JP4652277B2 - Assembling method of moisture-curing adhesive composition and speaker - Google Patents

Description

The present invention relates to a moisture curable adhesive composition and a method for assembling a speaker using the same.

As shown in FIG. 1, the speaker used in the audio equipment is composed of members such as 1 bottom plate, 2 magnets, 3 top plates, 4 frames, 6 cones, 8 voice coils, 9 dampers, 10 dust caps, These members are assembled to the speaker by being appropriately joined with an adhesive at the joint 10 or the like.

Conventionally, a chloroprene rubber adhesive has been widely used as an adhesive used for joining the joints 13 and the like. However, this chloroprene rubber adhesive has a high volatility such as toluene, that is, an inflammable. Since it is a solvent-type adhesive containing a low-point solvent, it exerts adhesive force only by volatilization of the solvent, so it takes a long time to obtain sufficient adhesive strength (fixing time is long). Since a large amount of solvent volatilized, there were problems in air pollution and worker health.

In order to solve these problems, there are proposals such as those using hot melt adhesives (Patent Document 1) and those using two-component acrylic adhesives (Patent Document 2).
JP-A-53-133301 Japanese Examined Patent Publication No.59-042519

However, those using hot melt adhesives require special melting and coating equipment, which causes workability problems, and those using two-component acrylic adhesives require two-component mixing operations. Therefore, there was a drawback of managing the mixing.

Furthermore, the one using a conventional moisture-curing adhesive (Patent Document 3) has an appropriate viscosity to improve the workability by containing an appropriate amount of solvent to reduce the viscosity, and the volatilization of the solvent. The initial curability is excellent, but it is necessary to pay particular attention to the volatilization of a solvent having a low flash point such as toluene, and there is a drawback that air pollution and indoor work environment deteriorate.
Japanese Examined Patent Publication No. 7-103358

Thus, the conventional speaker assembly adhesives have their merits and demerits, and none of them is fully satisfactory.

As a result of intensive studies to solve the above problems, the present inventor obtained knowledge that a moisture-curing adhesive having a specific composition can achieve the object of the present invention. Invented.

That is, the present invention includes (1) 100 parts by mass of a polyether polymer represented by the general formula (A) having a hydrolyzable silicon functional group at the end,
Formula (A)




(In the formula, ^{R 1} is a monovalent hydrocarbon group having 1 to 12 carbon atoms, ^{R 2} is a monovalent hydrocarbon group having 1 to 6 carbon atoms, n is an integer from 0 to 2. )
(2) 1 to 50 parts by mass of an aromatic ether compound which is one or more members selected from the group consisting of dibenzyl ether, diphenyl ether and butyl phenyl ether;
A moisture curable adhesive composition comprising:
Furthermore, (3) 0.5 to 15 parts by mass of organosilane (4) 0.5 to 5 parts by mass of a silanol compound condensation catalyst ,
Containing
This moisture curable adhesive composition is a moisture curable adhesive composition for speakers which is used for bonding dampers made of fibers or porous materials, and the component (1) is a methyldimethoxysilyl group-terminated polypropylene. One of the group consisting of oxide, component (2) is dibenzyl ether, and component (3) is vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane As described above, the component (4) is dibutyltin dilaurate, and the moisture-curable adhesive composition is used for bonding a damper made of cotton. The moisture-curable adhesive composition is used. This is a method of assembling a speaker.

The adhesive composition of the present invention prevents air pollution and deterioration of the working environment due to volatilization of the solvent contained in the adhesive composition, and is excellent in coating workability because it has a lower viscosity than conventional ones. In particular, since the penetrability into a fibrous material such as a damper of a speaker or a porous material is improved, a high adhesive force can be obtained at each joint portion.

And it becomes possible to assemble a speaker with high adhesive reliability and durability by applying the adhesive composition of the present invention as an adhesive to the joint portion of the speaker.

In the present invention, the polyether polymer represented by the general formula (A) having a hydrolyzable silicon functional group at the end has a main chain of —RO— (wherein R is a carbon atom having 2 to 4 carbon atoms). A polyether polymer having a group represented by the general formula (A) at least at one end of the main chain thereof is selected.
Formula (A)

(In the formula, ^{R 1} is a monovalent hydrocarbon group having 1 to 12 carbon atoms, ^{R 2} is a monovalent hydrocarbon group having 1 to 6 carbon atoms, n is an integer from 0 to 2. )

Examples of the polyether polymer include reaction products of an isocyanate-terminated polyether urethane prepolymer and γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-mercaptopropyltrimethoxysilane. It is done.

In the present invention, the specific polyether polymer contains a specific amount of one or more selected from the group consisting of an aromatic ether compound, an alcohol having 6 to 8 carbon atoms, and a paraffinic hydrocarbon solvent. Thus, it is possible to provide a moisture-curable adhesive composition that can be preferably applied to adhesion of a fibrous or porous material exemplified in speaker assembly.

In the present invention, the aromatic ether compound includes, for example, dibenzyl ether, diphenyl ether, butyl phenyl ether, etc. Among them, dibenzyl ether, butyl phenyl ether further reduces the viscosity of the moisture-curable adhesive composition. This is preferable because the penetrability into the shape and the porous material is improved.

Examples of the alcohol having 6 to 8 carbon atoms include 1-hexanol, 2-ethylhexanol, 2-methylcyclohexanol, 2-octanol, 2-heptyl alcohol and the like. Among these, 2-ethylhexanol, 2-methylcyclo Hexanol is preferred because it further reduces the viscosity of the moisture curable adhesive composition and improves the penetration into fibrous and porous materials.

In order to achieve the object of the present invention, among the aromatic ether compound and the alcohol having 6 to 8 carbon atoms, the aromatic ether compound is preferable, and in particular, dibenzyl ether effectively reduces the viscosity of the adhesive, Since the flash point is 61 ° C. or higher, the moisture-curable adhesive composition of the present invention can be handled stably against fire, and is specially designed based on the “Dangerous Goods Ship Transport and Storage Rules” and “Aeronautical Law”. It is still preferable because it can be packaged and transported without temperature control, and it is particularly preferable because of superior adhesive strength.

In the present invention, the mixing ratio of the component (1) and the component (2) is such that the total amount of the component (2) is 1.0 to 50 parts by mass, preferably 5 to 100 parts by mass of the component (1). 30 parts by mass. When the blending ratio of the component (2) is 1.0 part by mass or more, the viscosity of the moisture-curable adhesive composition is sufficiently low and the coating workability is good, and the penetration into the fibrous and porous materials is also good. If it is 50 parts by mass or less, the viscosity of the moisture curable adhesive composition will not be too low, and there will be no possibility that the coating operation cannot be performed stably.

In the adhesive composition used in the present invention, an organosilane represented by the general formula (B), which is a crosslinking agent and also serves as an adhesion imparting agent, can be used.
General formula (B)

Wherein R ³ and R ⁴ are each a monovalent hydrocarbon group having 1 to 4 carbon atoms, Y is a monovalent hydrocarbon group that may contain a substituent or a substituent atom, and a and b are each (It is an integer of 0-2, and the sum of a and b is 0-2.)

Examples of the organosilane represented by the general formula (B) in the present invention include dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, and phenyltrimethoxysilane. Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, vinyltris (β-methoxyethoxy) silane, aminomethyltriethoxysilane, N-β (aminoethyl) ) Aminomethyltrimethoxysilane, N-β (aminoethyl) methyltributoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopro Pyrmethyldiethoxysilane, γ-aminoisobutyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, {[N-β ( Aminoethyl)] N-β (aminoethyl)} γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane 3,4-epoxycyclohexylethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, etc. All I can get lost. These organosilanes may be used alone or in combination of two or more. Among these, N-β (aminoethyl) γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane are preferably selected because they have a high effect of imparting adhesiveness and are further rapidly cured.

The compounding ratio of the organosilane in the present invention is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (1). In order to effectively act as a crosslinking agent if it is 0.5 parts by mass or more, the moisture curable adhesive composition is fast-curing, and if it is 15 parts by mass or less, the effect of imparting adhesiveness is large, and further, it is fast-curing. is there.

In the present invention, as a condensation catalyst of a silanol compound, for example, metal salt of carboxylic acid such as organosilicon titanate, tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bisacetylacetate, dibutyltin oxide, Known silanol condensation catalysts such as organic tin oxides such as dioctyltin oxide and amino salts such as dibutylamine-2-ethylhexoate can be used.

The amount of the silanol compound condensation catalyst in the present invention is preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the component (1). In order to act as an effective condensation catalyst at 0.5 parts by mass or more, the moisture-curable adhesive composition is fast-curing, and at 5 parts by mass or less, it is further fast-curing.

In the adhesive composition of the present invention, in addition to the above-described components, fillers, plasticizers, colorants, anti-aging agents, ultraviolet absorbers, sagging inhibitors, etc. within a range that does not significantly impair the adhesive performance, etc. Can be blended.

Since the adhesive composition of the present invention has the specific composition described above, when the adhesive composition is applied to, for example, a portion to be joined between speaker members in the air, the adhesive composition (1) constituting the adhesive composition is used. -OH where the) (oR ²⁾ of the organosilane groups and the crosslinking agent (oR ⁴⁾ group generates an -OH group immediately undergo hydrolysis by moisture in the moisture and the adherend in the air, and the generated The groups immediately undergo a condensation reaction by the action of the condensation catalyst to form a three-dimensional network bond and cure.

At the same time, a part of the organosilane substituent and a part of the —OH group generated by reacting with moisture as described above exhibit a strong adhesion to an adherend such as metal or paper. Become.

In addition, the adhesive composition of the present invention is superior in coating workability because it has a lower viscosity than conventional ones, and particularly has good penetration into fibrous and porous materials such as speaker dampers. It becomes possible to obtain high adhesive strength at the part. Furthermore, since it does not contain a solvent with a low flash point, air pollution and indoor work environment will not deteriorate, so the speaker assembling method of the present invention is extremely efficient and assembles a speaker with high adhesive reliability. Demonstrate the effect that you can.

(Example 1, Reference Example 1, Comparative Examples 1 to 4)
The present invention will be described in more detail based on examples and comparative examples. In addition, the unit of the usage-amount of each use material is shown by a mass part. The following abbreviations are used for each material used.

(Materials used)
Polyether polymer: Methyldimethoxysilyl group-terminated polypropylene oxide (Kanebuchi Chemical Industry Co., Ltd., trade name: Silyl SAT200)
Aromatic ether compound: Dibenzyl ether (commercially available flash point 135 ° C)
C6-C8 alcohol: 2-ethylhexanol (commercially available flash point 79 ° C)
Propylene glycol: molecular weight 3000 (commercially available flash point 61 ° C or higher)
Toluene: Commercially available organosilane: Vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KMB1003 and N-β (aminoethyl) γ-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KMB603) and γ-glycid Xylpropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM403)
Filler: Fatty acid-treated calcium carbonate (Shiraishi Kogyo Co., Ltd. white gloss CCR)
Silanol compound condensation catalyst: Dibutyltin dilaurate (commercially available)
SPCC: Commercial product, SPCC-D blasted steel sheet Cotton: Commercial product, cotton canvas, cellulose

The physical properties were measured as follows.

[Cotton / SPCC peel strength]
In accordance with JIS K-6854, an adhesive was applied to a test piece (70 mm × 25 mm × 0.3 mm, SPCC-D sandblasting), and immediately the other test piece (JISL-3102 ordinary cotton canvas No. 1209 No. 9: 70 mm × 25 mm × 0.7 mm, non-treated) were laminated and bonded together, and then cured for 7 days in an environment of a temperature of 23 ° C. and a humidity of 50% was used as a sample. The peel strength (180 ° peel strength, unit: kN / m) of the sample was measured at a tensile speed of 50 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50%.

[viscosity]
In accordance with JIS K-7117, 500 ml of the adhesive was taken and left in a constant temperature bath at 25 ° C. for 24 hours to prepare a sample. The viscosity was measured continuously at 25 ° C. with a single cylindrical rotational viscometer for 2 minutes.

[Speaker damper adhesive strength]
The test was performed at 23 ° C. and 50% humidity. The speaker shown in FIG. 1 was assembled. Cotton was used as a material for the damper 9 (outer diameter 60 mm × inner diameter 20 mm × thickness 0.25 mm). These materials were impregnated with a phenol-based thermosetting resin composition and heat-molded into the shape of the damper 9 shown in FIG. The material of the frame 4 was iron whose surface was chromated. As the three-point portion of the speaker, the obtained damper 9 and the voice coil 8 (made of aluminum) wound with the paper tape 11 and the coil 12 shown in FIG. It was bonded via a portion indicated by a mark). Further, as the speaker damper portion, the damper 9 and the frame 5 are similarly bonded with the adhesive, thereby producing the speaker shown in FIG. 3 (the paper tape 11 and the adhesive composition 13 are not shown) and measuring the strength. A sample was prepared. As an adhesion method, an adhesive was applied to each joint portion (indicated by a circle in FIG. 2), and the adhesive was cured for 7 days in an environment of a temperature of 23 ° C. and a humidity of 50%. . The speaker damper part adhesive strength (unit: kg) was measured in an environment of a temperature of 23 ° C. and a humidity of 50%. A voice coil pulling jig 15 was inserted into the center of the voice coil 8, and the peripheral edge 5 of the frame was fixed to the peripheral edge of the frame fixing jig 14 (the location indicated by the circle in FIG. 3). The voice coil pulling jig 15 was pulled in the direction of the arrow at a pulling speed of 100 mm / min, and the adhesive strength of the speaker damper portion was measured.

[Adhesive odor]
The test was performed at 23 ° C. and 50% humidity. 100 g of the adhesive was taken into a 500 ml polyethylene container, and the odor was confirmed.

The materials used were mixed in the composition of Table 1 to prepare an adhesive composition, and the measurement results are also shown in Table 1.

The adhesive composition of the present invention can prevent air pollution and work environment deterioration due to volatilization of the solvent contained, and is excellent in coating workability due to its low viscosity, and also has good penetration into fibrous or porous materials. For example, it is possible to assemble a speaker with high adhesion reliability and durability because it is possible to obtain a high adhesive force at a joint portion such as a damper portion of the speaker. The nature is extremely large.

The speaker assembling method of the present invention uses the adhesive composition having the characteristics described above, so that it is possible to assemble a speaker having excellent adhesive workability and high adhesion reliability and durability. The availability of is extremely high.

Sectional drawing of a speaker. Sectional drawing which shows the structure of a speaker 3 point | piece part. The schematic diagram which shows the measuring method of the adhesive strength of the speaker damper part containing a speaker 3 point | piece part.

Explanation of symbols

1 Bottom plate 2 Magnet 3 Top plate 4 Frame 5 Frame peripheral edge 6 Cone 7 Cone peripheral edge (cone edge)
8 Voice coil 9 Damper 10 Dust cap 11 Paper tape 12 Coil 13 Joint and adhesive composition 14 Frame fixing jig 15 Voice coil tension jig

Claims (5)

(1) 100 parts by mass of a polyether polymer represented by the general formula (A) having a hydrolyzable silicon functional group at its end;
Formula (A)




(In the formula, ^{R 1} is a monovalent hydrocarbon group having 1 to 12 carbon atoms, ^{R 2} is a monovalent hydrocarbon group having 1 to 6 carbon atoms, n is an integer from 0 to 2. )
(2) 1 to 50 parts by mass of an aromatic ether compound which is one or more members selected from the group consisting of dibenzyl ether, diphenyl ether and butyl phenyl ether;
A moisture-curable adhesive composition comprising: Furthermore, (3) 0.5 to 15 parts by mass of organosilane (4) 0.5 to 5 parts by mass of a silanol compound condensation catalyst ,
The moisture-curable adhesive composition according to claim 1, comprising: The moisture-curable adhesive composition for speakers according to claim 1 or 2, wherein the use is for bonding a damper made of a fiber or a porous material. Component (1) is methyldimethoxysilyl group-terminated polypropylene oxide, Component (2) is dibenzyl ether, Component (3) is vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-glycidoxypropyl The moisture-curing adhesive composition according to claim 2 , wherein one or more members selected from the group consisting of methyldimethoxysilane, the component (4) is dibutyltin dilaurate, and the use is for use in bonding a damper made of cotton. A method for assembling a speaker, wherein the moisture-curable adhesive composition according to claim 1 is used.