JP2006096859A - Sealing material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing material composition giving cured products having low modulus and high elongation, used for joints of sand-like ceramic-based siding boards and harmonizing the surface of the sand-like siding board with the surface of the sealing material on the joint. <P>SOLUTION: The sealing material composition contains 1-20vol% balloons and nonspherical particles both having 100-500μm average particle size in 1/5-5/1 volume ratio. Preferably, the main ingredient is a hydrolyzable silyl group-containing polymer and an amine compound is added as a flatting agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a sealant composition, and more specifically, when used as a joint for a ceramic-type siding board with a sand-like surface, the sand-like surface appearance of the ceramic-type siding board and the surface state of the cured sealant composition are designed. The present invention relates to a sealing material composition that is harmonized without a sense of incongruity.

  In recent years, the surface of the ceramic siding board has been given a rough texture with a rough texture to create a solid and luxurious exterior wall image on the ceramic siding board. The ones that have been painted and given a sense of quality have come to be used. However, when the above-mentioned high-quality exterior wall material is used, if the conventional irregular sealing material is used, the surface of the sealing material is glossy and smooth. The problem of becoming. For this reason, the development of a sealing material having an appearance in harmony with the sand-like outer wall has been promoted by creating irregularities on the surface of the sealing material in order to harmonize with the surface of the siding board, or by further imparting matteness. For example, a method of blending an inorganic porous expanded body having an average particle size of 0.1 to 2.0 mm and a porosity of 40 to 85% (see Patent Document 1, page 2), an average particle size of 100 μm or more A method of blending a balloon and a primary and / or secondary amine having a melting point of 35 ° C. or higher is known (see Patent Document 2, page 2).

  Among the conventional methods described above, the method of blending a balloon having a particle diameter of 100 μm or more increases the modulus of the sealing material after curing as the amount of the balloon is increased, and the tendency to decrease the extensibility becomes strong. It is not preferable in applications where low modulus and high elongation cured material properties are required (for example, see Japanese Patent Application Laid-Open No. 10-219960) such as a joint of a siding board. On the other hand, even when non-spherical particles such as cinnabar sand having a particle diameter of 100 μm or more other than the balloon are used, the modulus of the sealing material after curing increases as the blending amount increases, and the tendency for the extensibility to decrease increases.

JP 2001-59083 A JP 2001-164237 A

  The present invention is a sealing material composition having an appearance harmonized with the outer wall when used for a sand-like ceramic siding board joint and having physical properties of low modulus and high elongation required for the ceramic siding board joint. It is an issue to provide.

The sealing material composition of the present invention is a sealing material composition imparted with rough texture or further matteness to solve the above problems.
That is, the present invention relates to a sealing material composition used for the joint of a sand-like ceramic siding board, and a total of 1 balloon and non-spherical particles having an average particle diameter of 100 to 500 μm are combined with the sealing material composition. The present invention relates to a sealing material composition comprising ˜20 vol% and having a volume ratio of balloon to non-spherical particles of 1/5 to 5/1, preferably 1/2 to 2/1.

  According to the sealing material composition of the present invention, the physical properties after curing have low modulus, high elongation, and uniform matteness throughout the four seasons, so it is suitable for joints of sand-like high-quality siding boards Can be used.

  Embodiments of the present invention will be described below. The sand-like ceramic siding board using the sealing material composition of the present invention is mainly used as a building exterior material which is molded and cured and cured into a plate shape using a cementitious raw material and a fibrous raw material as main raw materials. The board used is a board having a texture of a fine concavo-convex pattern having a rough surface. Examples of the board include a wood fiber reinforced cement board system, a fiber reinforced cement board system, and a fiber reinforced cement / calcium silicate board system. Further, the joint is a gap existing between the sand-like ceramic siding boards or at the joint between the sand-like ceramic siding boards and other members.

  Here, the sand tone means that the surface has a texture of fine unevenness with a rough feeling as described above, and is called sandstone tone, sand wall shape, sand blowing wind, sand blowing tone, chopping stone tone, etc. Also included. As a means for imparting a sand-like texture to the ceramic siding board, a method is generally used in which a paint containing an aggregate having a relatively large particle size is applied so that the aggregate appears on the painted surface. The ceramic siding board having a sand-like texture is called a sand-like ceramic siding board.

  The balloon used in the sealing material composition of the present invention is a spherical particle having a hollow inside. Examples of the balloon material include inorganic materials such as glass, silica, shirasu, and ceramic, and organic materials such as saran, epoxy resin, polystyrene, acrylic resin, and phenol resin. In addition, it is not limited only to these, What combined the inorganic material and the organic material, and what processed the surface of the balloon with various surface treatment agents can also be used. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide, etc., or an inorganic balloon may be surface treated with a silane coupling agent. The average particle size of the balloon used is 100 to 500 μm, and preferably the average particle size is 200 to 400 μm. When the average particle size is less than 100 μm, the unevenness on the surface of the sealing material composition becomes small and does not match the surface of the sand-like siding board. When the average particle size exceeds 500 μm, the unevenness on the cured surface of the sealing material composition becomes large and dust adheres. It tends to be easy to do.

  The non-spherical particles used in the sealing material composition of the present invention refer to particles having a shape other than a spherical body, and are not spherical, such as cubic, rectangular, scaly, fibrous, acicular, or indefinite. Irregularly shaped particles can be used. Non-spherical particle materials include cryolite, granular calcium carbonate, silica sand, silica stone powder, silica, glass powder, rubber powder, hardened crushed sealant, mica, plastic powder, wood powder, metal powder, fiber, etc. However, particles that are pulverized from those existing in nature are desirable. Further, from the viewpoint of cost, the use of inorganic particles is preferable, and the use of cryogenic stones or granular calcium carbonate that hardly affects the hue of the sealing material composition is particularly preferable. The non-spherical particles used have an average particle size of 100 to 500 μm, particularly preferably an average particle size of 200 to 400 μm. If the average particle size is less than 100 μm, the unevenness of the cured surface of the sealing material composition is too small to eliminate the sense of incongruity with the sand-like ceramic siding board. On the other hand, if it exceeds 500 μm, the unevenness is too large. It tends to stand out.

  Preferable non-spherical particles used in the sealing material composition of the present invention are cryogenic stones or granular calcium carbonate as described above, and the main component produced by pulverizing calcite, limestone, marble, etc. is composed of calcium carbonate. A white aggregate is mentioned. Cryosalt or granular calcium carbonate has low modulus and high elongation properties, and is suitable for a sealant composition for joints of sand-like siding boards. Moreover, since the hue is whitish, the color of the particles is not conspicuous, and the sealing material composition containing the particles can be adjusted to an arbitrary color tone.

  The content of the balloon and non-spherical particles used in the sealing material composition of the present invention is 1 to 20 vol% in total with respect to the sealing material composition, preferably 5 to 15 vol%. When the amount used is less than 1 vol%, it becomes difficult to impart design properties in harmony with the sand-like ceramic siding board to the surface of the sealing material composition. On the other hand, if it exceeds 20 vol%, the viscosity of the sealing material composition becomes too high, the workability is lowered, the physical properties of the cured product of the sealing material composition are hardened, and the elongation tends to be lowered. In some cases, it is not preferable as a sealing material composition used in the present invention.

Moreover, the volume ratio of the balloon to the non-spherical particles in the sealing material composition of the present invention is 1/5 to 5/1, preferably 1/2 to 2/1. When the volume ratio of the balloon / non-spherical particles is less than 1/5, the modulus of the cured product of the sealing material composition tends to be high. On the other hand, if it exceeds 5/1, the extensibility is lowered, the modulus is also increased and the extensibility tends to be lowered. By incorporating balloons and non-spherical particles in the sealing material composition at a constant volume ratio in this way, a low modulus and high elongation sealing that is optimal for ceramic siding board joint applications, which cannot be obtained with each individual compounding, is possible. A material composition can be obtained.
It is not clear why balloons and non-spherical particles are used in a certain range of volume ratios, resulting in a decrease in the modulus of the cured product of the sealing material composition and high elongation properties, but compared to blending the same kind of particles. It is conceivable that the use of particles of different shapes reduces the contact and interference between particles in the cured product of the sealing material composition, and the degree of freedom of deformation of the entire cured material of the sealing material composition increases.

  When the sealing material composition of the present invention contains an amine compound as a matting agent, it is preferable because it can impart matting properties to the cured sealing material and can further reduce discomfort with a siding board, and has excellent weather resistance. A sealant composition is obtained.

Examples of such amine compounds include 2-ethylhexylamine, octylamine, laurylamine, cocoalkylamine, tetradecylamine, pentadecylamine, cetylamine, stearylamine, trimethylcyclohexylamine, benzylamine, ethylenediamine, hexamethylenediamine. 1,7-heptanediamine, trimethylhexamethylenediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13 -Tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, , 19-nonadecanediamine, 1,20-eicosanediamine, 1,2-henticosanediamine, 1,2-docosanediamine, 1,3-tricosanediamine, 1,24-tetracosanediamine, isophoronediamine , Diaminodicyclohexylmethane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, xylenediamine, 4,4′-diaminodiphenylmethane, 2, 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminobiphenyl, 2,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,4- Diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylene Amine, 2,3-toluenediamine, 2,4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, 3,4-toluenediamine, diaminodiethylphenylmethane, polyoxyethylenediamine, polyoxypropylenediamine , Tri (methylamino) hexane, dilaurylamine, distearylamine, methyllaurylamine, N, N′-dilaurylpropylamine, N, N′-distearylbutylamine, N-butyl-N′-laurylethylamine, N-butyl-N′-laurylpropylamine, N-lauryl-N′-stearylbutylamine, N-laurylpropylenediamine, N-stearylpropylenediamine, diethylenetriamine, triethylenetetramine, methylaminopropylamine, etc. It can be.
These amine compounds can be used as one or a mixture of two or more, and it is preferable to use an amine compound having a melting point of 35 ° C. or higher and / or an amine compound having a melting point of 20 ° C. or lower. In particular, an amine compound having a melting point of 35 ° C. or higher (usually solid at normal temperature) and an amine compound having a melting point of 20 ° C. or lower (usually liquid at normal temperature) are used alone or in combination of two or more. It is preferable.

In the present invention, when an amine compound having a melting point of 35 ° C. or higher is used as a matting agent, excellent matting properties can be imparted even after curing in a high temperature atmosphere in summer.
As such an amine compound having a melting point of 35 ° C. or higher, any aromatic or aliphatic compound having a melting point of 35 ° C. or higher can be used. For example, 4,4′-diaminodiphenylmethane, 2,4′- Diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminobiphenyl, 2,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,4-diaminophenol, 2,5-diaminophenol, o-phenylenediamine, m-phenylenediamine, 2,3-toluenediamine, 2,4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, 3,4-toluene Aromatic amine compounds such as diamine, 1,12-dodecanediamine, 1,10-decanediamine, 1 , 8-octanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, stearylamine, and other aliphatic amine compounds.

A particularly preferred example of the amine compound used as the matting agent used in the sealing material composition of the present invention is a fine powder coating amine in which fine powder is fixed on the surface of a solid amine compound having a melting point of 35 ° C. or higher. By adhering the fine powder, the matte effect can be obtained stably and uniformly even in a higher temperature atmosphere. Therefore, the fine powder coated amine can impart excellent matte properties in summer, especially after curing at a high joint temperature of 60 ° C. or higher.
As a method for producing a fine powder coated amine, a fine powder having an average particle size of 2 μm or less is added to the solid amine compound having an average particle size of 20 μm or less, and a weight ratio of the solid amine compound to the fine powder is 1 / 0.001. It is fixed to 0.5 and coated with active amino groups on the surface. For example, a solid amine compound is pulverized to a central particle size of 20 μm or less, and at the same time, a fine powder is added to the central particle. Mixed and pulverized so as to have a diameter of 2 μm or less; or a high-speed impact mixing stirrer, compression-shear type mixing stirrer or spray together with a fine powder having a central particle size of 2 μm or less in advance with a solid amine compound finely pulverized to a central particle diameter of 20 μm or less It can be produced by fixing a fine powder on the surface of a solid amine compound using a drying apparatus (see JP-A No. 2000-117090). The solid amine compound is adjusted to have a center particle size of 20 μm or less, preferably 3 to 15 μm. As said fine powder, it can use arbitrarily from inorganic type fine powder or organic type fine powder. Examples of inorganic fine powders include titanium oxide, calcium carbonate, clay, silica, zirconia, carbon, alumina, talc, etc., and organic fine powders include polyvinyl chloride, polyacrylic resin, polystyrene, polyethylene, etc. One kind or a mixture of two kinds or more can be used. The amount used is selected so that the weight ratio of the solid amine compound to the fine powder is 1 / 0.001 to 0.5, preferably 1 / 0.002 to 0.4. The amount of the fine powder coating amine used is usually 0.05 to 3% by weight, preferably 0.1 to 2% by weight, based on the sealing material composition. If it is less than 0.05% by weight, the matte effect on the surface of the cured product at high temperature will not be sufficiently exerted, and if it exceeds 3% by weight, a whitening phenomenon will occur on the cured surface of the sealing material composition, resulting in surface appearance. Tend to be a difficult point.

The amine compound used as the matting agent may be an amine compound having a melting point of 20 ° C. or lower. When the amine compound is used, matting properties can be stably imparted to the sealing material even in a low temperature atmosphere in winter.
The amine compound having a melting point of 20 ° C. or lower that can be used in the sealing material composition of the present invention is preferably an amine compound having a saturated or unsaturated alkyl chain distribution having 8 to 18 carbon atoms, such as coconut oil (palm Oil), palm kernel oil, palm oil and other vegetable oils and fats. By using an amine compound having a saturated or unsaturated alkyl chain distribution of 8 to 18 carbon atoms and a melting point of 20 ° C. or less, the surface of the sealing material composition after curing is homogeneous even at a low temperature of 5 ° C. or less in winter. It is possible to achieve a 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. About 16 ° C. cocoalkylamine (coconutamine) containing a plurality of amine compounds having an alkyl chain distribution of about 18% stearyl chain having about 18 carbon atoms and about 6% oleyl chain having about 18 carbon atoms and having different melting points Etc.) can be used to provide stable and uniform excellent matting properties to the cured surface of the sealing material composition in winter, particularly even in a low temperature atmosphere of 5 ° C. or lower. The amount of the amine compound having a saturated or unsaturated alkyl chain distribution having 8 to 18 carbon atoms and a melting point of 20 ° C. or lower is usually 0.05 to 2% by weight, preferably 0.1%, based on the sealing material composition. What is necessary is just to contain in the range of -1 weight%. 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 2% by weight, the matte effect tends not to be exhibited.

  In particular, when an amine compound having a melting point of 35 ° C. or higher (particularly fine powder coating amine) and an amine compound having a melting point of 20 ° C. or lower (particularly cocoalkylamine) are used in combination as a matting agent, ℃) to low temperature (5 ° C), it can impart a uniform matte to the hardened surface of the sealant composition, and harmonizes the sand-like ceramic siding board surface with the joint sealant composition surface This is preferable. When used in combination, the weight ratio of the amine compound (especially fine powder coating amine) having a melting point of 35 ° C. or higher to the amine compound (especially cocoalkylamine) having a melting point of 20 ° C. or lower is 20/1 to 1/10. 4/1 to 1/2 is particularly preferable. When the weight ratio exceeds 20/1, it may be difficult to impart a uniform matte state to the cured surface of the sealing material composition at low temperature (5 ° C.). It tends to be difficult to impart a uniform matte state to the cured surface of the sealing material composition at (60 ° C.).

As the polymer used in the sealant composition of the present invention, any conventionally known polymer suitable for the sealant composition can be used as a main component. Specific examples of such polymers include modified silicone polymers, silicone polymers, polyurethane polymers, polysulfide polymers, modified polysulfide polymers, acrylic polymers, polyisobutylene polymers, rubber polymers such as SBR and butyl rubber, and the like. Contain and adjust as one-pack or two-pack. Especially, the sealing material composition which has a hydrolyzable silyl group containing polymer as a main component is preferable from viewpoints, such as a physical property, workability | operativity, a weather resistance, adhesiveness, and sclerosis | hardenability.
Examples of the hydrolyzable silyl group-containing polymer include a modified silicone polymer, an acrylic polymer having an alkoxysilyl group, and a polyisobutylene polymer having an alkoxysilyl group, and one or more of these are used for use. Good. When a modified silicone polymer and / or an acrylic polymer is used as the hydrolyzable silyl group-containing polymer, it can be adjusted to a low modulus, high elongation property, excellent weather resistance, and used as a sealant for ceramic siding board joints. It is preferable because a suitable one is obtained.

The modified silicone polymer used in the sealant composition of the present invention has a polyoxyalkylene ether as the main chain skeleton and a hydrolyzable group (for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate at the terminal or side chain). A liquid polymer having a silyl group having a group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group, etc.). 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 ester (alkyl number is preferably 2 to 4) (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) vinylalkoxysilanes (eg vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyldimethylmethoxysilane) and the like One or two selected from the group of (meth) acryloxyalkoxysilane (for example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc.) Radical copolymerization [usually α, α in the presence of mercaptoalkoxylane (c) (for example, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc.) as a chain transfer agent. Techniques such as known bulk polymerization and solution polymerization using polymerization initiators such as' -azobisisobutyronitrile (AIBN), α, α'-azobisisovaleronitrile, benzoyl peroxide, methyl ethyl ketone peroxide; or redox Produced by a catalyst, for example, a transition metal salt, a redox polymerization method combining an amine and a peroxide-based initiator] (usually number average molecular weight 3000 to 100,000, average alkoxysilyl group number in one molecule 1.5 to 3); and (ii) a vinyl resin disclosed in Japanese Examined Patent Publication No. 4-69667. Monomers such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, propyl acrylate, pentyl acrylate, stearyl acrylate, etc .; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, cyclohexyl Methacrylate such as methacrylate; Styrene or its derivatives (α-methyl styrene, chloromethyl styrene, etc.); Fumaric acid diesters such as diethyl fumarate, dibutyl fumarate, dipropyl fumarate; Vinyl chloride, vinylidene chloride, ethylene fluoride, fluorine Vinyl halides such as vinylidene fluoride and vinylene fluoride]] 100 parts (parts by weight, the same applies hereinafter) And an alkoxysilyl group-containing disulfide compound [for example, bis (trimethoxysilylmethyl) disulfide, bis (triethoxysilylmethyl) disulfide, bis (trimethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) disulfide, bis (methyldimethoxy Silylmethyl) disulfide, bis (methyldiethoxysilylmethyl) disulfide, bis (propyldimethoxysilylmethyl) disulfide, bis (propyldiethoxysilylmethyl) disulfide, bis (dimethylmethoxysilylpropyl) disulfide, bis (dimethylethoxysilylpropyl) Disulfide etc.] 0.05 to 50 parts is added, and if necessary in an organic solvent (toluene, xylene, hexane, ethyl acetate, dioctyl phthalate, etc.) And photopolymerization (normal temperature to 50 to 60 ° C., light irradiation for 4 to 30 hours).

［式中、ｎは５〜４００およびｍは５〜４００である］
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。 Further, the alkoxysilyl group-containing polyisobutylene-based polymer has a main chain skeleton composed of at least isobutylene units [if necessary, a monomer that can be copolymerized with isobutylene in addition to the isobutylene units (for example, having 4 to 12 carbon atoms). Olefins, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, etc.)], containing alkoxysilyl groups at both ends of the molecule, and preferably having a number average molecular weight of 1000 to 40000 In general, it can be produced by using an all-terminal functional isobutylene polymer obtained by a cationic polymerization method called an inifer method (see JP-A-8-231758). Representative commercial products include the formula:

[Wherein n is 5 to 400 and m is 5 to 400]
The “Epion” (registered trademark) series manufactured by Kaneka Co., Ltd. having the following chemical structure is exemplified.

  Use of a modified silicone polymer and / or an acrylic polymer as the hydrolyzable silyl group-containing polymer used in the sealing material composition of the present invention is preferred because it is excellent in weather resistance and can be adjusted to low modulus and high elongation properties. 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 can be improved by the interaction with the modified silicone polymer or the crosslinking reaction by hydrolysis of the alkoxysilyl group, and the low modulus, Since it can adjust to the physical property of high elongation, it is especially preferable.

In the present invention, in addition to the hydrolyzable silyl group-containing polymer, it is preferable to blend a solventless acrylic polymer having no room temperature liquid functional group obtained by continuous bulk polymerization at high temperature and high pressure. By using such a solventless acrylic polymer, the physical properties can be adjusted to low modulus and high elongation, and the workability is excellent. The solvent-free acrylic polymer having no functional group that is liquid at room temperature is an acrylic monomer having no functional group [for example, an acrylate or methacrylate used in the polymerization method (ii) of the alkoxysilyl group-containing acrylic polymer. Can be produced in a very short reaction time (about 5 minutes) by continuous bulk polymerization (very little or no initiator, no chain transfer agent) at a high temperature and high pressure around 400 ° C., for example. % Polymer and low Tg room temperature liquid, good compatibility with modified silicone polymer (narrow composition distribution and narrow molecular weight distribution), adjust viscosity and viscosity of sealing material to improve workability, , Improve the weather resistance, excellent. Examples of commercially available products include “ARUFON (registered trademark) UP-1000” manufactured by Toagosei Co., Ltd.
In addition, the acrylic polymer is an alkoxysilyl group-containing acrylic polymer polymerized in a modified silicone polymer, and a solvent-free acrylic polymer having no room temperature liquid functional group obtained by continuous bulk polymerization at high temperature and high pressure. Is preferably used in combination. Solvent-free acrylic polymers that do not have liquid functional groups at room temperature have a plasticizer replacement effect, and the cured sealant has low modulus and high elongation properties, and contributes to improved workability and weather resistance. To do.

Examples of other components that can be used in the sealing material composition of the present invention include various fillers, plasticizers, curing catalysts, and other additives other than the above components.
The filler is different from the above-described balloons and non-spherical particles having an average particle diameter of 100 to 500 μm, such as heavy calcium carbonate, fatty acid-treated calcium carbonate, fume silica, precipitated silica, carbon black, talc, Mica, clay, glass beads, glass balloons, glass balloons, silica balloons, plastic balloons and other balloons, glass fibers, inorganic fibers such as metal fibers, polyethylene fibers, organic fibers such as polypropylene fibers, aluminum borate, silicon carbide, nitriding Silicon, potassium titanate, graphite, acicular crystalline calcium carbonate, magnesium borate, titanium diboride, chrysotile, wollastonite and other acicular crystalline fillers can be used.
Examples of the plasticizer include phthalic acid diesters, epoxidized hexahydrophthalic acid diesters, alkylene dicarboxylic acid diesters, and alkylbenzenes.
Examples of the curing catalyst include tin catalysts such as tin dioctylate, dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin oxide, dibutyltin bisethoxysilicate, and dioctyltin oxide. And titanium-based catalysts such as tetraisopropyl titanate, tetra n-butyl titanate and partial hydrolysis condensates thereof, titanium diisopropyl bisacetyl acetate, titanium diisopropyl bisethyl acetoacetate, and the like.

Other additives include colorants (Bengara, titanium oxide, carbon black, other colored pigments, dyes, etc.), organic solvents (methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, ligroin, ethyl acetate, tetrahydrofuran, n-hexane, heptane, isoparaffinic high-boiling solvent, etc.), stabilizer (in the case of a sealing material composition mainly composed of alkoxysilyl group-containing polymer, methanol, ethanol, etc.), adhesive (aminosilane, mercaptosilane, epoxy) Silane coupling agents such as silane, epoxy compounds, etc.), anti-aging agents (hindered phenols, mercaptans, sulfides, dithiocarboxylates, thioureas, thiophosphates, thioaldehydes, etc.) Agents, water retention agents (water, hydrates of inorganic salts, etc.), UV absorbers / light stabilizers (benzotriazoles, hindered amines, etc.), antioxidants (hindered phenols, etc.), thixotropic agents ( Colloidal silica, organic bentonite, fatty acid amide, hydrogenated castor oil, etc.) can be used in an appropriate amount range.
The sealing material composition of the present invention having such a structure is a one-pack type in which the above-mentioned blending components are mixed together, or a two-pack type of a base containing a hydrolyzable silyl group-containing polymer and a curing catalyst-containing curing agent, or Furthermore, it can be used as a three-component type in which a toner comprising a colorant and a plasticizer is another component.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In Examples and the like, unless otherwise specified, the units described are based on weight.

[Production Example 1: Production of fine powder coated amine]
76.9 parts of 1,12-dodecanediamine (melting point 71 ° C.) having a center particle size of about 8 μm and 23.1 parts of ultrafine titanium oxide having a center particle size of about 0.02 μm were mixed together, and a high-speed impact mixing stirrer (day By combining with a Kiyo Engineering Co., Ltd. (Hi-X mixer), ultrafine titanium oxide having a center particle size of about 0.02 μm is formed on the surface of 1,12-dodecanediamine having a center particle size of about 8 μm. 100 parts of fine powder-coated amine fixed to be obtained.

[Example 1: Preparation of sealing material composition]
A planetary equipped with a heating and decompression device for fatty acid-treated calcium carbonate, calcium carbonate, modified silicone polymer, acrylic polymer, alkylbenzene, silane coupling agent, anti-aging agent, thixotropic agent shown in Example 1 in Table 1 below. The mixture was charged into a Lee mixer (planetary stirring mixer) and stirred for 30 minutes. Next, the mixture was stirred for 1 hour at 60 ° C. under vacuum under reduced pressure, and a stabilizer was added, followed by stirring and mixing under vacuum under reduced pressure for 5 minutes. After cooling to room temperature, a pigment, a curing catalyst, a balloon, cold water stone, and an amine compound were blended and mixed and stirred for 10 minutes under vacuum and reduced pressure to obtain a one-component sealant composition.

[Examples 2-3: Preparation of sealing material composition]
A sealing material composition was obtained in the same manner as in Example 1 except that the blending ratio of balloon and cryogenic stone in Example 1 was changed.
[Example 4: Preparation of sealing material composition]
A sealing material composition was obtained in the same manner as in Example 1 except that silica sand was added in place of the cryogenic stone in Example 1.
[Example 5: Preparation of sealing material composition]
A sealing material composition was obtained in the same manner as in Example 1 except that laurylamine was added instead of the cocoalkylamine in Example 1.
[Example 6: Preparation of sealing material composition]
A sealing material composition was obtained in the same manner as in Example 1 except that octylamine was added instead of cocoalkylamine in Example 1.
[Example 7: Preparation of sealing material composition]
A sealing material composition was obtained in the same manner as in Example 1 except that 1,12-dodecanediamine was blended in place of the fine powder coating amine in Example 1.
[Example 8: Preparation of sealing material composition]
A sealing material composition was obtained in the same manner as in Example 1 except that the cocoalkylamine in Example 1 was not blended.
[Example 9: Preparation of sealing material composition]
A sealing material composition was obtained in the same manner as in Example 1 except that the hydrolyzable silyl group-containing polymer B in Example 1 was replaced with the hydrolyzable silyl group-containing polymer B.
[Example 10: Preparation of sealing material composition]
A sealing material composition was obtained in the same manner as in Example 1 except that diisononyl phthalate was blended in place of the acrylic polymer in Example 1.
[Comparative Examples 1-3: Preparation of Sealant Composition]
A sealing material composition was obtained in the same manner as in Example 1 except that the volume ratio of the balloon and cryogenic stone in Example 8 was changed outside the range of 1/5 to 5/1.

In Table 1,
Note 1) “Calcy's PLS-505” (average particle size 0.1 μm), manufactured by Kamishima Chemical Industry Co., Ltd.
Note 2) “Heavy coal 300M” (average particle size 6.0 μm), manufactured by Bihoku Flour Industry Co., Ltd.
Note 3) “MS Polymer S-943” (manufactured by Kaneka Corporation) (an acrylic modified type modified silicone polymer obtained by polymerizing an acrylic polymer containing an alkoxysilyl group in the modified silicone polymer)
Note 4) "MS polymer S-203" (modified silicone polymer) manufactured by Kaneka Corporation
Note 5) “ARUFON (registered trademark) UP-1000” manufactured by Toagosei Co., Ltd. (solvent-free acrylic polymer having no functional group at room temperature obtained by continuous bulk polymerization at high temperature and high pressure)
Note 6) “Alkene 200P” manufactured by Shin Nippon Petrochemical Co., Ltd.
Note 7) Equivalent mixture of “Syra Ace (registered trademark) S-220”, “Syra Ace (registered trademark) S-210”, “Syra Ace (registered trademark) S-320” manufactured by Chisso Corporation Note 8) Asahi Denka Industrial Co., Ltd., "Adekastab (registered trademark) AO-60", "Adekastab (registered trademark) LA-62", "Adekastab (registered trademark) LA-32" equivalent mixture Note 9) Enomoto Kasei Co., Ltd. "Disbaron (registered trademark) # 6500" (polyamide wax)
Note 10) Methanol Note 11) Mixture of titanium oxide / iron yellow / petal / carbon black / diisononyl phthalate = 40/5/1 / 0.3 / 50 (weight ratio) Note 12) Dibutyltin bisacetylacetonate / dibutyltin bistriethoxysilicate = 1/2 (weight ratio) mixture Note 13) “Ecespheres (registered trademark) SL350” manufactured by Taiheiyo Cement Co., Ltd.
Note 14) “NSK-1” manufactured by Nichetsu Co., Ltd.
Note 15) Kao Corporation, “Farmin (registered trademark) CS”

  Table 2 shows the volume concentrations and volume ratios of balloons and non-spherical particles in the sealing material compositions in Examples 1 to 10 and Comparative Examples 1 to 3.

[performance test]
(1) Harmony with sand-like siding board Sand-like ceramic siding board "Moen" (thickness 12mm) made by Nichiha Co., Ltd. is cut into 50mm squares, and the two pieces are paralleled at 15mm intervals on a polyethylene sheet Line up. Each sealing material composition is placed on a joint having a width of 15 mm, a depth of 12 mm, and a length of 50 mm. Next, a 20 mm square polyethylene backup material is used to smooth the surface. The test specimen thus produced is subjected to the following test. The results are listed in Table 3.
i) Concavity and convexity The test specimen is allowed to stand at 23 ° C. for 24 hours to cure the sealing material composition, and the uneven state of the cured surface is visually determined.
Judgment criteria:
◯: Sand-like unevenness, x: No sand-like unevenness
ii) Matting property The test specimen is allowed to stand at 23 ° C., 50 ° C., 60 ° C. and 5 ° C. for 24 hours to cure the sealing material composition, and the presence or absence of gloss (gloss) on the cured surface is visually determined.
○: no gloss, △ slightly glossy, ×: glossy
iii) Color Tone The test specimen is allowed to stand at 23 ° C. for 24 hours to cure the sealing material composition, and the color tone of the cured surface is visually determined.
○: Uniform color tone, △: Color tone is not uniform, x: Color tone is not uniform

(2) Extrudability Tested in accordance with “5.14 Extrusion Test with Test Cartridge” of JIS A1439: 2004 “Testing Method of Sealant for Building”. The measurement temperature is 23 ° C.

(3) Tensile adhesiveness Tested in accordance with "5.20 Tensile adhesiveness test" in JIS A1439: 2004 "Testing methods for sealing materials for construction". The adherend uses an aluminum plate and “US-1” manufactured by Sunstar Giken Co., Ltd. as a primer. The heating condition in the heat resistance test is 80 ° C. × 14 days.

(4) Weather resistance Each sealing material composition was cast on a flexible board to a thickness of 0.2 mm, and after curing for 7 days at 20 ° C. and 35 ° C. and 95% relative humidity, a sunshine weather meter (black panel) Set at a temperature of 63 ° C and 18 minutes of 120 minutes of rainfall). Check the surface of the sealant to be whitened (whether the finger is white or not) over time. Time until the finger is white (h ) Is the end time.

  Table 3 shows the performance test results of the sealing material compositions in Examples 1 to 10 and Comparative Examples 1 to 3.

  From the results shown in Tables 1 to 3, when the balloon and non-spherical particles are contained within the scope of the present invention, surprisingly, an unexpected effect that the cured material properties of the sealing material composition are low modulus and high elongation is recognized. In addition, when blended with a fine powder coating amine with a melting point of 35 ° C or higher, it has excellent matting properties at high temperatures (50 ° C, 60 ° C), and when cocoalkylamine is used, it has matting properties at low temperatures (5 ° C). It is recognized that it can be granted. Moreover, it is recognized that it is excellent in weather resistance by using the acrylic polymer having an alkoxyl group.

Claims (13)

  In the sealing material composition used for the joint of the sand-like ceramic siding board, the balloon and the non-spherical particles having an average particle diameter of 100 to 500 μm are contained in a total of 1 to 20 vol% with respect to the sealing material composition, And the volume ratio of a balloon and a non-spherical particle | grain is 1/5-5/1, The sealing material composition characterized by the above-mentioned.   The sealing material composition according to claim 1, wherein the volume ratio of the balloon to the non-spherical particles is 1/2 to 2/1.   The sealant composition according to claim 1 or 2, wherein the sealant composition comprises an amine compound as a matting agent.   The sealing material composition according to claim 3, wherein the amine compound is an amine compound having a melting point of 35 ° C. or higher and / or an amine compound having a melting point of 20 ° C. or lower.   The sealing material composition according to claim 4, wherein the amine compound having a melting point of 35 ° C. or more is a fine powder coating amine obtained by fixing a fine powder on the surface of a solid amine.   The sealant composition according to claim 4 or 5, wherein the amine compound having a melting point of 20 ° C or lower is an amine compound having a saturated or unsaturated alkyl chain distribution having 8 to 18 carbon atoms.   The sealing material composition according to claim 6, wherein the amine compound having a C8-18 saturated or unsaturated alkyl chain distribution is a cocoalkylamine.   The sealing material composition according to any one of claims 1 to 7, wherein the non-spherical particles are cryolite or granular calcium carbonate.   The sealing material composition according to any one of claims 1 to 8, wherein a main component of the sealing material composition is a hydrolyzable silyl group-containing polymer.   The sealant composition according to claim 9, wherein the hydrolyzable silyl group-containing polymer is a modified silicone polymer and / or an acrylic polymer.   The sealing material composition according to claim 10, wherein the acrylic polymer is an alkoxysilyl group-containing acrylic polymer polymerized in a modified silicone polymer.   The sealing material composition according to claim 10, wherein the acrylic polymer is 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.   The acrylic polymer is an alkoxysilyl group-containing acrylic polymer polymerized in a modified silicone polymer, and a solvent-free acrylic polymer having no room temperature liquid functional group obtained by continuous bulk polymerization at high temperature and high pressure. The sealant composition according to claim 10, which is used in combination.