JP5554891B2 - Curable composition and method of using the same - Google Patents

Description

  The present invention relates to a curable composition useful as a moisture curable reactive hot melt adhesive. More specifically, the curable composition is excellent in workability, general-purpose adhesiveness, heat-resistant adhesiveness, and has a long usable time during construction, and further is toxic. The present invention relates to a curable composition useful as a moisture curable reactive hot melt adhesive with a low content.

  In general, hot melt adhesives have a high bonding speed, can automate production lines and can be omitted, and are widely used from the viewpoint of environmental compatibility because they are solvent-free. However, since the hot melt adhesive melts by heat and solidifies by cooling and develops an adhesive force, the adhesive force, particularly heat resistance, is limited, and the range of use is limited.

  Therefore, in recent years, as a means for improving the problems of hot melt adhesives, development of reactive hot melt adhesives using a crosslinking reaction after bonding has been actively conducted. A typical example is a urethane-based reactive hot melt adhesive that has a prepolymer having an isocyanate group in the molecule as a main component and has improved heat resistance using a crosslinking reaction of the isocyanate group after bonding. Are known. However, urethane type reactive hot melt adhesives use highly toxic isocyanate compounds, and there is a problem that they volatilize during the manufacturing process and use of the adhesive. Accordingly, a reactive hot melt adhesive using a polymer having a reactive silicon group has been developed as a reactive hot melt adhesive excluding an isocyanate compound.

  When a curable composition containing a polymer having a reactive silicon group is used as a reactive hot melt adhesive, the initial adhesive strength immediately after bonding the adherend is high, and adhesion to various substrates It is desired that the adhesive property is good and that the adhesiveness under high temperature conditions is excellent. In general, hot-melt adhesives are cooled and solidified immediately after coating, and therefore the pot life, that is, the time during which the adherend can be bonded tends to be very short. ing.

  Under such circumstances, Patent Documents 1, 2, and 3 disclose reactive hot melt adhesives using a polymer having a reactive silicon group. Patent Document 1 discloses a reactive hot-melt adhesive that is excellent in thermal stability and heat-resistant adhesiveness when heated by using an oxyalkylene-based polymer having a reactive silicon group and a (meth) acrylic acid alkyl ester-based (co) polymer. It is described that an agent is obtained. Patent Document 2 describes that a reactive hot-melt adhesive excellent in general-purpose adhesive and heat-resistant adhesiveness can be obtained from a polymer having a reactive silicon group and a room temperature solidifying resin. Furthermore, Patent Document 3 describes that the initial adhesive strength can be obtained in a short time by using a vinyl polymer having a specific reactive silicon group.

 However, the compositions described in Patent Documents 1 and 2 have the adhesive strength at a high temperature (80 ° C.) decreased to less than half that at room temperature (23 ° C.) as described in the examples of the patent. However, there remains a problem with respect to heat-resistant adhesiveness, particularly heat-resistant retention. Also, in Patent Documents 1, 2, and 3, the technology for extending the pot life that can be used for various practical applications and various bonding methods is very important for practical use. Nevertheless, it was not considered.

As described above, a reactive hot-melt adhesive using a polymer having a reactive silicon group with low toxicity, which has sufficient heat-resistant adhesive properties and has a long working life and excellent workability, has been obtained so far. The current situation was not.
JP-A-4-335080 JP-A-6-271834 JP 2004-292622 A

 In the curable composition using a polymer having a reactive silicon group with low toxicity, the present invention exhibits sufficient initial adhesive strength, general-purpose adhesiveness and heat-resistant adhesiveness, and has a long pot life during construction. A curable composition useful as a reactive hot melt adhesive is provided.

  As a result of intensive studies to solve the above problems, the present inventor mixed an oxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid alkyl ester (co) polymer at a specific ratio, Furthermore, it has been found that by adding a tackifying resin, it is possible to improve the short working time, which is a defect of the hot melt adhesive, while maintaining high initial adhesive strength. On the other hand, since the tackifying resin melts at a high temperature, the above composition tended to decrease the adhesive strength under high temperature conditions. However, by adding a filler and / or thixotropic agent, the initial adhesive strength was increased. The inventors have found that adhesion performance, particularly adhesion and adhesion retention under high temperature conditions can be greatly improved while maintaining the pot life, and the present invention has been completed.

That is, the present invention is, in the set Narubutsu, oxyalkylene polymer having a reactive silicon group (A), (meth) acrylic acid alkyl ester (co) polymer (B), tackifier resin (C) A curable composition comprising a filler (D) and / or a thixotropic agent (E), and a curing catalyst (F), wherein the oxyalkylene polymer (A) has a reactive silicon group. ) And (meth) acrylic acid alkyl ester-based (co) polymer (B) in a composition ratio of 20/80 to 65/35, and the total amount of ((A) + (B)) is 100 parts by weight. In contrast, 10 to 100 parts by weight of tackifier resin (C), 5 to 200 parts by weight of filler (D) and / or 1 to 60 parts by weight of thixotropic agent (E), and curing catalyst (F). It relates to a curable composition characterized in that it comprises 0.1 to 20 parts by weight
Oxyalkylene polymer having a reactivity silicon group (A) preferably has a group represented by the following general formula (1).
^{-NR 1 -C (= O) -} (1)
(In the formula, R ¹ is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)
Oxyalkylene polymer having a reactivity silicon group (A) preferably has a group represented by the following general formula (2).
—O—R ² — (Si (R ³ _2−b ) (X _b ) —O) _m —SiR ⁴ _3−a X _a (2)
(In the formula, R ² is an alkylene group having 2 to 20 carbon atoms. (M × (2-b)) R ³ and (3-a) R ⁴ are each independently 1 to 1 carbon atoms. 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms or (R ⁵ ) ₃ SiO— (three R ⁵ are monovalent hydrocarbons having 1 to 20 carbon atoms) .) Is at least one selected from the group consisting of triorganosiloxy groups, X is a hydroxyl group or a hydrolyzable group, a is 1 , 2 or 3. m (Si (R ^{B in 3} _2-b ) (X _b ) —O) is independently 0, 1 or 2. m is 0 or an integer of 1 to 19.)
It is preferable that the number average molecular weight of the oxyalkylene polymer having the reactivity silicon group (A) is 10,000～45,000.
It is preferred that the molecular weight distribution of the oxyalkylene polymer having the reactivity silicon group (A) is 1.6 or less.
Oxyalkylene polymer having a reactivity silicon group (A) preferably has a group represented by the following general formula (3).
-SiX ₃ (3)
(In the formula, X is a hydroxyl group or a hydrolyzable group.)
The ( meth) acrylic acid alkyl ester-based (co) polymer (B) preferably has a reactive silicon group represented by the following general formula (4) .
-SiR ⁴ _3-a X _a (4)
(In the formula, each R ⁴ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ⁵ ) ₃ SiO— (three R ⁵ is a monovalent hydrocarbon having 1 to 20 carbon atoms.) Is selected from the group consisting of triorganosiloxy groups, a is 1, 2 or 3, and X is a hydroxyl group Or a hydrolyzable group.)
It is preferable that the ( meth) acrylic acid alkyl ester-based (co) polymer (B) has a group represented by the following general formula (3) .
-SiX ₃ (3)
(In the formula, X is a hydroxyl group or a hydrolyzable group.)
Preferably contains a vinyl polymer (G) having a reactivity silicon group at the molecular terminal.
The main chain of the vinyl polymer having a reactivity silicon group at the molecular terminal (G) is from (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomer It is preferably produced by polymerizing at least one monomer selected from the group consisting of, and the polymerization method is preferably a living radical polymerization method or an atom transfer radical polymerization method .
It is preferred that the molecular weight distribution of the vinyl polymer (G) having a reactivity silicon group at the molecular terminal is less than 1.8.
Charge Hamazai (D) is calcium carbonate, titanium oxide, silica, kaolin, clay, is preferably at least one selected from the group consisting of talc.
Chi shit imparting agent (E) is hydrogenated castor oil derivatives, polyamides waxes is preferably at least one selected from the group consisting of metal soaps.
1 It is preferable that the viscosity at 20 ° C. is 100 Pa · s or less and the viscosity at 30 ° C. is 1000 Pa · s or more .
Further, the present invention is an adhesive for building components made using the curable composition, the adhesive for automotive parts, adhesives for electrical and electronic components, and, for textiles, leather, clothing Relating to adhesives .
Further, the present invention is a reactive hot melt adhesive formed using the curable composition , wherein the pot life in which the adherend can be bonded is 5 minutes or more under the condition of 23 ° C. and 50% RH. It is related with the reactive hot-melt-adhesive characterized by these .
Furthermore, the present invention is a method of bonding two types of adherends via a reactive hot melt adhesive formed using the curable composition, wherein the reactive hot melt adhesive is 60 to 180. After heating to 1 ° C., it is applied to one adherend, and after the reactive hot melt adhesive is 60 ° C. or less, the other adherend is bonded to the reactive hot melt adhesive. bonding wherein a method of bonding the two adherends through a reactive hot melt adhesive comprising using the curable composition, the reactive hot-melt adhesive of 60 to 180 After heating to 1 ° C., and then applying to one adherend, and after one minute or more has elapsed after application, the other adherend is pressure-bonded to the reactive hot melt adhesive , Through a reactive hot melt adhesive comprising a curable composition A method of adhering two types of adherends, wherein after applying a curable composition and bonding the adherends together, one of the bonded adherends is peeled off and then bonded again. The present invention relates to an adhesion method .
Furthermore, the present invention relates to a method for producing a molded body in which two types of adherends are bonded via a reactive hot melt adhesive comprising the curable composition, the reactive hot melt After the adhesive is heated to 60 to 180 ° C., it is applied to one adherend, and after the reactive hot melt adhesive becomes 60 ° C. or less, the other adherend is attached to the reactive hot melt adhesive. after crimping the agent relates to the production how a molded body, which comprises molding (heating).

  The present invention provides a curable composition useful as a moisture curable reactive hot melt adhesive that is excellent in workability, general-purpose adhesiveness, and heat-resistant adhesive, has a long pot life during construction, and has low toxicity. It is possible.

  The curable composition of the present invention contains an oxyalkylene polymer (A) having a reactive silicon group (hereinafter sometimes referred to as an oxyalkylene polymer (A)) as an essential component.

  The oxyalkylene polymer (A) has an average of 0.8 or more reactive silicon groups per molecule. Here, the reactive silicon group is an organic group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom.

  The oxyalkylene polymer (A) having a reactive silicon group has a characteristic that a siloxane bond is formed by a reaction accelerated by a silanol condensation catalyst and is crosslinked.

As the main chain skeleton of the polyoxyalkylene polymer (A) having a reactive silicon group,
It is a polymer having a repeating unit represented by —R—O— (R represents a divalent alkylene group having 2 to 4 carbon atoms).

Wherein R is not particularly limited as long as it is a divalent alkylene group having 2 to 4 carbon atoms, _{e.g., -CH 2 -, - CH 2} CH 2 -, - CH (CH 3) CH 2 -, - CH ( C ₂ H ₅ ) CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —C (CH ₃ ) ₂ CH ₂ — and the like. Of these, —CH (CH ₃ ) CH ₂ — is preferable because it is easily available. The oxyalkylene polymer (A) may be composed of only one type of repeating unit or may be composed of a plurality of types of repeating units.

  The oxyalkylene polymer (A) may be linear or branched, or a mixture thereof. Further, the main chain skeleton may contain a repeating unit other than —R—O— (R represents a divalent alkylene group having 2 to 4 carbon atoms).

  In addition, the repeating unit other than —R—O— (R represents a divalent alkylene group having 2 to 4 carbon atoms) is preferably 80% by weight or less, and 50% by weight or less in the polymer. Is more preferable. Further, the repeating unit represented by -ROO (R represents a divalent alkylene group having 2 to 4 carbon atoms) is preferably present in the polymer in an amount of 50% by weight or more, and is present in an amount of 80% by weight or more. More preferably.

The production method of the main chain skeleton of the oxyalkylene polymer is not particularly limited. For example, (a1) initiators such as dihydric alcohols, polyhydric alcohols, various oligomers having a hydroxyl group, and alkalis such as KOH and NaOH. Ring-opening polymerization of monoepoxides such as ethylene oxide and propylene oxide in the presence of known catalysts such as catalysts, acidic catalysts, composite metal cyanide complex catalysts such as aluminoporphyrin metal complexes and cobalt zinc zinc-glyme complex catalysts How to get by,
(A2) A chain extension reaction of a hydroxyl group-terminated polyether polymer with a bifunctional or higher functional alkyl halide such as CH ₂ Cl ₂ or CH ₂ Br _{2 in} the presence of a basic compound such as KOH, NaOH, KOCH ₃ , or NaOCH ₃ And a method obtained by subjecting a hydroxyl group-terminated polyether polymer to a chain extension reaction with a compound having two or more isocyanate groups.

  Among these, ring-opening polymerization of monoepoxide using a double metal cyanide complex catalyst in the method (a1) is preferable because a polymer having a narrow molecular weight distribution and a low viscosity can be obtained.

It does not specifically limit as a reactive silicon group, For example, group shown by General formula (5) is mentioned.
-(Si (R ³ _2-b ) (X _b ) -O) _m -SiR ⁴ _3-a X _a (5)
((M × (2-b)) R ³ and (3-a) R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Selected from the group consisting of a triorganosiloxy group represented by -20 aralkyl groups or (R ⁵ ) ₃ SiO— (three R ⁵ are each independently a monovalent hydrocarbon having 1 to 20 carbon atoms). X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different, a is 1 , 2 or 3, b represents 0, 1 or 2, respectively, and for b in m (Si (R ³ _2-b ) (X _b ) —O), they may be the same or different. M represents an integer of 0 to 19.)
R ³ and R ⁴ described in the general formula (5) are not particularly limited, and examples thereof include alkyl groups such as a methyl group and an ethyl group; aryl groups such as a phenyl group; Among these, a methyl group is particularly preferable.

  The hydrolyzable group represented by X in the general formula (5) is not particularly limited and includes conventionally known hydrolyzable groups such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, and a ketoximate group. Amino group, amide group, aminooxy group, mercapto group and the like. Among these, alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group are preferable because they are mildly hydrolyzable and easy to handle.

  Hydroxyl group or hydrolyzable group represented by X in the general formula (5) can be bonded to 1 to 3 silicon atoms, and hydrolysis contained in one molecule of the oxyalkylene polymer (A). (A + Σb) indicating the total number of sex groups and hydroxyl groups is preferably 3-5. The hydroxyl group and hydrolyzable group present in the reactive silicon group may be the same or different.

  The number of silicon atoms in the reactive silicon group may be one or two or more. In the case of a reactive silicon group in which silicon atoms are linked by a siloxane bond or the like, about 20 may be used.

The reactive silicon group is preferably a group represented by the following general formula (4) because of availability, and specifically, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group. Group, trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group and the like. Among these, a dimethoxymethylsilyl group, a trimethoxysilyl group, and a triethoxysilyl group are preferable because of high activity and good curability. Further, a group represented by the following general formula (3) is more preferable because of a high expression rate of adhesive strength, and specific examples include a trimethoxysilyl group and a triethoxysilyl group.
-SiR ⁴ _3-a X _a (4)
(In the formula, R ⁴ , X and a are the same as those in the general formula (5).)
-SiX ₃ (3)
(In the formula, R ⁴ , X and a are the same as those in the general formula (5).)
The average number of reactive silicon groups in the oxyalkylene polymer (A) is at least 0.8, preferably 0.8 to 3, more preferably 0.8 to 1.5. preferable. When the average number of reactive silicon groups contained in one molecule of the polymer is 0.8 to 1.5, the balance between curability and the crosslinked structure is good, and the resulting cured product has good adhesion, It has mechanical properties.

  The reactive silicon group may be present at the molecular chain terminal of the oxyalkylene polymer (A) or may be present inside, but if the reactive silicon group is present at the molecular chain terminal, a good machine Since it becomes easy to obtain the hardened | cured material which expresses a characteristic, it is preferable.

The method for introducing the reactive silicon group into the oxyalkylene polymer is not particularly limited, and various methods can be used.
For example, the method shown below is mentioned.

(A) A method in which an organic polymer having a functional group such as a hydroxyl group, an epoxy group, or an isocyanate group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group.
(B) An organic polymer having an unsaturated group by reacting an organic polymer having a functional group such as a hydroxyl group in the molecule with an organic compound having an active group and an unsaturated group that are reactive with the functional group. Get. Alternatively, for example, a monomer having an unsaturated group that does not participate in the polymerization reaction, such as ring-opening copolymerization of an epoxide having an unsaturated group to obtain an unsaturated group-containing organic polymer when ring-opening polymerization of epoxide is performed to obtain an organic polymer Are copolymerized to obtain an organic polymer having an unsaturated group. Next, the resulting reactive organism is reacted with hydrosilane having a reactive silicon group for hydrosilylation.
(C) A method of reacting a compound containing a mercapto group and a reactive silicon group with an organic polymer containing an unsaturated group obtained in the same manner as in the method (b).

Further, among the methods (a), a method of reacting a polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a reactive silicon group, or a polymer having an isocyanate group at a terminal, an amino group and a reactive silicon group The method of reacting a compound having a high molecular weight is preferable because a high addition rate can be obtained in a relatively short reaction time. The oxyalkylene polymer obtained by such a reaction becomes a polymer having a group represented by the following general formula (1) together with a reactive silicon group.
^{-NR 1 -C (= O) -} (1)
(In the formula, R ¹ is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)

  The oxyalkylene polymer (A) having the group represented by the general formula (1) can also be obtained by a method other than the above, for example, aromatic such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate. -Based isocyanates; diisocyanate compounds such as isophorone diisocyanate, hexamethylene diisocyanate; and the like; and -R-O- (R represents a divalent alkylene group having 2 to 4 carbon atoms). And those obtained from a chain extension reaction with a polyol having This is a polymer having a group of the general formula (1) regardless of the method for introducing a reactive silicon group.

  As a method of reacting a polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method (a), for example, the method disclosed in JP-A-3-47825 can be mentioned. There is no particular limitation. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanatepropylmethyldiethoxy. Although silane etc. are mentioned, it is not limited to these. Moreover, it does not specifically limit as a method with which the polymer which has an isocyanate group at the terminal, and the compound which has an amino group and a reactive silicon group are made, A conventionally well-known method can be used. Specific examples of the compound having an amino group and a reactive silicon group include N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) -γ-aminopropyltrimethyl. Ethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-phenylaminopropyltrimethoxysilane, ureidopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane , Γ-aminopropylmethyldiethoxysilane and the like, but are not limited thereto.

In the method (b), in order to introduce a reactive silicon group at a high introduction rate, an organic polymer having an unsaturated group represented by the following general formula (6) is represented by the following general formula (7). A method in which the hydrosilane compound is reacted in the presence of a Group 8 transition metal catalyst is preferred. Examples of the group 8 transition metal catalyst include H ₂ PtCl ₆ · H ₂ O, a platinum-vinylsiloxane complex, a platinum-olefin complex, and the like.
—O—R ⁷ —CR ⁶ ═CH ₂ (6)
(Wherein R ⁶ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁷ is an alkylene group having 0 to 20 carbon atoms)
H- (Si (R ³ _2-b ) (X _b ) -O) _m -SiR ⁴ _3-a X _a (7)
(R ³ , R ⁴ , X, a, b and m are the same as in the general formula (5).)
In addition, it is more preferable that R ⁶ described in the general formula (6) is hydrogen or a methyl group. Specific examples of the hydrosilane compound represented by the general formula (7) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, Alkoxysilanes such as methyldimethoxysilane, methyldiethoxysilane, and phenyldimethoxysilane; Acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; Bis (dimethylketoximate) methylsilane, Bis (cyclohexylketoximate) ) Examples include, but are not limited to, ketoximate silanes such as methylsilane. Among these, since the hydrolysis of the composition from which alkoxysilanes are obtained is gentle and easy to handle, it is preferable.

The oxyalkylene polymer obtained by such a reaction is a polymer having a group represented by the following general formula (2).
—O—R ² — (Si (R ³ _2−b ) (X _b ) —O) _m —SiR ⁴ _3−a X _a (2)
(In the formula, R ² is an alkylene group having 2 to 20 carbon atoms. (M × (2-b)) R ³ and (3-a) R ⁴ are each independently 1 to 1 carbon atoms. 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms or (R ⁵ ) ₃ SiO— (three R ⁵ are each independently monovalent carbon atoms having 1 to 20 carbon atoms) And at least one selected from the group consisting of triorganosiloxy groups represented by X. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they are the same. A is 1 , 2 or 3, b is 0, 1 or 2. b in m (Si (R ³ _2-b ) (X ^b ) —O) Are each independently 0, 1 or 2. m is 0 or an integer of 1 to 19.)
As a synthesis method of (c), for example, in the presence of a radical initiator and / or a radical generation source, a compound having a mercapto group and a reactive silicon group is introduced into an unsaturated bond site of an organic polymer by a radical addition reaction. However, it is not particularly limited. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropylmethyldiethoxysilane. However, it is not limited to these.

  Among the above methods, since the polymer obtained by the method (c) has a strong odor due to mercaptosilane, the method (a) or the method (b) is preferable. The methods (a) and (b) have advantages and disadvantages. The polyoxyalkylene polymer having a reactive silicon group obtained by the method (b) is a composition having a lower viscosity and better workability than the polymer obtained by the method (a), and a urethane bond, This is preferable in that it does not have an organic group that lowers heat resistance such as a urea bond, and further does not use a compound having an isocyanate group that is problematic in toxicity. On the other hand, the method (a) is preferable in that the introduction of a silyl group into the polymer can be prepared inexpensively and with good productivity. In addition, the oxyalkylene polymer obtained by the methods (a), (b), and (c) may be used singly or in combination of several kinds.

  The number average molecular weight of the oxyalkylene polymer (A) is preferably 10,000 to 100,000 in terms of polystyrene-reduced number average molecular weight (Mn) by gel permeation chromatography (GPC), and preferably 10,000 to 45,000. 000 is more preferable, and 15,000 to 30,000 is particularly preferable because of excellent balance between handling and physical properties such as adhesion and mechanical properties.

  Moreover, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is not particularly limited, is preferably 2.0 or less, and more preferably 1.6 or less. Further, it is particularly preferably 1.4 or less because the viscosity becomes low and handling becomes easy.

  The molecular weight distribution can be measured by various methods, but a method by gel permeation chromatography (GPC) is generally used.

  The curable composition of the present invention contains a (meth) acrylic acid alkyl ester-based (co) polymer (B) (hereinafter sometimes referred to as (co) polymer (B)) as an essential component.

  (Meth) acrylic acid alkyl ester (co) polymer is a polymer composed of one (meth) acrylic acid alkyl ester compound as a repeating unit, and a plurality of (meth) acrylic acid alkyl ester compounds as repeating units. And a copolymer composed of one or a plurality of (meth) acrylic acid alkyl ester compounds as repeating units and a compound copolymerizable therewith. In addition, the description method “(meth) acrylic acid alkyl ester” refers to an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester, and also has the same meaning in the subsequent description methods.

  The (meth) acrylic acid alkyl ester compound used as the repeating unit is not particularly limited and includes conventionally known compounds, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, and n-acrylic acid. -Butyl, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, undecyl acrylate, lauryl acrylate, tridecyl acrylate, myristyl acrylate, cetyl acrylate, acrylic Examples include stearyl acid, behenyl acrylate, and biphenyl acrylate.

  In addition, the methacrylic acid ester compound is not particularly limited, and examples thereof include conventionally known compounds, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid. Tert-butyl acid, n-hexyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, undecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, behenyl methacrylate, methacryl Examples include acid biphenyl.

  The main chain skeleton of the (meth) acrylic acid alkyl ester-based (co) polymer (B) is substantially composed of one or more (meth) acrylic acid alkyl ester compounds. Consisting of the above compound means that the proportion of repeating units derived from the (meth) acrylic acid alkyl ester compound present in the (co) polymer (B) exceeds 50%. Moreover, the ratio of the repeating unit derived from the (meth) acrylic acid alkyl ester compound present in the (co) polymer (B) is preferably 70% or more.

  Further, among the (meth) acrylic acid alkyl ester compounds, from the viewpoint of compatibility and stability, the molecular chain is substantially (b-1) an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms. A copolymer (hereinafter referred to as (co) polymer (B) -a) comprising an ester compound and (b-2) a (meth) acrylic acid alkyl ester compound having an alkyl group having 10 or more carbon atoms. ) Is preferred.

The (b) polymer (meth) acrylic acid alkyl ester compound having an alkyl group having 1 to 8 carbon atoms in the (co) polymer (B) -a has the general formula (8):
CH ² = C (R ⁸ ) COOR ⁹ (8)
(Wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents an alkyl group having 1 to 8 carbon atoms).

R ⁹ described in the general formula (8) is not particularly limited, and examples thereof include 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, and a 2-ethylhexyl group. 8, preferably 1-4, more preferably 1-2 alkyl groups.

Incidentally, not limited to necessarily one alkyl group R ⁹ contained in (co) polymer (B) -a.

Moreover, (b-2) the (meth) acrylic acid alkyl ester compound having an alkyl group having 10 or more carbon atoms in the (co) polymer (B) -a has the general formula (9):
CH ² = C (R ⁸ ) COOR ¹⁰ (9)
(Wherein R ⁸ is the same as in the general formula (8). R ¹⁰ represents an alkyl group having 10 or more carbon atoms.)

R ¹⁰ described in the general formula (9) is not particularly limited, and for example, lauryl group, tridecyl group, cetyl group, stearyl group, alkyl group having 22 carbon atoms, biphenyl group and the like having 10 or more carbon atoms, usually Includes 10-30, preferably 10-20 long chain alkyl groups. Incidentally, not limited to R ¹⁰ is not necessarily one kind of alkyl groups in the (co) polymer (B) -a.

  The molecular chain of the (co) polymer (B) -a is substantially composed of the compounds (b-1) and (b-2). )) Means that the proportion of repeating units derived from the compounds (b-1) and (b-2) present in the (co) polymer (B) -a exceeds 50%.

  The proportion of the repeating units derived from the compounds (b-1) and (b-2) present in the (co) polymer (B) -a is preferably 70% or more. An oxyalkylene polymer having a reactive silicon group when the proportion of repeating units derived from the compounds (b-1) and (b-2) present in the (co) polymer (B) -a is less than 50% There is a tendency that the compatibility of (A) and (co) polymer (B) -a is reduced, and it becomes cloudy, and the adhesive properties of the cured product are reduced.

  Moreover, the ratio of the repeating unit derived from the compounds (b-1) and (b-2) present in the (co) polymer (B) -a is the weight ratio (derived from (b-1): (b- 2) Origin) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40. When the ratio is larger than 95: 5, the compatibility is lowered, and when it is smaller than 40:60, the cost tends to be disadvantageous.

  Furthermore, in addition to the repeating unit derived from the (meth) acrylic acid alkyl ester compound, the (co) polymer (B) may contain a repeating unit derived from a compound having copolymerizability with these. The compound having copolymerizability with the (meth) acrylic acid alkyl ester compound is not particularly limited. For example, acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide Amide group such as, epoxy group such as glycidyl acrylate, glycidyl methacrylate, compounds containing amino group such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, And compounds derived from vinyl acetate, vinyl propionate, ethylene, and the like.

  Although there is no restriction | limiting in particular in the molecular weight of a (co) polymer (B) component, The thing of the number average molecular weight of 500 to 100,000 in polystyrene conversion in GPC is preferable, and the thing of 1,000-50,000 is more Those having a molecular weight of 2,000 to 20,000 are particularly preferred because they are easy to handle and have excellent adhesive properties.

  The method for producing the (co) polymer (B) is not particularly limited, and examples thereof include a usual vinyl polymerization method such as a solution polymerization method or a bulk polymerization method by radical reaction. The reaction is usually carried out at 50 to 150 ° C. by adding the above-mentioned compound, radical initiator, chain transfer agent, solvent and the like.

  Examples of the radical initiator include azobisisobutyronitrile and benzoyl peroxide. Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, and lauryl mercaptan, and halogen-containing compounds. Is mentioned. As the solvent, for example, non-reactive solvents such as ethers, hydrocarbons and esters are preferably used.

The (co) polymer (B) preferably has a reactive silicon group represented by the following general formula (4) because the cured product obtained has excellent adhesive strength and heat resistance.
-SiR ⁴ _3-a X _a (4)
(In the formula, R ⁴ , a and X are the same as in the general formula (2).)
The method for introducing a reactive silicon group into the (co) polymer (B) is not particularly limited, and various methods are exemplified.
(D) a method of copolymerizing a compound having a polymerizable unsaturated bond and a reactive silicon group together with the compounds (b-1) and (b-2),
(E) After copolymerizing a compound having a polymerizable unsaturated bond and a reactive functional group (hereinafter referred to as Y ′ group) (for example, acrylic acid) together with the compounds (b-1) and (b-2), A compound having a functional group (hereinafter referred to as Y ″ group) capable of reacting the produced copolymer with a reactive silicon group and a Y ′ group (for example, a compound having an isocyanate group and —Si (OCH ₃ ) ₃ group); How to react,
(F), a method of copolymerizing the compounds (b-1) and (b-2) in the presence of a mercaptan having a reactive silicon group as a chain transfer agent,
(G), a method of copolymerizing compounds (b-1) and (b-2) using an azobisnitrile compound or disulfide compound having a reactive silicon group as an initiator,
(H), a method in which the compounds (b-1) and (b-2) are polymerized by a living radical polymerization method, and a reactive silicon group is introduced into the molecular terminal.

  It is also possible to arbitrarily combine the methods (d) to (h). For example, as a combination of (d) and (f), a compound having a polymerizable unsaturated bond and a reactive silicon group in the presence of a mercaptan having a reactive silicon group as a chain transfer agent is added to the compound (b-1), It is also possible to take a method of copolymerizing with (b-2).

As the compound having a polymerizable unsaturated bond and a reactive silicon group described in (d), the general formula (10):
_{^{CH 2 = C (R 8)}} -COOR 11 - (Si (R 3 2-b) (X b) -O) m -SiR 4 3-a X a (10)
(In the formula, R ⁸ is the same as in the general formula (8). R ¹¹ represents a divalent alkylene group having 1 to 6 carbon atoms. R ³ , R ⁴ , X, a, b and m are represented by the general formula ( The same as 2).)
Or, general formula (11):
_{^{CH 2 = C (R 8)}} - (Si (R 3 2-b) (X b) -O) m -SiR 4 3-a X a (11)
(Wherein R ⁸ is the same as in the general formula (8), R ³ , R ⁴ , X, a, b and m are the same as in the general formula (2)).

R ¹¹ described in the general formula (10) is not particularly limited, and examples thereof include an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, and a propylene group, preferably 1 to 4 carbon atoms. .

  In the copolymerization, the compound represented by the general formula (10) or (11) may be used alone or in combination of two or more.

  The compound of the general formula (10) or (11) is not particularly limited, and examples thereof include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltriethoxysilane. γ-acryloxypropylalkyl polyalkoxysilane, γ-acryloxypropylalkylpolyalkoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, etc. Examples thereof include vinyl alkyl polyalkoxysilanes such as methoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane.

  Examples of the Y ′ group and Y ″ group described in (e) can be a combination of various groups. For example, as the Y ′ group, an amino group, a hydroxyl group, and a carboxylic acid group can be used as the Y ″ group. Mention may be made of isocyanate groups.

  As another example, as described in JP-A-62-70405, JP-A-09-272714, JP-A-59-168014, the Y ′ group is an allyl group, Y ″ Examples of the group include a silicon hydride group (H—Si). In this case, the Y ′ group and the Y ″ group can be bonded by a hydrosilylation reaction in the presence of a Group VIII transition metal.

  Examples of the mercaptan having a reactive silicon group used as the chain transfer agent described in (f) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropyltriethoxysilane. . Further, as described in JP-A-60-228516, the compounds (b-1) and (b-2) are made of a bifunctional radical polymerizable compound and a mercaptan having an alkoxysilyl group as a chain transfer agent. A method of copolymerization in the presence is also possible.

  Examples of the azobisnitrile compound or disulfide compound having a reactive silicon group described in (g) include alkoxysilyl compounds described in, for example, JP-A-60-23405 and JP-A-62-70405. Examples thereof include azobisnitrile compounds having a group and disulfide compounds having an alkoxysilyl group.

  Examples of the method described in (h) include the methods described in JP-A No. 09-272714.

  In addition, a method of using a mercaptan having a reactive silicon group and a radical polymerization initiator having a reactive silicon group as described in JP-A-59-168014, JP-A-60-228516, etc. is also mentioned. It is done.

  The number of reactive silicon groups in the (co) polymer (B) is not particularly limited, and an average of 0.1 per molecule of the (co) polymer (B) from the viewpoint of the effect on adhesive force and cost. The number is from 4.0 to 4.0, and more preferably from 0.5 to 2.0.

Moreover, it is preferable from the point of the expression rate of adhesive strength to have three hydroxyl groups and / or hydrolysable groups on one silicon atom shown by following General formula (3).
-SiX ₃ (3)
(In the formula, X is a hydroxyl group or a hydrolyzable group.)
The mixing ratio of the reactive silicon group-containing oxyalkylene polymer (A) and the (co) polymer (B) in the composition of the present invention is 100 parts by weight of the total amount of ((A) + (B)). Of these, it is necessary that the component (A) is 20 to 65 parts by weight, the component (B) is 35 to 80 parts by weight, and preferably the component (A) is 40 to 60 parts by weight and the component (B) is 40 to 60 parts by weight. When the oxyalkylene polymer (A) exceeds 65 parts by weight, the initial cohesive force immediately after coating the curable composition is insufficient, resulting in low adhesive strength, which can be obtained, and the oxyalkylene polymer (A). ) Is less than 20 parts by weight, the curable composition becomes too hard after coating, and the adherend cannot be bonded, or the resulting cured product becomes brittle, and good adhesiveness and durability tend not to be obtained. become.

The curable composition of the present invention contains a tackifier resin (C) as an essential component.
As tackifying resin (C) used for this invention, there is no restriction | limiting in particular and what is used normally 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).

  The amount of the tackifying resin (C) used needs to be 10 to 100 parts by weight with respect to 100 parts by weight of the total amount of the oxyalkylene polymer (A) and the (co) polymer (B). 80 parts by weight is more preferable, and 30 to 70 parts by weight is further preferable. If the amount is less than 10 parts by weight, sufficient adhesive strength and pot life may not be secured immediately after the curable composition is applied. If the amount is more than 100 parts by weight, the heat-resistant adhesiveness is lowered or the curing rate is slow. In addition, the workability tends to decrease because the viscosity increases.

  In the curable composition of the present invention, at least one of a filler (D) and a thixotropic agent (E) is an essential component. Here, the filler (D) and the thixotropic agent (E) play a role of increasing the initial cohesive force immediately after the application of the curable composition and further improving the adhesiveness and heat resistance of the obtained cured product.

  The filler (D) is not particularly limited. For example, calcium carbonate, magnesium carbonate, titanium oxide, carbon black, fused silica, precipitated silica, diatomaceous earth, white clay, kaolin, clay, talc, wood powder, walnut Shell powder, rice husk powder, silicic anhydride, quartz powder, aluminum powder, zinc powder, asbestos, glass fiber, carbon fiber, glass beads, alumina, glass balloon, shirasu balloon, silica balloon calcium oxide, magnesium oxide, silicon oxide, etc. Organic fillers such as inorganic fillers, woody fillers such as pulp and cotton chips, powder rubber, recycled rubber, fine powder of thermoplastic or thermosetting resin, and hollow bodies such as polyethylene. Among these, calcium carbonate, titanium oxide, silica, kaolin, clay, and talc are high in initial cohesive strength of the resulting curable composition, can provide high initial adhesive strength, and have good adhesiveness and heat resistance. It is preferable from the viewpoint of obtaining properties.

  Only 1 type may be added and a filler (D) may be added in combination of multiple types.

  When blending the filler (D), the blending amount should be 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the oxyalkylene polymer (A) and the (co) polymer (B). 50 to 180 parts by weight, more preferably 80 to 160 parts by weight. When the amount exceeds 200 parts by weight, workability tends to decrease due to an increase in viscosity, and the adhesive performance of the resulting cured product also tends to decrease. On the other hand, when the amount is less than 5 parts by weight, sufficient effects tend not to be obtained.

  The thixotropic agent (E) is not particularly limited, and examples thereof include hydrogenated castor oil derivatives, polyamide waxes, organic bentonite, calcium stearate, aluminum stearate, barium stearate and other metal soaps. These thixotropic agents (E) may be used alone or in combination of two or more. Among these, since the initial cohesive force of the curable composition obtained is particularly high, high initial adhesive strength is obtained, and further, good adhesiveness and heat resistance are obtained, hydrogenated castor oil derivatives, Polyamide waxes and metal soaps are preferred.

  When the thixotropic agent (E) is blended, the blending amount is 1 to 60 parts by weight based on 100 parts by weight of the total amount of the oxyalkylene polymer (A) and the (co) polymer (B). Is required, more preferably 2 to 40 parts by weight, and most preferably 5 to 20 parts by weight. When the blending amount exceeds 60 parts by weight, workability tends to decrease due to an increase in viscosity, and the adhesive performance of the resulting cured product also tends to decrease. On the other hand, if the amount is less than 1 part by weight, sufficient effects tend not to be obtained.

The curable composition of the present invention contains a curing catalyst (F) as an essential component.
The curing catalyst (F) is not particularly limited, and examples thereof include a silanol condensation catalyst that promotes a reaction of a commonly used reactive silicon group. For example, tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate, bis Titanium compounds such as acetylacetonatodiisopropoxytitanium; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate Dibutyl tin dioctyl maleate, dibutyl tin ditridecyl maleate, dibutyl tin dibenzyl maleate, dibutyl tin diacetate, dioctyl tin diethyl maleate, dioctyl tin dioctyl maleate , Dibutyltin dimethoxide, dibutyltin dinonylphenoxide, dibutenyltin oxide, dibutyltin diacetylacetonate, dibutyltin diethylacetoacetonate, reaction product of dibutyltin oxide and silicate compound, dibutyltin oxide and phthalate ester Tetravalent organotin compounds such as reactants of the above; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetraacetylacetonate It is done.

  In addition to the above compounds, amine compounds, acidic phosphate esters, reactants of acidic phosphate esters and amine compounds, saturated or unsaturated polyvalent carboxylic acids or acid anhydrides thereof, carboxylic acid compounds and amine compounds And reactants such as salts of lead, and lead octylate.

  The compounding quantity of a curing catalyst (F) needs to be 0.1-20 weight part with respect to 100 weight part of total amounts of oxyalkylene type polymer (A) and (co) polymer (B). If the blending amount is less than 0.1 parts by weight, the curing rate is slow, whereas if it is 20 parts by weight or more, the pot life is too short and the workability tends to be lowered. In order to obtain an appropriate curing rate, the blending amount is more preferably 0.5 to 8 parts by weight, and particularly preferably 1 to 5 parts by weight.

  The curable composition of the present invention desirably contains a vinyl polymer (G) having a reactive silicon group at the molecular end (hereinafter sometimes referred to as a vinyl polymer (G)). Since the reactive silicon group of the vinyl polymer (G) is at the terminal, a high molecular weight between crosslink points is obtained compared to the case where only the (co) polymer (B) is used. From the curable composition of the present invention, The obtained cured product becomes more elastic and tends to have high durability and adhesion. On the other hand, in order to increase the molecular weight between cross-linking points, it is also possible to increase the amount of the oxyalkylene polymer (A), but in this case, the initial adhesive strength of the curable composition decreases due to a decrease in cohesive force. There is a tendency. On the other hand, the vinyl polymer (G) can arbitrarily adjust the cohesion force by selecting the monomer, and can be used without impairing the initial cohesion force of the curable composition.

Hereinafter, the vinyl polymer (G) used in the present invention will be described.
<Vinyl monomer>
It does not specifically limit as a vinyl-type monomer which comprises the principal chain of the vinyl-type polymer (G) of this invention, Various things can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) N-octyl acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, tolyl (meth) acrylate , (Meth) acrylic acid benzyl, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3-meth Sibutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (Methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethylmethyl, (meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic acid 2-par Fluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoro (meth) acrylate Methylmethyl, 2-perfluoro (meth) acrylic acid (Meth) such as methyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Acrylic monomers; aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; Maleimide monomers such as imide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile-based monomers such as acrylonitrile, methacrylonitrile; acrylamide, Amide group-containing vinyl monomers such as methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene And the like; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized.

  The main chain of the vinyl polymer (G) is at least one monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that the polymer is mainly produced by polymerization. Here, “mainly” means that 50 mol% or more, preferably 70 mol% or more of the monomer units constituting the vinyl polymer (G) are the above monomers.

  Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. Acrylic acid ester monomers and methacrylic acid ester monomers are more preferable, an acrylic acid ester monomer is particularly preferable from the viewpoint of initial adhesive strength development, and butyl acrylate is still more preferable. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. . In the above expression format, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

<Molecular weight and molecular weight distribution>
The molecular weight distribution of the vinyl polymer (G) in the present invention, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is Although not particularly limited, it is preferably less than 1.8, more preferably 1.6 or less, and particularly preferably 1.3 or less. In the GPC measurement in the present invention, chloroform is usually used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.
The number average molecular weight of the vinyl polymer (G) in the present invention is not particularly limited, but when measured by GPC, a range of 500 to 1,000,000 is preferable, more preferably 5,000 to 50,000, Further, 15,000 to 40,000 is the most preferable because of excellent balance between workability and initial adhesive strength.

<Method of synthesizing the main chain>
In the present invention, the method for synthesizing the vinyl polymer (G) is not limited, and free radical polymerization may be used. However, since a polymer having a narrow molecular weight distribution is obtained, controlled radical polymerization is preferable, and living radical polymerization is performed. Are more preferred, and atom transfer radical polymerization is particularly preferred. These will be described below.

Living radical polymerization and atom transfer radical polymerization The atom transfer radical polymerization method is a kind of radical polymerization method and further living radical polymerization method.
Radical polymerization is generally considered to be difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. However, although living radical polymerization and atom transfer radical polymerization are radical polymerizations, a termination reaction hardly occurs and a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5) is obtained. The molecular weight can be freely controlled by the charge ratio of the initiator. Therefore, the living radical polymerization method can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. Particularly preferred as a method for producing the vinyl polymer (G).

  In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state. The definition in the present invention is also the latter. As this living polymerization, particularly atom transfer radical polymerization, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules ( Macromolecules) 1995, 28, 7901, Science 1996, 272, 866, WO96 / 30421, WO97 / 18247 or Sawamoto et al., Macromolecules 1995, 28. Volume, page 1721, JP 2000-44626 A, JP 2000-72809 A, JP 2000-191728 A, and the like.

Polymerization catalyst Examples of the catalyst used in this polymerization method include elements of Group 7, Group 8, Group 9, Group 10 or Group 11, preferably Group 8, Group 9, Group 10 of the Periodic Table. A transition metal catalyst having a group or group 11 element as a central metal is used. Examples of the central metal include iron, nickel, ruthenium, and copper. Among these, monovalent copper, divalent ruthenium, and divalent iron are preferable from the viewpoint of ease of polymerization control.
Examples of the ligand constituting the transition metal catalyst include 2,2′-bipyridyl, derivatives thereof, 1,10-phenanthroline, derivatives thereof, alkylamines such as tributylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyl. Examples include polyamines such as triethylenetetraamine, and triphenylphosphine. These may be used alone or in combination of two or more. Among these, polyamine and further pentamethyldiethylenetriamine are preferable from the viewpoint of reaction control.

Polymerization initiator Examples of the polymerization initiator used in this polymerization method include organic halides, particularly organic halides having a highly reactive carbon-halogen bond (for example, ester compounds having a halogen atom at the α-position, benzyl-positions). And the like, and halogenated sulfonyl compounds.
In addition, when an organic halide having a functional group other than a group for initiating polymerization or a sulfonyl halide compound is used, a polymer having a functional group introduced at the terminal can be obtained. Examples of such functional groups include alkenyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, silyl groups, and the like.
Furthermore, when an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator, a polymer having two or more terminals (for example, a multibranched / star polymer) can be obtained.

Solvent This polymerization can be carried out without solvent or in various solvents. These are not particularly limited, but for example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ethyl acetate and butyl acetate And ester solvents such as ethylene carbonate and propylene carbonate, and the like. These may be used alone or in admixture of two or more. A supercritical fluid may also be used.
In addition, although superposition | polymerization temperature is not specifically limited, It can carry out in the range of 0-200 degreeC, and it is more preferable to carry out at 50-150 degreeC.

<Functional group>
-Number of reactive silicon groups The vinyl polymer (G) has at least one reactive silicon group. Further, from the viewpoint of curability of the composition, adhesion, adhesive properties, and mechanical properties, the number of reactive silicon groups is preferably 1.1 or more and 4.0 or less, more preferably 1.2 or more. It is 3.0 or less.
-Position of reactive silicon group Since the hardened | cured material formed by hardening | curing the curable composition of this invention becomes elastic and high durability and adhesiveness are obtained, the reactive silicon group needs to exist in the terminal.

  Methods for producing the above-mentioned vinyl polymer having a reactive silicon group at the molecular end, in particular, a (meth) acrylic polymer are disclosed in JP-B-3-14068, JP-B-4-55444, and JP-A-6-221922. No. gazette and the like. However, since these methods are free radical polymerization methods using the above "chain transfer agent method", the resulting polymer has a relatively high proportion of crosslinkable functional groups at the molecular chain ends, while Mw / Mn The value of the molecular weight distribution represented by is generally as large as 2 or more, and the viscosity is increased. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio, the above “living radical polymerization method” is used. It is preferable.

These functional groups will be described below.
-Reactive silicon group As a reactive silicon group of the vinyl polymer (G) in this invention, general formula (12);
^{_{- [Si (R 12) 2}} -d (X) d O] l -Si (R 13) 3-c (X) c (12)
{Wherein R ¹² and R ¹³ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ¹² or When two or more R ¹³ are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different. c represents 1, 2, or 3, and d represents 0, 1, or 2. l is an integer of 0-19. However, it is assumed that c + ld ≧ 1. }
The group represented by these is mentioned.

  Examples of the hydrolyzable group include commonly used groups such as a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxy group, an amide group, and an aminooxy group are preferable, but an alkoxy group is particularly preferable in terms of mild hydrolyzability and easy handling.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (c + Σd) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms forming the reactive silicon group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less. In particular, the general formula (13)
-Si (R ¹³ ) _3-c (X) _c (13)
A reactive silicon group represented by the formula (wherein R ¹³ , X and c are the same as described above) is preferable because it is easily available.

  Although not particularly limited, c is preferably 2 or more in consideration of curability. In addition, it is preferable to use a compound having c of 3 (for example, a trimethoxy functional group) and a compound having 2 (for example, a dimethoxy functional group) because storage stability, curability, adhesion, and adhesive properties may be excellent.

-Reactive silicon group introduction | transduction method Although the reactive silicon group introduction | transduction method to the vinyl polymer (G) of this invention is demonstrated below, it is not limited to this.

As a method for synthesizing the vinyl polymer (G) having at least one reactive silicon group,
(I) a method of adding a hydrosilane compound having a reactive silicon group to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst,
(Nu) A method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a group capable of reacting with a hydroxyl group, such as a compound having a reactive silicon group and an isocyanate group in one molecule,
(L) When synthesizing a vinyl polymer by radical polymerization, a method of reacting a compound having both a polymerizable alkenyl group and a reactive silicon group in one molecule;
(E) A method in which a vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a compound having a reactive silicon group and a stable carbanion in one molecule.

  The vinyl polymer having at least one alkenyl group used in the method (i) can be obtained by various methods. Although the synthesis method is illustrated below, it is not necessarily limited to these.

(Li-a) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (14) To react as a second monomer.
_{^{H 2 C = C (R 14}} ) -R 15 -R 16 -C (R 17) = CH 2 (14)
(Wherein R ¹⁴ represents hydrogen or a methyl group, R ¹⁵ represents —C (O) O—, or o-, m-, p-phenylene group, and R ¹⁶ represents a direct bond, 20 represents a divalent organic group having 20 and may contain one or more ether bonds, R ¹⁷ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents -20 aralkyl groups)
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. It is preferable to react as the second monomer at the end or after completion of the reaction of the predetermined monomer.

  (Li-b) When a vinyl polymer is synthesized by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene after the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability such as

  (Li-c) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin on a vinyl polymer having at least one carbon-halogen bond having high reactivity. A method of replacing halogen by reaction.

(Li-d) A method of replacing a halogen by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group as shown in the general formula (15). .
^{M + C- (R 18) (} R 19) -R 20 -C (R 17) = CH 2 (15)
(Wherein R ¹⁷ is the same as above, and R ¹⁸ and R ¹⁹ are both electron-withdrawing groups that stabilize carbanion C-, or one is the electron-withdrawing group and the other is hydrogen or having 1 to 10 carbon atoms. Represents an alkyl group or a phenyl group, R ²⁰ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds, M ⁺ represents an alkali metal ion, Or a quaternary ammonium ion)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

  (Lee) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a metal alone or an organometallic compound such as zinc. A method of reacting with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group .

(Li-f) An oxyanion or carboxylate anion having an alkenyl group as represented by the general formula (16) or (17) is added to a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of replacing halogen by reaction.
_{^{H 2 C = C (R 17}} ) -R 21 -O-M + (16)
(In the formula, R ¹⁷ and M ⁺ are the same as above. R ²¹ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
_{^{H 2 C = C (R 17}} ) -R 22 -C (O) O-M + (17)
(In the formula, R ¹⁷ and M ⁺ are the same as above. R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.)
Etc.

  The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond is an atom transfer radical polymerization method using an organic halide as described above as an initiator and a transition metal complex as a catalyst. For example, but not limited to.

Further, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but are not limited thereto. .
In the hydroxyl group of a vinyl polymer having at least one hydroxyl group,
(Li-g) a method of reacting a base such as sodium methoxide and reacting with an alkenyl group-containing halide such as allyl chloride;
(Ri-h) a method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate,
(Li-i) a method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine,
(Li-j) A method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst, and the like.

  In the present invention, when halogen is not directly involved in the method of introducing an alkenyl group such as (Ri-a) or (Ri-b), it is preferable to synthesize a vinyl polymer by using a living radical polymerization method. . In view of easier control, the method (b) is more preferable.

  When introducing an alkenyl group by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl heavy polymer having at least one highly reactive carbon-halogen bond at the terminal, obtained by radical polymerization of a vinyl monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). It is preferable to use coalescence. The method (Re-f) is more preferable from the viewpoint of easier control.

Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a reactive silicon group, If a typical thing is shown, the compound shown by General formula (18) will be illustrated.
^{_{H- [Si (R 12) 2}} -d (X) d O] l -Si (R 13) 3-c (X) c (18)
{Wherein R ¹² and R ¹³ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R 'Is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different), and represents a triorganosiloxy group represented by R ¹² or When two or more R ¹³ are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different. c represents 1, 2, or 3, and d represents 0, 1, or 2. l is an integer of 0-19. However, it is assumed that c + ld ≧ 1. }
Among these hydrosilane compounds, in particular, the general formula (19)
H-Si (R ¹³ ) _3-c (X) _c (19)
(Wherein R ¹³ , X and c are the same as above)
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.

When the hydrosilane compound having a reactive silicon group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of transition metal catalysts include platinum alone; platinum solid dispersed in a carrier such as alumina, silica, carbon black; chloroplatinic acid; a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc .; platinum-olefin Complexes: platinum-divinyltetramethyldisiloxane complex and the like. Examples of the catalyst other than platinum _{compounds, RhCl (PPh 3) 3,} RhCl 3, RuCl 3, IrCl 3, FeCl 3, AlCl 3, PdCl 2 · H 2 O, NiCl 2, TiCl 4 , and the like.
Examples of the method for producing a vinyl polymer having at least one hydroxyl group used in the methods (nu) and (Li-g) to (Li-j) include the following methods. It is not limited.
(Nu-a) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (20) is used as the second monomer. How to react as.
^{_{H 2 C = C (R 14}} ) -R 15 -R 16 -OH (20)
(Wherein R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as above)
There is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, particularly in the case of living radical polymerization, when the rubber-like properties are expected, the end of the polymerization reaction or a predetermined monomer. After completion of the reaction, it is preferable to react as the second monomer.
(Nu-b) When a vinyl polymer is synthesized by living radical polymerization, an alkenyl alcohol such as 10-undecenol, 5-hexenol or allyl alcohol is reacted at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. How to make.
(Nu-c) A method in which a vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide disclosed in JP-A-5-262808.
(Nu-d) A method of radical polymerization of a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.
(Nu-e) A method in which a vinyl monomer is radically polymerized using an excessive amount of alcohol as disclosed in, for example, JP-A-6-116312.
(Nu-f) For example, a halogen of a vinyl polymer having at least one carbon-halogen bond having high reactivity is hydrolyzed or a hydroxyl group-containing compound by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at the terminal by reacting.
(Nu-g) A method in which a vinyl polymer having at least one carbon-halogen bond having high reactivity is reacted with a stabilized carbanion having a hydroxyl group as shown in the general formula (21) to substitute a halogen.
M ^<+>- C- (R ^{< 18 >} ) (R ^{< 19 >} )-R ^{< 20 >} -OH (21)
(In the formula, R ¹⁸ , R ¹⁹ and R ²⁰ are the same as above)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.
(Nu) h) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal or an organometallic compound such as zinc, and then aldehydes. Or a method of reacting ketones.
(Nu-i) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with, for example, an oxyanion or carboxylate anion having a hydroxyl group as shown in the general formula (22) or (23). To replace the halogen.
^{HO-R 21 -O-M +} (22)
(Wherein R ²¹ and M ⁺ are the same as above)
HO-R ^{< 22 >} -C (O) OM ^<+> (23)
(Wherein R ²² and M ⁺ are the same as above)
(Nu-j) When synthesizing a vinyl polymer by living radical polymerization, as the second monomer after the end of the polymerization reaction or after the completion of the reaction of the predetermined monomer, an alkenyl group and a hydroxyl group having low polymerizability in one molecule A method of reacting a compound having
Although it does not specifically limit as such a compound, The compound etc. which are shown by General formula (24) are mentioned.
^{_{H 2 C = C (R 14}} ) -R 21 -OH (24)
(Wherein R ¹⁴ and R ²¹ are the same as above)
Although it does not specifically limit as a compound shown by the said General formula (24), The alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable from availability.

  In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group such as (nu-a) to (nu-e) and (nu-j), a vinyl polymer is obtained by using a living radical polymerization method. It is preferable to synthesize. The method (nu-b) is more preferable in terms of easier control.

  When introducing a hydroxyl group by converting halogen in a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method). The method (nu-i) is more preferable from the viewpoint of easier control.

  Examples of the compound having a reactive silicon group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanate. Examples thereof include natopropyltriethoxysilane, and a generally known catalyst for urethanization reaction can be used if necessary.

Examples of the compound having a polymerizable alkenyl group and a reactive silicon group in one molecule used in the method (l) include, for example, γ-trimethoxysilylpropyl (meth) acrylate, γ-methyldimethoxysilylpropyl (meth) acrylate, and the like. What is shown by the following general formula (25) is mentioned.
_{^{H 2 C = C (R 14}} ) -R 15 -R 23 - [Si (R 12) 2-d (X) d O] l -Si (R 13) 3-c (X) c (25)
(In the formula, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , X, c, d, and l are the same as above. R ²³ is a direct bond or one divalent organic group having 1 to 20 carbon atoms. (The above ether bond may be included, provided that c + ld ≧ 1 is satisfied.)
There is no particular limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a reactive silicon group in one molecule. However, particularly in the case of living radical polymerization, when a rubber-like property is expected, the end of the polymerization reaction or a predetermined value is determined. It is preferable to make it react as a 2nd monomer after completion | finish of reaction of this monomer.

  The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond, which is used in the method (v), uses an organic halide as described above as an initiator, and a transition metal complex. Examples thereof include, but are not limited to, an atom transfer radical polymerization method using a catalyst.

Examples of the compound having both a reactive silicon group and a stabilized carbanion in one molecule include those represented by the general formula (26).
^{M + C- (R 18) (} R 19) -R 24 -C (H) (R 25) -CH 2 - [Si (R 12) 2-d (X) d O] l -Si (R 13) _3-c (X) _c (26)
(Wherein R ¹² , R ¹³ , R ¹⁸ , R ¹⁹ , X, c, d, 1 and M ⁺ are the same as above. R ²⁴ is a direct bond or a divalent organic group having 1 to 10 carbon atoms. R ²⁵ , which may contain one or more ether bonds, represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, provided that c + ld Satisfy that ≧ 1.)
As the electron withdrawing group for R ¹⁸ and R ¹⁹ , those having a structure of —CO ₂ R, —C (O) R and —CN are particularly preferable.

  When the vinyl polymer (G) having a reactive silicon group at the molecular end is blended, the blending amounts thereof are oxyalkylene polymer (A), (co) polymer (B), and vinyl polymer (G). ) Is 100 to 50 parts by weight, the component (A) is 20 to 60 parts by weight, the component (B) is 35 to 75 parts by weight, and the component (G) is 5 to 45 parts by weight. More preferably, the component (A) is 20 to 60 parts by weight, the component (B) is 35 to 75 parts by weight, and the component (G) is 5 to 20 parts by weight. When component (G) exceeds 45 parts by weight, characteristics derived from components (A) and (B) tend to be lost.

  In the curable composition of this invention, it is preferable that the viscosity in 120 degreeC is 100 Pa.s or less, and the viscosity in 30 degreeC is 1,000 Pa.s or more.

  When the viscosity at 120 ° C. exceeds 100 Pa · s, the coatability and workability deteriorate, or it is necessary to apply at a higher temperature to ensure the coatability and workability. In that case, the range of use is limited, for example, it becomes difficult to use the base material with low heat resistance. More preferably, the temperature at 120 ° C. is 50 Pa · s or less, and more preferably 20 Pa · s or less.

  On the other hand, when the viscosity at 30 ° C. is less than 1,000 Pa · s, the initial cohesive force immediately after application of the curable composition is insufficient, and high adhesive strength tends not to be obtained. More preferably, it is 10,000 Pa · s or more, and further preferably 50,000 Pa · s or more.

  Since the curable composition of the present invention uses a low-viscosity polymer, a polymer having high temperature sensitivity, or a resin, it can be applied as a hot melt adhesive at a relatively low temperature. In order to ensure good workability, the coating is preferably performed by heating to 60 to 180 ° C, more preferably 70 to 160 ° C, particularly preferably 90 to 140 ° C. When the temperature is lower than 60 ° C., sufficient workability cannot be ensured, and when the temperature is higher than 180 ° C., the stability of the curable composition is lowered, and the use range is limited such that it cannot be used for a substrate having low heat resistance. When heating and using a curable composition, the heating method can use a conventionally well-known method without a restriction | limiting in particular.

  The curable composition of the present invention preferably has a pot life of 5 minutes or longer under conditions of 23 ° C. and 50% RH after coating. Here, the pot life is the time during which the adherend can be bonded after being applied. After coating with a general hot melt adhesive, the adherend is solidified by cooling. Since it is impossible to bond, and even if bonded, sufficient wettability cannot be ensured, so there is a problem that sufficient adhesiveness cannot be finally obtained, so the pot life is several minutes until cooling and solidification It was normal to be limited to. On the other hand, since the curable composition of the present invention is solidified after passing through a semi-solidified state having an adhesive force after cooling for 5 minutes or more, and an adherend can be arbitrarily bonded during the semi-solidified state. It is characterized by a long pot life. In addition, the adhesive force during this time is not only high enough to fix the adherend, but it can be repositioned because it can be peeled off once like an adhesive and repositioned, etc. Workability can be improved.

The pot life in the present invention is defined as follows.
(I) In a plurality of samples in which a curable composition is applied and the adherend is bonded after an arbitrary time has elapsed after application, the shear bond strength immediately after the adherend is bonded is expressed by 0.5 Mpa or more ( Thickness of curable composition: 100 μm, base material: aluminum-aluminum (a curable composition is applied to one base material, and the other base material is bonded to each other after the elapse of time and the adhesive strength is measured), tensile speed; 50mm / min)
(II) Further, after curing for 2 weeks at 23 ° C. and 50% RH, a time zone during which cohesive failure occurs is defined as the pot life.

  The length of the pot life is desirably 5 minutes or longer, more preferably 15 minutes or longer, and further preferably 30 minutes or longer. More preferably, it is 60 minutes or more. If the pot life is too long, the time to reach the final bond strength tends to be longer. Moreover, it is preferable that the shear bond strength immediately after applying a curable composition and bonding a to-be-adhered body is 0.5 MPa or more, More preferably, it is 0.8 MPa or more, More preferably, it is 1.0 MPa or more.

  The curable composition of the present invention is used as a reactive hot melt adhesive for various uses and for bonding substrates. The use is not particularly limited, and examples thereof include architecture, automobiles, electricity / electronics, textiles / leathers / clothing. Among them, the curable composition of the present invention is solvent-free and excellent in environmental compatibility, high adhesive strength can be obtained immediately after coating, excellent adhesion to various adherends, heat resistant adhesiveness Since it has characteristics such as superiority, it is preferably used as an architectural application or an automobile application among the above applications, and most preferably used as an automobile application.

  As an example which uses the reactive hot-melt-adhesive agent formed using the curable composition of this invention for a motor vehicle use, the use to a motor vehicle interior material is mentioned, for example. An automotive interior material is a laminate in which a skin material and a base material are laminated via an adhesive layer, and a reactive hot melt adhesive using the curable composition of the present invention is suitable as the adhesive layer. used.

Here, as a method of laminating the skin material and the substrate through the reactive hot melt adhesive using the curable composition of the present invention,
(I) A method in which the curable composition is applied on the surface to be laminated of at least one member of the skin material and the base material, and is bonded to the other member before the curable composition is cooled and solidified,
(Ii) A method in which the curable composition is cooled and solidified on the layered surface of at least one member of the skin material and the base material, and then the layered surface of the other member is bonded to each other.

  In the case of a general hot melt adhesive, it is difficult to bond the adherend after cooling and solidification, but the curable composition of the present invention also adheres to the adherend after cooling and solidification as in the method (ii). Further, since a high adhesive strength can be obtained immediately after the bonding, it is possible to improve productivity and workability.

  The automobile interior material obtained by this method can be suitably used for instrument panels, door materials, seat sheets, ceiling materials, rear trays, pillars, and the like.

  The skin material is not particularly limited, for example, plastic materials such as polyvinyl chloride (PVC), thermoplastic plastic rubber, thermoplastic plastic olefin, textile materials such as cloth, nonwoven fabric, or the above various materials and various foams. A material formed by laminating a body, for example, a foam such as PP, polyethylene (PE), PVC, or polyurethane can be used.

  The base material is not particularly limited. For example, various plastics such as ABS, polypropylene (PP), polycarbonate, nylon, etc .; metals such as steel, iron, aluminum; woody material in which timber chips are hardened with a thermosetting resin Boards: Plant fiber sheets such as kenaf fiber, sisal hemp, corrugated cardboard, etc., molded articles formed into shapes for proper missions using boards, etc., or simply made of flat plates can be used.

  In addition to the above, the curable composition of the present invention may contain a silane coupling agent, a plasticizer, a stabilizer and the like as necessary.

  Specific examples of the silane coupling agent include amino group-containing silanes such as N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane. An epoxy group-containing silane such as γ-glycidoxypropyltrimethoxysilane; a vinyl-type unsaturated group-containing silane such as vinyltrimethoxysilane; an isocyanate group-containing silane such as γ-isocyanatopropyltrimethoxysilane; These silane coupling agents may be used alone or in combination of two or more. In particular, aminosilane, its reaction product, epoxy silane, and isocyanate silane are preferable from the viewpoint of adhesiveness.

  The silane coupling agent is preferably used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total amount of the oxyalkylene polymer (A), the (co) polymer (B) and the vinyl polymer (G). It is more preferable to use 2 to 10 parts by weight.

  Specific examples of the plasticizer include, for example, phthalic acid esters such as dioctyl phthalate and diisodecyl phthalate; aliphatic dibasic acid esters such as dioctyl adipate; and epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil Polyethers such as polypropylene glycol and derivatives thereof; vinyl polymers obtained by polymerizing vinyl monomers by various methods, and the like. These plasticizers may be used alone or in combination of two or more.

  The amount of the plasticizer used may be 5 to 100 parts by weight with respect to 100 parts by weight of the total amount of the oxyalkylene polymer (A), (co) polymer (B) and vinyl polymer (G). It is preferable to use 10 to 70 parts by weight. If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 100 parts by weight, the mechanical strength of the cured product will be insufficient, or sufficient adhesive strength after coating will not be obtained.

  Specific examples of the stabilizer include an antioxidant, a light stabilizer, and an ultraviolet absorber.

  When an antioxidant is used, the weather resistance and heat resistance of the cured product can be improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred.

  The amount of the antioxidant used is 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the oxyalkylene polymer (A), the (co) polymer (B) and the vinyl polymer (G). It is preferable to use 0.2 to 5 parts by weight.

  When a light stabilizer is used, photooxidation deterioration of the cured product can be prevented. Examples of the light stabilizer include benzotriazole-based, hindered amine-based, and benzoate-based compounds, and hindered amine-based compounds are particularly preferable.

  The light stabilizer is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the oxyalkylene polymer (A), (co) polymer (B) and vinyl polymer (G). It is preferable to use 0.2 to 5 parts by weight.

  When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, with benzotriazole being particularly preferred.

  The amount of the ultraviolet absorber used is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the oxyalkylene polymer (A), (co) polymer (B) and vinyl polymer (G). It is preferable to use 0.2 to 5 parts by weight.

  Further, it is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

  Furthermore, 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, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, Examples include solvents and fungicides. These various additives may be used alone or in combination of two or more.

  The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use.

  There is no particular limitation on the method of adjusting the curable composition to be applied by the application method of the present invention. Ordinary methods such as using a small amount of a solvent to dissolve and mixing the components can be used.

The curable composition of this invention is demonstrated based on an Example.
EXAMPLES Hereinafter, the present invention will be specifically described with reference to synthesis examples, production examples, and examples, but the present invention is not limited to these synthesis examples, production examples, and examples.

The synthesis example of the oxyalkylene polymer (A) having a reactive silicon group is shown below.
(Synthesis Example 1)
A polyoxypropylene diol having a number average molecular weight of 2,000 is used as an initiator, and propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a poly having a number average molecular weight of 14,500 (polystyrene conversion value determined from GPC). Oxypropylene diol was obtained. After the obtained polyoxypropylene diol and sodium methoxide were reacted, allyl chloride was reacted to convert the terminal hydroxyl group into an unsaturated group.

  0.75 mol of methyldimethoxysilane is reacted in the presence of a platinum divinyldisiloxane complex with respect to 1 mol of the unsaturated group of this unsaturated group-terminated polyoxypropylene polymer, and a number having a methyldimethoxysilyl group at the molecular end. An oxyalkylene polymer having a reactive silicon group having an average molecular weight of 15,000 (polystyrene conversion value determined from GPC) and a molecular weight distribution of 1.20 was obtained (Polymer A).

(Synthesis Example 2)
A polyoxypropylene diol having a number average molecular weight of 2,000 is used as an initiator, and propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a poly having a number average molecular weight of 25,500 (polystyrene conversion value determined from GPC). Oxypropylene diol was obtained. After the obtained polyoxypropylene diol and sodium methoxide were reacted, allyl chloride was reacted to convert the terminal hydroxyl group into an unsaturated group.

  A number having 0.71 mol of methyldimethoxysilane in the presence of platinum divinyldisiloxane complex to 1 mol of unsaturated group of this unsaturated group-terminated polyoxypropylene polymer, and having a methyldimethoxysilyl group at the molecular end An oxyalkylene polymer having a reactive silicon group having an average molecular weight of 26,000 (polystyrene conversion value determined from GPC) and a molecular weight distribution of 1.30 was obtained (Polymer B).

(Synthesis Example 3)
A polyoxypropylene diol having a number average molecular weight of 2,000 is used as an initiator, and propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a poly having a number average molecular weight of 20,000 (polystyrene conversion value determined from GPC). Oxypropylene diol was obtained. After the obtained polyoxypropylene diol and sodium methoxide were reacted, allyl chloride was reacted to convert the terminal hydroxyl group into an unsaturated group.

  A number having a trimethoxysilyl group at the molecular end by reacting 0.65 mol of trimethoxysilane in the presence of a platinum divinyldisiloxane complex with respect to 1 mol of the unsaturated group of this unsaturated group-terminated polyoxypropylene polymer. An oxyalkylene polymer having a reactive silicon group having an average molecular weight of 21,000 (polystyrene conversion value determined from GPC) and a molecular weight distribution of 1.28 was obtained (Polymer C).

(Synthesis Example 4)
A polyoxypropylene diol having a number average molecular weight of 2,000 is used as an initiator, and propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a poly having a number average molecular weight of 14,500 (polystyrene conversion value determined from GPC). Oxypropylene diol was obtained. A urethanation reaction is carried out by adding 0.7 mol of γ-isocyanatopropyltrimethoxysilane to 1 mol of hydroxyl group of the resulting polyoxypropylenediol, and the number average molecular weight having a trimethoxysilyl group at the molecular end is 15,500 ( A polyoxyalkylene polymer having a reactive silicon group with a molecular weight distribution of 1.40 was obtained (Polymer D) obtained from GPC (Polymer D).

The synthesis example of the (meth) acrylic-acid alkylester type | system | group (co) polymer (B) is shown below.
(Synthesis Example 5)
In 40 g of toluene heated to 105 ° C., 67 g of methyl methacrylate, 5 g of butyl acrylate, 15 g of stearyl methacrylate, 5 g of 3-methacryloxypropyltrimethoxysilane, 8 g of γ-mercaptopropylmethyldimethoxysilane, and 2 as a polymerization initiator A solution prepared by dissolving 3 g of 2,2′-azobisisobutyronitrile in 15 g of toluene was added dropwise over 5 hours, followed by stirring for 2 hours. Furthermore, by adding a solution prepared by dissolving 0.3 g of 2,2′-azobisisobutyronitrile in 10 g of toluene and stirring for 2 hours, a solid content concentration of 60% by weight and a number average molecular weight of 3,000 (GPC Further, an acrylic copolymer having a molecular weight distribution of 1.62 was obtained (Polymer E).

(Synthesis Example 6)
In 40 g of toluene heated to 105 ° C., 67 g of methyl methacrylate, 5 g of butyl acrylate, 15 g of stearyl methacrylate, 5 g of 3-methacryloxypropyltrimethoxysilane, 8 g of γ-mercaptopropyltrimethoxysilane, and 2 as a polymerization initiator A solution prepared by dissolving 3 g of 2,2′-azobisisobutyronitrile in 15 g of toluene was added dropwise over 5 hours, followed by stirring for 2 hours. Furthermore, by adding a solution prepared by dissolving 0.3 g of 2,2′-azobisisobutyronitrile in 10 g of toluene and stirring for 2 hours, a solid content concentration of 60% by weight and a number average molecular weight of 3,100 (GPC Further, an acrylic copolymer having a molecular weight distribution of 1.66 was obtained (Polymer F).

The synthesis example of the vinyl polymer (G) having reactive silicon at the molecular terminal is shown below.
(Synthesis Example 7)
(Method for producing n-butyl acrylate polymer having alkenyl group at terminal)
A stirrer, jacketed 250 L reactor was purged with nitrogen, CuBr (1.09 kg), acetonitrile (11.4 kg), n-butyl acrylate (26.0 kg) and diethyl 2,5-dibromoadipate (2.28 kg) ) And stirred at 70 ° C. for about 30 minutes. To this was added triamine (43.9 g) to initiate the reaction. During the reaction, n-butyl acrylate (104 kg) was continuously added dropwise. Triamine (176 g) was added in portions during the dropwise addition of n-butyl acrylate. Four hours after the start of the reaction, unreacted monomer and acetonitrile were devolatilized by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (45.7 kg), 1,7-octadiene (14.0 kg) and triamine (439 g) were added to the concentrate and stirring was continued for 8 hours. The mixture was heated and stirred at 80 ° C. under reduced pressure to devolatilize acetonitrile and unreacted 1,7-octadiene, and concentrated. Toluene (130 kg) was added to the concentrate to dissolve the polymer. Solid copper in the polymer mixture was filtered through a bag filter (manufactured by HAYWARD, nominal filter cloth pore diameter: 1 μm). Kyoward 500SH (manufactured by Kyowa Chemical Co., Ltd .: 0.5 parts by weight with respect to 100 parts by weight of the polymer) and Kyoward 700SL Kyowa Chemical Co., Ltd .: 0.5 parts by weight with respect to 100 parts by weight of the polymer) were added to the filtrate. The mixture was heated and stirred at 100 ° C. for 3 hours in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%). Insoluble matter in the mixture was filtered off. The filtrate was concentrated to obtain a polymer. The polymer was heated and devolatilized at 180 ° C. for 12 hours (the degree of vacuum was 10 torr or less) to remove the Br group from the polymer.

  Toluene (100 parts by weight with respect to 100 parts by weight of the polymer), Kyoward 500SH (manufactured by Kyowa Chemical Co., Ltd .: 1 part by weight with respect to 100 parts by weight of the copolymer), Kyoward 700SL Kyowa Chemical Co., Ltd .: polymer 100 1 part by weight with respect to parts by weight), hindered phenolic antioxidant (Irganox 1010; Ciba Specialty Chemicals 0.01 part), and 150 ° C. for 4 hours in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%) Stir with heating. Insoluble matter in the mixture was filtered off. The filtrate was concentrated to obtain an alkenyl group-terminated acrylic acid n-butyl polymer. The number average molecular weight of the obtained polymer was 24300, and the molecular weight distribution was 1.2. When the average number of alkenyl groups introduced per molecule of the copolymer was determined by 1H NMR analysis, it was 1.8.

(Method for producing n-butyl acrylate polymer having a crosslinkable silyl group at the terminal)
An alkenyl group-terminated n-butyl acrylate polymer (65 kg), dimethoxymethylhydrosilane (1.1 kg), methyl orthoformate (0.55 kg) obtained above in a 140 L reactor pressure-resistant reaction vessel with a stirrer and jacket, And a xylene solution of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum (10 mg as platinum with respect to 1 kg of the polymer). The mixture was heated and stirred at 100 ° C. for 1 hour under a nitrogen atmosphere. Reactive silyl group-terminated n-butyl acrylate polymer (Polymer G) was obtained by distilling off the volatile components of the mixture under reduced pressure. The number average molecular weight of the obtained polymer G was 24600 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.3. The average number of silyl groups introduced per molecule of the polymer was determined by 1H NMR analysis and found to be 1.8.

Production examples of the curable composition are shown below.
(One-part curable composition production examples 1 to 13)
(A), (B), (D), (E), (G) component, (C) component dissolved in toluene and a stabilizer after mixing in the ratio shown in Table 1 ((B) component is toluene. Toluene was devolatilized by heating under reduced pressure at 120 ° C. Next, the silane coupling agent shown in Table 1 was added and stirred for 5 minutes, and then component (F) was added and stirred for 5 minutes. Finally, it was degassed under reduced pressure, and the metal container was filled with the curable composition (Formulations 1 to 13).

Examples and comparative examples are shown below.
(Examples 1-8, Comparative Examples 1-5)
The following evaluation was performed using the obtained one-component curable compositions 1-13.
All the evaluations were performed in an atmosphere having a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 10%.
● Viscosity measurement;
The viscosity of the composition at 30 and 120 ° C. was measured.
● Adhesiveness
・ After applying a curable composition heated to an initial adhesive strength of 120 ° C. to an aluminum plate (thickness 100 μm, width 25 mm, length 25 mm), and taking an open time of 5 minutes, 15 minutes, 30 minutes, and 60 minutes After the aluminum plate was bonded and a 5 kg weight was applied for 1 minute and pressure bonded, the shear bond strength was measured with a tensile tester (tensile speed 50 mm / min).
・ Apply a curable composition heated to 120 ° C. of adhesive strength to an aluminum plate (thickness 100 μm, width 25 mm, length 25 mm). The weight was put on for 1 minute and crimped. After removing the weight, the shear bond strength after standing for 3 hours was measured with a tensile tester (tensile speed: 50 mm / min).
・ After applying a curable composition heated to a final adhesive strength of 120 ° C. to an aluminum plate (thickness: 100 μm, width: 25 mm, length: 25 mm), and taking an open time of 5, 15, 30, 60 minutes The aluminum plate was bonded and a 5 kg weight was put on it for 1 minute and pressure bonded. After removing the weight and curing at 23 ° C. and 50% RH for 14 days, the shear bond strength was measured with a tensile tester (tensile speed 50 mm / min).
・ Apply a curable composition heated to 120 ° C heat resistant adhesive strength to an aluminum plate (thickness 100 µm, width 25 mm, length 25 mm), and after 5 minutes of open time, paste the aluminum plate and apply a 5 kg weight Crimped for 1 minute. After removing the weight and curing at 23 ° C. and 50% RH for 14 days, the shear bond strength under the condition of 80 ° C. was measured with a tensile tester (tensile speed: 50 mm / min).
Expressing strength of at least 0.5Mpa in test-pot life the initial adhesive strength, and open time to be cohesive failure in the test of the final adhesive strength was pot life.
-Adhesiveness to base material for automobile interior material A curable composition heated to 120 ° C was applied to a base for automobile interior material (PP board), and the thickness was adjusted to 100 µm with an applicator. After taking an open time of 5 minutes, it was bonded to the back surface of a car interior material (surface: TPO, back surface: PP foam), and a 5 kg roller was applied twice. Subsequently, it was cured for 14 days under an atmosphere of 23 ° C. and 50% RH to obtain a laminate of automobile interior materials. The obtained laminate was cut into a 25 mm-wide strip to obtain a sample for evaluation, and the creep resistance (adhesion holding force) of the cured product laminated between the skin material and the substrate was measured by the method described later.
(Evaluation of creep resistance (holding power))
After fixing the base material horizontally, one end of the skin material is peeled off, and a weight (500 g / 25 mm) is hung so that a load is applied in the direction of 90 degrees with respect to the adhesive surface. Measurements were made at 23 ° C and 90 ° C. However, the time required to peel 60 mm was measured for those peeled 60 mm or more within 24 hours.

  The obtained evaluation results are shown in Table 1.

表１に示すように、実施例に記載の硬化性組成物は塗工後に十分な可使時間を確保することができるとともに、最終接着強度や耐熱接着性能に優れる硬化物を得ることができる。また、３つの加水分解性基をもつ反応性ケイ素基を導入したオキシアルキレン系重合体（Ａ）あるいは（共）重合体（Ｂ）を使用した場合では（実施例２、３、４）、被着体を貼り合わせてからの接着強度の発現速度が特に早く、３時間後には十分に実用に耐え得る強度を発現している。さらに、ビニル系重合体（Ｇ）を配合した場合では、粘度が低く良好な作業性が得られると共に高い接着強度、耐熱接着性が得られていることが分かる。また、さらに本発明の硬化性組成物は自動車内装材表皮材に対しても良好な接着性を示しており、本用途向け接着剤として有用であることがわかった。

As shown in Table 1, the curable compositions described in the examples can ensure a sufficient pot life after coating, and can obtain a cured product excellent in final adhesive strength and heat-resistant adhesive performance. In the case of using an oxyalkylene polymer (A) or (co) polymer (B) having a reactive silicon group having three hydrolyzable groups (Examples 2, 3, and 4), The rate of expression of the adhesive strength after the bonded bodies are bonded is particularly fast, and the strength that can withstand practical use is sufficiently developed after 3 hours. Furthermore, when the vinyl polymer (G) is blended, it can be seen that the viscosity is low and good workability is obtained, and high adhesive strength and heat resistant adhesiveness are obtained. Furthermore, the curable composition of the present invention also showed good adhesion to an automobile interior material skin material, and was found to be useful as an adhesive for this application.

Claims (23)

In the composition, an oxyalkylene polymer (A) having a reactive silicon group, a (meth) acrylic acid alkyl ester (co) polymer (B), a tackifying resin (C), a filler (D) and A curable composition comprising a thixotropic agent (E) and a curing catalyst (F), the oxyalkylene polymer (A) having a reactive silicon group and (meth) acrylic acid The composition ratio of the alkyl ester (co) polymer (B) is 20/80 to 65/35, and the total amount of ((A) + (B)) is 100 parts by weight. 10 to 100 parts by weight of C), 5 to 200 parts by weight of filler (D) and / or 1 to 60 parts by weight of thixotropic agent (E), and 0.1 to 20 parts by weight of curing catalyst (F) A curable composition comprising the curable composition. The curable composition according to claim 1, wherein the oxyalkylene polymer (A) having a reactive silicon group has a group represented by the following general formula (1).
^{-NR 1 -C (= O) -} (1)
(In the formula, R ¹ is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.) The curable composition according to claim 1, wherein the oxyalkylene polymer (A) having a reactive silicon group has a group represented by the following general formula (2).
—O—R ² — (Si (R ³ _2−b ) (X _b ) —O) _m —SiR ⁴ _3−a X _a (2)
(In the formula, R ² is an alkylene group having 2 to 20 carbon atoms. (M × (2-b)) R ³ and (3-a) R ⁴ are each independently 1 to 1 carbon atoms. 20 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms or (R ⁵ ) ₃ SiO— (three R ⁵ are monovalent hydrocarbons having 1 to 20 carbon atoms) .) Is at least one selected from the group consisting of triorganosiloxy groups, X is a hydroxyl group or a hydrolyzable group, a is 1 , 2 or 3. m (Si (R ^{B in 3} _2-b ) (X _b ) —O) is independently 0, 1 or 2. m is 0 or an integer of 1 to 19.) The curable composition according to any one of claims 1 to 3, wherein the number average molecular weight of the oxyalkylene polymer (A) having a reactive silicon group is 10,000 to 45,000. . The curable composition according to any one of claims 1 to 4, wherein the molecular weight distribution of the oxyalkylene polymer (A) having a reactive silicon group is 1.6 or less. The curable composition according to any one of claims 1 to 5, wherein the oxyalkylene polymer (A) having a reactive silicon group has a group represented by the following general formula (3). object.
-SiX ₃ (3)
(In the formula, X is a hydroxyl group or a hydrolyzable group.) The (meth) acrylic acid alkyl ester-based (co) polymer (B) has a reactive silicon group represented by the following general formula (4), according to any one of claims 1 to 6. Curable composition.
-SiR ⁴ _3-a X _a (4)
(In the formula, each R ⁴ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ⁵ ) ₃ SiO— (three R ⁵ is a monovalent hydrocarbon having 1 to 20 carbon atoms.) Is selected from the group consisting of triorganosiloxy groups, a is 1 , 2 or 3, and X is a hydroxyl group Or a hydrolyzable group.) The curing according to any one of claims 1 to 7, wherein the (meth) acrylic acid alkyl ester-based (co) polymer (B) has a group represented by the following general formula (3). Sex composition.
-SiX ₃ (3)
(In the formula, X is a hydroxyl group or a hydrolyzable group.) The curable composition according to any one of claims 1 to 8, comprising a vinyl polymer (G) having a reactive silicon group at a molecular end. The main chain of the vinyl polymer (G) having a reactive silicon group at the molecular end is composed of (meth) acrylic monomer, acrylonitrile monomer, aromatic vinyl monomer, fluorine-containing vinyl monomer and silicon-containing vinyl monomer. 10. The polymer according to claim 9, wherein the polymer is produced by mainly polymerizing at least one monomer selected from the group consisting of a living radical polymerization method and an atom transfer radical polymerization method. Curable composition. The curable composition according to claim 9 or 10, wherein the molecular weight distribution of the vinyl polymer (G) having a reactive silicon group at a molecular end is less than 1.8. The curing agent according to any one of claims 1 to 11, wherein the filler (D) is at least one selected from the group consisting of calcium carbonate, titanium oxide, silica, kaolin, clay, and talc. Sex composition. The thixotropic agent (E) is at least one selected from the group consisting of hydrogenated castor oil derivatives, polyamide waxes, and metal soaps. The curable composition as described. The curable composition according to any one of claims 1 to 13, wherein the viscosity at 120 ° C is 100 Pa · s or less and the viscosity at 30 ° C is 1000 Pa · s or more. The adhesive for building members which uses the curable composition of any one of Claims 1-14. The adhesive for motor vehicle parts which uses the curable composition of any one of Claims 1-14. The adhesive for electrical / electronic components which uses the curable composition of any one of Claims 1-14. The adhesive agent for fibers, leather, and clothing which uses the curable composition of any one of Claims 1-14. It is a reactive hot-melt-adhesive formed by using the curable composition of any one of Claims 1-14, Comprising: The pot life which can adhere an adherend together is 23 degreeC50% RH A reactive hot melt adhesive, characterized by being 5 minutes or longer under conditions. A method for adhering two types of adherends via a reactive hot melt adhesive comprising the curable composition according to claim 1, wherein the reactive hot melt After the adhesive is heated to 60 to 180 ° C., it is applied to one adherend, and after the reactive hot melt adhesive becomes 60 ° C. or less, the other adherend is attached to the reactive hot melt adhesive. A bonding method characterized in that the adhesive is pressure-bonded to the agent. A method for adhering two types of adherends via a reactive hot melt adhesive comprising the curable composition according to claim 1, wherein the reactive hot melt After the adhesive is heated to 60 to 180 ° C., it is applied to one adherend, and after one minute or more has elapsed after the application, the other adherend is pressure-bonded to the reactive hot melt adhesive. Adhesive method. A method for adhering two kinds of adherends via a reactive hot-melt adhesive using the curable composition according to any one of claims 1 to 14, wherein the curable composition is An adhesion method characterized in that after applying and bonding the adherends, one of the bonded adherends is once peeled off and then bonded again. A method for producing a molded body in which two types of adherends are bonded via a reactive hot melt adhesive using the curable composition according to any one of claims 1 to 14, The reactive hot melt adhesive is heated to 60 to 180 ° C. and then applied to one adherend. After the reactive hot melt adhesive is 60 ° C. or less, the other adherend is attached to the adherend. A method for producing a molded article, wherein the molded article is molded after being pressure-bonded to a reactive hot melt adhesive.