KR101554248B1 - Curable compositions - Google Patents

Abstract

Curing property, adhesiveness and storage stability, and also provides a curable composition which does not require an organotin-based catalyst and is excellent in safety.
(A) an organic polymer having an average of at least 0.8 crosslinkable silicon groups per molecule and having a main chain other than a polysiloxane, (B) a specific epoxy silane compound and a specific aminosilane compound, (C) a specific titanium catalyst, wherein the silane compound (B) is added to 100 parts by mass of the organic polymer (A) as the curable composition, and the silane compound is reacted in the range of 1.5 to 10 moles, 0.1 to 40 parts by mass, and (C) titanium catalyst in an amount of 0.1 to 40 parts by mass.

Description

Curable compositions [0001]

The present invention relates to a curable composition containing an organic polymer having a silicon-containing group (hereinafter also referred to as "crosslinkable silicon group") which can be crosslinked by forming a siloxane bond with a hydroxyl group or a hydrolyzable group bonded to a silicon atom .

The organic polymer containing at least one crosslinkable silicon group in the molecule is crosslinked by the formation of a siloxane bond accompanied by a hydrolysis reaction of a reactive silicon group by moisture or the like even at room temperature to give a rubbery cured product . Among these polymers having a crosslinkable silicon group, organic polymers whose backbone skeleton is a polyoxyalkylene polymer or a (meth) acrylic acid ester polymer are widely used for sealing materials, adhesives, paints and the like.

The curable composition used for sealing materials, adhesives, paints and the like and the rubbery cured products obtained by curing require various properties such as curability, adhesiveness, storage stability, mechanical properties such as modulus, strength and elongation, Have been studied to date.

The curable composition containing an organic polymer having such a crosslinkable silicon group is cured using a silanol condensation catalyst, and an organotin-based catalyst such as dibutyltin bis (acetylacetonate) is generally widely used.

Recently, however, organotin compounds have been pointed out to be toxic and development of inorganic tin catalysts is required.

Alcohol-type silicone compositions using titanium catalysts as the non-tin-based tin catalysts are already commercially available and widely used for various purposes (for example, Patent Documents 1 to 3).

However, a comparatively small number of examples in which a titanium catalyst is added to an organic polymer containing a crosslinkable silicon group are disclosed in Patent Documents 4 to 21 and the like. Such a curable composition using a titanium catalyst has a problem in that the curing rate is slow and the curing rate after storage lowers and viscosity increases.

In addition, a curable composition containing an organic polymer containing a crosslinkable silicon group is often used as an adhesive and a sealing material, and in this case, adhesion to various kinds of substrates is required. So-called aminosilane having a primary amino group and an alkoxy group in a molecule is usually used to secure this adhesion. However, when a one-part curable composition is prepared by adding aminosilane using an organic polymer containing a crosslinkable silicon group and a titanium catalyst, the viscosity of the composition is increased after storage for a certain period of time, And may not be used. Sealing materials and adhesives are used not only at the time of manufacture but also at a warehouse or store for many months, so that the curing property and viscosity are preferably constant before and after storage.

Publication No. 39-27643 U.S. Patent No. 3175993 U.S. Patent No. 3334067 Publication No. 58-17154 Publication No. 11-209538 Publication No. Hei 5-311063 Japanese Patent Application Laid-Open No. 2001-302929 Japanese Patent Application Laid-Open No. 2001-302930 Japanese Patent Application Laid-Open No. 2001-302931 Japanese Patent Application Laid-Open No. 2001-302934 Japanese Patent Application Laid-Open No. 2001-348528 Japanese Unexamined Patent Publication No. 2002-249672 Japanese Patent Application Laid-Open No. 2003-165916 Japanese Patent Application Laid-Open No. 2003-147220 Japanese Patent Application Laid-Open No. 2005-325314 WO2005 / 108492 WO2005 / 108498 WO2005 / 108494 WO2005 / 108499 WO2007 / 037368 Japanese Patent Application Laid-Open No. 2008-280434

An object of the present invention is to provide a curable composition which is excellent in curability, adhesiveness and storage stability, does not require an organotin-based catalyst, and is excellent in safety.

In order to solve the above problems, the present inventors have conducted intensive studies and have found that, as a curing catalyst, a specific epoxy silane compound and a specific aminosilane compound are reacted with an organic polymer containing 0.8 or more crosslinkable silicon groups on average per molecule By using the obtained silane compound and titanium chelate coordinated with? -Keto ester in combination, it is possible to obtain a room temperature moisture curing type curing composition which is excellent in curability, adhesiveness and storage stability, does not require an organotin-based catalyst, .

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 having a main chain excluding the polysiloxane, (B) an epoxy silane compound represented by the following formula (1) And a silane compound obtained by reacting an aminosilane compound represented by the following formula (2) in an amount of 1.5 to 10 moles of the epoxy silane compound per mole of the aminosilane compound, and (C) a silane compound represented by the following formula Titanium chelate, and titanium chelate represented by the following formula (4), wherein the amount of the silane compound (B) relative to 100 parts by mass of the organic polymer (A) 40 parts by weight of the titanium catalyst and 0.1 to 40 parts by weight of the titanium catalyst (C).

(Wherein 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, R ⁶ is an alkyl group, a is 0 , 1 or 2.)

(Wherein 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.)

(3), each of n R ^{21 s} is 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 carbon atom number 1 to 20 hydrocarbon groups, and 4-n R ²³ and 4-n R ²⁴ are each independently a substituted or unsubstituted hydrocarbon group 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 two R ^{26 s} are each independently a hydrogen atom or a substituted or unsubstituted 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.

The silane compound (B) is preferably a silane compound obtained by reacting the epoxy silane compound and the aminosilane compound at a reaction temperature of 40 to 100 ° C.

Wherein the organic polymer (A) is a polyoxyalkylene polymer having on average 0.8 or more crosslinkable silicon groups in one molecule, a saturated hydrocarbon polymer containing 0.8 or more crosslinkable silicon groups on average in one molecule, And (meth) acrylic acid ester-based aggregates containing on average 0.8 or more crosslinkable silicon groups.

The crosslinkable silicon group preferably includes a trimethoxysilyl group.

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

In the formula (12), R ⁴¹ is a methyl group or an ethyl group. When a plurality of R ^{41 s} exist, they are the same or different. R ⁴² is a methyl group or an ethyl group. When a plurality of R ^{42 s} exist, they are the same or different, R ⁴³ is a hydrocarbon group having 1 to 10 carbon atoms, m is 2 or 3, and n is 0 or 1.

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

The curable composition having excellent transparency can be obtained by matching the refractive index difference 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.

The curable composition having excellent transparency can be obtained by matching the refractive index difference so that the difference between the refractive index of the organic polymer liquid component (A) and the refractive index of the polymer powder is 0.1 or less.

It is preferable to add a refractive index adjusting agent to the organic polymer (A) so that the difference between the refractive index of the organic polymer liquid component (A) and the refractive index of the polymer powder is 0.1 or less.

Wherein the polymer powder is a polymer powder obtained by polymerizing a monomer selected from the group consisting of (meth) acrylic acid ester, vinyl acetate, ethylene and vinyl chloride singly or copolymerizing the monomer with one or more vinyl monomers as a raw material , And more preferably at least one selected from the group consisting of an acrylic polymer powder and a vinyl polymer powder.

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

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

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a curable composition which is excellent in curability, adhesiveness and storage stability, does not require an organotin-based catalyst, and is excellent in safety. Further, according to the present invention, a curable composition having excellent transparency can be obtained.

Embodiments of the present invention will now be described, but these are merely illustrative, 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 having on average 0.8 or more crosslinkable silicon groups in one molecule and having a main chain excluding the polysiloxane, (B) an epoxy silane compound represented by the formula (1) A silane compound obtained by reacting the aminosilane compound represented by the formula (2) with the epoxy silane compound in an amount of 1.5 to 10 moles per mole of the aminosilane compound, and (C) a silane compound represented by the formula (3) (B) a silane compound in an amount of from 0.1 to 100 parts by mass based on 100 parts by mass of the organic polymer (A), wherein the curing catalyst comprises at least one titanium catalyst selected from the group consisting of a chelate and a titanium chelate represented by the formula (4) , And 0.1 to 40 parts by mass of the titanium catalyst (C).

The organic polymer (A) is an organic polymer containing an average of at least 0.8 crosslinkable silicon groups in one molecule and having a main chain other than the polysiloxane, and may have various main chain skeletons except polysiloxane.

In particular, polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer and polyoxypropylene-polyoxybutylene copolymer; A copolymer of polyisoprene, isoprene or butadiene with acrylonitrile and / or styrene, a copolymer of polybutadiene, isoprene or butadiene, or a copolymer of polyisoprene and polyisoprene, A copolymer of acrylonitrile and styrene, and a hydrocarbon-based polymer such as a hydrogenated polyolefin-based polymer obtained by hydrogenating such a polyolefin-based polymer; Condensation of a dibasic acid such as adipic acid and glycol or ring-opening polymerization of lactones; (Meth) acrylate-based copolymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; Vinyl polymers obtained by radical polymerization of monomers such as (meth) acrylic acid ester monomers, vinyl acetate, acrylonitrile and styrene; A graft polymer obtained by polymerizing a vinyl monomer in the organic polymer; Polysulfide based polymers; 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, and ε-aminoundecanoic acid Nylon 11 by condensation polymerization, nylon 12 by ring-opening polymerization of? -Aminolaurolactam, and copolymerized nylon having two or more components of the nylon; For example, a polycarbonate-based polymer or diarylphthalate-based polymer produced by condensation polymerization of bisphenol A and carbonyl chloride.

In addition, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, and polyoxyalkylene polymers and (meth) acrylic acid ester copolymers have relatively low glass transition temperatures and the obtained cured products have low cold resistance It is preferable because it excelled. Further, the polyoxyalkylene polymer and the (meth) acrylate polymer are particularly preferable because they have a high permeability and are excellent in deep curability in the case of a one-pack type composition.

The crosslinkable silicon group of the organic polymer (A) used in the present invention is a group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and is crosslinked by forming a siloxane bond. As the crosslinkable silicon group, for example, groups represented by the following general formula (5) are suitable.

The formula (5) of the R ³¹ is an alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms of a cycloalkyl group, an aryl group of 6 to 20 carbon atoms, having a carbon number of 7-20 or an aralkyl group of R ³¹ ₃ SiO- (R ³¹ a is the ), And when two or more R ^{31 s} exist, 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. Also, e need not be the same in the following p general formula (6). p represents an integer of 0 to 19; However, d + (sum of e) ≥1.

The hydrolyzable group and the hydroxyl group may be bonded to one silicon atom in a range of 1 to 3, and the sum d + (e) is preferably in the range of 1 to 5. When two or more of the hydrolyzable group and the hydroxyl group are bonded in 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 may be about 20 in the case of a silicon atom bonded by a siloxane bond or the like.

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

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

Specific examples of R ³¹ include alkyl groups such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group, and triarylsiloxane groups represented by R ³¹ ₃ SiO- Time and so on. Of these, a methyl group is preferable.

The hydrolyzable group represented by X is not particularly limited, but any conventionally known hydrolyzable group may be used. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximethoxy group, an amino group, an amide group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group . Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoxime 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 desirable. An alkoxy group is particularly preferable from the viewpoint of being hydrolyzable and being easy to handle. Among the alkoxy groups, the smaller the number of carbon atoms is, the higher the reactivity is, and the higher the number of carbon atoms in the order of methoxy> ethoxy> propoxy group, the lower the reactivity. The methoxy group and the ethoxy group are generally used although they can be selected according to purpose or use.

Specific examples of the crosslinkable silicon group include dialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group [-Si (OR) ₃ ], methyldimethoxysilyl group, and methyldiethoxysilyl group. A silyl group [-SiR ¹ (OR) ₂ ], and a trimethoxysilyl group is more suitable. Wherein R is an alkyl group such as a methyl group and an ethyl group.

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

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

The organic polymer having a crosslinkable silicon group may be linear or branched and has a number average molecular weight of 500 to 100,000, more preferably 1,000 to 50,000, particularly preferably 3,000 to 30,000 in terms of polystyrene by GPC . When the number average molecular weight is less than 500, the elongation property of the cured product tends to be insignificant. When the number average molecular weight exceeds 100,000, the viscosity tends to be inadequate in view of workability.

In order to obtain a rubbery cured product exhibiting high strength, high elongation and low elastic modulus, it is preferable that 0.8 or more, preferably 1.1 to 5, crosslinkable silicon groups contained in the organic polymer are contained in one molecule of the polymer. When the average number of crosslinkable silicon groups contained in the molecule is less than 0.8, the curability becomes insufficient and it is difficult to exhibit good rubber elasticity behavior. The crosslinkable silicon group may be at the terminal or the end of the side chain of the main chain of the organic polymer molecule chain or may be present at both ends. Particularly, when the crosslinkable silicon group is present only at the end of the main chain of the molecular chain, since the effective meshes length of the organic polymer component contained in the finally formed cured product becomes long, it is possible to obtain a rubbery cured product exhibiting high strength, .

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, and is preferably a linear or branched alkylene group having 1 to 14 carbon atoms and 2 to 4 carbon atoms.

Specific examples of the repeating unit represented by the general formula (8)

_{-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-
And the like. The backbone skeleton of the polyoxyalkylene polymer may be a single repeating unit or two or more repeating units. Particularly, when it is used for a sealing material or the like, it is preferable to use a polymer mainly composed of a propylene oxide polymer because of its amorphousness and relatively low viscosity.

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Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, for example, Japanese Patent Application Laid-Open Nos. 61-197631, 61-215622, 61-215623, 61-215623 A polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting an organoaluminum compound such as that shown in JP-A No. 46-27250 and a porphyrin with a metal cyanide complex catalyst , But the present invention is not limited thereto. According to the polymerization method using an organoaluminum-porphyrin complex catalyst or the polymerization method using various metal cyanide complex catalysts, it is possible to obtain a polyoxyalkylene polymer having a number average molecular weight of 6,000 or more and a molecular weight distribution of Mw / Mn of 1.6 or less .

The main chain skeleton of the polyoxyalkylene polymer may include other components such as a urethane bonding component. Examples of the urethane bonding component include aromatic polyisocyanates such as toluene (toluylene) diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; A polyoxyalkylene polymer having an aliphatic polyisocyanate such as isophorone diisocyanate and hexamethylene diisocyanate and a hydroxyl group-containing polymer.

The introduction of the crosslinkable silicon group into the polyoxyalkylene polymer is carried out by reacting a polyoxyalkylene polymer having functional groups such as an unsaturated group, hydroxyl group, epoxy group and isocyanate group in the molecule with a functional group exhibiting reactivity with the functional group and a crosslinkable silicon group (Hereinafter referred to as a polymer reaction method).

As a specific example of the polymer reaction method, hydrosilylation and mercapto formation are carried out by reacting an unsaturated group-containing polyoxyalkylene polymer with a hydrosilane having a crosslinkable silicon group and a mercapto compound having a crosslinkable silicon group to obtain a poly And a method of obtaining an oxyalkylene-based polymer. The unsaturated group-containing polyoxyalkylene polymer can be obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an active group exhibiting a reaction with the functional group and an organic compound having an unsaturated group to obtain a polyoxyalkylene polymer containing an unsaturated group.

As another example of the polymer reaction method, there are a method of reacting a polyoxyalkylene polymer having a hydroxyl group at the terminal thereof with a compound having an isocyanate group and a crosslinkable silicon group and a method of reacting a polyoxyalkylene polymer having an isocyanate group at the terminal, Of a compound having an active hydrogen group and a crosslinkable silicon group. When the 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 are described in Japanese Patent Publication Nos. 45-36319, 46-12154, 50-156599, 54-6096, 55-13767, 57-164123 Japanese Patent Publication Nos. 3-2450, 2005-213446, 2005-306891, WO2007-040143, US Patent Nos. 3,632,557, 4,345,053 and 4,960,844, etc. .

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

The saturated hydrocarbon polymer is a polymer substantially containing no carbon-carbon unsaturated bond other than an aromatic ring. The polymer constituting the skeleton of the unsaturated hydrocarbon polymer includes (1) a polymer having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene, (2) by homopolymerizing a diene compound such as butadiene, isoprene or the like, or by copolymerizing with an olefin compound and hydrogenating it. However, it is also possible to use an isobutyl The hydrogenated polybutadiene-based polymer is preferred because it is easy to introduce a functional group at the terminal, is easy to control the molecular weight, can increase the number of terminal functional groups, and is particularly preferable.

When the main chain skeleton is a saturated hydrocarbon polymer, it is excellent in heat resistance, weather resistance, durability and moisture barrier property.

In the isobutylene polymer, all of the monomer units may be formed of isobutylene units or may be copolymers with other monomers, but it is preferable that they contain 50 mass% or more of repeating units derived from isobutylene in terms of rubber properties By mass, more preferably 80% by mass or more, and particularly preferably 90% to 99% by mass.

As a method of synthesizing a saturated hydrocarbon polymer, various polymerization methods have been reported in the past, but in recent years, so-called living polymerization has been developed in particular. In the case of a saturated hydrocarbon polymer, particularly an isobutylene polymer, it can be easily produced by using an initiator polymerization (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. It is known that a polymer having a molecular weight of about 500 to 100,000 can be polymerized at a molecular weight distribution of 1.5 or less and various functional groups can be introduced at the molecular end.

As a method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group, for example, Japanese Patent Publication Nos. 4-69659, 7-108928, 63-254149, 64-22904, Japanese Patent Publication No. 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, Japanese Patent Application Laid-Open No. 7-53882, and the like, but the present invention is not limited thereto.

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

The (meth) acrylic acid ester-based monomer constituting the main chain of the (meth) acrylic acid ester-based polymer is not particularly limited, and various ones can be used. (Meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, n-heptyl (meth) acrylate, n-pentyl (meth) acrylate, n-pentyl (Meth) acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, decyl acrylate, dodecyl acrylate, phenyl methacrylate, tolyl methacrylate, benzyl methacrylate, (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl , 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) di Methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, (meth) acryloyloxymethyldiethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, Acrylate, ethylene oxide adduct of acrylic acid, trifluoromethyl methyl (meth) acrylate, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoro (Meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoro Perfluorooctylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl Methacrylic acid-based monomers.

The (meth) acrylic ester polymer may be copolymerized with the following vinyl monomers together with the (meth) acrylic ester monomers. Examples of the vinyl-based monomer include styrene-based monomers such as styrene, vinyltoluene,? -Methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; Fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Monoalkyl esters and dialkyl esters of maleic anhydride, maleic acid, maleic acid; Monoalkyl esters and dialkyl esters of fumaric acid, fumaric acid; Maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide Monomers; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; Alkenes such as ethylene and propylene; Conjugated dienes such as butadiene and isoprene; Vinyl chloride, vinylidene chloride, aryl chloride, aryl alcohol, and the like.

These may be used alone, or a plurality of them may be copolymerized. Particularly, a polymer composed of a styrene-based monomer and a (meth) acrylic acid-based monomer is preferred because of the physical properties of the product and the like. More preferably, it is a (meth) acrylic polymer composed of an acrylic ester monomer and a methacrylic acid ester monomer, and particularly preferably an acrylic polymer composed of an acrylic acid ester monomer. Butyl acrylate monomer is more preferable in applications such as general building use because of the properties such as low viscosity of the compound, low modulus of the cured product, high elongation, weather resistance and heat resistance. On the other hand, in applications where oil resistance such as automotive uses is required, a copolymer mainly composed of ethyl acrylate is more preferable. This polymer centered on ethyl acrylate is excellent in oil resistance but tends to have a somewhat lowered low-temperature characteristic (cold resistance). Therefore, in order to improve its low-temperature characteristics, a part of ethyl acrylate can be substituted with butyl acrylate. However, the proportion of the butyl acrylate is increased, so that the good oil resistance is impaired. Therefore, in the application requiring oil resistance, the ratio is preferably 40% or less, more preferably 30% or less. It is also preferable to use 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group in order to improve the low-temperature characteristics and the like without impairing the oil resistance. The heat resistance tends to deteriorate by the introduction of an alkoxy group having an ether bond in the short side chain. Therefore, when heat resistance is required, the ratio is preferably 40% or less. An appropriate polymer can be obtained by changing the ratio in consideration of physical properties such as required oil resistance and heat resistance and low temperature characteristics depending on various applications and desired purposes. For example, ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (40 to 50/20 to 30/30 to 20 in mass ratio), which is not limited, but has excellent balance of physical properties such as oil resistance, heat resistance and low temperature characteristics, Copolymers are considered. In the present invention, such preferred monomers may be copolymerized with other monomers and then block-copolymerized, and it is preferable that such preferred monomers are contained in an amount of 40% or more based on the mass. In the above expression, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

The method for obtaining the (meth) acrylic acid ester polymer in the present invention is not particularly limited, and it is possible to use a known polymerization method (for example, Japanese Unexamined Patent Application Publication No. 63-112642, Japanese Unexamined Patent Publication No. 2007-230947, Japanese Unexamined Patent Publication No. 2001-40037, JP-A-2003-313397, etc.) can be used, and a radical polymerization method using a radical polymerization reaction is preferable. Examples of the radical polymerization method include a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, and a controlled radical polymerization method in which a reactive silyl group can be introduced at a controlled position such as a terminal . However, a polymer obtained by a general free radical polymerization method using an azo compound, a peroxide, or the like as a polymerization initiator has a problem that the molecular weight distribution generally has a value of 2 or more and a viscosity is increased. Accordingly, in order to obtain a (meth) acrylic ester polymer having a narrow molecular weight distribution and a low viscosity as a (meth) acrylic ester polymer having a crosslinkable functional group at the molecular chain end at a high ratio, it is preferable to use a controlled radical polymerization method.

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

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

The organic polymer having such a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, two or more kinds selected from the group consisting of a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic ester polymer having a crosslinkable silicon group are mixed May also be used.

A method for producing an organic polymer in which a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group are mixed is disclosed in JP-A-59-122541, JP-A-63-112642, Japanese Patent Application Laid-Open No. 6-172631, Japanese Patent Application Laid-Open No. 11-116763, etc., but the present invention is not limited thereto.

Preferred embodiments are those in which the molecular chain having a crosslinkable silicon group is substantially composed of a compound represented by the following general formula (9):

-CH ₂ -C (R ³⁵ ) (COOR ³⁶ ) - (9)

(Meth) acrylic acid ester monomer unit having an alkyl group having 1 to 8 carbon atoms represented by the following general formula (10): wherein R ³⁵ represents a hydrogen atom or a methyl group and R ³⁶ represents an alkyl group having 1 to 8 carbon atoms,

-CH ₂ -C (R ³⁵ ) (COOR ³⁷ ) - (10)

(Meth) acrylic acid ester monomer unit having an alkyl group having not less than 10 carbon atoms and represented by the following general formula (wherein R ³⁵ is as defined above and R ³⁷ represents an alkyl group having 10 or more carbon atoms) And an oxyalkylene-based polymer.

Examples of R ^{36 in the} above general formula (9) include those having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms such as methyl, ethyl, propyl, n-butyl, Preferably an alkyl group having 1 to 2 carbon atoms. The alkyl group of R ³⁶ may be used singly or in combination of two or more.

Examples of R ^{37 in} the general formula (10) include a long chain having 10 or more carbon atoms, usually 10 to 30, preferably 10 to 20 carbon atoms such as a lauryl group, a tridecyl group, a cetyl group, a stearyl group and a behenyl group Alkyl group. The alkyl group for R < ³⁷ > may be either a single compound or a mixture of two or more compounds as in the case of R < ³⁶ >.

The molecular chain of the (meth) acrylate-based copolymer is substantially a monomer unit of the formulas (9) and (10), but the term "substantially" 10) exceeds 50% by mass. The sum of the monomer units of the formulas (9) and (10) is preferably 70 mass% or more.

The ratio of the monomer units of the formula (9) to the monomer units of the formula (10) is preferably from 95: 5 to 40:60 by mass ratio, more preferably from 90:10 to 60:40.

Examples of the monomer unit (hereinafter referred to as another monomer unit) other than the formula (9) and the formula (10) that may be contained in the copolymer include an?,? - unsaturated carboxylic acid such as acrylic acid and methacrylic acid; Amide groups such as acrylamide, methacrylamide, N-methylol acrylamide and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, diethylaminoethyl acrylate, di Monomers containing amino groups such as ethylaminoethyl methacrylate and aminoethyl vinyl ether; And other monomer units derived from acrylonitrile, styrene,? -Methyl styrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

Another preferred (meth) acrylic acid ester polymer having a crosslinkable silicon group used in a process for producing an organic polymer in which a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic ester polymer having a crosslinkable silicon group are mixed Specific examples thereof include (a1) a (meth) acrylic acid methyl monomer unit and (a2) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 8 carbon atoms, as disclosed in Japanese Patent Application Laid-Open No. 2008-44975 And an acrylic polymer having a crosslinkable silicon group.

The molecular chain of the acrylic copolymer preferably contains 50 mass% or more of the total of the (a1) monomer unit and the (a2) monomer unit, and the total of the monomer units of (a1) and (a2) is 70 mass% Or more. The abundance ratio of (a1) and (a2) is preferably in the range of (a1) / (a2) = 90/10 to 20/80, more preferably 70/30 to 30/70 in mass ratio. By setting the mass ratio of (a1) / (a2) in the range of 90/10 to 20/80, transparency can be improved.

The acrylic copolymer may contain monomer units other than (a1) and (a2). As the monomer units other than (a1) and (a2), for example, the above-mentioned other monomer units in the description of the (meth) acrylic acid ester-based copolymer may be similarly used.

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 the above 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 based on 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 mixing a saturated hydrocarbon polymer having a crosslinkable silicon group and a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group are proposed in Japanese Patent Laid-Open Nos. 1-168764 and 2000-186176, But is not limited thereto.

The method for producing an organic polymer in which a (meth) acrylic acid ester-based copolymer having a crosslinkable silicon group is mixed is also a method for carrying out the polymerization of a (meth) acrylic acid ester-based monomer in the presence of an organic polymer having a crosslinkable silicon group use. This manufacturing method is specifically disclosed in Japanese Patent Application Laid-Open Nos. 59-78223, 59-168014, 60-228516, 60-228517, and the like, but the present invention is not limited thereto no.

When two or more kinds of polymers are used in combination, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a (meth) acrylic ester polymer having a crosslinkable silicon group is added to 100 parts by mass of a polyoxyalkylene polymer having a crosslinkable silicon group Is preferably 10 to 200 parts by mass, more preferably 20 to 80 parts by mass.

The silane compound (B) is obtained by reacting an epoxy silane compound represented by the following formula (1) and an aminosilane compound represented by the following formula (2) in an amount of 1.5 to 10 moles of the epoxy silane compound per 1 mole of the aminosilane compound Is a silane compound which is reacted.

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 preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylenerene group, an octylene group, a methyleneoxyethylene group, An oxybutylene group, an ethyleneoxyethylene group and an ethyleneoxypropylene group are preferable, and a butyl group, an octylene group and a methyleneoxypropylene group are more preferable. R ⁵ is a monovalent hydrocarbon group, and includes alkyl groups such as methyl group, ethyl group and propyl group; Alkenyl groups such as a vinyl group, an aryl group and a butenyl group; An aryl group such as a phenyl group or a trimethyl group is preferable, and a methyl group is more preferable. When a plurality of R < ⁵ > exist, they may be the same or different. R ⁶ is an alkyl group, preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group or an ethyl group. When a plurality of R < ⁶ > exist, 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, 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, more preferably a methyl group or an ethyl group. b is 0 or 1; 3-b R < ¹⁴ > may be the same or different.

As the epoxy silane compound, for example, 4-oxiranylbutyltrimethoxysilane, 8-oxiranyloxytitrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropyltriethoxysilane, and the like.

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

The reaction conditions of the epoxy silane compound and the aminosilane compound are such that the primary amino group of the aminosilane compound reacts with the epoxy silane compound to cause the primary amino group to become a secondary amino group or a tertiary amino group, .

The aminosilane compound is mixed with the epoxy silane compound in the presence or absence of a solvent, for example, at 25 ° C to 100 ° C, preferably 30 ° C to 90 ° C, more preferably 40 ° C To 80 < [deg.] ≫ C. By setting the reaction temperature within the above range, it is possible to stably proceed the reaction without congestion. When the reaction temperature is lower than 25 占 폚, the activity is lowered and the time required for achieving a sufficient reaction is prolonged, which is inefficient. The reaction time may be suitably set in consideration of the reaction temperature and the like. For example, under the above-described conditions, the reaction time is generally set within the range of 1 to 336 hours, preferably 24 to 72 hours .

The reaction ratio (molar ratio) of the epoxy silane compound to the aminosilane compound is adjusted so that the epoxy silane compound is 1.5 to 10 mol, preferably 1.6 to 5.0 mol, more preferably 1.7 to 2.4 mol, per mol of the aminosilane compound.

The epoxy silane compound and the aminosilane compound are subjected to a heating reaction at a reaction temperature of preferably 40 ° C or more, more preferably 40 to 100 ° C, and more preferably 40 to 80 ° C to produce an epoxy silane compound epoxy The ring is cleaved and the hydroxyl group produced by this reaction is cyclized by an alcohol exchange reaction with an alkoxy group in the aminosilane compound to obtain a carbacilatran derivative represented by the following formula (11). The carbacilatran derivative represented by the following formula (11) is a compound having a peak at 60 ppm-70 ppm of ²⁹ Si-NMR.

R ¹ to R ⁶ and a in the formula (11) are the same as those in the formula (1), R ⁷ to R ¹² are the same as those in the formula (2) , 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). Further, the alkoxy group bonded to the silicon atom may be partially substituted by an alcohol exchange reaction, and the silicon atom-bonded alkoxy group in the carbasilatran derivative produced by the reaction with the silicon atom-bonded alkoxy group of the raw material may not be the same.

The blending ratio of the silane compound (B) is 0.1 to 40 parts by mass of the silane compound (B) relative to 100 parts by mass of the organic polymer (A), preferably 0.3 to 30 parts by mass, More preferably 20 parts by mass. The silane compound (B) may be used alone or in combination of two or more.

The titanium catalyst (C) 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).

In the formula (3), each of n R ^{21 s} is 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 C1- 4-n R ²³ and 4-n R ²⁴ are each independently a substituted or unsubstituted hydrocarbon group 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 two R ^{26 s} each independently represent a hydrogen atom or a substituted or unsubstituted 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 of 1 to 20 carbon atoms.

The titanium chelate represented by the formula (3) or (4) includes, for example, titanium dimethoxide bis (ethylacetate), titanium diethoxide bis (ethylacetate), titanium diisopropoxide bis (Methyl acetoacetate), titanium diisopropoxide bis (methyl acetoacetate), titanium diisopropoxide bis (t-butyl acetoacetate), titanium diisopropoxide bis (methyl-3- Dimethylhexanoate), titanium diisopropoxide bis (ethyl-3-oxo-4,4,4-trifluorobutanoate), titanium di-n-butoxide bis (ethylacetate) Titanium diisobutoxide bis (ethylacetate), titanium di-t-butoxide bis (ethylacetate), titanium di-2-ethylhexoxide bis (ethylacetate), titanium bis (1-methoxy- - propoxide) (Ethyl acetoacetate), titanium bis (3-oxo-2-butoxide) bis (ethylacetate), titanium bis (3-diethylaminopropoxide) (Ethylacetate), titanium triisopropoxide (aryl acetoacetate), titanium triisopropoxide (methacryloxyacetylacetate), 1,2-dioxyethanetitanium bis (ethylacetate), 1 , 3-dioxypropane titanium bis (ethylacetate), 2,4-dioxypentanetanium bis (ethylacetate), 2,4-dimethyl-2,4-dioxypentanetanium bis (ethylacetate) (Ethyl acetoacetate), titanium bis (trimethylsiloxy) bis (acetylacetonate), and the like can be given. Among these, titanium diethoxide bis (ethylacetate), titanium diisopropoxide bis (ethylacetate), titanium dibutoxide bis (ethylacetate) and the like, and titanium diisopropoxide bis Ethyl acetoacetate) is more suitable.

Examples of the chelating agent capable of forming the chelate ligand of the titanium chelate include methyl acetate, ethyl acetate, t-butyl acetate, allyl acetate, acetoacetic acid (2-methacryloxyethyl), 3- Oxo-4,4-dimethylhexanoate and ethyl 3-oxo-4,4,4-trifluorobutanoate. Of these, methyl acetate and ethyl acetate are preferable, and acetates such as acetone Ethyl acetate is more preferable. When two or more chelating ligands are present, each chelating ligand may be the same or different.

The mixing ratio of the titanium catalyst (C) is 0.1 to 40 parts by mass of the titanium catalyst (C) relative to 100 parts by mass of the organic polymer (A), preferably 1 to 30 parts by mass, More preferably 20 parts by mass. The titanium catalyst (C) may be used singly or in combination of two or more. As a method of adding the titanium catalyst (C), in addition to directly adding the above-mentioned titanium chelate, a titanium compound capable of reacting with a chelating reagent such as titanium tetraisopropoxide and titanium dichloride diisopropoxide and A chelating agent such as ethyl acetate may be separately added to the composition of the present invention and chelated in the composition.

The curable composition of the present invention uses the above-mentioned (C) titanium catalyst as a curing catalyst, but other curing catalysts may be used in combination to the extent that the effect of the present invention is not impaired. Other curing catalysts include, for example, 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 , Organotin compounds such as dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin divisate, tin octylate and tin naphthenate; Dialkyltin oxides such as dimethyltin oxide, dibutyltin oxide, and dioctyltin oxide water; A reaction product of dibutyltin oxide and a phthalic acid ester; Titanate esters such as tetrabutyl titanate and tetrapropyl titanate; Organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetate and diisopropoxyaluminum ethylacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; Organic acid lead such as lead octylate and lead naphthenate; Organic acid bismuth such as bismuth octoate, bismuth neodecanoate and bismuth rosinate; And other acidic catalysts and basic catalysts known as silanol condensation catalysts. However, the organotin compound may be toxic to the curable composition obtained according to the addition amount.

The curable composition of the present invention preferably contains (D) a silane compound having one hydrolyzable silicon group and having a primary amino group in one molecule. (D) silane compound may be blended to further improve storage stability and tensile properties.

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

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

delete

In the formula (12), R ⁴¹ is a methyl group or an ethyl group, and when a plurality of R ^{41 s} exist, they are the same or different. R ⁴² is a methyl group or an ethyl group, and when a plurality of R ^{42 s} exist, they are the same or different. R ⁴³ is a hydrocarbon group of 1 to 10 carbon atoms. m is 2 or 3, and more preferably 3. n is 0 or 1;

Specific examples of the silane compound (D) include phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, triphenylmethoxysilane, 2-carboxyethylphenylbis (2-methoxyethoxy) Silane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenylaminomethyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Alkoxysilane containing an epoxy group such as 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane; 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methyl diethoxy silane, 3- isocyanate propyl methyl dimethoxy silane, (isocyanate methyl) Alkoxysilanes containing isocyanate groups such as ethoxymethylsilane, (isocyanatomethyl) triethoxysilane, (isocyanatomethyl) diethoxymethylsilane and the like; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane, mercapto Alkoxysilane containing a mercapto group such as methyltrimethoxysilane, mercaptomethyltriethoxysilane and the like; Carboxysilanes such as 2-carboxyethyltriethoxysilane and N-2- (carboxymethyl) aminoethyl-3-aminopropyltrimethoxysilane; Vinyl ethers such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane and the like Alkoxysilane containing a type-unsaturated group; Halogen-containing alkoxysilanes such as 3-chloropropyltrimethoxysilane; Isocyanate silanes such as tris (3-trimethoxysilylpropyl) isocyanate; N-benzyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl-3-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N Secondary amino groups such as N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, bis (3-trimethoxysilylpropyl) amine, N- / ≪ / RTI > alkoxy silane containing a tertiary amino group; (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- Ketimine type silanes such as propanamine; N-propoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetraethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, Tetraalkoxysilane (tetraalkyl silicate) such as butoxysilane, tetra-i-butoxysilane and tetra-t-butoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, tri Trialkoxysilane such as fluoropropyltrimethoxysilane; Dialkoxysilanes such as dimethyldimethoxysilane and diethyldimethoxysilane; Monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane; Alkyl isopropenoxysilanes such as dimethyl diisopropenoxysilane and methyltriisopropenoxysilane; And so on.

Examples of the compound represented by the formula (12) include dialkoxysilane such as dimethyldimethoxysilane and dimethyldiethoxysilane; Alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane and decyltrimethoxysilane; Alkoxysilane containing a phenyl group such as phenyltrimethoxysilane and phenyltriethoxysilane; Alkoxysilane containing a vinyl-type unsaturated group such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane. Among these alkoxysilanes, an alkoxysilane containing a phenyl group is more preferable.

The mixing ratio of the silane compound (D) is not particularly limited, but it is preferable to mix the silane compound (D) in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the organic polymer (A), more preferably 0.3 to 20 parts by mass , More preferably from 0.5 to 10 parts by mass. The above-mentioned (D) silane compounds may be used singly or in combination of two or more kinds.

The curable composition of the present invention preferably contains (E) a filler. The cured product can be reinforced by adding the filler (E).

As the filler (E), known fillers can be widely used, and there is no particular limitation, and examples thereof include calcium carbonate, magnesium carbonate, diatomaceous earth hydrate silicic acid, hydrated silicic acid, hydrous silicic acid, calcium silicate, fine powder silica, titanium dioxide Calcium carbonate, fine powder silica and polymer powders are preferable, and surface-treated calcium carbonate, amorphous silica having a particle diameter of 0.01 to 300 탆, and calcium carbonate, At least one selected from the group consisting of polymer powders having a particle size of 0.01 to 300 탆 are more preferable. It is also possible to use glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, silica balloons, glass balloons, silica balloons, An acrylic balloon is more preferable because of a small decrease in post-drawing.

As the above-mentioned calcium carbonate, any of calcium carbonate such as heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate and ground calcium carbonate can be used, but colloidal calcium carbonate is more suitable. These calcium carbonates may be used alone or in combination of two or more.

The primary particle diameter of the above-mentioned calcium carbonate is preferably 0.5 탆 or less, and more preferably 0.01 to 0.1 탆. Calcium carbonate having such a small particle diameter can be used to impart thixotropy to the curable composition.

Among the calcium carbonates, surface treated calcium carbonate is preferable from the viewpoints of imparting thixotropy and reinforcing effect on the cured product (cured coating), and more preferably, the surface treated fine calcium carbonate is used. Further, other calcium carbonate such as surface-treated fine calcium carbonate can be used in combination with the surface-treated fine calcium carbonate, for example, surface-treated heavy calcium carbonate such as calcium carbonate having a large particle size and surface treated calcium carbonate having a large particle size. When the surface-treated fine calcium carbonate is mixed with other calcium carbonate, the ratio (mass ratio) of the surface-treated fine calcium carbonate to other calcium carbonate is preferably 1: 9 to 9: 1, more preferably 3: 7 to 7: desirable.

A known surface treatment agent can be widely used without limitation to the surface treatment agent used in the surface treated calcium carbonate. Examples of the surface-treating agent include, but are not limited to, higher fatty acid compounds, resin acid compounds, aromatic carboxylic acid esters, anionic surfactants, cationic surfactants, nonionic surfactants, paraffin, titanate coupling agents and silane coupling agents And higher fatty acid-based compounds and paraffins are more preferable. These surface treatment agents may be used alone or in combination of two or more.

Examples of the higher fatty acid-based compounds include higher fatty acid-based alkali metal salts such as sodium stearate having 10 or more carbon atoms.

Examples of the resin acid compounds include abietic acid, neoabietic acid, d-pimic acid, i-d-pimic acid, vodecanoic acid, benzoic acid and cinnamic acid.

Examples of the aromatic carboxylic acid ester include esters of phthalic acid such as octyl alcohol, butyl alcohol, isobutyl alcohol and the like, lower alcohol esters of naphthoic acid, lower alcohol esters of rosin acid and aromatic dicarboxylic acids or maleic acid moieties of rosin acid Partially esterified products of aromatic polycarboxylic acids such as water, or heterogeneous alcohol esterified products.

Examples of the anionic surfactant include sulfuric acid ester type surfactants such as sodium dodecyl sulfate or sulfonic acid type anionic surfactants such as sodium dodecylbenzenesulfonate, sodium laurylsulfonate and dodecylbenzenesulfonic acid. have.

As the surface-treated calcium carbonate, known surface-treated calcium carbonate can be widely used, and there is no particular limitation. For example, Vigot 15 (manufactured by Shiraishi Calcium Co., Ltd.), hard calcium carbonate , Primary particle diameter 0.15 mu m), and the like; Vigot 10 (colloidal calcium carbonate surface-treated with fatty acid, product of Baekseok Calcium Co., Ltd., primary particle diameter 0.10 占 퐉), Baekchungwha DD (Baekseok Calcium Co., Ltd., colloidal calcium carbonate surface- , Primary particle diameter 0.05 占 퐉), colloidal calcium carbonate surface-treated with a fatty acid (product of Maruo Calcium Co., Ltd., primary particle diameter: 0.05 占 퐉), Neolite SS Colloidal calcium carbonate surface-treated with fatty acid, average particle diameter 0.04 m), Neolite GP-20 (colloidal calcium carbonate surface-treated with resin acid, available from Seiyu Chemical Industry Co., Ltd., average particle diameter 0.03 μm) Surface-treated colloidal calcium carbonate such as colloidal calcium carbonate surface-treated with fatty acid, average particle diameter 0.15 μm, manufactured by Karushiz P (Shindo Chemical Industry Co., Ltd.); MC coat P1 (heavy calcium carbonate surface-treated with paraffin, primary particle diameter 3.3 m), AFF-95 (manufactured by Phytatech Co., Ltd., heavy calcium carbonate surface with cationic polymer, Surface-treated heavy calcium carbonate such as AFF-Z (manufactured by FIMATEC Co., Ltd., a cationic polymer and a heavy calcium carbonate having a surface of an antistatic agent, primary particle diameter of 1.0 μm) have.

The surface-treated calcium carbonate is preferably blended in an amount of 0 to 500 parts by mass, more preferably 10 to 300 parts by mass, and more preferably 15 to 100 parts by mass with respect to 100 parts by mass of the organic polymer (A) Do. The surface-treated calcium carbonate may be used singly or in combination of two or more. Also, the surface-treated calcium carbonate can be used in combination with the surface-treated calcium carbonate.

As the amorphous silica, a known amorphous silica can be widely used, and there is no particular limitation, but the amorphous silica preferably has a particle size of 0.01 to 300 μm, more preferably 0.1 to 100 μm, and more preferably 1 to 30 μm.

Transparency can be further improved by using amorphous silica having a difference between the refractive index of the organic polymer (A) and the refractive index of the amorphous silica of 0.1 or less. 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 still more preferably 0.03 or less.

The amount of the amorphous silica is preferably 0 to 500 parts by mass, more preferably 1 to 200 parts by mass, and more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the organic polymer (A). The amorphous silica may be used singly or in combination of two or more kinds. In addition, amorphous silica having a particle diameter in the range of 0.01 to 300 탆 and crystalline silica having a different particle diameter from the above can be used in combination.

As the polymer powder, a known polymer powder can be widely used, and there is no particular limitation, but the particle diameter is preferably 0.01 to 300 μm, more preferably 0.1 to 100 μm, and further preferably 1 to 30 μm.

Examples of the polymer powder include polymers obtained by polymerizing monomers selected from the group consisting of (meth) acrylic acid esters, vinyl acetate, ethylene and vinyl chloride, or polymers obtained by copolymerizing the monomers with one or more vinyl monomers, Is preferably used. Acrylic polymer powder and vinyl polymer powder are more preferable, and acrylic polymer powder is more preferable.

In order to further improve the transparency of the curable composition of the present invention, the difference between the refractive index of the organic polymer liquid component (A) and the refractive index of the polymer powder is preferably 0.1 or less, more preferably 0.05 or less, and 0.03 or less More preferable.

The method of making the difference between the refractive index of the organic polymer liquid component (A) and the refractive index of the polymer powder to be not more than 0.1 is not particularly limited, but (1) a method of adjusting the refractive index of the organic polymer liquid component to the refractive index of the polymer powder , (2) a method of adjusting the refractive index of the polymer powder to the refractive index of the organic polymer (A), and the like.

With the above method (1), for example, there can be mentioned a method of mixing a required amount of a refractive index adjuster which is compatible with the organic polymer liquid component (A) and adjusting the refractive index of the liquid component. Specifically, in the case 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 high, (A) a refractive index adjusting agent having a refractive index higher than that of the organic polymer (for example, epoxy resin (Refractive index: 1.57), petroleum resin (e.g., FTR6100 (a copolymer of C5 and C9, product of Mitsui Petrochemical Co., Ltd., refractive index 1.56), terpene phenol resin (e.g., T145 (a product of Yasuhara Chemical Co., refractive index 1.59)] is heated and melted in the organic polymer (A).

As a method of (2) above, for example, a method of changing the monomer blend of the polymer powder by an enemy may be mentioned. Specifically, for example, a method of increasing the refractive index of the polymer powder in the aspect of (A) the organic polymer having a refractive index of about 1.46 to 1.48 and using the acrylic polymer powder as the polymer powder, for example, vinyl chloride (refractive index: 1.53 , And allylonitrile (refractive index: 1.52 (polymer)) are copolymerized with a (meth) acrylic acid ester monomer. Also, in the above embodiment, for example, lauryl methacrylate (refractive index 1.44 (monomer)), flyel methacrylate (refractive index 1.44 (monomer)), 2- (2- Ethoxyethoxy) ethyl acrylate (refractive index: 1.43 (monomer)) is copolymerized with a (meth) acrylic acid ester 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, and more preferably 1 to 50 parts by weight, based on 100 parts by weight of the organic polymer (A). The polymer powder may be used singly or in combination of two or more kinds.

In the curable composition of the present invention, the mixing ratio of the above (E) filler is not particularly limited, but it is preferable that 0 to 500 parts by mass of the above (E) filler is blended with 100 parts by mass of the organic polymer (A) More preferably 2 to 250 parts by mass, and more preferably 5 to 125 parts by mass. The filler (E) may be used singly or in combination of two kinds.

The curable composition of the present invention preferably further contains (F) a diluent. (F) The physical properties such as viscosity can be adjusted by adding a diluent.

(F) As the diluent, a known diluent may be widely used. But are not limited to, for example, an? -Olefin derivative represented by the following formula (I) such as a saturated hydrocarbon solvent such as normal paraffin or isoparaffin, a linear dimer (trade name, manufactured by Idemitsu Kosan Co., Ltd.) Aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol and diacetone alcohol, ethyl acetate, butyl acetate, amyl acetate and cellosolve , Ester solvents such as acetyl triethyl citrate and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

R ⁵¹ -ZR ⁵² (I)

(In the formula (I), R ⁵¹ and R ⁵² each independently represents a straight chain alkyl group having 2 to 20 carbon atoms, and Z represents a divalent group represented by any one of the following formulas (Ia) to (Ic).)

(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 (F) is not particularly limited. However, considering the safety of the obtained curable composition, the curable composition preferably has a high flash point and less volatile substances from the curable composition.

Therefore, the flash point of the (F) diluent is preferably 60 ° C or higher, more preferably 70 ° C or higher. When two or more (F) diluents are mixed and used, it is preferable that the combined diluent has a flash point of 70 ° C or higher. However, in general, a diluent having a high flash point tends to have a low dilution effect with respect to the curable composition, so that the flash point is preferably 250 ° C or lower.

In consideration of safety and dilution effect of the curable composition of the present invention, (F) a diluent is preferably a saturated hydrocarbon solvent, and normal paraffin and isoparaffin are more suitable. The number of carbon atoms of normal paraffin and isoparaffin is preferably 10 to 16. Concretely, it is preferable to use N-11 (normal paraffin, JX Ichimitsu Energy Co., Ltd., carbon number 11, flash point 68 캜), N-12 (normal paraffin, JX sunlight one star energy (Product name, product number 12, carbon number 85 ° C), IP solvent 2028 (paraffin, product of Idemitsu Kosan Co., Ltd., carbon number 10 to 16, flash point 86 ° C).

The mixing ratio of the (F) diluent is not particularly limited, but it is preferable to mix 0 to 50 parts by mass of the (F) diluent with respect to 100 parts by mass of the organic polymer (A), more preferably 0.1 to 30 parts by mass , More preferably from 0.1 to 15 parts by mass. The (F) diluent may be used singly or in combination of two or more.

The curable composition of the present invention preferably contains a metal hydroxide. The metal hydroxide is blended to impart flame retardancy to improve workability and to reinforce the cured product. In addition, the metal hydroxide has an effect that the safety is higher than other flame retardants such as halogen-based flame retardants. In particular, by using a metal hydroxide and a surface-treated calcium carbonate in combination, workability (rheological property) can be further improved and flame retardancy can be imparted. The metal hydroxide may be a metal hydroxide surface-treated with a surface treating agent.

Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide and the like, and aluminum hydroxide is more preferable.

There is no particular limitation on the mixing ratio of the metal hydroxide, but the metal hydroxide is preferably blended in an amount of 0 to 500 parts by weight, more preferably 2 to 250 parts by weight, based on 100 parts by weight of the organic polymer (A) More preferably 5 to 125 parts by mass. These metal hydroxides may be used alone or in combination of two or more. Other known flame retardants may be used in combination.

The curable composition of the present invention may contain, in addition to the above components, an ultraviolet absorber, an antioxidant, an antioxidant, an adhesion imparting agent, a physical property adjuster, a plasticizer, a thixotropic agent, a dehydrating agent (storage stability improver), a flame retardant, An anti-sagging agent, a colorant, and a radical polymerization initiator may be added, or other commonly used polymers may be mixed.

The antioxidant is used for preventing oxidation of the curable composition and improving weather resistance and heat resistance. Examples thereof include hindered amine type and hindered phenol type antioxidant. As the sterically hindered amine antioxidant, for example, N, N ', N' ', N' '' - tetrakis- (4,6-bis (butyl- (N-methyl- -Tetramethylpiperidin-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- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- 6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}, dimethyl succinate and 4-hydroxy-2,2 , Polymers of 6,6-tetramethyl-1-piperidine ethanol, decane diacid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidine) - reaction product of dimethylethyl hydroperoxide and octane (70%) - polypropylene (30%), bis (1,2,2,6,6-pentamethyl-4- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2, 2,6,6-pentamethyl-4-piperidyl sebacate (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl -7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, and the like, but the present invention is not limited thereto. , For example, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5- butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5- (1,1-dimethylethyl) -4-hydroxy C7-C9 branched alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, di Ethyl [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ' 4-a, a ', a "- (methylene-2,4,6-triyl) tri-p-cresol, calcium diethylbis [[[ (5-tert-butyl-4-hydroxy-methyl) phosphine], 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis Propyl] propionate], hexamethylene bis [3- (3,5-di-tert-butyl-4- hydroxyphenyl) propionate], 1,3,5- 4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) The reaction product of benzene amine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5- Amino) phenol, and the like, but are not limited thereto. The antioxidant may be used alone, or two or more of them may be used in combination.

The ultraviolet absorber is used for preventing light deterioration of the curable composition and improving weather resistance. Examples of the ultraviolet absorber include ultraviolet absorbers such as benzotriazole, triazine, benzophenone and benzoate. As ultraviolet absorbers, for example, 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol- 4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzoyl) 2- (2H-benzotriazol-2-yl) -6- (linear and / or cyclic diisocyanate) reaction product of 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- (hexyl) oxy-phenol and the like Benzophenone-based ultraviolet absorber such as octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, , But the present invention is not limited thereto. The ultraviolet absorber may be used alone or in combination of two or more.

The antioxidant is used for preventing the deterioration of the curable composition and improving the heat resistance. Examples thereof include an antioxidant such as an amine-ketone, an aromatic secondary amine-based antioxidant, a benzimidazole-based antioxidant, a thiourea- An antioxidant, an antioxidant antioxidant, and the like.

Examples of the antioxidant such as amine-ketone include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4- Quinoline, and amine-ketone such as a reaction product of diphenylamine and acetone. However, the present invention is not limited thereto.

Examples of the aromatic secondary amine-based antioxidant include N-phenyl-1-naphthylamine, alkylated diphenylamine, octyldiphenylamine, 4,4'-bis (?,? - dimethylbenzyl) N, N'-di-2-naphthyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N- (p-toluenesulfonamide) diphenylamine, -Phenylenediamine, N-phenyl-N '- (3-methacryloyloxy) -phenylenediamine, N-phenyl- 2-hydroxypropyl) -p-phenylenediamine, and the like, but the present invention is not limited thereto.

Examples of the benzimidazole antioxidants include benzimidazole compounds such as 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and zinc salts of 2-mercaptobenzimidazole. But is not limited thereto.

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

As the above phosphorous acid-based antioxidant, there may be mentioned, for example, phosphorous acid-based compounds such as tris (nonylphenyl) phosphite and the like, but the present invention is not limited thereto.

Although the amount of the antioxidant to be used is not particularly limited, it is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the organic polymer (A) It is suitable to use in the range of mass part.

The physical property adjuster is added for the purpose of improving the physical properties of the curable composition such as tensile properties. As examples of the physical property adjuster, a silicone compound having one silanol group in one molecule and having a primary amino group is suitably used. As the silicone compound, for example, triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, diphenylalkylsilanol and the like can be given.

The plasticizer is added for the purpose of enhancing elongation properties after curing and enabling low modulus. The kind of the plasticizer is not particularly limited, and examples thereof include phthalates such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, di-sodecyl phthalate and diisodecyl phthalate; Aliphatic dibasic acid esters such as dioctyl adipate, isodecyl succinate, dioctyl sebacate and dibutyl adipate; Glycol esters such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate and pentaerythritol ester; Aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; Phosphoric acid esters such as tricresyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, tributyl phosphate, and tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and benzyl epoxystearate; Polyester plasticizers such as polyesters of dibasic acid and dihydric alcohol; Polyethers such as polypropylene glycol and derivatives of polyethylene glycol; Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether; repeating units such as triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, and triethylene glycol diethyl ether; 3, tetraethylene glycol diethyl ether, tetraethylene glycol ethyl methyl ether, tetraethylene glycol diethyl ether and the like, and polyoxyethylene alkyl ethers such as polyoxyethylene dimethyl ether ; Polystyrene such as poly-alpha-methylstyrene and polystyrene; Hydrocarbon oligomers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, water-added polybutadiene, water-added polyisoprene, and process oil; Chlorinated paraffins; Acrylic plasticizers such as UP-1080 (manufactured by Dong-A Synthetic Chemical Co., Ltd.) and UP-1061 (manufactured by Dong-A Synthetic Chemical Co., Ltd.); Acryl-based plasticizers such as UP-2000 (manufactured by Donga Chemical Co., Ltd.) and UHE-2012 (manufactured by Donga Chemical Co., Ltd.); UC-3510 (manufactured by East Asia Co., Ltd.); Epoxy-group-containing acrylic polymers such as UG-4000 (manufactured by Dong-A Synthetic Chemical Co., Ltd.); Silyl group-containing acrylic polymers of less than 0.8, preferably less than 0.4, such as US-6110 (manufactured by Dong-A Synthetic Co., Ltd.) and US-6120 (manufactured by Dong-A Synthetic Chemical Industry Co., Ltd.); An oxyalkylene resin containing less than 0.8 and preferably less than 0.4 silyl groups, and the like.

Examples of the shrinkage agent include inorganic whitening agents such as colloidal silica and asbestos powder, organic bentonites, modified polyester polyols, organic whitening agents such as fatty acid amides, water-added castor oil derivatives, fatty acid amide waxes, aluminum stearate , Barium stearate, and the like.

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.

As the flame retardant, for example, a phosphorus flame retardant such as ammonium polyphosphate; Metal oxide flame retardants such as antimony trioxide; Brominated flame retardants; Chlorine-based flame retardants and the like.

The curable composition of the present invention may be of a one-component type or a two-component type, if necessary, although a one-component type may be suitably used. The curable composition of the present invention can be cured at room temperature by the humidity in the atmosphere and is suitably used as a room temperature moisture curable curable composition, but may be suitably heated as needed to accelerate curing.

The method for producing the curable composition of the present invention is not particularly limited and may be produced by mixing a predetermined amount of the above components (A) to (C), containing other compounding materials as required, have. The reaction of the epoxy silane compound with the aminosilane compound in the silane compound (B) can be carried out by reacting the silane compound (B) obtained by previously reacting the epoxy silane compound with the aminosilane compound, Or a mixture in which a part or all of an epoxy silane compound, an aminosilane compound, and other compound materials are mixed, an epoxy silane compound is reacted with an aminosilane compound in the mixture, A curable composition may be prepared.

There is no particular limitation on the mixing order of the components (A) to (C), but it is preferable to mix the components (B) and (C) in advance and obtain a mixture containing the components (B) and (C) It is preferable to blend the component (A), and it is more preferable that the curing catalyst obtained by aging the mixture containing the components (B) and (C) at a predetermined temperature is blended with the component (A). Here, the aging is carried out by transesterifying a part of the alkoxy group of the titanium catalyst (C) with a part of the alkoxy group of the silane compound (B) and / or a part of the silane compound (B) Is hydrolyzed and oligomerized with the above (C) titanium catalyst. It is preferable to reach the state of chemical equilibrium by the above aging.

When the mixture of the silane compound (B) and the titanium catalyst (C) is used in advance, the mixing ratio of the silane compound (B) to the titanium catalyst (C) The amount of the (B) silane compound is preferably in the range of 0.1 to 30 mols, more preferably 0.5 to 5.0 mols, still more preferably 0.5 to 3.0 mols. The titanium catalyst (C) and the silane compound (B) may be used individually or in combination of two or more.

A method for obtaining a mixture of the silane compound (B) and the titanium catalyst (C) is a method in which the silane compound (B) is reacted with the silane compound (C) (C) a titanium catalyst, and reacting the epoxy silane compound with an aminosilane compound in the mixture to prepare a mixture of the silane (B) and the silane compound A mixture of a compound and (C) a titanium catalyst may be obtained.

The reaction temperature condition for aging the mixture containing the silane compound (B) and the titanium catalyst (C) is not particularly limited, but the reaction between the silane compound (B) and the titanium catalyst (C) More preferably 30 ° C to 90 ° C, and even more preferably 40 ° C to 80 ° C. By setting the reaction temperature within the above range, it is possible to stably proceed the reaction without congestion. When the reaction temperature is lower than 30 占 폚, the activity is lowered, the time required for obtaining a sufficient reaction is prolonged, and it is inefficient. The reaction time can be suitably set in consideration of the reaction temperature and the like, but it is preferable to carry out the reaction at least until the equilibrium state is reached. For example, under the above conditions, the reaction time is generally 1 to 336 hours, It is preferable to set it within the range of 72 to 168 hours.

The mixing sequence of the compounding materials other than the components (A) to (C) may be suitably determined without any particular limitation. When a mixture in which the components (B) and (C) are premixed is used, a mixture may be obtained by mixing other components with the components (B) and (C) (B) and (C) may be blended to obtain a mixture. Alternatively, another compounding material may be added to the mixture containing the components (B) and (C) do. In the case of using a curing catalyst obtained by aging a mixture containing the components (B) and (C), it is preferable to add other compounding materials before the aging step and to subject the mixture containing the components (B), (C) Or other ingredients may be added after the aging step. Alternatively, other ingredients may be added after the aging step and aged at a predetermined temperature. Further, the composition containing all of the compounding materials may be aged at a predetermined temperature.

In the case of mixing the component (D) with another compounding material, there is no particular limitation on the mixing order, but it is possible to obtain a mixture in which the components (C) and (D) Or a mixture containing the components (C) and (D), for example, by mixing the component (A) with the mixture, after obtaining a mixture in which the components (B) It is preferable to blend the remaining compounding materials.

When a mixture of the titanium catalyst (C) and the silane compound (D) is used in advance, the mixing ratio of the titanium catalyst (C) to the silane compound (D) The amount of the silane compound (D) is preferably 0.1 to 30 mols, more preferably 0.5 to 5.0 mols, and still more preferably 0.5 to 3.0 mols. The titanium catalyst (C) and the silane compound (D) may be used individually or in combination of two or more.

When a silane compound having an alkoxysilyl group is used as the component (D), it is more preferable to blend a curing catalyst that ages the mixture containing the components (C) and (D) at a predetermined temperature with the remaining compounding materials. Here, the aging is carried out by transesterifying a part of the alkoxy group of the titanium catalyst (C) and a part of the alkoxy group of the silane compound (D) and / or by carrying out a transesterification reaction of a part of the silane compound (D) (C) a titanium catalyst to oligomerize a part thereof. By such aging, it is preferable to reach a state of chemical equilibrium.

The reaction temperature condition for aging the mixture containing the titanium catalyst (C) and the silane compound (D) is not particularly limited, but the reaction between the titanium catalyst (C) and the silane compound (D) at 30 ° C to 100 ° C More preferably 30 ° C to 90 ° C, and even more preferably 40 ° C to 80 ° C. By setting the reaction temperature within the above range, it is possible to stably proceed the reaction without congestion. When the reaction temperature is lower than 30 占 폚, the activity is lowered and the time required for achieving a sufficient reaction is prolonged and inefficient. The reaction time can be suitably set in consideration of the reaction temperature and the like, but it is preferable to carry out the reaction at least until the equilibrium state is reached. For example, under the above conditions, the reaction time is generally 1 to 336 hours, It is preferable to set it within the range of 72 to 168 hours.

In the present invention, the aging of the components (B) and (C) and the aging of the components (C) and (D) described above may or may not be satisfactory, but it is preferable to perform aging at least either, Is more preferable. In the case of aging, there is no limitation on the aging sequence, but since the production process is simplified, in terms of workability, it is preferable to simultaneously aging the mixture of components (B) to (D) at a predetermined temperature, The mixture containing one of the components (B) and (D) and the component (C) is aged at a predetermined temperature and then the other of the components (B) and (D) (B) and (C) are aged, and the components (B) and (D) are aged, and if necessary, further mixing The method of aging the mixture is preferred. By carrying out the above aging step, the storage stability can be further improved.

When the component (E) is contained in another compounding material, the mixing procedure may be suitably determined without any particular limitation. When the components (B) and (C) described above are aged and the components (C) and (D) are aged, it is preferable to blend the component (E) after the aging step.

In the case of mixing the component (F) with another compounding material, there is no particular limitation on the mixing order, but it is preferable to add one or both of the components (B) and (D) It is preferable to aged at a predetermined temperature. In this case, the mixture containing one or both of the components (B) and (D), the component (C) and the component (F) may be matured at the same temperature at the same time, or one of the components (B) and The mixture containing both components and component (C) may be aged simultaneously at a predetermined temperature, and then the component (F) may be added to the mixture, followed by aging at a predetermined temperature. It is more preferable to blend the component (F) after the aging step of the components (B) to (D), and to perform a further aging step so as to lower the change rate of the curing time after storage. By carrying out the above aging step, the storage stability can be further improved.

The curable composition of the present invention can be used as an adhesive, a sealant, a pressure-sensitive adhesive, a coating material, a potting material, a paint, a putty material and a primer. Since the curable composition of the present invention is excellent in adhesiveness, storage stability and curability, it is preferably used for an adhesive, but it can be used for various buildings, automobiles, civil engineering, electric and electronic fields, and the like.

(Example)

The present invention will be described in more detail with reference to the following examples, but it goes without saying that these examples are illustrative and are not to be construed as limiting.

In the synthesis examples, the examples and the comparative examples, analysis and measurement were carried out according to the following methods.

1) Number average molecular weight measurement

Was measured by gel permeation chromatography (GPC) under the following conditions. In the present invention, the molecular weight at the maximum frequency measured by GPC under the above measurement conditions and converted to standard polyethylene glycol is referred to as the number average molecular weight.

THF solvent measuring device

Analytical instrument: Alliance (Waters), 2410 type differential refractometer (Waters), 996 type multi-wavelength detector (Waters), Milleniam data processor (Waters)

Column: Plgel GUARD + 5 μm × 3 × (50 × 7.5 mm, 300 × 7.5 mm, manufactured by PolymerLab)

· Flow rate: 1 mL / min

· Converted polymer: Polyethylene glycol

· Measuring temperature: 40 ℃

FT-NMR measurement apparatus: JNM-ECA500 (500 MHz) manufactured by Japan Electronics Co.,

FT-IR measuring apparatus: FT-IR460Plus manufactured by Nippon Bunko K.K.

2) Storage stability test, curing (TFT) test and thixotropic test

The viscosity, curing time and structural viscosity index (SVI value) immediately after the combination of the curable composition were measured. The above conditions were referred to as initial, and the measured viscosity, curing time and SVI value were set as initial viscosity, initial TFT and initial SVI value, respectively.

The viscosity was measured by a BS type rotational viscometer (rotor No. 7-10 rpm) when the viscosity of the curable composition was 160 Pa · s or more. When the viscosity of the curable composition was less than 160 Pa · s, a BH type rotational viscometer (rotor No. 7-20 rpm ) (Measured temperature 23 캜).

The curing time was measured in accordance with JIS A 1439 5.19 Tack Free Test under the environment of 23 ° C RH and 50% RH.

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 curable composition is less than 160 Pa · s, The viscosity was calculated by dividing the viscosity at 2 rpm by the viscosity at 20 rpm using a rotational viscometer (rotor No. 7) (measurement temperature 23 캜). The required SVI value was used as an indicator of thixotropy.

Next, the curable composition in the sealed glass container was left under a 50 캜 atmosphere for 1, 2, or 4 weeks, and the viscosity, curing time, and SVI value were measured. The measured viscosity, time for curing and SVI value were defined as the viscosity after storage, the TFT after storage, and the SVI value after storage, respectively.

The viscosity after storage was divided by the initial viscosity to calculate the increase rate. The increase rate after storage for 1 week was evaluated as the following evaluation criteria.

?: Not less than 0.90 and not more than 1.40,?: Not less than 1.41 and not more than 1.50,?: Not less than 1.51 and not more than 1.60, and X: not less than 1.61 or not more than 0.89.

Further, the storage ratio of the TFT after storage was divided by the initial TFT, and the rate of change was calculated. The rate of change after one week of storage was evaluated as the following evaluation criteria.

?: Not less than 0.90 and not more than 1.10,?: Not less than 0.80 and not more than 0.89, or not less than 1.11 and not more than 1.30,?: Not less than 1.31 and not more than 1.40 or not less than 0.70 and not more than 0.79 X:

3) Surface hardening test

And allowed to stand for 7 days in an environment of 23 DEG C RH and 50% to prepare a cured product of a curable composition having a size of 100 mm x 100 mm x 3 mm and judge it as touching (hand-touch feeling). The evaluation criteria are as follows.

?: Not sticky at all,?: Not sticky,?: Sticky, X: very sticky.

4) Adhesion test

0.2 g of the curable composition was uniformly coated on the adherend and immediately bonded to an area of 25 mm x 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 being squeezed by eyeball clips in an atmosphere of 23 ° C RH and 50% for 7 days. Examples of the material to be adhered include a hard PVC, a polycarbonate (PC), a polystyrene (PS), an ABS resin (ABS), an acrylic resin (PMMA), a nylon 6 (Ny), a cold rolled steel sheet (SPCC) Aluminum (Al) was used. The fracture state of the adhesive surface was evaluated by the following evaluation criteria.

CF: Cohesive failure, AF: Adhesive failure, C10A90 to C90A10: An approximate percentage of the area of the fracture state of CF and AF, and CnA (100-n) represents the fracture state of CFn% and AF it means.

5) Transparency test

The curable composition was increased by using a spacer of 3 mm between acrylic plates having a thickness of 2 mm and the transparency was visually observed and evaluated according to the following evaluation criteria.

?: Colorless transparent,?: Colorless and slightly opaque, X: opaque state.

(Synthesis Example 1)

A flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer and a reflux condenser was charged with propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst with ethylene glycol as an initiator to obtain a hydroxyl group having a reduced molecular weight of 24,000, Distribution 1.3 Polyoxypropylene triol was obtained. A methanol solution of sodium methoxide was added to the obtained polyoxypropylene diol, and the methanol was distilled under heating and reduced pressure to convert the terminal hydroxyl groups of the polyoxypropylene triols to sodium alkoxide to obtain a polyoxyalkylene polymer M1.

Next, the polyoxyalkylene polymer M1 was reacted with allyl chloride at the compounding ratio shown in Table 1 to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. To the polyoxyalkylene polymer having an allyl group at the terminal thereof, trimethoxysilane, which is a silicon hydride compound, was added and reacted with 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt% to obtain a polyoxyalkylene group having a trimethoxysilyl group To obtain an alkylene-based polymer A1.

The molecular weight of the resulting polyoxyalkylene polymer A1 having a trimethoxysilyl group at the terminal thereof was measured by GPC to find that the peak top molecular weight was 25,000 and the molecular weight distribution was 1.3. According to H1-NMR measurement, the terminal trimethoxysilyl group was 1.7 per one molecule.

(Synthesis Example 2)

A flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer and a reflux condenser was charged with propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst with ethylene glycol as an initiator and the resulting hydroxyl group had a reduced molecular weight of 11000 and a molecular weight To obtain a polyoxypropylene diol having a distribution of 1.3. A methanol solution of sodium methoxide was added to the obtained polyoxypropylene triol, and the methanol was distilled under heating and reduced pressure to convert the terminal hydroxyl groups of the polyoxypropylene triols into sodium alkoxide, thereby obtaining a polyoxyalkylene polymer M2.

The polyoxyalkylene polymer M2 was reacted with allyl chloride at the compounding ratios shown in the following Table 1 to remove unreacted allyl chloride and purified to obtain a polyoxyalkylene polymer having an allyl group at the terminal. Trimethoxysilane, which is a silicon hydride compound, was added to 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt% to react with the polyoxyalkylene polymer having an allyl group at this end to obtain a polyoxyalkylene having a trimethoxysilyl group To thereby obtain a polymer A2 of the rhenylene group.

The molecular weight of the obtained polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal thereof was measured by GPC to find that the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3. According to H1-NMR measurement, the terminal trimethoxysilyl group was 1.7 per one molecule.

Synthetic Example No. One 2 Composition: (A) Polymer A1 A2 The polyoxyalkylene-based polymer M1 100.00 - The polyoxyalkylene polymer M2 - 100.00 Allyl chloride 0.74 1.53 Trimethoxysilane 1.17 2.44

In Table 1, the compounding amount of each compounding material is expressed in g. The polyoxyalkylene polymers M1 to M2 are the polyoxyalkylene polymers M1 to M2 obtained in Synthesis Example 1-2, respectively.

(Synthesis Example 3)

As shown in Table 2, 184 g of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, . In another container, 247 g of methyl methacrylate, 23 g of n-butyl acrylate, 56 g of lauryl methacrylate (trade name: LIGHT ESTER L, available from Kyorifu K.K.), 3 g of 3-acryloxypropyltrimethoxy 58.64 g of silane (trade name: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 26.21 g of 3-mercaptopropyltrimethoxysilane and 15.73 g of AIBN were mixed and stirred, . After completion of the dropwise addition, the mixture was further reacted for 3 hours to obtain a vinyl-based polymer A3 having a trimethoxysilyl group.

The molecular weight of the obtained vinyl polymer A3 was measured by GPC, and as a result, the peak top molecular weight was 3,000 and the molecular weight distribution was 1.6. It was 2.00 per molecule of trimethoxysilyl group contained by H1-NMR measurement.

(Synthesis Example 4)

As shown in Table 2, a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer and a reflux condenser was charged with 43.00 g of m-xylene, 80.00 g of methyl methacrylate, 2-ethylhexyl methacrylate ) Product, 20.00 g of acryloxymethyltrimethoxysilane (manufactured by Gelest), and 0.10 g of zirconocene dichloride as a metal catalyst were introduced, and the contents of the flask were heated to 80 캜 while introducing nitrogen gas . Subsequently, 3.65 g of mercaptopromethyltrimethoxysilane sufficiently purged with nitrogen gas was added to the flask under stirring at one time. After adding 3.65 g of mercaptomethyltrimethoxysilane, heating and cooling were carried out for 4 hours so that the temperature of the contents of the flask during stirring could be maintained at 80 캜. Further, 3.65 g of mercaptopromethyltrimethoxysilane sufficiently purged with nitrogen gas was further added to the flask over 5 minutes while stirring. Mercapto methyltrimethoxysilane was further added to the flask, and the mixture was reacted for 4 hours while cooling and warming the mixture so that the temperature of the content of the flask in the flask could be maintained at 90 캜. After the reaction for 8 hours and 5 minutes in total, the temperature of the reaction product was returned to room temperature, and 20.00 g of a benzoquinone solution (95% THF solution) was added to the reaction product to terminate the polymerization to obtain a vinyl polymer A4 having a trimethoxysilyl group.

The molecular weight of the obtained vinyl-based polymer A4 was measured by GPC, and as a result, the peak top molecular weight was 4000 and the molecular weight distribution was 1.6. The trimethoxysilyl group contained by the H1-NMR measurement was 2.00 per molecule.

(Synthesis Example 5)

As shown in Table 2, 400 g of a polyoxyalkylene polymer A1 having a trimethoxysilyl group at the terminal thereof obtained in Synthesis Example 1 was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, 200 g of a polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal thereof was added, and the mixture was heated to 80 占 폚. In another container, 247 g of methyl methacrylate (trade name: LIGHT ESTEER M, manufactured by Kyoeisha Co., Ltd.), 23 g of n-butyl acrylate, stearyl methacrylate (trade name: LIGHTESTER S, 45 g of 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, Shin-Etsu Chemical Co., Ltd.), 23.77 g of 3-mercaptopropyltrimethoxysilane, 10.56 g of AIBN, After mixing and stirring, the mixture was charged into a dropping device and dropped over 3 hours. After completion of the dropwise addition, the mixture was further reacted for 3 hours to obtain an organic polymer A5 having a trimethoxysilyl group as a mixture of a polyoxyalkylene polymer, a polyoxyalkylene polymer and a vinyl polymer.

The molecular weight of the organic polymer A5 having the trimethoxysilyl group thus obtained was measured by GPC, and as a result, the peak top molecular weight was 4000 and the molecular weight distribution was 1.6. According to H1-NMR measurement, the terminal trimethoxysilyl group was 2.35 per molecule.

(Synthesis Example 6)

As shown in Table 2, a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer and a reflux condenser was charged with 40.00 g of ethyl acetate, 70.00 g of methyl methacrylate, 2-ethylhexyl methacrylate ) Product, 12.00 g of 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, Shin-Etsu Chemical Co., Ltd.) and 0.10 g of titanocene dichloride as a metal catalyst were introduced into a flask While the contents of the flask were heated to 80 占 폚. Subsequently, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently purged with nitrogen gas was added at once to the flask under stirring. After adding 4.30 g of 3-mercaptopropyltrimethoxysilane, heating and cooling were carried out for 4 hours so that the temperature of the content in the flask while stirring could be maintained at 80 캜. Further, 4.30 g of 3-mercaptopropyltrimethoxysilane sufficiently purged with nitrogen gas was further added to the flask over 5 minutes under stirring. After the addition of the entire amount of 4.30 g of 3-mercaptopropyltrimethoxysilane, the reaction was carried out for 4 hours while further cooling and heating so that the temperature of the content in the flask in the flask under stirring could be maintained at 90 캜. After a total reaction time of 8 hours and 5 minutes, the temperature of the reaction product was returned to room temperature, and 20.00 g of a benzoquinone solution (95% THF solution) was added to the reaction product to terminate the polymerization to obtain a vinyl polymer A6 having a trimethoxysilyl group. The peak top molecular weight was 4000 and the molecular weight distribution was 2.4. The trimethoxysilyl group contained by the H1-NMR measurement was 2.00 per molecule.

Synthetic Example No. 3 4 5 6 Composition: (A) Polymer A3 A4 A5 A6 Methyl methacrylate 247.00 80.00 247.00 70.00 n-butyl acrylate 23.00 - 23.00 - Lauryl methacrylate 56.00 - - - Stearyl methacrylate - - 49.00 - 2-ethylhexyl methacrylate - 20.00 - 30.00 3-acryloxypropyltrimethoxysilane 58.64 - - - 3-methacryloxypropyltrimethoxysilane - - 45.00 12.00 Acryloxymethyltrimethoxysilane - 20.00 - 3-mercaptopropyltrimethoxysilane 26.21 - 23.77 8.60 Mercaptomethyltrimethoxysilane - 7.30 - - AIBN 15.73 - 10.56 - Zirconocene dichloride - 0.10 - - Titanocene dichloride - - - 0.10 Ethyl acetate 184.00 - - 40.00 m-xylene - 43.00 - - The polyoxyalkylene polymer A1 - - 400.00 - The polyoxyalkylene polymer A2 - - 200.00 -

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

(Synthesis Example 7)

As shown in Table 3, a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser was charged with 3-aminopropyltrimethoxysilane (trade name: Z-6610, manufactured by Toray Dow Corning Silicone Co., ) And 276 g of 3-glycidoxypropyltrimethoxysilane (trade name: Z-6040, manufactured by Dow Corning Silicone Co., Ltd.) were added, and the mixture was stirred at 50 캜 for 72 hours to obtain a silane compound B1.

In the obtained silane compound B1, the disappearance of a peak due to an epoxy group at about 910 cm ^-1 in FT-IR was confirmed, and a peak of a secondary amine near 1140 cm ^-1 was confirmed. Further, at ²⁹ Si- And the appearance of a new peak at 70 ppm was confirmed.

(Synthesis Example 8)

3-aminopropyltrimethoxysilane (trade name: Z-6610, manufactured by Dow Corning Silicone Co., Ltd.) was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, And 276 g of 3-glycidoxypropyl trimethoxysilane (trade name: Z-6040, manufactured by Toray Dow Corning Silicone Co., Ltd.) were added and stirred at 23 占 폚 for 168 hours to obtain a silane compound B2.

In the resulting silane compound B2, was made in a FT-IR confirmed the disappearance of the peak due to the epoxy group in the vicinity of 910cm ^-1 and confirmed that the peak of the secondary amine in the vicinity of 1140cm ^-1. No peak was observed at -60 ppm to -70 ppm by ²⁹ Si-NMR.

(Synthesis Example 9)

3-aminopropyltrimethoxysilane (trade name: Z-6610, manufactured by Dow Corning Silicone Co., Ltd.) was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, And 100 g of 3-glycidoxypropyltrimethoxysilane (trade name: Z-6040, manufactured by Dow Corning Toray Silicone Co., Ltd.) were added and stirred at 50 ° C for 72 hours to obtain a silane compound B3.

In the obtained silane compound B3, the disappearance of a peak due to an epoxy group at about 910 cm ^-1 in FT-IR was confirmed, and a peak of a secondary amine at about 1140 cm ^-1 was confirmed. Further, at ²⁹ Si- And the appearance of a new peak at 70 ppm was confirmed.

(Synthesis Example 10)

3-aminopropyltrimethoxysilane (trade name: Z-6610, manufactured by Dow Corning Silicone Co., Ltd.) was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, And 100 g of 3-glycidoxypropyltrimethoxysilane (trade name: Z-6040, manufactured by Toray Dow Corning Silicone Co., Ltd.) were added and stirred at 50 ° C for 72 hours to obtain a silane compound B4.

In the obtained silane compound B4, the disappearance of a peak due to an epoxy group at about 910 cm ^-1 in FT-IR was confirmed, and a peak of a secondary amine at around 1140 cm ^-1 was confirmed. Further, at ²⁹ Si- And the appearance of a new peak at 70 ppm was confirmed.

Synthetic Example No. 7 8 9 10 Composite: (B) Silane compound B1 B2 B3 B4 3-aminopropyltrimethoxysilane 100.00 100.00 44.62 31.61 3-glycidoxypropyltrimethoxysilane 276.00 276.00 100.00 100.00 Epoxy silane / aminosilane (molar ratio) 2.09 2.09 1.70 2.40 Reaction temperature condition (캜) 50 23 50 50

In Table 3, the compounding amount of each compounding material is expressed in g.

(Comparative Synthesis Example 1)

As shown in Table 4, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser (Product of Shin-Etsu Chemical Co., Ltd.) and 127.5 g of 3-glycidoxypropyltrimethoxysilane were added, and the mixture was stirred at 50 ° C for 72 hours to obtain a silane compound X1.

In the resulting silane compound, X1, from the FT-IR confirmed the disappearance of the peak of the amino group of 1410cm ^-1, 1120cm ^-1 vicinity, and confirmed the disappearance of the peak due to the epoxy group in the vicinity of 910cm ^-1. No peak was observed at -60 ppm to -70 ppm by ²⁹ Si-NMR.

(Comparative Synthesis Example 2)

As shown in Table 4, 3-aminopropyltrimethoxysilane (trade name: Z-6610, manufactured by Dow Corning Silicone Co.) was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, And 15.82 g of 3-glycidoxypropyltrimethoxysilane (trade name: Z-6040, manufactured by Toray Dow Corning Silicone Co., Ltd.) were added, and the mixture was stirred at 50 ° C for 72 hours to obtain a silane compound X2.

In the obtained silane compound X2. In the FT-IR confirmed the disappearance of the peak due to the epoxy group in the vicinity of and 910cm ^-1 was confirmed that the peak of the secondary amine in the vicinity of 1140cm ^-1, and verify the appearance of new peaks at -60ppm to -70ppm by ²⁹ Si-NMR I could.

(Comparative Synthesis Example 3)

As shown in Table 4, 3-aminopropyltrimethoxysilane (trade name: Z-6610, manufactured by Dow Corning Silicone Co.) was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, And 158.20 g of 3-glycidoxypropyltrimethoxysilane (trade name: Z-6040, manufactured by Toray Dow Corning Silicone Co., Ltd.) were further added and stirred at 50 ° C for 72 hours to obtain a silane compound X3.

In the obtained silane compound X3, the disappearance of a peak due to an epoxy group at about 910 cm ^-1 in FT-IR was confirmed, and a peak of a secondary amine at about 1140 cm ^-1 was confirmed. Further, at ²⁹ Si-NMR, And the appearance of a new peak at 70 ppm was confirmed.

Comparative Synthetic Example No. One 2 3 Compound: silane compound X1 X2 X3 3-aminopropyltrimethoxysilane - 10.00 10.00 N-2- (aminoethyl) -3-aminopropyltrimethoxysilane 50.00 - - 3-glycidoxypropyltrimethoxysilane 127.50 15.82 158.20 Epoxy silane / aminosilane (molar ratio) 2.40 1.20 12 Reaction temperature condition ℃ 50 50 50

In Table 4, the blending amount of each compounding material is expressed in g.

(Synthesis Example 11)

100 g of the silane compound B1 obtained in Synthesis Example 7 was placed in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device, and a reflux condenser, and then 100 g of Olgatix TC-750 [manufactured by Matsumoto Fine Chemicals Co., 63.1 g of titanium diisopropoxybis (ethylacetate)] was added and aged by heating at 70 캜 for 144 hours to obtain a titanium catalyst G1. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G1.

(Synthesis Example 12)

100 g of the silane compound B1 obtained in Synthesis Example 7 was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, 126.2 g of Olgitics TC-750 was added, And aged by heating with stirring for 144 hours to obtain a titanium catalyst G2. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G2.

(Synthesis Example 13)

In a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, 23.47 g of triethylamine, 10 g of titanium tetrachloride and 17.19 g of t-butyl alcohol were added. The mixture was stirred at room temperature for 2 hours, and the precipitate was filtered and distilled to obtain titanium tetra-t-octoxide. 10 g of the obtained titanium tetra-t-butoxide and 7.65 g of ethyl acetoacetate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were added and the mixture was stirred at room temperature for 2 hours and then at 70 ° C for 2 hours. After completion of the reaction, unreacted materials and the like were removed under reduced pressure to obtain a titanium catalyst C1.

Then, 19.85 g of the silane compound B1 obtained in Synthesis Example 7 was added to 14.12 g of the titanium catalyst C1 obtained as shown in Table 5, and the mixture was heated and agitated at 50 占 폚 for 72 hours for aging to obtain a titanium catalyst G3. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G3.

(Synthesis Example 14)

50 g of titanium tetraisopropoxide (trade name: Oligitics TA-10, manufactured by Matsumoto Fine Chemical Co., Ltd.) and 50 g of methyl acetoacetate (manufactured by Japan Synthetic Co., Ltd.) were charged in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser Ltd.) was added, and the mixture was stirred at room temperature for 2 hours and then at 70 ° C for 2 hours. After completion of the reaction, unreacted materials and the like were removed under reduced pressure to obtain a titanium catalyst C2.

Subsequently, 106.96 g of the silane compound B1 obtained in Synthesis Example 7 was added to 69.71 g of the obtained titanium catalyst C2 as shown in Table 5, and aged by heating at 60 캜 for 168 hours to obtain a titanium catalyst G4. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G4.

(Synthesis Example 15)

In a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, 50 g of titanium tetraisopropoxide and 50.72 g of isopropyl acetoacetate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Followed by stirring at 70 ° C for 2 hours. After completion of the reaction, unreacted materials and the like were removed under reduced pressure to obtain a titanium catalyst C3.

Then, 118.85 g of the silane compound B1 obtained in Synthesis Example 7 was added to 79.58 g of the obtained titanium catalyst C3 as shown in Table 5, and the mixture was agitated by heating at 70 캜 for 72 hours to obtain a titanium catalyst G5. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G5.

(Synthesis Example 16)

As shown in Table 5, a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device, and a reflux condenser was charged with 118.85 g of the silane compound B2 obtained in Synthesis Example 8, 100 g of vinyltrimethoxysilane (trade name: KBM1003, (Manufactured by Nippon Kayaku Co., Ltd.) and 78.88 g of Olgitics TC-750 were agitated by heating and stirring at 70 캜 for 144 hours to obtain a titanium catalyst G6. The change in fink was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G6.

(Synthesis Example 17)

184.28 g of the silane compound B2 obtained in Synthesis Example 8 and 100.00 g of the Oligitics TC-750 were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, And aged by heating with stirring to obtain titanium catalyst G7. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G7.

(Synthesis Example 18)

As shown in Table 5, 126.93 g of the silane compound B3 obtained in Synthesis Example 9 and 100.00 g of Olgytix TC-750 were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, The mixture was agitated by heating for a period of time to obtain a titanium catalyst G8. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G8.

(Synthesis Example 19)

156.37 g of the silane compound B4 obtained in Synthesis Example 10 and 100.00 g of Olgytix TC-750 were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, The mixture was agitated by heating with stirring for a period of time to obtain a titanium catalyst G9. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G9.

Synthetic Example No. 11 12 13 14 15 16 17 18 19 Compound: titanium catalyst G1 G2 G3 G4 G5 G6 G7 G8 G9 (B) Silane Compound B1 100.00 100.00 19.85 106.96 118.85 - - - - (B) Silane Compound B2 - - - - - 118.85 184.28 - - (B) Silane compound B3 - - - - - - - 126.93 - (B) Silane compound B4 - - - - - - - - 156.37 (C) Oligitics TC750 63.10 126.20 - - - 78.88 100.00 100.00 100.00 (C) Titanium Catalyst C1 - - 14.12 - - - - - - (C) titanium catalyst C2 - - - 69.71 - - - - - (C) titanium catalyst C3 - - - - 79.58 - - - - (D) Vinyltrimethoxysilane - - - - - 3.80 - - - (B) / (C) (molar ratio) 1.0 0.5 1.0 1.0 1.0 0.8 2.0 1.75 2.0

In Table 5, the compounding amount of each compounding material is expressed in g. The silane compounds B1 to B4 were the silane compounds B1 to B4 obtained in Synthesis Example 7-10, and the titanium catalysts C1 to C3 were the titanium catalysts C1 to C3 obtained in Synthesis Examples 13 to 15, respectively. same.

Oligitics TC-750: product name of Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis (ethylacetate).

Vinyltrimethoxysilane: Product name: KBM1003, manufactured by Shinwol Chemical Industry Co., Ltd.

(Synthesis Example 20)

As shown in Table 6, 10 g of the silane compound B1 obtained in Synthesis Example 7 and 40 g of Olgitt TC-750 were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, And aged by heating and stirring to obtain titanium catalyst G10. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G10.

(Synthesis Example 21)

60 g of the silane compound B1 obtained in Synthesis Example 7 and 40 g of Olgytix TC-750 were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, and the mixture was stirred at 70 DEG C for 144 hours After aging by heating and stirring, 100 g of normal paraffin (trade name: N-11, manufactured by JX Ikki Seiki Energy Co., Ltd.) was added and aged by heating at 70 캜 for 144 hours to obtain a titanium catalyst G11. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G11.

(Synthesis Example 22)

A titanium catalyst G12 was obtained in the same manner as in Synthesis Example 21 except that the compounding ratio of the compounding material was changed as shown in Table 6. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G12.

(Synthesis Example 23)

10 g of the silane compound B1 obtained in Synthesis Example 7 was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, and 10 g of (D) phenyltrimethoxysilane (trade name: KBM103 Manufactured by Shin-Etsu Chemical Co., Ltd.), 40 g of Olgytix TC-750 and 100 g of normal paraffin were added and aged by heating and stirring at 70 ° C for 144 hours to obtain a titanium catalyst G13. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G13.

(Synthesis Example 24)

A titanium catalyst G14 was obtained in the same manner as in Synthesis Example 23, except that the compounding ratio of the compounding material was changed as shown in Table 6. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G14.

(Synthesis Examples 25 to 28)

Titanium catalysts G15 to G18 were obtained in the same manner as in Synthesis Example 24 except that the (D) silane compound was changed as shown in Table 6. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalysts G15 to G18.

(Synthesis Example 29)

10 g of the silane compound B1 obtained in Synthesis Example 7 was added to a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, and 10 g of (D) phenyltrimethoxysilane (trade name: KBM103 (Manufactured by Shin-Etsu Chemical Co., Ltd.), 40 g of Olgitics TC-750 was added, and the mixture was aged by heating at 70 DEG C for 144 hours, aged. 100 g of normal paraffin was added and the mixture was heated and stirred at 70 DEG C for 144 hours And aged to obtain a titanium catalyst G19. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G19.

(Synthesis Example 30)

10 g of the silane compound B1 obtained in Synthesis Example 7 and 40 g of Olgytix TC-750 were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube, a thermometer, a dropping device and a reflux condenser, and heated at 70 DEG C for 144 hours 50 g of phenyltrimethoxysilane (trade name: KBM103, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane compound (D) and 100 g of normal paraffin were added to the mixture (D), and the mixture was heated and agitated at 70 DEG C for 144 hours To obtain a titanium catalyst G20. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G20.

(Synthesis Example 31)

Titanium catalyst G21 was obtained in the same manner as in Synthesis Example 29, except that the compounding ratio of the compounding material was changed as shown in Table 6. The change in peak was confirmed by ²⁹ Si-NMR in the obtained titanium catalyst G21.

Synthetic Example No. 20 21 22 23 24 25 26 27 28 29 30 31 composite:
Titanium catalyst G10 G11 G12 G13 G14 G15 G16 G17 G18 G19 G20 G21 (B) Silane Compound B1
10.00 60.00 84.00 10.00 47.00 47.00 47.00 47.00 47.00 10.00 10.00 48.00 (C) Oligitics TC750
40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 (D) phenyltrimethoxysilane - - - 50.00 25.00 - - - - 50.00 50.00 - (D) Vinyltrimethoxysilane - - - - - 19.00 - - - - - 4.00 (D) Methyltrimethoxysilane - - - - - - 17.00 - - - - - (D) 3-glycidoxypropyltrimethoxysilane - - - - - - - 30.00 - - - - (D) decyltrimethoxysilane - - - - - - - - 33.00 - - - (F) Normal paraffin
- 100 100 100 100 100 100 100 100 100 100 100

In Table 6, the compounding amount of each compounding material is expressed in g. The silane compound B1 is the silane compound B1 obtained in Synthesis Example 7, and the details of the other compounding materials are as follows.

Oligitics TC-750: product name of Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis (ethylacetate).

Phenyltrimethoxysilane: trade name: KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.

Vinyltrimethoxysilane: trade name: KBM-1003, manufactured by Shinwol Chemical Industry 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 Shinwol Chemical Industry Co., Ltd.

(Example 1)

50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 10 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Was mixed with 40 g of the vinyl-based polymer obtained in Synthesis Example 4 in terms of solid content of A4. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomer and m-xylene contained in the vinyl-based polymer A4 and cooled to room temperature. Thereafter, 16.5 g of the titanium catalyst G2 obtained in Synthesis Example 12 was added, and the mixture was degassed and stirred at 25 캜 to obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 8.

(Example 2)

50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 10 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Was mixed with 40 g in terms of solid content of vinyl polymer A3 obtained in Synthesis Example 3. The mixture was heated (120 ° C) and deaerated under reduced pressure to remove the remaining monomers and ethyl acetate contained in the vinyl-based polymer A3 and cooled to room temperature. Thereafter, 11.0 g of the titanium catalyst G3 obtained in Synthesis Example 13 was added, and the mixture was deaerated and stirred at 25 캜 to obtain a curing composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 8.

(Example 3)

50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 10 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Was mixed with 40 g in terms of solid content of vinyl polymer A3 obtained in Synthesis Example 3. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl-based polymer A3 and cooled to room temperature. Thereafter, 9.0 g of the titanium catalyst G4 obtained in Synthesis Example 14 was added, followed by degassing and stirring at 25 캜 to obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 8.

(Example 4)

As shown in Table 7, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 50 g of the polyoxyalkylene polymer obtained in Synthesis Example 2 were added to a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- A2 was mixed with 40 g in terms of solid content of the vinyl polymer A3 obtained in Synthesis Example 3. The mixture was heated (120 ° C) and deaerated under reduced pressure to remove the remaining monomers and ethyl acetate contained in the vinyl-based polymer A3 and cooled to room temperature. Thereafter, 11.0 g of the titanium catalyst G5 obtained in Synthesis Example 15 was placed and deaerated and stirred at 25 캜 to obtain a curing composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 8.

(Example 5)

As shown in Table 7, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 50 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- Was mixed with 40 g in terms of solid content of the vinyl-based polymer A3 obtained in Synthesis Example 3. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl polymer A3 and cooled to room temperature. Thereafter, 9.0 g of the titanium catalyst G6 obtained in Synthesis Example 16 was added, followed by degassing and stirring at 25 캜 to obtain a curing composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 8.

(Example 6)

100 g of the polymer A5 obtained in Synthesis Example 5, (E) 50 g of the MC coat P-1 as the surface-treated calcium carbonate, 1 g of Diparron # 6500 and 1 g of antioxidant Roncrack CD were added to the solution and heated (100 ° C), deaeration and stirring were continued for 1 hour, and the temperature was returned to room temperature (25 ° C) And 10 g of the titanium catalyst G1 obtained in Synthesis Example 11 were placed and further degassed and stirred to obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 8.

(Example 7)

As shown in Table 7, 100 g of the polymer A5 obtained in Synthesis Example 5 and 10.0 g of the titanium catalyst G7 obtained in Synthesis Example 17 were placed in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- Deg.] C to obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 8.

(Example 8)

100 g of the polymer A5 obtained in Synthesis Example 5 and 9.0 g of the titanium catalyst G8 obtained in Synthesis Example 18 were placed in a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water-cooled condenser, To obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 8.

(Example 9)

100 g of the polymer A5 obtained in Synthesis Example 5 and 9.0 g of the titanium catalyst G9 obtained in Synthesis Example 19 were placed in a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water-cooled condenser, To obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 8.

Example No. One 2 3 4 5 6 7 8 9 (A) Polymer A1 50.00 50.00 50.00 50.00 50.00 - - - - (A) Polymer A2 10.00 10.00 10.00 10.00 10.00 - - - - (A) Polymer A3 - 40.00 40.00 40.00 40.00 - - - - (A) Polymer A4 40.00 - - - - - - - - (A) Polymer A5 - - - - - 100.00 100.00 100.00 100.00 (B + C) titanium catalyst G1 - - - - - 10.00 - - - (B + C) titanium catalyst G2 16.50 - - - - - - - - (B + C) titanium catalyst G3 - 11.00 - - - - - - - (B + C) titanium catalyst G4 - - 9.00 - - - - - - (B + C) titanium catalyst G5 - - - 11.00 - - - - - (B + C + D) titanium catalyst G6 - - - - 9.00 - - - - (B + C) titanium catalyst G7 - - - - - - 10.00 - - (B + C) titanium catalyst G8 - - - - - - - 9.00 - (B + C) titanium catalyst G9 - - - - - - - - 9.00 (E) MC coat P-1 - - - - - 50.00 - - - (F) Acetyltriethyl citrate - - - - - 5.00 - - - Di Sparone # 6500
- - - - - 1.00 - - - No crack CD
- - - - - 1.00 - - -

In Table 7, the compounding amounts of the respective compounding materials are expressed in g, and the polymers A3 and A4 are represented by the blend amount in terms of solid content. The polymers A1 to A2 were the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Example 1-2, the polymers A3 to A4 were the vinyl polymers A3 to A4 obtained in Synthesis Example 3-4, respectively, and the polymer A5 was Synthesis Example 5 And titanium catalysts G1 to G9 are the titanium catalysts G1 to G9 obtained in Synthesis Examples 11 to 19, respectively. Details of other ingredients are as follows.

MC coat P-1: product name of Baekseok Ind. Co., colloidal calcium carbonate, surface paraffin wax treatment.

Diparron # 6500: Amide wax, trade name, available from Nambon Corporation.

Nocra CD: 4,4'-bis ([alpha], [alpha] -dimethylbenzyl) diphenylamine, product name of DAINI CHINA Co.,

Acetyltriethyl citrate: manufactured by Tokyo Kasei Kogyo Co., Ltd.

Example No. One 2 3 4 5 6 7 8 9 Initial TFT (min) 18 10 9 10 12 16 10 12 16 Initial viscosity (Pa · s) 60 130 110 100 96 120 148 90 70 After 1 week storage TFT (min) 18 10 9 10 12 16 10 12 16 Rate of change
evaluation 1.00
◎ 1.00
◎ 1.00
◎ 1.00
◎ 1.00
◎ 1.00
◎ 1.00
◎ 1.00
◎ 1.00
◎ Viscosity after storage for 1 week (Pa · s) 62 130 122 122 104 135 182 96 82 Increase rate
evaluation 1.03
◎ 1.00
◎ 1.11
◎ 1.22
◎ 1.08
◎ 1.13
◎ 1.23
◎ 1.07
◎ 1.17
◎ Surface hardenability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ○ Adhesion strength (N / mm ² ) PVC 4.1 3.9 3.7 3.8 3.7 3.9 2.6 3.4 3.1 PC 5.6 5.9 5.6 6.0 5.9 5.3 5.1 5.2 5.0 A1 6.2 6.1 5.9 6.0 5.7 5.5 5.7 5.9 4.8

(Example 10)

As shown in Table 9, 100 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1, 6 g of the silane compound B1 obtained in Synthesis Example 7, 6 g of an organosiloxane obtained in Synthesis Example 7, 4 g of Tix TC-750 were placed and stirred at 25 deg. C under stirring to obtain a curable composition. Table 10 shows the results of the storage stability test, the curing test, the surface hardening test and the adhesion test of the curable composition.

(Example 11)

50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 50 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- Was mixed with 40 g in terms of solid content of vinyl polymer A3 obtained in Synthesis Example 3. The mixture was heated (120 ° C) and deaerated under reduced pressure to remove the remaining monomers and ethyl acetate contained in the vinyl-based polymer A3 and cooled to room temperature. Thereafter, 6 g of the silane compound B1 obtained in Synthesis Example 7 and 4 g of Olgitics TC-750 were added, followed by deaeration and stirring at 25 캜 to obtain a curable composition. Table 10 shows the results of the storage stability test, the curing test, the surface hardening test and the adhesion test of the curable composition.

(Example 12)

50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 50 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Was mixed with 40 g of the vinyl-based copolymer obtained in Synthesis Example 3 in terms of A3 solid content. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl polymer A3 and cooled to room temperature. Then, 6 g of the silane compound B2 obtained in Synthetic Example 8 and 4 g of Olgitics TC-750 were added and deaerated and stirred at 25 DEG C to obtain a curable composition. Table 10 shows the results of the storage stability test, the curing test, the surface hardening test and the adhesion test of the curable composition.

Example No. 10 11 12 (A) Polymer A1 100.00 50.00 50.00 (A) Polymer A2 - 10.00 10.00 (A) Polymer A3 - 40.00 40.00 (B) Silane Compound B1 6.00 6.00 - (B) Silane Compound B2 - - 6.00 (C) Oligitics TC750 4.00 4.00 4.00

In Table 9, the compounding amount of each compounding material is expressed in g, and the amount of polymer A3 is expressed in terms of solid content. The polymers A1 to A2 were the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Example 1-2, the polymer A3 was the vinyl polymer A3 obtained in Synthesis Example 3, and the silane compounds B1 to B2 were synthesized in Synthesis Examples 7-8 The resulting silane compounds B1 to B2 were obtained, and Oligitics TC-750 was a product of Matsumoto Fine Chemical Co., Ltd. and titanium diisopropoxybis (ethylacetate).

Example No. 10 11 12 Initial TFT (min) 10 8 6 Initial viscosity (Pa · s) 42 110 90 After 1 week storage TFT (min) 8 10 20 Rate of change
evaluation 0.80
○ 1.25
○ 1.25
○ Viscosity after storage for 1 week (Pa · s) 58 160 142 Increase rate
evaluation 1.38
◎ 1.45
○ 1.58
△ Surface hardenability ○ △ △ Adhesion strength (N / mm ² ) PVC 1.1 2.2 2.3 PC 2.0 5.2 4.5 Al 3.1 2.2 2.3

(Comparative Example 1)

100 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 4 g of Olgitics TC-750 were placed in a 300-mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- To obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 12.

(Comparative Example 2)

As shown in Table 11, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 50 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Was mixed with 40 g in terms of solid content of the vinyl-based polymer A3 obtained in Synthesis Example 3. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the remaining monomers and ethyl acetate contained in the vinyl-based polymer A3 and cooled to room temperature. Then, 3 g of 3-glycidoxypropyltrimethoxysilane and 4 g of Olgitics TC-750 were added, followed by deaeration and stirring at 25 ° C to obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 12.

(Comparative Example 3)

As shown in Table 11, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 50 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Was mixed with 40 g in terms of solid content of the vinyl-based polymer A3 obtained in Synthesis Example 3. The mixture was heated (120 ° C) and deaerated under reduced pressure to remove the remaining monomers and ethyl acetate contained in the vinyl-based polymer A3 and cooled to room temperature. Thereafter, 5 g of QS-20 was added, and the mixture was heated and deaerated at 100 DEG C with stirring. The mixture was returned to room temperature (25 DEG C), 3 g of 3-glycidoxypropyltrimethoxysilane and 4 g of Olgitics TC- ≪ / RTI > The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 12.

(Comparative Example 4)

50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 10 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Was mixed with 40 g in terms of solid content of vinyl polymer A3 obtained in Synthesis Example 3. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl polymer A3 and cooled to room temperature. Thereafter, 50 g of Riton A-5 was added, followed by heating and degassing stirring at 100 占 폚. 6 g of the silane compound X1 obtained in Comparative Synthesis Example 1 and 4 g of Olgitic TC-750 were added, and the mixture was degassed and stirred at 25 DEG C to obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 12.

(Comparative Example 5)

50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 10 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Was mixed with 40 g in terms of solid content of vinyl polymer A3 obtained in Synthesis Example 3. The mixture was heated (120 ° C) and deaerated under reduced pressure to remove the remaining monomers and ethyl acetate contained in the vinyl-based polymer A3 and cooled to room temperature. Then, 6 g of the silane compound X2 obtained in Comparative Synthesis Example 2 and 4 g of Olgitic TC-750 were added, and the mixture was degassed and stirred at 25 DEG C to obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 12.

(Comparative Example 6)

50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 10 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- And 40 g in terms of solid content of vinyl polymer A3 obtained in Synthesis Example 3 were mixed. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl polymer A3 and cooled to room temperature. Thereafter, the mixture was heated and stirred at 100 ° C for degassing. 6 g of the silane compound X3 obtained in Comparative Synthesis Example 3 and 4 g of Olgytix TC-750 were added, and the mixture was degassed and stirred at 25 DEG C to obtain a curable composition. The results of the curing test, the storage stability test, the surface hardenability test and the adhesion test of the curable composition are shown in Table 12.

Comparative Example No. One 2 3 4 5 6 (A) Polymer A1 100.00 50.00 50.00 50.00 50.00 50.00 (A) Polymer A2 - 10.00 10.00 10.00 10.00 10.00 (A) Polymer A3 - 40.00 40.00 40.00 40.00 40.00 Silane compound X1
- - - 6.00 - - Silane compound X2
- - - - 6.00 - Silane compound X3
- - - - - 6.00 (E) QS-20
- - 5.00 - - - (E) Raiton A-5
- - - 50.00 - - (D) 3-glycidoxypropyltrimethoxysilane - 3.00 3.00 - - -

In Table 11, the compounding amount of each compounding material is represented by g, and the polymer A3 is represented by the blending amount in terms of solid content. The polymers A1 to A2 were the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Example 1-2, the polymer A3 was the vinyl polymer A3 obtained in Synthesis Example 3, and the silane compounds X1 to X3 were synthesized in Comparative Synthesis Examples 1-3 The obtained silane compounds X1 to X3, and the details of other compounding materials are as follows.

QS-20: Product name of Tokuyama Co., Ltd., primary particle size 5 ~ 50μm, non-surface treated hydrophilic dry silica.

Riton A-5: Product name of Baekseok Industry Co., Ltd., ground calcium carbonate, surface fatty acid treatment.

Oligitics TC-750: a product of Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis (ethylacetate).

Comparative Example No. One 2 3 4 5 6 Initial TFT (min) 12 15 30 17 15 15 Initial viscosity (Pa · s) 60 130 160 140 240 140 After 1 week storage TFT (min) 18 22 60 22 24 22 Rate of change
evaluation 1.50
X 1.47
X 2.00
X 1.33
△ 1.60
X 1.47
X Viscosity after storage for 1 week (Pa · s) 96 184 270 240 320 200 Increase rate
evaluation 1.60
△ 1.42
○ 1.69
X 1.71
X 1.33
◎ 1.43
○ Surface hardenability X X X X X X Adhesion strength (N / mm ² ) PVC 1.0 2.3 2.3 2.7 1.9 2.1 PC 2.2 3.3 2.1 5.5 2.2 3.3 A1 0.6 2.2 1.7 2.2 1.6 2.3

(Example 13)

45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 45 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- Were mixed with 35 g in terms of solid content of the vinyl polymer A6 obtained in Synthesis Example 6. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl-based polymer A6 and cooled to room temperature. Then, 1 g of the silane compound B1 obtained in Synthesis Example 7 and 4 g of Olgitic TC-750 were added and deaerated and stirred at 25 캜 to obtain a curable composition. Table 14 shows the results of the storage stability test, the curing test and the surface hardening test of the curable composition.

(Example 14)

A curable composition was prepared in the same manner as in Example 13 except that the mixing ratio of the compounding materials was changed as shown in Table 13. [ Table 14 shows the results of the storage stability test, the curing test and the surface hardening test of the curable composition.

(Example 15)

45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 45 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- Were mixed with 35 g in terms of solid content of the vinyl polymer A6 obtained in Synthesis Example 6. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl-based polymer A6 and cooled to room temperature. Then, 5 g of the titanium catalyst G10 obtained in Synthesis Example 20 was added and stirred at 25 deg. C for deaeration to obtain a curable composition. Table 14 shows the results of the storage stability test, the curing test and the surface hardening test of the curable composition.

(Example 16)

45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 45 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- Were mixed with 35 g in terms of solid content of the vinyl polymer A6 obtained in Synthesis Example 6. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl-based polymer A6 and cooled to room temperature. Then, 5 g of the titanium catalyst G10 obtained in Synthesis Example 20 and 5 g of phenyltrimethoxysilane were added and deaerated and stirred at 25 캜 to obtain a curable composition. Table 14 shows the results of the storage stability test, the curing test and the surface hardening test of the curable composition.

(Examples 17 to 19)

A curable composition was prepared in the same manner as in Example 16 except that the silane compound (D) was changed as shown in Table 13. Table 14 shows the results of the storage stability test, the curing test and the surface hardening test of the curable composition.

Example No. 13 14 15 16 17 18 19 (A) Polymer A1 45.00 45.00 45.00 45.00 45.00 45.00 45.00 (A) Polymer A2 20.00 20.00 20.00 20.00 20.00 20.00 20.00 (A) Polymer A6 35.00 35.00 35.00 35.00 35.00 35.00 35.00 (B) Silane Compound B1 1.00 6.00 - - - - - (C) Oligitics TC750 4.00 4.00 - - - - - (B + C) titanium catalyst G10
- - 5.00 5.00 5.00 5.00 5.00 (D) phenyltrimethoxysilane - - - 5.00 - - - (D) Vinyltrimethoxysilane - - - - 3.70 - - (D) decyltrimethoxysilane - - - - - 6.60 - (D) tetraethoxysilane - - - - - - 5.30

In Table 13, the compounding amount of each compounding material is represented by g, and the polymer A6 is represented by the blending amount in terms of solid content. The polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Example 1-2, the polymer A6 is the vinyl polymer A6 obtained in Synthesis Example 6, the silane Compound B1 is the silane compound B1 obtained in Synthesis Example 7 , The titanium catalyst G10 is the titanium catalyst G10 obtained in Synthesis Example 20, and the details of the other compounding materials are as follows.

Oligitics TC-750: a product of Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis (ethylacetate).

Phenyltrimethoxysilane: trade name: KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.

Vinyltrimethoxysilane: trade name: KBM-1003, manufactured by Shinwol Chemical Industry Co., Ltd.

Decyltrimethoxysilane: trade name: KBM-3013C, manufactured by Shinwol Chemical Industry Co., Ltd.

Tetraethoxysilane: trade name: KBE-04, manufactured by Shinwol Chemical Industry Co., Ltd.

Example No. 13 14 15 16 17 18 19 Initial TFT (min) 11.0 18.0 11.0 16.0 20.0 15.5 83.0 Initial viscosity (Pa · s) 223.8 113.1 255.2 59.6 48.8 41.2 44.2 After 1 week storage TFT (min) 9.0 15.0 11.0 20.5 26.0 19.0 87.0 Rate of change
evaluation 0.81
○ 0.83
○ 1.00
◎ 1.28
○ 1.30
○ 1.23
○ 1.05
◎ Viscosity after storage for 1 week (Pa · s) 338.4 164.1 314.7 82.8 63.0 55.9 52.5 Increase rate
evaluation 1.51
△ 1.45
○ 1.23
◎ 1.39
◎ 1.29
◎ 1.36
◎ 1.19
◎ After 2 weeks storage TFT (min) 8.5 19.5 8.5 20.0 26.5 18.0 120.0 Rate of change 0.8 1.1 0.8 1.3 1.3 1.2 1.4 Viscosity after storage for 2 weeks (Pa · s) 376.6 174.1 359.7 83.7 66.7 57.7 54.2 Increase rate 1.7 1.5 1.4 1.4 1.4 1.4 1.2 After 4 weeks storage TFT (min) 8.5 19.0 8.5 21.0 30.0 20.0 120.0 Rate of change 0.8 1.1 0.8 1.3 1.5 1.3 1.4 Viscosity after storage for 4 weeks (Pa · s) 387.2 180.5 390.6 85.5 64.4 59.6 56.3 Increase rate 1.7 1.6 1.5 1.4 1.3 1.4 1.3 Surface hardenability ○ ◎ ○ ○ ○ ○ ○

(Example 20)

27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 23 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- Were mixed with 21 g in terms of solid content of the vinyl polymer A6 obtained in Synthesis Example 6. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl-based polymer A6 and cooled to room temperature. Thereafter, 40 g of Phaiton SB (heavy calcium carbonate, average particle diameter 2.2 μm, product of Baekseok Calcium Co., Ltd.), 40 g of Carax 300 (calcium carbonate, primary particle diameter (electron microscope) 20 g of the titanium catalyst G11 obtained in Synthetic Example 21 was added to 20 g of the titanium catalyst G11 by heating (100 deg. C), degassing and stirring for 1 hour and returning to room temperature, followed by degassing and stirring at 25 deg. The results of the storage stability test, the curing test and the adhesion test of the curable composition are shown in Tables 16 and 17.

(Examples 21 to 27)

As shown in Table 15, a curable composition was prepared in the same manner as in Example 20 except that titanium catalysts G12 to G18 were used in place of the titanium catalyst G11. The results of the storage stability test, the curing test and the adhesion test of the curable composition are shown in Tables 16 and 17.

Example No. 20 21 22 23 24 25 26 27 (A) Polymer A1 27.00 27.00 27.00 27.00 27.00 27.00 27.00 27.00 (A) Polymer A2 52.00 52.00 52.00 52.00 52.00 52.00 52.00 52.00 (A) Polymer A6
21.00 21.00 21.00 21.00 21.00 21.00 21.00 21.00 (B + C + F) titanium catalyst G11 20.00 - - - - - - - (B + C + F) titanium catalyst G12 - 22.40 - - - - - - (B + C + D + F) titanium catalyst G13 - - 20.00 - - - - - (B + C + D + F) titanium catalyst G14 - - - 21.20 - - - - (B + C + D + F) titanium catalyst G15 - - - - 20.60 - - - (B + C + D + F) titanium catalyst G16 - - - - - 20.40 - - (B + C + D + F) titanium catalyst G17 - - - - - - 21.70 - (B + C + D + F) titanium catalyst G18 - - - - - - - 22.00 (E) Phyton SB
40.00 40.00 40.00 40.00 40.00 40.00 40.00 40.00 (E) The Carlex 300
20.00 20.00 20.00 20.00 20.00 20.00 20.00 20.00

In Table 15, the compounding amount of each compounding material is represented by g, and the polymer A6 is represented by the blending amount in terms of solid content. The polymers A1 to A2 were the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Example 1-2, the polymer A6 was the vinyl polymer A6 obtained in Synthesis Example 6, and the titanium catalysts G11 to G18 were the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Examples 21 to 28 Titanium catalysts G11 to G18, and the details of other compounding materials are as follows.

Phyton SB: Baekseok Calcium Co., Ltd., heavy calcium carbonate, average particle diameter 2.2μm.

Carlex 300: product of Tannum Calcium Co., fatty acid surface treated calcium carbonate, primary particle size (electron microscope) 0.05 μm.

Normal paraffin: Product name: N-11, JX IKEIJI ENERGY CO., LTD.

Example No. 20 21 22 23 24 25 26 27 Initial TFT (min) 9.0 13.0 13.0 14.0 12.0 14.5 12.0 10.0 Initial viscosity (Pa · s) 56.5 29.7 26.3 26.5 27.5 30.4 27.8 30.7 Initial SVI 3.0 2.5 3.0 2.3 2.8 3.0 2.7 2.8 After 1 week storage TFT (min) 7.5 13.0 15.0 14.0 12.0 18.0 14.0 13.0 Rate of change
evaluation 0.83
○ 1.00
◎ 1.15
○ 1.00
◎ 1.00
◎ 1.24
○ 1.17
○ 1.30
○ Viscosity after storage for 1 week (Pa · s) 83.3 41.9 37.4 35.5 35.3 37.5 33.8 37.2 Increase rate
evaluation 1.47
○ 1.41
○ 1.42
○ 1.34
◎ 1.28
◎ 1.23
◎ 1.22
◎ 1.21
◎ SVI after 1 week storage 2.5 2.3 3.1 2.5 2.8 2.8 2.8 2.6 After 2 weeks storage TFT (min) 7.0 13.0 18.0 15.0 13.0 18.0 14.0 14.0 Rate of change 0.8 1.0 1.4 1.1 1.1 1.2 1.2 1.4 Viscosity after storage for 2 weeks (Pa · s) 84.4 43.9 39.0 36.7 39.1 38.9 36.5 39.4 Increase rate 1.5 1.5 1.5 1.4 1.4 1.3 1.3 1.3 After 2 weeks SVI 2.6 2.5 3.1 2.6 2.8 2.9 2.8 2.6 After 4 weeks storage TFT (min) 7.0 16.0 21.0 15.0 13.0 18.0 14.0 14.0 Rate of change 0.8 1.2 1.6 1.1 1.1 1.2 1.2 1.4 Viscosity after storage for 4 weeks (Pa · s) 88.4 48.2 43.3 37.9 38.2 43.0 38.9 40.5 Increase rate 1.6 1.6 1.6 1.4 1.4 1.4 1.4 1.3 After 4 weeks SVI 2.4 2.4 3.0 2.5 2.8 2.8 2.8 2.6

Adhesion test: Adhesion strength (N / mm ² ) Example No. 20 21 22 23 24 25 26 27 PVC 2.3
C40A60 2.1
CF 1.6
C10A90 2.1
C20A80 1.8
C10A90 1.7
C20A80 2.3
C20A80 1.8
C10A90 PC 3.2
CF 2.0
CF 3.2
CF 2.9
CF 2.9
CF 2.5
CF 2.9
CF 2.7
CF PS 1.8
AF 1.5
C30A70 1.4
AF 2.0
AF 2.1
C20A80 1.8
AF 2.3
C20A80 1.9
AF ABS 1.3
AF 1.4
C40A60 1.3
AF 1.7
AF 1.3
AF 1.5
AF 1.7
C20A80 1.3
AF PMMA 2.5
C30A70 1.7
CF 1.9
C30A70 2.4
C70A30 2.5
C50A50 1.5
AF 2.5
C80A20 2.5
C30A70 6-Ny 1.7
C20A80 2.2
CF 1.1
AF 1.8
C20A80 1.4
AF 1.0
AF 2.2
C80A20 1.3
AF SPCC 4.3
C30A70 3.0
CF 2.2
AF 3.5
C50A50 3.4
AF 3.6
C30A70 4.2
CF 3.4
AF A1 4.6
CF 3.8
CF 2.8
AF 4.5
C60A40 4.0
C20A80 5.0
CF 4.4
CF 3.9
C80A20

(Example 28)

45 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 45 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- Were mixed in an amount of 35 g in terms of solid content of the vinyl polymer A6 obtained in Synthesis Example 6. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl-based polymer A6 and cooled to room temperature. Thereafter, 40 g of Phaiton SB as a filler (E) was added, heating (100 ° C), degassing and stirring were continued for 1 hour and returned to room temperature. 1 g of the silane compound B1 obtained in Synthetic Example 7, 4 g of Olgitt TC- To obtain a curable composition. The results of the storage stability test, the curing test and the adhesion test of the curable composition are shown in Tables 19 and 20.

(Examples 29 to 33)

As shown in Table 18, a curable composition was prepared in the same manner as in Example 28 except that the (E) filler was changed. The results of the storage stability test, the curing test and the adhesion test of the curable composition are shown in Tables 19 and 20.

Example No. 28 29 30 31 32 33 (A) Polymer A1 45.00 45.00 45.00 45.00 45.00 45.00 (A) Polymer A2 20.00 20.00 20.00 20.00 20.00 20.00 (A) Polymer A6 35.00 35.00 35.00 35.00 35.00 35.00 (B) Silane Compound B1 1.00 1.00 1.00 1.00 1.00 1.00 (C) Oligitics TC750 4.00 4.00 4.00 4.00 4.00 4.00 (D) phenyltrimethoxysilane 5.00 5.00 5.00 5.00 5.00 5.00 (E) Phyton SB 40.00 40.00 40.00 40.00 40.00 - (E) The Carlex 300 - 20.00 - - - 20.00 (E) Calpain 200 - - 20.00 - - - (E) Biscotti Excel-30 - - - 20.00 - - (E) MS-100M - - - - 20.00 - (E) MC coat P1 - - - - - 40.00

In Table 18, the compounding amount of each compounding material is represented by g, and the polymer A6 is represented by the blending amount in terms of solid content. The polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Example 1-2, the polymer A6 is the vinyl polymer A6 obtained in Synthesis Example 6, the silane Compound B1 is the silane compound B1 obtained in Synthesis Example 7 , And other ingredients are as follows.

Oligitics TC-750: product name of Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybis (ethylacetate).

Phenyltrimethoxysilane: trade name: KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.

Phytone SB: Product name of Baekseok Calcium Co., Ltd., heavy calcium carbonate, average particle diameter 2.2 탆.

Carlex 300: product name of Tannai Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.05 μm.

Calpine 200: Product name of Tannai Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.07 μm.

BISCO EXCEL-30: Product name of Baekseok Industry Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.03 μm.

MS-100M: product name of Tannic Calcium Co., Ltd., surface treated with fatty acid and resin acid, calcium carbonate, primary particle diameter (electron microscope) 0.05 μm.

MC coat P-1: product name of Baekseok Ind. Co., colloidal calcium carbonate, surface paraffin wax treatment, average particle diameter 3.0 탆.

Example No. 28 29 30 31 32 33 Initial TFT (min) 19.0 17.0 16.0 16.0 17.0 16.0 Initial viscosity (Pa · s) 112.4 235.6 214.8 374.2 258.9 218.3 Initial SVI 1.1 1.5 1.5 2.7 1.5 1.5 After 1 week storage TFT (min) 20.5 18.0 18.5 16.5 19.0 18.0 Rate of change
evaluation 1.08
◎ 1.06
◎ 1.12
○ 1.03
◎ 1.11
○ 1.13
○ Viscosity after storage for 1 week (Pa · s) 128.7 266.8 271.6 557.1 316.9 306.5 Increase rate
evaluation 1.15
◎ 1.13
◎ 1.26
◎ 1.49
○ 1.22
◎ 1.40
◎ SVI after 1 week storage 1.0 1.6 1.4 1.9 2.0 1.4 After 2 weeks storage TFT (min) 19.5 19.5 18.0 19.0 19.0 18.5 Rate of change 1.0 1.1 1.1 1.2 1.1 1.2 Viscosity after storage for 2 weeks (Pa · s) 116.1 281.6 279.9 562.3 324.6 298.9 Increase rate 1.0 1.2 1.3 1.5 1.3 1.4 After 2 weeks SVI 1.1 2.1 1.8 2.0 2.1 1.9 After 4 weeks storage TFT (min) 19.5 21.0 21.0 21.0 20.0 18.0 Rate of change 1.0 1.2 1.3 1.3 1.2 1.1 Viscosity after storage for 4 weeks (Pa · s) 124.7 284.1 282.6 400.0 330.9 296.2 Increase rate 1.1 1.2 1.3 1.1 1.3 1.4 After 4 weeks SVI 1.1 1.8 1.9 2.9 2.3 1.9

Adhesion test: Adhesion strength (N / mm ² ) Example No. 28 29 30 31 32 33 PVC 3.4
CF 3.2
CF 3.3
CF 3.2
CF 3.3
CF 3.5
CF PC 3.7
CF 3.5
CF 3.6
CF 3.8
CF 3.9
CF 3.2
CF PS 2.1
C30A70 2.6
C10A90 2.9
C40A60 2.9
C40A60 2.9
C30A70 2.8
C40A60 ABS 1.9
AF 2.5
C20A80 2.8
C30A70 2.9
C60A40 3.2
C40A60 3.0
C50A50 PMMA 3.5
C90A10 3.7
CF 3.8
CF 3.7
CF 3.7
CF 3.1
CF 6-Ny 2.2
C10A90 2.1
AF 3.2
C90A10 3.3
C60A40 3.4
C60A40 2.0
AF A1 5.8
CF 4.7
C20A80 4.3
C60A40 2.4
AF 4.4
C20A80 5.0
CF

(Example 34)

As shown in Table 21, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 27 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Were mixed with 21 g in terms of solid content of the vinyl polymer A6 obtained in Synthesis Example 6. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl-based polymer A6 and cooled to room temperature. Then, 40 g of Phyton SB as a filler (E), 20 g of Carlex 300 as a surface-treated calcium carbonate and 1 g of an antioxidant LoNcrack CD were placed and heated (100 캜), degassing and stirring were performed for 1 hour and then at room temperature (25 캜) And 10 g of the titanium catalyst G20 obtained in Synthesis Example 30 was added, followed by degassing and stirring to obtain a curable composition. The results of the curing test and the storage stability test of the curable composition are shown in Table 22.

(Example 35)

As shown in Table 21, a curable composition was prepared in the same manner as in Example 34 except that titanium catalyst G19 was used instead of titanium catalyst G20. The results of the curing test and the storage stability test of the curable composition are shown in Table 22.

(Example 36)

As shown in Table 21, 27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 27 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water- Were mixed with 21 g in terms of solid content of the vinyl polymer A6 obtained in Synthesis Example 6. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl-based polymer A6 and cooled to room temperature. 150 g of Alnolix B316 as aluminum hydroxide and 5 g of a noncracked CD as an antioxidant were added and heated (100 DEG C), degassed and stirred for 1 hour and returned to room temperature (25 DEG C) , 2.5 g of vinyltrimethoxysilane as a component (D) and 9.2 g of the titanium catalyst G21 obtained in Synthesis Example 31, and further deaerated and stirred to obtain a curable composition. The results of the curing test and the storage stability test of the curable composition are shown in Table 22, and the results of the adhesion test are shown in Table 23.

Example No. 34 35 36 (A) Polymer A1 27.00 27.00 27.00 (A) Polymer A2 52.00 52.00 52.00 (A) Polymer A6 21.00 21.00 21.00 (B + C + D + F) titanium catalyst G20 20.00 - - (B + C + D + F) titanium catalyst G19 - 20.00 - (B + C + D + F) titanium catalyst G21 - - 9.20 (D) Vinyltrimethoxysilane - - 2.50 (E) Phyton SB 40.00 40.00 - (E) The Carlex 300 20.00 20.00 - (F) I sofa -M - - 20.00 Alnorix B316 - - 150.00 No crack CD 1.00 1.00 5.00

In Table 21, the compounding amount of each compounding material is expressed by g, and the polymer A6 is represented by the blending amount in terms of solid content. Polymers A1 to A2 were the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Example 1-2, the polymer A6 was the vinyl polymer A6 obtained in Synthesis Example 6, and the titanium catalysts G19 to G21 were synthesized in Synthesis Examples 29 to 31 The obtained titanium catalysts G19 to G21, and the details of other compounding materials are as follows.

Vinyltrimethoxysilane: trade name: KBM-1003, manufactured by Shinwol Chemical Industry Co., Ltd.

Phytone SB: Product name of Baekseok Calcium Co., Ltd., heavy calcium carbonate, average particle diameter 2.2 탆.

Carlex 300: product name of Tannai Calcium Co., Ltd., fatty acid surface-treated calcium carbonate, primary particle diameter (electron microscope) 0.05 μm.

Almorix B316: Product name of Almorix Co., Ltd., aluminum hydroxide, average particle size 18 μm.

Isofa-M: Exxon Mobil Co., Ltd. Product name, paraffin.

No crack CD: 4,4'-bis ([alpha], [alpha] -dimethylbenzyl) diphenylamine.

Example No. 34 35 36 Initial TFT (min) 14.0 14.5 17.0 Initial viscosity (Pa · s) 26.8 27.3 53.2 Initial SVI 3.4 3.0 3.0 After 1 week storage TFT (min) 16.0 15.0 17.0 Rate of change
evaluation 1.14
○ 1.03
◎ 1.00
◎ Viscosity after storage for 1 week (Pa · s) 34.2 37.4 79.1 Increase rate
evaluation 1.28
◎ 1.37
◎ 1.49
○ SVI after 1 week storage 3.1 3.1 2.9 After 2 weeks storage TFT (min) 18.0 18.0 18.0 Rate of change 1.3 1.2 1.1 Viscosity after storage for 2 weeks (Pa · s) 42.3 39.0 81.5 Increase rate 1.6 1.4 1.5 After 2 weeks SVI 3.1 3.1 3.1 After 4 weeks storage TFT (min) 19.5 21.5 18.0 Rate of change 1.4 1.5 1.1 Viscosity after storage for 4 weeks (Pa · s) 40.4 40.3 85.0 Increase rate 1.5 1.5 1.6 After 4 weeks SVI 3.1 3.0 3.1

Adhesion test: Adhesion strength (N / mm ² ) Example No. 36 PVC 1.4
AF PC 2.7
CF PS 0.9
AF ABS 0.7
AF PMMA 1.1
C30A70 6-Ny 0.8
AF SPCC 1.8
AF A1 2.7
CF

(Example 37)

As shown in Table 24, 100 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 (E) was added to a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet pipe and a water-cooled condenser, 40 g of amorphous silica having an average particle diameter of 6 탆 was put into the reactor and stirred at 100 캜 and 10 mmHg for 1 hour and then cooled to 20 캜 to obtain a titanium catalyst G14 of 21.2 and the mixture was vacuum-mixed for 10 minutes to obtain a curable composition.

Table 25 shows the results of the storage stability test, the curing test, the surface hardening test, the adhesion test and the transparency test of the curable composition.

(Example 38)

27 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and 27 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 were added to a 300 ml flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer inlet tube and a water- Were mixed with 21 g in terms of solid content of the vinyl polymer A6 obtained in Synthesis Example 6. The mixture was heated (120 DEG C) and deaerated under reduced pressure to remove the residual monomers and ethyl acetate contained in the vinyl-based polymer A6 and cooled to room temperature. 20 g of MR13G (methacrylic acid ester polymer powder, average particle size of about 1 m) as the polymer powder (E) and 20 g of FTR8100 (manufactured by Mitsui Petrochemical Co., Ltd.) 21 g of the titanium catalyst G14 obtained in Synthesis Example 24 was added and the mixture was vacuum-mixed for 10 minutes to obtain a curable composition ≪ / RTI >

The blending amount of FTR8100 is determined as follows. First, FTR8100, which is a refractive index adjuster, is heated and melted in an appropriate ratio to the component (A), and the refractive index is measured with an Abbe refractometer at 20 deg. Take an X-Y plot of FTR8100 compounding ratio and refractive index. And a blending amount of FTR8100 which is in agreement with the refractive index of the powder to be the main filler is required.

Table 25 shows the results of the storage stability test, the curing test, the surface hardening test, the adhesion test and the transparency test of the curable composition.

(Example 39)

As shown in Table 24, a curable composition was prepared in the same manner as in Example 38 except that the compounding material was changed. Table 25 shows the results of the storage stability test, the curing test, the surface hardening test, the adhesion test and the transparency test of the curable composition.

Refractive index Example 37 38 39 (A) Polymer A1 1.45 100 27.00 27.00 (A) Polymer A2 1.45 - 52.00 52.00 (A) Polymer A6 1.48 - 21.00 21.00 (B + C + D + F) titanium catalyst G14 1.50 21.20 21.20 21.20 (E) MR13G 1.49 - 20.00 - (E) FuseLex E2 1.45 40.00 - - FTR8100 1.56 - 17.00 -

In Table 24, the compounding amount of each compounding material is expressed by g, and the polymer A6 is represented by the blending amount in terms of solid content. The polymers A1 to A2 are the polyoxyalkylene polymers A1 to A2 obtained in Synthesis Example 1-2, the polymer A6 is the vinyl polymer A6 obtained in Synthesis Example 6, and the titanium catalyst G14 is the titanium catalyst G14 obtained in Synthesis Example 24 , And other ingredients are as follows.

MR13G: trade name of JEON Chemical Co., Ltd., methacrylic acid ester polymer powder, average particle diameter about 1 μm.

Fusex (R) E-2: Amorphous silica, commercial name of YongSam Co., Ltd. Average particle size (50% weight average when measured by laser method): 6μm.

FTR8100: trade name of Samjung Petroleum Co., Ltd., and petroleum resin of C5 and C9.

Example No. 37 38 39 Initial TFT (min) 15 18 17 Initial viscosity (Pa · s) 37.1 24.0 14.0 After 1 week storage TFT (min) 14 20 21 Rate of change
evaluation 0.93
◎ 1.11
○ 1.24
○ Viscosity after storage for 1 week (Pa · s) 53.1 31.6 14.4 Increase rate
evaluation 1.43
○ 1.32
◎ 1.03
◎ Surface hardenability ○ ○ ○ Adhesion strength (N / mm ² ) PVC 2.0
AF 2.6
C9A1 1.3
AF PC 2.9
CF 3.3
CF 3.1
C8A2 A1 4.2
C8A2 3.3
AF 3.0
AF Transparency ◎ ◎ ◎

As shown in Tables 7-10 and 13 to 25, the curable composition of the present invention exhibited sufficient adhesiveness, storage stability and curability.

Claims (16)

(A) an organic polymer having an average of at least 0.8 crosslinkable silicon group in one molecule and having a main chain other than a polysiloxane,
(B) an epoxy silane compound represented by the following formula (1) and an aminosilane compound represented by the following formula (2) are reacted in an amount of 1.5 to 10 moles of the epoxy silane compound per mole of the aminosilane compound Silane compounds, and
(C) at least one titanium catalyst 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)
0.1 to 40 parts by mass of the silane compound (B) and 0.1 to 40 parts by mass of the titanium catalyst (C) are added to 100 parts by mass of the organic polymer (A)
Wherein the organic polymer (A) is a polyoxyalkylene polymer having an average of at least 0.8 crosslinkable silicon groups per molecule, a saturated hydrocarbon polymer containing an average of at least 0.8 crosslinkable silicon groups per molecule, and an average And (meth) acrylic acid ester-based polymers containing at least 0.8 crosslinkable silicon groups.
Curable composition.
Formula 1

(Wherein 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, R ⁶ is an alkyl group, and a is 0, 1 or 2)

(2)

(Wherein 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)

(3)

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

Formula 4

(In the formula (4), R ²⁵ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, and two R ^{26 s} are each independently a hydrogen atom or a substituted or unsubstituted carbon atom number of 1 And each of R ²⁷ and R ²⁸ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms) The method according to claim 1,
Wherein the silane compound (B) is a silane compound obtained by reacting the epoxy silane compound and the aminosilane compound at a reaction temperature of 40 to 100 占 폚.
Curable composition. delete The method according to claim 1,
Characterized in that the crosslinkable silicon group comprises a trimethoxysilyl group.
Curable composition. The method according to claim 1,
(D) a silane compound which has one hydrolyzable silicon group in one molecule and does not have a primary amino group.
Curable composition. 6. The method of claim 5,
Wherein the silane compound (D) is a compound represented by the following formula (12)
Curable composition.

Formula 5

(In the above formula (12), R ⁴¹ is a methyl group or an ethyl group, and when a plurality of R ^{41 s} exist, they may be the same or different,
R ⁴² is a methyl group or an ethyl group, and when a plurality of R ^{42 s} exist, 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 n is 0 or 1) The method according to claim 1,
(E) a filler.
Curable composition. 8. The method of claim 7,
Wherein the filler (E) is at least one selected from the group consisting of surface-treated calcium carbonate, amorphous silica having a particle diameter of 0.01 to 300 탆, and a polymer powder having a particle diameter of 0.01 to 300 탆.
Curable composition. 9. The method of claim 8,
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.
Curable composition. 9. The method of claim 8,
Wherein the difference between the refractive index of the organic polymer liquid phase component (A) and the refractive index of the polymer powder is 0.1 or less.
Curable composition. 11. The method of claim 10,
Wherein the refractive index adjusting agent is added to the organic polymer (A) so that the difference between the refractive index of the organic polymer liquid component (A) and the refractive index of the polymer powder is 0.1 or less.
Curable composition. 9. The method of claim 8,
Wherein the polymer powder is a polymer obtained by polymerizing a monomer selected from the group consisting of (meth) acrylic acid ester, vinyl acetate, ethylene, and vinyl chloride alone, or a copolymer obtained by copolymerizing the monomer and one or more vinyl monomers Characterized in that it is a powder.
Curable composition. 13. The method of claim 12,
Wherein the polymer powder is at least one selected from the group consisting of an acrylic polymer powder and a vinyl polymer powder.
Curable composition. The method according to claim 1,
(F) a diluent. ≪ RTI ID = 0.0 >
Curable composition. The method according to claim 1,
Characterized in that it further comprises a metal hydroxide.
Curable composition 16. The method of claim 15,
Characterized in that the metal hydroxide is aluminum hydroxide.
Curable composition.