U.S. patent application number 09/725255 was filed with the patent office on 2001-07-19 for composite molding and process for the production of the same.
Invention is credited to Inoue, Shin-ichi, Kanagawa, Tetsuo, Miyamatsu, Hiroki, Okamoto, Hiroshi, Sano, Masataka, Yoshida, Kimi.
Application Number | 20010008690 09/725255 |
Document ID | / |
Family ID | 26576814 |
Filed Date | 2001-07-19 |
United States Patent
Application |
20010008690 |
Kind Code |
A1 |
Okamoto, Hiroshi ; et
al. |
July 19, 2001 |
Composite molding and process for the production of the same
Abstract
A joining type composite molding is disclosed, containing an
internal component X and an external component Y, wherein the
internal component X is formed from a first resin (H); the external
component Y is formed from a second resin (L) compounded with at
least one functional component (A) selected from the group
consisting of a catechin, a saponin, a tea-leaf powder, a tea-leaf
extract and tannin (tannic acid), and a ceramics component (C); and
the first resin (H) and the second resin (L) are resins falling
into different categories respectively, or a resin of the same
category of a non-polyolefinic resin.
Inventors: |
Okamoto, Hiroshi;
(Owari-asahi-shi, JP) ; Inoue, Shin-ichi;
(Tokoname-shi, JP) ; Kanagawa, Tetsuo; (Otsu-shi,
JP) ; Sano, Masataka; (Hamamatsu-shi, JP) ;
Miyamatsu, Hiroki; (Hamamatsu-shi, JP) ; Yoshida,
Kimi; (Hamamatsu, JP) |
Correspondence
Address: |
ARMSTRONG,WESTERMAN, HATTORI,
MCLELAND & NAUGHTON, LLP
1725 K STREET, NW, SUITE 1000
WASHINGTON
DC
20006
US
|
Family ID: |
26576814 |
Appl. No.: |
09/725255 |
Filed: |
November 29, 2000 |
Current U.S.
Class: |
428/373 ;
264/171.26; 264/172.15; 264/173.16; 428/374 |
Current CPC
Class: |
Y10T 428/2929 20150115;
Y10T 428/2924 20150115; Y10T 428/2931 20150115; B29C 48/18
20190201; B29C 48/06 20190201 |
Class at
Publication: |
428/373 ;
428/374; 264/172.15; 264/173.16; 264/171.26 |
International
Class: |
D02G 003/00; B29C
047/06 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 30, 1999 |
JP |
340849/1999 |
Dec 9, 1999 |
JP |
350697/1999 |
Claims
What is claimed is:
1. A joining type composite molding comprising an internal
component X and an external component Y, the internal component X
being formed from a first resin (H); the external component Y being
formed from a second resin (L) compounded with at least one
functional component (A) selected from the group consisting of a
catechin, a saponin, a tea-leaf powder, a tea-leaf extract and
tannin (tannic acid), and a ceramics component (C); and the first
resin (H) and the second resin (L) being resins falling into
different categories respectively, or a resin of the same category
of a non-polyolefinic resin.
2. The composite molding as claimed in claim 1, wherein the first
resin (H) and the second resin (L) are resins falling into
different categories respectively, which is selected from
polyamide-based resins, polyester-based resins, polyolefinic
resins, polyurethane-based resins, polyvinyl chloride-based resins,
polyvinylidene chloride-based resins and acrylic resins, or a resin
of the same category of a non-polyolefinic resin
3. The composite molding as claimed in claim 1, wherein the
external component Y is formed from the second resin (L) having the
functional component (A) and the ceramics component (C) compounded
therein in a state of composite particles.
4. The composite molding as claimed in claim 1, which is a
core-sheath joining type composite molding comprising the internal
component X as a core component and the external component Y as a
sheath component.
5. The composite molding as claimed in claim 1, which is a bimetal
joining type composite molding constructed of the internal
component X and the external component Y in a Y/X or Y/X/Y
state.
6. The composite molding as claimed in claim 1, wherein the
ceramics component (C) is a silica gel obtained via a hydrous
silicate gel, a combination of an inorganic sintering aid and an
inorganic flocculent, a combination of ceramics particles, an
inorganic sintering aid and an inorganic flocculant, a
water-swelling clay mineral, or ceramics particles.
7. A process for the production of a composite molding comprising
co-extrusion forming a first resin (H) and a second resin (L)
compounded with at least one functional component (A) selected from
the group consisting of a catechin, a saponin, a tea-leaf powder, a
tea-leaf extract and tannin (tannic acid), and a ceramics component
(C) at a temperature higher than melting temperatures of the
respective components, such that the first resin (H) becomes an
internal component X and that the second resin (L) compounded with
the functional component (A) and the ceramics component (C) becomes
an external component Y, thereby obtaining a joining type composite
molding constructed of the internal component X and the external
component Y, where the first resin (H) and the second resin (L) are
resins falling into different categories, or a resin of the same
category of a non-polyolefinic resin.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a core-sheath joining type
or bimetal joining type composite molding (especially, filaments
and sheets) having superior functionalities (e.g., deodorizing
properties, antimicrobial properties, etc.), moldability (e.g.,
melt spinning properties, etc.), post-processing properties (e.g.,
stretching properties, etc.), physical properties (e.g., strength,
dimensional stability, etc.), and economy (i.e., cost), which is
useful for various applications including interior materials of
vehicles or interiors, clothes, matting materials, hygienic
materials, and filters of air conditioners or air cleaners, and to
a process for the production of the same.
[0003] 2. Description of the Conventional Art
[0004] (Filters Made of Polypropylene)
[0005] As filters to be incorporated into air conditioners or air
cleaners, filters made of a polypropylene filament that is not only
advantageous from the standpoint of production cost but also
superior in characteristics such as moldability, mechanical
strength, waterproof properties, and chemical resistance, are
widely used. It is also known that polypropylene for this filter is
incorporated with a synthetic bactericide or carried with a
catechin as a tea-extraction component, through external attachment
or internal addition.
[0006] For example, Japanese Patent Laid-Open No. 99656/1989
mentions an antibacterial electret filter comprising polypropylene
fibers having 0.1% or more of a bactericide incorporated therein.
However, the bactericide that is used in the examples of this
laid-open publication is thiabendazole as a synthetic
bactericide.
[0007] Further, Japanese Patent Laid-Open No. 148407/1995 describes
an antiviral filter comprising a filter impregnated with, or a
filter material incorporated with, a virus-inactivating agent
comprising, as an active ingredient, a tea-extraction component.
The tea-extraction component as referred to herein means a tea
polyphenol such as a catechin. In the examples of this patent
laid-open are given (A) an example in which the tea-extraction
component is dissolved in water to prepare an aqueous solution,
which is then impregnated and attached to an electret filter; and
(B) an example in which polypropylene is mixed with the
tea-extraction component, and the mixture is molten to form a film,
which is then cut and fabricated into a non-woven fabric.
[0008] Moreover, Japanese Patent Laid-Open No. 266828/1996
describes an antiviral filter comprising a dust-collecting filter
and a filter impregnated with a tea-extraction component. The
tea-extraction component as referred to herein means a tea
polyphenol such as a catechin. Further, the filer having a
tea-extraction component attached thereto as referred to herein
means electret filter, HEPA filter, high-performance filer,
middle-performance filter, bag filter, etc. (Composite
monofilaments made of polypropylene).
[0009] In general, a core-sheath joining type or bimetal joining
type composite monofilament per se is known. For instance, Japanese
Patent Publication No. 3969/1988 (Japanese Patent No. 1,456,233)
describes a composite monofilament comprising high-melting
polypropylene as a core component and a low-melting polyolefin as a
sheath component. This patent publication also mentions that this
monofilament is fabricated in a net-like state. However, this
patent publication does not describe that the monofilament is
carried with an active ingredient such as a bactericide. In this
monofilament, since not only a necessary strength is obtained by
the core component, but also heat fusion properties are obtained by
the sheath component, it is easy to fabricate it into a net-like
state or a non-woven fabric-like state.
[0010] In the case where the tea-extraction component is dissolved
in water to prepare an aqueous solution, which is then externally
impregnated and carried in a filter, namely, in the attachment and
carrying method by impregnation, the tea-extraction component is
compatible with water, and hence, fixing properties and waterproof
properties are not sufficient. Therefore, when this filter is used
in contact with water, or in washing with water, it involves such a
defect that the tea-extraction component as an attaching component
is readily lost.
[0011] In the method in which the tea-extraction component such as
a catechin is internally added to (i.e., incorporated into)
polypropylene as a filter material and then melt formed, since the
tea-extraction component such as a catechin, which is originally
soluble in water, is incompatible with polypropylene as a non-polar
resin, it is likely to bleed out onto the filament surface to
generate stains. Further, when the filament is dipped in water or
washed with water, a major part of the extraction component elutes
out, whereby the effect is drastically reduced. Even when the
internal addition amount is increased taking into consideration of
the bleeding-out, the elution amount is still high during contact
with water. Accordingly, it is inevitable that not only the
production cost is high, but also the spinning properties,
stretching properties and strength are decreased. In addition, in
this internal addition method, during the melt forming, a
considerable amount of an effective part of the tea-extraction
component is volatilized out, and hence, it is inevitable that the
relatively expensive active ingredient is lost.
SUMMARY OF THE INVENTION
[0012] Under such circumstances, the present invention is aimed to
provide a joining type (a core-sheath type or bimetal joining type)
composite molding, in which bleeding of the internally added
functional component is effectively inhibited; the internally added
functional component does not adversely affect moldability (e.g.,
melt spinning properties, etc.), post-processing properties (e.g.,
stretching properties, etc.), and physical properties (e.g.,
strength, dimensional stability, etc.); the internal addition
amount of the functional component can be greatly decreased,
leading to an advantage from the standpoint of production cost;
superior functionalities (e.g., deodorizing properties,
antimicrobial properties, etc.), which the functional component
inherently possesses, can be exhibited to the maximum extent; even
when used upon contact with water, the composite molding is durable
so that the functionalities can be kept over a long period of time;
and even when used upon contact with a human body, the composite
molding is high in safety. The present invention is also aimed to
provide a process for the production of the joining type composite
molding.
[0013] Specifically, the composite molding according to the present
invention is a joining type composite molding comprising an
internal component X and an external component Y, wherein the
internal component X is formed from a first resin (H); the external
component Y is formed from a second resin (L) compounded with at
least one functional component (A) selected from the group
consisting of catechin, saponin, tea-leaf powder, tea-leaf extract,
and tannin (tannic acid), and ceramics component (C); and the first
resin (H) and the second resin (L) are a resin falling within a
scope different from each other, or a resin falling into the same
scope of a non-polyolefinic resin.
[0014] The process for the production of the composite molding
according to the present invention is characterized by co-extrusion
forming a first resin (H) and a second resin (L) compounded with at
least one functional component (A) selected from the group
consisting of catechin, saponin, tea-leaf powder, tea-leaf extract,
and tannin (tannic acid), and ceramics component (C) at a melting
temperature higher than melting temperatures of the respective
components, such that the first resin (H) becomes an internal
component X and that the second resin (L) compounded with the
functional component (A) and the ceramics component (C) becomes an
external component Y, thereby obtaining a joining type composite
molding constructed of the internal component X and the external
component Y, wherein the first resin (H) and the second resin (L)
are a resin falling into a scope different from each other, or a
resin falling into the same scope of a non-polyolefinic resin.
BRIEF DESCRIPTION OF THE DRAWING
[0015] FIG. 1A is a schematically cross-sectional view of the
composite molding (composite filament) obtained in Example 1;
and
[0016] FIG. 1B is a schematically cross-sectional view of the
filament obtained in Comparative Example 1.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The present invention is described below in detail.
[0018] (Composite Molding)
[0019] The composite molding according to the present invention is
a joining type composite molding constructed of an internal
component X and an external component Y. The internal component X
is formed from a first resin (H), and the external component Y is
formed from a second resin (L) having a functional component (A)
and the ceramics component (C) compounded therein. And, it is
necessary that the first resin (H) and the second resin (L) are a
resin falling within a scope different from each other, or a resin
falling within the same scope of a non-polyolefinic resin.
Representative examples of the "joining type" are a core-sheath
joining type and a bimetal joining type.
[0020] (First Resin (H) and Second Resin (L))
[0021] As described above, it is necessary that the first resin (H)
and the second resin (L) are a resin falling within a scope
different from each other, or a resin falling within the same scope
of a non-polyolefinic resin. From the standpoint of practical use,
the first resin (H) and the second resin (L) are preferably a resin
selected from polyamide-based resins, polyester-based resins,
polyolefinic resins, polyurethane-based resins, polyvinyl
chloride-based resins, polyvinylidene chloride-based resins, and
acrylic resins. Of these are particularly preferred polyamide-based
resins, polyester-based resins and polyolefinic resins. However,
other various molding resins including polystyrenic resins
(including ABS (acrylonitrile-butadiene-styrene) resins and AS
(acrylonitrile-styrene) resins), polycarbonate-based resins,
ethylene-vinyl alcohol copolymer-based resins, various
heat-resistant resins, and various high-strength resins can also be
used. The resin also includes thermoplastic elastomers. In this
case, so far as these resins fall within the same scope, even when
the grade is different, or the resins are blended with and modified
by other resins, they are considered to be a resin falling within
the same scope. For example, a difference between polyamide-based
resins such as nylon 6 and nylon 66, or a difference between
polyolefinic resins such as polyethylene and polypropylene, is not
considered to be a difference in the scope of a resin. The reason
why the case where both the first resin (H) and the second resin
(L) are a polyolefinic resin is excluded from the scope of the
present invention is in the fact that the present inventor filed
previously an application for patent regarding such
combination.
[0022] Of the above-exemplified resins, examples of the
polyamide-based resins include nylon 6, nylon 66, nylon 6-66, nylon
610, nylon 612, nylon 11, nylon 12, nylon 46, nylon MXD6, and
polyamide-based thermoplastic elastomers. Examples of the
polyester-based resins include polyethylene terephthalate,
polybutylene terephthalate, polyethylene naphthalate, and
polyester-based thermoplastic elastomers. Examples of the
polyolefinic resins include homopolymers or copolymers of an
olefin, comprising, as the major component, ethylene or propylene,
such as low-density polyethylene, linear low-density polyethylene,
medium-density polyethylene, high-density polyethylene,
ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer,
ionomers, copolymers comprising ethylene as a major component with
propylene or .alpha.-olefins such as 1-butene, ethylene-1-butene
copolymer, polypropylene comprising propylene as major component
with ethylene or .alpha.-olefins such as 1-butene, and polyolefinic
thermoplastic elastomers. Examples of the polyurethane-based resins
include polyurethane-based thermoplastic elastomers. Examples of
the acrylic resins include homopolymers or copolymers comprising,
as the major component, (meth)acrylate or (meth)-acrylonitrile.
[0023] With respect to the melting points of the first resin (H)
which will become the internal component X and of the second resin
(L) which will become the external component Y, in many cases, the
internal component X is responsible to ensuring the strength and
stretching properties, while the external component Y is
responsible to having the functionalities. Accordingly, it is
possible to make the melting point of the first resin (H) higher
(for example, from 5.degree. C. to 10.degree. C. or higher) than
that of the second resin (L). In particular, when a resin having a
low melting point but capable of being subjected to melt forming is
used as the resin for the external component Y, there are
advantages that not only the external component Y can be made to
have heat fusion properties, but also the volatilization of the
active ingredient in the functional component (A) during the melt
forming can be suppressed. In this case, even when the melting
point of the first resin (H) is made equal to or lower than that of
the second resin (L), since the functional component (A) is
contained in the external component Y, there is a significant
advantage that the amount of the functional component (A) to be
used can be made small. Accordingly, the melting point of the first
resin (H) and that of the second resin (L) can be freely set up and
arbitrarily determined depending upon the purpose.
[0024] (Functional Component (A))
[0025] As the functional component (A) is used at least one member
selected from the group consisting of catechin, saponin, a tea-leaf
powder, tea-leaf extract, and tannin (tannic acid). In Particular,
catechin is important. These are a component having functionalities
such as deodorizing properties (e.g., deodorizing properties,
smell-eliminating properties, toxic gas-removing properties),
antimicrobial properties (e.g., antibacterial properties,
bactericidal properties, bacteriostatic properties, fungicidal
properties, antiviral properties), physiological activity (e.g.,
antiallergic properties), and antioxidation properties.
[0026] Of these, as the catechin, are used monomeric compounds and
oligomeric compounds (including theaflavin). Those that are
particularly important as the catechin are tea-originated catechin
formulations in which the catechin concentration is increased. The
major components of the catechin are epigallocatechin,
epigallocatechin gallate, epicatechin, epicatechin gallate, etc.
Since these components are not required to be isolated from each
other, a formulation containing the tea catechin in a high
concentration, comprising a mixture of these components (preferably
those containing 20% or more the tea catechin, and preferably those
containing 25% or more of the tea catechin), can be suitably used
as it stands. The tea-originated catechin formulation is readily
available because the commercially available tea-originated
catechin formulation includes 30% products, 50% products, 60%
products, 70% products, 80% products, and 90% products. The
catechin is contained in various kinds of plants other than teas,
such as catechu, and hence, catechins originated from such plants
are also useful.
[0027] Among the saponins, tea saponin can be obtained by
extracting a saponin-containing component with an organic solvent
or water from tea leaves or tea seeds and then repeatedly purifying
it by means of column chromatography, etc. Though the tea saponin
includes steroid-based saponin and triterepenoid-based saponin, any
of them can be used for the object of the present invention. Since
the saponin is also contained in various kinds of plants other than
teas, such as ginseng (ginseng radix), panacis japonici rhizoma,
soybean (Glycine max MERR.), bupleurum root (bupleuri radix),
hydrangeae dulcis folium, loofah (Luffa cylindrica M. Roemen),
polygala root (polygalae radix), platycodon root (platicodi radix),
senega (senegae radix), ophiopogon tuber (ophiopogonis tuber),
akebia stem (akebiae caulis), anemarrhena rhizome (anemarrhenae
rhizoma), achyranthes root (achyranthis radix), licorice root
(glycyrrhizae radix), and smilax rhizome (smilacis rhizoma),
saponins made from these plants can also be used.
[0028] Examples of the tea-leaf powder or tea-leaf extract which
can be used include powders or extracts of teas, such as the first
pick of tea, the second pick of tea, the third pick of tea, deeply
steamed tea, and kabusecha.
[0029] As the tannin (tannic acid), commercially available purified
tannic acid can be used. Extracts or semi-purified products of
natural plants containing tannic acid, such as Chinese gallotannin
and Turkish gallotannin, can be used as they stand.
[0030] (Ceramics Component (C))
[0031] As the ceramics component (C) are useful in various kinds of
ceramics. In this case, as described below in detail, a silica gel
obtained via a hydrous silicate gel, a combination of an inorganic
sintering aid and an inorganic flocculant, and a combination of
ceramics particles, inorganic sintering aid and an inorganic
flocculant are suitably used. When these ceramics are used, it is
possible to realize complexation with the functional component (A)
while utilizing a flocculation force.
[0032] As the silica gel is suitably used a silica gel obtained via
a hydrous silicate gel. At this time, an aqueous solution of a
silicate is mixed with an acid to adjust pH, and the thus obtained
hydrous gel is further washed with water to remove ions and then
dried to obtain a desired silica gel. Examples of the silicate
include sodium silicate represented by Na.sub.2O.nSiO.sub.2 and
potassium silicate represented by K.sub.2O.nSiO.sub.2, the former
sodium silicate being particularly important. A concentrated
aqueous solution of the silicate is generally called as a water
glass, and typical commercially available water glasses have an
SiO.sub.2 content of from 22 to 38% by weight and an Na.sub.2O
content of from 5 to 19% by weight.
[0033] Examples of the inorganic sintering aid include polyvalent
metal salts of an inorganic acid such as phosphoric acid, sulfuric
acid, nitric acid, and carbonic acid, and fluorides or
silicofluorides of an alkali metal or an alkaline earth metal. As
the polyvalent metal salts are suitably used those of aluminum,
zinc, magnesium, calcium, or manganese. They are usually put into
use in a state where a hydrous salt or hydrate is dissolved in
water.
[0034] Suitable examples of the inorganic flocculant include
inorganic flocculants in a state of sol or solution and
particularly, silicic anhydride in a state of sol, or silicates
(such as sodium silicate and potassium silicate) in a state of
solution. The silicic anhydride in a state of sol includes not only
usual colloidal silica that uses water as a medium but also an
organosilica sol that uses an organic solvent such as an alcohol,
as a medium.
[0035] Examples of the ceramics particles in the combination of
ceramics particles, inorganic sintering aid and inorganic
flocculant include various clay minerals, oxides, hydroxides,
composite oxides, nitrides, carbides, suicides, borides, zeolite,
cristobalite, diatomaceous earth, and polyvalent metal salts of
silicic acid. Examples of the clayminerals include kaolin,
agalmatolite, sericite, and bentonite. Examples of the oxides
include alumina, titania, silica, zirconia, magnesia, and zinc
oxide. Examples of the hydroxides include hydroxides of aluminum,
zinc, magnesium, calcium, and manganese. Examples of the composite
oxides include alums. Examples of the nitrides include silicon
nitride and boron nitride. Examples of the polyvalent metal salts
of silicic acid include aluminum salts, zinc salts, magnesium
salts, calcium salts, and manganese salts.
[0036] With respect to the proportion of the respective components,
in the combination of an inorganic sintering aid and an inorganic
flocculant the amount of the inorganic flocculant is in many cases
from about 100 to 300 parts by weight in terms of solids content,
or more, based on 100 parts by weight of the solids content of the
inorganic sintering aid. In the combination of ceramics particles,
inorganic sintering aid and inorganic flocculant, those amounts at
which the ceramics particles as the major component as well as the
inorganic sintering aid and the inorganic flocculant can play the
respective roles are employed. In many cases, the amounts of the
inorganic sintering aid and the inorganic flocculant are from about
0.5 to 20 parts by weight and from 0.5 to 25 parts by weight in
terms of solids content, respectively based on 100 parts by weight
of the ceramics particles.
[0037] As other examples of the ceramics component (C), clay
minerals having a nature of swelling upon absorption of water, such
as sepiolite, vermiculite, bentonite, sericite clay, and mica of a
water-swelling property, can be suitably used. Of these, sepiolite
having a specific fibrous structure is particularly important.
[0038] Further, as the ceramics component (C), fine powders of
ceramics particles such as silica, alumina, and titania can be used
as they are.
[0039] (Composite Particles of Functional Component (A) and
Ceramics Component (C))
[0040] As described previously, the internal component X is formed
from the first resin (H), and the external component Y is formed
from the second resin (L) having the functional component (A) and
the ceramics component (C) compounded therein. Of these, in the
external component Y, though the functional component (A) and the
ceramics component (C) may be respectively compounded in the second
resin (L), it is preferred that after composite particles
comprising the functional component (A) and the ceramics component
(C) have been prepared in advance, the composite particles are
compounded in the second resin (L).
[0041] In the case where the composite particles are prepared, when
the ceramics component (C) is a silica gel obtained via a hydrous
silicate gel, it is desired that the functional component (A) is
added to the system before, during or after mixing the silicate and
the acid but before the completion of the gelation reaction,
thereby containing the functional component (A) in the silica gel.
Thus, the ceramics can be flocculated in a state containing the
functional component (A).
[0042] In the case where the ceramics component (C) is a
combination of an inorganic sintering aid and an inorganic
flocculant, it is preferred that the ceramics are flocculated in a
state containing the functional component (A). One example is given
below. An aqueous solution of aluminum phosphate as an example of
the inorganic sintering aid is mixed with the functional component
(A) as a powder or an aqueous or alcoholic solution; the pH is
adjusted at from 3 to 4; and is further mixed with a colloid
solution of colloidal silica as an example of the inorganic
flocculant, thereby making the system to have pH to an
approximately neutral degree. At this time, since flocculation
takes place, the flocculation product is placed in a crucible or on
an evaporating dish and then subjected to a heat treatment in a
dryer or an electric furnace until it has become dried.
[0043] In the case where the ceramics component (C) is a
combination of ceramics particles, inorganic sintering aid and
inorganic flocculant, it is preferred that the ceramics are
flocculated in a state containing the functional component (A). One
example is given below. An aqueous solution of aluminum phosphate
as an example of the inorganic sintering aid is added to and
kneaded with particles of ceramics such as aluminum silicate,
alumina, and titania so as to have a viscosity to a degree of an
approximately stiff paste, and subsequently, the kneaded mixture is
mixed with the functional component (A) as a powder or an aqueous
or alcoholic solution (alternatively, after mixing the functional
component (A) with the ceramics particles, the inorganic sintering
aid is kneaded therewith). Further, an aqueous solution of aluminum
phosphate is additionally mixed, if desired. And, pH is adjusted at
from 3 to 4, and is further mixed with a colloid solution of
colloidal silica as an example of the inorganic flocculent, thereby
making the system to have pH to an approximately neutral degree. At
this time, since flocculation takes place, the flocculation product
is placed in a crucible or on an evaporating dish and then
subjected to a heat treatment in a dryer or an electric furnace
until it has become dried.
[0044] (Proportions of Each of the Components in External Component
Y)
[0045] With respect to the proportions of the second resin (L), the
functional component (A) and the ceramics component (C) accounting
for in the external component Y, it is desired that the total
amount of the functional component (A) and the ceramics component
(C) is from 1 to 40 parts by weight (preferably from 2 to 30 parts
by weight) based on 100 parts by weight of the second resin (L).
When the total amount of the functional component (A) and the
ceramics component (C) is too small, the desired functionalities
such as deodorizing properties, antimicrobial properties,
physiological activity, and antioxidation properties are not enough
exhibited. On the other hand, when the total amount of the
functional component (A) and the ceramics component (C) is too
large, negative features become conspicuous so that not only the
functionalities do not increase exceeding a certain extent, but
also the productivity of the composite molding having a shape of
filament or film is lowered, and the strength and drape are
decreased.
[0046] With respect to the relation between the functional
component (A) and the ceramics component (C), it is desired that an
amount of the functional component (A) is from 1 to 300 parts by
weight (preferably from 2 to 200 parts by weight, and more
preferably from 3 to 150 parts by weight) based on 100 parts by
weight of the ceramics component (C). When the amount of the
functional component (A) is too small, the desired functionalities
such as deodorizing properties, antimicrobial properties,
physiological activity, and antioxidation properties are not
sufficient. On the other hand, when the amount of the functional
component (A) is too large, a balance to the ceramics component (C)
is lost, leading to a disadvantage from the standpoint of cost.
[0047] (Joining Type)
[0048] The composite molding according to the present invention is
a joining type composite molding having structure of the internal
component X and the external component Y. In this connection,
examples of the joining type include a core-sheath type and a
bimetal (side-by-side) joining type. In the case of the core-sheath
joining type, the internal component X is a core component, and the
external component Y is a sheath component. The structure here may
be any of concentric core-sheath type, eccentric core-sheath type,
polycentric core-sheath type, and hollow core-sheath type. In the
case of the core-sheath type, even when the adhesion between the
first resin (H) as the internal component X and the second resin
(L) used for the external component Y is insufficient, it is
possible to ensure the adhesion between the internal and external
layers through choosing, as the second resin (L), a material having
a degree of shrinkage larger than that of the first resin (H). In
the case of the bimetal joining type, the type is in a Y/X or Y/X/Y
state (in the Y/X state, one is made of the internal component X,
wherein the other is made of the external component Y).
[0049] (Proportion of the Internal Component X to the External
Component Y)
[0050] When the composite molding is of a core-sheath joining type,
a suitable weight ratio of the internal component X as the core
component to the external component Y as the sheath component is
from 30:70 to 80:20, and particularly from 35:65 to 75:25. When the
proportion of the sheath component is too small, since the
proportion of the functional component (A) is too small, the
desired functionalities are not thoroughly exhibited. Further, when
the resulting molding is required to have heat adhesion, the heat
adhesion becomes insufficient. On the other hand, when the
proportion of the sheath component is too large, since the
proportion of the core component X is relatively too small, the
resulting molding is liable to be not satisfied from the
standpoints of moldability (e.g., spinning properties, etc.),
stretching properties, strength, dimensional stability, etc.
[0051] When the composite molding is of a bimetal joining type, a
suitable weight ratio of the internal component X to the external
component Y (in the Y1 X 1Y state, weight ratio of X to other Y is
from 30:70 to 95:5, and particularly from 35:65 to 90:10. Namely,
the proportion of the internal component X can be made larger, as
compared with the case of the core-sheath joining type. (Shape of
composite molding).
[0052] When the composite molding is of a core-sheath joining type,
a representative shape is in a filament state. Its cross-section
can be made not only circular but non-circular. It can also be made
hollow as the case may be. A thickness of the filament is arbitrary
in from an extra fine fibrous state to a monofilament state (from
an extra fine denier to an extra thick denier), or even up to a
state close to a thicker rod.
[0053] When the composite molding is of a bimetal joining type, a
representative shape is in a film or sheet state. The molding may
be slit into thin strips to form filaments. Further, the film or
sheet can also be split. In addition, the molding can be formed
into a container state, a plate state, or other state of various
parts.
[0054] (Production of Composite Molding)
[0055] When the first resin (H) and the second resin (L) are a
resin falling within a scope different from each other, or a resin
falling within the same scope of a non-polyolefinic resin, the
composite molding can be suitably produced in the following
manner.
[0056] Namely, the first resin (H) and the second resin (L)
compounded with the functional component (A), which is at least one
member selected from the group consisting of catechin, saponin,
tea-leaf powder, tea-leaf extract, and tannin (tannic acid), and
the ceramics component (C) are subjected to co-extrusion forming at
a temperature higher than melting temperatures of the respective
components, such that the first resin (H) becomes the internal
component X and that the second resin (L) compounded with the
functional component (A) and the ceramics component (C) becomes the
external component Y. There can be thus obtained a joining type
composite molding constructed of the internal component X and the
external component Y. In this case, the functional component (A)
can also be internally added to the first resin (H) that becomes
the internal component X.
[0057] The co-extrusion forming can be attained by discharging the
first resin (H) and the second resin (L) linear or sheet-like form
from composite dies using two or more extruders. Depending on
circumstances, the both resins are formed into a net-like form by
using rotating dies. In this connection, the second resin (L), a
master batch in which the concentration of the material to be
internally added is high may be previously prepared and then mixed
with the second resin (L), followed by providing for the
forming.
[0058] If desired, in both the first resin (H) and the second resin
(L), auxiliary agents such as antioxidants, ultraviolet light
absorbers, colorants, lubricants, antistatic agents, matting
agents, fluidity improvers, plasticizers, and flame retardants can
be internally added. In particular, it is preferred that, in the
second resin (L) compounded with the functional component (A) and
the ceramics component (C), forming aids effective for improving
the flocculation prevention or the dispersibility, inclusive of
metallic soaps, are compounded together with stabilizers such as
antioxidants, thereby ensuring homogenous dispersion of the
functional component (A) and the ceramics component (C)
(particularly, composite particles comprising the both). Further,
in order to improve supporting properties of the functional
component (A), suitable amounts of metal ion sources such as copper
salts, iron salts, calcium salts, titanium salts, aluminum salts,
silver salts, tin salts, zinc salts, chromium salts, and cobalt
salts can be made coexistent.
[0059] In the case where a filament-form material is obtained in
many cases drawing is carried out after the co-extrusion forming.
While the drawing ratio is not particularly limited, when the
drawing ratio is too small, the strength tends to be insufficient
depending on the use. The drawing ratio is usually 3 or more, and
particularly 4 or more. On the other hand, when the drawing ratio
is too large, a trouble in which ply separation is likely to occur
between the core and the sheath may be caused. Accordingly, an
upper limit of the drawing ratio is generally about 10. Further,
since the drawing is not required depending on the use, the drawing
is not always essential. When a film-form or sheet-form material is
to be obtained, drawing may also be carried out after co-extrusion
forming, if desired.
[0060] (Application and Use)
[0061] When the composite molding according to the present
invention is in a filament form, it is free to obtain from the
composite filament secondary products such as yarns, piles,
cotton-like materials, nets, ropes, belts, woven fabrics, non-woven
fabrics, and knitted fabrics. The composite filament or secondary
products thereof can be used in combination with fibers or
monofilaments such as natural fibers (cotton, hemp, silk, wool,
etc.), fibers or monofilaments of synthetic resins (polyesters,
acrylic reins, polypropylene, polyethylene, nylons, vinylons,
polyvinylidene chloride, polyvinyl chloride, polyurethane, etc.),
semi-synthetic fibers (acetate fibers, etc.), regenerated fibers
(rayon, etc.), and inorganic fibers (glass fibers, carbon fibers,
etc.), or secondary products thereof. When the composite molding
according to the present invention is film, sheet, or container,
the secondary products can also be obtained by lamination or the
like.
[0062] Examples of the use for which the composite molding or its
secondary products according to the present invention is applied
include interior materials of vehicles (sheet cloths, ceiling
materials, flooring materials, etc.), interior materials for rooms
(wall sheets, flooring materials, etc.), matting materials of rooms
or vehicles (mats, carpets, etc.), filters (for air conditioners,
air cleaners, vacuum cleaners, etc.), footwear materials,
industrial materials, clothing materials, bedding materials,
hygienic materials, medical materials, daily goods, kitchen
utensils, toiletry, and packaging materials.
[0063] (Heat Fused Article)
[0064] When the kind of the second resin (L) is chosen, or the
amount of the internally added material is regulated in order to
impart heat fusion properties to the external component Y of the
composite molding according to the present invention, heat fused
articles can be obtained. For example, when textile fabrics (e.g.,
nets, woven fabrics, knitted fabrics, etc.) or non-woven fabrics
are produced using composite filaments of a core-sheath joining
type, or filaments obtained by slitting a film of a bimetal joining
type into thin strips, crossover points of the filaments can be
fused upon heat fusion. Accordingly, an advantage is given that
mesh deviation occurred during the practical use or secondary
processing can be effectively prevented. Alternatively, the textile
fabrics or non-woven fabrics can be fixed to a frame or the
like.
[0065] The present invention is further described below with
reference to the following Examples. In these Examples, all parts
and percents are on a weight basis.
[0066] (Preparation of Materials)
[0067] As the first resin (H) was prepared the following
materials.
[0068] (H.sub.1): Polypropylene (PP) having a melting point of
163.degree. C. and a specific gravity of 0.91
[0069] As the second resin (L) was prepared the following
materials.
[0070] (L.sub.1): Polyethylene terephthalate (PET) having a melting
point of 265.degree. C. and a specific gravity of 1.4
[0071] As the functional component (A) to be internally added to
the second resin (L) were prepared the following materials.
[0072] (A.sub.1): 30% Product of tea catechin (a tea catechin
formulation originated from tea, containing about 30% in total of
epigallocatechin, epigallocatechin gallate, epicatechin and
epicatechin gallate)
[0073] (A.sub.2): Tea saponin having a purity of 70%
[0074] (A.sub.3): Green tea powder
[0075] (A.sub.4) Powder obtained by drying a hot water-extract of
green tea
[0076] (A.sub.5): Tannic acid having a purity of 85%
[0077] As a raw material of the ceramics component (C) to be
internally added to the second resin (L) were prepared the
following materials.
[0078] (C.sub.1): Silicate (water glass)
[0079] (C.sub.2): Aluminum phosphate and colloidal silica
[0080] (C.sub.3): Silica, aluminum phosphate and colloidal
silica
[0081] (Preparation of Functional Component (A)-Ceramics Component
(C) Composite Particles)
[0082] Composite particles comprising the functional component (A)
and the ceramics component (C) were produced in the following
manners.
[0083] (Method 1)
[0084] The raw material (C.sub.1) for the ceramics component (C)
was prepared in the following manner. That is, the functional
material (A) was added to a 1N sulfuric acid solution kept at
0.degree. C., and a 1N water glass solution was separately
prepared. Next, the 1N water glass solution was added dropwise over
several minutes while vigorously stirring the 1N sulfuric acid
solution containing the functional component (A). At this time, the
reaction mixture had a temperature of from 5 to 7.degree. C. The
mixed solution was washed with running water for one day, and then,
the water was well drained off. Thereafter, the residue was finely
ground and dried in vacuo in a dryer at a temperature of 50 to
60.degree. C., to obtain a powdered composite.
[0085] (Method 2)
[0086] The raw material (C.sub.2) for the ceramics component (C)
was prepared in the following manner. That is, the functional
material (A) was mixed with 200 parts of an aluminum phosphate
aqueous solution having a concentration of 25% to adjust pH at from
3 to 4, and the mixture was further mixed with 130 parts of a
colloid solution of colloidal silica (solids content: 40%) to make
the pH neutral. Since a slurry had gradually flocculated, it was
placed on an evaporating dish (or in a crucible) within a period in
which it could be handled and subjected to a heat treatment by
drying at from 100 to 300.degree. C. in a constant-temperature
dryer or an electric furnace. A rigid, amorphous flocculation
product was thus obtained. The obtained flocculation product was
finely ground in an automatic mortar (or a ball mill) and screened
by a sieve to obtain particles having a particle size of from 100
to 325 mesh. The particles of the flocculation product were then
subjected to a heat treatment in a constant-temperature dryer or an
electric furnace.
[0087] (Method 3)
[0088] The raw material (C.sub.3) for the ceramics component (C)
was prepared in the following manner. That is, 130 parts of the
functional component (A) was dry mixed with 400 parts by weight of
silica having a mean particle size smaller than 325 mesh, and 200
parts of an aluminum phosphate aqueous solution having a
concentration of 25% was added to and kneaded with the mixture to a
degree of an approximately stiff paste. The paste was further mixed
with 50 parts of a colloid solution of colloidal silica (solid
content: 40%) to make the pH neutral. Since flocculation occurred
step by step at this time, the mixture was placed on an evaporating
dish within a period in which it could be handled and then dried.
Thereafter, the dried product was subjected to dehydration and
hydrolysis at from 100 to 300.degree. C. and then finely
ground.
EXAMPLES 1 TO 7
[0089] The second resin (L) was mixed with the functional component
(A)-supported ceramics component (C) obtained in Method 1, 2 or 3
as described above, together with small amounts of an antioxidant
and a flocculation preventive (a dispersing agent), and the mixture
was melt extruded and pelletized. The thus obtained pellets were
used as the external component (sheath component) Y, and pellets of
the above-described first resin (H) were used as the internal
component (core component) X. The both pellets were subjected to
co-extrusion under temperature conditions of 70 to 90.degree. C.
higher than the melting point of the second resin (L) with respect
to the external component (sheath component) Y and under
temperature conditions of 60 to 90.degree. C. higher than the
melting point of the first resin (H) with respect to the internal
component (core component) X, respectively, from two extruders each
equipped with a composite die, followed by drawing in a drawing
ratio of about 6, thereby obtaining a composite filament (composite
molding). Thereafter, from this composite filament was prepared a
non-woven fabric. The conditions are shown in Table 1.
COMPARATIVE EXAMPLES 1 AND 2
[0090] To the second resin (L) was internally added the functional
component (A) and subjected to extrusion forming at a temperature
of 70 to 90.degree. C. higher than the melting point of the second
resin (L), followed by drawing in a drawing ratio of about 6,
thereby obtaining a filament. Using the thus obtained filament, a
non-woven fabric was prepared. The conditions are also shown in
Table 1.
COMPARATIVE EXAMPLES 3 AND 4
[0091] The same procedures as in Examples 1 to 7 were followed to
effect co-extrusion, except omitting the internal addition of the
ceramics component (C) to the second resin (L), followed by drawing
in a drawing ratio of about 6, thereby obtaining a filament
(composite filament) Using the thus obtained filament, a non-woven
fabric was prepared. The conditions are also shown in Table 1.
[0092] FIG. 1A is a schematically cross-sectional view of the
composite molding (composite filament) obtained in Example 1; and
FIG. 1B is a schematically cross-sectional view of the monofilament
obtained in Comparative Example 1.
1 TABLE 1 Internal component X External component Y Composite (H)
(A) (L) (A) (C) particles Comparative (See Note 1) (L.sub.1):94
(A.sub.1):6 -- -- Example 1 parts parts Comparative (See Note 1)
(L.sub.1):94 (A.sub.2):6 -- -- Example 2 parts parts Comparative
(H.sub.1):50 -- (L.sub.1):46 (A.sub.1):3 -- -- Example 3 parts
parts - parts Comparative (H.sub.1):50 -- (L.sub.1):46 (A.sub.2):3
-- -- Example 4 parts parts - parts Example 1 (H.sub.1):50 --
(L.sub.1):35 (A.sub.1):3 (C.sub.1):12 Method 1 parts parts parts
parts Example 2 (H.sub.1):50 -- (L.sub.1):35 (A.sub.2):3
(C.sub.1):12 Method 1 parts parts parts parts Example 3
(H.sub.1):50 -- (L.sub.1):35 (A.sub.3):3 (C.sub.1):12 Method 1
parts parts parts parts Example 4 (H.sub.1):50 -- (L.sub.1):35
(A.sub.1):3 (C.sub.2):12 Method 2 parts parts parts parts Example 5
(H.sub.1):50 -- (L.sub.1):35 (A.sub.4):3 (C.sub.2):12 Method 2
parts parts parts parts Example 6 (H.sub.1):50 -- (L.sub.1):35
(A.sub.5):3 (C.sub.3):12 Method 3 parts parts parts parts Example 7
(H.sub.1):50 -- (L.sub.1):35 (A.sub.1):3 (C.sub.3):12 Method 3
parts parts parts parts
[0093] Note 1: In Comparative Examples 1 and 2, monofilament
(non-composite filament)
[0094] Note 2: In Comparative Examples 3 and 4 and Examples 1 to 7,
core-sheath joining type composite filament
[0095] (Test)
[0096] Each of the non-woven fabrics as prepared above was dipped
in water at a normal temperature for 3 hours and then once taken
out, followed by spontaneous drying. Thereafter, the filter was
again dipped in water for 3 hours and then taken out, followed by
spontaneous drying. The amounts of the functional component (A)
before the first dipping in water and after the second dipping in
water were measured by thermal analysis by means of a differential
calorimeter (the temperature was elevated at a rate of 5.degree.
C./min in an electric furnace, and a heat balance (endothermic
heat/exothermic heat) of the sample during the heating step and an
accompanying increase or decrease in weight were analyzed). And,
the filters before and after the water washing were subjected to a
deodorizing properties test and an antimicrobial properties test
under the following conditions. The results obtained are shown
separately in Tables 2 and 3.
[0097] (Deodorizing Properties Test)
[0098] In a 1-m.sup.3 vessel was placed an air cleaner having each
of the non-woven fabrics as described above equipped therein, which
could be operated externally, and five cigarettes were installed in
a smoke absorber and ignited in the vessel. When the first
cigarette had burnt out, the operation of the air cleaner was
started. An ammonia concentration was measured by using a gas
detector tuber 5 minutes and 30 minutes after the start of the
operation. Then, a deodorizing rate was determined by the decreased
amount of concentration after 30 minutes, as compared with the
concentration (initial concentration) after 5 minutes.
[0099] (Antimicrobial Properties Test)
[0100] Each of the samples was examined for the antimicrobial
properties under the following conditions.
[0101] Test item: Test for rate of decrease in number of
bacteria
[0102] Test bacterium: Staphyloccus aureus ATCC 6538P
[0103] Test method: According to a uniform test method
[0104] Test results:
[0105] Number of planted bacteria (A):
1.0.times.10.sup.5 log A=5.0
[0106] Number of bacteria on non-processed cloth (B):
1.6.times.10.sup.7 log B=7.2
[0107] (A Standard Cotton Cloth was Used as the Non-Processed
Cloth.)
[0108] log B-log A=2.2>1.5 (the test was effective) Increase or
decrease value=log C-Log A Difference in increase or decrease
value=(log B-log A)-(log C-log A)
2 TABLE 2 Comparative Example 1 2 3 4 Before water washing Content
of (A) (%) 3.9 3.9 2.1 2.0 After dipping in water Content of (A)
(%) 0.6 0.7 0.2 0.2 Deodorizing rate of NH.sub.3 (%) 51 52 46 45
Antimicrobial properties Number of bacteria, log C 6.5 6.5 6.9 6.9
Increase or decrease value 1.5 1.5 1.9 1.9 Difference in increase
or decrease value 0.7 0.7 0.3 0.3
[0109] (For the Antimicrobial Properties Test, 0.2 g of the Sample
was Collected.)
3 TABLE 3 Example 1 2 3 4 5 6 7 Before water washing Content of (A)
(%) 2.7 2.7 2.6 2.6 2.7 2.6 2.6 After dipping in water Content of
(A) (%) 2.6 2.6 2.5 2.5 2.5 2.5 2.4 Deodorizing rate of 75 75 73 73
74 72 72 NH.sub.3 (%) Antimicrobial properties Number of bacteria,
3.8 3.9 3.9 3.9 4.0 4.2 3.9 log C Increase or decrease -1.2 -1.1
-1.1 -1.1 -1.0 -1.2 -1.1 value Difference in increase 3.4 3.3 3.3
3.3 3.2 3.0 3.3 or decrease value
[0110] (For the Antimicrobial Properties Test, 0.2 g of the Sample
was Collected.)
[0111] It is understood from Tables 2 and 3 that, in Comparative
Examples 1 and 2, even though the internal addition amount of the
functional component (A) is 6 parts, the functionalities after
dipping in water are insufficient. Further, it is understood that,
in Comparative Examples 3 and 4, since the functional component (A)
is internally added in the side of the sheath component Y as the
external layer, the functionalities after dipping in water are more
insufficient. Further, when drawn articles of a filament made of
the second resin (L.sub.1) only, in which the functional component
(A) is not internally added, the deodorizing rate of NH.sub.3 is
about 40%, and hence, a "(measured value)--40%" value is a
substantial deodorizing rate. Further, it is understood that, in
Comparative Examples 3 and 4, since the ceramics component (C) is
not co-existent, a considerable amount of the functional component
(A) was volatilized out during the extrusion forming, as compared
with Examples 1 to 7. Moreover, in Examples 1 to 7, since PP having
a low specific gravity is used for the core, and PET is used for
the sheath acting as a surface, there are merits that the surface
can have preferable drape, nerve, feeling (challis-like feeling),
heat resistance, and shrinkage resistance during laundry, which PET
possesses, while preventing an increase of the specific gravity of
the whole.
[0112] (Antiviral Properties Test)
[0113] Using each of the composite filaments obtained in Examples
1, 4 and 7 and of a composite filament (control) composed of the
first resin (H.sub.1) and the second resin (L.sub.1) in a weight
ratio of 1:1, a specimen (3 cm.times.3 cm) comprising a filter for
air conditioner was prepared. To the specimen was added by dropping
0.2 ml of an influenza virus-floating solution, followed by storing
at 25.degree. C. Twenty-four hours after the storage, the virus on
the specimen was washed away, and a logarithmic value of a virus
infection value (a 50% tissue culture infectious dose (TCID.sub.50)
per ml) was measured. The results obtained are shown in Table
4.
4 TABLE 4 log TCID.sub.50/ml At the start After 24 hours Control
5.3 5.3 Example 1 5.3 3.4 Example 4 5.3 3.4 Example 7 5.3 3.4
[0114] (Preparation of Materials)
[0115] As the first resin (H) were prepared the following
materials.
[0116] (Hi): Polypropylene (PP) having a melting point of
163.degree. C. and a specific gravity of 0.91
[0117] (H.sub.2): Nylon 6 (Ny6) having a melting point of
220.degree. C. and a specific gravity of 1.13
[0118] (H.sub.3): Polyethylene terephthalate (PET) having a melting
point of 265.degree. C. and a specific gravity of 1.4
[0119] As the second resin (L), were prepared the following
materials.
[0120] (L.sub.1): Polyethylene terephthalate (PET) having a melting
point of 265.degree. C. and a specific gravity of 1.4
[0121] (L.sub.2): Polypropylene (PP) having a melting point of
128.degree. C. and a specific gravity of 0.91
[0122] (L.sub.3) Nylon 6 (Ny6) having a melting point of
220.degree. C. and a specific gravity of 1.13
[0123] As the functional component (A) to be internally added to
the second resin (L) was prepared the following material.
[0124] (A.sub.1): 30% Product of tea catechin (a tea catechin
formulation originated from tea, containing about 30% in total of
epigallocatechin, epigallocatechin gallate, epicatechin and
epicatechin gallate)
[0125] As a raw material of the ceramics component (C) to be
internally added to the second resin (L), were prepared the
following materials.
[0126] (C.sub.3): Silica, aluminum phosphate and colloidal
silica
[0127] (C.sub.4): Sepiolite
[0128] (Preparation of Functional Component (A)-Ceramics Component
(C))
[0129] As to (C.sub.3), composite particles with (A.sub.1) were
produced according to Method 3 as described above. Further, as to
(C.sub.4), (A.sub.1) was dissolved or dispersed in water, into
which was then addede (C.sub.4), followed by mixing and drying
(referred to as "Method 4", hereinafter).
EXAMPLES 8 TO 11
[0130] The second resin (L) was mixed with the functional component
(A)-supported ceramics component (C) obtained in Method 3 or 4 as
described above, together with small amounts of an antioxidant and
a flocculation preventive (a dispersing agent), and the mixture was
melt extruded and pelletized. The thus obtained pellets were used
as the external component (sheath component) Y, and pellets of the
above-described first resin (H) were used as the internal component
(core component) X. The both pellets were subjected to co-extrusion
under temperature conditions of 70 to 90.degree. C. higher than the
melting point of the second resin (L) with respect to the external
component (sheath component) Y and under temperature conditions of
60 to 90.degree. C. higher than the melting point of the first
resin (H) with respect to the internal component (core component)
X, respectively, from two extruders each equipped with a composite
die, followed by drawing in a drawing ratio of about 6, thereby
obtaining a composite filament (composite molding). Thereafter,
from this composite filament, was prepared a non-woven fabric. The
conditions are shown in Table 5.
COMPARATIVE EXAMPLES 5 TO 7
[0131] To the second resin (L), was internally added the functional
component (A) and subjected to extrusion forming at a temperature
of 70 to 90.degree. C. higher than the melting point of the second
resin (L), followed by drawing in a drawing ratio of about 6,
thereby obtaining a filament. Using the thus obtained filament, a
non-woven fabric was prepared. The conditions are also shown in
Table 5.
COMPARATIVE EXAMPLES 8 TO 11
[0132] The same procedures as in Examples 8 to 11 were followed to
effect co-extrusion, except omitting the internal addition of the
ceramics component (C) to the second resin (L), followed by drawing
in a drawing ratio of about 6, thereby obtaining a filament
(composite filament). Using the thus obtained filament, a non-woven
fabric was prepared. The conditions are also shown in Table 5.
5 TABLE 5 Internal component External component X Y Composite (H)
(A) (L) (A) (C) particles Comparative (See Note 1) (L.sub.1):94
(A.sub.1):6 -- -- Example 5 parts parts Comparative (See Note 1)
(L.sub.2):94 (A.sub.1):6 -- -- Example 6 parts parts Comparative
(See Note 1) (L.sub.3):94 (A.sub.1):6 -- -- Example 7 parts parts
Comparative (H.sub.1):50 -- (L.sub.3):46 (A.sub.1):3 -- -- Example
8 parts parts - parts Comparative (H.sub.2):50 -- (L.sub.1):46
(A.sub.1):3 -- -- Example 9 parts parts - parts Comparative
(H.sub.3):50 -- (L.sub.2):46 (A.sub.1):3 -- -- Example 10 parts
parts - parts Comparative (H.sub.3):50 -- (L.sub.3):46 (A.sub.1):3
-- -- Example 11 parts parts - parts Example 8 (H.sub.1):50 --
(L.sub.3):35 (A.sub.1):3 (C.sub.3):12 Method 3 parts parts parts
parts Example 9 (H.sub.2):50 -- (L.sub.1):35 (A.sub.1):3
(C.sub.4):12 Method 3 parts parts parts parts Example 10
(H.sub.3):50 -- (L.sub.2):35 (A.sub.1):3 (C.sub.4):12 Method 4
parts parts parts parts Example 11 (H.sub.3):50 -- (L.sub.3):35
(A.sub.1):3 (C.sub.4):12 Method 4 parts parts parts parts In
Comparative Examples 1 to 3, monofilament (non-composite filament)
In Comparative Examples 8 to 11 and Examples 8 to 11, core-sheath
joining type composite filament
[0133] (Test)
[0134] The same tests as in Examples 1 to 7 were carried out. The
results obtained are shown in Tables 6 and 7.
6 TABLE 6 Comparative Example 5 6 7 8 9 10 11 Before water washing
3.8 4.0 4.0 2.2 2.0 2.2 2.2 Content of (A) (%) After dipping in
water Content of (A) (%) 0.6 0.8 0.5 0.2 0.2 0.2 0.1 Deodorizing
rate of NH.sub.3 (%) 50 54 48 44 44 45 40 Antimicrobial properties
Number of bacteria, log C 6.6 6.6 6.6 6.9 7.0 6.9 7.1 Increase or
decrease value 1.6 1.6 1.6 1.9 2.0 1.9 2.2 Difference in increase
or 0.6 0.6 0.6 0.3 0.2 0.3 0.1 Decrease value
[0135] (For the Antimicrobial Properties Test, 0.2 g of the Sample
was Collected.)
7 TABLE 7 Example 8 9 10 11 Before water washing Content of (A) (%)
2.6 2.4 2.6 2.7 After dipping in water Content of (A) (%) 2.5 2.3
2.2 2.3 Deodorizing rate of NH.sub.3 (%) 74 70 70 69 Antimicrobial
properties Number of bacteria, log C 3.9 4.1 4.1 4.1 Increase or
decrease value -1.1 -0.9 -0.9 -0.9 Difference in increase or
decrease value 3.3 3.1 3.1 3.1
[0136] (For the Antimicrobial Properties Test, 0.2 g of the Sample
was Collected.)
EXAMPLE 12
[0137] As raw materials of the first resin (H), the second resin
(L), the functional component (A) to be internally added to the
second resin (L), and the ceramics component (C) to be internally
added to the second resin (L), were prepared the following
materials. Further, composite particles comprising the functional
component (A) having the ceramics component (C) supported thereon
were obtained in the same procedures as in Method 1 as described
above.
[0138] (H.sub.1): Polypropylene (PP) having a melting point of
163.degree. C. and a specific gravity of 0.91
[0139] (L.sub.1): Polyethylene terephthalate (PET) having a melting
point of 265.degree. C. and a specific gravity of 1.4
[0140] (A.sub.1): 30% Product of tea catechin
[0141] (C.sub.1): Silicate (water glass)
[0142] The second resin (L) was mixed with the functional component
(A)-supported ceramics component (C) obtained in Method 1 as
described above, together with small amounts of an antioxidant and
a flocculation preventive (a dispersing agent), and the mixture was
melt extruded and pelletized. The thus obtained pellets were used
as the external component (sheath component) Y, and pellets of the
above-described first resin (H) were used as the internal component
(core component) X. The both pellets were subjected to co-extrusion
under temperature conditions of about 80.degree. C. higher than the
melting point of the second resin (L) with respect to the external
component (sheath component) Y and under temperature conditions of
about 80.degree. C. higher than the melting point of the first
resin (H) with respect to the internal component (core component)
X, respectively, from two extruders each equipped with a composite
die, thereby obtaining a bimetal joining type film-like composite
molding of a Y/X/Y layer construction. Thereafter, the resulting
film-like composite molding was slit into thin strips. Using the
thus obtained fibrous molding, a cloth was prepared. This cloth had
deodorizing properties and antimicrobial properties as in Example
1.
[0143] (Preparation of Materials)
[0144] As the first resin (H) and the second resin (L), were
prepared the following materials. (H.sub.3) is the same resin as
(L.sub.1)
[0145] (H.sub.3): Polyethylene terephthalate (PET) having a melting
point of 265.degree. C.
[0146] (L.sub.1): Polyethylene terephthalate (PET) having a melting
point of 265.degree. C.
EXAMPLES 13 TO 19
[0147] The second resin (L) of the external component Y was mixed
with the functional component (A)-supported ceramics component (C)
obtained in Method 1, 2 or 3 as described above, together with
small amounts of an antioxidant and a flocculation preventive (a
dispersing agent), and the mixture was melt extruded and
pelletized. The thus obtained pellets were used as the external
component (sheath component) Y, and pellets of the above-described
first resin (H) were used as the internal component (core
component) X. The both pellets were subjected to co-extrusion under
temperature conditions of 70 to 90.degree. C. higher than the
melting point of the resin (L) of the external component Y with
respect to the external component (sheath component) Y and under
temperature conditions of 70 to 90.degree. C. higher than the
melting point of the resin (H) of the internal component X with
respect to the internal component (core component) X, respectively,
from two extruders each equipped with a composite die, followed by
drawing as far as possible, thereby obtaining a composite filament
(composite molding). Thereafter, from this composite filament was
prepared a non-woven fabric. The conditions are shown in Table
8.
COMPARATIVE EXAMPLES 12 AND 13
[0148] To the same resin as the resin (L) of the external component
Y, was internally added the functional component (A) and subjected
to extrusion forming at a temperature of 70 to 90.degree. C. higher
than the melting point of that resin, followed by drawing as far as
possible, thereby obtaining a filament. Using the thus obtained
filament, a non-woven fabric was prepared. The conditions are also
shown in Table 8.
COMPARATIVE EXAMPLES 14 AND 15
[0149] The same procedures as in Examples 13 to 19 were followed to
effect co-extrusion, except omitting the internal addition of the
ceramics component (C) to the second resin (L) of the external
component Y, followed by drawing as far as possible, thereby
obtaining a filament (composite filament). Using the thus obtained
filament, a non-woven fabric was prepared. The conditions are also
shown in Table 8.
8 TABLE 8 Internal component External component X Y Composite (H)
(A) (L) (A) (C) particles Comparative (See Note 1) (L.sub.1):94
(A.sub.1):6 -- -- Example 12 parts parts Comparative (See Note 1)
(L.sub.1):94 (A.sub.2):6 -- -- Example 13 parts parts Comparative
(H.sub.3):50 -- (L.sub.1):46 (A.sub.1):3 -- -- Example 14 parts
parts - parts Comparative (H.sub.3):50 -- (L.sub.1):46 (A.sub.2):3
-- -- Example 15 parts parts - parts Example 13 (H.sub.3):50 --
(L.sub.1):35 (A.sub.1):3 (C.sub.1):12 Method 1 parts parts parts
parts Example 14 (H.sub.3):50 -- (L.sub.1):35 (A.sub.2):3
(C.sub.1):12 Method 1 parts parts parts parts Example 15
(H.sub.3):50 -- (L.sub.1):35 (A.sub.3):3 (C.sub.1):12 Method 1
parts parts parts parts Example 16 (H.sub.3):50 -- (L.sub.1):35
(A.sub.1):3 (C.sub.2):12 Method 2 parts parts parts parts Example
17 (H.sub.3):50 -- (L.sub.1):35 (A.sub.4):3 (C.sub.2):12 Method 2
parts parts parts parts Example 18 (H.sub.3):50 -- (L.sub.1):35
(A.sub.5):3 (C.sub.3):12 Method 3 parts parts parts parts Example
19 (H.sub.3):50 -- (L.sub.1):35 (A.sub.1):3 (C.sub.3):12 Method 3
parts parts parts parts In Comparative Examples 12 and 13,
monofilament (non-composite filament) In Comparative Examples 14
and 15 and Examples 13 to 19, core-sheath joining type composite
filament
[0150] (Test)
[0151] Using the non-woven fabrics as prepared above, various tests
were carried out in the same procedures as described above. The
results obtained are shown separately in Tables 9 and 10.
9 TABLE 9 Comparative Example 12 13 14 15 Before water washing
Content of (A) (%) 3.8 3.8 2.0 2.0 After dipping in water Content
of (A) (%) 0.6 0.6 0.2 0.2 Deodorizing rate of NH.sub.3 (%) 50 49
44 40 Antimicrobial properties Number of bacteria, log C 6.6 6.6
7.0 6.9 Increase or decrease value 1.6 1.6 2.0 1.9 Difference in
increase or decrease value 0.6 0.6 0.2 0.3
[0152] (For the Antimicrobial Properties Test, 0.2 g of the Sample
was Collected.)
10 TABLE 10 Example 13 14 15 16 17 18 19 Before water washing 2.6
2.6 2.5 2.5 2.6 2.5 2.5 Content of (A) (%) After dipping in water
Content of (A) (%) 2.4 2.4 2.3 2.3 2.5 2.2 2.3 Deodorizing rate of
73 73 72 71 73 70 71 NH.sub.3 (%) Antimicrobial properties Number
of bacteria, 3.8 3.9 4.1 4.0 4.0 4.2 4.0 log C Increase or decrease
-1.2 -1.1 -0.9 -1.0 -1.0 -0.8 -1.0 value Difference in increase 3.4
3.3 3.1 3.2 3.2 3.0 3.2 or decrease value
[0153] (For the Antimicrobial Properties Test, 0.2 g of the Sample
was Collected.)
[0154] It is understood from Tables 9 and 10 that, in Comparative
Examples 12 and 13, even though the internal addition amount of the
functional component (A) is 6 parts, the functionalities after
dipping in water are insufficient. Further, it is understood that,
in Comparative Examples 14 and 15, since the functional component
(A) is internally added in the side of the sheath component Y as
the external layer, the functionalities after dipping in water are
more insufficient. Further, when drawn articles of a filament made
of the second resin (L) only, in which the functional component (A)
is not internally added, the deodorizing rate of NH.sub.3 is about
40%, and hence, a "(measured value)--40%" value is a substantial
deodorizing rate. Further, it is understood that, in Comparative
Examples 14 and 15, since the ceramics component (C) is not
co-existent, a considerable amount of the functional component (A)
was volatilized out during the extrusion forming, as compared with
Examples 13 to 19. Moreover, in Examples 13 to 19, since PET is
used for the core (for the sheath, too), there are obtained
preferable drape, nerve, feeling (challis-like feeling) heat
resistance, and shrinkage resistance during laundry.
[0155] (Preparation of Materials)
[0156] As the first resin (H) and the second resin (L), were
prepared the following materials. (H.sub.2) is the same resin as
(L.sub.3); (H.sub.4) is the same resin as (L.sub.4); and (H.sub.5)
is the same resin as (L.sub.5), respectively.
[0157] (H.sub.2): Nylon 6 (Ny6) having a melting point of
220.degree. C.
[0158] (H.sub.4): Nylon 66 (Ny66) having a melting point of 260
[0159] (H.sub.5): Polyvinylidene chloride (a copolymer containing
15% of vinyl chloride) having a melting point of 175.degree. C.
[0160] (L.sub.3): Nylon 6 (Ny6) having a melting point of
220.degree. C.
[0161] (L.sub.4) Nylon 66 (Ny66) having a melting point of
260.degree. C.
[0162] (L.sub.5): Polyvinylidene chloride (a copolymer containing
15% of vinyl chloride) having a melting point of 175.degree. C.
[0163] As the functional component (A) to be internally added in
the resin (L) of the external component Y, was prepared the
following material.
[0164] (A.sub.1): 30% Product of tea catechin (a tea catechin
formulation originated from tea, containing about 30% in total of
epigallocatechin, epigallocatechin gallate, epicatechin and
epicatechin gallate)
[0165] As a raw material of the ceramics component (C) to be
internally added in the resin (L) of the external component Y, were
prepared the following materials.
[0166] (C.sub.3): Silica, aluminum phosphate and colloidal
silica
[0167] (C.sub.4): Sepiolite
[0168] (Preparation of Functional Component (A)-Ceramics Component
(C))
[0169] As to (C.sub.3), composite particles with (A.sub.1) were
produced according to Method 3 as described above. Further, as to
(C.sub.4), (A.sub.1) was dissolved or dispersed in water, into
which was then added (C.sub.4), followed by mixing and drying
(referred to as "Method 4", hereinafter).
EXAMPLES 20 TO 23
[0170] The second resin (L) of the external component Y was mixed
with the functional component (A)-supported ceramics component (C)
obtained in Method 3 or 4 as described above, together with small
amounts of an antioxidant and a flocculation preventive (a
dispersing agent), and the mixture was melt extruded and
pelletized. The thus obtained pellets were used as the external
component (sheath component) Y, and pellets of the above-described
first resin (H) were used as the internal component (core
component) X. The both pellets were subjected to co-extrusion under
temperature conditions of 70 to 90.degree. C. higher than the
melting point of the resin (L) of the external component Y with
respect to the external component (sheath component) Y and under
temperature conditions of 70 to 90.degree. C. higher than the
melting point of the resin (H) of the internal component X with
respect to the internal component (core component) X, respectively,
from two extruders each equipped with a composite die, followed by
drawing as far as possible, thereby obtaining a composite filament
(composite molding). Thereafter, from this composite filament, was
prepared a non-woven fabric. The conditions are shown in Table
11.
COMPARATIVE EXAMPLES 16 TO 18
[0171] To the resin same as the resin (L) of the external component
Y, was internally added the functional component (A) and subjected
to extrusion forming at a temperature of 70 to 90.degree. C. higher
than the melting point of the resin, followed by drawing as far as
possible, thereby obtaining a filament. Using the thus obtained
filament, a non-woven fabric was prepared. The conditions are also
shown in Table 11.
COMPARATIVE EXAMPLES 19 TO 21
[0172] The same procedures as in Examples 20 to 23 were followed to
effect co-extrusion, except omitting the internal addition of the
ceramics component (C) to the second resin (L) of the external
component Y, followed by drawing as far as possible, thereby
obtaining a filament (composite filament). Using the thus obtained
filament, a non-woven fabric was prepared. The conditions are also
shown in Table 11.
11 TABLE 11 Internal component External component X Y Composite (H)
(A) (L) (A) (C) particles Comparative (See Note 1) (L.sub.3):94
(A.sub.1):6 -- -- Example 16 parts parts Comparative (See Note 1)
(L.sub.4):94 (A.sub.1):6 -- -- Example 17 parts parts Comparative
(See Note 1) (L.sub.5):94 (A.sub.1):6 -- -- Example 18 parts parts
Comparative (H.sub.2):50 -- (L.sub.3):46 (A.sub.1):3 -- -- Example
19 parts parts - parts Comparative (H.sub.4):50 -- (L.sub.4):46
(A.sub.1):3 -- -- Example 20 parts parts - parts Comparative
(H.sub.5):50 -- (L.sub.5):46 (A.sub.1):3 -- -- Example 21 parts
parts - parts Example 20 (H.sub.2):50 -- (L.sub.3):35 (A.sub.1):3
(C.sub.3):12 Method 3 parts parts parts parts Example 21
(H.sub.4):50 -- (L.sub.4):35 (A.sub.1):3 (C.sub.4):12 Method 3
parts parts parts parts Example 22 (H.sub.2):50 -- (L.sub.4):35
(A.sub.1):3 (C.sub.4):12 Method 4 parts parts parts parts Example
23 (H.sub.5):50 -- (L.sub.5):35 (A.sub.1):3 (C.sub.4):12 Method 4
parts parts parts parts In Comparative Examples 16 to 18,
monofilament (non-composite filament) In Comparative Examples 19 to
21 and Examples 20 to 23, core-sheath joining type composite
filament
[0173] (Test)
[0174] The same tests as in Examples 20 to 23 were carried out. The
results obtained are shown in Tables 12 and 13.
12 TABLE 12 Comparative Example 16 17 18 19 20 21 Before water
washing Content of (A) (%) 4.2 4.2 4.4 2.3 2.3 2.4 After dipping in
water Content of (A) (%) 0.7 0.7 0.8 0.2 0.2 0.3 Deodorizing rate
of NH.sub.3 (%) 55 55 56 44 43 45 Antimicrobial properties Number
of bacteria, log C 6.5 6.5 6.5 7.0 7.0 6.8 Increase or decrease
value 1.5 1.5 1.5 2.0 2.0 1.8 Difference in increase or 0.7 0.7 0.7
0.2 0.2 0.4 Decrease value
[0175] (For the Antimicrobial Properties Test, 0.2 g of the Sample
was Collected.)
13 TABLE 13 Example 20 21 22 23 Before water washing 2.6 2.4 2.6
2.7 Content of (A) (%) After dipping in water Content of (A) (%)
2.4 2.3 2.4 2.6 Deodorizing rate of NH.sub.3 (%) 74 74 70 72
Antimicrobial properties Number of bacteria, log C 3.8 4.1 4.2 4.1
Increase or decrease value -1.2 -0.9 -0.8 -0.9 Difference in
increase or decrease value 3.4 3.1 3.0 3.1
[0176] (For the Antimicrobial Properties Test, 0.2 g of the Sample
was Collected.)
EXAMPLE 24
[0177] As raw materials of the resin (H) of the internal component
X, the resin (L) of the external component Y, the functional
component (A) to be internally added in the resin (L) of the
external component Y, and the ceramics component (C) to be
internally added in the resin (L) of the external component Y were
prepared the following materials. Further, composite particles
comprising the functional component (A) having the ceramics
component (C) supported thereon were obtained in the same
procedures as in Method 1 as described above.
[0178] (H.sub.3): Polyethylene terephthalate (PET) having a melting
point of 265.degree. C.
[0179] (L.sub.1): Polyethylene terephthalate (PET) having a melting
point of 265.degree. C.
[0180] (A.sub.1): 30% Product of tea catechin
[0181] (C.sub.1): Silicate (water glass)
[0182] The resin (L) in the side of the external component Y was
mixed with the functional component (A)-supported ceramics
component (C) obtained in Method 1 as described above, together
with small amounts of an antioxidant and a flocculation preventive
(a dispersing agent), and the mixture was melt extruded and
pelletized. The thus obtained pellets were used as the external
component (sheath component) Y, and pellets of the resin (H) of the
internal component X were used as the internal component (core
component) X. The both pellets were subjected to co-extrusion under
temperature conditions of 70 to 90.degree. C. higher than the
melting point of the resin (L) of the external component Y with
respect to the external component (sheath component) Y and under
temperature conditions of 70 to 90.degree. C. higher than the
melting point of the resin (H) of the internal component X with
respect to the internal component (core component) X, respectively,
from two extruders each equipped with a composite die, thereby
obtaining a bimetal joining type film-like composite molding of a
Y/X/Y layer construction. Thereafter, the resulting film-like
composite molding was slit into thin strips. Using the thus
obtained fibrous molding, a cloth was prepared. This cloth had
deodorizing properties and antimicrobial properties same as in
Example 13.
[0183] In the composite moldings according to the present
invention, necessary moldability (e.g., melt spinning properties,
etc.), next-processing properties (e.g., stretching properties,
etc.), and physical properties (e.g., strength, dimensional
stability, etc.), are obtained mainly by the internal component X,
and surface characteristics and functionalities such as deodorizing
properties, antimicrobial properties, physiological activity, and
antioxidation properties are obtained by the external component Y.
When the kind of the second resin (L) and the amount of the
internally added components are selected or controlled, preferred
heat fusion properties are obtained.
[0184] And, since in the external component Y, the functional
component (A) is fixed and made waterproof in the co-existence of
the ceramics component (C), bleeding of the functional component
(A) internally added is effectively inhibited. Further, due to the
functional component (A) present in the external component Y,
superior functionalities that the functional component (A)
inherently possesses, such as deodorizing properties and
antimicrobial properties, are exhibited at the maximum. Moreover,
even when the composite molding is used in a state in which it is
brought into contact with water or washed with water, since the
functional component (A) does not readily elute out, the
functionalities are maintained over a long period of time. The
presence of the ceramics component (C) also contributes to the
dimensional stability and heat resistance of the filament against
circumferential changes such as temperature and humidity
changes.
[0185] Further, since it is only a requirement that the functional
component (A) is present in the external component Y in the surface
side, the internal addition amount of the functional component (A)
can be largely reduced, leading to an advantage from the economic
standpoint.
[0186] In addition, since various combinations of resins for the
first resin (H) of the internal component X and the second resin
(L) of the external component Y can be employed, it is possible to
obtain composite moldings having mechanical characteristics,
thermal nature, and surface nature, which meet the needs.
[0187] Besides, since the functional component (A) is a component
contained in a tea or the like, it is safe even when the filament
is used in a state in which it is brought into contact with a human
body.
[0188] While the invention has been described in detail and with
reference to specific examples thereof, it will be apparent to one
skilled in the art that various changes and modifications can be
made therein without departing from the spirit and scope
thereof.
* * * * *