高分子材料の撥水化技術と

その可能性

神神 戸戸 大大 学学 工工 学学 部部

応用化学科応用化学科

西西 野野 孝孝

平成平成1818年年1111月月2222日日

tnishino@kobe-u.ac.jp

第第1919回建材情報交流会回建材情報交流会

ナノ技術等を用いた最新防汚技術V サスティナブル建築 Part-II

Bulk高分子表面・界面高強度・耐熱性・・・

接着剤・複合材料・フィルム・

繊維・バイオマテリアル・コーティング・・・バルク特性 保持

表面改質

疎水性 親水性

極性官能基の導入撥水性●物理的～荒れ ●湿式

●乾式～プラズマ●化学的～

表面自由エネルギー；低

剥離・耐水性（撥水・撥油）・防汚染・生体親和性

表面荒れ性

フラクタル表面→ 撥水・撥油表面

鄭・渡辺，化学，46，477 (1991)T.Onda, S.Shibuichi, N.Satoh, K.Tsujii,

Langmuir, 12, 2126 (1996).

高分子の表面性質

動的接触角 (Dynamic Contact Angle)

θθ

H2O H2O

水との接触角低 高

濡れる 撥く

疎水性 (撥水性)親水性

表面自由エネルギー高 低

1 nm10 nm

CF3

CF3CF3CF3 CF3 CF3CF3 CF3CF3CF3CF3 CF3 CF3CF3 CF3CF3CF3CF3 CF3 CF3CF3 CF3CF3CF3CF3 CF3 CF3CF3 CF3CF3CF3CF3 CF3 CF3CF3 CF3

-CF3 Regular AlignedHexagonal Closest Packing

Vapor DepositionPerfluoroeicosane ( CF3(CF2)18CF3 )

θ= 119゜(water)γ= 6.7 mJ / m2

The Lowest Surface Energy T. Nishino et al., Langmuir, 15 (1999) 4321

ＳｙｎｔｈｅｓｉｓＳｙｎｔｈｅｓｉｓ

(CF2)7CF3(CH2)2

CH3

CH2 CC O

O

2-perfluorooctylethyl methacrylate (PFEMA)

CH3

CH3

CH2 CC O

O

Methyl methacrylate(MMA)

Monomer

Living Anionic CopolymerizationAIBN, MIBK, 70°C, 24hs-BuLi, THF, -78°C

Radical Copolymerization

Copolymers Mna) PFEMA contentb)Mw/Mna)

Random 12800 1.51 17.6

Diblock 11900 1.08 15.2

a) : determined by GPC b) : determined by 1H-NMR (mol%)

Diblock Random

T.Nishino, Y.Urushihara, M.Meguro, K.NakamaeJ.Colloid and Interface Sci., 279, 364 (2004).

Surface free energyWater CH2I2Polymer (mJ/m2)(degree)

Diblock 120 103 7.8

Random 93 65 26.4

PTFE 98 70 18.0The Lowest 119 107 6.7

Low surface free energy

No self-assembly

Stable -CF3 surface

2

Random copolymer Diblock copolymer

Perfluoroalkyl side chain

CF3

15Å

7.8 mJ /cm ESCAFTIR RASGIXD

60

70

80

90

100

110

120

130

140

0.01 0.1 1.0 10 1000

水との動的接触角(°)

0.25wt%

共重合体の添加量 (wt%)

ランダム共重合体

PMMA

ジブロック共重合体

(CF2)7CF3(CH2)2

CH3

CH2 CC O

O

2-perfluorooctylethyl methacrylate (PFEMA)

CH3

CH3

CH2 CC O

O

375 ppm

45 ppm

15.2 mol%

PTFE

Diblock copolymer vs. Homopolymer

Homo CF3CF2CHCl2 118 100 8.5 ± 0.4100

Table. Dynamic contact angles and the surface free energy γs of diblock copolymer and homopolymer.

Polymer SolventWater CH2I2

Chloroform 120 103Diblock

(mJ/m2)

7.8± 0.2

γs

(degree)

PFEMA content

15.2

(mol%)

Homopolymer(CF3CF2CHCl2)

Diblock(chloroform)

Perfluoroalkyl side chain

CF3 group

15Å

Self-assembled structure at surface

Cast solvent effectCast solvent effectT.Nishino, Y.Urushihara, M.Meguro, K.Nakamae

J.Colloid and Interface Sci., vol.283, pp.533-538 (2005).

7.8Chloroform

9.9Ethyl acetate

11.7THF

11.8MEK

22.2Toluene

23.0Benzene

9.9HCFC-225

γs (mJ/m2)Solvent

10.8TFMB

8.1Trichloroethylene

Table. Surface free energies of the Diblock copolymer films cast and spin-coated from various solutions.

Cast film Spin-coated film

27.5

27.9

28.0

27.8

27.2

27.7

12.2

12.4

28.4

Chloroform

Ethyl acetate

THF

MEK

Toluene

Benzene

HCFC-225

Solvent

TFMB

Trichloroethylene

MMA segment

Solubility

PFEMA segment

(CF2)7 CF3(CH2)2

CH3

( CH2 C )CO

OCH3

CH3

( CH2 C )C O

O

m n

MicelleMicelle

Model of Air/Solution Interface

Low surface free energy

AirPFEMA segment

Solution

InterfaceInterface

Chloroform Toluene

UnimerUnimer

Micelle

7.8 mJ/m2 22.2 mJ/m2

Y.Urushihara，and T.Nishino, Langmuir, vol. 21, 2614-2618 (2005).

Molecular sequenceFilm-forming condition

Annealing effect

Surface propertiesstructureCast solvent effectFilm-forming technique

(CF2)7CF3(CH2)2

CH3( CH2 C )

COO

CH3

CH3( CH2 C )

COO

m n

Surface free energy γs (mJ/m2)

0.8

1.0

1.2

1.4

1.6

1.8

2.0

5 10 15 20 25 30

Ato

mic

rat

io F

/C

Fig. Relationship between the surface free energy and the atomicratio F/C on the film surface of the polymethacrylate with perfluoroalkyl side chains

西野 孝，科学と工業，80巻,512（2006）

C7F15COOH

PFOS: 3MC8F17SO3

-

PFOA: Du Pont

C8F17CH2CH2OH

Chemical & Engineering News (Feb.20,2006) p.26

フッ素系高分子ポリテロラフルオロエチレン (PTFE)

(CF2 CF2)n

撥水・撥油性

低摩擦性低誘電率耐溶剤性

成型加工性機械的強度価格生体蓄積性

低接着性・剥離性

(CF2)7CF3(CH2)2

CH3

( CH2 C )CO

OCH3

CH3( CH2 C )

COO

m n

高撥水性高撥水性 ++ 高接着性高接着性

Rf

RfRf Rf

PEO chains

CH2

CH3

CCO

OCH3

CH2(CH2)2(CF2)n CF3

H

CC OO

i

CH2

CH3

O

O-(CH2-CH2-O)m-CH3

CC

j k

Rf

撥水性撥水性 接着性接着性

Environmental Response

Rf Rf Rf

PEO Chain

Rf Rf

Matrix Resin

Matrix resin

Rf

疎水性

Matrix resin

Rf Rf

Rf

Water

親水性

可逆的

迅速

Adhesive Test ～90°Peel Strength to Epoxy Resin

0.0

0.5

1.0

1.5

2.0

2.5

40 60 80 100 120 140

Advancing contact angle of water (degree)

90°

peel

stre

ngth

(N/c

m)

PTFEPPPE

PVA

PET-2 PET-1

PMMAPET

MMA/PFEA/PMA-EO

0

Fig. Relationship between 90°peel strength and the advancing contact angle of water on various polymers.

PVC*Surface Modified Surface

Repellent property of ink marker

Wiping property of ink marker

Wiped with ethanol after 24hrs.

*PVC : polyvinylchloride

PFEA

CH2

(CH2)2 (CF2)7 CF3

H

CC O

Oji

CH2

CH3

CC

OOCH3

MMA PMA-DMSi

CH2

OSi

CH3

O

(CH2)3 n-BuSiCH3

CH3m

CH3

CH3

C

C O

k

Mn ; 5,000

PFEA

CH2

(CH2)2 (CF2)7 CF3

H

CC O

Oji

CH2

CH3

CC

OOCH3

MMA PMA-DMSi

CH2

OSi

CH3

O

(CH2)3 n-BuSiCH3

CH3m

CH3

CH3

C

C O

k

Mn ; 5,000