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JPH07135700

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DESCRIPTION JPH07135700
[0001]
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a
method of assembling a speaker which enables quick curing bonding without using a solvent and
without heating.
[0002]
2. Description of the Related Art As shown in FIG. 1, a speaker used in an audio apparatus is a
frame 1, cone paper 2, cone edge 3, gasket 4, voice coil 5, damper 6, dust cap 7, top plate 8, The
ferrite magnet 9 is composed of the members of the bottom plate 10 and the like, and these
members are appropriately joined with an adhesive at junctions a, b, c, d, e, f and g and
assembled into a speaker .
[0003]
Although a chloroprene-type adhesive was widely used as an adhesive used for joining of abovementioned a-e, this chloroprene-type adhesive takes a predetermined open time, and is expressed
after apply | coating an adhesive. In the case of contact-type adhesion in which adhesion is
carried out utilizing the tackiness, there is a disadvantage that the initial adhesion strength due to
adhesion can not be obtained in single-sided application.
[0004]
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1
In addition, there is a disadvantage that when bonding is performed immediately after
application, a jig for fixing is required until the initial adhesive strength is developed.
Furthermore, since chloroprene-based adhesives are solvent-based adhesives having a solid
content of 30 to 35% by weight, in the working environment, for example, there is a risk of losing
health due to volatilization of a large amount of solvent during solidification and causing a fire.
There was a problem.
[0005]
On the other hand, the joints f and g corresponding to the field part of the speaker are required
to have sufficient adhesive strength.
For this reason, as adhesives used for the joints f and g, adhesives such as epoxy adhesive,
microcapsule acrylic adhesive, two-component acrylic adhesive, α-cyanoacrylate adhesive and
the like can be used. There is also known a bonding method in which an α-cyanoacrylate
adhesive and a room-temperature moisture-curable adhesive (a conventional moisture-curable
adhesive without contact adhesion) are used (JP-A-1-129700). ).
[0006]
The commonly used cold setting epoxy adhesive requires special equipment for accurate
automatic measurement mixing of the two liquids, the time to reach practical strength is slow,
and a special heating furnace is required, etc. There was a drawback of In addition, since the
cured product is hard and brittle, there is a problem that the ferrite of the adhesive may be
broken.
[0007]
The microcapsule-type acrylic adhesive is excellent in workability because it cures in a short time
at room temperature with one solution, but it does not cure unless the microcapsules are broken,
so that the protruding part of the adhesive becomes uncured was there.
[0008]
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An epoxy / modified silicone two-component rapid curing elastic adhesive as represented by
Cemedine EP-001, etc., which is referred to as an elastic adhesive, is an improved product of the
brittleness of such an epoxy adhesive. Although known, this type of adhesive still has problems
such as slow curing speed not suitable for line assembly and extremely slow internal curing.
[0009]
The two-component acrylic adhesive has the advantage that it cures quickly and has excellent
assembly line suitability, but the cured product is hard and brittle, and therefore has the
disadvantage of breaking the ferrite of the adherend. .
[0010]
The α-cyanoacrylate adhesive is one solution, can be cured in a short time at normal
temperature, and is excellent in workability, but it has low impact adhesion, moisture resistance,
heat aging adhesion and adhesion performance. There was a disadvantage that it was inferior.
With conventional adhesives as described above, there was no adhesive that was fast curing and
also flexible.
[0011]
On the other hand, in the case of adhesion by combination of α-cyanoacrylate adhesive and
normal temperature moisture curing adhesive (conventional moisture curing adhesive without
contact adhesion), two solutions are applied, and these are not exactly overlapping. It has the
disadvantage of requiring special equipment for positioning.
[0012]
As described above, there are problems with the conventional bonding methods for assembling a
speaker, and none of them can be fully satisfied. In particular, bonding can be performed up to
the respective joints a to g of the speaker with one adhesive. There was no.
[0013]
SUMMARY OF THE INVENTION The inventor of the present invention has conducted intensive
studies to solve the above-mentioned problems with the above-mentioned bonding method for
assembling a speaker, and the two-component rapid curing elastic adhesive reacts and cures at
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room temperature to be tough. The present invention has been accomplished by actively utilizing
this property with a focus on being a flexible adhesive.
[0014]
The present invention, unlike conventional solvent-based rubber-based adhesives, does not
contain a solvent, so it is safe on fire from a hygienic point of view, it can be fixed immediately
because it is a room temperature rapid curing adhesive, and the bonding method is simple and
after bonding The temporary press is short, bonding is easy, any joints can be bonded, and a
special heating furnace is not required, and even if joints without proper humidity are bonded, it
takes less time. An object of the present invention is to provide a method of assembling a speaker
using an adhesive which is sufficiently hardened to the inside and is excellent in workability.
[0015]
[Means for Solving the Problems] In order to solve the above-mentioned problems, in the method
of assembling a speaker according to the present invention, a two-component rapid curing
comprising liquid A and liquid B at the joint of each member constituting the speaker An elastic
adhesive is applied, and the above-described members are immediately bonded.
[0016]
As a two-component rapid curing elastic adhesive used in the method of the present invention, a
curing accelerator for a polymer compound having a reactive silicon group, a radical
polymerizable monomer, and a polymer compound having a reactive silicon group and a radical
polymerizable monomer And a polymerization initiator of a radically polymerizable monomer as
essential components, wherein the polymerization initiator of the radically polymerizable
monomer is blended in either one of the solution A or the solution B, and the radically
polymerizable monomer What mix | blends a polymerization accelerator with the other of A
liquid or B liquid, and mix | blends the remaining essential component with one or both of A
liquid or B liquid is used.
[0017]
Further, as a two-component rapid curing elastic adhesive used in the method of the present
invention, a curing agent for a compound having an isocyanate group, a radical polymerizable
monomer, a curing agent for a compound having an isocyanate group, and a curing accelerator
for a compound having an isocyanate group A polymerization initiator of a polymerizable
monomer and a polymerization accelerator of a radical polymerizable monomer are contained as
essential components, and a polymerization initiator of the radical polymerizable monomer is
blended in either one of solution A and solution B, and radical polymerization What mixes the
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polymerization promoter of the sex monomer in the other of A liquid or B liquid, and mix | blends
the remaining essential component in one or both of A liquid or B liquid is used.
[0018]
Although all the joints of each member constituting the speaker may be adhered using the twocomponent rapid curing elastic adhesive of the present invention, at least one joint of these joints
is a two-component type of the present invention It may be adhered using a quick curing elastic
adhesive, and in this case, the remaining joints are joined using a conventionally known speaker
adhesive.
[0019]
The two-pack rapid curing elastic adhesive of the present invention cures depending on the type
of radically polymerizable monomer and the type and / or combination ratio of the compound
having a reactive silicon group and / or the isocyanate compound to be combined therewith.
Since various things are possible from the thing of the thing of a thing being flexible and flexible
to a thing hard and tough, it is possible to adjust and use the thing of each part of a speaker as
needed.
[0020]
Generally speaking, flexible types of adhesives tend to be used for the parts a to e of the
loudspeakers, and also for the glues used for the joints f and g that strike the field parts of the
loudspeakers There is a tendency for hard materials with high strength to be used.
[0021]
This is a part based on the unique policy of each company that manufactures speakers related to
the problem of acoustic characteristics, and it is a part where it becomes difficult to determine
the physical properties of the adhesive uniformly, but according to the present invention The
two-component rapid curing elastic adhesive can be widely used because the physical properties
can be easily adjusted by the above method.
[0022]
The two-component rapid curing elastic adhesive used in the method of the present invention is
not only applied by the two-component mixing method, but one of the two components on one of
the adherends and the other on the other of the adherends The other method is applied, and a
method of bonding can be used by superimposing adherends at the time of assembly.
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[0023]
In addition, it is possible to adopt the method of honeymoon type adhesion which is carried out
with 2 liquid type acrylic adhesive, apply the main component of the adhesive to one of the
adherends, and accelerate the curing of the adhesive. Take the form of adhesion, as is done with
an anaerobic adhesive, which is applied to the other component of the agent and to the other of
the adherends, and adhered together by overlapping the adherends at the time of assembly. Is
also possible.
[0024]
Furthermore, in the two-component rapid curing elastic adhesive of the present invention, radical
polymerizable monomers can be cured by ultraviolet light or electron beam, so these components
are instantaneously cured by these means to perform temporary fixing or adhesion. Is also
possible.
[0025]
(A) A combination of a compound having one or more radically polymerizable reactive groups in
the molecule and a compound having one or more reactive silicon groups in the molecule as the
two-component rapid curing elastic adhesive used in the present invention (A) Acrylic-modified
silicone type, two-component rapid curing elastic adhesive, (b) a compound having five or more
radically polymerizable reactive groups in the molecule and one or more isocyanate group in the
molecule And an acrylic-urethane-based two-component rapid-curing elastic adhesive comprising
the combination (B) of the compounds possessed.
[0026]
Specific examples of the compound having one or more radically polymerizable reactive groups
in the molecule used for the adhesive comprising the combination (A) include acrylate and / or
methacrylate, that is, as (meth) acrylate, for example, methyl Alkyl such as (meth) acrylate, ethyl
(meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate,
dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, etc. Or substituted
alkyl type-functional (meth) acrylate; ether type monofunctional (meth) (methoxyethyl (meth)
acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate,
etc.) Acrylate; alkylene type difunctional (meth) acrylates such as ethylene glycol di (meth)
acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc .;
diethylene glycol di (meth) acrylate, polyethylene glycol Ether-type difunctional (meth) acrylates
such as di (meth) acrylate, polypropylene glycol di (meth) acrylate, triethylene glycol di (meth)
acrylate, tetraethylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate ,
Trifunctional (meth) acrylates such as trimethylolethane tri (meth) acrylate; pentaerythritol tetra
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(meth) acrylate, dipentaerythritol poly Multifunctional (meth) acrylates such as meta) acrylate
and tetramethylolmethane tetra (meth) acrylate; 2-hydroxyethyl (meth) acrylate,
tetramethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 2,3 -Polar or
substituted atom-containing (meth) acrylates such as dibromopropyl (meth) acrylate,
tetrahydrofurfuryl (meth) acrylate, 2-chloroethyl (meth) acrylate, dimethylaminoethyl (meth)
acrylate; 2, 2-bis (4-acryloxy-diethoxyphenyl) propane di (meth) acrylate, bisoxypolyethylenated
bisphenol A-di (meth) acrylate, bisoxypropyleneated bisphenol A-di (meth) acrylate, Epoxy (meth)
acrylates such as bisoxy-2-hydroxyethylated bisphenol A-di (meth) acrylate; polyester type di
(meth) acrylates such as adipic acid-1,6-hexanediol-di (meth) acrylate; Meta) acrylate etc. are
mentioned.
[0027]
These (meth) acrylates may be used alone or in combination of two or more.
Further, in some cases, allyl compounds such as diallyl phthalate monomers other than (meth)
acrylates, styrene monomers, triallyl isocyanurate, bisphenol A-based unsaturated polyester
resin, and a reaction product of an isocyanate compound and allyl alcohol in these (meth)
acrylates Small amounts of polymerizable monomers can be used in combination.
When a solid monomer is used, it is desirable to use a liquid monomer such as 2-hydroxyethyl
methacrylate in combination.
[0028]
Specific examples of the compound having one or more reactive silicon groups in the molecule
include JP-A 50-156599, JP-A 52-73998, JP-A 58-10418, JP-A Organosilicone compounds
having at least two or more silicon atoms to which a hydrolyzable group is bonded, as disclosed
in JP-A-63-12677, and compounds as proposed in JP-A-62-230822 and the like Compound, an
oxyalkylene polymer having a silicon group and a (meth) acrylate having a silicon group, which
are proposed in JP-A-60-228516, JP-A-63-112642 and JP-A-1-31271 There is something like a
composition consisting of a polymer).
[0029]
Here, the reactive silicon group is a silicon-containing functional group that can be crosslinked
by forming a siloxane bond, and a representative example is represented by the following general
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formula (I).
[0031]
(Wherein R 1 is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon
atoms or a triorganosiloxy group, X is a hydroxyl group or a different or same hydrolyzable
group, a is 0, 1 or 2) And b is an integer of 0, 1, 2 or 3 and a = 2 and not b = 3, m is an integer of
0 to 18)
[0032]
Preferred reactive silicon functional groups from the viewpoint of economy and the like are
groups represented by the following general formula (II).
[0034]
(Wherein, R 1 is the same as above, and n is an integer of 0, 1 or 2).
)
[0035]
Furthermore, polyether polyols such as polyester polyol-based urethane prepolymers and
polyether polyol-based urethane prepolymers in which terminal isocyanate groups are blocked
with active hydrogen group-containing silane coupling agents such as mercaptosilanes,
aminosilanes, hydroxysilanes, etc. And what made isocyanate silane directly react with the
hydroxyl group of polyester polyol can be used.
[0036]
These high molecular compounds having reactive silicon may be used alone or in combination of
two or more.
Furthermore, depending on the case, you may use together polymerizable monomers, such as
(meth) acrylate.
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[0037]
The two-component rapid curing elastic adhesive used in the present invention comprises (a) a
combination of one or more radically polymerizable monomers in the molecule and a compound
having one or more reactive silicon groups in the molecule (A) 2) a combination of a (meth)
acrylate monomer and / or a (meth) acrylate oligomer and a modified silicone, it is a fast-curing,
tough and flexible two-liquid with improved defects, leaving each excellent part There is a mold
fast curing elastic adhesive.
[0038]
That is, as the adhesive of the combination (A) of the present invention, the solution A contains
the polymer compound having a reactive silicon group and the polymerization accelerator of the
radically polymerizable monomer as essential components, and the solution B is a radically
polymerizable monomer , A polymerization initiator of a radically polymerizable monomer, and a
curing accelerator of a polymer compound having a reactive silicon group as essential
components.
[0039]
The polymerization accelerator of the above-mentioned radical polymerizable monomer and the
polymerization initiator may be contained in either one of the solution A or the solution B. A
polymerization accelerator can also be included.
[0040]
The radical polymerizable monomer can also be contained in the solution A as it is contained in
the solution B.
In this case, the types and combinations of radically polymerizable monomers used in the A
solution and the B solution may be the same or different from each other.
[0041]
Furthermore, the liquid A contains a polymer compound having a reactive silicon group, a radical
polymerizable monomer, and a polymerization initiator of a radical polymerizable monomer as
essential components, and the liquid B has a polymer compound having a reactive silicon group
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It is also possible to include the curing accelerator of the above and a polymerization accelerator
of a radically polymerizable monomer as essential components.
[0042]
Also in this configuration, the polymerization accelerator for the radically polymerizable
monomer and the polymerization initiator may be contained in either one of the solution A or the
solution B. It is also possible to make the agent B contain a polymerization accelerator.
[0043]
Moreover, it is also possible to make only the polymerization accelerator of a radically
polymerizable monomer into an essential component of B liquid, and to make all the other
components be contained in A liquid.
Liquid B can also be used as a honeymoon-type adhesive, using it as a hardening acceleration
primer.
[0044]
There is no particular limitation on the mixing ratio of the solution A and the solution B, and any
mixing ratio can be used as long as the effects of the present invention can be achieved.
[0045]
As a method of curing the (meth) acrylate component of the adhesive of the combination (A) of
the present invention, methods which have already been used in two-component radically
polymerizable adhesives can be used.
[0046]
That is, as radical polymerization initiators, for example, diacyl peroxides such as benzoyl
peroxide and acetyl peroxide; hydroperoxides such as cumene hydroperoxide and t-butyl
hydroperoxide; methyl ethyl ketone peroxide and cyclohexanone peroxide Ketone peroxides;
dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide; peroxy esters such as t-butyl
peroxyacetate; thioglycerol and pyrazoles and / or pyrazolones And various other known radical
12-05-2019
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polymerization initiators.
The radical polymerization initiator may be used in combination of two or more.
[0047]
As a polymerization accelerator used in combination with a radical polymerization initiator for
curing the (meth) acrylate component of the composition of the present invention, for example,
N, N-dimethylaniline, N, N-dimethyl-P-toluidine, di- Tertiary amines such as isopropanol-Ptoluidine and triethylamine; polyamines such as diethylenetriamine, triethylenetetramine and
pentaethylenehexamine; thioureas such as thiourea, ethylenethiourea, benzoylthiourea,
acetylthiourea and tetramethylthiourea; Organic acid salts or inorganic acid salts of metals such
as copper, cobalt, manganese and vanadium and organic chelate compounds with acetylacetone
and the like; reducing organic compounds such as ascorbic acid and gallic acid; mercaptans;
known compounds such as saccharin and salts thereof Promoters can be mentioned.
These curing accelerators can also be used in combination of two or more.
[0048]
The amount of the radical polymerization initiator and the polymerization accelerator used in the
room temperature curable two-component composition of the present invention is the same as
that of the conventional one, and the total amount of both is usually 0.05 to 20% %, Preferably
about 0.1 to 10% by weight.
When the amount used is too small, the curing rate of polymerization is slowed, curing takes
time, and when it is too large, heat generation becomes large, and bubbles are contained in the
layer of the cured product to deteriorate physical properties of the cured product.
[0049]
In the room temperature-curable two-component composition of the present invention, as the
main component of the radically polymerizable monomer, if necessary, waxes such as paraffin
wax and rice wax, P-benzoquinone as a surface dryness improving material Quinone type
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stabilizers such as hydroquinone, hindered phenolic antioxidants such as butylhydroxytoluene,
inorganic and organic fillers, dyes, pigments, thixotropic agents, aminosilanes, epoxysilanes,
acidic phosphoric acid group-containing (meth) An adhesion promoter such as an acrylate
monomer can be contained.
[0050]
As a method of curing a polymer compound having a reactive silicon group which is the other
main component of the adhesive of the combination (A) of the present invention, a curing
accelerator which has already been put to practical use and is known at present It can be used.
As this curing accelerator, organotin compounds such as dibutyltin dilaurate, dioctyltin
dimaleate, dibutyltin phthalate, stannous octoate, dibutyltin methoxide, dibutyltin diacetyl
acetate, dibutyltin diversatate, etc .; tetrabutyl titanate, tetraisopropyl titanate Organic titanate
compounds such as triethanolamine titanate; metal carboxylates such as lead octylate and cobalt
naphthenate; aminosilanes such as γ-aminopropyltriethoxysilane and γaminopropyltrimethoxysilane; tetramethyl ammonium chloride And quaternary ammonium salts
such as penzalkonium chloride; organic phosphoric acid compounds such as monomethyl
phosphoric acid, di-n-butyl phosphoric acid, triphenyl phosphate etc. Be
[0051]
These may be used alone or in combination of two or more.
These compounds can be added to the component having a reactive silicon group, but it is
preferable to add them to a portion consisting of only a radically polymerizable monomer in
terms of storage stability etc. It has the advantage of being easy to handle.
It is sufficient for the amount of the curing accelerator used to be about the amount used
conventionally.
[0052]
In the portion mainly containing a reactive silicon group of the room temperature-curable two-
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component composition of the present invention, waxes such as paraffin wax and rice wax,
various kinds (Meta ) Acrylate monomers; P-benzoquinone, quinone type stabilizers such as
hydroquinone, hindered phenolic antioxidants such as butylhydroxyl toluene, inorganic and
organic fillers, dyes, pigments, thixotropic agents, antifoaming agents A leveling agent, a
thickener, a viscosity reducing agent such as a high boiling point solvent, and other various
additives can be blended.
[0053]
As the adhesive of the combination (A) which can be used in the present invention,
benzophenone, benzoyl isopropyl ether, benzyl, benzyl for the purpose of imparting ultraviolet
curing property to the radical polymerizable monomer in addition to the above-mentioned
adhesive A photopolymerization initiator such as dimethyl ketal can be added to impart
ultraviolet curability.
[0054]
Furthermore, when an acidic phosphoric acid compound such as di-n-butyl phosphoric acid or 2(meth) acroxyethyl phosphate giving extremely fast curing is used as a curing accelerator for
reactive silicon group, the reactive silicon group is Even after curing, if such an acid remains, it
acts as a depolymerization catalyst for the polymer, which may extremely reduce the heat aging
property, so it has a function to gradually react with the acid to neutralize it. It is recommended
to add an inorganic filler such as calcium oxide, calcium carbonate or magnesium oxide, or an
epoxy compound such as bisphenol A epoxy or bisphenol F epoxy.
Furthermore, an adhesion imparting agent such as epoxysilane or aminosilane can be contained.
[0055]
Two-component rapid curing comprising (b) a combination (B) of a compound having one or
more radically polymerizable reactive groups in the molecule and a compound having one or
more isocyanate groups in the molecule, which can be used in the present invention Specific
examples of the compound having one or more radically polymerizable reactive groups in the
molecule used for the elastic adhesive include, in combination (A), one or more radically
polymerizable reactive groups in the molecule to be used. The same kind of compound as the
compound can be used.
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[0056]
Examples of the compound having one or more isocyanate groups in the molecule which is the
other main component of the combination (B) include tolylene diisocyanate, MDI, crude MDI,
Desmodur R [Bayer A.1. G.
(Trade name of a compound having an NCO group, tris (isocyanatophenylmethane)) desmodur RF
[Bayer A. G.
Company trade names of compounds having an NCO group, tris (isocyanatophenyl)
thiophosphate], HDI trimers, IPDI trimers, HDI burettes and the like.
[0057]
Furthermore, urethane prepolymers containing terminal isocyanate groups obtained by reacting
an isocyanate and a polyol can also be included in this category.
[0058]
These isocyanate compounds may be used alone or in combination of two or more.
Furthermore, depending on the case, you may use together polymerizable monomers, such as
(meth) acrylate.
[0059]
The adhesive of the combination (B) used in the present invention is a combination of a (meth)
acrylate monomer and / or a methacrylate oligomer and an isocyanate compound, which are fastcuring, tough and flexible. There is a defect improved two-pack rapid curing elastic adhesive
leaving parts.
[0060]
That is, the adhesive (A) solution of the combination (B) of the present invention contains the
isocyanate compound and the polymerization accelerator of the radical polymerizable monomer
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as essential components, and the B solution has radical polymerization with the radical
polymerizable monomer. A monomer polymerization initiator, an isocyanate compound curing
agent and a curing accelerator are contained as essential components.
[0061]
The polymerization accelerator of the above-mentioned radical polymerizable monomer and the
polymerization initiator may be contained in either one of the solution A or the solution B, and
the polymerization initiator of the monomer is added to the solution A contrary to the above
configuration. And B can also contain a polymerization accelerator.
[0062]
The radical polymerizable monomer can also be contained in the solution A as it is contained in
the solution B.
In this case, the types and combinations of radically polymerizable monomers used in the
solutions A and B may be the same or different from each other.
[0063]
Furthermore, the liquid A contains an isocyanate compound, a radical polymerizable monomer,
and a polymerization initiator of the radical polymerizable monomer as essential components,
and the liquid B promotes the polymerization of the curing agent of the isocyanate compound
and the radical polymerizable monomer. An agent may be contained as an essential component.
[0064]
Also in this configuration, the polymerization accelerator of the radically polymerizable monomer
and the polymerization initiator may be contained in either one of the solution A or the solution
B. The initiator can also be added to the solution B containing a polymerization accelerator.
[0065]
Moreover, it is also possible to make all the components except for the curing agent of the
remaining isocyanate compound be contained in the solution A, with only the polymerization
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15
accelerator of the radically polymerizable monomer as the essential component of the solution B.
Liquid B can also be used as a honeymoon-type adhesive, using it as a hardening acceleration
primer.
[0066]
There is no particular limitation on the mixing ratio of solution A and solution B, and any mixing
ratio can be used as long as the effects of the present invention can be achieved.
[0067]
As the adhesive of the combination (B) which can be used in the present invention, additives
corresponding to various purposes can be used similarly to the adhesive of the combination (A).
Furthermore, it is also possible to add a photopolymerization initiator to impart ultraviolet
curability as in the case of the adhesive of the combination (A).
[0068]
As a curing agent of the isocyanate compound used for the combination (B) of the present
invention, a compound having one or more hydroxyl groups in the molecule can be used.
Examples of this include ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol,
low molecular weight polyols such as trimethylolpropane, polyether polyols such as polyethylene
glycol, polyoxypropylene glycol and polytetramethylene ether glycol, and poly There are
polyester polyols such as caprolactone, polymethyl valerolactone, and polyester produced by the
reaction of a diol and a dibasic acid, castor oil, liquid polybutadiene of terminal hydroxyl group,
polycarbonate diol, acrylic polyol, epoxy resin and the like.
[0069]
As a polymerization accelerator and a polymerization initiator of a compound having one or more
radically polymerizable groups in the molecule, used in the combination (B) used in the present
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invention, used in the case of the combination (A) You can use the same thing as
[0070]
As a curing accelerator for the isocyanate compound of the adhesive of the combination (B) used
in the present invention, compounds already used in the polymerization of urethane can be used.
[0071]
Examples of curing accelerators for isocyanates include known accelerators such as tertiary
amines such as triethylenediamine, organic tin compounds such as dibutyltin dilaurate, and
organic lead compounds such as lead stearate.
These promoters can also be used alone or in combination.
[0072]
As an adhesive which can be used in the present invention, particularly as a two-component
rapid curing elastic adhesive, a modified silicone type as a substance to be combined with a
(meth) acrylate compound [a compound having one or more radically polymerizable groups in
the molecule] The use of the compound makes it possible to achieve the object of the present
invention sufficiently since the storage stability is excellent and the moisture in the air does not
cause skin soaking and the handling becomes easy.
[0073]
The application of the adhesive may be performed on either or both sides of the adherend as in
the case of the rubber contact adhesive.
[0074]
In the method of assembling a speaker according to the present invention, sufficient adhesion
performance can be exhibited whether double-sided coating or single-sided coating is performed.
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The method of applying the adhesive is also not particularly limited, and known means such as
hand, spatula, roll coat, spray and the like may be used.
Heating can also be performed as needed to accelerate curing.
[0075]
In the method of assembling the speaker according to the present invention, the use of the twocomponent rapid curing elastic adhesive deteriorates the working environment due to the
volatilization of the solvent, which is a major problem of the solvent type rubber adhesive, earth
resources Help to solve the problem of wasting the
[0076]
Furthermore, in the adhesion of the field section, the conventional acrylic two-component
adhesive has the disadvantage that it is too hard to cause cracking of the ferrite which is the
adherend, but in the method of the present invention, low temperature (- It becomes possible to
obtain a durable good adhesive without cracking of the ferrite even if repeated thermal shocks
between 40 ° C. and high temperature (80 ° C.) are applied.
[0077]
EXAMPLES The present invention will be described by way of examples.
In the following examples, all parts and percentages are indicated on a weight basis unless
otherwise noted.
[0078]
The present invention relates to a two-component rapid curing elastic adhesive, and since two
types of liquid compositions are required, the following names are given to the two components
for convenience of explanation.
In the adhesive used in the present invention, (a) a combination of a compound having one or
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more radically polymerizable reactive groups in the molecule and a compound having one or
more reactive silicon groups in the molecule (A) A liquid type quick curing elastic adhesive,
wherein a liquid composition containing a compound having one or more radically polymerizable
reactive groups in the molecule is designated as (a-A) liquid, and one or more reactive silicon in
the molecule The following description will be made with a liquid composition containing a
compound having a group as the liquid (a-B).
Similarly, a two-component rapid curing elastic adhesive comprising a combination (B) is a liquid
composition containing one or more radically polymerizable compounds in the molecule as the
(b-A) solution, and one or more in the molecule. The following explanation is given for a
composition containing a compound having an isocyanate group as the liquid (b-B).
[0079]
Preparation Example 1 Preparation of Solution (a-A) 50 parts of dicyclopentenyl methacrylate,
50 parts of 2-hydroxypropyl methacrylate, 0.05 parts of vanadium acetylacetonate, 0.5 parts of
hydroquinone, 2 parts of 2-methacroxyethyl phosphate The solution was stirred using a lab
stirrer and dissolved and mixed to prepare solution (a-A).
[0080]
(A-B) Preparation of solution 100 parts of modified silicone S-303 (trade name of polymer
compound having reactive silicon, manufactured by Kanegafuchi Chemical Industry Co., Ltd.), 20
parts of dicyclopentenyl methacrylate, cumene hydroperoxide Solution (a-B) was prepared by
stirring and mixing 2 parts with a lab stirrer.
[0081]
The mixing ratio of the (a-A) liquid and the (a-B) liquid was 1: 1 (weight ratio) to obtain a twocomponent rapid curing elastic adhesive.
[0082]
Preparation Example 2 (b-A) Liquid Preparation 50 parts of dicyclopentenyl oxyethyl
methacrylate, 50 parts of polyoxypolopirenediol (molecular weight 500), 5 parts of
ethylenethiourea, 3 parts of dibutyltin dilaurate are stirred using a lab stirrer The mixture was
dissolved and mixed to prepare solution (b-A).
[0083]
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Preparation of (b-B) solution 50 parts of dicyclopentenyl methacrylate, 2 parts of cumene
hydroperoxide, 50 parts of crude MDI, 5 parts of molecular sieve powder are stirred using a lab
stirrer, dissolved and mixed, (b-B ) Solution was prepared.
[0084]
The mixing ratio of the (b-A) solution and the (b-B) solution was 1: 1 (weight ratio) to prepare a
two-component rapid curing elastic adhesive.
[0085]
Preparation Example 3 Preparation of Solution (a-A) 50 parts of dicyclopentenyl methacrylate,
50 parts of 2-hydroxypropyl methacrylate, 0.5 parts of dibutyltin diacetyl acetate and 1 part of
γ-aminopropyltriethoxysilane, as a lab stirrer The solution (a-A) was prepared by stirring and
mixing.
[0086]
Preparation of (a-B) solution It prepared similarly to preparation of the (a-B) solution of Example
1.
The mixing ratio of the (a-A) liquid and the (a-B) liquid was 1: 1 (weight ratio) to prepare a twocomponent rapid curing elastic adhesive.
[0087]
Preparation Example 4
[0088]
Preparation of solution (b-A) 50 parts of dicyclopentenyl methacrylate, 50 parts of
polyoxypropylene triol (molecular weight 1500), 5 parts of ethylenethiourea, 3 parts of
dibutyltin malate by stirring with a lab stirrer (b-A) ) Solution was prepared.
[0089]
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20
Preparation of solution (b-B) 50 parts of isobornyl methacrylate, 50 parts of a 4: 1 reaction
product of MDI and polytetramethylene ether glycol (molecular weight 1000), 2 parts of cumene
hydroperoxide by stirring with a lab stirrer Solution (b-B) was prepared.
The mixing ratio of the (b-A) liquid and the (b-B) liquid was 1: 1 (weight ratio) to prepare a twocomponent rapid curing elastic adhesive.
[0090]
Preparation Example 5 (a-A) Preparation of solution 50 parts of dicyclopentenyl oxyethyl
acrylate, 50 parts of hydroxyl acrylate, 1 part of dibutyltin diacetyl acetate, 5 parts of benzyl
dimethyl ketal, 5 parts of ethylenethiourea with a lab stirrer The solution (a-A) was prepared by
[0091]
(A-B) Preparation of solution 100 parts of modified silicone SAT-200 (trade name of a compound
having one or more reactive silicon groups in the molecule, manufactured by Kanegafuchi
Chemical Industry Co., Ltd.) 20 parts of iribornyl acrylate Solution (a-B) was prepared by stirring
and mixing 3 parts of cumene hydroperoxide and 5 parts of benzyldimethyl ketal with a lab
stirrer.
The mixing ratio of the (a-A) liquid and the (a-B) liquid was 1: 1 (weight ratio) to prepare a twocomponent rapid curing elastic adhesive.
[0092]
Example 1 (Joining of Joints f and g) The joint f between the top plate 8 and the ferrite magnet 9
shown in FIG. 1 using the two-component rapid curing elastic adhesive obtained by Preparation
Examples 1 to 4 And a joint g between the ferrite magnet 9 and the bottom plate 10 was
performed.
[0093]
That is, when the two-component rapid curing elastic adhesive composition obtained in each
preparation example is applied onto the top plate 8 and the bottom plate 10 having a diameter of
120 mm, respectively, the ferrite magnet 9 is immediately superposed and left for 5 minutes, The
adhesion is completed, and the initial adhesive strength which can be transferred to the next
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process is shown, and the adhesion of the top plate 8 to the ferrite magnet 9 and the adhesion of
the bottom plate 10 to the ferrite magnet 9 are completed.
[0094]
The joint is allowed to stand and aged at 20 ° C. for 1 day, and then subjected to 5 cycles of cold
heat repeating test at −40 ° C. for 2 hours and then at 120 ° C. for 2 hours to determine
presence or absence of generation of ferrite cracks. I observed it.
As a result, no crack was observed at all in any combination of joints.
[0095]
Moreover, when the same joint after leaving and curing at 20 ° C. for 1 day was repeatedly
dropped 20 times on a concrete surface from a height of 1 m, no joints were completely broken
at all. .
[0096]
Example 2 (Joining of Joint a) Bonding of a joint a between the cone edge 3 and the edge of the
frame 1 in FIG. The
Each adhesive composition is thinly coated on the edge of frame 1 on one side, and the cone
edge 3 is immediately superposed and left for 5 minutes to develop an initial adhesive strength
which can be transferred to the next step, 20 After leaving and curing at 1 ° C. for 1 hour, the
corn paper was pulled, and the corn paper was broken, and good adhesion strength was obtained
even with single-sided coating.
[0097]
Example 3 (Joining of Joint b) Using the two-component rapid curing elastic adhesive obtained in
Preparation Example 5, the joint b between the corn paper 2 and the lead wire was joined.
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The adhesive composition is coated on corn paper, and the lead wire is immediately superposed,
and irradiated with ultraviolet light for 10 seconds with an ultraviolet irradiation machine, the
protruding part of the adhesive is cured and the lead wire is fixed, and the next step It became
possible to move.
When the lead wire was pulled after one hour, the place where the ultraviolet light was not
applied was also cured, and the corn paper was broken.
When ultraviolet irradiation was not performed, when left to stand for 5 minutes, fixing was
completed and it was possible to move to the next step.
Also in this case, when the lead wire was pulled after one hour, the corn paper was broken.
[0098]
Example 4 (Joining of Joint c) The joint c between the caps 7 of FIG. 1 was joined using the twocomponent rapid curing elastic adhesive composition prepared in Preparation Examples 1 to 5.
When each adhesive composition is applied to corn paper 2 and the dust cap 7 is immediately
superposed and left for 5 minutes, the initial adhesion can be completed with any adhesive
composition and can be transferred to the next step. It showed strength and became handleable.
After curing the bonded product at 20 ° C. for 1 hour, when the dust cap 7 was pulled, the corn
paper 2 was broken in any adhesive composition.
[0099]
Example 5 (Joining of Joint d) The joint d between the damper 6 of FIG. 1 and the frame 1 is
joined using the two-component rapid curing elastic adhesive composition prepared in
Preparation Examples 1 to 5 The
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When each adhesive composition is applied to a frame and the damper 6 is immediately placed
on top of each other for 5 minutes, fixing is completed regardless of which adhesive composition
is used, and an initial stage can be transferred to the next step It shows adhesive strength and
can be handled.
After curing this bonded product at 20 ° C. for 1 hour, the damper 6 was pulled and the damper
was broken.
[0100]
Example 6 (joining of joint portion e) Three-point joining between the damper 6, the voice coil 5
and the cone paper 2 of FIG. 1 using the two-component rapid curing elastic adhesive
composition prepared in Examples 1 to 5 Bonding of part e was performed.
Each adhesive composition was applied to the contact portion between the damper 6 and the
voice coil 5 using a thin pipe, and the cone paper 2 was immediately superposed.
When it was left to stand for 5 minutes, fixing was completed regardless of which adhesive
composition was used, and it showed an initial adhesive strength which could be transferred to
the next step, and could be handled.
After curing this bonded product at 20 ° C. for 1 hour, the damper 6 was pulled, and the
damper 6 was broken.
[0101]
Comparative Example 1 (Joining of Joints g and f) Using a commercially available two-component
acrylic adhesive [Cemedine Co., Ltd., trade name Cemedine Y400], the same ferrite magnet 120
with a diameter of 120 mm as in Example 1 and Bonding of the joint f between the top plate 8
and the joint g between the bottom plate 10 and the ferrite magnet 9 was performed.
[0102]
Subsequently, when the bonded product which was left to stand and aged at 20 ° C. for 1 day
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was subjected to the same cold-heat repeated test as in Example 1, cracking occurred in the
ferrite.
[0103]
Comparative Example 2 (Joining of Joint a) Joining of joint a is performed in the same manner as
in Example 2 using a commercially available chloroprene rubber adhesive [Semedine Co., Ltd.,
trade name Cemedine CS 4503] for speaker assembly. The
Thinly apply Cemedine CS4503 to the edge of Frame 1, and after taking 10 minutes open time,
overlay cone edge 3 and compress for 5 seconds, and immediately pull corn paper 2. As it is
coated on one side, practical adhesion It did not reach strength.
When the corn paper 2 was pulled after 1 hour as in Example 2, the corn paper 2 was peeled off.
[0104]
Immediately after thinly applying the above chloroprene rubber adhesive [Cemedine CS4503
(trade name) made by Cemedine Co., Ltd.] to the edge of the frame 1 and overlaying the cone
edge 3, the evaporation of the solvent inside is slow and the curing is slow Therefore, even after
10 minutes, the initial practical strength was not reached.
[0105]
Furthermore, since the above-mentioned chloroprene rubber adhesive [Cemedine Co., Ltd.
product name: Cemedine CS4503] is a solvent type adhesive, a large amount of solvent is
volatilized in the air to solidify the adhesive, and the working environment It included the above
problems.
[0106]
Comparative Example 3 (Joining of Joints b to e) Using a commercially available chloroprene
rubber adhesive (Semedain Co., Ltd., trade name Cemedine CS4503) for speaker assembly,
bonding is performed in the same manner as in Examples 3 to 6 Bonding of parts b to e was
performed.
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Since the above-mentioned chloroprene rubber adhesive (made by Cemedine Co., Ltd., trade
name Cemedine CS4503) is a solvent type adhesive, a large amount of solvent is volatilized in the
air in order to solidify the adhesive, and in the working environment Problems included.
[0107]
Moreover, in the case of single-sided coating, a sufficient bonded product could not be obtained
with the above-mentioned chloroprene rubber-based adhesive (Cemedain Co., Ltd. product name:
Cemedine CS4503).
Furthermore, since the above-mentioned chloroprene rubber-based adhesive (CEMEDAINE CO.,
LTD., Trade name Cemedine CS4503) is a solvent type adhesive, the solvent volatilizes when the
adherend is superposed immediately after the application of the adhesive. There is a drawback
that it takes time to develop adhesion.
[0108]
As described above, according to the present invention, unlike the conventional solvent-based
rubber-based adhesive, a solvent-free two-component reaction-based adhesive is used, so that it
is safe in terms of hygiene and fire, Since the adhesive used is a quick curing type and can be
fixed immediately, the bonding method is simple and the bonding operation is easy, and unlike
the water-based contact type (water emulsion type) adhesive, the bonding portion is not limited,
and Adhesives can bond any joints, and do not require heating, except for certain applications
because they cure at room temperature, and because the cured physical properties have
elasticity so that cracking of the ferrite magnet does not occur, Great effects can be achieved.
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