JP2011079887A - Thixotropy-imparting agent and single-liquid moisture curable urethane resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thixotropy-imparting agent to be compounded into a single-liquid moisture curable urethane resin composition so as to impart excellent thixotropy to the composition, and to provide the single-liquid moisture curable urethane resin composition excellent in thixotropy, storage stability and curability. <P>SOLUTION: The composition contains a prepolymer obtained by reacting a polyol with a polyisocyanate, and a thixotropy-imparting agent containing a diamide expressed by general formula (I) and/or formula (II). In general formula (I), R<SP>1</SP>and R<SP>3</SP>are identical or different from each other, each representing a monovalent hydrocarbon group; and R<SP>2</SP>represents a divalent hydrocarbon group. In general formula (II), R<SP>4</SP>and R<SP>6</SP>are identical or different from each other, each representing a monovalent hydrocarbon group; and R<SP>5</SP>represents a divalent hydrocarbon group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a thixotropic agent blended in a one-component moisture-curable urethane resin composition that cures with moisture in the air, and a one-component moisture-curable urethane excellent in thixotropic properties, storage stability, and curability. The present invention relates to a resin composition.

Conventionally, in compositions such as paints, sealing agents, adhesives, coating agents and the like, thixotropic agents are blended for the purpose of suppressing sedimentation and dripping of specific components such as pigments.
For example, Patent Document 1 discloses an anti-sagging agent obtained by swelling a polyamide obtained by reacting a monocarboxylic acid, a hydrogenated castor oil fatty acid (12-hydroxystearic acid) and an aliphatic polyamine with a diluent. A coating composition containing is disclosed.
Patent Document 2 includes an isocyanate-terminated prepolymer obtained by using an aliphatic and / or alicyclic diisocyanate monomer, a polyether polyol, and the like, and a thixotropic agent, and is useful as a sealing agent composition. A curable polyisocyanate composition is disclosed. And as a thixotropic agent, hydrogenated castor oil fatty acid, amide wax, aluminum stearate, calcium stearate, zinc stearate, fine powder silica, organic bentonite, bentonic acid, silicic acid anhydride, urea derivative, aerosil, etc. The polyamide in Patent Document 1 is used as the amide wax.

In addition, moisture curable urethane resin compositions include civil engineering, architectural, vehicle and other adhesives, sealing agents, paints, coating agents and sealants, civil engineering or architectural resin coatings, woodworking, etc. It is used as a primer composition for
Patent Document 3 discloses an active isocyanate group-containing urethane prepolymer obtained by reacting a polyether polyol with an excess of polyisocyanate, and an activity obtained by reacting a polyester polyol with an excess of polyisocyanate. A polyurethane resin composition containing an isocyanate group-containing urethane prepolymer in a predetermined ratio, and a polyurethane resin composition containing these prepolymers and a thixotropic agent such as anhydrous silica are disclosed.
Further, Patent Document 4 was obtained by reacting an isocyanate group-containing urethane prepolymer obtained by using a polyether polyol, finely divided silica, and a compound having an organic isocyanate and a nitrogen atom bonded to a hydroxyl group. A curable composition comprising a thixotropic agent is disclosed.

Japanese Patent Laid-Open No. 6-166838 JP 2002-37835 A Japanese Patent Laid-Open No. 1-132662 JP 2007-45958 A

In recent years, a one-pack type curable resin composition has been increasing in demand because it is more workable than a two-pack type composition, a solvent-type composition, and the like. And since moisture-curable urethane resin composition is excellent in the adhesiveness and the selectivity of a viscosity, and the mechanical strength after hardening, utilization to the electric / electronic field | area of the one-pack type composition is examined. For example, the progress of downsizing, narrowing of the bonding area between members, etc. is remarkable, such as sufficient fixing and protection of electronic parts (including elements, substrates, etc.) that form recesses and projections Therefore, there is a need for a one-component moisture-curable urethane resin composition suitable for a sealing agent composition and an adhesive composition used for the purpose, a coating composition, and the like. There is also a need for a thixotropic agent that blends with such a composition to give excellent thixotropic properties.
In addition, since the one-pack type curable resin composition has come to be widely used as described above, its use environment and storage environment due to seasonality and the like are diversified. And when the physical property at the time of use of a composition changes greatly from the physical property immediately after manufacture of a composition, the effect with respect to a product may be impaired. For example, when it is assumed that a composition stored at a temperature exceeding 30 ° C. is used, the storage stability of the composition is determined between a composition containing a thixotropic agent and a composition not containing a thixotropic agent. In general, the former is inferior. Therefore, a one-component moisture-curable urethane resin composition excellent in the balance between thixotropy and storage stability of the composition is demanded.
An object of the present invention is to provide a thixotropic agent that imparts excellent thixotropy by blending with a one-pack type moisture-curable urethane resin composition, and a one-part type moisture that is excellent in thixotropic, storage stability and curability It is to provide a curable urethane resin composition.

（式中、Ｒ^１及びＲ^３は、それぞれ、同一又は異なって、１価の炭化水素基であり、Ｒ^２は、２価の炭化水素基である。）

（式中、Ｒ^４及びＲ^６は、それぞれ、同一又は異なって、１価の炭化水素基であり、Ｒ^５は、２価の炭化水素基である。）
２．更に、ポリウレアを含有する上記１に記載の揺変性付与剤。
３．［Ａ］ポリオールと、ポリイソシアネートとを反応させて得られたイソシアネート基（ＮＣＯ）を有するプレポリマーであって、該イソシアネート基（ＮＣＯ）の合計量の含有割合が、該プレポリマーの分子量に対して、２．５〜１１％であるプレポリマー、及び、［Ｂ］上記１又は２に記載の揺変性付与剤を含有することを特徴とする一液型湿気硬化性ウレタン樹脂組成物。
４．上記揺変性付与剤［Ｂ］の含有量が、上記プレポリマー［Ａ］１００質量部に対して、０質量部を超えて５０質量部以下である上記３に記載の一液型湿気硬化性ウレタン樹脂組成物。
５．上記ポリオールがエステル結合を有するポリオールを含み、該エステル結合含有ポリオールの数平均分子量が５００〜８，０００である上記３又は４に記載の一液型湿気硬化性ウレタン樹脂組成物。
６．上記エステル結合含有ポリオールが、ヒドロキシカルボン酸と、多価アルコールとから形成されたポリオール、及び、ヒドロキシカルボン酸と、多価アルコールのグリシジルエーテルとから形成されたポリオール、から選ばれた少なくとも１種である上記５に記載の一液型湿気硬化性ウレタン樹脂組成物。 The present invention is as follows.
1. A thixotropic agent blended in a one-part moisture-curable urethane resin composition, which is represented by the following general formula (I) and has a number average molecular weight of 500 to 3,000, And a thixotropic agent characterized by containing at least one of diamides (II) represented by the following general formula (II) and having a number average molecular weight of 500 to 3,000.

(In the formula, R ¹ and R ³ are the same or different and each is a monovalent hydrocarbon group, and R ² is a divalent hydrocarbon group.)

(In the formula, R ⁴ and R ⁶ are the same or different and each represents a monovalent hydrocarbon group, and R ⁵ represents a divalent hydrocarbon group.)
2. The thixotropic agent according to 1 above, further comprising polyurea.
3. [A] A prepolymer having an isocyanate group (NCO) obtained by reacting a polyol and a polyisocyanate, wherein the content ratio of the total amount of the isocyanate group (NCO) is relative to the molecular weight of the prepolymer. And a prepolymer that is 2.5 to 11% and [B] the thixotropy imparting agent according to 1 or 2 above, and a one-component moisture-curable urethane resin composition.
4). The one-component moisture-curable urethane according to 3 above, wherein the content of the thixotropic agent [B] is more than 0 parts by mass and 50 parts by mass or less with respect to 100 parts by mass of the prepolymer [A]. Resin composition.
5). 5. The one-component moisture-curable urethane resin composition according to 3 or 4 above, wherein the polyol includes a polyol having an ester bond, and the number average molecular weight of the ester bond-containing polyol is 500 to 8,000.
6). The ester bond-containing polyol is at least one selected from a polyol formed from a hydroxycarboxylic acid and a polyhydric alcohol, and a polyol formed from a hydroxycarboxylic acid and a glycidyl ether of a polyhydric alcohol. 6. The one-component moisture-curable urethane resin composition as described in 5 above.

According to the thixotropic agent of the present invention, a one-component moisture-curable urethane resin composition excellent in thixotropic properties can be provided.
Moreover, according to the one-component moisture-curable urethane resin composition of the present invention, the thixotropic property, storage stability, and curability are excellent.
In the one-component moisture-curable urethane resin composition of the present invention, the content of the thixotropic agent [B] is more than 0 parts by mass and 50 parts by mass with respect to 100 parts by mass of the prepolymer [A]. When it is below, it can be set as the composition excellent in thixotropic property and storage stability.
In the one-component moisture-curable urethane resin composition of the present invention, the polyol forming the prepolymer [A] contains a polyol having an ester bond, and the number average molecular weight of the ester bond-containing polyol is 500 to 8,000. In some cases, a cured product excellent in thixotropic property, storage stability and curability and excellent in electrical insulation can be obtained.

（式中、Ｒ^１及びＲ^３は、それぞれ、同一又は異なって、１価の炭化水素基であり、Ｒ^２は、２価の炭化水素基である。）

（式中、Ｒ^４及びＲ^６は、それぞれ、同一又は異なって、１価の炭化水素基であり、Ｒ^５は、２価の炭化水素基である。） 1. Thixotropic agent The thixotropic agent of the present invention is represented by the following general formula (I), and the diamide (I) having a number average molecular weight of 500 to 3,000, and the following general formula (II): And at least one of diamides (II) having a number average molecular weight of 500 to 3,000.

(In the formula, R ¹ and R ³ are the same or different and each is a monovalent hydrocarbon group, and R ² is a divalent hydrocarbon group.)

(In the formula, R ⁴ and R ⁶ are the same or different and each represents a monovalent hydrocarbon group, and R ⁵ represents a divalent hydrocarbon group.)

In the general formula (I) representing the diamide (I), R ¹ and R ³ are the same or different and each is a monovalent hydrocarbon group. The number of carbon atoms of this hydrocarbon group is preferably 6 to 50, more preferably 8 to 45, and still more preferably 10 to 40. The hydrocarbon group may be a group composed of an aliphatic hydrocarbon, or a group including a ring structure (a structure derived from an alicyclic hydrocarbon or an aromatic hydrocarbon).
R ² is a divalent hydrocarbon group, preferably having 6 to 50 carbon atoms, more preferably 8 to 45, and still more preferably 10 to 40. The hydrocarbon group may be a group composed of an aliphatic hydrocarbon, or a group including a ring structure (a structure derived from an alicyclic hydrocarbon or an aromatic hydrocarbon).

  The number average molecular weight of the diamide (I) is 500 to 3,000, preferably 600 to 2,000, more preferably 700 to 1,800. When the number average molecular weight is in the above range, the one-component moisture-curable urethane resin composition containing the diamide (I) is excellent in thixotropic properties. The number average molecular weight can be measured by gel permeation chromatography (GPC).

In the general formula (II) representing the diamide (II), R ⁴ and R ⁶ are the same or different and each is a monovalent hydrocarbon group. The number of carbon atoms of this hydrocarbon group is preferably 6 to 50, more preferably 8 to 45, and still more preferably 10 to 40. The hydrocarbon group may be a group composed of an aliphatic hydrocarbon, or a group including a ring structure (a structure derived from an alicyclic hydrocarbon or an aromatic hydrocarbon).
R ⁵ is a divalent hydrocarbon group, preferably having 6 to 50 carbon atoms, more preferably 8 to 45, and still more preferably 10 to 40. The hydrocarbon group may be a group composed of an aliphatic hydrocarbon, or a group including a ring structure (a structure derived from an alicyclic hydrocarbon or an aromatic hydrocarbon).

  The number average molecular weight of the diamide (II) is 500 to 3,000, preferably 600 to 2,000, more preferably 700 to 1,800. When the number average molecular weight is in the above range, the thixotropy when this diamide (II) is blended with a one-component moisture-curable urethane resin composition is excellent. The number average molecular weight can be measured by gel permeation chromatography (GPC).

The diamide in the thixotropic agent of the present invention may be either one of the above diamide (I) and diamide (II), or both.
When the diamide is composed of both diamide (I) and diamide (II), from the viewpoint of thixotropy and storage stability of the resulting composition, the content ratio of both is 100% by mass of the total. Preferably, they are 5-95 mass% and 5-95 mass%, More preferably, they are 10-90 mass% and 10-90 mass%, More preferably, they are 15-85 mass% and 15-85 mass%.

In the thixotropic agent of the present invention, the content of the diamide is 90% by mass or more, preferably 95% by mass or more. It may be 100% by mass. That is, the thixotropic agent of the present invention is usually composed of the above-mentioned diamide, but depending on the production method of this diamide, in order not to impair the effects of the present invention, a by-product is contained. There is.
In this case, the thixotropic agent of the present invention can be composed of the above diamide and polyurea. This polyurea does not greatly reduce the properties of the one-component moisture-curable urethane resin composition by the thixotropic agent having an upper limit of the content of 10% by mass.

（式中、Ｒ^７は、２価の有機基である。） The polyurea is a compound having a urea bond, but an example of a compound contained in the thixotropic agent of the present invention is a polyurea having a structure represented by the following general formula (III).

(In the formula, R ⁷ is a divalent organic group.)

In the general formula (III) representing the structure constituting the polyurea, R ⁷ is a divalent organic group, preferably has 2 to 50 carbon atoms, more preferably 4 to 45, still more preferably 6 to 40. The organic group includes an unsubstituted hydrocarbon group such as a group derived from an aliphatic hydrocarbon; a group containing a ring structure, that is, a group derived from an alicyclic hydrocarbon; derived from an aromatic hydrocarbon. Or a group in which one or more of the hydrogen atoms in the hydrocarbon group are substituted with a functional group such as a halogen atom or a hydroxyl group.

（式中、Ｒ^７及びＲ^８は、それぞれ、同一又は異なって、２価の有機基である。）

（式中、Ｒ^７は、２価の有機基であり、Ｒ^９は、１価の有機基である。） Specific examples of the polyurea are reaction products of a diamine and a polyisocyanate described later, that is, a reaction product of a polyurea having a structure represented by the following general formula (IV) and a monoamine and a polyisocyanate described later. Product, that is, polyurea represented by the following general formula (V). A compound in which one terminal is an amide group and the other terminal is an amino group is also included in the monoamine.

(Wherein R ⁷ and R ⁸ are the same or different and are divalent organic groups.)

(In the formula, R ⁷ is a divalent organic group, and R ⁹ is a monovalent organic group.)

R ⁸ in the general formula (IV) can be the same as R ⁷ .
R ⁹ in the general formula (V) is a monovalent organic group, and may be a hydrocarbon group that may have a substituent. The number of carbon atoms of the hydrocarbon group is preferably 2 to 50, more preferably 4 to 45, and still more preferably 6 to 40. The hydrocarbon group may be a group derived from an aliphatic hydrocarbon, or a group containing a ring structure, that is, a group derived from an alicyclic hydrocarbon or a group derived from an aromatic hydrocarbon. May be.

  The number average molecular weight of the polyurea is usually 200 to 2,000.

Hereafter, the manufacturing method of the thixotropic agent of this invention is demonstrated.
In the case of the thixotropic agent containing the diamine (I), the production method includes reacting a monoamine having 6 to 50 carbon atoms with a dicarboxylic acid having 6 to 50 carbon atoms to produce a diamide ( A diamide (I) synthesis step for generating I) is provided. In addition, when the unreacted raw material component remains in the reaction system, if this is used as it is as a thixotropic agent and blended with the one-component moisture-curable urethane resin composition, the effect of the present invention cannot be obtained. . Therefore, a post-process for eliminating unreacted raw material components can be further provided. For example, when monoamine remains in the reaction system, isocyanate can be added and reacted with the monoamine to produce the polyurea represented by the general formula (V).

  Examples of monoamines used in the diamide (I) synthesis step include aliphatic monoamine compounds, alicyclic monoamine compounds, and aromatic monoamine compounds. These may be used alone or in combination.

Aliphatic monoamine compounds include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine , Hexadecylamine, heptadecylamine, octadecylamine and the like.
Examples of the alicyclic monoamine compound include cyclopentylamine and cyclohexylamine.
In addition, examples of the aromatic monoamine compound include aniline, benzylamine, and phenethylamine.

  Examples of the dicarboxylic acid used in the diamide (I) synthesis step include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. These may be used alone or in combination.

Examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, decadicarboxylic acid, dodecanedicarboxylic acid, and dimer acid.
Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like.
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyldicarboxylic acid, 1,2-bisphenoxyethane-p, p′-dicarboxylic acid, and naphthalenedicarboxylic acid.

  The ratio (molar ratio) of the monoamine and dicarboxylic acid used in the diamide (I) synthesis step is usually 2: 1 to 2: 1.2, preferably 2: 1.05 to 2: 1. 1.

  The reaction conditions in the diamide (I) synthesis step are not particularly limited. For example, the diamide can be produced by reacting the raw material components charged in the above ratio under normal pressure or reduced pressure, preferably at a temperature in the range of 80 ° C to 240 ° C. The reaction time is usually 2 to 15 hours.

After the diamide (I) synthesis step, as described above, a post step for eliminating unreacted raw material components can be further provided.
When monoamine remains in the reaction system, isocyanate (described later) can be added to react with the monoamine. In this case, the reaction temperature is usually 40 ° C to 120 ° C.

  In the case of the thixotropic agent containing the diamine (II), the production method comprises reacting a diamine having 6 to 50 carbon atoms with a monocarboxylic acid having 6 to 50 carbon atoms to diamide. A diamide (II) synthesis step for generating (II) is provided. In addition, when the unreacted raw material component remains in the reaction system, if this is used as it is as a thixotropic agent and blended with the one-component moisture-curable urethane resin composition, the effect of the present invention cannot be obtained. . Therefore, a post-process for eliminating unreacted raw material components can be further provided. For example, when a diamine and / or a half amide (a compound in which one end is an amide group and the other end is an amino group) remains in the reaction system, an isocyanate is added to the diamine and / or half amide. The polyurea which has a structure represented by the said general formula (IV) can be produced | generated by making it react.

  Examples of the diamine used in the diamide (II) synthesis step include aliphatic diamine compounds, alicyclic diamine compounds, and aromatic diamine compounds. These may be used alone or in combination.

Examples of the aliphatic diamine compound include ethylenediamine, trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 2-methylpentamethylenediamine, and 1,7-heptamethylene. Diamine, 1,8-octamethylenediamine, N, N′-dimethyl-1,6-hexanediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 2,2,4- Trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,16-hexadecamethylenediamine, etc. Is mentioned.
Examples of the alicyclic diamine compound include 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, and the like.
Moreover, as an aromatic diamine compound, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4 , 6-Diethyl-1,3-phenylenediamine, 5-methyl-4,6-diethyl-1,3-phenylene-diamine, 1,5-diaminonaphthalene, bis (4-aminophenyl) methane, bis (4- Aminophenyl) propane, 2,4-bis (b-amino-tert-butyl) toluene, 1,3-diamino-4-isopropylbenzene, 4,4′-diaminodiphenylmethane, and the like.

  Examples of the monocarboxylic acid used in the diamide (II) synthesis step include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids. These may be used alone or in combination.

Aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid (valeric acid), caproic acid, caprylic acid, enanthic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecane Acid, tetradecanoic acid, heptadecanoic acid, hexadecanoic acid (palmitic acid), pentadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, trimethylacetic acid, oleic acid, undecenoic acid, lindelic acid, milli Examples include streic acid, palmitoleic acid, oleic acid, linoleic acid, elaidic acid, gadrenic acid, eicosapentaenoic acid, docosahexaenoic acid, erucic acid, brassic acid, and arachidonic acid.
Examples of alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, 1-methyl cyclohexane carboxylic acid, 2-methyl cyclohexane carboxylic acid, 3-methyl cyclohexane carboxylic acid, 4-methyl cyclohexane carboxylic acid, cycloheptane carboxylic acid. Etc.
Examples of aromatic monocarboxylic acids include benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, 4-tert-butylbenzoic acid, 1-naphthalenecarboxylic acid, and 2-naphthalenecarboxylic acid. 1-methyl-2-naphthoic acid, 2-isopropyl-1-naphthoic acid and the like.

  The ratio (molar ratio) of the diamine and monocarboxylic acid used in the diamide (II) synthesis step is usually 1: 2 to 1.2: 2, preferably 1.05: 2 to 1.1. : 2.

  The reaction conditions in the diamide (II) synthesis step are not particularly limited. For example, the diamide can be produced by reacting the raw material components charged in the above ratio under normal pressure or reduced pressure, preferably at a temperature in the range of 80 ° C to 240 ° C. The reaction time is usually 2 to 15 hours.

After the diamide (II) synthesis step, as described above, a post step for eliminating unreacted raw material components can be further provided.
When diamine remains in the reaction system, isocyanate (described later) can be added and reacted with diamine. In this case, the reaction temperature is usually 40 ° C to 120 ° C.

As the isocyanate, a polyisocyanate having two or more isocyanate groups is usually used.
Examples of the polyisocyanate include aliphatic isocyanate, aromatic isocyanate, and alicyclic isocyanate. These can be used alone or in combination of two or more.

  Examples of the aromatic isocyanate include diphenylmethane diisocyanate (MDI) such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2′-diphenylmethane diisocyanate; crude diphenylmethane diisocyanate; 2,4-toluene diisocyanate, 2 Tolylene diisocyanate (TDI) such as 1,6-toluene diisocyanate; 1,4-naphthalene diisocyanate, naphthalene diisocyanate (NDI) such as 1,5-naphthalene diisocyanate; 1,5-tetrahydronaphthalene diisocyanate; 1,2-phenylene diisocyanate, Phenylene diisocyanates (PDI) such as 1,3-phenylene diisocyanate and 1,4-phenylene diisocyanate; Diisocyanate (XDI); tetramethylxylylene diisocyanate (TMXDI); tolidine diisocyanate (TODI); 2,4,6-trimethylphenyl-1,3-diisocyanate, 2,4,6-triisopropylphenyl-1,3- Diisocyanate, chlorophenylene-2,4-diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate and the like.

Examples of the aliphatic isocyanate include ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHMDI), dodecamethylene diisocyanate, lysine diisocyanate (LDI), and lysine triisocyanate (LTI). Can be mentioned.
Examples of the alicyclic isocyanate include isophorone diisocyanate (IPDI), cyclohexylene diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate, hydrogenated XDI (H ₆ XDI), hydrogenated MDI (H ₁₂ MDI), norbornene diisocyanate. (NBDI) and the like.

  The thixotropic agent of the present invention is blended in a one-component moisture-curable urethane resin composition to give excellent thixotropic properties. As the curable urethane resin in the one-component moisture-curable urethane resin composition, any known resin can be applied. For example, (a) an isocyanate group-containing urethane prepolymer obtained by reacting a polyol containing more than 50% by weight of a polyether polyol with an excess of a polyisocyanate, and (b) 50% by weight of a polyether ester polyol. An isocyanate group-containing urethane prepolymer obtained by reacting an excess of polyol and excess polyisocyanate, (U) a polyol containing more than 50% by weight of polyester polyol, and an excess of polyisocyanate. The obtained isocyanate group-containing urethane prepolymer, (d) an isocyanate group-containing urethane prepolymer obtained by reacting a polyol containing more than 50% by mass of a polyol not having an ether bond with excess polyisocyanate, etc. Is mentioned. These isocyanate group-containing urethane prepolymers may be used alone or in combination of two or more. Furthermore, it can also be used in combination with curable urethane resins other than those described above.

  Of the above embodiments (a) to (d), as embodiment (c), the polyester polyol is preferably obtained by reacting a polyol containing 80% by mass or more, more preferably 90% by mass or more with excess polyisocyanate. When the isocyanate group-containing urethane prepolymer is used, the resulting one-component moisture-curable urethane resin composition is particularly excellent in the balance between thixotropy and storage stability.

2. One-component moisture-curable urethane resin composition The one-component moisture-curable urethane resin composition of the present invention is a prepolymer having an isocyanate group (NCO) obtained by reacting [A] polyol with polyisocyanate. A prepolymer (hereinafter also referred to as “component [A]”) in which the content ratio of the total amount of isocyanate groups (NCO) is 2.5 to 11% with respect to the molecular weight of the prepolymer. And [B] the thixotropic agent of the present invention (hereinafter also referred to as “component [B]”).

The polyol (hereinafter referred to as “polyol (A1)”) used for forming the component [A] is not particularly limited as long as it has two or more hydroxyl groups. The number of hydroxyl groups contained in the polyol (A1) is preferably 2 to 4 from the viewpoints of storage stability and curability (touch drying property) of the composition.
The average hydroxyl value of the polyol (A1) is preferably 30 to 250 mgKOH / g, more preferably 40 from the viewpoints of workability when handling the composition, curability (touch drying property), and storage stability. ~ 170 mg KOH / g. The hydroxyl value can be measured according to JIS K1557-1 or JIS K0070.
Furthermore, the number average molecular weight (hereinafter referred to as “Mn”) of the polyol (A1) is determined from the viewpoint of storage stability of the composition, curability (touch drying property), and workability when handling the composition. Preferably it is 500-8,000. When this Mn is too large, curability (touch drying property) and storage stability may be lowered. On the other hand, when Mn is too small, workability may be reduced.

Examples of the polyol (A1) include polyhydric alcohols; polyhydric phenols; alkanolamines having two or more hydroxyl groups; polyether polyols; polyester polyols; polyether ester polyols; acrylic polyols; Vegetable oil polyol (soybean oil polyol, castor oil polyol, etc.); polydiene polyol (polybutadiene polyol, etc.); silicone polyol; vinyl monomer in the presence of at least one compound (raw material polyol) selected from these polyols And polymer polyols obtained by polymerizing. These may be used alone or in combination of two or more.
In the present invention, since a composition excellent in thixotropic property, storage stability and curability is obtained, the polyol (A1) is a compound having an ester bond (hereinafter referred to as “polyol (A11)”). Preferably there is.

  The number of ester bonds contained in the polyol (A11) is not particularly limited. In addition, Mn of the polyol (A11) is preferably 500 to 8,000, more preferably 1,000 to 6,000, from the viewpoints of thixotropic property, storage stability, and curability (touch drying property). Preferably, it is 1,500 to 5,000.

  Examples of the polyol (A11) include polyester polyols and polyether ester polyols. These may be used individually by 1 type and may be used in combination of 2 or more type. Of these, polyester polyol is preferred.

  Examples of the polyester polyol include a compound obtained by reacting a carboxylic acid having at least one carboxyl group with a polyhydric alcohol (hereinafter referred to as “polyester polyol (A11a)”), a hydroxycarboxylic acid, and a polyvalent alcohol. Examples thereof include compounds obtained by reacting glycidyl ether of alcohol (hereinafter referred to as “polyester polyol (A11b)”).

  The case where the polyester polyol is a polyester polyol (A11a) formed from a carboxylic acid having at least one carboxyl group and a polyhydric alcohol will be described.

The carboxylic acid may have another functional group such as a hydroxyl group.
Examples of the polyhydric alcohol include a diol having two hydroxyl groups and a polyol having three or more hydroxyl groups.

  Among the polyhydric alcohols, diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, , 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8- Octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, polyoxyethylene glycol, dipropylene glycol , Tripropylene glycol, polyoxyp Aliphatic diols such as (poly) alkylene glycols such as pyrene glycol, ditetramethylene glycol, polytetramethylene ether glycol; cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol, hydrogenated bisphenol A and other alicyclic diols; hydroquinone, resorcin, dihydroxyphenyl, naphthalenediol, dihydroxydiphenyl ether, bisphenol A, bisphenol A, ethylene oxide, propylene oxide Adducts added with alkylene oxides such as diethoxylated bisphenol A, p-xylylene glycol, m-xylylene glycol, o-xylylene glycol 4,4'-bishydroxymethylbiphenyl, 4,2'-bishydroxymethylbiphenyl, 2,2'-bishydroxymethylbiphenyl, 4,3'-bishydroxymethylbiphenyl, 3,3'-bishydroxymethyl And aromatic diols such as biphenyl and 3,2′-bishydroxymethylbiphenyl. These may be used alone or in combination of two or more.

  Among the polyhydric alcohols, polyols include aliphatic triols such as alkanetriols such as glycerin, trimethylolpropane, trimethylolethane, hexanetriol; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc. Examples include aliphatic polyols such as alkane polyols. These may be used alone or in combination of two or more.

  As said polyester polyol (A11a), the compound (henceforth "polyester polyol (A11a-1)") obtained by carrying out dehydration condensation using hydroxycarboxylic acid together with a polyhydric alcohol as carboxylic acid; Carboxylic acid A compound obtained by dehydration condensation using a dicarboxylic acid as a polyhydric alcohol and a diol as a polyhydric alcohol (hereinafter referred to as “polyester polyol (A11a-2)”); a dicarboxylic acid as a carboxylic acid, a lower alcohol or the like Examples of the compound obtained by subjecting to a transesterification by using a diol that is a polyhydric alcohol; a lactone polyester polyol; a polycarbonate polyol and the like.

  Examples of the hydroxycarboxylic acid used for forming the polyester polyol (A11a-1) include 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 2-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 2-hydroxyoctanoic acid, 2 -Hydroxy-2-methylpropanoic acid, 2-hydroxy-2-methylbutanoic acid, 2-hydroxy-2-ethylbutanoic acid, 2-hydroxy-2-methylpentanoic acid, 2-hydroxy-2-ethylpentanoic acid, 2-hydroxy 2-propylpentanoic acid, 2-hydroxy-2-butylpentanoic acid, 2-hydroxy-2-methylhexanoic acid, 2-hydroxy-2-ethylhexanoic acid, 2-hydroxy-2-propylhexanoic acid, 2-hydroxy 2-butylhexanoic acid, 2-hydroxy-2-pentylhe Sanic acid, 2-hydroxy-2-methylheptanoic acid, 2-hydroxy-2-methylheptanoic acid, 2-hydroxy-2-ethylheptanoic acid, 2-hydroxy-2-propylheptanoic acid, 2-hydroxy-2-butyl Heptanoic acid, 2-hydroxy-2-pentylheptanoic acid, 2-hydroxy-2-hexylheptanoic acid, 2-hydroxy-2-methyloctanoic acid, 2-hydroxy-2-ethyloctanoic acid, 2-hydroxy-2-propyl Octanoic acid, 2-hydroxy-2-butyloctanoic acid, 2-hydroxy-2-pentyloctanoic acid, 2-hydroxy-2-hexyloctanoic acid, 2-hydroxy-2-heptyloctanoic acid, 3-hydroxypropanoic acid, 3 -Hydroxybutanoic acid, 3-hydroxypentanoic acid, 3-hydroxyhexanoic acid, 3-hydride Xyheptanoic acid, 3-hydroxyoctanoic acid, 3-hydroxy-3-methylbutanoic acid, 3-hydroxy-3-methylpentanoic acid, 3-hydroxy-3-ethylpentanoic acid, 3-hydroxy-3-methylhexanoic acid, 3- Hydroxy-3-ethylhexanoic acid, 3-hydroxy-3-propylhexanoic acid, 3-hydroxy-3-methylheptanoic acid, 3-hydroxy-3-ethylheptanoic acid, 3-hydroxy-3-propylheptanoic acid, 3- Hydroxy-3-butylheptanoic acid, 3-hydroxy-3-methyloctanoic acid, 3-hydroxy-3-ethyloctanoic acid, 3-hydroxy-3-propyloctanoic acid, 3-hydroxy-3-butyloctanoic acid, 3- Hydroxy-3-pentyloctanoic acid, 4-hydroxybutanoic acid, 4-hydroxypentanoic acid 4-hydroxyhexanoic acid, 4-hydroxyheptanoic acid, 4-hydroxyoctanoic acid, 4-hydroxy-4-methylpentanoic acid, 4-hydroxy-4-methylhexanoic acid, 4-hydroxy-4-ethylhexanoic acid, 4 -Hydroxy-4-methylheptanoic acid, 4-hydroxy-4-ethylheptanoic acid, 4-hydroxy-4-propylheptanoic acid, 4-hydroxy-4-methyloctanoic acid, 4-hydroxy-4-ethyloctanoic acid, 4 -Hydroxy-4-propyloctanoic acid, 4-hydroxy-4-butyloctanoic acid, 5-hydroxypentanoic acid, 5-hydroxyhexanoic acid, 5-hydroxyheptanoic acid, 5-hydroxyoctanoic acid, 5-hydroxy-5-methyl Hexanoic acid, 5-hydroxy-5-methylheptanoic acid, 5-hydroxy-5-e Luheptanoic acid, 5-hydroxy-5-methyloctanoic acid, 5-hydroxy-5-ethyloctanoic acid, 5-hydroxy-5-propyloctanoic acid, 6-hydroxyhexanoic acid, 6-hydroxyheptanoic acid, 6-hydroxyoctanoic acid 6-hydroxy-6-methylheptanoic acid, 6-hydroxy-6-methyloctanoic acid, 6-hydroxy-6-ethyloctanoic acid, 7-hydroxyheptanoic acid, 7-hydroxyoctanoic acid, 7-hydroxy-7-methyl Octanoic acid, 8-hydroxyoctanoic acid, 8-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, 11-hydroxystearic acid, 12-hydroxystearic acid, 8-hydroxypalmitic acid, 9-hydroxypalmitic acid 10-hydroxypalmichi Acid, 11-hydroxypalmitic acid, 12-hydroxypalmitic acid, ricinoleic acid (ricinoleic acid), castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, ε-hydroxycaproic acid, 2-hydroxynaphthalene-3-carboxylic acid 2-hydroxynaphthalene-6-carboxylic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolvaleric acid, 2,2-dimethylolpentanoic acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, 2-oxide A decanoic acid etc. are mentioned. These may be used alone or in combination of two or more.

  The manufacturing method of the polyester polyol (A11a-1) using hydroxycarboxylic acid and a polyhydric alcohol is not specifically limited, It can be based on a well-known method.

  The dicarboxylic acid used for forming the polyester polyol (A11a-2) may be any of aliphatic dicarboxylic acid, aromatic dicarboxylic acid and alicyclic dicarboxylic acid. The preferred number of carbon atoms of the dicarboxylic acid is 4 or more. Among the description of the method for producing the thixotropic agent of the present invention, the compounds exemplified as the dicarboxylic acid used in the diamide (I) synthesis step may be used alone or Two or more can be used in combination.

  Examples of the polyester polyol (A11a-2) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene-butylene adipate diol, polyneopentyl-hexamethylene adipate diol, poly 3- Methylpentane adipate diol, polyethylene terephthalate diol, polybutylene terephthalate diol, polyhexamethylene terephthalate diol, polyneopentyl terephthalate diol, polyethylene-butylene terephthalate diol, polyneopentyl-hexamethylene terephthalate diol, poly 3-methylpentane terephthalate diol, polyethylene Isophthalate diol, poly Butylene isophthalate diol, polyhexamethylene isophthalate diol, polyneopentyl Louis softer rate diol, polyethylene - butylene isophthalate diol, polyneopentyl - hexamethylene isophthalate diol, poly 3-methylpentane isophthalate diol.

  The manufacturing method of the polyester polyol (A11a-2) using dicarboxylic acid and a polyhydric alcohol is not specifically limited, It can be based on a well-known method.

  Next, the case where the polyester polyol is a polyester polyol (A11b) formed from hydroxycarboxylic acid and a glycidyl ether of a polyhydric alcohol will be described.

  The said hydroxycarboxylic acid can use the compound illustrated as hydroxycarboxylic acid used for formation of the said polyester polyol (A11a-1) individually or in combination of 2 or more.

  The glycidyl ether of the polyhydric alcohol can be a compound containing an aliphatic hydrocarbon chain, an alicyclic hydrocarbon chain or an aromatic hydrocarbon chain, such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, sorbitol polyglycidyl ether, polyglycerol poly Glycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether Le, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like. These may be used alone or in combination of two or more.

  The manufacturing method of the polyester polyol (A11b) using hydroxycarboxylic acid and the glycidyl ether of polyhydric alcohol is not specifically limited, It can be based on a well-known method.

  Examples of the polyether ester polyol include at least one compound selected from polyhydric alcohols, polyhydric phenols, and alkanolamines, ethylene oxide, propylene oxide, 1,2-, 2,3-, or 1,4-butylene. Compounds obtained by reacting a polyether polyol obtained by addition (block and / or random addition) of alkylene oxide such as oxide and a carboxylic acid having two or more carboxyl groups; polyethylene glycol, polypropylene glycol In addition, a polyalkylene polyol such as a propylene oxide adduct of glycerin is reacted with a carboxylic acid anhydride such as succinic anhydride, adipic anhydride or phthalic anhydride and a compound having a cyclic ether group such as ethylene oxide or propylene oxide. It is not include the compounds obtained.

  In the present invention, the polyol (A11) is particularly preferably a polyester polyol.

  The said polyol (A1) may consist only of a polyol (A11), and may consist of a polyol (A11) and another polyol. The lower limit of the content ratio of the polyol (A11) constituting the polyol (A1) is preferably 50% by mass, more preferably 80% by mass, and still more preferably 90% by mass with respect to 100% by mass of the polyol (A1). It is. The composition containing the component [A] obtained using the polyol (A1) containing the polyol (A11) is excellent in storage stability and thixotropic properties.

The polyisocyanate (hereinafter referred to as “polyisocyanate (A2)”) used for forming the component [A] is not particularly limited as long as it is a compound having two or more isocyanate groups.
As said polyisocyanate, the compound illustrated as isocyanate (polyisocyanate) used in order to make it react with a monoamine or diamine among description of the manufacturing method of the thixotropic agent of this invention mentioned above individually or in combination of 2 or more Can be used. Furthermore, modified products of these polyisocyanates can also be used.
Examples of the modified isocyanate include urethane-modified isocyanate compounds, dimers, trimers, carbodiimide-modified products, allophanate-modified products, burette-modified products, urea-modified products, isocyanurate-modified products, oxazolidone-modified products, and isocyanate group-terminated prepolymers. Examples thereof include polymers.

  The component [A] is a compound having an isocyanate group obtained by reacting the polyol (A1) with the polyisocyanate (A2). And this component [A] has moisture crosslinking reactivity. That is, this cross-linking reactivity is a property derived from a cross-linking reaction initiated by the reaction of the isocyanate group and moisture (water) of the component [A].

  From the viewpoint of curability of the one-component moisture-curable urethane resin composition of the present invention, the content ratio of the total amount (total atomic weight) of isocyanate groups (NCO) constituting the component [A] is the component [A]. The molecular weight is preferably 2.5 to 11%, more preferably 3 to 10.5%, and still more preferably 3.5 to 10%. When the said content rate is too high, there exists a tendency for storage stability to fall. On the other hand, when the said content rate is too low, there exists a tendency for workability | operativity at the time of handling a composition to fall.

In forming the component [A], the polyol (A1) and the polyisocyanate (A2) have an isocyanate group possessed by the polyisocyanate (A2) with respect to an active hydrogen group containing a hydroxyl group possessed by the polyol (A1). Used to be in excess.
Reaction of the said polyol (A1) and the said polyisocyanate (A2) can be advanced by heating and stirring at the temperature of 50 to 100 degreeC normally without a solvent. During or after the reaction of these compounds, a urethanization catalyst such as a metal salt, an organic tin compound, an organic bismuth compound, or an amine can be used in combination as necessary.
Moreover, in the case of reaction of the said polyol (A1) and the said polyisocyanate (A2), as long as these reactions are not inhibited, you may make the additive mentioned later coexist in a reaction system.

  Mn of the component [A] is preferably 500 to 8,000, more preferably 1,000 to 6,000, and still more preferably, from the viewpoint of storage stability of the composition and workability when handling the composition. 1,500 to 5,000.

The essential components in the one-component moisture-curable urethane resin composition of the present invention are the component [A] and the component [B] which is the thixotropic agent of the present invention.
The content of the component [B] in the one-component moisture-curable urethane resin composition of the present invention is preferably more than 0 parts by mass and 50 parts by mass or less with respect to 100 parts by mass of the component [A]. Preferably it is 0.05-40 mass parts, More preferably, it is 0.1-20 mass parts. If content of the said component [B] exists in the said range, it will be excellent in thixotropic property, storage stability, and sclerosis | hardenability.
In addition, the content of the component [B] in the one-component moisture-curable urethane resin composition of the present invention is preferably more than 0% by mass and 10% by mass or less, more preferably 1%, based on the entire composition. -10 mass%, More preferably, it is 1-5 mass%. If content of the said component [B] exists in the said range, it will be excellent in thixotropic property, storage stability, and sclerosis | hardenability.

  The one-component moisture-curable urethane resin composition of the present invention further comprises a curing catalyst, a filler, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, an antifoaming agent, depending on the purpose and application. Lubricants, weathering stabilizers, light stabilizers, heat stabilizers, colorants such as pigments and dyes, fluorescent brighteners, tackifiers, waxes, conductivity-imparting agents, antistatic agents, water repellents, oil repellents, antiseptics It can contain an agent.

  The curing catalyst may be a catalyst known per se, and examples thereof include tertiary amines and organotin compounds. These may be used alone or in combination of two or more.

  Examples of the tertiary amine include monoamine, diamine, triamine, polyamine, cyclic amine, alcohol amine, ether amine and the like. Specific compounds include triethylamine, tripropylamine, tributylamine, N, N-dimethylcyclohexylamine, triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′. -Tetramethylpropane-1,3-diamine, N, N, N ', N'-tetramethylhexane-1,6-diamine, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, tetramethylguanidine, N, N-dipolyoxyethylene stearylamine, N, N-dipolyoxyethylene tallow alkylamine, N, N′-dimethyl Piperazine, N-methyl-N ′-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N-ethyl Morpholine, N- (N ′, N′-dimethylaminoethyl) -morpholine, 1,2-dimethylimidazole, 2-methylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanol Amine, N-methyl-N ′-(2-hydroxyethyl) -piperazine, N- (2-hydroxyethyl) -morpholine, bis- (2-dimethylaminoethyl) ether, ethylene glycol bis- (3-dimethyl)- Aminopropyl ether, N, N′-dimethylbenzylamine, N, N′-dimethylcyclohexylamine, 1,4-diaza- (2,2,2) -bicyclooctane, tetramethylguanidine, 1,8-diazabicyclo [5 4.0] -7-undecene, 1,4-diazabicyclo 2.2.2] octane, bis (2-dimethylaminoethyl) ether. The tertiary amines can be used alone or in combination of two or more.

  Examples of the organic tin compound include butyltin trichloride, dibutyltin diacetate, dibutyltin dilaurate, dimethyltin mercaptide, dibutyltin mercaptide, dimethyltin dilaurate, stannous octoate, tin oleate, and the like. The said organotin compound can be used individually or in combination of 2 or more.

  When the one-component moisture-curable urethane resin composition of the present invention contains a tertiary amine as a curing catalyst, the content thereof is preferably 0.5 to 100 parts by mass of the component [A]. The amount is 5.0 parts by mass, more preferably 1.0 to 3.0 parts by mass, and still more preferably 1.2 to 2.0 parts by mass.

  When the one-component moisture-curable urethane resin composition of the present invention contains an organotin compound as a curing catalyst, the content thereof is preferably 0.05 to 100 parts by mass of the component [A]. 0.5 parts by mass, more preferably 0.1 to 0.3 parts by mass, and still more preferably 0.12 to 0.2 parts by mass.

  Examples of the filler include calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, magnesium hydroxide, carbon black, clay, talc, fumed silica, calcined silica, precipitated silica, ground silica, fused silica, kaolin, and diatom. Examples include soil, zeolite, titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide, aluminum oxide, magnesium oxide, aluminum sulfate, glass fiber, carbon fiber, glass balloon, shirasu balloon, saran balloon, and phenol balloon. The said filler can be used individually or in combination of 2 or more types.

  When the one-component moisture-curable urethane resin composition of the present invention contains a filler, the content is preferably 5 to 300 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the component [A]. It is 10-100 mass parts, More preferably, it is 20-50 mass parts.

  Examples of the plasticizer include phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, aliphatic monobasic acid ester, aliphatic dibasic acid ester, phosphoric acid ester, polyhydric alcohol ester, epoxy plasticizer, high Examples include molecular plasticizers and chlorinated paraffins. These can be used alone or in combination of two or more.

  Examples of phthalic acid esters include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, di-n-hexyl phthalate, dicyclohexyl phthalate, diheptyl phthalate, Di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, diphenyl phthalate, di (2-ethylhexyl) phthalate, di (2-butoxyethyl) phthalate Benzyl 2-ethylhexyl phthalate, benzyl n-butyl phthalate, benzylisononyl phthalate, dimethyl isophthalate and the like.

  Examples of trimellitic acid esters include tributyl trimellitic acid, trihexyl trimellitic acid, tri-n-octyl trimellitic acid, tri-2-ethylhexyl trimellitic acid, triisodecyl trimellitic acid, and the like.

  Examples of pyromellitic acid esters include tetrabutyl pyromellitic acid, tetrahexyl pyromellitic acid, tetra-n-octyl pyromellitic acid, tetra-2-ethylhexyl pyromellitic acid, and tetradecyl pyromellitic acid.

  Aliphatic monobasic esters include butyl oleate, methyl oleate, methyl octoate, butyl octoate, methyl dodecanoate, butyl dodecanoate, methyl palmitate, butyl palmitate, methyl stearate, butyl stearate, linole Examples thereof include methyl acid, butyl linoleate, methyl isostearate, butyl isostearate, methyl acetyl ricinolate, and butyl acetyl ricinolate.

  Examples of the aliphatic dibasic acid ester include dimethyl adipate, diethyl adipate, di-n-propyl adipate, diisopropyl adipate, diisobutyl adipate, di-n-octyl adipate, di (2-ethylhexyl) adipate, Diisononyl adipate, diisodecyl adipate, di (2-butoxyethyl) adipate, di (butyl diglycol) adipate, heptylnonyl adipate, dimethyl azelate, di-n-octyl azelate, di (2-ethylhexyl azelate) ), Diethyl succinate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, di (2-ethylhexyl) sebacate, dibutyl fumarate, di (2-ethylhexyl) fumarate, maleic acid Dimethyl, ma Diethyl ynoic acid, maleic di -n- butyl, maleate, di (2-ethylhexyl), and the like.

  Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-n-amyl phosphate, triphenyl phosphate, tri-o-cresyl phosphate, trixylenyl phosphate, diethyl 2-ethylhexyl phosphate, Examples thereof include diphenyl cresyl phosphate, tris phosphate (2-butoxyethyl), and tris phosphate (2-ethylhexyl).

  Examples of polyhydric alcohol esters include diethylene glycol diacetylate, diethylene glycol dibenzoate, glycerol monooleate, glycerol tributyrate, glycerol triacetate, glyceryl-tri (acetylricinoleate), and triethylene glycol diacetate.

Epoxy plasticizers include epoxidized vegetable oil plasticizers, epoxidized fatty acid alkyl esters, and the like.
Examples of the epoxidized vegetable oil-based plasticizer include epoxidized soybean oil and epoxidized linseed oil.
Examples of the epoxidized fatty acid alkyl ester include methyl epoxy stearate, butyl epoxy stearate, 2-ethylhexyl epoxy stearate and the like.
In addition, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2-epoxypropane, bisphenol A diglycidyl ether, vinyldicyclohexene diepoxide, 2,2-bis (4-hydroxy) And a polycondensate of phenyl) propane and epichlorohydrin.

  The polymer plasticizer preferably has a molecular weight of 500 or more, a liquid polyurethane resin, a polyester plasticizer obtained from dicarboxylic acid and glycol; an etherified or esterified product of polyalkylene glycol such as polyethylene glycol or polypropylene glycol A polyether plasticizer such as a saccharide polyether obtained by addition polymerization of an alkylene oxide such as ethylene oxide or propylene oxide to a saccharide polyhydric alcohol such as sucrose, and then etherification or esterification; poly-α- Examples thereof include polystyrene plasticizers such as methylstyrene; low-viscosity (meth) acrylic ester plasticizers, and the like.

As the plasticizer, a phosphate ester and a polymer type plasticizer are preferable from the viewpoint of controlling the viscosity of the composition.
When the one-component moisture-curable urethane resin composition of the present invention contains a plasticizer, the content thereof is preferably 10 to 300 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the component [A]. It is 12-100 mass parts, More preferably, it is 15-40 mass parts.

  The viscosity of the one-component moisture-curable urethane resin composition of the present invention is preferably 10 to 600 Pa · s, more preferably 50 to 400 Pa · s, when measured at a temperature of 25 ° C. and a rotation speed of 5 rpm. Since the viscosity of a composition exists in the said range, it is excellent in workability | operativity at the time of handling a composition.

  Since the one-component moisture-curable urethane resin composition of the present invention contains specific components [A] and [B], it is excellent in thixotropic property and moisture-curing property. And when a composition is stored at the temperature exceeding 30 degreeC, the change of physical properties, such as a viscosity, can be suppressed and the storage stability which was not in the conventional composition is provided. Therefore, the one-component moisture-curable urethane resin composition of the present invention has excellent thixotropic properties in the above viscosity range and is excellent in storage stability. The one-component moisture-curable urethane resin composition of the present invention has little change in physical properties over time in a temperature range of about 0 ° C. to 40 ° C. Leads to stable and efficient progress.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Physical property measuring method and evaluation method The physical property measuring method and the evaluation method according to the thixotropic agent and the one-component moisture-curable urethane resin composition are as follows.
1-1. Number average molecular weight (Mn)
Measurement was performed using a high-performance SEC dedicated system “Shodex GPC-104” (trade name) manufactured by Showa Denko KK. The eluent is tetrahydrofuran or chloroform.
1-2. Viscosity Immediately after the production of the one-pack type moisture curable urethane resin composition and the viscosity after standing for 10 days at a temperature of 40 ° C., the “RB80 type viscometer” (trade name) manufactured by Toki Sangyo Co., Ltd. Used, and measured at a temperature of 25 ° C. and a rotation speed of 5 rpm and 50 rpm.
1-3. Thixotropy Using the viscosity measured in the above section 1-2, the viscosity (V ¹¹ and V ¹² ) at 5 rpm and 50 rpm immediately after the production of the one-component moisture-curable urethane resin composition, V ¹¹ / V ¹² value was calculated, it was determined thixotropy to the following criteria.
A: V ¹¹ / V ¹² > 4 and extremely excellent in thixotropic property.
○: 3 ≦ V ¹¹ / V ¹² ≦ 4, and excellent thixotropic properties.
X: V ¹¹ / V ¹² <3, which is inferior to thixotropy.

◎：２０％未満であり、貯蔵安定性に極めて優れる。
○：２０％〜４０％であり、貯蔵安定性に優れる。
×：４０％を超えており、貯蔵安定性に劣る。 1-4. Storage stability Among the viscosities measured in the above section 1-2, the viscosity at the same rotational speed (viscosity V ¹¹ or V ¹² immediately after the production of the one-component moisture-curable urethane resin composition, and the temperature 40 The change rates S1 (%) and S2 (%) were calculated by the following formulas (1) and (2) using the viscosity V ²¹ or V ²² ) after standing at 10 ° C. for 10 days. Storage stability was determined according to the following criteria, with the higher of S1 and S2.

A: Less than 20% and extremely excellent in storage stability.
A: 20% to 40%, and excellent storage stability.
X: It exceeds 40% and is inferior in storage stability.

1-5. Curability The curability of the composition was evaluated by the touch-drying property according to the following method.
After the one-component moisture-curable urethane resin composition is applied to a flat substrate, the surface of the coating film is left every one minute from the coating film formation in a state of standing at a temperature of 25 ° C. and a humidity of 40%. Touched. Then, the time until the uncured product did not adhere to the finger was measured.
A: The tack free time is less than 10 minutes, and the touch dryness is extremely excellent.
A: Tack free time is 10 to 15 minutes, and the touch dryness is excellent.
X: The tack free time exceeds 15 minutes and is inferior to the touch dryness.
1-6. A one-component moisture-curing urethane resin composition is poured into an electrically insulating mold and allowed to stand for 24 hours under conditions of a temperature of 25 ° C. and a humidity of 40% to be cured, and a plate-shaped test piece of 100 mm × 100 mm × 3 mm Got. The volume resistivity was measured using the electrode “SME-8310” (model name) manufactured by Hioki Electric Co., Ltd. and the digital super insulation / microammeter “DSM-8104” (model name) manufactured by the company. Judged by criteria.
A: Volume resistance value exceeds 1.0E + 13 Ω · cm, and the electrical insulation is extremely excellent.
○: The volume resistance value is 1.0E + 11 to 1.0E + 13 Ω · cm, which is excellent in electrical insulation.
X: Volume resistance value is less than 1.0E + 11 Ω · cm, and is inferior in electrical insulation.

2. Thixotropic agent Example 1-1 (Synthesis of thixotropic agent (B-1) containing diamide (b-1))
620 parts of dimer acid and 640 parts of stearylamine were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas supply device, a water inspection device, and a heating device. Thereafter, while stirring these components and introducing nitrogen gas into the reaction system, the mixture was reacted at a temperature of 240 ° C. for 5 hours to obtain diamide (b-1) having Mn of 1,100. Next, 12 parts of tolylene diisocyanate (hereinafter referred to as “TDI”) is added to the reaction system and reacted with the remaining stearylamine to form polyurea, and thixotropic modification comprising the diamide (b-1) and polyurea. The imparting agent (B-1) was obtained. The content of diamide (b-1) contained in the thixotropic agent (B-1) is 99% (see Table 1).

Example 1-2 (synthesis of thixotropic agent (B-2) containing diamide (b-2))
230 parts of sebacic acid and 640 parts of stearylamine were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas supply device, a water inspection device, and a heating device. Then, while stirring these components and introducing nitrogen gas into the reaction system, the mixture was reacted at a temperature of 240 ° C. for 5 hours to obtain diamide (b-2) having Mn of 800. Next, 7 parts of TDI was added to the reaction system and reacted with the remaining stearylamine to form polyurea, whereby the thixotropic agent (B-2) comprising the diamide (b-2) and polyurea was obtained. The content ratio of diamide (b-2) contained in this thixotropic agent (B-2) is 99% (see Table 1).

Example 1-3 (Synthesis of thixotropic agent (B-3) containing diamide (b-3))
730 parts of behenic acid and 130 parts of hexamethylenediamine were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas supply device, a water inspection device, and a heating device. Then, while stirring these components and introducing nitrogen gas into the reaction system, the mixture was reacted at a temperature of 240 ° C. for 5 hours to obtain diamide (b-3) having Mn of 780. Next, 2 parts of TDI was added to the reaction system and reacted with the remaining hexamethylenediamine to form polyurea, whereby the thixotropic agent (B-3) composed of the diamide (b-3) and polyurea was obtained. The content ratio of diamide (b-3) contained in this thixotropic agent (B-3) is 99% (see Table 1).

Example 1-4 (Synthesis of thixotropic agent (B-4) containing diamide (b-4))
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas supply device, a water inspection device, and a heating device, 590 parts of behenic acid and 500 parts of dimer diamine were charged. Thereafter, while stirring these components and introducing nitrogen gas into the reaction system, the mixture was reacted at a temperature of 240 ° C. for 5 hours to obtain diamide (b-4) having Mn of 1,200. Next, 15 parts of TDI was added to the reaction system and reacted with the remaining dimer diamine to form polyurea, whereby the thixotropic agent (B-4) comprising the diamide (b-4) and polyurea was obtained. The content ratio of diamide (b-4) contained in this thixotropic agent (B-4) is 98% (see Table 1).

Example 1-5 (Synthesis of thixotropic agent (B-5) containing diamide (b-5))
620 parts of stearic acid and 160 parts of 1,3-bisaminocyclohexane were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas supply device, a water inspection device, and a heating device. Then, while stirring these components and introducing nitrogen gas into the reaction system, the mixture was reacted at a temperature of 240 ° C. for 5 hours to obtain diamide (b-5) having Mn of 700. Next, 7 parts of TDI was added to the reaction system, and reacted with the remaining 1,3-bisaminocyclohexane to form polyurea, and the thixotropic agent (B-5) comprising the diamide (b-5) and polyurea. Got. The content ratio of diamide (b-5) contained in this thixotropic agent (B-5) is 99% (see Table 1).

Example 1-6 (Synthesis of thixotropic agent (B-6) containing diamide (b-6))
630 parts of stearic acid, 45 parts of hexamethylenediamine and 110 parts of 1,3-bisaminocyclohexane were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas supply device, a water detection device and a heating device. Thereafter, while stirring these components and introducing nitrogen gas into the reaction system, the mixture was reacted at a temperature of 240 ° C. for 5 hours to obtain diamide (b-6) having Mn of 690. Next, 9 parts of TDI was added to the reaction system and reacted with the remaining hexamethylenediamine and 1,3-bisaminocyclohexane to form polyurea, which was a thixotropic agent comprising the diamide (b-6) and polyurea ( B-6) was obtained. The content ratio of diamide (b-6) contained in this thixotropic agent (B-6) is 99% (see Table 1).

Comparative Example 1-1 (Synthesis of thixotropic agent (B-7) containing diamide (b-7))
650 parts of lauric acid and 100 parts of ethylenediamine were charged into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas supply device, a water inspection device and a heating device. Thereafter, while stirring these components and introducing nitrogen gas into the reaction system, the mixture was reacted at a temperature of 240 ° C. for 5 hours to obtain diamide (b-7) having Mn of 460. Next, 2 parts of TDI was added to the reaction system and reacted with the remaining emethylenediamine to form polyurea, and the thixotropic agent (B-7) composed of the diamide (b-7) and polyurea was obtained. The content ratio of diamide (b-7) contained in this thixotropic agent (B-7) is 99% (see Table 1).

3. One-part moisture-curing urethane resin composition 3-1. Prepolymer The prepolymer used in the following synthesis example was used as the prepolymer used in the one-component moisture-curable urethane resin composition.

    Synthesis Example 1-1 (Synthesis of Prepolymer (A-1))

In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas supply device and a heating device, a castor oil-modified polyester polyol having a hydroxyl value of 85 mgKOH / g (trade name “# 1824”, manufactured by Ito Oil Co., Ltd., hereinafter “polyester polyol (a -1) ") 60 parts, 4,4'-diphenylmethane diisocyanate (trade name" Millionate MT ", manufactured by Nippon Polyurethane Industry Co., Ltd.), and tricresyl phosphate as a plasticizer (C-1) (product) 30 parts (name “TCP”, manufactured by Daihachi Chemical Industry Co., Ltd.) Thereafter, the temperature was raised while stirring these components, and the polyester polyol (a-1) and 4,4′-diphenylmethane diisocyanate were reacted at a temperature of 85 ° C. while introducing nitrogen gas into the reaction system (reaction). 3 hours). And the mixture (M-1) which consists of a prepolymer (A-1) whose content rate (NCO rate) of an isocyanate group is 4.0%, and Mn is 2,400, and tricresyl phosphate was obtained. .
The mass ratio of prepolymer (A-1) and tricresyl phosphate contained in this mixture (M-1) is 8: 3.

Synthesis Example 1-2 (Synthesis of prepolymer (A-2))
The content ratio of isocyanate groups is 6 in the same manner as in Synthesis Example 1-1 except that the amounts used of the polyester polyol (a-1) and 4,4′-diphenylmethane diisocyanate were 56 parts and 24 parts, respectively. The mixture (M-2) which consists of prepolymer (A-2) which is 0.0% and Mn is 1,600, and tricresyl phosphate was obtained.
The mass ratio of the prepolymer (A-2) and tricresyl phosphate contained in this mixture (M-2) is 8: 3.

Synthesis Example 1-3 (Synthesis of prepolymer (A-3))
The isocyanate group content is 8 as in Synthesis Example 1-1 except that the amounts of the polyester polyol (a-1) and 4,4′-diphenylmethane diisocyanate used are 52 parts and 28 parts, respectively. A mixture (M-3) consisting of a prepolymer (A-3) of 0.0% and Mn of 1,200 and tricresyl phosphate was obtained.
The mass ratio of prepolymer (A-3) and tricresyl phosphate contained in this mixture (M-3) is 8: 3.

Synthesis Example 1-4 (Synthesis of prepolymer (A-4))
The isocyanate group content is 12 in the same manner as in Synthesis Example 1-1 except that the amounts used of the polyester polyol (a-1) and 4,4′-diphenylmethane diisocyanate were 44 parts and 36 parts, respectively. A mixture (M-4) consisting of a prepolymer (A-4) of 0.0% and Mn of 800 and tricresyl phosphate was obtained.
The mass ratio of the prepolymer (A-4) and tricresyl phosphate contained in this mixture (M-4) is 8: 3.

Synthesis Example 1-5 (Synthesis of prepolymer (A-5))
The isocyanate group content is 3 in the same manner as in Synthesis Example 1-1 except that the amounts of the polyester polyol (a-1) and 4,4′-diphenylmethane diisocyanate are 63 parts and 17 parts, respectively. The mixture (M-5) which consists of a prepolymer (A-5) which is 0.0% and Mn is 3,200 and tricresyl phosphate was obtained.
The mass ratio of the prepolymer (A-5) and tricresyl phosphate contained in this mixture (M-5) is 8: 3.

Synthesis Example 1-6 (Synthesis of prepolymer (A-6))
In a reaction vessel equipped with a stirrer, thermometer, nitrogen gas supply device and heating device, 60 parts of the above polyester polyol (a-1), 4,4′-diphenylmethane diisocyanate (trade name “Millionate MT”, manufactured by Nippon Polyurethane Industry Co., Ltd. ) 20 parts and 30 parts of glyceryl-tri (acetylricinoleate) which is a plasticizer (C-2) were charged. Thereafter, the temperature was raised while stirring these components, and the polyester polyol (a-1) and 4,4′-diphenylmethane diisocyanate were reacted at a temperature of 85 ° C. while introducing nitrogen gas into the reaction system (reaction). 3 hours). And the mixture (M-) which the prepolymer (A-6) whose content rate (NCO rate) of an isocyanate group is 4.0%, and Mn is 2,400, and glyceryl-tri (acetyl ricinolate) 6) was obtained.
The mass ratio of the prepolymer (A-6) and glyceryl-tri (acetylricinoleate) contained in this mixture (M-6) is 8: 3.

Synthesis Example 1-7 (Synthesis of prepolymer (A-7))
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas supply device and a heating device, 300 parts of 1,6-hexanediol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd.) and 3,100 parts of ricinoleic acid (manufactured by Ito Oil Co., Ltd.) Was charged. Thereafter, these components were heated while being stirred, and reacted at a temperature of 210 ° C. while introducing nitrogen gas into the reaction system. When the acid value of the reaction system became 3 or less, the reaction was terminated (reaction time 20 hours), and had an average of 3.0 hydroxyl groups, a hydroxyl value of 55 mgKOH / g, and Mn of 3,000. A polyester polyol (a-2) was obtained.

Next, 60 parts of the above polyester polyol (a-2), 4,4′-diphenylmethane diisocyanate (trade name “Millionate MT”, Nippon Polyurethane Industry Co., Ltd.) was added to a reaction vessel equipped with a stirrer, thermometer, nitrogen gas supply device and heating device. 20 parts) and 30 parts of tricresyl phosphate (trade name “TCP”, manufactured by Daihachi Chemical Industry Co., Ltd.) which is a plasticizer (C-1) were charged. Thereafter, the temperature was increased while stirring these components, and the polyester polyol (a-2) and 4,4′-diphenylmethane diisocyanate were reacted at a temperature of 85 ° C. while introducing nitrogen gas into the reaction system (reaction). 3 hours). And the mixture (M-7) which consists of prepolymer (A-7) whose content rate (NCO rate) of isocyanate group is 4.0%, and Mn is 3,100, and tricresyl phosphate was obtained. .
The mass ratio of prepolymer (A-7) and tricresyl phosphate contained in this mixture (M-7) is 8: 3.

3-2. Preparation and Evaluation of One-Part Moisture-Curable Urethane Resin Composition Example 2-1
110 parts of the mixture (M-1) obtained in Synthesis Example 1-1 (consisting of 80 parts of the prepolymer (A-1) and 30 parts of the plasticizer (C-1)) was brought to 85 ° C. 3 parts of thixotropic agent (B-1) are added and dissolved, and 20 parts of aluminum hydroxide (trade name “Hijilite H-21”, Showa Denko KK) is used as a filler. As a catalyst, 1 part of triethylenediamine was blended and mixed. Subsequently, it cooled to room temperature and prepared the one-pack type moisture curable urethane resin composition (Table 2). The one-component moisture-curable urethane resin composition was evaluated, and the results are shown in Table 2.

Example 2-2
Instead of 110 parts of the mixture (M-1), 110 parts of the mixture (M-2) (consisting of 80 parts of prepolymer (A-2) and 30 parts of plasticizer (C-1)) was used. In the same manner as in Example 2-1, a one-component moisture-curable urethane resin composition was prepared and evaluated. The results are also shown in Table 2.

Example 2-3
Instead of 110 parts of mixture (M-1), 110 parts of mixture (M-3) (consisting of 80 parts of prepolymer (A-3) and 30 parts of plasticizer (C-1)) were used. In the same manner as in Example 2-1, a one-component moisture-curable urethane resin composition was prepared and evaluated. The results are also shown in Table 2.

Example 2-4
A one-component moisture-curable urethane resin composition was prepared in the same manner as in Example 2-1, except that the thixotropic agent (B-2) was used instead of the thixotropic agent (B-1). And evaluated. The results are also shown in Table 3.

Example 2-5
A one-component moisture-curable urethane resin composition was prepared in the same manner as in Example 2-1, except that the thixotropic agent (B-3) was used instead of the thixotropic agent (B-1). And evaluated. The results are also shown in Table 3.

Example 2-6
A one-component moisture-curable urethane resin composition was prepared in the same manner as in Example 2-1, except that the thixotropic agent (B-4) was used instead of the thixotropic agent (B-1). And evaluated. The results are also shown in Table 3.

Example 2-7
A one-component moisture-curable urethane resin composition was prepared in the same manner as in Example 2-1, except that the thixotropic agent (B-5) was used instead of the thixotropic agent (B-1). And evaluated. The results are also shown in Table 3.

Example 2-8
A one-component moisture-curable urethane resin composition was prepared in the same manner as in Example 2-1, except that the thixotropic agent (B-6) was used instead of the thixotropic agent (B-1). And evaluated. The results are also shown in Table 3.

Example 2-9
After 110 parts of the mixture (M-6) obtained in Synthesis Example 1-6 (consisting of 80 parts of prepolymer (A-6) and 30 parts of plasticizer (C-2)) was brought to 85 ° C., this 3 parts of thixotropic agent (B-1) are added and dissolved, and 20 parts of aluminum hydroxide (trade name “Hijilite H-21”, Showa Denko KK) is used as a filler. As a catalyst, 1 part of triethylenediamine was blended and mixed. Then, it cooled to room temperature and prepared the one-pack type moisture curable urethane resin composition (Table 3). The one-component moisture-curable urethane resin composition was evaluated, and the results are shown in Table 3.

Example 2-10
Instead of 110 parts of mixture (M-1), 110 parts of mixture (M-7) (consisting of 80 parts of prepolymer (A-7) and 30 parts of plasticizer (C-1)) were used. In the same manner as in Example 2-1, a one-component moisture-curable urethane resin composition was prepared and evaluated. The results are also shown in Table 3.

Comparative Example 2-1
A one-component moisture-curable urethane resin composition was prepared and evaluated in the same manner as in Example 2-1, except that the thixotropic agent was not blended. The results are also shown in Table 2.

Comparative Example 2-2
Instead of 110 parts of the mixture (M-1), 110 parts of the mixture (M-4) (consisting of 80 parts of the prepolymer (A-4) and 30 parts of the plasticizer (C-1)) was used. In the same manner as in Example 2-1, a one-component moisture-curable urethane resin composition was prepared and evaluated. The results are also shown in Table 2.

Comparative Example 2-3
Instead of 110 parts of mixture (M-1), 110 parts of mixture (M-5) (consisting of 80 parts of prepolymer (A-5) and 30 parts of plasticizer (C-1)) were used. In the same manner as in Example 2-1, a one-component moisture-curable urethane resin composition was prepared and evaluated. The results are also shown in Table 2.

Comparative Example 2-4
A one-component moisture-curable urethane resin composition was prepared in the same manner as in Example 2-1, except that the thixotropic agent (B-7) was used instead of the thixotropic agent (B-1). And evaluated. The results are also shown in Table 4.

Comparative Example 2-5
Instead of the thixotropic agent (B-1), fumed silica manufactured by Nippon Aerosil Co., Ltd. (trade name “Aerosil RY200”, hereinafter referred to as “thixotropic agent (B-8)”) was used. In the same manner as in Example 2-1, a one-component moisture-curable urethane resin composition was prepared and evaluated. The results are also shown in Table 4.

From the results in Tables 2 to 4, the following is clear.
Examples 2-1 to 2-10 are examples of a one-component moisture-curable urethane resin composition having the configuration of the present invention, and are excellent in thixotropic property, storage stability, and curability.
On the other hand, Comparative Example 2-1 was an example using a composition containing no thixotropic agent, and thixotropic properties were insufficient. Comparative Example 2-2 was an example using a composition containing a prepolymer having a total content of isocyanate groups of 12% relative to the molecular weight, and the storage stability was insufficient. . Comparative Example 2-3 was an example using a composition containing a prepolymer having a total content of isocyanate groups of 3% with respect to the molecular weight, and thixotropic property was insufficient. Comparative Example 2-4 is an example using a composition containing a thixotropic agent having Mn of 460, and thixotropic properties and storage stability were insufficient. Moreover, Comparative Example 2-5 is an example using a composition containing fumed silica as a thixotropic agent, and thixotropic properties and storage stability were insufficient.

The one-component moisture-curable urethane resin composition of the present invention is a cover for civil engineering or architectural resins, including adhesives, sealing agents, paints, coating agents, and sealants for civil engineering, construction, and vehicles. It is useful as a primer for woodworking. As a method of using as a sealing agent, for example, when an electronic component such as a semiconductor element is fixed at a predetermined position on a substrate, the semiconductor element is sealed by, for example, potting the composition against the electronic component. It can be carried out. Since the composition is excellent in thixotropic properties, a uniform moisture-cured film can be formed even when applied to an inclined portion, a side portion of a vertical member, or the like.
Moreover, it can also be used as a coating material for forming an electrically insulating protective film on electronic parts with overload, self-heating, etc., such as varistors, capacitors, resistors, and coils.

Claims (6)

A thixotropic agent blended in a one-part moisture-curable urethane resin composition, which is represented by the following general formula (I) and has a number average molecular weight of 500 to 3,000, And a thixotropic agent characterized by containing at least one of diamides (II) represented by the following general formula (II) and having a number average molecular weight of 500 to 3,000.

(In the formula, R ¹ and R ³ are the same or different and each is a monovalent hydrocarbon group, and R ² is a divalent hydrocarbon group.)

(In the formula, R ⁴ and R ⁶ are the same or different and each represents a monovalent hydrocarbon group, and R ⁵ represents a divalent hydrocarbon group.)   The thixotropic agent according to claim 1, further comprising polyurea.   [A] A prepolymer having an isocyanate group obtained by reacting a polyol and a polyisocyanate, wherein the content ratio of the total amount of the isocyanate group is 2.5 to 2.5 with respect to the molecular weight of the prepolymer. A one-component moisture-curable urethane resin composition comprising a prepolymer of 11% and the thixotropic agent according to claim 1 or 2.   The content of the thixotropic agent [B] is more than 0 parts by mass and 50 parts by mass or less with respect to 100 parts by mass of the prepolymer [A]. Urethane resin composition.   The one-component moisture-curable urethane resin composition according to claim 3 or 4, wherein the polyol includes a polyol having an ester bond, and the number average molecular weight of the ester bond-containing polyol is 500 to 8,000.   The ester bond-containing polyol is at least one selected from a polyol formed from a hydroxycarboxylic acid and a polyhydric alcohol, and a polyol formed from a hydroxycarboxylic acid and a glycidyl ether of a polyhydric alcohol. The one-component moisture-curable urethane resin composition according to claim 5.