WO2012057281A1

WO2012057281A1 - Curable composition

Info

Publication number: WO2012057281A1
Application number: PCT/JP2011/074849
Authority: WO
Inventors: 担渡辺; 岡村　直実; 齋藤　敦; 裕仁水野
Original assignee: セメダイン株式会社
Priority date: 2010-10-27
Filing date: 2011-10-27
Publication date: 2012-05-03
Also published as: JP6161103B2; JPWO2012057281A1

Abstract

Provided are: a curable composition which exhibits excellent curability, adhesiveness and storage stability and which does not necessitate an organotin-type catalyst and is therefore highly safe; and a process for manufacturing the curable composition. A curable composition comprising (A) an organic polymer that contains on average 0.8 or more crosslinking silicon group in one molecule and (B) an aged curing catalyst, wherein the aged curing catalyst (B) is a catalyst obtained by mixing (C) a silane compound obtained by reacting a specific epoxysilane compound with a specific aminosilane compound with (D) a specific titanium catalyst at a mixing ratio such that the amount of the silane compound (C) is 0.1 to 30mol relative to one mol of the titanium catalyst (D) and then aging the resulting mixture at a reaction temperature of 30 to 100°C.

Description

Curable composition

The present invention relates to an organic polymer having a silicon-containing group (hereinafter also referred to as “crosslinkable silicon group”) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. It relates to the curable composition containing this.

An organic polymer containing at least one crosslinkable silicon group in the molecule is crosslinked at room temperature by the formation of a siloxane bond accompanied by a hydrolysis reaction of a reactive silicon group due to moisture or the like. It is known to have the property of being obtained. Among these polymers having a crosslinkable silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a (meth) acrylate polymer are used for sealing materials, adhesives, paints, etc. Widely used.

The curable composition used for sealing materials, adhesives, paints, etc. and the rubber-like cured product obtained by curing have various properties such as curability, adhesiveness, storage stability, mechanical properties such as modulus, strength, and elongation. Properties are required, and many studies have been made on organic polymers containing crosslinkable silicon groups.

These curable compositions containing an organic polymer having a crosslinkable silicon group are cured using a silanol condensation catalyst. Usually, organic tin-based catalysts such as dibutyltin bis (acetylacetonate) are widely used. in use. However, in recent years, toxicity of organotin compounds has been pointed out, and development of non-organotin catalysts has been demanded.

As this non-organotin-based catalyst, a dealcohol-free silicone composition using a titanium catalyst is already on the market and is widely used for many applications (for example, Patent Documents 1 to 3).
However, there are relatively few examples of adding a titanium catalyst to an organic polymer containing a crosslinkable silicon group, which are disclosed in Patent Documents 4 to 21 and the like. The curable compositions using these titanium catalysts have a problem that the curing rate is slow, and the curing rate is lowered and the viscosity is increased after storage.

Further, a curable composition containing an organic polymer containing a crosslinkable silicon group is often used as an adhesive or a sealing material, and in that case, adhesion to various types of substrates is required. In order to ensure this adhesion, so-called aminosilane having a primary amino group and an alkoxy group in the molecule is usually used. However, when an organic polymer containing a crosslinkable silicon group and a titanium catalyst are used to produce a one-component curable composition by adding aminosilane, the composition is good after storage for a certain period, although the adhesiveness is good. If the viscosity of the product increases and is severe, it may harden in the container and not be used. Sealing materials and adhesives are not always used immediately after production, but are often stored for several months in warehouses or stores, and it is desired that their curability and viscosity be constant before and after storage. Yes.

Japanese Examined Patent Publication No. 39-27643 US Pat. No. 3,175,993 US Pat. No. 3,334,067 JP 58-17154 A JP-A-11-209538 JP-A-5-311063 JP 2001-302929 A JP 2001-302930 A JP 2001-302931 A JP 2001-302934 A JP 2001-348528 A JP 2002-249672 A JP 2003-165916 A JP 2003-147220 A JP 2005-325314 A WO2005 / 108492 WO2005 / 108498 WO2005 / 108494 WO2005 / 108499 WO2007 / 037368 JP 2008-280434 A

An object of the present invention is to provide a curable composition excellent in curability, adhesiveness and storage stability, and not requiring an organic tin-based catalyst and excellent in safety, and a method for producing the curable composition. .

In order to solve the above-mentioned problems, the present inventors have conducted intensive research and have identified, as a curing catalyst, an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule. By using an aging curing catalyst obtained by mixing a silane compound obtained by reacting an epoxy silane compound with a specific aminosilane compound and a titanium chelate coordinated with a β-ketoester at a predetermined mixing ratio and aging. The present inventors have found that a curable composition that is remarkably excellent in curability, adhesiveness, and storage stability and that does not require an organotin catalyst and that is excellent in safety can be obtained.

That is, the curable composition of the present invention comprises (A) an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule, and (B) an aging curing catalyst. A silane compound obtained by reacting (C) an epoxysilane compound represented by the following formula (1) with an aminosilane compound represented by the following formula (2): (D) one or more titanium catalysts selected from the group consisting of a titanium chelate represented by the following formula (3) and a titanium chelate represented by the following formula (4), In contrast, (C) a aging curing catalyst obtained by mixing at a mixing ratio of 0.1 to 30 mol of the silane compound and aging at a reaction temperature of 30 to 100 ° C.

(In the formula (1), R ¹ to R ³ are each a hydrogen atom or an alkyl group, R ⁴ is an alkylene group or an alkyleneoxyalkylene group, R ⁵ is a monovalent hydrocarbon group, and R ⁶ is An alkyl group, and a is 0, 1 or 2.)

(In the formula (2), R ⁷ to R ¹² are each a hydrogen atom or an alkyl group, R ¹³ is a monovalent hydrocarbon group, R ¹⁴ is an alkyl group, and b is 0 or 1. )

(In the formula (3), n R ^{21 s} are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4-n R ^{22 s} are each independently a hydrogen atom. Or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, wherein 4-n R ²³ and 4-n R ²⁴ are independently substituted or unsubstituted carbon atoms having 1 to 20 carbon atoms. And n is 0, 1, 2 or 3.)

(In the formula (4), R ²⁵ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and the two R ²⁶ are each independently a hydrogen atom or substituted or unsubstituted. The two R ²⁷ and the two R ²⁸ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.)

The aging is preferably performed at 40 ° C to 80 ° C.

It is preferable to blend 0.5 to 30 parts by mass of the (B) aging curing catalyst with respect to 100 parts by mass of the (A) organic polymer.

The (C) silane compound is preferably a silane compound obtained by reacting the epoxysilane compound in a range of 1.5 to 10 mol with respect to 1 mol of the aminosilane compound.
The (C) silane compound is preferably a silane compound obtained by reacting the epoxysilane compound and the aminosilane compound at a reaction temperature of 40 to 100 ° C.

The (A) organic polymer is preferably an organic polymer whose main chain is not polysiloxane.
The (A) organic polymer is a polyoxyalkylene polymer containing 0.8 or more crosslinkable silicon groups on average per molecule, and 0.8 or more crosslinks on average per molecule. Selected from the group consisting of a saturated hydrocarbon polymer containing a functional silicon group and a (meth) acrylic acid ester polymer containing an average of 0.8 or more crosslinkable silicon groups in one molecule. One or more are preferable.

It is preferable that the crosslinkable silicon group contains a trimethoxysilyl group.

The curable composition of the present invention preferably further contains (E) a silane compound having one hydrolyzable silicon group and one primary amino group in one molecule.
The (E) silane compound is preferably a compound represented by the following formula (12).

In the formula (12), R ⁴¹ is a methyl group or an ethyl group, and when a plurality of R ⁴¹ are present, they may be the same or different, and R ⁴² is a methyl group or An ethyl group, and when there are a plurality of R ⁴² , they may be the same or different, R ⁴³ is a hydrocarbon group having 1 to 10 carbon atoms, and m is 2 or 3 and n is 0 or 1.

The curable composition of the present invention preferably further contains (F) a filler. The filler (F) is at least one selected from the group consisting of surface-treated calcium carbonate, amorphous silica having a particle size of 0.01 to 300 μm, and polymer powder having a particle size of 0.01 to 300 μm. It is preferable.

A curable composition excellent in transparency by matching the difference in refractive index so that the difference between the refractive index of the organic polymer (A) and the refractive index of the amorphous silica is 0.1 or less. You can get things.

Further, the difference in refractive index between the liquid phase component (A) containing the organic polymer as a main component and the refractive index of the polymer powder is made to be equal to or less than 0.1. Thus, a curable composition having excellent transparency can be obtained.
By adding a refractive index adjusting agent to the (A) organic polymer, the difference between the refractive index of the liquid phase component mainly composed of the (A) organic polymer and the refractive index of the polymer powder is 0.1. The following is preferable.

The polymer powder polymerizes a monomer selected from the group consisting of (meth) acrylic acid ester, vinyl acetate, ethylene and vinyl chloride alone, or the monomer and one or more vinyl monomers The polymer powder is preferably a polymer powder obtained from a polymer obtained by copolymerization, and is at least one selected from the group consisting of an acrylic polymer powder and a vinyl polymer powder. More preferred.

The curable composition of the present invention preferably further contains (G) a diluent.

The curable composition of the present invention preferably further contains a metal hydroxide. It is preferable that the metal hydroxide is aluminum hydroxide.

The curable composition of the present invention preferably further contains a titanium chelate compound as a non-aged curing catalyst. The titanium chelate compound is preferably at least one titanium catalyst selected from the group consisting of a titanium chelate represented by the formula (3) and a titanium chelate represented by the formula (4).

The method for producing a curable composition of the present invention comprises (A) an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule, and (B) an aging curing catalyst. A method for producing a curable composition for producing a curable composition, wherein the (B) aging curing catalyst is represented by (C) an epoxysilane compound represented by the following formula (1) and the following formula (2): One or more types of titanium selected from the group consisting of a silane compound obtained by reacting an aminosilane compound, a titanium chelate represented by the following formula (3) and a titanium chelate represented by the following formula (4): An aging curing catalyst obtained by mixing a catalyst with 0.1 to 30 mol of the (C) silane compound with respect to 1 mol of the (D) titanium catalyst and aging at a reaction temperature of 30 to 100 ° C. It is characterized by being.

In the manufacturing method of the curable composition of this invention, it is preferable to mix | blend the said (A) organic polymer, the said (B) ageing hardening catalyst, and a titanium chelate compound, and manufacturing a curable composition.
It is preferable that the titanium chelate compound is at least one titanium catalyst selected from the group consisting of a titanium chelate represented by the formula (3) and a titanium chelate represented by the formula (4).

According to the present invention, it is possible to provide a curable composition excellent in curability, adhesiveness and storage stability, and not requiring an organic tin-based catalyst and excellent in safety, and a method for producing the curable composition. . Moreover, according to this invention, the curable composition excellent in standing | starting-up adhesiveness and the curable composition excellent in transparency can also be obtained.

Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

The curable composition of the present invention comprises (A) an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule, and (B) an aging curing catalyst. (B) an aging curing catalyst, (C) a silane compound obtained by reacting an epoxysilane compound represented by the formula (1) and an aminosilane compound represented by the formula (2), D) one or more titanium catalysts selected from the group consisting of a titanium chelate represented by the formula (3) and a titanium chelate represented by the formula (4), with respect to 1 mol of the titanium catalyst (D) (C) A aging curing catalyst obtained by mixing at a mixing ratio of 0.1 to 30 mol of the silane compound and aging at a reaction temperature of 30 to 100 ° C.

The organic polymer (A) is not particularly limited as long as it is an organic polymer containing one or more crosslinkable silicon groups in one molecule, but is an organic polymer in which the main chain is not polysiloxane. It is preferable to use those having various main chain skeletons excluding polysiloxane.

Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene Copolymers of acrylonitrile and styrene, etc., hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid and glycols A polyester polymer obtained by condensation of lactones or ring-opening polymerization of lactones; a (meth) acrylic acid ester polymer obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomer, vinyl polymer obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene; graft polymer obtained by polymerizing vinyl monomer in the organic polymer; polysulfide Polymer: Nylon 6 by ring-opening polymerization of ε-caprolactam, Nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, Nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-aminolaurolac by condensation polymerization of A polyamide polymer such as nylon 12 produced by ring-opening polymerization of a copolymer, a copolymer nylon having two or more components of the above-mentioned nylon; a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, for example; Examples include diallyl phthalate polymers.

Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers can be obtained with a relatively low glass transition temperature. The cured product is preferable because it is excellent in cold resistance. Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because of their high moisture permeability and excellent deep-part curability when made into one-component compositions.

The crosslinkable silicon group of the (A) organic polymer used in the present invention is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the following general formula (5) is preferable.

In the formula (5), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ³¹ ₃ represents a triorganosiloxy group represented by SiO— (R ³¹ is the same as above), and when two or more R ³¹ 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. d represents 0, 1, 2, or 3, and e represents 0, 1, or 2, respectively. Further, p in the following general formula (6) need not be the same. p represents an integer of 0 to 19. However, d + (sum of e) ≧ 1 is satisfied.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and d + (sum of e) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.
The number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.

As the crosslinkable silicon group, a crosslinkable silicon group represented by the following general formula (7) is preferable because it is easily available.

In the formula (7), R ³¹ and X are the same as those described above, and d is an integer of 1, 2 or 3. In view of curability, in order to obtain a curable composition having a sufficient curing rate, a in the formula (7) is preferably 2 or more, and more preferably 3.

Specific examples of R ³¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ³¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

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

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

Moreover, the crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group can be present in the main chain, the side chain, or both.

The number of silicon atoms forming the crosslinkable silicon group is one or more, but in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less.

The organic polymer having a crosslinkable silicon group may be linear or branched, and its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to 50,000. Particularly preferred is 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, the average number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more in one molecule of the polymer. 1.1 to 5 may be present. If the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the curability becomes insufficient and it becomes difficult to develop good rubber elastic behavior. The crosslinkable silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. In particular, when the crosslinkable silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the following general formula (8).
-R ³² -O- (8)
In the general formula (8), R ³² is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms. .

Specific examples of the repeating unit represented by the general formula (8) include
_{_{_{_{-CH 2 O -, - CH 2}}}} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, —CH ₂ CH ₂ CH ₂ CH ₂ O—
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used as a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferable because it is amorphous or has a relatively low viscosity.

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

The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of the urethane bond component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate, and polyoxyalkylene heavy compounds having a hydroxyl group. The thing obtained from reaction with coalescence can be mention | raise | lifted.

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

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

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

Specific examples of the polyoxyalkylene polymer having a crosslinkable silicon group include JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. No. 57-164123, Japanese Patent Publication No. 3-2450, Japanese Patent Application Laid-Open No. 2005-213446, No. 2005-306891, International Publication No. WO 2007-040143, US Pat. No. 3,632,557, No. 4,345,053, The ones proposed in the publications such as 4,960,844 can be listed.

The above polyoxyalkylene polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc. (2) Diene compounds such as butadiene and isoprene are homopolymerized or copolymerized with the above olefin compounds. After that, it can be obtained by a method such as hydrogenation. However, isobutylene polymers and hydrogenated polybutadiene polymers are easy to introduce functional groups at the terminals, control the molecular weight, and the number of terminal functional groups. Therefore, an isobutylene polymer is particularly preferable.

Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. Those containing at least mass% are preferred, those containing at least 80 mass% are more preferred, and those containing from 90 to 99 mass% are particularly preferred.

As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods have been reported so far, but many so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (J. P. Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843). It is known that a polymer having a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends.

Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-62-254149, JP-A-62-2904, Although described in each specification of Kaihei 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.

The above saturated hydrocarbon polymer having a crosslinkable silicon group may be used alone or in combination of two or more.

The (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer is not particularly limited, and various types can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, Ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2- (meth) acrylic acid 2- -Fluoroethyl ethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoro) (meth) acrylate Methyl) methyl, 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic And (meth) acrylic acid monomers such as 2-perfluorohexadecyl ethyl acid.

In the (meth) acrylic acid ester polymer, the following vinyl monomers can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomers include styrene 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 and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexyl Maleimide monomers such as maleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

These may be used alone or a plurality of them may be copolymerized. Especially, the polymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer. In applications such as general construction, a butyl acrylate monomer is more preferred from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less, and more preferably 30% or less. More preferably. It is also preferable to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the alkyl group in the side chain in order to improve low temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent balance of physical properties such as oil resistance, heat resistance, and low-temperature characteristics include ethyl acrylate / butyl acrylate / -2-methoxyethyl acrylate (40-50 / 20 by mass ratio). To 30/30 to 20). In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, it is preferable that these preferable monomers are contained in a mass ratio of 40% or more. . In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

In the present invention, the method for obtaining the (meth) acrylic acid ester polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112642, JP-A-2007-230947, JP-A-2001-40037). And a synthesis method described in JP-A-2003-313397), and a radical polymerization method using a radical polymerization reaction is preferable. As the radical polymerization method, a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator or a reactive silyl group is introduced at a controlled position such as a terminal. Possible controlled radical polymerization methods are mentioned. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate 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. It is preferable to use a controlled radical polymerization method.

Examples of the controlled radical polymerization method include free radical polymerization method and living radical polymerization method using a chain transfer agent having a specific functional group, such as an addition-cleavage transfer reaction (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable. A reaction using a thiol compound having a reactive silyl group and a reaction using a thiol compound having a reactive silyl group and a metallocene compound (Japanese Patent Laid-Open No. 2001-40037) are also suitable.

<Free radical polymerization method>
When the free radical polymerization method is used, the reaction is preferably carried out at 0 ° C. to 200 ° C. using a chain transfer agent and an initiator. More preferably, it is particularly preferably set within the range of 25 ° C to 150 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the free radical polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, the reaction time is usually 1 to 144 hours under the above conditions, preferably It is preferable to set within the range of 2 to 8 hours.

As the chain transfer agent, known chain transfer agents can be widely used and are not particularly limited. However, a thiol compound is preferable, and a thiol compound having a reactive silyl group is more preferable. For example, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyldimethylmethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethyldimethylethoxysilane, mercaptomethyltripropoxysilane, mercaptomethylmethyldisilane Propoxysilane, mercaptomethyldimethylpropoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxysilane, 3-mercaptopropyl-monomethyldimethoxysilane, 3-mercaptopropyl-monophenyldimethoxysilane, 3-mercaptopropyl -Dimethylmonomethoxysilane, 3-mercaptopropyl-monomethyldiethoxysilane, 4- Rukaputobuchiru - trimethoxysilane and 3-mercaptopropyl butyl - trimethoxysilane. These may be used alone or in combination of two or more.

The chain transfer agent can be appropriately set in consideration of molecular weight, molecular weight distribution, etc., but can be used in a normal amount, specifically, 100 mol parts of a polymerizable unsaturated compound to be polymerized. The amount is usually 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

The initiator is not particularly limited, and examples thereof include an azo initiator, a peroxide initiator, an ionic initiator, and a redox initiator. These may be used alone or in combination of two or more.

Examples of the azo initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis. (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobisisobutyronitrile (V-60, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylbutyronitrile) (V-59, manufactured by Wako Pure Chemical Industries, Ltd.), 1,1′-azobis (cyclohexane-1-carbonitrile) (V-40, Wako Pure) Yakuhin Kogyo Co., Ltd.), 1-[(1-cyano-1-methylethyl) azo] formamide (V-30, Wako Pure Chemical Industries, Ltd.), 2-phenylazo-4-methoxy-2,4 -Dimethyl-valeronitrile (V-19, manufactured by Wako Pure Chemical Industries, Ltd.) Zonitrile compound, 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide] (VA-080, manufactured by Wako Pure Chemical Industries, Ltd.) 2,2′-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide] (VA-082, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [ 2-methyl-N- [2- (1-hydroxybutyl)]-propionamide] (VA-085, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2-methyl-N- (2 -Hydroxyethyl) -propionamide] (VA-086, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropionamide) dihydrate (VA-088, manufactured by Wako Pure Chemical Industries, Ltd.) ), 2, 2 ' Azobis [N- (2-propenyl) -2-methylpropionamide] (VF-096, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (N-butyl-2-methylpropionamide) (VAm -110, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) (VAm-111, manufactured by Wako Pure Chemical Industries, Ltd.), 2 2,2′-azobis (2,4,4-trimethylpentane) (VR-110, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-methylpropane) (VR-160, Wako Pure Chemical) And alkylazo compounds such as those manufactured by Kogyo Co., Ltd.

Examples of the peroxide initiator include methyl ethyl ketone peroxide (Permec H, manufactured by NOF Corporation), cyclohexanone peroxide species (Perhexa H, manufactured by NOF Corporation), methylcyclohexanone peroxide (Perhexa Q). , Manufactured by NOF Corporation), methylacetoacetate peroxide (Percure SA, manufactured by NOF Corporation), ketone peroxides such as acetylacetone peroxide (Percure A, manufactured by NOF Corporation), 1,1 -Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (Perhexa TMH, manufactured by NOF Corporation), 1,1-bis (t-hexylperoxy) cyclohexane (Perhexa HC, NOF Corporation ), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane (per Oxa 3M, manufactured by NOF Corporation), 1,1-bis (t-butylperoxy) cyclohexane (Perhexa C, manufactured by NOF Corporation), 1,1-bis (t-butylperoxy) cyclododecane (Perhexa CD-R, manufactured by NOF Corporation), 2,2′-bis (t-butylperoxy) butane (Perhexa 22, manufactured by NOF Corporation), n-butyl 4,4-bis (t -Butylperoxy) valerate) perhexa V, manufactured by NOF Corporation), 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (pertetra A, manufactured by NOF Corporation), etc. Peroxyketals, t-butyl hydroperoxide (Perbutyl H-69, manufactured by NOF Corporation), p-menthane hydroperoxide (Permenta H, manufactured by NOF Corporation), diisopropylbenzene hydroperoxide ( Cumyl P, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutyl hydroperoxide (Perocta H, manufactured by NOF Corporation), cumene hydroperoxide (Park Mill H-80, NOF Corporation) ), Hydroperoxides such as t-hexyl hydroperoxide (Perhexyl H, NOF Corporation), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (Perhexin 25B, manufactured by NOF Corporation), di-t-butyl peroxide (Perbutyl DR, manufactured by NOF Corporation), t-butyl cumyl peroxy species (Perbutyl C, manufactured by NOF Corporation) ), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa 25B, manufactured by NOF Corporation), Dicumyl Peroxy species (Park Mill DR, manufactured by NOF Corporation), α, α'-bis (t- Dialkyl peroxides such as tilperoxy) diisopropylbenzene (perbutyl P, manufactured by NOF Corporation), octanoyl peroxy species (Perroyl O, manufactured by NOF Corporation), lauroyl peroxy species (Perroyl L, NOF Corporation) Co., Ltd.), stearoyl peroxy species (Perroyl S, manufactured by NOF Corporation), succinic acid peroxy species (Perloyl SA, manufactured by NOF Corporation), benzoyl peroxide (Nyper BW, NOF Corporation )), Isobutyryl peroxide (Perroyl IB, manufactured by NOF Corporation), 2,4-dichlorobenzoyl peroxy species (Nyper CS, manufactured by NOF Corporation), 3,5,5-trimethylhexanoyl Diacyl peroxides such as peroxy species (Perroyl 355, manufactured by NOF Corporation), di-n-propyl peroxydicarbonate (Perloy NPP-50M, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (Perroyl IPP-50, manufactured by NOF Corporation), bis (4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP, Nippon Oil Corporation) Fatty Co., Ltd.), di-2-ethoxyethyl peroxydicarbonate (Perroyl EEP, manufactured by NOF Corporation), di-2-ethoxyhexyl peroxydicarbonate (Perloyl OPP, manufactured by NOF Corporation) Di-2-methoxybutyl peroxydicarbonate (Perroyl MBP, manufactured by NOF Corporation), di (3-methyl-3-methoxybutyl) peroxydicarbonate (Perloyl SOP, manufactured by NOF Corporation), etc. Peroxydicarbonates, α, α'-bis (neodecanoylperoxy) diisopropylbenzene (Nyper ND-R, (Manufactured by NOF Corporation), cumyl peroxyneodecanoate (Park Mill ND-R, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylperoxyneodecanoate (perocta ND- R, manufactured by NOF Corporation), 1-cyclohexyl-1-methylethyl peroxyneodecanoate (percyclo ND-R, manufactured by NOF Corporation), t-hexylperoxyneodecanoate (perhexyl ND) -R, manufactured by NOF Corporation, t-butyl peroxyneodecanoate (perbutyl ND-R, manufactured by NOF Corporation), t-hexyl peroxypivalate (perhexyl PV, NOF Corporation) ), T-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Perocta O, NOF Corporation) ) Made 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane (Perhexa 250, manufactured by NOF Corporation), 1-cyclohexyl-1-methylethylperoxy-2-ethylhexano Ate (Percyclo O, manufactured by NOF Corporation), t-hexylperoxy-2-ethylhexanoate (Perhexyl O, manufactured by NOF Corporation), t-butylperoxy-2-ethylhexanoate ( Perbutyl O, manufactured by NOF Corporation), t-butyl peroxyisobutyrate (Perbutyl IB, manufactured by NOF Corporation), t-hexyl peroxyisopropyl monocarbonate (Perhexyl I, manufactured by NOF Corporation) T-butyl peroxymaleic acid (Perbutyl MA, manufactured by NOF Corporation), t-butylperoxy 3,5,5-trimethylhexanoate (Perb 355, manufactured by NOF Corporation), t-butyl peroxylaurate (Perbutyl L, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane (Perhexa 25MT, manufactured by NOF Corporation), t-butyl peroxyisopropyl monocarbonate (Perbutyl I, manufactured by NOF Corporation), t-butyl peroxy-2-ethylhexyl monocarbonate (Perbutyl E, NOF Corporation) Co., Ltd.), t-hexyl peroxybenzoate (Perhexyl Z, manufactured by NOF Corporation), 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane (Perhexa 25Z, manufactured by NOF Corporation) ), T-butyl peroxyacetate (Perbutyl A, manufactured by NOF Corporation), t-butylperoxy-m-toluoyl benzoate (Perbutyl ZT, manufactured by NOF Corporation) ), T-butyl peroxybenzoate (Perbutyl Z, manufactured by NOF Corporation), peroxyesters such as bis (t-butylperoxy) isophthalate (Perbutyl IF, manufactured by NOF Corporation), t- Butyl peroxyallyl monocarbonate (Peromer AC, manufactured by NOF Corporation), t-butyltrimethylsilyl peroxide (Perbutyl SM, manufactured by NOF Corporation), 3,3′-4,4′-tetra (t- Butyl peroxycarbonyl) benzophenone (BTTB-50, manufactured by NOF Corporation), 2,3-dimethyl-2,3-diphenylbutane (NOFMER BC, manufactured by NOF Corporation) and the like.

Examples of the ionic initiator include 2,2′-azobis [2- (phenylamidino) propane] dihydrochloride (VA-545, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2 -[N- (4-chlorophenyl) amidino] propane} dihydrochloride (VA-546, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyphenyl) amidino] Propane} dihydrochloride (VA-548, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (N-benzylamidino) propane] dihydrochloride (VA-552, Wako Pure Chemical Industries, Ltd.) 2,2′-azobis [2- (N-allylamidino) propane] dihydrochloride (VA-553, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis (2-amidino) Lopan) dihydrochloride (VA-50, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis {2- [N- (4-hydroxyethyl) amidino] propane} dihydrochloride (VA-558, Wako Pure) 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (VA-041, manufactured by Wako Pure Chemical Industries), 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (VA-044, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis [2- (4,5, 6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride (VA-054, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (3,4) , 5,6-Tetrahydropyrimidi -2-yl) propane] dihydrochloride (VA-058, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidine-2] -Yl) propane] dihydrochloride (VA-059, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane } Dihydrochloride (VA-060, manufactured by Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (VA-061, Wako Pure Chemical Industries, Ltd.) And anionic initiators such as potassium persulfate (KPS, manufactured by Wako Pure Chemical Industries, Ltd.) and ammonium persulfate (APS, manufactured by Wako Pure Chemical Industries, Ltd.).

Such redox initiators include, for example, systems based on organic peroxides and tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as cumene hydroperoxide. And systems based on cobalt naphthate.

The initiator can be appropriately set in consideration of molecular weight, molecular weight distribution, etc., but can be used in a normal amount, specifically, in 100 mol parts of the polymerizable unsaturated compound to be polymerized. On the other hand, it is usually used in an amount of 0.001 to 30 mol parts, preferably 0.01 to 20 mol parts.

<Addition-cleavage transfer reaction polymerization method>
When the addition-cleavage transfer reaction polymerization method is used, the reaction is preferably carried out at 0 ° C. to 200 ° C. using a chain transfer agent and an initiator. More preferably, it is particularly preferably set within the range of 25 ° C to 150 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the addition-cleavage transfer reaction polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 30 minutes to 144. The time is preferably set within the range of 1 to 24 hours.

Examples of the chain transfer agent include benzoyl-1-pyrrolecarbodithioate, benzoyldithiobenzoate, cyanoisopropyldithiobenzoate, cumyldithiobenzoate, methoxycarbonylphenylmethyldithiobenzoate, cyanobenzyldithiobenzoate, 1-phenylethyldithiobenzoate T-butyldithiobenzoate S- (thiobenzyl) thioglycolyl acid, 1-phenylethylphenyldithiobenzoate, 3-benzylsulfanylthiocarbonylsulfanyl-propionic acid, 2- (benzylsulfanylthiocarbonylsulfanyl) ethanol, 3-benzylsulfanylthio Carbonylsulfanylpropionic acid, S- (1-ethoxycarbonylethyl) O-ethylxanthate, D 2- (2-trifluoroethoxythiocarbonylsulfanyl) propionate, ethyl-2- (1-diethoxyphosphonyl-2,2,2-trifluoroethoxythiocarbonylsulfanyl) propionate, bisthiobenzoyl disulfide, bis ( 2,6-dimethylthiobenzoyl) disulfide, bis (2,4-dimethylthiobenzoyl) disulfide, bis (4-methoxythiobenzoyl) disulfide, bis (2,4dimethoxythiobenzoyl) disulfide, bis (4-fluorothiobenzoyl) ) Disulfide, bis (2,4-difluorothiobenzoyl) disulfide, bis (4-cyanothiobenzoyl) disulfide, bis (3,5-dicyanothiobenzoyl) disulfide, bis (3,5-bis (trifluorome Di) dithiobenzoate) disulfide, bis (2,3,4,5,6-pentafluorothiobenzoyl) disulfide, bis (4-phenylthiobenzoyl) disulfide, bis (2-naphthylthionyl) disulfide, bis (1- Naphthylthionyl) disulfide, triphenylmethyldithioisonicotinate, 2-cyanoisopropyl (2,6-dimethyl) dithiobenzoate, 2-cyanoisopropyl (2,4-dimethyl) dithiobenzoate, 2-cyanoisopropyl (4-methoxy) ) Dithiobenzoate, 2-cyanoisopropyl (2,4-dimethoxy) dithiobenzoate, 2-cyanoisopropyl (4-fluoro) dithiobenzoate, 2-cyanoisopropyl (2,4-difluoro) dithiobenzoate, 2-cyanoisopropyl Lopyldithioisonicotinate, 2-cyanoisopropyl 4-cyanodithiobenzoate, 2-cyanoisopropyl 3,5-dicyanodithiobenzoate, 2-cyanoisopropyl 3,5-bis (trifluoromethyl) dithiobenzoate, 2-cyanoisopropyl 2,3,4,5,6-pentafluorodithiobenzoate, 2-cyanoisopropyl 4-pyridinium dithiocarboxyate 4-toluenesulfonate salt, 2-cyanoisopropyl (4-phenyl) dithiobenzoate, 2-cyanoisopropyl- 2-naphthyl dithiolate, 2-cyanoisopropyl-1-naphthyl dithiolate, 2-cyano-4-methylpent-2-yldithiobenzoate, 2-cyano-4-methylpent-2-yl-4-cyanodithiobenzoate 2-cyano-4-methylpent-2-yl 3,5-bis-trifluoromethyl dithiobenzoate, and a 2-cyano-4-methylpent-2-yl-4-methoxy-phenyl dithiobenzoate. These may be used alone or in combination of two or more.

The initiator is not particularly limited, and examples thereof include an azo initiator, a peroxide initiator, and an ionic initiator. These may be used alone or in combination of two or more.

<Polymerization method using a thiol compound having a reactive silyl group and a metallocene compound>
It is preferable to use a metallocene compound as the metal catalyst, and further to react at 0 ° C. to 150 ° C. using a thiol compound having at least one reactive silyl group in the molecule. More preferably, it is particularly preferably set within the range of 25 ° C to 120 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 1 to 12 hours, preferably 2 It is preferable to set within a range of up to 8 hours.

The metallocene compound is not particularly limited. For example, dicyclopentadiene-Ti-dichloride, dicyclopentadiene-Ti-bisphenyl, dicyclopentadiene-Ti-bis-2,3,4,5,6-pentafluoropheny -1-yl, dicyclopentadiene-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadiene-Ti-bis-2,5,6-trifluorophen-1-yl Dicyclopentadiene-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadiene-Ti-bis-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2 , 3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2, , 5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluoro- Titanocene compounds such as 3- (pyr-1-yl) -phen-1-yl; dicyclopentadienyl-Zr-dichloride, dicyclopentadiene-Zr-bisphenyl, dicyclopentadiene-Zr-bis-2, 3,4,5,6-pentafluorophen-1-yl, dicyclopentadiene-Zr-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadiene-Zr-bis-2, 5,6-trifluorophen-1-yl, dicyclopentadiene-Zr-bis-2,6-difluorophen-1-yl, dicyclopentadi -Zr-bis-2,4-difluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl -Zr-bis-2,3,5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Zr-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Zr- Zirconocene compounds such as bis-2,6-difluoro-3- (pyr-1-yl) -phen-1-yl); dicyclopentadienyl-V-chloride, bismethylcyclopentadienyl-V-chloride Bispentamethylcyclopentadienyl-V-chloride, dicyclopentadienyl-Ru-chloride, dicyclopentadienyl-Cr-chlora Id etc. can be mentioned. These may be used alone or in combination of two or more.

The metallocene compound can be used in a usual catalytic amount. Specifically, it is usually 0.1 to 0.00001 mol part, preferably 100 to 100 mol part of the polymerizable unsaturated compound to be polymerized, preferably Used in an amount of 0.0001-0.00005 mol parts.

The thiol compound having a reactive silyl group is not particularly limited. For example, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyldimethylmethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldiethoxysilane, mercapto Methyldimethylethoxysilane, mercaptomethyltripropoxysilane, mercaptomethylmethyldipropoxysilane, mercaptomethyldimethylpropoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropyl-triethoxy Silane, 3-mercaptopropyl-monomethyldimethoxysilane, 3-mercaptopropyl-monophenyldimethoxysilane Down, 3-mercaptopropyl - dimethyl mono silane, 3-mercaptopropyl - monomethyl diethoxy silane, 4-mercaptomethyl-butyl - trimethoxysilane and 3-mercaptopropyl butyl - and tri methoxy silane. These may be used alone or in combination of two or more.

The amount of the thiol compound having a reactive silyl group can be appropriately set in consideration of the molecular weight of the polymer to be obtained, the polymerization rate, etc., but the reaction proceeds smoothly and does not run away. In this case, the metallocene compound and the thiol compound having a reactive silyl group are usually used in a molar ratio in the range of 100: 1 to 1: 50000, preferably in a molar ratio of 10: 1 to 1: 10000.

<Radical polymerization using transition metal complex>
When a radical polymerization method using a transition metal complex is used, it is preferable to perform the reaction at 0 ° C. to 200 ° C. using a transition metal complex, an organic halide and / or a ligand. More preferably, it is particularly preferably set within the range of 25 ° C to 150 ° C. By setting the polymerization reaction temperature within the above range, the reaction can proceed stably without causing runaway. Depending on the activity of the unsaturated group of the polymerizable unsaturated compound to be used, even when a relatively unsaturated acrylate-based polymerizable unsaturated compound is used, when the reaction temperature is less than 0 ° C, The activity is low, the time required to achieve a sufficient polymerization rate is lengthened, and the efficiency is poor. Further, even when a compound having a low polymerization activity such as a styrene type unsaturated compound is used, a sufficient polymerization rate can be achieved under the condition of 25 ° C. or higher. In the case of using the addition-cleavage transfer reaction polymerization method, the reaction time can be appropriately set in consideration of the polymerization rate, molecular weight, etc. For example, under the above conditions, the reaction time is usually 30 minutes to 144. The time is preferably set within the range of 1 to 24 hours.

It does not specifically limit as said transition metal complex, For example, what is described in WO97 / 18247 can be utilized. Among these, a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel is preferable. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When using cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, if necessary, zero-valent copper, cuprous chloride Dicopper, cupric bromide, and cupric iodide can also be used.
A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

When a copper compound is used as the catalyst, the ligand described in WO97 / 18247 can be used as the ligand. Although not particularly limited, amine-based ligands are preferable, and bipyridyl compounds such as 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, hexamethyltriethylenetetraamine, bispicolylamine , Ligands of aliphatic amines such as trialkylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine. In the present invention, among these, polyamine compounds, particularly aliphatic polyamines such as pentamethyldiethylenetriamine and hexamethyl (2-aminoethyl) amine are preferred. Moreover, when using a polyamine compound, a pyridine-type compound, or an aliphatic amine compound as a ligand in the case of using a copper compound as a catalyst, these ligands must have three or more amino groups. Is preferred. The amino group in the present invention represents a group having a nitrogen atom-carbon atom bond, and among these, a group in which the nitrogen atom is bonded only to a carbon atom and / or a hydrogen atom is preferable. The metallocene compounds listed above can also be used.

The amount of the ligand as described above is determined from the number of coordination sites of the transition metal and the number of groups coordinated by the ligand under the conditions of normal atom transfer radical polymerization, so that they are almost equal. Is set to For example, the amount of 2,2′-bipyridyl and its derivatives added to CuBr is usually twice as much as the molar ratio, and in the case of pentamethyldiethylenetriamine, it is once as large as the molar ratio. In the present invention, when a ligand is added to initiate polymerization and / or when a catalyst activity is controlled by adding a ligand, there is no particular limitation, but the metal atom is excessive with respect to the ligand. Is preferred. The ratio between the coordination position and the coordinating group is preferably 1.2 times or more, more preferably 1.4 times or more, particularly preferably 1.6 times or more, and particularly preferably 2 times or more. It is.

As an initiator, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position) or a sulfonyl halide is used. Used.
Specifically, C ₆ H ₅ —CH ₂ X, C ₆ H ₅ —C (H) (X) CH ₃ , C ₆ H ₅ —C (X) (CH ₃ ) ₂ , XCH ₂ — _{_{_{_{C 6 H 5 -CH 2 X,}}}} XC (H) (CH 3) -C 6 H5-C (H) (CH 3) X ( where in the above _formula, C 6 _{H 5} is a phenyl group, X is chlorine , Bromine, or iodine), R ³ —C (H) (X) —CO ₂ R ⁴ , R ³ —C (CH ₃ ) (X) —CO ₂ R ⁴ , R ³ —C (H) (X) -C (O) R ⁴ , R ³ -C (CH ₃ ) (X) -C (O) R ⁴ , R ³ -C ₆ H ₄ -SO ₂ X (wherein R ³ and R ⁴ are hydrogen atoms Or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine).

Aluminum radical chelates such as triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-t-butoxyaluminum, trisec-butoxyaluminum and dioctyltin in radical polymerization methods using transition metal complexes And divalent tin compounds such as diethylhexyltin and dibutyltin, and organic substances such as glucose and ascorbic acid can be used as additives for activating the polymerization.

In the synthesis of the (meth) acrylic acid ester polymer, the polymerization can be carried out without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene, xylene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketone solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ethyl acetate, butyl acetate, etc. Polyoxyalkylene polymers such as ester solvents, carbonate solvents such as ethylene carbonate and propylene carbonate, and the like can be mentioned, and these can be used alone or in admixture of two or more.

Further, by using a polyoxyalkylene polymer, a saturated hydrocarbon polymer or the like as a solvent, a subsequent degassing step or the like can be made unnecessary.

The above (meth) acrylic acid ester-based polymer having a crosslinkable silicon group may be used alone or in combination of two or more.

These organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, it comprises a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more selected from the group can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group is disclosed in JP-A-59-122541. Although proposed in Japanese Laid-Open Patent Publication No. 63-112642, Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763, the invention is not particularly limited thereto. Preferable specific examples include a crosslinkable silicon group and a molecular chain substantially having the following general formula (9):
—CH ₂ —C (R ³⁵ ) (COOR ³⁶ ) — (9)
(Wherein R ³⁵ represents a hydrogen atom or a methyl group, and R ³⁶ represents an alkyl group having 1 to 8 carbon atoms) (meth) acrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms Unit and the following general formula (10):
—CH ₂ —C (R ³⁵ ) (COOR ³⁷ ) — (10)
(Wherein R ³⁵ is the same as described above, and R ³⁷ represents an alkyl group having 10 or more carbon atoms) and is a copolymer comprising a (meth) acrylic acid ester monomer unit having an alkyl group having 10 or more carbon atoms. In this method, a polymer is blended with a polyoxyalkylene polymer having a crosslinkable silicon group.

R ^{36 in the} general formula (9) is, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, etc., having 1 to 8, preferably 1 to 4, More preferred are 1 to 2 alkyl groups. The alkyl group of R ³⁶ may alone, or may be a mixture of two or more.

R ^{37 in the} general formula (10) is, for example, a long-chain alkyl having 10 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10-30, preferably 10-20. Group. Incidentally, as with the alkyl group for R ³⁷ is the R ^36, alone may be, or may be a mixture of two or more.

The molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units of the formula (9) and the formula (10), and the term “substantially” here means the copolymer. It means that the total of the monomer units of the formula (9) and the formula (10) present therein exceeds 50% by mass. The total of the monomer units of the formula (9) and the formula (10) is preferably 70% by mass or more.

The abundance ratio of the monomer unit of formula (9) and the monomer unit of formula (10) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40, in terms of mass ratio.

Examples of monomer units other than the formulas (9) and (10) that may be contained in the copolymer (hereinafter also referred to as other monomer units) include α such as acrylic acid and methacrylic acid. , Β-unsaturated carboxylic acids; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether, etc. And other monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

Having a crosslinkable silicon group used in a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group (meta ) Other preferred specific examples of the acrylate polymer include, for example, (a1) a methyl (meth) acrylate monomer unit as disclosed in JP-A-2008-44975, and (a2) An acrylic polymer having a crosslinkable silicon group containing a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 8 carbon atoms.

The molecular chain of the acrylic copolymer preferably contains a total of 50% by mass or more of the monomer unit (a1) and the monomer unit (a2). It is more preferable that the total of the monomer units is 70% by mass or more. The abundance ratio of the (a1) and the (a2) is preferably (a1) / (a2) = 90/10 to 20/80, more preferably 70/30 to 30/70 in terms of mass ratio. When the mass ratio of (a1) / (a2) is in the range of 90/10 to 20/80, the transparency can be improved.
The acrylic copolymer may contain monomer units other than (a1) and (a2). As the monomer unit other than (a1) and (a2), for example, the other monomer units described above in the description of the (meth) acrylic acid ester-based copolymer can be used in the same manner.

The number average molecular weight of the acrylic copolymer is preferably 600 to 5000, more preferably 1000 to 4500. By setting the number average molecular weight within this range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group can be improved.
The acrylic copolymer is preferably used in an amount of 5 to 900 parts by mass with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group. These acrylic copolymers may be used alone or in combination of two or more.

Organic polymers obtained by blending a saturated hydrocarbon polymer having a crosslinkable silicon group and a (meth) acrylic acid ester copolymer having a crosslinkable silicon group are disclosed in JP-A-1-168774 and 2000-2000. Although it is proposed in Japanese Patent No. 186176, etc., it is not particularly limited thereto.

Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group, in the presence of an organic polymer having a crosslinkable silicon group ( A method of polymerizing a meth) acrylate monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

When two or more kinds of polymers are blended and used, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a crosslink with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group. The (meth) acrylic acid ester-based polymer having a functional silicon group is preferably used in an amount of 10 to 200 parts by weight, more preferably 20 to 80 parts by weight.

The curable composition of the present invention uses (B) an aging curing catalyst as a curing catalyst, and the (B) aging curing catalyst comprises (C) the epoxysilane compound represented by the formula (1) and the above A silane compound obtained by reacting an aminosilane compound represented by the formula (2), (D) a titanium chelate represented by the formula (3), and a titanium chelate represented by the formula (4). One or more titanium catalysts are mixed at a mixing ratio of 0.1 to 30 moles of the (C) silane compound with respect to 1 mole of the (D) titanium catalyst and aged at a reaction temperature of 30 to 100 ° C. Is an aging curing catalyst.

The (C) silane compound used for the (B) aging curing catalyst is a silane compound obtained by reacting an epoxysilane compound represented by the following formula (1) with an aminosilane compound represented by the following formula (2). .

In the formula (1), R ¹ to R ³ are each a hydrogen atom or an alkyl group, preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and more preferably a hydrogen atom. R ⁴ is an alkylene group or an alkyleneoxyalkylene group, and is a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, methyleneoxyethylene group, methyleneoxypropylene group, methyleneoxybutylene. Group, ethyleneoxyethylene group and ethyleneoxypropylene group are preferable, butylene group, octylene group and methyleneoxypropylene group are more preferable. R ⁵ is a monovalent hydrocarbon group, preferably an alkyl group such as a methyl group, an ethyl group or a propyl group; an alkenyl group such as a vinyl group, an allyl group or a butenyl group; an aryl group such as a phenyl group or a tolyl group; Groups are more preferred. When a plurality of R ⁵ are present, they may be the same or different. R ⁶ is an alkyl group, preferably a methyl group, an ethyl group, or a propyl group, and more preferably a methyl group or an ethyl group. When a plurality of R ⁶ are present, they may be the same or different. a is 0, 1 or 2, and 0 is preferable.

In the formula (2), R ⁷ to R ¹² are each a hydrogen atom or an alkyl group, preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and more preferably a hydrogen atom. R ¹³ is a monovalent hydrocarbon group, preferably an alkyl group or an alkoxy group, more preferably a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, or a propoxy group, and even more preferably a methoxy group or an ethoxy group. R ¹⁴ is an alkyl group, preferably a methyl group, an ethyl group, or a propyl group, and more preferably a methyl group or an ethyl group. b is 0 or 1. (3-b) R ¹⁴ may be the same or different.

Examples of the epoxysilane compound include 4-oxiranylbutyltrimethoxysilane, 8-oxiranyloctyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropyltriethoxysilane and the like.

Examples of the aminosilane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and the like.

The reaction condition between the epoxysilane compound and the aminosilane compound is that the primary amino group of the aminosilane compound reacts with the epoxysilane compound, the primary amino group becomes a secondary amino group or a tertiary amino group, What is necessary is just to make it react so that a primary amino group may not remain | survive.
As the reaction conditions for that purpose, for example, the aminosilane compound and the epoxysilane compound are mixed in the presence or absence of a solvent, and 25 ° C to 100 ° C, preferably 30 ° C to 90 ° C, more preferably 40 ° C. It is preferable to carry out the reaction at a reaction temperature of from 0 ° C to 80 ° C. By setting the reaction temperature within the above range, the reaction can proceed stably without causing runaway. When the reaction temperature is less than 25 ° C., the activity is low, the time required to achieve a sufficient reaction is lengthened, and the efficiency is poor. The reaction time can be appropriately set in consideration of the reaction temperature and the like. For example, under the above conditions, the reaction time is usually set in the range of 1 to 336 hours, preferably 24 to 72 hours. Is preferred.
The reaction ratio (molar ratio) between the epoxysilane compound and the aminosilane compound is preferably such that the epoxysilane compound is reacted in an amount of 1.5 to 10 moles with respect to 1 mole of the aminosilane compound. Is more preferable, and 1.7 to 2.4 mol is more preferable.

The epoxy silane compound and the amino silane compound are heated and reacted at a reaction temperature of preferably 40 ° C. or higher, more preferably 40 to 100 ° C., and still more preferably 40 to 80 ° C. Is cleaved and cyclized by an alcohol exchange reaction between the hydroxyl group produced by this reaction and the alkoxy group in the aminosilane compound, whereby a carbacyltolane derivative represented by the following formula (11) can be obtained. The carbacyltolane derivative represented by the following formula (11) is a compound having a peak from −60 ppm to −70 ppm in ²⁹ Si-NMR.

In Formula (11), R ¹ to R ⁶ and a are the same as in Formula (1), R ⁷ to R ¹² are the same as in Formula (2), and b in Formula (2) is When 0, R ¹⁵ is the same as OR ^{14 in the} formula (2), and when b in the formula (2) is 1, R ¹⁵ is the same as R ^{13 in the} formula (2). The alkoxy group bonded to the silicon atom may be partially substituted by an alcohol exchange reaction. The silicon atom-bonded alkoxy group of the raw material and the silicon atom-bonded alkoxy group in the carbacyltran derivative generated by the reaction May not be the same.

The (D) titanium catalyst used in the (B) aging curing catalyst is at least one selected from the group consisting of a titanium chelate represented by the following formula (3) and a titanium chelate represented by the following formula (4). is there.

In the formula (3), n R ^{21 s} are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4-n R ^{22 s} are each independently a hydrogen atom or A substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, wherein 4-n R ²³ and 4-n R ²⁴ are each independently substituted or unsubstituted C 1-20 carbon atoms. A hydrocarbon group and n is 0, 1, 2 or 3;

In the formula (4), R ²⁵ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and the two R ²⁶ are independently a hydrogen atom or a substituted or unsubstituted group. It is a hydrocarbon group having 1 to 20 carbon atoms, and two R ²⁷ and two R ²⁸ are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.

Examples of the titanium chelate represented by the formula (3) or the formula (4) include titanium dimethoxide bis (ethyl acetoacetate), titanium diethoxide bis (ethyl acetoacetate), and titanium diisopropoxide bis (ethyl). Acetoacetate), titanium diisopropoxide bis (methyl acetoacetate), titanium diisopropoxide bis (t-butyl acetoacetate), titanium diisopropoxide bis (methyl-3-oxo-4,4-dimethylhexano) Eth), titanium diisopropoxide bis (ethyl-3-oxo-4,4,4-trifluorobutanoate), titanium di-n-butoxide bis (ethyl acetoacetate), titanium diisobutoxide bis (ethyl acetoacetate) ) Titanium di-t-butoxide bis (ethyl acetoacetate), Titanium di-2-ethylhexoxide bis (ethyl acetoacetate), Titanium bis (1-methoxy-2-propoxide) bis (ethyl acetoacetate), Titanium bis (3-oxo-2-butoxide) bis (ethylacetoacetate), titanium bis (3-diethylaminopropoxide) bis (ethylacetoacetate), titanium triisopropoxide (ethylacetoacetate), titanium triisopropoxide (allyl) Acetoacetate), titanium triisopropoxide (methacryloxyethyl acetoacetate), 1,2-dioxyethane titanium bis (ethyl acetoacetate), 1,3-dioxypropane titanium bis (ethyl acetate) Toacetate), 2,4-dioxypentane titanium bis (ethyl acetoacetate), 2,4-dimethyl-2,4-dioxypentane titanium bis (ethyl acetoacetate), titanium tetrakis (ethyl acetoacetate), titanium bis (Trimethylsiloxy) bis (ethylacetoacetate), titanium bis (trimethylsiloxy) bis (acetylacetate), and the like. Among these, titanium diethoxide bis (ethyl acetoacetate), titanium diisopropoxide bis (ethyl acetoacetate), titanium dibutoxide bis (ethyl acetoacetate) and the like, titanium diisopropoxide bis (ethyl acetoacetate) ) Is more preferable.

Examples of the chelating reagent capable of forming the chelate ligand of the titanium chelate include, for example, methyl acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, allyl acetoacetate, acetoacetate (2-methacryloxyethyl), 3-oxo Examples include β-ketoesters such as methyl -4,4-dimethylhexanoate and ethyl 3-oxo-4,4,4-trifluorobutanoate, preferably methyl acetoacetate and ethyl acetoacetate, more preferably ethyl acetoacetate . When two or more chelate ligands are present, each chelate ligand may be the same or different.

The (B) aging curing catalyst is prepared by previously mixing the (C) silane compound in a mixing ratio of 0.1 to 30 mol with respect to 1 mol of the (D) titanium catalyst, and aging at a reaction temperature of 30 to 100 ° C. This is an aging curing catalyst. Here, aging means transesterification of a part of the alkoxy group of the (D) titanium catalyst and a part of the alkoxy group of the (C) silane compound and / or moisture contained in the air ( C) It means that a part of the silane compound is hydrolyzed with the (D) titanium catalyst to be oligomerized. It is preferable to reach the state of chemical equilibrium by the aging, or the state after reaching the state of chemical equilibrium.

The mixing ratio of the (D) titanium catalyst and the (C) silane compound is in the range of 0.1 to 30 mol of the (C) silane compound with respect to 1 mol of the (D) titanium catalyst. (D) In the range of 0.5 to 5.0 moles of the (C) silane compound relative to 1 mole of the titanium catalyst, more preferably, the (C) silane compound 0 relative to 1 mole of the (D) titanium catalyst. The range is from 5 to 3.0 mol. The (D) titanium catalyst and the (C) silane compound may be used singly or in combination of two or more.

The reaction temperature condition for aging the mixture of the (D) titanium catalyst and the (C) silane compound is such that the (D) titanium catalyst and the (C) silane compound are reacted at 30 to 100 ° C. 30 ° C. to 90 ° C. is preferable, and 40 ° C. to 80 ° C. is more preferable. By setting the reaction temperature within the above range, the reaction can proceed stably without causing runaway. When the reaction temperature is less than 30 ° C., the activity is low, the time required to achieve a sufficient reaction is lengthened, and the efficiency is poor. The reaction time can be appropriately set in consideration of the reaction temperature and the like, but it is desirable to carry out the reaction until at least an equilibrium state is reached. For example, the reaction time is usually 1 to 336 hours under the above conditions, preferably Is preferably set within a range of 72 to 168 hours.

The blending ratio of the (B) aging curing catalyst is not particularly limited, but it is preferable to blend 0.5 to 30 parts by mass of the (B) aging curing catalyst with respect to 100 parts by mass of the (A) organic polymer. More preferably, 5.0 to 20.0 parts by mass is blended. The (B) aging curing catalyst may be used alone or in combination of two or more.

The curable composition of the present invention uses the above-mentioned (B) aging curing catalyst as a curing catalyst, but may be used in combination with a non-aging curing catalyst or other aging curing catalyst that has not been aged. In particular, in addition to the (B) aging curing catalyst, it is preferable to use a titanium chelate compound in combination as a non-aging curing catalyst. (B) The rising adhesiveness can be improved by using an aging curing catalyst and a titanium chelate compound which has not been aged. The titanium chelate compound is not particularly limited, and a known titanium chelate compound can be used, and is selected from the group consisting of a titanium chelate represented by the formula (3) and a titanium chelate represented by the formula (4). One or more titanium catalysts are preferred. Further, other titanium chelate compounds such as titanium tetraacetylacetonate may be used.

The blending ratio of the titanium chelate compound used as the non-aged curing catalyst is not particularly limited, but 1 to 1 of the titanium chelate compound used as the non-aged curing catalyst with respect to 100 parts by mass of the (B) matured curing catalyst. It is preferable to mix 100 parts by mass, and it is more preferable to add 10 to 20 parts by mass. The titanium chelate compounds may be used alone or in combination of two or more.

The curable composition of the present invention can be used in combination with other curing catalysts to the extent that the effects of the present invention are not reduced. Examples of other curing catalysts include organometallic compounds and amines, and it is particularly preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate. , Dioctyltin dilaurate, dioctyltin diversate, organotin compounds such as tin octylate and tin naphthenate; dialkyltin oxides such as dimethyltin oxide, dibutyltin oxide and dioctyltin oxide; reaction products of dibutyltin oxide and phthalate, etc. ; Titanates such as tetrabutyl titanate and tetrapropyl titanate; aluminum trisacetylacetonate, aluminum trisethylate Organoaluminum compounds such as acetoacetate and diisopropoxyaluminum ethylacetoacetate; Chelate compounds such as zirconium tetraacetylacetonate; Leaded organic acids such as lead octylate and lead naphthenate; Bismuth octylate, bismuth neodecanoate and rosin Examples include organic acid bismuth such as bismuth acid; other acidic catalysts and basic catalysts known as silanol condensation catalysts. However, the toxicity of the resulting curable composition may increase depending on the amount of the organotin compound added.

It is preferable that the curable composition of the present invention further includes (E) a silane compound having one hydrolyzable silicon group and one primary amino group in one molecule. (E) By adding a silane compound, storage stability and tensile physical properties can be further improved.

As the (E) silane compound, known silane compounds having one hydrolyzable silicon group and one primary amino group in one molecule can be widely used. In the hydrolyzed silicon group of the silane compound (E), a known hydrolyzable group excluding a primary amino group can be used as the hydrolyzable group bonded to the silicon atom, but an alkoxyl group is preferred. In the component (E), in consideration of storage stability and tensile physical properties, the hydrolyzable silicon group is preferably a trialkoxysilyl group or a dialkoxysilyl group, and more preferably a trialkoxysilyl group.

As the (E) silane compound, a compound represented by the following formula (12) is more preferably used.

In the formula (12), R ⁴¹ is a methyl group or an ethyl group, and when a plurality of R ⁴¹ are present, they may be the same or different. R ⁴² is a methyl group or an ethyl group, and when a plurality of R ⁴² are present, they may be the same or different. R ⁴³ is a hydrocarbon group having 1 to 10 carbon atoms. m is 2 or 3, and 3 is more preferable. n is 0 or 1.

Specific examples of the (E) silane compound include phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, 2-carboxyethylphenylbis (2-methoxyethoxy) silane, and N-phenyl. -3-alkoxysilanes containing a phenyl group such as 3-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidyl Alkoxysilanes containing epoxy groups such as sidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane; Socyanate propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) dimethoxymethylsilane, (isocyanate) Alkoxysilanes containing isocyanate groups such as (methyl) triethoxysilane, (isocyanatemethyl) diethoxymethylsilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3- Mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltrimethoxysilane, Alkoxysilanes containing mercapto groups such as lucaptomethyltriethoxysilane; carboxysilanes such as 2-carboxyethyltriethoxysilane, N-2- (carboxymethyl) aminoethyl-3-aminopropyltrimethoxysilane; vinyltrimethoxy Alkoxysilanes containing vinyl unsaturated groups such as silane, vinyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane; 3-chloropropyltrimethoxy Alkoxysilane containing halogen such as silane; isocyanurate silane such as tris (3-trimethoxysilylpropyl) isocyanurate; N-benzyl-3-aminopropyltrimeth Xisilane, N-vinylbenzyl-3-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N, N′-bis [3- (trimethoxysilyl) propyl] Alkoxysilanes containing secondary amino groups and / or tertiary amino groups such as ethylenediamine, bis (3-trimethoxysilylpropyl) amine, N-ethyl-3-aminoisobutyltrimethoxysilane; N- (1,3- Ketimine type silanes such as dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine; Silane, tetraethoxysilane, ethoxytrimethoxysilane, Tetraalkoxysilanes such as methoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane ( Tetraalkyl silicate); methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltri Trialkoxysilanes such as methoxysilane; dialkoxysilanes such as dimethyldimethoxysilane and diethyldimethoxysilane; trimethylmethoxysilane and trimethylethoxysilane What monoalkoxysilanes; and the like can be given; dimethyl isopropenoxysilane silane, alkyl isopropenoxysilane silane such as methyltrimethoxysilane isopropenoxysilane silane.

Examples of the compound represented by the formula (12) include dialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and hexyltrimethoxysilane. Alkyl trialkoxysilanes such as decyltrimethoxysilane; alkoxysilanes containing phenyl groups such as phenyltrimethoxysilane and phenyltriethoxysilane; vinyl-type unsaturated groups such as vinyltrimethoxysilane and vinyltriethoxysilane Alkoxysilanes; alkoxysilanes containing epoxy groups such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane, etc. Shishiran is more preferable.

The blending ratio of the (E) silane compound is not particularly limited, but it is preferable to blend 0.1 to 20 parts by weight of the (E) silane compound with respect to 100 parts by weight of the (A) organic polymer. It is more preferable to add 0.3 to 20 parts by mass, and it is even more preferable to add 0.5 to 10 parts by mass. The (E) silane compound may be used alone or in combination of two or more.

The curable composition of the present invention preferably further contains (F) a filler. (F) A hardened | cured material can be reinforced by mix | blending a filler.
As the filler (F), known fillers can be widely used and are not particularly limited. For example, calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, anhydrous silicic acid, calcium silicate , Fine powder silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, zeolite, polymer powder, etc., calcium carbonate, fine powder silica and polymer powder are preferred, surface treated carbonic acid One or more selected from the group consisting of calcium, amorphous silica having a particle size of 0.01 to 300 μm, and polymer powder having a particle size of 0.01 to 300 μm are more preferable. In addition, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, silica balloons, saran balloons, acrylic balloons, etc. can be used. Among them, an acrylic balloon is more preferable from the viewpoint that the decrease in elongation after curing of the composition is small.

As the calcium carbonate, any of heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, ground calcium carbonate and the like can be used, but colloidal calcium carbonate is more preferable. These calcium carbonates may be used alone or in combination of two or more.
The primary particle diameter of the calcium carbonate is preferably 0.5 μm or less, more preferably 0.01 to 0.1 μm. By using such fine powdered calcium carbonate having a small particle diameter, thixotropy can be imparted to the curable composition.

Also, among calcium carbonates, surface-treated calcium carbonate is preferable from the viewpoint of imparting thixotropy and reinforcing effect on a cured product (cured film), and surface-treated fine calcium carbonate is more preferable. Furthermore, surface-treated fine powdered calcium carbonate is used in combination with other calcium carbonates such as heavy calcium carbonate that has not been surface-treated and has a large particle size, or surface-treated calcium carbonate with a large particle size. May be. When the surface-treated fine calcium carbonate and other calcium carbonate are used in combination, the ratio (mass ratio) between the surface-treated fine calcium carbonate and the other calcium carbonate is preferably 1: 9 to 9: 1. 3: 7 ~ 7: 3 is more preferred.

In the surface-treated calcium carbonate, the surface treatment agent to be used is not particularly limited, and known surface treatment agents can be widely used. Examples of the surface treatment agent include higher fatty acid compounds, resin acid compounds, aromatic carboxylic acid esters, anionic surfactants, cationic surfactants, nonionic surfactants, paraffin, and titanate couplings. And higher fatty acid compounds and paraffin are more preferable. These surface treatment agents may be used alone or in combination of two or more.

Examples of the higher fatty acid compounds include higher fatty acid alkali metal salts having 10 or more carbon atoms such as sodium stearate.
Examples of the resin acid compound include abietic acid, neoabietic acid, d-pimalic acid, id-pimalic acid, bodocarpic acid, benzoic acid, and cinnamic acid.
Examples of the aromatic carboxylic acid ester include phthalic acid octyl alcohol, butyl alcohol, isobutyl alcohol and the like, naphthic acid lower alcohol ester, rosin acid lower alcohol ester, and aromatic dicarboxylic acid or rosin acid malee. Examples thereof include partially esterified products of aromatic polycarboxylic acids such as acid adducts, and different alcohol esterified products.
Examples of the anionic surfactant include a sulfate ester type such as sodium dodecyl sulfate, or a sulfonic acid type anionic surfactant such as sodium dodecylbenzene sulfonate, sodium lauryl sulfonate, and dodecyl benzene sulfonic acid. Is mentioned.

As the surface-treated calcium carbonate, known surface-treated calcium carbonate can be widely used and is not particularly limited. For example, Vigot 15 (manufactured by Shiroishi Calcium Co., Ltd., light carbonate surface-treated with fatty acid) Surface treatment light calcium carbonate such as calcium, primary particle diameter 0.15 μm; Vigot 10 (manufactured by Shiroishi Calcium Co., Ltd., colloidal calcium carbonate surface treated with fatty acid, primary particle diameter 0.10 μm), white sinter flower DD (Shiraishi calcium Colloidal calcium carbonate surface-treated with resin acid, primary particle size 0.05 μm, Carlex 300 (manufactured by Maruo Calcium Co., Ltd., colloidal calcium carbonate surface-treated with fatty acid, primary particle size 0. 05μm), Neolite SS (manufactured by Takehara Chemical Co., Ltd.), surface-treated with fatty acid Loyal calcium carbonate, average particle size 0.04μm), Neolite GP-20 (manufactured by Takehara Chemical Industry Co., Ltd., colloidal calcium carbonate surface-treated with resin acid, average particle size 0.03μm), Calsees P (Kamishima Chemical Industry) Surface-treated colloidal calcium carbonate such as colloidal calcium carbonate surface-treated with fatty acid manufactured by Co., Ltd .; MC Coat P1 (manufactured by Maruo Calcium Co., Ltd., heavy carbonate surface-treated with paraffin) Calcium, primary particle size 3.3 μm), AFF-95 (manufactured by Pfematech Co., Ltd., heavy calcium carbonate surfaced with a cationic polymer, primary particle size 0.9 μm), AFF-Z (manufactured by Pmatech) Surface treatment heavy such as heavy calcium carbonate surfaced with cationic polymer and antistatic agent, primary particle diameter 1.0 μm) An example is calcium carbonate.

The surface-treated calcium carbonate is preferably added in an amount of 0 to 500 parts by weight, more preferably 10 to 300 parts by weight, and more preferably 15 to 100 parts by weight with respect to 100 parts by weight of the (A) organic polymer. More preferably. The said surface treatment calcium carbonate may be used by 1 type, and may be used in combination of 2 or more type. Moreover, you may use together the surface treatment calcium carbonate and the calcium carbonate which has not surface-treated.

As the amorphous silica, known amorphous silica can be widely used, and is not particularly limited. However, the particle size is preferably 0.01 to 300 μm, more preferably 0.1 to 100 μm. 1 to 30 μm is more preferable.
By using amorphous silica in which the difference between the refractive index of the organic polymer (A) and the refractive index of the amorphous silica is 0.1 or less, the transparency can be further improved. The difference between the refractive index of the organic polymer (A) and the refractive index of the amorphous silica is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0.03 or less.

The amorphous silica is preferably blended in an amount of 0 to 500 parts by weight, more preferably 1 to 200 parts by weight, and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the (A) organic polymer. More preferably. The amorphous silica may be used alone or in combination of two or more. In addition to amorphous silica having a particle size of 0.01 to 300 μm, amorphous silica or crystalline silica having a particle size different from the above may be used in combination.

As the polymer powder, known polymer powders can be widely used, and are not particularly limited. However, the particle size is preferably 0.01 to 300 μm, more preferably 0.1 to 100 μm. 1 to 30 μm is more preferable.

As the polymer powder, for example, a monomer selected from the group consisting of (meth) acrylic acid ester, vinyl acetate, ethylene and vinyl chloride is polymerized alone, or the monomer and one or more vinyl monomers are used. A polymer powder made from a polymer obtained by copolymerization of a polymer is preferably used, an acrylic polymer powder or a vinyl polymer powder is more preferred, and an acrylic polymer powder is further preferable.

In order to further improve the transparency of the curable composition of the present invention, the difference between the refractive index of the liquid phase component containing (A) the organic polymer as the main component and the refractive index of the polymer powder is 0.1. Preferably, it is preferably 0.05 or less, more preferably 0.03 or less.
The method for setting the difference between the refractive index of the liquid phase component containing (A) the organic polymer as the main component and the refractive index of the polymer powder to 0.1 or less is not particularly limited, but (1) high (A) a method of matching the refractive index of the liquid phase component containing an organic polymer as a main component with the refractive index of the molecular powder, and (2) (A) the refractive index of the polymer powder with the refractive index of the organic polymer. And the like.

As the method of (1), for example, (A) a method of adjusting a refractive index of a liquid phase component by blending a necessary amount of a compatible refractive index adjusting agent with a liquid phase component mainly composed of an organic polymer. Is mentioned. Specifically, in an embodiment where (A) the refractive index of the organic polymer is about 1.46 to 1.48 and the refractive index of the polymer powder is higher, it is higher than (A) the organic polymer. Refractive index adjusting agent having a refractive index {for example, epoxy resin [Example: Epicoat 828 (Bisphenol A, manufactured by Yuka Shell Epoxy Co., Ltd., refractive index 1.57)], petroleum resin [Example: FTR6100 (of C5 and C9 Copolymer, Mitsui Petrochemical Co., Ltd., refractive index 1.56)], terpene phenol resin [Example: Polystar T145 (Yasuhara Chemical Co., Ltd., refractive index 1.59)]} There is a method of heating and melting the coalescence.

Examples of the method (2) include a method of appropriately changing the monomer composition of the polymer powder. Specifically, in the embodiment where the refractive index of the organic polymer (A) is about 1.46 to 1.48 and acrylic polymer powder is used as the polymer powder, the refractive index of the polymer powder is As a method for increasing the viscosity, for example, a monomer such as vinyl chloride [refractive index 1.53 (polymer)] and allylonitrile [refractive index 1.52 (polymer)] is used as a single monomer of (meth) acrylate. The method of copolymerizing to a body is mentioned. In this embodiment, the method (E4) for reducing the refractive index of the polymer powder includes, for example, lauryl methacrylate [refractive index 1.44 (monomer)], allyl methacrylate [refractive index 1.44 (single Monomer)], and a monomer such as 2 (2-ethoxyethoxy) ethyl acrylate [refractive index of 1.43 (monomer)] is copolymerized with a meth) acrylate monomer.

The polymer powder is preferably blended in an amount of 0 to 500 parts by weight, more preferably 0.5 to 100 parts by weight, based on 100 parts by weight of the organic polymer (A). It is more preferable to blend. The polymer powder may be used alone or in combination of two or more.

In the curable composition of the present invention, the blending ratio of the filler (F) is not particularly limited, but the filler (F) is added in an amount of 0 to 500 masses per 100 mass parts of the organic polymer (A). It is preferably blended in an amount of 2 to 250 parts by weight, more preferably 5 to 125 parts by weight. The said (F) filler may be used by 1 type, and may be used in combination of 2 or more type.

The curable composition of the present invention preferably further contains (G) a diluent. (G) By blending a diluent, physical properties such as viscosity can be adjusted.
(G) As a diluent, a well-known diluent can be widely used, and there is no restriction | limiting in particular, For example, saturated hydrocarbon solvents, such as normal paraffin and isoparaffin, a linearlen dimer (Idemitsu Kosan Co., Ltd. brand name) Α-olefin derivatives represented by the following formula (I), aromatic hydrocarbon solvents such as toluene and xylene, alcohols such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, and diacetone alcohol Solvents, ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve, citrate solvents such as acetyl triethyl citrate, acetyl tributyl citrate and triethyl citrate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone Various solvents such as
R ⁵¹ -ZR ⁵² (I)
(In the formula (I), R ⁵¹ and R ⁵² each independently represents a linear alkyl group having 2 to 20 carbon atoms, and Z is represented by any one of the following formulas (Ia) to (Ic): Represents a valent group.)

(In the formula (Ib), R ⁵³ represents a hydrogen atom or a linear or branched alkyl group having 1 to 40 carbon atoms.)

The flash point of the diluent (G) is not particularly limited, but considering the safety of the resulting curable composition, it is desirable that the flash point of the curable composition is high. Volatile substances from the curable composition Is preferably less.
Therefore, the flash point of the (G) diluent is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. When two or more (G) diluents are mixed and used, the flash point of the mixed diluent is preferably 70 ° C. or higher. However, generally, a diluent having a high flash point tends to have a low dilution effect on the curable composition, and therefore, the flash point is preferably 250 ° C. or lower.

In consideration of both safety and dilution effect of the curable composition of the present invention, (G) a saturated hydrocarbon solvent is preferable as the diluent, and normal paraffin and isoparaffin are more preferable. Normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms. Specifically, N-11 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number 11, flash point 68 ° C.), N-12 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number) 12, flash point 85 ° C.), IP solvent 2028 (isoparaffin, manufactured by Idemitsu Kosan Co., Ltd., carbon number 10 to 16, flash point 86 ° C.) and the like.

The blending ratio of the (G) diluent is not particularly limited, but it is preferable to blend 0 to 50 parts by mass of the (G) diluent with respect to 100 parts by mass of the (A) organic polymer. 1 to 30 parts by mass is more preferable, and 0.1 to 15 parts by mass is even more preferable. The said (G) diluent may be used by 1 type, and may be used in combination of 2 or more type.

The curable composition of the present invention preferably further contains a metal hydroxide. By mix | blending the said metal hydroxide, a flame retardance can be provided, workability | operativity can be improved, and hardened | cured material can be reinforced. Furthermore, the metal hydroxide also has an effect of higher safety than other flame retardants such as halogen flame retardants. In particular, by using a metal hydroxide and surface-treated calcium carbonate in combination, workability (thixotropic properties) can be further improved and flame retardancy can be imparted. The metal hydroxide may be a metal hydroxide surface-treated with a surface treatment agent.
Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide, and aluminum hydroxide is more preferable.

The blending ratio of the metal hydroxide is not particularly limited, but 0 to 500 parts by weight of the metal hydroxide is preferably blended with respect to 100 parts by weight of the (A) organic polymer. More preferably, 5 to 125 parts by mass is added. The said metal hydroxide may be used independently and may be used together 2 or more types. Moreover, you may use together another well-known flame retardant.

In addition to the above-described components, the curable composition of the present invention includes an ultraviolet absorber, an antioxidant, an anti-aging agent, an adhesiveness imparting agent, a physical property modifier, a plasticizer, a thixotropic agent, and a dehydration agent as necessary. You may mix substances such as additives (storage stability improvers), flame retardants, tackifiers, anti-sagging agents, colorants, radical polymerization initiators, and blend with other compatible polymers. Good.

The antioxidant is used to prevent oxidation of the curable composition to improve weather resistance and heat resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. It is done. Examples of the hindered amine antioxidant include N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis- (2,2,6 , 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine · N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4- Peridyl) imino}], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis (2,2,6,6-tetramethyl-decanedioic acid) 1 (octyloxy) -4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane (70%)]-polypropylene (30%), bis (1,2,2,6,6- Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1- [2- [3- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9- Examples include, but are not limited to, tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, etc. Examples of hindered phenol-based antioxidants include penta Erythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-ter t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide), benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5, 5 ′, 5 ″ -hexane-tert-butyl-4-a, a ′, a ″-(mesitylene-2,4,6-tolyl) tri-p-cresol, calci Mudiethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 , 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzenamine Product of 2,4,4-trimethylpentene with 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5 Triazin-2-ylamino) phenol and the like, but not limited thereto. The antioxidants may be used alone or in combination of two or more.

The ultraviolet absorber is used to improve the weather resistance by preventing photodegradation of the curable composition, for example, ultraviolet absorption of benzotriazole, triazine, benzophenone, benzoate, etc. Agents and the like. Examples of the ultraviolet absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazole-2) -Il) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4 -Benzotriazole ultraviolet absorbers such as methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(he Sil) oxy] -phenol and other triazine ultraviolet absorbers, benzophenone ultraviolet absorbers such as octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. Examples include, but are not limited to, benzoate ultraviolet absorbers. The said ultraviolet absorber may be used independently or may use 2 or more types together.

The anti-aging agent is used for preventing heat deterioration of the curable composition and improving the heat resistance. For example, an anti-aging agent such as an amine-ketone type or an aromatic secondary amine type is used. Antiaging agents, benzimidazole type antiaging agents, thiourea type antiaging agents, phosphorous acid type antiaging agents and the like can be mentioned.

Examples of the amine-ketone-based anti-aging agent include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline. And amine-ketones such as a reaction product of diphenylamine and acetone, but are not limited thereto.

Examples of the aromatic secondary amine-based antiaging agent include N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (P-toluenesulfonylamide) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, etc. Secondary amines and the like can be mentioned, but the invention is not limited to these.

Examples of the benzimidazole antioxidant include benzimidazoles such as 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptobenzimidazole, and the like, but are not limited thereto. is not.

Examples of the thiourea antioxidant include, but are not limited to, thiourea such as 1,3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea.

Examples of the phosphorous acid-based antioxidant include, but are not limited to, a phosphorous acid-based material such as tris (nonylphenyl) phosphite.

The amount of the anti-aging agent is not particularly limited, but the anti-aging agent is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the (A) organic polymer. More preferably, it is used in the range of 0.2 to 5 parts by mass.

The physical property modifier is added for the purpose of improving physical properties of the curable composition such as tensile physical properties. As an example of the physical property adjusting agent, for example, a silicon compound having one silanol group and one primary amino group in one molecule is preferably used. Examples of the silicon compound include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, diphenylalkylsilanol and the like.

The plasticizer is added for the purpose of enhancing the stretched physical properties after curing or enabling low modulus. The type of the plasticizer is not particularly limited. For example, phthalates such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diisoundecyl phthalate; dioctyl adipate, isodecyl succinate, sebacine Aliphatic dibasic acid esters such as dioctyl acid and dibutyl adipate; Glycol esters such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate and pentaerythritol ester; Aliphatics such as butyl oleate and methyl acetylricinoleate Esters; Phosphate esters such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tributyl phosphate, tricresyl phosphate; Epoxy plasticizers such as modified soybean oil, epoxidized linseed oil, and epoxy benzyl stearate; Polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; Polyethers such as polypropylene glycol and polyethylene glycol derivatives Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, etc. with 2 repetitions, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol diethyl ether, etc. with 3 repetitions, tetraethylene glycol 4 repeats such as diethyl ether, tetraethylene glycol ethyl methyl ether, tetraethylene glycol diethyl ether, etc. , Polyoxyethylene alkyl ethers such as polyoxyethylene dimethyl ether, which are repeated further; polystyrenes such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, water Hydrocarbon oligomers such as hydrogenated polybutadiene, hydrogenated polyisoprene and process oil; chlorinated paraffins; acrylics such as UP-1080 (manufactured by Toagosei Co., Ltd.) and UP-1061 (manufactured by Toagosei Co., Ltd.) Hydroxyl group-containing acrylic plasticizers such as UP-2000 (manufactured by Toagosei Co., Ltd.), UHE-2012 (manufactured by Toagosei Co., Ltd.); UC-3510 (manufactured by Toagosei Co., Ltd.) Carboxyl group-containing acrylic polymers such as UG-4 Epoxy group-containing acrylic polymers such as 00 (manufactured by Toagosei Co., Ltd.); less than 0.8 such as US-6110 (manufactured by Toagosei Co., Ltd.), US-6120 (manufactured by Toagosei Co., Ltd.) Examples of the silyl group-containing acrylic polymer are preferably less than 0.4.

Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, and aluminum stearylate. And barium stearylate.

The dehydrating agent is added for the purpose of removing moisture during storage. Examples of the dehydrating agent include zeolite, calcium oxide, magnesium oxide, and zinc oxide.

Examples of the flame retardant include phosphorus flame retardants such as red phosphorus and ammonium polyphosphate; metal oxide flame retardants such as antimony trioxide; bromine flame retardants; chlorine flame retardants and the like.

The curable composition of the present invention can be a one-component type or a two-component type as required, and can be suitably used as a one-component type. The curable composition of the present invention can be cured at normal temperature by atmospheric moisture, and is suitably used as a normal temperature moisture-curable curable composition, but if necessary, curing is accelerated by heating as appropriate. You may let them.

The method for producing the curable composition of the present invention is not particularly limited. For example, the components (A) and (B) are blended in a predetermined amount, and other blended substances are blended as necessary, and deaerated and stirred. Can be manufactured.
There are no particular restrictions on the blending order of the blended substances other than the components (A) and (B), and they may be determined as appropriate. For example, for example, the components (A), (B) and other compounding substances may be compounded to produce the curable composition of the present invention, and other compounding substances may be added before the aging step of the component (B). You may mix | blend and may perform an aging process with respect to the mixture containing (C) silane compound, (D) titanium catalyst, and another compounding substance. Moreover, you may age | cure | ripen at the predetermined temperature further with respect to the composition which mix | blended all the compounding substances, and the composition containing a component (B). When a non-aged curing catalyst is used in combination, it is preferable to produce the curable composition so that the aging process is not performed after the addition of the non-aged curing catalyst.

When blending other compounding substances before the aging step of component (B), after obtaining a mixture containing (C) silane compound, (D) titanium catalyst and other compounding substances, the mixture may be aged. Well, after blending one of the (C) silane compound and (D) titanium catalyst with the other compounding material and performing an aging step as necessary, blend the other of (C) silane compound and (D) titanium catalyst And may be aged.

When the component (E) is blended as another blending substance, there is no particular limitation on the blending order, but after obtaining a composition containing the components (B) and (E), the composition and the component (A) are blended. After obtaining a composition containing components (B) and (E), it is preferable to blend the remaining compounding substances. The method for obtaining the composition containing the components (B) and (E) is not particularly limited, and the components (B) and (E) may be mixed, and as described above, the components before the aging step of the component (B) (E) may be blended.

The mixing ratio of the components (B) and (E) is not particularly limited, but the mixing ratio of the (D) titanium catalyst and the (E) silane compound is the (E) silane with respect to 1 mol of the (D) titanium catalyst. The compound is preferably in the range of 0.1 to 30 mol, more preferably in the range of 0.5 to 5.0 mol, and still more preferably in the range of 0.5 to 3.0 mol. (C) Silane compound, (D) titanium catalyst, and (E) silane compound may be used alone or in combination of two or more.

When a silane compound having an alkoxysilyl group is used as the component (E), (D) a curing catalyst obtained by aging a composition containing a titanium catalyst and (E) silane compound at a predetermined temperature is blended with the remaining compounding substances. More preferably. Here, the aging means transesterification of a part of the alkoxy group of the (D) titanium catalyst and a part of the alkoxy group of the (E) silane compound and / or the moisture contained in the air ( E) This means that a part of the silane compound is hydrolyzed with the titanium catalyst (D) and oligomerized. It is preferable to reach the state of chemical equilibrium by the aging.

The reaction temperature condition for aging the mixture containing the (D) titanium catalyst and the (E) silane compound is not particularly limited, but the (D) titanium catalyst and the (E) silane compound are heated at 30 ° C. to 100 ° C. The reaction is preferably carried out, more preferably from 30 ° C to 90 ° C, and even more preferably from 40 ° C to 80 ° C. By setting the reaction temperature within the above range, the reaction can proceed stably without causing runaway. When the reaction temperature is less than 30 ° C., the activity is low, the time required to achieve a sufficient reaction is lengthened, and the efficiency is poor. The reaction time can be appropriately set in consideration of the reaction temperature and the like, but it is desirable to carry out the reaction until at least an equilibrium state is reached. For example, the reaction time is usually 1 to 336 hours under the above conditions, preferably Is preferably set within a range of 72 to 168 hours.

In the present invention, when the aging step of the (D) titanium catalyst and (E) silane compound is performed, the aging of the (C) silane compound and (D) titanium catalyst, and the (D) titanium catalyst and (E) The order of aging of the silane compound is not limited, but since the manufacturing process is simplified, from the viewpoint of workability, a mixture of (C) silane compound, (D) titanium catalyst and (E) silane compound is mixed. On the other hand, it is preferable to ripen at a predetermined temperature at the same time. In addition, from the viewpoint of storage stability, rate of change in curing time, etc., one of (C) silane compound and (E) silane compound and (D) titanium catalyst is included. After the mixture is aged at a predetermined temperature, the other of (C) the silane compound and (E) the silane compound is blended and aged again at a predetermined temperature as necessary, or (C) the silane compound and (D) titanium Aged catalyst As was, (D) were mixed those aged titanium catalyst and (E) a silane compound, a method of further aging the mixture was the mixed as needed is preferred. By performing the aging step, the storage stability can be further improved.

When the component (F) is blended as another blending substance, there is no particular limitation on the blending order, and it may be determined as appropriate, but it is more preferable to blend the component (E) after the aging step.

When component (G) is blended as another blending substance, there is no particular limitation on the blending order, but in addition to (C) one or both of (C) silane compound and (E) silane compound, and (D) titanium catalyst, component It is preferable to age the mixture containing (G) at a predetermined temperature. In this case, a mixture containing one or both of (C) silane compound and (E) silane compound, (D) titanium catalyst, and component (G) may be aged at the same time at a predetermined temperature. After aging simultaneously at a predetermined temperature for a mixture containing one or both of a silane compound and (E) a silane compound and (D) a titanium catalyst, the mixture is blended with component (G), and again at a predetermined temperature. The aging step may be performed a plurality of times, such as by aging. Particularly, by blending the component (G) after the aging step of (C) silane compound, (D) titanium catalyst and (E) silane compound, and further performing the aging step, the rate of change in the curing time after storage is lowered. More preferred. By performing the aging step, the storage stability can be further improved.

The curable composition of the present invention can be used as an adhesive, a sealing material, an adhesive material, a coating material, a potting material, a paint, a putty material, a primer, and the like. Since the curable composition of the present invention is excellent in adhesiveness, storage stability, and curability, it is particularly preferable to use it as an adhesive, but for various other buildings, automobiles, civil engineering, electric / electronics. It can be used for fields.

Hereinafter, the present invention will be described more specifically with reference to examples. However, it is needless to say that these examples are shown by way of example and should not be interpreted in a limited manner.

Analysis and measurement in Synthesis Examples, Examples and Comparative Examples were performed according to the following methods.
1) Measurement of number average molecular weight It measured on the following conditions by the gel permeation chromatography (GPC). In the present invention, the maximum frequency molecular weight measured by GPC under the measurement conditions and converted with standard polyethylene glycol is referred to as the number average molecular weight.
THF solvent measuring device / analyzer: Alliance (manufactured by Waters), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Millenium data processing device (manufactured by Waters)
Column: Plgel GUARD + 5 μmMixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by Polymer Lab)
・ Flow rate: 1 mL / min ・ Converted polymer: Polyethylene glycol ・ Measurement temperature: 40 ° C.
FT-NMR measuring device: JNM-ECA500 (500 MHz) manufactured by JEOL Ltd.
FT-IR measuring device: FT-IR460Plus manufactured by JASCO Corporation

2) Storage stability test, curability (TFT) test, and thixotropy test Viscosity, curing time, and structural viscosity index (SVI value) immediately after blending the curable composition were measured. The conditions were referred to as initial, and the measured viscosity, curing time, and SVI value were defined as initial viscosity, initial TFT, and initial SVI value, respectively.

The viscosity is measured with a BS rotational viscometer (rotor No. 7-10 rpm) when the viscosity of the curable composition is 160 Pa · s or more, and when the viscosity of the curable composition is less than 160 Pa · s, the BH type. It was measured with a rotational viscometer (rotor No. 7-20 rpm) (measurement temperature 23 ° C.).
As for the curing time, the touch drying time (TFT) was measured in an environment of RH 50% at 23 ° C. according to JIS A 1439 5.19 tack-free test.
The SVI value is calculated by dividing the viscosity at 1 rpm by the viscosity at 10 rpm using a BS type rotational viscometer (rotor No. 7) when the viscosity of the curable composition is 160 Pa · s or more. When the viscosity of the product was less than 160 Pa · s, it was calculated by dividing the viscosity at 2 rpm by the viscosity at 20 rpm using a BH type rotational viscometer (rotor No. 7) (measurement temperature 23 ° C.). The obtained SVI value was used as an index indicating thixotropy.

Next, the curable composition in the sealed glass container was left in an atmosphere of 50 ° C. for 1, 2 or 4 weeks, and the viscosity, the curing time, and the SVI value were measured. The measured viscosity, curing time, and SVI value were the viscosity after storage, the TFT after storage, and the SVI value after storage, respectively.
The viscosity increase ratio was calculated by dividing the viscosity after storage by the initial viscosity. Moreover, the thickening rate after 1 week storage was evaluated according to the following evaluation criteria.
○: 0.90 or more and 1.40 or less, Δ: 1.41 or more and 1.50 or less, ×: 0.89 or less or 1.51 or more.
The rate of change was calculated by dividing the TFT after storage by the initial TFT. The rate of change after storage for 1 week was evaluated according to the following evaluation criteria.
A: 0.90 or more and 1.10 or less, B: 0.80 or more and 0.89 or less, or 1.11 or more and 1.30 or less, X: 0.79 or less or 1.31 or more.

3) Surface Curability Test A cured product of a curable composition having a size of 100 mm × 100 mm × 3 mm was prepared by leaving it in an environment of 23 ° C. and RH 50% for 7 days, and judged by finger touch. The evaluation criteria are as follows.
A: Not sticky at all, ○: Not sticky, △: Sticky, ×: Very sticky.

4) Adhesion test 0.2 g of the curable composition was uniformly applied on the adherend, and immediately bonded in an area of 25 mm × 25 mm. After bonding, the adhesive strength was measured in accordance with the tensile shear bond strength test method of JIS K 6850 rigid adherend immediately after pressing with a small eyeball clip for 24 hours or 7 days in an atmosphere of 23 ° C. and RH 50%. . Polycarbonate is used as an adherent for the adhesive strength test after 24 hours, and hard vinyl chloride (PVC), polycarbonate (PC), polystyrene (PS), ABS resin (adhesive for the adhesive strength test after 7 days ( ABS), acrylic resin (PMMA), nylon 6 (6-Ny), cold rolled steel plate (SPCC), or anodized aluminum (Al) was used. Further, the fracture state of the adhesive surface was evaluated according to the following evaluation criteria.
CF: cohesive failure, AF: adhesion failure, C10A90 to C90A10: The area of the fracture state of CF and AF is expressed as an approximate percentage. CnA (100-n) is CFn%, AF (100-n)% It means the destruction state.

5) Transparency test The curable composition was stretched using a 3 mm spacer between acrylic plates having a thickness of 2 mm, and the transparency was visually observed and evaluated according to the following evaluation criteria.
◎: colorless and transparent, ○: colorless and slightly cloudy, ×: cloudy.

(Synthesis Example 1)
Hydroxyl value obtained by reacting propylene oxide in a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser in the presence of ethylene glycol as an initiator and zinc hexacyanocobaltate-glyme complex catalyst A polyoxypropylene triol having a reduced molecular weight of 24,000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene triol, methanol is distilled off under heating and reduced pressure, and the terminal hydroxyl group of the polyoxypropylene triol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M1. It was.

Next, the polyoxyalkylene polymer M1 is reacted with allyl chloride at the blending ratio shown in Table 1 to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. Coalescence was obtained. This polyoxyalkylene polymer having an allyl group at the end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and trimethoxysilyl at the end. A polyoxyalkylene polymer A1 having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A1 having a trimethoxysilyl group by GPC, the peak top molecular weight was 25,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 2)
Hydroxyl value obtained by reacting propylene oxide in a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser in the presence of ethylene glycol as an initiator and zinc hexacyanocobaltate-glyme complex catalyst A polyoxypropylene triol having a converted molecular weight of 11000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene triol, methanol is distilled off under heating and reduced pressure, and the terminal hydroxyl group of the polyoxypropylene triol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M2. It was.

Next, the polyoxyalkylene polymer M2 is reacted with allyl chloride at the blending ratio shown in Table 1 to remove unreacted allyl chloride, and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. Coalescence was obtained. This polyoxyalkylene polymer having an allyl group at the end is reacted with trimethoxysilane, which is a silicon hydride compound, by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and trimethoxysilyl at the end. A polyoxyalkylene polymer A2 having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A2 having a trimethoxysilyl group by GPC, the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 3)
Hydroxyl value obtained by reacting propylene oxide in the presence of zinc hexacyanocobaltate-glyme complex catalyst in a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser in the presence of glycerin as an initiator A polyoxypropylene triol having a molecular weight of 14,000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene triol, methanol is distilled off under heating and reduced pressure, and the terminal hydroxyl group of the polyoxypropylene triol is converted to sodium alkoxide to obtain a polyoxyalkylene polymer M3. It was.

Next, the polyoxyalkylene polymer M3 is reacted with allyl chloride at the blending ratio shown in Table 1 to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. Coalescence was obtained. For this polyoxyalkylene polymer having an allyl group at its terminal, 3-mercaptopropyltrimethoxysilane (trade name: KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silyl compound, is used as a polymerization initiator. Reaction was performed using 2′-azobis-2-methylbutyronitrile (AIBN, manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a polyoxyalkylene polymer A3 having a trimethoxysilyl group at the terminal.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A3 having a trimethoxysilyl group by GPC, the peak top molecular weight was 15000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 4)
A polyoxypropylene diol having a number average molecular weight Mn = 3000 (trade name: Diol 3000, manufactured by Mitsui Chemicals, Inc.) is placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, and sodium methoxide is added. Of methanol was distilled off under reduced pressure by heating to convert the terminal hydroxyl group of polyoxypropylene triol into sodium alkoxide to obtain a polyoxyalkylene polymer M4.

Next, the polyoxyalkylene polymer M4 is reacted with allyl chloride at the blending ratio shown in Table 1 to remove unreacted allyl chloride, and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. Coalescence was obtained. The polyoxyalkylene polymer having an allyl group at the terminal is reacted with 3-mercaptopropyltrimethoxysilane, which is a silyl compound, using AIBN, which is a polymerization initiator, to form a polyoxyalkylene polymer having a trimethoxysilyl group at the terminal. An oxyalkylene polymer A4 was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A4 having a trimethoxysilyl group by GPC, the peak top molecular weight was 3,500 and the molecular weight distribution was 1.2. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis Example 5)
As shown in Table 1, a polyoxypropylene diol having a number average molecular weight of 10,000 (trade name: Preminol 4010, manufactured by Asahi Glass Co., Ltd.) was added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. 100.00 g, 3.95 g of m-xylene diisocyanate (trade name: Takenate 500, manufactured by Mitsui Chemicals, Inc.) were reacted at 90 ° C. for 3 hours with stirring and mixing in a nitrogen atmosphere to obtain urethane prepolymer 1.
A new flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was degassed under reduced pressure, replaced with nitrogen gas, and 2.69 g of 3-aminopropyltrimethoxysilane was added under a nitrogen stream. Subsequently, 3.76 g of n-butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at room temperature for 24 hours to obtain a reaction product (silylating agent 1).

The obtained silylating agent 1 was reacted with the obtained urethane prepolymer 1 at room temperature for 1 hour, then heated to 60 ° C. and stirred for 2 hours to have an isocyanate group and terminal trimethoxysilyl. A polyoxyalkylene polymer A5 having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A5 having a trimethoxysilyl group by GPC, the peak top molecular weight was 11,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 2.0 per molecule.

(Synthesis Example 6)
As shown in Table 1, a polyoxypropylene diol having a number average molecular weight of 10,000 (trade name: Preminol 4010, manufactured by Asahi Glass Co., Ltd.) was added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. 100.00 g of 2,4-tolylene diisocyanate (trade name: Cosmonate T-80, manufactured by Mitsui Chemicals Co., Ltd.) 3.49 g of urethane pre-reacted at 90 ° C. for 3 hours with stirring and mixing in a nitrogen atmosphere. Polymer 2 was obtained.
A new flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was degassed under reduced pressure, then replaced with nitrogen gas, and 1.54 g of n-butylamine was added under a nitrogen stream. 4.04 g of roxymethyltrimethoxysilane (manufactured by Gelest) was added and stirred at room temperature for 24 hours to obtain a reaction product (silylating agent 2).

The obtained silylating agent 2 was reacted with the obtained urethane prepolymer 2 at room temperature for 1 hour, then heated to 60 ° C. and stirred for 2 hours to have an isocyanate group and terminal trimethoxysilyl. A polyoxyalkylene polymer A6 having a group was obtained.
The molecular weight of the obtained polyoxyalkylene polymer A6 having a trimethoxysilyl group at the terminal was measured by GPC. As a result, the peak top molecular weight was 11,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 2.0 per molecule.

In Table 1, the compounding quantity of each compounding substance is shown by g. The polyoxyalkylene polymers M1 to M4 are the polyoxyalkylene polymers M1 to M4 obtained in Synthesis Examples 1 to 4, respectively. Silylating agents 1 and 2 are silylating agents 1 and 2 obtained in Synthesis Examples 5 and 6, respectively. * 1 is as follows.
* 1) Polyoxypropylenediol: Trade name: Preminol 4010, manufactured by Asahi Glass Co., Ltd.

(Synthesis Example 7)
As shown in Table 2, a polyoxyalkylene polymer having a trimethoxysilyl group at the terminal obtained in Synthesis Example 1 in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser. 400 g of A1 and 200 g of polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal obtained in Synthesis Example 2 were added and heated to 80 ° C. In another container, 247 g of methyl methacrylate (trade name: Light Ester M, manufactured by Kyoeisha Co., Ltd.), 23 g of n-butyl acrylate, 49 g of stearyl methacrylate (trade name: Light Ester S, manufactured by Kyoeisha Co., Ltd.), 3-methacryloxy 45 g of propyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 23.77 g of 3-mercaptopropyltrimethoxysilane and 10.56 g of AIBN are mixed, and after stirring, filled in a dropping device over 3 hours. It was dripped. After completion of the dropping, the reaction was further continued for 3 hours to obtain an organic polymer A7 having a trimethoxysilyl group, which is a mixture of a polyoxyalkylene polymer, a polyoxyalkylene polymer, and a vinyl polymer.
As a result of measuring the molecular weight of the obtained organic polymer A7 having a trimethoxysilyl group by GPC, the peak top molecular weight was 4000 and the molecular weight distribution was 1.6. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 2.35 per molecule.

(Synthesis Example 8)
As shown in Table 2, 184 g of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was put into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, and heated to 70 ° C. did. In another container, 247 g of methyl methacrylate, 23 g of n-butyl acrylate, 56 g of lauryl methacrylate (trade name: Light Ester L, manufactured by Kyoeisha), 3-acryloxypropyltrimethoxysilane (trade name: KBM5103, Shin-Etsu Chemical Co., Ltd.) 58.64 g), 3-mercaptopropyltrimethoxysilane 26.21 g, and AIBN 15.73 g were mixed, stirred, filled into a dropping device, and dropped over 3 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a vinyl polymer A8 having a trimethoxysilyl group.
As a result of measuring the molecular weight of the obtained vinyl polymer A8 by GPC, the peak top molecular weight was 3000 and the molecular weight distribution was 1.6. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 2.00 per molecule.

(Synthesis Example 9)
As shown in Table 2, 152.8 g of ethyl acetate was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, and heated to 70 ° C. In a separate container, 247 g of methyl methacrylate, 23 g of n-butyl acrylate, 56 g of lauryl methacrylate, 13.1 g of 3-acryloxypropyltrimethoxysilane, 12.60 g of 3-mercaptopropyltrimethoxysilane, and 4.68 g of AIBN are mixed and stirred. Then, it was filled in a dropping device and dropped over 3 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain a vinyl polymer A9 having a trimethoxysilyl group.
As a result of measuring the molecular weight of the obtained vinyl polymer A9 by GPC, the peak top molecular weight was 6000 and the molecular weight distribution was 1.6. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 2.11 per molecule.

(Synthesis Example 10)
As shown in Table 2, in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, m-xylene 43.00 g, methyl methacrylate 80.00 g, 2-ethylhexyl methacrylate (Tokyo Chemical Industry Co., Ltd.) )) 20.00 g, acryloxymethyltrimethoxysilane (manufactured by Gelest) 20.00 g, and 0.10 g of zirconocene dichloride as a metal catalyst were charged, and the contents of the flask were brought to 80 ° C. while introducing nitrogen gas into the flask. Heated. Subsequently, 20.00 g of mercaptomethyltrimethoxysilane sufficiently substituted with nitrogen gas was added all at once to the flask with stirring. After adding 20.00 g of mercaptomethyltrimethoxysilane, heating and cooling were performed for 4 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. Further, 20.00 g of mercaptomethyltrimethoxysilane sufficiently substituted with nitrogen gas was added to the flask over 5 minutes with stirring. After the addition of 20.00 g of the total amount of mercaptomethyltrimethoxysilane, the reaction was carried out for 4 hours while further cooling and heating so that the temperature of the contents in the stirring flask could be maintained at 90 ° C. After a total of 8 hours and 5 minutes of reaction, the temperature of the reaction product was returned to room temperature, 20.00 g of a benzoquinone solution (95% THF solution) was added to the reaction product to stop the polymerization, and a vinyl system having a trimethoxysilyl group Polymer A10 was obtained.
As a result of measuring the molecular weight of the obtained vinyl polymer A10 by GPC, the peak top molecular weight was 4000, and the molecular weight distribution was 1.6. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 2.00 per molecule.

(Synthesis Example 11)
As shown in Table 2, 166 g of ethyl acetate was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, and heated to 70 ° C. In a separate container, 247 g of methyl methacrylate, 23 g of n-butyl acrylate, 56 g of lauryl methacrylate, 33.7 g of 3-acryloxypropyltrimethoxysilane, 4.31 g of 3-methacryloxypropyltrimethoxysilane, 16-mercaptopropyltrimethoxysilane 16 .91 g and Perocta O (manufactured by NOF Corporation) 11.13 g were mixed, stirred, filled into a dropping device, and dropped over 3 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a vinyl polymer A11 having a trimethoxysilyl group.
As a result of measuring the molecular weight of the obtained vinyl polymer A11 by GPC, the peak top molecular weight was 4200, and the molecular weight distribution was 1.6. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 3.03 per molecule.

In Table 2, the compounding amount of each compounding substance is indicated by g. The polyoxyalkylene polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, respectively.

(Synthesis Example 12)
As shown in Table 3, 10 g of propylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. ) 30 g, n-butyl acrylate 100 g, lauryl acrylate (Tokyo Chemical Industry Co., Ltd.) 49 g, 3-acryloxypropyltrimethoxysilane 11.62 g, synthesized 3- (trimethoxysilyl) propyl-2-bromopropio 5.21 g of Nate and 4.74 g of CuBr as a transition metal catalyst, N, N, N ′, N ″, N ″ -pentamethylenediethylenetriamine as a ligand (trade name: Kao Raiser No. 3, manufactured by Kao Corporation) ) 2.86 g The contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. After the reaction for 12 hours, the temperature of the reaction product is returned to room temperature, the atmosphere is put in, the polymerization is stopped, the reaction product is precipitated and purified with dehydrated methanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and vinyl having a trimethoxysilyl group. A polymer A12 was obtained.
The number average molecular weight of the obtained vinyl polymer A12 was 10,000, and Mw / Mn = 1.1. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 2.0 per molecule.

(Synthesis Example 13)
As shown in Table 3, in a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 100 g of ethyl acetate, 60 g of methyl methacrylate, 10 g of n-butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 10 g of lauryl methacrylate, 14.05 g of 3-methacryloxypropyltrimethoxysilane, 5 g of synthesized 2-cyanoprop-2-yldithiobenzoate and 1.86 g of AIBN were charged, and the contents of the flask were kept at 80 ° C. while introducing nitrogen gas into the flask. Heated. Heating and cooling were performed for 8 hours so that the temperature of the contents in the stirring flask could be maintained at 80 ° C. After the reaction, the temperature of the reaction product was returned to room temperature to obtain a vinyl polymer A13 having a trimethoxysilyl group.
The number average molecular weight of the obtained vinyl polymer A13 was 4000, and Mw / Mn = 1.1. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 2.0 per molecule.

(Synthesis Example 14)
As shown in Table 3, 188 g of ethyl acetate was put into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, and heated to 70 ° C. In a separate container, 264 g of methyl methacrylate, 24 g of n-butyl acrylate, 48 g of lauryl methacrylate, 40 g of 2-ethylhexyl methacrylate, 25.17 g of acryloxymethyltrimethoxysilane, 10.68 g of methacryloxymethyltrimethoxysilane (manufactured by Gelest), mercapto Methyltrimethoxysilane (manufactured by Gelest) (15.48 g) and AIBN (6.71 g) were mixed, stirred, charged into a dropping device, and dropped over 3 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain a vinyl polymer A14 having a trimethoxysilyl group.
As a result of measuring the molecular weight of the obtained vinyl polymer A14 by GPC, the peak top molecular weight was 4500, and the molecular weight distribution was 1.6. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 3.21 per molecule.

(Synthesis Example 15)
As shown in Table 3, 40.00 g of ethyl acetate, 70.00 g of methyl methacrylate, 2-ethylhexyl methacrylate (Tokyo Chemical Industry Co., Ltd.) were placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. )) 30.00 g, 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 12.00 g, and titanocene diclyde 0.10 g as a metal catalyst were charged in a flask with nitrogen gas The contents of the flask were heated to 80 ° C. while introducing. Next, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently purged with nitrogen gas was added into the flask all at once with stirring. After adding 4.30 g of 3-mercaptopropyltrimethoxysilane, heating and cooling were performed for 4 hours so that the temperature of the contents in the flask under stirring could be maintained at 80 ° C. Further, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently substituted with nitrogen gas was added to the flask over 5 minutes with stirring. After an additional amount of 4.30 g of 3-mercaptopropyltrimethoxysilane was added, the reaction was performed for 4 hours while further cooling and heating so that the temperature of the contents in the stirring flask could be maintained at 90 ° C. . After a total of 8 hours and 5 minutes of reaction, the temperature of the reaction product was returned to room temperature, 20.00 g of a benzoquinone solution (95% THF solution) was added to the reaction product to stop the polymerization, and a vinyl system having a trimethoxysilyl group Polymer A15 was obtained. The peak top molecular weight was 4000, and the molecular weight distribution was 2.4. The number of trimethoxysilyl groups contained by H ¹ -NMR measurement was 2.00 per molecule.

In Table 3, the compounding amount of each compounding substance is indicated by g.

(Synthesis Example 16)
As shown in Table 4, 3-aminopropyltrimethoxysilane (trade name: Z-6610, Toray Dow Corning, Ltd.) was added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser. 100 g of Silicone Co., Ltd., 276 g of 3-glycidoxypropyltrimethoxysilane (trade name: Z-6040, manufactured by Toray Dow Corning Silicone Co., Ltd.), and stirred at 50 ° C. for 72 hours to give a silane compound C1 was obtained. With respect to the obtained silane compound C1, the disappearance of the peak due to the epoxy group near 910 cm ⁻¹ was confirmed by FT-IR, and the peak of the secondary amine near 1140 cm ⁻¹ was confirmed. ²⁹ Si-NMR Furthermore, the appearance of a new peak was confirmed from -60 ppm to -70 ppm.

(Synthesis Example 17)
As shown in Table 4, in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, 44.62 g of 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane 100 g was added and stirred at 50 ° C. for 72 hours to obtain a silane compound C2. With respect to the obtained silane compound C2, disappearance of a peak due to an epoxy group near 910 cm ⁻¹ was confirmed by FT-IR, a secondary amine peak near 1140 cm ⁻¹ was confirmed, and ²⁹ Si-NMR Furthermore, the appearance of a new peak was confirmed from -60 ppm to -70 ppm.

(Synthesis Example 18)
As shown in Table 4, in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, 31.61 g of 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane 100 g was added and stirred at 50 ° C. for 72 hours to obtain a silane compound C3. For the obtained silane compound C3, the disappearance of the peak due to the amino group near 1410 cm ⁻¹ and 1120 cm ⁻¹ was confirmed by FT-IR, and the peak of the secondary amine near 1140 cm ⁻¹ was confirmed. ^{From 29} Si-NMR, it was confirmed that a new peak appeared from −60 ppm to −70 ppm.

(Comparative Synthesis Example 1)
As shown in Table 4, in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, 50.00 g of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 127.5 g of 3-glycidoxypropyltrimethoxysilane was added and stirred at 50 ° C. for 72 hours to obtain a silane compound X1. The obtained silane compound X1, ^{1410 cm} -1 in FT-IR, to confirm the disappearance of a peak attributable to the amino groups in the vicinity of 1,120 cm ^-1, to confirm the disappearance of the peak due to the epoxy group in the vicinity of 910 cm ^-1 .

In Table 4, the compounding amount of each compounding substance is indicated by g.

(Synthesis Example 19)
As shown in Table 5, 100 g of the silane compound C1 obtained in Synthesis Example 16 was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser, followed by Olgatrix TC-750. 63.1 g of [trade name, titanium diisopropoxy bis (ethyl acetoacetate) manufactured by Matsumoto Fine Chemical Co., Ltd.] was added and aged by heating and stirring at 70 ° C. for 144 hours to obtain a titanium catalyst B1. With respect to the obtained titanium catalyst B1, change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 20)
As shown in Table 5, 100 g of the silane compound C1 obtained in Synthesis Example 16 was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser, followed by Olgatrix TC-750. Was aged by heating and stirring at 70 ° C. for 144 hours to obtain a titanium catalyst B2. With respect to the obtained titanium catalyst B2, change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 21)
As shown in Table 5, 100 g of the silane compound C1 obtained in Synthesis Example 16 was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser, followed by Olgatrix TC-750. Was aged by heating and stirring at 80 ° C. for 144 hours to obtain a titanium catalyst B3. With respect to the obtained titanium catalyst B3, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 22)
A flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser was charged with 23.47 g of triethylamine, 10 g of titanium tetrachloride, and then 17.19 g of t-butyl alcohol. The mixture was stirred at room temperature for 2 hours, and the precipitate was filtered and purified by distillation to obtain titanium tetra-t-butoxide. 10 g of the obtained titanium tetra-t-butoxide and 7.65 g of ethyl acetoacetate (manufactured by Nippon Gosei Co., Ltd.) were added and stirred at room temperature for 2 hours, and then stirred at 70 ° C. for 2 hours. After completion of the reaction, unreacted substances and the like were removed under reduced pressure to obtain a titanium catalyst D1.
Subsequently, as shown in Table 5, 19.85 g of the silane compound C1 obtained in Synthesis Example 16 was added to 14.12 g of the obtained titanium catalyst D1, and the mixture was aged by heating and stirring at 50 ° C. for 72 hours. A titanium catalyst B4 was obtained. With respect to the obtained titanium catalyst B4, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 23)
After adding 50 g of titanium tetraisopropoxide (trade name: Olgatyx TA-10, manufactured by Matsumoto Fine Chemical Co., Ltd.) and 40.85 g of methyl acetoacetate (manufactured by Nihon Gosei Co., Ltd.), the mixture was stirred at room temperature for 2 hours. The mixture was stirred at 70 ° C. for 2 hours. After completion of the reaction, unreacted substances and the like were removed under reduced pressure to obtain a titanium catalyst D2.
Subsequently, as shown in Table 5, the silane compound C1 obtained in Synthesis Example 16 was placed in 69.71 g of the obtained titanium catalyst D2, and aged by heating and stirring at 60 ° C. for 168 hours. A titanium catalyst B5 was obtained. With respect to the obtained titanium catalyst B5, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 24)
50 g of titanium tetraisopropoxide and 50.72 g of isopropyl acetoacetate (manufactured by Nihon Gosei Co., Ltd.) were added and stirred at room temperature for 2 hours, and then stirred at 70 ° C. for 2 hours. After completion of the reaction, unreacted substances and the like were removed under reduced pressure to obtain a titanium catalyst D3.
Subsequently, as shown in Table 5, the silane compound C1 obtained in Synthesis Example 16 was added to 79.58 g of the obtained titanium catalyst D3 and aged by heating and stirring at 70 ° C. for 72 hours. Catalyst B6 was obtained. With respect to the obtained titanium catalyst B6, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 25)
As shown in Table 5, 100 g of the silane compound C1 obtained in Synthesis Example 16 was added to a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, a dropping device, and a reflux condenser, and (E) vinyltrimethoxysilane ( 3.8 g of trade name: KBM1003, manufactured by Shin-Etsu Chemical Co., Ltd.) and 78.88 g of ORGATICS TC-750 were added, and the mixture was aged by heating and stirring at 70 ° C. for 144 hours to obtain a titanium catalyst B7. With respect to the obtained titanium catalyst B7, the change in peak was confirmed by ²⁹ Si-NMR.

In Table 5, the compounding amount of each compounding substance is indicated by g. The silane compound C1 is the silane compound C1 obtained in Synthesis Example 16, and ORGATICS TC-750 is a trade name, titanium diisopropoxybis (ethyl acetoacetate) manufactured by Matsumoto Fine Chemical Co., Ltd.

(Synthesis Example 26)
As shown in Table 6, 126.93 g of the silane compound C2 obtained in Synthesis Example 17 was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser, followed by Olgax TC. 100 g of −750 was added and aged by heating and stirring at 60 ° C. for 168 hours to obtain a titanium catalyst B8. With respect to the obtained titanium catalyst B8, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 27)
As shown in Table 6, 156.37 g of the silane compound C3 obtained in Synthesis Example 18 was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser, followed by Olgatics TC. 100 g of −750 was added and aged by heating and stirring at 70 ° C. for 168 hours to obtain a titanium catalyst B9. With respect to the obtained titanium catalyst B9, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 28)
As shown in Table 6, 184.28 g of the silane compound C3 obtained in Synthesis Example 18 was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser, followed by Olgax TC. 100 g of −750 was added and aged by heating and stirring at 70 ° C. for 168 hours to obtain a titanium catalyst B10. With respect to the obtained titanium catalyst B10, the change in peak was confirmed by ²⁹ Si-NMR.

In Table 6, the compounding amount of each compounding substance is indicated by g. Silane compounds C2 and C3 are the silane compounds C2 and C3 obtained in Synthesis Examples 17 and 18, respectively, and ORGATICS TC-750 is a trade name, titanium diisopropoxy bis (ethyl acetoacetate) manufactured by Matsumoto Fine Chemical Co. is there.

(Synthesis Example 29)
As shown in Table 7, 10 g of the silane compound C1 obtained in Synthesis Example 16 and 40 g of ORGATIC TC-750 were placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser. The mixture was aged by heating and stirring at 70 ° C. for 144 hours to obtain a titanium catalyst B11. With respect to the obtained titanium catalyst B11, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 30)
As shown in Table 7, 60 g of the silane compound C1 obtained in Synthesis Example 16 and 40 g of ORGATIC TC-750 were placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser. After maturing by heating and stirring at 70 ° C. for 144 hours, 100 g of normal paraffin (trade name: N-11, manufactured by JX Nippon Oil & Energy Corporation) is added and stirring is performed at 70 ° C. for 144 hours. To obtain a titanium catalyst B12. With respect to the obtained titanium catalyst B12, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 31)
As shown in Table 7, a titanium catalyst B13 was obtained by the same method as in Synthesis Example 30 except that the blending ratio of the blended materials was changed. With respect to the obtained titanium catalyst B13, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 32)
As shown in Table 7, 10 g of the silane compound C1 obtained in Synthesis Example 16 was added to a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, a dropping device, and a reflux condenser, and (E) 50 g of methoxysilane (trade name: KBM103, manufactured by Shin-Etsu Chemical Co., Ltd.), 40 g of Organics TC-750 and 100 g of normal paraffin were added, and the mixture was aged by heating and stirring at 70 ° C. for 144 hours, and the titanium catalyst B14 Got. With respect to the obtained titanium catalyst B14, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 33)
As shown in Table 7, a titanium catalyst B15 was obtained in the same manner as in Synthesis Example 32 except that the blending ratio of the blended materials was changed. With respect to the obtained titanium catalyst B15, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Examples 34 to 37)
As shown in Table 7, titanium catalysts B16 to B19 were obtained in the same manner as in Synthesis Example 32 except that (E) the silane compound was changed. With respect to the obtained titanium catalysts B16 to B19, the change in peak was confirmed by ²⁹ Si-NMR.

In Table 7, the compounding quantity of each compounding substance is shown by g. The silane compound C1 is the silane compound C1 obtained in Synthesis Example 16, and details of other compounding substances are as follows.
ORGATICS TC-750: trade name, titanium diisopropoxybis (ethyl acetoacetate) manufactured by Matsumoto Fine Chemical Co., Ltd.
Phenyltrimethoxysilane: Trade name: KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.
Vinyltrimethoxysilane: Trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.
Methyltrimethoxysilane: Trade name: KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.
3-Glycidoxypropyltrimethoxysilane: Trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.
Decyltrimethoxysilane: Trade name: KBM-3013C, manufactured by Shin-Etsu Chemical Co., Ltd.
Normal paraffin: Trade name: N-11, manufactured by JX Nippon Oil & Energy Corporation.

(Synthesis Example 38)
As shown in Table 8, 10 g of the silane compound C1 obtained in Synthesis Example 16 was added to a flask equipped with a stirrer, a nitrogen gas introduction tube, a thermometer, a dropping device, and a reflux condenser, and (E) 50 g of methoxysilane (trade name: KBM103, manufactured by Shin-Etsu Chemical Co., Ltd.) is added, followed by 40 g of ORGATICS TC-750, aging by heating and stirring at 70 ° C. for 144 hours, and then 100 g of normal paraffin. The mixture was aged by heating and stirring at 70 ° C. for 144 hours to obtain a titanium catalyst B20. With respect to the obtained titanium catalyst B20, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 39)
As shown in Table 8, 10 g of the silane compound C1 obtained in Synthesis Example 16 and 40 g of ORGATIC TC-750 were placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser. The mixture was aged by heating and stirring at 70 ° C. for 144 hours, and (E) 50 g of phenyltrimethoxysilane (trade name: KBM103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane compound and 100 g of normal paraffin were added. The mixture was aged by heating and stirring at 144 ° C. for 144 hours to obtain a titanium catalyst B21. With respect to the obtained titanium catalyst B21, the change in peak was confirmed by ²⁹ Si-NMR.

(Synthesis Example 40)
As shown in Table 8, a titanium catalyst B22 was obtained in the same manner as in Synthesis Example 37 except that the blending ratio of the blended materials was changed. With respect to the obtained titanium catalyst B22, the change in peak was confirmed by ²⁹ Si-NMR.

In Table 8, the compounding quantity of each compounding substance is shown by g. The silane compound C1 is the silane compound C1 obtained in Synthesis Example 16, and details of other compounding substances are as follows.
ORGATICS TC-750: trade name, titanium diisopropoxybis (ethyl acetoacetate) manufactured by Matsumoto Fine Chemical Co., Ltd.
Phenyltrimethoxysilane: Trade name: KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.
Vinyltrimethoxysilane: Trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.
Normal paraffin: Trade name: N-11, manufactured by JX Nippon Oil & Energy Corporation.

Example 1
As shown in Table 9, 100 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 19 were placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 10 g of the titanium catalyst B1 obtained in the above was added and degassed and stirred at 25 ° C. to obtain a curable composition. Table 10 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 2)
As shown in Table 9, 50 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 20 g of the polyoxyalkylene polymer A4 obtained in the above and 30 g of the vinyl polymer A10 obtained in Synthesis Example 10 and 10 g of the titanium catalyst B1 obtained in Synthesis Example 19 were degassed and stirred at 25 ° C. to obtain a curable composition. I got a thing. Table 10 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 3)
As shown in Table 9, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 3 were placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 20 g of the polyoxyalkylene polymer A3 obtained in the above and 30 g of the vinyl polymer A8 obtained in Synthesis Example 8 and 10 g of the titanium catalyst B1 obtained in Synthesis Example 19 were degassed and stirred at 25 ° C. to obtain a curable composition. I got a thing. Table 10 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

Example 4
As shown in Table 9, 90 g of the polyoxyalkylene polymer A5 obtained in Synthesis Example 5 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 10 g of the vinyl polymer A9 obtained in the above and 10 g of the titanium catalyst B1 obtained in Synthesis Example 19 were added and degassed and stirred at 25 ° C. to obtain a curable composition. Table 10 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

In Table 9, the compounding amount of each compounding substance is indicated by g. Polymers A1 to A5 are respectively polyoxyalkylene polymers A1 to A5 obtained in Synthesis Examples 1 to 5, and polymers A8 to A10 are vinyl polymers A8 to A10 obtained in Synthesis Examples 8 to 10, respectively. Yes, the titanium catalyst B1 is the titanium catalyst B1 obtained in Synthesis Example 19.

(Example 5)
As shown in Table 11, 100 g of the polyoxyalkylene polymer A6 obtained in Synthesis Example 6 and Synthesis Example 19 were placed in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube, and a water-cooled condenser. 10 g of the titanium catalyst B1 obtained in the above was added and degassed and stirred at 25 ° C. to obtain a curable composition. Table 12 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition. In addition, the initial viscosity in the storage stability test and the viscosity after storage were confirmed visually by tilting the glass container of the curable composition in the sealed glass container.

(Example 6)
As shown in Table 11, 60 g of the polyoxyalkylene polymer A6 obtained in Synthesis Example 6 and Synthesis Example 14 were placed in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube, and a water-cooled condenser. 40 g of the vinyl polymer A14 obtained in the above and 10 g of the titanium catalyst B1 obtained in Synthesis Example 19 were added and degassed and stirred at 25 ° C. to obtain a curable composition. The curable composition was tested in the same manner as in Example 5. The results are shown in Table 12.

In Table 11, the blending amount of each compounding substance is indicated by g. The polymer A6 is the polyoxyalkylene polymer A6 obtained in Synthesis Example 6, the polymer A14 is the vinyl polymer A14 obtained in Synthesis Example 14, and the titanium catalyst B1 is the titanium catalyst obtained in Synthesis Example 19. B1.

(Example 7)
As shown in Table 13, 100 g of vinyl polymer A12 obtained in Synthesis Example 12 was obtained in Synthesis Example 19 in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser. 10g of the titanium catalyst B1 was added and degassed and stirred at 25 ° C to obtain a curable composition. Table 14 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 8)
As shown in Table 13, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 4 were placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 10 g of the polyoxyalkylene polymer A4 obtained in the above and 40 g of the vinyl polymer A13 obtained in Synthesis Example 13 and 10 g of the titanium catalyst B1 obtained in Synthesis Example 19 were degassed and stirred at 25 ° C. to obtain a curable composition. I got a thing. Table 14 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

Example 9
As shown in Table 13, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above, 40 g of the polyoxyalkylene polymer A4 obtained in Synthesis Example 4, 30 g of the vinyl polymer A11 obtained in Synthesis Example 11, and titanium obtained in Synthesis Example 19. 10 g of the catalyst B1 was added and deaerated and stirred at 25 ° C. to obtain a curable composition. Table 14 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 10)
As shown in Table 13, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 70 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized. 10 g of the vinyl polymer A9 obtained in the above and 20 g of the vinyl polymer A13 obtained in Synthesis Example 13 and 10 g of the titanium catalyst B1 obtained in Synthesis Example 19 were degassed and stirred at 25 ° C. to obtain a curable composition. Obtained. Table 14 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 11)
As shown in Table 13, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above and 40 g of the vinyl polymer A10 obtained in Synthesis Example 10 and 16.5 g of the titanium catalyst B2 obtained in Synthesis Example 20 were deaerated and stirred at 25 ° C. and cured. Sex composition was obtained. Table 14 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 12)
As shown in Table 13, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above and 40 g of the vinyl polymer A10 obtained in Synthesis Example 10 and 7 g of the titanium catalyst B3 obtained in Synthesis Example 21 were degassed and stirred at 25 ° C. to obtain a curable composition. I got a thing. Table 14 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

In Table 13, the compounding amount of each compounding substance is indicated by g. Polymers A1 to A4 are respectively polyoxyalkylene polymers A1 to A4 obtained in Synthesis Examples 1 to 4, and Polymers A9 to A13 are vinyl polymers A9 to A13 obtained in Synthesis Examples 9 to 13, respectively. The titanium catalysts B1 to B3 are the titanium catalysts B1 to B3 obtained in Synthesis Examples 19 to 21, respectively.

(Example 13)
As shown in Table 15, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above and 40 g of the vinyl polymer A8 obtained in Synthesis Example 8 and 11 g of the titanium catalyst B4 obtained in Synthesis Example 22 were degassed and stirred at 25 ° C. I got a thing. Table 16 shows the results of the curability test, storage stability test, surface curability test, and adhesion test of the curable composition.

(Example 14)
As shown in Table 15, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above, 40 g of the vinyl polymer A8 obtained in Synthesis Example 8, and 9 g of the titanium catalyst B5 obtained in Synthesis Example 23 were degassed and stirred at 25 ° C. to obtain a curable composition. I got a thing. Table 16 shows the results of the curability test, storage stability test, surface curability test, and adhesion test of the curable composition.

(Example 15)
As shown in Table 15, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above, 40 g of the vinyl polymer A8 obtained in Synthesis Example 8, and 11 g of the titanium catalyst B6 obtained in Synthesis Example 24 were degassed and stirred at 25 ° C. to obtain a curable composition. I got a thing. Table 16 shows the results of the curability test, storage stability test, surface curability test, and adhesion test of the curable composition.

(Example 16)
As shown in Table 15, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above and 40 g of the vinyl polymer A8 obtained in Synthesis Example 8 and 9 g of the titanium catalyst B7 obtained in Synthesis Example 25 were degassed and stirred at 25 ° C. to obtain a curable composition. I got a thing. Table 16 shows the results of the curability test, storage stability test, surface curability test, and adhesion test of the curable composition.

(Example 17)
As shown in Table 15, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above and 40 g of the vinyl polymer A8 obtained in Synthesis Example 8 and 5 g of the titanium catalyst B1 obtained in Synthesis Example 19 were degassed and stirred at 25 ° C. to obtain a curable composition. I got a thing. Table 16 shows the results of the curability test, storage stability test, surface curability test, and adhesion test of the curable composition.

(Example 18)
As shown in Table 15, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above and 40 g of the vinyl polymer A8 obtained in Synthesis Example 8 and 20 g of the titanium catalyst B1 obtained in Synthesis Example 19 were degassed and stirred at 25 ° C. to obtain a curable composition. I got a thing. Table 16 shows the results of the curability test, storage stability test, surface curability test, and adhesion test of the curable composition.

In Table 15, the compounding amount of each compounding substance is indicated by g. Polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, respectively. Polymer A8 is the vinyl polymer A8 obtained in Synthesis Example 8, and titanium catalysts B1 and B4. To B7 are titanium catalysts B1 and B4 to B7 obtained in Synthesis Examples 19 and 22 to 25, respectively.

(Example 19)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, 100 g of the polymer A7 obtained in Synthesis Example 7 and 5 g of QS-20, Nocrack 1 g of CD and 0.5 g of TBSTA were added, heated (100 ° C.), degassed and stirred for 1 hour, returned to room temperature (25 ° C.), 5 g of triethyl citrate, and the titanium catalyst B1 obtained in Synthesis Example 19 10 g was added and deaerated and stirred at 25 ° C. to obtain a curable composition. Table 18 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 20)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser, 100 g of the polymer A7 obtained in Synthesis Example 7, 5 g of RY200S, and Nocrack CD Add 1 g, heat (100 ° C.), degas and stir for 1 hour, return to room temperature (25 ° C.), add 5 g of triethyl citrate and 10 g of titanium catalyst B1 obtained in Synthesis Example 19, and degas at 25 ° C. Air-stirring was performed to obtain a curable composition. Table 18 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 21)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, 100 g of polymer A7 obtained in Synthesis Example 7 and 2 g of RY200S, Ryton A- 5 (50 g), LA72 (1 g), heated (100 ° C.), degassed and stirred for 1 hour, returned to room temperature (25 ° C.), 5 g of triethyl citrate and 10 g of titanium catalyst B1 obtained in Synthesis Example 19 were added. Further, the mixture was deaerated and stirred at 25 ° C. to obtain a curable composition. Table 18 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 22)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 100 g of the polymer A7 obtained in Synthesis Example 7 and 50 g of MC coated P-1 were added. 1 g of Disparon # 6500 and 1 g of Nocrack CD were added, heated (100 ° C.), degassed and stirred for 1 hour, returned to room temperature (25 ° C.), 5 g of acetyltriethyl citrate, titanium obtained in Synthesis Example 19 10 g of the catalyst B1 was added, and further deaerated and stirred at 25 ° C. to obtain a curable composition. Table 18 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 23)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 100 g of the polymer A7 obtained in Synthesis Example 7 and 50 g of MC coated P-1 were added. 2 g of Disparon # 6500 and 1 g of Nocrack CD were added, heated (100 ° C.), degassed and stirred for 1 hour, returned to room temperature (25 ° C.), 5 g of acetyltributyl citrate, titanium obtained in Synthesis Example 19 10 g of the catalyst B1 was added, and further deaerated and stirred at 25 ° C. to obtain a curable composition. Table 18 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 24)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 100 g of polymer A7 obtained in Synthesis Example 7 and 30 g of Carlex 300, Almo 250 g of Lix B316 and 2 g of Nocrack CD were added, heated (100 ° C.), degassed and stirred for 1 hour, returned to room temperature (25 ° C.), 25 g of acetyltributyl citrate, titanium catalyst B1 obtained in Synthesis Example 19 10 g and 2 g of Olgatics TC750 were added, and the mixture was further deaerated and stirred at 25 ° C. to obtain a curable composition. Table 18 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 25)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 100 g of the polymer A7 obtained in Synthesis Example 7 and 40 g of MC coated P-1 were added. , 25 g of Carlex 300, 1 g of Nocrack CD, heated (100 ° C.), degassed and stirred for 1 hour, returned to room temperature (25 ° C.), 8 g of triethyl citrate, the titanium catalyst obtained in Synthesis Example 19 10 g of B1 and 1 g of ORGATICS TC750 were added and further deaerated and stirred at 25 ° C. to obtain a curable composition. Table 18 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

In Table 17, the compounding quantity of each compounding substance is shown by g. The polymer A7 is the organic polymer A7 obtained in Synthesis Example 7, and the titanium catalyst B1 is the titanium catalyst B1 obtained in Synthesis Example 19. Details of other compounding substances are as follows.
QS-20: trade name, manufactured by Tokuyama Corporation, primary dry particle size of 5 to 50 μm, surface-untreated hydrophilic dry silica.
RY200S: trade name manufactured by Nippon Aerosil Co., Ltd., hydrophobic silica, specific surface area 80 ± 15 m ² / g by BET method.
Ryton A-5: trade name manufactured by Shiroishi Kogyo Co., Ltd., ground calcium carbonate, surface fatty acid treatment.
MC coat P-1: Trade name manufactured by Shiroishi Kogyo Co., Ltd .: colloidal calcium carbonate, surface paraffin wax treatment.
Carlex 300: manufactured by Maruo Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.05 μm.
Armorix B316: trade name, aluminum hydroxide, average particle diameter of 18 μm, manufactured by Armorix Co., Ltd.
Disparon # 6500: trade name, amide wax, manufactured by Enomoto Kasei Co., Ltd.
NOCRACK CD: trade name, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, manufactured by Ouchi Shinko Co., Ltd.
LA72: Adeka Co., Ltd. trade name, hindered amine light stabilizer.
TBSTA: Tri-n-butoxytitanium monostearate manufactured by Nihon Kenta Co., Ltd.
Triethyl citrate: manufactured by Tokyo Chemical Industry Co., Ltd.
Acetyltriethyl citrate: manufactured by Tokyo Chemical Industry Co., Ltd.
Acetyltributyl citrate: manufactured by Tokyo Chemical Industry Co., Ltd.
ORGATICS TC-750: trade name, titanium diisopropoxybis (ethyl acetoacetate) manufactured by Matsumoto Fine Chemical Co., Ltd.

(Example 26)
As shown in Table 19, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser, 100 g of the polymer A7 obtained in Synthesis Example 7 was placed, heated (100 ° C.), The mixture was degassed and stirred for 1 hour, returned to room temperature (25 ° C.), 10 g of the titanium catalyst B8 obtained in Synthesis Example 26 was added, and degassed and stirred at 25 ° C. to obtain a curable composition. Table 20 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 27)
As shown in Table 19, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser, 100 g of the polymer A7 obtained in Synthesis Example 7 was placed, heated (100 ° C.), After deaeration and stirring for 1 hour, the temperature was returned to room temperature (25 ° C.), 9 g of titanium catalyst B9 obtained in Synthesis Example 27 was added, and the mixture was further deaerated and stirred at 25 ° C. to obtain a curable composition. Table 20 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Example 28)
As shown in Table 19, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser, 100 g of the polymer A7 obtained in Synthesis Example 7 was placed, heated (100 ° C.), The mixture was degassed and stirred for 1 hour, returned to room temperature (25 ° C.), 9 g of the titanium catalyst B10 obtained in Synthesis Example 28 was added, and degassed and stirred at 25 ° C. to obtain a curable composition. Table 20 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

In Table 19, the compounding amount of each compounding substance is indicated by g. The polymer A7 is the organic polymer A7 obtained in Synthesis Example 7, and the titanium catalysts B8 to B10 are the titanium catalysts B8 to B10 obtained in Synthesis Examples 26 to 28, respectively.

(Example 29)
As shown in Table 21, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized. 20 g of the polyoxyalkylene polymer A2 obtained in the above and 35 g of vinyl polymer A15 obtained in Synthesis Example 15 in terms of solid content were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomer and ethyl acetate contained in the vinyl polymer A15, and cooled to room temperature. Thereafter, 5 g of the titanium catalyst B11 obtained in Synthesis Example 29 was added and degassed and stirred at 25 ° C. to obtain a curable composition. Table 22 shows the results of the storage stability test, the curability test, and the surface curability test of the curable composition.

(Example 30)
As shown in Table 21, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized. 20 g of the polyoxyalkylene polymer A2 obtained in the above and 35 g of vinyl polymer A15 obtained in Synthesis Example 15 in terms of solid content were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomer and ethyl acetate contained in the vinyl polymer A15, and cooled to room temperature. Thereafter, 5 g of the titanium catalyst B11 obtained in Synthesis Example 29 and 5 g of phenyltrimethoxysilane were added and stirred at 25 ° C. to obtain a curable composition. Table 22 shows the results of the storage stability test, the curability test, and the surface curability test of the curable composition.

(Examples 31 to 33)
As shown in Table 21, a curable composition was prepared in the same manner as in Example 30 except that (E) the silane compound was changed. Table 22 shows the results of the storage stability test, the curability test, and the surface curability test of the curable composition.

In Table 21, the compounding quantity of each compounding substance is shown by g, and the polymer A15 is shown by the compounding quantity of solid content conversion. Polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, respectively. Polymer A15 is the vinyl polymer A15 obtained in Synthesis Example 15, and silane compound C1 is synthesized. It is the silane compound C1 obtained in Example 16, the titanium catalyst B11 is the titanium catalyst B11 obtained in Synthesis Example 29, and details of other compounding materials are as follows.
ORGATICS TC-750: trade name, titanium diisopropoxybis (ethyl acetoacetate) manufactured by Matsumoto Fine Chemical Co., Ltd.
Phenyltrimethoxysilane: Trade name: KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.
Vinyltrimethoxysilane: Trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.
Decyltrimethoxysilane: Trade name: KBM-3013C, manufactured by Shin-Etsu Chemical Co., Ltd.
Tetraethoxysilane: Trade name: KBE-04, manufactured by Shin-Etsu Chemical Co., Ltd.

(Example 34)
As shown in Table 23, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 2 were placed in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube, and a water-cooled condenser. 52 g of the polyoxyalkylene polymer A2 obtained in the above and 21 g of the vinyl polymer A15 obtained in Synthesis Example 15 were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomer and ethyl acetate contained in the vinyl polymer A15, and cooled to room temperature. Thereafter, 40 g of Whiten SB (manufactured by Shiraishi Calcium Co., Ltd., heavy calcium carbonate, average particle size 2.2 μm), Carlex 300 (manufactured by Maruo Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle size (electronic) (Microscope) 0.05 μm) was added, heated (100 ° C.), degassed and stirred for 1 hour, returned to room temperature, 20 g of titanium catalyst B12 obtained in Synthesis Example 30 was charged, degassed and stirred at 25 ° C., A curable composition was obtained. Tables 24 and 25 show the results of the storage stability test, curability test, surface curability test, and adhesion test of the curable composition.

(Examples 35 to 41)
As shown in Table 23, a curable composition was prepared in the same manner as in Example 34 except that the titanium catalysts B13 to B19 were used instead of the titanium catalyst B12. Tables 24 and 25 show the results of the storage stability test, curability test, surface curability test, and adhesion test of the curable composition.

In Table 23, the compounding quantity of each compounding substance is shown by g, and polymer A15 is shown by the compounding quantity of solid content conversion. The polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Examples 1 and 2, respectively. The polymer A15 is the vinyl polymer A15 obtained in Synthesis Example 15, and the titanium catalysts B12 to B19. Are titanium catalysts B12 to B19 obtained in Synthesis Examples 30 to 37, and details of other compounding materials are as follows.
Whiteon SB: Shiraishi Calcium Co., Ltd., heavy calcium carbonate, average particle size 2.2 μm.
Carlex 300: manufactured by Maruo Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.05 μm.
Normal paraffin: Trade name: N-11, manufactured by JX Nippon Oil & Energy Corporation.

(Example 42)
As shown in Table 26, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 52 g of the polyoxyalkylene polymer A2 obtained in the above and 21 g of the vinyl polymer A15 obtained in Synthesis Example 15 were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomer and ethyl acetate contained in the vinyl polymer A15, and cooled to room temperature. Thereafter, 40 g of whiten SB as a filler, 20 g of Carlex 300 as a surface-treated calcium carbonate, and 1 g of NOCRACK CD as an anti-aging agent were added, heated (100 ° C.), degassed, and stirred for 1 hour, and room temperature (25 C.), 10 g of the titanium catalyst B21 obtained in Synthesis Example 39 was added, and the mixture was further deaerated and stirred to obtain a curable composition. Table 27 shows the results of the curability test, the storage stability test, and the surface curability test of the curable composition.

(Example 43)
As shown in Table 26, a curable composition was prepared in the same manner as in Example 42 except that the titanium catalyst B20 was used instead of the titanium catalyst B21. Table 27 shows the results of the curability test, the storage stability test, and the surface curability test of the curable composition.

(Example 44)
As shown in Table 26, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was synthesized in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 52 g of the polyoxyalkylene polymer A2 obtained in the above and 21 g of the vinyl polymer A15 obtained in Synthesis Example 15 were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomer and ethyl acetate contained in the vinyl polymer A15, and cooled to room temperature. Thereafter, 150 g of Almorix B316 as aluminum hydroxide and 5 g of NOCRACK CD as anti-aging agent were added, heated (100 ° C.), degassed and stirred for 1 hour, returned to room temperature (25 ° C.), and ISOPAR M as a diluent. 20 g, 2.5 g of vinyltrimethoxysilane as component (E) and 9.2 g of the titanium catalyst B22 obtained in Synthesis Example 40 were added and further deaerated and stirred to obtain a curable composition. Table 27 shows the results of the curability test, storage stability test and surface curability test of the curable composition, and Table 28 shows the results of the adhesion test.

In Table 26, the compounding quantity of each compounding substance is shown by g, and polymer A15 is shown by the compounding quantity of solid content conversion. The polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Examples 1 and 2, respectively. The polymer A15 is the vinyl polymer A15 obtained in Synthesis Example 15, and the titanium catalysts B20 to B22. Are titanium catalysts B20 to B22 obtained in Synthesis Examples 38 to 40, respectively, and details of other compounding materials are as follows.
Vinyltrimethoxysilane: Trade name: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.
Whiteon SB: trade name, heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd., average particle size 2.2 μm.
Carlex 300: trade name manufactured by Maruo Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.05 μm.
Armorix B316: trade name, aluminum hydroxide, average particle diameter of 18 μm, manufactured by Armorix Co., Ltd.
Isopar M: trade name, isoparaffin, manufactured by ExxonMobil Co., Ltd.
NOCRACK CD: trade name, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, manufactured by Ouchi Shinko Co., Ltd.

(Example 45)
As shown in Table 29, 100 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was used as a filler in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. Fuselex (registered trademark) E-2 [made by Tatsumori Co., Ltd., amorphous silica with an average particle diameter of 6 μm] 40 g was added, mixed at 100 ° C. and 10 mmHg for 1 hour, cooled to 20 ° C., and synthesis example 21.2 g of the titanium catalyst B15 obtained in No. 33 was added and vacuum mixed for 10 minutes to obtain a curable composition.
Table 30 shows the results of the storage stability test, the curability test, the surface curability test, the adhesion test, and the transparency test of the curable composition.

(Example 46)
As shown in Table 29, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 2 were placed in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging tube and a water-cooled condenser. 52 g of the polyoxyalkylene polymer A2 obtained in the above and 21 g of the vinyl polymer A15 obtained in Synthesis Example 15 were mixed. The mixture was heated (120 ° C.) and degassed under reduced pressure to remove residual monomer and ethyl acetate contained in the vinyl polymer A15, and cooled to room temperature. Thereafter, 20 g of MR13G (manufactured by Soken Chemical Co., Ltd., polymer powder powder, polymer powder having an average particle size of about 1 μm) as a filler, and FTR8100 (manufactured by Mitsui Oil Co., Ltd., C5) as a refractive index adjuster. And C9 copolymer petroleum resin) were mixed at 100 ° C. and 10 mmHg for 1 hour, cooled to 20 ° C., and 21.2 g of the titanium catalyst B15 obtained in Synthesis Example 33 was added and vacuum mixed for 10 minutes. Thus, a curable composition was obtained.

In addition, the compounding quantity of FTR8100 is determined by the following method. First, FTR8100 serving as a refractive index adjusting agent is heated and melted to the component (A) at an appropriate ratio, and the refractive index is measured with an Abbe refractometer at 20 ° C. An XY plot of FTR8100 compounding ratio and refractive index is taken. The FTR8100 blending amount that matches the refractive index of the powder serving as the main filler is the blending amount.

Table 30 shows the results of the storage stability test, curability test, surface curability test, adhesion test and transparency test of the curable composition.

(Example 47)
As shown in Table 29, a curable composition was prepared in the same manner as in Example 46 except that the compounding substances were changed. Table 30 shows the results of the storage stability test, the curability test, the surface curability test, the adhesion test, and the transparency test of the curable composition.

In Table 29, the compounding quantity of each compounding substance is shown by g, and polymer A15 is shown by the compounding quantity of solid content conversion. Polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, respectively, Polymer A15 is the vinyl polymer A15 obtained in Synthesis Example 15, and titanium catalyst B15 is synthesized. The details of the titanium compound B15 obtained in Example 33 and other compounding materials are as follows.
MR13G: trade name manufactured by Soken Chemical Co., Ltd., methacrylic acid ester polymer powder, average particle size of about 1 μm.
Fuselex (registered trademark) E-2: trade name, manufactured by Tatsumori Co., Ltd., amorphous silica, average particle size (50% weight average when measuring particle size distribution by laser method): 6 μm.
FTR8100: trade name of Mitsui Oil Co., Ltd., C5 and C9 copolymer petroleum resin.

(Comparative Example 1)
As shown in Table 31, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, 100 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Olgax TC 4g of -750 was added and degassed and stirred at 25 ° C to obtain a curable composition. Table 32 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Comparative Example 2)
As shown in Table 31, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 2 were placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above, 40 g of the vinyl polymer A8 obtained in Synthesis Example 8, 3 g of 3-glycidoxypropyltrimethoxysilane, and 4 g of Orgatyx TC-750 were added at 25 ° C. The mixture was deaerated and stirred to obtain a curable composition. Table 32 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Comparative Example 3)
As shown in Table 31, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 2 were placed in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser. 10 g of the polyoxyalkylene polymer A2 obtained in the above and 40 g of the vinyl polymer A8 obtained in Synthesis Example 8 and 5 g of QS-20 were heated and degassed and stirred at 100 ° C., and returned to room temperature (25 ° C.). Then, 3 g of 3-glycidoxypropyltrimethoxysilane and 4 g of Orgatyx TC-750 were added and degassed and stirred at 25 ° C. to obtain a curable composition. Table 32 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Comparative Example 4)
As shown in Table 31, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was used in Synthesis Example 2. 10 g of the obtained polyoxyalkylene polymer A2 and 40 g of the vinyl polymer A8 obtained in Synthesis Example 8 and 50 g of Ryton A-5 were added, and the mixture was heated and deaerated and stirred at 100 ° C. The mixture was returned to room temperature (25 ° C.), 6 g of the silane compound C1 obtained in Synthesis Example 16 and 4 g of ORGATICS TC-750 were put in, and degassed and stirred at 25 ° C. to obtain a curable composition. Table 32 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

(Comparative Example 5)
As shown in Table 31, in a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube, and water-cooled condenser, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 was used in Synthesis Example 2. 10 g of the obtained polyoxyalkylene polymer A2 and 40 g of the vinyl polymer A8 obtained in Synthesis Example 8 and 50 g of Ryton A-5 were added, and the mixture was heated and deaerated and stirred at 100 ° C. The mixture was returned to room temperature (25 ° C.), 6 g of the silane compound X1 obtained in Comparative Synthesis Example 1 and 4 g of ORGATIC TC-750 were added, and degassed and stirred at 25 ° C. to obtain a curable composition. Table 32 shows the results of the curability test, the storage stability test, the surface curability test, and the adhesion test of the curable composition.

In Table 31, the compounding amount of each compounding substance is indicated by g. Polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Examples 1 and 2, respectively, and the polymer A8 is the vinyl polymer A8 obtained in Synthesis Example 8, and the silane compounds C1 and X1 Are the silane compounds C1 and X1 obtained in Synthesis Example 16 and Comparative Synthesis Example 1, respectively, and ORGATICS TC-750 is a trade name, titanium diisopropoxybis (ethyl acetoacetate) manufactured by Matsumoto Fine Chemical Co., Ltd. The details of other compounding substances are the same as in Table 17.

As shown in Tables 9 to 30, all of the curable compositions of the present invention exhibited sufficient adhesion, storage stability and curability. Further, as shown in Tables 17 and 18, when an aging curing catalyst and a non-aging curing catalyst are used in combination, the TFT becomes faster, but the storage stability is good, and in particular, the adhesive strength after 24 hours is very high. Excellent characteristics of high.

Claims

(A) an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule, and (B) an aging curing catalyst,
A curable composition containing
The (B) aging curing catalyst comprises (C) a silane compound obtained by reacting an epoxysilane compound represented by the following formula (1) and an aminosilane compound represented by the following formula (2), and (D) the following formula ( 3) one or more titanium catalysts selected from the group consisting of a titanium chelate represented by the following formula (4) and a titanium chelate represented by the following formula (4): A curable composition comprising an aging curing catalyst prepared by mixing silane compounds at a mixing ratio of 0.1 to 30 mol and aging at a reaction temperature of 30 to 100 ° C.

(In the formula (1), R 1 to R 3 are each a hydrogen atom or an alkyl group, R 4 is an alkylene group or an alkyleneoxyalkylene group, R 5 is a monovalent hydrocarbon group, and R 6 is An alkyl group, and a is 0, 1 or 2.)

(In the formula (2), R 7 to R 12 are each a hydrogen atom or an alkyl group, R 13 is a monovalent hydrocarbon group, R 14 is an alkyl group, and b is 0 or 1. )

(In the formula (3), n R 21 s are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4-n R 22 s are each independently a hydrogen atom. Or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, wherein 4-n R 23 and 4-n R 24 are independently substituted or unsubstituted carbon atoms having 1 to 20 carbon atoms. And n is 0, 1, 2 or 3.)

(In the formula (4), R 25 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and the two R 26 are each independently a hydrogen atom or substituted or unsubstituted. The two R 27 and the two R 28 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.)
2. The curable composition according to claim 1, wherein the aging is performed at 40 ° C. to 80 ° C.
The curable composition according to claim 1 or 2, wherein 0.5 to 30 parts by mass of the (B) aging curing catalyst is blended with 100 parts by mass of the (A) organic polymer.
4. The silane compound according to claim 1, wherein the (C) silane compound is a silane compound obtained by reacting the epoxysilane compound in a range of 1.5 to 10 mol with respect to 1 mol of the aminosilane compound. The curable composition according to claim 1.
5. The silane compound according to claim 1, wherein the (C) silane compound is a silane compound obtained by reacting the epoxysilane compound and the aminosilane compound at a reaction temperature of 40 to 100 ° C. Curable composition.
6. The curable composition according to claim 1, wherein the organic polymer (A) is an organic polymer whose main chain is not polysiloxane.
The (A) organic polymer is a polyoxyalkylene polymer containing 0.8 or more crosslinkable silicon groups on average per molecule, and 0.8 or more crosslinks on average per molecule. Selected from the group consisting of a saturated hydrocarbon polymer containing a functional silicon group and a (meth) acrylic acid ester polymer containing an average of 0.8 or more crosslinkable silicon groups in one molecule. The curable composition according to any one of claims 1 to 6, wherein the curable composition is one or more.
The curable composition according to any one of claims 1 to 7, wherein the crosslinkable silicon group contains a trimethoxysilyl group.
9. The curing according to claim 1, further comprising (E) a silane compound having one hydrolyzable silicon group and one primary amino group in one molecule. Sex composition.
The curable composition according to claim 9, wherein the (E) silane compound is a compound represented by the following formula (12).

(In the formula (12), R 41 is a methyl group or an ethyl group, and when a plurality of R 41 are present, they may be the same or different, and R 42 is a methyl group. Or when there are a plurality of R 42 s , they may be the same or different, R 43 is a hydrocarbon group having 1 to 10 carbon atoms, and m is 2 Or 3 and n is 0 or 1.)
The curable composition according to any one of claims 1 to 10, further comprising (F) a filler.
The filler (F) is at least one selected from the group consisting of surface-treated calcium carbonate, amorphous silica having a particle size of 0.01 to 300 μm, and polymer powder having a particle size of 0.01 to 300 μm. The curable composition according to claim 11.
The curable composition according to claim 12, wherein the difference between the refractive index of the organic polymer (A) and the refractive index of the amorphous silica is 0.1 or less.
14. The curability according to claim 12 or 13, wherein the difference between the refractive index of the liquid phase component (A) composed mainly of the organic polymer and the refractive index of the polymer powder is 0.1 or less. Composition.
By adding a refractive index adjusting agent to the (A) organic polymer, the difference between the refractive index of the liquid phase component mainly composed of the (A) organic polymer and the refractive index of the polymer powder is 0.1. It is set as follows, The curable composition of Claim 14 characterized by the above-mentioned.
The polymer powder polymerizes a monomer selected from the group consisting of (meth) acrylic acid ester, vinyl acetate, ethylene and vinyl chloride alone, or the monomer and one or more vinyl monomers. The curable composition according to any one of claims 12 to 15, wherein the curable composition is a polymer powder made from a polymer obtained by copolymerization.
The curable composition according to claim 16, wherein the polymer powder is at least one selected from the group consisting of an acrylic polymer powder and a vinyl polymer powder.
The curable composition according to any one of claims 1 to 17, further comprising (G) a diluent.
The curable composition according to any one of claims 1 to 18, further comprising a metal hydroxide.
20. The curable composition according to claim 19, wherein the metal hydroxide is aluminum hydroxide.
The curable composition according to any one of claims 1 to 20, further comprising a titanium chelate compound as a non-aged curing catalyst.
The titanium chelate compound is one or more titanium catalysts selected from the group consisting of a titanium chelate represented by the formula (3) and a titanium chelate represented by the formula (4). The curable composition as described.
A curable composition for producing a curable composition by blending (A) an organic polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule and (B) an aging curing catalyst. A manufacturing method of
The (B) aging curing catalyst comprises (C) a silane compound obtained by reacting an epoxysilane compound represented by the following formula (1) and an aminosilane compound represented by the following formula (2), and (D) the following formula ( 3) one or more titanium catalysts selected from the group consisting of a titanium chelate represented by the following formula (4) and a titanium chelate represented by the following formula (4): A method for producing a curable composition, which is an aging curing catalyst obtained by mixing silane compounds at a mixing ratio of 0.1 to 30 mol and aging at a reaction temperature of 30 to 100 ° C.

(In the formula (1), R 1 to R 3 are each a hydrogen atom or an alkyl group, R 4 is an alkylene group or an alkyleneoxyalkylene group, R 5 is a monovalent hydrocarbon group, and R 6 is An alkyl group, and a is 0, 1 or 2.)

(In the formula (2), R 7 to R 12 are each a hydrogen atom or an alkyl group, R 13 is a monovalent hydrocarbon group, R 14 is an alkyl group, and b is 0 or 1. )

(In the formula (3), n R 21 s are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and 4-n R 22 s are each independently a hydrogen atom. Or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, wherein 4-n R 23 and 4-n R 24 are independently substituted or unsubstituted carbon atoms having 1 to 20 carbon atoms. And n is 0, 1, 2 or 3.)

(In the formula (4), R 25 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and the two R 26 are each independently a hydrogen atom or substituted or unsubstituted. The two R 27 and the two R 28 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.)
24. The method for producing a curable composition according to claim 23, wherein the curable composition is produced by blending the (A) organic polymer, the (B) aging curing catalyst, and a titanium chelate compound.
25. The titanium chelate compound is one or more titanium catalysts selected from the group consisting of a titanium chelate represented by the formula (3) and a titanium chelate represented by the formula (4). The manufacturing method of curable composition of description.