JP2020201237A - Performance evaluation method of sealant composition, sealant composition, sealing joint structure, and construction method of sealing joint structure - Google Patents

Abstract

To provide a new performance evaluation method of a sealant composition which is mainly used for outdoor joints suitable for the usage environment (actual exposure) of sealing joints, and to provide a sealant composition excellent in weather resistance and durability without discoloration, peeling and/or breakage in a test joint.SOLUTION: The performance evaluation method of a sealant composition in the invention includes: (1) a step of spectroscopic irradiation exposure test using an open frame carbon arc lamp for 2,000 hours conforming to JISA1415 (2013) 6.2; and (2) a step of enlarging/reducing the test joint by 20% 4,000 cycles. Step (1) and step (2) are repeated 1-5 cycles.SELECTED DRAWING: Figure 1

Description

The present invention relates to a performance evaluation method of a sealing material composition mainly used for outdoor joints, a sealing material composition, a sealing joint structure and a method of constructing a sealing joint structure.

There is a method of ensuring airtightness and watertightness by providing sealing joints at joints between members of buildings and civil engineering structures. Since the sealing joints of buildings and civil engineering structures are often outdoors and are affected by sunlight and rainwater, the sealing materials used for the joints are required to have excellent weather resistance. Further, since the sealing joint repeatedly expands and contracts as the member expands and contracts in volume due to the influence of temperature and humidity, the sealing material used for the joint is required to sufficiently follow the expansion and contraction of the joint. For this reason, as a sealing material used for joints, a sealing material having improved weather resistance by blending a weather resistance imparting agent, and a rubber material after curing of the sealing material are made highly stretchable with low modulus to prevent expansion and contraction of joints. Sealants with improved followability have been proposed (Patent Documents 1 and 2).
As an evaluation test of the followability of the sealing material to the expansion and contraction of the joint, for example, JIS A 1439 (2016) Test method 5.12 Durability test of the building sealing material is specified. The JIS durability test is a test method that takes into consideration the temperature and expansion and contraction of the sealing joint. On the other hand, sealing materials for construction and civil engineering are often used outdoors, and since the sealing materials deteriorate over time due to ultraviolet rays, not only evaluation of temperature and expansion and contraction but also evaluation of weather resistance are performed in duplicate. A method is required. In addition, as a sealing material used for construction and civil engineering, from the viewpoint of extending the life of buildings and civil engineering structures, defects such as peeling and breakage may occur even if a load such as expansion and contraction and ultraviolet rays are applied to the sealing joint. There is a demand for a sealant composition that does not occur and has a long service life.

Japanese Unexamined Patent Publication No. 2001-342341 Japanese Unexamined Patent Publication No. 2009-67717

An object of the present invention is to provide a new performance evaluation method suitable for the usage environment (actual exposure) of a sealing joint in a performance evaluation method of a sealing material composition mainly used for outdoor joints. Further, a sealing material composition that conforms to the performance evaluation and is excellent in weather resistance and durability, a sealing joint structure in which the sealing material composition is filled and cured in the joint, and the sealing material composition is filled in the joint and cured. It is to provide a construction method of a sealing joint structure.

As a result of diligent studies, the present inventor conducted a step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using JIS A 1415 (2013) 6.2 open frame carbon arc lamp, and 20% of the test piece joints. Including the step (2) of performing the expansion / contraction cycle 4,000 times, the step (1) and the step (2) are performed 1 to 5 cycles, or JIS A 1415 (2013) 6.2 open. The above-mentioned steps include a step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using a frame carbon arc lamp, and a step (2) of performing a cycle of expanding / contracting the test piece joint by 30% 4,000 times. It has been found that performance evaluation suitable for the usage environment (actual exposure) of the outdoor sealing joint can be performed by performing the step (1) and the step (2) for 1 to 4 cycles, and the present invention has been completed. That is, the present invention is shown in the following [1] to [6].
[1] A method for evaluating the performance of a sealing material composition.
JIS A 1415 (2013) 6.2 A step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using an open frame carbon arc lamp, and
The performance evaluation method comprising 1 to 5 cycles of the step (1) and the step (2) including a step (2) of performing a cycle of expanding / contracting a test piece joint by 20% 4,000 times.
[2] A method for evaluating the performance of a sealing material composition.
JIS A 1415 (2013) 6.2 A step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using an open frame carbon arc lamp, and
The performance evaluation method, which comprises a step (2) of performing a cycle of enlarging / reducing a test piece joint by 30% 4,000 times, and performing the step (1) and the step (2) for 1 to 4 cycles.
[3] In the performance evaluation method according to [1], after performing the above steps (1) and the above steps (2) for 1 to 5 cycles, discoloration, peeling, and breakage occur at the test piece joints in any of the cycles. A sealant composition that meets the performance evaluation.
[4] In the performance evaluation method described in [2], after performing the above steps (1) and the above steps (2) for 1 to 4 cycles, discoloration, peeling, and breakage occur at the test piece joints in any of the cycles. A sealant composition that meets the performance evaluation.
[5] A sealing joint structure in which the joints are filled with the sealing material composition according to [3] or [4] and cured.
[6] A step of forming a joint by providing a joint bottom with a base material to which a backup material, a hat joiner, or a bond breaker is attached in a gap between the adherends.
A step of applying a primer composition to an adherend surface of an adherend to form a primer layer,
The step of filling the gaps between the joints with the sealant composition according to [3] or [4] and curing the mixture.
Construction method of sealing joint structure including.

According to the performance evaluation method of the sealing material composition of the present invention, it is possible to evaluate the performance mainly suitable for the usage environment (actual exposure) of the sealing joint outdoors. Since the performance can be properly evaluated before using the sealing material composition, it is easy to predict the sealing joint defect, and the defect rate of the sealing joint can be reduced. Further, in the performance evaluation method of the sealing material composition of the present invention, by using the sealing material composition in which no defects of discoloration, peeling, and breaking are observed as the sealing joint, the life of the building and the civil engineering structure can be extended. Can contribute.

It is sectional drawing which shows the concept of the sealing joint structure which filled the joint with the sealing material composition of this invention and hardened. It is sectional drawing which shows the concept of the sealing joint structure which filled the joint with the sealing material composition of this invention and hardened. It is sectional drawing which shows the concept of the sealing joint structure which filled the joint with the sealing material composition of this invention and hardened. It is sectional drawing which shows the concept of the sealing joint structure which filled the joint with the sealing material composition of this invention and hardened. It is sectional drawing which shows the concept of the sealing joint structure which filled the joint with the sealing material composition of this invention and hardened.

Hereinafter, the present invention will be described in detail according to an embodiment.

The present invention includes a step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using JIS A 1415 (2013) 6.2 open frame carbon arclamp, and a cycle of expanding / contracting the joint of the test piece by 20%. A method for evaluating the performance of a sealing material composition in which the step (1) and the step (2) are carried out for 1 to 5 cycles including the step (2) performed 4,000 times, or JIS A 1415 (2013) 6.2. The process includes a step (1) of performing spectral irradiation for 2,000 hours by an exposure test method using an open frame carbon arc lamp, and a step (2) of performing a cycle of expanding / contracting the joint of the test piece by 30% 4,000 times. A method for evaluating the performance of a sealing material composition in which the steps (1) and (2) are performed for 1 to 4 cycles. It is a construction method of a material composition, a sealing joint structure in which the sealing material composition is filled in a joint and cured, and a sealing joint structure in which the sealing material composition is filled in a joint and cured. First, the performance evaluation method of the sealing material composition of the present invention will be described in detail.

The performance evaluation method of the sealant composition of the present invention includes a step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using JIS A 1415 (2013) 6.2 open frame carbon arc clamp, and a test body joint. This is a method in which the step (1) and the step (2) are carried out for 1 to 5 cycles, including a step (2) in which the cycle of 20% enlargement / reduction is carried out 4,000 times.
Further, the performance evaluation method of the sealant composition of the present invention includes a step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using JIS A 1415 (2013) 6.2 open frame carbon arclamp and a test. This is a method in which the step (1) and the step (2) are performed 1 to 4 cycles, including a step (2) of performing a cycle of expanding / contracting the body joint by 30% 4,000 times.

The test piece used in performing the performance evaluation method of the sealant composition will be described. As the test body, a joint material between adjacent adherends is filled with a sealing material composition and cured. Conventionally known specimen shapes and sizes can be used, but specifically, JTC S-0001 ceramic siding sealing material (NPO corporation housing exterior technical center standard, established 2004.09) Examples include 5.1.6a) type I test piece of .01) and b) type II test piece. In addition, as the curing conditions of the sealing material composition, standard curing conditions described in JIS and the like can be mentioned. Specifically, when the sealant composition is a one-component type, it can be cured at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH for 14 days, and then at a temperature of 30 ± 2 ° C. for 14 days. .. Further, when the sealing material composition is a two-component type, there is a condition that it is cured at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH for 7 days and then at a temperature of 50 ± 2 ° C. for 7 days.

The step (1) can be performed in accordance with the exposure test method using JIS A 1415 (2013) 6.2 open frame carbon arc lamp. As the test conditions of the exposure test method, both WS-A and WS-B can be adopted, but it is preferable to carry out with WS-A assuming direct outdoor exposure.

The step (2) can be performed by a method according to JIS A 1439 (2016) 5.12 Durability test procedure 9 (expansion / reduction of joint width). The joint width of the test piece can be enlarged or reduced at any of ± 10%, ± 20%, and ± 30% of the initial joint width in terms of deformation rate. Assuming that the sealant composition is used for a working joint (joint), the deformation rate is preferably ± 20% or ± 30%.
The speed of the cycle for expanding / contracting the test piece joint in the step (2) is preferably 5 ± 1 time / min. Further, it is preferable to use the same testing machine as the JIS A 1439 (2016) 5.12.1g) repeating testing machine.

It is the outdoor sealing joint that the cycle of spectroscopic irradiation for 2,000 hours by the open frame carbon arc lamp in the step (1) and the expansion / contraction of the test piece joint in the step (2) 4,000 times is performed. It is assumed that the load will be applied for about 10 years.

The order of the steps (1) and (2) is not particularly limited, but the step (1) was performed in order to evaluate the discoloration, peeling, and breaking state of the sealant composition (test piece joint). After that, the order in which the step (2) is performed is preferable. By adopting this order, it is possible to apply the load of the weather resistance factor to the sealant composition and then the load of the deformation (enlargement / reduction) factor, and the load at the time of the deformation factor becomes larger. Therefore, the sealing material composition is more likely to cause breakage or peeling due to the load when the deformation factor is applied than when the load of the weather resistance factor is not applied, and the performance evaluation method of the present invention is to evaluate the performance of the sealing material composition having a long service life. It is useful for doing.

In the performance evaluation of the sealing material composition of the present invention, after performing the above steps (1) and the above steps (2) for 1 to 5 cycles or 1 to 4 cycles, the joints of the test piece are visually observed and discolored. Check for cracks and peeling. The cracks and peeling can also be visually observed when the test joint joint is expanded in the expansion / contraction cycle of the step (2).

The sealant composition of the present invention will be described in detail below.
The sealant composition of the present invention contains a room temperature curable resin. The room temperature curable resin is one in which the curable resin reacts with an active hydrogen-containing compound (for example, water such as humidity) at room temperature to be crosslinked and cured. In the present invention, the normal temperature means the normal temperature (5 to 35 ° C.) described in JIS Z 8703 (1983). A curable resin that reacts with an active hydrogen-containing compound and is cross-linked and cured at a temperature of less than 5 ° C or higher than 35 ° C, but is a curable resin that reacts with an active hydrogen-containing compound and is cross-linked and cured at room temperature (5 to 35 ° C). If present, it is contained in the room temperature curable resin.

The room temperature curable resin is not particularly limited as long as it is crosslinked and cured by reacting with an active hydrogen-containing compound at room temperature. Specific examples thereof include isocyanate group-containing resins and crosslinkable (hydrolyzable) silyl group-containing resins.

The isocyanate group-containing resin is a resin having one or more isocyanate groups in the resin, and the isocyanate group reacts with an active hydrogen (group) to form a urethane bond, a urea bond, or the like and crosslink and cure. The isocyanate group-containing resin is simply "urethane prepolymer" including an isocyanate group-containing urethane prepolymer (hereinafter, an isocyanate group-containing urethane prepolymer and an isocyanate group-containing urethane prepolymer having a photoreactive unsaturated bond introduced later). In some cases,) can be preferably mentioned.

The isocyanate group-containing urethane prepolymer reacts an organic isocyanate compound and an active hydrogen-containing compound all at once or sequentially in a range where the molar ratio of isocyanate group / active hydrogen is 1.2 to 10, preferably 1.2 to 5. It can be produced so that the isocyanate group remains in the urethane prepolymer. If the molar ratio is less than 1.2, the viscosity of the urethane prepolymer becomes high, and the workability of the sealant composition deteriorates. On the other hand, when the molar ratio exceeds 10, the amount of carbon dioxide gas generated when the isocyanate group reacts with water increases, which causes foaming during curing.

The isocyanate group content in the isocyanate group-containing urethane prepolymer is preferably 0.3 to 15% by mass, and particularly preferably 0.5 to 5% by mass. When the isocyanate group content is less than 0.3% by mass, the viscosity of the urethane prepolymer becomes high, and the workability of the sealant composition deteriorates. When the isocyanate group content exceeds 15% by mass, the amount of carbon dioxide gas generated when the isocyanate group reacts with water increases, which causes foaming during curing.

The number average molecular weight of the isocyanate group-containing urethane prepolymer is preferably 1,500 or more, more preferably 1,500 to 20,000, further preferably 1,500 to 15,000, and particularly preferably 1,500 to 10,000. preferable. The number average molecular weight in the present invention is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

As a method for producing the isocyanate group-containing urethane prepolymer, a conventionally known method can be used. Specifically, a method in which an organic isocyanate compound and an active hydrogen-containing compound are charged in a reaction vessel made of glass or stainless steel, a reaction catalyst or an organic solvent is used as necessary, and the reaction is carried out while stirring at 50 to 120 ° C. Can be mentioned. At this time, since the urethane prepolymer thickens when the isocyanate group reacts with water such as moisture, it is preferable to replace the inside of the container with nitrogen gas in advance or to carry out the reaction under a nitrogen gas stream.

Examples of the organic isocyanate compound include organic polyisocyanate. The organic polyisocyanate is a compound having two or more isocyanate groups in the compound, and specifically, a toluene polyisocyanate such as 2,4-toluene diisocyanate or 2,6-toluene diisocyanate, 4,4'-. Diphenylmethane diisocyanate such as diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 1,2-phenylenediocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 2,4,6 Phenylene polyisocyanates such as −trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl-1,3-diisocyanate, naphthalene polyisocyanates such as 1,4-naphthalenediocyanate and 1,5-naphthalenediocyanate, Fragrances such as chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate Polyisocyanate can be mentioned. In addition, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl- Aromatic polyisocyanates such as 1,6-hexamethylene diisocyanate, decamethylene diisocyanate, and lysine diisocyanate, aromatic aliphatic polyisocyanates such as o-xylylene diisocyanate, m-xylylene diisocyanate, and p-xylylene diisocyanate, 1,4- Examples thereof include alicyclic polyisocyanates such as cyclohexyldiisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Further, polypeptide isocyanates such as polymethylene polyphenyl polyisocyanate and crude toluene diisocyanate can be mentioned. Furthermore, modified polyisocyanates having one or more uretdione bond, isocyanurate bond, allophanate bond, burette bond, uretonimine bond, carbodiimide bond, urethane bond or urea bond obtained by modifying these organic polyisocyanates can be mentioned. .. All of these can be used alone or in combination of two or more.

Of these, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, alicyclic polyisocyanates, and modified polyisocyanates obtained by modifying these organic polyisocyanates are preferable because the sealant composition is excellent in weather resistance. ..

Moreover, organic monoisocyanate can be used together with organic polyisocyanate. That is, a mixture of organic polyisocyanate and organic monoisocyanate can be used as the above-mentioned organic isocyanate compound. The organic monoisocyanate is a compound having one isocyanate group in the compound, and specifically, n-butyl monoisocyanate, n-hexyl monoisocyanate, n-hexadecyl monoisocyanate, n-octadecyl monoisocyanate and the like. Examples of the aliphatic monoisocyanate, p-isopropylphenylmonoisocyanate, and p-benzyloxyphenylmonoisocyanate.

An active hydrogen-containing compound is a compound having one or more active hydrogens (groups) in the compound. Specific examples thereof include high molecular weight polyols, high molecular weight polyamines, low molecular weight polyols, low molecular weight amino alcohols, low molecular weight polyamines, high molecular weight and low molecular weight monools.

Examples of the polymer polyol include polyester polyol, polycarbonate polyol, polyoxyalkylene-based polyol, poly (meth) acrylic polyol, hydrocarbon-based polyol, animal and plant-based polyol, and copolyol thereof. In the present invention, "(meth) acrylic" means "acrylic and / or methacrylic".

The number average molecular weight of the polymer polyol is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

Examples of polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, trimellitic acid and the like. Polycarboxylic acids, one or more of these anhydrides or carboxylic acids including alkyl esters such as methyl esters and ethyl esters, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2. -Butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8 Low-molecular-weight polyols such as -octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylpropane, glycerin, pentaerythritol, etc. Examples thereof include polyester polyols obtained by reacting with one or more of the above. In addition to these carboxylic acids and low molecular weight polyols, low molecular weight polyamines such as butyrene diamine, hexamethylenediamine, xylylenediamine and isophoronediamine, and one of low molecular weight amino alcohols such as monoethanolamine and diethanolamine. A polyesteramide polyol obtained by reacting with the above can also be mentioned. Furthermore, lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low-molecular-weight polyols, low-molecular-weight polyamines, and low-molecular-weight amino alcohols as initiators are also available. Can be mentioned.

As the polycarbonate polyol, a dehydrochloration reaction between the low molecular weight polyols used in the synthesis of the polyester polyol described above and phosgene, or a transesterification reaction between the low molecular weight polyols described above and diethylene carbonate, dimethyl carbonate, diethyl carbonate, or diphenyl carbonate. Can be obtained from.

Examples of the polyoxyalkylene-based polyol include low-molecular-weight polyols, low-molecular-weight polyamines, and low-molecular-weight amino alcohols similar to those used for the synthesis of the above-mentioned polyester polyols; sorbitol, mannitol, sucrose, glucose and the like. Sugar-based low-molecular-weight polyhydric alcohols; starting with one or more low-molecular-weight polyvalent phenols such as bisphenol A and bisphenol F, and using one or more cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Ring-opening addition polymerization or copolymerization of polyoxyethylene-based polyol, polyoxypropylene-based polyol, polyoxybutylene-based polyol, polyoxytetramethylene-based polyol, poly- (oxyethylene)-(oxypropylene) -random or block Examples thereof include copolymerized polyols, polyester ether polyols using the above-mentioned polyester polyols and polycarbonate polyols as initiators, and polycarbonate ether polyols. Further, a polyol obtained by reacting these various polyols with an organic isocyanate compound with an excess hydroxyl group with an isocyanate group to have a hydroxyl group at the molecular end can be mentioned. The number of alcoholic hydroxyl groups in the polyoxyalkylene-based polyol is preferably 2 or more, more preferably 2 to 4, and particularly preferably 2 to 3 in one molecule.

The catalyst for synthesizing the polyoxyalkylene-based polyol is an alkali metal compound catalyst such as a sodium-based catalyst or a potassium-based catalyst, a cationic polymerization catalyst, a composite metal cyanation complex catalyst such as a glyme complex or a diglyme complex of zinc hexacyanocovalent, Examples include phosphazene compound catalysts. Of these, alkali metal compound catalysts and composite metal cyanide complex catalysts are preferable. Further, a polyoxyalkylene-based polyol synthesized by using a composite cyanide complex catalyst is preferable because it has a low total unsaturation degree and a low viscosity of the polyol.

Further, for modification of urethane prepolymers, polyoxypropylene-based products obtained by ring-opening addition polymerization of cyclic ether compounds such as propylene oxide using low-molecular-weight monoalcohols such as methyl alcohol, ethyl alcohol and propyl alcohol as initiators. Polyoxyalkylene-based monools such as oars can also be used. The number average molecular weight of the polyoxyalkylene monool is preferably 1,000 to 10,000.

The "system" of the above-mentioned polyoxyalkylene-based polyol or polyoxyalkylene-based monool is 50% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass of the portion of the molecule excluding the hydroxyl group. As mentioned above, particularly preferably, if 95% by mass or more is composed of polyoxyalkylene, it means that the remaining portion may be modified with ester, urethane, polycarbonate, polyamide, poly (meth) acrylate, polyolefin or the like. To do. In the present invention, "(meth) acrylate" means "acrylate and / or methacrylate".

The poly (meth) acrylic polyol is a radical polymerization of a hydroxyl group-containing (meth) acrylic monomer and another ethylenically unsaturated compound in the presence or absence of a solvent, such as a batch type or continuous polymerization. It is obtained by copolymerization by the method of. A product obtained by performing a continuous massive copolymer reaction at a high temperature of 150 to 350 ° C. and further to 210 to 250 ° C. in the absence of a solvent is preferable because the molecular weight distribution of the reaction product is narrow and the viscosity is low. In this copolymerization reaction, it is preferable to use the hydroxyl group-containing (meth) acrylic monomer so that the average number of hydroxyl groups per molecule of the poly (meth) acrylic polyol is 1.2 to 4. The glass transition point (Tg) of the poly (meth) acrylic polyol is preferably 50 ° C. or lower, more preferably 0 ° C. or lower, further preferably −70 to −20 ° C., and particularly preferably −70 to −30 ° C.

The hydroxyl group-containing (meth) acrylic monomer is a (meth) acrylic monomer having at least one hydroxyl group in the molecule, and specifically, hydroxyethyl (meth) acrylate and hydroxypropyl (meth). Hydroxyalkyl (meth) acrylates such as acrylates and hydroxybutyl (meth) acrylates; pentaerythritol tri (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dipentaerythritol penta (meth). ) Mono (meth) acrylates of polyhydric alcohols such as acrylates, ditrimethylolpropantri (meth) acrylates, polypropylene glycol mono (meth) acrylates, and polyvalent (meth) acrylates with residual hydroxyl groups. These can be used alone or in combination of two or more. Of these, hydroxyalkyl (meth) acrylates are preferable, and hydroxyethyl (meth) acrylates are more preferable because the viscosity of the (meth) acrylic polyol is low and the reactivity with the isocyanate group is good.

Examples of the ethylenically unsaturated compound other than the hydroxyl group-containing (meth) acrylic monomer include (meth) acrylic monomer and other ethylenically unsaturated compounds. Examples of the ethylenic compound other than the (meth) acrylic monomer include vinyl compounds such as ethylene, propylene, isobutylene, butadiene, chloroprene, styrene, chlorostyrene, 2-methylstyrene, and divinylbenzene. Examples of the (meth) acrylic monomer include (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylate. 2-Ethylhexyl, benzyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, tridecyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tripropylene Examples thereof include glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycidyl tri (meth) acrylate, and trimethyl propantri (meth) acrylate. These can be used alone or in combination of two or more. Of these, the monomer of the (meth) acrylic acid ester-based compound is preferable in that the viscosity of the (meth) acrylic polyol is low, and further, methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate are preferred. In the present invention, "(meth) acrylic acid" means "acrylic acid and / or methacrylic acid".

Examples of the hydrocarbon-based polyol include polyolefin polyols such as polybutadiene polyols and polyisoprene polyols; polyalkylene polyols such as hydrogenated polybutadiene polyols and hydrogenated polyisoprene polyols; halogenated polyalkylene polyols such as chlorinated polypropylene polyols and chlorinated polyethylene polyols. Can be mentioned.

Examples of animal and plant-based polyols include castor oil-based polyols and silk fibroin.

Any of the above-mentioned polymer polyols can be used alone or in combination of two or more. Of these, polyoxyalkylene-based polyols and poly (meth) acrylic polyols are preferable because the physical properties of the rubber after curing of the sealing material composition are good.

The isocyanate group-containing urethane prepolymer can also introduce a photoreactive unsaturated bond into the urethane prepolymer for the purpose of imparting weather resistance. The urethane prepolymer in which a photoreactive unsaturated bond is introduced acts as a curing component in the sealing material composition of the present invention, and also gives the cured composition good adhesiveness to the adherend surface and excellent weather resistance. It is a thing. The above-mentioned photoreactive unsaturated bond is an unsaturated bond that causes a chemical change such as polymerization in a relatively short time when exposed to light. Specific examples thereof include unsaturated bonds derived from a vinyl group, a vinylene group, and a (meth) acryloyl group. In the present invention, the "(meth) acryloyl group" means "acryloyl group and / or methacryloyl group".

The isocyanate group of the isocyanate group-containing urethane prepolymer into which a photoreactive unsaturated bond has been introduced reacts with an active hydrogen-containing compound and is crosslinked and cured. In addition, the photoreactive unsaturated bond of the isocyanate group-containing urethane prepolymer into which a photoreactive unsaturated bond has been introduced undergoes a polymerization reaction when exposed to light, forming a cured film having excellent weather resistance on the surface of the sealant composition. Form. It is considered that this cured film imparts excellent weather resistance to the sealing material composition. As the photoreactive unsaturated bond, an unsaturated bond derived from a (meth) acryloyl group is preferable because it has a high effect of imparting weather resistance.

Examples of the method for introducing a photoreactive unsaturated bond into an isocyanate group-containing urethane prepolymer include the following methods.
(B) Organic isocyanate compounds, high molecular weight active hydrogen-containing compounds (number average molecular weight of 1,000 or more), and low-molecular-weight active hydrogen-containing compounds (number) having active hydrogen and photoreactive unsaturated bonds in the molecule. (Average molecular weight less than 1,000) is reacted with the total amount of active hydrogen under the condition of excess isocyanate group;
(B) An organic isocyanate compound and an active hydrogen-containing compound of a polymer (number average molecular weight of 1,000 or more) having an active hydrogen and a photoreactive unsaturated bond in the molecule (for example, a mono (meth) of polyoxyalkylene triol. ) A method obtained by reacting an acrylate, an alkylene oxide adduct of (meth) acrylic acid, a polybutadiene polyol) with an excess amount of isocyanate groups with respect to the total amount of active hydrogen;
(C) An organic isocyanate compound, a low molecular weight (number average molecular weight less than 1,000) active hydrogen-containing compound (for example, (meth) acryloyl isocyanate) having a photoreactive unsaturated bond and an isocyanate group in the molecule, and A method obtained by reacting a high molecular weight (number average molecular weight of 1,000 or more) active hydrogen-containing compound with the total amount of active hydrogen under the condition of excess isocyanate group;
Of these methods, the method (a) described above is preferable in terms of availability of raw materials and ease of reaction.

In the reaction of introducing a photoreactive unsaturated bond into an isocyanate group-containing urethane prepolymer, the raw materials may be charged and reacted in a batch, or the raw materials may be charged and reacted in sequence. The molar ratio (isocyanate group / active hydrogen) of the isocyanate group of the organic isocyanate compound to the active hydrogen of the active hydrogen-containing compound (including the compound having an active hydrogen and a photoreactive unsaturated bond) is 1.2 to 10 Is preferable, and 1.2 to 5 is more preferable. The isocyanate group content in the isocyanate group-containing urethane prepolymer into which a photoreactive unsaturated bond has been introduced is preferably 0.3 to 15% by mass, more preferably 0.5 to 5% by mass. When the isocyanate group content is less than 0.3% by mass, the molecular weight becomes too large, the viscosity increases, and the workability deteriorates. In addition, since the number of cross-linking points in the urethane prepolymer is reduced, sufficient adhesiveness cannot be obtained. If the isocyanate group content exceeds 15% by mass, the amount of carbon dioxide gas generated when the isocyanate group reacts with water increases, which causes foaming during curing.

The concentration of the photoreactive unsaturated bond in the isocyanate group-containing urethane prepolymer into which the photoreactive unsaturated bond has been introduced is preferably 0.01 mmol / g or more, more preferably 0.03 to 1 mmol / g, and particularly preferably 0.03 to 1 mmol / g. It is preferably 0.05 to 0.5 mmol / g.

The active hydrogen-containing compound (low molecular weight and high molecular weight) having the above-mentioned active hydrogen and a photoreactive unsaturated bond has an active hydrogen (group) such as a hydroxyl group, an amino group or a carboxyl group and a vinyl group in the compound. , Vinylene group, (meth) acryloyl group and other compounds having both photoreactive unsaturated bonds. A compound having a hydroxyl group and a (meth) acryloyl group is preferable in terms of ease of reaction and high effect of imparting weather resistance. Further, the molecular weight of the compound having an active hydrogen (group) and a photoreactive unsaturated bond is preferably one having a number average molecular weight of less than 1,000 in terms of easy reaction.

Examples of the active hydrogen-containing compound having a hydroxyl group and a (meth) acryloyl group include 2-hydroxyethyl (meth) acrylate, which is a monoester of alkylene glycol such as ethylene glycol, propylene glycol, butylene glycol and (meth) acrylic acid. , 2-Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, 6-hydroxyhexyl ( Monohydroxymono (meth) acrylates such as meta) acrylates, hydroxyheptyl (meth) acrylates and hydroxyoctyl (meth) acrylates, trifunctional or higher alkylene polyols such as glycerin, trimethylolpropane and pentaerythritol, and (meth) acrylic acid Monohydrokipoly (meth) acrylates such as glycerin di (meth) acrylate, trimethylpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and glycerin mono, which are polyesters such as monoesters or diesters and triesters. Polyhydrokimono (meth) acrylates such as (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and polyhydrokipoly (meth) acrylates such as pentaerythritol di (meth) acrylate Can be mentioned. In addition to these, monohydroxymonos (meth) such as diethylene glycol, dipropylene glycol, polyoxyethylene polyol, polyoxypropylene polyol, and polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to bisphenol A and bisphenol F. ) Acrylate, polyhydroxymono (meth) acrylate, polyhydroxypoly (meth) acrylate, ethylene oxide, propylene oxide, active hydrogen of hydroxyalkyl (meth) acrylate such as (meth) acrylic acid and hydroxyethyl (meth) acrylate. , Butylene oxide and other compounds to which alkylene oxide is added and having a hydroxyl group, and caprolactone-modified products of hydroxyethyl acrylate and which have a hydroxyl group can also be mentioned. These can be used alone or in combination of two or more. Of these, monohydroxypoly (meth) acrylates and dihydroxypoly (meth) acrylates are preferable in that the viscosity of the urethane prepolymer can be suppressed to a low level and the effect of imparting weather resistance can be enhanced.

The sealant composition of the present invention can contain an oxazolidine compound together with an isocyanate group-containing urethane prepolymer. The oxazolidine compound is a compound having one or more, preferably 2 to 4, and more preferably 2 to 3 oxazolidine rings, which are heterocycles of saturated 5-membered rings containing an oxygen atom and a nitrogen atom. The oxazolidine compound reacts with water such as moisture and is hydrolyzed, and the oxazolidine ring produces (regenerates) a secondary amino group and an alcoholic hydroxyl group, thereby functioning as a latent curing agent for the isocyanate group-containing urethane prepolymer. It is a thing. When the isocyanate group of the urethane prepolymer reacts with water such as moisture, it forms a urea bond and cures. At this time, carbon dioxide gas is also generated, and bubbles due to carbon dioxide gas are generated in the cured product to deteriorate the appearance and cure. Problems such as breakage of objects and deterioration of adhesiveness may occur. On the other hand, when the sealant composition using the isocyanate group-containing urethane prepolymer and the oxazolidine compound in combination is reacted with water, the water reacts preferentially with the oxazolidine compound, and the oxazolidine ring of the oxazolidine compound becomes a secondary amino group. Generates an alcoholic hydroxyl group (active hydrogen group). Next, since the generated active hydrogen group (particularly the secondary amino group) reacts preferentially with the isocyanate group, the generation of carbon dioxide gas due to the reaction between water and the isocyanate group is suppressed, and foaming of the sealing material composition during curing is suppressed. Can be prevented.

If the organic polyisocyanate used in producing the isocyanate group-containing urethane prepolymer is an aliphatic polyisocyanate or an alicyclic polyisocyanate, the curing of the sealant composition may be delayed. When the isocyanate group-containing urethane prepolymer and the oxazolidine compound are used in combination with the sealant composition, the curing of the sealant composition can be accelerated, and the amount of the curing acceleration catalyst described later can be reduced.

Examples of the oxazolidine compound include a urethane bond-containing oxazolidine compound, an ester group-containing oxazolidine compound, an oxazolidine silyl ether compound, and a carbonate group-containing oxazolidine compound. These oxazolidine compounds can be obtained by reacting the hydroxyl group of a compound having a hydroxyl group and an oxazolidine ring with the isocyanate group of an organic polyisocyanate and the carboxyl group of an organic carboxylic acid compound. Of these oxazolidine compounds, urethane bond-containing oxazolidine compounds are preferable because they are easy to produce.

Specific examples of the compound having a hydroxyl group and an oxazolidine ring include N-hydroxyalkyloxazolidine obtained by a dehydration condensation reaction between a secondary amino group of an alkanolamine and a carbonyl group of a ketone compound or an aldehyde compound. As a method for producing the compound having a hydroxyl group and an oxazolidine ring, 1 mol or more, preferably 1 to 1.5 mol, more preferably 1 mol, preferably 1 to 1.5 mol of the carbonyl group of the aldehyde compound or the ketone compound is made with respect to 1 mol of the secondary amino group of the alkanolamine. Is used, and a method of performing a dehydration condensation reaction while heating and refluxing in a solvent such as toluene or xylene to remove by-produced water can be mentioned. Excess aldehyde compounds and ketone compounds may be removed by distillation.

Examples of alkanolamines include diethanolamine, dipropanolamine, and N- (2-hydroxyethyl) -N- (2-hydroxypropyl) amine. Examples of the ketone compound include acetone, diethyl ketone, isopropyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl-tert-butyl ketone, diisobutyl ketone, cyclopentanone and cyclohexanone. Examples of the aldehyde compound include acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, barrelaldehyde, isobarrelaldehyde, 2-methylbutylaldehyde, n-hexylaldehyde, 2-methylpentylaldehyde, n-octylaldehyde, 3,5. , 5-Trimethylhexylaldehyde and other aliphatic aldehyde compounds; examples thereof include aromatic aldehyde compounds such as benzaldehyde, methylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, isopropylbenzaldehyde, isobutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde and trimethoxybenzaldehyde. All of these can be used alone or in combination of two or more.

Of these, diethanolamine is preferable as the alkanolamine, and the ketone compound or the aldehyde compound is preferable because it is easy to produce a compound having a hydroxyl group and an oxazolidine ring and is excellent in preventing foaming when the sealant composition is cured. Of these, aldehyde compounds are preferable, and isobutylaldehyde, 2-methylpentylaldehyde, and benzaldehyde are more preferable.

Compounds having a hydroxyl group and an oxazolidine ring include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, and 2-phenyl-3- (2). -Hydroxyethyl) Oxazolidine can be mentioned.

As the urethane bond-containing oxazolidine compound, the isocyanate group of the organic polyisocyanate and the hydroxyl group and the hydroxyl group of the compound having an oxazolidine ring have an isocyanate group / hydroxyl group molar ratio of 0.9 to 1.2, preferably 0.95 to 1. Preferable examples thereof include those obtained by reacting the mixture at a temperature of 50 to 120 ° C. in the presence or absence of an organic solvent so as to be 05.

Examples of the organic polyisocyanate used for producing the urethane bond-containing oxazolidine compound include the same organic polyisocyanates used for producing the urethane prepolymer described above. Of these, aromatic aliphatic polyisocyanates and aliphatic polyisocyanates are preferable, and xylylene diisocyanate and hexamethylene diisocyanate are particularly preferable.

The ester group-containing oxazolidine compound can be obtained by reacting the above-mentioned compound having a hydroxyl group and an oxazolidine ring with a lower alkyl ester of a dicarboxylic acid or a polycarboxylic acid.

The oxazolidine silyl ether compound includes the above-mentioned compound having a hydroxyl group and an oxazolidine ring, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 3-glycidoxypropyltri. It is obtained by a dealcohol reaction with an alkoxysilane such as methoxysilane and 3-glycidoxypropyltriethoxysilane.

The carbonate group-containing oxazolidine compound can be obtained by reacting the above-mentioned compound having a hydroxyl group and an oxazolidine ring with a carbonate such as diallyl carbonate using a polyhydric alcohol such as diethylene glycol or glycerin.

All of these oxazolidine compounds can be used alone or in combination of two or more.

The oxazolidine compound preferably does not have an active hydrogen-containing functional group such as an amino group or a hydroxyl group that reacts with the isocyanate group of the urethane prepolymer, or an isocyanate group. This is to prevent an increase in the viscosity of the urethane prepolymer and a decrease in the foaming prevention performance of the oxazolidine compound. However, in the production of the above-mentioned urethane bond-containing oxazolidine compound, a small amount of active hydrogen-containing functional group or isocyanate group may remain in the molecule depending on the selection of the molar ratio. In this case, in order to achieve the object of the present invention. It can be considered that it does not have. The "small amount" means that the amount of the active hydrogen-containing functional group or isocyanate group remaining in the molecule is preferably 0.05 mmol or less, more preferably 0.02 mmol or less per 1 g of the oxazolidine compound.

The blending amount of the oxazolidine compound is preferably 0.1 to 1 mol of the active hydrogen of the secondary amino group produced (regenerated) by hydrolysis of the oxazolidine compound with respect to 1 mol of the isocyanate group of the urethane prepolymer. , 0.3 to 1 mol, and particularly preferably 0.5 to 1 mol. If the amount of active hydrogen of the secondary amino group produced (regenerated) by hydrolysis of the oxazolidine compound is less than 0.1 mol, foaming prevention is insufficient, which is not preferable.

A crosslinkable silyl group-containing resin is a resin having one or more crosslinkable (hydrolytable) silyl groups in the resin, and the crosslinkable silyl group reacts with an active hydrogen (group) to form a siloxane bond. It is crosslinked and cured to become a cured product. Examples of the crosslinkable silyl group-containing resin include those generally called silicone resin or modified silicone resin. Since the rubber has excellent physical properties after curing, a modified silicone resin can be preferably mentioned.

The silicone resin has an organopolysiloxane as the main chain and has a crosslinkable silyl group in the resin. Specifically, a one-component silicone resin containing an organopolysiloxane having a silanol group at the terminal as a main component and a crosslinkable silyl group-containing low molecular weight compound as a cross-linking component, and an organopoly having a silanol group at the terminal as a main component. Examples thereof include a two-component silicone resin containing siloxane and aminoxylalkylsilane as a curing agent. Examples of the crosslinkable silyl group-containing low molecular weight compound include acyloxyalkylsilane, aminoxyalkylsilane, and alkoxyalkylsilane.

Examples of the modified silicone resin include JP-A-52-73998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, and JP-A-61-234033. Japanese Patent Application Laid-Open No. 63-6003, Japanese Patent Application Laid-Open No. 63-112642, Japanese Patent Application Laid-Open No. 3-79627, Japanese Patent Application Laid-Open No. 4-283259, Japanese Patent Application Laid-Open No. 5-287186, Japanese Patent Application Laid-Open No. 11-80571 Examples thereof are those disclosed in JP-A-11-116763 and JP-A-11-130931. Specifically, an aliphatic carbon having one or more crosslinkable silyl groups in the resin and having a main chain of a vinyl polymer, a polyoxyalkylene polymer, polyisobutylene, polyisobutylene, polybutanediene or the like. Examples thereof include hydrogen hydrate-based polymers, polyester-based polymers, and polysulfide polymers. In addition, a copolymer of the above-mentioned polymer and a mixture of the polymers can be mentioned. All of these can be used alone or in combination of two or more.

The main chain of the modified silicone resin is a polyoxyalkylene polymer or a polyoxyalkylene polymer which may be (meth) acrylic-modified in that the rubber properties such as modulus and elongation of the cured composition are good. , (Meta) acrylic copolymer is preferable.

In the present invention, "may be (meth) acrylic modified" refers to a polyoxypropylene-based polymer obtained by blocking or pendant copolymerizing a (meth) acrylic-based monomer, or a polyoxyalkylene-based polymer. It means a mixture of a (meth) acrylic copolymer and a polymer of a (meth) acrylic monomer in a polyoxyalkylene polymer having a crosslinkable silyl group introduced therein.

（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のアリール基または炭素数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およびアミノオキシ基より選ばれる加水分解性の基であり、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、メトキシ基またはエトキシ基が最も好ましい。ａは０、１または２の整数であり、０または１が最も好ましい。） From the viewpoint of curability and physical properties after curing of the sealing material composition, the crosslinkable silyl group is preferably contained in an amount of one or more, and more preferably one to three.
The crosslinkable silyl group is preferably one represented by the following general formula, which is easy to crosslink and easy to produce.

(In the formula, 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. Reactive groups are hydrolyzable groups selected from halogen atoms, hydrogen atoms, hydroxyl groups, alkoxy groups, acyloxy groups, ketoximate groups, amide groups, acid amide groups, mercapto groups, alkenyloxy groups and aminooxy groups. When there are a plurality of Xs, X may be the same group or different groups. Of these, X is preferably an alkoxy group, most preferably a methoxy group or an ethoxy group. A is 0, 1 or 2. It is an integer of 0 or 1 is most preferable.)

The crosslinkable silyl group can be introduced into the main chain, specifically, for example, by the following known method.
(A) An organic compound (for example, allyl isocyanate) having an active group and an unsaturated group that are reactive with this functional group in a polyoxyalkylene-based or vinyl-based polymer having a functional group such as a hydroxyl group at the terminal. The reaction product is then hydrosilylated by allowing hydrosilane having a hydrolyzable group to act on the obtained reaction product.
(B) A compound having a functional group and a crosslinkable silyl group that are reactive with this functional group in a polyoxyalkylene-based or vinyl-based polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group at the terminal. How to react.
Examples of the compound having a reactive functional group and a crosslinkable silyl group include amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, vinyl-type unsaturated group-containing silanes, chlorine atom-containing silanes, and isocyanates. Examples include group-containing silanes and hydrosilanes.
(C) Compounds having a polymerizable unsaturated bond and a crosslinkable silyl group (for example, CH ₂ = CHSi (OCH ₃ ) ₃ or CH ₂ = CHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ ) and (meth) acrylic A method of copolymerizing with an acid alkyl ester monomer.
(D) A compound having a polymerizable unsaturated bond and a functional group (for example, hydroxyethyl (meth) acrylate or allyl (meth) acrylate) is added to the (meth) acrylic acid alkyl ester monomer and copolymerized. then compound the copolymer produced with a reactive functional group and a crosslinking silyl group of the (for example, a compound having an isocyanate group and -Si (OCH _{3) 3} group, trimethoxysilane, hydrolysis, such as triethoxy silane A method of reacting with hydrosilanes having a degradable group.

In the present invention, the number average molecular weight of the silicone resin and the modified silicone resin is preferably 1,000 or more, and particularly preferably 6,000 to 30,000. Further, when the molecular weight distribution is narrow, the viscosity of the sealing material composition is low, and the physical properties of the rubber after curing are low modulus and high elongation, which is preferable.

The sealant composition of the present invention may contain various additives in addition to the above-mentioned components, if necessary, as long as the object of the present invention is not impaired. Additives are added to the sealant composition and used to improve various performances such as viscosity adjustment, curing acceleration, and adhesiveness of the sealant composition. Specific examples thereof include a curing accelerator, a plasticizer, a weather-resistant stabilizer, a filler, a rocking denaturing agent, an adhesiveness improving agent, a storage stability improving agent (dehydrating agent), a coloring agent, and an organic solvent. All of these can be used alone or in combination of two or more.

The curing acceleration catalyst is used to promote cross-linking curing of a room temperature curable resin by reacting with an active hydrogen-containing compound (for example, water such as humidity). The curing acceleration catalyst can also be used as a reaction catalyst during the production of the above-mentioned urethane prepolymer and urethane bond-containing oxazolidine compound. When the curing accelerating catalyst is used as a reaction catalyst during the production of the urethane prepolymer and the urethane bond-containing oxazolidine compound, the reaction catalyst remaining in them may act as a curing accelerating catalyst of the sealing material composition.

Examples of the curing acceleration catalyst include metal-based catalysts and amine-based catalysts.

Examples of the metal-based catalyst include a salt of a metal and an organic acid, a salt of an organic metal and an organic acid, and a metal chelate compound. Examples of the salt of the metal and the organic acid include salts of various metals such as tin, bismuth, zirconium, zinc and manganese and organic acids such as octyl acid, neodecanoic acid, stearic acid and naphthenic acid. Specific examples thereof include tin octylate, tin naphthenate, bismuth octylate, and zirconium octylate. Salts of organic metals and organic acids include dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin oxide and phthalates. Things can be mentioned. Examples of the metal chelate compound include a tin chelate compound, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound, a bismuth chelate compound, and an iron chelate compound. Specifically, dibutyltin bis (acetylacetonate), EXCESTAR C-501 manufactured by Asahi Glass Co., Ltd., which is a tin chelate compound, zirconium tetrakis (acetylacetonate), titanium tetrakis (acetylacetoneate), aluminum tris (acetylacetonate). , Aluminum tris (ethylacetacetate), bismastris (2-ethylhexanoate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismus, acetylacetone nickel, acetylacetone zinc, acetylacetone manganese.

Examples of amine-based catalysts include tertiary amines. Examples of tertiary amines include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), and 1,4-diazabicyclo [2.2.2]. Examples include octane (DABCO) and salts of these tertiary amines and organic carboxylic acids.

Any of these curing acceleration catalysts can be used alone or in combination of two or more.

Of these, salts of metals and organic acids, salts of organic metals and organic acids, and metal chelate compounds are preferable, and salts of tin and organic acids, and bismuth, because the sealant composition is excellent in curability. Salts with organic acids, salts with organic tin and organic acids, salts with organic bismuth and organic acids, tin chelate compounds, bismuth chelate compounds, and iron chelate compounds are preferred.

The amount of the curing acceleration catalyst used is preferably 0.005 to 5 parts by mass, particularly preferably 0.005 to 2 parts by mass with respect to 100 parts by mass of the room temperature curable resin.

In addition to the above-mentioned metal catalysts and amine catalysts, organic carboxylic acid catalysts, phosphoric acid ester catalysts, p-toluenesulfonyl monoisocyanates, and reaction products of p-toluenesulfonyl monoisocyanates and water can be used. The organic carboxylic acid catalyst, the phosphoric acid ester catalyst, the p-toluenesulfonyl monoisocyanate, and the reaction product of the p-toluenesulfonyl monoisocyanate and water are the oxazolidin rings of the oxazolidine compound when the oxazolidine compound is blended in the sealant composition. It is a hydrolysis promoting catalyst (ring-opening catalyst) that promotes the hydrolysis of. By promoting the hydrolysis of the oxazolidine ring, the generated secondary amino group and alcoholic hydroxyl group (active hydrogen group) react with the isocyanate group of the urethane prepolymer, and the curing of the sealant composition is promoted.

Examples of the organic carboxylic acid-based catalyst include formic acid, acetic acid, propionic acid, caproic acid, oxalic acid, succinic acid, adipic acid, 2-ethylhexanoic acid (octyl acid), octenoic acid, lauric acid, oleic acid, stearic acid and the like. Α, β-unsaturated carboxylic acids such as aliphatic carboxylic acids, maleic acids and acrylic acids, aromatic carboxylic acids such as phthalic acid, benzoic acid and salicylic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and methyltetrahydrophthalic acid , Methylhexahydrochloride phthalic acid, methylnadic acid anhydride, dimethylbutenyltetrahydrochloride phthalic acid and other alicyclic acid anhydrides.

Examples of the phosphoric acid ester-based catalyst include a normal phosphoric acid ester compound and a phosphite ester compound. Examples of the orthophosphoric acid ester compound include acidic phosphoric acid ester compounds such as ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, and oleyl acid phosphate, and examples of the phosphite ester compound include triethyl phosphate. Sub-acid triester compounds such as triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylmonodecylphosphite, dilaurylhydrogenphosphite, diorail Examples thereof include phosphite diester compounds such as hydrogen phosphite and diphenylhydrogen phosphite.

The reaction product of p-toluenesulfonyl monoisocyanate and water may be one in which p-toluenesulfonyl monoisocyanate is reacted with water in advance before being blended into the sealant composition of the present invention, or p-. Water may be added and reacted while the toluenesulfonyl monoisocyanate is blended and prepared in the sealant composition, or water present in the sealant composition (water contained in the raw material). Etc.) and may be reacted at the time of preparation or after preparation.

The amount of the hydrolysis promoting catalyst (ring-opening catalyst) used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the oxazolidine compound.

The plasticizer is used for the purpose of lowering the viscosity of the sealing material composition to improve workability and adjusting the physical properties of the rubber after curing of the sealing material composition. Specifically, phthalates such as dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sevacinate, and butyl oleate. Kind.

The weather-resistant stabilizer is used for the purpose of preventing oxidation, photodegradation, and heat deterioration of the sealant composition to further improve weather resistance and heat resistance. Examples of the weather resistance stabilizer include a hindered amine-based light stabilizer, a hindered phenol-based antioxidant, and an ultraviolet absorber. Any of these weather-resistant stabilizers can be used alone or in combination of two or more.

As hindered amine-based light stabilizers, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis decanoate (2,2,6,6-tetramethyl-1 (octyloxy) -4 -Piperidyl) ester, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, Methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,3) 5-Di-tert-Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6 6-Tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl 1- (2-hydroxyethyl) succinate-4-hydroxy-2,2,6,6-tetramethyl Piperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetra) Methyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-Butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, as well as ADEKA's Adecastab LA- Examples thereof include 63P and LA-68LD.

Examples of hindered phenolic antioxidants include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl). -4-Hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propioamide], benzenepropanoic acid 3,5-bis Examples thereof include (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester and 2,4-dimethyl-6- (1-methylpentadecyl) phenol.

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

Of these, hindered amine-based photostabilizers and hindered phenol-based antioxidants are preferable because they are highly effective in improving weather resistance. The weather resistance stabilizer is preferably used in an amount of 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the room temperature curable resin.

The filler is used for the purpose of increasing the amount of the sealing material composition and reinforcing the physical properties of the cured product. Specifically, mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, silicic anhydride, fine quartz powder, aluminum powder, zinc powder, synthetic silica such as precipitated silica, calcium carbonate, carbon dioxide. Inorganic powder fillers such as magnesium, alumina, calcium oxide and magnesium oxide; fibrous fillers such as glass fibers and carbon fibers; inorganic balloon fillers such as glass balloons, talc balloons, silica balloons and ceramic balloons; wood Powder, walnut shell powder, fir shell powder, pulp powder, cotton chips, rubber powder, fine powder of thermoplastic or thermosetting resin, powder such as polyethylene or hollow body, organic balloon-like filling such as saran microballoon; water Examples thereof include flame-retardant fillers such as magnesium oxide and aluminum hydroxide. The particle size of the filler is preferably 0.01 to 1,000 μm.

The rock denaturing agent is used for the purpose of preventing sagging (slump) of the sealing material composition. Specific examples thereof include inorganic shake denaturing agents such as fine powder silica and fatty acid surface-treated calcium carbonate; organic shaking denaturing agents such as urea compounds, organic bentonite, and fatty acid amide. All of these can be used alone or in combination of two or more.

Examples of the fine powder silica include hydrophilic silica and hydrophobic silica. All of these can be used alone or in combination of two or more.

Examples of the hydrophilic silica include natural silica obtained by finely pulverizing quartz, silica sand and the like, and synthetic silica such as dry silica and wet silica. Dry silica is obtained by burning a silane gas such as silicon tetrachloride in an oxyhydrogen flame, and is sometimes referred to as fumed silica. In addition, wet silica includes precipitation-type silica in which silica is precipitated in a solution by neutralizing sodium silicate with a mineral acid, and is sometimes referred to as white carbon.

Examples of the hydrophobic silica include those obtained by surface-treating the hydrophilic silica with an organosilicon compound reactive with the hydrophilic silica to make it hydrophobic.

The urea compound is a compound having at least one urea bond (-NHCONH-) in the compound, and examples thereof include a reaction product of an organic isocyanate compound and an amine compound.

Examples of the organic isocyanate compound include the same organic isocyanate compounds as those used in the production of the urethane prepolymer described above.

Examples of the amine compound include compounds having at least one amino group in the molecule. Examples of the amino group include a primary amino group and a secondary amino group. Examples of monoamines having a primary amino group include butylamine, isobutylamine, hexylamine, heptylamine, 2-ethylhexylamine, octylamine, 3-methoxypropylamine, tetradecylamine, cetylamine, stearylamine, oleylamine, and trimethylcyclohexylamine. , Benzylamine, aniline and the like. Examples of the diamine having a primary amino group include ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 1,7-diaminoheptane, and trimethylhexamethylenediamine. , 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-diaminoheptadecan, 1,18-diaminooctadecane, isophorone diamine, diaminodicyclohexylmethane, 3,9-bis (3-aminopropyl)- Examples thereof include 2,4,8,10-tetraoxaspiro (5,5) undecane, xylene diamine, phenylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, polyoxyethylenediamine, and polyoxypropylenediamine. Examples of the triamine having a primary amino group include tri (methylamino) hexane. Examples of monoamines having a secondary amino group include diethylamine, dipropylamine, diisopropylamine, dibutylamine, dihexylamine, di-2-ethylhexylamine, diphenylamine, dilaurylamine, distearylamine, and methyllaurylamine. Examples of the diamine having a secondary amino group include N, N'-dilaurylpropyl diamine, N, N'-distearylbutyldiamine, N-butyl-N'-laurylethyldiamine, and N-butyl-N'-lauryl. Examples thereof include propyldiamine and N-lauryl-N'-stearylbutyldiamine. Examples of polyamines having a primary amino group and a secondary amino group include diethylenetriamine, triethylenetetramine, and methylaminopropylamine. Any of these amine compounds can be used alone or in combination of two or more.

Fatty acid surface-treated calcium carbonate is obtained by treating the surface of heavy calcium carbonate, light calcium carbonate, and colloidal calcium carbonate with fatty acids such as fatty acids, fatty acid alkyl esters, fatty acid metal salts, and fatty acid organic salts. Examples of fatty acids include fatty acids having 10 to 25 carbonic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the metal salt include sodium salt, potassium salt, calcium salt, aluminum salt, and examples of the organic salt include ammonium salt.

The adhesiveness improver is used for the purpose of improving the adhesiveness of the sealant composition. Specific examples thereof include various coupling agents such as silane-based, aluminum-based, and zirco-aluminate-based, and partial hydrolysis condensates thereof. Of these, the silane coupling agent and its partially hydrolyzed condensate are preferable because they have excellent adhesiveness.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3-mercaptopropyltrimethoxysilane. 3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) Examples thereof include compounds having an alkoxysilyl group such as -3-aminopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane and having a number average molecular weight of 500 or less. In addition, compounds having a number average molecular weight of 200 to 3,000, which are partially hydrolyzed condensates of one or more of these silane-based coupling agents, can be mentioned. All of these can be used alone or in combination of two or more.

The storage stability improver (dehydrating agent) is used for the purpose of improving the storage stability of the sealant composition. Specific examples thereof include vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate (PTSI), which react with water present in the sealant composition and act as a dehydrating agent. All of these can be used alone or in combination of two or more.

The colorant is used for the purpose of coloring the sealant composition and imparting design to the cured product. Specific examples thereof include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black. All of these can be used alone or in combination of two or more.

The organic solvent is used for the purpose of lowering the viscosity of the sealant composition and improving the extrudability and workability during casting and coating. The organic solvent can be used without particular limitation as long as it has good compatibility with other components in the sealing material composition and does not react with other components. Specifically, carbonate-based solvents such as dimethyl carbonate, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, aliphatic solvents such as n-hexane, and alicyclic solvents such as cyclohexane. Examples thereof include solvents, aromatic solvents such as toluene and xylene, and organic solvents such as petroleum distillate solvents such as mineral spirit and industrial gasoline. All of these can be used alone or in combination of two or more.

Since the sealant composition of the present invention reacts with an active hydrogen-containing compound (for example, water such as moisture) and is crosslinked and cured, it can be used as a one-component sealant composition. Further, the room temperature curable resin of the present invention can be used as a main agent, and a curing agent can be mixed with the main agent to be used as a two-component sealing material composition.

Examples of the method of mixing the two-component sealant composition include a method of uniformly mixing each component using a mixer such as a hand mixer, a vacuum defoaming mixer, or a drum rotary mixer.

The method for producing the sealing material composition of the present invention is not particularly limited and can be carried out by a known method. As a method for producing the one-component sealant composition, specifically, a room temperature curable resin and, if necessary, an oxazolidine compound and an additive are mixed with a stirrer such as glass, stainless steel, or iron. (Kneading) A method of charging the mixture in a container, blocking water such as moisture, and stirring and mixing in a batch or continuous manner under a dry nitrogen stream can be mentioned. As a method for producing a two-component sealant composition, the main agent and the curing agent are separated and each of the above components is placed in a mixing (kneading) container equipped with a stirrer to block water such as moisture, and under a dry nitrogen stream. Examples thereof include a method of manufacturing by stirring and mixing in a batch type or a continuous type.

When the sealing material composition of the present invention is used as a one-component sealing material composition, the room temperature curable resin may react with water such as humidity to thicken and harden. It is preferably packed in a container that can be blocked and sealed for storage. The container is not particularly limited as long as it can block water such as humidity. Specific examples thereof include metal and resin cans, aluminum bags, and paper and resin cartridges. Even when it is used as a two-component sealant composition, it is preferable to pack each component of the main agent and the curing agent in a container capable of blocking water such as moisture and store it in a sealed container.

By blending the above-mentioned components, the sealing material composition of the present invention is subjected to spectroscopic irradiation for 2,000 hours by an exposure test method using JIS A 1415 (2013) 6.2 open frame carbon arclamp after curing. The step (1) and the step (2) of performing the cycle of expanding / contracting the joint of the test piece by 20% 4,000 times are included, and the step (1) and the step (2) are performed 1 to 5 cycles. After that, no discoloration, peeling or breakage occurs at the test piece joint in any of the cycles.
Further, in the sealant composition of the present invention, the cured composition is subjected to spectroscopic irradiation for 2,000 hours by an exposure test method using JIS A 1415 (2013) 6.2 open frame carbon arclamp (1). Including the step (2) of performing the cycle of expanding / contracting the joint of the test piece by 30% 4,000 times, after performing the step (1) and the step (2) for 1 to 4 cycles, in any cycle. Also, the joints of the test piece will not be discolored, peeled or broken.

The sealing joint structure of the present invention will be described. The sealing joint structure of the present invention includes a step (1) of performing spectral irradiation for 2,000 hours by an exposure test method using a JIS A 1415 (2013) 6.2 open frame carbon arc lamp, and a 20% enlargement of the test joint joint. Including the step (2) of performing the reduction cycle 4,000 times, after performing the step (1) and the step (2) for 1 to 5 cycles, discoloration, peeling, and discoloration and peeling of the test piece joint are performed in each cycle. It is a sealing joint structure in which a sealing material composition that does not break is filled in the joint and cured.
Further, the sealing joint structure of the present invention includes a step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using JIS A 1415 (2013) 6.2 open frame carbon arc lamp, and 30% of the test joint joint. Including the step (2) of performing the expansion / contraction cycle 4,000 times, after performing the step (1) and the step (2) for 1 to 4 cycles, the joints of the test piece are discolored in each cycle. It is a sealing joint structure in which a joint is filled with a sealing material composition that does not cause peeling and breaking and is cured.
The sealing joint structure will be specifically described with reference to FIGS. 1 to 5. The sealing joint structure of the present invention is not construed as being limited to FIGS. 1 to 5.

FIG. 1 is an example of a cross section showing the concept of a sealing joint structure. In FIG. 1, a backup material 4 is loaded in the gap between the adherend 1 and the adherend 2 to provide a joint base. A primer layer 9 is formed on the adherend surfaces of the adherend 1 and the adherend 2, and the sealing material 10 is filled in the gap between the joints.

FIG. 2 is an example of a cross section showing the concept of a sealing joint structure. In FIG. 2, a gap and a joint basement are provided on the convex side surface of the hat joiner 5 so that the adherend 1 and the adherend 2 face each other. A primer layer is formed on the adherend surfaces of the adherend 1 and the adherend 2, and the sealing material 10 is filled in the gap between the joints.

FIG. 3 is an example of a cross section showing the concept of a sealing joint structure. In FIG. 3, a gap is provided in the base material 6 forming the joint bottom with the adherend 1 and the adherend 2 facing each other. A primer layer 9 is formed on the adherend surfaces of the adherend 1 and the adherend 2, and the sealing material 10 is filled in the gap between the joints. A bond breaker 7 having a mold release performance with respect to the sealing material 10 is attached to the bottom of the joint.

FIG. 4 is an example of a cross section showing the concept of the sealing joint structure. In FIG. 4, a backup material 4 is loaded in the gap between the adherend 2 and the adherend 3 to provide a joint base. A primer layer 9 is formed on the adherend surfaces of the adherend 2 and the adherend 3, and the sealing material 10 is filled in the gap between the joints.

FIG. 5 is an example of a cross section showing the concept of a sealing joint structure. In FIG. 5, a gap and a joint basement are provided on the convex side surface of the one-sided hat joiner 8 so that the adherend 2 and the adherend 3 face each other. A primer layer 9 is formed on the adherend surfaces of the adherend 2 and the adherend 3, and the sealing material 10 is filled in the gap between the joints.

As described above, the sealing material 10 shown in FIGS. 1 to 5 is a composition containing a room temperature curable resin, and the room temperature curable resin reacts with the active hydrogen-containing compound to form a rubber-like cured product.

The adherend 1, the adherend 2, and the adherend 3 in the present invention are not particularly limited as long as they are members capable of forming joints. Specifically, for example, ceramic siding, metal siding, concrete, mortar, glass, tile, natural stone, artificial stone, wood board, resin board, ALC (Autoclaved Light-weight Concrete), gypsum board, metal sash, resin sash, Examples include metal sashes and resin sashes. The members of the adherend 1, the adherend 2 and the adherend 3 may be the same or different.

The backup material 4 in the present invention is not particularly limited as long as it can be inserted into the gap between the adherends and the joint base can be formed. Specifically, for example, a backup material made of foamed polyethylene having a mold release performance with respect to the sealing material 10 can be mentioned. Examples of the shape of the backup material include a rod-shaped or string-shaped one having a quadrangular, round, or elliptical cross section. It is preferable to appropriately use a width of the backup material suitable for the joint design.

The hat joiner 5 in the present invention is not particularly limited as long as a gap between adherends and a joint base can be formed. Specific examples thereof include hat joiners made of metal and resin. It is preferable that the upper surface of the convex portion of the hat joiner 5 has a mold release performance with respect to the sealing material 10. Such hat joiners include those in which an olefin-based or fluorine-based tape is attached to the upper surface of the convex portion of a metal or resin hat joiner, or an olefin-based or fluorine-based coating material is applied to the upper surface of the convex portion for coating. Examples include those in which layers are formed. Further, among the resin hat joiners, those made of an olefin-based or fluorine-based material are preferable because they have mold release performance with respect to the sealing material 10 without forming the tape or coating layer on the upper surface of the convex portion. It is preferable that the width and height of the convex portion of the hat joiner are appropriately used for the design of the joint. Further, the convex portion of the hat joiner may have a flat upper surface or a curved upper surface.

The base material 6 in the present invention is not particularly limited as long as the joint base between the adherends can be formed. Specific examples thereof include concrete, mortar, glass, tile, natural stone, artificial stone, wood board, resin board, metal board, ALC (Autoclaved Light-weight Concrete), and gypsum board.

The bond breaker 7 in the present invention is not particularly limited as long as it has a mold release performance with respect to the sealing material 10. Specifically, for example, an olefin-based or fluorine-based material is used on the surface in contact with the sealing material 10, and a tape-like material having an adhesive layer on the surface in contact with the base material 6 and being able to be attached to the base material 6 can be mentioned.

The single hat joiner 8 in the present invention is not particularly limited as long as a gap between adherends and a joint base can be formed. The one-sided hat joiner 8 is formed by forming the legs at both ends of the convex portion of the hat joiner 5 with only one of them. Specific examples thereof include metal and resin single hat joiners. It is preferable that the upper surface of the convex portion of the one-sided hat joiner 8 has a mold release performance with respect to the sealing material 10. Such single-hat joiners include those in which an olefin-based or fluorine-based tape is attached to the upper surface of the convex portion of a metal or resin single-hat joiner, or an olefin-based or fluorine-based coating material is applied to the upper surface of the convex portion. Examples thereof include those in which a coating layer is formed. Further, among the resin-made single hat joiners, those made of an olefin-based or fluorine-based material are preferable because they have a mold release performance with respect to the sealing material 10 without forming the tape or coating layer on the upper surface of the convex portion. It is preferable that the width and height of the convex portion of the one-sided hat joiner 8 are appropriately used for the design of the joint. Further, the convex portion of the one-sided hat joiner 8 may have a flat upper surface or a curved upper surface.

The primer layer 9 in the present invention will be described. The primer layer improves the adhesiveness and adhesion between the adherend 1, the adherend 2, and the adherend 3 and the sealing material 10. Further, the primer layer 9 prevents substances such as water and plasticizer contained in the adherend from being transferred to the sealing material 10, and the substance such as plasticizer contained in the sealing material 10 is transferred to the adherend. It prevents you from doing so. Further, when the surface of the adherend is fragile, the surface can be strengthened by forming the primer layer 9 on the surface of the adherend. The primer layer 9 can be formed by applying a primer composition to the adherend surface of an adherend and drying and / or reaction curing.

As the primer composition, conventionally known ones can be used without particular limitation. In particular, it is preferable to use a primer composition recommended by the sealant manufacturer in which the adhesiveness between the adherend, the primer and the sealant has been confirmed in advance.

The components of the primer composition will be described. The primer composition is a composition containing a binder and an organic solvent. The binder is dried and / or reactively cured to form a primer layer. The binder may be a high molecular weight compound having a number average molecular weight of 1,000 or more, or a low molecular weight compound having a number average molecular weight of less than 1,000.

Examples of the binder include an isocyanate group-containing compound, an isocyanate group-crosslinkable silyl group-containing compound, and a crosslinkable silyl group-containing compound. These can be used alone or in combination of two or more.

The organic solvent will be described. The organic solvent is used to dissolve and dilute the binder and the additives described below to adjust the primer composition to a viscosity suitable for the coating operation. The organic solvent is preferably one that dissolves the binder and the additive and is inert to the binder and the additive and does not react. Further, the organic solvent preferably has an appropriate volatility that does not hinder the securing of an open time (usually about 10 to 60 minutes at 5 to 35 ° C.) after application of the primer composition. ..

Specific examples of the organic solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, butyl stearate, and methyl benzoate. , Ethyl benzoate, propyl benzoate, butyl benzoate, γ-butyrolactone, diethyl malonate and other ester solvents; diethyl ether, dipropyl ether, dibutyl ether, dioxane, tetrahydrofuran and other ether solvents; N, N-dimethyl Amid solvents such as acetoamide and N-methylpyrrolidone; ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, butyl methyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone, and acetophenone: ethylene glycol monomethyl ether acetate. , Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl-1,3-butylene glycol acetate and other acetate solvents can be mentioned. These can be used alone or in combination of two or more.

In addition, n-hexane, 2-methylpentane, n-heptane, n-octane, 2,2,3-trimethylpentane, 2,2,4-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, Aliper hydrocarbon solvents such as n-decane and n-dodecane; alicyclic hydrocarbon solvents such as cyclohexane; xylene, ethylbenzene, trimethylbenzene, isopropylbenzene, butylbenzene, diethylbenzene, pentylbenzene, dipentylbenzene, cyclohexylbenzene , Naphthalene, tetraline, biphenyl and other aromatic hydrocarbon solvents; dimethylsulfoxide, mineral spirit, petroleum naphtha, coal tar naphtha, solvent naphtha, ligroin, and mixtures thereof can be used in combination with the above-mentioned organic solvents.

Additives can be added to the primer composition, if necessary. Examples of the additive include an adhesiveness-imparting agent and a curing acceleration catalyst. Examples of the adhesive imparting agent include a silane coupling agent. Examples of the curing acceleration catalyst include those similar to the curing acceleration catalyst that can be blended in the sealing material composition.

The construction method of the sealing joint structure of the present invention will be described. The method for constructing the sealing joint structure of the present invention is a step of forming a joint by providing a joint bottom with a base material to which a backup material, a hat joiner or a bond breaker is attached in a gap between the adherends, and the adherend. A step of applying the primer composition to the adherend surface of the joint to form a primer layer, and 2,000 hours of spectroscopic irradiation is performed on the gaps between the joints by an exposure test method using JIS A 1415 (2013) 6.2 open frame carbon arclamp. After performing the step (1) and the step (2) for 1 to 5 cycles including the step (1) and the step (2) of performing the cycle of expanding / contracting the joint of the test piece by 20% 4,000 times. This is a method for constructing a sealing joint structure, which comprises a step of filling and curing a sealing material composition that does not cause discoloration, peeling, or breaking in the test joint in any cycle.
Further, the method of constructing the sealing joint structure of the present invention is a step of forming a joint by providing a joint bottom with a base material to which a backup material, a hat joiner or a bond breaker is attached in a gap between the adherends. A step of applying the primer composition to the adherend surface of the joint to form a primer layer, and a 2,000-hour spectroscopic irradiation method of exposure test using JIS A 1415 (2013) 6.2 open frame carbon arclamp in the joint gap. The step (1) and the step (2) of performing the cycle of expanding / contracting the joint of the test piece by 30% 4,000 times are included, and the step (1) and the step (2) are performed 1 to 4 cycles. After that, it is a method of constructing a sealing joint structure including a step of filling and hardening a sealing material composition that does not cause discoloration, peeling, or breaking in the test joint in any cycle.

As a method of constructing the sealing joint structure, first, the adherend surface and the joint bottom of the adherend are cleaned with a brush or a waste cloth to remove chips and dust. If the adherend surface of the adherend is wet, wipe it off thoroughly and dry it. When the joint base is provided with a hat joiner or a single hat joiner, the hat joiner or the single hat joiner is attached to the base or the like before installing the adherend. When the joint bottom is provided with a backup material or a base material to which a bond breaker is attached, the adherend and the adherend should be installed facing each other so as to have a gap as designed. After the adherend is installed, a backup material is inserted into the gap between the adherends so that the joint depth is as designed, or a bond breaker is attached to the surface of the base material which is the base material. The hat joiner, one-sided hat joiner, backup material, and base material to which the bond breaker is attached are appropriately selected and used according to the joint design.
Next, a masking tape, a curing tape such as a polymasker, or the like is attached to the joint (the surface of the adherend). If the joint surface of the adherend is uneven, attach it without gaps, being careful not to create gaps between the adherend and the curing tape.
Next, the primer composition is applied to the adherend surface of the adherend, that is, the adhesive surface between the adherend and the sealant composition by brush, felt, spray or the like. The primer may be applied in 2 to 3 times in order to prevent uncoated areas and uneven coating of the primer composition. After applying the primer, allow an open time to dry-cure and / or react-cure the primer composition.
Next, the sealing material composition of the present invention is prepared, and the nozzle tip of the cartridge or the dedicated gun is attached to the bottom of the joint, and the sealing material composition is filled (cast) without gaps so that no gaps remain in the gaps between the joints. After filling the sealant composition, the surface of the sealant is smoothed with a spatula or the like. A surface coating agent may be applied to the surface of the sealing material to prevent the surface of the sealing material from becoming dirty.
Next, the curing tape near the joint is peeled off, and it is confirmed whether or not the sealing material composition adheres to a portion other than the sealing joint. If the sealant composition adheres to unnecessary parts, remove it cleanly.
As described above, the sealing material composition of the present invention is a composition containing a room temperature curable resin, and the room temperature curable resin reacts with an active hydrogen-containing compound or the like to form a rubber-like cured product. In the case of a one-component sealant composition, it reacts with moisture in the air and gradually hardens from the surface of the sealant (the surface in contact with air). In the case of a two-component sealing material composition, the main agent and the curing agent react, and the entire sealing material is gradually cured. That is, the sealing material composition of the present invention becomes a rubber-like cured product if the surface of the sealing material composition is smoothed with a spatula or the like after being placed and cured as it is, and a sealing joint structure can be formed.

Examples of the present invention are shown below, but the present invention is not construed as being limited to the examples.

[Example 1]
A one-component urethane sealant composition (Orton Exceed, manufactured by Auto Chemical Industries, Ltd.) was used.

The following performance evaluation was performed using the sealant composition of Example 1. The evaluation results are shown in Table 1.

[Tensile Adhesive Test A]
In accordance with JIS A 1439 (2016) Tensile Adhesion Test of 5.20 Tensile Adhesion Test of Building Sealant, Tensile Adhesion Test after Curing was performed, and 50% tensile stress (M ₅₀ ) of the sealant composition, maximum. Tensile stress (T _max ) and elongation at maximum load (E _max ) were determined. As the test body, a mortar having a size of 50 mm × 50 mm × 25 mm was used. A one-component urethane primer composition (OP-2019, manufactured by Auto Chemical Industry Co., Ltd.) was applied in advance to the surface to be adhered to the sealing material composition of Example 1 and dried and cured.
[Tensile Adhesive Test B]
NPO corporation housing exterior technical center standard JTC S-0001 Ceramic siding sealing material (established: 2004.09.01) conforms to the 5.3.2 tensile adhesive test, and after curing, the tensile adhesive test is performed. The 50% tensile stress (M ₅₀ ), maximum tensile stress (T _max ), and elongation at maximum load (E _max ) of the sealant composition were determined. As the adherend, a ceramic siding (manufactured by Toray ACE) having a size of 50 mm × 50 mm × 14 mm was used. A one-component urethane primer composition (OP-2019, manufactured by Auto Chemical Industry Co., Ltd.) was applied in advance to the surface to be adhered to the sealing material composition of Example 1 and dried and cured. The test piece was an I-type test piece.

[Weather resistance test A]
NPO corporation housing exterior technical center standard JTC S-0001 Ceramics siding sealant (establishment: 2004.09.01) 5.1.6b) Based on the preparation of type II test piece, type II test piece was prepared. .. An aluminum plate having a length of 50 mm, a width of 30 mm, and a thickness of 15 mm is used as the adherend, and a one-component urethane-based primer composition (OP-2019, OP-2019,) is previously applied to the adherend surface with the sealant composition of Example 1. (Manufactured by Auto Chemical Industry Co., Ltd.) was applied and dried and cured. The sealant composition was cured at 23 ° C. and 50% RH for 14 days and then at 30 ° C. for 14 days to cure. The joint shape of the sealing material was 40 mm in length × 10 mm in width × 10 mm in depth.
Using the prepared test piece, the step (1) of performing spectroscopic irradiation for 2,000 hours was performed in accordance with the exposure test method (WS-A) using JIS A 1415 (2013) 6.2 open frame carbon arc lamp. .. Irradiation was continuous irradiation, water spray was 18 minutes per 120 minutes, and an exposure test was conducted until the irradiation time reached 2,000 hours.
After the step (1), the test piece was installed in a repetitive tester specified in JIS A 1439 (2016) 5.12.1 g), and the joint of the test piece was expanded 4,000 times with a deformation rate of ± 20%. The reduction was repeated to carry out step (2).
Steps (1) and (2) were carried out for 1 to 5 cycles to prepare a weather resistance test of the sealant composition.
[Weather resistance test B]
NPO corporation housing exterior technical center standard JTC S-0001 Ceramics siding sealant (establishment: 2004.09.01) 5.1.6b) Based on the preparation of type II test piece, type II test piece was prepared. .. An aluminum plate having a length of 50 mm, a width of 30 mm, and a thickness of 15 mm is used as the adherend, and a one-component urethane-based primer composition (OP-2019, OP-2019,) is previously applied to the adherend surface with the sealant composition of Example 1. (Manufactured by Auto Chemical Industry Co., Ltd.) was applied and dried and cured. The sealant composition was cured at 23 ° C. and 50% RH for 14 days and then at 30 ° C. for 14 days to cure. The joint shape of the sealing material was 40 mm in length × 10 mm in width × 10 mm in depth.
Using the prepared test piece, the step (1) of performing spectroscopic irradiation for 2,000 hours was performed in accordance with the exposure test method (WS-A) using JIS A 1415 (2013) 6.2 open frame carbon arc lamp. .. Irradiation was continuous irradiation, water spray was 18 minutes per 120 minutes, and an exposure test was conducted until the irradiation time reached 2,000 hours.
After the step (1), the test piece was installed in a repetitive tester specified in JIS A 1439 (2016) 5.12.1 g), and the joint of the test piece was expanded 4,000 times with a deformation rate of ± 30%. The reduction was repeated to carry out step (2).
Steps (1) and (2) were carried out for 1 to 4 cycles to prepare a weather resistance test of the sealant composition.
The state of the test piece after each cycle was visually observed, and the weather resistance test A and the weather resistance test B were evaluated according to the following criteria.
◯: No discoloration, peeling or breakage is observed at the test piece joint Δ: No discoloration is observed at the test piece joint, but peeling or breakage is observed at a depth of less than 5 mm ×: Discoloration is observed at the test piece joint. Alternatively, peeling or breaking at a depth of 5 mm or more is observed.

From the results in Table 1, the sealant composition of Example 1 had a 50% tensile stress (M ₅₀ ) of less than 0.2 N / mm ^{2 and} an elongation rate at maximum load (E) in tensile adhesiveness tests A and B. It can be seen that _max ) is 700% or more, and the rubber has excellent physical properties with low modulus and high elongation.
Further, it can be seen that the sealant composition of Example 1 is excellent in weather resistance and durability because no discoloration, peeling and breakage are observed in the test body joints after 1 to 5 cycles in the weather resistance test A. ..
Further, it can be seen that the sealant composition of Example 1 is excellent in weather resistance and durability, as no discoloration, peeling or breakage is observed in the test body joint after 1 to 4 cycles in the weather resistance test B. ..

Since the sealant composition of the present invention has low modulus, high elongation, and is excellent in weather resistance and durability, it can be suitably used as a sealant composition for construction and civil engineering. In particular, the sealing material composition of the present invention can be suitably used as a sealing material composition for working joints. The sealing material composition of the present invention can also be used as a putty material or an adhesive.

1 Adhesive body 2 Adhesive body 3 Adhesive body 4 Backup material 5 Hat joiner 6 Base material 7 Bond breaker 8 Single hat joiner 9 Primer layer 10 Sealing material (hardened material)

Claims (6)

It is a performance evaluation method for the sealant composition.
JIS A 1415 (2013) 6.2 A step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using an open frame carbon arc lamp, and
The performance evaluation method comprising 1 to 5 cycles of the step (1) and the step (2) including a step (2) of performing a cycle of expanding / contracting a test piece joint by 20% 4,000 times. It is a performance evaluation method for the sealant composition.
JIS A 1415 (2013) 6.2 A step (1) of performing spectroscopic irradiation for 2,000 hours by an exposure test method using an open frame carbon arc lamp, and
The performance evaluation method, which comprises a step (2) of performing a cycle of enlarging / reducing a test piece joint by 30% 4,000 times, and performing the step (1) and the step (2) for 1 to 4 cycles. In the performance evaluation method according to claim 1, after performing the steps (1) and the steps (2) for 1 to 5 cycles, no discoloration, peeling, or breakage occurs at the test piece joint in any of the cycles, and the performance is improved. A sealant composition that meets the evaluation. In the performance evaluation method according to claim 2, after performing the steps (1) and the steps (2) for 1 to 4 cycles, no discoloration, peeling or breakage occurs at the test piece joint in any of the cycles, and the performance is improved. A sealant composition that meets the evaluation. A sealing joint structure in which the joints are filled with the sealing material composition according to claim 3 or 4 and cured. A process of forming a joint by providing a joint base with a backup material, a hat joiner, or a base material to which a bond breaker is attached in the gap between the adherends.
A step of applying a primer composition to an adherend surface of an adherend to form a primer layer,
The step of filling the gap between the joints with the sealant composition according to claim 3 or 4 and curing the composition.
Construction method of sealing joint structure including.

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