DESCRIPTION
SPUNBONDED NONWOVEN FABRIC, PRODUCTION PROCESS FOR THE FABRIC
AND USE THEREOF
TECHNICAL FIELD
[0001]
The present invention relates to a spunbonded nor-woven
fabric which comprises long fibers comprising a thermoplastic
10 polyurethane elastomer having a low hardness, specifically it
relates to a spunbonded noimwoven fabric which comprises long
fibers comprising athermoplastic polyurethane elastomer having
a low hardness and long fibers comprising a thermoplastic polymer
other than the above thermoplastic polyurethane elastomer, The
15 present invention further relates to a laminate containing the
spunbonded non-woven fabric and to sanitary materials obt-ainable
by using the same.
TECHNICAL BACKGROUND
[0002]
20 In recent years, non-woven fabrics are used widely for
various kinds of uses because of having excellent permeability
and flexibility. On this account, non-woven fabrics are
required to have various properties according to their, uses and
the properties are required to be further improved.
SF-2364 2
[0003]
For example, nonwoven fabrics used for sanitary
materials such as paper diapers, sanitary napkins and the like,
and base fabric such as wet compress pack materials and the like
5 are required to have water resistance and excellent moisture
permeability. Furthermore, the normwoven fabrics are required
to have stretchability and bulk properties according to a portion
for use.
[0004]
10 Examples of a method of adding stretchability to the
nonwoven fabrics are a method of using athermoplastic elastomer
as a material for a spunbonded nonwoven fabric (referred to
Patent document 1), a method of using mixed fibers which comprise
fibers made of a polymer containing athermoplastic polyurethane
15 elastomer and fibers made of a thermoplastic polymer other than
the thermoplastic polyurethane elastomer as fibers for forming
a nonwoven fabric (referred to Patent document 2) o Moreover,
differing to the addition of stretchability, a long fiber
nonwoven fabric obtainable by combining adhesive fibers made
20 of a hydrogenated styrene block copolymer and nonadhesive
fibers and the like are variously proposed (referred to Patent
document 3)
[0005]
Mixing the fibers made of the thermoplastic polyurethane
SF2364 3
elastomer, stretchability is added, Moreover, stretchability
(elastic recovery properties) is desired according to the use.
As a method of increasing stretchability, there is a method of
using a thermoplastic polyurethane elastomer having a low
hardness and excellent elastic recovery properties.
[0006]
However, a thermoplastic polyurethane elastomer having
a low hardness is soft. In producing a spunbonded non-woven
fabric by mixing fibers made of a thermoplastic polyurethane
10 elastomer having a low hardness , the fibers prepared just after
deposition are easily deformed by a rotational device that a
linear pressure is applied on the deposited fibers such as
calendar roller ( for example, referred to Patent document 4),
or a conveyer , and thereby the contact area is increased. In
15 the case that fusion bonding of the fibers is insufficient, there
is a possibility that the fibers adhere to the rotational device
and the insufficient fusion bonding has an industrial problem.
For example , in a process that a web which comprises only
long fibers made of a thermoplastic polyurethane elastomer,
20 prepared by a spun bonding method are fusion bonded each other
completely or no completely and unified in the step of contacting
the web with a rotational device, since a force of generating
a peeling force higher than an adhesion force functions in a
mechanical direction , fusion bonding is hard to be caused. In
SFm2364 4
the case of producing a spunbonded nonwoven fabric which
comprises long fibers made of a thermoplastic polyurethane
elastomer and long fibers made of a thermoplastic polymer other
than the thermoplastic polyurethane elastomer, the fibers are
5 hardly fusion bonded each other in the step of collecting the
fibers on a conveyor after opening, and heterogeneous fibers
are only deposited and the web is not unified, When the web is
contacted with a rotational device such as a calendar roller
and the like, the long fibers made of a thermoplastic
10 polyurethane elastomer are adhered on the rotational device at
the beginning and the whole web is frequently wound around the
rotational device in the end. The production has an industrial
problem.
In a process of using mixed fibers which comprise fibers
15 made of a polymer containing a thermoplastic polyurethane
elastomer and fibers made of a thermoplastic polymer other than
the thermoplastic polyurethane elastomer, a method of coating
the roll surface with a silicon resin having a low surface free
energy or a material of fluororesin is usually used in order
20 to prevent adhesion of fibers to a roll and the like o The coating
is worn away with progressing of the production, and at the time
that the surface of a base layer is exposed, the fibers have
a possibility of adhesion of the fibers to a roil and the like.
The method is not preferred because of having an industrial
SF°2364 5
problem.
PRIOR ARTS
PATENT DOCUMENT
[0007]
O Patent document 1: WO°H7°503502
Patent document 20 JP°A°2004°244791
Patent document 3m JP°A°2004°197291
Patent document 4: JP--A°2004244793
SUMMARY OF THE INVENTION
10 SUBJECT TO BE SOLVED BY THE INVENTION
[0008]
It is an object of the present invention to provide a
spunbonded nonwoven fabric having excellent productivity such
that fibers are not adhered on a roll and the like just after
15 fiber deposition, and having excellent stretchability, touch
and fuzz resistance.
MEANS FOR SOLVING THE SUBJECT
[0009]
The present invention provides a spunbonded nonwoven
20 fabric which comprises long fibers made of a thermoplastic
polyurethane elastomer (A) containing ethylene bis°oleic acid
amide and/or crosslinked organic fine particles, having a
hardness of 75 to 85 and obtainable by using
1,4 bis(2-hydroxyethoxy)benzene as a chain extender, and
SF- 2364 6
further provides a spunbonded nonwoven fabric which comprises
log fibers made of the thermoplastic polyurethane elastomer (A)
and long fibers made of a thermoplastic resin (B) other than
the thermoplastic polyurethane elastomer (A) and provides uses
thereof.
EFFECT OF THE INVENTION
[0010]
Since the spunbonded nonwoven fabric of the present
invention comprises long fibers made of a thermoplastic
10 polyurethane elastomer_ having a relatively low hardness and has
high stretching physical properties, good touch, fuzz resistance,
it is suitable for sanitary materials made of the spunbonded
nonwoven fabric such as paper diapers and the like.
[0011]
15 Since the long fibers made of the thermoplastic
polyurethane elastomer having a relatively low b<=rdness
contained in the spunbonded nonwoven fabric of the present
invention contain ethylene bis^oleic acid amide and/or
crosslinked organic fine particles, the spunbonded nonwoven
20 fabric can be produced stably with no adhesion thereof to a roll
and the like just after fiber deposition during the production.
BRIEF DESCRIPTION OF DRAWING
[0012]
Fig. 1 is a schematic view of a gear stretching device.
SF 2364 7
EMBODIMENT FOR CARRYING OUT THE INVENTION
[0013]
Thermoplastic polyurethane elastomer (A)
The thermoplastic polyurethane elastomer (A) of the
5 present invention (hereinafter, abbreviated to "TPU(A)") is a
thermoplastic polyurethane elastomer (hereinafter, abbreviated
to "TPU(a)") having a hardness (measured in JIS K°-7311 by an
A type durometer) of 75 to 85, preferably 80 to 85, more
preferably 80 to 83 and containing ethylene bis^oleic acid amide
10 and/or crosslinked organic fine particles. The thermoplastic
polyurethane elastomer is known generically may be abbreviated
as "TPU
[0014]
Even when TPU having a hardness of less than 75 is mixed
15 with ethylene bis^oleic acid amide and/or crosslinked organic
fine particles and mixed with long fibers made of a thermoplastic
resin (B) other than TPU (hereinafter referred to "thermoplastic
resin (B)"), a resulting spunbonded nonwoven fabric has a
possibility that the fabric is adhered on a roll and the like
20 just after fiber deposition. On the other hand, when TPU having
a hardness of over 85 is mixed with long fibers made of the
thermoplastic resin (B) and molded by spun bonding, a resulting
spunbonded nonwoven fabric has a problem that the
stretchability is poor.
SF2364
[0015]
8
In the thermoplastic polyurethane elastomer (A) of the
present invention, it is preferred to use a thermoplastic
polyurethane elastomer (A2) which comprises the thermoplastic
5 polyurethane elastomer [TPU(a)] which is a thermoplastic
polyurethane elastomer_ [TPU(a2)] obtainable by using
1, 4®bis (2-hydroxyethoxy) benzene as a chain extender and further
comprises ethylene bis-oleic acid amide and/or cros,sli_nked
organic fine particles, because when it is used as a material
10 of a spunbonded non-woven fabric, and mixed with long fibers
of the thermoplastic resin (B) to prepare a spunbonded nonwoven
fabric, the resulting spunbonded nonwoven fabric has excellent
stretchability.
[0016]
15 The raw material of TPU(A) according to the present
invention, namely the thermoplastic polyurethane elastomer
[TPU(a)] prepared before adding ethylene bis oleic acid amide
and/or crosslinked organic fine particles has a fluid
initiation temperature of preferably not lower than 155° C, more
20 preferably 155 to 170° Co The thermoplastic polyurethane
elastomer [TPtJ(a2)] obtainable by using
1,4 bis(2^hydroxyethoxy)benzene as a chain extender used for
the thermoplastic polyurethane elastomer [TPU(a)] has a fluid
initiation temperature of preferably not lower than 160 ° C, more
SF 2364 9
preferably 160 to 175° Co Using TPU having a fluid initiation
temperature in the above range, a spunbonded non-woven fabric
having excellent productivity, stretchability, touch and fuzz
resistance can be produced.
[0017]
The expression "TPU(a)" may include the thermoplastic
polyurethane elastomer TPU(a2) obtainable by using
1,4 bis(2-hydroxyeLhoxy)benzene as a chain extender unless
otherwise provided notification.
10 [0018]
TPU(a) of the present invention has a weight average
molecular weight (Mw) of preferably from 125000 to 200000, more
preferably 130000 to 180000, and a melt viscosity of from 09
x 104 to L4 x 109 (dPa s)o The thermoplastic polyurethane
10 elastomer [TPU(a2)] obtainable by using
1,4-bis(2-hydroxyet.hoxy)benzene as a chain extender ued for
TPU (a) has a weight average molecular weight (Mw) of preferably
from 95000 to 200000, more preferably 95000 to 170000, and a
melt viscosity of from 04 x 109 to L3 x 109 (dPa s) a Using
20 TPU having Mw and a melt viscosity in the above ranges as TPU (a),
a spunbonded nonwoven fabric can be produced stably.
[0019]
TPU (a) of the present invention is preferred because the
amount of massive matters such as fish eyes or gel generated
SF 2364 10
during the production of TPU is small. These massive matters
can be measured by a known method, for example, the method as
described in JPmAa2004--2447914 These massive matters are
components caused by the raw materials for TPU and by the chemical
5 reaction of the raw materials, such as a component derived from
a hard segment condensate of TPU and a component obtainable by
crosslinking a hard segment and/or a soft segment with
allophanate bonding or burret bonding. When the amount of the
massive matters is large, thread breakage and the like are caused
10 and thereby the spunbonded nonwoven fabric cannot be produced
stably
[0020]
Polyol
A Polyol which is one component for constituting TPU(a)
15 according to the present invention is a polymer having at least
two hydroxyl groups in one molecule and examples therc,of are
polyoxyalkylene Polyol, polytetramethylene ether glycol,
polyester polyol, polycaprolactone Polyol and polycarbonate
diole These polyols may be used singly or two or more may be
20 mixed for use. Among these polyols, polyoxyalkylene Polyol,
polytetramethylene ether glycol and polyester Polyol are
preferred.
[0021]
It is preferred that these polyols be sufficiently
SF 2364 11
dehydration treated with heating under reduced pressure to
decrease the moisture thereof. These polyols have a moisture
content of preferably not more than 0005 % by weight, more
preferably not more than 0. 03 % by weight, furthermore preferably
5 not more than 0.02 % by weight.
[0022]
Polyoxyalkylene Polyol
Examples of polyoxyalkylene polyol are polyoxyalkylene
glycols obtainable by addition polymerizing one or two or more
10 bivalent alcohols having a relatively low molecular weight on
an alkylene oxide such as propylene oxide, ethylene oxide,
butylenes oxide and styrene oxide. In the addition
polymerization, preferable examples of a polymerization
catalyst are an alkali metal compound such as cesium hydroxide
15 and rubidium hydroxide, and a compound having a P=N bond.
[0023]
Among the alkylene oxides, propylene oxide and ethylene
oxide are particularly preferred. When two or more alkylene
oxides are used, the amount of propylene oxide is preferably
20 not less than 40 % by weight, more preferably not less than 50 %
by weight based on the total amount of alkylene oxides. Using
an alkylene oxide containing propylene oxide in the above amount,
polyoxy alkylene polyol can have an oxy propylene group content
of not less than 40 by weight.
SF-2364 12
[0024]
In order to improve durability and mechanical properties,
TPU(a) of the present invention has a rate of primary
hydroxylation at a molecule end of polyoxyalkylene polyol of
5 preferably not less than 50 % by mol, more preferably not less
than 60 % by molo In order to improve the rate of primary
hydroxylation, ethylene oxide is preferably copolymerized at
a molecule end.
[0025]
10 Polyoxyalkylene polyol has a number average molecular
weight of preferably from 200 to 8000, more preferably 500 to
5000 o In order to improve lowering of the glass transition point
and fluidity of TPU (a) , TPU (a) is preferably produced by mixing
two or more polyoxyalkylene polyols having a different molecular
15 weight and a different content of oxyalkylene group.
Furthermore, the polyoxyalkylene polyol preferably contains a
smaller amount of a mono-ol having an unsaturated group at a
molecule end generated by a side reaction of the propylene oxide
addition polymerization. The monocol content in
20 polyoxyalkylene polyol is represented by a degree of total
unsaturation as determined in JIS K-1557. The degree of total
unsaturation of polyoxyalkylene polyol is preferably not more
than 0. 03 meq/g, more preferably not more than 0. 02 meq/g. When
the degree of total unsaturation is more than 0.03 meq/g, the
SF-2364 13
heat resistance and durability of TPU are lowered. The lower
limit of the degree of total u.nsaturation is preferably about
0.001 meq/g from the viewpoint of industrial production of
polyoxyalkylene polyol.
5 [0026]
Polytetramethylene etherglycol
For TPU(a) of the present invention, it is possible to
use, as a polyol, polytetramethylene ether glycol (here: rafter
abbreviated to "PTMEG") obtainable by ring--opening
10 polymerization of tetrahydrofuraneo PTMEG has a number average
molecular weight of preferably about 250 to 4000, more preferably
about 250 to 3000.
[0027]
Polyesterpolyol
15 Examples of polyesterpolyol are polyesterpolyols
obtainable by condensation polymerization of one or two or more
polyols having a low molecular weight with one or two or more
carboxylic acid such as dicarboxylic acid having a low molecular
weight and oligomeric acid.
20 [0028]
Examples of polyols having a low molecular weight are
ethylene glycol, diethylene glycol, propylene glycol,
dipropylene glycol, 1,3--propane diol, 1,4--butane diol,
1, 5--pentane diol, 1, 6-hexane diol, glycerin, trimethyol propane,
SF-2364 14
3-methyl-1,5-pentane diol, hydrogenated bisphenol A and
hydrogenated bisphenol F. Examples of dicarboxylic acid
having a low molecular weight are glutaric acid, adipic acid,
sebacic acid, terephthalic acid, isophthalic acid and dimer acid.
Specific examples thereof are polyethylene butylenes adipate
polyol, polyethylene adipate polyol, polyethylene propylene
adipate polyol and polypropylene adipate polyol.
[0029]
Polyester polyol has a number average molecular weight
10 of preferably about 500 to 4000, more preferably about 800 to
3000.
[0030]
Polycaprolactone polyol
Polycaprolactone polyol is obtainable by ring-opening
15 polymerization of s-caprolactone.
[0031]
Polycarbonate diol
Examples of polycarbonate diol are polycarbonate diols
obtainable by condensation reaction of a bivalent alcohol such
20 as 1, 4-butanedi_ol and 1, 6--hexanediol with a carbonate compound
such as dimethyl carbonate, diethyl carbonate and diphenyl
carbonate. Polycarbonate diol has a number average molecular
weight of preferably about 500 to 3000, more preferably about
800 to 2000.
SF-2364 15
[0032]
Isocyanate compound
Examples of the isocyanate compound which is one
component constituting TPU(a) according to the present invention
5 are compounds of aromatic group, aliphatic group and alicyclic
group which compounds have two or more isocyanate groups in one
molecule.
[0033]
Aromatic polyisocyanate
10 Examples of aromatic polyisocyanates are 2,4---tolylene
diisocyanate, 2,6--tolylene diisocyanate, a tolylene
diisocyanate isomeric mixture containing 2,4-type and 2,6---type
in a weight ratio of 80 to 20 (TDI-80/20) , a tolylene diisocyanate
isomeric mixture containing 2,4-type and 2,6-type in a weight
15 ratio of 65 to 35 (TDI°65/35), 4,4' -diphenylmethanediisocyanate,
2,4'®diphenylmetharie diisocyanate, 2,2'-diphenylrnethane
diisocyanate, and their diphenylmethane diisocyanate isomeric
mixtures, tolylene diisocyanate, xylylene diisocyanate,
tetramethylxylylene diisocyanate, paraphenylene diisocyanate,
20 naphthalene diisocyanate,
[0034]
Aliphatic polyisocyanate
Examples of aliphatic polyisocyanates are ethylene
diisocyanate, trimethylene diisocyanate, tetramethylene
SF-2364 16
diisocyanate, hexamethylene diisocyanate, octamethylene
diisocyanate, nonamethylene diisocyanate,
2,2'-dirnethylpentane diisocyanate, 2,2,4-trimethylhexane
diisocyanate, decamethylene diisocyanate, butene diisocyanate,
5 1,3-butadiene-1, 4-diisocyanate, 2,4,4-trimethylhexamethylene
diisocyanate, 1, 6,11-undecamethylene triisocyanate,
1,3,6®hexamethylene triisocyanate,
1, 8-diisocyanate-4-isocyanate methyloctane,
2, 5, 7--trimethyl-1, 8--diisocyanate-5-isocyanate methyloctane,
10 bis(isocyanate ethyl) carbonate, bis(isocyanate ethyl) ether,
1, 4-butyleneglycohol dipropylether- co,on' -diisocyanate, lysine
isocyanate methyl ester, lysine triisocyanate, 2--isocyanate
ethyl-2,6-diisocyanate hexanoate, 2iisocyanate
propyl-2,6-diisocyanate hexanoate and
15 bis(4-isocyanate-n-butylidene)pentaerythritol.
[0035]
Alicyclic polyisocyanate
Examples of alicyclic polyisocyanates are isophorone
diisocyanate, bis(isocyanate methyl)cyclohexane,
20 dicylohexylmethane diisocyanate, cyclohexane diisocyanate,
methylcyclohexane diisocyanate,
2,2'-dimethyldicyclohexylmethane diisocyanate, dimmer acid
diisocyanate, 2,5.-diisocyanate methyl--bicyclo[2,2,1]--heptane,
2,6-ndiisocyanate methyl-bicyclo[2,2,1] heptane,
SF-2364 17
2-isocyana-temethyl-2-(3-isocyanatepropyl)--5--isocyanate
met-hyl-bicyclo [2, 2, 1] m-heptane,
2-isocyanatemethyl-2-(36Oisocyanatepropyl)-.6---isocyanate
methyl---bicyclo[2,2,1]°heptane,
5 2-isocyanatemethyl-3_. (3-isocyanatepropyl) -5- (2--isocyanate
ethyl)®bicyclo[2,2,1]-heptane,
2-isocyanatemethyl®3- (3-isocyanatepropyl) -6®(2®isocyanate
ethyl)-bicyclo[2.2.1]®heptane,
2-isocyanatemethyl-2- (3-isocyana-tepropyl) -.5-- (2--isocyanate
10 ethyl) ----bicyclo [2 0 2 0 1] --heptane and 2-isocyanate
methyl-2-.(3--isocyanatepropyl) -6-(2-isocyanate ethyl) ----
bicyclo [ 2., 2, 1 ] c_heptane
[0036]
Furthermore, examples of polyisocyanates are modified
15 polyisocyanates such as urethane modified polyisocyanate,
carbodiimide modified polyisocyanate, urethoimine modified
polyisocyanate, biuret modified polyisocyanate, allophanate
modified polyisocyanate and isocyanurate modified
polyisocyanate.
20 [0037]
Of these polyisocyanates, it is preferred to use
4, 41 -diphenylmethane diisocyanate (hereinafter abbreviated to
"MDI"), hydrogenated MDI (dicyclohexylmethane diisocyanate,
hereinafter abbreviated to "HMDI"), paraphenylene diisocyanate
SF-2364 18
(hereinafter abbreviated to "PPDI"), naphthalene diisocyanate
(hereinafter abbreviated to "NDI"), hexamethylene diisocyanate
(hereinafter abbreviated to "HDI"), isophorone diisocyanate
(hereinafter abbreviated to "IPDI"),
5 2,5-diisocyanatemethyl-bicyclo[2,2,1]-heptane (hereinafter
abbreviated to "2, 5-=NBDI") , 2, 6-m-diisocyanate
methyl-bicyclo[2,2,1]---heptane (hereinafter abbreviated to
"2, 6-NBDI") It is more preferred to use MDI, HDI, HMDI, PPDI,
2,5--NBDI and 2,6-NBDI. Moreover, it is also preferred to use
10 modified diisocyanates of above preferred diisocyanates, such
as urethane modified diisocyanate, carbodiimide modified
diisocyanate, urethoimine modified diisocyanate and
isocyanurate modified diisocyanate.
[0038]
15 Chain extender
Examples of the chain extender used for the production
of TPU(a) are preferably aliphatic, aromatic, complex cyclic
or alicyclic polyols having at least two hydroxyl groups in one
molecule and a low molecular weight. The chain extender
20 preferably has a decreased content of moisture by sufficiently
carrying out dehydration treatment with heating under reduced
pressure. The chain extender has a moisture content of
preferably not more than 0.05 % by weight, more preferably not
more than 0. 03 % by weight, furthermore preferably not more than
SF-2364 19
0002 % by weight.
[0039]
Examples of aliphatic polyols are ethylene glycol,
propylene glycol, 1,3-propane diol, 1,4-butane diol,
5 1,5-pentane diol, 1,6-hexane diol, glycerin and trimethylol
propane. Examples of aromatic, complex cyclic and alicyclic
polyols are paraxylene glycol, bis(2-hydroxyethyl)
terephthalate, bis(2mhydroxyethyl)isophtlieelate,
1, 4-bis(2-hydroxyethoxy)benzene,
10 1,3-bis(2-hydroxyethoxy)benzene, resorcin, hydroquinone,
2, 2' -bi_ s (4 -hydroxycyclohexyl) propane,
3, 9-bis (1, l-dimethyl---2-hydroxyethyl) --2, 4, 8, 10-tetraoxaspiro
[5,5]undecane, 1,4°cyclohexane dimethanol and 1,4-cyclohexane
diol.
15 [0040]
These chain extenders may be used singly or two or more
may be mixed for use.
[0041]
Among these chain extenders, 1,4-bis(2-hydroxyethoxy)
20 benzene is preferably used because the spunbonded non--woven
fabric having more excellent stretchability can be produced
stably without adhesion of the fabric to a roll and the like.
[0042]
Ethylene bisoleic acid amide
SF-2364 20
Ethylene bisoleic acid amide which is one component for
adding to TPU (a) according to the present invention is a compound
obtainable from ethylene diamine and oleic acid.
[0043]
5 To TPU(a), ethylene bisoleic acid amide according to the
present invention is added in an amount of usually 0.3 to 2.0 %
by mass, preferably 0,4 to 008 % by mass. Adding to ethylene
bisoleic acid amide in the above amount, TPU (a) can be extruded
stably and adhesion of the fabric to a roll and the like can
10 be prevented stably in the production of the spunbonded non---woven
fabric.
[0044]
Crosslinked organic fine particles
The crosslinked organic fine particles which are one
15 component for adding to TPU(a) according to the present invention
are fine particles which are not molten in melt spinning TPU (a) ,
have an average particle diameter of usually 0.5 to 8 fp.m,
preferably 1 to 4 pm and comprise a crosslinked polymer.
[0045]
20 Examples of the crosslinked organic fine particles
comprise a crosslinked polymer obtainable by polymerizing one
or two or more of the following compounds with the following
crosslinking agent. Examples of the compounds are-
(rneth)acrylates such as (meth)acrylic acid,
SF--w2364 21
methyl(meth)acrylat.e, ethyl(meth)acrylate,
n-propyl(meth)acrylate, iso-propyl(meth)acrylate,
nP-butyl (meth) acrylate, iso--butyl (meth) acrylate,
t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,
5 cyclohexyl(meth)acrylate, benzyl(meth)acrylate,
hydroxyethyl(meth)acrylate and hydroxypropyl(meth)acrylate;
styrenes such as styrene, p-methyl styrene, vinyltoluene
and p-t-butylstyrene;
maleimides such as N-phenyl maleimide, N-cyclohexyl
10 maleimide and NVbenzyl maleimide;
(meth)acrylamides such as (meth)acrylamide and
Namethylol (meth)acrylamide;
acrylo nitriles such as (meth)acrylo nitrite and the
like; and N-vinyl pyrrolidone.
15 Examples of the crosslinking agent are polyfunctional
(meth)acrylates such as, ethylene glycol di(meth)acrylate,
diethylene glycol di(meth)acrylate, propylene glycol
di(meth)acrylate, neopentylglycol di(meth)acrylate,
trimethylol propane tri(meth)acrylate and bishydroxyethyl
20 bisphenol A di(meth)acrylate;
radical polymerizable crosslinking agents such as
divinyloxy ethoxy (meth)acrylate, diallylphthalate,
al.lyf(meth)acrylate and divinyl benzene;
polyfunctional epoxy compounds such as bisphenol A
SF---2364 22
diglycidyl ether, diethylene glycol diglycidyl ether and
neopentylglycol diglycidyl ether;
polyfunctional isocyanate compounds such as tolylene
diisocyanate, xylylene diisocyanate and isophorone
5 diisocyanate; N-methylol melamine and N-methylol
benzoguanamine. The crosslinked organic fine particles
preferably comprise a crosslinked acryl resin containing a
(meth) acrylate as a main component because of having excellent
heat resistance.
10 [0046]
The crosslinked organic fine particles according to the
present invention are added in an amount of usually 0.3 to 2.0 %
by mass, preferably 0.4 to 2.0 % by mass, more preferably 0.8
to 1. 0 % by mass to TPU (a) When the crosslinked organic fine
15 particles are added in the above amount, TPU (a) can be extruded
stably and adhesion of the fabric to a roll and the like can
be stably prevented in the production of the spunbonded non-woven
fabric.
[0047]
20 In the combined use of ethylene bisoleic acid amide and
the crosslinked organic fine particles, the total amount thereof
is from 0.3 to 2.0 % by mass, preferably 0.4 to 2.0 % by mass,
more preferably 0.8 to 1.0 % by mass or the above amount may
apply each of ethylene bisoleic acid amide and the crosslinked
SF-2364 23
organic fine particles.
[0048]
Other thermoplastic elastomer
TPU (A) or TPU (a) according to the present invention may
5 be mixed with various known thermoplastic elastomers such as
a polystyrene elastomer, a polyolefin elastomer, a
polyvinylchloride elastomer, a polyester elastomer, a polyamide
elastomer and a thermoplastic polyurethane elastomer other than
TPU (a) within not missing the object of the present invention.
10 [0049]
Additive
To TPU (A) or TPU (a) according to the present invention,
various known additives such as an antioxidant, a heat stabilizer,
a weather stabilizer, an antistatic agent, a slipping agent,
15 an antifogging agent, a lubricant, a dye, a pigment, a natural
oil, a synthetic oil and a wax may be added within not missing
the object of the present invention.
[0050]
Examples of the additives are a hindered phenol
20 antioxidant such as 2, 6- dim-t--.butyll4-methylphenol (BHT),
pent aerythritol
tetrakis [3- (3, 5-di-_.,t-_butyl-_4-hydroxyphenyl) propionate]
(Trade name. Irganox1010 manufactured by Ciba Specialty Inc.),
6 -- (3, 5--di---t-butyl-4---hydroxyphenyl) propionic acid alkyl ester
SF-2364 24
and 2 , 2 ` ---oxamide
bis[ethyl-3-(3,5¢-di---tf-butyl-4-hydroxyphenyl)] propionate; an
aliphatic acid metal salt such as zinc stearate, calcium
stearate and 1, 2-hydroxystreari.c acid calcium; and a
5 polyvalent alcohol aliphatic acid ester such as glycerin
monostearate, glycerin distearate, pentaerythritol
monostearate, pentaerythritol distearate and pentaerythritol
tristearateo These may be used singly or two or more may be
combined for use.
10 [0051]
Process for producing thermoplastic polyurethane elastomer (a)
The TPU(a) of the present invention is produced by
selecting polyole, an isocyanate compound and a chain extender
each having an optimum chemical structure as the raw materials
15 of TPU(a)a In the production, the hard segment amount is
preferably 20 to 60 % by weight, more preferably 22 to 50 % by
weight, most preferably 25 to 35 % by weight wherein the hard
segment amount is a weight percent value (% by weight) obtainable
by dividing the total amount of the isocyanate compound and the
20 chain extender used in the production of TPU by the total amount
of polyol, the isocyanate compound and the chain extender, and
multiplying 100.
[0052]
Examples of the process for producing TPU(a) are (i) a
SF-2364 25
process of allowing an end isocyanate group-having prepolymer
prepared by allowing polyol to react with a isocyanate compound
(hereinafter, referred to "prepolymer") to react with the chain
extender (hereinafter, referred to "prepolymer process") and
5 (ii) a process of mixing polyol with the chain extender and
allowing the resulting mixture to react with an isocyanate
compound (hereinafter, referred to "one shot process"). Of
these production processes, it is preferred to prepare `I'PU by
the prepolymer process from the viewpoint of mechanical
10 properties and quality of the resulting TPU.
[00 53 1
In the prepolymer process, the prepolymer is produced by
mixing polyol and the isocyanate compound with stirring at a
reaction temperature of about 40 to 2500 C for 30 sec to 8 hr
15 in the presence of an inert gas. Next, the prepolymer and the
chain extender are thoroughly mixed with stirring at a h.i qh rate
in an amount such that the isocyanate index is preferably from
0. 9 to 1. 2, more preferably 0. 95 to 1. 15, furthermore preferably
0.97 to 1.08. The prepolymer and the chain extender are mixed
20 and polymerized at a temperature of usually 80 to 300° C,
preferably 80 to 260° C, most preferably 90 to 220° C although
the temperature is properly determined according to the melting
point of the chain extender and the viscosity of the prepolymer.
The polymerization time is preferably from 2 sec to 1 hr.
SF--2364 26
[0054]
In the one shot process, polyol and the chain extender
are mixed and defoamed, and the mixture and the isocyanate
compound are mixed with stirring at a temperature of 40 to 280°
5 C, more preferably 100 to 260° C for 30 sec to 1 hr and thereby
the polymerization reaction is progressed. In the one shot
process, the isocyanate index is preferably in the same range
as that in the prepolymer process.
[0055]
10 Process for producing thermoplastic polyurethane elastorner (A)
TPU (A) of the present invention is prepared by adding the
desired amounts of ethylene bisoleic acid amide and/or the
crosslinked organic fine particles to TPU(a) prepared by the
above production process. An example of the process of adding
15 ethylene bisoleic acid amide and/or the crosslinked organic fine
particles to TPU (a) is a process of pulverizing TPU (a), adding
the desired amounts of ethylene bisoleic acid amide and/or the
crosslinked organic fine particles and melt kneading them using
an extruder.
20 [0056]
Thermoplastic resin (B)
For the thermoplastic resin (B) which is a raw material
other than TPU(a) for forming long fibers of the spunbonded
non-woven fabric of the present invention, various known
SF-2364 27
thermoplastic resins other than TPU(a) can be used. The
thermoplastic resin (B) is a resinous polymer different from
TPU(a) and is usually a crystalline polymer having a melting
point (Tm) of not lower than 100° C or a noncrystalline polymer
having a glass transition temperature of not lower than 100°
C. The thermoplastic resin (B) is preferably the crystalline
thermoplastic resin.
[0057]
As the thermoplastic resin (B), a thermoplastic resin
10 (extendable thermoplastic resin) having such properties that
the non-woven fabric prepared by a known process for producing
a spunbonded non--woven fabric has a maximum point elongation
of not less than 50%, preferably not less than 700, more
preferably not less than 100%, and has little elastic recovery
15 is preferred because when a spunbonded non-woven fabric prepared
by mixing the thermoplastic resin and the long fibers of TPU (a)
is stretched and processed, more bulkiness is expressed and the
touch is better and further the elongation end function can be
add to the spunbonded nonwoven fabric. The upper limit of the
20 maximum point elongation of the spunbonded nonwoven fabric made
of the thermoplastic resin (B), which is not particularly limited,
is usually not more than 300%.
[0058]
Examples of the thermoplastic resin (B) are a polyolefin
SF-2364 28
which is a homopolymer or copolymer of a-olefins such as
ethylene, propylene, 1-butene, l-hexene, 4-methyl-l-pentene
and l-octene such as, high pressure low density polyethylene,
linear low density polyethylene (LLDPE), high density
5 polyethylene (HDPE), polypropylene (propylene homopolymer), a
polyolefin (such as polypropylene random copolymer,
poly®l®butene, poly-4-methyl®l-®pentene, ethylene/propylene
random copolymer, ethylene/l-butene random copolymer and
propylene/1-butene random copolymer);
10 a polyester (such as polyethylene terephthalate,
polybutylene terephthalate and polyethylene naphthal.ate), a
polyamide (such as nylon-6, nylon-66 and polymethaxylene
adipamide), polyvinylchloride, polyimide,
ethylene/vinylacetate copolymer,
15 ethylene/vinylacetate/vinylalcohol copolymer,
ethylene/(meth)acrylic acid copolymer,
ethylene-acrylate-=carbon monoxide copolymer,
polyacrylonitrile, polycarbonate, polystyrene, ionomer and
their mixtures.
20 More preferable examples are high---pressure low-density
polyethylene, linear low-density polyethylene (LLDPF), high
density polyethylene, a propylene polymer such as polypropylene
and a polypropylene random copolymer, polyethylene
terephthalate and polyamide.
SF-2364 29
[0059]
Of these thermoplastic resins (B), polyolefin is
preferred and a propylene polymer is particularly preferred from
the viewpoint of spinning stability at the time of molding and
stretching processability of the nonwoven fabric.
[0060]
Preferable examples of the propylene polymer are a
propylene homopolymer having a melting point (Tm) of not lower
than 155° C, preferably 157 to 165 C and a copolymer of propylene
10 and a slight amount of at least one or two or more a -olefins
having at least two carbon atoms (excluding 3 carbon atoms),
preferably 2 to 8 carbon atoms (excluding 3 carbon atoms) such
as ethylene, 1-butene, 1- -pentene, 1-hexene, lmoctene and
4-methyl-l-pentene.
15 [0061]
The melt flow rate (MFR: ASTM D-1238, 230° C, a load of
2160 g) of the propylene polymer is not particularly limited
as long as melt spinning can be carried out. The melt flow rate
of the propylene polymer is usually 1 to 1000 g/10 min, preferably
20 5 to 500 g/10 min, more preferably 10 to 100 g/10 min. The
propylene polymer of the present invention has a ratio Mw/Mn
of weight average molecular weight (Mw) to number average
molecular weight (Mn) of usually 1.5 to 5.0. Furthermore, the
ratio is preferably in the range of 1,5 to 3.0 because the
SF-2364 30
spinning properties are good and fibers having more excellent
fiber strength can be prepared. Mw and Mn can be measured using
GPC (gel permeation chromatography) by a known method.
[0062]
5 The olefin polymer composition prepared by adding HDPE
in a small amount of 1 to 20 % by weight, preferably 2 to 15 %
by weight, furthermore preferably 4 to 10 % by weight based on
100 % by weight of the total amount of the propylene polymer
and HDPE to the propylene polymer is preferred from the viewpoint
10 of spinning properties and stretching processability because
it is possible to further improve the stretching processing
properties of the resulting spunbonded non--woven fabric.
[0063]
HDPE for adding to the propylene has a density, which is
15 not particularly limited, of usually 0494 to 0,97 g/cm3,
preferably 0 0 95 to 0.97 g/cm3, more preferably 0.96 to 097 g/cm3
Moreover, HDPE has a melt flow rate, which is not particularly
limited as long as it has spinning properties, of usually 041
to 100 g/10 min, preferably 005 to 50 g/10min, more preferably
20 1 to 30 g/10 min from the viewpoint of expressing elongation
properties, wherein the melt flow rate MFR is determined by ASTM
D-1238 at 190°C under a load of 2160 g. The expression "good
spinning properties" in the present invention means that fiber
cut is not caused and fiber fusion is not caused at the time
SF-2364 31
of outputting from a spinning nozzle and during stretching.
[0064]
Additive
To the thermoplastic resin (B) of the present invention,
5 various known additives such as an antioxidant, a heat stabilizer,
a weather stabilizer, an antistatic agent, a slipping agent,
an antifogging agent, a lubricant, a dye, a pigment, a natural
oil, a synthetic oil and a wax can be added previously as an
optional component within not missing the object of the present
10 invention.
[0065]
Examples of the additives are a hindered phenol
antioxidant such as 2,6Gdi-t-butyl-4--methylphenol (BHT),
pentaerythritol
15 totrakis[3-(3,5-dict-butyl-c4-hydroxyphenyl)propionate]
(Trade name: Irganox"1010, manufactured by Ciba Specialty Tnca) ,
6- (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester,
2,2'-oxamide bis[ethyl-3-(3,5-di.-t-butyl-4-hydroxyphenyl)]
propionate; an aliphatic acid metal salt such as zinc stearate,
20 calcium stearate and 1,2-hydroxycalcium stearate; a
polyvalent alcohol aliphatic acid ester such as glycerin
monostearate, glycerin distearate, pentaerythritol
monostearate, pentaerythritol distearate and pentaerythritol
tristearateo These may be used singly or two or more may be
SF-2364 32
combined for use.
[0066]
Spunbonded nonwoven fabric
The spunbonded non-woven fabric of the present invention
5 is a spunbonded non-woven fabric containing long fibers of TPU (A)
It is not particularly limited as long as it contains the long
fibers of TPU (A) o It comprises only the long fibers of TPU (A)
or furthermore comprises other fibers additionally.
[0067]
10 The spunbonded nonwoven fabric of the present invention
preferably comprises the long fibers of TPU(A) and the long
fibers of the thermoplastic resin (B), and more preferably
comprises the long fibers of TPU (A) and the long fibers of the
thermoplastic resin (B) in a proportion of 10/90 % by mass to
15 90/10 % by mass based on 100 % by weight of the total weight
of (A) and (B) a When the spunbonded nonwoven fabric contains
other resins in addition to the long fibers of TPU(A), it has
improved touch and flexibility and can be suitably used for
sanitary materials such as paper diapers and the like.
20 [0068]
The spunbonded non-woven fabric of the present invention
more preferably comprises the long fibers of TPU (A) in an amount
of preferably not less than 20 % by mass, more preferably not
less than 30 % by mass from the viewpoints of stretchability
,SF-2364 33
and flexibility, and it furthermore comprise the long fibers
of TPU (A) in an amount of preferably not more than 70 % by mass,
more preferably not more than 60 % by mass from the viewpoint
of processing properties (resistance to tackiness).
[0069]
The spunbonded nonwoven fabric of the present invention
has excellent stretching properties (hereinafter sometimes
referred to "stretching properties (I) ") as compared wit.1-1 those
of conventional spunbonded nonwoven fabrics because of
10 containing the long fibers of TPU(A) The stretching properties
are represented by a stress ratio (S1/S2) in the following way.
For example, a specimen having a size of 200 mm(MD) x 25 mm (CD)
is prepared from the spunbonded nonwoven fabric. Using a
universal tensile testing machine (IM-201 type, manufactured
15 by Intesco Co., Ltd.), the specimen is stretched by 100% in a
sample width of 25 mm, in a chuck distance of 100 Arun at a I ensile
rate of 300 mm/min and thereafter, the specimen is recovered
until the original size at the same rate. This cycle is repeated
twice. The value after the two cycle repetition (stress at the
20 time of 50% stretching (S1) stress at the time of 50% recovery
(S2)), namely, stress ratio (S1/S2) is taken as the stretching
properties.
[0070]
As the stretching properties (I) are smaller, they are
SF--2364 34
more excellent. Furthermore, the stretching properties depend
on the amount of the long fibers of TPU(A) contained in the
spunbonded nonwoven fabric. For example, when the amount of
the long fibers of TPU(A)is 70 % by mass and the stretching
5 properties are not more than 1. 72, when it is 55 % by mass and
the stretching properties are not more than 1.82, when it is
50 % by mass and the stretching properties are not more than
1087, when it is 40 % by mass and the stretching properties
are not more than 1. 94, or when it is 30 % by mass and the
10 stretching properties are not more than 2.01, the resulting
spunbonded non-woven fabric has excellent stretching properties
even after stretching. Furthermore,
1,4rybis(2-hydroxyethoxy)benzene is preferably used as the chain
extender because the resulting spunbonded nonwoven fabric has
15 more excellent stretching properties.
[0071]
The long fibers of TPU(A) and the long fibers of the
thermoplastic resin (B) for forming the spunbonded nonwoven
fabric according to the present invention each have an average
20 fiber diameter of usually not more than 50 pm, preferably not
more than 40 I_Lm, more preferably not more than 30 jim. The fiber
diameter of the long fibers of TPU(A) may be the same as or
different from that of the long fibers of the thermoplastic resin
(B).
ISF-2364 35
The spunbonded non-woven fabric of the present invention
has a basis weight in terms of the total laminate of usually
not more than 120 g/m2, preferably not more than 80 g/m2, more
preferably not more than 50 g/m2, furthermore preferably 40 to
15 g/m2 from the viewpoints of flexibility and permeability in
the sanitary material use such as diapers and the like.
[0072]
The spunbonded non-woven fabric of the present invention
may be a single layer or a laminate of two or more layers. When
10 the spunbonded non-woven fabric is the laminate of two or more
layers, one laminate has such a proportion (fiber combining
ratio) of the long fibers of TPU (A) and the long fibers of the
thermoplastic resin (B) in the spunbonded non-woven fabric of
each layer such that it may be same as or different from that
15 of the other layer.
[0073]
When spunbonded non-woven fabrics having a different
fiber combining ratio are laminated, the laminate may comprise
a spunbonded non-woven fabric containing only the long fibers
20 of TPU(A), a spunbonded non-woven fabric containing over 90 %
by mass of the long fibers of TPU(A), a spunbonded non-woven
fabric containing only the long fibers of the thermoplastic resin
(B) or a spunbonded non-woven fabric containing over 90 % by
mass of the long fibers of the thermoplastic resin (B)a When
SF'--2364 36
the laminate comprises a layer of a spunbonded non--woven fabric
having a proportion of the long fibers of TPU (A) or a proportion
of the long fibers of the thermoplastic resin (B) beyond the
above range, the proportion of the long fibers of TPU (A) in the
whole laminate is preferably in the above range.
[0074]
The fiber-combining ratio indicates a proportion of
specific kinds of fibers in a layer of a spunbonded non--woven
fabric obtainable by mixing two or more kinds of fibers or a
10 mixing proportion of each kind of fibers in the nonwoven fabric
layer. That is to say, in the layer of a spunbonded non-woven
fabric which comprises TPU (A) and the thermoplastic resin (B),
the fiber-combining ratio of the long fibers of TPU(A) is
determined by dividing the weight of the long fibers of TPU (A)
15 with the total weight of the long fibers of TPU (A) and the long
fibers of the thermoplastic resin (B) [the weight of the long
fibers of TPU(A) / (the weight of the long fibers of TPU(A) +
the weight of the long fibers of the thermoplastic resin (B) ) ]
The fiber-combining ratio of the long fibers of the thermoplastic
20 resin (B) is determined by dividing the weight of the long fibers
of the thermoplastic resin (B) with the total weight of the long
fibers of TPU (A) and the long fibers of the thermoplastic resin
(B) [the weight of the long fibers of thermoplastic resin (B)
/ (the weight of the long fibers of TPU (A) + the weight of the
SF--2364 37
long fibers of the thermoplastic resin (B))]. Furthermore,
in the layers of the spunbonded non-woven fabrics formed from
TPU (A) and the thermoplastic resin (B), the expression that the
fiber combining ratio is different means that the fiber combining
ratio of (A) and (B) is different in each of the non-woven fabric
layers.
[0075]
In the spunbonded non-woven fabric laminate having at
least two layers, at least one layer is preferably a spunbonded
10 non-woven fabric layer (C-1) which comprises the long fibers
of TPU (A) in an amount of preferably 40 to 95 % by weight, more
preferably 40 to 90 % by weight, furthermore preferably 50 to
80 % by weight and the long fibers of the thermoplastic resin
(B) in an amount of preferably 60 to 5 % by weight, more preferably
15 60 to 10 % by weight, furthermore preferably 50 to 20 % by weight
provided that the total of (A) and (B) is 100 % by weighi o The
other layer is preferably a spunbonded non-woven fabric layer
(C-2) which comprises the long fibers of TPU(A) in an amount
of preferably 10 to 60 % by weight, more preferably 10 to 55 %
20 by weight, furthermore preferably 10 to 50 % by weight and the
long fibers of the thermoplastic resin (B) in an amount of
preferably 90 to 40 % by weight, more preferably 90 to 45 % by
weight, furthermore preferably 90 to 50 % by weight provided
that the total of (A) and (B) is 100 % by weight.
SF-2364
[0076]
38
The spunbonded non-woven fabric layers (Ca=1) and (Cc2)
may be laminated continuously or may be laminated through another
spunbonded non-woven fabric layer, a melt blown non-woven f abric
layer, a film layer or an adhesive layer.
[0077]
As another embodiment of the present invention, there is
a non-woven f abr ic laminate having three layers of fiber combined
spunbonded non-woven fabrics such that the laminate has at least
10 three layers containing the long fibers of TPU (A) and the long
fibers of the thermoplastic resin (B) , and the fiber mixed
spunbonded non-woven fabric layer placed in the middle of the
three spunbonded nonwoven fabric layers (intermediate layer)
has a fiber combining ratio of the thermoplastic elastomer (A)
15 larger than that of each of the other two layers.
[0078]
In the other spunbonded nonwoven fabric layers placed
on both sides of the intermediate layer, the fiber combining
ratio of the long fibers of -the thermoplastic elastomer (A) may
20 be the same as or different from each other. It is unnecessary
that the three fiber combined spunbonded layers are laminated
continuously„ The three fiber combined spunbonded layers may
be laminated through another spunbonded non---woven fabric layer,
a melt blown non--woven fabric, a film layer or an adhesive layer.
SF'-2364 39
Moreover, on at least one outside or both outsides of the three
layered laminate, another fiber combined nonwoven fabric layer
may be laminated and the fiber combined nonwoven fabric layer
has a fiber combining ratio of TPU(A) larger than or smaller
than that of the intermediate layer.
[0079]
Specifically, the intermediate layer is preferably a
spunbonded nonwoven fabric layer (D--1) which comprises the long
fibers of TPU (A) in an amount of preferably 40 to 100 % by weight,
1_0 more preferably 40 to 95 % by weight, furthermore preferably
50 to 90 % by weight and the long fibers of the thermoplastic
resin (B) in an amount of preferably 60 to 0 % by weight, more
preferably 60 to 5 % by weight, furthermore preferably 50 to
10 % by weight provided that the total of (A) and (B) is 100 %
15 by weight
[0080]
The two spunbonded non-woven fabric layers which are
placed on both sides of the intermediate layer are a spunbonded
non-woven fabric layer (D-2) which comprises the long fibers
20 of TPU (A) in an amount of preferably 10 to 60 % by weight, more
preferably 10 to 55 % by weight, furthermore preferably 10 to
50 % by weight and the long fibers of the thermoplastic resin
(B) in an amount of preferably 90 to 40 % by weight, more
preferably 90 to 45 % by weight, furthermore preferably 90 to
SF-2364 40
50 % by weight, and a spunbonded non-woven fabric layer (D--3)
which comprises the long fibers of TPU(A) in an amount of
preferably 10 to 60 % by weight, more preferably 10 to 55 % by
weight, furthermore preferably 10 to 50 % by weight and the long
5 fibers of the thermoplastic resin (B) in an amount of preferably
90 to 40 % by weight, more preferably 90 to 45 % by weight,
furthermore preferably 90 to 50 % by weight provided that the
total of (A) and (B) is 100 % by weight.
[0081]
10 In the spunbonded nonwoven fabric laminate, the
intermediate layer (DN1) has a fiber combining rate of the long
fibers of TPU(A) larger than those of the spunbonded non---woven
fabric layers (D-2) and (D-3)a
[0082]
15 The fiber combining ratios of the long fibers of TPU (A) in
the two spunbonded non-woven fabric layers (D-2) and (D-3) which
are placed on both sides of the intermediate layer (D-1) may
be same as or different each other. It is preferred that the
difference between the fiber combining ratios of the long fibers
20 of TPU(A)in the two spunbonded nonwoven fabric layers (D-2)
and (D-3) be preferably not more than 40 %, more preferably not
more than 30 %, furthermore preferably not more than 20 %,
specially preferably 10 to 0 % and the difference between the
basis weights of (D72) and (D-3), namely the values of
,SF--2364 41
(Di)/(D2) and (Di)/(D-3) be preferably 2 to 05, more
preferably 1.5 to 0067, furthermore preferably 1.2 to 0083,
specially preferably 101 to 0.91 because the productivity can
be enhanced.
5 [0083]
Process for producing spunbonded non-woven fabric
The spunbonded non-woven fabric of the present invention
can be produced using TPU(A) or TPU(A) and the thermoplastic
resin (B) by a known production process of spunbonded non-woven
10 fabrics, for example, the process as described in
JP-A-2004--244791
[0084]
Specifically, the spunbonded nonwoven fabric can be
produced by the following process of:
15 (1) a step of melting the thermoplastic polyurethane elastomer
(A) containing ethylene bisoleic acid amide and/or cross linked
organic fine particles and having a hardness of 75 to 85, or
TPU(A)and the thermoplastic resin (B) other than the
thermoplastic polyurethane elastomer (A) respectively,
20 (I1) a step of extruding the thermoplastic polyurethane
elastomer (A), or TPU(A)and the thermoplastic resin (B)
respectively from different nozzles provided on the same die
simultaneously and depositing mixed fibers of long fibers of
the thermoplastic polyurethane elastomer (A), or long fibers
SF-2364 42
of TPU(A)and long fibers of the thermoplastic resin (B) by
spinning, and
(III) a step of partly fusing the deposit prepared in the above.
[0085]
5 More specifically, TPU (A) or TPU (A) and the thermoplastic
resin (B) are melted by different extruders respectively, and
the molten polymers are introduced respectively into dies
equipped with a large number of spinning nozzles. TPU(AA) and
the thermoplastic resin (B) are output simultaneously from
10 different spinning holes respectively. Thereafter, the long
fibers of TPU (A) and the long fibers of the thermoplastic resin
(B) molten and spun are introduced into a cooling room and cooled
with cool air. The long fibers are stretched by stretching air
and are deposited on a movable collecting surface. The melting
15 temperature of the polymers is not particularly limited as long
as it is higher than the softening temperature or melting
temperature of each polymer and lower than the thermolysis
temperature, and it can be determined by the polymer for use.
The die temperature depends on the polymer for use. For example,
20 when a propylene polymer or an olefin polymer composition of
a propylene polymer and HDPE is used as the thermoplastic resin
(B), the die temperature is determined in the range of usually
180 to 2400 C, preferably 190 to 230° C, more preferably 200 to
225° C.
SF-2364
[0086]
43
The temperature of the cooling air is not particularly
limited as long as the polymer can be solidified. For example,
the temperature of the cooling air is in the range of usually
5 to 50° C, preferably 10 to 40° C, more preferably 15 to 30°
C. The air rate of the stretching air is in the range of usually
100 to 10,000 m/min, preferably 500 to 10,000 m/mina
[0087]
The mixed fibers are deposited in a web form on the movable
10 collecting surface by the above method, and then the deposit
is transported by contacting with a rotational device such as
a belt, a nip roll and the like. Thereafter, the deposit is
subjected to confounding treatment by needle punch, water jet
or ultrasonic sealing, or heat fusion treatment by heat embossing
15 roll and thereby the deposit is fused partly. It is preferred
to employ heat fusion treatment by heat embossing roll. The
embossing temperature is usually from 50 to 160° C, preferably
60 to 150° C. The embossed area ratio by embossing roll can be
determined appropriately. The embossed area ratio is
20 preferably 5 to 30%.
[0088]
Stretchable spunbonded non-woven fabric
The stretchable spunbonded non-woven fabric of the present
invention is a non-woven fabric obtainable by stretching the
SF-2364 44
above spunbonded nonwoven fabric. Since the spunbonded
non-woven fabric comprises the long fibers of TPU (A) and other
fibers, the nonwoven fabric obtainable by stretching has
excellent touch, flexibility and stretchability and can be
favorably used for sanitary materials such as paper diapers and
the like.
[0089]
A specimen is prepared from the stretchable spunbonded
nonwoven fabric. Using a universal tensile testing machine
10 (IM-201 type, manufactured by Intesco Co., Ltd.), the specimen
is stretched by 100% in a sample width of 25 mm, in a chuck distance
of 100 mm at a tensile rate of 300 mm/min and thereafter, the
specimen is recovered until the original size at the same rate.
This cycle is carried out. The value after the cycle (stress
15 at the time of 50% stretching (S1) - stress at the time of 50%
recovery (S2) , namely, stress ratio (S1/S2) is taken s the
stretching properties (hereinafter sometime referred to
"stretching properties (II))o The stretchable spunbonded
nonwoven fabric of the present invention has a more excellent
20 stress ratio (S1/S2) than that of the spunbonded nonwoven fabric
containing the long fibers of TPU(A) before stretching.
[0090]
Similar to the stretching properties (I), the stretching
properties (II) depends on the amount of the long fibers of TPU (A)
SF--2364 45
For example, when the amount of the long fibers of TPU (A) is 70 %
by mass and the stretching properties are not more than "1.61,
when it is 55 % by mass and the stretching properties are not
more than 1071, when it is 50 % by mass and the stretching
5 properties are not more than L75, when it is 40 % by mass and
the stretching properties are not more than 1088, or when it
is 30 % by mass and the stretching properties are not more than
1.89, the resulting spunbonded nonwoven fabric has excellent
stretching properties. TPU(A2) is preferably used as TPU(A)
10 because the resulting stretchable spunbonded non-woven fabric
has more excellent stretching properties.
[0091]
Process for producing stretchable spunbonded non-woven fabric
The stretchable spunbonded nonwoven fabric of the
15 present invention can be obtained by stretching processing the
above spunbonded non-woven fabric. As the process for
stretching processing, conventionally known processes are
applicable. It may be a partly stretching process or an overall
stretching process. Moreover, it may be mono axial stretching
20 or biaxial stretching. As the process for stretching in a
machine flow direction (MD) , for example, the partly fused mixed
fibers are passed through two or more nip rolls.. During passing
the fibers, the partly fused mixed fibers can be stretched by
increasing the rotation rates of the nip rolls in order of the
SF-2364 46
MD direction. Fig. 1 shows a gear stretching device equipped
with a pair of gear rolls. Using the gear stretching device as
shown in Fig®1, the spunbonded non-woven fabric 2 can be
processed with gear stretching.
[0092]
The stretching magnification is preferably not less than
50%, more preferably not less than 100%, furthermore preferably
not less than 200%, and preferably not more than 10001";, more
preferably not more than 400%. In the case of mono-axial
10 stretching, the preferred stretching magnification is carried
out in any of the MD direction and the CD direction vertical
to the MD direction. In the case of two-axial stretching, the
preferred stretching magnification is carried out in both of
the MD direction and the CD direction vertical to the MD direction.
15 Carrying out the stretching processing in such a stretching
magnification, the stretchable non-woven fabric has to fiber
diameter of usually not more than 50 μm, preferably not more than
40 μm, more preferably not more than 30 μm.
[0093]
20 The stretchable non-woven fabric thus prepared has
excellent fuzz resistance, touch and stretchability which are
suitable for sanitary materials such as disposable diapers,
sanitary napkins, bladder control pads and the like.
Particularly, the stretchable non-woven fabric having more
SF 2364 47
excellent effects can be prepared by stretching and processing
the mixed fibers containing the long fibers of TPU(A) and the
long fibers of the polymers of polyethylene and/or polypropylene
and having expansion properties in the above stretching
magnification.
[0094]
The spunbonded non-woven fabric of the present invention
may be laminated on one side or both sides thereof with other
layers. The other layers laminated on the spunbonded nonwoven
10 fabric are particularly not limited and various kinds of layers
can be laminated thereon according to the use.
[0095]
Examples of the other layers are knitting fabrics, woven
fabrics, non-woven fabrics and films. When the other layers are
15 laminated (adhered) to the nonwoven fabric laminate of the
present invention, it is possible to employ various known methods,
for example, a heat fusion method such as heat embossing
processing and ultrasonic fusion, a mechanical confounding
method such as needle punch and water jet, a method of using
20 an adhesive agent such as a hot melt adhesive agent and a urethane
adhesive agent, and extrusion laminating.
[0096]
Examples of the non--woven fabric laminated on the
spunbonded nonwoven fabric of the present invention may include
SF--2364 48
various known non-woven fabrics such as a spunbonded non-woven
fabric other than the spunbonded non-woven fabric of the present
invention, a melt blown non-woven fabric, a wet non-woven fabric,
a dry non-woven fabric, a dry pulp nonwoven fabric, a flash
5 spinning non-woven fabric and split non-woven fabric. These
non-woven fabrics may be non-stretchable non-woven fabrics.
The non-stretchable non-woven fabrics have a MD or CD elongation
at rupture of about. 50% and do not cause return stress after
stretching.
1 0 [00 971
The film laminated on the spunbonded non-woven fabric of
the present invention is preferably a film having permeability
(moisture permeability) which can make the best use of the
permeability of the spunbonded non-woven fabric of the present
15 invention. As the film having permeability, various known films
having permeability are used. Specific examples thereof are
films made of a thermoplastic elastomer having moisture
permeability such as polyurethane elastomer, polyester
elastomer and polyamide elastomer, and porous films obtainable
20 by stretching films made of a thermoplastic resin containing
inorganic or organic fine particles. Examples of the
thermoplastic resin preferably used for the porous films are
polyolefins such as high pressure low density polyethylene,
linear low density polyethylene (namely, LLDPE), high density
SF-2364 4 9
polyethylene, polypropylene, polypropylene random copolymer
and compositions thereof.
[0098]
The laminate with the film having permeability can be made
5 into a cloth-like complex material having very high water
resistance and capable of making the best use of flexibility
and stretchability of the spunbonded non-woven fabric of the
present invention.
EXAMPLE
10 [0099]
The present invention is described in more detail with
reference to the following examples, but it should not be limited
by them.
[0100]
15 The physical properties in the examples and comparative
examples were determined by the following methods,
[0101]
(1) Basis weight [g/m2]
Six specimens having a size of 200 mm (machine direction-
20 MD) x 50 mm (crosswise direction: CD) were collected from a
spunbonded non-woven fabric and/or a spunbonded non-woven fabric
laminate. The specimens were collected in any 3 places in the
MD direction or CD direction (total 6 places) F Next, the mass
(g) of each of the specimens was measured using an electronic
SF--2364 50
even balance (manufactured by Kensei Co., Ltd.). The average
of the masses of each specimen was determined. From the average,
each mass was converted to the mass (g) per I m2 and the value
was rounded off the second decimal place and taken as the basis
weight [g/m2] of each non-woven fabric specimen.
[0102]
(2) Maximum strength [N/ 50 mm] and maximum point elongation
1%]
The measurement was carried out according to JIS L1906.
10 Six specimens having a size of 200 mm (machine direction: MD)
x 50 mm (crosswise direction: CD) were collected from a
spunbonded nonwoven fabric and/or a spunbonded non-woven fabric
laminate. The specimens were collected in any 3 places in the
MD direction or CD direction (total 6 places) Next, each
15 specimen was subjected to tensile test at a spun width 10 of
100 mm at tensile rate of 100 mm/min using a universal '1-ensile
testing machine (IM-201 type, manufactured by Intesco Co 4 , Ltd 4 )
The maximum strength [N/ 50 mm] and the maximum point elongation
[%] were determined. The maximum strength was determined by
20 averaging the values on the 6 places (MD, CD each 3 places) and
rounding the average off the second decimal place. The maximum
point elongation was determined by averaging the values on the
6 places (MD, CD each 3 places) and rounding the average off
the first decimal place.
SF-2364 51
[0103]
(3) Stretching properties (I)
The measurement was carried out using a universal tensile
testing machine (IM-201 type, manufactured by Intesco Co., Ltda)o
5 A specimen having a size of 200 mm (MD) x 25 mm (CD) was collected
from a spunbonded nonwoven fabric and/or a spunbonded nonwoven
fabric laminate. The specimen was stretched by 100% in a sample
width of 25 mm, in a chuck distance of 100 mm at a tensile rate
of 300 mm/mm and thereafter, the specimen was recovered until
10 the original size at the same rate. This cycle was repeated twice.
The value after the two cycle repetition (stress at the time
of 50% stretching (Si) - stress at the time of 50% recovery (S2) ) ,
namely, stress ratio (S1/S2) was determined and taken as the
criterion of the stretching properties. When the stress ratio
15 is smaller, the stretching properties are more excellent. The
specimen was collected in any 3 places in the MD direct.i.on or
CD direction and each average was determined and rounded off
in the third decimal place. As the stress ratio, a higher value
was used in each average value in the MD direction and the CD
20 direction.
[0104]
(4) Stretching treatment
The measurement was carried out using a universal tensile
testing machine (IM-201 type, manufactured by Intesco Co,, Ltd.)
SF-2364 52
A specimen having a size of 200 mm (MD) x 25 mm (CD) was collected
from a spunbonded non-woven fabric and/or a spunbonded nonwoven
fabric laminate. The specimen was stretched by 150% in a sample
width of 25 mm, in a chuck distance of 100 mm at a tensile rate
5 of 300 mm/min and -thereafter, the specimen was recovered until
the original size at the same rate.
[0105]
(5) Stretching properties (II)
The spunbonded non-woven fabric prepared by stretching
10 treatment (stretchable spunbonded nonwoven fabric) was
evaluated in accordance with the measuring method of the
stretching properties (I) The specimen was stretched by 100%
in a sample width of 25 mm, in a chuck distance of 100 mm at
a tensile rate of 300 mm/min and thereafter, the specimen was
15 recovered until the original size at the same rate. After this
cycle, the value ( Lress at the time of 50% stretching (Si)
stress at the time of 50% recovery (S2)), namely, stress ratio
(Sl/S2) was determined and taken as the criterion of the
stretching physical properties. When the stress ratio is smaller,
20 the stretching properties are more excellent. The specimen was
collected in any 3 places in the MD direction and CD direction
and each average was determined and rounded off in the third
decimal place. As the stress ratio, a higher value was used
in each average value in the MD direction and the CD direction
SF=2364 53
[0106]
(6) Tackiness
Ten panelists touch on the spunbonded nonwoven fabric
and/or the spunbonded non-woven fabric laminate with their hands
5 and evaluated the tackiness in the following criterion.
Furthermore, the condition before (4) stretching treatment
indicates before stretching treatment and the condition after
measurement indicates after stretching treatment.
[0107]
10 Very good: 10 panelists felt no tackiness and fine touch.
[0108]
Good: 9 to 7 panelists of 10 panelists felt no tackiness and
fine touch.
[0109]
15 Somewhat good: 6 to 3 panelists of 10 panelists felt no tackiness
and fine touch.
[0110]
No good: 2 to 0 panelists of 10 panelists felt no tackiness and
fine touch.
20 [0111]
(7) Spinning properties
The spinning condition around the nozzle surface of a
device of producing the spunbonded non--woven fabric was observed
visually. The number of fiber break per 5 min was counted (unit:
SF--2364 54
times/5 min).
[0112]
(8) Adhesion
In the device for producing the spunbonded non-woven
5 fabric, the mixed fibers were deposited on a belt and derived
for 5 mine When the web was passed through metal made nip rolls,
the web adhesion condition was evaluated as the adhesion to rolls
(I)
[0113]
10 Good: Web adhesion was not confirmed at all visually.
[0114]
Somewhat good: Web adhesion was not nearly confirmed visually.
[0115]
No good: Web adhesion was confirmed visually, or the web was
15 wound.
[0116]
In the above method, when the mixed fibers were deposited
on the belt and then derived for 10 min, the web condition was
evaluated as the adhesion to rolls (2)0
20 [0117]
(9) Hardness
The hardness of TPU was measured using a type A durometer
in accordance with JIS K-7311,
[0118]
SF-2364 55
(10) Molecular weight
The molecular weight of TPU was determined in the
following manner. TPU was dissolved in a concentration of 0. 4 %
by mass using a high-power GPC column (TSKgel GMHXL manufactured
5 by Tohso Coo, Ltd.) and measured in conditions that the sample
injected amount was 100 μl and the flow rate of the elution THE
was 1.0 ml/min using GPC device. From the resulting elution
curve, the number average molecular weight (Mn) , weight average
molecular weight (Mw) and Mw/Mn were determined using
10 polystyrene as a standard.
[0119]
(11) Melt viscosity
TPU was dried. at 100° C for 2 hr and about 2 g of a specimen
was weighed. Using an elevated flow tester (manufactured by
15 Shimadzu Corporation), the melt viscosity of the specimen was
measured under a load of 30 kgf/cm2 using a dice of 1 rr_tt0 x 1
mml for a preheating time of 4 min at a measuring temperature
of 200° C (unit. 104dPa- s)
(12) Fluid initiation temperature
20 TPU was dried at 1000 C for 2 hr and about 2 g of a specimen
was weighed. Using an elevated flow tester (manufactured by
Shimadzu Corporation), the fluid initiation temperature of the
specimen was measured under a load of 30 kgf/cm2 using a dice
of 1 mmO x 1 mml for a preheating time of 10 min by increasing
5E--2364 56
the temperature from 1000 C (unit: 0 C)
[0121]
TPU Production Example 1
71 0 1. parts by weight of polyester polyol having a number
average molecular weight of 1932, 408 parts by weight
1,4-butane diol (hereinafter abbreviated to "BD"), 0a3 part by
weight of pentaerythritol
tetr_akis [3- (3, 5-di-_trybutyl-4--hyd.r_oxyphenyl) propionate]
(hereinafter abbreviated to "antioxidant-l") and 003 part by
10 weight of polycarbone diimide were mixed. To the mixture, 22.9
parts by weight of MDI was added and mixed with highly stirring
sufficiently and reacted at 160°C for 1 hr. The reactant was
pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, 002 part by weight of ethylene bisstearic
15 acid amide, 0,5 part by weight of triethylene
glycol®bis-[3-(3,5-di-t-butyl®4®hydroxyphenyl)propioni-ate]
(hereinafter abbreviated to"antioxidant-2"), 0.4 part by weight
of ethylene bisoleic acid amide (hereinafter abbreviated to
"EOA") and 0. 8 part by weight of fine particles having an average
20 particle diameter of 2. 0 jtm were mixed. Thereafter, the mixture
was melt kneaded using an extruder at a set temperature of 210°C
and thereby granulated to prepare a thermoplastic polyurethane
elastomer [TPU (A-- 1) ] .
[0122]
SF-2364 57
The physical properties of TPU (A-1) were measured by the
above methods. The results are shown in Table 1.
[0123]
TPU Production Example 2
5 71.7 parts by weight of polyester polyol having a number
average molecular weight of 1932, 408 parts by weight of BD,
0.3 part by weight of antioxidant-1 and 0.3 part by weight of
polycarbone diiimide were mixed. To the mixture, 22.9 parts by
weight of MDI was added and mixed with highly stirring
10 sufficiently and reacted at 160°C for 1 hr. The reactant was
pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, 008 part by weight of ethylene bisstearic
acid amide, 0.5 part by weight of antioxidant-2 and 008 part
by weight of EOA were mixed. Thereafter, the mixture was melt
15 kneaded using an extruder at a set temperature of 210°C and
thereby granulated to prepare a thermoplastic polyurethane
elastomer [TPU(A-2)]o
[0124]
The physical properties of TPU (A'2) were measured by the
20 above methods. The results are shown in Table 1.
[0125]
TPU Production Example 3
63.8 parts by weight of polyester polyol having a number
average molecular weight of 1932, 7..3 parts by weight of BD,
SF-2364 58
0.3 part by weight of antioxidant-1 and 0.3 part by weight of
polycarbone diimide were mixed. To the mixture, 28.3 parts by
weight of MDI was added and mixed with highly stirring
sufficiently and then reacted at 160°C for 1 hr. The reactant
5 was pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, 0.4 part by weight of ethylene bisstearic
acid amide and 0.5 part by weight of antioxidant-2 were mixed
Thereafter, the mixture was melt kneaded using an extruder at
a set temperature of 210°C and thereby granulated to prepare
10 a thermoplastic polyurethane elastomer [TPU(E--1)].
[0126]
The physical properties of TPU (E-1) were measured by the
above methods. The results are shown in Table 1.
[0127]
15 TPU Production Example 4
71 0 7 parts by weight of polyester polyol having a number
average molecular weight of 1932, 408 parts by weight of BD,
003 part by weight of antioxidant-1 and 0.3 part by weight of
polycarbone diimide were mixed. To the mixture, 22.9 parts by
20 weight of MDI was added and mixed with highly stirring
sufficiently and then reacted at 160°C for 1 hr. The reactant
was pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, 004 part by weight of ethylene bisstearic
acid amide and 0.5 part by weight of antioxidant-2 were mixed
SF-2364 59
ti
Thereafter, the mixture was melt kneaded using an extruder at
a set temperature of 210°C and thereby granulated to prepare
a thermoplastic polyurethane elastomer [TPU(E-2)].
[0128]
The physical properties of TPU (E-2) were measured by the
above methods. The results are shown in Table 10
[0129]
Example -I
Preparation of thermoplastic resin composition for spunbonded
10 non-woven fabric
96 Parts by weight of a propylene homopolymer having an
MFR (measured in accordance with ASTM D1238 at 230°C under a
load of 2016 kg) of 60 g/10 min, a density of 0091 g/cm3 and a
melting point of 160°C (hereinafter abbreviated to "PP-1") was
15 mixed with 8 parts by weight of high density polyethylene having
an MFR (measured in accordance with ASTM D1238 at 190°c' under
a load of 2.16 kg) of 5 g/10 min, a density of 0097 g/cm3 and
a melting point of 134°C (hereinafter abbreviated to "HDPE")
to prepare a thermoplastic resin composition (B-1)o
20 [0130]
Production of spunbonded non-woven fabric
Each of TPU (A---1) and B-1 prepared in Production Example
1 was independently melted using an extruder of '75 mmo and an
extruder of 50 mmo and then melt spun using a spunbonded non-woven
SF--2364 60
fabric molding machine having a spinning port (length vertical
to the machine flow direction on colleting surface- 800 mm) in
such conditions that the resin temperature and the die
temperature were each 205°C and the cooling air temperature was
5 20°C and the stretching air rate was 3200 m/min to deposit a
web of the mixed long fibers formed from long fibers A of TPU (A-1)
and long fibers B of B-1 on the collecting surface. The spinning
port has a nozzle pattern such that output holes for TPU(A®1)
and output holes for B-1 were arranged one after the other. The
10 nozzle diameter for TPU (A--1) (fibers A) was 0.75 mmo and the
nozzle diameter for B--1 (fibers B) was 006 mmo. The nozzle pitch
in the vertical direction was 8 mm and the nozzle pitch in the
horizontal direction was 11 mm, and the ratio of the nozzle number
for fibers A to the nozzle number for fibers B was 1 e 1045.
15 The output amount of one hole for fibers A was 0.82 g/ (min ° hole )
and the output amount of one hole for fibers B was 0,56
g/(min -hole).
[0131]
The web of the mixed long fibers deposited was deposited
20 on a moving belt and passed through between a metal made nip
roll and a belt with a linear pressure of 15 kg/cm to prepare
a mixed spunbonded nonwoven fabric. The resulting mixed
spunbonded non--woven fabric had a basis weight of 30 g/m2 The
web of the mixed long fibers deposited had a large fiber diameter
SF-2364 61
of 27.1 μm and a small fiber diameter of 2202 μ.m. In results,
it was considered that the fiber diameter of TPU(A-1) was 27.1
pm and the fiber diameter of B-1 was 22.2 rim.
[0132]
5 The web was released from the moving belt and subjected
to heat embossing with an embossing pattern such that the area
rate was 18% and the embossed area was 0.41 mm2 at an average
heating temperature of 95°C at a linear pressure of 70 kg/cm
to prepare a spunbonded nonwoven fabric.
10 [0133]
The resulting spunbonded non---woven fabric was evaluated
by the above methods. The stretching properties (I) were
measured using the spunbonded non-woven fabric prepared before
stretching treatment, and the stretching properties (II) were
15 measured using the spunbonded non-woven fabric prepared after
stretching treatment namely using the stretchable spunnbonded
nonwoven fabric. The evaluation results are shown in Table 1 .
[0134]
Example 2
20 The procedure of Example 1 was repeated except for using
TPU(A-2) prepared in TPU production example 2 in place of
TPU(A-al) used in Example 1 to prepare a spunbonded non-woven
fabric. The resulting non-woven fabric was evaluated in the
same methods as those of Example 1. The results are shown in
SE'rn2364 62
Table 1.
[0135]
Example 3
The procedure of Example 2 was repeated except that the
5 individual hole output amount of fibers A was 0. 60 g/ min ° hole
and the individual hole output amount of fibers B was 0061 g/
min a hole to prepare a spunbonded non--woven fabric. The
resulting nonwoven fabric was evaluated in the same methods
as those of Example 2. The results are shown in Table 1.
10 [0136]
Example 4
The procedure of Example 2 was repeated except that the
individual hole output amount of fibers A was 0. 94 g/ min ° hole
and the individual hole output amount of fibers B was 0.53 g/
15 min ° hole to prepare a spunbonded non-woven fabric. The
resulting non-woven fabric was evaluated in the same methods
as those of Example 2. The results are shown in Table 1.
[0137]
Comparative Example 1
20 The procedure of Example 1 was repeated except for using
TPU(E-1) prepared in TPU production example 3 in place of
TPU(A-1) used in Example 1 to prepare a spunbonded nonwoven
fabric. In the case of judging the adhesion (I) as no good,
molding of the non--woven fabric was carried out by winding a
SE-2364 63
release paper to a metal made roll. The resulting non-woven
fabric was evaluated in the same methods as those of Example
1. The results are shown in Table 1.
[0138]
Comparative Example 2
The procedure of Comparative Example 1 was repeated
except for using TPU(E-2) prepared in TPU production example
4 in place of TPU (E-- 1) used in Comparative Example 1. to prepare
a spunbonded non-woven fabric. The resulting non-woven fabric
10 was evaluated in the same methods as those of Comparative Example
1. The results are shown in Table 1.
[0139]
Example 5
The procedure of Example 1 was repeated except for
15 changing the individual hole output amount of fibers B into 0
g/ min ® hole, namely using only TPU (A-1) to prepare a spur-bonded
non-woven fabric. The spinning properties and adhesion (I) were
evaluated as good. The resulting non-woven fabric had
stretching properties (I) of 1044 and had excellent
20 stretchability.
[0140]
Comparative Example 3
The procedure of Comparative Example 1_ was repeated
except that the individual hole output amount of fibers A was
SF-2364 64
0. 60 g/ min ° hole and the individual hole output amount of fibers
B was 0. 61 g/ min ° hole to prepare a spunbonded non-=woven fabric.
The resulting non--woven fabric was evaluated in the same methods
as those of Comparative Example 10
The results are shown in Table 1.
[0141]
Comparative Example 4
The procedure of Comparative Example 1 was repeated
except that the individual. hole output amount of fibers A was
10 0. 94 g/ min @ hole and the individual hole output amount of fibers
B was 0. 53 g/ min ° hole to prepare a spunbonded non.-,woven fabric.
The resulting non-woven fabric was evaluated in the same methods
as those of Comparative Example 1.
The results are shown in Table 1.
15
SF--2364
[0142]
65
Table 1-1
Ex_ le 1 Ex le 2 Exam le 3 Example 4
TPU
Composition A-1 A-2 A-2 A-2
Fiber weight ratio 50% 50% 40% 55%
Hardness 81 81 81 81
Molecular weight 164824 152028 152028 152028
EOA/fine particles 004/008 0.8/-- 0e8/- 0,8/-
Melt viscosity 009 181 1.1 101
Fluid initiation
temperature
156 155 155 155
Evaluation
Basis weight 30 30 30 30
Maximum strength MD 30,6 26.8 2708 2608
Maximum strength CD 1209 10.5 12.0 1007
Maximum point elongation
MD
207 201 186 197
Maximum point elongation
CD
225 211 200 214
Spinning properties Good Good Good Good
Adhesion (1) Good Good Good Good
Adhesion (2) No good Good Good Good
Stretching properties I 1.82 1075 1.94 1.82
Tackiness before
stretching treatment
Good Good Good Good
Stretching ro er_ties II 1070 1864 1888 1071
Tackiness after
stretching treatment
Very
good
Very
good
Very
ood
Very
good
SF-2364 66
Table 1-2
Compar.
Example 1
Compares
Example 2
Compar.
Ex le 3
Compares
Exam le 4
TPU
Composition E-1 Ew2 EW-1 E---1
Fiber weig_h_t ratio 50% 50% 40% 55%
Hardness 87 82 87 87
Molecular weight 151515 170167 151515 151515
EOA/fine particles a/-
Melt viscosity 1.1 1.4 1.1 1.1
Fluid initiation
temperature
173 157 173 173
Evaluation
Basis weight 30 30 30 30
Maximum strength MD, 24.1 29.7 28.0 26.0
Maximum strength CD 11.4 12.3 12.8 9.7
Maximum point elongation
MD
171 200 151 180
Maximum point elongation
CD
211 233 180 220
Spinning properties Good Good Good Good
Adhesion (1) No good No good No good No good
Adhesion (2) No good No ood No good No good
Stretching properties I 1.98 1.82 2.21 1086
Tackiness before
stretching treatment
Good Somewhat
good
Good
_
Good
Stretching ro erties II 1.86 1.70 2.10 1075
Tackiness after
stretching -treatment
Very
_ ood
good very
good
Very
_good
[0143]
TPU Production Example 5
5 73.8 parts by weight of polyester polyol having a number
average molecular weight of 1932, 6.9 parts by weight of
1, 4-bis (2-hydroxyethoxy) benzene (hereinafter abbreviated to
"BHEB"), 0.3 part by weight of pentaerythritol
tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate]
10 (hereinafter abbreviated to "antioxidant-l") and 0.3 part by
weight of polycarbone diimide were mixed. To the mixture, 18.7
parts by weight of MDT was added and mixed with highly stirring
SF'--2364 67
sufficiently and then reacted at 160°C for 1 hr. The reactant
was pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, 0.2 part by weight of ethylene bisstearic
acid amide, 0.5 part by weight of triethylene
5 glycol-bis-w[3-(3,5Gdi-t--butyl--4-h_ydroxyphenyl)propionate]
(hereinafter abbreviated to"antioxidant-2"), O.4 part by weight
of ethylene bisoleic acid amide (hereinafter abbreviated to
"EOA") and 0. 8 part by weight of crosslinked acryl fine particles
having an average particle diameter of 2.0 μm (hereinafter
10 abbreviated to "fine particles") were mixed. Thereafter, the
mixture was melt kneaded using an extruder at a set temperature
of 210°C and thereby granulated to prepare a thermoplastic
polyurethane elastomer [TPU(A2-=1)].,
[0144]
15 The physical properties of TPU (A2-1) were measured by the
above methods. The results are shown in Table 2.
[0145]
TPU Production Example 6
72 a 3 parts by weight of polyester polyol having a number
20 average molecular weight of 1932, 7,7 parts by weight of BHEB,
003 part by weight of antioxidant1 and 003 part by weight of
polycarbone da_imide were mixed. To the mixture, 19.4 parts by
weight of MDT was added and mixed with highly stirring
sufficiently and then reacted at 160°C for 1 hr. The reactant
SF 2364 68
was pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, Oat part by weight of ethylene bisstearic
acid amide, 0.5 part by weight of antioxidant---2, 0.4 part by
weight of EOA and 0.8 part by weight of fine particles having
5 an average particle diameter of 2. 0 EAm were mixed. Thereafter,
the mixture was melt kneaded using an extruder at a set
temperature of 210°C and thereby granulated to prepare a
thermoplastic polyurethane elastomer [TPU(A2-2)].
[0146]
10 The physical properties of TPU (A2-2) were measured by the
above methods. The results are shown in Table 2.
[0147]
TPU Production Example 7
72 0 3 parts by weight of polyester polyol having a number
15 average molecular weight of 1932, 7.7 parts by weight of BHEB,
0.3 part by weight of antioxidant-1 and 003 part by weight of
polycarbone diimide were mixed. To the mixture, 1904 parts by
weight of MDI was added and mixed with highly stirring
sufficiently and then reacted at 160°C for 1 hr. The reactant
20 was pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, 003 part by weight of ethylene bisstearic
acid amide, 005 part by weight of antioxidant---2 and 044 part
by weight of EOA were mixed. Thereafter, the mixture was melt
kneaded using an extruder at a set temperature of 210°C and
SF-2364 69
thereby granulated to prepare a thermoplastic polyurethane
elastomer [TPU(A2-3)].
[0148]
The physical properties of TPU (A2-3) were measured by the
5 above methods. The results are shown in Table 2.
[0149]
TPU Production Example 8
72 0 3 parts by weight of polyester polyol having a number
average molecular weight of 1932, 7.7 parts by weight of BHEB,
10 0.3 part by weight of antioxidant-1 and 0.3 part by weight of
polycarbone diimide were mixed. To the mixture, 19.4 parts by
weight of MDI was added and mixed with highly stirring
sufficiently and then reacted at 160°C for 1 hr. The reactant
was pulverized. Thereafter, to 100 parts by weight of the
15 pulverized matter, 008 part by weight of ethylene bisstearic
acid amide, 005 part by weight of antioxidant-2 and 0,8 part
by weight of EOA were mixed. Thereafter, the mixture was melt
kneaded using an extruder at a set temperature of 210°C and
thereby granulated to prepare a thermoplastic polyurethane
20 elastomer [TPU(A2-4)]s
[0150]
The physical properties of TPU (A2-4) were measured by the
above methods. The results are shown in Table 2.
[0151]
SF-2364 70
TPU Production Example 9
72.3 parts by weight of polyester polyol having a number
average molecular weight of 1932, 7.7 parts by weight of BHEB,
0.3 part by weight of antioxidant-1 and 0.3 part by weight of
5 polycarbone diimide were mixed. To the mixture, 1904 parts by
weight of MDI was added and mixed with highly stirring
sufficiently and then reacted at 160 °C for `1 hr. The reactant
was pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, 0.8 part by weight of ethylene bisstearic
10 acid amide, 0.5 part by weight of antioxidant2, 008 part by
weight of EOA and 008 part by weight of fine particles having
an average particle diameter of 200 μm were mixed. Thereafter,
the mixture was melt kneaded using an extruder at a set
temperature of 210°C and thereby granulated to prepare a
15 thermoplastic polyurethane elastomer [TPU(A2w-5)]o
[0152]
The physical properties of TPU (A2m,5) were measured by the
above methods. The results are shown in Table 2.
[0153]
20 TPU Production Example 10
72 e 3 parts by weight of polyester polyol having a number
average molecular weight of 1932, 707 parts by weight of BHEB,
003 part by weight of antioxidant--1 and 0.3 part by weight of
polycarbone diimide were mixed. To the mixture, 19.4 parts by
SF'--2364 71
weight of MDI was added and mixed with highly stirring
sufficiently and then reacted at 160°C for 1 hr. The reactant
was pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, 0.2 part by weight of ethylene bisstearic
5 acid amide and 0.5 part by weight of antioxidant-2 were mixed.
Thereafter, the mixture was melt kneaded using an extruder at
a set temperature of 210°C and thereby granulated to prepare
a thermoplastic polyurethane elastomer [TPU(Dm1)].
[0154]
10 The physical properties of TPU (D-1) were measured by the
above methods. The results are shown in Table 3.
[0155]
TPU Production Example 11
66.4 parts by weight of polyester polyol having a number
15 average molecular weight of 1932, 10.4 parts by weight of BHEB,
0,3 part by weight of antioxidant-1 and 003 part by weight of
polycarbone diimide were mixed. To the mixture, 2206 parts by
weight of MDI was added and mixed with highly stirring
sufficiently and then reacted at 160°C for 1 hr. The reactant
20 was pulverized. Thereafter, to 100 parts by weight of the
pulverized matter, 0„3 part by weight of ethylene bisstearic
acid amide, 045 part by weight of antioxidant--2 and 0.4 part
by weight of EOA were mixed. Thereafter, the mixture was melt
kneaded using an extruder at a set temperature of 210°C and
SF-2364 72
thereby granulated to prepare a thermoplastic polyurethane
elastomer [TPU (Em-5) ] .
[0156]
The physical properties of TPU(E-5) were measured by the
5 above methods. The results are shown in Table 3.
[0157]
Example 6
Preparation of thermoplastic resin composition for spunbonded
non-woven fabric
10 96 Parts by weight of a propylene homopolymer having an
MFR (measured in accordance with ASTM D1238 at 230°C under a
load of 2.16 kg) of 60 g/10 min, a density of 0.91 g/cm3 and a
melting point of 160°C (hereinafter abbreviated to "PP-1") was
mixed with 8 parts by weight of high density polyethylene having
15 an MFR (measured in accordance with ASTM D1238 at 190°C under
a load of 2.16 kg) of 5 g/10 min, a density of 0.97 g/cm3 and
a melting point of 134°C (hereinafter abbreviated to "HDPE")
to prepare a thermoplastic resin composition (B-1).
[0158]
20 Production of spunbonded non-woven fabric
Each of TPU(A2--1) prepared. in Production Example 5 and
above B-1 was independently melted using an extruder of 75 mmo
and an extruder of 50 mmo and then melt spun using a spunbonded
non-woven fabric molding machine having a spinning port (length
SF--2364 '73
vertical to the machine flow direction on collecting surface:
800 mm) in such conditions that the resin temperature and the
die temperature were each 205°C, the cooling air temperature
was 200 C and the stretching air rate was 3200 m/min to deposit
5 a web of the mixed long fibers formed from long fibers A of
TPU (A2°1) and long fibers B of B-1 on the collecting surface.
The spinning port has a nozzle pattern such that output holes
for TPU (A2-l) and an output holes for B-1 were arranged one after
the other. The nozzle diameter of TPU (A2--1) (fibers A) was 0.75
10 mmo and the nozzle diameter of Bw-1 (fibers B) was 0.6 mmO. The
nozzle pitch in the vertical direction was 8 mm and the nozzle
pitch in the horizontal direction was 11 mm, and the ratio of
the nozzle number for fibers A to the nozzle number for fibers
B was 1 : 1.45. The output amount of one hole for fibers A was
15 0.82 g/ (min ° hole) and the output amount of one hole for fibers
B was 0.56 g/(min-Bole)
[0159]
The web of the mixed long fibers deposited was deposited
on a moving belt and passed through between a metal made nip
20 roll and a belt with a linear pressure of 15 kg/cm to prepare
a mixed spunbonded non-woven fabric. The resulting mixed
spunbonded non--woven fabric had a basis weight of 30 g/m2. The
web of the mixed long fibers deposited had a large fiber diameter
of 2701 μm and a small. fiber diameter of 22.2 Jtm.. In results,
SF-2364 74
it was considered that the fiber diameter of TPU (A2-=-1) was 2V.1
p,tm and the fiber diameter of B-1 was 2202 μm.
[0160]
The web was released from the moving belt and subjected
5 to heat embossing with an embossing pattern such that the area
rate was 18% and the embossed area was 0.41 mm2 at an average
heating temperature of 85°C at a linear pressure of 70 kg/cm
to prepare a spunbonded non-woven fabric.
[0161]
10 The resulting spunbonded non-woven fabric was evaluated
by the above methods. The stretching properties (I) were
measured using the spunbonded non-woven fabric prepared before
stretching treatment, and the stretching properties (II) were
measured using the spunbonded non-woven fabric prepared after
15 stretching treatment namely using the stretchable spunbonded
non-woven fabric. The evaluation results are shown in TI-lble 2
[0162]
Example 7
The procedure of Example 6 was repeated except for using
20 TPU(A2-2) prepared in TPU production example 6 in place of
TPU(A2°1) used in Example 6 to prepare a spunbonded non-woven
fabric. The resulting non-woven fabric was evaluated in the
same methods as those of Example 6.
The results are shown in Table 2.
SF-2364 75
[0163]
Example 8
The procedure of Example 6 was repeated except for using
TPU (A2--3) prepared in TPU production example 7 in place of
TPU(A2-1) used in Example 6 to prepare a spunbonded nonwoven
fabric. The resulting nonwoven fabric was evaluated in the
same methods as those of Example 6.
The results are shown in Table 2.
[0164]
10 Example 9
The procedure of Example 6 was repeated except for using
TPU(A2-4) prepared in TPU production example 8 in place of
TPU(A2°1) used in Example 6 to prepare a spunbonded non-woven
fabric. The resulting non--woven fabric was evaluated in the
15 same methods as those of Example 6.
The results are shown in Table 2.
[0165]
Example 10
The procedure of Example 6 was repeated except that
20 TPU (A2`3) prepared in TPU production example 7 was used in place
of TPU (A2-1) used in Example 6, the individual hole output amount
of fibers A was 0. 60 g/ min ® hole and the individual hole output
amount of fibers B was 0. 61 g/ min - hole to prepare a spunbonded
non--woven fabric. The. resulting non---woven fabric was evaluated
SF--2364 76
in the same methods as those of Example 6.
The results are shown in Table 2.
[0166]
Example 11
The procedure of Example 6 was repeated except that
TPU (A2-5) prepared in TPU production example 9 was used in place
of TPU (A2-1) used in Example 6, the individual hole output amount
of fibers A was 0. 94 g/ min ® hole and the individual hole output
amount of fibers B was 0. 53 g/ min ® hole to prepare a spunbonded
10 non--woven fabric. The resulting non-woven fabric was evaluated
in the same methods as those of Example 6.
The results are shown in Table 2.
SF-2364
[0167]
77
Table 2
Ex, 6 Exa7 Exn 8 Exo9 Exe10 Ex.11
TPU
Composition A2-1 A2-2 A2-3 A2-4 A2-3 A2-5
Fiber wei ht ratio 50% 50% 50% 50% 40% 55%
Hardness 80 83 82 83 82 83
Molecular weight 153555 168483 126421 121053 126421 160882
EOA/fine
particles
0,4/
0.8
0.4/
0.8
0e4/= 0,8/ 0.4/- 0.8/
0.8
Melt viscosity 0.4 0.8 0.4 0.5 0.4 1.3
Fluid initiation
temperature
162 170 168 168 168 164
Evaluation
Basis weight 30 30 30 30 30 30
Maximum strength
MD
25.6 29.6 24.5 25.6 27.8 26.8
Maximum strength
CD
10.1 12.5 10.0 10.1 12.0 10.7
Maximum point
elongation MD
206 201 200 187 186 197
Maximum point
elongation CD
218 200 225 208 200 214
Spinning
properties
Good Good Good Good Good Good
Adhesion (1) Good Good Good Good Good Good
Adhesion (2) Good Good Good Good Good Good
Stretching
properties I
1071 1.54 1.64 1.70 1.77 1.60
Tackiness before
stretching
treatment
Good Good Good Good Good Good
Stretching
proper-Lies II
1.60 1.44 1.53 1.59 1.66 1.51
Tackiness after
stretching
treatment
Very
good
Very
good
Very
good
Very
good
Very
good
Very
good
[0168]
5 Comparative Example 5
The procedure of Example 6 was repeated except for using
TPU(D-1) prepared in TPU production example 10 in place of
TPU (A2--1) used in Example 6 to prepare a spunbonded non----woven
fabric. In the case of judging the adhesion (II) as no good,
SF-2364 '78
molding of the nonwoven fabric was carried out by winding a
release paper to a metal made roll. The resulting non-woven
fabric was evaluated in the same methods as those of Example
6. The results are shown in Table 3.
5 [0169]
Comparative Example 6
The procedure of Comparative Example 5 was repeated
except for using TPU(E®5) prepared in TPU production example
11 in place of TPU (Dml) used in Comparative Example 5 to prepare
10 a spunbonded nonwoven fabric. The resulting nonwoven fabric
was evaluated in the same methods as those of Comparative Example
5. The results are shown in Table 3.
[0170]
Example 12
15 The procedure of Example 1 was repeated except that the
individual hole out put amount of fibers B was 0 g/ min - hole to
prepare a spunbonded non-woven fabric only formed from TPU (A2-1)
The resulting nonwoven fabric was evaluated with the result
that the spinning properties, the adhesion (1) and the adhesion
20 (2) were good. Furthermore, the stretching properties (I) were
1.44 and the stretchability was excellent.
SF-2364 79
[0171]
Table 3
Compar.
Ex. 5
Compar. Ex. 6
TPU
Composition D-l E-5
Fiber wei ht ratio 50% 50%
Hardness 83 87
Molecular weight 195408 92743
EOA/fine articles 0.4/
Melt viscosity 1.1 1.7
Fluid initiation temperature 171 173
Evaluation
Basis weight 30 30
Maximum strength MD 26.3 Failure for
evaluation
Maximum strength CD 11.3 Failure for
evaluation
Maximum point elongation MD 188 Failure for
evaluation
Maximum point elongation CD 205 Failure for
evaluation
S innin ro ernes Good No good
Adhesion (1) No good Failure for
evaluation
Adhesion (2) No good Failure for
evaluation
Stretching properties 1 1.64 Failure for
evaluation
Tackiness before stretching
treatment
Somewhat
good
Failure for
evaluation
Stretching properties II 1.53
Tackiness after stretching
treatment
Good
POSSIBILITY FOR INDUSTRIAL USE
[0172]
5 The spunbonded nonwoven fabric of the present invention
comprises the long fibers of the thermoplastic polyurethane
elastomer having a relatively low hardness and has high
stretching physical properties, good touch and fuzz resistance.
The spunbonded non-woven fabric of the present invention is
10 suitably used for sanitary materials such as paper diapers and
SF-2364 80
the like.
DESCRIPTION OF NUMERALS
[0173]
1: Gear roll of gear stretching device
2: Spunbonded non-woven fabric
SF'-2364 81

CLAIMS
1. A spunbonded nonwoven fabric comprising long fibers
which comprise a thermoplastic polyurethane elastomer (A)
containing ethylene bisoleic acid amide and/or crosslinked
organic fine particles and having a hardness of 75 to 850
2. The spunbonded nonwoven fabric according to claim 1
further comprising long fibers which comprise a thermoplastic
10 resin (B) other than the thermoplastic polyurethane elastomer
(A).
3. The spunbonded nonwoven fabric according to claim 2
wherein the long fibers which comprise the thermoplastic resin
15 (B) are non-stretchable fibers.
4. The spunbonded nonwoven fabric according to claim 2
which comprises 10 to 90 % by mass of the long fibers of the
thermoplastic polyurethane elastomer (A) and 90 to 10 % by mass
20 of the long fibers of the thermoplastic resin (B)a
5. The spunbonded non-woven fabric according to any one
of claims 2 to 4 wherein the thermoplastic resin (B) is a polymer
containing polyethylene arid/or polypropylene.
6. The spunbonded non-woven fabric according to any one
of claims 1 to 5 wherein the thermoplastic polyurethane elastomer
(A) is a thermoplastic polyurethane elastomer (A2) obtainable
5 by using 1, 4-bis (2-hydroxyethoxy) benzene as a chain extender.
7e The spunbonded non-woven fabric according to claim 1
or 2 wherein the thermoplastic polyurethane elastomer (A) has
a fluid initiation temperature of not lower than 155°C.
10
8. The spunbonded non-woven fabric according to claim 6
wherein the thermoplastic polyurethane elastomer (A2) has a
fluid initiation temperature of not lower than 160° C.
15 9. A stretchable spunbonded non-woven fabric obtainable
by stretching and processing a spunbonded non-woven fabric as
claimed in any one of claims 1 to 8.
10. A laminate comprising at least one layer which
20 comprises a stretchable spunbonded non-woven fabric as claimed
in claim 9.
11. A sanitary material comprising a stretchable
spunbonded non-woven fabric as claimed in claim 9.