JP6282450B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition containing a reactive silicon group-containing polymer, the curable composition exhibits fast curability, and the cured product has excellent flexibility and a good restoration rate, It can be used for many purposes.

  Reactive silicon group-containing polymers are known as moisture-reactive polymers and are included in many industrial products such as adhesives, sealing agents, coating agents, paints, and adhesives, and are used in a wide range of fields. (Patent Document 1).

  As a polymer component of such a reactive silicon group-containing polymer, the main chain skeleton has various polymers such as a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester copolymer. In particular, polyoxyalkylene polymers have a relatively low viscosity at room temperature and are easy to handle, and a cured product obtained after the reaction also exhibits good elasticity.

  The curable composition using the reactive silicon group-containing polyoxyalkylene-based polymer sometimes has insufficient cured product elongation and surface tack under certain compounding compositions and use conditions. On the other hand, the method of satisfying both the elongation and surface tack of hardened | cured material by adding a specific silicon compound has already been found (patent documents 2 and 3).

  On the other hand, a method for synthesizing a polyoxyalkylene polymer having a plurality of reactive silicon groups at one terminal is also known (Patent Documents 4 and 5).

Patent 1801280 Japanese Patent Laid-Open No. 05-117521 Japanese Patent Application Laid-Open No. 2004-91771 JP 2005-272733 A JP-A-3-79627

  However, as a result of intensive studies by the present inventors, it has been found that in the techniques described in Patent Documents 2 and 3, the obtained cured product tends to relieve stress, that is, there is room for further improvement in resilience.

  In addition, in the techniques described in Patent Documents 6 and 7, description is also suggested regarding the addition of a specific silicon compound in addition to the polyoxyalkylene polymer having a plurality of reactive silicon groups at one terminal. There is no.

  The present invention has been completed as a result of intensive studies of the above circumstances, and the purpose thereof is a curing that can obtain a cured product that is fast-curing and exhibits excellent flexibility and a good restoration rate. It is to obtain a sex composition.

In order to solve the above problems, the present invention comprises the following arrangement. That is, the present invention relates to a reactive silicon group-containing polymer (A) having an average of more than 1.0 reactive silicon group at one end,
General formula (1):
R ₃ Si-
(Wherein R is a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom each independently), and a silicon compound (B) that generates R ₃ SiOH by hydrolysis,
Silanol condensation catalyst (C),
The curable composition containing this.

  The curable composition concerning this invention contains a specific silicon compound (B) with the reactive silicon group containing polymer (A). Thereby, the modulus of the cured product of the curable composition is reduced, the tensile properties are improved (high elongation), and the residual tack is improved (low adhesion).

  On the other hand, when the reactive silicon group-containing polymer used in combination is not devised, the curing rate of the curable composition is slowed down, particularly the curing rate inside the cured product (depth curing rate) is slowed and cured. There is concern that the restoration rate of things will decrease.

  However, in the curable composition according to the present invention, the reactive silicon group-containing polymer (A) that uses the silanol condensation catalyst (C) and is used in combination with a specific silicon compound has one reactive silicon group. It has an average of more than 1.0 at the end. As a result, the curable composition according to the present invention has fast curability, while the cured product exhibits good flexibility, a restoration rate, and high weather resistance. The reason why such an effect can be obtained can be estimated as follows.

  Polymers that have reactive groups such as carbon-carbon unsaturated bonds and reactive silicon groups at the ends of the polymer chain can be used to extend the polymer chain or build a crosslinked network using the reaction of the reactive group be able to. Such a polymer is used in various applications by utilizing this property to change the property of the polymer to exhibit adhesive performance or to form a rubber-like cured product. In this case, it is known that the reactive group advantageously works at the end of the polymer chain. For the purpose of extending the polymer chain and imparting adhesive performance, the molecular chain can be extended efficiently by having a reactive group at the terminal. In addition, when a cured product is obtained by three-dimensional crosslinking, the molecular weight between crosslinking points can be ensured by having a reactive group at the end of the molecular chain, and the characteristics of the polymer main chain structure are improved in the cured product properties. As a result, a tough cured product can be obtained.

  Here, a generally known reactive silicon group-containing polymer is obtained by adding a silyl group to a carbon-carbon unsaturated bond to a polymer having only one carbon-carbon unsaturated bond at a terminal. (Hydrosilylation reaction) is generally synthesized by introducing a reactive silicon group. However, in such a hydrosilylation reaction, it is known that isomerization of a carbon-carbon unsaturated bond occurs as a side reaction and an internal olefin is produced. For this reason, it is difficult to introduce a 100% reactive silicon group with respect to the carbon-carbon unsaturated bond. That is, when a reactive silicon group is introduced into a polymer having only one carbon-carbon unsaturated bond at the terminal by a hydrosilylation reaction, it is difficult to introduce a 100% reactive silicon group at all terminals. . Therefore, the reaction of the obtained reactive silicon group-containing polymer inevitably causes defects. When trying to obtain a cured product using a reactive silicon group-containing polymer having defects, defects may occur in chain extension reaction and three-dimensional crosslinking, and as a result, the expected characteristics may not be obtained.

  On the other hand, the reactive silicon group-containing polymer (A) contained as a main component in the curable composition according to the present invention has more than 1.0 carbon-carbon unsaturated bonds at one terminal site, as will be described later. A terminal structure polymer having a hydrogen atom is produced as a starting material, and the finally obtained reactive silicon group also has an average of more than 1.0 at one terminal site. That is, the reactive silicon group-containing polymer (A) contained as a main component in the curable composition according to the present invention has no defects and has an average of more than 1.0 reactive silicon groups on one terminal site. Therefore, by using together with the specific silicon compound (B) and the silanol condensation catalyst (C), a synergistic effect of these three is exhibited. As a result, while the curable composition according to the present invention has fast curability, the cured product of the curable composition containing such a polymer has excellent flexibility, good restoration rate, and high weather resistance. Indicates.

（式中、Ｒ^１，Ｒ^３はそれぞれ独立に２価の炭素数１〜６の結合基であり、隣接するそれぞれの炭素原子と結合する原子は、炭素、酸素、窒素のいずれかである。Ｒ^２，Ｒ^４はそれぞれ独立に水素、または炭素数１から１０の炭化水素基である。ｎは１から１０の整数である。Ｒ^５はそれぞれ独立に、炭素原子数１から２０の置換あるいは非置換の炭化水素基である。Ｙは水酸基または加水分解性基である。ａは１、２、３のいずれかである。）で表される構造を有することが好ましい。 In the curable composition, the terminal portion of the reactive silicon group-containing polymer (A) is represented by the general formula (2):

(Wherein R ¹ and R ³ are each independently a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to each adjacent carbon atom is any one of carbon, oxygen and nitrogen. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10. R ⁵ is independently substituted or substituted with 1 to 20 carbon atoms, It is an unsubstituted hydrocarbon group, Y is a hydroxyl group or a hydrolyzable group, and a is any one of 1, 2, and 3).

  In the curable composition, the main chain of the reactive silicon group-containing polymer (A) is preferably a polyoxyalkylene polymer.

  In the curable composition described above, the reactive silicon group-containing polymer (A) causes a polymer having a hydroxyl group at the terminal to act on an alkali metal salt of 0.6 equivalent or more with respect to the hydroxyl group, and then carbon-carbon. After reacting with an epoxy compound having an unsaturated bond and further reacting with a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond, a reactive silicon group is formed on the carbon-carbon unsaturated group by a hydrosilylation reaction. It is preferable to be obtained by introduction.

  In the curable composition, 0.1 to 10 parts by weight of the silicon compound (B) and 0.001 to 20 of the silanol condensation catalyst (C) with respect to 100 parts by weight of the reactive silicon group-containing polymer (A). It is preferable to contain by weight.

The present invention also relates to a reactive silicon group-containing polymer (A) having an average of more than 1.0 reactive silicon group at one end,
General formula (1):
R ₃ Si-
(Wherein R is the same or different and is a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom), a silicon compound (B) that generates R ₃ SiOH by hydrolysis,
A agent containing
B agent containing silanol condensation catalyst (C),
The curable composition of the multi-liquid mixing type | mold which consists of a 2 or more-component composition containing this.

  Furthermore, this invention relates to the hardened | cured material obtained by hardening the curable composition in any one of the said.

  In the curable composition according to the present invention, the reactive silicon group-containing polymer (A) having an average of more than 1.0 reactive silicon groups at one end, the specific silicon compound (B) and silanol Three of the condensation catalysts (C) are used in combination. As a result, due to the synergistic effect of these three factors, the curable composition according to the present invention exhibits fast curability, while the resulting cured product exhibits excellent flexibility and good restoration rate.

The curable composition according to the present invention comprises a reactive silicon group-containing polymer (A) having an average of more than 1.0 reactive silicon group at one end,
General formula (1):
R ₃ Si-
(Wherein R is a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom each independently), and a silicon compound (B) that generates R ₃ SiOH by hydrolysis,
Silanol condensation catalyst (C),
Containing. The reactive silicon group-containing polymer (A) is characterized in that it has an average of more than 1.0 reactive silicon groups at one terminal.

  In the present invention, the term “end” includes the chain end in the polymer molecular chain and the vicinity thereof. More specifically, it may be defined as a group that substitutes on the number of atoms corresponding to 20%, more preferably 10%, from the terminal of the bonding atoms constituting the polymer molecular chain. In terms of the number of bonded atoms, the terminal site may be defined as the terminal site of 30 atoms, more preferably 20 atoms from the end of the polymer molecular chain.

<< Reactive silicon group-containing polymer (A) >>
The reactive silicon group-containing polymer (A) of the present invention has an average of more than 1.0 reactive silicon groups at one end.

  The reactive silicon group-containing polymer (A) may have an average of more than 1.0 reactive silicon group at one end, preferably 1.1 or more. More preferably, it is 5 or more, and more preferably 2.0 or more. Further, the upper limit is preferably 5 or less, and more preferably 3 or less.

  Reactive silicon group-containing polymer (A) The number of terminal structures having more than 1.0 reactive silicon groups contained in one molecule is preferably 0.5 or more on average. More preferably, it is 1.1 or more, and most preferably 1.5 or more. The upper limit is preferably 4 or less, and more preferably 3 or less.

  The reactive silicon group-containing polymer (A) may have a reactive silicon group in addition to the terminal site, but preferably has only a terminal site.

（式中、Ｒ^１，Ｒ^３はそれぞれ独立に２価の炭素数１〜６の結合基であり、隣接するそれぞれの炭素原子と結合する原子は、炭素、酸素、窒素のいずれかである。Ｒ^２，Ｒ^４はそれぞれ独立に水素、または炭素数１から１０の炭化水素基である。ｎは１から１０の整数である。Ｒ^５はそれぞれ独立に、炭素原子数１から２０の置換あるいは非置換の炭化水素基である。Ｙは水酸基または加水分解性基である。ａは１、２、３のいずれかである。）であることが好ましい。

In the present invention, the terminal site of the reactive silicon group-containing polymer (A) is represented by the general formula (2):

(Wherein R ¹ and R ³ are each independently a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to each adjacent carbon atom is any one of carbon, oxygen and nitrogen. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10. R ⁵ is independently substituted or substituted with 1 to 20 carbon atoms, An unsubstituted hydrocarbon group, Y is a hydroxyl group or a hydrolyzable group, and a is any one of 1, 2, and 3).

Examples of R ¹ include CH ₂ OCH ₂ , CH ₂ O, and CH ₂ , and CH ₂ OCH ₂ is preferable.

Examples of R ² include a hydrogen atom, a methyl group, and an ethyl group, and a hydrogen atom and a methyl group are preferable.

Examples of R ³ include CH ₂ and CH ₂ CH ₂ , and CH ₂ is preferable.

Examples of R ⁴ include a hydrogen atom, a methyl group, and an ethyl group, and a hydrogen atom and a methyl group are preferable.

Examples of R ⁵ include a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, and an N, N-diethylaminomethyl group, and a methyl group, an ethyl group, and a chloromethyl group are preferable. Preferably, they are a methyl group and an ethyl group.

  Examples of Y include a hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, and alkenyloxy group. Of these, alkoxy groups such as a methoxy group and an ethoxy group are more preferable, and a methoxy group and an ethoxy group are particularly preferable because they are mildly hydrolyzable and easy to handle.

Specific examples of the reactive silicon group (SiR ⁵ _3-a Y _a ) of the reactive silicon group-containing polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, and tris (2-propenyloxy) silyl. Group, triacetoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxy Examples include, but are not limited to, methyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) diethoxysilyl group, and the like. Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N- Diethylaminomethyl) dimethoxysilyl group is preferable because it exhibits high activity and a cured product having good mechanical properties. From the viewpoint of activity, trimethoxysilyl group, (chloromethyl) dimethoxysilyl group, and (methoxymethyl) dimethoxysilyl group are particularly preferable. From the viewpoint of stability, methyldimethoxysilyl group, methyldiethoxysilyl group, triethoxysilyl group Is particularly preferable, and from the viewpoint of safety, a methyldiethoxysilyl group and a triethoxysilyl group are particularly preferable, and a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable because of easy production.

<Main chain structure>
The main chain structure of the reactive silicon group-containing polymer (A) may be linear or may have a branched chain. Since the reactive silicon group-containing polymer (A) of the present invention is characterized in that a reactive group is localized at the terminal, the main chain structure is preferably linear.

  The main chain skeleton of the reactive silicon group-containing polymer (A) is not particularly limited, and those having various main chain skeletons can be used. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, Polyoxyalkylene polymers such as polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer; ethylene-propylene copolymer, polyisobutylene, isobutylene and isoprene, etc. Copolymer, polychloroprene, polyisoprene, isoprene or a copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or a copolymer of butadiene and acrylonitrile, styrene, and the like. Saturated hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenation of the body; polyester polymers obtained by condensation of dibasic acids such as adipic acid with glycols or ring-opening polymerization of lactones Combined; (meth) acrylic acid ester-based polymer, (meth) acrylic acid-based monomer, vinyl acetate obtained by radical polymerization of (meth) acrylic acid ester-based monomers such as ethyl (meth) acrylate and butyl (meth) acrylate Vinyl polymers such as polymers obtained by radical polymerization of monomers such as acrylonitrile and styrene; graft polymers obtained by polymerizing vinyl monomers in the polymers; polysulfide polymers; ε-caprolactam Polyamide 6 by polycondensation of polyamide 6, hexamethylenediamine and adipic acid by ring-opening polymerization. Of the above polyamides, polyamide 6 · 10 by condensation polymerization of hexaamidediamine and sebacic acid, polyamide 11 by condensation polymerization of ε-aminoundecanoic acid, polyamide 12 by ring-opening polymerization of ε-aminolaurolactam, Polyamide polymers such as copolymer polyamides having two or more components; for example, polycarbonate polymers produced by condensation polymerization from bisphenol A and carbonyl chloride; organic polymers such as diallyl phthalate polymers . Each of the above polymers may be mixed in a block shape, a graft shape or the like. Of these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylate polymers have relatively low glass transition temperatures. The resulting cured product is preferable because it is excellent in cold resistance, and a polyoxyalkylene polymer is more preferable.

  The reactive silicon group-containing polymer (A) may have any one main chain skeleton among the various main chain skeletons described above, and is a mixture of polymers having different main chain skeletons. Also good. Moreover, about a mixture, what manufactured each polymer separately may be mixed, and you may manufacture simultaneously so that it may become arbitrary mixed compositions.

  The glass transition temperature of the reactive silicon group-containing polymer (A) is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and particularly preferably −20 ° C. or lower. preferable. When the glass transition temperature is higher than 20 ° C., the viscosity in winter or in a cold region may be increased, which may make it difficult to handle, and the flexibility of the cured product may be decreased, and the elongation may be decreased. The glass transition temperature can be determined by DSC measurement according to the measurement method specified in JISK7121.

  Organic polymers such as saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth) acrylic ester polymers are used as adhesive groups for low molecular weight components when used as a base polymer for adhesives and sealants. It is preferable because there is little contamination due to transfer to materials.

  Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are preferred because they have high moisture permeability and are excellent in deep part curability and further in adhesion when made into one-component compositions. An oxyalkylene polymer is particularly preferable.

  The number average molecular weight of the reactive silicon group-containing polymer (A) is 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30 in terms of polystyrene equivalent molecular weight in GPC. , 000. When the number average molecular weight is less than 3,000, the amount of reactive silicon groups introduced is increased, which may be inconvenient in terms of production cost. When the number average molecular weight exceeds 100,000, the viscosity becomes high and the workability is increased. Tend to be inconvenient.

  Regarding the molecular weight of the reactive silicon group-containing polymer (A), the organic polymer precursor before introduction of the reactive silicon group is obtained by measuring the hydroxyl value of JIS K 1557 and the iodine value specified in JIS K 0070. The end group concentration is directly measured by titration analysis based on the principle of the measurement method, and the end group equivalent molecular weight is calculated in consideration of the structure of the organic polymer (degree of branching determined by the polymerization initiator used). You can also The molecular weight of the reactive silicon group-containing polymer is calculated based on the number average molecular weight obtained by general GPC measurement of the organic polymer precursor and a calibration curve of the above-mentioned terminal group-converted molecular weight. It is also possible to obtain the number average molecular weight obtained by GPC of the coalesced in terms of the terminal group equivalent molecular weight.

  The molecular weight distribution (Mw / Mn) of the reactive silicon group-containing polymer (A) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, and further preferably 1.5 or less. Preferably, 1.4 or less is particularly preferable, and 1.2 or less is most preferable. The molecular weight distribution of the reactive silicon group-containing polymer (A) can be determined from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

<Synthesis Method of Reactive Silicon Group-Containing Polymer (A)>
Next, a method for synthesizing the reactive silicon group-containing polymer (A) will be described.

  The reactive silicon group-containing polymer (A) reacts with a carbon-carbon unsaturated bond after introducing two or more carbon-carbon unsaturated bonds at one end of a hydroxyl-terminated polymer obtained by polymerization. It is preferably obtained by reacting a reactive silicon group-containing compound.

  More specifically, the reactive silicon group-containing polymer (A) is obtained by reacting a polymer having a hydroxyl group at the terminal with an alkali metal salt of 0.6 equivalent or more relative to the hydroxyl group, After reacting with an epoxy compound having a saturated bond and further reacting with a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond, a reactive silicon group is introduced into the carbon-carbon unsaturated group by a hydrosilylation reaction. It is preferable that it is obtained by doing.

  The preferred synthesis method will be described below.

(polymerization)
In the case of using a polyoxyalkylene polymer as the main chain of the reactive silicon group-containing polymer (A), an initiator having a hydroxyl group using a complex metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex The method of polymerizing an epoxy compound is preferable because a hydroxyl-terminated polymer having a small molecular weight distribution (Mw / Mn) can be obtained.

  The initiator having a hydroxyl group has at least one hydroxyl group such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polypropylene glycol, polyoxypropylene triol, allyl alcohol, polypropylene monoallyl ether, polypropylene monoalkyl ether, etc. Things.

  Examples of the epoxy compound include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Of these, propylene oxide is preferable.

(Introduction of carbon-carbon unsaturated bond)
As a method for introducing two or more carbon-carbon unsaturated bonds at one terminal, an alkali metal salt is allowed to act on a hydroxyl group-containing polymer, and then an epoxy compound having a carbon-carbon unsaturated bond first. It is preferable to use a method in which a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted. By using this method, it is possible to efficiently and stably introduce reactive groups while controlling the molecular weight and molecular weight distribution of the polymer main chain according to the polymerization conditions.

  In the present invention, when an epoxy compound having a carbon-carbon unsaturated bond is reacted with a hydroxyl group-containing polymer, an alkali metal salt is used. By using an alkali metal salt, the terminal sites of all polymers are used. Can be reacted with an epoxy compound having a carbon-carbon unsaturated bond uniformly. When a double metal cyanide complex catalyst is used instead of an alkali metal salt, an epoxy compound having a carbon-carbon unsaturated bond selectively reacts with a polymer having a low molecular weight. This is not preferable because a carbon-carbon unsaturated bond is locally introduced into the terminal portion.

  Examples of the alkali metal salt used in the present invention include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. In view of ease of handling and solubility, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide and potassium ethoxide are preferable, and sodium methoxide and potassium methoxide are more preferable. Sodium methoxide is particularly preferred from the standpoint of availability. You may use an alkali metal salt in the state melt | dissolved in the solvent.

  As the addition amount of the alkali metal salt used in the present invention, the lower limit of the molar ratio of the polymer to the hydroxyl group is preferably 0.5 or more, more preferably 0.6 or more, and more preferably 0.7 or more and 0.8 or more. preferable. The upper limit is preferably 1.2 or less, and more preferably 1.0 or less. If the addition amount of the alkali metal salt is too small, the reaction does not proceed sufficiently, and if the addition amount is too large, the alkali metal salt remains as an impurity and the side reaction may proceed.

  Alkali metal salts are used to alkoxylate hydroxyl groups in polyoxyalkylene polymers. In order to make this reaction proceed efficiently, water and alcohol other than hydroxyl group-containing polymers are removed from the reaction system. It is preferable to remove. In order to remove, a known method may be used, for example, heat evaporation, vacuum devolatilization, spray vaporization, thin film evaporation, azeotropic devolatilization, or the like.

  As temperature at the time of making an alkali metal salt act, 50 to 150 degreeC is preferable and 110 to 140 degreeC is more preferable. As time for making an alkali metal salt act, 10 minutes or more and 5 hours or less are preferable, and 30 minutes or more and 3 hours or less are more preferable.

（式中のＲ^１、Ｒ^２は上記と同じである。）で表される化合物が好適に使用できる。具体的には、アリルグリシジルエーテル、メタリルグリシジルエーテル、グリシジルアクリレート、グリシジルメタクリレート、ブタジエンモノオキシド、１，４−シクロペンタジエンモノエポキシドが反応活性の点から好ましく、アリルグリシジルエーテルが特に好ましい。 As an epoxy compound having a carbon-carbon unsaturated bond used in the present invention, in particular, the general formula (3):

A compound represented by the formula (R ¹ and R ² are the same as above) can be preferably used. Specifically, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide are preferable from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferable.

  The addition amount of the epoxy compound having a carbon-carbon unsaturated bond used in the present invention can be any amount in consideration of the introduction amount and reactivity of the carbon-carbon unsaturated bond to the polymer. In particular, the lower limit of the molar ratio with respect to the hydroxyl group contained in the polymer is preferably 0.2 or more, and more preferably 0.5 or more. The upper limit is preferably 5.0 or less, and more preferably 2.0 or less.

  In the present invention, the reaction temperature when the ring-opening addition reaction of the epoxy compound having a carbon-carbon unsaturated bond to the polymer containing a hydroxyl group is preferably 60 ° C. or more and 150 ° C. or less, More preferably, the temperature is 110 ° C. or higher and 140 ° C. or lower. If it is low, the reaction hardly proceeds, and if it is too high, the main chain of the polyoxyalkylene polymer may be decomposed. The reaction time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 3 hours.

（式中のＲ^３、Ｒ^４は上記と同じである。Ｘはハロゲン原子である。）で表される化合物が好適に使用できる。具体的には、塩化ビニル、塩化アリル、塩化メタリル、臭化ビニル、臭化アリル、臭化メタリル、ヨウ化ビニル、ヨウ化アリル、ヨウ化メタリルなどが挙げられ、取り扱いの容易さから塩化アリル、塩化メタリルを用いることがより好ましい。 As the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond used in the present invention, in particular, the general formula (4):

A compound represented by the formula (wherein R ³ and R ⁴ are the same as described above. X is a halogen atom) can be preferably used. Specific examples include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, methallyl iodide, and allyl chloride, More preferably, methallyl chloride is used.

  The amount of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is not particularly limited, but the lower limit of the molar ratio with respect to the hydroxyl group contained in the polyoxyalkylene polymer is 0.7 or more. Is preferable, and 1.0 or more is more preferable. The upper limit is preferably 5.0 or less, and more preferably 2.0 or less.

  As temperature at the time of making the halogenated hydrocarbon compound which has a carbon-carbon unsaturated bond react, 50 to 150 degreeC is preferable and 110 to 140 degreeC is more preferable. The reaction time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 3 hours.

  The number of hydroxyl groups contained in one molecule of the polymer having a carbon-carbon unsaturated bond obtained after the reaction is preferably 0.3 or less in order to maintain sufficient stability even when stored for a long period of time. 1 or less is more preferable.

(Introduction of reactive silicon groups)
Next, a method for introducing a reactive silicon group will be described.

The method for introducing the reactive silicon group is not particularly limited, and a known method can be used. The introduction method is illustrated below.
(Ii) A method of adding a hydrosilane compound to a polymer having a carbon-carbon unsaturated bond by a hydrosilylation reaction.
(Ii) a polymer having a carbon-carbon unsaturated bond and a compound having both a group capable of forming a bond by reacting with the carbon-carbon unsaturated bond and a reactive silicon group (also referred to as a silane coupling agent). How to react. Examples of silane coupling agents that react with carbon-carbon unsaturated bonds to form bonds include, but are not limited to, mercapto groups.

  The method (i) is preferable because the reaction is simple, the adjustment of the amount of reactive silicon groups introduced, and the physical properties of the resulting reactive silicon group-containing polymer are stable. The method (ii) has many reaction options, and it is easy and preferable to increase the rate of introduction of reactive silicon groups.

  A part of hydrosilane compound used by the method of (i) is illustrated. Halogenated silanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl) dichlorosilane, (dichloromethyl) dichlorosilane, bis (chloromethyl) chlorosilane, (methoxymethyl) dichlorosilane; Silane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, (chloromethyl) methylmethoxysilane, (chloromethyl) dimethoxysilane, (chloromethyl) Diethoxysilane, bis (chloromethyl) methoxysilane, (methoxymethyl) methylmethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) Ethoxysilane, (ethoxymethyl) diethoxysilane, (3,3,3-trifluoropropyl) dimethoxysilane, (N, N-diethylaminomethyl) dimethoxysilane, (N, N-diethylaminomethyl) diethoxysilane, [( Chloromethyl) dimethoxysilyloxy] dimethylsilane, [(chloromethyl) diethoxysilyloxy] dimethylsilane, [(methoxymethyl) dimethoxysilyloxy] dimethylsilane, [(diethylaminomethyl) dimethoxysilyloxy] dimethylsilane, [(3 , 3,3-trifluoropropyl) dimethoxysilyloxy] dimethylsilane and the like; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; bis (dimethylketoximate) methyl Isopropenyloxysilanes such as lanthanum, ketoxymate silanes such as bis (cyclohexylketoxymate) methylsilane, triisopropenyloxysilane, (chloromethyl) diisopropenyloxysilane, (methoxymethyl) diisopropenyloxysilane (Deacetone type).

  The amount of hydrosilane used is preferably from 0.05 to 10 in terms of reactivity in terms of the molar ratio to the unsaturated groups in the polymer that is the precursor (number of moles of hydrosilane / number of moles of unsaturated groups). .3 to 2 are more preferable from the viewpoint of economy.

The hydrosilylation reaction is accelerated by various catalysts. As the hydrosilylation catalyst, known catalysts such as various complexes such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium may be used. For example, platinum supported on a carrier such as alumina, silica, carbon black, chloroplatinic acid; chloroplatinic acid complex composed of chloroplatinic acid and alcohol, aldehyde, ketone, etc .; platinum-olefin complex [eg Pt (CH _{2 = CH 2) 2 (PPh} 3), Pt (CH 2 = CH 2) 2 Cl 2]; platinum - vinylsiloxane complex _{[Pt {(vinyl) Me 2} SiOSiMe 2 (vinyl)}, Pt {Me (vinyl) SiO} ₄ ]; platinum-phosphine complex [Ph (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ]; platinum-phosphite complex [Pt {P (OPh) ₃ } ₄ ] and the like can be used. From the viewpoint of reaction efficiency, it is preferable to use a platinum catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex. The temperature conditions for the silylation reaction are not particularly limited, but it is preferable to carry out the reaction under heating conditions for the purpose of lowering the viscosity of the reaction system or improving the reactivity, and the reaction is carried out in the range of 50 ° C to 150 ° C. Is more preferable, and 70 to 120 ° C. is particularly preferable. If the reaction time is longer than necessary, the polymer main chain may deteriorate, and it is preferable to adjust the reaction time together with the temperature. Although the temperature and reaction time are affected by the main chain structure of the polymer to be produced, it is preferably 30 minutes or more and 5 hours or less from the viewpoint of increasing the efficiency of the production process, and more preferably 3 hours or less. preferable.

  Since the reactive silicon group-containing polymer (A) has a high content of reactive silicon groups, the hydrolytic condensation reaction of the reactive silicon groups proceeds at the same time as hydrosilylation. The viscosity may increase during storage for a period of time.

  Therefore, in the production method by hydrosilylation of the reactive silicon group-containing polymer (A), the use of orthocarboxylic acid trialkyl ester can improve the viscosity and storage stability during silylation.

  Specific examples of the orthocarboxylic acid trialkyl ester include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate and the like. Trimethyl orthoformate and trimethyl orthoacetate are more preferred.

  The amount of orthocarboxylic acid trialkyl ester used is 0.1 to 10 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the polymer having a carbon-carbon double bond. If the amount used is small, the effect cannot be obtained sufficiently and the viscosity of the polymer may increase. Moreover, when there is too much usage-amount, it is economically disadvantageous, and the work amount of the process of removing orthoester increases.

  The reactive silicon group-containing polymer (A) of the present invention serves as a raw material for the curable composition, and the cured product of the curable composition exhibits excellent flexibility, good restoration rate, and high weather resistance. Below, each component used as the raw material of the curable composition concerning this invention other than a reactive silicon group containing polymer (A) is demonstrated.

<< Silicon Compound (B) >>
In the present invention, the silicon compound (B) is added particularly in order to achieve high elongation and low adhesion of the cured product. The silicon compound (B) has the following general formula (1):
R ₃ Si-
(Wherein R is independently a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom), and R ₃ SiOH is generated by hydrolysis.

（式中、Ｒは一般式（１）におけるＲと同一であり、Ｑは炭素数１〜２０の置換又は非置換の１価の炭化水素基）、あるいは Among them,

(Wherein R is the same as R in formula (1), Q is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms), or

（式中、Ｒは一般式（１）におけるＲと同一であり、Ｚは炭素数１〜２０の置換又は非置換の１価の有機基）で示されるシリコン化合物を用いることが好ましい。

(Wherein R is the same as R in formula (1), and Z is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms).

  Specific examples are shown below, but the silicon compound as the component (B) is not limited thereto.

Examples of the compound represented by [Chemical Formula 5] include R is an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, an aryl group such as a phenyl group, or a substituted group thereof.

などが挙げられる。

Etc.

  As the compound represented by [Chemical Formula 6], for example,

などが挙げられる。

Etc.

  In addition, although it does not belong to the above [Chemical 5] or [Chemical 6],

なども使用し得る。

Etc. can also be used.

Further, it is a derivative of a polyhydric alcohol having 3 or more hydroxyl groups such as trimethylolpropane, glycerin, pentaerythritol or sorbitol described in JP-A-11-241029, and R ₃ SiOH such as trimethylsilanol by hydrolysis. The compound which produces | generates the silicon compound which produces | generates can also be used suitably.

In addition, a compound that is a derivative of an oxypropylene polymer as described in JP-A-7-258534 and generates a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis is also preferably used. Can do. Furthermore, a polymer having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can be converted into a monosilanol-containing compound by hydrolysis as described in JP-A-6-279893 can also be used.

  Among the silicon compounds (B) described above,

、などの１価のアルコールやフェノールの誘導体が好ましい。また、アルコールのトリメチルシリル誘導体であって分子量が１４０、好ましくは１５０以上の化合物が好ましい。特開平１１−２４１０２９号公報に記載されているトリメチロールプロパン、グリセリン、ペンタエリスリトールあるいはソルビトールなどの水酸基数が３以上の多価アルコールのトリメチルシリル誘導体、特開平７−２５８５３４号公報に記載されているようなオキシプロピレン重合体のトリメチルシリル誘導体が望ましい。特に、トリメチロールプロパンのトリメチルシリル誘導体とフェノキシトリメチルシラン（［化１３］の最初の化合物）の混合物も用いることができる。

Monohydric alcohol and phenol derivatives such as A trimethylsilyl derivative of alcohol having a molecular weight of 140, preferably 150 or more is preferred. Trimethylsilyl derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as trimethylolpropane, glycerin, pentaerythritol or sorbitol described in JP-A-11-241029, as described in JP-A-7-258534 Trimethylsilyl derivatives of such oxypropylene polymers are desirable. In particular, a mixture of a trimethylsilyl derivative of trimethylolpropane and phenoxytrimethylsilane (the first compound of [Chemical Formula 13]) can also be used.

  The amount of the silicon compound (B) used is not particularly limited, and the amount used may be freely changed according to the expected properties of the cured product. Usually, the reactive silicon group-containing polymer (A) The amount is 0.1 to 10 parts, preferably 0.5 to 5 parts per 100 parts (parts by weight, the same applies hereinafter). If the amount is less than 0.1 parts, the effect is small, and the use exceeding 10 parts is not desirable in terms of the balance between cost and performance due to the use of expensive silicon compounds.

  The method of mixing the reactive silicon group-containing polymer (A) and the silicon compound (B) of the present invention is roughly divided into three types.

  One is a method in which the silicon compound (B) is simply added to the reactive silicon group-containing polymer (A). Depending on the properties of the silicon compound (B), the heating and stirring conditions may be adjusted to uniformly disperse and dissolve. In this case, it is not necessary to have a completely uniform state, and even if it is in an opaque state, the object can be sufficiently achieved if it is dispersed. Moreover, you may use a dispersibility improving agent, for example, surfactant, etc. together as needed.

  The second method is a method in which a predetermined amount of the compound is mixed when the final product is used. For example, when used as a two-component type sealing material, the compound can be mixed and used as a third component in addition to the base and the curing agent.

  In the third method, the compound is reacted with an organic polymer in advance. If necessary, a tin-based, titanate-based, acid or basic catalyst is used in combination, and a necessary amount of water is added. The purpose is achieved by heating and devolatilization under reduced pressure.

<< Silanol condensation catalyst (C) >>
In the present invention, the reactive silicon group-containing polymer (A) is reacted with reactive silicon groups in the curable composition for the purpose of accelerating the reaction of hydrolyzing and condensing the reactive silicon groups and extending or cross-linking the polymer. A silanol condensation catalyst (C) is blended together with the group-containing polymer (A).

  As the silanol condensation catalyst (C), it is already known that a large number of catalysts can be used, and examples thereof include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, and inorganic acids.

  Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis ( Ethyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (Ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonyl phenoxide), dibutenyl tin oxide, dibutyl tin oxide, dibutyl tin bis (acetylacetonate), dioctyl tin bis ( Cetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dioctyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate, etc. Can be mentioned. From the recent increase in interest in the environment, it is preferable to use a dioctyltin compound rather than a dibutyltin compound.

  Specific examples of the carboxylate metal salt include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, Examples thereof include manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, and cerium carboxylate. As the carboxylic acid group, the following carboxylic acid and various metals can be combined. As the metal species, divalent tin, bismuth, divalent iron, trivalent iron, zirconium and titanium are preferable because of high activity, and divalent tin is most preferable.

  Specific examples of the amine compound include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, Aliphatic primary amines such as cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine Aliphatic secondary amines such as distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine; Aliphatic tertiary amines such as amylamine, trihexylamine and trioctylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aromatic amines such as aniline, laurylaniline, stearylaniline and triphenylamine; Pyridine, 2-aminopyridine, 2- (dimethylamino) pyridine, 4- (dimethylaminopyridine), 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine, 2- Piperidinemethanol, 2- (2-piperidino) ethanol, piperidone, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 6- (Dibutylamino) -1,8 Diazabicyclo [5,4,0] undecene-7 (DBA-DBU), 6- (2-hydroxypropyl) -1,8-diazabicyclo [5,4,0] undec-7-ene (OH-DBU), OH -Compounds in which the hydroxyl group of DBU is modified by urethanation, etc., 1,5-diazabicyclo [4,3,0] nonene-5 (DBN), 1,4-diazabicyclo [2,2,2] octane (DABCO), aziridine Nitrogen-containing heterocyclic compounds such as: DBU phenol salt (specifically, trade name: U-CAT SA1 (manufactured by San Apro)), DBU octylate (specifically, trade name: U-CAT SA102) (Product of San Apro)), DBU p-toluenesulfonate (specifically, trade name: U-CAT SA506 (product of San Apro)), DBN octylate (specifically , Trade name: U-CAT 1102 (manufactured by San-Apro)) and other amines such as monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine , Ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, 2- (2-aminoethylamino) Ethanol, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2- 1-piperazinyl) ethylamine, xylylenediamine, amines such as 2,4,6-tris (dimethylaminomethyl) phenol; guanidines such as guanidine, phenylguanidine, diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide, And biguanides such as 1-phenylbiguanide.

  Among these, amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU and DBN; guanidines such as guanidine, phenylguanidine and diphenylguanidine; butylbiguanide, 1 Biguanides such as -o-tolyl biguanide and 1-phenyl biguanide are preferable because they exhibit high activity, and aryl group-substituted biguanides such as 1-o-tolyl biguanide and 1-phenyl biguanide can be expected to have high adhesiveness. preferable.

  Further, the amine compound is basic, but an amine compound having a pKa value of the conjugate acid of 11 or more is preferably high in catalytic activity, and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBN and the like are particularly preferable because the pKa value of the conjugate acid is 12 or more and high catalytic activity is exhibited.

  In the present invention, as an amine compound used for the silanol condensation catalyst (C), an amino group-containing silane coupling agent (sometimes referred to as aminosilane) and a ketimine compound that generates the amine compound by hydrolysis are also used. it can.

  Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, pivalic acid, 2,2-dimethylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid and the like can be mentioned. 2-Ethylhexanoic acid, neodecanoic acid, and versatic acid have high activity and are preferable from the viewpoint of availability. In addition, carboxylic acid derivatives such as carboxylic acid anhydrides, alkyl carboxylates, amides, nitriles, and acyl halides can also be used.

  Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate), Aluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate, zirconium compounds such as zirconium tetrakis (acetylacetonate), hafnium compounds such as tetrabutoxyhafnium Kind.

Other silanol condensation catalysts (C) include organic sulfonic acids such as trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid and boronic acid; boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride ethylamine Boron trifluoride complexes such as complexes; ammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, cesium fluoride, ammonium hydrogen fluoride, 1,1,2,3,3,3-hexafluoro-1-diethylamino Fluorine anion-containing compounds such as propane (MEC81, commonly known as Ishikawa reagent), potassium hexafluorophosphate, Na ₂ SiF ₆ , K ₂ SiF ₆ , (NH ₄ ) ₂ SiF ₆ can be mentioned.

  A photoacid generator or a photobase generator that generates an acid or a base by light can also be used as the silanol condensation catalyst (C). Examples of the photoacid generator include triarylsulfonium salts such as p-phenylbenzylmethylsulfonium salt, p-hydroxyphenylbenzylmethylsulfonium salt, triphenylsulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt, 4,4 -Bis [di (β-hydroxyethoxy) phenylsulfonio] phensulfide bishexafluoroantimonate, diphenyliodonium salt, bis (4-tert-butylphenyl) iodonium salt, (4-tert-butoxyphenyl) phenyliodonium salt, Onium salt photoacid generators such as iodonium salts such as (4-methoxyphenyl) phenyliodonium salts, benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthra 2-sulfonate, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, sulfonic acid derivatives such as N- (trifluoromethylsulfonyloxy) naphthylimide, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexyl) Sulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, Diazomethanes such as methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, carboxylic acid esters, Examples thereof include iron arene complexes.

  The silanol condensation catalyst (C) may be used in combination of two or more different types of catalysts. For example, the combined use of the amine compound and the carboxylic acid may improve the reactivity. There is sex. The catalytic activity can also be increased by using an acid such as carboxylic acid in combination with a phosphonium salt compound such as tetrabutylphosphonium hydroxide. Moreover, there is a possibility that the reactivity may be improved by using a halogen-substituted aromatic compound such as pentafluorophenol or pentafluorobenzaldehyde and an amine compound in combination.

  As a usage-amount of a silanol condensation catalyst (C), 0.001-20 weight part is preferable with respect to 100 weight part of reactive silicon group containing polymers (A), Furthermore, 0.01-15 weight part is more. Preferably, 0.01-10 weight part is especially preferable. If the amount of the silanol condensation catalyst (C) is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, when the blending amount of the silanol condensation catalyst (C) exceeds 20 parts by weight, the reaction rate is too fast, so that the workable time is shortened because the usable time of the composition is shortened, and the storage stability tends to be deteriorated. There is. Furthermore, in the silanol condensation catalyst (C), after the curable composition is cured, it may ooze out on the surface of the cured product or contaminate the cured product surface. In such a case, the amount of the silanol condensation catalyst (C) used is 0.01 to 2.0 parts by weight, so that the surface state of the cured product can be kept good while ensuring curability.

<< Other additives >>
In the composition of the present invention, as other additives, adhesiveness imparting agent, plasticizer, solvent, diluent, silicate, filler, sagging inhibitor, antioxidant, light stabilizer, ultraviolet absorber, physical property adjustment An agent, a tackifier resin, a compound containing an epoxy group, a photocurable material, an oxygen curable material, a surface property improver, an epoxy resin, other resins, a flame retardant, and a foaming agent may be added. Moreover, you may add various additives to the curable composition of this invention as needed for the purpose of adjustment of various physical properties of a curable composition or hardened | cured material. Examples of such additives include, for example, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, fungicides, and the like. It is done.

<Adhesive agent>
An adhesiveness imparting agent can be added to the composition of the present invention.

  As the adhesion-imparting agent, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added.

  Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltris (2-propoxy) silane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropyl. Methyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltriisopropoxysilane, N-β- (β-aminoethyl) aminoethyl-γ-aminopropyltri Methoxysilane, N-6-aminohexyl-γ-aminop Pyrtrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltri Methoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, (aminomethyl) dimethoxymethylsilane, (aminomethyl) trimethoxysilane, (phenylaminomethyl) dimethoxymethylsilane, (phenylamino) Amino group-containing silanes such as methyl) trimethoxysilane, bis (3-trimethoxysilylpropyl) amine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; γ-isocyanatopropyltrimethoxysilane; Isocyanate group-containing silanes such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, α-isocyanatemethyldimethoxymethylsilane; γ- Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc. Group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Epoxy group-containing silanes such as β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) silane, N-β- (carboxy Carboxysilanes such as methyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysila Vinyl type unsaturated group-containing silanes such as γ-chloropropyltrimethoxysilane and other halogen-containing silanes; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; methyl (N-dimethoxymethylsilylmethyl) carbamate , Carbamate silanes such as methyl (N-trimethoxysilylmethyl) carbamate, methyl (N-dimethoxymethylsilylpropyl) carbamate, methyl (N-trimethoxysilylpropyl) carbamate, etc .; (methoxymethyl) dimethoxymethylsilane, (methoxymethyl) ) Alkoxy group-containing silanes such as trimethoxysilane, (ethoxymethyl) trimethoxysilane, (phenoxymethyl) trimethoxysilane; 3- (trimethoxysilyl) propyl succinic anhydride, 3- (triethoxy Acid anhydride-containing silane such as Lil) propyl succinic anhydride, and the like. In addition, these partial condensates and derivatives thereof, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc. It can be used as a ring agent.

  The above silane coupling agents may be used alone or in combination.

  Moreover, the reaction material of various silane coupling agents can also be used. Reaction products include isocyanate silane and hydroxyl group-containing compound, isocyanate silane and amino group-containing compound; amino silane and acrylic group-containing compound, methacryl group-containing compound (Michael addition reaction product); amino silane and epoxy group Examples include a reaction product with a containing compound, a reaction product with an epoxy silane and a carboxylic acid group-containing compound, and an amino group-containing compound. Reaction products of silane coupling agents such as isocyanate silane and amino silane, amino silane and (meth) acrylic group-containing silane, amino silane and epoxy silane, amino silane and acid anhydride-containing silane can also be used.

  Specific examples of the adhesion-imparting agent other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.

  0.1-20 weight part is preferable with respect to 100 weight part of reactive silicon group containing polymers (A), and, as for the usage-amount of a silane coupling agent, 0.5-10 weight part is especially preferable.

<Plasticizer>
A plasticizer can be added to the composition of the present invention. By adding a plasticizer, the viscosity, slump property of the composition, and mechanical properties such as hardness, tensile strength, and elongation of the cured product obtained by curing the curable composition can be adjusted. Specific examples of the plasticizer include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, and the like; bis (2-ethylhexyl) ) Terephthalic acid ester compounds such as 1,4-benzenedicarboxylate (specifically, trade name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester ( Specifically, trade name: Hexamol DINCH (manufactured by BASF)); dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributy acetyl citrate Aliphatic carboxylic acid ester compounds such as; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyl ricinoleate; alkylsulfonic acid phenyl esters (specifically, trade name: Mesamol (manufactured by LANXESS)); Phosphate ester compounds such as zil phosphate and tributyl phosphate; Trimellitic ester compounds; Chlorinated paraffins; Hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; Process oils; Epoxidized soybean oil, Epoxy benzyl stearate, etc. Epoxy plasticizers, and the like.

  Moreover, a polymeric plasticizer can be used. When a high molecular plasticizer is used, the initial physical properties can be maintained over a long period of time compared to the case where a low molecular plasticizer is used. Furthermore, the drying property (paintability) when an alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; number average molecular weight of 500 or more Furthermore, more than 1,000 polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxy group of these polyether polyols Polystyrenes such as polystyrene and polymethyl -α- methyl styrene; group, polyethers such as derivatives obtained by converting the like ether groups polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, polychloroprene, and the like. Various polymers can be provided with physical properties by copolymerizing a reactive group-containing monomer. For example, it is known that the adhesion improvement effect and the elastic recovery rate are improved by using polybutadiene grafted with maleic acid.

  The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing polymer (A). If it is less than 5 parts by weight, the effect as a plasticizer is not expressed, and if it exceeds 150 parts by weight, the mechanical strength of the cured product is insufficient. A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

<Solvent, Diluent>
A solvent or diluent can be added to the composition of the present invention. Although it does not specifically limit as a solvent and a diluent, Aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether etc. can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. . The said solvent or diluent may be used independently and may be used together 2 or more types.

<Silicate>
Silicates can be added to the composition of the present invention. This silicate acts as a cross-linking agent and has a function of improving the restorability, durability, and creep resistance of the cured product obtained from the curable composition of the present invention. Furthermore, it has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane and alkylalkoxysilane or partial hydrolysis condensates thereof can be used.

  Specific examples of the silicate include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxy. Examples thereof include tetraalkoxysilanes (tetraalkyl silicates) such as silane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

  The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the restoring effect, durability, and creep resistance improvement effect of the present invention are greater than those of tetraalkoxysilane.

  Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis. A commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

  When using a silicate, the usage-amount is 0.1-20 weight part with respect to 100 weight part of reactive silicon group containing polymers (A), Preferably it is 0.5-10 weight part.

<Filler>
Various fillers can be mix | blended with the composition of this invention. Fillers include heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, Examples thereof include fillers such as resin powder such as activated zinc white, PVC powder and PMMA powder; and fibrous fillers such as asbestos, glass fibers and filaments.

  The amount of the filler used is preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A).

  An organic balloon or an inorganic balloon may be added to improve the workability (such as sharpness) of the composition. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

  The balloon is a spherical filler with a hollow inside. The balloon can be added for the purpose of reducing the weight (lowering the specific gravity) of the composition. Examples of the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran, but are not limited thereto. In addition, an inorganic material and an organic material can be combined, or a plurality of layers can be formed by stacking. An inorganic or organic balloon or a combination of these can be used. The balloons used may be the same balloon or a mixture of different types of balloons. Furthermore, the balloon can be used by processing or coating the surface thereof, or can be used by treating the surface with various surface treatment agents. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide, or the like, or an inorganic balloon may be surface treated with a silane coupling agent.

  Specific examples of balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113073, JP-A-9-53063, JP-A-10-10. -251618, JP-A 2000-154368, JP-A 2001-164237, WO 97/05201, and the like.

  Moreover, the thermally expansible fine particle hollow body as described in Unexamined-Japanese-Patent No. 2004-51701, 2004-66749, etc. can be used. The thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylindene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape. By heating the bonding part using this composition, the gas pressure in the shell of the thermally expandable fine hollow body increases, and the volume of the polymer outer shell material softens, so that the volume expands dramatically and the bonding interface is Plays the role of peeling. By adding the thermally expandable fine hollow body, it is possible to obtain an adhesive composition that can be easily peeled off without destroying the material simply by heating when not necessary, and can be peeled off without using any organic solvent.

<Anti-sagging agent>
An anti-sagging agent may be added to the composition of the present invention as needed to prevent sagging and improve workability. The sagging inhibitor is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These anti-sagging agents may be used alone or in combination of two or more.

  The amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing polymer (A).

<Antioxidant>
An antioxidant (antiaging agent) can be used in the composition of the present invention. If an antioxidant is used, the weather resistance of the cured product can be increased. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB944LD, CHIMASSORB119FL (all of which are manufactured by Ciba Japan Co., Ltd.); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68 All are manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.) Hindered amine light stabilizers can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.

  0.1-10 weight part is preferable with respect to 100 weight part of reactive silicon group containing polymers (A), and, as for the usage-amount of antioxidant, 0.2-5 weight part is especially preferable.

<Light stabilizer>
A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred.

  0.1-10 weight part is preferable with respect to 100 weight part of reactive silicon group containing polymers (A), and, as for the usage-amount of a light stabilizer, 0.2-5 weight part is especially preferable.

  When a photocurable substance is blended in the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. Tertiary amine-containing hindered amine light stabilizers include Tinuvin 622LD, Tinuvin 144, Tinuvin 770, CHIMASSORB119FL (all manufactured by BASF); Adekastab LA-57, LA-62, LA-67, LA-63 (all stock Examples include light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.).

<Ultraviolet absorber>
An ultraviolet absorber can be used in the composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of UV absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, but benzotriazole is particularly preferable, and commercially available names are Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (above, manufactured by BASF) can be mentioned. 2- (2H-1,2,3-benzotriazol-2-yl) -phenolic compounds are particularly preferred. Furthermore, it is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole ultraviolet absorber in combination.

  0.1-10 weight part is preferable with respect to 100 weight part of reactive silicon group containing polymers (A), and, as for the usage-amount of a ultraviolet absorber, 0.2-5 weight part is especially preferable.

<Tackifying resin>
In the present invention, a tackifying resin can be added for the purpose of enhancing the adhesion and adhesion to the substrate, or as necessary. The tackifying resin is not particularly limited, and those that are usually used can be used.

  Specific examples include terpene resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenation thereof, terpene-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, modified phenol resins, xylene-phenols. Resin, cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon) Resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin and the like. These may be used alone or in combination of two or more.

  The styrenic block copolymer and its hydrogenated product are not particularly limited. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene. Examples include butylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and styrene-isobutylene-styrene block copolymer (SIBS).

  Of these, terpene-phenol resins are preferred because they are highly compatible with polymers and provide a high adhesion effect. On the other hand, when the color tone is important, a hydrocarbon resin is preferable.

  The amount of tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and 5 to 30 parts by weight per 100 parts by weight of the reactive silicon group-containing polymer (A). Is more preferable. When the amount is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion effects to the substrate, and when the amount exceeds 100 parts by weight, the viscosity of the composition may be too high and handling may be difficult.

<Compound containing epoxy group>
In the composition of the present invention, a compound containing an epoxy group can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing polymer (A).

<Photo-curing substance>
A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. A photocurable substance is a substance in which the molecular structure undergoes a chemical change in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like.

  Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) dimethacrylate and oligoesters having a molecular weight of 10,000 or less. Specifically, for example, Aronix M-210 of special acrylate (bifunctional), Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, (Multifunctional) Aronix M-400, etc., but particularly compounds containing an acrylic functional group In addition, a compound containing an average of 3 or more functional groups in one molecule is preferable (all Aronix is a product of Toa Gosei Chemical Co., Ltd.).

  Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

  The photocurable substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A). Below the part by weight, there is no effect of improving the weather resistance, and above 20 parts by weight, the cured product tends to be too hard and tends to crack.

<Oxygen curable substance>
An oxygen curable substance can be used in the composition of the present invention. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering. Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene and 1,3-pentadiene Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferable. Moreover, the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds.

  The amount of the oxygen curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A). Part. If the amount used is less than 0.1 parts by weight, the improvement of the contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

<Surface property improver>
A surface property improving agent can be added to the composition of the present invention. Examples of surface property improvers include long-chain alkylamines such as laurylamine, 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, tris (2,4-di-t-butylphenyl). ) Phosphorus compounds such as phosphites, oxazolidine compounds and the like.

  It is preferable to use the surface property improver in a range of 0.3 to 10 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing polymer (A).

<Epoxy resin>
A reactive silicon group-containing polymer (A) and an epoxy resin can be used in combination in the composition of the present invention. A composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles. Epoxy hydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited to these, and generally used epoxies Resins can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferred are bisphenol A type epoxy resins or novolac type epoxy resins.

  These epoxy resins and reactive silicon group-containing polymers are used in a weight ratio of (A) / epoxy resin = 100/1 to 1/100. When the ratio of (A) / epoxy resin is less than 1/100, it is difficult to obtain an effect of improving the impact strength and toughness of the cured epoxy resin, and the ratio of (A) / epoxy resin exceeds 100/1. And the intensity | strength of a polymer hardened | cured material will become inadequate. The preferred use ratio varies depending on the use of the curable resin composition and cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin The reactive silicon group-containing (A) is used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. On the other hand, when improving the intensity | strength of hardened | cured material, it is good to use 1-200 weight part of epoxy resins with respect to 100 weight part of reactive silicon group containing (A), More preferably, it is 5-100 weight part.

  When an epoxy resin is added, the composition of the present invention can naturally be used in combination with a curing agent that cures the epoxy resin. There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols ; Fe Lumpur acids; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. Further, the curing agents may be used alone or in combination of two or more.

  When the epoxy resin curing agent is used, the amount used is in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Ketimine can be used as a curing agent for the epoxy resin. Ketimine is stably present in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. When ketimine is used, a one-component composition can be obtained. Such a ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

  For the synthesis of ketimine, known amine compounds and carbonyl compounds may be used. For example, as amine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino Polyvalent amines such as ethyl) amine and tetra (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene-based polyamines; γ-aminopropyltri Tokishishiran, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, aminosilanes such as N-(beta-aminoethyl)-.gamma.-aminopropyl methyl dimethoxy silane; and it may be used. Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane And the like can be used.

  When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like.

  These ketimines may be used alone or in combination of two or more, and are used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin, and the amount used is the kind of epoxy resin and ketimine It depends on.

<Flame Retardant>
A flame retardant such as a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added to the composition of the present invention. The said flame retardant may be used independently and may be used together 2 or more types.

  The flame retardant is used in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the reactive silicon group-containing polymer (A).

<Foaming agent>
The composition of the present invention can be used as a foam material using a foaming agent. For example, a liquefied gas such as butane, propane, ethane, methane or dimethyl ether can be used as an aerosol propellant. Moreover, you may use compressed gas, such as air, oxygen, nitrogen, and a carbon dioxide. A propellant containing pentane, hexane, or heptane can be used as a hydrocarbon solvent having a boiling range of 10 to 100 ° C. Moreover, a siloxane oxyalkylene copolymer can be used as a foam stabilizer. The amount of the blowing agent used can be 5 to 100 ml, preferably 5 to 50 ml, and more preferably 5 to 20 ml with respect to 100 g of the reactive silicon group-containing polymer (A).

<< Preparation of curable composition >>
The curable composition containing the reactive silicon group-containing polymer (A) of the present invention may be prepared as a one-component type in which all the blending components are preliminarily blended and stored and cured by moisture in the air after construction. A component such as a silanol condensation catalyst (C), a filler, a plasticizer, water and the like is separately blended as a B agent as a curing agent, and the blended material and the organic polymer composition are mixed before use 2 It can also be prepared as a component type. From the viewpoint of workability, a one-component type is preferable.

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is of a two-component type, it is not necessary to add a silanol condensation catalyst (C) to the organic polymer (A) having a reactive silicon group and the main agent (agent A) containing a silicon compound. Even if a slight amount of water is contained in the compounding agent, there is little concern about increase in viscosity or gelation of the compound, but dehydration drying is preferable when long-term storage stability is required. As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of silicon compound that can react with water, such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the reactive silicon group-containing polymer (A). A range of 5 to 10 parts by weight is preferred.

  The method for preparing the composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader, or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing can be employed.

  The composition containing the reactive silicon group-containing polymer (A) of the present invention is a moisture-reactive composition in which the reaction proceeds by moisture, but a thermosetting resin, a photocurable resin, a radiation curable resin, It can also be used as a so-called dual curable composition used in combination. Specifically, it is possible to use a curable resin utilizing an ene-thiol addition reaction, a radical polymerization reaction of a (meth) acryl group, a ring-opening polymerization reaction of an epoxy group, an addition reaction by hydrosilylation, a urethanization reaction, or the like. it can.

<< Usage >>
The composition of the present invention is suitable for use as a curable composition or a pressure-sensitive adhesive composition, and is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproof material, and a waterproof coating material. It can be used for mold preparations, vibration-proof materials, vibration-damping materials, sound-proof materials, foam materials, paints, spray materials, etc. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, among these, it is more preferable to use it as a sealing material or an adhesive.

  Also, electrical / electronic component materials such as solar cell backside sealing materials, electrical / electronic components such as insulation coating materials for electric wires and cables, electrical insulation materials for devices, acoustic insulation materials, elastic adhesives, binders, contact type Adhesives, spray-type sealing materials, crack repair materials, tile adhesives, adhesives for asphalt waterproofing materials, powder coatings, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical equipment Sealing materials, dental impression materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, anti-slip coating materials, cushioning materials, primers, conductive materials for shielding electromagnetic waves, thermal conductive materials, hot melt materials , Potting agents for electrical and electronic use, films, gaskets, concrete reinforcements, adhesives for temporary fixing, various molding materials, and meshed glass and laminated glass end faces Liquid sealant used in sealing parts for rust prevention and waterproofing of cutting parts, large vehicle parts such as automobile parts, trucks, buses, train car parts, aircraft parts, marine parts, electrical parts, various machine parts, etc. It can be used for various purposes. Taking automobiles as an example, it can be used in a wide variety of applications such as plastic covers, trims, flanges, bumpers, window attachments, interior attachments, and exterior attachments. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . Further, the curable composition of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for electrical / electronic / precision equipment assembly, leather, textile products, adhesives for bonding fabrics, paper, board and rubber, reactive post-crosslinking pressure sensitive adhesives, direct It can also be used as a sealing material for glazing, a sealing material for double-glazed glass, a sealing material for SSG method, a sealing material for building working joints, a civil engineering material, and a bridge material. Furthermore, it can be used as an adhesive material such as an adhesive tape or an adhesive sheet.

  Examples of the method of the present invention will be specifically described below, but the present invention is not limited to these examples.

  The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.

Liquid feeding system: Tosoh HLC-8120GPC
Column: Tosoh TSK-GEL H type Solvent: THF
Molecular weight: Polystyrene conversion Measurement temperature: 40 ° C
The molecular weight in terms of end groups in the examples is determined by measuring the hydroxyl value by the measuring method of JIS K 1557 and the iodine value by the measuring method of JIS K 0070, and calculating the structure of the organic polymer (the degree of branching determined by the polymerization initiator used). This is the molecular weight determined in consideration.

The average number of carbon-carbon unsaturated bonds introduced per terminal of the polymer (Q) shown in the examples was calculated by the following formula.
(Average number of introductions) = [Unsaturated group concentration of polymer (Q) determined from iodine value (mol / g) −Unsaturated group concentration of precursor polymer (P) determined from iodine value (mol / g)] / [Hydroxyl concentration of precursor polymer (P) determined from hydroxyl value (mol / g)].

  The average number of silyl groups introduced per terminal of the polymer (A) shown in the examples was calculated by NMR measurement.

(Synthesis Example 1)
Polyoxypropylene glycol having a number average molecular weight of about 2,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight having a hydroxyl group at both ends is 27,900 (in terms of end group) Polyoxypropylene (P-1) having a molecular weight of 17700) and a molecular weight distribution of Mw / Mn = 1.21 was obtained. Subsequently, 0.5 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene (P-1). After distilling off methanol by vacuum devolatilization, 0.5 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-1) and reacted at 130 ° C. for 2 hours. Thereafter, a methanol solution of 0.28 molar equivalent of sodium methoxide was added to remove methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl group into an allyl group. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, water was removed by centrifugation, and the resulting hexane solution was obtained. Further, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. As described above, polyoxypropylene (Q-1) having an average of more than 1.0 carbon-carbon unsaturated bonds at one terminal was obtained. The polymer (Q-1) was found to have an average of 1.5 carbon-carbon unsaturated bonds introduced at one terminal site.

  50 μl of platinum divinyldisiloxane complex solution is added to 500 g of polyoxypropylene (Q-1) having an average of 1.5 carbon-carbon unsaturated bonds at one terminal site, and dimethoxymethylsilane is added with stirring. 0 g was slowly added dropwise. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain a number average having more than 1.0 dimethoxymethylsilyl groups on one end on average. Polyoxypropylene (polymer A) having a molecular weight of about 28,400 was obtained. The polymer (Polymer A) was found to have an average of 1.2 dimethoxymethylsilyl groups at one end and an average of 2.4 per molecule.

(Synthesis Example 2)
1.2 mole equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the hydroxyl group-terminated polyoxyalkylene (P-1) obtained in Synthesis Example 1. After distilling off methanol by vacuum devolatilization, 1.5 mol equivalent of allyl chloride was further added to the hydroxyl group of the polymer (P-1) to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, water was removed by centrifugation, and the resulting hexane solution was added. Further, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. Thus, a polyoxypropylene polymer (Q-2) having an allyl group at the terminal site was obtained. To 500 g of this polymer (Q-2), 150 μl of platinum divinyldisiloxane complex solution was added, and 4.8 g of dimethoxymethylsilane was slowly added dropwise with stirring. After the mixed solution was reacted at 100 ° C. for 6 hours under 6% oxygen condition, unreacted dimethoxymethylsilane was distilled off under reduced pressure to average 1.0 or less dimethoxymethyl at one end. Polyoxypropylene (polymer B) having a silyl group and a number average molecular weight of about 28,500 was obtained. The polymer (Polymer B) was found to have an average of 0.8 dimethoxymethylsilyl groups at one end and an average of 1.6 per molecule.

(Synthesis Example 3)
A polyoxypropylene triol having a number average molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight 26200 having a hydroxyl group at the end (terminal group equivalent molecular weight 17400) Polyoxypropylene (P-2) having a molecular weight distribution Mw / Mn = 1.34 was obtained. 1.2 mole equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the obtained hydroxyl-terminated polyoxyalkylene (P-2). After distilling off methanol by vacuum devolatilization, 1.5 mol equivalent of allyl chloride was added to the hydroxyl group of the polymer (P-2) to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, water was removed by centrifugation, and the resulting hexane solution was added. Further, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. Thus, a polyoxypropylene polymer (Q-3) having an allyl group at the terminal site was obtained. To 500 g of this polymer (Q-3), 150 μl of a platinum divinyldisiloxane complex solution was added, and 5.5 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 100 ° C. for 6 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure to obtain a number average molecular weight of about 27,7 having an average of 1.0 or less dimethoxymethylsilyl group at one end. 500 polyoxypropylenes (Polymer C) were obtained. The polymer (Polymer C) was found to have an average of 0.7 dimethoxymethylsilyl groups at one end and an average of 2.1 per molecule.

Example 1
2. 0.75 parts by weight of TMSP (manufactured by Toray Dow Corning Co., Ltd .: trimethylphenoxysilane), Neostan U-28 (manufactured by Nitto Kasei Co., Ltd .: tin octylate) with respect to 100 parts by weight of polymer polymer A After 0 parts by weight, 0.5 parts by weight of laurylamine (dodecylamine) and 0.6 parts by weight of water were added and sufficiently mixed with a spatula, they were uniformly mixed and defoamed using a rotating and rotating mixer.

(Hardened physical properties)
The obtained composition was filled in a mold and cured at 23 ° C. and 50% RH for 3 days, and further at 50 ° C. for 4 days to produce a sheet-like cured product having a thickness of about 3 mm. The sheet-like cured product was punched into a No. 3 dumbbell mold, and a tensile strength test was performed at 23 ° C. and 50% RH, and the modulus at 100% elongation was measured. The measurement was performed using a Shimadzu autograph (AGS-J) at a tensile speed of 200 mm / min. The results are shown in Table 1.

(Example 2)
A curable composition was prepared in the same manner as in Example 1 except that TMSP was changed to 0.53 parts by weight of AZ6170 (manufactured by Dow Corning Toray: Tris ((trimethylsiloxy) methyl) propane), Evaluation was performed. The results are shown in Table 1.

(Comparative Example 1)
A curable composition was prepared and evaluated in the same manner as in Example 1 except that TMSP was not added. The results are shown in Table 1.

(Comparative Example 2)
A curable composition was prepared and evaluated in the same manner as in Example 1 except that the polymer was changed to polymer B. The results are shown in Table 1.

(Comparative Example 3)
A curable composition was prepared and evaluated in the same manner as in Example 1 except that the polymer was changed to polymer B and TMSP was not added. The results are shown in Table 1.

  According to Table 1, when a silicon compound is added to a reactive silicon group-containing polymer (A) having an average of more than one reactive silicon group at one end, the reactive silicon group is averaged at one end. It can be seen that the modulus decreases as in the case of the reactive silicon group-containing polymer having one or less.

(Example 3, Comparative Examples 4 and 5)
TMSP 0.75 part by weight, DIDP (manufactured by Kyowa Hakko Kogyo Co., Ltd .: diisodecyl phthalate), Sansosizer E-PS (manufactured by Shin Nippon Rika Co., Ltd .: epoxy) with respect to 100 parts by weight of the polymer in Table 2 20 parts by weight of hexahydrophthalic acid di-2-ethylhexyl), 20 parts by weight of white glaze CCR (manufactured by Shiraishi Calcium Co., Ltd .: precipitated calcium carbonate), 20 parts by weight of Whiten SB (manufactured by Shiraishi Kogyo Co., Ltd .: heavy calcium carbonate) 3 parts by weight of Disparon # 308 (manufactured by Enomoto Chemical Co., Ltd .: hydrogenated castor oil), Tinuvin 326 (manufactured by BASF: 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol ) 1 part by weight, Sanol LS770 (manufactured by Ciba Specialty Chemicals: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate) 1 Parts by weight, 3 parts by weight of Aronix M309 (manufactured by Toagosei Co., Ltd .: 1,1,1-trimethylolpropane triacrylate), 3.0 parts by weight of neostan U-28, 0.6 parts by weight of laurylamine , 6.4 parts by weight of DIDP, 15 parts by weight of Whiten SB, 5 parts by weight of ASP170 (manufactured by BASF: Kaolin), 4 parts by weight of DIDP, 5 parts by weight of Tyco R820 (manufactured by Ishihara Sangyo Co., Ltd .: titanium oxide) as a color The base material, the curing agent and the color were mixed and defoamed.

(Skinning time)
The obtained composition was filled into a mold having a thickness of about 5 mm using a spatula, the time when the surface was flattened was set as the curing start time, the surface was touched with the spatula, and the evaluation composition adhered to the spatula. Curing time was measured with the time when it disappeared as the skinning time. The results are shown in Table 2.

(Hardened physical properties)
The obtained composition was filled in a mold and cured at 23 ° C. and 50% RH for 3 days, and further at 50 ° C. for 4 days to produce a sheet-like cured product having a thickness of about 3 mm. The sheet-like cured product was punched into a No. 3 dumbbell mold and subjected to a tensile strength test at 23 ° C. and 50% RH to measure the modulus at 100% elongation, the strength at break, and the elongation. The measurement was performed using a Shimadzu autograph (AGS-J) at a tensile speed of 200 mm / min. The results are shown in Table 2.

(Restoration rate)
Marked lines with a spacing of 20 mm are drawn on the constricted part of the dumbbell-shaped cured product for measuring the physical properties of the cured product, and the stretched line is fixed so that the distance between the marked lines is 40 mm, and left standing at 23 ° C. and 50% RH for 24 hours. . After fixing, the restoration rate after 1 hour, 1 day, and 1 week was measured. The restoration rate was calculated by the following formula. The results are shown in Table 2.

Restoration rate (%) = (40-distance between marked lines (mm)) / 20

Claims (5)

Reactive silicon group-containing polymer (A) having an average of more than 1.0 reactive silicon group in the group which substitutes on the number of atoms corresponding to 20% from the end of the bonding atoms constituting the polymer molecular chain ,
General formula (1):
R ₃ Si-
(Wherein R is a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom each independently), and a silicon compound (B) that generates R ₃ SiOH by hydrolysis,
Silanol condensation catalyst (C),
Contain,
The terminal portion of the reactive silicon group-containing polymer (A) is represented by the general formula (2):

(Wherein R ¹ and R ³ are each independently a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to each adjacent carbon atom is any one of carbon, oxygen and nitrogen. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10. R ⁵ is independently substituted or substituted with 1 to 20 carbon atoms, An unsubstituted hydrocarbon group, Y is a hydroxyl group or a hydrolyzable group, a is any one of 1, 2, and 3).
A curable composition in which the main chain of the reactive silicon group-containing polymer (A) is a polyoxyalkylene polymer . Against reactive silicon group-containing polymer (A) 100 parts by weight of the silicon compound (B) 0.1 to 10 parts by weight, claim 1 containing 0.001 to 20 parts by weight of silanol condensation catalyst (C) the curable composition according to. Reactive silicon group-containing polymer (A) having an average of more than 1.0 reactive silicon group in the group which substitutes on the number of atoms corresponding to 20% from the end of the bonding atoms constituting the polymer molecular chain ,
General formula (1):
R ₃ Si-
(In the formula, R is the same or different and contains a group represented by a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom), and contains a silicon compound (B) that generates R ₃ SiOH by hydrolysis. And
The terminal portion of the reactive silicon group-containing polymer (A) is represented by the general formula (2):

(Wherein R ¹ and R ³ are each independently a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to each adjacent carbon atom is any one of carbon, oxygen and nitrogen. R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10. R ⁵ is independently substituted or substituted with 1 to 20 carbon atoms, An unsubstituted hydrocarbon group, Y is a hydroxyl group or a hydrolyzable group, a is any one of 1, 2, and 3).
A agent whose main chain of the reactive silicon group-containing polymer (A) is a polyoxyalkylene polymer ,
B agent containing silanol condensation catalyst (C),
A multi-component mixed curable composition comprising a composition of two or more liquids containing Cured product formed by curing the curable composition according to any one of claims 1-3. Reactive silicon group-containing polymer (A) having an average of more than 1.0 reactive silicon group in the group which substitutes on the number of atoms corresponding to 20% from the end of the bonding atoms constituting the polymer molecular chain ,
General formula (1):
R ₃ Si-
(Wherein each R is independently a substituted or unsubstituted monovalent hydrocarbon group or hydrogen atom), and R is obtained by hydrolysis. ₃ Silicon compound (B) for generating SiOH,
Silanol condensation catalyst (C),
A method for producing a curable composition containing
The terminal portion of the reactive silicon group-containing polymer (A) is represented by the general formula (2):

(Wherein R ¹ , R ³ Are each independently a divalent linking group having 1 to 6 carbon atoms, and the atom bonded to each adjacent carbon atom is any one of carbon, oxygen and nitrogen. R ² , R ⁴ Are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. n is an integer of 1 to 10. R ⁵ Each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. Y is a hydroxyl group or a hydrolyzable group. a is one of 1, 2, and 3. )
The main chain of the reactive silicon group-containing polymer (A) is a polyoxyalkylene polymer,
An epoxy compound having a carbon-carbon unsaturated bond after the reactive silicon group-containing polymer (A) is caused to act on a polymer having a hydroxyl group at the terminal with an alkali metal salt of 0.6 equivalent or more with respect to the hydroxyl group. Obtained by reacting with a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond, and then introducing a reactive silicon group into the carbon-carbon unsaturated group by a hydrosilylation reaction A method for producing a curable composition.