JP5388121B2 - Speaker assembly method - Google Patents

Description

  The present invention relates to a method for assembling a speaker using an adhesive, and more particularly to a method for assembling a speaker in which a bonded member provides a speaker having high adhesive strength at high temperatures.

  As shown in FIG. 1, the speaker used in the audio equipment includes a frame 1, cone paper 2, cone edge 3, gasket 4, voice coil 5, damper 6, dust cap 7, top plate 8, ferrite magnet 9, and bottom. Each of the members of the plate 10 is configured, and these members are joined to the speaker by appropriately joining them with an adhesive at the joints a, b, c, d, e, f, and g.

  Various adhesives are used as the adhesive, and Patent Document 1 proposes an adhesive composition for speaker assembly containing a polyether polymer having a crosslinkable silicon group. This adhesive composition has the advantages that it does not require the use of a solvent, can be used as a one-component composition that does not require a two-component mixing operation, and can be bonded in a short time at room temperature.

  Patent Document 2 proposes a speaker assembling method in which a moisture-curing adhesive is applied to a speaker member and bonded after the tack is developed. This method uses a moisture curable adhesive as a contact adhesive, and has an advantage that a member can be fixed directly after the tack is developed and a temporary presser is not required.

  In paragraph 0015 of Patent Document 2, a polyether polymer having a crosslinkable silicon group is disclosed as a moisture curable adhesive to be used. In particular, in paragraph 0016, an oxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group (acrylic acid ester and / or methacrylic acid ester are (meth) acrylic acid esters) It is disclosed that an excellent product can be obtained by using a curable composition comprising

  Patent Document 3 proposes a speaker assembling method using a two-pack type fast-curing adhesive using a radical polymerizable monomer such as an acrylate ester in addition to a polymer having a crosslinkable silicon group. When this method is used, the member can be fixed directly after the tack is developed, and there is an advantage that the inner part can be cured in a short time in addition to the advantage that a temporary holding is not required.

  On the other hand, heat resistance is required for adhesives for speakers. This is because the temperature of the voice coil may rise to 100 ° C. or higher by continuous operation. In particular, the temperature tends to rise in a vehicle-mounted speaker mounted on an automobile. Therefore, it is desirable that the adhesive used for assembling the speaker has an adhesive strength in a high temperature atmosphere, particularly a peel strength (hot peel strength) in a high temperature atmosphere.

  Furthermore, as a matter of course, the speaker is required to have good sound quality. The adhesive used affects the sound quality of the speaker, and the sound quality improves as the hardness of the cured adhesive increases. Therefore, it is desirable that the adhesive used for assembling the speaker has a large hardness. Usually, as the hardness increases, the loss tangent (tan δ) decreases.

Japanese Patent Application Laid-Open No. 64-045486 Japanese Patent Laid-Open No. 04-220899 JP 07-135700 A

  It is an object of the present invention to apply heat resistance, particularly hot, in a speaker assembly method in which an adhesive composition containing a polymer having a crosslinkable silicon group is applied to a joint portion of each member constituting a speaker and the members are bonded together. An object of the present invention is to provide a speaker assembly method capable of manufacturing a speaker having improved peel strength.

  Another object of the present invention is to provide a method for assembling a speaker in which an adhesive composition containing a polymer having a crosslinkable silicon group is applied to a joint portion of each member constituting the speaker and the members are bonded together. An object of the present invention is to provide a method for assembling a loudspeaker capable of producing a loudspeaker having a cured product having a high hardness and improved sound quality.

  In paragraph 0054 of Patent Document 3, an acidic phosphoric acid compound can be used as a curing catalyst (curing accelerator) for a polymer having a crosslinkable silicon group. In this case, it is recommended to add calcium oxide as a neutralizing agent. ing.

  Even when the present inventors use a curing catalyst other than an acidic phosphoric acid compound as a curing catalyst for a polymer having a crosslinkable silicon group, a polymer composition having a crosslinkable silicon group to which calcium oxide has been added. As a result, the present inventors have found that a speaker having a high hardness can be produced by using a cured adhesive which is expected to have a high hot peel strength and excellent sound quality at the joint, and thus the present invention has been achieved. That is, the present invention relates to the following speaker assembling method and speaker assembling adhesive composition.

  (1) Other than organic polymers having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture, calcium oxide and acidic phosphate compounds A method for assembling a speaker, wherein a curable composition containing a curing catalyst is applied to a joint portion of each member constituting the speaker and the members are bonded together.

（式中、Ｒ^１は、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基またはＲ^１ _３ＳｉＯ−（Ｒ^１は、前記と同じ）で示されるトリオルガノシロキシ基を示し、Ｒ^１が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｘは水酸基または加水分解性基を示し、Ｘが２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。ａは０、１、２または３を、ｂは０、１または２を、それぞれ示す。またｎ個の式（２）：

におけるｂは同一である必要はない。ｎは０〜１９の整数を示す。但し、ａ＋（ｂの和）≧１を満足するものとする。） (2) The speaker assembling method according to (1), wherein the crosslinkable silicon group is a group represented by the following formula (1).

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ¹ ₃ SiO— (R ¹ is the same as above), and when two or more R ¹ are present, they may be the same or different, and X is a hydroxyl group or a hydrolysis. When two or more X are present, they may be the same or different, a is 0, 1, 2 or 3, b is 0, 1 or 2; And n equations (2):

B in need not be the same. n shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied. )

（式中、Ｒ^１、Ｘは前記におなじ、ａは１、２又は３の整数である。） (3) The method for assembling a speaker according to (2), wherein the crosslinkable silicon group is a group represented by the following formula (3).

(Wherein R ¹ and X are the same as defined above, and a is an integer of 1, 2 or 3.)

  (4) The method for assembling a speaker according to (3), wherein a is 2 or 3 in the crosslinkable silicon group.

  (5) The method for assembling a speaker according to (4), wherein a is 3 in the crosslinkable silicon group.

  (6) The speaker assembling method according to any one of (1) to (5), wherein the hydrolyzable group in the crosslinkable silicon group is an alkoxy group.

  (7) The speaker assembling method according to (6), wherein the hydrolyzable group in the crosslinkable silicon group is a methoxy group.

  (8) The speaker assembly method according to any one of (1) to (7), wherein the organic polymer having a crosslinkable silicon group is an oxyalkylene polymer having a crosslinkable silicon group.

  (9) The speaker assembly method according to any one of (1) to (7), wherein the organic polymer having a crosslinkable silicon group is a (meth) acrylic acid ester polymer having a crosslinkable silicon group.

  (10) The organic polymer having a crosslinkable silicon group is a mixture of an oxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group (1) ) To (7).

  (11) The organic polymer having a crosslinkable silicon group is a polymer obtained by polymerizing a (meth) acrylate monomer in the presence of an oxyalkylene polymer having a crosslinkable silicon group. And (1) to (7).

  (12) The speaker assembly method according to any one of (1) to (11), wherein the calcium oxide is calcium oxide that has not been surface-treated.

  (13) The speaker assembling method according to any one of (1) to (12), wherein the curing catalyst other than the acidic phosphate compound is a tin-based compound.

  (14) An organic polymer having a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond with moisture, a curing catalyst other than calcium oxide and an acidic phosphate compound An adhesive composition for assembling speakers.

  When the speaker assembly method of the present invention is used, an organic polymer having a hydrolyzable group bonded to a silicon atom and having a crosslinkable silicon group that can be crosslinked by forming a siloxane bond with moisture is used. In addition to advantages such as that it can be used as a one-part composition that does not require the use of a solvent, does not require a two-component mixing operation, and can be bonded in a short time at room temperature, A speaker with improved sound quality can be manufactured.

It is a longitudinal cross-sectional view of the typical speaker containing the speaker assembled using the assembly method of this invention.

（式中、Ｒ^１は、炭素数１〜２０のアルキル基、炭素数３〜２０のシクロアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基またはＲ^１ _３ＳｉＯ−（Ｒ^１前期と同じ）で示されるトリオルガノシロキシ基を示し、Ｒ^１が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｘは水酸基または加水分解性基を示し、Ｘが２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。ａは０、１、２または３を、ｂは０、１または２を、それぞれ示す。またｎ個の式（２）：

におけるｂは同一である必要はない。ｎは０〜１９の整数を示す。但し、ａ＋（ｂの和）≧１を満足するものとする。）で表わされる基があげられる。 The crosslinkable silicon group of the organic polymer having a crosslinkable silicon group used in the present invention is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. As a representative example, the formula (1):

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ¹ ₃ SiO— (R ^{1 represents the} same as the previous period), and when two or more R ¹ are present, they may be the same or different, and X is a hydroxyl group or a hydrolyzable group. And when two or more X are present, they may be the same or different, a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. Also, n formulas (2):

B in need not be the same. n shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied. ).

  The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (sum of b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.

（式中、Ｒ^１，Ｘ，ａは前記と同じ）で表わされる架橋性珪素基が、入手が容易である点から好ましい。また、硬度が大きく、音質が向上したスピーカーを得るには、式（３）の架橋性珪素基においてａが３である場合が好ましい。 The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.
Formula (3):

A crosslinkable silicon group represented by the formula (wherein R ¹ , X and a are the same as described above) is preferable from the viewpoint of easy availability. In order to obtain a speaker having high hardness and improved sound quality, it is preferable that a is 3 in the crosslinkable silicon group of formula (3).

Specific examples of R ¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

  It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group, an amide group, and an aminooxy group are more preferable. An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

  In the case of the crosslinkable silicon group represented by the formula (3), a is preferably 2 or more in consideration of curability. Usually, when a is 3, compared with the case where a is 2, the curing rate is increased and the hardness of the cured product is increased, but the hot peel strength is decreased. However, in the present invention, even when a is 3, sufficient hot peel strength required for the joint portion of the speaker can be obtained, the hardness of the cured product is large, and the sound quality of the speaker is excellent.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups such as a trimethoxysilyl group and a triethoxysilyl group, dialkoxysilyl groups such as —Si (OR) ₃ , a methyldimethoxysilyl group, and a methyldiethoxysilyl group. Group, —SiR ¹ (OR) ₂ . Here, R is an alkyl group such as a methyl group or an ethyl group.

  Further, the crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group can be present in the main chain, the side chain, or both. It is preferable that a crosslinkable silicon group is present at the end of the molecular chain in view of excellent cured product properties such as tensile properties of the cured product.

  At least one crosslinkable silicon group may be present in one molecule of the polymer, preferably 1.1 to 5. When the number of crosslinkable silicon groups contained in the molecule is less than one, the curability is insufficient, and when the number is too large, the network structure becomes too dense, and good mechanical properties are not exhibited.

  The main chain skeleton of the organic polymer having a crosslinkable silicon group used in the present invention is not particularly limited, and those having various main chain skeletons can be used. Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene Copolymers of acrylonitrile and / or styrene, etc., and hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; adipic acid, terephthalic acid Polyester polymers such as condensation polymers of polybasic acids such as succinic acid and polyhydric alcohols such as bisphenol A, ethylene glycol and neopentyl glycol, and ring-opening polymers of lactones; by ring-opening polymerization of ε-caprolactam Nylon 6, Nylon 6 · 6 by condensation polymerization of hexamethylenediamine and adipic acid, Nylon 6 · 10 by condensation polymerization of hexamethylenediamine and sebacic acid, Nylon 11 by condensation polymerization of ε-aminoundecanoic acid, ε-aminolaurolactam Nylon 12 by ring-opening polymerization of the above, polyamide-based polymer such as copolymer nylon having two or more components among the above nylons; polyacrylic obtained by ion polymerization or radical polymerization of monomers such as ethyl acrylate and butyl acrylate Acid ester, ethyl acrylate, butyl acetate An acrylic acid ester-based polymer such as an acrylic acid ester copolymer of an acrylic acid ester such as a rate and vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc .; obtained by polymerizing a vinyl monomer in the organic polymer Examples include graft polymers; polysulfide polymers; polycarbonate polymers produced by condensation polymerization from bisphenol A and carbonyl chloride, diallyl phthalate polymers, and the like.

  Of the polymers having the main chain skeleton, polyester polymers, acrylate polymers, polyoxyalkylene polymers, hydrocarbon polymers, polycarbonate polymers and the like are preferable. In particular, it is easy to introduce a crosslinkable silicon group into the molecular chain end, is relatively low in viscosity and inexpensive, has a low glass transition temperature, and the resulting cured product has excellent cold resistance, heat resistance and weather resistance. Acrylic acid alkyl ester polymers that are excellent in properties and adhesiveness are preferred.

  Furthermore, since the mixture of the polyoxyalkylene polymer and the alkyl acrylate ester polymer has excellent mechanical strength of the cured product and excellent heat resistance and adhesion to the substrate, Especially suitable. When a mixture of an oxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group is used, (meth) acrylic acid is used with respect to 100 parts by weight of the oxyalkylene polymer. The ester polymer is preferably used in an amount of 10 to 200 parts by weight, more preferably 20 to 80 parts by weight.

  The organic polymer having a crosslinkable silicon group may be linear or branched, and preferably has a number average molecular weight of about 500 to 50,000, more preferably 1,000 to 30,000. As the molecular weight increases, the hot peel strength increases, but the hardness tends to decrease.

（式中、Ｒ^２は２価の有機基）
式（４）におけるＲ^２は、炭素数１〜１４の、さらには２〜４の、直鎖状もしくは分岐状アルキレン基が好ましい。式（４）で示される繰り返し単位の具体例としては、例えば、

等があげられる。ポリオキシアルキレン系重合体の主鎖骨格は、１種類だけの繰り返し単位からなってもよいし、２種類以上の繰り返し単位からなってもよい。特にオキシプロピレンを主成分とする重合体から成るのが好ましい。 Among the above polymers, the polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the formula (4).

(Wherein R ² is a divalent organic group)
R ² in Formula (4) is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the formula (4) include, for example,

Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, it is preferably made of a polymer mainly composed of oxypropylene.

  As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, for example, JP-A Nos. 61-197631, 61-215622, 61-215623, and 61-215623 can be used. Polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting an organoaluminum compound and a porphyrin as shown, for example, a double metal cyanide complex shown in JP-B-46-27250 and JP-B-59-15336 Examples of the polymerization method using a catalyst include, but are not limited to, a polymerization method. According to the polymerization method using an organic aluminum-porphyrin complex catalyst or the polymerization method using a double metal cyanide complex catalyst, the number average molecular weight is 6,000 or more, the Mw / Mn is 1.6 or less, the high molecular weight, and the molecular weight distribution is narrow. Coalescence can be obtained.

  The main chain skeleton of the polyoxyalkylenes may contain other components such as a urethane bond component. Examples of the urethane bond component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; and polyoxyalkylenes having a hydroxyl group. What can be obtained from this reaction can be mentioned.

  The introduction of a crosslinkable silicon group into an oxyalkylene polymer is reactive to this functional group in an oxyalkylene polymer having a functional group such as an unsaturated group, hydroxyl group, epoxy group or isocyanate group in the molecule. It can be performed by reacting a compound having a functional group having a crosslinkable silicon group. This method (hereinafter referred to as polymer reaction method) is also suitably used for polyester polymers, polyamide polymers, and polymers of unsaturated monomers obtained by living polymerization. This is because these polymers have a functional group such as a hydroxyl group at the end of the molecular chain, and therefore it is easy to introduce a crosslinkable silicon group at the end.

  As a specific example of the polymer reaction method, a hydrosilane or mercapto compound is produced by reacting an unsaturated group-containing oxyalkylene polymer with a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to form a crosslinkable silicon group. The method of obtaining the oxyalkylene type polymer which has can be mention | raise | lifted. The unsaturated group-containing oxyalkylene polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group, The contained oxyalkylene polymer can be obtained.

  Other specific examples of the polymer reaction method include a method of reacting an oxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or an oxyalkylene polymer having an isocyanate group at a terminal. And a method of reacting a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group. When an isocyanate compound is used, an oxyalkylene polymer having a crosslinkable silicon group can be easily obtained. The polymer reaction method can be applied to polymers other than oxyalkylene polymers.

  Specific examples of the oxyalkylene polymer having a crosslinkable silicon group include JP-B Nos. 45-36319 and 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. No. 57-164123, Japanese Patent Publication No. 3-2450, Japanese Patent Application Laid-Open No. 2005-213446, Japanese Patent Application No. 2005-306871, International Patent Publication No. WO 2007-040143, US Pat. Nos. 3,632,557, 4,345,053, 4 , 960, 844, and the like.

（式中、Ｒ^３は水素原子またはメチル基、Ｒ^４はアルキル基を示す）
式（５）におけるＲ^４はアルキル基であり、炭素数１〜３０のアルキル基が好ましい。Ｒ^４は直鎖状であってもよく、分岐状であってもよい。また、ハロゲン原子やフェニル基等を有する置換アルキル基でもよい。Ｒ^４の例としては、メチル基、エチル基、プロピル基、ｎ−ブチル基、ｔ−ブチル基、２−エチルヘキシル基、ラウリル基、トリデシル基、セチル基、ステアリル基、ベヘニル基等をあげることができる。 The (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group is essentially a polymer having a repeating unit represented by the formula (5).

(Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group)
R ⁴ in Formula (5) is an alkyl group, and an alkyl group having 1 to 30 carbon atoms is preferable. R ⁴ may be linear or branched. Moreover, the substituted alkyl group which has a halogen atom, a phenyl group, etc. may be sufficient. Examples of R ⁴ include methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, and behenyl group. it can.

  The molecular chain of the (meth) acrylic acid alkyl ester polymer consists essentially of the monomer unit of the formula (5), and the term “essentially” as used herein means that of the formula (5) present in the polymer. It means that the total of monomer units exceeds 50% by weight. The total of the monomer units of the formula (5) is preferably 70% by weight or more.

  Examples of monomer units other than formula (5) include acrylic acid such as acrylic acid and methacrylic acid; amide groups such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide, glycidyl acrylate, and glycidyl methacrylate. Monomers containing amino groups such as epoxy group such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene The monomer unit resulting from etc. is mention | raise | lifted.

（式中、Ｒ^３は前記に同じ、Ｒ^５は炭素数１〜５のアルキル基を示す）で表される（メタ）アクリル酸エステル単量体単位と、下記式（７）：

（式中、Ｒ^３は前記に同じ、Ｒ^６は炭素数６以上のアルキル基を示す）で表される（メタ）アクリル酸エステル単量体単位からなる共重合体が好ましい。 As described above, the (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group may be used in combination with an oxyalkylene polymer. In this case, in terms of high compatibility with the oxyalkylene polymer having a crosslinkable silicon group, the molecular chain having a crosslinkable silicon group has the following formula (6):

(Wherein R ³ is the same as above, R ⁵ represents an alkyl group having 1 to ⁵ carbon atoms) and a (meth) acrylate monomer unit represented by the following formula (7):

(Wherein R ³ is the same as described above, and R ⁶ represents an alkyl group having 6 or more carbon atoms). A copolymer comprising a (meth) acrylic acid ester monomer unit is preferred.

As R < ⁵ > of said Formula (6), C1-C5, such as a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group, etc., Preferably it is 1-4, More preferably, it is 1-2. Of the alkyl group. Incidentally, R ⁵ may be a kind, or may be a mixture of two or more.

R ^{6 in the} formula (7) is, for example, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group and the like having 6 or more carbon atoms, usually 7-30, preferably 8-20. Long chain alkyl groups. R ⁶ may be a single type or a mixture of two or more types. Moreover, the weight ratio of the monomer unit of the formula (6) and the monomer unit of the formula (7) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40.

  The (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group can usually be obtained by radical copolymerization of a (meth) acrylic acid alkyl ester and a (meth) acrylic acid alkyl ester having a crosslinkable silicon group. . Further, when an initiator having a crosslinkable silicon group or a chain transfer agent having a crosslinkable silicon group is used, the crosslinkable silicon group can be introduced into the molecular chain terminal.

  JP 2001-040037 A, JP 2003-048923 A and JP 2003-048924 A have a crosslinkable silicon group (meth) obtained by using a mercaptan having a crosslinkable silicon group and a metallocene compound. Acrylic acid alkyl ester polymers are described. Moreover, the synthesis example of Unexamined-Japanese-Patent No. 2005-026881 describes the (meth) acrylic-acid alkylester type polymer which has a crosslinkable silicon group by high temperature continuous polymerization.

  As disclosed in JP-A-2000-086999, a (meth) acrylic acid alkyl ester-based polymer having a crosslinkable silicon group, in which a crosslinkable silicon group is introduced at a high ratio at the molecular chain terminal, Are known. Since such a polymer is produced by living radical polymerization, a crosslinkable silicon group can be introduced into the molecular chain terminal at a high rate. In the present invention, a (meth) acrylic acid alkyl ester polymer as described above can be used.

  Specific examples of a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and a mixture of this polymer and an oxyalkylene polymer having a crosslinkable silicon group are disclosed in JP-A Nos. 59-122541 and 63-112642. And in each publication such as JP-A-6-172631. JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. disclose oxyalkylene polymers having a crosslinkable silicon group. (Meth) acrylic acid ester-based monomer is polymerized in the presence of a mixture of an oxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group. The method of obtaining is described.

  Calcium oxide used in the method of the present invention is an inorganic substance represented by a chemical formula (CaO) and also functions as a filler, also called quick lime or calcined lime. A surface treated with a fatty acid, a surfactant or the like is suitable for rubber, but in the present invention, calcium oxide not subjected to a surface treatment is more preferable because the heat resistance of the cured product can be further improved. The amount of calcium oxide used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and particularly preferably 5 to 30 parts by weight with respect to 100 parts by weight of the organic polymer having a crosslinkable silicon group. Calcium oxide is sold by Omi Chemical under the trade name such as CML.

  In the present invention, a curing catalyst other than the acidic phosphoric acid compound is used to cure the organic polymer having a crosslinkable silicon group. Acidic phosphoric acid compounds are likely to cause metal corrosion and are not suitable for assembling loudspeakers with many metal parts. Moreover, when an acidic phosphoric acid compound is used as a curing catalyst for a one-component curable composition, the composition has poor storage stability.

  Examples of curing catalysts other than acidic phosphate compounds include titanates such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, 4 such as dibutyltin diacetylacetonate, dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanate (dioctyltin diversate), dioctyltin oxide, reaction product of dibutyltin oxide and phthalate, etc. Organotin compounds such as divalent tin compounds such as valent tin compounds, tin octylate, tin naphthenate, tin stearate, tin dineodecanoate (tin versatic acid tin); aluminum tris Organoaluminum compounds such as cetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; bismuth salts such as bismuth-tris (2-ethylhexoate), bismuth-tris (neodecanoate) and organic carboxylic acids Or a reaction product with an organic amine, etc .; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; an organic lead compound such as lead octylate; an organic iron compound such as iron naphthenate; an organic vanadium compound; Octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine , Benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, Amine compounds such as 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) or salts thereof with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess The reaction product of a polyamine and an epoxy compound is exemplified.

  These curing catalysts may be used alone or in combination of two or more. Of these curing catalysts, organometallic compounds or a combined system of organometallic compounds and an amine compound are preferred from the viewpoint of curability. Furthermore, dibutyltin maleate, a reaction product of dibutyltin oxide and a phthalate ester, dibutyltin diacetylacetonate, and dioctyltin dineodecanate are preferred because of their high curing speed. Moreover, a dioctyl tin compound is preferable from the viewpoint of environmental problems. The curing catalyst is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the organic polymer having a crosslinkable silicon group.

  Various additives such as a filler, a plasticizer, an adhesiveness-imparting agent, a solvent, and a tackifier can be used in combination with the curable composition used in the present invention as necessary.

  Fillers include reinforcing fillers such as fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, kaolin, titanium oxide, Fillers such as bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, glass balloon, shirasu balloon, organic balloon, organic fiber, and inorganic fiber can be used.

  When it is desired to obtain a cured product having high strength by using these fillers, mainly fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and When a filler selected from activated zinc white is used in an amount of 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer having a crosslinkable silicon group, preferable results are obtained. In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like is used. If it is used in the range of 5 to 500 parts by weight per 100 parts by weight of the same polymer, preferable results can be obtained. These fillers may be used alone or in combination of two or more.

  Plasticizers include phthalates such as diisodecyl phthalate, diundecyl phthalate, diisoundecyl phthalate, dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate; aliphatics such as dioctyl adipate, isodecyl succinate, dibutyl sebacate, etc. Dibasic acid esters; Glycol esters such as diethylene glycol dibenzoate and pentaerythritol ester; Aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; Epoxidized soybean oil, epoxidized linseed oil, epoxy benzyl stearate, etc. Epoxy plasticizers such as: polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; polyethers such as polypropylene glycol and derivatives thereof; poly-α Polystyrenes such as methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polyisobutene, paraffin hydrocarbons, naphthene hydrocarbons, paraffin-naphthene mixed hydrocarbons, chlorinated paraffins, etc. The plasticizer can be optionally used alone or in the form of a mixture of two or more. In particular, polyether plasticizers such as polypropylene glycol and its derivatives, polyisobutene, paraffin and the like that do not contain an unsaturated bond in the polymer main chain are preferable from the viewpoint of weather resistance.

  Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- Amino group-containing silanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane; Epoxy group-containing silanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Gamma-mercaptopropyltrimethoxysilane Mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane Silanes; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; Isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; methyldimethoxysilane, trimethoxysilane, methyldi Specific examples include hydrosilanes such as ethoxysilane, but are not limited thereto.

  If the adhesiveness-imparting agent is added too much, the modulus of the cured product becomes high, and if it is too small, the adhesiveness decreases, so 0.1 to 15 weights with respect to 100 parts by weight of the crosslinkable silicon group-containing organic polymer. It is preferable to add part, more preferably 0.5 to 10 parts by weight.

  You may mix | blend a solvent and a diluent for the improvement of workability | operativity, the fall of a viscosity, etc. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Examples of the diluent include normal paraffin, isoparaffin, and the like.

  The tackifier is preferable for improving the wettability to the adherend and increasing the peel strength. Examples include, but are not limited to, petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin and its phenolic resin copolymer, phenol / phenol novolac resin-based tackifier resin, etc. It is not something.

  Examples of other additives include sagging inhibitors such as hydrogenated castor oil, organic bentonite, and calcium stearate, colorants, antioxidants, ultraviolet absorbers, and light stabilizers. Furthermore, additives such as other resins such as epoxy resins, curing agents such as epoxy resin curing agents, physical property modifiers, storage stability improvers, lubricants, and foaming agents can be added as necessary. .

  The curable composition used in the present invention may be a one-component composition comprising all components as a mixture, or a two-component composition comprising a resin component having a crosslinkable silicon group and a curing catalyst component as separate components. Can be used. In general, a two-part composition can provide a cured product having excellent characteristics. However, since an operation of mixing a resin component and a curing catalyst component is required at the time of assembling a speaker, a one-part composition is required for work. preferable.

  As shown in FIG. 1, the speaker joint includes a joint a between the cone edge 3 and the edge of the frame 1, a joint b between the cone paper 2 and the lead wire, a joint c between the caps 7, and a damper 6. Joint d between frames 1, three-point joint e between damper 6, voice coil 5 and cone paper 2, joint f between top plate 8 and ferrite magnet 9, and joint between ferrite magnet 9 and bottom plate 10 Although there is a part g and the like, the assembling method of the present invention can be used for any joint part.

  In order to assemble a speaker using the curable composition of the present invention, the curable composition may be applied to the joint and bonded together. After applying the curable composition to the joint, it is possible to take an open time as necessary, and after bonding, it can be cured as necessary.

(Synthesis Example 1)
A methanol solution of sodium methoxide (NaOMe) was added to polyoxypropylene diol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group to an allyl group. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added, and trimethoxysilane is reacted. The weight average molecular weight in terms of PPG (polypropylene glycol) is about 25,000, and 1.5 per molecule. A polyoxypropylene-based polymer having a number of terminal trimethoxysilyl groups was obtained.

(Synthesis Example 2)
Add a methanol solution of sodium methoxide (NaOMe) to polyoxypropylene diol having a molecular weight smaller than that of the polyoxypropylene diol used in Synthesis Example 1 to distill off the methanol, and then add allyl chloride to remove the terminal hydroxyl group. Converted to the base. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added and reacted with trimethoxysilane, and the weight average molecular weight in terms of PPG is about 15000, and 1.5 terminal trioxyls per molecule. A polyoxypropylene polymer having a methoxysilyl group was obtained.

(Synthesis Example 3)
In a flask, 40 parts by weight of ethyl acetate as a solvent, 59 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl methacrylate, 22 parts by weight of γ-methacryloxypropyltrimethoxysilane, and 0.1 part by weight of ruthenocene dichloride as a metal catalyst were added. The mixture was heated to 80 ° C. while introducing charged nitrogen gas. Then, 8 parts by weight of 3-mercaptopropyltrimethoxysilane was added to the flask and reacted at 80 ° C. for 6 hours. After cooling to room temperature, 20 parts by weight of a benzoquinone solution (95% THF solution) was added to terminate the polymerization. The solvent and unreacted substances were distilled off to obtain an acrylate polymer having a trimethoxysilyl group having a polystyrene-equivalent weight average molecular weight of about 6000.

  The measuring methods of hot peel strength, hardness and loss tangent (tan δ) in Examples and Comparative Examples are as follows.

(Hot peel strength)
The adhesive composition is applied to an aluminum plate having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm to a thickness of 200 μm on a portion having a length of 75 mm from one end. On the other hand, the adhesive composition is applied twice to a portion having a length of 75 mm from one end of the No. 5 campus having a width of 25 mm and a length of 200 mm twice. Laminate the coated parts so that they overlap, and tighten them 3 times with a hand roller. This was cured at 23 ° C. and 50% RH for 1 week as a test piece. The 180 ° peel strength of the campus is measured under a predetermined temperature atmosphere (tensile speed 200 mm / min).

(hardness)
In accordance with JIS K6253, the adhesive composition was cured at 23 ° C. and 50% RH for 1 week, and a JIS A hardness was measured.

(Loss tangent (tan δ))
A sheet having a thickness of 2 mm was prepared from the adhesive composition. The dynamic viscoelasticity test was performed on a 2 mm sheet using a DMS6100 manufactured by Seiko Instruments Inc. at a measurement temperature of 23 ° C., a frequency of 100 Hz, and a distortion rate of 0.1%, and then the loss tangent (tan δ) was reduced. Obtained by the formula.
tan δ = E ″ / E ′
(E ': storage elastic modulus, E ": loss elastic modulus)

(Examples 1-2, Comparative Example 1)
Each compounding substance was mixed and stirred with the composition shown in Table 1 to prepare an adhesive composition. Table 1 shows the hardness and hot peel strength of the cured product of the adhesive composition. As is clear from the comparison between Examples 1 and 2 and Comparative Example 1, it can be seen that the addition of calcium oxide instead of calcium carbonate improves the peel strength, particularly the peel strength at high temperatures. Moreover, it turns out that hardness becomes large. In Examples 1 and 2 and Comparative Example 1, the compositions were prepared so that the total amount of calcium oxide and calcium carbonate was the same.

(Examples 3 to 7, Comparative Example 2)
As is clear from the comparison between Examples 3 to 7 and Comparative Example 2 as in Examples 1 to 3, by adding calcium oxide instead of calcium carbonate, peel strength, in particular, peel strength after heat treatment It can be seen that is improved. Moreover, it turns out that hardness becomes large. Furthermore, it can be seen from the comparison between Example 4 and Example 5 that the peel strength at high temperature is superior in the case of calcium oxide that has not been surface-treated as compared with the case of calcium oxide that has been surface-treated.

(Example 8, Comparative Example 3)
As is clear from the comparison between Example 8 and Comparative Example 3 as in Examples 1 to 3, the peel strength, particularly the peel strength at high temperatures, is improved by adding calcium oxide instead of calcium carbonate. I understand that Moreover, it turns out that hardness becomes large. Furthermore, especially in comparison with Example 4 and Example 8, by decreasing the molecular weight of the organic polymer having a crosslinkable silicon group, the hot peel strength tends to decrease, but the hardness increases. Recognize.

(Example 9, Comparative Example 4)
As is clear from the comparison between Example 9 and Comparative Example 4 as in Examples 1 to 3, the peel strength, particularly the peel strength at high temperatures, is improved by adding calcium oxide instead of calcium carbonate. I understand that Unlike the other examples, the crosslinkable silicon group in the oxyalkylene polymer or (meth) acrylate polymer is a trimethoxysilyl group, whereas in Example 9, it is a methyldimethoxysilyl group. . From a comparison between Examples 1, 2, and 8 and Example 9, when a bifunctional crosslinkable silicon group such as a dimethoxysilyl group was used, a trifunctional crosslinkable silicon group such as a trimethoxysilyl group was used. It can be seen that the hot peel strength is improved as compared with the case where is used. Moreover, it turns out that hardness becomes large.

(Example 10)
The speaker was assembled using the adhesive composition used in Example 8 at the joints excluding the joints f and g (joints between the top plate 8 and the bottom plate 10 and the ferrite magnet 9). Adhesive strength was sufficient even when heated, and the sound quality of the obtained speaker was good.

The compounding amounts of the compounding substances in Table 1 are shown in parts by weight, and * 1 to * 11 are as follows.
* 1: A mixture of Kaneka Co., Ltd. polymer with a main chain of polyoxypropylene and a dimethoxy group at the molecular end, and a polymer with a main chain of polymethacrylic acid ester and a dimethoxysilyl group in the molecule. Product name: Silyl MA440
* 2: Omi Chemical Co., Ltd., surface-treated calcium oxide, product name: CML-35S
* 3: Omi Chemical Co., Ltd., fatty acid-treated calcium oxide, product name: CML-31
* 4: Nitto Kasei Co., Ltd., dioctyl tin-based curing catalyst, trade name: Neostan U-830
* 5: Nitto Kasei Co., Ltd. dibutyltin curing catalyst, product name: Neostan U-220H
* 6: Heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd., Product name: Whiten SB
* 7: Maruo Calcium Co., Ltd., fatty acid-treated calcium carbonate, product name: Calfine 200
* 8: Ciba Japan Co., Ltd., hindered phenol antioxidant, product name: Irganox 245
* 9: Tetraethoxysilane, product name: Ethyl silicate 28, manufactured by Colcoat Co., Ltd.
* 10: Made by Japan Energy Co., Ltd., paraffinic diluent, product name: Cactus normal paraffin N-11
* 11: Shin-Etsu Chemical Co., Ltd., N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, trade name: Shin-Etsu Silicone KBM603

1 Frame 2 Cone paper 3 Cone edge 4 Gasket 5 Voice coil 6 Dumbar 7 Dust cap 8 Top plate 9 Ferrite magnet 10 Bottom plate a, b, c, d, e, f, g Joint part of each member

Claims (14)

Having bound hydroxyl group or a hydrolyzable group to the silicon atom, moisture by an organic polymer having a crosslinkable silicon group capable of crosslinking by forming a siloxane bond, and calcium oxide, hardened non acid phosphate compound A method for assembling a speaker, wherein a curable composition containing a catalyst is applied to a joint portion of each member constituting the speaker and the members are bonded together. 2. The speaker assembling method according to claim 1, wherein the crosslinkable silicon group is a group represented by the following formula (1).

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ¹ ₃ SiO— (R ¹ is the same as above), and when two or more R ¹ are present, they may be the same or different, and X is a hydroxyl group or a hydrolysis. When two or more X are present, they may be the same or different, a is 0, 1, 2 or 3, b is 0, 1 or 2; And n equations (2):

B in need not be the same. n shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied. ) The speaker assembling method according to claim 2, wherein the crosslinkable silicon group is a group represented by the following formula (3).

(Wherein R ¹ and X are the same as defined above, and a is an integer of 1, 2 or 3.)   4. The method for assembling a speaker according to claim 3, wherein a is 2 or 3 in the crosslinkable silicon group.   5. The speaker assembling method according to claim 4, wherein a is 3 in the crosslinkable silicon group. 6. The speaker assembling method according to claim 1 , wherein the hydrolyzable group in the crosslinkable silicon group is an alkoxy group.   The speaker assembling method according to claim 6, wherein the hydrolyzable group in the crosslinkable silicon group is a methoxy group. The speaker assembling method according to any one of claims 1 to 7 , wherein the organic polymer having a crosslinkable silicon group is an oxyalkylene polymer having a crosslinkable silicon group. 8. The speaker assembling method according to claim 1 , wherein the organic polymer having a crosslinkable silicon group is a (meth) acrylic acid ester polymer having a crosslinkable silicon group. 8. The organic polymer having a crosslinkable silicon group is a mixture of an oxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. The method for assembling a speaker according to any one of the above. The organic polymer having a crosslinkable silicon group is a polymer obtained by polymerizing a (meth) acrylic acid ester monomer in the presence of an oxyalkylene polymer having a crosslinkable silicon group. Item 8. The method for assembling a speaker according to any one of Items 1 to 7. The speaker assembling method according to claim 1 , wherein the calcium oxide is calcium oxide that has not been surface-treated. The speaker assembling method according to claim 1 , wherein the curing catalyst other than the acidic phosphoric acid compound is a tin-based compound. Having hydrolyzable groups bonded to a silicon atom, and an organic polymer having a crosslinkable silicon group capable of crosslinking by forming a siloxane bond by moisture, and calcium oxide, and a curing catalyst other than the acid phosphoric acid compound An adhesive composition for assembling speakers.

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