U.S. patent application number 10/512864 was filed with the patent office on 2006-05-11 for polyurethane-based anhydrous sizing compositions for glass fibres, glass fibres obtained and composite materials comprising said fibres.
This patent application is currently assigned to Saint-Gobain Vetroex France. Invention is credited to Patrick Moireau, Christelle Pousse.
Application Number | 20060099417 10/512864 |
Document ID | / |
Family ID | 29414962 |
Filed Date | 2006-05-11 |
United States Patent
Application |
20060099417 |
Kind Code |
A1 |
Moireau; Patrick ; et
al. |
May 11, 2006 |
Polyurethane-based anhydrous sizing compositions for glass fibres,
glass fibres obtained and composite materials comprising said
fibres
Abstract
The invention relates to a sizing composition consisting of a
solution comprising less than 5% by weight of solvent and
comprising a curable base system, said system comprising at least
50% by weight of a mixture of: one or more components containing at
least one isocyanate reactive functional group; one or more
components containing at least one hydroxyl reactive functional
group; and optionally, one or more components containing at least
one amine reactive functional group. A subject of the invention is
also the glass strands coated with the aforementioned sizing
composition. The glass strands obtained can be used to reinforce
organic or inorganic materials.
Inventors: |
Moireau; Patrick; (Curienne,
FR) ; Pousse; Christelle; (Paris, FR) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Saint-Gobain Vetroex France
Chambery
FR
73000
|
Family ID: |
29414962 |
Appl. No.: |
10/512864 |
Filed: |
May 21, 2003 |
PCT Filed: |
May 21, 2003 |
PCT NO: |
PCT/FR03/01537 |
371 Date: |
January 9, 2006 |
Current U.S.
Class: |
428/375 |
Current CPC
Class: |
C03C 25/25 20180101;
Y10T 428/2933 20150115; C03C 25/326 20130101 |
Class at
Publication: |
428/375 |
International
Class: |
D02G 3/00 20060101
D02G003/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 22, 2002 |
FR |
02/06197 |
Claims
1. A glass strand coated with a sizing composition consisting of a
solution comprising less than 5% by weight of solvent and
comprising a curable base system, said system comprising at least
50% by weight of a mixture of: one or more components comprising at
least one isocyanate reactive functional group; one or more
components comprising at least one hydroxyl reactive functional
group; and optionally, one or more components comprising at least
one amine reactive functional group.
2. The glass strand as claimed in claim 1, wherein the curable base
system represents 60 to 100% by weight of the composition.
3. The glass strand as claimed in claim 2, in that wherein the base
system represents 75 to 90% by weight of the composition.
4. The glass strand as claimed in claim 1, wherein the base system
consists of 75% and up to 100% by weight of one or more isocyanate
components, one or more hydroxyl components and one or more amine
components.
5. The glass strand as claimed in claim 1, wherein the base system
comprises at least 70% by weight of one or more components of
molecular mass less than 750.
6. The glass strand as claimed in claim 1, wherein the ratio r of
the number of isocyanate reactive sites to the number of hydroxyl
reactive sites is between 0.1 and 6.
7. The glass strand as claimed in claim 1, wherein the ratio r' of
the number of isocyanate reactive sites to the sum of the number of
hydroxyl reactive sites and of the number of amino reactive sites
is between 0.1 and 6.
8. The glass strand as claimed in claim 1, wherein the content of
isocyanate component(s) is between 10 and 50%, by weight of the
sizing composition.
9. The glass strand as claimed in claim 1, wherein the content of
hydroxyl component(s) is between 15 and 55%, by weight of the
sizing composition.
10. The glass strand as claimed in claim 1, wherein the content of
amine component(s) is less than or equal to 30%, by weight of the
sizing composition.
11. The glass strand as claimed in claim 1, wherein the composition
comprises from 0 to 5% by weight of a catalyst.
12. The glass strand as claimed in claim 1, wherein the composition
comprises from 0 to 30% by weight of a coupling agent.
13. The glass strand as claimed in claim 1, wherein the composition
comprises from 0 to 30% by weight of a textile processing aid.
14. The glass strand as claimed in claim 1, wherein the base system
consists of one or more isocyanate components comprising at least
two isocyanate reactive functional groups, one or more hydroxyl
components comprising at least one hydroxyl reactive functional
group and, optionally, one or more amine components comprising at
least one amine reactive functional group.
15. The glass strand as claimed in claim 14, wherein the base
system consists of one or more isocyanate components comprising
three isocyanate reactive functional groups and one or more
hydroxyl components comprising one to three hydroxyl reactive
functional groups.
16. The glass strand as claimed in claim 14, wherein the base
system consists of one or more isocyanate components comprising
three isocyanate reactive functional groups, one or more hydroxyl
components comprising a hydroxyl reactive functional unit and one
or more amine components comprising two primary amine reactive
functional groups.
17. A sizing composition, consisting of a solution comprising less
than 5% by weight of solvent and comprising a curable base system,
said system comprising at least 50% by weight of a mixture of: one
or more components comprising at least one isocyanate reactive
functional group; one or more components comprising at least one
hydroxyl reactive functional group; and optionally, one or more
components comprising at least one amine reactive functional
group.
18. A composite comprising at least one organic and/or inorganic
material and sized glass strands, wherein all or some of the glass
strands comprises the glass strand as claimed in claim 1.
19. (canceled)
20. A method for forming a cloth, said method comprising forming
said cloth which comprises said glass strand as claimed in claim 1.
Description
[0001] The present invention relates to a sizing composition for
glass strands, to the glass strands obtained and to the composites
incorporating said glass strands. More precisely, it relates to an
anhydrous sizing composition comprising compounds with isocyanate
reactive functional groups and compounds with hydroxyl and/or amine
functional groups that are capable of reacting to form
polyurethanes and/or polyureas.
[0002] The manufacture of glass reinforcing strands is carried out
in a known manner using molten glass streams emanating from the
orifices of bushings. These streams are drawn in the form of
continuous filaments, and then these filaments are brought together
as base strands that are then collected in various forms: bobbins
of continuous strands, continuous- or chopped-strand mats, chopped
strands, etc.
[0003] Before they are brought together in the form of strands, the
filaments are coated with a size by being passed them over a sizing
member. The application of a size is necessary, on the one hand,
for obtaining strands and, on the other hand, for producing
composites that combine said strands as reinforcing agent with
other organic and/or inorganic materials.
[0004] The size serves in the first place as a lubricant and
protects the strands from the abrasion resulting from high-speed
friction of the strands on the various members encountered in the
aforementioned process. It is important for the glass strand to
possess a slippability (or "slip") sufficient to withstand the
subsequent conversion operations, such as unwinding from and
winding onto appropriate supports, or weaving, so as to minimize
any friction liable to break the filaments.
[0005] The size also has the function of giving the aforementioned
strands integrity, that is to say of binding the filaments together
within the strands. This integrity is more particularly desirable
in textile applications in which the strands are subjected to high
mechanical, especially tensile, stresses. Thus, when the filaments
are poorly bonded together, they have a tendency to break more
easily when they are stressed, resulting in the formation of fuzz
that disrupts the operation of the textile machines, or even
requires them to be completely shut down. In addition, non-integral
strands are considered as being tricky to handle, especially when
they are to be used to form bobbins, as broken filaments then
appear along the sides. Apart from the unsatisfactory esthetic
appearance, it is more difficult to unwind the strands removed from
these packages.
[0006] The size also has the role of promoting the wetting and/or
impregnation of the strands with the materials to be reinforced, by
creating bonds between the strands and these materials. The quality
of the adhesion of the material to the strands and the wettability
and/or impregnability of the strands by the material depend on the
mechanical properties of the resulting composites. In most cases,
the size makes it possible to obtain composites having improved
mechanical properties.
[0007] The sizing compositions must also be compatible with the
strand production conditions that in particular impose high
filament drawing rates, which may be up to several tens of meters
per second. They must also withstand the shear forces induced by
the passage of the filaments, especially as regards the viscosity,
which must not appreciably fluctuate, and be capable of correctly
wetting the surface of the filaments so as to obtain uniform
sheathing over their entire length.
[0008] Sizing compositions that contain components capable of
curing after being deposited on the glass must furthermore remain
stable at the temperatures (around 60 to 100.degree. C.) beneath
the bushing. In particular, it is desirable to ensure that the
curable constituents possess a low vapor pressure at the
temperatures indicated, so as to avoid any problem of a
concentration variation resulting from the volatilization of
certain constituents. It is also important to control the degree of
conversion defined by the ratio of the number of functional groups
that have reacted in the size to the number of initial reactive
functional groups in order to guarantee that sized glass strands of
constant quality are obtained. The degree of conversion must
especially be very close to the expected theoretical value in order
to prevent the size from changing over time.
[0009] As a general rule, the sizing compositions are chosen so as
to fulfill the aforementioned functions and so as not to undergo
chemical reactions causing a substantial increase in the viscosity,
both during storage at room temperature and under the higher
temperature conditions beneath the bushing.
[0010] The sizes most commonly employed are low-viscosity aqueous
sizes. Although very easy to use, they do have disadvantages. In
particular, these sizes contain a very large proportion of water,
generally more than 80%, the water having to be removed after
deposition on the glass since water results in a reduction in
adhesion between the strands and the material to be reinforced. A
well-known means consists in drying the glass strands thermally,
but this is a lengthy and expensive operation that needs to be
matched perfectly to the strand manufacturing conditions. Moreover,
this treatment is not neutral with respect to the strand. In
particular, when the sized strand is in the form of packages, what
may occur is a change in the distribution of the constituents of
the size, by irregular and/or selective migration, a coloration of
the strand and a deformation of the package.
[0011] Aqueous sizing compositions containing polyurethanes have
already been proposed. Thus, EP-A-0 554 173 discloses a size
intended for coating glass strands used in the construction of
molded composites, the bonding agent of which is formed from one or
more polyurethane resins, optionally combined with one or more
polyepoxides. JP-2000044793 proposes the reinforcement of
thermoplastics by means of glass strands treated with a sizing
composition comprising a polyurethane resin in emulsion, a coupling
agent and a lubricant.
[0012] Moreover, "anhydrous" sizing compositions are known, that is
to say those comprising less than 5% by weight of solvent and
consisting of a base system formed from curable components.
[0013] In FR-A-2 727 972, the sizing composition is capable of
curing under the action of UV radiation or an electron beam. The
curable base system contains at least one component of molecular
mass less than 750, having at least one epoxy functional group and
comprising at least 60% by weight of one or more components of
molecular mass less than 750 having at least one epoxy, hydroxyl,
vinyl ether, acrylic or methacrylic functional group.
[0014] FR-A-2 772 369 discloses a sizing composition for glass
strands that does not require a heat treatment step after
deposition on the strand. It comprises at least 60% by weight of
components capable of curing, these components being, in the case
of at least 60% of them, components of molecular mass less than 750
and these curable components comprising at least one mixture of one
of more components having at least one acrylic and/or methacrylic
reactive functional group and of one or more components having at
least one primary amine and/or secondary amine functional group, at
least 20% by weight of these components possessing at least two
acrylic, methacrylic, primary amine and/or secondary amine reactive
functional groups.
[0015] One object of the present invention is to propose a
thermally curable anhydrous sizing composition for coating glass
strands, which involves the reaction of one or more compounds
containing one or more isocyanate functional groups and one or more
compounds containing one or more hydroxyl functional groups and,
optionally, of one or more compounds containing one or more amine
functional groups.
[0016] Another object of the present invention is to propose a
sizing composition in which the reaction time of the curable system
may range, in order to be adapted to the application conditions,
from a system able to crosslink relatively slowly, in one or a few
hours, to an extremely reactive system having a gel time of around
ten minutes.
[0017] Another object of the invention is to propose a sizing
composition that makes it possible to control the texture of the
glass strands, that is to say their stiffness and their
integrity.
[0018] Another object of the invention is to propose glass strands
coated with a size that makes them suitable for undergoing an
operation for increasing their volume ("bulking" operation).
[0019] The sizing composition according to the invention consists
of a solution comprising less than 5% by weight of solvent and
comprising a curable base system, said system comprising at least
50% by weight of a mixture of:
[0020] one or more components containing at least one isocyanate
reactive functional group;
[0021] one or more components containing at least one hydroxyl
reactive functional group; and
[0022] optionally, one or more components containing at least one
amine reactive functional group.
[0023] In the present invention, the expressions below have the
following meanings:
[0024] "solvent" is understood to mean water and organic solvents
capable of being used to dissolve certain curable components. The
presence of one or more solvents in a limited amount does not
require any particular treatment in order to remove them. In most
cases, the sizes according to the invention are completely free of
solvent;
[0025] "cure", "curable", "curing", etc. are understood to mean
"cure and/or crosslink", "curable and/or crosslinkable", "curing
and/or crosslinking", etc., respectively;
[0026] "reactive functional group" is understood to mean a
functional group that can act in the size curing reaction, it being
possible for the curing to take place at the usual strand
production temperature (around 20 to 100.degree. C.) with no
additional supply of energy, or else at a higher temperature, up to
about 150.degree. C. (thermal curing); and
[0027] "curable base system" is understood to mean the combination
of essential components that allow the expected
polyurethane/polyurea structure of the size to be obtained.
[0028] Hereafter, the expressions "one or more isocyanate
components", "one or more hydroxyl components" and "one or more
amine components" are understood to mean "one or more components
containing at least one isocyanate reactive functional group", "one
or more components containing at least one hydroxyl reactive
functional group" and "one or more components containing at least
one amine reactive functional group", respectively.
[0029] The sizing composition according to the invention is
compatible with the glass strand production conditions imposed by
the direct process, the viscosity of the composition being adapted
according to the draw speed and the diameter of the filaments made
to pass through the sizing composition. As a general rule, it is
desirable for the viscosity not to exceed 400 mPas, preferably 150
mPas, so that the sizing composition can be uniformly distributed
over the surface of the glass filaments. The composition according
to the invention also has a strand wetting rate compatible with the
strand draw rate.
[0030] As a general rule, the curable base system represents 50 to
100% by weight of the sizing composition according to the
invention, mainly 60 to 100% by weight of the composition and, in
most cases, 75 to 90% by weight of the composition.
[0031] The base system consists predominantly (preferably 75% by
weight and up to 100% by weight in most cases) of one or more
isocyanate components and one or more hydroxyl components, and
where appropriate one or more amine components, the use of this
mixture of components allowing polyurethane or poly(urethane-urea)
polymers to be obtained by the reaction of the various isocyanate,
hydroxyl and amine functional groups of the initial constituents.
It is these polymers that predominantly participate in the
structure of the size, and it is from this structure that the
properties of the sized glass strands directly stem.
[0032] Furthermore, the base system comprises a majority
(preferably at least 70% by weight and better still at least 80% by
weight) of one or more components of molecular mass less than 750,
this component or these components normally forming part, in most
cases, of the aforementioned isocyanate, hydroxyl and amine
components.
[0033] Preferably, and in general according to the invention, the
aforementioned components of molecular mass less than 750 are of
molecular mass less than 600.
[0034] When the base system contains components of molecular mass
less than 750, it advantageously includes one or more isocyanate
and/or hydroxyl and/or amine components of molecular mass greater
than 1000 (prepolymers). The total content of these components is
generally less than 20% by weight of the sizing composition,
preferably less than 15%, as above this content the viscosity and
the reactivity of the composition become too high to allow the size
to be deposited on the glass strands under the conditions of the
abovementioned process.
[0035] In general, the reactivity of the base system is varied in
order to be adapted to the application conditions. In particular,
the gel time has a major influence on the size deposition quality
and on the construction of the packages when the strand is
collected in the form of bobbins. The gel time must not be less
than about 10 minutes in order to allow the size to be deposited
beneath the bushing by means of sizing rolls with no significant
risk of the size gelling on the rolls. Moreover, the gel time must
not exceed 1.5 hours so that it is possible to obtain strand
packages that can be handled on leaving the winder. Gel times
varying from 15 to 45 minutes prove to be very satisfactory.
[0036] According to certain embodiments, the base system according
to the invention may optionally include a small proportion (less
than 20%) of one or more components participating in the structure
of the cured size, but having no isocyanate, hydroxyl or amine
functional groups and/or a molecular mass greater than or equal to
1000. Preferably, the proportion of these components is less than
15%.
[0037] According to the preferred embodiment of the invention,
which allows particularly satisfactory results to be obtained, the
base system consists of one or more isocyanate components
containing at least two isocyanate reactive functional groups, one
or more hydroxyl components containing at least one hydroxyl
reactive functional group and, optionally, one or more components
containing at least one amine reactive functional group.
Particularly advantageously, the base system consists either of one
or more isocyanate components containing three isocyanate reactive
functional groups and one or more hydroxyl components containing
one to three hydroxyl reactive functional groups, or one or more
isocyanate components containing three isocyanate reactive
functional groups, one or more hydroxyl components containing a
hydroxyl reactive functional group and one or more amine components
containing two primary amine reactive functional groups.
[0038] According to the invention, all or some of the hydroxyl
components of the base system may contain one or more hydroxyl
reactive functional groups and one or more amine reactive
functional groups.
[0039] The isocyanate component or components of the base system
may especially be chosen from: [0040] aliphatic or cycloaliphatic
isocyanates, such as hexyl isocyanate, dodecyl isocyanate,
hexadecyl isocyanate, cyclohexyl isocyanate, 1-adamantyl
isocyanate, 1,6-hexamethylene diisosyanate (HDI),
1,12-dodecamethylene diisocyanate, isophorone diisocyanate (IPDI),
1,1-methylenebis(4-isocyanatocyclohexane) (HMDI), transcyclohexane
1,4-diisocyanate (CHDI), esters, such as butyl isocyanatoacetate
and 3-ethyl isocyanatopropionate, or ethers, such as
trifluoroacetyl isocyanate; [0041] aromatic isocyanates, such as
3,5-dimethylphenyl isocyanate, 4-methoxybenzyl isocyanate,
4-dimethylaminophenyl isocyanate, 4-methoxyphenyl isocyanate,
4-ethoxyphenyl isocyanate, xylylene diisocyanate (XDI), toluene
diisocyanate (TDI), naphthalene-1,5-diisocyanate (NDI),
4,4'-diphenylmethane diisocyanate (MDI) and tetramethylxylene
diisocyanate (TMXDI); and [0042] isocyanate-terminated prepolymers
(NCO-prepolymers), for example TOLONATE.RTM. HDT and TOLONATE.RTM.
HDB (NCO content: 20-25%; sold by Rhodia), products resulting from
the reaction between polyethers and isocyanates, such as
polytetramethylene glycol/TDI prepolymers, for example
CASTOMER.RTM. E 1009 and CASTOMER.RTM. E 1004 (NCO content:
[0043] 4.2 and 9.3% respectively; sold by Baxenden); polypropylene
glycol/TDI prepolymers, for example TRIXENE.RTM. DP9B/1534 (NCO
content: 4.4%; sold by Baxenden) and products resulting from the
reaction between polyesters and isocyanates, especially TDI, for
example CASTOMER.RTM. DP9A/956 (NCO content: 4%; sold by
Baxenden).
[0044] Among the isocyanates that have just been mentioned, some
are monomers whose vapor pressure is relatively high, making them
potentially toxic to humans. This is why isocyanates in the form of
prepolymers of molecular mass at least equal to 400 and preferably
at least equal to 450 are preferred. Advantageously, the molecular
mass is less than or equal to 2000, preferably less than or equal
to 1200, since above this the prepolymers have a high melting point
or a high viscosity, which make the sizing composition difficult to
apply to the glass filaments. Advantageously, the prepolymer has a
content of free isocyanate reactive functional groups (NCO content)
at least equal to 3%, preferably less than 25% and advantageously
greater than or equal to 5%.
[0045] As a general rule according to the invention, the proportion
of isocyanate component(s) in the base system represents 15 to 75%,
and preferably 30 to 60%, by weight. Preferably, at least 10% of
the isocyanate components are polyisocyanates, and advantageously
100% of the isocyanate components are polyisocyanates.
[0046] The content of isocyanate component(s) in the composition is
generally between 10 and 50% and preferably between 20 and 40% by
weight.
[0047] The hydroxyl component or components of the base system may
be chosen from: [0048] aliphatic or cycloaliphatic alcohols, such
as hexanol, octanol, dodecanol, cyclohexanol, 1,2-propanediol,
2-ethyl-2-hydroxymethyl-1,3-propanediol, butanediol, butenediol,
pentanediol, hexanediol, cyclohexandiol, 1,4-cyclohexanedimethanol,
glycerol, trimethylolpropane and pentaerythritol; [0049] tertiary
alkanolamines, such as 2-(diisopropylamino)ethanol,
3-dimethylamino-1-propanol, 3-diethylamino-1,2-propanediol,
3-diisopropylamino-1,2-propanediol, N-butyl-diethanolamine,
triethanolamine and triisopropanolamine, [0050] monohydroxylated
components of the hydroxyl-terminated polyester type, obtained by
reaction between a fatty acid and a poly(alkylene oxide), such as
polyethylene glycol isostearate or polypropylene glycol
isostearate, components of the hydroxyl-terminated polyether type
obtained by reaction between a fatty alcohol and ethylene oxide
and/or propylene oxide, for example lauric alcohol having 4
ethylene oxide units, or by reaction between an alkyl phenol and
ethylene oxide and/or propylene oxide, for example nonyl phenol
having 8 ethylene oxide units; and [0051] poly(oxyalkylene)polyols,
for example poly(oxyethylene)polyols, poly(oxypropylene)polyols,
poly(oxyethylene)(oxypropylene)polyols,
poly(tetrahydrofuran)polyols and poly(caprolactone)polyols, the
molecular mass of which is preferably less than 1500.
[0052] Among the hydroxyl compounds that have just been mentioned,
those containing more than 5 carbon atoms are preferred. Compounds
having a smaller number of carbon atoms may be employed when it is
desired to lower the viscosity of the base system and/or to limit
the chain length during curing.
[0053] Preferably according to the invention, the hydroxyl
components are chosen from alcohols containing at least two
hydroxyl reactive functional groups, and better still two or three
hydroxyl functional groups.
[0054] As indicated above, the hydroxyl components may include one
or more amine functional groups. Examples of such components are
given later.
[0055] Within the context of the invention, it is also possible to
use, as hydroxyl components, components containing one or more
epoxide functional groups, the epoxy ring of which may be opened by
the action of a catalyst in order to generate a secondary hydroxyl.
The catalyst that can be used for this purpose may be any catalyst
known to those skilled in the art, as indicated later.
[0056] As examples of such components, mention may be made of
components containing an epoxy functional group such as cyclohexene
monoxide, glycidyl ethers, particularly C.sub.4-C.sub.20 alkyl
glycidyl ethers, phenyl glycidyl ether, alkyl phenyl glycidyl
ethers, monoglycidyl ethers of derivatives of bisphenol A,
especially of acryloxybisphenol A, and components containing
several epoxy functional groups, such as polyglycidyl ethers, in
particular 1,4-butanediol diglycidyl ether, neopentyl glycol
diglycidyl ether, cyclohexanedimethanol diglycidyl ether,
resorcinol diglycidyl ether, bisphenol A or bisphenol F diglycidyl
ether, polybutadiene diglycidyl ether, polyglycol diepoxydes,
trimethylolpropane triglycidyl ether and polyglycidyl ethers of
alkyl polyesters.
[0057] As a general rule according to the invention, the proportion
of hydroxyl component(s) varies from 15 to 60%, and preferably 20
to 50%, by weight of the base system. Preferably, at least 15%, and
advantageously at least 20%, of the hydroxyl component(s) are
components comprising at least two hydroxyl reactive functional
groups.
[0058] The content of hydroxyl component(s) in the composition is
generally between 15 and 55%, and preferably between 25 and 45%, by
weight.
[0059] The number of reactive sites of the hydroxyl components that
can react with the reactive sites of the isocyanate components may
vary greatly. In general, the ratio r of the number of isocyanate
reactive sites to the number of hydroxyl reactive sites varies from
0.1 to 6 and preferably from 0.3 to 4, it being understood that an
isocyanate functional group counts as one isocyanate reactive site
and that a hydroxyl functional group counts as one hydroxyl
reactive site.
[0060] The amine component or components of the base system may be
chosen from components containing one or more primary and/or
secondary amine functional groups, such as components having
linear, branched or cyclic hydrocarbon chain components, for
example, N,N-dibutylamine, N,N-dicyclohexylamine,
aminoethylpiperazine, 2(2-aminoethoxy)ethanol, 3-amino-1-propanol,
2-amino-2-ethyl-1-propanol, N-(2-aminoethyl)ethanolamine,
2-amino-2-ethyl-1,3-propanediol, aromatic components, for example
1,3-diphenylguanidine and 3,4-diaminotoluene, and amine-terminated
polymers, for example (polybutadiene)diamine. According to the
invention, some of the aforementioned amine compounds contain one
or more hydroxyl functional groups as mentioned above.
[0061] Preferably, the amine components are chosen from components
containing at least two primary and/or secondary amine functional
groups. So as to reduce the reactivity of the amine compounds, it
may be envisaged to add a small amount (around 2 to 15% by weight
of the composition) of a ketone, in particular a diketone such as
pentanediene, dibenzoylmethane, 2,2,6,6-trifluoro-3,5-heptanedione,
dimethyl-1,4-cyclohexanedione-2,5-dicarboxylate,
4,4,4-trifluoro-1-(2-naphtyl)-1,3-butanedione,
thenoyltrifluoroacetone,
2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione,
3-methyl-2,4-pentanedione, 1-(2-furyl)-1,3-butanedione and
2,6-dimethyl-3,5-heptanedione. Pentanedione, dibenzoylmethane,
3-methyl-2,4-pentanedione and 2,6-dimethyl-3,5-heptanedione are
preferred.
[0062] As a general rule according to the invention, the proportion
of amine component(s) represents 0 to 30% by weight of the base
system and in most cases it is between 5 and 30%.
[0063] The content of amine component(s) in the composition is
generally between 0 and 30%, and preferably between 0 and 20%, by
weight.
[0064] The number of reactive sites of the amine components that
can react with the reactive sites of the isocyanate components may
vary greatly. As a general rule, the ratio r' of the number of
isocyanate reactive sites to the sum of the number of hydroxyl
reactive sites and of the number of amine reactive sites varies
from 0.1 to 6, and preferably from 0.3 to 4, it being understood
that an isocyanate functional group counts as one isocyanate site,
that a hydroxyl functional group counts as one hydroxyl reactive
site, that a primary amine functional group counts as two amine
reactive sites and that a secondary amine functional group counts
as one amine reactive site.
[0065] The sizing composition may include, in addition to the base
system, at least one catalyst promoting size curing. This may, for
example, be a specific catalyst for the synthesis of polyurethanes,
such as 1,4-diazabicyclo[2.2.2]octane and
1,8-diazabiscyclo[5.4.0]undec-7-ene, or else a catalyst suitable
for epoxy components, such as tris(N,N-dimethylaminomethyl)benzene,
tris(N,N-dimethylaminopropyl)triazine, N,N-dimethylbenzylamine and
2-propylimidazole.
[0066] The content of components acting only as catalysts for the
base system (that is to say those not participating in the
structure of the cured size) is generally less than 5% by weight of
the sizing composition, preferably less than 3% and in most cases
around 0.5% by weight.
[0067] The sizing composition may also include, within the limits
indicated above, a solvent for helping to dissolve certain
components of the base system. As examples of such a solvent,
mention may be made of ethyl acetate, N-methyl pyrrolidone and
tetrahydrofuran.
[0068] The sizing composition may include one or more components
(hereafter called additives) in addition to the aforementioned
components that essentially participate in the structure of the
cured size, and where appropriate to the catalysts and to the
solvent. These additives give the size particular properties and,
when the composite is deposited in two steps, as is preferred, they
may be provided by one or both of the constituent compositions of
the size.
[0069] The composition according to the invention may include, as
additive, at least one coupling agent for bonding the size to the
glass. The coupling agent may be a component of the base system, in
which case it participates in the curing reaction, or a component
acting only as additive.
[0070] The proportion of coupling agent(s) is generally between 0
and 30% by weight of the sizing composition and in most cases is
greater than 5% by weight. Preferably, it is between 10 and 25% of
the composition.
[0071] The coupling agent is generally chosen from silanes such as
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-acryloxypropyltrimethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
poly(oxyethylene/oxypropylene)trimethoxysilane,
.gamma.-aminopropyltriethoxysilane, vinyltrimethoxysilane,
phenylaminopropyltrimethoxysilane,
styrylaminoethylaminopropyltrimethoxysilane or
terbutylcarbamoylpropyltrimethoxysilane, siloxanes, titanates,
zirconates and mixtures of these compounds. Preferably, silanes are
chosen.
[0072] The composition may include, as additive, at least one
textile processing aid acting essentially as lubricant, and it is
in many cases necessary for the composition to have the functions
of a size.
[0073] The proportion of textile processing aid is generally
between 0 and 30%, preferably between 3 and 20%, by weight of the
composition.
[0074] The textile processing aid is generally chosen from
optionally alkoxylated fatty esters, such as decyl laurate,
isopropyl palmitate, cetyl palmitate, isopropyl stearate, isobutyl
stearate, trimethylolpropane trioctanoate, trimethylolpropane
tridecanoate, alkyl phenol derivatives, such as ethoxylated nonyl
phenol, optionally alkoxylated fatty alcohols, such as
methyl-terminated polyethylene glycol laurate or stearate
advantageously containing fewer than 10 oxyethylene units, mixtures
based on mineral oils, and mixtures of these compounds. The
processing aids are preferably free of functional groups liable to
act preferentially with isocyanate, hydroxyl and/or amine
functional groups.
[0075] The composition according to the invention may be deposited
on the glass filaments in one or more steps.
[0076] When they are deposited in one step, all of the curable
constituents are contained in the sizing composition and it is then
imperative to block either the isocyanate functional groups or the
hydroxyl and amine functional groups so as to prevent the
composition from curing prematurely before it is deposited on the
glass filaments. The preferred solution in this embodiment consists
in using polyisocyanates whose isocyanate reactive functional
groups are blocked by protective groups, it being possible for the
functional groups to be unblocked by the addition of an unblocking
agent. As examples of such polyisocyanates, mention may be made of
derivatives of TDI, HDI, IPDI, and MDI (for example sold by
Baxenden under the references BI 7673, BI 7772, BI 7950, BI 7962,
BI 7983, BI 7960, which may be unblocked by
3,5-dimethylpyrazole).
[0077] The composition according to the invention is preferably
deposited in several steps, for example under the conditions of the
process described in FR-A-2 763 328. In that process, molten glass
streams flowing out of orifices placed at the base of one or more
bushings are drawn into the form of one or more sheets of
continuous filaments and then the filaments are brought together as
one or more strands that are collected on one or more moving
supports. The size is deposited by applying to the filaments a
first stable composition of viscosity between 0.5 and 300 mPas and
at least one second stable composition of viscosity between 0.5 and
250 mPas, supplied separately from the first composition.
[0078] The second composition may be deposited on the filaments as
soon as possible after the first composition has been deposited or
on the strands as late as possible during their collection on the
supports. The difference in viscosity between the compositions is
generally less than 150 mPas.
[0079] The composition according to the invention is preferably
applied in two steps, the first composition preferably comprising
the polyisocyanate component(s) and optionally one or more
additives, and the second composition comprising the hydroxyl
component(s) and/or the amine component(s) and optionally one or
more additives, especially the curing catalyst or catalysts.
[0080] Deposition of the size in two steps is particularly
advantageous. It allows better control of the curing reactions and
consequently the size has a uniform quality over the entire length
of the strands, while ensuring a high productivity with less risk
of the strands breaking.
[0081] As a general rule, the size deposited on the strand requires
no additional supply of energy for it to cure. However, it is
possible to subject the strand, after fiberizing, to a heat
treatment at various stages in the process for the purpose of
accelerating the curing reaction. This treatment may be applied to
strands collected in the form of a package, to sheets of continuous
or chopped strands, or else to strands in combination with an
organic material for producing composites. As an illustration, for
a roving weighing about 20 kg, a treatment at a temperature of
around 120 to 140.degree. C. for about 8 hours proves to be
satisfactory. For chopped strands, the treatment time does not
exceed around ten minutes at an equivalent temperature.
[0082] The actual integrity of the strands through the binding
together of the constituent filaments that is obtained after the
size has cured is particularly important when the amount of size on
the strands is relatively low. The loss on ignition of the strands
coated with the sizing composition according to the invention does
not in fact exceed 3% by weight, preferably 1.5% and advantageously
0.8% by weight.
[0083] The sized strands are generally collected in the form of
packages on rotating supports, such as cakes, rovings and cops.
Whatever the state of cure of the size and the crossing angle, even
when the latter is small (less than 1.5.degree.), it is easy to
unwind the strands from the packages and handle them.
Straight-sided packages retain their dimensional characteristics
over time and undergo no deformation. The strands may also be used
subsequently for producing meshes, fabrics, braids, tapes, etc.
[0084] The strands may also be collected on receiving supports
moving in translation. In particular, they may be thrown, by a
member that also serves to attenuate them, toward the collecting
surface moving transversely to the direction of the thrown strands,
for the purpose of obtaining a web of intermingled continuous
strands or mat. The strands may also be chopped before collection
by a member serving also to attenuate them.
[0085] The presence of polyurethane or poly(urethane-urea) polymers
in the size provides a certain flexibility in the bonding and
allows the filaments to be able to move relative to one another. In
this way, the integrity of the glass strands is improved. The
strands coated with the size according to the invention prove to be
particularly advantageous for producing fabrics or for applications
requiring them to be chopped, such as in the simultaneous spray
molding technique. Another advantage due directly to the presence
of the aforementioned polymers is that the strands have a better
impact strength than other sized strands, while remaining
compatible with many of the thermoplastics to be reinforced.
[0086] The sized glass strand according to the invention is
noteworthy in that it can be treated so as to increase its volume
and obtain what is commonly called a "bulked" strand. The treatment
consists in making the strand pass through a system comprising one
or more nozzles through which a flow of air passes, then in
collecting the strand in the form of a package on a suitable
device. This strand can then be woven in particular to form wall
fabrics to be painted.
[0087] The glass filaments constituting these strands have a
diameter that can vary widely, usually from 5 to 30 .mu.m. They may
be made of any glass whatsoever, the most common in the field of
reinforcing strands being E-glass and AR-glass.
[0088] The strands obtained according to the invention may
advantageously be used to reinforce various materials for the
purpose of obtaining composites having high mechanical properties.
The composites are obtained by combining at least the glass strands
according to the invention with at least one organic and/or
inorganic material, the glass content in the final composite
generally varying from 1 to 5% by weight (cementicious matrix) and
from 20 to 80%, preferably 30 to 70%, by weight (organic
matrix).
[0089] The examples that follow allow the invention to be
illustrated without, however, limiting it. In these examples, the
following analytical methods are used for measuring the physical
properties.
[0090] In the case of sizing compositions: [0091] the viscosity is
measured by means of a SOFRASER MIVI 4000 apparatus sold by
Sofraser. It is expressed in mPas; [0092] the gel time, expressed
in minutes, is measured on the mixture of compositions A and B by
means of a TROMBOMAT device (sold by Prodemat S.A.), which plots
the curve of the viscosity of the sizing composition as a function
of time. On this curve, the point of intersection of the tangent at
the point of inflexion and the x-axis corresponds to the gel
time.
[0093] In the case of strands coated with the sizing composition
according to the invention: [0094] the loss on ignition is measured
according to the ISO 1887 standard. It is expressed in %; [0095]
the amount of fuzz allows the abrasion resistance of a strand to be
assessed. It is measured by weighing the amount of material that
becomes detached from the strand after it passes over a series of
eight ceramic cylindrical turn rolls arranged in such a way that
the angle of deflection of the strand at each turn roll is equal to
90.degree.. The amount of fuzz is given in mg per 1 kg of strand
tested; [0096] the stiffness or rigidity is measured under the
conditions defined by the ISO 3375 standard, on ten specimens
before and after undergoing the abovementioned abrasion resistance
test. The stiffness is expressed in mm and denoted by x(y), x and y
that represent the value measured before and the value measured
after the strand passes over the turn rolls, respectively. The
value y allows the integrity of the strand, and indirectly its
ability to be impregnated with a material, more particularly a
polymer-type organic material, to be pre-assessed. In general, a
sized strand whose y value is less than 100 mm, and preferably
close to 60 mm (the lowest value that can be obtained) is used more
for applications requiring good impregnation by the matrix. A
strand having an x value greater than or equal to 120 and a y value
of greater than or equal to 100 is suitable for a use requiring
high strand integrity, for example for weaving, and optionally in
the case of chopping; [0097] the tensile strength is measured under
the conditions defined by the ISO 3341 standard. It is expressed in
g/tex.
[0098] For composites containing glass strands coated with the
sizing composition: [0099] the flexural strength and the flexural
modulus are measured under the conditions defined by the ISO 178
standard, before and after aging by immersion in water at
100.degree. C. for 24 hours (polyester resin composites) and 72
hours (epoxy resin composites). It is expressed in MPa; [0100] the
shear strength is measured under the conditions defined by the ISO
4585 standard, before and after aging by immersion in water at
100.degree. C. for 24 hours (polyester resin composites) and 72
hours (epoxy resin composites). It is expressed in MPa.
EXAMPLE 1
[0101] Filaments 13.6 .mu.m in diameter obtained by drawing strands
of molten E-glass flowing from a bushing (800 orifices) were coated
with a first composition A and then with a second composition B (in
percentages by weight): TABLE-US-00001 Composition A
triisocyanate.sup.(1) 35
.gamma.-methacryloxypropyltrimethoxysilane.sup.(2) 10
.gamma.-glycidoxypropyltrimethoxysilane.sup.(3) 10 isopropyl
palmitate 5 Composition B 1,5-pentanediol 15
3-dimethylamino-1-propanol 11.5 polyethyleneglycol
isostearate.sup.(4) 13 1,4-diazabicyclo[2.2.2]octane 0.5
[0102] Compositions A and B had a viscosity of 49 mPas (at
21.degree. C.) and 58 mPas (at 22.5.degree. C.), respectively.
[0103] Parallel with the sizing of the filaments, a mixture
containing equal parts of compositions A and B was produced. The
mixture had a viscosity of 1000 Pas after one hour and a gel time
of 21 minutes.
[0104] The ratios r and r' of the sizing composition had the same
value: 0.487.
[0105] The filaments were brought together to form a strand that
was wound on a rotating support so as to obtain a direct roving of
14 kg. The strand had a linear density of 297 tex and a loss on
ignition of 0.65%.
[0106] This strand had a tensile strength equal to 38.7 g/tex, a
stiffness equal to 162 mm (122 mm) and an amount of fuzz equal to 8
mg.
[0107] From the strand thus obtained, two series of composite
panels having parallel strands were produced according to the ISO
9291 standard using two different resins. The first resin was an
epoxy resin consisting of 100 parts by weight of epoxy
resin.sup.(5), 90 parts by weight of phthalic anhydride.sup.(6) and
0.5 parts by weight of tertiary amine.sup.(7). The second resin was
an unsaturated polyester resin consisting of 100 parts by weight of
isophthalic polyester.sup.(8) and 1.5 parts by weight of
peroxide.sup.(9).
[0108] The values of the mechanical properties of these composites
are given below: TABLE-US-00002 Epoxy resin Polyester resin
Flexural strength (MPa) Before treatment 2555.6 2738.4 After
treatment 2039.9 1718.2 Flexural modulus (MPa) Before treatment
39982 37051 After treatment 37957 35339 Shear strength (MPa) Before
treatment 67.3 45.4 After treatment 47.3 25.8
[0109] Although the abovementioned mechanical properties are
inferior to those that may be obtained with known aqueous sizing
compositions especially suitable for epoxy or polyester resins,
they are, however, significant. Their level of performance is
average, comparable to that of most current strands, and in any
case it remained satisfactory for the applications envisioned
here.
EXAMPLE 2
[0110] In this example, the conditions of Example 1 were repeated,
using the following: TABLE-US-00003 Composition A
trilsocyanate.sup.(1) 35
.gamma.-methacryloxypropyltrimethoxysilane.sup.(2) 10
.gamma.-glycidoxypropyltrimethoxysilane.sup.(3) 10 isopropyl
palmitate 5 Composition B polyglycol (molecular mass MW =
1000).sup.(10) 15 3-dimethylamino-1-propanol 11.5
polyethyleneglycol isostearate.sup.(4) 13
1,4-diazabicyclo[2.2.2]octane 0.5
[0111] Parallel with sizing of the filaments, a mixture containing
equal parts of compositions A and B was produced. The mixture had a
viscosity of 2000 Pas after 1 hour and a gel time of 20
minutes.
[0112] Compositions A and B had a viscosity of 49 cP (at 21.degree.
C.) and 68 cP (at 22.5.degree. C.), respectively.
[0113] The ratios r and r' of the sizing composition had the same
value: 0.998.
[0114] The filaments were brought together to form a strand that
was wound on a rotating support so as to obtain a direct roving of
14 kg. The strand had a linear density of 286 tex and a loss on
ignition of 0.76%.
[0115] This strand had a tensile strength equal to 34.5 g/tex, a
stiffness equal to 157 mm (110 mm) and an amount of fuzz equal to 5
mg.
EXAMPLE 3
[0116] In this example the conditions of Example 1 were repeated,
using the following compositions A and B: TABLE-US-00004
Composition A triisocyanate.sup.(1) 35
.gamma.-methacryloxypropyltrimethoxysilane.sup.(2) 10
.gamma.-glycidoxypropyltrimethoxysilane.sup.(3) 10 isopropyl
palmitate 5 Composition B 1,5-pentanediol 18 N-butyldiethanolamine
11 polyethylene glycol (molecular mass MW = 300) 10
1,4-diazabicyclo[2.2.2]octane 1
[0117] Compositions A and B had a viscosity of 49 cP (at 21.degree.
C.) and 58 cP (at 22.5.degree. C.), respectively.
[0118] The ratios r and r' of the sizing composition had the same
value: 0.375.
[0119] Parallel with sizing of the filaments, a mixture containing
equal parts of compositions A and B was produced. The mixture had a
viscosity of 60 Pas after 1 hour and a gel time of 26 minutes.
[0120] A strand of 287 tex linear density was formed and collected
on a series of bobbins. This strand underwent a "bulking" treatment
under the following conditions: the strands extracted from two
bobbins were brought together and made to pass in succession over a
first drawing godet (speed: 220 m/min), through a nozzle (inlet and
outlet diameters of 0.7 and 2.2 mm, respectively; air pressure:
6-6.5 bar), over a second draw godet (speed: 183.5 m/min) and
finally over a winding device (pressure: 2.5 bar).
[0121] The strand obtained had a linear density of 640 tex, a
stiffness before the turn roll of 110 mm, a loss on ignition of
0.21% and it left no visible sticky deposit.
[0122] The strand obtained had sufficient tensile strength to be
able to be woven. The fabric formed had a good "coverage" (was
"closed"), was highly hydrophobic and possessed good
impregnabability by polyvinyl acetate (loss on ignition about 17%).
It could be used as cloth to be painted.
EXAMPLE 4
[0123] In this example, the conditions of Example 1 were repeated,
using the following: TABLE-US-00005 Composition A
triisocyanate.sup.(1) 35
.gamma.-methacryloxypropyltrimethoxysilane.sup.(2) 10
.gamma.-glycidoxypropyltrimethoxysilane.sup.(3) 10 isopropyl
palmitate 5 Composition B polyethylene glycol isostearate.sup.(4) 9
etherified lauric alcohol (4 ethylene oxide units).sup.(12) 9.5
triethanolamine 17 1,4-diazabicyclo[2.2.2]octane 0.5
1-methyl-2-pyrrolydinone 4
[0124] The ratios r and r' of the sizing composition have identical
values of 0.589.
[0125] Parallel with the sizing of the filaments, a mixture
consisting of equal parts of compositions A and B was produced. The
mixture had a viscosity of 2800 Pas after 1 hour and a gel time of
32 minutes.
[0126] The filaments were brought together into 51 tex strands that
were wound as cakes. From the strands extracted from 24 cakes, a
1400 tex strand having a loss on ignition of 1.28% was formed.
[0127] The strand had moderate integrity and a moderate stiffness
and could be easily chopped. Its ability to be impregnated with a
polyester resin was evaluated to be 1, measured visually on a scale
ranging from 0 (poor; absence of wetting) to 5 (excellent; strand
invisible in the resin).
[0128] The strand could be used as reinforcement in materials of
the SMC (sheet molding compound) type.
EXAMPLE 5
[0129] Filaments 14 .mu.m in diameter obtained by drawing molten
strands of E-glass flowing from a bushing (800 orifices) were
coated with a first composition A and then with a second
composition B (in percentages by weight): TABLE-US-00006
Composition A triisocyanate.sup.(1) 35
.gamma.-methacryloxypropyltrimethoxysilane.sup.(2) 15 isopropyl
palmitate 7 1-methyl-2-pyrrolydinone 3 Composition B etherified
lauric alcohol (4 ethylene oxide units).sup.(12) 16
polybutadienediamine (molecular mass = 1200).sup.(13) 15 isopropyl
palmitate 8 1,8-diazabiscyclo[5.4.0]undec-7-ene 1
[0130] The ratios r and r' of the sizing composition were 4.71 and
3.01, respectively.
[0131] Parallel with sizing of the filaments, a mixture consisting
of equal parts of compositions A and B was produced. The mixture
had a viscosity of 716 Pas after 1 hour and a gel time of 10.5
minutes.
[0132] The filaments were brought together to form a strand that
was wound on a rotating support so as to obtain a direct roving of
20 kg. The strand had a linear density of 315 tex and a loss on
ignition of 0.57%. It possessed a tensile strength equal to 31.3
g/tex, a stiffness equal to 170 mm (80 mm) and an amount of fuzz
equal to 1.6 mg.
[0133] The strand thus obtained was woven and the fabric used for
reinforcing epoxy, polyester and phenolic matrices.
(1) Sold under the reference TOLONATE HDT LV by Rhodia;
(2) Sold under the reference SILQUEST A 174 by Witco-Crompton;
(3) Sold under the reference SILQUEST A 187 by Witco-Crompton;
(4) Sold under the reference LDM 1018 by Seppic;
(5) Sold under the reference LY 556 by Ciba-Geigy;
(6) Sold under the reference ARALDITE HY 917 by Ciba-Geigy;
(7) Sold under the reference ARALDITE DY 070 by Ciba-Geigy;
(8) Sold under the reference SYNOLIT 1717 by DSM;
(9) Sold under the reference HTM 60 by Ciba-Geigy;
(10) Sold under the reference POLYGLYCOL 1000 by Clariant;
(11) Sold under the reference TOLONATE HDB LV by Rhodia;
(12) Sold under the reference SIMULSOL P4 by Seppic;
(13) Sold under the reference PolyBd-diamine by Atofina.
* * * * *