阅读说明：本技术 固化性组合物和涂膜防水剂 (Curable composition and water repellent for coating film ) 是由 池内拓人 于 2019-01-11 设计创作，主要内容包括：本发明提供橡胶弹性、涂膜强度、涂布性和对防水衬底等的密合性优异的固化性组合物。本发明的固化性组合物包含具有水解性甲硅烷基的聚环氧烷、和平均粒径为0.01～100μm的长石类,优选进一步含有碳酸钙,并且优选长石类含有霞石正长岩(Nepheline Syenite),所述组合物具有低粘度并且涂布性优异,同时可以形成具有优异的橡胶弹性和涂膜强度并且具有优异的密合性的固化物。(The invention provides a curable composition having excellent rubber elasticity, coating film strength, coating property and adhesion to a waterproof substrate and the like. The curable composition of the present invention comprises a polyalkylene oxide having a hydrolyzable silyl group and a feldspar having an average particle diameter of 0.01 to 100 [ mu ] m, preferably further contains calcium carbonate, and preferably the feldspar contains Nepheline Syenite (Nepheline Syenite), has a low viscosity and excellent coatability, and can form a cured product having excellent rubber elasticity and coating film strength and excellent adhesion.)

1. A curable composition comprising:

a polyalkylene oxide having a hydrolyzable silyl group, and

feldspar having an average particle diameter of 0.01 to 100 μm.

2. The curable composition according to claim 1, wherein the feldspar based material is contained in an amount of 1 to 800 parts by mass based on 100 parts by mass of the polyalkylene oxide.

3. A water repellent for coating films comprising the curable composition according to claim 1 or claim 2.

Technical Field

The present invention relates to a curable composition and a coating film water repellent.

Background

Conventionally, a coating film for waterproofing is formed on a house of a concrete building. Patent document 1 discloses a polyurethane elastic foam which is composed ofThe urethane elastic foam has a foaming ratio of 2 to 10 times, an elongation of 200 to 1000%, and a tensile strength of 20 to 100kg/cm²The urethane waterproof material of (1).

Disclosure of Invention

Technical problem to be solved by the invention

However, since the urethane material used in the construction of the urethane waterproofing material disclosed in patent document 1 contains a solvent, it is considered to use a solvent-free material in order to reduce the burden on the work environment and the global environment.

Further, the waterproof coating film is required to have rubber elasticity that can accommodate not only expansion and contraction accompanying a temperature change of a concrete building as a waterproof backing but also elongation of the waterproof backing due to cracks accompanying deterioration with time. Further, the waterproof coating film is required to have adhesion to a waterproof substrate.

Therefore, among the solvent-free materials, it is conceivable to use a modified silicone resin.

However, although the modified polysiloxane resin has excellent rubber elasticity, the coating film strength is low. Therefore, when a filler is added to improve the strength of the coating film, another problem occurs in that the coatability is lowered.

The invention provides a curable composition having excellent rubber elasticity, coating film strength, coating property and adhesion to a waterproof substrate and the like.

Means for solving the problems

The curable composition of the present invention comprises a polyalkylene oxide having a hydrolyzable silyl group and a feldspar having an average particle diameter of 0.01 to 100 [ mu ] m.

[ polyalkylene oxide ]

The polyalkylene oxide contained in the curable composition has a hydrolyzable silyl group. The hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable groups are bonded to a silicon atom.

The hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and examples thereof include: a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a Ketoximate (Ketoximate) group, an amino group, an amide (Acid amide) group, an aminooxy group, a mercapto group, an alkenyloxy group, and the like.

Among these, alkoxysilyl groups are preferable because the hydrolysis reaction is mild. Examples of the alkoxysilyl group include: trialkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, triisopropoxysilyl and triphenoxysilyl; dialkoxysilyl groups such as dimethoxysilyl, diethoxysilyl, methyldimethoxysilyl, and methyldiethoxysilyl; and monoalkoxysilyl groups such as dimethylmethoxysilyl and dimethylethoxysilyl groups. Among them, a dialkoxysilyl group is more preferable, and a methyldimethoxysilyl group is particularly preferable.

Preferably, the polyalkylene oxide has 1 to 4 hydrolyzable silyl groups on average in 1 molecule. When the number of hydrolyzable silyl groups in the polyalkylene oxide is 1 or more, the curability of the curable composition is improved. When the number of hydrolyzable silyl groups in the polyalkylene oxide is 4 or less, the curable composition can form a cured product having excellent rubber elasticity.

The average number of hydrolyzable silyl groups per 1 molecule in the polyalkylene oxide may be determined by¹The concentration of hydrolyzable silyl groups in the polyalkylene oxide determined by H-NMR and the number average molecular weight of the polyalkylene oxide determined by GPC method were calculated.

As the polyalkylene oxide, there are preferably mentioned: the main chain containing a compound of the formula- (R-O)_nA polymer having a repeating unit represented by the formula (I) (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). The main chain skeleton of the polyalkylene oxide may contain only one kind of repeating unit, or may contain two or more kinds of repeating units.

Examples of the main chain skeleton of the polyalkylene oxide include: polyethylene oxide, polypropylene oxide, polybutylene oxide, 1, 4-polybutylene oxide (Polytetramethylene oxide), a polyethylene oxide-polypropylene oxide copolymer, a polypropylene oxide-polybutylene oxide copolymer, and the like. Among them, polypropylene oxide is preferred. The curable composition can form a cured product having excellent rubber elasticity if it is based on polypropylene oxide.

The number average molecular weight of the polyalkylene oxide is preferably 3000 to 50000, more preferably 10000 to 30000. When the number average molecular weight of the polyalkylene oxide is 10000 or more, the rubber elasticity of a cured product of the curable composition is improved. When the number average molecular weight of the polyalkylene oxide is 50000 or less, the coatability of the curable composition is improved.

In the present invention, the number average molecular weight of the polyalkylene oxide is a value in terms of polystyrene measured by a GPC (gel permeation chromatography) method. For the measurement by the GPC method, shodex kf800D manufactured by TOSOH, for example, is used as a GPC column, and chloroform or the like is used as a solvent.

The polyalkylene oxide having a hydrolyzable silyl group may be any one of those commercially available. Examples thereof include: trade names MS Polymer S-203 and S-303 manufactured by KANEKA corporation; SAILIRU (サイリル) Polymer SAT-200, SAT-350, SAT-400; trade names EXCETAR ESS-3620, ESS-2420, ESS2410, ESS3430, etc., manufactured by Asahi glass company.

[ feldspar series ]

The curable composition contains feldspar. Feldspathic includes feldspar and feldspar-like, preferably feldspar-like.

Examples of the feldspar include: alkaline feldspars such as orthoclase, diaclase, microcline, askew, etc.; anorthite, melilite, labradorite, anorthite, etc.

Examples of the feldspar analogue include: kalsilite (Kalsilite), Cancrinite (Cancrinite), and like Nepheline (Nepheline), Nepheline Syenite (Nepheline Syenite), Leucite (Leucite), Sodalite (Sodalite), kyanite (Hauyne), laponite (lasonite), tetrahedrite (Nosean), melilite (melilite), and the like, preferably Nepheline Syenite (Nepheline Syenite). It should be noted that Nepheline Syenite (Nepheline Syenite) is sometimes referred to as Syenite.

The feldspar having an average particle diameter of 0.01 to 100 μm, preferably 0.1 to 50 μm, more preferably 1 to 25 μm, particularly preferably 2 to 15 μm, and more particularly preferably 3 to 10 μm. When the average particle diameter of the feldspar is 0.01 μm or more, the curable composition can form a cured product having excellent coating film strength. When the average particle diameter of the feldspar is 100 μm or less, the feldspar can be uniformly dispersed in the curable composition, and the curable composition can form a cured product having excellent coating film strength. The average particle size of the feldspar is a value measured by image analysis using a transmission electron microscope. Specifically, a photograph of the feldspar by 100 × magnification is taken with a transmission electron microscope, arbitrary 50 feldspar are extracted, the diameter of each feldspar is measured, and the arithmetic average of the diameters of the feldspar is defined as the average particle diameter of the feldspar. The diameter of the feldspar member is a diameter of a complete circle that can surround the minimum diameter of the feldspar member.

The content of the feldspar in the curable composition is preferably 1 to 800 parts by mass, more preferably 30 to 600 parts by mass, still more preferably 50 to 450 parts by mass, and particularly preferably 80 to 300 parts by mass, based on 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. When the content of the feldspar in the above range, the curable composition can form a cured product having excellent rubber elasticity and coating film strength while having excellent coatability.

[ plasticizer ]

Preferably, the curable composition further contains a plasticizer. The curable composition containing a plasticizer can form a cured product having excellent rubber elasticity and excellent followability.

Examples of the plasticizer include: phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, di-n-hexyl phthalate, bis (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, and dibutylbenzyl phthalate; polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol. Among them, polyalkylene glycol is preferable, and polypropylene glycol is more preferable.

The number average molecular weight of the polyalkylene glycol is preferably 1000 to 10000, more preferably 2000 to 5000. When the number average molecular weight of the polyalkylene glycol is within the above range, the curable composition containing such a polyalkylene glycol can form a cured product having excellent rubber elasticity and excellent followability.

The number average molecular weight of the polyalkylene glycol is a value measured in terms of polystyrene by a GPC (gel permeation chromatography) method. The specific measurement method and measurement conditions are the same as those of the above-mentioned polyalkylene oxide having a hydrolyzable silyl group.

The content of the plasticizer in the curable composition is preferably 1 to 100 parts by mass, more preferably 10 to 80 parts by mass, particularly preferably 15 to 60 parts by mass, and most preferably 20 to 50 parts by mass, based on 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group.

[ Filler ]

The curable composition may further contain a filler. When the curable composition contains a filler, a curable composition that can give a cured product having excellent rubber elasticity can be provided.

The filler is not particularly limited, and examples thereof include: calcium carbonate, magnesium carbonate, calcium oxide, hydrous silicic acid, silicic anhydride, fine silica powder, calcium silicate, titanium dioxide, clay, talc, carbon black, glass spheres, and the like, with calcium carbonate being preferred and ground calcium carbonate being more preferred. The fillers may be used alone or in combination of two or more.

The average particle diameter of the filler is preferably 0.01 to 5 μm, more preferably 0.05 to 2.5 μm. The filler having such an average particle diameter can provide a curable composition capable of forming a cured product having excellent adhesion to a waterproof substrate or the like. The average particle diameter of the filler is a value measured by image analysis using a transmission electron microscope. Specifically, a photograph of the filler taken by a transmission electron microscope at a magnification of 100 is taken, arbitrary 50 fillers are extracted, the diameter of each filler is measured, and the arithmetic average of the diameters of the fillers is defined as the average particle diameter of the filler. The diameter of the filler is a diameter of a complete circle that can surround the minimum diameter of the filler.

Further, calcium carbonate is preferably surface-treated with fatty acid, fatty acid ester, or the like. The surface-treated calcium carbonate is a calcium carbonate which is surface-treated with a fatty acid, a fatty acid ester, or the like, and can impart thixotropy to the curable composition and inhibit aggregation of the calcium carbonate.

The content of the filler in the curable composition is preferably 1 to 700 parts by mass, more preferably 10 to 200 parts by mass, and particularly preferably 20 to 150 parts by mass, based on 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. When the content of the filler in the curable composition is 1 part by mass or more, the effect of the addition of the filler can be sufficiently obtained. When the content of the filler in the curable composition is 700 parts by mass or less, a cured product obtained by curing the curable composition has excellent adhesion to a waterproof substrate or the like.

[ dehydrating agent ]

Preferably, the curable composition further contains a dehydrating agent. The dehydrating agent can inhibit the curing of the curable composition by moisture contained in the air or the like when the curable composition is stored.

Examples of the dehydrating agent include: silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane and diphenyldimethoxysilane; and ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate. These dehydrating agents may be used alone, or two or more of them may be used in combination. Among them, vinyltrimethoxysilane is preferable.

The content of the dehydrating agent in the curable composition is preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass, based on 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. When the content of the dehydrating agent in the curable composition is 0.5 parts by mass or more, the effect of the dehydrating agent can be sufficiently obtained. Further, when the content of the dehydrating agent in the curable composition is 20 parts by mass or less, the curable composition has excellent curability.

[ silanol condensation catalyst ]

The curable composition preferably contains a silanol condensation catalyst. The silanol condensation catalyst is a catalyst for promoting a dehydration condensation reaction between silanol groups formed by hydrolysis of hydrolyzable silyl groups or the like contained in the polyalkylene oxide.

Examples of the silanol condensing catalyst include: organotin compounds such as 1,1,3, 3-tetrabutyl-1, 3-dilauryloxycarbonyl-distannoxane, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, dibutyltin bis (laurate), dibutyltin bis (acetylacetonate), dibutyltin bis (monoester malate), tin octylate, dibutyltin octylate, dioctyltin oxide, dibutyltin bis (triethoxysilicate), bis (dibutylbis triethoxysilicate) oxide, and dibutyltin oxybis diethoxysilicates; organic titanium compounds such as tetra-n-butoxy titanate and tetra-isopropoxy titanate. These silanol condensing catalysts may be used alone, or two or more of them may be used in combination.

The silanol condensation catalyst is preferably 1,1,3, 3-tetrabutyl-1, 3-dilauryloxycarbonyl distannoxane. The curing rate of the curable composition can be easily adjusted by using such a silanol condensation catalyst.

The content of the silanol condensation catalyst in the curable composition is preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, based on 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. When the content of the silanol condensation catalyst in the curable composition is 1 part by mass or more, the curing speed of the curable composition can be increased, and the time required for curing the curable composition can be shortened. Further, when the content of the silanol condensation catalyst in the curable composition is 10 parts by mass or less, the curable composition can be provided with an appropriate curing speed, and the storage stability and the handling property of the curable composition can be improved.

[ other additives ]

The curable composition may contain other additives such as thixotropy imparting agents, antioxidants, ultraviolet absorbers, pigments, dyes, anti-settling agents, and solvents. Among them, preferred are: thixotropy-imparting agents, ultraviolet absorbers and antioxidants.

The thixotropy-imparting agent may be any agent that can cause the curable composition to exhibit thixotropy. As the thixotropy imparting agent, preferred are: hydrogenated castor oil, fatty acid bisamides, fumed silica, and the like.

The content of the thixotropy imparting agent in the curable composition is preferably 0.1 to 200 parts by mass, more preferably 1 to 150 parts by mass, based on 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group. When the content of the thixotropy-imparting agent in the curable composition is 0.1 part by mass or more, thixotropy can be effectively imparted to the curable composition. When the content of the thixotropy-imparting agent in the curable composition is 200 parts by mass or less, the curable composition has an appropriate viscosity, and the workability of the curable composition is improved.

Examples of the ultraviolet absorber include: triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers and the like, and benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers are preferable, and benzotriazole-based ultraviolet absorbers are more preferable. The content of the ultraviolet absorber in the curable composition is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group.

Examples of the antioxidant include: hindered phenol antioxidants, monophenol antioxidants, bisphenol antioxidants, polyphenol antioxidants, and the like, and preferable examples thereof include hindered phenol antioxidants. The content of the antioxidant in the curable composition is preferably 0.1 to 20 parts by mass, and more preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group.

[ light stabilizer ]

The curable composition preferably contains a light stabilizer, and more preferably contains a hindered amine light stabilizer. Based on the hindered amine light stabilizer, a curable composition capable of maintaining excellent rubber elasticity and coating film strength for a longer period of time after curing can be provided.

Examples of the hindered amine-based light stabilizer include: a mixture of bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate and methyl 1,2,2,6, 6-pentamethyl-4-piperidinyl sebacate, bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, dibutylamine 1,3, 5-triazin.n, N' -bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine and N- (2,2,6, 6-tetramethyl-4-piperidinyl) butylamine, a polycondensate of poly [ {6- (1,1,3, 3-tetramethylbutyl) amino-1, 3, 5-triazin-2, 4-diyl } { (2,2,6, 6-tetramethyl-4-piperidyl) imino } hexamethylene { (2,2,6, 6-tetramethyl-4-piperidyl) imino } ], a polycondensate of dimethyl succinate and 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidylethanol, and the like.

As the hindered amine light stabilizer, a NOR type hindered amine light stabilizer is preferably used. The NOR type hindered amine light stabilizer can provide a curable composition which can suppress the deterioration of rubber elasticity and coating film strength with time after curing.

The NOR-type hindered amine light stabilizer has a NOR structure in which an alkyl group (R) is bonded to a nitrogen atom (N) included in a piperidine ring skeleton via an oxygen atom (O). The number of carbon atoms of the alkyl group in the NOR structure is preferably 1 to 20, more preferably 1 to 18, and particularly preferably 18. Examples of the alkyl group include: linear alkyl groups, branched alkyl groups, and cyclic alkyl groups (saturated alicyclic hydrocarbon groups).

Examples of the linear alkyl group include: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, and the like. Examples of the branched alkyl group include: isopropyl, isobutyl, sec-butyl, tert-butyl, and the like. Examples of the cyclic alkyl group (saturated alicyclic hydrocarbon group) include: cyclopentyl, cyclohexyl, cyclooctyl, and the like. Further, the hydrogen atom constituting the alkyl group may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a hydroxyl group, etc.

Examples of the NOR type hindered amine light stabilizer include a hindered amine light stabilizer represented by the following formula (I).

[ chemical formula 1]

When the NOR-type hindered amine light stabilizer is used, it is preferable to use the NOR-type hindered amine light stabilizer in combination with a benzotriazole-based ultraviolet absorber or a triazine-based ultraviolet absorber. Thus, a curable composition can be provided which can further suppress the deterioration of rubber elasticity and coating film strength with time after curing.

The content of the light stabilizer in the curable composition is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the polyalkylene oxide having a hydrolyzable silyl group.

The curable composition can be produced by uniformly mixing a polyalkylene oxide having a hydrolyzable silyl group and a feldspar, and additives added as needed. The curable composition preferably does not contain a solvent (for example, alcohol, xylene, toluene, or the like).

The curable composition has excellent adhesiveness and can form a cured product capable of maintaining excellent rubber elasticity and coating film strength for a long time, and thus, can be used for various applications such as coating film waterproofing agents, coating materials, and paints. Among them, it is preferably used as a coating film waterproofing agent.

As described above, the curable composition is preferably used as a waterproofing agent for coating films, and specifically, the curable composition is applied to a concrete surface forming a waterproof backing, such as a house of a concrete building. In this case, the curable composition is excellent in coatability, and thus can be smoothly and uniformly coated on a waterproof substrate. Further, a waterproof coating film can be formed by curing and curing the curable composition.

By using the curable composition, a waterproof structure comprising a waterproof substrate and a waterproof coating film that is provided on the surface of the waterproof substrate and comprises a cured product of the curable composition can be constituted.

The waterproof coating film obtained has excellent rubber elasticity, coating film strength and excellent adhesion to a waterproof substrate and the like, and therefore, the waterproof coating film can smoothly follow expansion and contraction caused by temperature change of the waterproof substrate and can smoothly follow extension of the waterproof substrate caused by cracking of the waterproof substrate which is deteriorated with the passage of time, and the waterproof coating film can maintain excellent waterproof performance without cracking for a long time.

Effects of the invention

The curable composition of the present invention has a low viscosity and is excellent in coatability, and at the same time, can form a cured product having excellent rubber elasticity and coating film strength and excellent adhesion.

Detailed Description

The present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.