JP7448212B2 - curable composition - Google Patents

Description

The present invention relates to curable compositions.

A joint structure of an architectural structure is constructed by filling a joint part formed between wall members constituting a wall part with a sealant.

In the joint structure described above, since the sealant is an organic substance, it is vulnerable to combustion, and in the event of a fire, the cured sealant material may fall off from the joint and flames may enter from the joint, causing damage to the walls of the building structure. The problem is that the fire resistance is insufficient.

Patent Document 1 describes (A) a polyalkylene ether having a silicon-containing functional group that can form a silanol group at its terminal by hydrolysis, (B) microencapsulated ammonium polyphosphate powder, (C) calcium carbonate powder, and (D ) A fire retardant sealant comprising a silanol condensation catalyst is disclosed.

Patent No. 3848379

However, the above-mentioned fireproof sealing materials foam due to the heat of a fire and then form a carbonized layer, but the foaming makes the combustion residue brittle, so it is easily destroyed by the wind pressure of the combustion flame and falls off from the joints. The problem is that the fire resistance of the walls of building structures is still insufficient.

The present invention provides a curable composition that can produce a cured product with excellent fire resistance. The present invention reliably maintains the filled state in sealing parts such as joints even in the event of a fire, prevents flames from penetrating through the sealing parts, and provides excellent fire resistance to the walls of building structures. The present invention provides a curable composition that can be used suitably as a sealing material.

The curable composition of the present invention comprises a polyalkylene oxide polymer having a urethane bond or a urea bond in the molecule and a hydrolyzable silyl group;
including glass frit.

[Polyalkylene oxide polymer]
The polyalkylene oxide polymer has a urethane bond (-NHCOO-) or a urea bond (-NHCONH-) in the molecule and a hydrolyzable silyl group.

As a polyalkylene oxide polymer, the main chain has the general formula: -(R-O) _n - (wherein R represents an alkylene group having 1 to 14 carbon atoms, and n is the number of repeating units. and is a positive integer) are preferred. The main chain skeleton of the polyalkylene oxide polymer may consist of only one type of repeating unit, or may consist of two or more types of repeating units.

The main chain refers to a polymer unit that accounts for 50% by mass or more in a molecule. A polymer unit is one formed by polymerizing monomers. In addition, the monomer constituting the polymer unit refers to a monomer containing two or more molecules in the polymer unit. When the polymer unit is composed of a plurality of monomers, the polymer unit may be composed of either random polymerization or block polymerization. When a plurality of polymer units are bonded to each other to form a molecular chain, and the molecular chain accounts for 50% by mass or more in the molecule, the entirety of the mutually bonded polymer units is defined as the main chain. When a plurality of polymer units are combined to form a molecular chain, the molecular structure existing between the polymer units is considered to be included in the main chain.

Examples of the main chain skeleton of polyalkylene oxide-based polymers include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer. It will be done. Among them, polypropylene oxide is preferred. According to polypropylene oxide, excellent fire resistance can be imparted to the cured product of the curable composition.

The main chain skeleton of the polyalkylene oxide polymer may contain urethane bonds, urea bonds, etc. in addition to the repeating unit represented by the above-mentioned general formula: -(RO) _n -. It is preferable that the repeating unit does not contain a urea bond, and is preferably a repeating unit represented by -(RO) _n -.

The number average molecular weight of the polyalkylene oxide polymer is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. The number average molecular weight of the polyalkylene oxide polymer is preferably 100,000 or less, more preferably 80,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. When the number average molecular weight of the polyalkylene oxide polymer is 2000 or more, the flexibility of the cured product of the curable composition is improved. If the number average molecular weight of the polyalkylene oxide polymer is 100,000 or less, the distance between crosslinking points in the cured product of the curable composition becomes small, the crosslinking density of the cured product becomes high, and it burns and becomes a residue. It retains its pre-combustion form even after burning, and has excellent fire resistance.

In the present invention, the number average molecular weight of the polyalkylene oxide polymer is a value measured by GPC (gel permeation chromatography) in terms of polystyrene. Specifically, 6 to 7 mg of a polyalkylene oxide-based polymer is collected, the collected polyalkylene oxide-based polymer is supplied to a test tube, and 0.05% by mass of BHT (dibutylhydroxytoluene) is added to the test tube. A diluted solution is prepared by adding an o-DCB (orthodichlorobenzene) solution containing the polyalkylene oxide polymer to a concentration of 1 mg/mL.

Using a dissolution filtration device, shake the diluted solution at 145° C. and a rotational speed of 25 rpm for 1 hour to dissolve the polyalkylene oxide polymer in the o-DCB solution containing BHT and use it as a measurement sample. . Using this measurement sample, the number average molecular weight of the polyalkylene oxide polymer can be measured by the GPC method.

The number average molecular weight of a polyalkylene oxide polymer can be measured, for example, using the measuring device and measurement conditions described below.
Measuring device manufactured by TOSOH, product name “HLC-8121GPC/HT”
Measurement conditions Column: TSKgelGMHHR-H(20)HT x 3
TSKguardcolumn-HHR(30)HT×1 piece
Mobile phase: o-DCB 1.0mL/min
Sample concentration: 1mg/mL
Detector: Blyth type refractometer
Standard material: Polystyrene (manufactured by TOSOH, molecular weight: 500-8420000)
Elution conditions: 145℃
SEC temperature: 145℃

The polyalkylene oxide polymer has a hydrolyzable silyl group in the molecule. The polyalkylene oxide polymer preferably has a hydrolyzable silyl group at at least one of both ends of its main chain, and preferably has a hydrolysable silyl group at both ends of its main chain. It is more preferable. When the polyalkylene oxide polymer has a hydrolyzable silyl group at at least one of both ends of the main chain, the cured product of the curable composition remains unburned even after it burns and becomes a residue. It maintains its shape and has excellent fire resistance.

A hydrolyzable silyl group is a group formed by bonding 1 to 3 hydrolyzable groups to a silicon atom. The hydrolyzable silyl group contained in the polyalkylene oxide polymer is not particularly limited, and examples include hydrogen atoms, halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, and amide groups. group, acid amide group, aminooxy group, mercapto group, alkenyloxy group, etc.

Among these, as the hydrolyzable silyl group, an alkoxysilyl group is preferable because the hydrolysis reaction is mild. Examples of alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; propyldimethoxysilyl group, methyldimethoxysilyl group, and methyldiethoxysilyl group. dialkoxysilyl groups such as; and monoalkoxysilyl groups such as dimethylmethoxysilyl group and dimethylethoxysilyl group. Among these, dialkoxysilyl groups and trialkoxysilyl groups are preferred, and dimethoxysilyl groups and trimethoxysilyl groups are more preferred.

In the polyalkylene oxide polymer, the average number of hydrolyzable silyl groups in one molecule is preferably 1 to 5, more preferably 1.4 to 4, and even more preferably 2.1 to 3. When the number of hydrolyzable silyl groups in the polyalkylene oxide polymer is within the above range, the cured product of the curable composition retains its pre-combustion form even after being burned to become a residue, resulting in an excellent It has fire resistance.

The average number of hydrolyzable silyl groups per molecule in the polyalkylene oxide polymer is determined by the concentration of hydrolyzable silyl groups in the polyalkylene oxide polymer determined by ¹ H-NMR and GPC. It can be calculated based on the number average molecular weight of the polyalkylene oxide polymer determined by the method.

Polyalkylene oxide polymers have urethane bonds (-NHCOO-) or urea bonds (-NHCONH-) in their molecules. Because the polyalkylene oxide polymer has urethane bonds or urea bonds in the molecule, the cured product of the curable composition retains its pre-combustion form even after it burns and becomes a residue, giving it excellent properties. It has fire resistance.

The polyalkylene oxide polymer preferably has a hydrolyzable silyl group at at least one end of the main chain. The hydrolyzable silyl group is preferably bonded to at least one of the ends of the main chain via a urethane bond or a urea bond. When a hydrolyzable silyl group is bonded to the end of the main chain via a urethane bond or a urea bond, the cured product of the curable composition more reliably retains its pre-combustion form even after it burns and becomes a residue. and has excellent fire resistance.

It is preferable that an alkylene group is interposed between the hydrolyzable silyl group and the urethane bond or urea bond. Due to the presence of alkylene groups, the cured product of the curable composition more reliably retains its pre-combustion form even after being burned to become a residue, and has excellent fire resistance.

The alkylene group is represented by -CnH _2m - (m is a natural number), for example, methylene group, ethylene group, n-propylene, n-butylene group, n-hexylene group, n-heptylene group, n-octylene group. , n-dodecylene group, etc., preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and an alkylene group having 1 to 4 carbon atoms. An alkylene group having 1 to 3 is more preferred.

The viscosity of the polyalkylene oxide polymer at 23° C. is preferably 50,000 Pa·s or less, more preferably 40,000 Pa·s or less, and preferably 35,000 Pa·s or less. When the viscosity of the polyalkylene oxide polymer at 23°C is 50,000 Pa·s or less, the cured product of the curable composition more reliably retains its pre-combustion form even after being burned to become a residue, resulting in an excellent It has fire resistance.

The viscosity of the polyalkylene oxide polymer at 23°C was measured using a B-type viscometer at a temperature of 23°C and a rotation speed of 20 rpm in accordance with the Japan Adhesive Industry Association standard JAI-7-1999. The melt viscosity obtained by The B-type viscometer is commercially available from Brookfield Co., Ltd. under the trade name "B-type viscometer digital rheometer DVII (rotor No. 29)."

[Glass frit]
The curable composition contains glass frit as a binder component in order to bond together the combustion residues of the polyalkylene oxide polymer in the combustion residues of the cured product of the curable composition.

Examples of the glass constituting the glass frit include phosphoric acid glass, boric acid glass, bismuth oxide glass, silicate glass, and sodium oxide glass. is preferred, and phosphate glass is more preferred. These glass frits include B ₂ O ₃ , P ₂ O ₅ , ZnO, SiO ₂ , Bi ₂ O ₃ , Al ₂ O ₃ , BaO, CaO, MgO, MnO ₂ , ZrO ₂ , TiO ₂ , CeO ₂ , SrO , V ₂ O ₅ , SnO ₂ , Li ₂ O, Na ₂ O, K ₂ O, CuO, Fe ₂ O ₃ and the like by adjusting a predetermined component ratio. Note that the glass frit may be used alone or in combination of two or more types.

The softening point of the glass constituting the glass frit is preferably 350° C. or higher, more preferably 360° C. or higher, because it can more effectively bond the combustion residues of the polyoxyalkylene polymer during combustion. The temperature is more preferably 370°C or higher, and even more preferably 380°C or higher. The softening point of the glass constituting the glass frit is preferably 650° C. or lower, more preferably 560° C. or lower, because it can more effectively bond the combustion residues of the polyoxyalkylene polymer during combustion. The temperature is more preferably 540°C or lower, and even more preferably 520°C or lower. Note that the softening point of the glass constituting the glass frit is the temperature at which the viscosity of the glass becomes 107.6 dPa·s (log η = 7.6).

The content of glass frit in the curable composition is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and 60 parts by mass based on 100 parts by mass of the polyalkylene oxide polymer. The amount is more preferably 70 parts by mass or more, and more preferably 70 parts by mass or more. The content of glass frit in the curable composition is preferably 200 parts by mass or less, more preferably 170 parts by mass or less, more preferably 150 parts by mass or less, and 120 parts by mass based on 100 parts by mass of the polyalkylene oxide polymer. The amount is more preferably 100 parts by mass or less, and more preferably 100 parts by mass or less. When the content of glass frit is 10 parts by mass or more, the cured product of the curable composition more reliably retains its pre-combustion form even after being burned and becomes a residue, and has excellent fire resistance. ing. When the content of the glass frit is 200 parts by mass or less, the cured product of the curable composition more reliably retains its pre-combustion form even after being burned and becomes a residue, and has excellent fire resistance. ing.

When the curable composition contains feldspars described below, the ratio of the feldspar content to the glass frit content (feldspar content/glass frit content) in the curable composition. is preferably 0.1 or more, more preferably 0.5 or more, more preferably 0.8 or more, and more preferably 1 or more. When the curable composition contains feldspars described below, the ratio of the feldspar content to the glass frit content (feldspar content/glass frit content) in the curable composition. is preferably 20 or less, more preferably 15 or less, more preferably 12 or less, and more preferably 6 or less. When the ratio of the feldspar content to the glass frit content (feldspar content/glass frit content) is 0.1 or more, the cured product of the curable composition burns and becomes a residue. It maintains its pre-combustion form more reliably even after burning, and has excellent fire resistance. When the ratio of the feldspar content to the glass frit content (feldspar content/glass frit content) was 20 or less, the cured product of the curable composition burned and became a residue. It maintains its pre-combustion form more reliably even after combustion, and has excellent fire resistance.

[Feldspars]
Preferably, the curable composition contains feldspars. Feldspars include feldspar and semi-feldspar, with semi-feldspar being preferred. Note that feldspars may be used alone or in combination of two or more types.

Examples of feldspars include alkali feldspars such as orthoclase, sanidine, microcline, and anorthoclase; and plagioclase such as albite, albite, neutral feldspar, albite, anorthite, and anorthite. It will be done.

Semi-feldspars include, for example, nepheline such as calcilite, cancrinite, nepheline syenite, leucite, and soda. Examples include sodalite, auinite, lazurite, nozeanite, melilite, and nepheline syenite is preferred. In addition, nepheline syenase is sometimes described as syenite.

The average particle diameter of the feldspars is preferably 0.01 μm or more, more preferably 0.1 μm or more, more preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more.
The average particle diameter of the feldspars is preferably 100 μm or less, more preferably 50 μm or less, more preferably 25 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. When the average particle size of the feldspar is 0.01 μm or more, the cured product of the curable composition more reliably retains its pre-combustion form even after being burned and becomes a residue, and has excellent fire resistance. are doing. When the average particle size of the feldspar is 100 μm or less, it can be uniformly dispersed in the curable composition, and the cured product of the curable composition retains its pre-combustion form even after it is burned and becomes a residue. Holds more securely and has excellent fire resistance.

Note that the average particle diameter of feldspars refers to a value measured by image analysis using a transmission electron microscope. Specifically, we took an enlarged photograph of feldspars using a transmission electron microscope at a magnification of 100 times, extracted 50 arbitrary feldspars, measured the diameter of each feldspar, and calculated the diameter of each feldspar. The arithmetic mean value of is taken as the average particle size of feldspars. Note that the diameter of feldspar refers to the diameter of the smallest perfect circle that can surround the feldspar.

The content of feldspars in the curable composition is preferably 1 part by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and 80 parts by mass based on 100 parts by mass of the polyalkylene oxide polymer. The amount is more preferably 100 parts by mass or more, and more preferably 100 parts by mass or more. The content of feldspars in the curable composition is preferably 800 parts by mass or less, preferably 600 parts by mass or less, more preferably 450 parts by mass or less, and 300 parts by mass based on 100 parts by mass of the polyalkylene oxide polymer. The following is more preferable, and 200 parts by mass or less is more preferable. When the content of feldspars is 1 part by mass or more, the combustion residue of the cured product of the curable composition does not become too hard or crack, and can maintain its pre-combustion form. When the content of feldspars is 800 parts by mass or less, the combustion residue of the cured product of the curable composition does not become too hard or crack, and can maintain its pre-combustion form.

[Silanol condensation catalyst]
Preferably, the curable composition contains a silanol condensation catalyst. The silanol condensation catalyst is a catalyst for promoting a dehydration condensation reaction between silanol groups formed by hydrolyzing the hydrolyzable silyl groups contained in the polyalkylene oxide polymer.

Examples of silanol condensation catalysts include 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin lauric acid). ) oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(monoester malate), tin octylate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis(triethoxysilicate), bis(dibutyltin bistriethoxysilicate) ) oxide and organic tin compounds such as dibutyltinoxybisethoxysilicate; organic titanium compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate. These silanol condensation catalysts may be used alone or in combination of two or more.

As the silanol condensation catalyst, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane is preferred. According to such a silanol condensation catalyst, the curing speed of the curable composition can be easily adjusted.

The content of the silanol condensation catalyst in the curable composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and 0.5 parts by mass based on 100 parts by mass of the polyalkylene oxide polymer. The above is more preferable. The content of the silanol condensation catalyst in the curable composition is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the polyalkylene oxide polymer. When the content of the silanol condensation catalyst in the curable composition is 0.1 part by mass or more, the curing speed of the curable composition is increased, and the time required for curing the curable composition is shortened. Can be done. When the content of the silanol condensation catalyst in the curable composition is 10 parts by mass or less, the curable composition has an appropriate curing rate, and the storage stability and handleability of the curable composition can be improved. can.

[Other additives]
The curable composition may also contain other additives such as thixotropic agents, antioxidants, ultraviolet absorbers, pigments, dyes, antisettling agents, aminosilane coupling agents, thixotropic agents, and solvents. Among these, thixotropy imparting agents, ultraviolet absorbers, and antioxidants are preferred.

Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers, with benzotriazole ultraviolet absorbers being preferred. The content of the ultraviolet absorber in the curable composition is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyalkylene oxide polymer.

Examples of the antioxidant include hindered phenolic antioxidants, monophenolic antioxidants, bisphenol antioxidants, and polyphenolic antioxidants, with hindered phenolic antioxidants being preferred. It will be done. The content of the antioxidant in the curable composition is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the polyalkylene oxide polymer.

The curable composition can be produced by mixing a polyalkylene oxide polymer, a glass frit, and, if necessary, feldspars and additives.

Gaps formed between members that make up a building structure, or gaps formed between parts of members that make up a building structure (hereinafter, these may be collectively referred to as "gaps") ) is filled with a curable composition, cured, and cured by moisture contained in the air or components to produce a cured product, which can be used for building structures and the components that make up the building structures. Can provide excellent fire resistance. The resulting fireproof structure includes mutually adjacent members or parts of the members, and a cured product of the curable composition filled in the gaps formed between the mutually adjacent members or between the parts of the members.

The members constituting the building structure are not particularly limited, and include, for example, wall members (for example, outer wall members, inner wall members, ceiling members, etc.), door members, partition members, and the like.

The cured product of the curable composition generates a strong combustion residue when burned, and even in the event of a fire, this combustion residue fills the gap and reliably maintains the closed state, preventing the flame from spreading through the gap. This makes it possible to impart excellent fire resistance to the building structure or the members constituting the building structure.

The curable composition of the present invention is cured by moisture contained in the air or in a member with which the curable composition is in contact to produce a cured product. The cured product of the curable composition retains its pre-combustion form even after being burned and becomes a residue, and has excellent fire resistance.

The combustion residue of the cured product of the curable composition reliably maintains the closed state of the gap even in the event of a fire, prevents the flame from penetrating through the gap, and protects the building structure or this building structure. It is possible to impart excellent fire resistance to materials such as

The present invention will be explained in more detail below using Examples, but the present invention is not limited thereto.

The following raw materials were used in producing the curable compositions of Examples and Comparative Examples.

・Polyalkylene oxide polymer 1 that has urethane bonds in the molecule and hydrolyzable silyl groups at both ends of the main chain (Polyalkylene oxide polymer 1, main chain skeleton: polypropylene oxide, urethane in the main chain skeleton) Does not have bonds or urea bonds, number average molecular weight: 17,400, has methyldimethoxysilyl groups at both ends of the main chain via urethane bonds, average number of methyldimethoxysilyl groups in one molecule: 3.0 pieces , has a methylene group between the methyldimethoxysilyl group and the urethane bond, viscosity at 23°C: 500 mPa・s, manufactured by Asahi Kasei Wacker Silicone Co., Ltd., product name "XT-50")

・Polyalkylene oxide polymer 2 that has urethane bonds in the molecule and hydrolyzable silyl groups at both ends of the main chain (Polyalkylene oxide polymer 2, main chain skeleton: polypropylene oxide, urethane in the main chain skeleton) Does not have bonds or urea bonds, number average molecular weight: 17,900, has methyldimethoxysilyl groups at both ends of the main chain via urethane bonds, average number of methyldimethoxysilyl groups in one molecule: 2.0 pieces , having a methylene group between the methyldimethoxysilyl group and the urethane bond, viscosity at 23°C: 10000 mPa・s, manufactured by Asahi Kasei Wacker Silicone Co., Ltd., product name "GENIOSIL STP-E10")

・Polyalkylene oxide polymer 3 that has urethane bonds in the molecule and hydrolyzable silyl groups at both ends of the main chain (Polyalkylene oxide polymer 3, main chain skeleton: polypropylene oxide, urethane in the main chain skeleton) Does not have bonds or urea bonds, number average molecular weight: 30,300, has methyldimethoxysilyl groups at both ends of the main chain via urethane bonds, average number of methyldimethoxysilyl groups in one molecule: 2.0 pieces , has a methylene group between the methyldimethoxysilyl group and the urethane bond, viscosity at 23°C: 30000 mPa・s, manufactured by Asahi Kasei Wacker Silicone Co., Ltd., product name "GENIOSIL STP-E30")

・Polyalkylene oxide polymer 4 that has a urea bond in the molecule and hydrolyzable silyl groups at both ends of the main chain (Polyalkylene oxide polymer 4, main chain skeleton: polypropylene oxide, urethane in the main chain skeleton) Has a bond or urea bond, number average molecular weight: 22,300, has trimethoxysilyl groups at both ends of the main chain via urea bonds, average number of trimethoxysilyl groups in one molecule: 3.0. , has a propylene group between a trimethoxysilyl group and a urea bond, viscosity at 23°C: 2500 mPa・s, manufactured by Momentive Performance Materials Japan LLC, product name "SPUR3030")

・Polyalkylene oxide polymer 5 that has a urea bond in the molecule and hydrolyzable silyl groups at both ends of the main chain (Polyalkylene oxide polymer 5, main chain skeleton: polypropylene oxide, urethane in the main chain skeleton) Has a bond or a urea bond, number average molecular weight: 22,500, has trimethoxysilyl groups at both ends of the main chain via a urea bond, average number of trimethoxysilyl groups in one molecule: 3.0. , has a propylene group between the trimethoxysilyl group and the urea bond, viscosity at 23°C: 7000 mPa・s, manufactured by Momentive Performance Materials Japan LLC, product name "SPUR3040")

・Polyalkylene oxide polymer 6 having hydrolyzable silyl groups at both ends of the main chain (polyalkylene oxide polymer 6, does not have urethane bonds or urea bonds in the molecule, main chain skeleton: polypropylene oxide, number average) Molecular weight: 5200, having methyldimethoxysilyl groups at both ends of the main chain, average number of methyldimethoxysilyl groups in one molecule: 1.4, viscosity at 23°C: 600 mPa・s, manufactured by Kaneka, product name "SAT010" ”)

・Polyalkylene oxide polymer 7 having hydrolyzable silyl groups at both ends of the main chain (Polyalkylene oxide polymer 7, does not have urethane bonds or urea bonds in the molecule, main chain skeleton: polypropylene oxide, number average Molecular weight: 4000, having methyldimethoxysilyl groups at both ends of the main chain, average number of methyldimethoxysilyl groups in one molecule: 2.1, viscosity at 23°C: 600 mPa・s, manufactured by Kaneka, product name "SAT015" ”)

・Polyalkylene oxide polymer 8 having hydrolyzable silyl groups at both ends of the main chain (polyalkylene oxide polymer 8, having no urethane bonds or urea bonds in the molecule, main chain skeleton: polypropylene oxide, number average) Molecular weight: 15,000, having methyldimethoxysilyl groups at both ends of the main chain, average number of methyldimethoxysilyl groups in one molecule: 2.1, viscosity at 23°C: 600 mPa・s, manufactured by AGC, product name "S6250" ”)

[Glass frit]
・Glass frit (phosphoric acid glass, “VY0144” manufactured by Nippon Frit Co., Ltd., main components: P ₂ O ₅ , AI ₂ O ₃ and R ₂ O, R is an alkali metal atom, softening point: 404°C)

[Feldspars]
・Semi-feldspar (average particle size: 5 μm, nepheline cyanite, manufactured by Shiraishi Calcium Co., Ltd., product name “Nesper”)

[Antioxidant]
・Hindered phenol antioxidant (manufactured by BASF Japan, product name “Irganox 1010”)

[Silanol condensation catalyst]
・Silanol condensation catalyst (1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, manufactured by Nitto Kasei Co., Ltd., trade name "Neostane U-130")

(Examples 1 to 7 and Comparative Examples 1 to 3)
Polyalkylene oxide polymers 1 to 8, glass frit, quasi-feldspar, hindered phenol antioxidant, and silanol condensation catalyst were mixed in the amounts shown in Table 1, and were mixed in a vacuum atmosphere using a planetary mixer. A curable composition was obtained by mixing for 60 minutes until uniform.

The rubber elasticity and dumbbell elongation after combustion of the obtained curable composition were measured by the following methods, and the results are shown in Table 1.

(Rubber elasticity after combustion)
The rubber elasticity of the curable composition after combustion was measured in the following manner. Specifically, the curable composition was coated onto a polyethylene film to a thickness of 10 mm and cured for 14 days under conditions of an ambient temperature of 23° C. and a relative humidity of 50% to prepare a test piece. The test piece was left in a muffle furnace set at 600°C for 30 minutes, and the test piece (combustion residue) after combustion was taken out of the muffle furnace, and the combustion residue was left in an atmosphere at 23°C for 3 hours. The obtained combustion residue was pressed against the surface using a durometer A based on JIS K6253, and the value after 15 seconds was measured as Shore A.
A: Shore A was 50 or more.
B: Shore A was less than 50 and 30 or more.
C: Shore A was less than 30.

(dumbbell growth rate)
After coating the curable composition on a release-treated substrate to a thickness of 3 mm, the curable composition was cured for one month at 23° C. and 50% relative humidity. A test piece was prepared by cutting the cured product of the curable composition into a No. 3 dumbbell conforming to JIS K6251.

A tensile test was conducted using the obtained test piece at a tensile speed of 200 mm/min. The distance between the scores in the tensile direction of the No. 3 dumbbell (initial distance between the scores) was 20 mm, and the distance between the scores (distance between the scores after tension) changed by the tensile test was measured. The dumbbell elongation rate was calculated based on the following formula and evaluated based on the following criteria.
Dumbbell elongation rate (%) = 100 x distance between scores after tension/distance between initial scores A: Dumbbell elongation rate 200% or more.
B: Dumbbell elongation rate less than 200% and 100% or more.
C: Dumbbell elongation rate less than 100%.

Claims (6)

A polyalkylene oxide polymer having a urethane bond or a urea bond in the molecule, a dialkoxysilyl group and/or a trialkoxysilyl group as a hydrolyzable silyl group, and a number average molecular weight of 17,400 or more and 80,000 or less. Combination and
A curable composition comprising a glass frit. The curable composition according to claim 1, which contains 10 to 200 parts by mass of glass frit per 100 parts by mass of the polyalkylene oxide polymer. The curable composition according to claim 1 or 2, characterized in that it contains feldspars. Curing according to any one of claims 1 to 3, wherein the polyalkylene oxide polymer has a hydrolyzable silyl group bonded to the end of the main chain via a urethane bond or a urea bond. sexual composition. The curable composition according to any one of claims 1 to 4, wherein the urethane bond or urea bond and the hydrolyzable silyl group are bonded via an alkylene group. The curable composition according to any one of claims 1 to 5, wherein the polyalkylene oxide polymer has a viscosity of 10,000 Pa·s or less at 23°C.