U.S. patent application number 16/079239 was filed with the patent office on 2019-02-28 for nonwoven fabric.
This patent application is currently assigned to DAIKIN INDUSTRIES, LTD.. The applicant listed for this patent is DAIKIN INDUSTRIES, LTD.. Invention is credited to Kazuya KAWAHARA, Eiji MASUDA, Kazuki SAKAMI.
Application Number | 20190062969 16/079239 |
Document ID | / |
Family ID | 59789683 |
Filed Date | 2019-02-28 |
United States Patent
Application |
20190062969 |
Kind Code |
A1 |
MASUDA; Eiji ; et
al. |
February 28, 2019 |
NONWOVEN FABRIC
Abstract
Provided is a nonwoven fabric which is formed from a resin
composition and has improved antifouling properties, sound
insulation properties, coefficient of friction, and texture. This
nonwoven fabric is formed from a resin composition which contains
(1) a thermoplastic resin and (2) a fluorine-containing copolymer,
and wherein: the thermoplastic resin (1) is a polypropylene; and
the fluorine-containing copolymer (2) is a copolymer which has (a)
a repeating unit that is formed of a fluorine-containing monomer
represented by formula CH.sub.2.dbd.C(--X)--C(.dbd.O)--Y--Z--Rf and
(b) a repeating unit that is formed of a non-fluorine monomer
having a hydrocarbon group with 14 or more carbon atoms, and which
has a weight average molecular weight of 2,500-20,000.
Inventors: |
MASUDA; Eiji; (Osaka-shi,
Osaka, JP) ; SAKAMI; Kazuki; (Osaka-shi, Osaka,
JP) ; KAWAHARA; Kazuya; (Osaka-shi, Osaka,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DAIKIN INDUSTRIES, LTD. |
Osaka-shi, Osaka |
|
JP |
|
|
Assignee: |
DAIKIN INDUSTRIES, LTD.
Osaka-shi, Osaka
JP
|
Family ID: |
59789683 |
Appl. No.: |
16/079239 |
Filed: |
March 6, 2017 |
PCT Filed: |
March 6, 2017 |
PCT NO: |
PCT/JP2017/008680 |
371 Date: |
August 23, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D04H 1/56 20130101; D04H
1/544 20130101; D04H 3/16 20130101; D10B 2509/00 20130101; D10B
2401/021 20130101; D04H 1/565 20130101; D04H 1/4291 20130101; D10B
2321/02 20130101; D04H 3/007 20130101; D04H 1/4318 20130101; D10B
2321/042 20130101; D01D 5/0985 20130101 |
International
Class: |
D04H 1/4291 20060101
D04H001/4291; D04H 1/4318 20060101 D04H001/4318; D04H 1/56 20060101
D04H001/56; D04H 3/007 20060101 D04H003/007; D04H 3/16 20060101
D04H003/16 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 11, 2016 |
JP |
2016-048579 |
Claims
1. A nonwoven fabric comprising a resin composition comprising: (1)
a thermoplastic resin, and (2) a fluorine-containing copolymer,
wherein the thermoplastic resin (1) is polypropylene, and the
fluorine-containing copolymer (2) is a copolymer which comprises:
(a) a repeating unit formed from a fluorine-containing monomer
represented by the formula:
CH.sub.2.dbd.C(--X)--C(.dbd.O)--Y--Z--Rf wherein X is a hydrogen
atom, a monovalent organic group or a halogen atom, Y is --O-- or
--NH--, Z is a direct bond or an divalent organic group, and Rf is
a fluoroalkyl group having 4 to 6 carbon atoms, and (b) a repeating
unit formed from a fluorine-free monomer containing a hydrocarbon
group having at least 14 carbon atoms, and which has a
weight-average molecular weight of 2,500 to 20,000.
2. The nonwoven fabric according to claim 1, wherein, in the
fluorine-containing monomer (a), X is a methyl group and Z is a
linear alkylene group or branched alkylene group having 1-20 carbon
atoms.
3. The nonwoven fabric according to claim 1, wherein the
fluorine-free monomer (b) is a (meth)acrylate ester in which an
acryloyloxy group is bonded to a monovalent non-cyclic hydrocarbon
group or cyclic hydrocarbon group having 14-30 carbon atoms.
4. The nonwoven fabric according to claim 1, wherein the
fluorine-free monomer (b) is an acrylate ester in which an
alpha-position is a hydrogen atom.
5. The nonwoven fabric according to claim 1, wherein the
fluorine-containing copolymer (2) further comprises (c) a repeating
unit formed from a fluorine-free crosslinkable monomer, and the
amount of the monomer (c) is 0.1 to 100 parts by weight, based on
100 parts by weight of the total of the monomer (a) and the monomer
(b).
6. The nonwoven fabric according to claim 1, wherein the
fluorine-containing copolymer (2) has a weight-average molecular
weight of 3,000 to 15,000.
7. The nonwoven fabric according to claim 1, wherein, in the
fluorine-containing copolymer (2), a weight ratio of the
fluorine-containing monomer (a) to the fluorine-free monomer (b) is
35:65 to 70:30 and the amount of the fluorine-containing monomer
(a) is at least 25 wt %, based on the fluorine-containing
copolymer.
8. The nonwoven fabric according to claim 1, wherein the resin
composition has a melt flow rate (MFR) of at least 600 g/10
minutes.
9. The nonwoven fabric according to claim 1, wherein a fiber in the
nonwoven fabric has an average fiber diameter of 0.1 to 5
micrometers.
10. The nonwoven fabric according to claim 1, wherein the amount of
the fluorine-containing copolymer (2) is 0.01 to 50 parts by
weight, based on 100 parts by weight of the thermoplastic resin
(1).
11. A method of producing a nonwoven fabric, comprising steps of:
(i) mixing a thermoplastic resin (1) with a fluorine-containing
copolymer (2) to obtain a resin composition; and (ii) spinning
fibers from a melt of the resin composition which is pressure-fed
to a die by a melt blowing method, with a nozzle having a large
number of arranged small holes, wherein the thermoplastic resin (1)
is polypropylene, and the fluorine-containing copolymer (2) is a
copolymer which comprises: (a) a repeating unit formed from a
fluorine-containing monomer represented by the formula:
CH.sub.2.dbd.C(--X)--C(.dbd.O)--Y--Z--Rf wherein X is a hydrogen
atom, a monovalent organic group or a halogen atom, Y is --O-- or
--NH--, Z is a direct bond or an divalent organic group, and Rf is
a fluoroalkyl group having 4 to 6 carbon atoms, and (b) a repeating
unit formed from a fluorine-free monomer containing a hydrocarbon
group having at least 14 carbon atoms, and which has a
weight-average molecular weight of 2,500 to 20,000.
Description
TECHNICAL FIELD
[0001] The present invention relates to a nonwoven fabric formed
from a resin composition comprising a thermoplastic resin and a
fluorine-containing copolymer.
BACKGROUND ART
[0002] Hitherto, disclosed is a technology of nonwoven fabric which
adding a fluorine-containing polymer to a thermoplastic resin.
[0003] WO 01/053585A discloses a nonwoven fabric prepared by adding
a lubricant comprising a vinylidene fluoride/hexafluoropropylene
copolymer as processing aid to polypropylene. However, there is no
surface modification effect in this nonwoven fabric comprising the
fluorine-containing copolymer.
[0004] JP H09-511700A discloses a method of increasing a
head-of-water pressure and an intensity to a nonwoven fabric having
an average fiber diameter of at least 10 micrometers comprising a
specific fluorocarbon. JP 2002-521586A discloses a method of giving
water repellency and alcohol repellency to a nonwoven fabric
surface by adding a fluorine-containing additive agent to a
specific region. These methods have a surface modification effect,
but other effects cannot be seen.
[0005] JP 2006-37085A discloses a method of mixing a
fluorine-containing copolymer with a thermoplastic resin to
performing a surface modification. However, only water- and
oil-repellency specialized in alcohol repellency is indicated as an
effect, but other effects cannot be seen.
PRIOR ART DOCUMENT
Patent Document
[0006] Patent document 1: WO 01/053585 A
[0007] Patent document 2: JP H09-511700A
[0008] Patent document 3: JP 2002-521586A
[0009] Patent document 4: JP 2006-37085A
SUMMARY OF THE INVENTION
Problem to be Solved by the Invention
[0010] An object of the present invention is to provide a nonwoven
fabric formed from a resin composition having improved antifouling
property, sound insulation property, friction coefficient and touch
feeling property.
Means for Solving Problem
[0011] The present invention relates to a nonwoven fabric formed
from a resin composition comprising (1) a thermoplastic resin, and
(2) a fluorine-containing copolymer.
[0012] The present invention provides a nonwoven fabric formed from
a resin composition comprising:
(1) a thermoplastic resin, and (2) a fluorine-containing copolymer,
wherein the thermoplastic resin (1) is polypropylene, and the
fluorine-containing copolymer is a copolymer which comprises:
[0013] (a) a repeating unit formed from a fluorine-containing
monomer represented by the formula:
CH.sub.2.dbd.C(--X)--C(.dbd.O)--Y--Z--Rf
wherein X is a hydrogen atom, a monovalent organic group or a
halogen atom,
Y is --O-- or --NH--,
[0014] Z is a direct bond or an divalent organic group, and Rf is a
fluoroalkyl group having 4 to 6 carbon atoms, and
[0015] (b) a repeating unit formed from a fluorine-free monomer
containing a hydrocarbon group having at least 14 carbon atoms,
and
[0016] which has a weight-average molecular weight of 2,500 to
20,000.
[0017] In addition, the present invention provides a method of
producing a nonwoven fabric, comprising steps of:
(i) mixing a thermoplastic resin (1) with a fluorine-containing
copolymer (2) to obtain a resin composition; and (ii) spinning a
melt of the resin composition which is pressure-fed to a die by a
melt blowing method, from a nozzle having a large number of
arranged small holes.
Effect of the Invention
[0018] In the present invention, the resin composition (or the
antifouling resin composition) can be processed into a nonwoven
fabric with high processing characteristics. A melt flow rate (MFR)
of the resin composition is improved. Further, processing stability
at the time of preparation of the nonwoven fabric is high, and the
productivity of the nonwoven fabric is high.
[0019] According to the present invention, a surface-modified
nonwoven fabric is obtained. The nonwoven fabric of the present
invention has excellent antifouling properties, sound insulation
properties, and water-proof pressure. Furthermore, the nonwoven
fabric of the present invention has excellent wiping easiness and
scratch resistance. In addition, the nonwoven fabric has a good
touch feeling due to a decrease in a coefficient of friction.
[0020] According to the present invention, a nonwoven fabric having
a small fiber diameter and a high density can be obtained.
MODES FOR CARRYING OUT THE INVENTION
(1) Thermoplastic Resin
[0021] The thermoplastic resin is polypropylene.
[0022] Examples of polypropylene are isotactic polypropylene,
syndiotactic polypropylene, atactic polypropylene, and amorphous
polypropylene.
[0023] The isotactic polypropylene is a highly crystalline
polypropylene based on isotactic polypropylene prepared by a
Ziegler-Natta catalyst or a metallocene catalyst.
[0024] The amorphous polypropylene is, for example, propylene
having extremely low crystallinity prepared by using a metallocene
catalyst. The amorphous polypropylene may be a mixture of
polypropylene having extremely low crystallinity (for example, at
least 50 wt % of a total amount of the mixture) produced by using a
metallocene catalyst, with other propylene. The amorphous
polypropylene is available as, for example, TAFTHREN T-3512 and
T-3522 manufactured by Sumitomo Chemical Co., Ltd., and L-MODU
S-400, S-600 and S-901 manufactured by Idemitsu Kosan Co., Ltd.
[0025] In the present invention, the thermoplastic resin may be one
or a combination of at least two.
(2) Fluorine-Containing Copolymer
[0026] The fluorine-containing copolymer (2) is a copolymer having
a repeating unit formed from the fluorine-containing monomer (a)
and a repeating unit formed from the fluorine-free monomer (b). The
fluorine-containing monomer (a) is a monomer containing a
fluoroalkyl group having 4 to 6 carbon atoms. The fluorine-free
monomer (b) is a monomer containing a non-cyclic or cyclic
hydrocarbon group having at least 14 carbon atoms, which may
contain a nitrogen, oxygen and/or sulfur atom. The
fluorine-containing copolymer (2) may have a repeating unit formed
from another monomer (c) other than the fluorine-containing monomer
(a) and the fluorine-free monomer (b).
[0027] The fluorine-containing monomer (a) is a monomer of the
formula:
CH.sub.2.dbd.C(--X)--C(.dbd.O)--Y--Z--Rf
wherein X is a hydrogen atom, a monovalent organic group or a
halogen atom,
Y is --O-- or --NH--,
[0028] Z is a direct bond or an divalent organic group, and Rf is a
fluoroalkyl group having 4 to 6 carbon atoms.
[0029] X is, for example, a hydrogen atom, a methyl group, a
halogen atom, a linear or branched alkyl group having 2 to 21
carbon atoms, a CFX.sup.1X.sup.2 group (where each of X.sup.1 and
X.sup.2 is a hydrogen atom, a fluorine atom, a chlorine atom, a
bromine atom or an iodine atom), a cyano group, a linear or
branched fluoroalkyl group having 1 to 21 carbon atoms, a
substituted or unsubstituted benzyl group or a substituted or
unsubstituted phenyl group.
[0030] In the fluorine-containing copolymer of the present
invention, X is preferably a hydrogen atom, a methyl group, a
fluorine atom, or a chlorine atom. X is especially a methyl group,
since antifouling property is high.
[0031] Y is preferably --O--.
[0032] Z is, for example, a direct bond,
a linear alkylene group or branched alkylene group having 1-20
carbon atoms, such as a group represented by the formula
--(CH.sub.2).sub.x-- wherein x is 1 to 10, a group represented by
the formula --SO.sub.2N(R.sup.1)R.sup.2-- or the formula
--CON(R.sup.1)R.sup.2-- wherein R.sup.1 is an alkyl group having 1
to 10 carbon atoms and R.sup.2 is a linear alkylene group or
branched alkylene group having 1 to 10 carbon atoms, a group
represented by the formula --CH.sub.2CH(OR.sup.3)CH.sub.2-- wherein
R.sup.3 is a hydrogen atom or an acyl group having 1 to 10 carbon
atoms (for example, a formyl group or an acetyl group),
--Ar--(CH.sub.2).sub.r-- wherein Ar is an arylene group optionally
having a substituent group, and r is 0 to 10, or a
--(CH.sub.2).sub.m--SO.sub.2--(CH.sub.2).sub.n-- group or a
--(CH.sub.2).sub.m--S--(CH.sub.2).sub.n-- group wherein m is 1-10,
and n is 0-10.
[0033] In the fluorine-containing copolymer of the present
invention, Z is preferably a direct bond, an alkylene group having
1-20 carbon atoms, or --SO.sub.2N(R.sup.1)R.sup.2--, particularly
preferably --(CH.sub.2).sub.2--.
[0034] The Rf group is preferably a perfluoroalkyl group, but may
be a fluoroalkyl group having a hydrogen atom. The carbon number of
the Rf group is preferably 4 or 6. The carbon number of the Rf
group is particularly preferably 6. Examples of the Rf group
include --CF.sub.2CF.sub.2CF.sub.2CF.sub.3,
--CF.sub.2CF(CF.sub.3).sub.2, --C(CF.sub.3).sub.3,
--(CF.sub.2).sub.5CF.sub.3 and
--(CF.sub.2).sub.3CF(CF.sub.3).sub.2.
[0035] Specific examples of the fluorine-containing monomer (a)
include, but are not limited to, the followings: [0036]
CH.sub.2.dbd.C(--H)--C(.dbd.O)--O--(CH.sub.2).sub.2--Rf [0037]
CH.sub.2.dbd.C(--H)--C(.dbd.O)--O--C.sub.6H.sub.4--Rf [0038]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--Rf [0039]
CH.sub.2.dbd.C(--H)--C(.dbd.O)--O--(CH.sub.2).sub.2N(--CH)SO.sub.2--Rf
[0040]
CH.sub.2.dbd.C(--H)--C(.dbd.O)--O--(CH.sub.2).sub.2N(--C.sub.2H.su-
b.5)SO.sub.2--Rf [0041]
CH.sub.2C(--H)--C(.dbd.O)--O--CH.sub.2CH(--OH)CH(--OH)CH.sub.2--Rf
[0042]
CH.sub.2.dbd.C(--H)--C(.dbd.O)--O--CH.sub.2CH(--OCOCH.sub.3)CH.sub.2--Rf
[0043] CH.sub.2.dbd.C(--H)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--Rf
[0044]
CH.sub.2.dbd.C(--H)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2--
-Rf [0045]
CH.sub.2.dbd.C(--H)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--- Rf
[0046]
CH.sub.2.dbd.C(--H)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2--(-
CH.sub.2).sub.2--Rf [0047]
CH.sub.2.dbd.C(--H)--C(.dbd.O)--NH--(CH.sub.2).sub.2--Rf [0048]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--Rf
[0049] CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--C.sub.6H.sub.4--Rf
[0050]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2N(--CH.sub.3)SO-
.sub.2--Rf [0051]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2N(--C.sub.2H.su-
b.5)SO.sub.2--Rf [0052]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--CH.sub.2CH(--OH)CH.sub.2--Rf
[0053]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--CH.sub.2CH(--OCOCH.sub.3-
)CH.sub.2--Rf [0054]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--Rf
[0055]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--(CH.sub.2)-
.sub.2--Rf [0056]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--Rf
[0057]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub-
.2--(CH.sub.2).sub.2--Rf [0058]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2).sub.2--Rf
[0059] CH.sub.2.dbd.C(--F)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--Rf
[0060]
CH.sub.2.dbd.C(--F)--C(O)--O--(CH.sub.2)--S--(CH.sub.2).sub.2--Rf
[0061]
CH.sub.2.dbd.C(--F)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2--Rf
[0062]
CH.sub.2.dbd.C(--F)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2--(CH.sub.2)-
.sub.2--Rf [0063]
CH.sub.2.dbd.C(--F)--C(.dbd.O)--NH--(CH.sub.2).sub.2--Rf [0064]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--Rf [0065]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--(CH.sub.2).sub.2-
--Rf [0066]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2--Rf
[0067]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2--(CH.sub.2-
).sub.2--Rf [0068]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--NH--(CH.sub.2).sub.2--Rf [0069]
CH.sub.2.dbd.C(--CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--Rf
[0070]
CH.sub.2.dbd.C(--CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--(CH.sub.2)-
.sub.2--Rf [0071]
CH.sub.2.dbd.C(--CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2--Rf
[0072]
CH.sub.2.dbd.C(--CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub-
.2--(CH.sub.2).sub.2--Rf [0073]
CH.sub.2.dbd.C(--CF.sub.3)--C(.dbd.O)--NH--(CH.sub.2).sub.2--Rf
[0074]
CH.sub.2.dbd.C(--CF.sub.2H)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--Rf
[0075]
CH.sub.2.dbd.C(--CF.sub.2H)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--(CH.sub.2-
).sub.2--Rf [0076]
CH.sub.2.dbd.C(--CF.sub.2H)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2--Rf
[0077]
CH.sub.2.dbd.C(--CF.sub.2H)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.su-
b.2--(CH.sub.2).sub.2--Rf [0078]
CH.sub.2.dbd.C(--CF.sub.2H)--C(.dbd.O)--NH--(CH.sub.2).sub.2--Rf
[0079] CH.sub.2.dbd.C(--CN)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--Rf
[0080]
CH.sub.2.dbd.C(--CN)--C(.dbd.O)--O--(CH.sub.2).sub.2S--(CH.sub.2).sub.2---
Rf [0081]
CH.sub.2.dbd.C(--CN)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2---
Rf [0082]
CH.sub.2.dbd.C(--CN)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.sub.2---
(CH.sub.2).sub.2--Rf [0083]
CH.sub.2.dbd.C(--CN)--C(.dbd.O)--NH--(CH.sub.2).sub.2--Rf [0084]
CH.sub.2.dbd.C(--CF.sub.2CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--S--Rf
[0085]
CH.sub.2.dbd.C(--CF.sub.2CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2-
--S--(CH.sub.2).sub.2--Rf [0086]
CH.sub.2.dbd.C(--CF.sub.2CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.su-
b.2--Rf [0087]
CH.sub.2.dbd.C(--CF.sub.2CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.su-
b.2--(CH).sub.2--Rf [0088]
CH.sub.2.dbd.C(--CF.sub.2CF.sub.3)--C(.dbd.O)--NH--(CH.sub.2).sub.2--Rf
[0089] CH.sub.2.dbd.C(--F)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--Rf
[0090]
CH.sub.2.dbd.C(--F)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--(CH.sub.2).sub.2--
-Rf [0091]
CH.sub.2.dbd.C(--F)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--- Rf
[0092]
CH.sub.2.dbd.C(--F)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--(-
CH.sub.2).sub.2--Rf [0093]
CH.sub.2.dbd.C(--F)--C(.dbd.O)--NH--(CH.sub.2).sub.3--Rf [0094]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--Rf [0095]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--(CH.sub.2).sub.2-
--Rf [0096]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--Rf
[0097]
CH.sub.2.dbd.C(--Cl)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--(CH.sub.2-
).sub.2--Rf [0098]
CH.sub.2.dbd.C(--CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--Rf
[0099]
CH.sub.2.dbd.C(--CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--(CH.sub.2)-
.sub.2--Rf [0100]
CH.sub.2.dbd.C(--CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--Rf
[0101]
CH.sub.2.dbd.C(--CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub-
.2--(CH.sub.2).sub.2--Rf [0102]
CH.sub.2.dbd.C(--CF.sub.2H)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--Rf
[0103]
CH.sub.2.dbd.C(--CF.sub.2H)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--(CH.sub.2-
).sub.2--Rf [0104]
CH.sub.2.dbd.C(--CF.sub.2H)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--Rf
[0105]
CH.sub.2.dbd.C(--CF.sub.2H)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.su-
b.2--(CH.sub.2).sub.2--Rf [0106]
CH.sub.2.dbd.C(--CN)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--Rf [0107]
CH.sub.2.dbd.C(--CN)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--(CH.sub.2).sub.2-
--Rf [0108]
CH.sub.2.dbd.C(--CN)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--Rf
[0109]
CH.sub.2.dbd.C(--CN)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.sub.2--(CH.sub.2-
).sub.2--Rf [0110]
CH.sub.2.dbd.C(--CF.sub.2CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.3--S--Rf
[0111]
CH.sub.2.dbd.C(--CF.sub.2CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.3-
--S--(CH.sub.2).sub.2--Rf [0112]
CH.sub.2.dbd.C(--CF.sub.2CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.3--SO.su-
b.2--Rf [0113]
CH.sub.2.dbd.C(--CF.sub.2CF.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--SO.su-
b.2--(CH.sub.2).sub.2--Rf wherein Rf is a fluoroalkyl group having
4 to 6 carbon atoms.
[0114] The fluorine-containing copolymer has the repeating unit
formed from the fluorine-free monomer (b) in addition to the
repeating unit formed from the fluorine-containing monomer (a).
[0115] The fluorine-free monomer (b) is a monomer which contains a
hydrocarbon group (a non-cyclic hydrocarbon group or a cyclic
hydrocarbon group) having at least 14 carbon atoms. The lower limit
of the number of carbon atoms may be 16 or 17. The upper limit of
the number of carbon atoms of the hydrocarbon group may be 30, for
example 25, especially 20.
[0116] The fluorine-free monomer (b) is preferably a
(meth)acrylate. The fluorine-free monomer (b) is preferably a
(meth)acrylate ester wherein an acryloyloxy group is bonded to a
monovalent hydrocarbon group. Particularly preferably, the
fluorine-free monomer (b) is an acrylate ester in which an
alpha-position is a hydrogen atom.
[0117] The fluorine-free monomer (b) may be a fluorine-free
non-crosslinkable monomer (b1). A specific example of the
fluorine-free non-crosslinkable monomer (b1) may be a compound of
the formula:
CH.sub.2.dbd.CA-T
wherein A is a hydrogen atom, a methyl group, or a halogen atom
other than a fluorine atom (for example, a chlorine atom, a bromine
atom, and an iodine atom), T is a hydrocarbon group having 14 to 30
carbon atoms, or an organic group having 15 to 31 carbon atoms and
an ester bond.
[0118] Examples of the hydrocarbon group having 14-30 carbon atoms
are a linear or branched saturated or unsaturated (for example,
ethylenically unsaturated) aliphatic hydrocarbon group having 14 to
30 carbon atoms, a saturated or unsaturated (for example,
ethylenically unsaturated) cycloaliphatic hydrocarbon group having
14 to 30 carbon atoms, an aromatic hydrocarbon group having 14-30
carbon atoms, and an araliphatic hydrocarbon group having 14-30
carbon atoms.
[0119] Examples of the organic group having 15 to 31 carbon atoms
and an ester bond are: --C(.dbd.O)--O-Q and --O--C(.dbd.O)-Q
wherein Q is a linear or branched saturated or unsaturated (for
example, ethylenically unsaturated) aliphatic hydrocarbon group
having 14 to 30 carbon atoms, a saturated or unsaturated (for
example, ethylenically unsaturated) cycloaliphatic hydrocarbon
group having 14 to 30 carbon atoms, an aromatic hydrocarbon group
having 14-30 carbon atoms, or an araliphatic hydrocarbon group
having 14-30 carbon atoms.
[0120] The fluorine-free non-crosslinkable monomer (b1) may be a
(meth)acrylate ester monomer.
[0121] Examples of the (meth)acrylate ester monomer may be a
compound represented by the formula:
CH.sub.2.dbd.CA.sup.21-C(.dbd.O)--O-A.sup.22
wherein A.sup.21 is a hydrogen atom, an organic group, a halogen
atom other than a fluorine atom, and A.sup.22 is a hydrocarbon
group having 14-30 carbon atoms.
[0122] A.sup.21 is preferably a hydrogen atom, a methyl group or a
chlorine atom.
[0123] A.sup.22 (hydrocarbon group) may be a non-cyclic hydrocarbon
group having 14 to 30 carbon atoms and a cyclic hydrocarbon group
having 14 to 30 carbon atoms. A.sup.22 (hydrocarbon group) is
preferably a non-cyclic hydrocarbon group, particularly a chain
hydrocarbon group having 14 to 30 carbon atoms.
[0124] Specific examples of the (meth)acrylate ester monomer having
a non-cyclic hydrocarbon group include cetyl (meth)acrylate,
stearyl (meth)acrylate and behenyl (meth)acrylate.
[0125] The fluorine-containing copolymer according to the present
invention may consist of the fluorine-containing monomer (a) and
the fluorine-free monomer (b) or may comprise another monomer (c)
other than the fluorine-containing monomer (a) and the
fluorine-free monomer (b). The other monomer (c) is preferably free
from a fluorine atom. Examples of the other monomer (c) are (c1) a
fluorine-free crosslinkable monomer or (c2) a halogenated olefin
monomer.
[0126] The fluorine-free crosslinkable monomer (c1) is a monomer
free from a fluorine atom. The fluorine-free crosslinkable monomer
may be a fluorine-free compound having at least one reactive group
and/or olefinic carbon-carbon double bond (preferably a
(meth)acrylate group). The fluorine-free crosslinkable monomer may
be a compound which has at least two olefinic carbon-carbon double
bonds (preferably (meth)acrylate groups) or a compound which has at
least one olefinic carbon-carbon double bond and at least one
reactive group. Examples of the reactive group include a hydroxyl
group, an epoxy group, a chloromethyl group, a blocked isocyanate
group, an amino group, a carboxyl group and a glycidyl group.
[0127] The fluorine-free crosslinkable monomer may be a
mono(meth)acrylate, di(meth)acrylate, or mono(meth)acrylamide
having a reactive group. Alternatively, the fluorine-free
crosslinkable monomer may be di(meth)acrylate.
[0128] Examples of the fluorine-free crosslinkable monomer include,
but are not limited to, diacetone(meth)acrylamide,
N-methylol(meth)acrylamide, hydroxymethyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate,
3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl
(meth)acrylate, butadiene, isoprene, chloroprene, monochlorovinyl
acetate, vinyl methacrylate, glycidyl (meth)acrylate,
1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,
1,9-nonanediol di(meth)acrylate, and neopentylglycol
di(meth)acrylate.
[0129] The fluorine-free crosslinkable monomer may be, for example,
an isocyanatoacrylate monomer. Specific examples of the
isocyanatoacrylate monomer include 2-isocyanatoethyl
(meth)acrylate, 3-isocyanatopropyl (meth)acrylate,
4-isocyanatobutyl (meth)acrylate, 2-butanone oxime adduct of
2-isocyanatoethyl (meth)acrylate, a pyrazole adduct of
2-isocyanatoethyl (meth)acrylate, 3,5-dimethylpyrazole adduct of
2-isocyanatoethyl (meth)acrylate, a 3-methylpyrazole adduct of
2-isocyanatoethyl (meth)acrylate, an epsilon-caprolactam adduct of
2-isocyanatoethyl (meth)acrylate, 2-butanone oxime adduct of
3-isocyanatopropyl (meth)acrylate, a pyrazole adduct of
3-isocyanatopropyl (meth)acrylate, 3,5-dimethylpyrazole adduct of
3-isocyanatopropyl (meth)acrylate, a 3-methylpyrazole adduct of
3-isocyanatopropyl (meth)acrylate, an epsilon-caprolactam adduct of
3-isocyanatopropyl (meth)acrylate, 2-butanone oxime adduct of
4-isocyanatobutyl (meth)acrylate, a pyrazole adduct of
4-isocyanatobutyl (meth)acrylate, 3,5-dimethylpyrazole adduct of
4-isocyanatobutyl (meth)acrylate, a 3-methylpyrazole adduct of
4-isocyanatobutyl (meth)acrylate, and an epsilon-caprolactam adduct
of 4-isocyanatobutyl (meth)acrylate.
[0130] The halogenated olefin monomer (c2) is a monomer free from a
fluorine atom.
[0131] The halogenated olefin monomer may be an olefin having 2-20
carbon atoms and substituted by 1-10 chlorine atoms, bromine atoms
or iodine atoms. Preferably, the halogenated olefin monomer is a
chlorinated olefin having 2-20 carbon atoms, particularly an olefin
having 2-5 carbon atoms and having 1-5 chlorine atoms. Preferable
examples of the halogenated olefin monomer are a vinyl halide such
as vinyl chloride, vinyl bromide and vinyl iodide, and a vinylidene
halide such as vinylidene chloride, vinylidene bromide and
vinylidene iodide.
[0132] The term "(meth)acrylate" as used herein means an acrylate
or methacrylate, and the term "(meth)acrylamide" as used herein
means an acrylamide or methacrylamide.
[0133] Each of the monomers (a)-(c) may be used one alone or in a
combination of at least two. The fluorine-containing copolymers (2)
may be one alone or in a combination of at least two.
[0134] The fluorine-containing copolymer (2) of the present
invention is preferably free from a repeating unit formed from a
fluorine-free monomer containing a hydrocarbon group having at most
13 carbon atoms, for example, a (meth)acrylate ester containing a
hydrocarbon group having at most 13 carbon atoms, particularly a
(meth)acrylate ester containing a non-cyclic hydrocarbon group
having at most 13 carbon atoms. For example, the
fluorine-containing copolymer (2) of the present invention is
preferably free from a repeat unit formed from lauryl acrylate.
High water- and oil-repellency is obtained by being free from these
repeat units.
[0135] A weight ratio of the fluorine-containing monomer (a) to the
fluorine-free monomer (b) in the fluorine-containing copolymer (2)
is preferably 35:65 to 70:30, more preferably 40:60 to 60:40,
particularly 42.5:57.5 to 58:42. The amount of the
fluorine-containing monomer (a) may be at least 25% by weight, for
example, at least 35% by weight, particularly 35 to 60% by weight,
based on the fluorine-containing copolymer.
[0136] The amount of the monomer (c) may be at most 100 parts by
weight, for example, 0.1 to 30 parts by weight, particularly 1 to
20 parts by weight, based on 100 parts by weight of the total of
the monomer (a) and the monomer (b).
[0137] The weight-average molecular weight of the
fluorine-containing polymer may be 2,500 to 20,000, preferably
3,000 to 15,000, for example, 5,000 to 12,000 in terms of
polystyrene, as measured by GPC (gel permeation chromatography).
The polymer of the present invention may be a random copolymer or a
block copolymer, but is generally a random copolymer.
[0138] The amount of the fluorine-containing copolymer (2) may be
0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight,
particularly 0.2 to 10 parts by weight, for example, 1.0 to 8 parts
by weight, more preferably 1.2 to 5.0 parts by weight, based on 100
parts by weight of the thermoplastic resin (1).
[0139] The fluorine-containing copolymer may be obtained by
polymerizing by a known method using a polymerization initiator, a
solvent, and optionally a chain transfer agent.
[0140] The fluorine-containing copolymer and the fluorine-free
polymer in the present invention can be produced by any of
conventional polymerization methods and the polymerization
condition can be optionally selected. The polymerization method
includes, for example, a solution polymerization, a suspension
polymerization and an emulsion polymerization.
[0141] In the solution polymerization, there can be used a method
of dissolving the monomer(s) into an organic solvent in the
presence of a polymerization initiator, replacing the atmosphere by
nitrogen, and stirring the mixture with heating at the temperature
within the range from 30.degree. C. to 120.degree. C. for 1 hour to
10 hours. Examples of the polymerization initiator include
azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide,
lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and
diisopropyl peroxydicarbonate. The polymerization initiator may be
used in the amount within the range from 0.01 to 20 parts by
weight, for example, from 0.01 to 10 parts by weight, based on 100
parts by weight of total of the monomers.
[0142] The organic solvent is inert to the monomer, and dissolves
the monomer, and examples of the organic solvent include an ester
(for example, an ester having 2-30 carbon atoms, specifically ethyl
acetate and butyl acetate), a ketone (for example, a ketone of 2-30
carbon atoms, specifically methyl ethyl ketone and diisobutyl
ketone), and an alcohol (for example, an alcohol having 1-30 carbon
atoms, specifically isopropyl alcohol). Specific examples of the
organic solvent include acetone, chloroform, HCHC225, isopropyl
alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene,
toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane,
methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone,
ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane,
1,1,1-trichloroethane, trichloroethylene, perchloroethylene,
tetrachlorodifluoroethane and trichlorotrifluoroethane. The organic
solvent may be used in the amount within the range from 10 to 2,000
parts by weight, for example, from 50 to 1,000 parts by weight,
based on 100 parts by weight of total of the monomers.
[0143] In the emulsion polymerization, there can be used a method
of emulsifying monomers in water in the presence of a
polymerization initiator and an emulsifying agent, replacing the
atmosphere by nitrogen, and polymerizing with stirring, for
example, at the temperature within the range from 50.degree. C. to
80.degree. C. for 1 hour to 10 hours. As the polymerization
initiator, for example, water-soluble initiators such as benzoyl
peroxide, lauroyl peroxide, t-butyl perbenzoate,
1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide,
acetyl peroxide, azobisisobutylamidine dihydrochloride,
azobisisobutyronitrile, sodium peroxide, potassium persulfate and
ammonium persulfate and oil-soluble initiators such as
azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide,
lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and
diisopropyl peroxydicarbonate can be used. The polymerization
initiator may be used in the amount within the range from 0.01 to
10 parts by weight, based on 100 parts by weight of the
monomers.
[0144] In order to obtain a polymer dispersion in water, which is
superior in storage stability, it is preferable that the monomers
are dispersed in water by using an emulsifying device capable of
applying a strong shearing energy (e.g., a high-pressure
homogenizer and an ultrasonic homogenizer) and then polymerized. As
the emulsifying agent, various emulsifying agents such as an
anionic emulsifying agent, a cationic emulsifying agent and a
nonionic emulsifying agent can be used in the amount within the
range from 0.5 to 20 parts by weight, based on 100 parts by weight
of the monomers. The anionic emulsifying agent and/or the cationic
emulsifying agent and/or the nonionic emulsifying agent are
preferable. When the monomers are not completely compatibilized, a
compatibilizing agent capable of sufficiently compatibilizing them
(e.g., a water-soluble organic solvent and a low-molecular weight
monomer) is preferably added to these monomers. By the addition of
the compatibilizing agent, the emulsifiability and polymerizability
can be improved.
[0145] Examples of the water-soluble organic solvent include
acetone, methyl ethyl ketone, ethyl acetate, propylene glycol,
dipropylene glycol monomethyl ether, dipropylene glycol,
tripropylene glycol and ethanol. The water-soluble organic solvent
may be used in the amount within the range from 1 to 50 parts by
weight, e.g., from 10 to 40 parts by weight, based on 100 parts by
weight of water. Examples of the low-molecular weight monomer are
methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl
methacrylate. The low-molecular weight monomer may be used in the
amount within the range from 1 to 50 parts by weight, e.g., from 10
to 40 parts by weight, based on 100 parts by weight of total of
monomers.
[0146] A chain transfer agent may be used in the polymerization.
The molecular weight of the polymer can be changed according to the
amount of the chain transfer agent used. Examples of the chain
transfer agent include a mercaptan group-containing compound
(especially alkyl mercaptan (for example, having 1-30 carbon
atoms)), such as lauryl mercaptan, thioglycol, and thioglycerol,
and an inorganic salt such as sodium hypophosphite and sodium
hydrogen sulfite. The amount of the chain transfer agent may be
within the range from 0.01 to 10 parts by weight, for example, from
0.1 to 5 parts by weight, based on 100 parts by weight of total of
the monomers.
[0147] A liquid medium is removed from a liquid (solution or
dispersion) containing the fluorine-containing copolymer to obtain
the fluorine-containing copolymer. For example, a dispersion of
fluorine-containing copolymer (an aqueous dispersion or an organic
solvent-dispersion) can be precipitated into water or an organic
solvent, and dried to obtain the fluorine-containing copolymer.
[0148] The resin composition may consist of the thermoplastic resin
(1) and the fluorine-containing copolymer (2), or may comprise
another component. Examples of the other component include
additives (that is, auxiliary agents) such as a dye, a pigment, an
antistatic agent, an antioxidant, a light stabilizer, an
ultraviolet light-absorbing agent, a neutralizing agent, a
nucleating agent, an epoxy stabilizer, a lubricant, an
antibacterial agent, a flame retardant and plasticizer.
[0149] The resin composition can be obtained by kneading (for
example, melt-kneading) the thermoplastic resin (1) and the
fluorine-containing copolymer (2). Generally, the thermoplastic
resin (1) and the fluorine-containing copolymer (2) are heated at a
temperature of 100-320.degree. C., for example, 200-300.degree. C.
to produce the nonwoven fabric. Preferably, the resin composition
is heated to spin the fiber.
[0150] The method for producing the nonwoven fabric may be a wet
method such as a paper-making method, and a dry method such as a
melt-blown method, a spunbond method, a chemical bond method, a
needle-punching method, a water punching method and a thermal
bonding method. The melt-blown method and the spun-bond method are
preferable, and the melt-blow method is particularly
preferable.
[0151] In the melt-blow method, in general, a molten material of
the resin composition pressure-fed to the die is spun from a nozzle
having a large number of arranged small holes to give fibers. A
discharge amount in the single hole is 0.1 to 20 g/minute, and a
high-speed air amount may be 10 to 1000 Nm.sup.3/hr/m.
[0152] Polypropylene as a base of the nonwoven fabric of the
present invention may have a melt flow rate (MFR) of at least 600
g/10 min, preferably 650 to 2,500 g/10 min, more preferably 700 to
2,200 g/10 min, for example, 800 to 1,800 g/10 min. The MFR is
measured under a load of 2.16 kg at a temperature of 230.degree. C.
in accordance with ASTM D1238. The addition of the
fluorine-containing copolymer to the polypropylene according to the
present invention has the effect of giving a higher MFR. The higher
MFR has the advantages that fluidity of the resin is high, and the
processing performance is stabilized because of low discharge
pressure during extrusion, the discharge is smooth to improve the
flowability, and it is easy to narrow the diameter of the fiber. A
method of thinning the fiber diameter includes a method of
improving a shape of a nozzle or reducing a nozzle diameter, a
method of increasing the MFR of polypropylene as the base. The
addition of the fluorine-containing copolymer according to the
present invention can increase the resin fluidity and can give a
nonwoven fabric having a decreased fiber diameter.
[0153] An average fiber diameter of fibers in the nonwoven fabric
is 0.1 to 5 micrometers, preferably 0.2 to 3 micrometers, more
preferably 0.2 to 2.6 micrometers. The fiber diameter of the
nonwoven fabric can be thin, since a surface-modified resin
composition is used. A basis weight of the nonwoven fabric may be 5
to 300 g/m.sup.2, for example, 10 to 200 g/m.sup.2. The basis
weight is a value showing a weight per 1 m.sup.2 of the nonwoven
fabric prepared.
[0154] The nonwoven fabric of the present invention can be used for
a clothes and health material such as operation clothes, paper
diaper, sanitary napkin; a filter such as a cell filter, a
dust-proof mask filter, a filter of an air cleaner and air
conditioner; a separator for battery; a packaging material; a
nonwoven fabric wiper and an exterior material and interior
material of automobile such as a door trim, an instrument panel, a
tire house, a bumper, a floor cover, a hood cover and a roof cover;
and a building material. The nonwoven fabric of the present
invention is suitable for a medical use. For example, the nonwoven
fabric can be used for a surgical gown, a surgical drape, a sheet,
a bandage, a wiping cloth, a pillow cover, a mask, and a covering
cloth.
EXAMPLES
[0155] Hereinafter, the present invention will be illustrated in
detail by the following Examples, which do not limit the present
invention.
[0156] In the following Examples, parts and % are parts by weight
and % by weight, unless otherwise specified.
[0157] Properties were measured in the following manner.
Weight-Average Molecular Weight of Fluorine-Containing Polymer
[0158] A fluorine-containing polymer (0.1 g) and tetrahydrofuran
(THF) (19.9 g) were mixed and then filtered by a filter after
standing for one hour to prepare a THF solution of the
fluorine-containing polymer. This sample was measured by a gel
permeation chromatograph (GPC) set to the following device and
condition. Instrument: SHODEX GPC-104 (manufactured by SHOWA DENKO
K. K.)
Column:
[0159] Sample side: GPC LF-G, GPC LF604, GPC LF604, GPC KF601 and
GPC KF601 (all manufactured by SHOWA DENKO K. K.) were connected in
this order.
[0160] Reference side: GPC KF600RL, GPC KF600RL, GPC KF600RH and
GPC KF600RH (all manufactured by SHOWA DENKO K. K.) were connected
in this order.
Mobile phase: THF Mobile phase flow rate: 0.6 mL/min in both sample
side and reference side Column temperature: 40.degree. C. Detection
unit: Differential refractometer (RI)
Basis Weight
[0161] A weight and an area of a nonwoven fabric were measured to
determine a weight per 1 m.sup.2 of the nonwoven fabric.
Average Fiber Diameter
[0162] An electron microscope was used to prepare a picture of a
nonwoven fabric taken by a magnification of 5,000.times.. 200
fibers were chosen at random from the fibers of the nonwoven fabric
in the picture, and the diameters of the fibers were measured and
an average value was calculated to give an average fiber
diameter.
Antifouling Property Evaluation
[0163] After putting 3 g of the following test liquid on a nonwoven
fabric and standing for 4 hours, the test liquid was wiped off with
a cloth, and a degree of stain remaining after wiping off was
visually estimated.
Test liquid: Mustard [0164] Ketchup [0165] Canned coffee [0166]
Milky lotion
Evaluation Method
[0167] Excellent: Test liquid can all be wiped off to give no trace
remainder.
[0168] Good: Test liquid can all be wiped off, but trace remains
very slightly.
[0169] Fair: Test liquid cannot all be wiped off, and trace
remains.
[0170] Bad: Test liquid cannot be wiped off at all, and trace
remains distinctly.
Oleic Acid Repellency
[0171] 3 mL of oleic acid was put on a nonwoven fabric, and time
until a liquid droplet begins to sink into the nonwoven fabric was
measured. The oleic acid repellency is 0 second, if the liquid
droplet penetrates immediately.
Touch Feeling:
[0172] A nonwoven fabric was touched by an index finger to evaluate
a feel.
Evaluation Method:
[0173] Good: Slides with no feeling of catch.
[0174] Fair: Slides with slight feeling of catch.
[0175] Bad: Not slide with a feeling of catch.
Friction Coefficient
[0176] A surface measuring instrument was used by using a steel
ball as a friction element to measure a static friction
coefficient, according to ASTM D1894.
Water-Proof Pressure
[0177] A water penetration test machine was used so that water
adjusted to 25.degree. C. was pressurized from a back of a nonwoven
fabric kept at a ring. A height (cm) of a column of water was
measured at the time of three liquid droplets appearing on the
surface.
Processability
[0178] Discharge pressure: A pressure applied at a tip of an
extrusion machine was measured at the time of a nonwoven fabric
processing. The evaluation is "unstable" if a pressure value is
gradually changed in 10 seconds or less, and "stable" if a pressure
value is not changed in more than 10 seconds.
[0179] Rolling-up property: When a prepared nonwoven fabric was
rolled-up from a wire part, the evaluation is "unstable" if the
nonwoven fabric remains on a wire without separating smoothly from
the wire part, and "stable" if the nonwoven fabric is separated
smoothly from the wire part.
Flowability
[0180] A pressure applied to a gear pump controlling a discharge
amount of the resin from a tip of an extrusion machine was measured
at the time of producing a nonwoven fabric.
Sound Insulating Property
[0181] A device for generating a sound by vibration was surrounded
by a sound-insulated box having an opening part of a 10 cm.times.10
cm, and the opening part was closed by a three-sheet pile of a
nonwoven fabric. The sound was generated by the vibration, a noise
meter was placed at a distance of 5 cm from the nonwoven fabric
dosing the opening part, to measure a degree of noise (dB).
Tensile Test
[0182] A tensile test was conducted according to JIS L1913. A
tensile strength, for example, was measured under the conditions of
a width of a nonwoven fabric test piece of 50 mm, a distance
between chucks of 200 mm and a tensile speed of 100 mm/min.
Preparative Example 1
[0183]
CH.sub.2.dbd.C(--CH.sub.3)--C(.dbd.O)--O--(CH.sub.2).sub.2--(CF.sub-
.2).sub.5CF.sub.3 (hereinafter referred to as "C6SFMA") (26.80 g),
stearyl acrylate (hereinafter referred to as "StA") (40.20 g) and
isopropyl alcohol (hereinafter referred to as "IPA") (100.50 g) as
solvent were charged into a 300 mL flask, an internal temperature
was set to be 65.degree. C. with stirring, azobisisobutyronitrile
(hereinafter referred to as "AIBN") (0.82 g) was added and a
mixture was kept for 10 hours. The solvent was removed to obtain a
fluorine-containing copolymer.
Preparative Example 2
[0184] A fluorine-containing copolymer was obtained in the same
manner as in Preparation Example 1 except that C6SFMA was 28.81 g,
StA was 38.19 g, IPA was 102.51 g and AIBN was 0.47 g.
Preparative Example 3
[0185] A fluorine-containing copolymer was obtained in the same
manner as in Preparation Example 1 except that C6SFMA was 30.15 g,
StA was 36.85 g, IPA was 102.51 g and AIBN was 0.74 g.
Preparative Example 4
[0186] A fluorine-containing copolymer was obtained in the same
manner as in Preparative Example 1 except that C6SFMA was 33.50 g,
StA was 33.50 g, IPA was 101.84 g and AIBN was 0.60 g.
Preparative Example 5
[0187] A fluorine-containing copolymer was obtained in the same
manner as in Preparative Example 1 except that C6SFMA was 38.86 g,
StA was 28.14 g, IPA was 89.11 g and AIBN was 0.47 g.
Preparative Example 6
[0188] A fluorine-containing copolymer was obtained in the same
manner as in Preparative Example 1 except that C6SFMA was 43.55 g,
StA was 23.45 g, IPA was 100.50 g and AIBN was 0.67 g.
Comparative Preparative Example 1
[0189] A fluorine-containing copolymer was obtained in the same
manner as in Preparation Example 1 except that C6SFMA was 32.16 g,
StA was 34.84 g, IPA was 134.00 g and AIBN was 1.34 g.
Comparative Preparative Example 2
[0190] A fluorine-containing copolymer was obtained in the same
manner as in Preparation Example 1 except that IPA was 67.00 g and
AIBN was 0.47 g.
Comparative Preparative Example 3
[0191] A fluorine-containing copolymer was obtained in the same
manner as in Preparation Example 1 except that C6SFMA was 32.16 g,
lauryl acrylate (hereinafter referred to as "LA") was 34.84 g, IPA
was 93.80 g and AIBN was 0.54 g.
[0192] A monomer ratio and molecular weight of the
fluorine-containing polymer obtained in Preparative Examples 1-6
and Comparative Preparative Examples 1-3 are shown in Table 1.
TABLE-US-00001 TABLE 1 Monomer Ratio Fluorine- Fluorine- Fluorine-
Fluorine- containing free containing free Molecular monomer monomer
monomer monomer weight Pre. Ex. 1 C6SFMA StA 40 60 7000 Pre. Ex. 2
C6SFMA StA 43 57 10000 Pre. Ex. 3 C6SFMA StA 45 55 7000 Pre. Ex. 4
C6SFMA StA 50 50 9000 Pre. Ex. 5 C6SFMA StA 58 42 14000 Pre. Ex. 6
C6SFMA StA 65 35 7000 Com. Pre. C6SFMA StA 48 52 2000 Ex. 1 Com.
Pre. C6SFMA StA 48 52 25000 Ex. 2 Com. Pre. C6SFMA LA 48 52 9000
Ex. 3
Examples 1 to 8
[0193] Each fluorine-containing copolymer obtained in Preparative
Examples 1 to 6 was melt-mixed with polypropylene (hereinafter
referred to as "PP800") having MFR of 800 at a temperature of
160.degree. C. by a twin screw extruder to give a
fluorine-containing copolymer content of 20%, and the mixture was
cooled with water and cut by a cutting machine to obtain
pellets.
[0194] The polypropylene containing 20% of the fluorine-containing
copolymer (hereinafter referred to as "fluorine-containing PP") was
further mixed with PP800 in a pellet mix amount shown in Table 2,
to give a target content of the fluorine-containing copolymer. This
mixture was melt-mixed by a nonwoven fabric processing machine set
at 240.degree. C., and discharged on a wire part by a gear pump
adjusting an amount of discharge which was set at 15 rpm equipped
with a nozzle having a caliber of .25 mm, to obtain a nonwoven
fabric. A target basis weight amount was set by changing a
rolling-up speed of the wire part under the same discharge
condition.
Comparative Example 1
[0195] PP800 was melt-mixed by a nonwoven fabric processing machine
set at 240.degree. C., and discharged on a wire part by a nozzle
having a caliber of .25 mm, to obtain a nonwoven fabric having a
basis weight of 30 g/m.sup.2.
Comparative Examples 2 to 4
[0196] Each fluorine-containing copolymer of Preparative
Comparative Examples 1 to 3 was melt-mixed with polypropylene
(hereinafter referred to as "PP800") having MFR of 800 at a
temperature of 160.degree. C. by a twin screw extruder to give a
fluorine-containing copolymer content of 20%, and the mixture was
cooled with water and cut by a cutting machine to obtain
pellets.
[0197] A nonwoven fabric was obtained in the same manner as in
Examples 1 to 8 except the above.
Example 9
[0198] A fluorine-containing copolymer of Preparative Example 3 was
melt-mixed with PP800 at a temperature of 160.degree. C. by a twin
screw extruder to give a fluorine-containing copolymer content of
20%, and the mixture was cooled with water and cut by a cutting
machine to obtain pellets.
[0199] The polypropylene containing 20% of the fluorine-containing
copolymer (hereinafter referred to as "fluorine-containing PP") was
further mixed with polypropylene (hereinafter referred to as
"PP1800") having MFR of 1800 in a pellet mix amount shown in Table
2, to give a target content of the fluorine-containing copolymer.
This mixture was melt-mixed by a nonwoven fabric processing machine
set at 240.degree. C., and discharged on a wire part by a gear pump
adjusting an amount of discharge which was set at 15 rpm equipped
with a nozzle having a caliber of .25 mm with adjusting a
rolling-up speed in the wire part, to obtain a nonwoven fabric
having a basis weight of 30 g/m.sup.2 or 5 g/m.sup.2.
Comparative Example 5
[0200] PP1800 was melt-mixed by a nonwoven fabric processing
machine set at 240.degree. C., and discharged on a wire part by a
nozzle having a caliber of .25 mm, to obtain a nonwoven fabric
having a basis weight of 30 g/m.sup.2.
TABLE-US-00002 TABLE 2 Pellet mix amount (kg) Ratio Fluorine-
Fluorine- Fluorine- Basis containing containing containing weight
PP copolymer PP PP PP copolymer g/m.sup.2 Com. Ex. 1 PP800 -- 100
-- 100 -- 30 Ex. 1 PP800 Pre. Ex. 1 100 25 100 5 30 Ex. 2 PP800
Pre. Ex. 2 100 25 100 5 30 Ex. 3 PP800 Pre. Ex. 3 100 25 100 5 30
Ex. 4 PP800 Pre. Ex. 3 100 25 100 5 5 Ex. 5 PP800 Pre. Ex. 4 100 25
100 5 30 Ex. 6 PP800 Pre. Ex. 5 100 25 100 5 30 Ex. 7 PP800 Pre.
Ex. 5 100 25 100 5 5 Ex. 8 PP800 Pre. Ex. 6 100 25 100 5 30 Com.
Ex. 2 PP800 Com. Pre. 100 25 100 5 30 Ex. 1 Com. Ex. 3 PP800 Com.
Pre. 100 25 100 5 30 Ex. 2 Com. Ex. 4 PP800 Com. Pre. 100 25 100 5
30 Ex. 3 Com. Ex. 5 PP1800 -- 100 -- 100 -- 30 Ex. 9 PP1800 Pre.
Ex. 3 100 25 100 5 30
[0201] These test results are shown in Table 3.
TABLE-US-00003 TABLE 3 Antifouling property Oleic acid Friction
Canned Milky repellency. coefficient Touch Mustard Ketchup coffee
lotion (Second) Com. Ex. 1 1.20 Bad Bad Bad Bad Bad 0 Ex. 1 1.09
Fair Good Good Fair Fair 4 Ex. 2 1.05 Good Excellent Fair Good Good
4 Ex. 3 1.03 Good Excellent Excellent Good Excellent 5 Ex. 4 1.03
Good Excellent Excellent Good Excellent 5 Ex. 5 1.03 Good Excellent
Excellent Good Excellent 5 Ex. 6 1.03 Good Excellent Good Good Good
5 Ex. 7 1.03 Good Excellent Good Good Good 5 Ex. 8 1.07 Fair Good
Good Good Fair 5 Com. Ex. 2 1.20 Bad Bad Fair Bad Fair 1 Com. Ex. 3
1.19 Bad Fair Fair Fair Bad 2 Com. Ex. 4 1.23 Bad Bad Bad Bad Bad 0
Com. Ex. 5 1.30 Bad Bad Bad Bad Bad 0 Ex. 9 1.06 Excellent
Excellent Good Fair Excellent 5
Examples 10 to 19
[0202] Each fluorine-containing copolymer of Preparative Examples 3
and 4 was melt-mixed with PP800 at a temperature of 160.degree. C.
by a twin screw extruder to give a fluorine-containing copolymer
content of 20%, and the mixture was cooled with water and cut by a
cutting machine to obtain pellets.
[0203] The polypropylene containing 20% of the fluorine-containing
copolymer (hereinafter referred to as "fluorine-containing PP") was
further mixed with PP800 in a pellet mix amount shown in Table 4,
to give a target content of the fluorine-containing copolymer. This
mixture was melt-mixed by a nonwoven fabric processing machine set
at 240.degree. C., and discharged on a wire part by a gear pump
adjusting an amount of discharge was set at 15 rpm equipped with a
nozzle having a caliber of .25 mm with adjusting a rolling-up speed
in the wire part, to obtain a nonwoven fabric having a basis weight
of 15 g/m.sup.2.
Comparative Example 8
[0204] A nonwoven fabric was obtained in the same manner as in
Comparative Example 1 except a basis weight was 15 g/m.sup.2.
Comparative Example 9
[0205] A nonwoven fabric was obtained in the same manner as in
Comparative Example 7 except a basis weight was 15 g/m.sup.2.
TABLE-US-00004 TABLE 4 Pellet mix amount (kg) Ratio Fluorine-
Fluorine- Fluorine- containing containing containing PP copolymer
PP PP PP copolymer Com. Ex. 6 PP800 -- 100 -- 100 -- Ex. 10 PP800
Pre. Ex. 3 100 2.5 100 0.5 Ex. 11 PP800 Pre. Ex. 3 100 6.0 100 1.2
Ex. 12 PP800 Pre. Ex. 3 100 15.0 100 3 Ex. 13 PP800 Pre. Ex. 3 100
25.0 100 5 Ex. 14 PP800 Pre. Ex. 3 100 40.0 100 8 Ex. 15 PP800 Pre.
Ex. 6 100 2.5 100 0.5 Ex. 16 PP800 Pre. Ex. 6 100 6.0 100 1.2 Ex.
17 PP800 Pre. Ex. 6 100 15.0 100 3 Ex. 18 PP800 Pre. Ex. 6 100 25.0
100 5 Ex. 19 PP800 Pre. Ex. 6 100 40.0 100 8 Com. Ex. 7 PP1800 --
100 -- 100 -- Ex. 20 PP1800 Pre. Ex. 3 100 25.0 100 5
[0206] These test results are shown in Table 5.
TABLE-US-00005 TABLE 5 Tension test Fiber Workability Maximum
diameter Dis- Rolling- Sound- Water- Elastic Maximum point (micro-
charge up prop- proofing proof modulus point stress elongation
meter) pressure erty (dB) pressure (MPa) (MPa) (%) Com. Ex. 6 3.1
Unstable Unstable 86 332 17.0 1.40 57.0 Ex. 10 2.7 Unstable Stable
83 350 17.3 1.33 50.0 Ex. 11 2.5 Stable Stable 80 378 18.0 1.20
43.0 Ex. 12 2.2 Stable Stable 80 380 17.9 1.20 44.0 Ex. 13 2.2
Stable Stable 78 390 17.7 1.25 45.7 Ex. 14 2.2 Stable Stable 76 389
17.8 1.24 45.8 Ex. 15 2.9 Unstable Stable 84 345 17.3 1.32 52.8 Ex.
16 2.7 Stable Stable 82 362 17.9 1.20 44.0 Ex. 17 2.5 Stable Stable
81 369 18.0 1.22 43.8 Ex. 18 2.5 Stable Stable 81 371 17.9 1.23
45.1 Ex. 19 2.5 Stable Stable 80 370 18.0 1.24 45.0 Com. Ex. 7 2.8
Unstable Unstable 87 340 16.8 1.41 59.0 Ex. 20 1.6 Stable Stable 78
400 18.0 1.26 46.8
Example 21 and Comparative Example 8
[0207] A nonwoven fabric was obtained in the same manner as in
Example 3 and Comparative Example 1 except a basis weight was 5
g/m.sup.2. A pellet mix amount and test results are shown in Table
6.
TABLE-US-00006 TABLE 6 Pellet mix amount Flowability Average
Fluorine- Fluorine- Gear Basis Fiber containing containing pump
Pressure weight diameter PP copolymer PP PP (rpm) (Mpa) (g/m.sup.2)
(micrometer) Com. Ex. 8 PP800 -- 100 -- 15 1.22 5 3.1 Ex. 21 PP800
Pre. Ex. 3 100 25 15 0.87 5 2.5
[0208] In the case that a nonwoven fabric was prepared under the
same conditions, when the fluorine-containing copolymer is added, a
pressure was decreased. This is because the mobility of resin is
improved by adding the fluorine-containing copolymer. The addition
of the fluorine-containing copolymer has also the effect that the
diameter of the fiber is thinner.
Example 22 and Comparative Example 9
[0209] A nonwoven fabric was obtained in the same manner as in
Example 9 and Comparative Example 5 except a basis weight was 3
g/m.sup.2. A pellet mix amount and test results are shown in Table
7.
TABLE-US-00007 TABLE 7 Pellet mix amount Flowability Average
Fluorine- Fluorine- Gear Basis Fiber containing containing pump
Pressure weight diameter PP Copolymer PP PP (rpm) (Mpa) (g/m.sup.2)
(micrometer) Com. Ex. 9 PP800 -- 100 -- 15 0.89 3 1.1 Ex. 22 PP800
Pre. Ex. 3 100 25 15 0.52 3 0.7
Example 23 and Comparative Example 10
[0210] A nonwoven fabric was obtained in the same manner as in
Example 22 and Comparative Example 9 except a nozzle diameter was
0.15 mm. A pellet mix amount and test results are shown in Table
8.
TABLE-US-00008 TABLE 8 Pellet mix amount Flowability Average
Fluorine- Fluorine- Gear Basis Fiber containing containing pump
Pressure weight diameter PP Copolymer PP PP (rpm) (Mpa) (g/m.sup.2)
(micrometer) Com. Ex. 10 PP800 -- 100 -- 15 0.92 3 0.5 Ex. 23 PP800
Pre. Ex. 3 100 25 15 0.58 3 0.3
[0211] The fiber diameter can be thin by increasing the MFR of
polypropylene used as a base, and also by decreasing the nozzle
caliber. It is shown that the fiber diameter is thinner by adding
the fluorine-containing copolymer according to the present
invention.
INDUSTRIAL APPLICABILITY
[0212] The nonwoven fabric of the present invention can be used as,
for example, a clothes and sanitary material (for example,
operation clothes, a paper diaper, a sanitary napkin), a filter
(for example, a battery filter, a filter of a dust-proof mask, a
filter of an air-conditioner or an air purifier), a separator for
batteries, a packaging material, a nonwoven fabric wiper, an
automotive interior material or exterior material (for example, a
door trim, an instrument panel, a tire house, a bumper, a floor
cover, a bonnet cover, a roof cover), and a building material. The
nonwoven fabric of the present invention is suitable for a medical
use. For example, the nonwoven fabric can be used for a surgical
gown, an operation drape, a sheet, a bandage, a wiping cloth, a
pillow cover, a mask and a covering cloth.
* * * * *