JP4529665B2 - Urethane resin composition - Google Patents

Description

  The present invention relates to a urethane resin composition.

Urethane resin compositions are used for sealing materials, waterproofing agents, adhesives, and the like, but when used in such applications, thixotropic properties (thixotropy and slump resistance) are required.
In order to satisfy this requirement, a technique is known in which colloidal silica is added to the urethane resin composition or various additives are added in combination with colloidal silica (for example, Patent Documents 1 to 3). reference.)
However, with the addition of colloidal silica or the like, there is a problem that the resulting urethane resin composition thickens during storage or foaming or cracking occurs on the adhesive surface during curing.

In order to solve these problems, the present applicant has proposed a one-component thixotropic polyurethane composition containing a fatty acid ester-modified silicone oil as an active ingredient (see Patent Document 4).
However, in the invention described in Patent Document 4, it is necessary to add a considerable amount of fatty acid ester-modified silicone oil (at least about 1 part by mass with respect to 100 parts by mass of the urethane prepolymer) in order to obtain a predetermined thixotropy. Further, thixotropy imparted by addition of fatty acid ester-modified silicone oil may be insufficient under the current required characteristics.

Japanese Patent Publication No. 51-11656 Japanese Patent Publication No.53-5899 Japanese Patent Publication No. 3-15669 Japanese Patent Laid-Open No. 6-80755

  Therefore, the present invention is a urethane resin composition that is excellent in thixotropic properties, that is, thixotropy and slump resistance, is excellent in storage stability when used as one liquid, and further suppresses foaming and cracking during curing. The issue is to provide goods.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have added a silicone oil having a carboxy group (hereinafter also referred to as “carboxy-modified silicone oil”), so that the resulting composition has excellent thixotropic properties. Further, the present invention has been completed by finding a urethane resin composition that is excellent in storage stability when used as a single liquid and that further suppresses foaming and cracking during curing.
That is, this invention provides the urethane resin composition shown to the following (I)-(III).

(I) 100 parts by mass of urethane prepolymer (A), 0.1 to 20 parts by mass of silicone oil (B) composed of at least one silicone oil represented by the following general formula (1), calcium carbonate and / or Or the urethane resin composition containing 1-200 mass parts of silicas.

Where R ¹ And R ² Each independently represents an alkyl group or an aryl group, R ³ Represents a single bond or an alkylene group having 1 to 30 carbon atoms, m represents 0 or a positive integer, and n represents an integer of 1 or more. Also, multiple R ¹ , R ² And R ³ May be the same or different.

(II) The urethane resin composition according to claim 1, wherein the urethane prepolymer (A) uses a polyether polyol as a raw material polyol compound.

(III) The urethane resin composition according to (I) or (II), which is used for a sealing material, a waterproof material or an adhesive .

  As described below, according to the present invention, a urethane resin composition excellent in thixotropic properties, excellent in storage stability when used as one liquid, and further suppressed in foaming and cracking during curing. It is useful because it can be provided.

The present invention is described in detail below.
The urethane resin composition of the present invention is a urethane resin composition containing a urethane prepolymer (A) and a carboxy-modified silicone oil (B).
Next, the urethane prepolymer (A) and the carboxy-modified silicone oil (B) used in the urethane resin composition of the present invention will be described in detail.

<Urethane prepolymer (A)>
The urethane prepolymer (A) used in the present invention comprises a polyol compound and an excess polyisocyanate compound (that is, an excess isocyanate (OH) with respect to a hydroxyl (OH) group in the same manner as in a normal one-pack type polyurethane resin composition. NCO) group) is a reaction product obtained by reaction, and generally contains 0.5 to 10% by mass of NCO groups at the molecular ends.
Such an NCO group of the urethane prepolymer (A) reacts with moisture in the air to form a crosslinking point, and a crosslinked structure having rubber elasticity having a flexible main chain of the prepolymer as a matrix is formed.

The polyisocyanate compound for producing such a urethane prepolymer (A) is not particularly limited as long as it is a compound having two or more NCO groups in the molecule. Specific examples thereof include 2,4-tolylene diisocyanate ( 2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4 ' -MDI), 1,4-phenylene diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI) and other aromatic polyisocyanates; hexa Methylene diisocyanate (HDI , Trimethyl hexamethylene diisocyanate (TMHDI), lysine diisocyanate, aliphatic polyisocyanates such as norbornane diisocyanate methyl (NBDI); trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H ₆ XDI (hydrogenated XDI) Alicyclic polyisocyanates such as H ₁₂ MDI (hydrogenated MDI) and H ₆ TDI (hydrogenated TDI); polyisocyanate compounds such as polymethylene polyphenylene polyisocyanate; carbodiimide-modified polyisocyanates of these isocyanate compounds; Isocyanurate-modified polyisocyanates of compounds; urethane prepolymers obtained by reacting these isocyanate compounds with polyol compounds described below ; And the like, may be used in combination of two or more even with these alone.
A monoisocyanate compound having only one NCO group in the molecule can also be used by mixing with a diisocyanate compound or the like.

  Further, the molecular weight and the skeleton of the polyol compound for producing such a urethane prepolymer (A) are not particularly limited as long as it is a compound having two or more OH groups. Examples thereof include monohydric alcohols, polyether polyols, polyester polyols, other polyols, and mixed polyols thereof.

  Here, specific examples of the low-molecular polyhydric alcohols include ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, and (1,3- or 1,4-) butanediol. , Pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, low molecular polyols such as pentaerythritol; sorbitol, etc. Saccharides; and the like.

Polyether polyols and polyester polyols are usually derived from the above low-molecular polyhydric alcohols. In the present invention, those derived from the following aromatic diols, amines and alkanolamines are also preferably used. be able to.
Specific examples of the aromatic diols include resorcin (m-dihydroxybenzene), xylylene glycol, 1,4-benzenedimethanol, styrene glycol, 4,4′-dihydroxyethylphenol; Bisphenol A structure (4,4'-dihydroxyphenylpropane), bisphenol F structure (4,4'-dihydroxyphenylmethane), brominated bisphenol A structure, hydrogenated bisphenol A structure, bisphenol S structure, bisphenol AF structure And those having a bisphenol skeleton.

  Specific examples of amines include ethylenediamine and hexamethylenediamine. Specific examples of alkanolamines include ethanolamine and propanolamine.

The polyether polyol derived from any one of the low molecular polyhydric alcohols, the aromatic diols, the amines and the alkanolamines includes low molecular polyhydric alcohols, aromatic diols, amines and alkanols. Obtained by adding at least one selected from alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide (tetramethylene oxide), tetrahydrofuran, and styrene oxide to at least one selected from the compounds exemplified above as amines Polyols which can be used.
Specific examples of such polyether polyols include polyethylene glycol, polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), sorbitol-based polyol, and the like.
Specific examples of polyether polyols having a bisphenol skeleton include polyether polyols obtained by adding ethylene oxide and / or propylene oxide to bisphenol A (4,4′-dihydroxyphenylpropane).

Similarly, as the polyester polyol, a condensate of one of the low molecular polyhydric alcohols, the aromatic diols, the amines and the alkanolamines with a polybasic carboxylic acid (condensation polyester polyol); lactone System polyol; polycarbonate polyol; and the like.
Specific examples of the polybasic carboxylic acid that forms the condensed polyester polyol include glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, sebacic acid, phthalic acid, Examples include hydroxycarboxylic acids such as terephthalic acid, isophthalic acid, dimer acid, pyromellitic acid, other low-molecular carboxylic acids, oligomeric acids, castor oil, and a reaction product of castor oil and ethylene glycol (or propylene glycol). . Specific examples of the lactone-based polyol include ring-opening polymers such as propionlactone and valerolactone.
Specific examples of the lactone polyol include ring-opening polymerization of lactones such as ε-caprolactone, α-methyl-ε-caprolactone, and ε-methyl-ε-caprolactone with an appropriate polymerization initiator. The thing which has a hydroxyl group at both ends is mentioned.
Examples of the polyester polyol having a bisphenol skeleton include condensed polyester polyols obtained by using a diol having a bisphenol skeleton instead of the low molecular polyhydric alcohols or together with the low molecular polyhydric alcohols. Specific examples include polyester polyols obtained from bisphenol A and castor oil, polyester polyols obtained from bisphenol A, castor oil, ethylene glycol, and propylene glycol.

  Specific examples of other polyols include acrylic polyols; polybutadiene polyols; polymer polyols having carbon-carbon bonds in the main chain skeleton such as hydrogenated polybutadiene polyols.

  In the present invention, the various polyol compounds exemplified above may be used alone or in combination of two or more.

  As described above, the urethane prepolymer (A) used in the urethane resin composition of the present invention is obtained by reacting a polyol compound with an excess of a polyisocyanate compound. The thing by the combination of the various polyol compounds illustrated and the various polyisocyanate compounds is mentioned.

In the present invention, the urethane prepolymer (A) has a polyether structure in the main chain, and the urethane polymer (A) is synthesized with a low viscosity and contains the urethane resin composition of the present invention. Is preferred for reasons such as flexibility.
Therefore, it is preferable to use a polyether polyol as the raw material polyol compound of the urethane prepolymer (A).

<Carboxy-modified silicone oil (B)>
The carboxy-modified silicone oil (B) used in the present invention is not particularly limited as long as it is a silicone oil having a carboxy group. Here, the silicone oil refers to a linear polymer composed of siloxane bonds.
Specific examples of such carboxy-modified silicone oil (B) include silicone oils represented by the following general formulas (1) to (3). More than one species may be used in combination.

In the formula, R ¹ and R ² each independently represent an alkyl group or an aryl group, R ³ represents a single bond or an alkylene group having 1 to 30 carbon atoms, m represents 0 or a positive integer, and n represents 1 It represents the above integer. The plurality of R ¹ , R ² and R ³ may be the same or different.

Here, the alkyl group or aryl group of R ¹ and R ² is preferably an alkyl group or an aryl group because it is easy to produce and easily available.
Specific examples of the alkylene group having 1 to 30 carbon atoms of R ³ include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a nonamethylene group, Examples of the urethane resin composition of the present invention that can be easily obtained include a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, a tetradecamethylene group, a pentadecamethylene group, and a hexadecamethylene group. A methylene group, an ethylene group, and a propylene group are more preferable because of thixotropic improvement.
Furthermore, m represents 0 or a positive integer, and is preferably an integer of 3 or more, and more preferably 3 to 500 so that the volatility does not become too high. n represents an integer of 1 or more, and is more preferably set to be an introduction amount of 0.005% by mass or more in order to develop sufficient thixotropy.

Specifically, as the silicone oil represented by the general formula (1), for example, R ¹ and R ² are both methyl groups, R ³ is a methylene group, and the weight average molecular weight is 100 to 100. Examples include silicone oils in which m (0 or a positive integer) and n (an integer of 1 or more) are set so as to be about 10,000.
Similarly, as the silicone oil represented by the general formula (2), specifically, for example, R ¹ and R ² are both methyl groups, R ³ is a methylene group, and the weight average molecular weight is Examples include silicone oil in which n (an integer of 1 or more) is set so as to be about 100 to 10,000.
Similarly, as the silicone oil represented by the general formula (3), specifically, for example, R ² is a methyl group, R ³ is a methylene group, and the weight average molecular weight is about 100 to 10,000. Silicone oil in which n (integer of 1 or more) is set to be mentioned.

  In the present invention, a commercially available product can be used as such a carboxy-modified silicone oil (B). Specifically, as the silicone oil represented by the general formula (1), Shin-Etsu Chemical Co., Ltd. X22-3701 and X22-3701E are mentioned, and the silicone oil represented by the general formula (3) includes X22-162C manufactured by Shin-Etsu Chemical Co., Ltd.

By using such a carboxy-modified silicone oil (B), the urethane resin composition of the present invention obtained has a high thixo index (TI), good slump resistance, and very excellent thixotropic properties. Specifically, the viscosity ratio at 1 rpm and 10 rpm measured by a B-type viscometer is 5.0 or more, and the slump test specified in 4.1 of “Testing method of sealing material for building” of JIS A 1439: 1997. The slump measured at is substantially 0 mm at a measurement temperature of 20 ° C., 2 mm or less at 60 ° C., and 5 mm or less at 80 ° C.
In addition, the urethane resin composition of the present invention is excellent in storage stability when used as one liquid because of its high thixo index after storage promotion, and further suppresses the occurrence of foaming and cracks during curing. Become.

The content of the carboxy-modified silicone oil (B) is preferably 0.1 to 20 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A). Is more preferable.
In the present invention, even if the content of the carboxy-modified silicone oil (B) is as small as 0.1 part by mass, the above-described effects can be obtained. On the other hand, as shown in the examples described later, when a conventionally known ester-modified silicone oil is used, a content of about 30 times is required in order to obtain an effect equivalent to the effect of the present invention. As the content increases, the storage stability deteriorates.

  The urethane resin composition of the present invention is one of the preferred embodiments containing calcium carbonate and / or silica.

The calcium carbonate used in the present invention is not particularly limited, and examples thereof include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), and colloidal calcium carbonate.
Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used.
Specifically, Ryton A-4 (manufactured by Bihoku Flour Chemical Co., Ltd.) is preferably exemplified as the heavy calcium carbonate, and white glaze A (manufactured by Shiraishi Kogyo Co., Ltd.) is suitably exemplified as the colloidal calcium carbonate. .
In addition, as calcium carbonate surface-treated with fatty acid, whiten 305 (heavy calcium carbonate, manufactured by Shiroishi Calcium Co., Ltd.), white luster CCR (collagen calcium carbonate, manufactured by Shiroishi Kogyo Co., Ltd.), Calfine 200 (colloidal calcium carbonate, Maruo Calcium) As a calcium carbonate surface-treated with a fatty acid ester, Snowlite SS (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.), Siletz 200 (collagen calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) and the like are preferably used.
These may be used alone or in combination of two or more.

The silica used in the present invention is not particularly limited, and examples thereof include fumed silica, calcined silica, precipitated silica, pulverized silica, and fused silica.
These may be used alone or in combination of two or more.

  The content of calcium carbonate and / or silica is preferably 1 to 200 parts by mass and more preferably 3 to 80 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A). This content is the total content of both calcium carbonate and silica.

  The urethane resin composition of the present invention can contain various additives as necessary in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of additives include fillers other than calcium carbonate and silica, plasticizers, softeners, adhesion promoters, pigments (dyes), anti-aging agents, antioxidants, antistatic agents, flame retardants, stabilizers, solvents Etc.

As fillers other than calcium carbonate and silica, those having various shapes can be used. Specifically, for example, organic or inorganic fillers such as wax stone clay, kaolin clay, calcined clay; fumed silica, calcined silica, precipitated silica, ground silica, fused silica; graphite, metal powder, talc, zeolite, silica Soil; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; organic or inorganic filler such as carbon black; vinyl chloride paste resin; glass balloon, vinylidene chloride resin balloon; these fatty acids , Resin acid, fatty acid ester treated product, fatty acid ester urethane compound treated product.
The content of such a filler is preferably 1 to 200 parts by mass and more preferably 3 to 80 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A).

Specific examples of the plasticizer or softener include, for example, diisononyl phthalate (DINP), dioctyl phthalate, dibutyl phthalate, dibenzyl phthalate; dioctyl adipate, isodecyl succinate; diethylene glycol dipenzoate, pentaerythritol Esters: butyl oleate, methyl acetylricinoleate; tricresyl phosphate, trioctyl phosphate; propylene glycol polyester adipate, butylene glycol polyester adipate; petroleum-based softeners such as paraffinic oil, naphthenic oil, and aroma oil It is done.
The content of such a plasticizer or softener is preferably 30 parts by mass or less and more preferably 20 parts by mass or less with respect to 100 parts by mass of the urethane prepolymer (A).

  Specific examples of the adhesion-imparting agent include silane coupling agents; terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.

  Specific examples of the silane coupling agent include amino silane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, and mixtures or reactants thereof.

  Here, the aminosilane is not particularly limited as long as it is a compound having an amino group or imino group and a hydrolyzable silicon-containing group. Specific examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy. Silane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2 -(Ami Ethyl) -3-aminopropyl ethyldiethoxysilane and the like.

Specific examples of vinylsilane include vinyltrimethoxysilane, vinyltriethoxysilane, and tris- (2-methoxyethoxy) vinylsilane.
Specific examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4- Epoxycyclohexyl) ethylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
Specific examples of methacrylic silane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Can be mentioned.
Specific examples of the isocyanate silane include isocyanate propyltriethoxysilane.
Specific examples of the ketimine silane include ketiminated propyltrimethoxysilane.

  The content of such an adhesion-imparting agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A).

  Specific examples of pigments (dyes) include inorganic substances such as titanium dioxide, titanium white, zinc oxide, carbon black, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate. Pigments; organic pigments such as azo pigments and copper phthalocyanine pigments.

Specific examples of the anti-aging agent include hindered phenol compounds and hindered amine compounds.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Specific examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the stabilizer include hindered phenol compounds and triazole compounds.

Specific examples of the solvent include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and octane; petroleum solvents (for example, mineral spirits) ranging from gasoline to kerosene fractions. Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether esters such as cellosolve acetate and butylcellosolve acetate;
The content of such a solvent is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A).

  In the urethane resin composition of the present invention, these various additives can be used in appropriate combination.

  The method for producing the urethane resin composition of the present invention from each component as described above is not particularly limited, but the urethane prepolymer (A), the carboxy-modified silicone oil (B) and various additives added as desired ( (Including calcium carbonate and silica) by a roll, a kneader, an extruder, a universal stirrer, or the like.

The urethane resin composition of the present invention is moisture curable and can be used as a one-component composition. In addition, if necessary, the urethane prepolymer (A) is used as a main agent (liquid A) side, and a curing agent (for example, water, polyether polyol, amine) used as desired is used as a two-liquid type. You can also. In addition, when using as one liquid, it isolate | separates and stores with the water in air.
Such a urethane resin composition of the present invention can be suitably used as a joint material, a sealing material, an adhesive, and a coating agent.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Urethane prepolymer A1>
As urethane prepolymer A1, 1270 g of polypropylene diol (Excenol 3020, manufactured by Asahi Glass Co., Ltd., number average molecular weight 3200) and 863 g of polypropylene triol (Excenol 5030, manufactured by Asahi Glass Co., Ltd., number average molecular weight 5000) are added to NCO group / OH group (one hydroxyl group). 138 g of xylylene diisocyanate (XDI, manufactured by Mitsui Takeda Chemical Company) and diphenylmethane diisocyanate (MDI, manufactured by Mitsui Takeda Chemical Company) 115 so that the index represented by the number of isocyanate groups per unit) is 1.8. A urethane prepolymer synthesized by mixing and reacting at 80 ° C. for 18 hours in a nitrogen stream in the presence of a tin catalyst was used.

(Examples 1-4 and Comparative Examples 1-4)
Each component shown in Table 1 below is blended with the composition (parts by mass) shown in Table 1 with respect to 100 parts by mass of the urethane prepolymer A1, and the urethane is uniformly dispersed with a high viscosity mixing mixer. A resin composition was obtained.
Each urethane resin composition obtained was evaluated for thixotropy and slump resistance as follows. The results are shown in Table 1 below.

<Thixotropic>
(1) Initial stage About each obtained urethane resin composition, the thixo index (TI) after leaving for 1 day under 20 degreeC after adjustment (dispersion) was measured at 20 degreeC, and thixotropy was evaluated. Here, TI is a ratio of viscosity (Pa · s) measured at a rotation speed of 1 rpm and 10 rpm using a B-type viscometer (No. 7 rotor) at 20 ° C. [TI = (viscosity at 1 rpm) / (Viscosity at 10 rpm)].
(2) After storage promotion About each obtained urethane resin composition, after adjusting (dispersing), TI after standing at 70 degreeC for one day was measured at 20 degreeC, and thixotropy was evaluated.

<Slump resistance>
About each obtained urethane resin composition, the slump test prescribed | regulated to 4.1 of "the test method of the sealing material for construction" of JISA1439: 1997 is performed in the environment of 20 degreeC, 60 degreeC, and 80 degreeC. The slump amount (mm) was measured.
Specifically, each urethane resin composition obtained in the groove portion of the groove-shaped container is used for each groove-shaped container (slump (vertical)) defined in JIS A 1439: 1997 4.1.1. The sample was filled with care so that bubbles would not enter under a temperature environment, and the surface after filling was smoothed to prepare a test specimen. Immediately after the preparation of the test body, the test body was suspended vertically and placed in each temperature environment for 24 hours. The distance from the lower end of the groove portion of the groove-based container to the tip of the urethane resin composition filled in each test body was measured as a slump amount in a straight scale.

The components shown in Table 1 are as follows.
Calcium carbonate: Sealet 200, manufactured by Maruo Calcium Co., Ltd. Carboxy-modified silicone oil B1: X22-3701E, functional group equivalent 4000, manufactured by Shin-Etsu Chemical Co., Ltd. Carboxy-modified silicone oil B2: X22-3701, functional group equivalent 1250, Shin-Etsu Chemical -Kogyo-modified silicone oil B3: X22-162C, functional group equivalent 2300, manufactured by Shin-Etsu Chemical Co., Ltd.-Dimethyl silicone oil: KF96, manufactured by Shin-Etsu Chemical Co., Ltd.-Ester-modified silicone oil: KF910, manufactured by Shin-Etsu Chemical Co., Ltd.

As is clear from Table 1, the urethane resin compositions obtained in Examples 1 to 4 have higher initial viscosity and thixo index than the urethane resin compositions obtained in Comparative Examples 1 and 2, In addition, since the amount of slump was small under each temperature environment, it was found that thixotropy and slump resistance were excellent. In addition, when the urethane resin composition obtained in the example and the urethane resin composition obtained in Comparative Examples 3 and 4 are compared, in order to obtain thixotropy and slump resistance equivalent to those in Example 1. The ester-modified silicone oil must be added so that the content is 30 times the content of the carboxy-modified silicone oil B1 (Comparative Example 3), and the content of the carboxy-modified silicone oil B1 added in Example 2 It was found that when the ester-modified silicone oil having the same content as was added, the thixotropy and slump resistance were inferior (Comparative Example 4).

Claims (3)

100 parts by mass of urethane prepolymer (A), 0.1 to 20 parts by mass of silicone oil (B) composed of at least one silicone oil represented by the following general formula (1), calcium carbonate and / or silica 1 A urethane resin composition containing ~ 200 parts by mass.

(Wherein R ¹ and R ² each independently represents an alkyl group or an aryl group, R ³ represents a single bond or an alkylene group having 1 to 30 carbon atoms, m represents 0 or a positive integer, and n represents Represents an integer of 1 or more, and the plurality of R ¹ , R ² and R ³ may be the same or different. The urethane resin composition according to claim 1, wherein the urethane prepolymer (A) uses a polyether polyol as a raw material polyol compound .   The urethane resin composition according to claim 1 or 2, which is used for a sealing material, a waterproof material or an adhesive.