U.S. patent application number 16/499083 was filed with the patent office on 2020-02-06 for fibers to which silicone has been fixed, and production method thereof.
The applicant listed for this patent is KURASHIKI BOSEKI KABUSHIKI KAISHA, SHIN-ETSU CHEMICAL CO., LTD.. Invention is credited to Shinji IRIFUNE, Tomoya KANAI, Kunihiro OHSHIMA, Minoru SUGIYAMA, Masaki TANAKA.
Application Number | 20200040520 16/499083 |
Document ID | / |
Family ID | 64107696 |
Filed Date | 2020-02-06 |
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United States Patent
Application |
20200040520 |
Kind Code |
A1 |
IRIFUNE; Shinji ; et
al. |
February 6, 2020 |
FIBERS TO WHICH SILICONE HAS BEEN FIXED, AND PRODUCTION METHOD
THEREOF
Abstract
In one embodiment, the present invention relates to
silicone-fixed fibers including fibers and silicone fixed to the
fibers. The silicone includes an acrylic-modified
organopolysiloxane (A) having two or more acrylic groups per
molecule. A rate of decrease in the amount of Si after the
silicone-fixed fibers are washed 10 times is less than 50%. The
present invention relates to a method for producing silicone-fixed
fibers. The method includes coating or impregnating the fibers with
a fiber treatment agent containing silicone, and irradiating the
fibers coated or impregnated with the fiber treatment agent with an
electron beam so that the silicone is fixed to the fibers. The
silicone includes an acrylic-modified organopolysiloxane (A) having
two or more acrylic groups per molecule. Thus, the present
invention provides silicone-fixed fibers that include fibers to
which silicone is fixed by electron beam irradiation and have a
good texture even after washing, and a method for producing the
silicone-fixed fibers.
Inventors: |
IRIFUNE; Shinji; (Gunma,
JP) ; KANAI; Tomoya; (Gunma, JP) ; TANAKA;
Masaki; (Tokyo, JP) ; SUGIYAMA; Minoru;
(Osaka, JP) ; OHSHIMA; Kunihiro; (Osaka,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHIN-ETSU CHEMICAL CO., LTD.
KURASHIKI BOSEKI KABUSHIKI KAISHA |
Tokyo
Kurashiki-shi, Okayama |
|
JP
JP |
|
|
Family ID: |
64107696 |
Appl. No.: |
16/499083 |
Filed: |
March 16, 2018 |
PCT Filed: |
March 16, 2018 |
PCT NO: |
PCT/JP2018/010486 |
371 Date: |
September 27, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D06M 15/643 20130101;
D06M 14/24 20130101; D06M 14/20 20130101; D06M 15/356 20130101;
D06M 15/6436 20130101; D06M 15/3568 20130101; D06M 14/22
20130101 |
International
Class: |
D06M 15/643 20060101
D06M015/643; D06M 14/20 20060101 D06M014/20 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2017 |
JP |
2017-072061 |
Jun 14, 2017 |
JP |
2017-117114 |
Claims
1. Silicone-fixed fibers comprising fibers and silicone fixed to
the fibers, wherein the silicone comprises an acrylic-modified
organopolysiloxane (A) having two or more acrylic groups per
molecule, and a rate of decrease in an amount of Si after the
silicone-fixed fibers are washed 10 times is less than 50%.
2. The silicone-fixed fibers according to claim 1, wherein the
silicone further comprises an amino-modified organopolysiloxane (B)
having one or more amino groups per molecule.
3. The silicone-fixed fibers according to claim 1, wherein the
fibers comprise one or more natural fibers selected from the group
consisting of cotton, silk, hemp, wool, angora, and mohair.
4. The silicone-fixed fibers according to claim 1, wherein the
fibers are in at least one form selected from the group consisting
of staple, filament, tow, yarn, woven fabric, knitted fabric,
wadding, and nonwoven fabric.
5. A method for producing silicone-fixed fibers comprising fibers
and silicone fixed to the fibers, the method comprising: coating or
impregnating the fibers with a fiber treatment agent comprising
silicone; and irradiating the fibers coated or impregnated with the
fiber treatment agent with an electron beam so that the silicone is
fixed to the fibers, wherein the silicone comprises an
acrylic-modified organopolysiloxane (A) having two or more acrylic
groups per molecule.
6. The method according to claim 5, wherein the silicone further
comprises an amino-modified organopolysiloxane (B) having one or
more amino groups per molecule.
7. The method according to claim 5, wherein the fiber treatment
agent is a solution in which the silicone is diluted with an
organic solvent, or an emulsion in which the silicone is dispersed
in water as a dispersion medium.
8. The method according to claim 5, comprising a drying process
before irradiating the fibers coated or impregnated with the fiber
treatment agent with the electron beam.
9. The method according to claim 6, wherein the fiber treatment
agent is a solution obtained by diluting the acrylic-modified
organopolysiloxane (A) and the amino-modified organopolysiloxane
(B) simultaneously with an organic solvent, or an emulsion obtained
by dispersing the acrylic-modified organopolysiloxane (A) and the
amino-modified organopolysiloxane (B) simultaneously in water as a
dispersion medium.
10. The method according to claim 6, wherein the fiber treatment
agent is prepared by diluting the acrylic-modified
organopolysiloxane (A) and the amino-modified organopolysiloxane
(B) separately with an organic solvent to form solutions and then
mixing the solutions together, or by dispersing the
acrylic-modified organopolysiloxane (A) and the amino-modified
organopolysiloxane (B) separately in water as a dispersion medium
to form emulsions and then mixing the emulsions together.
11. The method according to claim 5, wherein the fibers comprise
one or more natural fibers selected from the group consisting of
cotton, silk, hemp, wool, angora, and mohair.
12. The method according to claim 5, wherein the fibers are in at
least one form selected from the group consisting of staple,
filament, tow, yarn, woven fabric, knitted fabric, wadding, and
nonwoven fabric.
13. The silicone-fixed fibers according to claim 1, wherein the
acrylic-modified organopolysiloxane (A) has two or more acrylic
groups per molecule and contains a unit represented by the
following general formula (1) in the molecule: ##STR00006## (in the
general formula (1), R.sup.1 represents the same or different
substituted or unsubstituted monovalent hydrocarbon group having 1
to 18 carbon atoms, R.sup.2 represents a hydrogen atom, m is an
integer of 1 to 8, and a and b are positive numbers and satisfy
a+b.ltoreq.3).
14. The silicone-fixed fibers according to claim 2, wherein the
amino-modified organopolysiloxane (B) has one or more amino groups
per molecule, as represented by the following general formula (2):
##STR00007## (in the general formula (2), a plurality of R.sup.3s
represent the same or different substituted or unsubstituted
monovalent hydrocarbon group having 1 to 18 carbon atoms, a
hydroxyl group, an alkoxy group, or an amino group, a plurality of
R.sup.4s represent the same or different substituted or
unsubstituted monovalent hydrocarbon group having 1 to 18 carbon
atoms or an amino group, at least one of R.sup.3s and R.sup.4s is
an amino group, and n is a positive number).
15. The method according to claim 5, wherein the acrylic-modified
organopolysiloxane (A) has two or more acrylic groups per molecule
and contains a unit represented by the following general formula
(1) in the molecule: ##STR00008## (in the general formula (1),
R.sup.1 represents the same or different substituted or
unsubstituted monovalent hydrocarbon group having 1 to 18 carbon
atoms, R.sup.2 represents a hydrogen atom, m is an integer of 1 to
8, and a and b are positive numbers and satisfy a+b.ltoreq.3).
16. The method according to claim 6, wherein the amino-modified
organopolysiloxane (B) has one or more amino groups per molecule,
as represented by the following general formula (2): ##STR00009##
(in the general formula (2), a plurality of R.sup.3s represent the
same or different substituted or unsubstituted monovalent
hydrocarbon group having 1 to 18 carbon atoms, a hydroxyl group, an
alkoxy group, or an amino group, a plurality of R.sup.4s represent
the same or different substituted or unsubstituted monovalent
hydrocarbon group having 1 to 18 carbon atoms or an amino group, at
least one of R.sup.3s and R.sup.4s is an amino group, and n is a
positive number).
Description
TECHNICAL FIELD
[0001] The present invention relates to fibers to which silicone is
fixed and a method for producing the fibers. Specifically, the
present invention relates to fibers to which silicone is fixed by
electron beam irradiation and a method for producing the
fibers.
BACKGROUND ART
[0002] A wide variety of organopolysiloxanes such as a
dimethylpolysiloxane, an epoxy group containing organopolysiloxane,
and an amino group containing organopolysiloxane have been used as
a fiber treatment agent for imparting softness, smoothness, etc. to
various fibers and fiber products. In particular, the amino group
containing organopolysiloxane provides good softness and is used in
a larger amount than any other organopolysiloxane. The fiber
treatment agent is generally in the form of an emulsion containing
water as a dispersion medium. In the most common method for the
treatment of fibers, the fibers are coated or impregnated with the
emulsion, and then dried by heating. The fibers treated with
silicone have an excellent texture immediately after the treatment.
However, the effective component (silicone) of the treatment agent
is washed away from the fibers after washing several times, and
thus the texture will be reduced. The reason for this may be that
the above silicone treatment agent is unable to react with the
fibers, and the silicone is not fixed to the fiber surface, but is
present on the fiber surface due to a weak adsorption effect of the
amino group on the fibers.
[0003] Therefore, e.g., further studies have been made to
incorporate silicone oil into synthetic resins to form synthetic
fibers such as polyester fibers, nylon fibers, and acrylic fibers.
However, since the compatibility between the silicone and these
synthetic resins is low, it is very difficult to form uniform
fibers in which the synthetic resins and the silicone are mixed
together. Accordingly, the use of silicone having a functional
group that may react with a functional group present on the fiber
surface, such as an epoxy group or an alkoxy group, has also been
considered. However, if the silicone having such a functional group
is in the form of an emulsion, the emulsion has poor stability over
time, so that the treatment agent cannot be used because it becomes
thickened before use.
[0004] To deal with the issue, there is a method for forming a
silicone rubber film on the surface. The rubber film is composed of
a curable silicone emulsion composition, which is conventionally
known to have various compositions. For example, Patent Document 1
proposes a silicone emulsion composition that includes an
anionically stabilized hydroxylated diorganopolysiloxane, colloidal
silica, and an organotin compound or an organic amine compound and
has a pH of 9 to 11.5. Patent Document 2 discloses a silicone latex
composition that includes a siloxane block copolymer having
dimethylsiloxane units and monophenylsiloxane units, water, a
cationic surfactant, a filler, and an aminosilane. Patent Document
3 proposes a silicone emulsion composition that includes a hydroxyl
group containing organopolysiloxane, a Si--H group containing
organopolysiloxane, colloidal silica, an amide group and carboxyl
group containing silane, an epoxy group containing silane, and a
curing catalyst. Patent Document 4 proposes a silicone emulsion
composition that includes an alkenyl group containing
organopolysiloxane, a Si--H group containing organopolysiloxane,
colloidal silica, a reaction product of an aminosilane and an acid
anhydride, an epoxysilane, and an addition reaction catalyst.
Patent Document 5 proposes a silicone emulsion composition that
includes a hydrogen siloxane in which the molecular terminal is
blocked with a hydroxyl group, an emulsifier, water, and a curing
catalyst. Patent Documents 6 to 8 propose a silicone emulsion
composition that includes a colloidal silica-silicone core-shell
body, a curing catalyst, an emulsifier, and water. Patent Document
9 proposes a silicone emulsion composition that includes a hydroxyl
group containing organopolysiloxane, colloidal silica, an amide
group and carboxyl group containing silane, an epoxy group
containing silane, a curing catalyst, and a photocatalytic oxide.
Patent Document 10 proposes a silicone emulsion composition that
includes a hydroxyl group containing organopolysiloxane, colloidal
silica, an amide group and carboxyl group containing silane, and an
epoxy group containing silane.
PRIOR ART DOCUMENTS
Patent Documents
[0005] Patent Document 1: JP S56(1981)-16553 A [0006] Patent
Document 2: U.S. Pat. No. 3,817,894 [0007] Patent Document 3: JP
H8(1996)-85760 A [0008] Patent Document 4: JP H9(1997)-208826 A
[0009] Patent Document 5: JP H9(1997)-208900 A [0010] Patent
Document 6: JP H9(1997)-208901 A [0011] Patent Document 7: JP
H9(1997)-208902 A [0012] Patent Document 8: JP H9(1997)-208903
A
[0013] Patent Document 9: JP 2002-363494 A
[0014] Patent Document 10: JP 2008-231276 A
DISCLOSURE OF INVENTION
Problem to be Solved by the Invention
[0015] In Patent Documents 1 to 10, organotin compounds are
typically used as a curing catalyst. However, the use of organotin
compounds is being restricted or regulated in applications, fields,
and countries because of its toxicity. Therefore, the replacement
of dibutyltin compounds by octyltin compounds, and further the
replacement of octyltin compounds by inorganic tin compounds or
other metal compounds have been proposed, but no effective catalyst
system has been found yet. Thus, it is still required that the
effect of the silicone treatment agent can be maintained even after
washing without using, e.g., toxic metal catalysts.
[0016] In order to solve the above problems, the present invention
provides silicone-fixed fibers that include fibers to which
silicone is fixed and have a good texture even after washing, and a
method for producing the silicone-fixed fibers.
Means for Solving Problem
[0017] In one embodiment, the present invention relates to
silicone-fixed fibers including fibers and silicone fixed to the
fibers. The silicone includes an acrylic-modified
organopolysiloxane (A) having two or more acrylic groups per
molecule. A rate of decrease in the amount of Si after the
silicone-fixed fibers are washed 10 times is less than 50%.
[0018] In one embodiment, the present invention relates to a method
for producing silicone-fixed fibers including fibers and silicone
fixed to the fibers. The method includes the following: coating or
impregnating the fibers with a fiber treatment agent containing
silicone; and irradiating the fibers coated or impregnated with the
fiber treatment agent with an electron beam so that the silicone is
fixed to the fibers. The silicone includes an acrylic-modified
organopolysiloxane (A) having two or more acrylic groups per
molecule.
Effects of the Invention
[0019] The present invention can provide silicone-fixed fibers that
include fibers to which silicone is firmly fixed and that have a
good texture even after washing. The production method of the
present invention can provide silicone-fixed fibers that include
fibers to which silicone is firmly fixed by electron beam
irradiation and that have a good texture even after washing.
DESCRIPTION OF THE INVENTION
[0020] The present inventors conducted many studies to fix silicone
to fibers so as to give them a good texture even after washing.
Consequently, the present inventors found that when fibers were
coated or impregnated with a fiber treatment agent containing an
acrylic-modified organopolysiloxane (A) having two or more acrylic
groups per molecule, and then the treated fibers were irradiated
with an electron beam, silicone was firmly fixed to the fibers and
the fibers could have a soft texture of silicone even after
washing. Based on these findings, the present inventors have
reached the present invention. In this specification, the term
"silicone" means a compound in which the main skeleton is composed
of a siloxane bond of silicon and oxygen, and an organic group is
attached to the silicon. Since the acrylic-modified
organopolysiloxane (A) having two or more acrylic groups per
molecule is used as the silicone, radicals are generated by
electron beam irradiation and a crosslinking reaction of the
silicones proceeds.
[0021] The acrylic-modified organopolysiloxane (A) having two or
more acrylic groups per molecule is not particularly limited and
may be, e.g., an acrylic-modified organopolysiloxane that has two
or more acrylic groups per molecule and contains a unit represented
by the following general formula (1) in the molecule.
##STR00001##
[0022] In the general formula (1), R.sup.1 represents the same or
different substituted or unsubstituted monovalent hydrocarbon group
having 1 to 18 carbon atoms, R.sup.2 represents a hydrogen atom, m
is an integer of 1 to 8, and a and b are positive numbers and
satisfy a+b.ltoreq.3. The substituted or unsubstituted monovalent
hydrocarbon group having 1 to 18 carbon atoms is not particularly
limited. Examples of the substituted or unsubstituted monovalent
hydrocarbon group having 1 to 18 carbon atoms include the
following: alkyl groups such as methyl, ethyl, propyl, and butyl
groups; alkenyl groups such as vinyl and allyl groups; aryl groups
such as phenyl and tolyl groups; and substituted forms of these
groups in which some or all hydrogen atoms bonded to carbon atoms
are substituted by halogen atoms or cyano groups, including, e.g.,
chloromethyl group, trifluoropropyl group, and cyanoethyl group. In
the general formula (1), R.sup.1 is more preferably a methyl
group.
[0023] The viscosity of the acrylic-modified organopolysiloxane (A)
is preferably 50 to 5000 mPas at 25.degree. C. If the viscosity is
less than 50 mPas, the acrylic-modified organopolysiloxane (A) is
not likely to adhere to the fibers. If the viscosity is more than
5000 mPas, the composition will have a higher viscosity, and thus
the treatment of the fibers tends to be difficult. The viscosity of
the acrylic-modified organopolysiloxane (A) is more preferably 100
to 1000 mPas at 25.degree. C. The acrylic-modified
organopolysiloxane (A) may be either a single acrylic-modified
organopolysiloxane or a mixture of a plurality of acrylic-modified
organopolysiloxanes which differ in the degree of polymerization
and the amount of functional groups.
[0024] In one embodiment of the present invention, from the
viewpoint of improving the softness of the fibers, it is preferable
that the silicone further includes an amino-modified
organopolysiloxane (B) having one or more amino groups per
molecule, as represented by the following general formula (2).
##STR00002##
[0025] In the general formula (2), a plurality of R.sup.3s
represent the same or different substituted or unsubstituted
monovalent hydrocarbon group having 1 to 18 carbon atoms, a
hydroxyl group, an alkoxy group, or an amino group. A plurality of
R.sup.4s represent the same or different substituted or
unsubstituted monovalent hydrocarbon group having 1 to 18 carbon
atoms or an amino group. At least one of R.sup.3s and R.sup.4s is
an amino group. Moreover, n is a positive number. Examples of the
substituted or unsubstituted monovalent hydrocarbon group having 1
to 18 carbon atoms may be the same as those described above. In the
general formula (2), the amino group represented by R.sup.3 or
R.sup.4 is not particularly limited and may be, e.g., an amino
group represented by the following general formula (3).
[Chemical Formula 3]
--R.sup.6(NR.sup.6CH.sub.2CH.sub.2)cNR.sup.7R.sup.6 (3)
[0026] In the general formula (3), R.sup.5 represents a substituted
or unsubstituted divalent hydrocarbon group having 1 to 8 carbon
atoms, R.sup.6, R.sup.7, and R.sup.8 each represent a hydrogen
atom, a substituted or unsubstituted monovalent hydrocarbon group
having 1 to 4 carbon atoms, or --CH.sub.2CH(OH)CH.sub.2OH, and c is
an integer of 0 to 4. Examples of the divalent hydrocarbon group
having 1 to 8 carbon atoms include the following: alkylene groups
such as ethylene, trimethylene, tetramethylene, hexamethylene, and
isobutylene groups; methylene-phenylene group; and
methylene-phenylene-methylene group. Among them, the trimethylene
group is preferred. Examples of the substituted or unsubstituted
monovalent hydrocarbon group having 1 to 4 carbon atoms include the
following: alkyl groups such as methyl, ethyl, propyl, and butyl
groups; alkenyl groups such as vinyl and allyl groups; and
substituted forms of these groups in which some of hydrogen atoms
bonded to carbon atoms are substituted by halogen atoms. Among
them, the methyl group is particularly preferred in terms of water
repellency, smoothness and softness.
[0027] The viscosity of the amino-modified organopolysiloxane (B)
is preferably 50 to 5000 mPas at 25.degree. C. If the viscosity is
less than 50 mPas, the amino-modified organopolysiloxane (B) is not
likely to adhere to the fibers. If the viscosity is more than 5000
mPas, the composition will have a higher viscosity, and thus the
treatment of the fibers tends to be difficult. The viscosity of the
amino-modified organopolysiloxane (B) is more preferably 100 to
1000 mPas at 25.degree. C.
[0028] In one embodiment of the present invention, from the
viewpoint of improving the fixing properties of the silicone to the
fibers and the texture of the fibers, when the total mass of the
acrylic-modified organopolysiloxane (A) and the amino-modified
organopolysiloxane (B) is 100% by mass, the blending amount of the
acrylic-modified organopolysiloxane (A) is preferably, but not
limited to, 10 to 95% by mass, and more preferably 30 to 90% by
mass and the blending amount of the amino-modified
organopolysiloxane (B) is preferably, but not limited to, 5 to 90%
by mass, and more preferably 10 to 70% by mass.
[0029] In the present invention, a rate of decrease in the amount
of Si after the fibers to which silicone is fixed (i.e., the
silicone-fixed fibers) are washed 10 times is less than 50%,
preferably 35% or less, more preferably 15% or less, and further
preferably 10% or less. With this configuration, the silicone-fixed
fibers can have a good texture even after washing. In the
silicone-fixed fibers of the present invention, as will be
described later, the fibers are coated or impregnated with a fiber
treatment agent containing the acrylic-modified organopolysiloxane
(A) or a fiber treatment agent containing the acrylic-modified
organopolysiloxane (A) and the amino-modified organopolysiloxane
(B), and then the treated fibers are irradiated with an electron
beam, so that silicone can be fixed to the fibers. In one
embodiment of the present invention, the amount of Si in the fibers
may be measured in the following manner.
[0030] The fibers are not particularly limited and may be either
natural fibers or synthetic fibers. The natural fibers are not
particularly limited and may be, e.g., cotton, silk, hemp, wool,
angora, or mohair. The synthetic fibers are not particularly
limited and may be, e.g., polyester fibers, nylon fibers, acrylic
fibers, or spandex. From the viewpoint of improving the fixing
properties of the silicone to the fibers, the fibers preferably
include one or more natural fibers selected from the group
consisting of cotton, silk, hemp, wool, angora, and mohair.
[0031] The form of the fibers is not particularly limited. The
fibers may be in any form such as staple, filament, tow, yarn,
woven fabric, knitted fabric, wadding, nonwoven fabric, paper,
sheet, or film.
[0032] The silicone-fixed fibers may be produced, e.g., by coating
or impregnating the fibers with a fiber treatment agent containing
silicone, and irradiating the fibers coated or impregnated with the
fiber treatment agent with an electron beam so that the silicone is
fixed to the fibers. As described above, the silicone includes the
acrylic-modified organopolysiloxane (A) or a mixture of the
acrylic-modified organopolysiloxane (A) and the amino-modified
organopolysiloxane (B).
[0033] The silicone, i.e., the acrylic-modified organopolysiloxane
(A) or the mixture of the acrylic-modified organopolysiloxane (A)
and the amino-modified organopolysiloxane (B) (also referred to
simply as a "silicone component" in the following) may be directly
used as the fiber treatment agent.
[0034] In one embodiment of the present invention, from the
viewpoint of handleability, the silicone (silicone component) may
be diluted with an organic solvent to form a solution, and this
solution may be used as a fiber treatment agent. Any organic
solvent that can dissolve the silicone may be used. Examples of the
organic solvent include the following; aromatic hydrocarbon
solvents such as toluene and xylene; aliphatic hydrocarbon solvents
such as hexane, octane, and isoparaffin; ether solvents such as
diisopropyl ether and 1,4-dioxane; and a mixed solvent thereof. The
aromatic hydrocarbon solvents such as toluene and xylene and the
aliphatic hydrocarbon solvents such as hexane, octane, and
isoparaffin are particularly preferred. The dilute concentration of
the silicone component is not particularly limited. For example,
the concentration of the acrylic-modified organopolysiloxane (A) or
the total concentration of the acrylic-modified organopolysiloxane
(A) and the amino-modified organopolysiloxane (B) may be 1 to 60%
by mass, and more preferably 1 to 20% by mass.
[0035] In one embodiment of the present invention, the silicone
component may be dispersed in water as a dispersion medium to form
an emulsion, and this emulsion may be used as a fiber treatment
agent for electron beam fixing. The emulsification may use, e.g., a
nonionic surfactant, an anionic surfactant, a cationic surfactant,
or an amphoteric surfactant. The nonionic surfactant is not
particularly limited and may be, e.g., polyoxyethylene alkyl ether,
polyoxyethylene alkyl phenyl ether, sorbitan alkylate, or
polyoxyethylene sorbitan alkylate. The anionic surfactant is not
particularly limited and may be, e.g., alkylbenzene sulfonate or
alkyl phosphate. The cationic surfactant is not particularly
limited and may be, e.g., quaternary ammonium salts or alkylamine
salts. The amphoteric surfactant is not particularly limited and
may be, e.g., alkyl betaine or alkyl imidazoline. These surfactants
may be used individually or in combinations of two or more. There
is no particular limitation to the surfactants. However, from the
viewpoint of ease of emulsification of the silicone, the HLB
(hydrophilic-lipophilic balance) of the surfactants is preferably
11 to 18, and more preferably 13 to 16.
[0036] The amount of the surfactant used is preferably 5 to 50
parts by mass, and more preferably 10 to 30 parts by mass with
respect to 100 parts by mass of the silicone component, i.e., the
acrylic-modified organopolysiloxane (A) or the mixture of the
acrylic-modified organopolysiloxane (A) and the amino-modified
organopolysiloxane (B). Any suitable amount of water may be used
for emulsification. However, water may be used in an amount such
that the concentration of the acrylic-modified organopolysiloxane
(A) or the total concentration of the acrylic-modified
organopolysiloxane (A) and the amino-modified organopolysiloxane
(B) is generally 1 to 60% by mass, and preferably 1 to 20% by mass.
The emulsification may be performed by mixing the acrylic-modified
organopolysiloxane (A) or the acrylic-modified organopolysiloxane
(A) and the amino-modified organopolysiloxane (B) with the
surfactant, and emulsifying the mixture with an emulsifier such as
a homomixer, a homogenizer, a colloid mill, or a line mixer.
[0037] In one embodiment of the present invention, when both the
acrylic-modified organopolysiloxane (A) and the amino-modified
organopolysiloxane (B) are used as the silicone component, these
components may be mixed in advance to form a solution or an
emulsion. Alternatively, these components may be separately formed
in advance into solutions or emulsions, and then the respective
solutions or emulsions may be mixed together.
[0038] In one embodiment of the present invention, other agents for
fibers such as an anticrease agent, a flame retardant, an
antistatic agent, and a heat resistant agent may be added to the
fiber treatment agent as long as the properties of the fiber
treatment agent are not impaired.
[0039] First, the fibers are coated or impregnated with the fiber
treatment agent containing the silicone. The fibers that serve as a
base material are not particularly limited and may be the same as
those described above.
[0040] In this case, any known method such as roll coating, gravure
coating, wire doctor coating, air knife coating, or dipping may be
used to coat or impregnate the fibers with the fiber treatment
agent. The coating or impregnation amount is preferably 0.01 to
20.0 g/m.sup.2, and more preferably 0.01 to 5 g/m.sup.2. When the
coating or impregnation amount is within the above range, the
adhesion of the silicone to the fibers can be improved.
[0041] In one embodiment of the present invention, when the fiber
treatment agent is a solution obtained by diluting the silicone
with an organic solvent, or an emulsion obtained by dispersing the
silicone in water, the fibers coated or impregnated with the fiber
treatment agent may be dried to vaporize the organic solvent or the
water (the dispersion medium of the emulsion). The drying may be
performed, e.g., by blowing hot air on the fibers or using a
heating furnace. The drying temperature and the drying time may be
determined as desired so as not to affect the fibers. For example,
the drying temperature may be 100 to 150.degree. C. and the drying
time may be 10 sec to 5 min.
[0042] Next, the fibers coated or impregnated with the fiber
treatment agent are irradiated with an electron beam so that the
silicone is fixed to the fibers. The electron beam irradiation
apparatus is not particularly limited and may be, e.g., a curtain
system, a scanning system, or a double scanning system. The
acceleration voltage of the electron beam by the electron beam
irradiation is not particularly limited and may be, e.g., 100 to
1000 kV. If the acceleration voltage is less than 100 kV, there may
be a lack of energy transmission. If the acceleration voltage is
more than 1000 kV, economic efficiency may be reduced. Moreover,
the irradiation amount of the electron beam is not particularly
limited and may be, e.g., 5 to 100 kGy. If the irradiation amount
is less than 5 kGy, curing failure may occur. If the irradiation
amount is 100 kGy or more, the fibers may be degraded. When the
fiber treatment agent is a solution obtained by diluting the
silicone with an organic solvent, the fibers may be immersed
(washed) in the organic solvent that has been used for dilution of
the silicone, after the electron beam irradiation, thereby removing
unreacted silicone. On the other hand, when the fiber treatment
agent is an emulsion obtained by dispersing the silicone in water,
the fibers may be washed with water after the electron beam
irradiation, thereby removing unreacted silicone.
EXAMPLES
[0043] Next, embodiments of the present invention will be described
in detail based on examples. However, the present invention is not
limited to the following examples. In the following examples and
comparative examples, the term "part" indicates "part by mass" and
the physical property values indicate measured values by the
following test methods.
[0044] (Measurement of Initial Amount of Si)
[0045] Using an X-ray fluorescence analyzer ZSX100e manufactured by
Rigaku Corporation, the mass of all elements (W0t) and the mass of
Si atoms (W0s) contained in each sample before washing were
measured by the EZ-scan method, and the initial amount of Si was
calculated by the following formula.
Initial amount of Si (% by mass)=(W0s)/(W0t).times.100
[0046] (Measurement of Amount of Si after Washing)
[0047] The samples were washed 10 times or 50 times in accordance
with the JIS L 0217 103 method (detergent: JAFET) and dried. Then,
using the X-ray fluorescence analyzer ZSX100e manufactured by
Rigaku Corporation, the mass of all elements (W10t or W50t) and the
mass of Si atoms (W10s or W50s) contained in the individual samples
after 10 times washing or 50 times washing were measured by the
EZ-scan method, and the amount of Si after 10 times washing and the
amount of Si after 50 times washing were calculated by the
following formulas.
Amount of Si after 10 times washing (% by
mass)=(W10s)/(W10t).times.100
Amount of Si after 50 times washing (% by
mass)=(W50s)/(W50t).times.100
[0048] (Rate of Decrease in Amount of Si after 10 Times
Washing)
Rate of decrease in amount of Si after 10 times washing (%)=(W0s
%-W10s %)/W0s %.times.100
[0049] In the formula, W0s % indicates the initial amount of Si and
W10s % indicates the amount of Si after 10 times washing.
[0050] (Initial Texture)
[0051] Three panelists touched the samples by hand to check the
softness of the samples and evaluated them based on the following
criteria.
[0052] A: very good
[0053] B: good
[0054] C: poor
[0055] (Texture after Washing)
[0056] The samples were washed 10 times or 50 times in accordance
with the JIS L 0217 103 (detergent: JAFET). Subsequently, three
panelists touched the samples by hand to check the softness of the
samples after washing and evaluated them based on the following
criteria.
[0057] A: very good
[0058] B: good
[0059] C: poor
Example 1
[0060] First, an acrylic-modified organopolysiloxane (A1)
represented by the following average molecular formula (4) was
diluted with toluene to prepare a fiber treatment agent (a) in
which the concentration of the acrylic-modified organopolysiloxane
(A1) was 10% by mass. Next, a broadcloth made of 100% by mass of
cotton (manufactured by KURABO) was immersed in the fiber treatment
agent (a), squeezed by a mangle roller at a squeeze rate of 100%,
and dried at 110.degree. C. for 90 seconds. Then, the broadcloth
was irradiated with an electron beam of 40 kGy at an acceleration
voltage of 200 kV in a nitrogen atmosphere using an area beam type
electron beam irradiation apparatus EC250/15/180L (manufactured by
IWASAKI ELECTRIC CO., LTD.). The fibers (i.e., the broadcloth made
of 100% by mass of cotton) thus treated with the electron beam were
immersed in toluene for 1 minute and then squeezed by a mangle
roller at a squeeze rate of 60%. Further, the fibers were again
immersed in fresh toluene for 1 minute, squeezed by a mangle roller
at a squeeze rate of 60%, and dried at 110.degree. C. for 90
seconds. Thus, silicone-fixed fibers were produced.
##STR00003##
Example 2
[0061] An acrylic-modified organopolysiloxane (A2) represented by
the following average molecular formula (5) was diluted with
toluene to prepare a fiber treatment agent (b) in which the
concentration of the acrylic-modified organopolysiloxane (A2) was
10% by mass. A broadcloth made of 100% by mass of cotton
(manufactured by KURABO) was immersed in the fiber treatment agent
(b), squeezed by a mangle roller at a squeeze rate of 60%, and
dried at 110.degree. C. for 90 seconds. Then, the broadcloth was
irradiated with an electron beam of 40 kGy at an acceleration
voltage of 200 kV in a nitrogen atmosphere using an area beam type
electron beam irradiation apparatus EC250/30/90L (manufactured by
IWASAKI ELECTRIC CO., LTD.). The fibers (i.e., the broadcloth made
of 100% by mass of cotton) thus treated with the electron beam were
immersed in toluene for 1 minute and then squeezed by a mangle
roller at a squeeze rate of 60%. Further, the fibers were again
immersed in fresh toluene for 1 minute, squeezed by a mangle roller
at a squeeze rate of 60%, and dried at 110.degree. C. for 90
seconds. Thus, silicone-fixed fibers were produced.
##STR00004##
Example 3
[0062] First, 300 g of the acrylic-modified organopolysiloxane (A2)
used in Example 2, 7.8 g of polyoxyethylene (4) lauryl ether
(product name "EMULGEN 104P" manufactured by Kao Corporation,
nonionic surfactant, HLB value: 9.6), and 22.2 g of polyoxyethylene
(23) lauryl ether (product name "EMULGEN 123P" manufactured by Kao
Corporation, nonionic surfactant, HLB value: 16.9) were charged in
a 2 L polyethylene jug and sufficiently mixed at a high speed with
a homomixer. Then, 18 g of phase-inverted water (ion-exchanged
water) was added to the mixture and kneaded. Subsequently, 280 g of
ion-exchanged water was added to the mixture and mixed at 2500 rpm
for 20 minutes with a homomixer. Thus, an oil-in-water emulsion (I)
in which the concentration of the acrylic-modified
organopolysiloxane (A2) was 50% by mass was obtained. The
oil-in-water emulsion (I) was further diluted with ion-exchanged
water to prepare a fiber treatment agent (c) in which the
concentration of the acrylic-modified organopolysiloxane (A2) was
10% by mass. A broadcloth made of 100% by mass of cotton
(manufactured by KURABO) was immersed in the fiber treatment agent
(c), squeezed by a mangle roller at a squeeze rate of 60%, and
dried at 110.degree. C. for 90 seconds. Then, the broadcloth was
irradiated with an electron beam of 40 kGy at an acceleration
voltage of 200 kV in a nitrogen atmosphere using an area beam type
electron beam irradiation apparatus EC250/30/90L (manufactured by
IWASAKI ELECTRIC CO., LTD.). The fibers (i.e., the broadcloth made
of 100% by mass of cotton) thus treated with the electron beam were
washed with water, squeezed by a mangle roller at a squeeze rate of
60%, and dried at 110.degree. C. for 90 seconds. Thus,
silicone-fixed fibers were produced.
Example 4
[0063] First, 300 g of an amino-modified organopolysiloxane (B1)
represented by the following average molecular formula (6), 1.8 g
of polyoxyethylene (4) lauryl ether (product name "EMULGEN 104P"
manufactured by Kao Corporation, nonionic surfactant, HLB value:
9.6), and 4.2 g of polyoxyethylene (23) lauryl ether (product name
"EMULGEN 123P" manufactured by Kao Corporation, nonionic
surfactant, HLB value: 16.9) were charged in a 2 L polyethylene jug
and sufficiently mixed at a high speed with a homomixer. Then, 18 g
of phase-inverted water (ion-exchanged water) was added to the
mixture and kneaded. Subsequently, 280 g of ion-exchanged water was
added to the mixture and mixed at 2500 rpm for 20 minutes with a
homomixer. Thus, an oil-in-water emulsion (II) in which the
concentration of the amino-modified organopolysiloxane (B1) was 50%
by mass was obtained. The oil-in-water emulsion (II) was mixed with
the oil-in-water emulsion (I) prepared in the same manner as
Example 3 at a ratio of the oil-in-water emulsion (I) to the
oil-in-water emulsion (II) of 50 parts by mass/50 parts by mass to
form an oil-in-water emulsion (III). The oil-in-water emulsion
(III) was diluted with ion-exchanged water to prepare a fiber
treatment agent (d) in which the concentration of the
organopolysiloxane (i.e., the total concentration of the
acrylic-modified organopolysiloxane (A2) and the amino-modified
organopolysiloxane (B1)) was 10% by mass. A broadcloth made of 100%
by mass of cotton (manufactured by KURABO) was immersed in the
fiber treatment agent (d), squeezed by a mangle roller at a squeeze
rate of 60%, and dried at 110.degree. C. for 90 seconds. Then, the
broadcloth was irradiated with an electron beam of 40 kGy at an
acceleration voltage of 200 kV in a nitrogen atmosphere using an
area beam type electron beam irradiation apparatus EC250/30/90L
(manufactured by IWASAKI ELECTRIC CO., LTD.). The fibers (i.e., the
broadcloth made of 100% by mass of cotton) thus treated with the
electron beam were washed with water, squeezed by a mangle roller
at a squeeze rate of 60%, and dried at 110.degree. C. for 90
seconds. Thus, silicone-fixed fibers were produced.
##STR00005##
Comparative Example 1
[0064] First, a dimethylpolysiloxane having no organic group other
than a methyl group and having a viscosity of 1000 mm.sup.2/s was
diluted with toluene to prepare a fiber treatment agent (Z) in
which the concentration of the dimethylpolysiloxane was 10% by
mass. A broadcloth made of 100% cotton (manufactured by KURABO) was
immersed in the fiber treatment agent (Z), squeezed by a mangle
roller at a squeeze rate of 60%, and dried at 110.degree. C. for 90
seconds. Then, the broadcloth was irradiated with an electron beam
of 40 kGy at an acceleration voltage of 200 kV in a nitrogen
atmosphere using an area beam type electron beam irradiation
apparatus EC250/30/90L (manufactured by IWASAKI ELECTRIC CO.,
LTD.). The fibers (i.e., the broadcloth made of 100% cotton) thus
treated with the electron beam were immersed in a toluene solution
for 1 minute and then squeezed by a mangle roller at a squeeze rate
of 60%. Further, the fibers were again immersed in a fresh toluene
solution for 1 minute, squeezed by a mangle roller at a squeeze
rate of 60%, and dried at 110.degree. C. for 90 seconds.
Comparative Example 2
[0065] A fiber treatment agent (c) was prepared in the same manner
as Example 3. A broadcloth made of 100% cotton (manufactured by
KURABO) was immersed in the fiber treatment agent (c), squeezed by
a mangle roller at a squeeze rate of 60%, and dried at 110.degree.
C. for 90 seconds. Then, the fibers (i.e., the broadcloth made of
100% cotton) thus treated with the fiber treatment agent (c) were
washed with water, squeezed by a mangle roller at a squeeze rate of
60%, and dried at 110.degree. C. for 90 seconds.
Comparative Example 3
[0066] An oil-in-water emulsion (II) in which the concentration of
an amino-modified organopolysiloxane (B1) was 50% by mass was
prepared in the same manner as Example 4. The oil-in-water emulsion
(II) was diluted with ion-exchanged water to prepare a fiber
treatment agent (Y) in which the concentration of the
amino-modified organopolysiloxane (B1) was 10% by mass. A
broadcloth made of 100% cotton (manufactured by KURABO) was
immersed in the fiber treatment agent (Y), squeezed by a mangle
roller at a squeeze rate of 60%, and dried at 110.degree. C. for 90
seconds. Then, the fibers (i.e., the broadcloth made of 100%
cotton) thus treated with the fiber treatment agent (Y) were washed
with water, squeezed by a mangle roller at a squeeze rate of 60%,
and dried at 110.degree. C. for 90 seconds.
[0067] The initial amount of Si (the amount of Si before washing),
the amount of Si after 10 times washing, the amount of Si after 50
times washing, the initial texture, and the texture after washing
of the respective fibers (i.e., the broadcloths made of 100%
cotton) obtained in Examples 1 to 4 and Comparative Examples 1 to 3
were measured in the above manner. Table 1 shows the results.
TABLE-US-00001 TABLE 1 Rate of decrease in Amount of Si (% by mass)
amount of Texture Before After After Si after 10 After 10 After 50
washing 10 times 50 times times washing Before times times
(initial) washing washing (%) washing washing washing Ex. 1 0.520
0.343 0.140 34.0 B B C Ex. 2 0.541 0.548 0.441 0 B B B Ex. 3 0.880
0.788 -- 10.5 B B B Ex. 4 1.250 1.130 0.738 9.6 A A A Comp. 0.037
0.015 0.006 59.5 B C C Ex. 1 Comp. 0.056 0.025 -- 55.4 B C C Ex. 2
Comp. 0.520 0.190 -- 63.5 A C C Ex. 3
[0068] In Examples 1 and 2, the fibers had been impregnated with
the fiber treatment agent, in which the acrylic-modified
organopolysiloxane (A) having two or more acrylic groups per
molecule was dissolved in the organic solvent, and then irradiated
with the electron beam. Consequently, these fibers had good
softness, and the acrylic-modified organopolysiloxane (A) was fixed
to the fibers even after washing. Specifically, a considerable
amount of the acrylic-modified organopolysiloxane was fixed to the
fibers after they were washed 10 times. In particular, in Example
2, a certain amount of the acrylic-modified organopolysiloxane was
fixed to the fibers even after they were washed 50 times. The
fixing properties of the acrylic-modified organopolysiloxane (A) to
the fibers were higher in Example 2 than in Example 1, since the
acrylic-modified organopolysiloxane (A) used in Example 2 had a
large number of acrylic groups as compared to the acrylic-modified
organopolysiloxane (A) used in Example 1.
[0069] In Example 3, the fibers had been treated with the fiber
treatment agent, in which the acrylic-modified organopolysiloxane
(A) having two or more acrylic groups per molecule was emulsified.
Consequently, the fibers also had good softness. Comparing Example
3 and Example 4 shows that when the acrylic-modified
organopolysiloxane (A) having two or more acrylic groups per
molecule was used in combination with the amino-modified
organopolysiloxane (B) having one or more amino groups per
molecule, the initial amount of silicone fixed to the fibers was
increased, the softness of the fibers was very good, and the
organopolysiloxane was sufficiently fixed to the fibers even after
they were washed 10 times.
[0070] On the other hand, in Comparative Example 1, the fibers had
been treated with the dimethylpolysiloxane having no acrylic group.
Consequently, the initial amount of dimethylpolysiloxane adhering
to the fibers was small, and almost no dimethylpolysiloxane was
left after the fibers were washed 10 times or 50 times. In
Comparative Example 2, the fibers had been treated with the fiber
treatment agent in which the acrylic-modified organopolysiloxane
(A) having two or more acrylic groups per molecule was emulsified,
but had not been subjected to electron beam irradiation.
Consequently, the amount of the acrylic-modified organopolysiloxane
(A) adhering to the fibers was small, and the softness of the
fibers was poor. In Comparative Example 3, the fibers had been
treated with the fiber treatment agent, in which the amino-modified
organopolysiloxane (B) having one or more amino groups per molecule
was emulsified. Consequently, although a considerable amount of the
amino-modified organopolysiloxane (B) adhered to the fibers at the
initial stage (washing), the amount of the amino-modified
organopolysiloxane (B) was significantly reduced after washing, and
the softness of the fibers became poor.
[0071] In the Examples, it was found that the acrylic-modified
organopolysiloxane (A) was graft-polymerized onto the fibers, and
crosslinking between the silicone components also proceeded, so
that the silicone was firmly fixed to the fibers, and thus the
fibers had good softness even after washing. On the other hand, in
the Comparative Examples, it was found that the silicone was not
fixed to the fibers.
* * * * *