JP5891756B2 - One-pack type moisture curable composition, sealing material comprising this composition, and solar cell module using this sealing material - Google Patents

Description

  The present invention relates to a one-component moisture-curable composition. In particular, one liquid containing a saturated hydrocarbon polymer having a crosslinkable silicon group in the molecule, and a polycarboxylic acid ester having two or more ester bonds of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms. Type moisture-curable composition.

Conventionally, saturated hydrocarbon polymers having a crosslinkable silicon group in the molecule are widely known. For example, the following polymers having a crosslinkable silicon group such as a methyldimethoxysilyl group at both ends of the organic polymer chain are known.
_{CH 3 (CH 3 O) 2} Si~~~ ( organic polymer _{chain) ~ (OCH 3) 2 CH} 3

  Usually, since this polymer is in a liquid state, it can be applied to a substrate and can be filled into a gap or a mold. In the above polymer, since the silicon atom is bonded to a methoxy group which is a hydrolyzable group, if it is allowed to stand after coating and filling, it undergoes hydrolysis reaction and silanol condensation reaction due to moisture in the air. The polymers are cross-linked by a siloxane bond to produce a rubber-like cured product. The polymer is also excellent in heat resistance, water resistance, moisture barrier properties, and weather resistance. Therefore, the said polymer is utilized for the adhesive agent and the sealing material, and is utilized especially as a sealing material for construction.

  By the way, since the said polymer has moisture barrier property, there exists a subject that hardening time is long. In particular, when filling a cylindrical shape having a depth, there is a problem that it takes a very long time until only the surface is cured first and the bottom is cured.

  In order to solve this problem, various curable compositions have been proposed. For example, a curable composition containing a saturated hydrocarbon polymer having a crosslinkable silicon group and a compound having a silanol group or a polymer having a silanol group is used, and the silanol compound is used as a crosslinking agent instead of water. Thus, it has been proposed that deep part curability can be improved (see Patent Documents 1 and 2). Further, it has been proposed that the deep curability can be improved by using a curable composition comprising a saturated hydrocarbon polymer having a crosslinkable silicon group and a hydrate of water or a metal salt ( (See Patent Documents 3 to 5). Moreover, by using a saturated hydrocarbon polymer having a crosslinkable silicon group, an amine, and a carbonyl compound as a curable composition, water generated by the reaction of the amine and the carbonyl compound is utilized. It has been proposed that deep part curability can be improved (see Patent Document 6).

  However, in the above curable composition, when an organic polymer having a crosslinkable silicon group is mixed with a silanol compound or water, a chemical reaction starts immediately and curing begins. I can't. That is, the curable composition is not a one-component type. Especially for architectural purposes, if it is not a one-pack type, multiple types of raw materials must be weighed and mixed on-site, resulting in inferior workability and variations in the quality of the resulting composition. There is a problem of getting. Further, since the raw materials must be mixed at a constant mixing ratio, there is a problem that at least one of the raw materials is left and the raw materials are wasted. Further, considering the time (pot life) from mixing a plurality of types of raw materials to curing the mixture, there is also a problem that the raw materials must be mixed little by little. In addition, after the work is completed, the container in which the raw materials are mixed must be washed, and each empty can containing multiple types of raw materials must be discarded. There is also the problem of being accompanied.

  Regarding this problem, it has been proposed to encapsulate one of the reaction components (see Patent Documents 7 and 8). In addition, a single-component sealant composition (one-component polyurethane, one-component modified silicone, or one-component polyisobutylene) having a viscosity of 10,000 to 10 million CP (centipoise) has a number of independent properties. It has been proposed to uniformly disperse bubbles (see Patent Document 9). Further, (a) 150 parts by weight of a polyisobutylene polymer having hydrolyzable silyl group terminals, (b) 150 parts by weight of calcium carbonate excellent in water dispersibility, (c) 2 parts by weight of a curing catalyst, and (f) A curable composition comprising as essential components 50 parts by weight of a polyether polymer having hydrolyzable silyl group ends and 50 parts by weight of a plasticizer compatible with the isobutylene polymer has a temperature of 23 ° C. and humidity. It has been proposed that when cured at 65% for 24 hours, it can be cured to a depth of 1.2 mm and can be stored in a sealed container at 50 ° C. for 1 week (Example 8 of Patent Document 10). Furthermore, when the adhesion imparting agent is (e) an aminosilane in which a hydrolyzable group is propoxylated, the deep-part curability is improved to 1.6 mm (same Example 7), and (d) newly excellent in compatibility with water. When a solvent is added, the deep part curability is improved to 2.0 mm (same Example 6).

Japanese Patent Laid-Open No. 2-196842 Japanese Patent Laid-Open No. 7-53882 JP-A-2-185565 JP-A-10-204303 Japanese Patent Application Laid-Open No. 11-209639 JP 2001-303024 A JP 2002-309114 A JP 2004-307723 A Japanese Patent Laid-Open No. 2001-132646 JP 2000-344982 A

  However, in the inventions described in Patent Documents 7 and 8, since one of the reaction components is microencapsulated, the microcapsule must be destroyed when the curable composition is cured. Moreover, in the invention described in Patent Document 9, in order to improve the deep part curability, a large number of closed cells must be uniformly dispersed in the one-pack type sealing material composition. That is, in the inventions described in Patent Documents 7 to 9, it is necessary to go through a process that is not performed with a normal one-component curable composition, an extraction process for extracting the curable composition from the container, and the extracted curing. There is a need to provide a one-component moisture-curable composition that can be used simply by performing an application step of applying an adhesive composition.

  In addition, according to the invention described in Patent Document 10, it is disclosed that it can be stored in a sealed container at 50 ° C. for one week. However, it is required to provide a one-pack type moisture curable composition having further storage stability. ing. In addition, the deep curability and the curing rate after storage for a longer period are unknown.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have (A) a saturated hydrocarbon polymer having a crosslinkable silicon group, (B) a polycarboxylic acid, and a monocarboxylic acid having 1 to 4 carbon atoms. A process that is not performed in a normal one-component curable composition such as destruction of microcapsules by containing a polycarboxylic acid ester having two or more ester bonds with alcohol and (C) an inorganic filler. It has been found that a one-component moisture-curable composition that can be stored for a long time without performing the process, and has excellent deep-part curability and curing speed even after long-term storage, has led to the completion of the present invention. . Specifically, the present invention provides the following.

（式中、Ｇは分子引力定数、ΣＧは分子中の原子と原子団のＧの総和、ｄは密度、Ｍは分子量を示す。） (1) The present invention provides (A) a saturated hydrocarbon polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one crosslinkable silicon group capable of crosslinking by forming a siloxane bond. 100 parts by weight and (B) a polycarboxylic acid and a C1-C4 monoalcohol having two or more ester bonds, and a solubility parameter δ calculated by the Small method shown in the following (Equation 1) is 8.9 (cal / cm ³ ) ^{½ to} 10.5 (cal / cm ³ ) ^{1 to} 150 parts by weight of a polycarboxylic acid ester within a range of ^½ or less, and (C) an inorganic filler 1 to It is a one-component moisture-curable composition containing 300 parts by weight.

(In the formula, G is a molecular attraction constant, ΣG is the sum of G of atoms and atomic groups in the molecule, d is density, and M is molecular weight.)

（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のアラルキル基又は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は水酸基又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。ｎは０〜１９の整数を示す。ａは０〜３の整数を示し、ｂは０〜２の整数を示すが、ａとｂとの和は１以上である。なお、上記一般式（Ｉ）を構成する一般式（ＩＩ）

における全てのｂが同一である必要はない。） (2) Moreover, this invention is a composition as described in (1) with which the said crosslinkable silicon group is represented by the following general formula (I).

(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 hydrolyzable group. And when X is 2 or more, they may be the same or different, n represents an integer of 0 to 19, a represents an integer of 0 to 3, and b represents An integer of 0 to 2 is shown, and the sum of a and b is 1 or more, and the general formula (II) constituting the above general formula (I)

It is not necessary that all b's in are the same. )

  (3) Moreover, this invention is a composition as described in (2) whose said X is an alkoxy group.

  (4) Moreover, this invention is a composition as described in (3) whose said X is a methoxy group.

  (5) Moreover, this invention is a composition in any one of (1) to (4) whose said saturated hydrocarbon type polymer is an isobutylene type polymer or a hydrogenated polybutadiene type polymer.

  (6) Moreover, this invention is a composition in any one of (1) to (5) in which the said saturated hydrocarbon type polymer has the said crosslinkable silicon group at the terminal of a polymer molecular chain.

(7) In the present invention, the monoalcohol having 1 to 4 carbon atoms is methanol, and the δ is 9.0 (cal / cm ³ ) ^1/2 or more 10.1 (cal / cm ³ ) ^{1 /} It is a composition in any one of (1) to (6) which exists in the range of ² or less.

  (8) Moreover, this invention is a composition in any one of (1) to (7) whose said polycarboxylic acid is aliphatic polycarboxylic acid.

  (9) Moreover, this invention is a composition in any one of (1) to (8) whose said polycarboxylic acid is dicarboxylic acid.

  (10) Moreover, this invention is a composition in any one of (1) to (9) whose said inorganic filler is calcium carbonate.

  (11) Moreover, this invention is a composition as described in (10) whose said calcium carbonate is surface-treated calcium carbonate.

  (12) Moreover, this invention is a composition in any one of (1) to (11) which further contains 1-30 weight part of the (meth) acrylic acid ester type polymer which has a crosslinkable silicon group. .

  (13) Moreover, this invention is a sealing material which consists of a composition in any one of (1) to (12).

  (14) Moreover, this invention is a solar cell module with which the edge part and fixing member of the solar cell panel were adhere | attached through the sealing material as described in (13).

  (15) Moreover, this invention is a solar cell module which uses the sealing material as described in (13) as an edge part processing agent of a solar cell panel.

  According to the present invention, it can be stored for a long time without performing a process that is not performed with a normal one-component curable composition, such as breakage of microcapsules, and deep curable and even after long-term storage. A one-component moisture curable composition having an excellent curing rate can be provided.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

<One-pack type moisture curable composition>
The one-component moisture-curable composition of the present invention contains a saturated hydrocarbon polymer, a polycarboxylic acid ester, and an inorganic filler as essential components. In addition to the essential components, other organic polymers having a crosslinkable silicon group and various additives can be used in combination as necessary. Hereinafter, these components will be described.

（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のアラルキル基又は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は水酸基又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又は３を、ｂは０、１又は２を、それぞれ示す。またｎ個の式（ＩＩ）：

における全てのｂが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。） [(A) Saturated hydrocarbon polymer]
First, as component (A), a saturated hydrocarbon polymer having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having at least one crosslinkable silicon group capable of crosslinking by forming a siloxane bond will be described. To do. A representative example of the crosslinkable silicon group is a group represented by the formula (I).

(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 hydrolyzable group. Represents a group, and when two or more X are present, they may be the same or different, a represents 0, 1, 2 or 3, b represents 0, 1 or 2; And n formulas (II):

It is not necessary that all b's in are 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。 The number of silicon atoms forming the crosslinkable silicon group is 1 or more and 20 or less.
Formula (III):

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.

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. In these, a methyl group is preferable at the point which has a practical reaction rate.

  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 used from the viewpoint of obtaining a practical reaction rate and storage stability. 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 small number of carbon atoms have high reactivity, and the reactivity decreases 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 application, a methoxy group or an ethoxy group is usually used.

  In the case of a crosslinkable silicon group represented by the formula (III), a is preferably 2 or more in consideration of curability. Usually, when a is 3, the curing rate is higher than when a is 2.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups such as a trimethoxysilyl group and a triethoxysilyl group, dialkoxy such as —Si (OR ² ) ₃ , a methyldimethoxysilyl group, and a methyldiethoxysilyl group. And a silyl group, —SiR ² ₁ (OR ² ) ₂ .

Here, R ² is an alkyl group, preferably an alkyl group having 10 or less carbon atoms, and more preferably a methyl group or an ethyl group. Among these, the methyldimethoxysilyl group has mild reactivity and is also used as a crosslinkable silicon group in industrially produced saturated hydrocarbon polymers. A trimethoxysilyl group having high reactivity is known as a crosslinkable silicon group, and may be used as a crosslinkable silicon group in the saturated hydrocarbon polymer of the present invention.

  One type of crosslinkable silicon group may be used, or two or more types may be used in combination. The crosslinkable silicon group may 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 from the viewpoint of excellent cured product properties such as tensile properties of the cured product.

  At least one, preferably 1.1 to 5, crosslinkable silicon groups may be present in one molecule of the component (A) polymer. 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 crosslinkable silicon group may be present at the terminal of the saturated hydrocarbon polymer molecular chain, may be present inside, or may be present in both. In particular, when a crosslinkable silicon group is present at the end of the molecular chain, the amount of the effective network chain of the saturated hydrocarbon polymer component contained in the finally formed cured product increases, so that the strength and elongation are high. This is preferable from the viewpoint of easily obtaining a rubber-like cured product. Further, these saturated hydrocarbon polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

The polymer that forms the skeleton of the saturated hydrocarbon polymer having a crosslinkable silicon group used in the present invention,
(1) polymerizing olefinic compounds having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene and the like as main monomers (2) homopolymerizing diene compounds such as butadiene and isoprene; It can be obtained by a method such as copolymerization of the olefinic compound and diene compound and then hydrogenation, but it is easy to introduce a functional group at the terminal, easy to control the molecular weight, and the number of terminal functional groups. From the standpoint that it can be increased, it is preferably an isobutylene polymer or a hydrogenated polybutadiene polymer.

  In addition, the saturated hydrocarbon polymer referred to in this specification is a concept that means a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring.

  In the isobutylene polymer, all of the monomer units may be formed from isobutylene units, and the monomer units copolymerizable with isobutylene are preferably 50% (weight%, in the isobutylene polymer). The same shall apply hereinafter), more preferably 30% or less, particularly preferably 10% or less.

  Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. Specific examples of such copolymer components include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, and vinyl. Cyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-vinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane , Vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinyl Examples thereof include silane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane and the like.

  When vinyl silanes or allyl silanes are used as monomers copolymerizable with isobutylene, the silicon content increases, the number of groups that can act as a silane coupling agent increases, and the adhesion of the resulting composition is improved. To do.

  In the hydrogenated polybutadiene polymer and other saturated hydrocarbon polymers, as in the case of the isobutylene polymer, other monomer units are included in addition to the main monomer unit. May be.

  In addition, the saturated hydrocarbon polymer used in the present invention contains a small amount of monomer units such that a double bond remains after polymerization, such as a polyene compound such as butadiene and isoprene, to the extent that the object of the present invention is achieved. Preferably, it may be contained in a range of 10% or less, further 5% or less, and particularly 1% or less.

  The number average molecular weight of the saturated hydrocarbon polymer, preferably an isobutylene polymer or hydrogenated polybutadiene polymer, is preferably 500 to 30,000, particularly 1,000 to 15,000. It is preferable from the viewpoint of easy handling. If the number average molecular weight is less than 500, the elongation characteristics of the cured product are lowered, which is not preferable. When the number average molecular weight exceeds 30,000, the polymer is unfavorable in that the fluidity is impaired and the convenience of handling is lacking. The saturated hydrocarbon polymer (A) may be used alone or in combination of two or more.

  Among the isobutylene polymers having a crosslinkable silicon group, an inbutylene polymer having a crosslinkable silicon group at the end of the molecular chain is a polymerization method called an inifer method (initiator and chain transfer agent both used as an inifer). And a terminal functional type, preferably all terminal functional type isobutylene polymer obtained by a cationic polymerization method using a specific compound. Such production methods are described, for example, in JP-A-63-006041, JP-A-63-006003, JP-A-63-254149, JP-A-01-038407, and the like.

  An isobutylene polymer having a crosslinkable silicon group in the molecular chain is produced by adding a vinylsilane or allylsilane having a crosslinkable silicon group to a monomer mainly composed of isobutylene and copolymerizing them.

  Furthermore, in the polymerization for producing an isobutylene polymer having a crosslinkable silicon group at the molecular chain end, the terminal is obtained by copolymerizing vinylsilanes or allylsilanes having a crosslinkable silicon group in addition to the main component isobutylene monomer. By introducing a crosslinkable silicon group into an isobutylene-based polymer having a crosslinkable silicon group at the terminal and inside the molecular chain.

  Specific examples of the vinyl silanes and allyl silanes having a crosslinkable silicon group include, for example, vinyl trichlorosilane, vinyl methyl dichlorosilane, vinyl dimethyl chlorosilane, vinyl dimethyl methoxy silane, divinyl dichloro silane, divinyl dimethoxy silane, allyl trichloro silane, Examples include allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, diallyldichlorosilane, diallyldimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane.

  An isobutylene polymer having a crosslinkable silicon group is manufactured and sold by Kaneka Corporation under the brand name of EPION.

（式中、Ｙは塩素原子、ヨウ素原子等のハロゲン原子、Ｒ^３は−Ｒ^４−、

（式中、Ｙは塩素原子、ヨウ素原子等のハロゲン原子、Ｒ^３は−Ｒ^４−、
（Ｒ^４は炭素数１〜２０の２価の炭化水素基で、好ましい具体例としてはアルキレン基、シクロアルキレン基、アリーレン基、アラルキレン基があげられる）で示される２価の有機基で、―ＣＨ_２―、

（Ｒ″は炭素数１〜１０の炭化水素基）より選ばれた２価の基がとくに好ましい）で示される有機ハロゲン化合物を反応させることにより、末端オレフィン基を有する水添ポリブタジエン系重合体（以下、末端オレフィン水添ポリブタジエン系重合体ともいう）が製造される。 In the hydrogenated polybutadiene polymer, for example, the hydroxyl group of the terminal hydroxy hydrogenated polybutadiene polymer is first converted to an oxymetal group such as -ONa or -OK, and then the formula (IV):

Wherein Y is a halogen atom such as a chlorine atom or an iodine atom, R ³ is —R ⁴ —,

Wherein Y is a halogen atom such as a chlorine atom or an iodine atom, R ³ is —R ⁴ —,
(R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, and preferred specific examples include an alkylene group, a cycloalkylene group, an arylene group, and an aralkylene group) CH _2- ,

A hydrogenated polybutadiene-based polymer having a terminal olefin group is reacted with an organic halogen compound represented by (R ″ is a divalent group selected from hydrocarbon groups having 1 to 10 carbon atoms). Hereinafter, it is also referred to as a terminal olefin hydrogenated polybutadiene polymer).

The method for converting the terminal hydroxyl group of the terminal hydroxy-hydrogenated polybutadiene polymer to an oxymetal group includes alkali metals such as Na and K; metal hydrides such as NaH; metal alkoxides such as NaOCH ₃ ; caustic alkalis such as caustic soda and caustic potash. And the like.

  In the above method, a terminal olefin hydrogenated polybutadiene polymer having almost the same molecular weight as that of the terminal hydroxy hydrogenated polybutadiene polymer used as a starting material is obtained. Before reacting the organic halogen compound (4), a polyvalent organic halogen compound containing two or more halogen atoms in one molecule, such as methylene chloride, bis (chloromethyl) benzene, bis (chloromethyl) ether, etc. When reacted, the molecular weight can be increased. After that, when reacted with the organic halogen compound represented by the formula (4), a hydrogenated polybutadiene polymer having a higher molecular weight and having an olefin group at the terminal can be obtained. Can do.

  Specific examples of the organic halogen compound represented by the formula (4) include, for example, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether. , Allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, l-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene, and the like, but are not limited thereto. Of these, allyl chloride is preferred because it is inexpensive and easily reacts.

As in the case of the isobutylene polymer having a crosslinkable silicon group at the molecular chain end, the introduction of the crosslinkable silicon group into the terminal olefin hydrogenated polybutadiene polymer is, for example, a hydrogen atom in the group represented by the formula (I). Is a hydrosilane compound, preferably of the formula:

(Wherein R ¹ , X, and a are the same as described above) are produced by subjecting the compound represented by the addition reaction to a platinum catalyst.

  Specific examples of the hydrosilane compound in which a hydrogen atom is bonded to the group represented by the formula (I) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxy Alkoxysilanes such as silane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoxy) Mate) ketoximate silanes such as methyl silane, and the like, but are not limited thereto. Among these, halogenated silanes and alkoxysilanes are preferable because of high reactivity, and alkoxysilanes are more preferable because of high safety as well as reactivity.

（式中、Ｇは分子引力定数、ΣＧは分子中の原子と原子団のＧの総和、ｄは密度、Ｍは分子量を示す。） [(B) Polycarboxylic acid ester]
In the present invention, in order to improve the deep curability of the curable composition, (B) two or more ester bonds with a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms, and the Small shown in the following (Equation 2) A polycarboxylic acid ester having a solubility parameter δ calculated by the method of 8.9 in the range of 8.9 (cal / cm ³ ) ^{1/2 to} 10.5 (cal / cm ³ ) ^1/2 is used. Use of this compound improves the deep curability of the curable composition, but does not reduce the storage stability of the curable composition. For this reason, it can be suitably used for a one-component curable composition containing a saturated hydrocarbon polymer having a crosslinkable silicon group.

(In the formula, G is a molecular attraction constant, ΣG is the sum of G of atoms and atomic groups in the molecule, d is density, and M is molecular weight.)

(Polycarboxylic acid)
The polycarboxylic acid constituting the acid portion of the polycarboxylic acid ester is preferably a dicarboxylic acid or a tricarboxylic acid, and more preferably a dicarboxylic acid. The polycarboxylic acid may be an aliphatic polycarboxylic acid or an aromatic polycarboxylic acid, but is preferably an aliphatic polycarboxylic acid in terms of good weather resistance and compatibility with the component (A). Polycarboxylic acids are more preferred.

  Examples of saturated aliphatic polycarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic acid, acetic acid, propionic acid, etc. And adipic acid is preferred in that the workability of the composition is good. Examples of the unsaturated aliphatic polycarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid and the like. Examples of the aromatic polycarboxylic acid include benzoic acid and cinnamic acid.

  Among the above-mentioned acids, adipic acid is particularly preferable in that the deep part curability and the workability of the composition are good.

(Monoalcohol)
The alcohol used for esterification of the polycarboxylic acid is preferably a monoalcohol having 1 to 4 carbon atoms. When the number of carbons exceeds 5, it is not preferable in the case that proper deep curability may not be obtained when stored for a long time in a one-pack type. Moreover, it is not preferable that it is not monoalcohol but alcohol having two or more hydroxyl groups in that it may cause poor curing after long-term storage as a composition.

  Examples of the monoalcohol having 1 to 4 carbon atoms constituting the alcohol part of the polycarboxylic acid ester include methanol, ethanol, n-propanol, i-propanol, n-butanol, s-butanol, and t-butanol. Among these, monoalcohols having 1 to 3 carbon atoms are preferable, methanol and ethanol are more preferable, and methanol is particularly preferable.

(ester)
The polycarboxylic acid ester is obtained by a condensation reaction between the polycarboxylic acid and the monoalcohol. The polycarboxylic acid ester is preferably a complete ester of polycarboxylic acid. The partial ester is not preferable because of poor storage stability. Moreover, a partial ester body is not preferable also at the point which a composition tends to thicken during storage.

In the polycarboxylic acid ester, the solubility parameter δ calculated by the Small method shown in (Expression 2) is 8.9 (cal / cm ³ ) ^1/2 or more and 10.5 (cal / cm ³ ) ^1/2. It is preferably in the following range, more preferably in the range of 9.0 (cal / cm ³ ) ^1/2 or more and 10.1 (cal / cm ³ ) ^1/2 or less. If δ is less than 8.9, the compatibility with water is inferior, and the deep part curability is not preferred. When δ exceeds 10.5, it is not preferable in that it may not be able to obtain appropriate adhesiveness when stored for a long period of time.

  In the present embodiment, the solubility parameter δ uses a value obtained by the Small method. The calculation method by the method of Small is described in Ichiro Shibazaki, “Adhesion Encyclopedia (above)” published by Kobunshi Publishing, March 25, 1975, page 31, line 5 to page 33, line 1. This embodiment Then, the solubility parameter δ is calculated based on the description in the same document.

Among polycarboxylic acid esters in which δ is in the range of 8.9 (cal / cm ³ ) ^1/2 or more and 10.5 (cal / cm ³ ) ^1/2 or less, as a specific example of aliphatic carboxylic acid methyl ester Dimethyl succinate (δ = 10.0), dimethyl glutarate (δ = 9.9), dimethyl adipate (δ = 9.6), and dimethyl sebacate (δ = 9.1). Examples of the lower fatty acid methyl ester include methyl acetate (δ = 9.3) and methyl propionate (δ = 9.1). Examples of the aromatic carboxylic acid methyl ester include methyl benzoate (δ = 10.1) and methyl cinnamate (δ = 10.0). Among them, dimethyl adipate is preferable because it is an ester of an aliphatic polycarboxylic acid and methanol and has a low molecular weight, and thus has excellent deep-part curability when stored for a long time in a one-pack type. The polycarboxylic acid ester may be one type or a mixture of two or more types.

On the other hand, as an example of a polycarboxylic acid ester in which δ is not in the range of 8.9 (cal / cm ³ ) ^1/2 or more and 10.5 (cal / cm ³ ) ^1/2 or less, trimethyl citrate (δ = 11 .5), methyl butyrate (δ = 8.8), methyl valerate (δ = 8.6), and trimethyl trimellitic acid (δ = 11.1).

  These polycarboxylic acid esters of component (B) may be used alone or in combination of two or more. Of these, dimethyl adipate is preferred. The amount of the polycarboxylic acid ester used as the component (B) is 1 to 150 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the polymer (A). More preferably, it is used in the range of 10 to 75 parts by weight. If it is less than 1 part by weight, it is not preferable in that a blending effect cannot be obtained, and good deep part curability cannot be obtained. Moreover, when it exceeds 150 weight part, when it preserve | saves for a long time with a solvent-free one-pack type, it is unpreferable at the point from which appropriate adhesiveness is not acquired.

[(C) inorganic filler]
In the present invention, an inorganic filler is used as the component (C). By using the inorganic filler, the one-component moisture-curable composition containing the polymer of the component (A) and the polymer of the component (B) is prevented from lowering the adhesiveness during storage. Examples of inorganic fillers include fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, fine calcium carbonate, heavy calcium carbonate or surface treated products thereof such as calcium carbonate, alumina, aluminum hydroxide, carbonic acid. Fillers such as magnesium, diatomaceous earth, calcined clay, clay, talc, kaolin, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, glass balloon, shirasu balloon and inorganic fiber can be used. .

  These fillers may be used alone or in combination of two or more. Of these, calcium carbonate and alumina are preferable. In particular, calcium carbonate is preferable because it is inexpensive. The calcium carbonate may be colloidal calcium carbonate having an average particle size of 1 micron or less, or may be heavy calcium carbonate having an average particle size of more than 1 micron.

  These calcium carbonates may or may not be surface-treated. As surface-treated calcium carbonate, calcium carbonate surface-treated with a higher fatty acid or a derivative such as a metal salt or ester thereof is well known. In the present invention, calcium carbonate surface-treated with a higher fatty acid or a derivative thereof can be used, but acrylic acid and / or polyacrylic acid, which is a slightly special surface-treated calcium carbonate, or a metal salt or ester thereof, etc. It is preferable to use calcium carbonate surface-treated with a derivative of When calcium carbonate surface-treated with acrylic acid and / or polyacrylic acid or a derivative thereof is used, the detailed reason is unknown, but when using calcium carbonate treated with an untreated or higher fatty acid derivative In comparison with the above, it is possible to obtain a composition in which the deep curability of the curable composition is excellent. In particular, calcium carbonate surface-treated with polyacrylic acid or a derivative such as a metal salt or ester thereof is preferred.

  The amount of the inorganic filler used is in the range of 1 to 300 parts, preferably 50 to 300 parts, more preferably 100 to 200 parts of the inorganic filler of component (C) with respect to 100 parts of polymer of component (A). Used. In particular, when 100 parts or more of the inorganic filler is used, the effect that the adhesiveness does not decrease after storage of the composition is remarkable. When it is less than 1 part by weight, it is not preferable in that a proper adhesiveness cannot be obtained when it is stored for a long time in a solventless one-component type. Moreover, when it exceeds 300 weight part, since the viscosity of a composition will become high and workability | operativity will fall, it is unpreferable.

[Other organic polymers]
Another organic polymer having a crosslinkable silicon group may be used in combination with the one-component moisture-curable composition of the present invention. Examples of such polymers include (meth) acrylic acid ester polymers; condensation polymers of polybasic acids such as adipic acid, terephthalic acid, and succinic acid and polyhydric alcohols such as bisphenol A, ethylene glycol, and neopentyl glycol. Polyester polymers such as ring-opening polymers of lactones and lactones; Nylon 6 by ring-opening polymerization of ε-caprolactam, Nylon 6,6 by condensation polymerization of hexamethylenediamine and adipic acid, polycondensation of hexamethylenediamine and sebacic acid Nylon 6 · 10 by nylon, nylon 11 by condensation polymerization of ε-aminoundecanoic acid, nylon 12 by ring-opening polymerization of ε-aminolaurolactam, and polyamides such as copolymer nylon having two or more components among the above nylons Polymer; polysulfide polymer; for example, bisphenol A and calcium chloride Polycarbonate-based polymers produced by condensation polymerization from sulfonyl, diallyl phthalate polymers, and the like.

  When a polymer other than a saturated hydrocarbon polymer having a crosslinkable silicon group or a (meth) acrylic acid ester polymer having a crosslinkable silicon group is used in combination, a saturated hydrocarbon polymer having a crosslinkable silicon group; The total amount of the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more of the total amount of the organic polymer having a crosslinkable silicon group. .

  As the other organic polymer having a crosslinkable silicon group, a (meth) acrylic acid ester polymer having a crosslinkable silicon group is preferable. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. When a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is used in combination, when the curable composition of the present invention is used as an adhesive or a sealing material, the adhesiveness of the cured product to the substrate is improved. This improvement in adhesion occurs when the inorganic filler of component (C) is present, and when there is no inorganic filler, the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is used in combination. However, the adhesion is not improved.

((Meth) acrylic acid ester polymer having a crosslinkable silicon group)
Hereinafter, the case where the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is used in combination will be described. The crosslinkable silicon group contained in the (meth) acrylic acid ester polymer is the same group as the crosslinkable silicon group contained in the saturated hydrocarbon polymer (A) described above.

  As in the case of the saturated hydrocarbon polymer (A), at least one crosslinkable silicon group is present in one molecule of the (meth) acrylic acid ester polymer, preferably 1.1 to 5, and (meth) It may be present at the end of the acrylate polymer chain, may be present inside, or may be present in both. When the number of crosslinkable silicon groups in one molecule of the (meth) acrylic acid ester polymer is less than 1, it is not preferable because sufficient adhesiveness may not be obtained. When the number of crosslinkable silicon groups exceeds 5, it is not preferable in that the viscosity of the composition may be too high. These (meth) acrylic acid ester-based polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  The polymer that forms the skeleton of the (meth) acrylic acid ester polymer used in the present invention is copolymerizable with the (meth) acrylic acid ester monomer, if necessary. The content of the (meth) acrylic acid ester monomer unit is preferably 50% or more, more preferably 70% or more. When the ratio of the (meth) acrylic acid ester monomer unit is less than 50%, the glass transition temperature (Tg) decreases, and the heat resistance and the elastic modulus tend to decrease.

（式中、Ｒ^５は１価の炭素数１〜３０の置換又は非置換の炭化水素基、Ｒ^６は水素原子又はメチル基を示す）で表わされる単位である。 The (meth) acrylic acid ester monomer unit has the formula (VIII):

(Wherein R ⁵ is a monovalent substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and R ⁶ is a hydrogen atom or a methyl group).

Specific examples of the monovalent substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms as R ⁵ in the formula (VIII) include, for example, methyl group, ethyl group, n-butyl group, isobutyl group, 1 -Ethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, isooctyl group, 3,5,5-trimethylhexyl group, 2-ethylhexyl Group, decyl group, dodecyl group, tridecyl group, hexadecyl group, stearyl group, allyl group and other branched or unbranched alkyl groups having 1 to 30 carbon atoms, alkylene groups, benzyl groups and the like having 1 to 30 carbon atoms Examples thereof include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms such as a substituted alkyl group, a phenyl group, and a chlorophenyl group.

  Among these, an alkyl group is preferable because it is easily available, and an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-butyl group, and an isobutyl group is particularly preferable.

  Specific examples of the monomer copolymerizable with the (meth) acrylic acid ester monomer used if necessary include acrylic acid monomers such as acrylic acid and methacrylic acid; di (meth) Ethylene glycol acrylate, di (meth) acrylic acid triethylene glycol, di (meth) acrylic acid tetraethylene glycol, di (meth) acrylic acid-1,3-butylene glycol, tri (meth) acrylic acid trimethylolpropane, etc. Polyfunctional (meth) acrylic acid ester monomers; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and methylenebisacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, diethylaminoethyl acrylate, Diethylamino Monomers containing amino groups such as til methacrylate and aminoethyl vinyl ether; other γ-acryloyloxypropyltriethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, maleic anhydride, acrylonitrile, methacrylonitrile, iminol methacrylate, As monomers having a copolymerizability with monomers such as diallyl phthalate, styrene, α-methylstyrene, vinyl pyridine, alkyl vinyl ether, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, ethylene, propylene, isobutylene, etc. Examples thereof include olefins having 4 to 12 carbon atoms, conjugated dienes, vinyl ethers, vinyl silanes, allyl silanes and the like already described.

  The method for producing the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is disclosed in JP-A-60-31556, 61-34067, 57-36109, 57-55954, Although disclosed in JP-A-61-225205, etc., among these polymers, a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group at the molecular chain end is produced, for example, by the following method. Can do.

That is,
(I) (meth) acrylic acid ester monomer contained if a monomer having copolymerizability with a (meth) acrylic acid ester monomer is required using a radical polymerization initiator containing a crosslinkable silicon group Polymerize the body,
(Ii) polymerizing the (meth) acrylic acid ester monomer of (i) using a radical polymerization chain transfer agent containing a crosslinkable silicon group;
(Iii) The (meth) acrylic acid ester monomer of (i) is polymerized by using the radical polymerization initiator and the radical polymerization chain transfer agent used in (i) and (ii) together,
(Iv) using a radical polymerization initiator and / or a radical polymerization chain transfer agent containing a functional group (hereinafter referred to as a Z group) such as a carboxyl group, a hydroxyl group, a halogen atom, an amino group, and an epoxy group; By polymerizing the (meth) acrylic acid ester monomer, a polymer having a Z group at the polymer molecule end is produced, or the Z group is reacted with a polyfunctional compound such as triisocyanate to produce a polymer. An isocyanate group, carboxyl group, hydroxyl group, halogen atom, amino group, which can react with the Z group or Z ′ group by producing a polymer having a functional group (hereinafter referred to as Z ′ group) at the terminal of the polymer molecule This is a method in which a silicon compound having a functional group such as an epoxy group, a mercapto group, and an acrylic group and having a crosslinkable silicon group is reacted with a Z group or a Z ′ group at the end of the polymer.

等のアゾ系のラジカル重合開始剤や、

等の過酸化物系のラジカル重合開始剤等があげられる。
前記架橋性珪素基を有するラジカル重合連鎖移動剤としては、

等があげられる。 Specific examples of the radical polymerization initiator having a crosslinkable silicon group are disclosed in, for example, JP-A-60-31558.

Azo radical polymerization initiators such as

And peroxide-based radical polymerization initiators.
As the radical polymerization chain transfer agent having a crosslinkable silicon group,

Etc.

  In addition, (meth) acrylic acid ester-based polymers having a crosslinkable silicon group in the molecular chain are vinylsilanes and allylsilanes having a crosslinkable silicon group in monomers mainly composed of (meth) acrylate monomer units. And the like are added and copolymerized.

  Further, the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group at the molecular chain terminal and inside is further crosslinked when the (meth) acrylic acid polymer having a crosslinkable silicon group at the molecular terminal is produced. It is manufactured by adding vinyl silanes and allyl silanes having a functional silicon group and copolymerizing them.

  Specific examples of vinyl silanes and allyl silanes having a crosslinkable silicon group include those similar to those used in the production of the above-mentioned isobutylene polymer having a crosslinkable silicon group in the molecular chain. It is done.

  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. Such a polymer can be used as the (meth) acrylic acid ester polymer used in the present invention.

  Further, as disclosed in JP 2000-086999 A, a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group, in which a crosslinkable silicon group is introduced at a high rate at the molecular chain terminal. Coalescence is also 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. Such a polymer can be used as the (meth) acrylic acid ester polymer used in the present invention.

  In the present invention, a (meth) acrylic acid alkyl ester polymer as described above can be used. Among these, a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group obtained by using a mercaptan having a crosslinkable silicon group and a metallocene compound is preferable in that the workability of the composition is good. .

  The number average molecular weight of the (meth) acrylic acid ester polymer is preferably 500 to 100,000 from the viewpoint of ease of handling, and more preferably 1,000 to 75,000. If the number average molecular weight is less than 500, the elongation characteristics of the cured product are not good, which is not preferable. When the number average molecular weight exceeds 100,000, the viscosity is high, the viscosity of the composition is increased, and the workability is lowered.

  The use ratio of the saturated hydrocarbon polymer (A) and the (meth) acrylic acid ester polymer is an arbitrary ratio depending on the use of the composition, workability, required properties of the cured product or composition, cost, etc. However, it is usually used in the range of 1 to 30 parts of a (meth) acrylic acid ester polymer with respect to 100 parts (parts by weight) of the component (A). If the amount of the (meth) acrylic acid ester polymer is less than 1 part by weight, sufficient adhesiveness cannot be obtained, which is not preferable. When the amount of the (meth) acrylic acid ester polymer exceeds 30 parts by weight, the viscosity is high, the viscosity of the composition is increased, and workability is lowered, which is not preferable.

[Curing catalyst]
In the one-component moisture-curable composition of the present invention, various additives such as a curing catalyst (silanol condensation catalyst), a plasticizer, an adhesiveness imparting agent, a diluent, and a tackifier may be used in combination as necessary. it can.
Curing catalysts include tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate, etc .; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide Dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanate (dioctyltin diversate), dioctyltin oxide, tetravalent tin compounds such as dibutyltin oxide and phthalate, tin octylate, naphthenate Organic tin compounds such as divalent tin compounds such as tin oxide, tin stearate, and tin neodecanoate (tin versatic acid); aluminum trisacetylacetonate, aluminum Organic aluminum compounds such as umtris ethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate; bismuth salts such as bismuth-tris (2-ethylhexoate), bismuth-tris (neodecanoate) and 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, diethylamine Nopropylamine, 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 acid, etc .; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; excess polyamine and epoxy Examples of reaction products with compounds; acidic phosphate compounds and the like.

  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 a saturated hydrocarbon polymer having a crosslinkable silicon group. If it is less than 0.5 part by weight, it is not preferable in that a sufficient curing rate cannot be obtained. If it exceeds 10 parts by weight, it cannot be said that the curing rate is faster than the case of 0.5 to 10 parts by weight, which is not preferable in that a useless curing catalyst is generated.

[Plasticizer]
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 (meth) acrylate plasticizers such as alkyl acrylates; polystyrenes such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymers, polychloroprene, polyisoprene, polyisobutene, paraffinic carbonization Plasticizers such as hydrogen, naphthenic hydrocarbons, paraffin-naphthene mixed hydrocarbons and chlorinated paraffins can be used alone or in the form of a mixture of two or more.

  In particular, polyether plasticizers such as polypropylene glycol and its derivatives, poly (meth) acrylate plasticizers, polyisobutene, paraffin and the like that do not contain an unsaturated bond in the polymer main chain are preferred from the viewpoint of weather resistance. In particular, polyether plasticizers such as polypropylene glycol and derivatives thereof and poly (meth) acrylate plasticizers, which are polymer plasticizers, are preferable. In addition, when an ester of a polybasic acid and an alcohol having 1 to 3 carbon atoms, such as dimethyl adipate, particularly an ester of a polybasic acid and methanol is used, the deep curability is improved when the composition is cured. There is. When using a plasticizer, it is preferable to add 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, based on 100 parts by weight of a saturated hydrocarbon polymer having a crosslinkable silicon group.

[Adhesive agent]
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. It is preferable to add 1 to 15 parts by weight, and it is more preferable to add 0.5 to 10 parts by weight.

[Tackifier]
A tackifier may be added to improve the wettability to the adherend and to increase the peel strength. Examples include petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin, phenolic resin copolymer thereof, and phenol / phenol novolac resin-based tackifier resin.

[Other additives]
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 (dehydrating agents), lubricants and foaming agents should be added as necessary. Is possible.

[Usage]
As described above, the one-component moisture-curable composition of the present invention has good storage stability and workability, is cured by moisture in the air at room temperature, and has weather resistance, water resistance, heat resistance, strength, elongation characteristics, Gives rubber-like elastic bodies and cured products with good paintability and adhesion. Therefore, it can be suitably used as a paint, a waterproofing agent, a potting material, an adhesive, a sealing material or the like that gives a coating film having elasticity. In particular, it is useful as a potting material, an adhesive, and a sealing material.

<Seal material>
The one-component moisture curable composition of the present invention is particularly suitable as a sealing material.
Conventionally, hot-melt butyl rubber sealing materials have been mainly used. However, although this sealant has good moisture resistance, it does not involve cross-linking, so that there is a problem that the temperature rises and the seal is deformed when exposed to direct sunlight.
In order to solve this problem, a crosslinkable polyisobutylene-based sealing material has also been proposed. However, there has been a problem that deep part curing is slow and adhesion to an adherend such as glass or aluminum is low.
When the one-component moisture-curable composition according to the present invention is used as a sealant, it is a crosslinkable polyisobutylene system, so that the seal can be prevented from being deformed even when installed in a place exposed to direct sunlight, and deep curing is performed. There is a special effect that it has sufficient adhesion to adherends such as glass and aluminum.

<Solar cell module>
The sealing material is preferably used as an end treatment agent for solar cell panels. In that case, the said sealing material will be used with respect to a solar cell module, Specifically, it will be used for the use which fixes the edge part and fixing member of a solar cell panel. Since the solar cell panel is installed in a place exposed to direct sunlight, prevention of seal deformation is required. Deep sealability is also required for the sealing material for solar cell panels. In this respect, the sealing material is preferably used for a solar cell module.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

<Example 1>
(A) 100 parts by weight of methyldimethoxysilyl group-terminated polyisobutylene (trade name “Epion EP505S”, manufactured by Kaneka Corporation) as a saturated hydrocarbon polymer having a crosslinkable silicon group, and (B) δ is 8.9 or more and 10 Dimethyl adipate as an ester of a polycarboxylic acid and a mono-alcohol having 1 to 4 carbon atoms in the range of .5 or less (solubility parameter δ = 9.0 (cal / cm ³ ) calculated by the method of Small) ^{1 / 2} ) 50 parts by weight, (C) 30 parts by weight of heavy calcium carbonate (trade name “Whiten SB Red”, average particle size: 1.8 μm, manufactured by Shiroishi Kogyo Co., Ltd.) as an inorganic filler, and an antioxidant 1 part by weight of a hindered phenol compound (trade name “Irganox 1010”, manufactured by Ciba Japan) was kneaded with a Dalton type mixer (manufactured by Shinagawa Kogyo Co., Ltd.). Thereafter, 3 parts by weight of ethyl silicate (trade name “ethyl silicate 28”, manufactured by Colcoat Co., Ltd.) as a dehydrating agent and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (trade name “KBM” as an adhesion-imparting agent are used. -603 ", manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 parts by weight of an organotin compound (trade name" Neostan U-700ES ", manufactured by Nitto Kasei Co., Ltd.) as a curing catalyst are added, and kneading and defoaming are performed. Thus, a one-component curable composition of Example 1 was obtained.

<Example 2>
(B) As an ester of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms in which δ is in the range of 8.9 to 10.5, dimethyl sebacate (δ = 9) is used instead of the dimethyl adipate. 0.1 (cal / cm ³ ) ^1/2 ) was used in the same manner as in Example 1 except that 50 parts by weight was used.

<Example 3>
(B) As an ester of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms, where δ is in the range of 8.9 to 10.5, dibutyl adipate (δ = 8) instead of the above dimethyl adipate .9 (cal / cm ³ ) ^1/2 ) was used in the same manner as in Example 1 except that 50 parts by weight was used.

<Comparative Example 1>
(B) Dioctyl adipate (δ = 8.5 (cal / cm) instead of an ester of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms, where δ is in the range of 8.9 to 10.5. ³ ) A composition of Comparative Example 1 was obtained in the same manner as in Example 1 except that 50 parts by weight of ^1/2 ) was used.

<Example 4>
(B) As an ester of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms, where δ is in the range of 8.9 to 10.5, dimethyl phthalate (δ = 10) instead of the dimethyl adipate .5 (cal / cm ³ ) ^1/2 ) was used in the same manner as in Example 1 except that 50 parts by weight was used.

<Example 5>
(B) As an ester of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms in which δ is in the range of 8.9 to 10.5, dibutyl phthalate (δ = 9) instead of the dimethyl adipate .5 (cal / cm ³ ) ^1/2 ) was used in the same manner as in Example 1 except that 50 parts by weight was used.

<Comparative Example 2>
(B) Dioctyl phthalate (δ = 8.9 (cal / cm) instead of an ester of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms, where δ is in the range of 8.9 to 10.5. ³ ) A composition of Comparative Example 2 was obtained in the same manner as in Example 1 except that 50 parts by weight of ^1/2 ) was used.

<Comparative Example 3>
(B) Paraffin type diluent (trade name “Cactus normal paraffin N—” instead of ester of polycarboxylic acid and monoalcohol having 1 to 4 carbon atoms, where δ is in the range of 8.9 to 10.5. 11 ”, normal paraffin having 11 carbon atoms, δ = 7.7 (cal / cm ³ ) ^1/2 , manufactured by JX Nippon Oil & Energy Corporation) was used in the same manner as in Example 1. Thus, a composition of Comparative Example 3 was obtained.

<Evaluation of storage stability>
The storage stability was evaluated for the compositions of the examples and comparative examples. First, the curable composition was left in a sealed container (cartridge) at 23 ° C. for 24 hours, and the viscosity of the curable composition at this time was measured. This viscosity is the initial viscosity. Thereafter, the curable composition was allowed to stand in a dryer set at 50 ° C. for 2 weeks, and then left at 23 ° C. for 24 hours in order to bring the liquid temperature to 23 ° C. And the viscosity of the curable composition at this time was measured. This viscosity is the viscosity after storage. The viscosity was set to 20 rpm using a BH rotor No. 7 manufactured by Toki Sangyo Co., Ltd., which is a measuring device conforming to 5.4 “viscosity” of JIS K6833-1. The value of the ratio of the viscosity after storage to the initial viscosity (viscosity after storage / initial viscosity) was defined as storage stability. The results are shown in Table 2. A value of less than 1.4 was designated as “◯”, and a value of 1.4 or more was designated as “x”.

<Evaluation of deep curability>
About the composition of each Example and the comparative example, deep part sclerosis | hardenability was evaluated. A curable composition stored under the same storage conditions as used in the evaluation of storage stability was filled into a polyethylene container having a diameter of 40 mm and a depth of 20 mm, and the surface was smoothed. It was placed in a humid environment for 24 hours. After 24 hours, the cured part was taken out and the thickness from the surface was measured with a micro gauge. The results are shown in Table 2. Practically, the thickness of the cured portion after 24 hours is required to be 1.0 mm or more. Therefore, the case where the thickness is 1.0 mm or more is “◯”, and the case where the thickness is less than 1.0 mm is “×”.

<Evaluation of curing rate after storage>
In order to evaluate the curing rate after storage, the tack-free time retention after storage was evaluated for the compositions of each Example and Comparative Example. The tack-free time was measured according to JIS A 1439 5.19. First, two types of samples (composition) immediately after production and after storage for 56 days in a dryer set at 50 ° C. are placed on a glass plate, taking care not to contain bubbles. While using a spatula, the specimen was flattened to a thickness of about 3 mm to prepare a test specimen. The prepared specimen was placed at 23 ° C. and 50% RH. The fingertips cleaned with ethyl alcohol were lightly touched at three locations on the surface of the specimen. Then, the time required for the sample (composition) to stop sticking to the fingertip after flattening was measured, and the time required for the sample after storage at 50 ° C. for 56 days / the sample immediately after production was required. The time value was defined as the tack-free time retention after storage. The results are shown in Table 2. The case where the tack free time retention rate is less than 1.3 is “◎”, the case where it is 1.3 or more and less than 1.6 is “◯”, and the case where it is 1.6 or more and less than 1.9 is “△” ", And a case where it was 1.9 or more was marked as" x ".

(A) 100 parts by weight of a saturated hydrocarbon polymer having a crosslinkable silicon group, and (B) two or more ester bonds of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms. 1 to 150 parts by weight of a polycarboxylic acid ester having a calculated solubility parameter δ in the range of 8.9 (cal / cm ³ ) ^{1/2 to} 10.5 (cal / cm ³ ) ^1/2 ; C) By containing 1 to 300 parts by weight of the inorganic filler, it can be stored for a long time without performing a process that is not performed with a normal one-component curable composition such as destruction of microcapsules, and for a long time. It was confirmed that even after storage, a one-component moisture-curable composition that is excellent in both deep curability and curing speed can be provided (Examples 1 to 5). In particular, it has two or more ester bonds of aliphatic polycarboxylic acid and methanol, and the solubility parameter δ is 9.0 (cal / cm ³ ) ^1/2 or more 10.1 (cal / cm ³ ) ^1/2 When the polycarboxylic acid methyl ester in the following range is used as the component (B) (Examples 1 and 2), compared to the case of using a monoalcohol having a large number of carbons (Example 3), the curing rate after storage is increased. It was excellent and it was confirmed that it is excellent in adhesiveness compared with the case where aromatic polycarboxylic acid is used (Examples 4 and 5).

  On the other hand, when the number of carbon atoms of the alcohol constituting the ester exceeds 5, it was confirmed that there is a possibility that appropriate deep curability may not be obtained when stored for a long time in a one-pack type (Comparative Examples 1 and 2). . That is, since the compositions described in Examples 6 to 8 of Patent Document 10 are based on dioctyl phthalate as a raw material, the compositions described in the same document are obtained from the conditions described in the same document (50 ° C., 1 week). Furthermore, it was confirmed that the deep curability as in the examples of the present invention may not be obtained when stored for a long time (50 ° C., 2 weeks). In addition, since the composition as described in the other Example of the said patent document 10 does not contain the polycarboxylic acid used as the frame | skeleton of said (B) polycarboxylic acid ester, deep part curability is less than 1.0 mm, Not as much as the embodiment of the present invention.

  Moreover, when paraffin type diluent was used instead of polycarboxylic acid ester, when it was preserve | saved for a long time by the one-pack type, it was confirmed that appropriate deep part sclerosis | hardenability may not be obtained (comparative example 3).

<Synthesis of (meth) acrylic acid ester-based polymer having a crosslinkable silicon group>
78 parts by weight of methyl methacrylate, 22 parts by weight of γ-methacryloxypropyltrimethoxysilane (trade name “KBM-503”, manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.1 part by weight of ruthenocene dichloride as a metal catalyst, The mixture was placed in a flask together with 40 parts by weight of ethyl acetate as a solvent, and heated to 80 ° C. while introducing nitrogen gas. Subsequently, 8 parts by weight of 3-mercaptopropyltrimethoxysilane (trade name “KBM-803”, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the flask and heated 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. The weight average molecular weight (polystyrene conversion) of this polymer was about 6000.

<Example 6>
A composition of Example 6 was obtained in the same manner as in Example 1 except that 10 parts by weight of the acrylate polymer obtained by the above synthesis was further added.

<Comparative example 4>
(B) The dioctyl adipate was used in an amount of 50 parts by weight instead of the ester of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms, where δ is in the range of 8.9 to 10.5, And the composition of the comparative example 4 was obtained by the method similar to Example 1 except having further added 10 weight part of acrylic ester polymers obtained by the said synthesis | combination.

  The compositions of Example 6 and Comparative Example 4 were similarly evaluated for storage stability, deep part curability and adhesiveness. The results are shown in Table 4.

(A) 100 parts by weight of a saturated hydrocarbon polymer having a crosslinkable silicon group, and (B) two or more ester bonds of a polycarboxylic acid and a monoalcohol having 1 to 4 carbon atoms. 1 to 150 parts by weight of a polycarboxylic acid ester having a calculated solubility parameter δ in the range of 8.9 (cal / cm ³ ) ^{1/2 to} 10.5 (cal / cm ³ ) ^1/2 ; C) In addition to 1 to 300 parts by weight of the inorganic filler, and further containing (D) 1 to 30 parts by weight of a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group, destruction of microcapsules, etc. One-part moisture that can be stored for a long time without performing steps that are not possible with ordinary one-part curable compositions, and is excellent in both deep curable and adhesive properties even after long-term storage Can provide a curable composition It was confirmed (Example 6). When Example 1 was compared with Example 6, it was confirmed that the adhesiveness after long-term storage was particularly excellent (Example 6).

  On the other hand, when the number of carbon atoms of the alcohol constituting the ester exceeds 5, even if 1 to 30 parts by weight of (D) a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group is added, the improvement in deep curability is observed. (Comparative Example 4).

Claims (15)

(A) An isobutylene polymer and / or hydrogenated polybutadiene-based polymer having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having at least one crosslinkable silicon group that can be crosslinked by forming a siloxane bond. 100 parts by weight of coalescence ,
(B) It has two or more ester bonds of polycarboxylic acid and monoalcohol having 1 to 4 carbon atoms, and the solubility parameter δ calculated by the Small method shown in the following (Equation 1) is 8.9 (cal / Cm ³ ) ^{1/2 to} 10.5 (cal / cm ³ ) ^{1/2 in} the range of 1 to 150 parts by weight of a polycarboxylic acid ester,
(C) 1 to 300 parts by weight of an inorganic filler ;
(D) A one-component moisture-curable composition containing 1 to 30 parts by weight of a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group .

(In the formula, G is a molecular attraction constant, ΣG is the sum of G of atoms and atomic groups in the molecule, d is density, and M is molecular weight.) The composition according to claim 1, wherein the crosslinkable silicon group is represented by the following general formula (I).

(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 hydrolyzable group. And when X is 2 or more, they may be the same or different, n represents an integer of 0 to 19, a represents an integer of 0 to 3, and b represents An integer of 0 to 2 is shown, and the sum of a and b is 1 or more, and the general formula (II) constituting the above general formula (I)

It is not necessary that all b's in are the same. )   The composition according to claim 2, wherein X is an alkoxy group.   The composition according to claim 3, wherein X is a methoxy group.   The composition according to any one of claims 1 to 5, wherein the saturated hydrocarbon polymer has the crosslinkable silicon group at an end of a polymer molecular chain. The mono-alcohol having 1 to 4 carbon atoms is methanol, and the δ is in a range of 9.0 (cal / cm ³ ) ^1/2 or more and 10.1 (cal / cm ³ ) ^1/2 or less. Item 7. The composition according to any one of Items 1 to 6.   The composition according to any one of claims 1 to 7, wherein the polycarboxylic acid is an aliphatic polycarboxylic acid.   The composition according to claim 1, wherein the polycarboxylic acid is a dicarboxylic acid.   The composition according to any one of claims 1 to 9, wherein the inorganic filler is calcium carbonate.   The composition according to claim 10, wherein the calcium carbonate is a surface-treated calcium carbonate. The total of the (A) isobutylene polymer and / or hydrogenated polybutadiene polymer and the (D) (meth) acrylate polymer is 50% by weight or more of the total amount of the organic polymer having a crosslinkable silicon group. The composition according to claim 1, wherein The number average molecular weight of the (A) isobutylene polymer and / or hydrogenated polybutadiene polymer is 500 or more and 30,000 or less,
The number average molecular weights of the said (D) (meth) acrylic acid ester type polymer are 500 or more and 100,000 or less, The composition of Claims 1-11.   A sealing material comprising the composition according to claim 1.   The solar cell module by which the edge part and fixing member of the solar cell panel were adhere | attached through the sealing material of Claim 13.   The solar cell module which used the sealing material of Claim 13 as an edge part processing agent of a solar cell panel.