U.S. patent number 3,849,840 [Application Number 05/399,114] was granted by the patent office on 1974-11-26 for method for imparting pressure sensitive adhesion to velvet type fasteners.
This patent grant is currently assigned to Kanebo Limited. Invention is credited to Yoshihiro Fukuda, Toru Uraya, Fukuo Yamada.
United States Patent |
3,849,840 |
Yamada , et al. |
November 26, 1974 |
METHOD FOR IMPARTING PRESSURE SENSITIVE ADHESION TO VELVET TYPE
FASTENERS
Abstract
Velvet type fasteners are imparted with pressure sensitive
adhesion by applying to the respective back surfaces of the male
and female pieces of a velvet type fastener, a composition
consisting of: 100 parts by weight of a polymer, containing at
least 65 percent mol of an ester of an acrylic acid or methacrylic
acid and from 0.2 to 5 parts by weight of glycidyl ester of an
unsaturated organic acid; from 0.5 to 5 parts by weight of a
zirconyl salt of organic acid, and; from 0.01 to 0.1 part by weight
of a volatile acid addition salt of organic amine.
Inventors: |
Yamada; Fukuo (Osaka,
JA), Fukuda; Yoshihiro (Osaka, JA), Uraya;
Toru (Kobe, JA) |
Assignee: |
Kanebo Limited (Tokyo,
JA)
|
Family
ID: |
14178234 |
Appl.
No.: |
05/399,114 |
Filed: |
September 20, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Sep 26, 1972 [JA] |
|
|
47-96937 |
|
Current U.S.
Class: |
24/448; 24/450;
156/330; 428/100; 525/329.5; 525/370; 526/273; 528/361; 156/66;
156/332; 273/DIG.30; 525/327.3; 525/329.9; 526/212; 526/916;
554/72 |
Current CPC
Class: |
A44B
18/0023 (20130101); Y10T 428/24017 (20150115); Y10S
273/30 (20130101); Y10T 24/2775 (20150115); Y10T
24/2758 (20150115); Y10S 526/916 (20130101) |
Current International
Class: |
A44B
18/00 (20060101); C09j 001/00 (); C09j 003/14 ();
C09j 007/04 () |
Field of
Search: |
;156/66,72,330,332
;117/122PA,161ZB,161UC ;24/DIG.18,204 ;161/53 ;2/DIG.6 ;46/DIG.1
;260/2EC:47EC,45.75R,8L,82.72,86.1E,88.3A,414 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kendall; Ralph S.
Assistant Examiner: Albrecht; Dennis L.
Claims
What we claim is:
1. A method for imparting pressure sensitive adhesion to velvet
type fasteners, comprising applying to the respective back surfaces
of the male and female pieces of a velvet type fastener composed of
synthetic fibers, a composition consisting of: 100 parts by weight
of a polymer, containing at least 65 percent mol of an ester of an
acrylic acid or methacrylic acid and from 0.2 to 5 parts by weight
of glycidyl ester of an unsaturated organic acid; from 0.5 to 5
parts by weight of a zirconyl salt of organic acid, and; from 0.01
to 0.1 part by weight of a volatile acid addition salt of an
organic amine.
2. A method for imparting pressure sensitive adhesion to velvet
type fasteners according to claim 1, wherein the composition is
adjusted to a pH below 6, preferably below 5, and optionally by
adding an acid selected from hydrochloric acid and acetic acid.
3. A method for imparting pressure sensitive adhesion to velvet
type fasteners according to claim 1, wherein the ester of the
acrylic acid or methacrylic acid is a member selected from the
group consisting of ethyl acrylate, butyl methacrylate, butyl
acrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate.
4. A method for imparting pressure sensitive adhesion to velvet
type fasteners according to claim 1, wherein the polymer is mainly
composed of a copolymer of an ester of acrylic acid or methacrylic
acid a monomer selected from the group consisting of vinyl acetate,
methyl methacrylate and styrene.
5. A method for imparting pressure sensitive adhesion to velvet
type fasteners according to claim 1, wherein the glycidyl ester of
the unsaturated organic acid is a member selected from the group
consisting of acrylic acid glycidyl ester, methacrylic acid
glycidyl ester, and crotonic acid glycidyl ester.
6. A method for imparting pressure sensitive adhesion to velvet
type fasteners according to claim 1, wherein the zirconyl salt of
organic acid is a member selected from the group consisting of
zirconyl acetate, zirconyl caprate and zirconyl stearate.
7. A method for imparting pressure sensitive adhesion to velvet
type fasteners according to claim 1, wherein the volatile acid
addition salt of the organic amine is a salt the group consisting
of selected from the salts of mono-, di- or triethanolamine or
mono-, di- or tripropanolamine with hydrochloric acid and acetic
acid.
8. A velvet type fastener composed of synthetic fibres which has
applied to the respective back surfaces of the male and female
pieces thereof a composition consisting of: 100 parts by weight of
a polymer, containing at least 65 percent mol of an ester of an
acrylic acid or methacrylic acid and from 0.2 to 5 parts by weight
of a glycidyl ester of an unsaturated organic acid; from 0.5 to 5
parts by weight of a zirconyl salt of an organic acid, and; from
0.01 to 0.1 part by weight of a volatile acid addition salt of an
organic amine.
Description
The present invention relates to a method for imparting pressure
sensitive adhesion to velvet type fasteners. More particularly, it
relates to a method for imparting pressure sensitive adhesion to
the respective back surfaces of the male and female pieces of
velvet type fasteners.
It is well known that there are two different kinds of velvet type
fasteners. One of them is a fastener composed of a male piece
having a plurality of upright hook elements disposed on a base
fabric and a female piece having a plurality of loop elements
formed on a working surface of a base fabric. In the other kind of
velvet type fastener, a male element is provided with a laterally
expanded cap formed at the top end portion of a stem is utilized
instead of the hook element. As to the materials for making these
kinds of fasteners, synthetic fibers such as polyamides polyesters,
polypropylene and polyoxymethylene fibers have been preferably
utilized. This is because the synthetic fibers mentioned above have
desirable physical properties such as elasticity, rigidity,
flexibility, thermal stability and strength. The term "velvet type
fastener" or "fastener" used herein refers to the above-mentioned
two kinds of fasteners.
It is also known that the velvet type fastener has been widely
utilized for clothing, interior decorations and industrial
materials, including woven and knitted fabrics of various types,
because of the velvet type fastener's easily detachable fastening
of a pair of articles.
Generally, the male and female pieces have been secured on woven
and knitted fabrics by sewing. However, it has been difficult to
carry out such a sewing operation owing to the presence of the
engaging elements of the male and female pieces and, in addition,
the engaging elements of these pieces have many times been partly
sewn in by the sewing thread. The inevitable consequences of these
problems have been lower securing efficiency and poorer fastening
effect. For thick or stiff materials such as carpet, natural or
synthetic wood and shaped resinous articles, it has been very
difficult or impossible to effect the above-mentioned sewing
operation.
To overcome the above problems, it has been proposed to impart heat
sensitive adhesion or pressure sensitive adhesion to the back
surface of each piece of the fastener. In the former method, the
heat sensitive adhesion is imparted by coating a heat meltable
resin layer onto the respective back surfaces of the male and
female pieces. However, it is necessary that each piece of the
fastener obtained by this method be secured by being pressed under
an elevated temperature satisfactory to melt the resin. This often
results in damage to the pieces from both or either the pressure
and/or the heat applied. On the other hand, the fastener obtained
with pressure sensitive adhesive agents according to the latter
method is not subject to the above-mentioned drawbacks and each
piece is easily secured to the desired materials. However, in the
case where the fastener is composed of synthetic fibers, the
conventional pressure sensitive adhesive agents tend to loose their
adhesion to the back surfaces of the pieces of the fastener during
repeated fastening. In addition, shear between the fastener and the
material secured to the fastener often occurs owing to creep of the
adhesive agent when the fastener and the material are subjected to
even a weak shearing force for a long period of time.
The principal object of the present invention is to provide a
method for imparting pressure sensitive adhesion which enables a
velvet type fastener to be secured easily and quickly to the
material on which the fastener is used said fastener and possessing
excellent adhesive strength and creep resistance in practical
use.
The object of the present invention can be accomplished by applying
an adhesive composition of the nature disclosed hereinafter to the
velvet type fastener.
The method according to the present invention is a novel method for
imparting pressure sensitive adhesion to velvet type fasteners,
comprising applying to the respective back surfaces of the male and
female pieces of a velvet type fastener composed of synthetic
fibers, a composition consisting of: 100 parts by weight of a
polymer, containing at least 65 percent mol of an ester of acrylic
acid or methacrylic acid and from 0.2 to 5 parts by weight of a
glycidyl ester of an unsaturated organic acid; from 0.5 to 5 parts
by weight of a zirconyl salt of organic acid, and; from 0.01 to 0.1
part by weight of a volatile acid addition salt of an organic
amine.
It has been found that the method of the present invention can
suitably impart superior and stable adhesive strength and creep
resistance to the velvet type fastener. The velvet type fastener to
which the adhesive composition according to the present invention
has been applied can be secured easily and quickly to the desired
materials.
The velvet type fasteners composed of synthetic fibers and usable
for the method of the present invention include fasteners composed
of the fibers such as polyamides, polyesters and polyolefins. For
example, woven or knitted multifilament yarn fabrics of polyamides
or polyesters may be suitably used for the loop elements and the
base fabric of the female piece, and woven or knitted fabrics of
densified polyethylene, polypropylene or polyvinyl chloride as well
as fabrics of polyamides or polyesters may be suitably used for the
base fabric of the male piece, because of their desirable
properties such as tensile strength and elasticity. For the male
elements which may be in hook form or in the laterally expanded cap
form at the top end portion of the stem, a monofilament yarn of
polyamides, polypropylene polyethylene, polyoxymethylene or the
like may be suitably used in view of the necessity of excellent
elasticity and rigidity. Of the above, the polyamides are
preferably utilized for the loop elements of the female piece and
the base fabrics of the male and female pieces and also
polypropylene is preferably utilized for the engaging male elements
of the male piece.
The ester of the acrylic acid or methacrylic acid usable for the
adhesive composition according to the present invention includes
acrylic and methacrylic esters having at least two carbon atoms in
the alkyl moiety, such as ethyl acrylate, butyl methacrylate, butyl
acrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate.
Preferably, butyl acrylate and 2-ethylhexyl acrylate are used. For
the polymer containing at least 65 percent mol of acrylic or
methacrylic ester, copolymers of an acrylic or methacrylic ester
with a polymerizable monomer such as vinyl acetate, methyl
methacrylate and styrene may be used. The copolymers may optionally
comprise unsaturated acids such as acrylic acid, methacrylic acid,
crotonic acid and itaconic acid. The acrylic or methacrylic ester
mainly participate in the pressure sensitive adhesion. When the
ester is present in an amount of less than 65 percent mol in the
polymer, the pressure sensitive adhesion of the fastener with the
adhesive composition applied is undesirably reduced. The monomers
copolymerized with the above ester participate in yielding "hard"
polymers. The monomers serve to control the tacking, improve the
cohesive adhesion and also to elevate the creep resistance, of the
adhesive composition.
The glycidyl ester of unsaturated organic acid which is a component
of and usable for the polymer in the pressure sensitive adhesive
composition may be the glycidyl esters of acids such as acrylic
acid, methacrylic acid and crotonic acid. These glycidyl esters
impart creep resistance and thermal stability to the adhesive
composition and are suitably used in an amount of from 0.2 to 5
parts based on the weight of 100 parts of the polymer. The glycidyl
esters also react with a zirconyl compound as described
hereinafter. When the glycidyl esters are used in an amount of less
than 0.2 parts, it is difficult to obtain appropriate cohesive
adhesion and creep resistance, while when the glycidyl esters are
used in an amount of more than 5 parts, the stability of the
composition and the durability of the pressure sensitivity are
reduced, more or less depending on the amount of the added zirconyl
compound.
It should be noted that the most important features of the method
of the present invention are that a specific amount of the zirconyl
salt of an organic acid is added in the composition, and that the
volatile acid addition salt of the organic amine is also used as an
accelerator for the reaction of the zirconyl compound with the
polymer. The resinous composition comprising the polymer containing
mainly the acrylic or methacrylic ester and partly the glycidyl
ester of unsaturated organic acid, but not comprising the
above-mentioned zirconyl compound and amine compound, is known as a
reactive acrylic resin. These known types of resinous compositions
are generally utilized in the flocking of textile articles.
However, these known compositions cannot be utilized for the
purpose of the present invention, because they are inferior in
adhesion to the fastener, in durability of the adhesion and also in
creep resistance. In addition, it is necessary that these
compositions be cured at a high temperature for a long period of
time, after coating, for the prevention of the gelation of the
composition owing to the change of viscosity during practical use
thereof.
The zirconyl salts of the organic acid usable for the present
invention include, for example, zirconyl acetate, zirconyl
propionate, zirconyl caprate and zirconyl stearate. Particularly,
zirconyl salts of higher fatty acids are preferably used. The
suitable amount of the zirconyl salts is from 0.5 to 5 parts based
on the weight of 100 parts of the polymer, while they are
preferably used in a range between 70 and 120 percent, based on the
weight of the glycidyl ester of unsaturated organic acid. In the
case where the zirconyl compounds are used in an amount of less
than 0.5 part based on the weight of 100 parts of the polymer, or
less than 70 percent based on the weight of the glycidyl ester,
appropriate adhesion and durability of adhesion of the resultant
composition cannot be obtained. On the other hand, when the
zirconyl compounds are used in an amount of more than 5 parts,
based on the weight of 100 parts of the polymer, durability of
pressure sensitivity of the composition becomes inferior and the
obtained fastener feels unpreferably hard. The use of the zirconyl
compounds in an amount of more than 120 percent based on the weight
of the glycidyl ester does not, to a large extent, increase the
effects for adhesion or creep resistance and, therefore, is
uneconomical.
It should also be noted that the other important features of the
present invention are that the adhesive composition used in the
present method is stable under acidic conditions and that the
composition is in the acidic pH range owing to the presence of the
acid addition salt of the organic amine. The composition is very
stable at a pH below 6, preferably at a pH below 5.
The volatile acid addition salts of the organic amines include, for
example, the salts of mono-, di- or triethanolamine or mono-, di-
or tripropanolamine with acids, readily and relatively volatilized
by heat, such as hydrochloric acid and acetic acid. These acid
addition salts exhibit acidic properties and can control the
cohesive adhesion and the durability of adhesion of the resultant
composition as mentioned above. Therefore, the composition
containing the acid addition salts is slowly reacted while
volatilizing the acid after being coated onto the fastener and
produces excellent adhesion and creep resistance. When the
composition is heated after being coated, it rapidly volatilizes
the acid and also produces the above-mentioned effects. For such
effects, the composition according to this invention may optionally
comprise a small amount of hydrochloric acid, acetic acid or the
like. The acid, addition salts of organic amine are suitably used
in an amount of from 0.01 to 0.1 part based on the weight of 100
parts of the polymer. When the amount of the acid addition salts is
less than 0.01 part, the increasing of the cohesive adhesion of the
composition cannot be obtained; while when the amount of the acid
addition salts is more than 0.1 part, the pressure sensitivity of
the adhesion is lost and the stability during storage becomes
slightly inferior.
The adhesive compositions usable for the method of the present
invention may be prepared as follows. The polymer is firstly
prepared by known emulsion polymerization or solution
polymerization procedures. The emulsion polymerization may be
effected by reacting the desired monomers as mentioned
hereinbefore, at a reflux temperature or in a redox system for from
2 to 10 hours, in the presence of from 0.01 to 1 percent, based on
the weight of the monomer, of a watersoluble initiator such as
hydrogen peroxide, potassium persulfate and ammonium perborate and
from 0.1 to 10 percent, based on the weight of the monomer, of an
emulsifying and dispersing agent. The emulsifying and dispersing
agent may be, for example, nonionic surface active compounds such
as a polyoxyethylene alkyl ether, a polyoxyethylene alkylphenyl
ether and polyoxyethylene sorbitan monoalkylate; anionic surface
active compounds such as sodium dodecylbenzenesulfonate and sodium
lauryl sulfate; cationic surface active compounds such as
polyoxyethylene laurylamine and lauryl trimethyl-ammonium chloride,
and; water-soluble polymers such as polyvinyl alcohol, hydroxyethyl
cellulose and carboxymethyl cellulose. These may be used alone or
as a mixture. In the above reaction, the glycidyl ester of
unsaturated organic acid should be added toward the end of the
reaction.
The solution polymerization may be effected according to
conventional methods in a medium such as methanol, ethanol and
ethyl acetate in the presence of an initiator such as benzoyl
peroxide and azobisisobutyronitrile. In general, the polymer
obtained by solution polymerization can give better adhesive
strength to the resultant composition than the polymer obtained by
emulsion polymerization, and solution polymerization is more
capable of controlling the operations of the production than the
emulsion polymerization.
To the remaining emulsion or solution, a solution or dispersion of
the volatile acid addition salt of organic amine in water,
alcohols, ethers, ketones or other hydrocarbons are added and
stirred so as to be uniformly mixed. Thus, the desired adhesive
composition can be obtained.
The adhesive composition this obtained may then be coated on the
respective back surfaces of the male and female pieces of a velvet
type fastener by conventional coating methods such as doctor
coating, roll coating and spray coating. The suitable amount of the
coated composition is in general between 80 and 400 g, preferable
120 and 250 g, based on the dry weight of the composition, per
square meter. The coated surfaces of the fastener may then be
secured to a releasing paper. Alternatively, the composition may be
coated onto a releasing paper and, after semi-drying, the coated
surface of the releasing paper is secured to the respective back
surfaces of the two pieces of a velvet type fastener. Then, the
composition which may be sandwiched between the fastener and the
releasing paper is dried at a temperature below 80.degree.C,
preferably below 60.degree.C. The fastener thus obtained and the
releasing paper may then be rolled up together.
The features of the adhesive composition and the structure of the
velvet type fastener according to the present invention are further
illustrated with reference to the accompanying drawings,
wherein:
FIG. 1 is a graph showing ductility (heat flowability) of the
composition heat treated at various temperatures plotted against
the pH of the original composition prior to the drying and the heat
treatment;
FIG. 2 is a partial section view of the male and the female piece
of the fastener obtained by the method of the present
invention.
Referring to FIG. 1 ductility (heat flowability) of the composition
dried at room temperature and heat treated at the indicated
temperatures is plotted against the pH of the original composition
prior to the drying and the heat treatment. The composition was
prepared by adding 2 parts by weight of zirconyl stearate to 250
parts by weight of a 40 percent emulsion of a polymer of 86 parts
by weight of acrylic acid butyl ester, 12 parts by weight of
styrene and 2 parts by weight of acrylic acid glicidyl ester. To
the mixture 0.05 parts by weight of monopropanolamine hydrochloride
was added and then hydrochloric acid or ammonia was added. Five
kinds of compositions having respective pHs of 3.2, 5.4, 6.2, 7.1
and 8.7 were produced from the obtained composition. Each of the
compositions was flowed onto a glass sheet and dried at room
temperature and then heat treated at 30.degree., 50.degree.,
80.degree., 100.degree. and 150.degree.C, respectively. The heat
treatment was effected for 5 seconds and 20 seconds. The species of
the compositions thus obtained were then subjected to the following
test for ductility. The species of 5 .times. 5 mm were pressed by a
load weighing 14 kg/cm.sup.2, at 40.degree.C, and for 1 minute,
their ductility by percentage was determined. In FIG. 1, the solid
lines show the ductility on the heat treatment for 5 seconds and
the dotted lines show the ductility on the heat treatment for 20
seconds.
From FIG. 1, it is evident that the self-cohesion of the
composition according to the present invention is intimately
connected with the pH and the heat treatment temperature. It is
also evident that the heat treatment of the composition can
desirably impart excellent cohesive adhesion to the composition by
volatilizing the volatile acid from the acid addition salt of
organic acid. The suitable heat treatment temperature is from
80.degree. to 160.degree.C, preferably 100.degree. to 130.degree.C
and the suitable heat treatment time is from 15 seconds to 3
minutes. Heat treatment at a temperature higher than 160.degree.C
risks damaging the fibers of the fastener. The composition, the
ductility of which is below 100 percent, gives an undesirable hard
feel to the fastener.
Referring to FIG. 2, a velvet type fastener according to the
present invention comprises a male piece 1 and a female piece 2.
The male piece 1 is composed of a base fabric 3, a plurality of
engaging elements 4 projecting perpendicular to the face surface of
the base fabric 3, a pressure sensitive adhesive composition layer
5 covering the back surface of the base fabric 3 and a releasing
paper 6 secured provisionally to the composition layer 5. Each
engaging element is provided with a laterally expanded cap formed
at the tip portion. However, in the fastener according to the
invention, the engaging element may also be in a hook form. On the
other hand, the female piece 2 is composed of a base fabric 7, a
plurality of upright loops 8 projecting from the face surface of
the base fabric 7, a pressure sensitive adhesive composition 9
covering the back surface of the base fabric 7 and a releasing
paper 10 secured provisionally to the composition layer 9.
According to the method of the present invention, excellent
pressure sensitive adhesion can be imparted to velvet type
fasteners composed of synthetic fibers. The fasteners can be easily
and quickly secured by hand pressure to various materials such as
textile fabrics, wood, synthetic resin articles, glass and metals.
That is, they can be secured even to materials to which velvet type
fasteners could not previously be secured by sewing or heat
melting. The velvet type fasteners imparted with pressure sensitive
adhesion by the method of the present invention possess
satisfactorily good strength of adhesion and creep resistance. On
repeated usages, the fasteners do not tend to lose their adhesion
to the secured materials and, also the adhesive composition does
not tend to lose its adhesion to the surfaces of the fastener to
which it is applied. The adhesion of the applied composition
becomes greater with the aging thereof. The method of the present
invention can be effectively applied to the fasteners wherein the
base fabric of the male piece is composed of polyamides and the
male elements thereof are composed of polypropylene. The male
elements composed of polypropylene do not slip out of the base
fabric, a common trouble with fasteners to which conventional
adhesive compositions are applied. The fasteners obtained by the
present method are preferably heated with an iron, hot air or the
like which imparts more effective adhesion, creep resistance and
wash fastness of the adhesion. The heat treatment is particularly
effective in the case where the fasteners are to be exposed to
heavy loads or to repeated washings. The fasteners advantageously
have desirable softness and flexiblity even after the heat
treatment, and these properties are particularly preferable when
the fasteners are utilized for clothing.
It is another advantage of the fasteners obtained by the present
method that it is not necessary to apply backings to the fasteners.
The fasteners possess sufficient adhesion and flexiblity as well as
good dimensional stability, and these properties are advantageously
improved by the abovementioned heat treatment. Therefore, backings
are not needed except in the case where high dimensional stability
is desired. Compared with this, backings with thermosetting resins
such as aminoplasts or modified thermosetting resins are generally
required for the conventional fasteners for the purpose of
rendering dimensional stability thereto or fixing the male elements
to the base fabric.
As is disclosed hereinbefore, the method of the present invention
can advantageously impart excellent pressure sensitive adhesion to
the velvet type fasteners composed of synthetic fibers. Further,
the fasteners obtained by the method of the present invention can
be utilized for clothing such as underwear, as well as for interior
decorations and industrial materials, because of their excellent
adhesive strength and flexiblity and their easily detachable
fastening.
The following examples further illustrate the method and the
fasteners according to the present invention, wherein parts are
indicated by weight. In the Examples, the creep resistance was
determined by securing the adhesive surface of a sample of the
fastener having an adherence dimension of 6.25 cm.sup.2 (2.5
.times. 2.5 cm), to a perpendicularly fixed substrate attaching a
load of 200 g to the fastening piece and then measuring the shear
in mm after 24 hours. The friction strength was determined by
tensile test with a Schopper's tensile tester for a sample of the
fastener having an adherence dimension of 6.25 cm.sup.2 (2.5
.times. 2.5 cm). The stripping strength was determined at an angle
of 180.degree.C by a Schopper's tensile tester for a sample of the
fastener of 2 cm width and 10 cm length. Further, the repeated
fastening test was carried out, wherein one piece of the fastener
was engaged, by pressing with 50 g/cm.sup.2 of pressure, with the
other piece, the adhesive surface of which had been secured to a
fixed substance and then the former piece was rapidly released from
the latter piece. The engaging and detaching was repeated 300
times. In the above test, the adhesive surface of the latter piece
had dimensions of 2 cm width and 5 cm length.
EXAMPLE 1
20 Parts of vinyl acetate, 77 parts of 2-ethylhexyl acrylate, 3
parts of methacrylic acid glycidyl ester, 80 parts of methyl
alcohol and 1 part of benzoyl peroxide were added to a three neck
glass flask of 2 liters, provided with a stirrer, a reflux
condenser and a thermometer, and heated at 60.degree. to
65.degree.C for 8 hours with stirring. As the polymerization
proceeded, a translucent viscous polymer solution was obtained.
Then, 45 parts of 10 percent solution of zirconyl caprate in a
mixture of 50 parts of ethyl acetate with 100 parts of toluole and
0.004 part of monoethanolamine hydrochloride were added to the
polymer solution and the resulting mixture was stirred until whole
mixture became satisfactorily homogeneous. The obtained composition
was of a pH of 5.7, a resin concentration of about 35 percent and a
viscosity of 3,000 centi-poises. The composition was then coated
over the back surfaces of the male and female pieces of a velvet
type fastener by means of a flow coater in such a way that the
weight of the component polymer of the coated composition was 160 g
per square meter. The solvent was removed by drying in a hot air
dryer at 48.degree. to 52.degree.C for 10 minutes and silicone
coated releasing papers were attached onto the respective back
surfaces of the male and female pieces through the coated resin
layers. As to the fastener used herein, the base fabrics of the
male and female pieces were composed of Nylon 6 yarn of 210
denier/12 filaments and the engaging elements of the male piece
were composed of a polypropylene monofilament yarn of 0.2
millimeter diameter, the top of the element being in a laterally
expanded cap form.
The male piece and the female piece of one fastener thus coated
were each secured to a plain woven fabric composed of 65 percent
polyester and 35 percent cotton by pressing with by hand. The male
piece and the female piece of another fastener thus coated were
also each secured to a fabric of the same type as the above by
pressing by hand and thereafter heating for 15 seconds over the
back surface of the secured plain fabric with an iron maintained at
130.degree.C. Then, these specimens were subjected to the tests for
strength of adhesion, creep resistance and strength of adhesion on
repeated fastening of the male and female pieces. The results are
shown in Table I.
For comparison, three other specimens were prepared and tested in a
manner similar to that stated above, except that the following
respective procedures were employed. Comparison 1: 80 parts of
2-ethylhexyl acrylate and 20 parts of vinyl acetate were used
instead of 20 parts of vinyl acetate, 77 parts of 2-ethylhexyl
acrylate, 3 parts of methacrylic acid glycidyl ester. Comparison 2:
zirconyl caprate and monoethanolamine hydrochloride were not used.
In this case, the composition coated fastener was cured at
150.degree.C for 3 minutes after being secured to the fabric by
hand pressure. Comparison 3: monoethanolamine hydrochloride was not
used. The results are also shown in Table I.
Table I
__________________________________________________________________________
Creep Friction Strip- resist- strength ping Repeated fastening No.
ance strength test (mm) (kg/cm) (kg/cm)
__________________________________________________________________________
1. The 0.7 25 3.2 Appearance not changed invention stripping
strength: (not heated) 2.9 kg/cm 2. The trace 32 4.9 Appearance not
changed invention stripping strength: (heated) 4.5 kg/cm 3.
Comparison Fastener released 1 4.6 17 1.2 from the object after
about 180 times of repetition 4. Comparison Fastener released 2 6.3
14 0.7 from the object after about 60 times of repetition 5.
Comparison Fastener released 3 5.9 13 0.9 from the object after
about 80 times of repetition
__________________________________________________________________________
From Table I, it is evident that the fastener to which the adhesive
composition was applied, according to the present invention,
exhibits superior and stable strength of adhesion and creep
resistance. Further, the fastener indicated as No. 2 in Table I was
subjected to the following washing test. The fastener was washed
with water containing 0.2 percent of Monogen (fatty alcohol ester,
Daiichi Kogyo Seiyaku Kabushiki Kaisha, Japan) and 0.2 percent of
washing soda at 40.degree.C, for 15 minutes, by a conventional
washing machine, and dried with air at 30.degree.C for 30 minutes.
After five repeated washing tests, the friction strength and the
stripping strength were reduced about 10 percent and about 20
percent, respectively. However, the fastener was satisfactory for
practical use.
EXAMPLE 2
Adhesive compositions were prepared by the same process as in
Example 1 by adding triethanolamine hydrochloride and zirconyl
stearate each in amounts as indicated in Table II, to the polymer
solution prepared as in Example 1, except that 83 parts of butyl
acrylate, 16 parts of styrene and 1 part of acrylic acid glycidyl
ester were used instead of 20 parts of vinyl acetate, 77 parts of
2-ethylhexyl acrylate and 3 parts of methacrylic acid glycidyl
ester. Each of the adhesive compositions was coated onto the
releasing surface of a silicone coated releasing paper by roll
coating and the coated paper was dried at 50.degree.C for 6
minutes. Then, the adhesive composition thus coated was secured to
the respective back surfaces of the male and female pieces of a
velvet type fastener of the same type as in Example 1, together
with the releasing paper, and further dried at 40.degree.C for 10
minutes. One piece of the fastener was secured to a plywood
consisting of lauan and the other piece of the fastener was secured
to a twill woven fabric composed of Nylon 6, by pressing each piece
by hand, and these were heated by hot air at 120.degree.C for 15
minutes. The obtained specimens were subjected to the tests as in
Example 1. The results are shown in Table II.
Table II
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Creep Friction Composition resistance (mm) strength (kg/cm)
Repeated fastening test zirconyl amine plywood fabric plywood
fabric compound compound
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Comparison 0.4 0.06 6.2 7.3 14 8 Fastener released from the object
after about 140 times of repetition The 0.6 0.06 0.9 1.0 24 22
Appearance not changed invention Comparison 2.0 0 3.2 4.1 12 10
Fastener released from the object after about 30 times of
repetition The Appearance not changed invention 2.0 0.02 0.7 0.9 25
21 The 2.0 0.06 trace trace 32 29 Appearance not changed invention
The 2.0 0.08 trace trace 34 31 Appearance not changed invention
Comparison 2.0 0.12 trace trace 33 30 Appearance not changed (rough
and hard feel in hands) The invention 4.0 0.06 0.4 0.6 35 31
Appearance not changed Comparison 6.0 0.06 trace trace 35 32
Appearance not changed (rough and hard feel in hands)
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As is evident from Table II, there are certain ranges for the
appropriate amounts of organic amine hydrochlorides and zirconyl
salts of organic acids. In addition the use of organic amine
hydrochlorides and zirconyl salts of organic acids in large amounts
does not result in increasing the effect on the friction strength
of adhesion, though the creep resistance generally becomes better.
The specimens indicated as Nos. 7, and 9 in Table II felt very hard
and, therefore, were unsuitable for practical use.
* * * * *