WO2007105258A1

WO2007105258A1 - Thixotropy-imparting agent, hardenable resin composition making use of the same and method of using the hardenable resin composition

Info

Publication number: WO2007105258A1
Application number: PCT/JP2006/304336
Authority: WO
Inventors: Kaoru Kawami; Kenji Shiota; Hiroyuki Hosoda; Kazunori Ishikawa; Misaki Yamamoto
Original assignee: The Yokohama Rubber Co., Ltd.
Priority date: 2006-03-07
Filing date: 2006-03-07
Publication date: 2007-09-20

Abstract

A thixotropy-imparting agent that even when added in a small amount as compared with those of conventional thixotropy-imparting agents, can impart satisfactory thixotropy to hardenable resin compositions. There is provided a thixotropy-imparting agent comprising a urethane-urea compound obtained by reacting a polyisocyanate with a diamine compound and hydroxy compound.

Description

Specification

Thixotropic agent, curable resin composition using the same, and method of using curable resin composition

Technical field

[0001] The present invention relates to a thixotropic agent, a curable resin composition using the same, and a method of using the curable resin composition.

Background art

[0002] Various curable resin compositions such as waterproofing materials, sealing materials, adhesives, paints and the like have been used in the fields of architecture and civil engineering. For example, as a waterproofing material, when applied to a horizontal surface, a low-viscosity curable resin composition is suitable because it is necessary to form a uniform-thickness coating film and finish the surface smoothly. Used. On the other hand, when it is constructed on an inclined surface such as a vertical surface, a curable resin composition having thixotropic properties is used to prevent dripping from the construction site. Therefore, conventionally, it was necessary to prepare separate water-proofing materials for the horizontal surface and the inclined surface.

On the other hand, a method is known in which a powder such as silica is added to a low-viscosity waterproofing material for horizontal surface, is given a thixotropic property to droop, and is used as a material for an inclined surface. However, when waterproofing materials are used outdoors, it is very difficult to weigh and add powder, especially lightweight ones such as silica, due to the effects of wind.

On the other hand, liquid additives have been proposed in order to solve the above-mentioned problems caused by wind. For example, a liquid wrinkle-modifying imparting agent using a polyether'ester-type polyvalent carboxylic acid can be mentioned, but those capable of imparting sufficient thixotropic activity have been strong.

[0003] By the way, in Patent Document 1, it is easy to manufacture, and various organic liquids can be gelled with a small amount of addition without polluting the environment, and it is homogeneous and is suitable for long-term storage and temperature changes. An organic liquid gelling agent, such as a diurea compound, which also comprises a specific diisocyanate and monoamine, for the purpose of high stability is described.

[0004] Patent Document 2 describes a thickening and viscosity adjusting agent for the purpose of exhibiting excellent thickening and thixotropic properties. Patent Document 1: Japanese Patent Application Laid-Open No. 2003-64346

Patent Document 2: JP 2002-69430 A

Disclosure of the invention

Problems to be solved by the invention

[0006] However, the gelling agent described in Patent Document 1 cannot exhibit sufficient thixotropy without sufficient gelling ability. Patent Document 1 describes that as a method of gelling an organic solvent, the gelling agent is added to the organic solvent and, if desired, heated to 80 to 180 ° C. and stirred until dissolved. Yes. In other words, since this gelling agent has two urea bonds and is therefore highly polar and powdery, it needs to be heated when uniformly dispersed in a curable resin composition such as a waterproof material. There are cases. Therefore, it was not practical to add this gelling agent during construction of the waterproof material as described above.

Further, Patent Document 2 describes the force that a solvent may be added. It is assumed that the thickening / viscosity modifier described in Patent Document 2 is used in water-based paint compositions and the like. Therefore, there is room for studying a solvent that is highly compatible with the curable resin composition used in the above-described waterproofing material and that can dissolve the thickening and viscosity modifier.

Accordingly, an object of the present invention is to provide a thixotropic agent that can impart sufficient thixotropy to a curable resin composition with a small amount of addition compared to conventional wrinkle modifiers. Another object of the present invention is to provide a thixotropic agent that has the above-described properties and is suitably used for outdoor use.

Another object of the present invention is to provide a curable resin composition using the thixotropic agent.

Means for solving the problem

[0008] As a result of intensive studies, the present inventor has obtained a conventional polyether ester by using a reaction product (urethane-urea compound) obtained by reacting a polyisocyanate with a diamine compound and a hydroxy compound. Compared to wrinkle modification imparting agents using type polycarboxylic acid

It has been found that it becomes a thixotropic agent capable of imparting sufficient thixotropic properties in a small amount. Furthermore, it was found that a urethane-urea compound obtained by reacting polyisocyanate, 1,4 xylylenediamine, and a specific hydroxy compound can give higher thixotropic properties. It was.

In addition, when the urethane-urea compound is dissolved in a specific polar solvent, it can be easily mixed with a curable resin composition that does not need to be heated, so that it can be suitably used for outdoor use. I found out. The present inventor completed the present invention based on these findings.

That is, the present invention provides the following (1) to (11).

(1) A thixotropic agent containing a urethane-urea compound obtained by reacting a polyisocyanate with a diamine compound and a hydroxy compound.

(2) The thixotropic agent according to (1) above, wherein the diamine compound is 1,4-xylylenediamine.

(3) The thixotropic agent according to (1) or (2) above, wherein the hydroxy compound contains a hydroxy compound having at least one ether bond.

(4) Hydroxy compounding power having at least one ether bond The wrinkle-modifying agent according to (3), which is ethylene glycol monoisopropyl ether.

(5) The thixotropic agent according to any one of (1) to (4) above, wherein the polyisocyanate is tolylene diisocyanate.

(6) The thixotropic agent according to (1), wherein the urethane-urea compound is a compound represented by the following formula (1).

[Chemical 1]

(In the formula, R ¹ is a residue obtained by removing two isocyanate groups from the polyisocyanate, and R ² is a hydrocarbon group having 1 to 22 carbon atoms which may have an ether bond. )

(7) In the above (6), R ² is a hydrocarbon group having 1 to 22 carbon atoms having an ether bond. The thixotropic agent described.

(8) The thixotropic agent according to (6) or (7) above, wherein R ¹ is a residue obtained by removing two isocyanate groups from tolylene diisocyanate.

(9) the urethane-urea compound,

At least one polar solvent selected from the group consisting of N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone and dimethylsulfoxide;

The thixotropic agent according to any one of (1) to (8) above, comprising

(10) at least one resin selected from the group consisting of urethane resin, modified silicone resin, polysulfide resin, silicone resin, polyisobutylene resin and epoxy resin;

The thixotropic agent according to any one of (1) to (9) above and

A curable resin composition containing

(11) When the curable resin composition described in (10) is used, the thixotropic agent described in any one of (1) to (9) above is excluded from the curable resin composition. A method for using a curable resin composition, wherein the thixotropic agent is added to the ingredients.

The invention's effect

The wrinkle modification imparting agent of the present invention can impart sufficient thixotropy with a small amount of addition compared with a wrinkle modification imparting agent using conventional polyether ester type polycarboxylic acid. In particular, when a specific urethane-urea compound is used, higher thixotropic properties can be imparted.

Moreover, the thixotropic agent of the present invention in which the thixotropic agent is dissolved in a specific polar solvent has the above-described properties, and can be suitably used for outdoor use.

In addition, since the curable resin composition of the present invention has thixotropic properties, it can also be used on inclined surfaces. In particular, according to the method of using the curable resin composition of the present invention, the construction site It is not necessary to prepare a curable resin composition having different viscosities even when the oil reaches a horizontal surface and an inclined surface.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The thixotropic agent of the present invention is a urethane-urea compound obtained by reacting a polyisocyanate with a diamine compound and a hydroxy compound (hereinafter also simply referred to as “urethane-urea compound (A)”). It contains.

[0012] The polyisocyanate used in the urethane-urea compound (A) is not particularly limited as long as it has two or more isocyanate groups, and a known polyisocyanate can be used. Specifically, for example, 2, 4 tolylene diisocyanate (2, 4-TDI), 2, 6 tolylene diisocyanate (2, 6-TDI), 4, 4'-diphenylmethane diiso Cyanate (4, 4 '— MDI), 2, 4' — dimethanemethane diisocyanate (2, 4 '— MDI), 1, 4 phenol diisocyanate, polymethylene polyphenylene poly Aromatics such as isocyanate, xylylene diisocyanate (XDI), 1,5 naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, tris (isocyanate phenol) thiophosphate Polyisocyanate; hexamethylene diisocyanate (HDI), norbornane disoocyanate methyl (NBDI), 1, 6, 11-undecane triisocyanate, 1, 3, 6 hexamethylene triiso Aliphatics such as cyanate and bicycloheptane triisocyanate Riisoshia sulfonate; isophorone iso Xia sulfonate (IPDI), H XDI (hydrogenated XDI)

6, H MDI (hydrogenated MDI

12

And alicyclic polyisocyanates such as carbocyclic imide-modified polyisocyanates of the above-mentioned polyisocyanates or trifunctional polyisocyanates such as these isocyanurate-modified polyisocyanates.

Further, an isocyanate compound having at least one isocyanate group having a large steric hindrance can also be used. Specific examples include TMXDI (diisocyanate compound) and saicene (triisocyanate compound) manufactured by Mitsui Cytec.

These may be used alone or in combination of two or more.

Among these, tolylene diisocyanate (TDI) is preferable from the viewpoint of imparting thixotropy and the stability of the resulting thixotropic agent itself. In view of these characteristics, 2,4-TDI having isocyanate groups having different reactivities is more preferable. Industrially, a mixture of 2,4—body 100%, or 2,4—body Z2,6—body = 85Z15 can be suitably used.

[0013] The diamine compound used in the urethane-urea compound (A) has 2 amino groups in one molecule. If it is a compound having one, it is not particularly limited. The amino group or imino group of the diamine compound reacts with the isocyanate group of the polyisocyanate to form a urea bond.

. Specifically, for example, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3 bisaminomethylcyclohexane, bis (4aminohexyl) methane, norbornene diamine. , 1,2 diaminocyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, 1,3 phenol-diamine, 1,4 phenol Examples include rangeamine, 1,3 xylylenediamine, 1,4 xylylenediamine, and the like. These may be used alone or in combination of two or more.

In particular, the use of 1,4 xylylenediamine, 1,4 phenylene diamine, 4,4'-diaminodiphenylmethane, which has an aromatic ring and has good symmetry, imparts higher wrinkle modification. Liked from the point that it will be possible.

[0014] The hydroxy compound used in the urethane-urea compound (A) is not particularly limited as long as it is a compound having at least one hydroxy group in one molecule, but has at least one ether bond in addition to the hydroxy group. It is also preferable to have a point power that is excellent in dispersibility in cocoa butter that has a large effect of imparting thixotropy. In particular, a hydroxy compound containing an isopropyl ether moiety is more preferable from the viewpoint of sterically suppressing hydrogen bonding and maintaining the stability of the resulting thixotropic agent itself. Specific examples of the hydroxy compound containing an isopropyl ether moiety include ethylene glycol monoisopropyl ether and diethylene glycol monoisopropyl ether. In particular, ethylene glycol monoisopropyl ether is preferable.

The hydroxy group of the hydroxy compound reacts with the isocyanate group of the polyisocyanate to form a urethane bond.

Specific examples of the hydroxy compound include methanol, ethanol, propanol, isopropanol, butanol, t-butanol (2-methyl-2-propanol), hexanol, 2-ethylhexanol, octanol, Dodecanol, octade cannole, allylic alcohol, ethylene glycol monomethyl ether, ethylene glycol mononomonoethylenoreethenore, ethyleneglycolenomonopropinoreethenore, ethyleneglycol Monoremonoisopropinoreethenole, ethyleneglycololebutenoleetenore, diethyleneglycololemonomethinoreatenore, diethyleneglycolenomonotinoreatenore, diethyleneglycolmonopropylether, diethyleneglycolmonoisopropylether, diethyleneglycol Mono-monobutyl ether, triethyleneglycol monomethinoate ethere, triethyleneglycol monobutinoleether, tetraethyleneglycol monomethyl ether ether, tetraethylene glycol monobutyl ether, dipropylene glycol butyrether, etc. Hydroxy compounds; dihydroxy compounds such as ethylene glycol, diethylene glycol, and triethylene glycol. These may be used alone or in combination of two or more.

[0016] Above all, from the viewpoint of increasing the effect of imparting thixotropy, the residue excluding the hydroxy group may have an ether bond, and may be a hydroxy group having 1 to 22 carbon atoms. A composite is preferred. Specifically, ethylene glycol, diethylene glycol, triethylene glycol and their monoalkyl ethers are preferable. Particularly preferred is a hydroxy compound in which the residue excluding the hydroxy group is a hydrocarbon group having 1 to 22 carbon atoms having an ether bond, because of its excellent dispersibility in resin.

[0017] The method for producing the urethane-urea compound (A) is not particularly limited. For example, the polyisocyanate, the diamine compound and the hydroxy compound are reacted by a known method. Obtainable. Each of these components may be reacted at the same time. In particular, a method of reacting a diisocyanate with a polyisocyanate and a hydroxy compound is preferred.

The urethane-urea compound (A) is produced by the isocyanate group (X) of the polyisocyanate, the amino group (Y) of the diamine compound, and the hydroxy group (Z) of the hydroxy compound. It is preferable to carry out by mixing each component so that the equivalent ratio [XZ (Y + Z)] is 100Z80 to: L00Z120.

Urethane-urea compound (Α) has a urea bond and a urethane bond, and these bonds form hydrogen bonds between the molecules, forming a network of urethane-urea compound (Α) and thought to be able to impart thixotropic properties. It is done.

Therefore, when the equivalent ratio is in the above range, the isocyanate of the polyisocyanate is Almost all of the nate groups become urethane-urea compounds (A) in which urea bonds and urethane bonds are formed, so that the effect of imparting thixotropy is increased. From these characteristics, the equivalent force iti, 100 / 90˜: LOO / 110 force S is preferred <100 / 95˜: LOO / 105 is more preferred.

[0018] Further, the mixing is carried out so that the equivalent ratio (YZZ) of the amino group (Y) of the diamine compound and the hydroxy group (Z) of the hydroxy compound is 100Z50 to: L00Z200. Good. When the equivalent ratio is within this range, the ratio of urea bonds to urethane bonds in the urethane-urea compound (A) becomes appropriate, and the effect of imparting thixotropy increases. From the standpoint of this characteristic, the equivalent ratio is more preferably 100/75 to: LOO / 150.

[0019] The urethane-urea compound (A) is preferably a compound represented by the following formula (1) because it has a great effect of imparting thixotropy.

[0020] [Chemical 2]

In the above formula (1), R ¹ is a residue obtained by removing two isocyanate groups from a polyisocyanate, and preferably obtained by removing two isocyanate groups from tolylene diisocyanate. Residue. Specific examples include those obtained by removing the isocyanate group from the above-mentioned polyisocyanate such as 2,4-TDI. Two R ^{1 s} in the above formula (1) may be the same or different!

R ² is a hydrocarbon group having 1 to 22 carbon atoms which may have an ether bond, and preferably a hydrocarbon group having 1 to 22 carbon atoms having an ether bond. Specifically, for example, the residues obtained by removing the hydroxy group compound hydroxy group exemplified above may be mentioned. Two R ² in the above formula (1) may be the same or different.

[0022] The compound represented by the above formula (1) has a urea bond and a urethane bond, and has a high polarity, so it is difficult to dissolve in a nonpolar solvent. Also for polar solvents such as hydroxy compounds and water Although it does not dissolve, it dissolves easily in the polar solvent used in the thixotropic agent of the present invention described later.

[0023] In the compound represented by the above formula (1), the residue obtained by removing the hydroxy group from the 1,4 xylylenediamine and the hydroxy compound is an ether bond to the polyisocyanate. It can be obtained by reacting a hydroxy compound which is a hydrocarbon group having 1 to 22 carbon atoms which may have a carbon atom. As this polyisocyanate, those having isocyanate groups having different reactivities are preferred. For example, TDI etc. are mentioned.

The use of 1,4 xylylenediamine in the production of the compound represented by the above formula (1) is particularly effective for the development of thixotropy because it is easy to form an appropriate hydrogen bond network.

In addition, the hydroxy compound used for the production of the compound represented by the above formula (1) preferably contains at least one ether bond in addition to the hydroxy group. As the hydroxy compound, ethylene glycol and Z or polyethylene glycol monoalkyl ether are preferably used.

[0024] The thixotropic agent of the present invention is a group catalyst comprising the urethane-urea compound (A) described above and N-methylbiridone, dimethylacetamide, dimethylformamide, 1,3 dimethyl-2-imidazolidinone, and dimethyl sulfoxide. And at least one polar solvent selected from the above. The polar solvent used in the thixotropic agent of the present invention may be used alone or in combination of two or more. The mixing ratio when used in combination is not particularly limited.

These polar solvents can easily dissolve the urethane-urea compound (A), particularly the compound represented by the above formula (1), and can be used for waterproofing materials, sealing materials, adhesives, paints, etc. For example, since it is excellent in compatibility with urethane resin, modified silicone resin, polysulfide resin, silicone resin, polyisobutylene resin, epoxy resin, etc., it can be easily mixed without heating.

[0025] The thixotropic agent of the present invention may contain, in addition to the above-mentioned components, an ester plasticizer that does not impair the solubility of the decolorizing agent in the rosin component! Yo ヽ. Specific examples of ester plasticizers include phthalates, adipates, 2, 2, 4 trimethyl Examples include 1,3 pentanediol diisoptylate.

[0026] thixotropic agent of the present invention, the polar solvent, the urethane one Urea compound (A), urethane - Urea Compound (A) and 5 to 70 mass relative to the sum of the polar solvent ^_0/0 It is preferable to contain. Within this range, an effect can be obtained by adding a small amount of the wrinkle-modifying agent, and the load on the environment can be reduced by reducing the amount of solvent used. In view of these characteristics, it is more preferable to contain 8 to 60% by mass.

[0027] The thixotropic agent of the present invention contains, in addition to the above-described components, various additives such as a filler, a dehydrating agent, a stabilizer, and a colorant, as long as the object of the present invention is not impaired. can do.

Examples of the filler include finely divided silica (Aerosil 200, manufactured by Toshin Kaisei Co., Ltd.), acrylic powder (F350, manufactured by Nippon Zeon Co., Ltd.), and the like.

[0028] The addition amount of the thixotropic agent of the present invention can be appropriately adjusted according to the type of the resin component and the required thixotropic property. In general, the thixotropic agent according to the present invention in an amount of 0.1 to 10 parts by mass of the urethane-urea compound (A) is added to 100 parts by mass of the resin component. Is preferable in that sufficient thixotropy can be imparted. In view of these characteristics, the urethane-urea compound (A) is more preferably contained in an amount of 0.5 to 5 parts by mass.

[0029] The thixotropic agent of the present invention has a urethane-urea compound (A) having a urea bond and a urethane bond, so that it can be used as a wrinkle-modifying agent using a conventional polyether ester type polyvalent carboxylic acid. Compared with a small amount of addition, sufficient thixotropy can be imparted. In particular, when a compound represented by the above formula (1) is used, higher thixotropic properties can be imparted. Further, when the urethane urea compound (A) synthesized using a hydroxy compound having at least one ether bond is contained, the dispersibility in the resin is particularly excellent. In addition, when the urethane-urea compound (A) synthesized using TDI is contained, the thixotropic property imparting agent and the stability of the resulting wrinkle-modifying agent itself are excellent.

Further, when the thixotropic agent of the present invention contains the urethane-urea compound (A) and the specific polar solvent described above, the curable resin composition is not affected by wind and does not need to be heated. Can be easily mixed with each other, so that it is preferably used for outdoor use. [0030] The thixotropic agent of the present invention can be used for curable rosin compositions, water-based paint compositions, fats and oils, etc., and has excellent properties as described above. It can be suitably used for curable resin compositions such as sealing materials, adhesives, and paints. Specific examples of such a curable resin composition include, for example, a moisture curable polyurethane composition described in JP-A-6-239953 and a two-component composition described in JP-A-2000-19203. A normal temperature curable waterproofing material composition etc. are mentioned.

[0031] Next, the curable resin composition of the present invention will be described.

The curable resin composition of the present invention comprises at least one resin selected from the group consisting of urethane resin, modified silicone resin, polysulfide resin, silicone resin, polyisobutylene resin and epoxy resin. And the above-described thixotropic agent of the present invention (hereinafter referred to as “the composition of the present invention”).

[0032] Urethane resin, modified silicone resin, polysulfide resin, silicone resin, polyisobutylene resin and epoxy resin used in the composition of the present invention are generally waterproof, sealing material, adhesive, The well-known thing used for the resin composition, such as a coating material, can be used.

For example, examples of the urethane resin (urethane prepolymer) include those suitably used for waterproofing resin compositions, and the same urethane urethane as used in ordinary one-component polyurethane resin compositions. A urea prepolymer that is the reaction product of a polyol compound and an excess of a polyisocyanate compound (ie, an excess of isocyanate groups relative to hydroxy groups), generally 0. 5 is also of the containing 10 mass ^_0/0 of Isoshianeto group.

[0033] Specific examples of urethane prepolymers used in the water-repellent resin composition include, for example, isocyanate-terminated urethane prepolymers described in JP-A No. 2000-19920. This isocyanate-terminated urethane prepolymer is produced by the reaction of TDI with polyol. As TDI, either 2, 4-TDI or 2, 6-TDI can be used. However, prepolymers using TDI with a low 2,4-TDI content tend to shorten the working time. Therefore, in order to obtain a pot life, the content of 2,4-TDI is preferably 65 to 100% by mass, more preferably 80% by mass. [0034] Examples of the polyol include polyhydric alcohols, amines, alkanolamines, polyhydric phenols and the like that are used for producing ordinary urethane prepolymers. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, and pentaerythritol, and examples of amines include ethylenediamine and hexamethylenediamine. Examples of the alkanolamines include ethanolamine and propanolamine, and examples of the polyhydric phenols include resorcin and bisphenols.

[0035] Specifically, polyether polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol and polyoxybutylene glycol, polyolefin polyols such as polybutadiene polyol and polyisoprene polyol, etc. Polyester polyols such as adipate polyols, latathone polyols, and castor oil are preferred, and these polyols can be used in combination as required. Among these, polypropylene glycol (PPG) is preferable. These compounds may be used singly or in combination of two or more. However, since the viscosity of the resulting urethane prepolymer is increased and the mechanical strength of the cured product may be insufficient, Those having an average molecular weight of about 400 to 8000 are preferred.

[0036] The equivalent ratio of TDI to polyol in the production of the urethane prepolymer is NCOZOH = l.5 to 2.1, which is the equivalent ratio of isocyanate groups in TDI to hydroxyl groups in the polyol. When the equivalent ratio is within this range, the viscosity of the urethane prepolymer obtained is low, and it is preferable because there are few unreacted isocyanate groups. Isoshianeto content of the resulting Isoshianeto terminated urethane prepolymer 1. 5 to 6. 0 mass ^_0/0. When the isocyanate content is in this range, the resulting composition can obtain the heat resistance and mechanical strength (breaking strength, breaking elongation, tear strength) that the waterproofing material specified in JIS A-6021 should have. Sufficient pot life can be taken. Preferably it is 2.0-4.0 mass%. The production conditions for urethane prepolymers may be those for ordinary urethane prepolymers. That is, the above-mentioned TDI and polyol are reacted at a reaction temperature of 50-: about LOO ° C under normal pressure!

[0037] As a non-described resin component, urethane resin and the like described in JP-A-6-239953 can be suitably used. Each of the above-mentioned coffins may be used in combination of two or more depending on the required properties.

[0038] The composition of the present invention includes various fillers, plasticizers, curing catalysts, dehydrating agents, softening agents, stabilizers, and colorants, in addition to the above-described components, as long as the object of the present invention is not impaired. In addition, known additives such as flame retardants, reinforcing agents, anti-aging agents, antioxidants, ultraviolet absorbers, and dyes' pigments can be blended.

[0039] The composition of the present invention contains the thixotropic agent of the present invention in an amount of 0.1 to 10 parts by mass of the urethane-urea compound (A) with respect to 100 parts by mass of the resin. It is preferable that it is capable of imparting sufficient thixotropy with a small amount. In view of these characteristics, the urethane-urea compound (A) is more preferably contained in an amount of 0.5 to 5 parts by mass.

[0040] The curable resin composition of the present invention can be used as a one-component curable resin composition, a two-component curable resin composition, or a three-component curable resin composition described later. .

The one-pack type curable rosin composition of the present invention contains the above rosin component, the thixotropic agent of the present invention, and an additive that is optionally added, and is cured by moisture in the air. Excellent workability. In addition, since it has thixotropic properties, it can also be used on inclined surfaces, and there is no need for mixing during use.

[0041] A first aspect of the two-component curable resin composition of the present invention includes a first solution containing the above-described resin component and an additive that is optionally added, and the thixotropic agent of the present invention. And a second liquid containing. According to this two-component curable resin composition, the first and second liquids can be mixed as needed during construction (during use), so that the construction site reaches the horizontal and inclined surfaces. However, it is preferable because it is not necessary to prepare curable resin compositions having different viscosities. The thixotropic agent of the present invention used for the second liquid is also referred to as “second liquid” for convenience when it is a solid that does not contain the specific polar solvent described above.

[0042] A second embodiment of the two-component curable resin composition of the present invention includes a first solution containing the above-described resin component, a curing agent generally used for the resin component, and the shaking of the present invention. It consists of a second liquid containing a denaturation-imparting agent, and an additive may be added to the first liquid and Z or the second liquid as necessary. This two-part curable resin composition is excellent in deep part curability and the like, which has a fast curing rate, and requires less labor to mix than the three-part curable resin composition described below. Also, with the second liquid Separately, by preparing a hardener, the hardener is mixed with the first liquid for horizontal surfaces and the second liquid and second liquid for inclined surfaces, even when the construction site extends to the horizontal and inclined surfaces. By mixing and using one liquid, the point force that is suitably used for both the horizontal surface and the inclined surface is also preferable.

[0043] The three-component curable resin composition of the present invention includes a first liquid containing the above-mentioned resin component, a second liquid containing a curing agent generally used for this resin component, and the present invention. And a third liquid containing the thixotropic agent. If necessary, an additive may be added to the first liquid and / or the second liquid. According to this three-component curable resin composition, the first and second liquids and the third liquid can be mixed as needed during construction (during use), so that the construction location can be reduced. Even in the case of a horizontal plane and an inclined plane, it is preferable because it is not necessary to prepare curable resin compositions having different viscosities. Furthermore, it is excellent in deep part curability and the like where the curing speed is high. The thixotropic agent of the present invention used for the third liquid is also referred to as “third liquid” for convenience when it is a solid that does not contain the specific polar solvent described above.

[0044] The composition of the present invention can be produced by a known method. For example, in the first aspect of the two-component curable resin composition, the urethane resin (urethane prepolymer) and the additive that is optionally added are required under reduced pressure or in an inert atmosphere. Accordingly, the mixture is sufficiently kneaded using a mixing device such as a ball mill and uniformly dispersed to form the first liquid, and the thixotropic agent of the present invention described above can be obtained as the second liquid.

[0045] Next, a method for using the curable resin composition of the present invention will be described.

The method of using the curable resin composition of the present invention is not particularly limited, but when the curable resin composition of the present invention described above is used, the above-described oscillating composition of the present invention is used. It is preferable to add this thixotropic agent to the component excluding the denaturing agent.

[0046] According to the method of using the curable resin composition of the present invention, it is not necessary to prepare a curable resin composition having different viscosities even when the construction site covers a horizontal surface and an inclined surface. Specifically, for example, by adding a specific amount of the wrinkle-modifying imparting agent of the present invention to a waterproof urethane urethane resin composition for a horizontal surface having a thixo index of 2.0 or less, the thixo index is 3.0 or more. It is possible to form a coating film with a thickness of 2. Omm or more on the vertical surface. Accordingly, by adding the thixotropic agent of the present invention to a urethane resin composition for waterproofing materials for horizontal surfaces, it can be used as a urethane resin composition for waterproofing materials for inclined surfaces. There is no need to prepare a urethane resin composition for water material. In addition, since the thixotropic agent of the present invention containing the urethane-urea compound (A) and the polar solvent is a liquid, the curable resin composition is not affected by wind and is not heated. Therefore, the curable resin composition of the present invention is suitably used for outdoor use.

[0047] In the present specification, the thixo index is a viscosity ratio obtained by measuring the viscosity (cps) at lrpm and lOrpm at 20 ° C using a BH viscometer No. 6 rotor. lr pm / 10rpm).

[0048] As described above, since the curable resin composition of the present invention has thixotropic properties, it can be used on inclined surfaces, and in particular, the use of the curable resin composition of the present invention. According to the method, it is not necessary to prepare a curable resin composition having different viscosities even when the application location extends over a horizontal plane and an inclined plane.

[0049] The use of the curable resin composition of the present invention is not particularly limited, but is suitable for waterproofing materials, sealing materials, adhesives, paints and the like from the viewpoint of excellent characteristics as described above. Used.

Example

[0050] (Preparation of thixotropic agent ( _a ) of the present invention)

2, 4— TDI (Cosmonate T100, manufactured by Mitsui Chemicals Co., Ltd.) 17. In a solution of 4 g dissolved in 3-6 g of Ν-methylpyrrolidone (Kanto Chemical Co., Ltd.), ethylene glycol monoisopropyl ether (Tokyo) Kasei Kogyo Co., Ltd.) 5. 2 g and triethylene glycol monomethyl ether (Tokyo Kasei Kogyo Co., Ltd.) 8. 2 g of the mixture was added dropwise under ice cooling. After completion of dropping, the reaction was allowed to proceed for 6 hours at room temperature. Next, 6.8 g of 1,4 xylylenediamine (PXDA, Showa Denko KK) was slowly added to this solution and reacted at room temperature for 1 hour. The solvent was removed under reduced pressure, and the following formula (2 The compound presumed to have a structure represented by) was obtained. For this compound, the disappearance of the isocyanate group peak was confirmed by FTIR. The obtained composite was used as the thixotropic agent (a) of the present invention.

[0051] [Chemical 3]

NHC 0 (CH ₂ CH ₂ 0) ₃ CH ₃

[0052] (Preparation of thixotropic agent (b) of the present invention)

The reaction was basically carried out in the same manner as the thixotropic agent (a) of the present invention, but the removal of the solvent was strong. That is, the thixotropic agent (b) of the present invention was obtained by dissolving the thixotropic agent (a) of the present invention in N-methylpyrrolidone so as to be a 50% by mass solution.

[0053] (Preparation of thixotropic agents ( _c ) to (j) of the present invention)

The reaction was basically performed in the same manner as the thixotropic agent (b) of the present invention except that the hydroxy compound shown in Table 1 below was used as the hydroxy compound in the amount (g) shown in Table 1. The thixotropic agents ( _c ) to (j) of the present invention shown in Table 1 were obtained.

(Preparation of thixotropic agent (k) of the present invention)

The reaction was carried out basically in the same manner as the thixotropic agent (a) of the present invention, but the amount of solvent removed was adjusted, and the thixotropic agent (a) of the present invention was added to N-methylpyrrolidone at 25 mass. The thixotropic agent (k) of the present invention was obtained by dissolving to a% solution.

[0055] [Table 1] 1

[0056] (Examples 1 to 3)

1-component urethane resin waterproofing composition (Europol, Yokohama Rubber Co., Ltd., Thixoindettas 1.1, the same shall apply hereinafter) and the thixotropic agent of the present invention obtained as described above ( b) and were mixed in the composition shown in Table 2 and dispersed uniformly to obtain each composition shown in Table 2. In Table 2, the mass part of the thixotropic agent (b) of the present invention of Examples 1 to 4 represents the total mass part of the compound represented by the above formula (2) and N-methylpyrrolidone. The mass part of the compound represented by the above formula (2) corresponds to about one half of the mass part of the thixotropic agent.

After mixing each of the above components, each composition obtained was allowed to stand at 20 ° C. and 50% RH for 10 minutes, and then the viscosity was measured by the above method to calculate the thixo index, and the thixotropic properties of each composition were reduced. Evaluated by Chitaso index. The higher the thixo index, the higher the wrinkle denaturation.

The results are shown in Table 2.

[Example 4]

The main component and curing agent of a two-component urethane waterproofing resin composition (U-8000, manufactured by Yokohama Rubber Co., Ltd., thixo-index 1.1), and the thixotropic agent (b) of the present invention, The composition shown in Table 2 was mixed and dispersed uniformly to obtain the composition of Example 4.

With respect to the composition of Example 4 immediately after mixing the above components, the tita indentation was calculated by the above-described method, and thixotropy of the composition of Example 4 was evaluated using a thixo index. The results are shown in Table 2.

[0058] (Example 5)

Mixing as it is without dissolving 0.7 parts by mass of the thixotropic agent (a) of the present invention in 100 parts by mass of the one-component urethane-based waterproofing agent composition used in Examples 1 to 3 Thus, the composition of Example 5 was obtained.

After mixing each component, the composition of Example 5 was allowed to stand at 20 ° C. and 50% RH for 10 minutes, and then the thixo index was calculated by the above method, and wrinkle modification of the composition of Example 5 was determined by thixo index. It was evaluated by.

The results are shown in Table 2.

[0059] (Examples 6 to 13) A one-component urethane-based waterproofing resin composition and the thixotropic agents (c) to (j) of the present invention obtained as described above are mixed in the composition shown in Table 2, Each composition shown in Table 2 was obtained by uniformly dispersing.

In Table 2, the mass parts of the thixotropic agents (c) of the present invention of Examples 6 to 13 are the total mass parts of each urethane-urea compound synthesized by the above method and N-methylpyrrolidone. The mass part of each urethane-urea compound corresponds to about one half of the mass part of the thixotropic agent.

After mixing each component, each composition obtained was allowed to stand at 20 ° C. and 50% RH for 10 minutes, and then the thixo index was calculated by the above method, and wrinkle modification of each composition was evaluated by the thixo index.

The results are shown in Table 2.

[Example 14]

The main component and curing agent of a two-component urethane waterproofing resin composition (U-8000, manufactured by Yokohama Rubber Co., Ltd., thixo-index 1.1), and the thixotropic agent (k) of the present invention, The composition shown in Table 2 was mixed and dispersed uniformly to obtain the composition of Example 14.

Table 2 shows the results of calculating the tita indentation by the above-described method and evaluating the wrinkle modification of the composition of Example 14 using the thixo index for the composition of Example 14 immediately after mixing the above components. Show.

[0061] (Comparative Examples 1-2)

100 parts by mass of a one-component or two-component urethane waterproofing agent resin composition used in the Examples, and a conventional liquid thixotropic agent (Disparon 3600N) mainly composed of a polyether ester type polycarboxylic acid The composition of Comparative Example 1 and Comparative Example 2 was obtained by mixing 5 parts by mass (solid content 50% by mass, manufactured by Enomoto Chemical Co., Ltd.) and 5 parts by mass (solid content 2.5 parts by mass).

After mixing each component, the composition of Comparative Example 1 was allowed to stand at 20 ° C. and 50% RH for 10 minutes, then the viscosity was measured by the above method to calculate the thixo index, and the composition of Comparative Example 1 was shaken. Denaturation was assessed by thixo index.

Further, the viscosity of the composition of Comparative Example 2 immediately after mixing the above components was measured by the above method. The thixo index was calculated, and thixotropic properties of the composition of Comparative Example 2 were evaluated using the thixo index.

The results are shown in Table 2.

[¾2]

[0063] [Table 3]

[0064] As is apparent from the results shown in Table 2, the single-component urethane-based waterproofing resin composition 100 A composition containing 1 part by mass and the thixotropic agent of the present invention (b) 1.4 parts by mass (containing 0.7 parts by mass of the compound represented by the above formula (2)) (Example 1), Compared with a composition using a conventional liquid thixotropic agent (Comparative Example 1), a thixoindasse of 3.0 or more could be obtained with the addition of a small amount of wrinkle modifier.

In addition, a composition (Example 5) containing a one-component urethane-based waterproofing resin composition and the thixotropic agent (a) of the present invention containing no N-methylpyrrolidone is a small amount of thixotropic agent. The ability to obtain a thixo index of 3.0 or more by the addition of the imparting agent. The thixo index was low compared to the composition of Example 1. This is because, in the composition of Example 1, since the compound represented by the formula (2) is dissolved in N-methylpyrrolidone, the thixotropic agent is used as the oil component compared to the composition of Example 5. It is considered that the effect of the thixotropic agent was sufficiently exerted by being easily mixed and uniformly dispersed.

Further, the compositions (Examples 2 and 3) in which the amount of the thixotropic agent (b) of the present invention was increased from that of Example 1 had a higher thixo index than the composition of Example 1. .

In addition, the composition (Examples 4 and 14) containing the two-component urethane waterproofing resin composition and the thixotropic agent (b) or (k) of the present invention is a conventional liquid thixotropic agent. Compared with the composition using the imparting agent (Comparative Example 2), it had a high thixo index, and had a thixo index equivalent to that when using the one-component urethane-based waterproofing resin composition.

In addition, the thixotropic index of the compositions (Examples 6 to 13) containing any of the thixotropic agents (c) to (j) of the present invention is 4.5 to 6.5. It has a higher V 且 thixo index than the yarn of Example 1! /.

Claims

The scope of the claims

[1] A thixotropic agent containing a urea urea compound obtained by reacting a polyisocyanate with a diamine compound and a hydroxy compound.

[2] The thixotropic agent according to [1], wherein the diamine compound is 1,4 xylylenediamine.

[3] The thixotropic agent according to claim 1 or 2, wherein the hydroxy compound comprises a hydroxy compound having at least one ether bond.

[4] The wrinkle modification-imparting agent according to claim 3, wherein the compound is a hydroxy compound having at least one ether bond, ethylene glycol monoisopropyl ether.

[5] The thixotropic agent according to any one of claims 1 to 4, wherein the polyisocyanate is tolylene diisocyanate.

[6] The thixotropic agent according to claim 1, wherein the urethane-urea compound is a compound represented by the following formula (1).

[Chemical 4]

[7] The thixotropic agent according to [6], wherein R ² is a hydrocarbon group having 1 to 22 carbon atoms having an ether bond.

8. The thixotropic agent according to claim 6 or 7, wherein R ¹ is a residue obtained by removing two isocyanate groups from tolylene diisocyanate.

[9] The urethane urea eye compound,

N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3 dimethyl At least one polar solvent selected from the group power consisting of 2-imidazolidinone and dimethyl sulfoxide;

The thixotropic agent according to claim 1, comprising:

[10] At least one resin selected from the group consisting of urethane resin, modified silicone resin, polysulfide resin, silicone resin, polyisobutylene resin and epoxy resin, and any one of claims 1 to 9 A thixotropic agent as described in

A curable resin composition containing

[11] When the curable resin composition according to claim 10 is used, the thixotropic agent according to any one of claims 1 to 9 is excluded from the curable resin composition. A method for using a curable resin composition, wherein the thixotropic agent is added to a component.