JP4841828B2 - Curable composition and sealant composition - Google Patents

Description

  The present invention relates to a curable composition and a sealing material composition that are cured by moisture in the air or the like to become a rubber-like elastic body, and particularly excellent in durability and surface contamination prevention effect. The present invention also relates to a curable composition and a sealing material composition having a glossy and rough appearance.

Conventionally, it is generally called a modified silicone resin as a moisture-curing resin component used in curable compositions such as waterproof sealants for buildings, civil engineering, and automobiles, adhesives, and paints. Resins such as chain polyethers containing a crosslinkable silyl group in the molecule and polyurethane resins are widely used because of their excellent workability and adhesiveness.
Also, in recent years, in detached houses, the outer wall material has a high-quality image that has been calmed by lowering the glossiness of the surface of the outer wall material, or the surface of the outer wall material has been erased and sand. Exterior wall materials with a heavy image that simulates natural rough rocks have been used with sandstone-like decorations coated with sandstones and sandstone-like decorations that imitate the irregularities of rocks.
The joints of the exterior wall material that has been painted to reduce the glossiness of the surface, or the sandstone-like decoration that mimics the surface glossiness and has a matte surface that has been matted, If a (surface) glossy or glossy sealant is used on the joints of the outer wall material that imitates natural rough rocks, the sealant will appear to stand out from the outer wall material, and the joint will stand out. The aesthetic feature is reduced, and the appearance of the outer wall of the building as a whole is impaired. Therefore, for example, in Patent Document 1, a room temperature curable composition in which a glossy surface is cured by blending a propylene oxide polymer having a hydrolyzable silyl group with an amine compound having a melting point of 10 to 200 ° C. Proposed. Further, Patent Document 2 proposes a sealing material composition having a rough feeling in which a balloon having an average particle size of 100 μm or more is blended in the sealing material composition.
Japanese Patent Laid-Open No. 9-100408 JP-A-10-251618

  However, in recent years, in the fields of buildings, civil engineering, automobiles, etc., there has been a growing need for so-called ultra-long life that maintains performance over a long period of time. For sealing materials, adhesives, paints, etc. used in these However, further improvements in durability such as adhesion, heat resistance, water resistance, and weather resistance are required. Workability is good in sealing materials, adhesives, paints, and the like containing conventionally known modified silicone resins, but various physical properties such as elongation after curing are still insufficient, and in particular, the surface after curing is not sticky. Since it remains, it has an aesthetic defect that dust or the like adheres to it, and there is a problem that a special device is required for synthesizing the modified silicone resin, making it difficult and expensive to manufacture.

Moreover, although the said method of mix | blending an amine compound with a room temperature curable composition can provide the matte effect of a hardened surface, there exists a problem that a weather resistance is inferior.
Furthermore, the above-mentioned method of blending a balloon with a sealing material composition is not suitable for the surface of the sealing material after curing, although the surface feels rough as if it was covered with sand, but the irregularities are large and the irregular reflection of light is insufficient. The surface is still high-gloss, with the above-mentioned exterior wall material, the surface is matt and the sandstone-like decoration imitating the sand and the unevenness of the rocks When used as a sealing material for joints of outer wall materials with a profound image imitating rocks, the sealing material appears to stand out from the outer wall materials, which also reduces the aesthetic characteristics of the outer wall materials and impairs the appearance of the building outer wall as a whole There is a problem that it ends up.

The object of the present invention is to solve the above-mentioned problems of the prior art, and is easy to manufacture and good in storage stability, cured by moisture in the atmosphere, etc., and has high tensile strength, low modulus and large elongation. It is to provide a one-component moisture-curing curable composition and a sealing material composition that are excellent in adhesiveness, in particular, surface contamination prevention effect and weather resistance.
Another object of the present invention is a one-part moisture-curing type curing that has a rough appearance with relatively large irregularities such as dust covered with sand that is sufficiently glossy and glossy in addition to the above characteristics. Providing an adhesive composition and a sealant composition.

  In order to achieve the object, the present invention includes the following (1) to (4).

(1) A curable composition containing a crosslinkable silyl group-containing resin and an amine, wherein the crosslinkable silyl group-containing resin, Sutaira average molecular weight of 1,000 to 30,000, Tg is 0 ℃ or less, A polyacrylic and / or methacrylic polyol (excluding fluorine-containing polyacrylic and / or methacrylic polyol ) having a viscosity at 25 ° C. of 100,000 mPa · s or less and a crosslinkable silyl group-containing isocyanate compound are converted into an isocyanate group. / Crosslinkable silyl group-containing polyacrylic and / or methacrylic resin (a-1) obtained by reacting in the range where the equivalent ratio of hydroxyl group is 0.1 to 1.5 / 1.0, and polyoxyalkylene polyol A crosslinkable silyl group-containing polyoxyalkylene resin (o-1) obtained by reacting a crosslinkable silyl group-containing isocyanate compound A mixture of and, wherein the amine is to be a mixture of melting point 30 ° C. or more aliphatic primary amine with a melting point 30 ° C. or more aliphatic secondary Kyua amine, said curable characterized by Composition.

(2) The curable composition according to (1), further containing an additive.

(3) The curable composition according to (2), wherein the additive is a polyacrylic and / or methacrylic plasticizer.

(4) A sealant composition containing a crosslinkable silyl group-containing resin and an amine, wherein the crosslinkable silyl group-containing resin, Sutaira average molecular weight of 1,000 to 30,000, Tg is 0 ℃ or less, A polyacrylic and / or methacrylic polyol (excluding fluorine-containing polyacrylic and / or methacrylic polyol ) having a viscosity at 25 ° C. of 100,000 mPa · s or less and a crosslinkable silyl group-containing isocyanate compound are converted into an isocyanate group. / Crosslinkable silyl group-containing polyacrylic and / or methacrylic resin (a-1) obtained by reacting in the range where the equivalent ratio of hydroxyl group is 0.1 to 1.5 / 1.0, and polyoxyalkylene polyol And a crosslinkable silyl group-containing polyoxyalkylene resin obtained by reacting a crosslinkable silyl group-containing isocyanate compound ( -1) a mixture of, and, said Amin is it a mixture of melting point 30 ° C. or more aliphatic primary amine with a melting point 30 ° C. or more aliphatic secondary Kyua Min, and wherein The sealing material composition.

  Since the crosslinkable silyl group-containing resin in the present invention has a low modulus, a large elongation and a high tensile strength after curing, the curable composition containing the resin has excellent storage stability and workability. The later adhesiveness is excellent. In addition to the above properties, the curable composition of the present invention is particularly excellent in surface contamination prevention effect and weather resistance, so it is sufficient for ultra-long life and high performance of recent buildings, civil engineering, automobiles, etc. Can adapt.

  Furthermore, the cured composition and sealant composition of the present invention imparted with a dull performance, or a dull and rough feel, in addition to the above properties, the cured surface is dull or dull. In particular, the coating or sealing of low-gloss outer wall materials, etc. with low surface glossiness, or matte and natural, rough rocks with low surface glossiness. When used for coating or sealing the outer wall material, the applied part and the joint of the sealing material are not conspicuous, and the characteristic aesthetics of the outer wall material having a high-quality image that is calm as a whole are not impaired.

The present invention will be described in detail below.
Since the crosslinkable silyl group-containing resin as a curing component in the present invention is significantly superior in weather resistance in spite of its low modulus as compared with a conventionally known crosslinkable silyl group-containing resin generally called a modified silicone, The curable composition and the sealing material composition containing this also have extremely good weather resistance. Furthermore, when balloons and granular materials are blended to give a rough feeling described later, the resin that covers the balloons and granular materials raised on the cured surface becomes a thin film, and the weather resistance of conventional modified silicone resins deteriorates. Since the crosslinkable silyl group-containing resin in the present invention has a high weather resistance, the weather resistance does not deteriorate even if a rough feeling is imparted.

The crosslinkable silyl group-containing resin as a curing component of the present invention is a specific polyacrylic and / or methacrylic type (hereinafter, “acrylic and / or methacrylic” is referred to as a (meth) acrylic type) polyol (provided that fluorine is contained). The same applies hereinafter except for polyacrylic and / or methacrylic polyols) or a polyoxyalkylene polyol and a crosslinkable silyl group-containing isocyanate compound. Specifically, in the case of a reaction between a specific poly (meth) acrylic polyol and a crosslinkable silyl group-containing isocyanate compound, the isocyanate group / hydroxyl group equivalent ratio is 0.1 to 1.5 / 1.0, Preferably, the reaction is performed within a range of 0.3 to 1.0 / 1.0, and more preferably 0.3 to 0.8 / 1.0, and a crosslinkable silyl group-containing poly (meth) acrylic resin ( In the case of synthesizing a-1) and reacting the polyoxyalkylene polyol with the crosslinkable silyl group-containing isocyanate compound, the equivalent ratio of isocyanate group / hydroxyl group is preferably 0.1 to 1.5 / 1.0. Is reacted in the range of 0.6 to 1.0 / 1.0 to synthesize a crosslinkable silyl group-containing polyoxyalkylene resin (o-1). Subsequently, these can be mixed and the said crosslinkable silyl group containing resin can be manufactured suitably. This method is preferable because the reaction can be easily controlled and the physical properties can be easily adjusted.
In these reactions, metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese and iron with organic acids such as octenoic acid and naphthenic acid, dibutyltin dilaurate, dioctyltin dilaurate, etc. Known urethanization catalysts such as organic metal compounds, organic amines such as triethylenediamine, triethylamine, and tri-n-butylamine and salts thereof can be used, and among them, dibutyltin dilaurate is preferable.
Further, a known organic solvent can also be used.

The poly (meth) acrylic polyol has a polystyrene-reduced number average molecular weight of 1,000 to 30,000, preferably 1,000 to 15,000, and Tg of 0 ° C. or less by gel permeation chromatography (GPC). A poly (meth) acrylic polyol having a viscosity at −70 to −20 ° C., particularly preferably −70 to −30 ° C. and 25 ° C. of not more than 100,000 mPa · s, particularly preferably not more than 50,000 mPa · s. is there. When the number average molecular weight exceeds 30,000, the viscosity at Tg 0 ° C., and the viscosity at 25 ° C. exceeds 100,000 mPa · s, the workability of the curable composition is deteriorated. This poly (meth) acrylic polyol is an ethylenically unsaturated compound containing at least a hydroxyl group-containing (meth) acrylic monomer in the presence or absence of a polymerization initiator and in the presence or absence of a solvent. in the lower, by the method known radical polymerization such as batch or continuous polymerization, preferably 150 to 350 ° C., more preferably those obtained by high temperature continuous polymerization reaction at 210 to 250 ° C., the molecular weight distribution of the reaction products Is preferable because it has a narrow and low viscosity. The poly (meth) acrylic polyol may be obtained by polymerizing a hydroxyl group-containing (meth) acrylic monomer alone, or may be obtained by copolymerizing two or more of these. Furthermore, it may be obtained by copolymerizing one or more of these and an ethylenically unsaturated compound other than these. Among these, from the point that it is easy to adjust the hydroxyl group content of the poly (meth) acrylic polyol and the physical properties of the cured resin can be easily selected, one of the hydroxyl group-containing (meth) acrylic monomers or What is obtained by copolymerizing 2 or more types and 1 type, or 2 or more types of ethylenically unsaturated compounds other than these is preferable. At the time of this copolymerization, each of the one or more hydroxyl group-containing (meth) acrylic monomers has an average hydroxyl functionality of 1.1 to 10 per molecule of the poly (meth) acrylic polyol. It is preferably used so as to contain 1.2 to 6, more preferably 1.5 to 3 in particular. When the average hydroxyl group functionality exceeds 10, the physical properties after curing become too hard and the rubbery elasticity is lost.

As the hydroxyl group-containing (meth) acrylic monomer, from the low reactivity of the crosslinkable silyl group-containing isocyanate compound and the isocyanate group of the organic monoisocyanate, and the low viscosity of the resulting crosslinkable silyl group-containing resin, Alcoholic hydroxyl group-containing (meth) acrylic monomers are preferred, specifically hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, etc. Hydroxyalkyl methacrylates, pentaerythritol triacrylate, glycerin monoacrylate, pentaerythritol diacrylate monostearate, dipentaerythritol Mono- or hydroxyl group-retained polyacrylates such as rupentaacrylate, ditrimethylolpropane triacrylate, polypropylene glycol monoacrylate, pentaerythritol trimethacrylate, glycerin monomethacrylate, pentaerythritol dimethacrylate monostearate, dipentaerythritol pentamethacrylate Polymethacrylates of polyhydric alcohols such as ditrimethylolpropane trimethacrylate and polypropylene glycol monomethacrylate, residual hydroxyl group polymethacrylates, adducts of epoxide and acrylic acid such as adducts of cyclohexene oxide and acrylic acid, cyclohexene oxide and methacrylic acid An adduct of epoxide and methacrylic acid such as an adduct of
Examples of other ethylenically unsaturated compounds include ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, vinyl acetate, acrylonitrile, styrene, chlorostyrene, 2-methylstyrene, divinyl. Benzene, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, methacrylic acid 2 -Ethylhexyl, benzyl methacrylate, glycidyl methacrylate, acrylamide, methacrylamide, ethoxylated phenol acrylate, ethoxylated paracumylphenol Acrylate, ethoxylated nonylphenol acrylate, propoxylated nonylphenol acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, N-vinyl-2-pyrrolidone, isobornyl acrylate, ethoxylated bisphenol F diacrylate, ethoxylated bisphenol A diacrylate, tripropylene Glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, polyurethane diacrylate, acrylic acid dimer, polyester polyacrylate, 1, 6 Hexanediol diacrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, lauryl acrylate, 2-phenoxy acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone diacrylate, zinc diacrylate, neopentyl glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, propoxylated glycerin Triacrylate, ethoxylated pentae Rithritol tetraacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, Link methacrylate, trimethylol propane trimethacrylate and the like. Among these, as the ethylenically unsaturated compound, from the viewpoint of weather resistance and characteristics after curing, monomers of acrylic acid ester compounds, monomers of methacrylic acid ester compounds, acrylamide, methacrylamide, acrylonitrile, etc. ) Acrylic compounds are preferred, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate. Is more preferable.
These can be used alone or in admixture of two or more.

Examples of the polyoxyalkylene polyol include those obtained by ring-opening addition polymerization of alkylene oxide and those obtained by ring-opening addition polymerization of alkylene oxide in an initiator.
Initiators include low-molecular-weight compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, and shoelacese. Examples include alcohols, polyhydric phenols such as bisphenol A, low molecular polyamines such as ethylenediamine, and low molecular amino alcohols such as diethanolamine.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran.
That is, the polyoxyalkylene polyol specifically includes, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, poly (oxyethylene) -poly (oxypropylene) -glycol, poly (oxyethylene)- Poly (oxybutylene) -glycol can be mentioned, among which polyoxypropylene glycol is particularly preferred. Further, there may be mentioned those obtained by reacting these various polyols with polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like with an excess of hydroxyl groups with respect to the isocyanate groups, and having molecular ends as hydroxyl groups.
These can be used alone or in admixture of two or more.
The polyoxyalkylene polyol preferably has a number average molecular weight of 1,000 to 30,000, more preferably 8,000 to 30,000, from the viewpoint of high elongation of the cured product. The number is preferably from 1 to 8, particularly preferably from 2 to 4, and more preferably a narrow molecular weight distribution having a total unsaturation value of 0.07 meq / g or less, particularly 0.04 meq / g or less.

  The crosslinkable silyl group-containing isocyanate compound may contain at least one or more isocyanate groups and one or more crosslinkable silyl groups in the molecule, but it is easy to control the reaction and has a rubber elasticity after curing. From a good point, a compound containing one isocyanate group and one crosslinkable silyl group in the molecule is preferable. The crosslinkable silyl group is preferably one represented by the following general formula which is easy to produce and easy to crosslink.

（式中、Ｒは炭化水素基であり、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基が好ましく、メチル基が最も好ましい。Ｘで示される反応性基はハロゲン原子、水素原子、水酸基、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、メルカプト基、アルケニルオキシ基及びアミノオキシ基より選ばれる基であり、Ｘが複数の場合には、Ｘは同じ基であっても異なった基であってもよい。このうちＸはアルコキシ基が好ましく、メトキシ基が最も好ましい。ａは０、１又は２の整数であり、０又は１が最も好ましい。）

Wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group is a group selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, and an aminooxy group. In this case, X may be the same group or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group, a is an integer of 0, 1 or 2, 1 is most preferred.)

  Specific examples of the crosslinkable silyl group-containing isocyanate compound include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3 -Isocyanatopropylisopropoxysilane, isocyanate trimethoxysilane, diisocyanate dimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types. Of these, 3-isocyanatopropyltrimethoxysilane is preferred.

In the curable composition and the sealing material composition of the present invention, the blending ratio of the crosslinkable silyl group-containing poly (meth) acrylic resin / crosslinkable silyl group-containing polyoxyalkylene resin is 1 part by weight / 99 parts by weight or more. 99 parts by weight / 1 part by weight, more preferably 20 parts by weight / 80 parts by weight / 80 parts by weight / 20 parts by weight, and particularly preferably 20 parts by weight / 80 parts by weight / 60 parts by weight / 40 parts by weight.

By adding the amine in the present invention to the curable composition and the sealing material composition, the amine migrates to the surface after curing and has the effect of preventing surface contamination, and at the same time, the diffuse reflection of light is sufficiently increased to give a dull appearance. all SANYO to exhibit the effect, a mixture of melting point 30 ° C. or more aliphatic primary amine with a melting point 30 ° C. or more aliphatic secondary Kyua Min. Primary amine aliphatic melting point 30 ° C. or higher, since the rate of migration from the interior sealing material to the surface is fast, that is excellent in surface contamination prevention effect after outdoor exposure. With a primary amine aliphatic melting point 30 ° C. or higher, a combination of a melting point 30 ° C. or more aliphatic secondary Kyua Min Then, aliphatic primary amines immediately after application of melting point 30 ° C. or more sealant to the surface migrated relatively exhibit surface contamination prevention effect of short-term, then, mp 30 ° C. or more aliphatic secondary Kyua Min is shifted to the front surface, the surface contamination preventing effect over a long period of time lasts.
Examples of the aliphatic primary amine having a melting point of 30 ° C. or higher include tetradecylamine, pentadecylamine, cetylamine, stearylamine and the like as monoamines. Examples of diamines include hexamethylenediamine, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1 , 16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 1,2-diaminohenticosane, 1,22- Diaminodocosane, 1,23-diaminotrico Emissions, 1,24- diamino tetra co Sun, polyoxyethylenediamine, and the like. Aliphatic melting point 30 ° C. or more as the secondary amine, dilauryl amine, Ru can be exemplified monoamines such as distearyl amine.
These may be used alone or in combination of two or more.
The amine is preferably used in an amount of 0.1 to 50 parts by weight, particularly 1 to 20 parts by weight, based on a total of 100 parts by weight of the crosslinkable silyl group-containing resin.

In the present invention, the aliphatic primary and secondary amines having a melting point of 30 ° C. or higher are aliphatic primary amines having a melting point of 30 ° C. or higher and / or aliphatics having a melting point of 30 ° C. or higher by reacting with water. Compounds that produce secondary amines can also be used. Specifically, compounds that react with water to produce aliphatic primary and / or secondary amines having a melting point of 30 ° C. or higher include easy availability of raw materials, storage stability, and reactivity with water. In terms of the point, an aliphatic primary and / or secondary amine ketimine compound, enamine compound, and / or aldimine compound having a melting point of 30 ° C. or higher can be preferably exemplified. These ketimine compounds, enamine compounds, and aldimine compounds can be obtained by dehydration reaction between ketones or aldehydes and aliphatic primary and / or secondary amines having a melting point of 30 ° C. or higher.
Examples of the ketones include methyl ethyl ketone, methyl isopropyl ketone, methyl tert-butyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 4-methyl-2-pentanone, 2-heptanone, 4-heptanone, diisopropyl ketone. , Aliphatic ketones such as diisobutyl ketone, aromatic ketones such as propiophenone and benzophenone, cyclic ketones such as cyclopentanone, cyclohexanone and methylcyclohexanone, and β-dicarbonyl compounds such as ethyl acetoacetate. Examples of aldehydes include butyraldehyde, isobutyraldehyde, hexyl aldehyde, and the like. These can be used alone or in admixture of two or more. Of these, 4-methyl-2-pentanone is preferred from the same points as described above.
An aliphatic primary and / or secondary amine having a melting point of 30 ° C. or more generated by reacting with water is 0.1 to 50 parts by weight, particularly 1 to 50 parts by weight based on 100 parts by weight of the total crosslinkable silyl group-containing resin. It is preferable to use an amount of 20 parts by weight.
When a compound that reacts with water to produce an aliphatic primary and / or secondary amine having a melting point of 30 ° C. or higher is used, the surface tackiness after curing of the curable composition and the sealing material composition is eliminated, and the like It has the effect of preventing contamination due to adhesion.

Next, the additive in the curable composition and the sealing material composition of the present invention will be described.
Examples of the additive in the present invention include a plasticizer, an antioxidant, an ultraviolet absorber, a crosslinking catalyst, a filler, a coupling agent, a thixotropic agent, a storage stability improving agent (dehydrating agent), and a coloring agent.

  Plasticizers are used to improve workability by lowering the viscosity of curable compositions and sealant compositions, and antioxidants and ultraviolet absorbers prevent oxidation, light degradation, and thermal degradation of cured resins. Thus, it is used to further improve not only the weather resistance but also the heat resistance. Specific examples of the antioxidant include hindered amine and hindered phenol antioxidants.

Specific examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate, dicarboxylic acid adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Etherification of esters, alcohol esters such as pentaerythritol esters, phosphate esters such as trioctyl phosphate and tricresyl phosphate, chlorinated paraffins, and polyoxyalkylene polyols used in the synthesis of the crosslinkable silyl group-containing resins Or esterified polyoxyalkylenes that do not contain hydroxyl groups, especially etherified or esterified polyoxyalkylene polyols obtained by addition polymerization of ethylene oxide or propylene oxide to saccharide polyhydric alcohols such as sucrose Saccharide-based polyoxyalkylenes not containing hydroxyl groups, poly-α-methylstyrene, polystyrene oligomers such as polystyrene, poly (meth) acrylic resins, polybutadiene, butadiene-acrylonitrile copolymers, polychloroprene, polyisoprene, Plasticizers that do not react with isocyanate groups such as oligomers such as polybutene and hydrogenated polybutene, and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate Polyesters such as polyesters from dibasic acids and dihydric alcohols And plasticizers that react with isocyanate groups such as hydroxyl group-containing polyethers such as polyoxypropylene glycols.
Among these, a poly (meth) acrylic resin is preferable, and further, ethylene exemplified by the polymerization method exemplified in the synthesis of the poly (meth) acrylic polyol used for the synthesis of the crosslinkable silyl group-containing resin. A poly (meth) acrylic resin not containing a hydroxyl group obtained by polymerizing a compound containing no hydroxyl group among the unsaturated unsaturated compounds, having a number average molecular weight of 500 to 2,000, Tg of −70 to −20 ° C., and Those having a viscosity at −70 to −30 ° C. and 25 ° C. of 5,000 mPa · s or less are particularly preferable because they have an effect of lowering the viscosity without deteriorating the weather resistance of the curable composition and the sealing material composition.
The plasticizer is preferably blended in an amount of 1 to 200 parts by weight, particularly 2 to 50 parts by weight, based on a total of 100 parts by weight of the crosslinkable silyl group-containing resin.

  Examples of the hindered amine antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and [bis (2,2,6,6-tetramethyl-1 decanedioate) (octyloxy). ) -4-piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl Malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propio Ruoxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl succinate 1- (2-hydroxyethyl) -4-hydroxy-2 , 2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {( 2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (3-amino (Propyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate Can be mentioned. In addition, high molecular weight hindered amine antioxidants such as those manufactured by Asahi Denka Kogyo Co., Ltd. and trade names ADK STAB LA-63P and LA-68LD are also included.

  Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide], benzenepropanoic acid 3 , 5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol.

  Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (4,6-diphenyl- Triazine-based UV absorbers such as 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone-based UV absorbers such as octabenzone, 2,4-di-tert-butylphenyl Examples include benzoate-based ultraviolet absorbers such as -3,5-di-tert-butyl-4-hydroxybenzoate.

  Each of the antioxidant and the ultraviolet absorber is preferably blended in an amount of 0.1 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on a total of 100 parts by weight of the crosslinkable silyl group-containing resin.

The cross-linking catalyst is a catalyst for cross-linking (curing) the cross-linkable silyl group-containing resin. Specific examples include organometallic compounds and amines. Among these, organotin compounds having an excellent cross-linking speed are used. preferable. Specifically, this organic tin compound includes stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin Among them, dibutyltin, dioctyltin diversate, etc. Among them, dibutyltin diacetylacetonate is most preferable because it is a liquid having a high crosslinking rate and a relatively low toxicity and radiance.
The crosslinking catalyst is preferably blended in an amount of 0.01 to 10 parts by weight, particularly 0.05 to 5 parts by weight, based on a total of 100 parts by weight of the crosslinkable silyl group-containing resin.

  A filler, a coupling agent, a thixotropic agent, a storage stability improving agent (dehydrating agent), a coloring agent, and the like may be added to the curable composition of the present invention as necessary for improving adhesiveness, reinforcing, preventing drooling, and the like. And it can mix | blend and use for a sealing material composition.

Fillers include inorganic powders such as heavy calcium carbonate, light calcium carbonate, clay, talc, silica, slate powder, mica, kaolin, zeolite, diatomaceous earth, bentonite, magnesium carbonate, meteorite, and fatty acid-treated calcium carbonate. Among them, those having a particle diameter of 0.01 μm or more are preferable, and among these, fatty acid-treated calcium carbonate is more preferable.
In the present invention, a filler that gives a design appearance to the surface after curing of the curable composition and the sealing material composition has a glossy appearance with relatively large irregularities such as sanding. It is preferable to use a balloon and / or a granular material.
Examples of the balloon (micro hollow body) include inorganic balloons such as ceramic balloons, glass balloons, shirasu balloons and silica balloons, or balloons made of organic materials such as phenol resin, urea resin, polystyrene and saran. However, the present invention is not limited to these, and an inorganic material and an organic material may be combined, or may be laminated to form a plurality of layers.
In addition, a balloon whose surface is processed or coated can be used, and a balloon whose surface is treated with various surface treatment agents can be used. Specifically, for example, an organic balloon coated with calcium carbonate, talc, titanium oxide or the like, and an inorganic balloon surface-treated with an organic acid or a silane coupling agent can be used. Of these, inorganic balloons are preferable from the viewpoint of low specific gravity and high strength, and ceramic balloons are particularly preferable.
In addition, examples of the granular material include granular materials other than the balloon, and specifically, inorganic powders exemplified as the filler such as heavy calcium carbonate, and organic powders such as rubber, nylon, and polyethylene. Among them, coarse particles having a relatively large particle size can be mentioned. Among these, coarse heavy calcium carbonate is particularly preferable.
The average particle diameter of the balloon and / or the granular material is 100 μm or more, preferably 200 to 600 μm. When the average particle size of the balloon and / or the granular material is less than 100 μm, even when blended in a large amount, only the viscosity of the curable composition and the sealing material composition is increased, and a rough feeling is not expressed.
In the present invention, it is preferable to use 1 to 200 parts by weight, particularly 10 to 100 parts by weight of the balloon and / or the granular material with respect to a total of 100 parts by weight of the crosslinkable silyl group-containing resin. If it is less than 1 part by weight, the surface of the cured product cannot be given a rough feeling, and if it exceeds 200 parts by weight, the workability of the curable composition and the sealing material composition is deteriorated.

Examples of the coupling agent include silane-based, aluminum-based, and zircoaluminate-based compounds, and among them, the silane-based coupling agent is preferable because of its excellent adhesiveness.
Specific examples of the silane coupling agent include N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- ( β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and other alkoxysilyl group-containing molecular weights of 500 or less, preferably 400 or less And low molecular weight compounds.

  Examples of the thixotropic agent include colloidal silica, asbestos powder, inorganic thixotropic agents such as the above-mentioned fatty acid-treated calcium carbonate, and organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide.

  Examples of the storage stability improver include low-molecular crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane that react with moisture present in the composition, and calcium oxide.

  Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.

  The total amount of the filler, the coupling agent, the thixotropic agent, the storage stability improving agent, and the colorant is 1 to 500 parts by weight, particularly 50 to 50 parts per 100 parts by weight of the total of the crosslinkable silyl group-containing resin. A range of 300 parts by weight is preferred.

  In the curable composition and the sealing material composition of the present invention, each of the components can be used alone or in combination of two or more.

  In the curable composition and the sealing material composition of the present invention, if necessary, an ester solvent such as ethyl acetate, a ketone solvent such as methyl ethyl ketone, an aliphatic solvent such as n-hexane, and an alicyclic group such as cyclohexane. Any known organic solvent such as an organic solvent or an aromatic solvent such as toluene or xylene can be used as long as it does not react with the crosslinkable silyl group and isocyanate group. These can be used alone or in admixture of two or more. The kind and amount of use may be appropriately determined according to the use of the curable composition and the sealing material composition.

  The curable composition and the sealing material composition of the present invention are preferably used as a one-component moisture curable type from the viewpoint of workability. However, the curable composition and the sealing material composition of the present invention are used as a main agent, and water It can also be used as a two-component curing type in which a curing agent such as is mixed and cured.

Hereinafter, the present invention will be described in more detail with reference to examples and the like.
Here, although the sealing material composition was shown as an example of a curable composition, it is not limited to this.

Synthesis example 1
A polyoxypropylene glycol (number average molecular weight 16,000, total unsaturation 0.02 meq / g, manufactured by Asahi Glass Co., Ltd.) in a warming reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and condenser PML-4016) was charged in an amount of 800 g (OH equivalent: 0.1), and 16.4 g (NCO equivalent: 0.08) of 3-isocyanatepropyltrimethoxysilane (Y-5187 manufactured by Nihon Unicar Co., Ltd., molecular weight 205.4) with stirring. ) (R value (NCO equivalent / OH equivalent) = 0.8) and 0.08 g of dibutyltin dilaurate were added, and the mixture was heated and stirred at 70 to 80 ° C. for 1 hour, and the peak of the isocyanate group was observed by FTIR. After confirming disappearance, the reaction was terminated by cooling to room temperature.
The obtained trimethoxysilyl group-containing polyoxypropylene resin was a translucent liquid at room temperature with a viscosity of 16,400 mPa · s / 25 ° C. This resin is referred to as O-1.

Synthesis example 2
A poly (meth) acrylic polyol (number average molecular weight 4,900, weight average molecular weight 13,000, hydroxyl value 20.5 mgKOH / g, average number of hydroxyl groups under a nitrogen gas stream in a warming reaction vessel similar to Synthesis Example 1 1.8 pieces, 800 g (OH equivalent: 0.292) of UH-2000 manufactured by Toagosei Chemical Industry Co., Ltd. were charged, and 3-isocyanatopropyltrimethoxysilane (Y-5187 manufactured by Nihon Unicar Co., Ltd., molecular weight 205.4) with stirring. ) After adding 30 g (NCO equivalent: 0.146) (R value (NCO equivalent / OH equivalent) = 0.5) and 0.08 g of dibutyltin dilaurate, the mixture was heated and stirred at 70-80 ° C. for 3 hours. After confirming the disappearance of the peak of the isocyanate group by FTIR, the reaction was terminated by cooling to room temperature.
The obtained trimethoxysilyl group-containing poly (meth) acrylic resin was a liquid having a theory of transparency at room temperature, a measured isocyanate group content of 0.00 mass% by titration, and a viscosity of 14,000 mPa · s / 25 ° C. . This resin is referred to as A-1.

Example 1
In a kneading container equipped with a heating and cooling device, 40 g of a trimethoxysilyl group-containing poly (meth) acrylic resin A-1, 80 g of a trimethoxysil group-containing polyoxypropylene resin O-1 and a poly (meth) acrylic plasticizer ( UP-1000 manufactured by Toagosei Co., Ltd., no hydroxyl group, Tg-55 ° C.) 12 g, hindered phenol antioxidant: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] (Irganox 1010 manufactured by Ciba Specialty Chemicals), 2.5 g of benzotriazole ultraviolet absorber: 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole ( Ciba Specialty Chemicals TINUVIN 327) 2.5g, fatty acid Surface) treated calcium carbonate (Maruo Calcium Co., Ltd. N-2) 120 g, stearylamine (manufactured by Kao Corporation Farmin 80) 6 g, distearyl amine (manufactured by Kao Corporation Farmin D86) were charged 6 g, stirring until the contents became homogeneous, Mixed. Thereafter, pressure dehydration was performed at 110 ° C. for 1 hour, and after cooling, 0.1 g of dibutyltin diacetylacetonate (Neostan U-220 manufactured by Nitto Kasei Co., Ltd.) and N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane (Chisaso Sila Ace S310) 0.5 g was charged, stirred and mixed to prepare a sealing material composition .

Comparative Example 1
A sealing material composition was prepared in the same manner as in Example 1 except that stearylamine and distearylamine were not used.

Comparative Example 2
In Example 1, instead of 40 g of trimethoxysilyl group-containing poly (meth) acrylic resin A-1 and 80 g of trimethoxysilyl group-containing polyoxypropylene resin O-1, dimethoxysilyl group-containing polyoxypropylene resin (Asahi Glass) ES-S3630) (120 g) was used, and a sealing material composition was prepared in the same manner except that stearylamine and distearylamine were not used.

〔performance test〕
Using sealant compositions prepared in Example 1 and the ratio Comparative Examples 1 and 2 were subjected to the following tests.
(1) Surface contamination Using a slate plate having a thickness of 5 mm, a joint having a depth of 5 mm, a width of 25 mm, and a length of 150 mm is prepared, a sealing material composition is placed on the joint, and the excess sealing material is removed with a spatula. The test piece was prepared by scratching and flattening the surface and curing for 3 days at 23 ° C. and 50% relative humidity.
After exposing the cured specimen to the outdoors for 1 month, 6 months, and 12 months, sprinkle black quartz sand (particle size 70-110 μm) on the surface, immediately turn the specimen over and lightly touch the bottom by hand. The extra black quartz sand was dropped. The state of the black silica sand (dirt) remaining on the surface was visually observed to determine the surface contamination of the specimen.
Criteria ○: no adhesion of black sand to cure the surface of the sealing material clean
X: State in which a large amount of black silica sand adheres to the cured surface of the sealing material and becomes black and dirty (2) Extrudability According to “4.14 Extrusion test with a test cartridge” in JIS A1439: 1997 “Testing method of sealing material for building” Measurement was performed in accordance with the measurement temperature (23 ° C.).
(3) Slump The slump (longitudinal) was measured in accordance with “4.1 slump test” in JIS A1439: 1997 “Testing method of sealing material for building” (measurement temperature: 23 ° C.).
(4) Tensile adhesiveness In accordance with "4.21 tensile adhesiveness test" of JIS A1439: 1997 "Testing method of sealing material for building", a tensile test was performed on the specimen after curing.
The specimen was prepared by treating the slate with a primer (OP2531, manufactured by Auto Chemical Industry Co., Ltd.), placing and curing the sealing material composition.
Modulus, what the value is less than 30.0 N / cm ² at 4.0 N / cm ² or more to 50% tensile stress (M50) ○, was evaluated as × 30.0 N / cm ² or more.
In the tensile test, the elongation was evaluated as ○ when the Emax was 200% or more, and × when the Emax was less than 200%.
(5) Weather resistance The sealing material composition is formed into a sheet and cured for 14 days at 23 ° C. and 50% relative humidity to prepare a sheet having a thickness of 5 mm. Using a sunshine weatherometer according to JIS K6266: 1996 The state of the surface of the test piece after 1000 hours irradiation, 2000 hours irradiation, 3000 hours irradiation, and 6000 hours irradiation was visually observed.
A sample having no or few hair cracks on the surface of the test piece was evaluated as ○, and a sample having many hair cracks on the surface of the test piece was evaluated as ×.
(6) Surface characteristics The sealing material composition was cured into a sheet and cured at 23 ° C. and 50% relative humidity for 7 days to produce a sheet having a thickness of 5 mm.
The smoothness and gloss of the surface of this sheet were measured visually.
In addition,
Surface characteristics of matte-type outer wall material Surface smoothness Smooth luster None Surface characteristics of matte sand-blasting type or matte rock-like type outer wall material Surface smoothness Unevenness Luster None Summarizing these results and the composition of the sealing material composition Table 1 shows.

  The curable composition of the present invention is an adhesive for building members, automobile parts, coating materials, waterproofing materials, sealing materials, especially for building outer wall joints, civil joints, automobile joints, etc. Suitable for performance sealing materials.

Claims (4)

A curable composition containing a crosslinkable silyl group-containing resin and an amine,
The crosslinkable silyl group-containing resin, Sutaira average molecular weight of 1,000 to 30,000, Tg is 0 ℃ or less, a viscosity at 25 ° C. The following 100,000 mPa · s polyacrylic and / or methacrylic polyol (except , Fluorine-containing polyacrylic and / or methacrylic polyols ) and a crosslinkable silyl group-containing isocyanate compound are reacted within a range where the isocyanate group / hydroxyl group equivalent ratio is 0.1 to 1.5 / 1.0. Crosslinkable silyl group-containing polyoxy obtained by reacting a crosslinkable silyl group-containing polyacrylic and / or methacrylic resin (a-1), a polyoxyalkylene polyol and a crosslinkable silyl group-containing isocyanate compound. A mixture with an alkylene-based resin (o-1), and
Wherein the amine is to be a mixture of melting point 30 ° C. or more aliphatic primary amine with a melting point 30 ° C. or more aliphatic secondary Kyua Min,
Said curable composition characterized by these.   The curable composition according to claim 1, further comprising an additive.   The curable composition according to claim 2, wherein the additive is a polyacrylic and / or methacrylic plasticizer. A sealing material composition containing a crosslinkable silyl group-containing resin and an amine,
The crosslinkable silyl group-containing resin, Sutaira average molecular weight of 1,000 to 30,000, Tg is 0 ℃ or less, a viscosity at 25 ° C. The following 100,000 mPa · s polyacrylic and / or methacrylic polyol (except , Fluorine-containing polyacrylic and / or methacrylic polyols ) and a crosslinkable silyl group-containing isocyanate compound are reacted within a range where the isocyanate group / hydroxyl group equivalent ratio is 0.1 to 1.5 / 1.0. Crosslinkable silyl group-containing polyoxy obtained by reacting a crosslinkable silyl group-containing polyacrylic and / or methacrylic resin (a-1), a polyoxyalkylene polyol and a crosslinkable silyl group-containing isocyanate compound. A mixture with an alkylene-based resin (o-1), and
Said Amin is a mixture of melting point 30 ° C. or more aliphatic primary amine with a melting point 30 ° C. or more aliphatic secondary Kyua Min,
The said sealing material composition characterized by these.