JP5392564B2 - Adhesive for speaker assembly using a plurality of polyoxyalkylene polymers - Google Patents

Description

  The present invention relates to an adhesive for speaker assembly using a polyoxyalkylene-based polymer having a crosslinkable silicon group, and in particular, a polyoxyalkylene having a crosslinkable silicon group that provides a speaker in which the bonded member has high adhesive strength at high temperatures. The present invention relates to an adhesive for speaker assembly using a polymer.

  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 each of these members is assembled to the speaker by being appropriately joined with an adhesive at the joint portions a, b, c, d, e, f, and g.

  Various adhesives are used as speaker assembly adhesives. Patent Document 1 discloses a speaker assembly adhesive containing a polyether polymer (polyoxyalkylene polymer) having a crosslinkable silicon group. Proposed. This adhesive 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 at room temperature in a short time.

  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, paragraph 0016 includes a polyoxyalkylene 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 is (meth) acrylic). It is disclosed that an adhesive having excellent adhesive properties can be obtained by using a curable composition comprising an acid ester).

  Patent Document 3 discloses a speaker that uses a two-component fast-cure adhesive that uses a radical polymerizable monomer such as (meth) acrylic acid ester in addition to a polymer such as a polyoxyalkylene polymer having a crosslinkable silicon group. Assembling methods have been proposed. When this adhesive 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 presser is not required.

  As described above, the adhesive using the polyoxyalkylene polymer having a crosslinkable silicon group has an advantage that it is cured at room temperature and does not require the use of a solvent, and is suitably used for assembling a speaker. . 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

  An object of the present invention is to provide an adhesive for speaker assembly containing a polyoxyalkylene polymer having a crosslinkable silicon group, which has a high adhesive strength in a cured product, particularly a high adhesive strength in a high temperature atmosphere. There is to do. Another object of the present invention is to provide an adhesive for speaker assembly containing a polyoxyalkylene polymer having a crosslinkable silicon group, the cured product having a high hardness.

  The inventors of the present invention have (A) a polyoxyalkylene polymer having a crosslinkable silicon group at the molecular end as a polymer and (B) a polyoxyalkylene polymer having (A) a component having a crosslinkable silicon group at the molecular end. An adhesive using a polyoxyalkylene polymer having a molecular weight smaller than that of a polymer and using an oxide of at least one element selected from Group 2 elements such as calcium oxide and Group 12 elements as a filler is large. It has been found that it has a peel strength, particularly a hot peel strength, and a high hardness, and has led to the present invention. That is, the present invention relates to the following speaker assembly adhesive.

(1) has a bound hydroxyl group or a hydrolyzable group in (A) of silicon atoms, a crosslinkable silicon group capable of crosslinking possess the molecular ends by forming a siloxane bond, the weight of the polyoxyalkylene polymer Polyoxyalkylene polymer having an average molecular weight of 10,000 to 50,000 , (B) a crosslinkable silicon group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond A weight average molecular weight of 5,000 to 30,000, (A) a polyoxyalkylene polymer having a molecular weight smaller than that of the component polyoxyalkylene polymer, and (C) an adhesive for speaker assembly containing calcium oxide A polymer having a total amount of 100 parts by weight of component (A) and component (B) and a crosslinkable silicon group other than components (A) and (B) In the case of containing, the adhesive for speaker assembly which contains 2-100 weight part of (C) component with respect to 100 weight part of polymers which have all the crosslinkable silicon groups.

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

  (5) The speaker assembly adhesive according to (4), wherein a is 3 in the crosslinkable silicon group.

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

  (7) The adhesive for speaker assembly as set forth in (6), wherein the hydrolyzable group in the crosslinkable silicon group is a methoxy group.

( 8 ) A (meth) acrylic acid ester polymer 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. 100 parts by weight of the total amount of the component and the component (B), 100 parts by weight of the polymer having all the crosslinkable silicon groups when containing a polymer having a crosslinkable silicon group other than the components (A) and (B), The adhesive for speaker assembly according to any one of (1 ) to (7) , further comprising 10 to 200 parts by weight based on

( 9 ) The speaker assembly adhesive according to any one of (1) to ( 8 ), wherein the calcium oxide is an oxide that has not been surface-treated.

( 10 ) When containing 2 to 200 parts by weight of calcium carbonate, 100 parts by weight of the total amount of components (A) and (B), and a polymer having a crosslinkable silicon group other than components (A) and (B) 100 parts by weight of the polymer, to 10 to 200 parts by weight, more 請 Motomeko (1), characterized in that it contains - (9) speaker assembly adhesive according with all of the crosslinkable silicon group.

(11) A speaker in which a joint portion of the speaker is bonded by the speaker assembly adhesive according to any one of (1) to (10).

(12) has a bound hydroxyl group or a hydrolyzable group in (A) of silicon atoms, a crosslinkable silicon group capable of crosslinking possess the molecular ends by forming a siloxane bond, the weight of the polyoxyalkylene polymer Polyoxyalkylene polymer having an average molecular weight of 10,000 to 50,000 , (B) a crosslinkable silicon group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond A polyoxyalkylene polymer having a weight average molecular weight of 5000 to 30000, a weight average molecular weight of 3000 or less than the polyoxyalkylene polymer of the component (A), and (C) calcium oxide. A method for producing an adhesive for assembling a speaker, comprising a total amount of 100 parts by weight of components (A) and (B), (A) and (B) Of the adhesive for speaker assembly containing 2 to 100 parts by weight of the component (C) with respect to 100 parts by weight of the polymer having all the crosslinkable silicon groups. Production method.

  The adhesive for speaker assembly of the present invention is a one-component composition obtained when a polyoxyalkylene polymer having a crosslinkable silicon group is used, which does not require the use of a solvent and does not require a two-component mixing operation. In addition to the advantages that it can be used as a product and can be bonded at room temperature, the cured product has the effect of having a high hot peel strength and a high hardness.

It is a longitudinal cross-sectional view of the typical speaker assembled using the adhesive agent for speaker assembly 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 polyoxyalkylene polymer having a crosslinkable silicon group used in the present invention has a hydroxyl group or hydrolyzable group bonded to a silicon atom, and is a group that can be crosslinked 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 hardness of the cured product is increased, but the hot peel strength is decreased. However, in the present invention, even when a is 3, it has a sufficient hot peel strength, the hardness of the cured product is large, and the sound quality of the speaker is excellent.

Specific structures of the crosslinkable silicon group include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group, dialkoxysilyl groups such as —Si (OR) ₃ , methyldimethoxysilyl group, and 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. In the present invention, a polyoxyalkylene polymer having a crosslinkable silicon group at the molecular chain terminal is used. When a crosslinkable silicon group is present at the end of the molecular chain, the cured product properties such as tensile properties and adhesive properties of the cured product are excellent. It is not necessary that a crosslinkable silicon group is present at all terminals of the polyoxyalkylene polymer, and at least one of the molecular terminals, preferably 1.1 or more and less than 2, may be present. 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. If a crosslinkable silicon group is present at the molecular chain end of the polyoxyalkylene polymer, it may be present other than at the molecular chain end, but it is preferable that the crosslinkable silicon group is substantially absent other than at the molecular chain end. .

（式中、Ｒ^２は２価のアルキレン基） The polyoxyalkylene polymer used in the present invention is essentially a polymer having a repeating unit represented by the formula (4).

(Wherein R ² is a divalent alkylene group)

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。 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.

  The polyoxyalkylene polymer having a crosslinkable silicon group may be linear or branched, but is preferably linear. In particular, the polymer of component (A) is preferably linear.

  In the present invention, polyoxyalkylene polymers having different molecular weights are used. The polyoxyalkylene polymer (A), which is a high molecular weight component, preferably has a weight average molecular weight of 10,000 to 50,000, more preferably 20,000 to 40,000. The polyoxyalkylene polymer (B), which is a low molecular weight component, has a weight average molecular weight of 5,000 to 30,000, more preferably 10,000 to 20,000. The polyoxyalkylene polymer (B), which is a low molecular weight component, is preferably at least 3000, more preferably 5000, particularly 10,000 in weight average molecular weight than the polyoxyalkylene polymer (A) which is a high molecular weight component. As long as a polymer having such a molecular weight range is used as the polymer (A) or the polymer (B), it is possible to use a polyoxyalkylene polymer having a molecular weight outside this range in combination.

  When a high molecular weight polyoxyalkylene polymer having a crosslinkable silicon group is used, a cured product having excellent peel strength including hot peel strength can be obtained. When a low molecular weight polyoxyalkylene polymer having a crosslinkable silicon group is used, the peel strength decreases, but the hardness of the cured product increases. This is thought to be because a cured product of a polyoxyalkylene polymer having a crosslinkable silicon group at the molecular chain terminal is a brittle cured product but has a high hardness because the molecular weight between crosslinking points is small. . Thus, desired peel strength and hardness can be obtained by using together the polyoxyalkylene type polymer which has a crosslinkable silicon group from which molecular weight differs, and adjusting molecular weight and a composition ratio.

  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. A polyoxyalkylene system having a narrow molecular weight distribution with a high molecular weight having a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less according to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst A polymer can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer 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, xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; The thing obtained from reaction with coalescence can be mention | raise | lifted.

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be performed on a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule. The reaction can be carried out by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has can be mention | raise | lifted. An unsaturated group-containing polyoxyalkylene 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, A polyoxyalkylene polymer containing can be obtained.

  Other specific examples of the polymer reaction method include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene system having an isocyanate group at a terminal. Examples thereof include a method of reacting a polymer with 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, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  Specific examples of the polyoxyalkylene polymer having a crosslinkable silicon group include JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. No. 57-164123, JP-B No. 3-2450, JP-A No. 2005-213446, No. 2005-306891, International Publication No. WO2007-040143, US Pat. No. 3,632,557, No. 4,345,053, The ones proposed in the publications such as 4,960,844 can be listed.

  The speaker assembly adhesive of the present invention may be used in combination with a polymer other than the polyoxyalkylene polymer having a crosslinkable silicon group. As an example of such a polymer, a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group can be given. When a (meth) acrylic acid alkyl ester-based polymer having a crosslinkable silicon group is used in combination, the cured product has excellent mechanical strength and also has excellent heat resistance and adhesion to a substrate. The combined use is particularly suitable for the present invention.

（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） 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 essentially consists of the monomer unit of the formula (5). The term “essentially” as used herein refers to the formula (5) present in the polymer. ) Of the 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 the formula (5) include monomer units derived from (meth) acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide Monomer units derived from monomers containing amide groups such as: monomer units derived from monomers containing epoxy groups such as glycidyl acrylate and glycidyl methacrylate; diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether Monomer units derived from monomers containing amino groups such as acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc. can give.

（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であることが好ましい。 When a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group is used by mixing with a polyoxyalkylene polymer, the compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group is high. In that respect, the molecular chain having a crosslinkable silicon group has the following formula (6):

(Wherein R ³ is the same as above, and R ⁵ is an alkyl group having 1 to ⁵ carbon atoms)
(Meth) acrylic acid ester monomer unit represented by the following formula (7):

(Wherein R ³ is the same as above, and R ⁶ is an alkyl group having 6 or more carbon atoms)
It is preferable that it is a copolymer which consists of a (meth) acrylic acid ester monomer unit represented by these.

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 as 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. Japanese Patent Laid-Open No. 2005-082681 describes a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group by continuous polymerization at high temperature.

  A (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group, in which a crosslinkable silicon group is introduced at a high ratio at the molecular chain terminal, is also disclosed in JP-A-2000-086999. . 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 the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and a mixture of this polymer and a polyoxyalkylene polymer having a crosslinkable silicon group are disclosed in JP-A-59-122541 and 63-. No. 112642, JP-A-6-172631, and the like. Further, JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, and the like disclose polyoxyalkylene series having a crosslinkable silicon group. Polymerization of a (meth) acrylic acid ester monomer in the presence of a polymer, a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group A method for obtaining a mixture of is described.

  When a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group is used in combination, the (meth) acrylic acid having a crosslinkable silicon group is used with respect to 100 parts by weight of the polyoxyalkylene polymer having a crosslinkable silicon group. The ester polymer is preferably used in an amount of 10 to 200 parts by weight, more preferably 20 to 80 parts by weight.

  Examples of the oxide of at least one element selected from (C) Group 2 element and Group 12 element used in the present invention include calcium oxide, magnesium oxide, zinc oxide, beryllium oxide, strontium oxide, barium oxide, Cadmium oxide is mentioned. Among these, calcium oxide, magnesium oxide, and zinc oxide are preferable because they are easily available and easy to handle, and calcium oxide is particularly preferable. These oxides may be surface-treated with a fatty acid, a surfactant or the like, but in the present invention, oxides that are not surface-treated are preferred because the heat resistance of the cured product can be further improved.

  Calcium oxide is sold by Omi Chemical Industry Co., Ltd. under a trade name such as CML. Magnesium oxide is sold by Kamishima Chemical Industry Co., Ltd. under the trade name of Starmag and Kyowa Chemical Industry Co., Ltd. under the trade name of Kisuma. Zinc oxide is sold as Zinc Oxide or Zinc Hana from Shodo Chemical Industry Co., Ltd., Sakai Chemical Industry Co., Ltd., Toho Zinc Co., Ltd., and Mitsui Mining Co., Ltd.

  The amount of oxide of at least one element selected from Group 2 elements and Group 12 elements is 100 weights of the total amount of polyoxyalkylene polymer having crosslinkable silicon groups of component (A) and component (B). The amount 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. In addition, when another polymer having a crosslinkable silicon group is used in combination, the amount of an oxide of at least one element selected from Group 2 elements and Group 12 elements is an oxyalkylene type having a crosslinkable silicon group. The amount 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 polymer including all crosslinkable silicon groups including the polymer.

  Various additives such as a curing catalyst, a filler, a plasticizer, an adhesion imparting agent, a solvent, and a tackifier can be used in combination with the adhesive of the present invention as necessary.

  The curing catalyst is used for rapidly curing a polymer such as a polyoxyalkylene polymer having a crosslinkable silicon group.

  Examples of curing catalysts include tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanate esters such as titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, Tetravalent tin compounds such as dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanate (dioctyltin diversate), dioctyltin oxide, reaction product of dibutyltin oxide and phthalate, octyl acid Organotin compounds such as divalent tin compounds such as tin, tin naphthenate, tin stearate, tin neodecanoate (tin versatic acid); aluminum trisacetylacetonate, Organoaluminum compounds such as luminium trisethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate; bismuth salts such as bismuth-tris (2-ethylhexoate), bismuth-tris (neodecanoate) and an organic carboxylic acid or organic amine; Reaction products, etc .; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organic lead compounds such as lead octylate; organic iron compounds such as iron naphthenate; organic vanadium compounds; butylamine, octylamine, lauryl Amine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diamine Tylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8 -Amine compounds such as 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 polyamines Examples include reaction products with epoxy compounds.

  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-based compounds such as dibutyltin maleate, a reaction product of dibutyltin oxide and a phthalate ester, and dibutyltin diacetylacetonate are preferable from the viewpoint of a high curing rate. Further, although the catalytic activity is slightly lowered, dioctyltin compounds such as dioctyltin dineodecanate and dioctyltin oxide are preferred from the viewpoint of environmental problems. Since dioctyltin oxide has a low catalytic activity, it is difficult to cure at the time of production of the adhesive. Therefore, it is easy to produce an adhesive containing this, but the curing time becomes long. For this reason, as disclosed in International Publication No. WO2005-012426, the adhesive can be heat-treated in order to improve the catalytic activity after the production of the adhesive.

  The polyoxyalkylene polymer having a crosslinkable silicon group in which a is 3 in the formula (3) has high reactivity and a high curing rate. When a highly active curing catalyst is used for this polymer, the curing rate becomes too high, and there are cases where problems such as curing during the production of the adhesive and smooth adhesion work during the use of the adhesive may occur. In such a case, it is preferable to use a dioctyltin compound such as the above-mentioned dioctyltin dineodecanate, or to use dioctyltin oxide by heat treatment after production of the adhesive.

  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 polyoxyalkylene polymer having a crosslinkable silicon group of the component (A) and the component (B). In addition, when other polymers having a crosslinkable silicon group are used in combination, 0.5 parts by weight per 100 parts by weight of the polymer having all crosslinkable silicon groups including the oxyalkylene polymer having a crosslinkable silicon group. It is preferable to use 10 to 10 parts by weight.

  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, A filler such as bentonite, organic bentonite, ferric oxide, glass balloon, shirasu balloon, organic balloon, organic fiber and inorganic fiber can be used.

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

  Among these fillers, when surface-treated calcium carbonate is used, an inexpensive and high-strength cured product can be obtained. Therefore, an oxide of at least one element selected from Group 2 elements and Group 12 elements and surface-treated calcium carbonate Are preferably used in combination. In particular, it is preferable to use calcium oxide, magnesium oxide or zinc oxide in combination with surface-treated calcium carbonate. The amount of the surface-treated calcium carbonate used is in the range of 1 to 200 parts by weight, preferably 5 to 100 parts by weight, and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the polymer having all crosslinkable silicon groups. .

  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.

  The plasticizer is preferably added in an amount of 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, based on 100 parts by weight of the polymer having all crosslinkable silicon groups.

  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 Γ-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 will be high, and if it is too low, the adhesiveness will be lowered. Therefore, from 0.1 to 100 parts by weight of the polymer having all crosslinkable silicon groups. 15 parts by weight is preferably added, 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 solvent or diluent is preferably added in an amount of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polymer having all crosslinkable silicon groups.

  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. The tackifier is preferably added in an amount of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polymer having all crosslinkable silicon groups.

  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 adhesive of the present invention can be used as a one-component adhesive comprising all components as a mixture, or as a two-component adhesive comprising a resin component having a crosslinkable silicon group and a curing catalyst component as separate components. it can. Two-part adhesives can generally provide adhesives with excellent characteristics, but the operation of mixing the resin component and the curing catalyst component is necessary when assembling the speaker. preferable.

  The method for producing the adhesive of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, a roll, a kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. The usual methods, such as melt | dissolving a component and mixing, are mentioned.

  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 are parts g and the like, the adhesive of the present invention can be used for any joint part.

  In order to assemble a speaker using the adhesive of the present invention, the adhesive may be applied to the joint and bonded together. After applying the adhesive to the joint, it is possible to take an open time as needed, 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 method of the curing rate, hot peel strength, hardness and loss tangent (tan δ) in the examples is as follows.

(Curing speed)
The curing rate was evaluated by the skinning time. Fill a cylindrical container with an inner diameter of 60 mm to a thickness of 5 mm, immediately place it in a constant temperature and humidity chamber at 23 ° C. and 50% RH, touch the surface with a finger, and measure the time until the composition does not adhere to the finger To do.

(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 cured at 23 ° C. and 50% RH for 1 week was used as a test piece.
A hardness is measured.

(Loss tangent (tan δ))
A sheet having a thickness of 2 mm is prepared from the adhesive. 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)

The adhesives of the examples were prepared by mixing and agitating each compounding substance with the compositions shown in Tables 1 and 2. In Tables 1 and 2, the actual values and ratios indicate examples and comparative examples, respectively. In addition, in the adhesives of Examples, Comparative Examples, Reference Examples, and Reference Comparative Examples, the following additives are commonly added in addition to the formulations shown in Table 1.
Antioxidant: Ciba Japan Co., Ltd., hindered phenol antioxidant, trade name: Irganox 245, 1 part by weight.
Dehydrating agent: Colcoat Co., Ltd., tetraethoxysilane, trade name: ethyl silicate 28, 1 part by weight.
Diluent: manufactured by Japan Energy Co., Ltd., paraffinic diluent, trade name: Cactus normal paraffin N-11, 10 parts by weight.
Adhesiveness imparting agent: manufactured by Shin-Etsu Chemical Co., Ltd., N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, trade name: Shin-Etsu Silicone KBM603, 6 parts by weight.

(Example 1-2, Comparative Example 1-2)
In Examples 1-2 and Comparative Examples 1-2, the polyoxyalkylene polymer synthesis example the polymer obtained in Synthesis Example obtained polymer were mixed with 2 in 1 as having a crosslinkable silicon group Are used. In Comparative Example 1, calcium oxide is not used. In Comparative Example 2, an oxide (titanium oxide) of an element that is not a Group 2 element or a Group 12 element is used. Table 1 shows the curing rate, hot peel strength, hardness, and loss tangent of the adhesive. In these examples and comparative examples, compositions are prepared so that the total amount of calcium oxide and calcium carbonate is the same. This is because calcium oxide is considered to act as a filler.

As is clear from the comparison between Examples 1 and 2 and Comparative Example 1, it can be seen that the use 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.

  As is apparent from the comparison between Example 2 and Comparative Example 2 in which 20 parts by weight of oxide is used in common, when titanium oxide is used instead of calcium oxide or the like, the peel strength, particularly at high temperatures, It can be seen that the peel strength decreases. Moreover, it turns out that hardness also becomes small.

(Example 3 , Comparative Examples 3-6)
In Example 3 and Comparative Example 3, the polymer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 2 were mixed and used as a polyoxyalkylene polymer having a crosslinkable silicon group. However, the amount of the polymer having a small molecular weight obtained in Synthesis Example 2 is increased. In Comparative Examples 4 to 6, only one type of polymer is used as the polyoxyalkylene polymer, and no mixture is used. Table 1 shows the curing rate, hot peel strength, hardness, and loss tangent of the adhesive.

As is apparent from the hardness values of Comparative Example 4, Example 2 and Example 3 in which 20 parts by weight of calcium oxide are commonly used, the polyoxyalkylene polymer of Synthesis Example 2 having a small molecular weight is increased. It can be seen that the hardness increases with time. Further, as is clear from the comparison between Example 3 and Comparative Example 3 and the comparison between Comparative Examples 4 and 5 and Comparative Example 6, also in this case, by adding calcium oxide instead of calcium carbonate, It can be seen that the peel strength and hardness at the time are improved.

(Examples 4 to 6 )
In Examples 4 to 6 , a surface-treated product of calcium oxide is used. Table 2 shows the curing rate, hot peel strength, hardness and loss tangent of the adhesive. In particular, the comparison between Example 2 and Example 4 shows that in the case of an oxide that has not been surface-treated, the peel strength at high temperatures and the hardness of the cured product are greater than in the case of an oxide that has been surface-treated. Recognize.

(Examples 7 to 8 , Comparative Example 7 )
In Examples 7 to 8 and Comparative Example 7 , dioctyltin oxide was used as a curing catalyst instead of dioctyltin diversate. However, in order to improve the catalytic activity, the adhesive composition was heated after the production of the adhesive composition. Table 2 shows the curing rate, hot peel strength, hardness and loss tangent of the adhesive. As is clear from the comparison between Examples 7 to 8 and Comparative Example 7 , even when other catalysts are used, the peel strength and hardness at high temperatures are improved by adding calcium oxide instead of calcium carbonate. I understand.

(Comparative Examples 8-9)
In Comparative Examples 8 to 9, a polymer having a dialkoxysilyl group instead of a trialkoxysilyl group as a crosslinkable silicon group is used. When a dialkoxysilyl group is used as the crosslinkable silicon group, the curing rate is reduced as compared with the case where a trialkoxysilyl group is used. Instead of dioctyltin diversate, dibutyltin bisacetylacetonate having high catalytic activity is used. Also in this case, it can be seen that the peel strength and hardness at high temperature are improved by adding calcium oxide instead of calcium carbonate.

(Example 9 )
A speaker was assembled using the adhesive composition used in Example 3 at a joint portion excluding the joint portions f and g (joint portions 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 Tables 1 and 2 are shown in parts by weight, and * 1 to * 12 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 : Sakai Chemical Industry Co., Ltd., non-surface-treated rutile titanium oxide, trade name: DAIAWHITE TCR-10
* 5 : Heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd., Product name: Whiten SB
* 6 : Maruo Calcium Co., Ltd., fatty acid-treated calcium carbonate, trade name: Calfine 200
* 7 : manufactured by Nitto Kasei Co., Ltd., dioctyltin diversate curing catalyst, trade name: Neostan U-830
* 8 : Nitto Kasei Co., Ltd., dioctyl tin oxide curing catalyst, product name: Neostan U-800P
* 9 : Nitto Kasei Co., Ltd. dibutyltin bisacetylacetonate curing catalyst, product name: Neostan U-220H

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 (12)

(A) has a bound hydroxyl group or a hydrolyzable group to a silicon atom, a crosslinkable silicon group capable of crosslinking by forming siloxane bonds possess a molecular end, the weight-average molecular weight of the polyoxyalkylene polymer is A polyoxyalkylene polymer of 10,000 to 50,000 , (B) a hydroxyl group or hydrolyzable group bonded to a silicon atom, and a crosslinkable silicon group that can be crosslinked by forming a siloxane bond at the molecular end A weight average molecular weight of 5000 to 30000, (A) a polyoxyalkylene polymer having a weight average molecular weight of 3000 or more smaller than the polyoxyalkylene polymer of the component, and (C) a speaker assembly containing calcium oxide Adhesive, 100 parts by weight of total amount of component (A) and component (B), crosslinkable silicon group other than components (A) and (B) The adhesive for speaker assembly containing 2-100 weight part of (C) component with respect to 100 weight part of polymers which all have a crosslinkable silicon group, when the polymer which has this is contained. The adhesive for assembling a speaker 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 assembly adhesive 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.)   The speaker assembly adhesive according to claim 3, wherein a is 2 or 3 in the crosslinkable silicon group.   The adhesive for speaker assembly according to claim 4, wherein a is 3 in the crosslinkable silicon group.   The adhesive for speaker assembly according to claim 1, wherein the hydrolyzable group in the crosslinkable silicon group is an alkoxy group.   The adhesive for speaker assembly according to claim 6, wherein the hydrolyzable group in the crosslinkable silicon group is a methoxy group. A (meth) acrylic acid ester polymer 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, The total amount of B) component is 100 parts by weight, and when it contains a polymer having a crosslinkable silicon group other than components (A) and (B), it is 10 parts per 100 parts by weight of the polymer having all crosslinkable silicon groups. 200 parts by weight, more speaker assembly adhesive of claim 1 to 7, wherein the contained. Speaker assembly adhesive of claim 1-8, wherein the calcium oxide is an oxide that is not treated surfaces. 2 to 200 parts by weight of calcium carbonate, 100 parts by weight of the total amount of the component (A) and the component (B), and a polymer having a crosslinkable silicon group other than the components (A) and (B) 100 parts by weight of the polymer having a crosslinkable silicon group, to 10 to 200 parts by weight, more speaker assembly adhesive of claim 1 to 9, wherein the containing. A speaker in which a joint portion of the speaker is bonded by the speaker assembly adhesive according to claim 1. (A) has a bound hydroxyl group or a hydrolyzable group to a silicon atom, a crosslinkable silicon group capable of crosslinking by forming siloxane bonds possess a molecular end, the weight-average molecular weight of the polyoxyalkylene polymer is A polyoxyalkylene polymer of 10,000 to 50,000 , (B) a hydroxyl group or hydrolyzable group bonded to a silicon atom, and a crosslinkable silicon group that can be crosslinked by forming a siloxane bond at the molecular end A weight average molecular weight of 5000 to 30000, (A) a polyoxyalkylene polymer having a weight average molecular weight of 3000 or more smaller than the polyoxyalkylene polymer of the component, and (C) a speaker assembly containing calcium oxide A method for producing an adhesive comprising 100 parts by weight of the total amount of the component (A) and the component (B), and a bridge other than the components (A) and (B). A method for producing an adhesive for speaker assembly containing 2 to 100 parts by weight of component (C) with respect to 100 parts by weight of a polymer having all crosslinkable silicon groups when a polymer having a bridging silicon group is contained. .

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