JP2006137804A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which gives a good surface-matting state, after cured, without being affected by temperature on curing , especially also at a low temperature. <P>SOLUTION: This curable composition comprises a hydrolysable silyl group-containing polymer as a main component, an amine originating from a natural product and having a freezing point of ≤34°C, and an amine compound having a melting point of ≥35°C. The amine compound is preferably coated with fine powder. The composition exhibits a good matting property and a non-self staining property (free from surface tackiness). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a curable composition, and in particular, when a curable composition is applied to, for example, a building sealant, the surface after curing can be matted without being affected by the temperature during curing. About.
The present invention can also obtain good matting properties and good non-self-contaminating properties (no surface tack and no dust or dust adherence) after curing without deteriorating its physical properties. The present invention relates to a curable composition.

Sealing materials using various polymer materials are conventionally known, and these are used for a wide variety of applications such as civil engineering, construction, and electrical machinery. These sealing materials are required to have a matte surface after curing depending on the purpose and place of use.
For example, when a sealing material is applied to a building, the matte surface has recently been matted without degrading the physical properties of the sealing material in order to avoid the so-called “shine” feeling that excessively glosses on the hardened surface after sealing. Measures to grant are desired.

  As one of methods for imparting matting, it is known to add a filler or a porous material having a relatively large particle size. Examples of such fillers and porous materials include glass beads having an average particle size of 10 to 80 μm, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloons, glass balloons, Silica balloons, Saran balloons, acrylic balloons and the like are included (see Patent Documents 1 to 3). However, when such a filler or porous material is added, the tensile physical properties are lowered, and it is difficult to obtain a material having sufficient physical properties as a sealing material.

  In order to cope with the above problem, for example, Patent Document 1 discloses a room temperature curable composition having a matte surface after curing, a propylene oxide polymer having a crosslinkable hydrolyzable silyl group at the end, and a melting point. An amine compound having a melting point of 10 to 200 ° C, an amide compound having a melting point of 10 to 200 ° C, a fatty acid having a melting point of 10 to 200 ° C, an alcohol having a melting point of 10 to 200 ° C, and a melting point of 10 to 200 ° C A room temperature curable composition comprising one or more compounds selected from the group consisting of fatty acid esters is disclosed. However, it has been pointed out that such a room temperature curable composition is insufficient in weather resistance although the matting effect is not a problem (Patent Document 4).

  Patent Document 4 discloses a crosslinkable silyl group-containing organic polymer and an acrylic polymer for the purpose of providing improved weather resistance, excellent storage stability, and sufficient matte and antifouling properties after storage. A curable composition containing a compound that reacts with water to produce an amine compound and a curing catalyst is disclosed.

Japanese Patent Laid-Open No. 9-100408 JP 2001-164237 A Japanese Patent Laid-Open No. 7-113073 JP 2004-124093 A

However, when a composition containing these matting agents is used, when a sealing material is applied at a normal temperature including summer, a good matte surface can be obtained, but at a low temperature in winter (for example, At 5 ° C., it may be difficult to obtain a sufficient matte surface.
Therefore, it is possible to obtain a sufficiently matte surface after curing, even when the sealant is applied without being affected by the temperature during curing, particularly at low temperatures in winter (for example, 5 ° C.). There was a problem to develop a functional composition.

  The object of the present invention is achieved by a curable composition containing an amine compound having a saturated and / or unsaturated alkyl chain distribution.

When the curable composition of the present invention is applied to a sealing material for construction, for example, it is not affected by the temperature at the time of curing, and preferably cured at a temperature in the range of 5 to 50 ° C., it is good after curing. A matte surface can be obtained.
When the curable fine product of the present invention further containing an amine compound is applied to a sealing material, the surface of the cured product has good matte property and good non-self-contamination property (no surface tack) without deteriorating its physical properties. , The property that dust and dust do not adhere).

  In the curable composition of the present invention, any conventionally known polymer suitable for a sealing material can be used as its main component. Specific examples of such polymers include silicone polymers, modified silicone polymers, acrylic polymers based on acrylic acid esters, polysulfide polymers, polyurethane polymers, rubber polymers such as SBR and butyl rubber, and alkyds. Based polymers and the like. Especially, the curable composition which has a hydrolyzable silyl group containing polymer as a main component is preferable. The hydrolyzable silyl group-containing polymer is preferably a modified silicone polymer and / or an alkoxysilyl group-containing acrylic polymer.

  The modified silicone polymer in the present invention has a polyoxyalkylene ether as a main chain skeleton, and a hydrolyzable group (for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, a terminal or a side chain, A liquid polymer having a silyl group having an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, or the like is designated. Among them, those having polyoxypropylene ether as the main chain and a number average molecular weight of 9000 to 25000 are preferable. Representative commercial products of the modified silicone polymer include, for example, MS polymer series (“MS polymer S-203”, etc.) manufactured by Kaneka Corporation and “Exester” (registered trademark) series, manufactured by Asahi Glass Co., Ltd.

The acrylic polymer having an alkoxysilyl group is composed of at least a (meth) acrylic acid ester unit in the main chain skeleton [if necessary, in addition to the (meth) acrylic acid ester unit, (meth) acrylic acid ester and Units of monomers that can be copolymerized (for example, olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, etc.)], containing alkoxysilyl groups in the molecule For example,
(I) disclosed in JP-B-3-80829, (a) alkyl acrylate (preferably having 2 to 4 alkyl carbon atoms) (for example, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl) Acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, etc.) and (b) vinyl alkoxysilane (eg, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyldimethylmethoxysilane, etc.) And (meth) acryloxyalkoxysilane (for example, γ monomethacryloxypropyltrimethoxysilane, γmonomethacryloxypropylmethyldimethoxysilane, etc.) Radical copolymerization with a species or a mixture of two or more species in the presence of mercaptoalkoxylane (c) (eg, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc.) as a chain transfer agent [usually, Methods such as known bulk polymerization and solution polymerization using polymerization initiators such as α, α'-azobisisobutyronitrile (AIBN), α, α'-azobisisovaleronitrile, benzoyl peroxide, methyl ethyl ketone peroxide Or a redox catalyst such as a transition metal salt, a redox polymerization method combining an amine and a peroxide-based initiator] (usually having a number average molecular weight of 3000 to 100000 per molecule) Average number of alkoxysilyl groups 1.5-3); and

(Ii) vinyl monomers disclosed in JP-B-4-69667 [for example, acrylates such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, propyl acrylate, pentyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, Methacrylates such as butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, cyclohexyl methacrylate; styrene or its derivatives (α-methylstyrene, chloromethylstyrene, etc.); diethyl fumarate, dibutyl fumarate, dipropyl fumarate, etc. Fumaric acid diester; vinyl chloride, vinylidene chloride, ethylene fluoride, vinylidene fluoride, vinylene fluoride, etc. Of 100 parts by weight (the same applies hereinafter) to an alkoxysilyl group-containing disulfide compound [for example, bis (trimethoxysilylmethyl) disulfide, bis (triethoxysilylmethyl) disulfide, bis (trimethoxysilylpropyl) ) Disulfide, bis (triethoxysilylpropyl) disulfide, bis (methyldimethoxysilylmethyl) disulfide, bis (methyldiethoxysilylmethyl) disulfide, bis (propyldimethoxysilylmethyl) disulfide, bis (propyldiethoxysilylmethyl) disulfide, Bis (dimethylmethoxysilylpropyl) disulfide, bis (dimethylethoxysilylpropyl) disulfide, etc.] is added in an amount of 0.05 to 50 parts, and an organic solvent (toluene, , Hexane, ethyl acetate, photopolymerization in dioctyl phthalate, etc.) (at room temperature to 50-60 ° C., include those prepared by subjecting by subjecting to light irradiation) of 4 to 30 hours.

  When such an alkoxysilyl group-containing acrylic polymer is used as a main component of the curable composition, it is possible to improve thin film weather resistance (suppression of whitening phenomenon of the thin layer portion) when applied to, for example, a sealing material.

In place of or in addition to the above-mentioned alkoxysilyl group-containing acrylic polymer, a solventless acrylic polymer that does not have a normal-temperature liquid functional group obtained by continuous bulk polymerization at high temperature and high pressure may be used.
Such a solvent-free acrylic polymer uses an acrylic monomer having no functional group [for example, acrylate or methacrylate used in the polymerization method (ii) of the alkoxysilyl group-containing acrylic polymer], for example, around 400 ° C. The polymer can be produced in a very short reaction time (about 5 minutes) by continuous bulk polymerization (preferably with very little or no initiator and no chain transfer agent) at a high temperature and high pressure. Such a polymer exhibits a low-molecular-weight polymer of 100% solvent-free and a low-temperature liquid with a low Tg, and has good compatibility with the modified silicone polymer (having a narrow composition distribution and molecular weight distribution) and is excellent. Weather resistance can be imparted.

［式中、ＲとＲ’は同一もしくは異なって、炭素数１〜５の低級アルキル；およびｃは１〜３の整数である］
のアルコキシシリル基を含有し、好ましくは数平均分子量１０００〜４００００で常温ワックス状ないし高粘度液状のものを指称し、一般に、イニファー法と呼ばれるカチオン重合法で得られる全末端官能型イソブチレン系ポリマーを用いることにより製造することができる（特開平８−２３１７５８号公報参照）。代表的な市販品としては、式：

の化学構造を有する、（株）カネカ製の「エピオン」（登録商標）シリーズが例示される。 The hydrolyzable silyl group-containing polymer in the present invention also includes a hydrolyzable silyl group-containing isobutylene polymer (hereinafter simply referred to as an isobutylene polymer). The isobutylene-based polymer has a main chain skeleton composed of at least isobutylene units. [If necessary, in addition to the isobutylene units, monomers that can be copolymerized with isobutylene (for example, olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyls) Compounds, vinyl silanes, allyl silanes, etc.) units]], hydrolyzable silyl groups at both ends of the molecule, for example the formula:

[Wherein, R and R ′ are the same or different, and are lower alkyl having 1 to 5 carbon atoms; and c is an integer of 1 to 3]
An all-terminal functional isobutylene polymer obtained by a cationic polymerization method called an inifer method is generally designated as a wax-like or high-viscosity liquid having a number average molecular weight of 1,000 to 40,000. It can be manufactured by use (see JP-A-8-231758). Representative commercial products include the formula:

The “Epion” (registered trademark) series manufactured by Kaneka Co., Ltd. having the following chemical structure is exemplified.

  As the hydrolyzable silyl group-containing polymer used in the sealant composition of the present invention, it is preferable to use a modified silicone polymer and / or an acrylic polymer because the weather resistance and physical properties are excellent and the surface of the cured product is uniformly matted. In particular, an acrylic modified modified silicone polymer commercially available as an acrylic polymer containing an alkoxysilyl group obtained by polymerization in a modified silicone polymer (for example, “MS polymer S-943” manufactured by Kaneka Corporation). Etc.), the compatibility of the components in the sealing composition is good, the weather resistance and physical properties are excellent due to the interaction with the modified silicone polymer and the crosslinking reaction by hydrolysis of the alkoxysilyl group, and it cures even at low temperatures. It is particularly preferable that the surface of the object is uniformly matted.

The curable composition of the present invention contains an amine compound having a saturated and / or unsaturated alkyl chain distribution. The amine compound having a saturated and / or unsaturated alkyl chain distribution used in the curable composition of the present invention is for imparting a good matte surface to the sealing material after curing.
In the present invention, the amine compound having a saturated and / or unsaturated alkyl chain distribution means saturated or unsaturated octyl chain, decyl chain, lauryl chain, tetradecyl chain, pentadecyl chain, cetyl chain, stearyl chain, oleyl chain, etc. This refers to an amine compound having a plurality of alkyl chains. An amine compound having an alkyl chain distribution can be obtained by combining amines having different alkyl chain lengths by a method such as mixing, or by synthesizing amines based on amine raw materials such as fats and oils having an alkyl chain distribution.
In particular, it is preferable to use a monoalkyl primary amine compound having a saturated and / or unsaturated alkyl chain distribution because of excellent matting effect.

In the present invention, it is preferable to use a naturally-derived amine compound as the amine compound having a saturated and / or unsaturated alkyl chain distribution in terms of matting properties at low temperatures.
In the present invention, the naturally-occurring amine compound refers to an amine compound obtained by extraction or synthesis from a raw material obtained from a natural material such as an animal or a plant, such as petroleum or coal produced in nature. It does not indicate an amine compound synthesized from fossil raw materials.
Examples of naturally-occurring amine compounds having a saturated and / or unsaturated alkyl chain distribution include amine compounds obtained from natural fats and oils such as coconut oil (palm oil), palm kernel oil, and palm oil. .
Among them, the use of a naturally-occurring amine compound having a saturated and / or unsaturated alkyl chain distribution and having a freezing point of 34 ° C. or lower is a cured surface of a sealing material composition in winter, particularly in a low temperature atmosphere of 5 ° C. It is preferable in that it can provide a stable, homogeneous and excellent matting property.
As such a naturally-occurring amine compound having a saturated and / or unsaturated alkyl chain distribution and a freezing point of 34 ° C. or lower, an amine compound having an alkyl chain distribution of 8 to 18 carbon atoms is preferable, and 5 ° C. in winter. Even at the following low temperatures, the surface of the cured sealing material composition can be in a uniform matte state. In particular, about 8% octyl chain with 8 carbon atoms, about 7% decyl chain with 10 carbon atoms, about 51% lauryl chain with 12 carbon atoms, about 19% tetradecyl chain with 14 carbon atoms, 8% cetyl chain with 16 carbon atoms. A cocoalkylamine having a distribution of alkyl chains of about 18% stearyl chain having 18 carbon atoms and 6% oleyl chain having 18 carbon atoms and having a freezing point of about 16 ° C. (coconut oil, also called coconut amine) When amine is used as a raw material, it can provide a stable and uniform matte and excellent non-self-contaminating property to the cured surface of the sealing material composition even in winter, especially in a low temperature atmosphere of 5 ° C. or lower. .
The amount of such an amine compound used in the curable composition of the present invention is usually 0.05 to 5% by weight, preferably 0.1 to 2% by weight, based on the sealing material composition. That's fine. If it is less than 0.05% by weight, the matte effect on the cured surface of the sealing material composition may not be exhibited, and if it exceeds 5% by weight, the matte effect tends not to be exhibited.

In one embodiment of the present invention, a curable composition for imparting good matting and / or non-self-contaminating properties (no surface tack and no dust or dust adhesion) to the cured surface. It is preferable to further mix other amine compounds, preferably an amine compound having a melting point of 35 ° C. or higher.
The content of such an amine compound in the curable composition of the present invention is from the viewpoint of imparting good mattness and / or non-self-contaminating property to the surface after curing without reducing its physical properties. It is preferably 0.02 to 10% by weight, and more preferably 0.1 to 8% by weight. In addition, the total amount of the amine compound contained in the curable composition of the present invention is preferably 0.15 to 9% by weight from the viewpoint of matteness and non-self-contaminating property of the cured surface.
Moreover, it is 5-50 degreeC atmospheric temperature that it is set to 1: 9-9: 1 as the content ratio (weight basis) of the naturally-derived amine compound whose freezing point is 34 degrees C or less and the melting point is 35 degrees C or more. From the viewpoints of the matte state and non-self-contaminating property of the cured surface when cured below. A more preferable content ratio is 2: 8 to 8: 2, particularly 3: 7 to 7: 3.

As such an amine compound, any conventionally known compound suitable for the curable composition can be used. Specific examples thereof include amine compounds having a melting point of 35 ° C. to 200 ° C. such as stearylamine, tribenzylamine, 1,10-decanediamine, 1,12-dodecanediamine (see, for example, JP-A-9-100408). included.
As the amine compound, it is preferable to use a fine powder coating amine having a melting point of 35 ° C. or higher, preferably 50 ° C. or higher, in which fine powder is fixed on the amine surface, without deteriorating its physical properties. This is particularly preferable from the viewpoint of imparting matte properties and good non-self-contamination properties (see, for example, JP-A-2002-30227).

  The fine powder-coated amine that can be preferably used in the present invention comprises a fine powder having a central particle diameter of 2 μm or less on the surface of a solid amine having a melting point of 50 ° C. or more and a central particle diameter of 20 μm or less, and the weight ratio of the solid amine to the fine powder is The surface is fixed so as to be 1 / 0.001 to 0.5 and the active amino group on the surface is coated. Such a fine powder coated amine is obtained by, for example, pulverizing a solid amine to a central particle size of 20 μm or less and simultaneously adding fine powder to the mixture to pulverize the central particle to have a central particle size of 2 μm or less; Solid amine finely pulverized to a diameter of 20 μm or less and fine powder with a center particle diameter of 2 μm or less are fixed to the surface of the solid amine using a high-speed impact mixing stirrer, compression shear mixing stirrer or spray dryer. Can be produced (see JP-A No. 2000-117090).

  As the solid amine, any of aromatic or aliphatic compounds having a melting point of 50 ° C. or higher may be used. For example, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,3′-diamino Diphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o- Aromatic amine compounds such as phenylenediamine, m-phenylenediamine, 2,3-toluenediamine, 2,4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, 3,4-toluenediamine, , 12-dodecanediamine, 1,10-decanediamine, 1,8-octanediamine , 1,14 tetradecane diamine, 1,16-hexadecane diamine, aliphatic amine compounds such as stearylamine and the like, may be subjected to one kind of them or a mixture of two or more in use. The solid amine is adjusted to have a center particle size of 20 μm or less, preferably 3 to 15 μm.

The fine powder can be arbitrarily used from inorganic or organic materials, such as titanium oxide, calcium carbonate, clay, silica, zirconia, carbon, alumina, talc, etc., and organic materials as inorganic materials. Examples thereof include polyvinyl chloride, polyacrylic resin, polystyrene, and polyethylene, and one or a mixture of two or more of these is used. The amount used is selected so that the weight ratio of the solid amine to the fine powder is 1 / 0.001 to 0.5, preferably 1 / 0.002 to 0.4.
The amount of such fine powder coating amine is usually selected in the range of 0.5 to 5 parts, preferably 1 to 3.5 parts, based on 100 parts of the polymer used in the curable composition of the present invention. . If it is less than 0.5 part, the matte effect on the surface of the cured product may not be sufficiently exhibited, and if it exceeds 5 parts, whitening phenomenon will occur remarkably on the surface of the cured product, which tends to be a difficult point on the surface appearance. is there.

The curable composition according to the present invention comprises the above-mentioned predetermined proportion of polymer, an amine compound having a saturated and / or unsaturated alkyl chain distribution, and, if necessary, an amine compound such as fine powder coating amine. In general, a curing catalyst and a colorant are added to this, and the system is dissolved in an organic solvent.
Examples of the curing catalyst include tin compounds such as tin dioctylate, dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin oxide, dibutyltin bisethoxysilicate, and dioctyltin oxide. Examples of the catalyst include titanium catalysts such as a catalyst, tetraisopropyl titanate, tetra n-butyl titanate and partial hydrolysis condensates thereof, titanium diisopropyl bisacetyl acetate, and titanium diisopropyl bisethyl ethyl acetoacetate.
Examples of the colorant include bengara, titanium oxide, carbon black, other color pigments, and dyes.
Examples of the organic solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, ligroin, ethyl acetate, tetrahydrofuran, n-hexane, heptane, and an isoparaffin-based high boiling point solvent.

The curable composition of the present invention is a particle having an average particle size of 30 to 500 μm (more preferably 70 to 400 μm) in order to impart designability to the cured product, particularly when used as a sealing material for construction. It is preferable to further contain. Such particles may be composed of inorganic and / or organic substances, and have any shape such as spherical (true sphere, elliptical sphere, flat sphere, hollow sphere), granular, chain or fibrous. Can be used. Specific examples thereof include particles of alumina, silicon carbide, zirconia, silicon nitride, ceramic, synthetic ruby, sapphire, glass, phenolic resin, acrylic resin, polyacrylonitrile, silica, urethane resin, calcium carbonate, silica sand, cryolite, etc. Can be mentioned.
Among them, when organic particles composed of acrylic resin are used, the curing agent composition can be imparted with heat resistance, solvent resistance or weather resistance, and the matte finish or matte finish finish can be applied to the cured surface. Design properties suitable for an outer wall, a yuzu skin finish painted outer wall, or a sandstone-like painted outer wall can be imparted. Such acrylic resin particles preferably have a heat resistant temperature of 150 to 300 ° C., and such particles are preferably composed of a polymer such as cross-linked polymethyl methacrylate and polyacrylonitrile. Examples of such commercially available crosslinked acrylic resin particles include Tufic (registered trademark) AR650LL manufactured by Toyobo Co., Ltd.
The inorganic particles and organic particles can be used alone or in combination of two or more, and the content in the curable composition is preferably 0.1 to 30% by weight, more preferably 2 to 20% by weight. It is preferable.

  Further, if necessary, the curable composition of the present invention may be added to a normal filler (heavy calcium carbonate, fatty acid-treated calcium carbonate, fume silica, precipitated silica, carbon black, talc, titanium oxide, etc.), plasticizer ( Phthalic acid diesters, epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylic acid diesters, alkylbenzenes, etc.), adhesives (epoxy compounds, silane coupling agents, etc.), anti-aging agents (hindered phenols, mercaptans, Sulfides, dithiocarboxylates, thioureas, thiophosphates, thioaldehydes, etc.), thixotropic agents (such as colloidal silica, organic bentonite, fatty acid amide, polyamid wax, hydrogenated castor oil), moisture retention agents ( Water, inorganic salt hydrates, etc.), UV absorbers Light stabilizers (benzotriazoles, etc. hindered amine), may be blended with an appropriate amount range such as an antioxidant (hindered phenols, etc.).

  The curable composition of the present invention composed of the above components is a one-pack type in which the above-described blending components are mixed together, or contains the above polymer, an amine compound having a saturated and / or unsaturated alkyl chain distribution, particles, and the like. And a two-component type configured to form a toner liquid containing a curing catalyst, a colorant, a fine powder coating amine, or the like, or further separated as a separate component from the colorant. Alternatively, it may be used as a three-part type.

Even when the curable composition of the present invention is cured at a low temperature in winter (for example, 5 ° C.), a sufficient matte surface can be obtained after curing. That is, the curable composition of the present invention is characterized in that the cured surface is matted when cured at an ambient temperature of 5 ° C.
The curable composition of the present invention can obtain a sufficiently matte surface after curing when it is preferably cured in the range of 5 to 50 ° C. without being affected by the temperature during curing. That is, the curable composition of the present invention is characterized in that the cured surface is matted when cured at 50 ° C. ambient temperature.

  The curable composition of the present invention composed of the above components is particularly effective when applied to a sealing material for construction, and particularly for matte finish paint outer walls, yuzu skin finish paint outer walls, or sandstone tone paint outer walls. It can be suitably used as a sealing material. The curable composition of the present invention can be applied to sealing materials for automobiles, electrical appliances, civil engineering, and other adhesives, paints, coating materials, potting materials, molded products, etc., in addition to the above-described architectural sealing materials. it can.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

[Example 1]
(1) Production of fine powder coated amine 76.9 parts of 1,12-dodecanediamine (melting point 71 ° C.) having a center particle diameter of about 8 μm and 23.1 parts of ultrafine titanium oxide having a center particle diameter of about 0.02 μm were mixed , By a composite treatment using a high-speed impact mixing stirrer (Hi-X mixer, manufactured by Nissin Engineering Co., Ltd.), the surface of 1,12-dodecanediamine having a center particle size of about 8 μm is formed on the surface of the center particle size. 100 parts of a fine powder coating amine obtained by adhering 0.02 μm ultrafine titanium oxide was obtained.

(2) Substrate Each component was blended in the following amounts (% by weight with respect to the total curable composition amount) to obtain a substrate.

(3) Toner liquid Each component was blended in the following amounts (% by weight with respect to the total amount of the curable composition) to obtain a toner liquid.

^{* 1} Calsees PLS-505 [manufactured by Kamishima Chemical Co., Ltd.] (average particle size 0.1 μm)
^{* 2} S-943 [manufactured by Kaneka Corporation] (acrylic modified silicone polymer)
^{* 3} Alkene 200P [Shin Nippon Petrochemical Co., Ltd.]
^{* 4} ARUFON (registered trademark) UP-1000 [manufactured by Toagosei Co., Ltd.] (solvent-free acrylic polymer obtained by continuous bulk polymerization at high temperature and high pressure and having no functional groups in the liquid state at room temperature)
^{* 5} ADK STAB (registered trademark) AO-60 [Asahi Denka Kogyo Co., Ltd.]
^{* 6} ADK STAB (registered trademark) LA-62 [Asahi Denka Kogyo Co., Ltd.]
^{* 7} ADK STAB (registered trademark) LA-32 [Asahi Denka Kogyo Co., Ltd.]
^{* 8} Sila Ace (registered trademark) S-220 [manufactured by Chisso Corporation]
^{* 9} Disparon (registered trademark) # 6500 [Enomoto Kasei Co., Ltd.]
^{* 10} Tuftic (registered trademark) AR650LL [manufactured by Toyobo Co., Ltd.] (average particle size 150 μm)
^{* 11} Mixture of titanium oxide / iron yellow / petal / carbon black / diisononyl phthalate = 40/5/1 / 0.3 / 50 (weight ratio)

(4) Adjustment of sealing material The base material of (2) above, the toner liquid of (3) above, and other blending components are blended in the weight percentages shown in Table 1 below, mixed using a planetary stirrer, and cured. Sex composition was obtained.

[Examples 2 and 3]
A curable composition was prepared in the same manner as in Example 1 except that the type and amount of the amine compound having a saturated and / or unsaturated alkyl chain distribution to be blended were changed.

[Comparative Example 1]
In Example 1, a curable composition was prepared in the same manner except that cocoalkylamine was not blended.
[Comparative Examples 2 to 5]
A curable composition was prepared in the same manner as in Example 1 except that the type of amine compound having a saturated and / or unsaturated alkyl chain distribution was changed.

^{* 12} Farmin (registered trademark) CS [manufactured by Kao Corporation], monoalkyl primary amine with a freezing point of 16 ° C
^{* 13} Farmin (registered trademark) 08D (manufactured by Kao Corporation), monoalkyl primary amine with a freezing point of -1 ° C
^{* 14} Farmin (registered trademark) 20D (manufactured by Kao Corporation), monoalkyl primary amine with a freezing point of 27 ° C
^{* 15} Farmin® 80 (manufactured by Kao Corporation), monoalkyl primary amine with a melting point of 50 ° C
^{* 16} Armin (registered trademark) OD [manufactured by Lion Akzo Co., Ltd.], monoalkyl primary amine with a freezing point of 13 ° C
^{* 17} Fine powder coated amine produced in Example 1 (1)

About the curable composition obtained by each Example and the comparative example, the performance test was done using the following evaluation method. The evaluation results are shown in Table 2.
[Evaluation method of performance test]
Each curable composition was used as a sealing material and placed on a flexible board provided with a groove of about 3 mm (depth) × 30 mm (width) and immediately subjected to the following test. The results are listed in Table 2.
A) Matting property test After standing for 3 days in a 5 ° C atmosphere or 24 hours in a 50 ° C atmosphere, the presence or absence of gloss (gloss) on the cured surface was visually determined.
○: no gloss,
Δ: Somewhat glossy,
X: Glossy B) Non-self-contamination test After standing in a 5 ° C atmosphere for 3 days or in a 50 ° C atmosphere for 24 hours, immediately sprinkle with volcanic ash and drop the test specimen's small face on the floor three times to remove excess After shaking the volcanic ash, it was determined whether or not the volcanic ash was attached.
○: No adhesion
Δ: Slight adhesion,
×: Adhering in large amounts C) Cured property test Curing composition shown in Table 2 based on JIS K6251: 2004, using a sheet of 2 mm thickness cured by curing for 14 days at 20 ° C. and 65% relative humidity. Physical properties were measured. However, the shape of the test piece was dumbbell No. 3, and the tensile speed was 200 mm / min.

As can be seen from the results of Tables 1 and 2, the curable composition obtained in each Example corresponding to the curable composition of the present invention obtained a good surface matte state after curing, particularly at low temperatures. However, the curable composition obtained in each Comparative Example was insufficient in the surface matte state.
In addition, according to the curable composition of the present invention containing a predetermined amine compound, the matte property of the surface after curing and the good non-self-contaminating property (there is no surface tack) without deteriorating its physical properties. It can be seen that a property that dust and dust do not adhere) can be obtained.
Furthermore, although not described in Table 2, since the crosslinked acrylic particles are blended, fine unevenness is formed on the surface of the cured composition in all examples and comparative examples, and the matte finish painted outer wall, yuzu skin The design was in harmony with the finished or outer wall.

Claims (11)

  A curable composition containing an amine compound having a saturated and / or unsaturated alkyl chain distribution.   The curable composition according to claim 1, wherein the amine compound having a saturated and / or unsaturated alkyl chain distribution is a naturally derived amine compound.   The curable composition according to claim 2, wherein the freezing point of the naturally occurring amine compound is 34 ° C or lower.   The curable composition according to claim 3, wherein the naturally-derived amine compound having a freezing point of 34 ° C or lower is cocoalkylamine.   The curable composition according to claim 3 or 4, further comprising an amine compound having a melting point of 35 ° C or higher.   The curable composition according to claim 5, wherein the content ratio (by weight) of a naturally occurring amine compound having a freezing point of 34 ° C. or lower and an amine compound having a melting point of 35 ° C. or higher is 1: 9 to 9: 1. The curable composition according to claim 5 or 6, wherein the amine compound having a melting point of 35 ° C or higher is a fine powder coating amine in which fine powder is fixed on the amine surface.   The curable composition according to any one of claims 1 to 7, wherein the cured surface when cured at an ambient temperature of 5 ° C is in a matte state.   The curable composition according to any one of claims 1 to 8, wherein a cured surface when cured at a temperature of 50 ° C is matted.   The curable composition according to any one of claims 1 to 9, comprising a hydrolyzable silyl group-containing polymer as a main component.   The curable composition according to claim 10, wherein the hydrolyzable silyl group-containing polymer is a modified silicone polymer and / or an alkoxysilyl group-containing acrylic polymer.