capacity.7JK^-1mol^-1The following is preferred. The lower limit is usually6JK^-1mol^-1It is.
The primary average particle diameter of the low heat capacity inorganic particles (d) is preferably 2 μm or more and 12 μm or less from the viewpoint of dispersibility.
[0057]
As such low heat capacity inorganic particles (d), carbon black, which is a simple substance of carbon, particularly crystalline carbon black is particularly preferable.
[0058]
In addition, when mix | blending a low heat capacity inorganic particle (d), the reason is unknown, However, Sliding property improves further irrespective of the presence or absence of water repellency. Moreover, the effect | action which makes easy defrosting at the time of having formed frost can also be anticipated.
[0059]
The solvent (e) is useful from the viewpoint of facilitating uniform mixing of each component of the surface treatment composition, facilitating the formation of a coating film, and further uniformly dispersing various components in the water-repellent binder resin (a). . Accordingly, the solvent (e) is selected in consideration of the other components (a), (b), (c) and (d).
[0060]
The solvent (e) may be an inorganic solvent system such as water, but an organic solvent system is preferable from the above viewpoint. The organic solvent system may be a single solvent or a mixed solvent system of two or more. When using 2 or more types, it is desirable from the point which can disperse | distribute other each component further uniformly that a polar organic solvent and a nonpolar organic solvent are included.
[0061]
Examples of the polar organic solvent include butyl acetate, ethyl acetate, acetone, methyl isobutyl ketone, ethanol, isopropanol, butanol, and ethylene glycol monoalkyl ether.
[0062]
Examples of the nonpolar organic solvent include toluene, xylene, n-hexane, cyclohexane, heptane, and terpenes that are petroleum spirits.
[0063]
In particular, by using a mixture of butyl acetate and a petroleum solvent (toluene, xylene, n-hexane, cyclohexane, heptane, terpene, etc.), the lubricity of the resulting coating film can be adjusted. The mixing ratio varies depending on the type of solvent to be combined and is arbitrary, but the same weight or a higher amount of butyl acetate is preferred from the viewpoint of good lubricity.
[0064]
A preferred blending ratio in the surface treatment composition of the present invention is 100 parts by weight or more and 200 parts by weight of PTFE particles (b) with respect to 100 parts by weight of the water-repellent binder resin (a) (hereinafter the same unless otherwise specified). The dispersant (c) is 5 parts by weight or more and 30 parts by weight or less. The inorganic particles (d) having a low heat capacity are preferably 25 to 200 parts by weight and the solvent (e) is preferably 400 to 2000 parts by weight.
[0065]
Such a surface treatment composition can be prepared in various forms as long as it can form a coating film. However, it is preferable to prepare a solvent-type coating from the viewpoint of easy formation of the coating film, and it is easy to apply and disperse. Therefore, the solid content concentration is preferably 5 to 40% by weight, particularly preferably 15 to 30% by weight. Moreover, you may mix | blend various additives, such as a pigment, other resin, a flow regulator, a color separation inhibitor, antioxidant, a ultraviolet absorber, unless the objective of this invention is impaired.
[0066]
Preparation of the composition for surface treatment as a solvent-type paint is performed by adding each component to the solvent (e) and stirring sufficiently. The stirring method is not particularly limited, but an ultrasonic stirring method, a forced stirring method, or the like is preferable from the viewpoint that particle components such as PTFE particles (b) and low heat capacity inorganic particles (d) can be easily and uniformly dispersed.
[0067]
The coating method is not particularly limited, and for example, methods such as a dip coating method, a bar coating method, a roll coating method, and a spray method can be employed. After coating, the film is dried at room temperature or, if necessary, dried by heating to form a cured film.
[0068]
The thickness of the coating film may be appropriately selected depending on the application part, but is usually 10 μm or more, more preferably 30 μm or more, 0.2 mm or less, and further preferably 0.1 mm or less.
[0069]
The base material to apply | coat is not specifically limited, It determines with the heat exchanger from which frost formation becomes a problem. For example, aluminum, stainless steel, copper, various alloys, ceramics and the like are fried.
[0070]
The coating film thus obtained (surface structure forming the heat exchange surface) gives surface portions A and surface portions B to the heat exchange surface and has frost and ice peelability.
Furthermore, the coating film can have a sliding angle (4 μl water droplet) on the heat exchange surface of 10 degrees or less, more preferably 5 degrees or less, and the water contact angle on the coating film surface is 140 degrees or more. Is 145 degrees or more, particularly 150 degrees or more, and even minute water droplets formed on the water-repellent surface easily slide down, do not form frost nuclei, and improve the effect of preventing frost formation.
[0071]
(Test example)
Next, a test example in which a surface structure is formed by the coating film will be described. In addition, the coating-film formation method which concerns on this invention is not limited to the formation method used for the following test example.
[0072]
Comparative Test Example 1
Zaffle GK-510 manufactured by Daikin Industries, Ltd. as the water-repellent binder resin (a), and Cefral Lube manufactured by Central Glass Co., Ltd. as the PTFE particles (b) (modified PTFE having an average primary particle size of 5-10 μm. Weight Average molecular weight 1500-20000), Unidyne TG-656 manufactured by Daikin Industries, Ltd. was used as the dispersant (c), and the amounts listed in Table 1 were added to the organic solvent (e) shown in Table 1 and ultrasonically stirred. The composition for surface treatment was prepared by stirring and mixing by the method.
[0073]
The obtained surface treatment composition was applied on an aluminum plate (JIS 1200 A1200 series, 100 mm × 100 mm) by spraying, allowed to stand at room temperature for 1 day, and then dried without washing the coating surface. Thus, a test coating plate (film thickness of 20 μm) was prepared.
[0074]
With respect to this coated plate, the contact angle with water and the sliding angle (4 μl) were examined by the following method. The results are shown in Table 1.
[0075]
The contact angle with water was measured as follows.
According to JISR3257, it measured with the contact angle meter (CA-VP, brand name) by Kyowa Interface Science Co., Ltd. at the temperature of 15-20 degreeC and the relative humidity of 50-70%. The greater the water contact angle, the higher the water repellency.
[0076]
The sliding angle was measured as follows.
A sample placed horizontally in a contact angle meter (CA-VP, trade name) manufactured by Kyowa Interface Science Co., Ltd. and placed in an environment with a temperature of 17 ± 1 ° C and a relative humidity of 60 ± 2%. 4 μl of distilled water was dropped on the plate to form water droplets, and then the sample plate was tilted at an angle of 0.1 degree, and the angle of the sample plate when the water droplets started to roll was measured. The measured value shown in the table is the first sliding angle. The smaller the sliding angle, the better the water droplet sliding property (sliding property).
[0077]
[Table 1]

[0078]
Test example 1
In the above Comparative Test Example 1, the mixing ratio of the components (a), (b), (c) and (e) is set to the ratio shown in Table 2, and further the particles shown in Table 2 as the low heat capacity inorganic particles (d) A surface treatment composition was prepared and coated in the same manner as in Test Example 1 except that the amount shown in Table 1 was added to prepare a test plate. The stirring method was an ultrasonic stirring method.
[0079]
For this coated plate, the water contact angle and the sliding angle were examined in the same manner as in Comparative Test Example 1. The results are shown in Table 2. From this result, it is understood that the sliding property can be improved by adding the inorganic particles (d) having a low heat capacity.
[0080]
The low heat capacity inorganic particles (d) in Table 2 are as follows.
CB: carbon black (manufactured by Sigma-Aldrich, primary average particle diameter of 2 to 12 μm)
GF: natural graphite (primary average particle diameter of about 3 μm)
[0081]
[Table 2]

[0082]
Test example 2
In Experiment No. 2-2 (carbon black particles) and Experiment No. 2-8 (natural graphite particles) of Test Example 1, the obtained coating film was heat-cured at 120 ° C. for 10 hours to prepare a test coated plate.
[0083]
For this heat-cured coated plate, the contact angle with water and the sliding angle were examined in the same manner as in Comparative Test Example 1. The results are shown in Table 3. It can be seen that this test example 2 can also improve the sliding property as compared with the comparative test example 1.
[0084]
[Table 3]

[0085]
Test example 3
4.0 g of Zaffle GK-510 manufactured by Daikin Industries, Ltd. as the water-repellent binder resin (a), and Cefral Lube manufactured by Central Glass Co., Ltd. (trade name. Average primary particle diameter of 5-10 μm) as PTFE particles (b). Modified PTFE, 4.0 g of weight average molecular weight 1500 to 20000), 4.0 g of Unidyne TG-656 manufactured by Daikin Industries, Ltd. as a dispersant (c), and carbon black (Sigma) as inorganic particles (d) having a low heat capacity -A product for surface treatment was prepared by using 2.0 g of Aldrich (average particle size 2 to 12 μm) and adding it to a mixed solvent of 20 g of butyl acetate and 20 g of heptane and stirring and mixing by ultrasonic stirring.
[0086]
The obtained surface treatment composition was applied on an aluminum plate (JIS H4000 A1200 series, 100 mm × 100 mm) by spraying, allowed to stand at room temperature for 1 day, and then dried without washing the coating surface. Thus, a test plate (film thickness 20-30 μm) was prepared.
[0087]
With respect to this coated plate, the water contact angle and sliding angle (4 μl) were measured by the same method as in Comparative Test Example 1 described above. The water contact angle was 152.1 degrees and the sliding angle was 4.6 degrees. Met.
[0088]
Next, the frost formation (frost) -defrost (defrost) test was conducted in the following manner.
First, the sample plate is fixed vertically in the wind tunnel, and the surface temperature of the sample plate is maintained at −7 ± 2 ° C. Air containing a humidity of 87 ± 3% relative humidity (temperature 7 ± 0.2 ° C.) flows in this wind tunnel parallel to the surface of the sample plate at a wind speed of 1 m / second to forcibly frost the sample plate surface. . This frost operation lasts 20 minutes.
Immediately after the frost operation, the sample plate surface temperature is heated to 5 ° C. and the defrost operation is started. Use the same air flow under the same conditions as in frost operation. The defrost operation lasts 2 minutes.
Such a frost operation-defrost operation is defined as one cycle, and this is continuously performed for two cycles.
The above is the point of the frost (frost) -defrost (defrost) test.
[0089]
The following results were obtained by the frost (frost) -defrost (defrost) test.
(1) Frosting began 10 minutes after the start of the first cycle frost operation. The photograph of the surface of the sample plate at the start of frosting taken with a CCD camera (CN401 manufactured by ELMO, trade name) is shown in FIG. 1 (entire) and FIG. 2 (enlarged, magnification is 1.2 times, the same applies hereinafter). Show.
Moreover, the photograph which image | photographed the frosting state of the sample plate surface at the time of completion | finish of frost operation 20 minutes after the frost operation start with a CCD camera is shown in FIG. 3 (whole) and FIG. 4 (enlarged). As can be seen from this photograph, the frost or ice formed on the surface of the sample plate was cotton-like (aggregate of acicular crystals).
[0090]
(2) In the first cycle defrost operation, frost or ice that has formed frost immediately after the start of the defrost operation began to peel off. A photograph of the state of the surface of the sample plate at the start of the frost or ice peeling with a CCD camera is shown in FIG. 5 (entire) and FIG. As can be seen from these photographs, in Test Example 3, the ice is falling in a lump. In the conventional heat exchanger, the ice was almost thawed, and the ice lump did not fall off before the ice was almost thawed.
Further, at the end of the defrost operation 2 minutes after the start of the first cycle defrost operation, frost or ice was completely peeled off from the surface of the sample plate. FIGS. 7 (overall) and FIG. 8 (enlarged) show photographs taken with a CCD camera of the state of the sample plate surface at the end of the defrost operation. As can be seen from these photographs, no water droplets observable with the naked eye were observed on the surface of the sample plate at the end of the defrost operation.
[0091]
(3) In the subsequent second cycle, frosting started 6 minutes after the start of frost operation.
9 (entire) and FIG. 10 (enlarged) show photographs taken with the CCD camera of the state of the sample plate surface at the end of the frost operation 20 minutes after the start of the frost operation in the second cycle. As can be seen from these photographs, there is no change compared to the state of the first frost operation.
(4) In the second cycle defrost operation performed next, frost or ice began to peel immediately after the start of the defrost operation. A photograph taken with a CCD camera of the state of the sample plate surface at the start of the frost or ice peeling is shown in FIG. 11 (entire).
Further, after 30 seconds from the start of the second cycle defrost operation, the frost or ice adhering to the surface of the sample plate was peeled off almost completely. A photograph taken with a CCD camera of the state of the sample plate surface when the frost or ice is almost completely peeled off is shown in FIG. As can be seen from these photographs, even during the second cycle defrost operation, the frost or ice is falling in a lump.
Moreover, the photograph which image | photographed the state of the sample plate surface at the time of completion | finish of a defrost operation 2 minutes after the defrost operation start of a 2nd cycle with a CCD camera is shown in FIG. 13 (whole) and FIG. As can be seen from these photographs, no water droplets that could be observed with the naked eye were observed on the surface of the sample plate even after the end of the second cycle defrost operation.
[0092]
Comparative test example 2
In Test Example 3, a sample plate was prepared using a surface treatment composition prepared in the same manner except that the low heat capacity inorganic particles (d) were not blended, and frosting (frosting) -defrosting was performed in the same manner. A (defrost) test was conducted. The results were as follows.
[0093]
(1) Frosting started about 5 minutes after the start of the first cycle frost operation, and almost the entire surface was frozen about 10 minutes after the start of the first cycle frost operation. FIGS. 15 (overall) and FIG. 16 (enlarged) show photographs taken with a CCD camera of the state of the surface of the sample plate in the entire frost state about 10 minutes after the start of the frost operation.
Moreover, the photograph which image | photographed the frost formation state on the sample plate surface at the time of completion | finish of frost operation 20 minutes after the frost operation start of the 1st cycle with a CCD camera is shown in FIG. 17 (whole) and FIG.
Compared to Test Example 3 described above, it can be seen that the amount of frost formation is large at the end of the frost operation. This shows that in Test Example 3, water droplets condensed on the surface of the sample plate are swept down by the wind pressure or easily dropped downward, so that there are few water droplets frozen on the surface of the sample plate due to frost operation. Can be interpreted.
[0094]
(2) In the first cycle defrost operation, frost or ice that has formed frost immediately after the start of the defrost operation began to melt. FIGS. 19 (entire) and 20 (enlarged) show photographs of the surface of the sample plate at the start of melting of the frost or ice with a CCD camera. As can be seen from these photographs, when the ice is peeled off, water droplets with polka dots are attached and the frost or ice is completely melted, and the ice mass is displaced as in Test Example 3 above. It is different from the falling situation.
In addition, frost or ice was completely melted at the end of the defrost operation 2 minutes after the start of the first cycle defrost operation. The photograph which image | photographed the state of the sample plate surface at the time of this defrost operation completion is shown in FIG. 21 (whole) and FIG. 22 (enlarged). As can be seen from these photographs, unlike the above-described Test Example 3, many small and large water droplets that can be observed with the naked eye were observed on the surface of the sample plate after completion of the defrost operation.
[0095]
(3) In the subsequent second cycle, frosting began 6 minutes after the start of operation.
The photograph which image | photographed the state of the sample plate surface at the time of completion | finish of frost operation 20 minutes after the start of frost operation of the 2nd cycle with a CCD camera is shown in FIG. 23 (whole) and FIG. From these photographs, it can be seen that large water droplets are frozen. In this respect, it can be seen that there is a large change compared to the state during the first frost operation. This is probably because large water droplets adhering to the surface of the sample plate after completion of the first defrost operation were frozen.
(4) In the second cycle defrost operation performed next, frost or ice began to melt immediately after the start of the defrost operation. FIG. 25 (entire) shows a photograph of the state of the surface of the sample plate at the start of melting of frost or ice immediately after the start of the defrost operation with a CCD camera. Further, frost or ice was almost completely melted 1 minute after the start of the defrost operation. A photograph of the state of the sample plate surface at this time is shown in FIG. 26 (entire). As can be seen from these photographs, the attached frost or ice melts without falling off as a lump.
Moreover, the photograph which image | photographed the state of the sample plate surface at the time of completion | finish of a defrost operation 2 minutes after the start of a defrost operation in a 2nd cycle with a CCD camera is shown in FIG. 27 (whole) and FIG. As can be seen from these photographs, more and more water droplets remained on the surface than at the end of the first defrost operation.
[0096]
As described above, when the surface structure according to the present invention is applied to the heat exchange surface, the heat exchange surface is excellent in water repellency, water slidability, and easy frost ice peelability.
[0097]
(Embodiment 1)
The first embodiment will be described with reference to FIGS. FIG. 29 is a configuration diagram of the heat exchange device according to the first embodiment. FIG. 30 is a state diagram in which the refrigerant blocking mechanism for the upper refrigerant passage of the heat exchanger is closed. FIG. 31 is a state diagram in which the refrigerant blocking mechanism for the intermediate refrigerant passage of the heat exchange device is closed. FIG. 32 is a state diagram in which the refrigerant shut-off mechanism for the lower refrigerant passage of the heat exchange device is closed.
[0098]
The heat exchange apparatus according to Embodiment 1 is used for an outdoor heat exchanger of a separate heat pump type air conditioner. Moreover, the heat exchanger 1 uses an air-to-air heat exchanger 1, and a heat exchange pipe 2 a is inserted into a flat plate fin 2. Further, the surface structure is formed on the heat exchange surface of the flat plate fin 2 by coating the surface treatment product. Furthermore, a flow divider 4 is arranged in the inlet side pipe 3 of the air heat exchanger 1, and the flow divider 4 branches into three flow dividing pipes 5 a, 5 b, 5 c. In addition, refrigerant dividing mechanisms 6a, 6b, and 6c are provided in the diversion pipes 5a, 5b, and 5c connected to the flow divider 4, respectively. The air heat exchanger 1 includes an upper refrigerant passage 11, an intermediate refrigerant passage 12, and a lower refrigerant passage 13 that are connected to the respective branch pipes 5 a, 5 b, and 5 c. The upper refrigerant passage 11, the intermediate refrigerant passage 12, and the lower refrigerant passage 13 are assembled by the outlet header 7, and are configured to transfer the refrigerant to the next device via the outlet header 7.
[0099]
The flat plate fin 2 is divided into three parts, upper, middle, and lower, so that heat does not move between the three refrigerant passages 11, 12, and 13. Further, as the refrigerant blocking mechanism 6a for the upper refrigerant path, the refrigerant blocking mechanism 6b for the intermediate refrigerant path, and the refrigerant blocking mechanism 6c for the lower refrigerant path, specifically, an electromagnetic on-off valve or an electric valve is used.
[0100]
When this heat exchange device acts as an evaporator during heating operation, such as when used as an outdoor heat exchanger of a heat pump air conditioner, for example, the air temperature (usually outside air) When the temperature decreases, frost forms on the heat exchange surface. However, in the case of this heat exchanging device, heat exchange is performed by disposing two types of surface portions, the surface portion A having a low heat capacity and the surface portion B having low binding or adhesion to frost or ice. The surface is excellent in water repellency and sliding property. For this reason, the condensed water condensed on the heat exchange surface of the heat exchange device has a spherical shape and is easily scattered by the wind pressure passing through the heat exchanger 1 for air, and is in a supercooled state and hardly freezes. Therefore, the growth time of frost adhering to the heat exchange surface is reduced, and the refrigeration operation (heating operation in the case of a heat pump air conditioner) up to the amount of frost that requires defrosting is extended.
[0101]
Further, when the anti-air heat exchanger 1 is frosted, in this heat exchange device, first, the refrigerant blocking mechanism 6a for the upper refrigerant passage 11 is blocked, and the circulation of the refrigerant to the upper refrigerant passage 11 is stopped. As a result, the upper refrigerant passage 11 is heated as the ambient air of the air-to-air heat exchanger 1 flows, and defrosting is performed on the heat exchange surface of the upper refrigerant passage 11 as follows.
[0102]
That is, since the surface portion A and the surface portion B are dispersedly arranged on the heat exchange surface of the upper refrigerant passage 11 portion, during the defrosting operation (operation for closing the refrigerant blocking mechanism 6a for the upper refrigerant passage 11). First, frost or ice on the interface portion that contacts the surface portion A melts by absorbing the heat of the surrounding air, and the frost or ice on the surface portion A peels off. Then, the peeled frost or ice and the frost or ice on the surface portion B are at least partially combined, and the frost or ice on the surface portion B is peeled by its own weight.
Therefore, in the dehumidifying operation of the upper refrigerant passage 11 portion, it is not necessary to completely melt the frost or ice adhering to the heat exchange surface as in the prior art, and the defrosting operation time is shortened. Moreover, since it defrosts using the thermal energy which ambient air has, energy efficiency is good.
[0103]
In addition, since the heat exchange surface of the heat exchanger 1 for air has easy frost and ice detachability, during the defrosting operation, frost or ice on the heat exchange surface peels off (removes) from the surface as a lump by its own weight, and frost Alternatively, no water droplets remain on the heat exchange surface after the ice is melted or peeled off. For this reason, the amount of frost formation or the amount of freezing after resumption of freezing operation reduces, and it can continue making the extension of freezing operation time and shortening of defrosting operation time continue. Therefore, less heat energy is required for defrosting and the defrosting operation time is shortened.
[0104]
The defrosting operation (operation for closing the refrigerant blocking mechanism 6a) of the upper refrigerant passage 11 described above is set by a timer so that the defrosting is completed by continuing for a predetermined time. When this predetermined time elapses, the refrigerant shut-off mechanism 6a is opened, the upper refrigerant passage 11 part acts as an evaporator, and the defrosting operation (the refrigerant shut-off mechanism 6b is closed) of the next intermediate refrigerant passage 12 part. ) For a predetermined time. When the defrosting operation for the intermediate refrigerant passage 12 is completed, the refrigerant blocking mechanism 6b is opened to allow the upper refrigerant passage 11 to act as an evaporator, and further the defrosting operation (refrigerant blocking mechanism for the lower refrigerant passage 13). 6c is closed for a predetermined time. The defrosting operation of the heat exchanger for air 1 is performed as described above. The order among the defrosting operation of the upper refrigerant passage 11 portion, the defrosting operation of the intermediate refrigerant passage 12 portion, and the defrosting operation of the lower refrigerant passage 13 portion is not particularly limited. For example, the defrosting operation for the lower refrigerant passage 13 may be performed after the defrosting operation for the upper refrigerant passage 11 portion.
[0105]
Thus, according to Embodiment 1, since the heating operation time is extended and the defrosting operation time is shortened, the heating comfort sensitivity is improved and the energy efficiency is improved.
[0106]
(Embodiment 2)
In the second embodiment, the air heat exchanger 1 is formed in a large number of refrigerant passages 21 to 29. A large number of refrigerant passages 21 to 29 are grouped into a plurality of refrigerant passage groups, in this case, an upper refrigerant passage group 31, an intermediate refrigerant passage group 32, and a lower refrigerant passage group 33. In addition, the block diagram of the heat exchange apparatus which concerns on FIG. 32 at Embodiment 2 is shown.
In addition, it is comprised so that the one branch pipe 5a, 5b, 5c may be connected for every these refrigerant | coolant channel groups 31,32,33. In addition, similar to the case of the first embodiment, refrigerant blocking mechanisms 6a, 6b, and 6c are provided in the branch pipes 5a, 5b, and 5c connected to the flow divider 4.
[0107]
In the defrosting operation in the second embodiment, the upper refrigerant passage group 31, the intermediate refrigerant passage group 32, and the lower refrigerant passage group 33 are replaced with the upper refrigerant passage 11, the intermediate refrigerant passage 12, and the lower refrigerant in the first embodiment. This is done by handling in the same way as the passage 13.
[0108]
Since the second embodiment is configured as described above, in the case of the large heat exchanger for air 1, the number of the branch pipes 5a, 5b, and 5c is reduced, and the refrigerant cutoff mechanisms 6a, 6b, and 6c are reduced. Therefore, the equipment can be simplified and an increase in cost can be suppressed.
[0109]
【The invention's effect】
According to the heat exchange device of the present invention, since the surface structure with excellent water repellency and sliding property is formed on the heat exchange surface, frost formation is delayed, defrosting operation time is shortened, and it is necessary for defrosting. Thermal energy can be reduced. In addition, since the defrosting operation is performed by stopping the circulation of the refrigerant for each part of the heat exchange device, the defrosting operation is performed while continuously operating the refrigeration operation and using the thermal energy of the ambient air of the heat exchange device. And the fall of the freezing operation effect (For example, the fall of the heating pleasant sensitivity in the case of applying to a heat pump type air conditioner) can be avoided, and the improvement of energy efficiency can be aimed at.
[Brief description of the drawings]
FIG. 1 is a photograph taken with a CCD camera of the state of a sample plate surface at the start of frosting 10 minutes after the start of frost operation in the first cycle in Test Example 3.
FIG. 2 is a partially enlarged photograph of FIG.
FIG. 3 is an overall photograph taken with a CCD camera of the frosting state on the surface of a sample plate at the end of frost operation 20 minutes after the start of frost operation in the first cycle in Test Example 3;
4 is a partially enlarged photograph of FIG. 3;
FIG. 5 is an overall photograph taken with a CCD camera of the peeling state of the sample plate surface at the start of peeling of frost or ice immediately after the start of defrosting operation in the first cycle in Test Example 3;
6 is a partially enlarged photograph of FIG.
7 is an overall photograph taken with a CCD camera of the state of the surface of the sample plate at the end of the defrost operation 2 minutes after the start of the defrost operation in the first cycle in Test Example 3. FIG.
8 is a partially enlarged photograph of FIG.
FIG. 9 is an overall photograph taken with a CCD camera of the state of the sample plate surface at the end of the frost operation 20 minutes after the start of the frost operation in the second cycle in Test Example 3;
10 is a partially enlarged photograph of FIG. 9;
FIG. 11 is an overall photograph taken with a CCD camera of the state of the surface of the sample plate at the start of frost or ice peeling immediately after the start of the defrost operation of the second cycle in Test Example 3;
FIG. 12 is an overall photograph taken with a CCD camera of the state of the surface of the sample plate when the peeling is almost completed, 30 seconds after the start of the second cycle defrost operation in Test Example 3.
FIG. 13 is an overall photograph taken with a CCD camera of the state of the sample plate surface at the end of the defrost operation, 2 minutes after the start of the defrost operation of the second cycle in Test Example 3.
14 is a partially enlarged photograph of FIG.
FIG. 15 is an overall photograph taken with a CCD camera of the state of the surface of a sample plate in a full frost state about 10 minutes after the start of frost operation in the first cycle in Comparative Test Example 2;
16 is a partially enlarged photograph of FIG.
FIG. 17 is an overall photograph taken with a CCD camera of the state of the sample plate surface at the end of the frost operation 20 minutes after the start of the frost operation in the first cycle in Comparative Test Example 2;
18 is a partially enlarged photograph of FIG.
FIG. 19 is an overall photograph taken with a CCD camera of the state of the sample plate surface at the start of frost or ice melting immediately after the start of the first cycle defrost operation in Comparative Test Example 2.
20 is a partially enlarged photograph of FIG.
FIG. 21 is an overall photograph taken with a CCD camera of the state of the sample plate surface at the end of the defrost operation, 2 minutes after the start of the defrost operation in the first cycle of Comparative Test Example 2;
22 is a partially enlarged photograph of FIG. 21. FIG.
FIG. 23 is an overall photograph taken with a CCD camera of the state of the sample plate surface at the end of the frost operation 20 minutes after the start of the frost operation in the second cycle of Comparative Test Example 2;
24 is a partially enlarged photograph of FIG. 23. FIG.
FIG. 25 is an overall photograph taken with a CCD camera of the state of the surface of the sample plate at the start of frost or ice melting immediately after the start of the defrost operation in the second cycle of Comparative Test Example 2;
FIG. 26 is an overall photograph taken with a CCD camera of the state of the surface of the sample plate 1 minute after the start of the defrost operation in the second cycle of Comparative Test Example 2.
FIG. 27 is an overall photograph taken with a CCD camera of the state of the sample plate surface at the end of the defrost operation, 2 minutes after the start of the defrost operation in the second cycle of Comparative Test Example 2;
28 is a partially enlarged photograph of FIG. 27. FIG.
29 is a configuration diagram of a heat exchange device according to Embodiment 1. FIG.
FIG. 30 is a state diagram in which the refrigerant shut-off mechanism for the upper refrigerant passage of the heat exchange device is closed.
FIG. 31 is a state diagram in which a refrigerant blocking mechanism for an intermediate refrigerant passage of the heat exchange device is closed.
FIG. 32 is a state diagram in which the refrigerant shut-off mechanism for the lower refrigerant passage of the heat exchange device is closed.
33 is a configuration diagram of a heat exchange device according to Embodiment 2. FIG.
[Explanation of symbols]
1 Heat exchanger for air
2 Flat plate fins
4 Shunt
5a Shunt pipe
5b Shunt pipe
5c Shunt pipe
6a Refrigerant shut-off mechanism
6b Refrigerant shut-off mechanism
6c Refrigerant shut-off mechanism
11 Upper refrigerant passage
12 Intermediate refrigerant passage
13 Lower refrigerant passage
21-29 Refrigerant passage
31 Upper refrigerant passage group
32 Intermediate refrigerant passage group
33 Lower refrigerant passage group

Claims (7)

Surface portion A having a molar heat capacity of 6JK ⁻¹ mol ^{−1 to} 7JK ⁻¹ mol ⁻¹ and having a conductive material as a main component, and a surface having water repellent binder resin and polytetrafluoroethylene particles as main components An evaporator comprising a fin having a heat exchange surface with air for part B and an air-to-air heat exchanger having a plurality of refrigerant passages;
A shunt for diverting the refrigerant into a plurality of refrigerant passages;
A plurality of shunt pipes connecting the refrigerant flow passage formed in the evaporator and the shunt;
A refrigerant shut-off mechanism provided in each shunt pipe,
When the evaporator is frosted, a part of the refrigerant shut-off mechanism is closed, and after a predetermined time, the shut-off mechanism is opened and the defrosting is performed by switching so that the other refrigerant shut-off mechanisms are sequentially closed. Heat exchange device. Molar heat capacity is 6JK ^-1 mol ^-1 ~ 7JK ^-1 mol ^-1 The heat exchange apparatus according to claim 1, wherein the substance having conductivity is carbon black. 3. The water repellent binder resin is a fluororesin, and the polytetrafluoroethylene particles have a weight average molecular weight of 500 to 200,000 and an average particle diameter of 0.1 [mu] m or more. The heat exchange apparatus as described. The heat exchange device according to any one of claims 1 to 3, wherein the number of the branch pipes is a number corresponding to the number of refrigerant passages so as to be connected to the respective refrigerant passages formed in the evaporator. . 4. The flow dividing pipe according to claim 1, wherein a plurality of refrigerant passages formed in the evaporator are grouped into a plurality of refrigerant passage groups, and one branch pipe is connected to each refrigerant passage group. The heat exchange device according to item. The heat exchanger according to any one of claims 1 to 5, wherein the refrigerant shut-off mechanism comprises an electromagnetic on-off valve or an electric valve. A refrigeration apparatus using the heat exchange apparatus according to any one of claims 1 to 6.

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