JPS6321715B2 - - Google Patents
Info
- Publication number
- JPS6321715B2 JPS6321715B2 JP55066393A JP6639380A JPS6321715B2 JP S6321715 B2 JPS6321715 B2 JP S6321715B2 JP 55066393 A JP55066393 A JP 55066393A JP 6639380 A JP6639380 A JP 6639380A JP S6321715 B2 JPS6321715 B2 JP S6321715B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- group
- segment
- oil
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000005871 repellent Substances 0.000 claims description 24
- 230000002940 repellent Effects 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 10
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- -1 hydroxyalkyl acrylates Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 1
- QQHQTCGEZWTSEJ-UHFFFAOYSA-N 1-ethenyl-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C=C)C=C1 QQHQTCGEZWTSEJ-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- RHZIVIGKRFVETQ-UHFFFAOYSA-N butyl 2-methylpropaneperoxoate Chemical compound CCCCOOC(=O)C(C)C RHZIVIGKRFVETQ-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Graft Or Block Polymers (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、高度の耐久性を有する撥水撥油剤に
関し、更に詳しく言えば、ブロツク化されたポリ
フルオロアルキル基を有する枝セグメントが特定
の幹セグメントに結合してなるポリマーからな
り、低濃度処理でも高い撥水撥油性を付与可能で
あり高度の耐摩擦など耐久性を有する撥水撥油剤
に関する。
パーフルオロアルキル基(Rf基)を含有した
アクリレート類、又はメタクリレート類の如きポ
リフルオロアルキル基含有の重合し得る化合物の
重合体、あるいはこれとアルキルアクリレート、
無水マレイン酸、クロロプレン、ブタジエン、メ
チルビニルケトン、塩化ビニルの如き他の重合し
得る化合物との共重合体よりなる撥水撥油剤は知
られている。而して、かゝる従来の撥水撥油剤
は、一般的にランダム共重合体からなるものが多
く、ポリエステル繊維のような反応活性点を持た
ない繊維に対して高度の耐久性、例えば耐摩擦
性、耐洗たく性、耐ドライクリーニング性を持つ
ものは少ない。即ち、ランダム共重合体の場合に
は、たとえ繊維との接着性の優れた成分をコモノ
マーとして用いても、ポリマー鎖中にRf基と混
在することになり、かゝる親水親油基である接着
性基と撥水撥油基であるRf基が相互にその機能
を阻害し、耐久性が高く、且つ高度の撥水撥油性
を有するポリマーを得るのは困難である。
前記の如き難点を解消するため、即ち、相反す
る機能を両立させるため、接着性基と撥水撥油性
基をブロツク化させた構造のポリマーを撥水撥油
剤とすることが提案されている。例えば接着性基
を持つポリマーを幹ポリマーとして、これにRf
基を含有したモノマー類をグラフト共重合したポ
リマー、あるいはRfセグメントと接着セグメン
トからなるブロツク共重合体などである。かゝる
ブロツク化された構造のポリマーで繊維を処理す
ると、高度の撥水撥油性と優れた耐久性を付与し
得るものである。特公昭52―43955号公報、特開
昭54―132694号公報、特公昭37―10090号公報、
特公昭37―18627号公報、特公昭38―10394号公報
などを参照。
本発明者は、ブロツク化構造を有する撥水撥油
剤について種々の研究、検討を重ねた結果、ブロ
ツク化されたRf基を有する枝セグメントが接着
性を有する幹ポリマーにグラフト結合した構造の
ポリマーが前記目的に良く合致し、しかも幹ポリ
マーの選択が非常に重要であることを見出した。
即ち、ポリエステル繊維の如き場合にも高度の耐
久性を付与可能な幹ポリマーとしては、アルキル
アクリレート類とヒドロキシアルキルアクリレー
ト又はメタクリレート類とを主成分とするものが
有効であり、両者の割合が特定範囲にあることが
重要であることを見出したものである。
かくして、本発明は、前記知見に基づいて完成
されたものであり、ブロツク化されたポリフルオ
ロアルキル基を有する枝セグメントが幹セグメン
トに結合してなるポリマーからなる撥水撥油剤に
おいて、幹セグメントが
〔A〕CH2=CHCOOR(但し、Rはアルキル基)
と〔B〕
The present invention relates to a water and oil repellent having a high degree of durability, and more specifically, it is made of a polymer in which branch segments having blocked polyfluoroalkyl groups are bonded to specific trunk segments, and is treated with low concentration treatment. However, the present invention relates to a water and oil repellent that can impart high water and oil repellency and has durability such as high friction resistance. A polymer of a polymerizable compound containing a polyfluoroalkyl group such as acrylates containing a perfluoroalkyl group (R f group) or methacrylates, or this and an alkyl acrylate,
Water and oil repellents comprising copolymers with other polymerizable compounds such as maleic anhydride, chloroprene, butadiene, methyl vinyl ketone, and vinyl chloride are known. Therefore, such conventional water and oil repellents are generally made of random copolymers, and have a high degree of durability, such as resistance to fibers that do not have reactive active sites such as polyester fibers. There are few materials that have abrasion resistance, wash resistance, and dry cleaning resistance. In other words, in the case of a random copolymer, even if a component with excellent adhesion to fibers is used as a comonomer, it will coexist with R f groups in the polymer chain, and such hydrophilic and lipophilic groups A certain adhesive group and the R f group, which is a water- and oil-repellent group, mutually inhibit their functions, making it difficult to obtain a polymer that is highly durable and has a high degree of water- and oil-repellency. In order to solve the above-mentioned difficulties, that is, to make contradictory functions compatible, it has been proposed to use a polymer having a block structure of an adhesive group and a water/oil repellent group as a water/oil repellent. For example, if a polymer with adhesive groups is used as a backbone polymer, R f
These include polymers obtained by graft copolymerization of group-containing monomers, or block copolymers consisting of an R f segment and an adhesive segment. Treatment of fibers with polymers having such a blocked structure can impart a high degree of water and oil repellency and excellent durability. JP 52-43955, JP 54-132694, JP 37-10090,
See Special Publications No. 18627, No. 10394, etc. As a result of various studies and studies on water and oil repellents having a blocked structure, the present inventors discovered a polymer with a structure in which a branch segment having a blocked R f group is graft-bonded to a trunk polymer having adhesive properties. It has been found that the above-mentioned purpose is met well, and that the selection of the backbone polymer is very important.
That is, as a backbone polymer capable of imparting high durability even to polyester fibers, it is effective to use a material whose main components are alkyl acrylates and hydroxyalkyl acrylates or methacrylates, and the ratio of both is within a certain range. It was discovered that it is important to have the following. Thus, the present invention was completed based on the above findings, and provides a water and oil repellent agent comprising a polymer in which a branch segment having a blocked polyfluoroalkyl group is bonded to a trunk segment. [A] CH 2 = CHCOOR (however, R is an alkyl group)
and [B]
【式】(但し、
R1は水素原子又はメチル基、R2は水素原子又は
アルキル基)とを主成分として構成され、
〔A〕/〔B〕の重量比が10/90〜90/10である
ことを特徴とする撥水撥油剤を新規に提供するも
のである。
本発明の撥水撥油剤は、低濃度処理においても
高度の撥水撥油性を繊維表面などに付与可能であ
り、更に摩擦、洗たくなどの耐久性も非常に良好
である。そして、従来の撥水撥油剤では耐摩擦、
耐洗たくなど耐久性の付与が困難であつたポリエ
ステル繊維などの処理においても、本発明の撥水
撥油剤は高度の耐久性付与が可能である。
本発明においては、ブロツク化されたポリフル
オロアルキル基を有する枝セグメントが、特定の
幹セグメントと結合していることが重要である。
そして、特定の幹セグメントは、
〔A〕CH2=CHCOORと〔B〕
[Formula] (where R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or an alkyl group),
The present invention provides a new water and oil repellent characterized by a weight ratio of [A]/[B] of 10/90 to 90/10. The water and oil repellent of the present invention can impart a high degree of water and oil repellency to fiber surfaces even when treated at low concentrations, and also has very good durability against friction and washing. Conventional water and oil repellents have abrasion resistance,
The water and oil repellent of the present invention can impart a high degree of durability even in the treatment of polyester fibers, etc., which have been difficult to impart durability, such as washing resistance. In the present invention, it is important that a branch segment having a blocked polyfluoroalkyl group is bonded to a specific trunk segment.
And the specific stem segment is [A] CH 2 = CHCOOR and [B]
【式】とを主成分とす
る共重合体からなる。Rはアルキル基であり、通
常は炭素数1〜8個のアルキル基、好ましくは炭
素数1〜3個の低級アルキル基である。〔A〕成
分はアクリレートであることが重要であり、メタ
クリレートの場合には耐久性付与効果が不充分と
なる。R1は水素原子又はメチル基のいずれでも
良く、R2は水素原子又はアルキル基、好ましく
は水素原子又はメチル基など低級アルキル基であ
る。特に好適な幹セグメントは、Rがエチル基、
R1,R2が水素原子であるエチルアクリレートと
2―ヒドロキシエチルアクリレートを主成分とす
る共重合体である。
本発明における幹セグメントは、〔A〕/〔B〕
の重量比が10/90〜90/10、好ましくは20/80〜
80/20、特に50/50〜75/25であるものが採用さ
れる。そして、幹セグメントは〔A〕及び〔B〕
の主成分のみからなるものでも良く、他の架橋成
分、グラフト活性成分など〔X〕を含んでいても
良い。〔X〕の含有量は幹セグメント100重量部当
り0〜20重量部、好ましくは2〜10重量部程度の
範囲から選定され得る。〔X〕としては、〔B〕成
分をそのまゝグラフトあるいは架橋成分とするこ
ともできるが、N―メチロールアクリルアミド、
N―ブトキシメチルアクリルアミド、グリシジル
メタクリレートの如き架橋成分や、グラフト手段
の必要に応じてアリルメタクリレート、P―イソ
プロピルスチレンなどを選択しても良い。
本発明において、幹セグメントの〔A〕,〔B〕
主成分が、ポリエステル繊維などに対して耐久性
向上に有効な理由は必ずしも明確でないが、繊維
素材との界面張力が小さい(特に〔A〕成分)、
OH基が水素結合する(〔B〕成分)、ガラス転移
点が低くフイルム化が容易であるなど、繊維素材
との接着に有利な要因を含んでいるためと考えら
れる。かゝる説明は、本発明の理解を助けるため
のものであり、本発明を何ら限定しないことは勿
論である。
本発明における枝セグメントは、ブロツク化さ
れたポリフルオロアルキル基を有している。ポリ
フルオロアルキル基(以下、PFA基と略記する
ことがある)は、通常炭素数4〜20個のものが選
定され、パーフルオロアルキル基であることが好
ましい。特に、炭素数6〜18個のパーフルオロア
ルキル基が好適である。そして、かゝるPFA基
が複数個、好適には3個以上、特に5個以上で枝
セグメントに含まれている。PFA基のブロツク
化手段は各種採用され得る。例えば、幹ポリマー
にPFA基含有モノマーをグラフト重合せしめる
方法がある。かゝる枝セグメントとしては、CH2
=C(R1)COOQRfの単独重合体、あるいはこれ
とアルキルアクリレート、アルキルメタクリレー
ト、スチレンなどとの共重合体が例示可能であ
る。R1は水素原子又はメチル基、Qは炭素数1
〜10個の二価のアルキレン基、Rfは炭素数6〜
18個のパーフルオロアルキル基であり、好適には
R1がメチル基、Qが―CH2CH2―である。枝セ
グメントとしてCH2=C(R1)COOQRfと共重合
させる成分としては、CH2=C(CH3)COOR3
(R3は炭素数1〜4個のアルキル基)が好適であ
る。好適な実施態様では、枝セグメントとして
CH2=C(R1)COOQRf/CH2=C(CH3)
COOR3の重量比が70/30〜100/0、特に80/20
〜95/5のものを選定するのが望ましい。
前記の如き幹セグメントへ枝セグメントがグラ
フトされたポリマーの合成法としては、通常の溶
液重合、乳化重合などによつて合成した幹セグメ
ントに対し、(1)連鎖移動法、(2)ポリマーラジカル
開始法、(3)Ce()による開始法、(4)高分子反応
法などが例示され、これらは下記に示される。
尚、以下の例では、CH2=C(CH3)COOQRf
をFMAにて示す。
(1) 連鎖移動法
(2) ポリマーラジカル開始法
(3) Ce()による開始法
(4) 高分子反応法
又、本発明においては、ブロツク化された
PFA基を有する枝セグメントをもつたモノマー
(以下、マクロマーと呼ぶ)を合成し、該マクロ
マーを幹セグメントの主成分〔A〕,〔B〕と共重
合させることによつても、本発明の撥水撥油剤が
製造され得る。
(5) マクロマー法
かゝるマクロマーを他のモノマーと共重合させ
る方法としては、通常の重合方法、例えば溶液重
合、乳化重合等を用いることができる。溶液重合
においては、該マクロマーを溶解する溶媒、例え
ばベンゾトリフロライド、1,1,2―トリフロ
ロトリクロロエタン、アセトン、テトラヒドロフ
ラン、酢酸エチル又はこれらの混合溶媒を用い、
30〜120℃で重合するのが通例である。乳化重合
においても、同様にこれら溶媒共存下で行なうの
が望ましい。
次に、本発明の実施例について更に具体的に説
明するが、かゝる説明によつて本発明が何ら限定
されるものでないことは勿論である。尚、撥水性
はJIS L―1005、撥油性はAATCC―TM118
(1966)により測定した。耐摩擦性は、東洋精機
アクセラローターを使用し、2000rpmにて所定時
間処理した後の撥水性、撥油性を測定して評価し
た。また、耐洗たく性は、家庭用電気洗たく機を
使用し、洗剤(ブルーダイヤ:商品名)55gr、浴
量20、40℃、10分間洗たくした後、10分間すす
ぎ、次いで乾燥するという工程を1回とし、所定
回数後の撥水性、撥油性を測定して評価した。
実施例 1
撹拌機、冷却管、温度計、窒素ガス導入管を備
えた300mlの四ツ口フラスコに、テトラヒドロフ
ラン(THF)80mlを入れ、窒素ガスを流し約30
分間脱気した。エチルアクリレート(EA)30gr、
2―ヒドロキシエチルアクリレート(HEA)
20gr及びアリルメタクリレート(AM)2.5grを
仕込み、さらに脱気を続け、温度を30℃にした。
開始剤ジーイソプロピルパーオキシジカーボネー
ト0.25grを加え、温度を28〜30℃に保ち18時間反
応させると、EA,HEA,AMの転化率はガスク
ロマトグラフイーにより100%であつた。反応終
了後、THFが還流するまで温度を上げ、CnF2o+1
CH2CH2OCOC(CH3)=CH2(=8.9,FMA)
110gr、メチルメタクリレート(MMA)11gr、
及び開始剤ブチルパーオキシイソブチレート
0.5grを加え、温度を70〜72℃に保ちながら反応
させると、18時間でFMA,MMAの転化率がガ
スクロマトグラフイーで100%になつたので、反
応を停止させた。
かくして得られた反応液をトリクロロトリフル
オロエタン/メタノール(70/30:容量比)混合
溶媒によつて所定濃度に希釈調整し、この希釈液
にポリエステル布を1分間浸漬し、30分間風乾、
次いで150℃で3分間熱処理して、撥水撥油加工
処理を行なつた。このように処理した布につい
て、初期及び摩擦後、洗たく後の撥水性、撥油性
を下記第1表に示す。比較として、Rf基を有す
るランダム共重合体からなる撥水撥油剤(市販
品)の性能についても、下記第1表に示す。撥油
性/撥水性の表示で示している。It consists of a copolymer whose main component is [Formula]. R is an alkyl group, usually an alkyl group having 1 to 8 carbon atoms, preferably a lower alkyl group having 1 to 3 carbon atoms. It is important that component [A] is an acrylate; if it is a methacrylate, the durability imparting effect will be insufficient. R 1 may be a hydrogen atom or a methyl group, and R 2 is a hydrogen atom or an alkyl group, preferably a hydrogen atom or a lower alkyl group such as a methyl group. Particularly preferred trunk segments include R being an ethyl group;
It is a copolymer mainly composed of ethyl acrylate and 2-hydroxyethyl acrylate in which R 1 and R 2 are hydrogen atoms. The trunk segment in the present invention is [A]/[B]
The weight ratio is 10/90 to 90/10, preferably 20/80 to
80/20, especially 50/50 to 75/25 is adopted. And the trunk segments are [A] and [B]
It may consist only of the main component, or it may contain other crosslinking components, graft active components, etc. [X]. The content of [X] can be selected from a range of 0 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the trunk segment. As [X], component [B] can be used as a graft or crosslinking component, but N-methylol acrylamide,
Crosslinking components such as N-butoxymethylacrylamide and glycidyl methacrylate, allyl methacrylate and P-isopropylstyrene may be selected depending on the necessity of the grafting means. In the present invention, [A], [B] of the trunk segment
The reason why the main components are effective in improving the durability of polyester fibers etc. is not necessarily clear, but the interfacial tension with the fiber material is small (especially the [A] component),
This is thought to be because it contains factors that are advantageous for adhesion to fiber materials, such as hydrogen bonding of OH groups (component [B]), low glass transition point, and ease of forming into a film. It goes without saying that such explanations are provided to aid understanding of the present invention, and do not limit the present invention in any way. The branch segment in the present invention has a blocked polyfluoroalkyl group. The polyfluoroalkyl group (hereinafter sometimes abbreviated as PFA group) is usually selected from those having 4 to 20 carbon atoms, and is preferably a perfluoroalkyl group. In particular, perfluoroalkyl groups having 6 to 18 carbon atoms are preferred. A plurality of such PFA groups, preferably three or more, particularly five or more, are contained in the branch segment. Various means for blocking the PFA group may be employed. For example, there is a method of graft polymerizing a PFA group-containing monomer to a backbone polymer. As a branch segment, CH 2
A homopolymer of =C(R 1 )COOQR f or a copolymer of this with alkyl acrylate, alkyl methacrylate, styrene, etc. can be exemplified. R 1 is a hydrogen atom or a methyl group, Q is 1 carbon number
~10 divalent alkylene groups, R f has ~6 carbon atoms
18 perfluoroalkyl groups, preferably
R 1 is a methyl group, and Q is -CH 2 CH 2 -. As a component to be copolymerized with CH 2 =C(R 1 )COOQR f as a branch segment, CH 2 =C(CH 3 )COOR 3
(R 3 is an alkyl group having 1 to 4 carbon atoms) is preferable. In a preferred embodiment, as a branch segment
CH2 =C( R1 ) COOQRf / CH2 =C( CH3 )
COOR 3 weight ratio is 70/30 to 100/0, especially 80/20
It is desirable to select one with a rating of ~95/5. Methods for synthesizing polymers in which branch segments are grafted onto trunk segments as described above include (1) chain transfer method, (2) polymer radical initiation, for trunk segments synthesized by conventional solution polymerization, emulsion polymerization, etc. (3) Ce() initiation method, (4) polymer reaction method, etc., and these are shown below. In addition, in the following example, CH 2 =C(CH 3 )COOQR f
is shown in FMA. (1) Chain transfer method (2) Polymer radical initiation method (3) Starting method with Ce() (4) Polymer reaction method In addition, in the present invention, blocked
The repellent of the present invention can also be obtained by synthesizing a monomer having a branch segment having a PFA group (hereinafter referred to as a macromer) and copolymerizing the macromer with the main components [A] and [B] of the trunk segment. Water and oil repellents can be produced. (5) Macromer method As a method for copolymerizing such a macromer with other monomers, conventional polymerization methods such as solution polymerization and emulsion polymerization can be used. In solution polymerization, a solvent that dissolves the macromer, such as benzotrifluoride, 1,1,2-trifluorotrichloroethane, acetone, tetrahydrofuran, ethyl acetate, or a mixed solvent thereof, is used,
It is customary to polymerize at 30-120°C. Emulsion polymerization is also preferably carried out in the presence of these solvents. Next, embodiments of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations. In addition, water repellency is JIS L-1005, oil repellency is AATCC-TM118.
(1966). Abrasion resistance was evaluated by measuring water repellency and oil repellency after processing at 2000 rpm for a predetermined time using a Toyo Seiki Accela rotor. In addition, the washing resistance was determined by washing once for 10 minutes at 40℃ using a household electric washing machine using 55g of detergent (Blue Diamond: product name), bath volume 20, rinsing for 10 minutes, and then drying. The water repellency and oil repellency were measured and evaluated after a predetermined number of times. Example 1 80 ml of tetrahydrofuran (THF) was placed in a 300 ml four-necked flask equipped with a stirrer, cooling tube, thermometer, and nitrogen gas inlet tube, and nitrogen gas was passed through it for about 30 minutes.
Degassed for a minute. Ethyl acrylate (EA) 30gr,
2-Hydroxyethyl acrylate (HEA)
20 gr and allyl methacrylate (AM) 2.5 gr were charged, and degassing was continued to bring the temperature to 30°C.
After adding 0.25 gr of initiator diisopropyl peroxydicarbonate and reacting for 18 hours while maintaining the temperature at 28-30°C, the conversion rate of EA, HEA, and AM was 100% as determined by gas chromatography. After the reaction is complete, increase the temperature until THF refluxes, and CnF 2o+1
CH 2 CH 2 OCOC (CH 3 ) = CH 2 (=8.9, FMA)
110gr, methyl methacrylate (MMA) 11gr,
and initiator butyl peroxyisobutyrate
When 0.5 gr was added and the reaction was carried out while maintaining the temperature at 70 to 72°C, the conversion of FMA and MMA reached 100% by gas chromatography in 18 hours, so the reaction was stopped. The reaction solution thus obtained was diluted to a predetermined concentration with a mixed solvent of trichlorotrifluoroethane/methanol (70/30: volume ratio), a polyester cloth was immersed in this diluted solution for 1 minute, and air-dried for 30 minutes.
Next, it was heat treated at 150°C for 3 minutes to make it water and oil repellent. The water repellency and oil repellency of the cloth treated in this manner are shown in Table 1 below, including initially, after rubbing, and after washing. For comparison, the performance of a water and oil repellent (commercially available) made of a random copolymer having an R f group is also shown in Table 1 below. Indicated by oil repellency/water repellency.
【表】
実施例 2〜11
実施例1と同様の方法で種々の組成の幹セグメ
ント及び枝セグメントを持つ共重合体を合成し、
0.05%希釈液でポリエステル布を撥水撥油加工処
理した場合の性能について、下記第2表に示す。
尚、幹セグメント/枝セグメントの重量比は30/
70である。[Table] Examples 2 to 11 Copolymers having trunk segments and branch segments of various compositions were synthesized in the same manner as in Example 1,
Table 2 below shows the performance of polyester cloth treated with a water- and oil-repellent treatment using a 0.05% diluted solution.
The weight ratio of trunk segment/branch segment is 30/
It is 70.
【表】
実施例 12
実施例1と同様の四ツ口フラスコに、イオン交
換水120gr、ジメチルスルホキシド60gr、EA/ヒ
ドロキシプロピルアクリレート(HPA)共重合
体(EA/HPAの重量比60/40)20gr、及び
FA20grを入れ、40℃にて脱気を行なつた。約30
分後に、(NH4)2Ce(NO3)6を0.40gr加え、更に撹
拌しながら25〜40℃の温度を保つた。3時間後に
ガスクロマトグラフイーによりFAの転化率が100
%となつていることが判つたので、反応を停止
し、生成した白色固体沈澱を別、洗浄、乾燥し
て、ポリマー固体38.6grを得た。この固体をトリ
クロロトリフルオロエタン/THF(70/30:容量
比)の混合溶媒に溶解し、0.05%希釈液で実施例
1と同様の方法によりポリエステル布を撥水撥油
加工処理し、耐摩擦性を評価した。尚、比較例と
して同一組成のランダム共重合体の性能も評価し
た。評価結果を下記第3表に示す。[Table] Example 12 In a four-necked flask similar to Example 1, add 120 gr of ion exchange water, 60 gr of dimethyl sulfoxide, and 20 gr of EA/Hydroxypropyl acrylate (HPA) copolymer (EA/HPA weight ratio 60/40). ,as well as
FA20gr was added and degassed at 40°C. about 30
After minutes, 0.40 gr of (NH 4 ) 2 Ce(NO 3 ) 6 was added and the temperature was maintained at 25-40° C. with further stirring. After 3 hours, gas chromatography showed that the conversion rate of FA was 100.
%, the reaction was stopped, and the white solid precipitate formed was separated, washed, and dried to obtain 38.6 gr of polymer solid. This solid was dissolved in a mixed solvent of trichlorotrifluoroethane/THF (70/30: volume ratio), and polyester cloth was treated with a water- and oil-repellent treatment using a 0.05% diluted solution in the same manner as in Example 1. The gender was evaluated. As a comparative example, the performance of a random copolymer having the same composition was also evaluated. The evaluation results are shown in Table 3 below.
【表】
実施例 13
実施例1と同様の四ツ口フラスコに、テトラヒ
ドロフラン(THF)を80gr、FMA72gr、
MMA8gr、チオグリコール酸(TGA)0.64grを
入れ約30分間窒素下で脱気した。脱気後、温度を
60℃に上げ、α,α′―アゾビスイソブチロニトリ
ル(AIBN)0.2grを入れ、低重合反応を行わせ
た。18時間後、ガスクロマトグラフイーでFMA,
MMAが99%以上反応していることを確認した
後、反応混合液を800grのメタノール中に再沈さ
せ、生成枝セグメントポリマーを得、これを減圧
下で乾燥させ、73.6grの淡黄色固体を得た。
この枝セグメント70grと、エチルアクリレー
ト/ヒドロキシエチルアクリレート共重合体(重
量比80/20)70grをベンゾトリフロライド500gr
中に入れ、パラトルエンスルホン酸7grを加え、
生成する水を除去しながら100〜110℃でエステル
化反応を行わせた。
得られたポリマーの性能は実施例10のポリマー
と同等であつた。
実施例 14
実施例13と同様の方法で、チオグリコール酸の
代わりにチオグリコールを用いて枝セグメントを
得た。この枝セグメント70grを1,1,2―トリ
フロロトリクロロエタン/THF(50/50重量比)
混合溶媒140grに溶かし、さらにピリジン3.25gr
を加えた。反応液を30〜35℃に保つように、アク
リル酸クロライド3.72grを滴下し、エステル化反
応を行わせた。4時間後、反応混合物を2100grの
メタノール中に再沈させ、得られた沈澱を減圧下
で乾燥させると、淡黄色固体を71.2gr得た。
この生成物のベンゾトリフロライド中での核磁
気共鳴スペクトルを測定すると、ビニル性プロト
ン(CH2=CH―)がσ価3.4〜4.4に観察され、
二重結合を有するマクロマーであることが確認さ
れた。
実施例1と同様の四ツ口フラスコに、このマク
ロマー35gr、エチルアクリレート(EA)21gr、
ヒドロキシエチルアクリレート(HEA)14gr、
ベンゾトリフロライド280grを入れ、脱気後温度
を60℃にし、AIBN0.2grを加えて重合反応を行
わせた。10時間後に、ガスクロマトグラフイーに
よつてEA,HEAが完全に反応していることを確
認した。
生成したポリマーの性能は実施例11のものと同
等であつた。[Table] Example 13 In a four-necked flask similar to Example 1, 80gr of tetrahydrofuran (THF), 72gr FMA,
MMA8gr and thioglycolic acid (TGA) 0.64gr were added and degassed under nitrogen for about 30 minutes. After degassing, reduce the temperature
The temperature was raised to 60°C, and 0.2g of α,α′-azobisisobutyronitrile (AIBN) was added to carry out a low polymerization reaction. After 18 hours, FMA was detected by gas chromatography.
After confirming that 99% or more of MMA has reacted, the reaction mixture was reprecipitated into 800gr of methanol to obtain the resulting branched segment polymer, which was dried under reduced pressure to produce 73.6gr of pale yellow solid. Obtained. 70gr of this branch segment, 70gr ethyl acrylate/hydroxyethyl acrylate copolymer (weight ratio 80/20), and 500gr benzotrifluoride.
Put it inside, add 7gr of paratoluenesulfonic acid,
The esterification reaction was carried out at 100 to 110°C while removing the produced water. The performance of the obtained polymer was comparable to that of the polymer of Example 10. Example 14 A branch segment was obtained in the same manner as in Example 13 using thioglycol instead of thioglycolic acid. 70gr of this branch segment was mixed with 1,1,2-trifluorotrichloroethane/THF (50/50 weight ratio)
Dissolve in 140gr of mixed solvent and add 3.25gr pyridine.
added. 3.72 gr of acrylic acid chloride was added dropwise while maintaining the reaction solution at 30 to 35°C to carry out the esterification reaction. After 4 hours, the reaction mixture was reprecipitated into 2100 gr of methanol and the resulting precipitate was dried under reduced pressure to obtain 71.2 gr of a pale yellow solid. When the nuclear magnetic resonance spectrum of this product in benzotrifluoride was measured, a vinylic proton (CH 2 =CH-) was observed at a σ value of 3.4 to 4.4.
It was confirmed that it is a macromer with a double bond. In a four-neck flask similar to Example 1, 35 gr of this macromer, 21 gr of ethyl acrylate (EA),
Hydroxyethyl acrylate (HEA) 14gr,
280gr of benzotrifluoride was added, and after degassing, the temperature was raised to 60°C, and 0.2gr AIBN was added to carry out a polymerization reaction. After 10 hours, complete reaction of EA and HEA was confirmed by gas chromatography. The performance of the produced polymer was comparable to that of Example 11.
Claims (1)
有する枝セグメントが幹セグメントに結合してな
るポリマーからなる撥水撥油剤において、幹セグ
メントが[A]CH2=CHCOOR(但し、Rはアル
キル基)と【式】 (但し、R1は水素原子又はメチル基、R2は水素原
子又はアルキル基)とを主成分として構成され、
[A]/[B]の重量比が10/90〜90/10であり、
枝セグメントがポリフルオロアルキル基を5個以
上有していることを特徴とする撥水撥油剤。 2 ポリフルオロアルキル基が炭素数6〜18個の
パーフルオロアルキル基である特許請求の範囲第
1項記載の撥水撥油剤。 3 幹セグメント/枝セグメントの重量比が20/
80〜70/30である特許請求の範囲第1項記載の撥
水撥油剤。 4 枝セグメントがCH2=C(R1)COOQRf(但
し、R1は水素原子又はメチル基、Qは炭素数1
〜10個の二価のアルキレン基、Rfは炭素数6〜
18個のパーフルオロアルキル基)を主成分として
構成されている特許請求の範囲第1項記載の撥水
撥油剤。[Scope of Claims] 1. A water and oil repellent made of a polymer in which a branch segment having a blocked polyfluoroalkyl group is bonded to a trunk segment, wherein the trunk segment is [A]CH 2 =CHCOOR (where R is an alkyl group) and [Formula] (where R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or an alkyl group),
The weight ratio of [A]/[B] is 10/90 to 90/10,
A water- and oil-repellent agent characterized in that the branch segments have five or more polyfluoroalkyl groups. 2. The water and oil repellent according to claim 1, wherein the polyfluoroalkyl group is a perfluoroalkyl group having 6 to 18 carbon atoms. 3 Weight ratio of trunk segment/branch segment is 20/
The water and oil repellent according to claim 1, which has a ratio of 80 to 70/30. 4 The branch segment is CH 2 = C (R 1 ) COOQR f (where, R 1 is a hydrogen atom or a methyl group, and Q is a carbon number of 1
~10 divalent alkylene groups, R f has ~6 carbon atoms
18. The water and oil repellent according to claim 1, which is composed mainly of 18 perfluoroalkyl groups.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6639380A JPS56163183A (en) | 1980-05-21 | 1980-05-21 | Highly durable water- and oil-repellant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6639380A JPS56163183A (en) | 1980-05-21 | 1980-05-21 | Highly durable water- and oil-repellant |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS56163183A JPS56163183A (en) | 1981-12-15 |
JPS6321715B2 true JPS6321715B2 (en) | 1988-05-09 |
Family
ID=13314522
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6639380A Granted JPS56163183A (en) | 1980-05-21 | 1980-05-21 | Highly durable water- and oil-repellant |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS56163183A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2811183B2 (en) * | 1988-08-25 | 1998-10-15 | 株式会社リコー | Fluorine-containing graft copolymer |
KR101159536B1 (en) * | 2004-07-06 | 2012-06-26 | 가부시키가이샤 노다스크린 | Graft copolymer, coating material, and method of forming coating film |
US7402624B2 (en) | 2004-11-08 | 2008-07-22 | E.I. Du Pont De Nemours & Company | Graft copolymers with segmented arms and their preparation and use |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5243955A (en) * | 1975-10-02 | 1977-04-06 | Tokuyama Soda Co Ltd | System link method |
JPS54132694A (en) * | 1978-04-07 | 1979-10-15 | Asahi Glass Co Ltd | Preparation of high-performance water- and oil-repellent |
-
1980
- 1980-05-21 JP JP6639380A patent/JPS56163183A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5243955A (en) * | 1975-10-02 | 1977-04-06 | Tokuyama Soda Co Ltd | System link method |
JPS54132694A (en) * | 1978-04-07 | 1979-10-15 | Asahi Glass Co Ltd | Preparation of high-performance water- and oil-repellent |
Also Published As
Publication number | Publication date |
---|---|
JPS56163183A (en) | 1981-12-15 |
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