JP2007297532A - Curable resin composition and sealing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition excellent in low tack property and workability. <P>SOLUTION: The curable resin composition comprises a urethane prepolymer, a drying oil and/or a polymerized product thereof having an iodine value of at least 130 and bearing a conjugated double bond in its molecule, the number of which is at least 25% of the number of double bonds contained in one molecule, a polysiloxane derivative bearing at least one siloxane unit represented by formula (1) and calcium carbonate. In the formula, R<SP>1</SP>is at least one selected from the group consisting of methyl, ethyl and phenyl groups; and R<SP>2</SP>is a 1-30C saturated hydrocarbon group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable resin composition and a sealing material.

Conventionally, urethane resin compositions are used for sealing materials, waterproofing materials, adhesives, and the like.
A composition containing a urethane prepolymer and an unsaturated compound capable of reacting with oxygen as a urethane resin composition having little stickiness on the surface after curing, that is, low tackiness (see, for example, Patent Documents 1 to 3). Has been proposed.

JP 2003-119382 A JP 2002-37846 A JP 2000-178533 A

However, the present inventors have found that there is room for improvement in workability, such as the composition described in Patent Documents 1 to 3 being attached to the spatula and pulling the thread over time during construction. I found it.
Then, an object of this invention is to provide the curable resin composition excellent in low tack property and workability | operativity.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have made the urethane prepolymer contain a specific drying oil and / or a polymer of the drying oil and a specific polysiloxane derivative, thereby reducing the tackiness and work. The present invention was completed by finding that a curable resin composition having excellent properties can be obtained.

That is, the present invention provides the following (1) to (5).
(1) a urethane prepolymer;
Dry oil having an iodine value of 130 or more, having a conjugated double bond in the molecule, and the number of the conjugated double bonds being 25% or more of the number of double bonds contained in one molecule and / or the drying oil A polymer of
A polysiloxane derivative having at least one siloxane unit represented by the following formula (1);
A curable 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 curable 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 drying oil and / or the polymer of the drying oil is 0.5 to 20 parts by mass,
The polysiloxane derivative is 0.5 to 30 parts by mass,
Curable resin composition as described in said (1) or (2) whose said calcium carbonate is 20-400 mass parts.
(4) The curable resin composition according to any one of (1) to (3), further comprising an active hydrogen-containing compound capable of reacting with the urethane prepolymer.
(5) A sealing material using the curable resin composition according to any one of (1) to (4) above.

  The curable resin composition of the present invention is excellent in low tack and workability.

The present invention will be described in detail below.
First, the curable resin composition of the present invention will be described.
The curable resin composition of the present invention is
Urethane prepolymer,
Dry oil having an iodine value of 130 or more, having a conjugated double bond in the molecule, and the number of the conjugated double bonds being 25% or more of the number of double bonds contained in one molecule and / or the drying oil A polymer of
A polysiloxane derivative having at least one siloxane unit represented by the following formula (1);
It is a 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.)

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 polyols; polyester polyols such as castor oil are listed.

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 the number of isocyanate groups of the isocyanate group-containing compound to the number of hydroxy groups of the polyol compound (NCO / OH) is 1.0 in the ratio of mixing the polyol compound and the isocyanate group-containing compound in the production of the urethane prepolymer. 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 drying oil and the polymer of the drying oil will be described below.
The composition of the present invention comprises:
A drying oil having an iodine value of 130 or more, having a conjugated double bond in the molecule, and having 25% or more of the number of conjugated double bonds in one molecule and / or said drying oil Contains polymer.
In the present invention, the number of conjugated double bonds in the molecule of the drying oil or the drying oil polymer is the number of individual double bonds involved in conjugation. For example, when the conjugated double bond is —CH ₂ —CH═CH—CH═CH—CH ₂ —, the number of conjugated double bonds is counted as two.

The drying oil will be described below.
The drying oil contained in the composition of the present invention has an iodine value of 130 or more, has a conjugated double bond in the molecule, and the number of conjugated double bonds is 25, the number of double bonds contained in one molecule. % Or more.

The drying oil contained in the composition of the present invention has an iodine value of 130 or more.
The iodine value of the drying oil is preferably 140 or more. When the iodine value is within this range, it is more excellent in low tack.

  The drying oil contained in the composition of the present invention has conjugated double bonds in the molecule, and the number of conjugated double bonds in the molecule is 25% of the number of double bonds contained in one molecule. That's it.

  Further, the number of conjugated double bonds contained in one molecule of drying oil is preferably 30% or more, more preferably 50% or more of the total number of double bonds contained in one molecule. When the ratio of the number of conjugated double bonds contained in one molecule of drying oil is within such a range, the tackiness is more excellent.

In the present invention, the drying oil contains an ester of a fatty acid having a conjugated double bond in the molecule.
Examples of the fatty acid having a conjugated double bond include eleostearic acid and octadecadienoic acid.

In the present invention, the drying oil contains, for example, a fatty acid having one double bond, a fatty acid having two or more unconjugated double bonds, and a saturated fatty acid in addition to the fatty acid having a conjugated double bond. Can be included.
The fatty acid having one double bond, the fatty acid having two or more unconjugated double bonds, and the saturated fatty acid are not particularly limited. For example, a conventionally well-known thing is mentioned.

Examples of the dry oil contained in the composition of the present invention include dehydrated castor oil and tung oil.
The drying oil is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. Specifically, for example, it can be produced by dehydrating a drying oil (for example, castor oil) containing a fatty acid ester having a hydroxy group.

  Further, the polymer of the drying oil contained in the composition of the present invention has an iodine value of 130 or more, has a conjugated double bond in the molecule, and the number of the conjugated double bonds contained in one molecule is 1. 25% or more of the number of double bonds contained in the molecule.

The polymer of the drying oil has an iodine value of 130 or more, has a conjugated double bond in the molecule, and the number in the conjugated double bond contained in one molecule is the number of double bonds contained in one molecule. If it is what polymerized the dry oil which is 25% or more, it will not restrict | limit in particular.
A drying oil having an iodine value of 130 or more, having a conjugated double bond in the molecule, and the number of conjugated double bonds contained in one molecule being 25% or more of the number of double bonds contained in one molecule is Are the same as above.
There is no particular limitation on the polymerization of the drying oil. For example, a conventionally well-known thing is mentioned. Specifically, for example, the drying oil can be polymerized by applying heat to the drying oil or irradiating light.

  Examples of the polymer of drying oil include a polymer of dehydrated castor oil and a polymer of tung oil.

  The drying oil and / or the drying oil polymer may be used alone or in combination of two or more.

  The content of the drying oil and / or the polymer of the drying oil is preferably 0.5 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer. More preferably, it is 0.5-5 mass parts. When the content of the drying oil and / or the polymer of the drying oil is within this range, the workability and the low tack property are excellent.

When the composition of the present invention is applied, the drying oil and / or polymer of the drying oil contained in the composition of the present invention bleeds out to the surface of the coating film to form a film, thereby The composition of the present invention is excellent in workability and low tack.
In particular, when the composition of the present invention is exposed outdoors, the drying oil and / or the polymer of the drying oil are further polymerized by light, so that the film formation is accelerated and the low tack property is 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 more excellent in workability.

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 group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 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. In addition, the molar ratio [isopropylene group: ethylene group] of isopropylene group [—CH ₂ CH (CH ₃ ) —] and ethylene group is 60:40 to 20:80, which is more excellent in workability. 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 workability is 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 workability. In the total amount of the siloxane unit and the siloxane unit represented by the 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 a 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 workability 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.
Of these, esters of higher fatty acids having 8 or more carbon atoms are preferred from the viewpoint of workability. 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, it is more excellent in workability.

The composition of the present invention may contain an active hydrogen-containing compound that can react with the urethane prepolymer.
The active hydrogen-containing compound is not particularly limited as long as it is a compound that contains active hydrogen and can react with the urethane prepolymer.

  Examples of the active hydrogen-containing compound include compounds having at least two substituents selected from the group consisting of sulfide bonds, hydroxy groups, mercapto groups, and amino groups. Specific examples include polysulfide polymers, polyhydric alcohols, amines, alkanolamines, and polyhydric phenols. Polyhydric alcohols, amines, alkanolamines, and polyhydric phenols have the same meanings as described above.

  The active hydrogen-containing compounds can be used alone or in combination of two or more.

  The amount of the active hydrogen-containing compound used is preferably 0 to 500 parts by mass and more preferably 0 to 300 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

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.

  The inorganic filler other than calcium carbonate is 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, anthanthrone 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 / methylphosphonate, 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.

The composition of the present invention can be produced and used as a one-pack type or a two-pack type.
When the composition of the present invention is a one-component type, as a production method thereof, for example,
[1] A mixing step of mixing a urethane prepolymer, calcium carbonate and a polysiloxane derivative to form a mixture, and adding a drying oil and / or a polymer of drying oil to the resulting mixture to obtain a curable resin composition. An addition step (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 a polysiloxane derivative and drying oil and / or a polymer of drying oil are simultaneously added to the mixture to obtain a curable resin composition. A method comprising an adding step,
[3] A method in which a urethane prepolymer, calcium carbonate, a polysiloxane derivative, and a drying oil and / or a drying oil polymer are simultaneously added and mixed may be mentioned.

  Of these, the production method A is preferable from the viewpoint of excellent workability and low tackiness.

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.

  In the addition step after the mixing step, a drying oil and / or a polymer of drying oil is added to obtain a curable resin composition.

In the addition step, a solvent and an additive can be further mixed.
In the addition step, the means for mixing the mixture with the drying oil and / or the polymer of the drying oil 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 curable resin composition can be stored, for example, in a container replaced with nitrogen gas, with the container sealed.

Further, when the composition of the present invention is a two-component type, for example, a first liquid containing a urethane prepolymer, a drying oil and / or a drying oil polymer, and a polysiloxane derivative, and calcium carbonate are included. It can be set as the 2 liquid type composition which has a 2nd liquid.
When the composition of the present invention further contains an active hydrogen-containing compound, the active hydrogen-containing compound can be added to the second liquid.
When the composition of the present invention is a one-component type, the storage stability is excellent.
The first liquid and the second liquid obtained by mixing each can be separately put into two containers replaced with, for example, nitrogen gas, and the containers can be sealed and stored.

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 workability | operativity and low tack property, it can be used conveniently as a sealing material composition.

The method for using the composition of the present invention will be described below.
Examples of the method of using the composition of the present invention include a method comprising 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.

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.
As a method of applying the composition of the present invention to a material to be coated, various methods can be used, 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 drying oil and / or the polymer of the drying oil proceeds by light and bleeds out on the surface of the composition to form a film faster, by irradiating with ultraviolet rays (for example, outdoor exposure) It is preferable to cure.
Outdoor exposure is not particularly limited, and from the viewpoint that workability and low tack are more excellent, the outdoor composition (preferably a place exposed to sunlight) is left for one day or more. Is preferred.

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 can be obtained, for example, by filling a joint of a building material such as a tile or an outer wall panel with the composition of the present invention and curing it.
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, when light is irradiated (for example, outdoor exposure), the polymerization reaction of the drying oil and / or the polymer of the drying oil is accelerated by light, and the film bleeds out to the surface of the composition to form a film. It is preferable to cure.
The outdoor exposure is not particularly limited, and from the viewpoint of better workability and low tackiness, the outdoor application (preferably in a place exposed to sunlight) is left for one day or more. Is preferred.

The inventor presumes the reason why the composition of the present invention is excellent in workability and low tackiness 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, whereby the drying oil and / or the polymer of the drying oil reacts with and / or coordinates with the calcium carbonate to form the urethane prepolymer. A film that prevents wetting and prevents the thixo-index of the composition from decreasing and increasing in viscosity over time, while increasing the low tack property by the film forming property of drying oil and / or a polymer of drying oil. The present inventor presumes that this can be formed on the surface of the composition.
Further, in the composition of the present invention, by adding the polysiloxane derivative to the urethane prepolymer and calcium carbonate prior to the drying oil and / or the polymer of the drying oil, the carboxylic acid that can be generated from the polysiloxane derivative is calcium carbonate. More effectively, the drying oil and / or the polymer of the drying oil reacts with and / or coordinates with calcium carbonate to promote wetting of the urethane prepolymer and calcium carbonate. The inventor speculates that this can be prevented.
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 167 g of hexamethylene diisocyanate was added to 800 g of polypropylene diol (Excenol 2020, manufactured by Asahi Glass Co., Ltd.) having a dehydrated average molecular weight of 2000 and 200 g of polypropylene triol having a dehydrated average molecular weight of 3000 (Excenol 3030, manufactured by Asahi Glass Co., Ltd.) (NCO / OH = 2.0) in the presence of a catalyst at 80 ° C. for 2 hours to obtain a urethane prepolymer having an NCO content of 3.75% by mass.
The resulting urethane prepolymer was used in the examples.

2. Drying oil The drying oil used in Examples and Comparative Examples is shown in Table 1 below.
In Table 1, the conjugated double bond content indicates the ratio of the number of conjugated double bonds in the molecule to the number of double bonds in one molecule of drying oil.
Dry oil 1 is a glyceride containing 9,11-octadecadienoic acid having a conjugated double bond.
In Table 1, the content of the conjugated double bond of the drying oil 1 is 35%, which means that the number of the conjugated double bonds of one molecule of the drying oil 1 is equal to that of one molecule of the drying oil 1. It is 35% of the number of double bonds.
Dry oil 2 also has a conjugated double bond derived from octadecadienoic acid.

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)
About the 1st liquid, each component of following Table 2 was stirred and mixed by the composition (mass part) shown in Table 2 under nitrogen stream, and the 1st liquid was obtained.
About the 2nd liquid, each component of following Table 2 was stirred and mixed by the composition (mass part) shown in Table 2 under nitrogen stream, and the 2nd liquid was obtained.
The first liquid and the second liquid were mixed at the time of use to prepare a composition.

5). Evaluation Viscosity, slump and tack were evaluated by the following methods using the obtained compositions. The results are shown in Table 2.

(1) Viscosity / Viscosity 1: Viscosity after 10 minutes from mixing The first and second liquids are mixed and placed under conditions of 23 ° C. and 50% RH for 10 minutes after mixing. And a viscosity at 10 rpm were measured using a B-type viscometer. The obtained two viscosities are set to viscosity 1 (1 rpm) and viscosity 1 (10 rpm). The thixo index 1 (1 rpm / 10 rpm) was determined from the viscosity 1 (1 rpm) and the viscosity 1 (10 rpm).
-Viscosity 2: Viscosity 120 minutes after mixing The first and second liquids are mixed, placed under conditions of 23 ° C and 50% RH for 120 minutes after mixing, and the viscosity of 1 rpm and 10 rpm of the composition 120 minutes later. Were measured using a B-type viscometer. The obtained two viscosities are viscosity 2 (1 rpm) and viscosity 2 (10 rpm). Thixo index 2 (1 rpm / 10 rpm) was determined from viscosity 2 (1 rpm) and viscosity 2 (10 rpm).

(2) Slump Using the jig defined in JIS A 1439 4.1, the obtained composition was subjected to a slump test in an environment of 23 ° C.
In the slump test, the first liquid and the second liquid were mixed under each temperature environment, and the composition that had been placed for 120 minutes after mixing was filled with care so that bubbles do not enter the groove of the slip jig, and the surface was Smoothened. 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) Tack Using a slate plate with a width of 50 mm x length of 50 mm x height of 5 mm, a primer (No. 40, manufactured by Yokohama Rubber Co.) is applied to the surface of the slate plate within a range of width 30 mm x length 30 mm. 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 5 mm, flattened with a spatula, and in an environment of 23 ° C. and 50% RH. The composition was allowed to cure for 28 days.
After curing, the tack was judged by finger touch.
The judgment criteria are as follows.
A: Tack is not felt.
○: Tack is hardly felt.
Δ: Tack is slightly felt.
X: Tack is felt.

The components shown in Table 2 are as follows.
-Urethane prepolymer: prepared as described above-Drying oils 1-3: Drying oil described above-Polysiloxanes 1-2: prepared as described above-Active hydrogen-containing compounds: polysulfide polymer, LP-282, Toraythiocol -Calcium carbonate 1: Calfine 200, manufactured by Maruo Calcium Co.-Calcium carbonate 2: Colloidal calcium carbonate, trade name Neolite SPT, Takehara Chemical Industry Co., Ltd.-Calcium carbonate 3: Heavy calcium carbonate, trade name Ryton 4, Bihoku・ Plasticizer: diisononyl phthalate, DINP, manufactured by Jplus ・ Catalyst: tin catalyst, Stann-BL, manufactured by Sansha Kogyo Co., Ltd.

As is apparent from the results shown in Table 2, the composition containing no drying oil (Comparative Example 1) was tacky.
The composition containing no polysiloxane derivative (Comparative Example 2) had poor workability because the thixo-index after 120 minutes from mixing was low, so that the pot life was short and slump was generated.
The composition (Comparative Example 3) containing a drying oil (linseed oil) with a low ratio of conjugated double bonds was somewhat tacky.
On the other hand, the compositions of Examples 1 to 4 have a high thixo index after 10 minutes or 120 minutes from mixing, so that the pot life is long, no slump is generated, the workability is excellent, and tack is felt. The low tack property was excellent.

Claims (5)

Urethane prepolymer,
Dry oil having an iodine value of 130 or more, having a conjugated double bond in the molecule, and the number of the conjugated double bonds being 25% or more of the number of double bonds contained in one molecule and / or the drying oil A polymer of
A polysiloxane derivative having at least one siloxane unit represented by the following formula (1);
A curable 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.)   The curable 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 drying oil and / or the polymer of the drying oil is 0.5 to 20 parts by mass,
The polysiloxane derivative is 0.5 to 30 parts by mass,
The curable resin composition according to claim 1 or 2, wherein the calcium carbonate is 20 to 400 parts by mass.   Furthermore, the curable resin composition in any one of Claims 1-3 containing the active hydrogen containing compound which can react with the said urethane prepolymer.   The sealing material which uses the curable resin composition in any one of Claims 1-4.