JP2019065277A - One-liquid type curable composition and cured product of one-liquid type curable composition - Google Patents

Abstract

To provide a one-liquid type curable composition that has high transparency and weather resistance, does not impair the beauty of a building appearance, and does not stain the surrounding area for a long time.SOLUTION: A one-liquid type curable composition contains an isocyanate group-containing urethane prepolymer (A) and a thixotropy imparting agent (B). A cured product of the one-liquid type curable composition has a haze value of 40% or less in accordance with ASTM D1003-97.SELECTED DRAWING: None

Description

  The present invention relates to a one-component curable composition containing an isocyanate group-containing urethane prepolymer and a cured product of the one-component curable composition.

  In general, since the Building Standards Act requires the installation of a ventilation system capable of replacing the air of a building such as a house in a predetermined time, a ventilation system is often provided in the building. The ventilating apparatus includes a duct communicating with the outside, and the tip of the duct is connected to a vent opening opened in the outer wall surface. A vent cap is attached to the ventilating port in order to prevent rainwater and the like from entering the ventilating port. Here, if there is a slight gap between the vent cap and the outer wall, rain water or the like will enter from this gap. Therefore, in order to prevent rainwater and the like from entering the gap between the vent cap and the outer wall, a sealing material is filled in the gap, and a waterproof seal portion is formed by the sealing material.

  In addition, along with the recent increase in the design of detached houses, outer walls colored in various patterns and tones are used. On the other hand, the sealing material used for the gap between the vent cap and the outer wall is usually white alone or only a few colors are prepared, and in many cases, the one relatively close to the color tone of the outer wall is used. When such a sealing material is used for an exterior wall with high designability, only the area around the vent cap may stand out, which may impair the aesthetic appearance of the entire building.

  On the other hand, there are cases where sealing materials used in the joint portion of the outer wall are provided with sealing materials of various colors, but in general, the contractor of the vent cap usually uses the sealing material at the joint portion of the outer wall It is often different from the vendor that fills the In fact, it is not realistic for the contractor of the vent cap to prepare a sealing material used only for the waterproof seal portion of the vent cap for each building having a different pattern or color tone.

  Although a transparent type is also marketed as a sealing material used for the clearance gap between a vent cap and an outer wall in order to solve the said problem, the transparency is low and it may still spoil the aesthetics of a building. In addition, since the above-mentioned sealing material of the transparent type can not use a pigment such as titanium oxide having high concealability from the viewpoint of transparency, the weather resistance is insufficient, and in the present situation, the high durability of the entire building is advanced. It is a problem.

  Most of this type of sealing materials are silicone-based and modified silicone-based (Patent Document 1), and there is also a problem that water repellent contamination by molecules of the silicone precursor after application and contamination around the periphery due to contained plasticizers .

JP 2001-055799

  The present invention was made to solve such problems, and has a high degree of transparency and weatherability, and does not contaminate the surroundings for a long time without impairing the appearance of the building appearance. It aims to provide goods.

An aspect of the present invention is a one-component curable composition comprising an isocyanate group-containing urethane prepolymer (A) and a thixotropic agent (B), which is a cured product of the one-component curable composition ASTM
It is a one-pack type curable composition whose haze value in D1003-97 is 40% or less.

  An aspect of the present invention is a one-part curable composition further comprising a compound (C) which is hydrolyzed with moisture to form an active hydrogen-containing functional group.

  An aspect of the present invention is that the isocyanate group-containing urethane prepolymer (A) is a reaction product of an organic isocyanate compound (a) and an active hydrogen-containing compound (b), and the active hydrogen-containing compound (b) is Active hydrogen-containing (meth) acrylic polymer (b-1), compound (b-2) having at least one active hydrogen and at least one photocurable ethylenic unsaturated group, and number average molecular weight of 1000 or more It is a one-component curable composition containing a polyol (b-3) of

  The aspect of the present invention is a liquid containing 1.0 mass% or more and 7.0 mass% or less of the active hydrogen-containing (meth) acrylic polymer (b-1) in the active hydrogen-containing compound (b) It is a mold-curable composition.

  An aspect of the present invention is that in the active hydrogen-containing compound (b), 1.0% by mass of the compound (b-2) having the at least one active hydrogen and at least one photocurable ethylenic unsaturated group It is a one-component curable composition containing not less than 7.0% by mass.

  An aspect of the present invention is a one-part curable composition wherein the organic isocyanate compound (a) contains an alicyclic polyisocyanate compound.

  An aspect of the present invention is a one-component curable composition, wherein the thixotropic agent (B) contains finely powdered silica.

  An embodiment of the present invention is the one-component curable composition, wherein the compound (C) which is hydrolyzed with moisture to form an active hydrogen-containing functional group is an oxazolidine compound.

  An aspect of the present invention is the one-component curable composition in which the isocyanate group-containing urethane prepolymer (A) has an isocyanate group of 0.10% by mass or more and 15% by mass or less.

  The aspect of this invention is that the isocyanate group of the said organic isocyanate compound (a) of the said isocyanate group containing urethane prepolymer (A) is 1.0 mol with respect to 1.0 mol of active hydrogen of the said active hydrogen containing compound (b). It is a one-component curable composition which is a reaction product of 5 mol or more and 8.0 mol or less.

  One aspect of the present invention is a one-component curable composition comprising 0.50 parts by mass or more and 20 parts by mass or less of the thixotropic agent (B) relative to the isocyanate group-containing urethane prepolymer (A) (solid content) It is.

  An embodiment of the present invention is a wet compound (C) which is hydrolyzed with the moisture to generate an active hydrogen-containing functional group with respect to 1.0 mol of the isocyanate group of the isocyanate group-containing urethane prepolymer (A). It is a one-component curable composition in which the active hydrogen of the active hydrogen-containing functional group generated by reacting with a component is 0.10 to 1.5 mol.

  An aspect of the present invention is a cured product of the above one-part curable composition.

  According to the embodiment of the present invention, the cured product of the one-component curable composition containing the isocyanate group-containing urethane prepolymer (A) and the thixotropic agent (B) has a haze value according to ASTM D1003-97 of 40% By being the following, it is possible to obtain a one-component curable composition which has high transparency and weather resistance, does not spoil the appearance of the building appearance, and does not contaminate the surroundings for a long period of time.

  According to the aspect of the present invention, the active hydrogen-containing compound (b) of the isocyanate group-containing urethane prepolymer (A), which is a reaction product of the organic isocyanate compound (a) and the active hydrogen-containing compound (b), is activated A hydrogen-containing (meth) acrylic polymer (b-1), a compound (b-2) having at least one active hydrogen and at least one photocurable ethylenic unsaturated group, and a number average molecular weight of 1,000 or more By including the polyol (b-3), the transparency and the weatherability can be further improved, and a cured product that does not contaminate the surroundings for a long period of time more reliably without impairing the appearance of the building appearance One-part curable compositions can be obtained.

  According to the aspect of the present invention, the active hydrogen-containing (meth) acrylic polymer (b-1) is contained in the active hydrogen-containing compound (b) in an amount of 1.0% by mass or more and 7.0% by mass or less A cured product having further improved weatherability and rubber physical properties can be obtained.

  According to the aspect of the present invention, 1.0% by mass of the compound (b-2) having at least one active hydrogen and at least one photocurable ethylenically unsaturated group in the active hydrogen-containing compound (b) By containing at least 7.0% by mass or less, a cured product with further improved weatherability and rubber physical properties can be obtained.

  According to the aspect of the present invention, when the organic isocyanate compound (a) contains an alicyclic polyisocyanate compound, the transparency and the weather resistance can be further improved, and a cured product having durability can be obtained.

  According to the aspect of the present invention, when the thixotropic agent (B) contains finely powdered silica, the transparency can be more reliably improved.

It is a top view explaining the test method of the contamination nature in an example and a comparative example. It is a side view explaining the test method of the contamination property in an Example and a comparative example. It is a photograph which shows the test result of the weather resistance in an Example and a comparative example.

  Next, the details of the one-component curable composition of the present invention will be described. The one-component curable composition of the present invention is a one-component curable composition comprising an isocyanate group-containing urethane prepolymer (A) and a thixotropic agent (B), and the one-component curable composition The haze value in ASTM D1003-97 of the cured product of the composition is 40% or less.

  The haze value according to ASTM D1003-97 of the cured product of the one-component curable composition of the present invention is not particularly limited as long as it is 40% or less, but from the viewpoint of the balance between ease of production and excellent transparency. 8% or more and 30% or less is preferable, and 12% or more and 25% or less is particularly preferable.

  Next, the components of the one-component curable composition of the present invention will be described below.

Isocyanate group-containing urethane prepolymer (A)
The isocyanate group-containing urethane prepolymer (A) comprises an organic isocyanate compound (a) and an active hydrogen-containing compound (b), and the number of moles of isocyanate groups of the organic isocyanate compound (a) is the activity of the active hydrogen-containing compound (b) It is a compound obtained by blending and reacting at a molar ratio that is in excess with respect to the number of moles of hydrogen. The isocyanate group-containing urethane prepolymer (A) is a curing component.

  The content of the isocyanate group in the isocyanate group-containing urethane prepolymer (A) is not particularly limited, but the lower limit thereof is 0.10 from the viewpoint of the workability and adhesiveness of the resulting one-component curable composition. % By mass is preferable, 0.20% by mass is more preferable, and 0.40% by mass is particularly preferable. On the other hand, the upper limit value of the content of the isocyanate group in the isocyanate group-containing urethane prepolymer (A) is from the viewpoint of foaming at the time of curing of the one-component curable composition to be obtained and physical properties of the cured product. 0 mass% is preferable, 12.0 mass% is more preferable, and 10.0 mass% is particularly preferable.

  Further, the number of moles of isocyanate groups of the organic isocyanate compound relative to 1.0 mole of active hydrogen of the active hydrogen-containing compound is not particularly limited as long as the number of moles of isocyanate groups is excessive. From the viewpoint of workability and adhesiveness of the curable composition, 1.5 mol is preferable, 2.0 mol is more preferable, 3.0 mol is more preferable, and 4.0 mol is particularly preferable. On the other hand, the upper limit thereof is preferably 8.0 moles, more preferably 6.0 moles, more preferably 5.0 moles, from the viewpoint of foaming upon curing of the obtained one-component curable composition and physical properties of the cured product. Is particularly preferred.

Organic isocyanate compound (a)
The organic isocyanate compound (a) is not particularly limited, and an organic polyisocyanate may be mentioned, and an organic monoisocyanate may be mentioned as an isocyanate group-containing urethane prepolymer (A) modification which may be used if necessary. Be Examples of the organic polyisocyanate include aromatic polyisocyanates in which an isocyanate group is bonded to an aromatic hydrocarbon, and aliphatic polyisocyanates in which an isocyanate group is bonded to an aliphatic hydrocarbon.

  As aromatic polyisocyanates, diphenylmethane diisocyanates (MDIs) such as 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate; toluene diisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDIs); phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate and the like can be mentioned.

  Aliphatic polyisocyanates such as xylylene diisocyanate; aliphatic polyisocyanates such as propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate and pentamethylene diisocyanate; cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate), isophorone diisocyanate Etc. can be mentioned.

  Further, carbodiimide-modified products, biuret-modified products, allophanate-modified products, dimers, trimers, polymethylene polyphenyl polyisocyanates (crude MDI or polymeric MDI) and the like of these diisocyanates can also be mentioned. These may be used alone or in combination of two or more. Among these, with respect to the cured product of the one-component curable composition of the present invention, while the transparency is further improved, the generation of defects such as cracking, discoloration and chalking is prevented over a long period to further improve the weatherability. Furthermore, from the viewpoint of imparting durability, alicyclic polyisocyanates and araliphatic polyisocyanates are preferable, alicyclic polyisocyanates are more preferable, and isophorone diisocyanate is particularly preferable.

  The organic monoisocyanate used to modify the isocyanate group-containing urethane prepolymer (A) is not particularly limited, and examples thereof include aliphatic mono-isocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate and n-octadecyl monoisocyanate. And isocyanates. These may be used alone or in combination of two or more.

Active hydrogen-containing compound (b)
As the active hydrogen-containing compound (b), a compound (b-) having an active hydrogen-containing (meth) acrylic polymer (b-1), at least one active hydrogen and at least one photocurable ethylenically unsaturated group 2) Polyol having a number average molecular weight of 1,000 or more (hereinafter sometimes referred to as "polymeric polyol") (b-3), low molecular polyol, amino alcohol, polyamine and the like. Among these, in the one-component curable composition of the present invention, as the active hydrogen-containing compound (b), an active hydrogen-containing (meth) acrylic polymer (b-1), at least one active hydrogen and at least one light It is preferable to use a compound containing a curable ethylenically unsaturated group (b-2) and a polyol having a number average molecular weight of 1000 or more (polyol of high molecular weight) (b-3).

  At least a part of the active hydrogen-containing compound (b) constituting the isocyanate group-containing urethane prepolymer (A), an active hydrogen-containing (meth) acrylic polymer (b-1), at least one active hydrogen and at least one An isocyanate group-containing urethane prepolymer (A) by using a compound (b-2) having one photocurable ethylenic unsaturated group and a polyol (b-3) having a number average molecular weight of 1000 or more in combination Weather resistance can be further improved. In addition, in the one-component curable composition in which a compound (C) that generates an active hydrogen-containing functional group by hydrolysis with the below-described moisture to produce an active hydrogen-containing functional group is optionally added to the isocyanate group-containing urethane prepolymer (A). The rubber composition can be rapidly cured without deteriorating the workability and without foaming, and can impart excellent rubber physical properties. Furthermore, the cured product of the one-component curable composition of the present invention has excellent transparency and weatherability, and can suppress surrounding contamination over a long period of time without impairing the aesthetic appearance of the building.

Active hydrogen-containing (meth) acrylic polymer (b-1)
Examples of the active hydrogen-containing (meth) acrylic polymer (b-1) include poly (meth) acrylic polyols. The poly (meth) acrylic polyol comprises an ethylenically unsaturated compound containing at least a hydroxyl group-containing (meth) acrylic monomer, in the presence or absence of a polymerization initiator, and in the presence or absence of a solvent. The molecular weight of the reaction product is obtained by continuous high temperature polymerization reaction, preferably at 150 to 350 ° C., more preferably at 210 to 250 ° C., by a known radical polymerization method such as batch system or continuous polymerization. It is preferable in that the distribution is narrow and the viscosity is low.

  The poly (meth) acrylic polyol may be one obtained by polymerizing one kind of hydroxyl group-containing (meth) acrylic monomer, and may be obtained by copolymerizing two or more kinds of hydroxyl group-containing (meth) acrylic monomer And may be obtained by copolymerizing one or more hydroxyl group-containing (meth) acrylic monomers and an ethylenically unsaturated compound other than hydroxyl group-containing (meth) acrylic monomers It may be something. Among these, it is easy to adjust the hydroxyl content of the poly (meth) acrylic polyol and it is easy to select the physical properties of the cured product, and one or two of the hydroxyl group-containing (meth) acrylic monomers What is obtained by copolymerizing one or more species of species and one or more ethylenically unsaturated compounds other than hydroxyl group-containing (meth) acrylic monomers is preferable. Among these, one or two or more of hydroxyl group-containing (meth) acrylic monomers having 9 or less carbon atoms and one or two or more hydroxyl group-containing (meth) acrylic monomers having 10 or more carbon atoms Those obtained by copolymerizing 50% by mass or more in total of one or more species of an ethylenically unsaturated compound other than a hydroxyl group-containing (meth) acrylic monomer with 50% by mass or less More preferably, one or more types of hydroxyl group-containing (meth) acrylic monomers having 9 or less carbon atoms and one or more types of hydroxyl group-containing (meth) acrylic monomers having 10 or more carbon atoms Particularly preferred are those obtained by copolymerizing 70% by mass or more in total and 30% by mass or less of one or more ethylenically unsaturated compounds other than hydroxyl group-containing (meth) acrylic monomers.

  At the time of the copolymerization, one or two or more kinds of hydroxyl group-containing (meth) acrylic monomers are used, and the average number of hydroxyl functional groups is 1.0 to 10 per molecule of poly (meth) acrylic polyol. It is preferable to use it as such, and it is particularly preferable to use 1.2 to 3 pieces. When the average number of hydroxyl functional groups exceeds 10, the physical properties after curing may be so hard that sufficient rubbery elasticity may not be obtained.

  Moreover, the number average molecular weight of polystyrene conversion by gel permeation chromatography (GPC) of poly (meth) acryl-type polyol is not specifically limited, However, 1000-30000 are preferable and 1000-15000 are especially preferable. The Tg of the poly (meth) acrylic polyol is not particularly limited, but is preferably 0 ° C. or less, more preferably −70 to −20 ° C., and particularly preferably −70 to −30 ° C. The viscosity at 25 ° C. of the poly (meth) acrylic polyol is not particularly limited, but 100,000 mPa · s or less is preferable, and 50,000 mPa · s or less is particularly preferable. When the viscosity of the poly (meth) acrylic polyol has a number average molecular weight of 30,000, a Tg of 0 ° C., and a viscosity at 25 ° C. of more than 100,000 mPa · s, the workability at the time of application may decrease.

  The content of the active hydrogen-containing (meth) acrylic polymer in the active hydrogen-containing compound is not particularly limited, but the weatherability and transparency of the one-component curable composition containing the isocyanate group-containing urethane prepolymer (A) From the viewpoint of further improving the properties and rubber physical properties, 1.0% by mass or more and 7.0% by mass or less is preferable, and 2.0% by mass or more and 6.0% by mass or less is particularly preferable.

Compound (b-2) having at least one active hydrogen and at least one photocurable ethylenically unsaturated group
The compound (b-2) having at least one active hydrogen and at least one photocurable ethylenically unsaturated group has one or more active hydrogens that react with the isocyanate group of the isocyanate group-containing urethane prepolymer (A). And a compound having one or more photocurable ethylenically unsaturated groups.

  As said active hydrogen, a hydroxyl group, a primary amino group, a secondary amino group, a carboxyl group, a mercapto group etc. are mentioned, for example. Among these, a hydroxyl group is preferable from the viewpoint of easy reaction with the isocyanate group of the isocyanate group-containing urethane prepolymer and a relatively small increase in viscosity. As said photocurable ethylenic unsaturated group, a vinyl group, vinylene group, cinnamoyl group, acryloyl group, methacryloyl group etc. are mentioned, for example. Among these, an acryloyl group and a methacryloyl group are preferable in that they are polymerized in a relatively short time by exposure to light to form a film having excellent weather resistance.

  Examples of compounds having one or more hydroxyl groups as active hydrogen groups and one or more acryloyl and / or methacryloyl groups as photocurable ethylenic unsaturated groups include, for example, "ALONIX" series manufactured by Toagosei Co., Ltd. And “KAYARAD” series manufactured by Nippon Kayaku Co., Ltd., “epoxy ester” series manufactured by Kyoeisha Chemical Co., Ltd., and the like.

  Although the content of the compound having at least one active hydrogen and at least one photocurable ethylenic unsaturated group in the active hydrogen-containing compound is not particularly limited, it contains an isocyanate group-containing urethane prepolymer (A) From the point of further improving the weather resistance, transparency and rubber physical properties of the one-component curable composition, 1.0 mass% or more and 7.0 mass% or less is preferable, and 2.0 mass% or more and 6.0 mass% or less Is particularly preferred.

Polyol having a number average molecular weight of 1000 or more (b-3)
As a polyol (polymeric polyol) having a number average molecular weight of 1000 or more (b-3), for example, polyester-based polyol, polycarbonate polyol, polyoxyalkylene-based polyol, hydrocarbon-based polyol, animal and vegetable-based polyol, copolyol thereof, etc. It can be mentioned. The polyol (b-3) having a number average molecular weight of 1,000 or more is an active hydrogen-containing (meth) acrylic polymer (b-1) and at least one active hydrogen and at least one photocurable ethylenically unsaturated group. It means high molecular polyols other than the compound (b-2) which has

  In the present specification, high molecular weight polyols and high molecular weight monools mean polyols and monools having a number average molecular weight of 1,000 or more in terms of polystyrene conversion by gel permeation chromatography (GPC), respectively. The low molecular weight monol and the low molecular weight amino alcohol mean polyols, monools and amino alcohols each having a polystyrene-reduced number average molecular weight of less than 1000 by gel permeation chromatography (GPC).

  When the number average molecular weight of the high molecular weight polyol is 1,000 or more, it is possible to obtain more excellent rubber elasticity after curing. The lower limit value of the number average molecular weight of the high molecular weight polyol is preferably 1,500, more preferably 2,000, from the viewpoint of further improving the rubber elasticity and obtaining excellent adhesion performance. On the other hand, the upper limit thereof is not particularly limited, but, for example, from the viewpoint of preventing the viscosity increase of the isocyanate group-containing urethane prepolymer (A) and obtaining excellent workability, 100000 is preferable, 30000 is more preferable, and 20000 Is particularly preferred.

  Examples of polyester-based polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalene dicarboxylic acid, Polycarboxylic acids such as trimellitic acid; alkyl ester compounds such as methyl esters and ethyl esters of these polycarboxylic acids; One or more kinds of acid anhydrides of these polycarboxylic acids such as 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- Cutandiol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, low molecular weight polyol such as trimethylolpropane, glycerin, pentaerythritol, etc .; Low molecular weight polyamines such as butylene diamine, hexamethylene diamine, xylylene diamine, isophorone diamine (polyamines with polystyrene-equivalent number average molecular weight less than 1000 by GPC); at least one of low molecular weight amino alcohols such as monoethanolamine and diethanolamine And polyester polyols, polyester amide polyols and the like obtained by the dehydration condensation reaction with In addition, lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using a low molecular weight polyol and a low molecular weight amino alcohol as an initiator.

  As polycarbonate polyol, for example, dehydrochlorination reaction of low molecular weight polyol used for synthesis of the above-mentioned polyester polyol and phosgene, or transesterification reaction of the above low molecular weight polyol and diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate etc. What is obtained etc. are mentioned.

  Examples of polyoxyalkylene-based polyols include low-molecular-weight polyols used in the synthesis of the above-mentioned polyester polyols, low-molecular-weight aminoalcohols, polycarboxylic acids, and low-molecular-weight saccharides such as sorbitol, mannitol, sucrose (sucrose) and glucose. (Polystyrene-equivalent number average molecular weight by GPC is less than 1000) Low molecular weight polyhydric alcohol, bisphenol A, bisphenol F etc. (Polystyrene-equivalent number average molecular weight by GPC is less than 1000) One or more polyhydric phenols as initiator Ring-opening addition polymerization or copolymerization (hereinafter, "polymerization or copolymerization" may be referred to as "co-polymerization"), one or more kinds of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran Ren-based polyols, polyoxypropylene polyols, polyoxybutylene polyols, polyoxytetramethylene polyols, poly - (oxyethylene) - (oxypropylene) -, such as a random or block copolymer based polyol. Moreover, as a polyoxyalkylene type polyol, the polyester ether polyol which used the said polyester polyol and polycarbonate polyol as an initiator, a polycarbonate ether polyol etc. are mentioned, for example. Furthermore, the polyol which made the said low molecular weight polyol and organic isocyanate react by excess amount of hydroxyl groups with respect to an isocyanate group is mentioned, for example.

  The number of alcoholic hydroxyl groups in the polyoxyalkylene polyol is not particularly limited, but an average of more than 2 per molecule is preferable, an average of more than 2 per one molecule is more preferable, and an average of more than 2 per molecule is more preferable Three is more preferred. Among these, polyoxyalkylene type diols, polyoxyalkylene type triols, and mixtures of polyoxyalkylene type diols and polyoxyalkylene type triols are particularly preferable in view of excellent adhesion performance after curing and rubber elasticity.

  As a catalyst used at the time of preparation of a polyoxyalkylene type polyol, for example, cesium alkoxide such as cesium hydride, cesium methoxide, cesium ethoxide, cesium type compounds such as cesium hydroxide, diethyl zinc, iron chloride, metal porphyrin, And phosphazenium compounds, glyme complexes of zinc hexacyanocobaltate and complex metal cyanide complexes such as diglyme complexes.

  In addition, as necessary, for modifying the isocyanate group-containing urethane prepolymer (A), cyclic ether compounds such as propylene oxide described above are used with a low molecular weight monoalcohol such as methyl alcohol, ethyl alcohol and propyl alcohol as an initiator. It is also possible to use polyoxyalkylene monools such as ring-opening addition (co) polymerized polyoxypropylene monools.

  In addition, "system", such as polyoxyalkylene type polyol and polyoxyalkylene type monool, means that 50 mass% or more of the part except the hydroxyl group in 1 mol of molecules is comprised by polyoxyalkylene. Do. Thus, the remainder may be modified with other structures such as esters, urethanes, polycarbonates, polyamides, poly (meth) acrylates, polyolefins and the like. The portion composed of polyoxyalkylene is not particularly limited as long as it is 50% by mass or more, but 80% by mass or more is preferable, 90% by mass or more is more preferable, and 95% by mass or more is particularly preferable.

  Examples of hydrocarbon-based polyols include polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; polyalkylene polyols such as hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol; halogenated poly such as chlorinated polypropylene polyol and chlorinated polyethylene polyol Alkylene polyol etc. are mentioned.

  As an animal and vegetable type polyol, a castor oil type diol etc. are mentioned, for example. Moreover, as the chain extender, for example, in addition to the low molecular weight polyol and low molecular weight amino alcohol used for the synthesis of the above-mentioned polyester-based polyol, it is the above-mentioned polyoxyalkylene-based polyol and having number average molecular weight of less than 1000 Can be mentioned.

  The various polymer polyols described above may be used alone or in combination of two or more.

  The total degree of unsaturation of the polymer polyol is not particularly limited, but is preferably 0.1 meq / g or less, more preferably 0.07 meq / g or less, and particularly preferably 0.04 meq / g or less. Also, the molecular weight distribution of the polymer polyol [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) in terms of polystyrene by GPC = Mw / Mn] is not particularly limited, but the isocyanate group-containing urethane prepolymer (A 1.0-1.6 are preferable, and 1.0-1.3 are especially preferable from the point which reduces the viscosity of 1.) and the rubber elasticity after hardening improves more.

  Among the above-mentioned high molecular weight polyols, polyoxyalkylene type polyols are preferable from the viewpoint of rubber elasticity and adhesion performance, and among these, polyoxypropylene type polyols are particularly preferable.

  The content of the high molecular weight polyol in the active hydrogen-containing compound is not particularly limited, but the weatherability, transparency and rubber properties of the one-component curable composition containing the isocyanate group-containing urethane prepolymer (A) are further improved. From the point of making it do, 30 mass% or more and 70 mass% or less are preferable, and 40 mass% or more and 60 mass% or less are especially preferable.

  In the isocyanate group-containing urethane prepolymer (A) to be blended in the one-component curable composition of the present invention, the component (b-1), the component (b-2) and the component (b) can be used as the active hydrogen-containing compound (b) In addition to the component b-3), if necessary, a polyol having a number average molecular weight of less than 1000 (low molecular weight polyol), an amino alcohol, a polyamine or the like may be used.

  The low molecular weight polyol includes the low molecular weight polyhydric alcohol having a number average molecular weight of less than 1000 mentioned as a raw material for producing the polyester polyol.

  Examples of amino alcohol include monoethanolamine, diethanolamine, N-methyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine and the like.

  Examples of the polyamine include high-molecular weight polyamines such as polyoxyalkylene polyamines in which the terminal of a polyoxyalkylene type polyol has an amino group at a number average molecular weight of 1000 or more, such as terminal diaminoation of polypropylene glycol. Examples of the polyamine further include low molecular weight polyamines having a number average molecular weight of less than 500, such as ethylene diamine, hexamethylene diamine, isophorone diamine, diaminophenyl methane, diethylene triamine and the like.

  The isocyanate group-containing urethane prepolymer (A) used in the present invention includes zinc such as stannous octylate and tin octylate, tin, lead, zirconium, metal such as bismuth, cobalt, manganese, iron and octylic acid, Metal salts with organic acids such as octenoic acid and naphthenic acid (metal organic acid salts), dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, metals such as EXCESTARC-501 (manufactured by AGC Co., Ltd.) which is a tin-based chelate compound Well-known urethanization catalysts can be used such as chelate compounds, organic metal compounds such as dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine, triethylamine, tri-n-butylamine and salts thereof. Among these urethanization catalysts, metal organic acid salts and organic metal compounds are preferable. Furthermore, known organic catalysts can also be used.

  The production method of the isocyanate group-containing urethane prepolymer (A) is not particularly limited, and a batch feeding reaction method, a multi-step feeding reaction method, etc. can be used, and for example, it is active in a glass or stainless steel reaction vessel. The hydrogen-containing compound (b) and the organic isocyanate compound (a) are charged, and if necessary, a reaction catalyst and an organic solvent are added, and the reaction is carried out with stirring at 50 to 120 ° C. At this time, since the isocyanate group may react with moisture to thicken the obtained isocyanate group-containing urethane prepolymer (A), if necessary, it blocks moisture such as nitrogen gas substitution or under nitrogen gas flow. The reaction may be carried out in the state of

Thixotropic agent (B)
The thixotropic agent (B) imparts thixotropy to the one-component curable composition of the present invention to fill the one-component curable composition on a vertical surface such as a vent cap or an exterior material of a building. It is used to prevent slumping when applied. The thixotropic agent (B) is a very important component when the one-part curable composition is used as a sealing material for buildings.

  As the thixotropic agent (B), for example, calcium carbonate surface-treated with an organic acid compound, hydrophilic fine powder silica, hydrophilic fine powder silica, monomethyltrichlorosilane, dimethyldichlorosilane, ureylene Inorganic based thixotropic agents such as surface-treated fine powder silica treated with a group-containing organic group and a hydrolyzable silyl group-containing compound, etc .; organic based thixotropic agents such as organic bentonite and fatty acid amide. These may be used alone or in combination of two or more.

  Examples of finely divided silica include natural silica obtained by pulverizing quartz, silica sand, diatomaceous earth and the like into fine powder, wet silica such as precipitated silica, and synthetic silica such as dry silica such as fumed silica, etc. Be

  In the one-component curable composition of the present invention, the haze value (ASTM D1003-97) of the cured product of the one-component curable composition is 40% or less, that is, from the viewpoint of improving the transparency, Hydrophilic powdery silica, surface-treated powdery silica and fatty acid amide are preferable, and surface-treated powdery silica and fatty acid from the viewpoint that stable thixotropy can be maintained even in the presence of the curing catalyst of the one-component curable composition. Amide is particularly preferred.

  The compounding amount of the thixotropic agent (B) is not particularly limited with respect to 100 parts by mass (solid content) of the isocyanate group-containing urethane prepolymer (A), but the lower limit thereof is 0. 5 parts by weight are preferred, 2.5 parts by weight are particularly preferred. On the other hand, the upper limit thereof is preferably 20.0 parts by mass, particularly preferably 12.0 parts by mass, from the viewpoint of the workability of the one-component curable composition.

Compound (C) which is hydrolyzed with moisture to form an active hydrogen-containing functional group
In the one-component curable composition of the present invention, if necessary, a compound (C) which is hydrolyzed with moisture to generate an active hydrogen-containing functional group may be further blended. Examples of the compound (C) which is hydrolyzed by moisture to form an active hydrogen-containing functional group include ketimine compounds, enamine compounds, and the like which are hydrolyzed by moisture to form a primary and / or secondary amine. The aldimine compound, a compound having an oxazolidine ring which is hydrolyzed by moisture to form a hydroxyl group and an amino group, and a silicate compound which can be hydrolyzed by moisture to form a polyol can be mentioned. Among these, compounds having an oxazolidine ring are preferable because they are excellent in the storage stability of the one-component curable composition and excellent in the non-foaming property and curability by the reduction of the gas generation amount at the time of curing.

  The compound having an oxazolidine ring is a compound having one or more, preferably 2 to 6 oxazolidine rings in a molecule, which is a saturated 5-membered heterocyclic ring containing an oxygen atom and a nitrogen atom. The compound having an oxazolidine ring reacts with moisture (moisture) in the atmosphere and the like to undergo hydrolysis, whereby the oxazolidine ring forms (regenerates) a secondary amino group and an alcoholic hydroxyl group, whereby an isocyanate group-containing urethane pre It functions as a latent curing agent for the polymer (A).

  When the isocyanate group of the isocyanate group-containing urethane prepolymer (A) reacts with moisture (moisture) such as in the atmosphere, it forms a urea bond and cures, but carbon dioxide gas is also generated at this time, and the cured product is carbon dioxide Air bubbles are generated to cause defects such as deterioration of appearance, breakage of cured product, and reduction of adhesion. However, when a mixture of an isocyanate group-containing urethane prepolymer (A) and a compound having an oxazolidine ring is exposed to water, the oxazolidine ring of the compound having an oxazolidine ring is a water before the water and the isocyanate group react. The compound is hydrolyzed by the reaction to form active hydrogen (in the case of a compound having an oxazolidine ring, a secondary amino group and an alcoholic hydroxyl group). When the generated active hydrogen reacts with the isocyanate group and cures, carbon dioxide gas is not generated, so that foaming of the one-component curable composition of the present invention due to carbon dioxide gas can be prevented.

  Also, in the case of an isocyanate group-containing urethane prepolymer (A) using isophorone diisocyanate as the organic isocyanate compound (a), when reacting only with water (moisture), the curing rate is extremely delayed; By using a compound having an oxazolidine ring as the compound (C) that hydrolyzes to form an active hydrogen-containing functional group, a secondary amino group formed by the reaction of a compound having an oxazolidine ring and water (moisture) The reaction with the isophorone diisocyanate-derived isocyanate group also has the effect of being able to accelerate the curing rate since the reaction rate is higher than the reaction with water (moisture).

  Examples of the compound having an oxazolidine ring include a urethane bond-containing oxazolidine compound which is a reaction product of a hydroxyl group of a compound having a hydroxyl group and an oxazolidine ring and an isocyanate group of an organic isocyanate compound, and a hydroxyl group and a carbonic acid of a compound having a hydroxyl group and an oxazolidine ring. The ester bond containing oxazolidine compound which is a reaction product with the carboxyl group of an acid compound, oxazolidine silyl ether, carbonate group containing oxazolidine etc. are mentioned. Among these, urethane bond-containing oxazolidine compounds are preferable in terms of ease of production and low viscosity.

  As the urethane bond-containing oxazolidine compound, for example, the hydroxyl group of the compound having a hydroxyl group and an oxazolidine ring and the isocyanate group of the organic isocyanate compound have an isocyanate group / hydroxyl group molar ratio of 0.9 to 1.2 / 1.0. The compound having a hydroxyl group and an oxazolidine ring and an organic isocyanate compound are blended so as to be in the range of preferably 0.95 to 1.05 / 1.0, and an organic solvent is added if necessary, What is obtained by reacting at a temperature of ° C. may be mentioned.

  As an organic isocyanate compound used for the synthesis of a urethane bond-containing oxazolidine compound, an aromatic polyisocyanate having an isocyanate group bonded to an aromatic hydrocarbon, an aromatic ring having an isocyanate group bonded to an aliphatic hydrocarbon group Aromatic aliphatic polyisocyanates, aliphatic polyisocyanates consisting only of isocyanate groups and aliphatic hydrocarbon groups, and the like.

  As aromatic polyisocyanate, diphenylmethane diisocyanates (MDIs) such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, or a mixture thereof; 2,4-toluene diisocyanate, 2,6-toluene Toluene diisocyanates (TDIs) such as diisocyanates or mixtures thereof; other aromatic polyisocyanates include phenylene diisocyanate, diphenyl diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate and the like.

  The aromatic aliphatic polyisocyanate may, for example, be xylylene diisocyanate.

  Aliphatic polyisocyanates include aliphatic polyisocyanates such as hexamethylene diisocyanate, pentamethylene diisocyanate, propylene diisocyanate and butylene diisocyanate; and alicyclic polyisocyanates such as cyclohexane diisocyanate, methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. .

  Further, carbodiimide-modified products, biuret-modified products, allophanate-modified products, dimers, trimers, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI) and the like of the above-mentioned various polyisocyanates can also be mentioned. These can be used alone or in combination of two or more.

  Among these, aliphatic polyisocyanates are preferred and hexamethylene diisocyanate is particularly preferred in that the crystallinity of the urethane bond-containing oxazolidine compound can be lowered and the workability of the resulting one-component curable composition can be made favorable. .

  As a compound which has a hydroxyl group and an oxazolidine ring, N-hydroxyalkyl oxazolidine obtained by the dehydration condensation reaction of the secondary amino group of an alkanolamine, and the carbonyl group of a ketone compound or an aldehyde compound is mentioned, for example.

  Examples of alkanolamines include diethanolamine, dipropanolamine, N- (2-hydroxyethyl) -N- (2-hydroxypropyl) amine and the like. Examples of the ketone compound include acetone, diethyl ketone, isopropyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, isobutyl ketone, methyl t-butyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and the like. . As the aldehyde compound, for example, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, 2-methylbutyraldehyde, n-hexylaldehyde, 2-methylpentyl aldehyde, n-octyl aldehyde, Aliphatic aldehyde compounds such as 3,5,5-trimethylhexyl aldehyde; and aromatic aldehyde compounds such as benzaldehyde, methyl benzaldehyde, trimethyl benzaldehyde, ethyl benzaldehyde, isopropyl benzaldehyde, isobutyl benzaldehyde, methoxy benzaldehyde, dimethoxy benzaldehyde, trimethoxy benzaldehyde and the like Etc.

  Among these, diethanolamine is preferable as the alkanolamine in that it is excellent in the ease of production of a compound having a hydroxyl group and an oxazolidine ring and the antifoaming property when the resulting one-component curable composition is cured. Among the compound and the aldehyde compound, an aldehyde compound is preferable, and among the aldehyde compounds, isobutyraldehyde, 2-methylpentyl aldehyde and benzaldehyde are preferable.

  Specific examples of the compound having a hydroxyl group and an oxazolidine ring include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 2- (1-methylbutyl) -3- (2-hydroxyethyl) oxazolidine, 2-phenyl-3 -(2- hydroxyethyl) oxazolidine etc. are mentioned.

  As a method of synthesizing a compound having a hydroxyl group and an oxazolidine ring, for example, the carbonyl group of the ketone compound or the aldehyde compound is 1.0 mol or more, preferably 1.0 to 1.0 mol of the secondary amino group of the alkanolamine. A method of using 1.5 mol, particularly preferably 1.0 to 1.2 mol, heating and refluxing in a solvent such as toluene and xylene, and conducting a dehydration condensation reaction while removing by-produced water is mentioned. .

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

  Examples of oxazolidine silyl ethers include compounds having a hydroxyl group and an oxazolidine ring as described above, trimethoxysilane, tetramethoxysilane, triethoxysilane, dimethoxydimethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyl It can be obtained by a dealcoholization reaction with an alkoxysilane such as trimethoxysilane or 3-glycidoxypropyltriethoxysilane.

  The carbonate group-containing oxazolidine can be obtained by reacting the above-described 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.

  The active hydrogen (oxazolidine ring formed by hydrolysis of the compound (C) which is hydrolyzed with moisture to form an active hydrogen-containing functional group with respect to 1.0 mol of isocyanate group-containing urethane prepolymer (A) The total amount of the secondary amino group and the alcoholic hydroxyl group is not particularly limited in the compound having one, but the lower limit thereof is preferably 0.1 mol from the viewpoint of more reliably preventing the generation of carbon dioxide gas, 0.2 mol Is more preferable, and 0.3 mol is particularly preferable. On the other hand, the upper limit thereof is preferably 1.5 moles, particularly preferably 1.0 moles, from the viewpoint of the physical properties of the cured product.

  Moreover, you may add the hydrolysis catalyst of the compound (C) (for example, compound which has an oxazolidine ring) which hydrolyzes with moisture and produces | generates an active hydrogen containing functional group as needed. As said hydrolysis catalyst, the hydrolysis catalyst of an oxazolidine ring can be mentioned, for example. The hydrolysis catalyst of the oxazolidine ring promotes the reaction (hydrolysis) of the compound having the oxazolidine ring with moisture to generate (regenerate) active hydrogen, or the generated (regenerate) active hydrogen and the urethane group containing isocyanate group. The reaction of the polymer (A) with the isocyanate group can be promoted to improve the curing rate of the one-component curable composition of the present invention. Examples of the hydrolysis catalyst of the oxazolidine ring include organic metal catalysts, organic carboxylic acid catalysts, acid anhydrides thereof, p-toluenesulfonyl isocyanate, a reaction product of p-toluenesulfonyl isocyanate and water, organic phosphoric acid ester compounds And the like. These can be used alone or in combination of two or more.

  Although the compounding quantity of the hydrolysis catalyst of an oxazolidine ring is not specifically limited, 0.001-10 mass parts is preferable with respect to 100 mass parts (solid content) of an isocyanate group containing urethane prepolymer (A), and 0.1-0.1 mass part is preferable. 5 parts by weight is particularly preferred. If the amount is less than 0.001 part by mass, the effect of promoting the hydrolysis of the compound having an oxazolidine ring is not sufficient. If the amount exceeds 10 parts by mass, the storage stability of the one-component curable composition may be affected.

  In the one-component curable composition of the present invention, additives such as a filler, an adhesion improver, a storage stability improver (dehydrating agent), and a colorant can be further added, if necessary.

  As the filler, mica, kaolin, zeolite, graphite, clay, clay, talc, slate powder, anhydrous silicic acid, aluminum powder, zinc powder, inorganic powdery filler such as magnesium carbonate, alumina, magnesium oxide, etc .; glass fiber, Fibrous fillers such as carbon fibers; inorganic fillers such as inorganic balloon-like fillers such as glass balloons, shirasu balloons and ceramic balloons; fillers obtained by treating the surface of the above inorganic fillers with organic substances such as fatty acids; Organic powdery fillers such as wood flour, walnut flour, rice husk flour, pulp flour, cotton chips, rubber powder, fine powder of thermoplastic or thermosetting resin, polyethylene powder, etc .; Polyethylene hollow body, Saran microballoon, etc. In addition to organic fillers such as organic balloon-like fillers, magnesium hydroxide and aluminum hydroxide And flame retardant fillers such um can also be mentioned. These may be used alone or in combination of two or more. The particle size of the filler is not particularly limited, but is preferably 0.01 to 1000 μm from the viewpoint of coatability.

  Examples of the adhesion improver include a coupling agent. As a coupling agent, coupling agents, such as a silane type, an aluminum type, zirco aluminate type | system | group, etc. or its partial hydrolytic condensate can be mentioned. Among these, silane coupling agents or partial hydrolytic condensates thereof are preferable from the viewpoint of adhesion performance.

  Specific examples of the silane coupling agent include, for example, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc. Molecular weight 500 or less having alkoxysilyl group such as Preferably mention may be made of 400 following compounds, one or more compounds having a molecular weight of 200 to 3000 with two or more partial hydrolysis condensate of the silane coupling agent. These may be used alone or in combination of two or more.

  As the storage stability improver, vinyltrimethoxysilane, calcium oxide, p-toluenesulfonyl isocyanate, etc., which react with the water present in the one-part curable composition, may be mentioned. These may be used alone or in combination of two or more. In addition, since it acts as a hardening accelerator when using the compound (C) which hydrolyzes with moisture and produces | generates an active hydrogen containing functional group as above-mentioned, it is especially preferable, as above-mentioned.

  Examples of the colorant include inorganic pigments such as titanium oxide, iron oxide and carbon black, and organic pigments such as copper phthalocyanine. These may be used alone or in combination of two or more.

  The compounding amounts of the various additives are selected so that the haze value of the cured product of the one-component curable composition is 40% or less.

  0-500 mass parts is preferable with respect to 100 mass parts of isocyanate group containing urethane prepolymers (A), and, as for the sum total of the compounding quantity of an adhesiveness improving agent and a storage stability improving agent, 5-300 mass parts is especially preferable.

  In the one-component curable composition of the present invention, the additives may be used alone or in combination of two or more.

  EXAMPLES Next, examples of the present invention will be described, but the present invention is not limited to these examples as long as the purpose of the present invention is not exceeded.

Synthesis of urethane bond-containing oxazolidine compound O-1 (compound (C) which is hydrolyzed with moisture to form an active hydrogen-containing functional group) Synthesis Example 1
While flowing nitrogen gas into a reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube, ester tube and heating / cooling device, 420 g of diethanolamine (molecular weight 105), 177 g of toluene and isobutyraldehyde (molecular weight 72.1) 317 g was charged, heated with stirring, and a reflux dehydration reaction was performed at 110 to 150 ° C. while removing by-produced water (71.9 g) out of the system. After distilling of water is not observed, the reaction product is further heated under reduced pressure (50 to 70 hPa) to remove toluene and unreacted isobutyraldehyde to obtain N-hydroxyethyl-2-isopropyloxazolidine as an intermediate reaction product. I got Then, 336 g of hexamethylene diisocyanate (molecular weight 168) is further added to 636 g of the obtained N-hydroxyethyl-2-isopropyloxazolidine, and the mixture is heated at 80 ° C. for 8 hours, and the measured NCO content by titration is 0.0 mass%. The reaction was terminated when it reached to obtain a urethane bond-containing oxazolidine compound O-1 (molecular weight 487) having two oxazolidine rings in the molecule. The obtained urethane bond-containing oxazolidine compound O-1 was liquid at normal temperature.

Preparation of one-component curable composition A-1 used in Example 1 A naphthenic solvent (Maruzen Petrochemicals) while flowing a nitrogen gas into a kneading / reaction vessel equipped with a stirring rod, a thermometer, a nitrogen seal pipe and a heating / cooling device. 55 g of SWACLEAN 150, manufactured by Co., Ltd., 330 g of polyoxypropylene diol (manufactured by AGC Co., Ltd., trade name: Exenol 3021, number average molecular weight 3300), active hydrogen-containing (meth) acrylic polymer (TOA SYNTHESIS) Made in Japan, trade name: ARUFON UH 2041, weight average molecular weight 2500) 140 g, a compound having at least one active hydrogen and at least one photocurable ethylenic unsaturated group (manufactured by Nippon Kayaku Co., Ltd., KAYARADR- Then, 25 g of a 167, average molecular weight 374) was charged and mixed with stirring. Then, 176.5 g of isophorone diisocyanate and 0.1 g of inorganic bismuth (Neosto Kasei Kogyo Co., Ltd., Neostan U-600) as a reaction catalyst were charged while stirring, and the mixture was heated and reacted at 70 to 75 ° C. for 1 hour. After cooling to room temperature, 15 g of a hindered phenolic antioxidant (manufactured by BASF Japan Ltd., IRGANOX 245), 15 g of a hindered amine light stabilizer (manufactured by ADEKA, Adekastab LA-63P), a polyvinyl methyl ether (Senca stock) 15 g of polyvinyl methyl ether-65 D, 66 g of hydrophobized finely powdered silica (Leosil MT-10, manufactured by Tokuyama Co., Ltd.) and 115 g of a urethane bond-containing oxazolidine compound O-1 are added, and 30 more until uniform The mixture was kneaded for a minute, further degassed under reduced pressure, packed in a container, and sealed to prepare a one-component curable composition A-1. The obtained one-component curable composition A-1 was prepared from No. 1 at 25 ° C. using a B-type rotational viscometer immediately after preparation. The viscosity at 20 revolutions per minute with a rotor of 6 was 90 to 140 Pa · s. Moreover, the obtained one-component curable composition A-1 was in the form of a colorless and transparent paste.

Preparation of One-Component Curable Composition A-2 Used in Example 2 In Example 1, 45 g of hydrocarbon solvent (Exsol D40, manufactured by EMG Marketing GK) and 250 g of polyoxypropylene diol instead of the naphthenic solvent 250 g of an active hydrogen-containing (meth) acrylic polymer (manufactured by Toagosei Co., Ltd., trade name: ARUFON UH 2000, weight-average), 250 g of polyoxypropylene triol (manufactured by AGC Co., Ltd., trade name: Exenol 4030, number average molecular weight 4000) Except using 160 g of molecular weight 4900), 13 g of a compound having at least one active hydrogen and at least one photocurable ethylenic unsaturated group, 95.3 g of isophorone diisocyanate and 66 g of a urethane bond-containing oxazolidine compound O-1 Similarly, one-part curing The composition A-2 was prepared. The obtained one-component curable composition A-2 was prepared from No. 1 at 25 ° C. using a B-type rotational viscometer immediately after preparation. The viscosity at 20 revolutions per minute with a rotor of 6 was 120 to 160 Pa · s. Moreover, the obtained one-component curable composition A-2 was in the form of a colorless and transparent paste.

  As a one-component curable composition of Comparative Example 1, commercially available sealing material-1: (Konishi Co., Ltd., modified silicone coke clear, one-component modified silicone system), a one-component curable composition of Comparative Example 2 Commercially available sealing material-2: (Cemedine Co., Ltd., Cemedine 8000 clear, one-component silicone system) was used.

Test Preparation of Sheet for Measurement A square frame is formed on a release paper using a square backer having a thickness of 3 mm, and the one-component curable composition prepared in Examples 1 and 2 and Comparative Examples 1 and 2 are contained in the frame. The commercial product used in Next, the excess one-part curable composition was removed with a spatula, and the surface was leveled to obtain a sheet which was aged for 7 days under an atmosphere of 23 ° C. and 50% RH.

Evaluation Item (1) Measurement of Haze The haze of the measurement sheet was measured according to Procedure D of ASTM D1003-97.
(2) Measurement of tensile properties Based on JIS K6251: 2010, a dumbbell-shaped No. 4 test piece was produced from a sheet for measurement. A tensile test (tensile speed 500 mm / min) is performed using a tensile tester (trade name STROGRAPH VG10-E, manufactured by Toyo Seiki Seisaku-sho, Ltd.) under an atmosphere of 23 ° C. using the obtained test piece, and cutting is performed. The tensile elongation Eb (%) and the tensile strength Tb (N / mm ² ) were measured.
(3) Measurement of Contamination As shown in FIG. 2, Example 1 in the shape shown in FIG. 1 using a square backer of 10 mm on the coated surface of siding (painted surface: white colored by Keimu Co., Ltd.) , And the commercial products used in Comparative Examples 1 and 2 were cast with a width of 10 mm and a height of 10 mm. After the placement, place in a room at 23 ° C and 50% relative humidity for 7 days, remove the backer and near the intersection where there is a lot of outdoor traffic, with the surface of the siding board facing the road, in the length direction The surface of the one-part curable composition and the surface of the lower siding plate of a commercial product after visual installation with a vertical position of 3 and a vertical position was visually observed to evaluate the contamination according to the following criteria.
○: There is no or very little clear contamination on the surface.
X: A large number of distinct contaminations are observed on the surface.
(4) Measurement of weather resistance A test piece is taken from the measurement sheet, and the exposure test method by "6.2 open frame carbon arc lamp" of JISA 1415: 2013 "Test method for exposure of polymer building materials with laboratory light source" According to the WS-A method of "the sunshine weather meter (Suga Test Instruments Co., Ltd. make, S80 type)", it tested. The test body was taken out for every irradiation for 1000 hours to 5000 hours, the surface was visually observed, and the weather resistance was evaluated by the following judgment criteria.
○: There are no or very few abnormalities such as clear cracks, discoloration, or chalking on the surface.
X: A large number of abnormalities such as clear cracks, discoloration, and chalking on the surface.

  The evaluation results are shown in Table 1 below and FIG.

  From Table 1 above, an active hydrogen-containing compound comprising an isocyanate group-containing urethane prepolymer which is a reaction product of isophorone diisocyanate and an active hydrogen-containing compound, a thixotropic agent, and a urethane bond-containing oxazolidine compound O-1 One-component type comprising an active hydrogen-containing (meth) acrylic polymer, a compound having at least one active hydrogen and at least one photocurable ethylenically unsaturated group, and a polyol having a number average molecular weight of 1000 or more In Examples 1 and 2 which are curable compositions, haze was reduced and excellent transparency was obtained. Furthermore, from Table 1 and FIG. 3, in Examples 1 and 2, both of the weather resistance and the stain resistance were excellent. In Examples 1 and 2, the tensile strength (Tb) was improved without impairing the tensile elongation (Eb) at the time of cutting, and the excellent durability was obtained.

  On the other hand, Comparative Example 1 which is a one-component type curable silicone-based one-component curable composition which is a commercially available sealing material, and Comparative Example 2 which is a one-component-type one-component silicone-based curable composition Even if it was transparent, haze increased and transparency was not obtained. In general, a sealing material which is a silicone-based one-component curable composition is superior in weatherability to a sealing material which is a urethane-based one-component-curable composition, and it is a silicone-based one. In Comparative Examples 1 and 2 in which the one-component curable composition is used, from Table 1 and FIG. 3, abnormalities such as discoloration, cracking, and choking occur, so that weather resistance can not be obtained, and tensile strength (Tb ) Was not obtained. In addition, in Comparative Example 2, no contamination resistance could be obtained.

  The one-component curable composition of the present invention has high transparency and weatherability, and can obtain a cured product that does not contaminate the surroundings for a long time without impairing the aesthetic appearance of the building appearance, and thus sealing of the building. It can be used as a material, for example, a sealing material for vent caps.

1 siding 2 one-part curable composition

Claims (13)

  A one-part curable composition comprising an isocyanate group-containing urethane prepolymer (A) and a thixotropic agent (B), the haze according to ASTM D1003-97 of the cured product of the one-part curable composition One-component curable composition having a value of 40% or less.   The one-component curable composition according to claim 1, further comprising a compound (C) which is hydrolyzed with moisture to form an active hydrogen-containing functional group. The isocyanate group-containing urethane prepolymer (A) is a reaction product of an organic isocyanate compound (a) and an active hydrogen-containing compound (b),
The active hydrogen-containing compound (b) is a compound having an active hydrogen-containing (meth) acrylic polymer (b-1) and at least one active hydrogen and at least one photocurable ethylenically unsaturated group (b) The one-component curable composition according to claim 1 or 2, which comprises -2) and a polyol (b-3) having a number average molecular weight of 1000 or more.   The active hydrogen-containing (meth) acrylic polymer (b-1) is contained in an amount of 1.0% by mass or more and 7.0% by mass or less in the active hydrogen-containing compound (b). One-component curable composition according to item 1.   1.0% by mass or more and 7.0% by mass or more of the compound (b-2) having the at least one active hydrogen and the at least one photocurable ethylenically unsaturated group in the active hydrogen-containing compound (b) The one-component curable composition according to any one of claims 1 to 4, which is contained below.   The one-component curable composition according to any one of claims 1 to 5, wherein the organic isocyanate compound (a) contains an alicyclic polyisocyanate compound.   The one-part curable composition according to any one of claims 1 to 6, wherein the thixotropic agent (B) contains finely powdered silica.   The one-component curable composition according to any one of claims 2 to 7, wherein the compound (C) which is hydrolyzed with moisture to form an active hydrogen-containing functional group is an oxazolidine compound.   The one-component curable composition according to any one of claims 1 to 8, wherein the isocyanate group-containing urethane prepolymer (A) has an isocyanate group of 0.10% by mass or more and 15% by mass or less.   The isocyanate group of the organic isocyanate compound (a) is 1.5 mol or more to 8.0 mol of the isocyanate group-containing urethane prepolymer (A) per 1.0 mol of active hydrogen of the active hydrogen-containing compound (b) The one-component curable composition according to any one of claims 1 to 9, which is a reaction product of a molar amount or less.   The said thixotropic property imparting agent (B) is 0.50 mass part or more and 20 mass parts or less with respect to the said isocyanate group containing urethane prepolymer (A) (solid content), The any one of Claim 1 thru | or 10 One-part curable composition.   The compound reacts with moisture of the compound (C) which is hydrolyzed with the moisture to generate an active hydrogen-containing functional group with respect to 1.0 mole of the isocyanate group of the isocyanate group-containing urethane prepolymer (A). The one-component curable composition according to any one of claims 1 to 11, wherein the active hydrogen of the active hydrogen-containing functional group is from 0.10 to 1.5 mol.   A cured product of the one-component curable composition according to any one of claims 1 to 12.