JP4884070B2 - One-component moisture-curing urethane resin composition and sealing material - Google Patents

Description

  The present invention relates to a one-component moisture-curable urethane resin composition and a sealing material.

Conventionally, urethane resin compositions are used for sealing materials, waterproofing materials, adhesives, and the like.
Among these, the urethane sealant is often sprayed with a paint on the urethane sealant, and the adhesion between the sealant and the paint is required.
Regarding paint adhesion, a composition containing a urethane prepolymer and a compound having an unsaturated group capable of air oxidation (see Patent Documents 1 and 2) has been proposed.

JP 2005-306921 A JP-A-2005-206722

However, the present inventor found that the compositions described in Patent Documents 1 and 2 are inadequate although some effects are seen in paint adhesion, and there is room for improvement due to poor long-term storage stability. I found out.
Therefore, an object of the present invention is to provide a one-component moisture-curable urethane resin composition that is excellent in paint adhesion and storage stability.

  As a result of diligent research to solve the above problems, the present inventor, as a result of containing a specific varnish and a specific polysiloxane derivative, is a one-component moisture-curable urethane resin composition having excellent paint adhesion and storage stability. As a result, the present invention was completed.

That is, the present invention provides the following (1) to (5).
(1) a urethane prepolymer;
A varnish having a viscosity at 25 ° C. of 9 poise or more obtained by polymerizing a drying oil having an iodine value of more than 170;
A polysiloxane derivative having at least one siloxane unit represented by the following formula (1);
A one-component moisture-curable urethane resin composition containing calcium carbonate.

(In the formula, R ¹ is at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, and R ² represents a saturated hydrocarbon group having 1 to 30 carbon atoms.)
(2) The one-component moisture-curable urethane resin composition according to (1), wherein the number of carbon atoms is 10 to 30.
(3) For 100 parts by mass of the urethane prepolymer,
The varnish is 0.5 to 20 parts by mass,
The polysiloxane derivative is 0.5 to 30 parts by mass,
The one-component moisture-curable urethane resin composition according to (1) or (2), wherein the calcium carbonate is 20 to 400 parts by mass.
(4) One-component moisture curing according to any one of (1) to (3), which can be obtained by adding the varnish to a mixture containing the urethane prepolymer, the calcium carbonate, and the polysiloxane derivative. Type urethane resin composition.
(5) A sealing material using the one-component moisture-curable urethane resin composition according to any one of (1) to (4) above.

  The one-component moisture-curable urethane resin composition of the present invention is excellent in paint adhesion and storage stability.

The present invention will be described in detail below.
First, the one-component moisture-curable urethane resin composition of the present invention will be described.
The one-component moisture-curable urethane resin composition of the present invention is
Urethane prepolymer,
A varnish having a viscosity at 25 ° C. of 9 poise or more obtained by polymerizing a drying oil having an iodine value of more than 170;
A polysiloxane derivative having at least one siloxane unit represented by the following formula (1);
It is a composition containing calcium carbonate.

In Formula (1), R ¹ is at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, and R ² represents a saturated hydrocarbon group having 1 to 30 carbon atoms.

The urethane prepolymer will be described below.
The urethane prepolymer contained in the composition of the present invention is not particularly limited, and for example, a urethane prepolymer obtained by reacting a polyol compound and an isocyanate group-containing compound can be used.

  The polyol compound used in the production of the urethane prepolymer is not particularly limited as long as it is a compound containing two or more hydroxy groups. Examples thereof include a product obtained by addition polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran to an active hydrogen-containing compound having two or more active hydrogens in the molecule.

Examples of the active hydrogen-containing compound include polyhydric alcohols, amines, alkanolamines, and polyhydric phenols.
Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane, and pentaerythritol.
Examples of amines include ethylenediamine and hexamethylenediamine.
Examples of alkanolamines include ethanolamine and propanolamine.
Examples of the polyhydric phenols include resorcin and bisphenols.

  Examples of the polyol compound include polyether polyols such as polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene glycol, and polyoxybutylene glycol; polyolefin polyols such as polybutadiene polyol and polyisoprene polyol; adipate polyols; Lactone type polyols; Polyester type polyols such as castor oil; Polycarbonate polyols.

In addition, the polyol compound preferably has a weight average molecular weight of about 500 to 10,000, more preferably about 2000 to 6,000, from the viewpoint that the resulting urethane prepolymer has a low viscosity and excellent workability.
A polyol compound can be used individually or in combination of 2 types or more, respectively.

  The isocyanate group-containing compound used in the production of the urethane prepolymer is not particularly limited. For example, a conventionally well-known thing is mentioned. Specifically, for example, TDI such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate; MDI such as 4,4′-diphenylmethane diisocyanate and 2,4′-diphenylmethane diisocyanate; tetramethylxylylene diisocyanate (TMXDI) ), Trimethylhexamethylene diisocyanate (TMHMDI), 1,5-naphthalene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI, o-xylylene diene) Isocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate), triphenylmethane Isocyanates, diisocyanates having norbornane skeleton (NBDI), and, these modified Hinto thereof.

Of these, TDI, XDI, HDI, and MDI are preferable. Since these polyisocyanates are general-purpose, they are inexpensive and easily available.
An isocyanate group containing compound can be used individually or in combination of 2 types or more, respectively.

  The ratio of mixing the polyol compound and the isocyanate group-containing compound during the production of the urethane prepolymer is such that the ratio of the number of isocyanate groups in the isocyanate group-containing compound to the number of hydroxy groups in the polyol compound (NCO / OH) is 1.0. It is preferable that it is above, and it is more preferable that it is 1.5-2.0.

  The urethane prepolymer is not particularly limited for its production. For example, it can be performed in the same manner as a normal urethane prepolymer. Specifically, a method in which an isocyanate group-containing compound and a polyol compound in a predetermined amount ratio are mixed and heated and stirred at 60 to 100 ° C. under normal pressure.

The varnish will be described below.
The varnish contained in the composition of the present invention has a viscosity at 25 ° C. of 9 poise or more obtained by polymerizing a drying oil having an iodine value of more than 170.

The drying oil used when producing the varnish has an iodine value of more than 170.
The iodine value of the drying oil is preferably greater than 170 and 210 or less, and more preferably greater than 170 and 190 or less. When the iodine value is within this range, the resulting composition is more excellent in paint adhesion.

Examples of the dry oil having an iodine value exceeding 170 include linseed oil and sesame oil.
Of these, linseed oil is preferred because it is more excellent in paint adhesion.
The drying oil used when manufacturing a varnish can be used individually or in combination of 2 or more types, respectively.

  The method for polymerizing the drying oil is not particularly limited, and examples thereof include conventionally known ones. Specifically, for example, the drying oil can be polymerized by applying heat or irradiating light.

The varnish contained in the composition of the present invention has a viscosity at 25 ° C. of 9 poise or more. When the viscosity of the varnish at 25 ° C. is 9 poise or more, the varnish bleeds out on the surface of the coating film of the composition as compared with a non-polymerized drying oil or a varnish having a low viscosity (low polymerization degree). Is fast and has excellent paint adhesion.
The viscosity at 25 ° C. of the varnish is preferably 9 to 130 poise, more preferably 9 to 60 poise from the viewpoint that the paint adhesion is excellent and the workability can be maintained without excessively increasing the viscosity.

Moreover, a commercial item can be used for the varnish. Examples of commercially available products include linseed oil No. 4 varnish and linseed oil No. 5 varnish (both manufactured by Cosmo Oil Chemical Co., Ltd.).
A varnish can be used individually or in combination of 2 or more types, respectively.

  The content of the varnish is preferably 0.5 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the urethane prepolymer. More preferably. When the content of the varnish is within this range, the paint adhesion and storage stability are more excellent.

When the composition of the present invention is applied, the varnish contained in the composition of the present invention quickly bleeds out on the surface of the coating film to form a film, whereby the composition of the present invention adheres to the paint. Excellent in properties.
In particular, when the composition of the present invention is exposed outdoors, the varnish is further polymerized by light, so that the formation of the coating film becomes faster and the paint adhesion is more excellent.

The polysiloxane derivative will be described below.
The polysiloxane derivative contained in the composition of the present invention is a polysiloxane having at least one siloxane unit represented by the following formula (1).

In Formula (1), R ¹ is at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, and R ² represents a saturated hydrocarbon group having 1 to 30 carbon atoms.

R ¹ is at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group.
R ² represents a saturated hydrocarbon group having 1 to 30 carbon atoms. The saturated hydrocarbon group preferably has 10 to 30 carbon atoms. In such a range, it is excellent in long-term storage stability.

When the polysiloxane derivative has two or more siloxane units represented by the formula (1), R ¹ may be the same or different, and R ² may be the same or different.

  Examples of the saturated hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, n-pentyl, 1-methylbutyl, and 2-methylbutyl. Group, 3-methylbutyl group, t-pentyl group, neopentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2 -Ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl Group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2,2-dimethylpentyl group, 3,3- Methylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, octyl group , Nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group (20 carbon atoms. Below, in parentheses in this paragraph) The numbers are the number of carbon atoms.), Heicosyl group (21), docosyl group (22), tricosyl group (23), tetracosyl group (24), pentacosyl group (25), hexacosyl group (26), heptacosyl group (27 ), Octacosyl group (28), nonacosyl group (29), and triacontyl group (30). It is.

  As a siloxane unit represented by Formula (1), the siloxane unit represented by each following formula is mentioned, for example.

  The siloxane units represented by the formula (1) can be used alone or in combination of two or more.

  The polysiloxane derivative can have a siloxane unit other than the siloxane unit represented by the formula (1). Examples of such siloxane units include siloxane units represented by the following formula (4).

In the formula, R ³ represents at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, R ⁴ represents a divalent hydrocarbon group having 2 or 3 carbon atoms, and R ⁵ represents Represents a divalent hydrocarbon group having 2 to 4 carbon atoms, R ⁶ represents a monovalent hydrocarbon group, and r is an integer of 1 or more.

R ³ represents at least one selected from the group consisting of a methyl group, an ethyl group and a phenyl group, preferably a methyl group or a phenyl group.
R ⁴ represents a divalent hydrocarbon group having 2 or 3 carbon atoms.
The divalent hydrocarbon group having 2 or 3 carbon atoms is an ethylene group, a propylene group, or an isopropylene group, and among them, a propylene group is preferable.

R ⁵ represents a divalent hydrocarbon group having 2 to 4 carbon atoms.
Examples of the divalent hydrocarbon group having 2 to 4 carbon atoms include an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and a 1,1-dimethylethylene group. Of these, an ethylene group and an isopropylene group are preferable.
r is preferably 5 or more, more preferably 10 to 50.
When r is 2 or more, the plurality of R ⁵ may be the same or different.
When r is 2 or more and a plurality of R ⁵ are different, a combination of a plurality of R ⁵ is, for example, a combination of an isopropylene group [—CH ₂ CH (CH ₃ ) —] and an ethylene group. As mentioned. In such a case, the number of isopropyleneoxy groups is preferably 10-40, and the number of ethyleneoxy groups is preferably 10-40. Further, the molar ratio [isopropylene group: ethylene group] of isopropylene group [—CH ₂ CH (CH ₃ ) —] and ethylene group is 60:40 to 20:80, from the viewpoint of imparting thixotropy. To preferred.

R ⁶ represents a monovalent hydrocarbon group. Preferably, it is a C1-C10 hydrocarbon group. Specifically, for example, a saturated hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a palmityl group or a stearyl group; an aromatic carbon group such as a phenyl group or a benzyl group A hydrogen group etc. are mentioned.
In the siloxane unit represented by the formula (4), each repeating unit may be contained in either or both of the inside of the molecule and the end of the molecule.

The polysiloxane derivative can have a siloxane unit represented by —Si (R ³ ) ₂ —O—. R ³ in the formula is independent and has the same meaning as described above.
Examples of —Si (R ³ ) ₂ —O— include —Si (CH ₃ ) ₂ —O—.

  When the polysiloxane derivative has a siloxane unit other than the siloxane unit represented by the formula (1), the arrangement of the siloxane units is not particularly limited. For example, the arrangement is random, block, or a mixture of random and block. Can be mentioned.

The polysiloxane derivative is not particularly limited with respect to the molecular terminals. Examples of the terminal groups, for example, siloxane units represented by -SiR ⁷ _3.
The polysiloxane derivative may be mentioned as one of preferred embodiments having groups represented by —SiR ⁷ ₃ on both sides of the polysiloxane derivative as terminal groups.

In —SiR ⁷ ₃ , R ⁷ represents at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, and may be the same or different.
Among them, the R ⁷ are all methyl group as one of the preferred embodiments.

The polysiloxane derivative has at least one siloxane unit represented by the formula (1).
The amount of the siloxane unit represented by the formula (1) is preferably 20 mol% or more, and more preferably 50 mol% or more in the total amount of siloxane units of the polysiloxane derivative. When the amount of the siloxane unit represented by the formula (1) is in such a range, the long-term storage stability is more excellent.
When the polysiloxane derivative further has a siloxane unit represented by the formula (4), the content of the siloxane unit represented by the formula (1) is represented by the formula (1) from the viewpoint of storage stability. In the total amount of the siloxane unit represented and the siloxane unit represented by Formula (4), it is preferably 20 mol% or more, and more preferably 50 mol% or more.

  Moreover, it is preferable that the polymerization degree is 5-1000, and, as for a polysiloxane derivative, it is more preferable that it is 10-100. When the degree of polymerization of the polysiloxane derivative is within such a range, it is preferable from the viewpoint of workability when used as an additive of the sealing material composition.

As a preferred embodiment, the polysiloxane derivative is composed of a siloxane unit represented by the formula (1), a siloxane unit represented by the formula (4), and a terminal group represented by -SiR ⁷ _3. Can be mentioned.

  As a polysiloxane derivative, the compound represented by following formula (5) is mentioned, for example.

In formula (5), R ¹ , R ³ and R ⁷ each independently represent at least one selected from the group consisting of a methyl group, an ethyl group and a phenyl group, and R ² has 1 to 30 carbon atoms. Represents a saturated hydrocarbon group, each R ⁴ independently represents a divalent hydrocarbon group having 2 or 3 carbon atoms, and each R ⁵ independently represents a divalent carbon atom having 2 to 4 carbon atoms. Represents a hydrogen group, R ⁶ independently represents a monovalent hydrocarbon group, r represents an integer of 1 or more, m represents an integer of 1 or more, and n represents an integer of 0 or more.

R < ¹ > -R < ⁷ >, r in Formula (5) is synonymous with the above.
In formula (5), m is preferably 10 to 100.
In formula (5), n is preferably 1 to 10.

As a compound represented by Formula (5), what is represented by following formula (6)-Formula (8) is mentioned, for example.
In formula (6), m ¹ is 50. In the formula (7), m ² is 50.

In the formula (8), R ² represents —C ₇ H ₁₅ and / or —C ₁₇ H ₃₅ , R ⁴ represents — (CH ₂ ) ₃ —, and R ^5a represents —CH ₂ CH (CH ₃ ). R ^5b represents —CH ₂ CH ₂ —, R ⁶ represents a butyl group, m represents an integer of 10 to 100, n represents an integer of 1 to 10, and p represents 10 to 20 An integer is represented, and q represents an integer of 10 to 20.

Polysiloxane derivatives can be used alone or in combination of two or more.
The polysiloxane derivative is not particularly limited with respect to its production method. For example, a conventionally well-known thing is mentioned.

  In the composition of the present invention, the content of the polysiloxane derivative is preferably 0.5 to 30 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer. . When the amount of the polysiloxane derivative is within such a range, the long-term storage stability is excellent and the cost is excellent.

The calcium carbonate will be described below.
The composition of the present invention contains calcium carbonate.
Calcium carbonate is not particularly limited. In addition, surface-treated calcium carbonate can be used.
The surface-treated calcium carbonate is not particularly limited.
Examples of the surface treatment agent used for the surface treatment of calcium carbonate include fatty acid esters.

The fatty acid ester used for the surface treatment of calcium carbonate is not particularly limited.
Among these, esters of higher fatty acids having 8 or more carbon atoms are preferable from the viewpoint of storage stability. Specific examples include stearyl stearate, lauryl stearate, stearyl palmitate, lauryl palmitate, glyceride tristearate, glyceride tripalmitate, and the like.
Further, tripalmitic acid glyceride is preferable in terms of thermal stability of the surface treatment and thixotropic properties.
A surface treating agent can be used individually or in combination of 2 or more types, respectively.

The method for surface treatment of calcium carbonate is not particularly limited, and for example, a conventionally known method can be used.
Calcium carbonate can be used alone or in combination of two or more.

  The content of calcium carbonate is preferably 20 to 400 parts by mass and more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the urethane prepolymer. In such a range, workability is excellent.

The composition of the present invention can further contain a solvent.
The solvent is not particularly limited. Specifically, for example, aromatic hydrocarbons such as benzene, xylene and toluene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate and butyl acetate; diethyl ether, tetrahydrofuran and dioxane And ethers.
A solvent can be used individually or in combination of 2 types or more, respectively.

  0.01-20 mass parts is preferable with respect to 100 mass parts of urethane prepolymers, and 0.01-10 mass parts is more preferable.

The composition of this invention can contain an additive in the range which does not impair the objective of this invention as needed.
Examples of additives include inorganic fillers other than calcium carbonate, reaction retarders, antioxidants, antioxidants, pigments (dyes), plasticizers, thixotropic agents, ultraviolet absorbers, flame retardants, and surfactants. (Including leveling agents), dispersing agents, dehydrating agents, adhesion-imparting agents, and antistatic agents.

  Inorganic fillers other than calcium carbonate are not particularly limited. For example, silica, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, wax stone clay, kaolin Examples include clay, fired clay, and carbon black.

  Specific examples of the reaction retarder include alcohol-based compounds.

Specific examples of the anti-aging agent include hindered phenol compounds.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Specific examples of the pigment include inorganic pigments such as titanium oxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, sulfate, etc .; azo pigment, phthalocyanine pigment, quinacridone Pigment, quinacridone quinone pigment, dioxazine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, perinone pigment, diketopyrrolopyrrole pigment, quinonaphthalone pigment, anthraquinone pigment, thioindigo pigment, benzimidazolone Examples thereof include organic pigments such as pigments, isoindoline pigments, and carbon black.

  Specific examples of the plasticizer include, for example, dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; phosphorus Examples include tricresyl acid, trioctyl phosphate; propylene glycol polyester adipate, butylene glycol polyester adipate, and the like.

Specific examples of the thixotropic agent include Aerosil (manufactured by Nippon Aerosil Co., Ltd.), Dispalon (manufactured by Enomoto Kasei Co., Ltd.), and the like.
Specific examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and the like.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methyl phosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, and the like.
Examples of the antistatic agent generally include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

As a method for producing the composition of the present invention, for example,
[1] A mixing step of mixing a urethane prepolymer, calcium carbonate, and a polysiloxane derivative to form a mixture, and an adding step of adding a varnish to the obtained mixture to form a one-component moisture-curable urethane resin composition A method (hereinafter referred to as “manufacturing method A”),
[2] A mixing step in which a urethane prepolymer and calcium carbonate are mixed to form a mixture, and an addition step in which a polysiloxane derivative and varnish are simultaneously added to the mixture to form a one-component moisture-curable urethane resin composition. A method comprising:
[3] A method of simultaneously adding and mixing a urethane prepolymer, calcium carbonate, a polysiloxane derivative, and a varnish.

  Especially, the manufacturing method A is preferable from a viewpoint that it is excellent by coating-material adhesiveness and storage stability.

Manufacturing method A will be described below.
First, in the mixing step, a urethane prepolymer, calcium carbonate, and a polysiloxane derivative having at least one siloxane unit represented by the formula (1) are mixed to obtain a mixture.
The order of addition of the urethane prepolymer, calcium carbonate, and polysiloxane derivative is not particularly limited, and one preferred embodiment is to add the polysiloxane derivative after mixing the urethane prepolymer and calcium carbonate.

In the mixing step, a solvent and an additive can be further mixed.
In the mixing step, the means for mixing the urethane prepolymer, calcium carbonate and the polysiloxane derivative having at least one siloxane unit represented by the formula (1) is not particularly limited. For example, an agitator such as a mixing mixer can be used.
In the mixing step, the conditions are not particularly limited. It is preferable to carry out under reduced pressure (for example, 20 Torr or less) from the viewpoint of preventing moisture curing of the urethane prepolymer and preventing air entrainment in the composition.

  After the mixing step, in the addition step, a one-component moisture-curable urethane resin composition obtained by polymerizing a dry oil having an iodine value exceeding 170 in the addition step and adding a varnish having a viscosity at 25 ° C. of 9 poise or more. And

In the addition step, a solvent and an additive can be further mixed.
In the addition step, the means for mixing the mixture and the varnish is not particularly limited. For example, an agitator such as a mixing mixer can be used.
In the addition step, the conditions are not particularly limited. From the viewpoint of preventing moisture curing of the urethane prepolymer and preventing air entrainment into the composition, it is preferably carried out under reduced pressure.

  After the addition step, the obtained one-component moisture-curable urethane resin composition can be stored, for example, in a container replaced with nitrogen gas and sealed in the container.

In the composition of the present invention, the polysiloxane derivative can generate a carboxylic acid by hydrolyzing an ester bond in the polysiloxane derivative due to, for example, moisture in the air.
The carboxylic acid that can be generated is a carboxylic acid having R ² in formula (1).
For example, when the polysiloxane derivative is a compound represented by the following formula (6), the carboxylic acid that can be produced is stearic acid, and when the polysiloxane derivative is a compound represented by the following formula (7), it can be produced. The carboxylic acid is considered to be octanoic acid. In the formula, m ¹ and m ² are 50, respectively.

Examples of the use of the composition of the present invention include a sealing material, a waterproof material, and an adhesive.
Especially, since the composition of this invention is excellent in coating-material adhesiveness, it can be used conveniently as a sealing material composition.

The method for using the composition of the present invention will be described below.
As a method of using the composition of the present invention, for example, a urethane curing step in which the composition of the present invention is applied to a material to be coated and cured to obtain a cured product, and the obtained cured product is applied with a paint, The method of comprising the coating process which makes the laminated body which has hardened | cured material and a coating material is mentioned.

First, in the urethane curing step, the composition of the present invention is applied to a material to be coated and cured to obtain a cured product.
Examples of the material to be coated include tile, panel, concrete, mortar, aluminum, and ALC.
Various methods can be used as a method of applying the composition of the present invention to a material to be applied, and examples thereof include extrusion with a caulking gun.

The composition of the present invention is not particularly limited with respect to its curing. Usually, after applying the composition of the present invention to a material to be coated, it can be cured by leaving it to stand for 5 hours or more in an environment of 23 ° C. and 50% RH.
In particular, since the polymerization reaction of the varnish proceeds by light and bleeds out on the surface of the composition to form a film, it is preferable to cure by irradiating light (for example, outdoor exposure).
Outdoor exposure is not particularly limited, and from the viewpoint of better paint adhesion, it is preferable to leave the outdoor composition (preferably a place exposed to sunlight) for at least one day.

After the urethane curing step, in the coating step, a coating can be applied to the surface of the obtained cured product to obtain a laminate having the cured product and the coating.
The coating material used in the painting process is not particularly limited, and can be appropriately selected depending on the application. Specific examples include acrylic silicone paints, acrylic paints, urethane paints, acrylic urethane paints, and fluorine paints.
Of these, acrylic silicone paints are preferred because they are more excellent in adhesion to the composition of the present invention.
The range to which the paint is applied includes part or all of the surface of the cured product of the composition, and may include a portion where the composition of the present invention is not applied.

Various methods can be used as a method of applying the paint to the cured product, and examples thereof include bar coater coating, spin coating, spray coating, and dip coating.
The time for curing the paint is not particularly limited. From the viewpoint of coating film formation, 12 hours or more is preferable.

Next, the sealing material of the present invention will be described below.
The sealing material of the present invention is formed using the composition of the present invention.
The composition used for the sealing material of the present invention is not particularly limited as long as it is the composition of the present invention.

The sealing material of the present invention is not particularly limited for its production. For example, it can be obtained by filling joints of building materials such as tiles and panels for outer walls with the composition of the present invention and curing them.
The sealing material of the present invention is not particularly limited with respect to its curing. Usually, after applying the composition of the present invention to a material to be coated, it can be cured by leaving it to stand for 5 hours or more in an environment of 23 ° C. and 50% RH.
In particular, since the polymerization reaction of the varnish proceeds by light and bleeds out on the surface of the composition to form a film, it is preferable to cure by irradiating light (for example, outdoor exposure).
The outdoor exposure is not particularly limited, and from the viewpoint of better paint adhesion, it is preferable to leave the outdoor composition (preferably a place exposed to sunlight) for at least one day.

Moreover, the sealing material of this invention can apply | coat a coating material on it.
When the paint is applied to the surface of the sealing material, the paint that can be used has the same meaning as described above.
The method for applying the paint on the surface of the sealing material is not particularly limited.
The time for curing the paint is not particularly limited. From the viewpoint of coating film formation, 12 hours or more is preferable.

Conventionally, when the urethane composition used as a sealing material, a waterproof material, an adhesive, or the like does not contain an unsaturated compound capable of reacting with oxygen, this urethane composition has low adhesion to the paint, The present inventors have found that when a coating material is applied on the sealing material after the sealing material obtained from the urethane composition is exposed outdoors, the adhesion of the coating material is lowered.
The present inventor uses a varnish having a viscosity at 25 ° C. of 9 poise or more obtained by polymerizing a dry oil having an iodine value of more than 170 as an unsaturated compound capable of reacting with oxygen. Succeeded in improving adhesion.
However, the present inventor has found that there is room for improvement in the long-term storage stability of the composition by using such a specific varnish.
The present inventor has further studied to solve this problem, and is obtained by polymerizing a dry oil having an iodine value of more than 170, and is a one-component moisture-curing type containing a varnish having a viscosity at 25 ° C. of 9 poise or more. It has been found that when the urethane resin composition further contains a polysiloxane derivative represented by the formula (1), the composition has excellent long-term storage stability.
Furthermore, the present inventor, when producing the composition, by adding a varnish to the mixture of urethane prepolymer, calcium carbonate and polysiloxane derivative, the paint adhesion of the one-part moisture-curable urethane resin composition, It has been found that the storage stability becomes better.

The inventor presumes the reason why the composition of the present invention is excellent in paint adhesion and storage stability as follows.
That is, the polysiloxane derivative contained in the composition of the present invention generates carboxylic acid by hydrolysis of the ester bond of the polysiloxane derivative, and the generated carboxylic acid covers the surface of calcium carbonate. When calcium carbonate is surface-treated with a surface treatment agent in advance, the surface of calcium carbonate is more coated with the generated carboxylic acid.
In this way, the surface of the calcium carbonate is coated with the carboxylic acid generated from the polysiloxane derivative, thereby preventing the varnish from reacting with and / or coordinated with the calcium carbonate to cause wetting with the urethane prepolymer. In the present invention, it is possible to suppress a decrease in time and increase in viscosity of the thixo index of the varnish, and on the other hand, a film that improves the adhesion of the paint due to the film-forming property of the varnish can be formed on the surface of the composition. Guess.
Further, in the composition of the present invention, by adding the polysiloxane derivative to the urethane prepolymer and calcium carbonate prior to the varnish, the carboxylic acid that can be generated from the polysiloxane derivative can more effectively surface-treat calcium carbonate. The present inventors speculate that it is possible to more effectively prevent the varnish from reacting and / or coordinating with calcium carbonate and promoting wetting of the urethane prepolymer and calcium carbonate.
Even a mechanism different from the above is within the scope of the present invention.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

1. Synthesis of urethane prepolymer 138 g of xylylene diisocyanate and 115 g of diphenylmethane diisocyanate were added to 1270 g of polypropylene diol having an average molecular weight of 3200 (Exenol 3020, manufactured by Asahi Glass) and 863 g of polypropylene triol having an average molecular weight of 5000 (Exenol 5030, manufactured by Asahi Glass) (NCO / OH = 1.8) and a reaction was carried out at 80 ° C. for 18 hours in the presence of a catalyst to obtain a urethane prepolymer having an NCO content = 1.44% by mass.
The obtained urethane prepolymer was used in the following Examples and Comparative Examples.

2. Varnishes The varnishes used in Examples and Comparative Examples are as shown in Table 1 below.

3. Synthesis of polysiloxane derivatives (1) Polysiloxane 1
100 g of 2.5% chloroplatinic acid hexahydrate isopropyl alcohol solution was added to 50 g of methyl hydrogen polysiloxane (KF99, manufactured by Shin-Etsu Chemical Co., Ltd.) and 20 g of a dried alkenyl group-containing polyether (Unisafe PKA5016, manufactured by NOF Corporation). Was added and reacted at 90 ° C. for 2 hours. Next, 214 g of dried stearic acid was added and reacted at 85 ° C. for 2 hours, 90 ° C. for 2 hours, and further at 110 ° C. for 2 hours to obtain polysiloxane. The obtained polysiloxane is designated as polysiloxane 1. Polysiloxane 1 is a mixture of compounds represented by the following formula (9).

In formula (9), R ² represents —C ₁₇ H ₃₅ , R ⁴ represents — (CH ₂ ) ₃ —, R ^5a represents —CH ₂ CH (CH ₃ ) —, and R ^5b represents — CH ₂ CH ₂ - represents, R ⁶ represents a butyl group, m represents an integer of 10 to 100, n represents an integer of 1 to 10, p is an integer of 10 to 20, q is 10 to Represents an integer of 20.

(2) Polysiloxane 2
A polysiloxane was obtained by synthesizing in the same manner as the synthesis of polysiloxane 1 except that 214 g of stearic acid was replaced with 109 g of octanoic acid. The obtained polysiloxane is designated as polysiloxane 2. Polysiloxane 2 is a mixture of compounds represented by the following formula (10).

In formula (10), R ² represents —C ₇ H ₁₅ , R ⁴ represents — (CH ₂ ) ₃ —, R ^5a represents —CH ₂ CH (CH ₃ ) —, and R ^5b represents — CH ₂ CH ₂ - represents, R ⁶ represents a butyl group, m represents an integer of 10 to 100, n represents an integer of 1 to 10, p is an integer of 10 to 20, q is 10 to Represents an integer of 20.

4). Preparation of compositions (Examples and Comparative Examples)
The components shown in Table 3 below were mixed in the composition (parts by mass) shown in Table 3 to obtain the compositions shown in Table 3.

  In Examples 1 to 3 and Comparative Examples 1 and 3 to 5, a urethane prepolymer, calcium carbonate, and a polysiloxane derivative were charged in a nitrogen stream, and the contents were uniform in a high viscosity mixing mixer for 30 minutes at room temperature. The mixture was stirred under reduced pressure (10 to 20 Torr) and mixed. Next, a solvent and a varnish were added, and the mixture was further stirred for 30 minutes at room temperature under reduced pressure (10 to 20 Torr) to prepare a composition.

  In Example 4, a composition was prepared in the same manner as in Example 1, except that the varnish was charged together with the urethane prepolymer, calcium carbonate, and polysiloxane derivative.

  In Comparative Example 2, a composition was prepared in the same manner as in Example 1 except that no polysiloxane derivative was used.

5. Evaluation Using each of the obtained compositions, the viscosity, slump property and paint adhesion were evaluated by the following methods. The results are shown in Table 3.

(1) Viscosity measurement (initial viscosity)
About each obtained composition which was left to stand at 23 degreeC for 1 day (24 hours), the viscosity of 1 rpm and 10 rpm was measured on 23 degreeC and 50% RH conditions using the B-type viscosity meter. The thixo index (1 rpm / 10 rpm) was determined from the measured viscosity.
(Viscosity after storage acceleration 1)
Each composition obtained was allowed to stand at 23 ° C. for 1 day, then left at 70 ° C. for 1 day, and left at 23 ° C. for 1 day to return the material temperature to 23 ° C. Measured and determined thixo index.
(Viscosity after accelerated storage 2)
Each composition obtained was allowed to stand at 23 ° C. for 1 day, further left at 50 ° C. for 14 days, and left at 23 ° C. for 1 day to return the material temperature to 23 ° C. Measured and determined thixo index.

(2) Slump Using the jig defined in 4.1 of JIS A 1439, each composition obtained was allowed to stand at 23 ° C. for 1 day (initial), and each composition was allowed to stand at 23 ° C. for 1 day. Then, a slump test was conducted in an environment at 23 ° C. for those left for 14 days at 50 ° C. (after storage promotion).
In the slump test, the sealing material was filled with care so that bubbles did not enter the groove portion of the slip jig under each temperature environment, and the surface was smoothed. After filling, the slip jig was left suspended for 12 hours or more at each temperature so that the groove portion was vertical.
After leaving, the distance (mm) from the lower end portion of the groove portion of the slip jig to the lower end portion of the sealing material slipped in the downward direction was measured, and the value of this distance was defined as the slump amount of the sealing material.

(3) Paint adhesion Using a slate plate with a width of 70 mm x length of 70 mm x height of 10 mm, a primer (No. 40, manufactured by Yokohama Rubber Co., Ltd.) within the range of width 50 mm x length 50 mm Was applied and left at 23 ° C. and 50% RH for 1 hour.
Next, each composition obtained on the applied primer was placed using a caulking gun to a thickness of 1 mm, leveled with a trowel, and the following sealing material curing conditions 1-3 The composition was cured with either.

-Sealing material curing condition 1: (23 ° C, 50% RH) x 3 days-Sealing material curing condition 2: (23 ° C, 50% RH) x 3 days + outdoor exposure x 14 days-Sealing material curing condition 3: ( 23 ° C, 50% RH) x 3 days + outdoor exposure x 28 days

  After that, on the cured product of the composition to which each composition was applied, the paint was applied according to the coating specifications shown in Table 2, and the paint was cured and dried for 14 days in an environment of 23 ° C. and 50% RH. A test specimen was obtained. The drying time in Table 2 is the drying time for the undercoat.

Next, a two-component epoxy resin adhesive (Quick Mender, manufactured by Konishi Co., Ltd., solvent-free system) was applied to the surface of the aluminum tension jig having a width of 35 mm and a length of 35 mm.
Next, an aluminum pulling jig is placed on the coating surface of the test piece so that the coating surface of the two-component epoxy resin adhesive faces downward, and the coating material and the two-component epoxy resin adhesive are bonded. And cured at 23 ° C. and 50% RH for 5 hours. Here, the two-pack type epoxy resin adhesive has sufficient adhesiveness without damaging the coating film.
Next, a cut was made in the paint application surface of the test specimen along the adhesion surface (width 35 mm × length 35 mm) of the aluminum tension jig adhered to the test specimen.
Thereafter, the test specimen is fixed to an autograph (AG5000E, manufactured by Shimadzu Corporation), and an aluminum tension jig is pulled at a rate of 3 mm / min in the vertical direction with respect to the coating surface of the test specimen, and the maximum tension is obtained. The load was measured. The obtained maximum tensile load is defined as a maximum tensile load T.
The maximum tensile load T was divided by the adhesion area (3.5 × 3.5 = 12.25 cm ² ) of the aluminum tension jig to determine the adhesion strength A [see formula (1). ].

Adhesion strength A (N / cm ² ) = maximum tensile load T (N) /12.25 (cm ² ) (1)

In Table 3, the adhesion strength A is “70 <” means that when the test specimen is pulled with a force corresponding to 70 N / cm ² , the paint and the cured product of each composition obtained are peeled off. Indicates not.
In the present invention, when the adhesion strength A is greater than 70 N / cm ² , the paint adhesion is good.

The components shown in Table 3 are as follows.
-Urethane prepolymer: prepared as described above-Calcium carbonate: Sealet 200, manufactured by Maruo Calcium Co., Ltd. What was dried at 110 ° C. for 24 hours.
Solvent: Xylene, manufactured by Kanto Chemical Co., Ltd. Varnish: See Table 1.
Polysiloxane 1-2: synthesized as described above.

As is clear from the results shown in Table 3, the composition containing no varnish (Comparative Example 1) had low paint adhesion.
The composition containing no polysiloxane derivative (Comparative Example 2) had a low thixo index after a long period of time (50 ° C., 14 days), slump occurred, and storage stability was poor.
The composition containing the non-polymerized drying oil (Comparative Examples 3 and 5) and the composition containing the varnish having a viscosity at 25 ° C. of less than 9 poise (Comparative Example 4) had low paint adhesion.
On the other hand, the compositions of Examples 1 to 4 had high initial viscosity and thixo-index after storage promotion, did not generate slump, and were excellent in storage stability and paint adhesion.
Especially, Examples 1-3 which added the varnish to the mixture of a urethane prepolymer, calcium carbonate, and a polysiloxane derivative were excellent by storage stability and paint adhesion.

Claims (11)

Urethane prepolymer,
A varnish having a viscosity at 25 ° C. of 9 poise or more obtained by polymerizing linseed oil having an iodine value of more than 170 with heat or light ;
A polysiloxane derivative having at least one siloxane unit represented by the following formula (1);
Containing calcium carbonate, one-moisture-curable urethane resin composition.

(In the formula, R ¹ is at least one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group, and R ² represents a saturated hydrocarbon group having 1 to 30 carbon atoms.)   The one-component moisture-curable urethane resin composition according to claim 1, wherein the number of carbon atoms is 10 to 30. For 100 parts by mass of the urethane prepolymer,
The varnish is 0.5 to 20 parts by mass,
The polysiloxane derivative is 0.5 to 30 parts by mass,
The one-component moisture-curable urethane resin composition according to claim 1 or 2, wherein the calcium carbonate is 20 to 400 parts by mass.   The one-component moisture-curable urethane resin composition according to any one of claims 1 to 3, which can be obtained by adding the varnish to a mixture containing the urethane prepolymer, the calcium carbonate, and the polysiloxane derivative.   The one-component moisture-curable urethane resin composition according to any one of claims 1 to 4, wherein the iodine value is greater than 170 and 210 or less.   The one-component moisture-curable urethane resin composition according to any one of claims 1 to 5, wherein the viscosity is 9 to 130 poise.   The one-pack type moisture curable urethane resin composition according to any one of claims 1 to 6, wherein the polysiloxane derivative is a compound represented by the following formula (5).

[In formula (5), R ¹ , R ^Three , R ⁷ Each independently represents at least one selected from the group consisting of a methyl group, an ethyl group and a phenyl group; ² Represents a saturated hydrocarbon group having 1 to 30 carbon atoms, R ^Four Each independently represents a divalent hydrocarbon group having 2 or 3 carbon atoms; ^Five Each independently represents a divalent hydrocarbon group having 2 to 4 carbon atoms; ⁶ Each independently represents a monovalent hydrocarbon group, r is an integer of 1 or more, m represents an integer of 1 or more, and n represents an integer of 0 or more. ]   The one-component moisture-curable urethane resin composition according to any one of claims 1 to 7, wherein the calcium carbonate is surface-treated with a surface treatment agent. Sealing material made using one-moisture-curable urethane resin composition according to any one of claims 1-8.   The sealing material according to claim 9, which is obtained by irradiating the one-component moisture-curable urethane resin composition with light.   The laminated body which has the sealing material of Claim 9 or 10, and the coating material on the said sealing material.