JP2015183185A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition including a reactive silicon group-containing polymer and drying-oil or its derivative and satisfactory in storage stability.SOLUTION: Provided is a curable composition comprising: a polymer (A) obtained by introducing a reactive silicon group into a precursor polymer (A`) having a functional group into which a reactive silicon group can be introduced; a compound (B) being one or more kinds selected from the group consisting of drying-oil and the derivative thereof, in which the average functional group number of the polymer (A`) is 2.0 to 3.0, the molecular weight per functional group is 5,000 to 20,000, also, the molecular weight distribution is 1.01 to 1.50, at least a part of the functional group being a hydroxyl group, the content of the compound (B) is 0.1 to 8.0 pts.mass to 100 pts.mass of the polymer (A), and the content of sodium is above zero and 5.0 ppm or more to the polymer (A).

Description

  The present invention relates to a curable composition containing a polymer having a reactive silicon group.

  A polymer having a reactive silicon group (hereinafter also referred to as a modified silicone polymer) is liquid at room temperature and is cured by a hydrolysis reaction to form a flexible rubber-like cured product. Curable compositions containing such modified silicone polymers are widely used as sealing materials, adhesives, coating agents and the like.

In the case of curable compositions generally used for sealing materials, adhesives, etc., the surface immediately after curing is tacky (tack) in order to prevent dirt and other dirt from adhering to the surface after curing. It is required not to remain. Moreover, it is preferable that the drying property of the coating material coated on the hardened | cured material surface is favorable, and a crack and whitening are not produced on the surface. As a countermeasure against these, a method is known in which at least one compound selected from drying oil and derivatives thereof is blended in the composition.
For example, Patent Document 1 discloses that by including a drying oil such as tung oil or linseed oil in a curable composition containing a modified silicone polymer, it is possible to improve the drying property when an alkyd paint is applied to the surface of the cured product. Is described.
Patent Document 2 describes that the addition of drying oil contributes to the suppression of cracks and whitening in the cured product.

JP-A-1-198661 JP2013-6887A

In addition, the curable composition containing the modified silicone polymer is required to have high storage stability and hardly increase viscosity in the storage state from the viewpoint of workability.
However, according to the knowledge of the present inventors, when a drying oil is contained in a curable composition containing a polymer having a reactive silicon group, the viscosity may increase during storage.

  An object of the present invention is to provide a curable composition having a good storage stability, comprising a polymer having a reactive silicon group and a drying oil or a derivative thereof.

  As a result of intensive studies on the cause of the increase in viscosity during storage, the present inventors have found that when sodium and dry oil remaining in the polymer having a reactive silicon group coexist in excess of a specific amount, storage is performed. It was found that thickening inside occurred. Then, by controlling the residual amount of sodium and the amount of drying oil added to a predetermined amount or less, it was found that stability during storage could be improved and viscosity increase could be suppressed, and the present invention was completed. .

The present invention includes the following [1] to [4].
[1] A polymer (A) obtained by introducing a reactive silicon group represented by the following formula (1) into a precursor polymer (A ′) having a functional group capable of introducing a reactive silicon group; Containing one or more compounds (B) selected from the group consisting of oil and derivatives thereof, the average number of functional groups of the precursor polymer (A ′) is 2.0 to 3.0, per functional group A group having a molecular weight of 5,000 to 20,000, a molecular weight distribution of 1.01 to 1.50, at least a part of the functional group being a hydroxyl group, and the compound (B) comprising a drying oil and a derivative thereof. And the content of the compound (B) is 0.1 to 8.0 parts by mass with respect to 100 parts by mass of the polymer (A), and the sodium content is Curable group characterized by being more than 0 and 5.0 ppm or less with respect to coalesced (A) Thing.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X ¹ represents a hydroxyl group or a hydrolyzable group. . Two X ¹ may be the same or different from each other. ]

[2] In the presence of an alkylene oxide ring-opening polymerization catalyst, the precursor polymer (A ′) opens an alkylene oxide on one or both of an initiator having two hydroxyl groups and an initiator having three hydroxyl groups. The curable composition according to [1], which is a hydroxyl group-containing polyoxyalkylene polymer obtained by addition.
[3] The curable composition according to [2], wherein the alkylene oxide ring-opening polymerization catalyst is a double metal cyanide complex catalyst in which t-butyl alcohol is coordinated as an organic ligand.
[4] The polymer (A) reacts with a hydroxyl group of the precursor polymer (A ′) with sodium or a sodium-containing compound, and then reacts with a halogen compound having an unsaturated group to introduce an unsaturated group. The curable composition according to any one of [1] to [3], which is a polymer obtained by reacting the unsaturated group with a hydrosilane compound having the reactive silicon group.

  ADVANTAGE OF THE INVENTION According to this invention, the polymer which has a reactive silicon group, and drying oil are included, and while the stickiness of the surface of hardened | cured material is suppressed, the curable composition excellent in storage stability is obtained.

In the present specification, the mass average molecular weight (Mw, hereinafter also referred to as “Mw”) and the number average molecular weight (Mn, hereinafter also referred to as “Mn”) are polystyrene-converted molecular weights measured by gel permeation chromatography (GPC). is there. The molecular weight distribution (hereinafter also referred to as “Mw / Mn”) is a value calculated from Mw and Mn measured by the above method, and the ratio of the mass average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn). ).
In this specification, when the functional group is a hydroxyl group, the molecular weight per functional group is a value obtained by dividing 56,100 by the hydroxyl value.
The hydroxyl value in this specification is a value measured by a method based on JIS K1557-1.
In this specification, when the functional group is a group other than a hydroxyl group, the molecular weight per functional group is a value determined by gel permeation chromatography (GPC). Specifically, a molecular weight per functional group is calculated by drawing a calibration curve with a polymer whose molecular weight per functional group is known and measuring the measurement object.

Sodium in the curable composition of the present invention means sodium detected by the following measurement method.
30 g of the curable composition is weighed in a platinum dish, burned and incinerated using a gas burner, and then completely incinerated in an electric furnace at 600 ° C. The obtained ashing residue is dissolved in 2 ml of 6N hydrochloric acid, and distilled water is added to make 100 ml. The sodium content of the ashing residue is measured using an atomic absorption photometer (manufactured by Shimadzu Corporation, product name: AA-6200). The quantification of the sodium content is determined from a calibration curve prepared with a metal standard solution.

<Polymer (A)>
The polymer (A) is a polymer obtained by introducing a reactive silicon group into a precursor polymer (A ′) having a functional group capable of introducing a reactive silicon group.
In the precursor polymer (A ′), functional groups capable of introducing reactive silicon groups are present at the ends of the entire main chain. In the polymer (A), the reactive silicon group is present at the end of the main chain. When the reactive silicon group of the polymer (A) is at the end of the main chain, the elongation property, internal curability and surface curability of the cured product are likely to be good.
In the polymer (A), among the functional groups capable of introducing the reactive silicon group of the precursor polymer (A ′), the ratio of the functional group substituted with a group containing a reactive silicon group is referred to as a silylation rate.
In the present specification, the “main chain” of a polymer refers to a polymer chain formed by linking two or more monomers. The main chain end is the end of each main chain, and there are two main chain ends in a polymer in which the main chain is linear. The “total main chain end” of the polymer means all the main chain ends of the polymer.
In this specification, the average number of functional groups of the precursor polymer (A ′) is the average value of “functional groups capable of introducing reactive silicon groups” per molecule. The average number of functional groups of the precursor polymer (A ′) is equal to the average number of main chain ends per molecule.
In the present specification, the average number of functional groups of the polymer (A) means the average of the ends of the main chain per molecule, and is equal to the average number of functional groups of the precursor polymer (A ′).
When the precursor polymer (A ′) or the polymer (A) is a mixture, the average value after mixing is the average number of functional groups of the precursor polymer (A ′) or the polymer (A).

The reactive silicon group of the polymer (A) is represented by the following formula (1).
-SiX ¹ ₂ R ¹ (1)
In Formula (1), R ¹ represents a monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group) which may have a substituent. R ¹ is preferably a hydrocarbon group having 8 or less carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and a phenyl group. A methyl group and a phenyl group are more preferable, and a methyl group is particularly preferable.

In the formula (1), X ¹ represents a hydroxyl group or a hydrolyzable group. Two X ¹ existing in one molecule may be the same as or different from each other.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. X ¹ is particularly preferably an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms. More specifically, X ¹ is particularly preferably a methoxy group or an ethoxy group.

<Precursor polymer (A ')>
The average number of functional groups of the precursor polymer (A ′) is 2.0 to 3.0. That is, the average number of functional groups of the polymer (A) is 2.0 to 3.0. When the average functional group number of the polymer (A) is 2.0, the main chain of the polymer (A) is linear. When the average number of functional groups of the polymer (A) is 2.0 or more, good strength in the cured product is easily obtained.
On the other hand, when the average functional group number of the polymer (A) is 3.0 or less, good flexibility in the cured product is easily obtained.

The molecular weight per functional group of the precursor polymer (A ′) is 5,000 to 20,000, and the molecular weight distribution is 1.01 to 1.50.
When the molecular weight of the precursor polymer (A ′) is not less than the lower limit of the above range, the elongation property and flexibility of the cured product are likely to be good. When the amount is not more than the upper limit of the above range, the curable composition tends to have a low viscosity, which is preferable for obtaining good workability. The molecular weight per functional group of the precursor polymer (A ′) is preferably 7,000 to 18,500, more preferably 7,500 to 17,000.
When the molecular weight distribution of the precursor polymer (A ′) is within the above range, the flexibility of the cured product tends to be good, and the curable composition tends to have a low viscosity. When the number average molecular weight is the same, the narrower the molecular weight distribution, the lower the viscosity. The reason is that when the molecular weight distribution is wide, a large number of high molecular weight substances are present, which causes high viscosity. Alternatively, when the flexibility is the same, the narrower the molecular weight distribution, the better the elongation properties. The reason is considered to be that when the molecular weight distribution exceeds 1.50, the amount of low molecular weight polymer components increases, and therefore the distance between cross-linking points becomes short and it becomes difficult to extend. Therefore, the molecular weight distribution is preferably narrower, more preferably 1.01-1.40, and still more preferably 1.01-1.30. The molecular weight distribution (Mw / Mn) of the precursor polymer (A ′) can be controlled by the type of catalyst and polymerization conditions (temperature, stirring conditions, pressure, etc.).

The functional group capable of introducing the reactive silicon group of the precursor polymer (A ′) is at least one selected from a group having an active hydrogen or an unsaturated group. The group having active hydrogen is preferably a hydroxyl group.
An unsaturated group is a monovalent group containing an unsaturated double bond. Specific examples of the unsaturated group are preferably alkenyl groups having 6 or less carbon atoms such as allyl group, isopropenyl group, 1-butenyl group, methallyl group, allyl group (—CH ₂ —CH═CH ₂ ), methallyl group. Is more preferable.
It is preferable that at least a part of the functional groups of the precursor polymer (A ′) is a hydroxyl group, and all the hydroxyl groups are a hydroxyl group.

  In the polymer (A), after reacting the hydroxyl group of the precursor polymer (A ′) with sodium or a sodium-containing compound, the unsaturated compound is introduced by reacting with a halogen compound having an unsaturated group. A polymer obtained by reacting a silylating agent with a group is preferred. The silylating agent is a compound having both a group that reacts with an unsaturated group and a reactive silicon group.

Examples of the method for introducing an unsaturated group into the hydroxyl group of the precursor polymer (A ′) using sodium or a sodium-containing compound include the following methods (I) and (II). These can be performed using a known method.
(I) The precursor polymer (A ′) is reacted with sodium or a sodium-containing compound to convert the terminal hydroxyl group to —ONa, and this is reacted with a halogenated compound having an unsaturated group to react with the terminal hydroxyl group. A method for introducing a saturated group. In this method, sodium halide is by-produced.
(II) When the precursor polymer (A ′) has one unsaturated group and one hydroxyl group as terminal functional groups, the precursor polymer (A ′) is reacted with sodium or a sodium-containing compound, A method of obtaining a polymer in which all terminals are unsaturated groups by converting a terminal hydroxyl group to -ONa and then dimerizing or multiplying using a polyvalent halogen compound. This method also produces sodium halide as a by-product.

In the above method (I) or (II), the sodium-containing compound is preferably NaH, NaOR (R represents an alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl), or sodium hydroxide.
As halogen, chlorine or bromine is preferable. As the halogen compound having an unsaturated group, alkenyl halides are preferable, and alkenyl chlorides such as allyl chloride and methallyl chloride are more preferable. Examples of the polyvalent halogen compound include dichloro hydrocarbons having 1 to 2 carbon atoms and trichloro hydrocarbons having 1 to 2 carbon atoms.
For example, in the method (I), when sodium alkoxide and allyl chloride are used, sodium chloride (NaCl) is by-produced.

By-product sodium halide can be removed by a known purification method.
For example, water and a surfactant are added to a reaction product containing sodium halide as a by-product, followed by dehydration to obtain a crude liquid containing crystals of sodium halide (crystallization process). By separating the liquid, sodium halide crystals can be removed.
As the surfactant, those generally known as nonionic surfactants can be used. In particular, a compound having 5% by mass or more of oxyethylene group (—O—C ₂ H ₄ —) in the molecule is preferable.
Examples of nonionic surfactants include polyoxyethylene aliphatic alkyl ether, polyoxyethylene polyoxypropylene aliphatic alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene monoaliphatic carboxylic acid ester, sorbitan mono or poly Aliphatic ester, polyoxyethylene sorbitan mono fatty acid ester, polyoxyethylene oxypropylene block copolymer, oxyethylene or polyoxyethylene aliphatic amine, fatty acid dialkanolamide, glycerol mono fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, Examples include pentaerythritol fatty acid esters.
The molecular weight of the surfactant is preferably 1,000 to 10,000, and more preferably 4,000 to 6,000. 5-50 mass% is preferable and, as for content of the oxyethylene group in surfactant, 10-30 mass% is more preferable.
The amount of the surfactant used is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the polymer into which the unsaturated group has been introduced.

As a method for obtaining a polymer (A) by reacting a silylating agent with an unsaturated group of a polymer into which an unsaturated group has been introduced, the following method [1] or [2] can be used. The method [1] is preferred in that there is no problem of odor of the polymer (A).
[1] A method in which an unsaturated group is reacted with a hydrosilane compound represented by the following formula (2) in the presence of a catalyst. However, X ¹ and R ¹ in the formula (2) are the same as in the above formula (1).
HSiX ¹ ₂ R ¹ (2)
[2] A method of reacting an unsaturated group with a mercapto group of a silicon compound represented by the following formula (3).
W ¹ R ² —SiX ¹ ₂ R ¹ (3)
X ¹ and R ¹ in the formula (3) are the same as those in the above formula (1). R ² is a divalent organic group, and W ¹ is a mercapto group.

The silylation rate in the polymer (A) is preferably 45 to 100 mol%, more preferably 50 to 84 mol%, and still more preferably 63 to 84 mol%.
When two or more kinds of polymers corresponding to the polymer (A) are mixed and used, the silylation rate in the mixture after mixing may be within the above range, and one of the polymers (A) before mixing. A part having a silylation rate of less than 70% may be used.

  The value of the silylation rate in this specification can be measured by NMR analysis. Ordinarily, a side reaction occurs in the reaction between the precursor polymer (A ′) produced using allyl chloride and the silylating agent. Approximately 10 mol% of the allyl group of the precursor polymer (A ′) produced using allyl chloride is isomerized and not silylated, so that 100% silylation is difficult. However, in a silylation with a silylation rate of up to 90%, the reaction rate can be regarded as almost 100%. Therefore, when the silylation rate of the polymer (A) to be obtained by the reaction between the precursor polymer (A ′) produced using allyl chloride and the silylating agent is less than 90%, the polymer ( As the value of the silylation rate in A), a value calculated from the charged amount of the silylating agent with respect to the charged amount of the precursor polymer (A ′) may be used.

The main chain of the precursor polymer (A ′) and the polymer (A) is not particularly limited, and a known main chain can be used in the polymer having a reactive silicon group. For example, a main chain composed of one or more polyoxyalkylene units, one or more polyester units, one or more polycarbonate units, or a combination thereof is preferable.
The main chains of the precursor polymer (A ′) and the polymer (A) preferably have at least a chain of alkylene oxide monomer units, that is, a polyoxyalkylene chain.
When the polymer (A) has a polyoxyalkylene chain, there are advantages such as low temperature dependence, easy flexibility of the cured product, and excellent price.
The reactive functional group in the initiator is a group having active hydrogen, and preferably a hydroxyl group. The average functional group number of the initiator, the average functional group number of the precursor polymer (A ′), and the average functional group number of the polymer (A) are the same.

[Hydroxyl-containing polyoxyalkylene polymer]
The precursor polymer (A ′) is preferably a linear or branched hydroxyl group-containing polyoxyalkylene polymer having a polyoxyalkylene chain and having all main chain terminals terminated by hydroxyl groups.
Specifically, in the presence of an alkylene oxide ring-opening polymerization catalyst, a hydroxyl group-containing product obtained by ring-opening addition of alkylene oxide to one or both of an initiator having two hydroxyl groups and an initiator having three hydroxyl groups Polyoxyalkylene polymers are preferred.
[Initiator]
Specific examples of the compound having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol. Of these, propylene glycol and dipropylene glycol are more preferable.
Specific examples of the initiator having three hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane and the like. Of these, glycerin is particularly preferable.
Further, polyoxyalkylene diols or polyoxyalkylene triols having a molecular weight of 80 to 10,000 per hydroxyl group obtained by ring-opening addition polymerization of alkylene oxide to these compounds having 2 or 3 hydroxyl groups Is preferably used as an initiator. An initiator may be used individually by 1 type and may use 2 or more types together.
[Alkylene oxide]
The alkylene oxide used for the synthesis of the precursor polymer (A ′) or the initiator preferably has 2 to 20 carbon atoms, and specific examples include propylene oxide, butylene oxide, and ethylene oxide. Propylene oxide is particularly preferred. An alkylene oxide may be used individually by 1 type, and may use 2 or more types together. When the polyoxyalkylene chain is composed of two or more oxyalkylene monomer units, the arrangement of the monomer units may be block or random.
[Alkylene oxide ring-opening polymerization catalyst]
Examples of the alkylene oxide ring-opening polymerization catalyst include an alkali metal catalyst, a double metal cyanide complex catalyst, and a metal porphyrin. In particular, a double metal cyanide complex catalyst is preferable in that the molecular weight distribution of the precursor polymer (A ′) and the polymer (A) tends to be small.
The double metal cyanide complex is preferably a double metal cyanide complex having an organic ligand.
The organic ligand is preferably an ether ligand or an alcohol ligand. Specific examples of the ether-based ligand include ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), and triethylene glycol dimethyl ether. Specific examples of the alcohol-based ligand include tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol, and ethylene glycol mono-tert-butyl ether. It is done.
In particular, a double metal cyanide complex catalyst in which t-butyl alcohol is coordinated as an organic ligand is preferable.
As the double metal cyanide complex, zinc hexacyanocobaltate is particularly preferable.

<Compound (B)>
The curable composition of this invention contains the compound (B) which is 1 or more types chosen from the group which consists of drying oil and its derivative (s). The compound (B) is a compound having an unsaturated group (oxidation-curable unsaturated group) that undergoes polymerization due to oxygen in the air. When compound (B) is contained in the curable composition, stickiness (tack) on the surface of the cured product is suppressed.
Examples of drying oils include linseed oil, tung oil, soybean oil, asa seed oil, isano oil, urushi kernel oil, egoma oil, pear oil, kaya oil, walnut oil, poppy oil, cherry seed oil, pomegranate seed oil, sacrificial oil Examples include flower oil, tobacco seed oil, spruce seed oil, rubber seed oil, sunflower seed oil, grape kernel oil, spinach seed oil, and honey bee seed oil.
Examples of drying oil derivatives include various alkyd resins obtained by modifying drying oil; reaction products of drying oil and functional polyoxyalkylene; reaction products of drying oil and isocyanate compound (urethanized oil) An acrylic polymer modified with a drying oil, an epoxy resin, a silicone resin; and the like.
As the drying oil, linseed oil, tung oil, or poppy oil is preferable in that good drying property (curability) is easily obtained. In particular, tung oil is preferable because it has a fast drying property (curability) compared to poppy oil, is excellent in surface tack reduction effect, has a high antifouling effect, and is less susceptible to yellowing than linseed oil. Tung oil is also preferable because it is relatively inexpensive and easily available.

In the curable composition of the present invention, the content of the compound (B) is 8.0 parts by mass or less, preferably 7.0 parts by mass or less, with respect to 100 parts by mass of the polymer (A). 0 parts by mass or less is more preferable. When the amount is 8.0 parts by mass or less, good storage stability of the curable composition is easily obtained.
The lower limit of content of a compound (B) is 0.1 mass part or more, 0.2 mass part or more is preferable and 0.4 mass part or more is more preferable. When the amount is 0.1 part by mass or more, a sticking suppression effect on the surface of the cured product can be easily obtained.

<Other polymers>
The curable composition of the present invention may contain other polymers having a known reactive silicon group in addition to the polymer (A). Other polymers may contain sodium, but preferably do not contain sodium.
Of the total of the polymers having reactive silicon groups contained in the curable composition, the proportion of the polymer (A) is preferably 50% by mass or more, and preferably 70% by mass or more in terms of the great effect of the present invention. More preferably, 90 mass% or more is further more preferable.

<Other ingredients>
The curable composition of this invention can contain a well-known component in a curable composition other than said polymer (A), a compound (B), and another polymer. Specific examples thereof include additives such as a curing catalyst, a co-catalyst, a filler, a plasticizer, a thixotropic agent, a stabilizer, an adhesion promoter, and a modulus modifier. These additive components may contain sodium but preferably do not contain it.
The method for preparing such a curable composition containing an additive component is not particularly limited, and the additive component may be added once or several times at an appropriate time during or after the production of the curable composition. What is necessary is just to add separately.

[Curing catalyst]
The curing catalyst is not particularly limited as long as it is a compound that catalyzes a hydrolysis reaction of a reactive silicon group. A salt of a metal (tin, bismuth, etc.) and an organic acid (octyl acid, octenoic acid, naphthenic acid, etc.); organic Metal complexes and the like are preferable. The organic acid salt is preferably stannous octylate, bismuth tris (2-ethylhexanoate), or the like.
The use amount of the curing catalyst is preferably 0.01 to 15.0 parts by mass, more preferably 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the polymer having reactive silicon groups. 1 type may be used independently and may be used together 2 or more types.

[Cocatalyst]
A curing catalyst and a co-catalyst may be used in combination. The cocatalyst is preferably an amine, carboxylic acid, or phosphoric acid, and an amine is particularly preferable from the viewpoint of fast curability of the curable composition and mechanical properties of the cured product.
The amine is not particularly limited, and a primary amine is preferable. Specific examples of amines include aliphatic monoamines such as butylamine, hexylamine, octylamine, decylamine, laurylamine, N, N-dimethyloctylamine; ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. An amine having a hydrolyzable silyl group, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane. A promoter may be used individually by 1 type, and may be used together 2 or more types. Especially, combined use of a bivalent tin compound and a primary amine compound is preferable, and combined use of stannous octylate and laurylamine is more preferable.
The cocatalyst is preferably used in an amount of 0.01 to 15 parts by weight, particularly preferably 0.1 to 5 parts by weight, based on a total of 100 parts by weight of the polymer having reactive silicon groups.

[Filler]
As the filler, heavy calcium carbonate having an average particle diameter of 1 to 20 μm, light calcium carbonate having an average particle diameter of 1 to 3 μm produced by a precipitation method, colloidal calcium carbonate whose surface is treated with a fatty acid or a resin acid organic substance, Fumed silica; precipitated silica; surface silicone-treated silica fine powder; silicic anhydride; hydrous silicic acid; carbon black; magnesium carbonate; diatomaceous earth; calcined clay; clay; talc; Bentonite; Ferric oxide; Zinc oxide; Active zinc white; Shirasu balloon, Perlite, Glass balloon, Silica balloon, Fly ash balloon, Alumina balloon, Zirconia balloon, Carbon balloon and other inorganic hollow bodies; Phenol resin balloon, Epoxy resin Balloon, urea resin balloon, sa Organic resin hollow bodies such as orchid balloons, polystyrene balloons, polymethacrylate balloons, polyvinyl alcohol balloons, styrene-acrylic resin balloons, polyacrylonitrile balloons; resin beads, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, Examples thereof include powdery fillers such as graphite, fine aluminum powder, and flint powder; and fibrous fillers such as glass fiber, glass filament, carbon fiber, Kevlar fiber, and polyethylene fiber.
These fillers may be used alone or in combination of two or more. The amount of the filler used is preferably 1 to 1000 parts by mass and more preferably 50 to 250 parts by mass with respect to 100 parts by mass in total of the polymer having reactive silicon groups.

[Plasticizer]
Plasticizers include phthalate esters such as di (2-ethylhexyl) phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate; dioctyl adipate, bis (2-methylnonyl) succinate, dibutyl sebacate, olein Aliphatic carboxylic acid esters such as butyl acid; Alcohol esters such as pentaerythritol ester; Phosphate esters such as trioctyl phosphate and tricresyl phosphate; Epoxidized soybean oil, 4,5-epoxycyclohexane-1,2-dicarboxylic acid Epoxy plasticizers such as di-2-ethylhexyl and epoxy benzyl stearate; Chlorinated paraffins; Isoparaffins; Polyester plasticizers such as polyesters obtained by reacting dibasic acids with dihydric alcohols; Polyethers such as polyoxyalkylene polyols A polyether derivative in which the hydroxyl group of polyoxypropylene glycol is sealed with an alkyl ether; an oligomer of polystyrene such as poly-α-methylstyrene and polystyrene; a polybutadiene, a butadiene-acrylonitrile copolymer, a polychloroprene, a polyisoprene, Examples include oligomers such as polybutene, hydrogenated polybutene, and epoxidized polybutadiene.
Paraffin hydrocarbons can also be used as a plasticizer and are effective in improving the surface stickiness (tack) of the cured product. Paraffinic hydrocarbons having 6 or more carbon atoms, more preferably 8 to 18 carbon atoms are preferred, because a remarkable effect can be easily obtained.
A plasticizer may be used individually by 1 type and may use 2 or more types together. 0.1-150 mass parts is preferable with respect to a total of 100 mass parts of the polymer which has a reactive silicon group, and, as for the usage-amount of a plasticizer, 10-120 mass parts is more preferable.

[Thixotropic agent]
The sagging property of the curable composition is improved by the addition of the thixotropic agent. Examples of the thixotropic agent include hydrogenated castor oil, fatty acid amide, calcium stearate, zinc stearate, fine powder silica, and organic acid-treated calcium carbonate.
The thixotropic agent is preferably added in an amount of 0.5 to 10 parts by mass with respect to a total of 100 parts by mass of the polymer having reactive silicon groups.

[Stabilizer]
Stabilizers (anti-aging agents) include antioxidants, UV absorbers, light stabilizers, and hindered amines, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, hindered phenols Phosphorus and sulfur compounds can be used. In particular, it is preferable to use a combination of two or more of light stabilizers, antioxidants, and ultraviolet absorbers. By using such a method, the anti-aging effect can be improved as a whole by making use of the respective characteristics.
Specifically, it is particularly effective to combine two or more selected from tertiary and secondary hindered amine light stabilizers, benzotriazole ultraviolet absorbers, hindered phenols, and phosphite antioxidants. is there.
Products commercially available as antioxidants, ultraviolet absorbers, or light stabilizers can be used as appropriate.
It is preferable that the usage-amount of antioxidant, a ultraviolet absorber, and a light stabilizer is 0.1-10 mass parts, respectively with respect to a total of 100 mass parts of the polymer which has a reactive silicon group. If the amount is less than 0.1 parts by mass, the anti-aging effect is not sufficiently exhibited, and if it exceeds 10 parts by mass, it is economically disadvantageous.

[Adhesive agent]
An adhesion-imparting agent may be used for improving the adhesion. Specific examples of the adhesiveness-imparting agent include organic silane coupling agents such as silane having a (meth) acryloyloxy group, silane having an amino group, silane having an epoxy group, and silane having a carboxyl group; Organometallic coupling agents such as aminoethyl-aminoethyl) propyltrimethoxytitanate, 3-mercaptopropyltrimethotitanate; and epoxy resins.
When adding the said organosilane coupling agent to a curable composition, it is preferable that the addition amount is 0.1-30 mass parts with respect to a total of 100 mass parts of the polymer which has a reactive silicon group.
When adding the said epoxy resin to a curable composition, the addition amount is 100 mass parts or less with respect to a total of 100 mass parts of the polymer which has a reactive silicon group, and 10-80 mass parts is more preferable.

<Curable composition>
The curable composition of this invention contains a polymer (A) and a compound (B) at least.
A two-component type curing in which a main component containing a polymer (A) and a compound (B) and a curing agent composition containing components such as a curing catalyst, a filler and water are prepared separately and mixed at the time of use. It is good also as a sex composition. In the case of the two-component type, a colorant such as toner may be added and mixed when the main agent and the curing agent are mixed.
Alternatively, the polymer (A), the compound (B), and all necessary blending components may be blended in advance and stored in a sealed state, and may be a one-component curable composition that is cured by moisture in the air when used. .

<Sodium content in curable composition>
The curable composition contains sodium as an impurity, and the content thereof is more than 0 and 5.0 ppm or less with respect to the polymer (A).
Sodium may be derived from the polymer (A) or may be derived from a component other than the polymer (A) or the compound (B).

The polymer (A) produced through the step of introducing an unsaturated group into the hydroxyl group of the precursor polymer (A ′) using sodium or a sodium-containing compound contains sodium halide produced as a by-product. Sodium halide, which is a by-product salt, can be removed by a purification method in which it is extracted and crystallized with water, but as shown in the examples described later, the polymer (A) after such purification is performed. Sodium is also contained therein, and when a drying oil is added thereto to form a curable composition, the resulting curable composition tends to thicken during storage.
The reason is considered as follows. When the step of introducing an unsaturated group using sodium or a sodium-containing compound is completed, if unreacted sodium or sodium-containing compound remains, the water added in the subsequent purification step and the unreacted product The reactant reacts to produce sodium hydroxide. That is, it is considered that the purified polymer (A) contains sodium hydroxide.
On the other hand, since the drying oil which is the compound (B) is an ester compound, it contains an acid that is partly hydrolyzed. For this reason, when a drying oil is added to the polymer (A), the acid in the drying oil reacts with sodium hydroxide in the polymer (A), and these reaction products act as a catalyst, so It is considered that the hydrolysis reaction of the union (A) is likely to proceed, and as a result, thickening during storage occurs.

According to the present invention, as shown in the examples below, the sodium content in the curable composition is 5.0 ppm or less with respect to the polymer (A), thereby increasing the viscosity during storage. It can be kept low. Moreover, the surface stickiness inhibitory effect of hardened | cured material by adding drying oil or its derivative (s) is also acquired.
The sodium content relative to the polymer (A) is preferably 4.0 ppm or less, and more preferably 2.5 ppm or less. The lower limit of the sodium content in the curable composition is more than zero.
In particular, the content of the compound (B) is preferably 5.0 parts by mass or less and the sodium content is 4.0 ppm or less with respect to the polymer (A), and the content of the compound (B) Is more preferably 5.0 parts by mass or less and the sodium content is 2.5 ppm or less.

In the step of introducing an unsaturated group, sodium or a sodium-containing compound is usually used in an amount of 1.05 mol equivalent or more, preferably 1.05 to 1.10 mol, relative to the amount of hydroxyl group of the precursor polymer (A ′). An equivalent amount is used.
The sodium content in the curable composition (X) can be controlled by the amount of the halide having an unsaturated group used in the step of introducing an unsaturated group.
The added amount of the halide having an unsaturated group is, for example, preferably a molar ratio (molar equivalent) to —ONa group converted from a hydroxyl group of the precursor polymer (A ′) is 1.15 molar equivalent or more. 1.25 mole equivalent or more is more preferable.

  The curable composition of the present invention comprises a sealant (elastic sealant for building, sealant for multi-layer glass, etc.), sealant (anti-rust / waterproof sealant for glass edge, solar cell back surface seal It is useful as an adhesive used in the fields of electrical insulating materials (insulating coatings for electric wires and cables).

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
In the following Reference Production Examples 1 and 2, a zinc chloride aqueous solution prepared by dissolving 10 g of zinc chloride in 15 mL of water, and a potassium hexacyanocobaltate aqueous solution prepared by dissolving 4 g of potassium hexacyanocobaltate in 80 mL of water, used.

(Reference Production Example 1: Production of double metal cyanide complex catalyst whose ligand is t-butyl alcohol)
A potassium hexacyanocobaltate aqueous solution was added dropwise at 40 ° C. over 30 minutes to a zinc chloride aqueous solution in which 10 g of zinc chloride was dissolved in 15 mL of water. After the dropwise addition, 80 mL of t-butyl alcohol and 80 mL of water were added, and the mixture was stirred and aged at 60 ° C. for 1 hour. After aging, the complex was filtered off.
To the obtained complex, 40 mL of t-butyl alcohol and 80 mL of water were added, stirred for 30 minutes, washed and filtered. Further, 100 mL of t-butyl alcohol was added, and the mixture was stirred for 30 minutes and filtered. After drying under reduced pressure until the mass became constant at 50 ° C., pulverization was performed to obtain a double metal cyanide complex catalyst (z-hexacyanocobaltate t-butyl alcohol complex catalyst) whose ligand was t-butyl alcohol. .

(Reference Production Example 2: Production of double metal cyanide complex catalyst whose ligand is glyme)
In the same zinc chloride aqueous solution as in Reference Production Example 1, a potassium hexacyanocobaltate aqueous solution prepared by dissolving 4 g of potassium hexacyanocobaltate in 80 mL of water was added dropwise at 40 ° C. over 30 minutes. After completion of the dropwise addition, 80 mL of glyme and 80 mL of water were added, and after stirring at 60 ° C. for 1 hour, the complex was separated by filtration.
To the resulting complex, 80 mL of glyme and 80 mL of water were added and stirred for 30 minutes, followed by filtration. Further, 100 mL of glyme and 10 mL of water were added and stirred, followed by filtration. After drying at 80 ° C. for 4 hours and pulverizing, a double metal cyanide complex catalyst (zinc hexacyanocobaltate glyme complex catalyst) having a ligand of glyme was obtained.

In the following Production Examples 1 to 5, hydroxyl group-containing polyoxyalkylene polymers (A′1) to (A′5) were produced as the precursor polymer (A ′).
(Production Example 1: Production of hydroxyl-containing polyoxyalkylene polymer (A′1))
As a trifunctional initiator, polyoxypropylene triol obtained by ring-opening addition polymerization of propylene oxide to glycerin (molecular weight 3,000 per functional group, hereinafter referred to as initiator A) was used.
As a bifunctional initiator, polyoxypropylene diol (molecular weight 2,000 per functional group, hereinafter referred to as initiator B) obtained by ring-opening addition polymerization of propylene oxide to propylene glycol was used.
First, in the presence of a zinc hexacyanocobaltate t-butyl alcohol complex catalyst (0.08 g), a mixture of initiator A (131 g) and initiator B (44 g) was mixed with propylene oxide (1425 g) at 120 ° C. The reaction was continued until the pressure in the reaction system did not drop. Thus, a hydroxyl group-containing polyoxyalkylene polymer (A′1) having a polyoxypropylene chain, having a functional group (hydroxyl group) at the end of the entire main chain, and having an average functional group number of 2.75 per molecule. Got. Mn of the (A′1) measured by GPC was 27,000, and Mw / Mn was 1.20. The molecular weight per functional group calculated from the hydroxyl value was 8,200.

(Production Example 2: Production of hydroxyl group-containing polyoxyalkylene polymer (A′2))
In the presence of zinc hexacyanocobaltate glyme complex catalyst (0.32 g), initiator A (182 g) was reacted with propylene oxide (1418 g) at 120 ° C. until the pressure of the reaction system did not drop. Thus, a hydroxyl group-containing polyoxyalkylene polymer (A′2) having a polyoxypropylene chain, having a functional group (hydroxyl group) at all main chain ends, and having an average number of functional groups per molecule of 3.0. Got. Mn of the (A′2) measured by GPC was 26,000, and Mw / Mn was 1.41. The molecular weight per functional group calculated from the hydroxyl value was 7,300.

(Production Example 3: Production of hydroxyl group-containing polyoxyalkylene polymer (A′3))
In Production Example 2, the initiator A (235 g) was replaced with propylene oxide (1365 g) in the same manner as in Production Example 2, having a polyoxypropylene chain, and having functional groups (hydroxyl groups) at the ends of all main chains. And a hydroxyl group-containing polyoxyalkylene polymer (A′3) having an average number of functional groups per molecule of 3.0 was obtained. Mn of the (A′3) measured by GPC was 20,000, and Mw / Mn was 1.39. The molecular weight per functional group calculated from the hydroxyl value was 5,700.

(Production Example 4: Production of hydroxyl-containing polyoxyalkylene polymer (A′4))
In the presence of zinc hexacyanocobaltate t-butyl alcohol complex catalyst (0.08 g), initiator A (156 g) was reacted with propylene oxide (1444 g) at 120 ° C. until the pressure of the reaction system was not reduced. . As a result, a hydroxyl group-containing polyoxyalkylene polymer (A′4) having a polyoxypropylene chain, having hydroxyl groups at all main chain ends, and having an average number of functional groups per molecule of 3.0 was obtained. Mn of the (A′4) measured by GPC was 34,000, and Mw / Mn was 1.15. The molecular weight per functional group calculated from the hydroxyl value was 9,300.

(Production Example 5: Production of hydroxyl group-containing polyoxyalkylene polymer (A'5))
In Production Example 4, the initiator A (128 g) was changed to propylene oxide (1472 g) in the same manner as in Production Example 4, having a polyoxypropylene chain, and having functional groups (hydroxyl groups) at all main chain terminals. Thus, a hydroxyl group-containing polyoxyalkylene polymer (A′5) having an average number of functional groups per molecule of 3.0 was obtained. Mn of the (A′5) measured by GPC was 41,000, and Mw / Mn was 1.18. The molecular weight per functional group calculated from the hydroxyl value was 11,300.

(Examples 1 to 35)
Using each of the hydroxyl group-containing polyoxyalkylene polymers (A′1) to (A′5) obtained above, a polymer (A) into which a reactive silicon group has been introduced is produced, and tung oil is added thereto. Thus, a curable composition (X) was produced. Main production conditions and evaluation results are shown in Tables 1 to 3.
Examples 1 to 8, 14 to 19, and 26 to 30 are examples, and examples 9 to 13, 20 to 25, and 31 to 35 are comparative examples.

[Allyl group introduction step]
First, a methanol solution containing sodium methoxide was added to the hydroxyl group-containing polyoxyalkylene polymers (A′1) to (A′5) under a nitrogen atmosphere and reacted at 130 ° C. The amount of sodium methoxide added was 1.05 (1.05 molar equivalent) in terms of the molar ratio of the hydroxyl group-containing polyoxyalkylene polymers (A′1) to (A′5) to the hydroxyl group amount. By this reaction, the hydroxyl groups at the ends of the entire main chain of the hydroxyl group-containing polyoxyalkylene polymer are converted into —ONa groups, and methanol is by-produced.
Then, after distilling off methanol under reduced pressure, allyl chloride was added and reacted at 110 ° C. The amount of allyl chloride added is the molar ratio (molar equivalent) of the hydroxyl group-containing polyoxyalkylene polymers (A′1) to (A′5) to the —ONa group converted from the hydroxyl group as shown in Tables 1 to 3. Was set to be. By this reaction, the terminal —ONa group is converted to —O—CH ₂ CH═CH ₂ group, and NaCl is by-produced.
Next, unreacted allyl chloride was removed under reduced pressure to obtain an allyl group-terminated polyoxyalkylene polymer having allyl groups at the ends of all main chains (including NaCl as a by-product salt).

[Purification process]
Next, 1 part by mass of polyoxyethyleneoxypropylene block copolymer as a surfactant and 3 parts by mass of water with respect to 100 parts by mass of the allyl group-terminated polyoxyalkylene polymer (including NaCl as a by-product salt) in the reactor. A by-product salt was extracted from the polymer with water by adding and stirring and mixing at a liquid temperature of 60 ° C. in a nitrogen atmosphere.
Next, while flowing nitrogen into the reactor, the mixture was heated to 80 ° C. and held for 5 hours to evaporate water and precipitate NaCl crystals (crystallization), followed by filtration. By degassing under reduced pressure, a purified allyl group-terminated polyoxyalkylene polymer was obtained.

[Reactive silyl group introduction step]
Next, dimethoxymethylsilane was added to the purified allyl group-terminated polyoxyalkylene polymer in the presence of chloroplatinic acid hexahydrate and reacted at 70 ° C. for 5 hours. Thereafter, unreacted dimethoxymethylsilane was removed under reduced pressure to obtain a polymer having a dimethoxymethylsilyl group at the main chain terminal (polymer (A) having a reactive silicon group).
The addition amount of dimethoxymethylsilane was set so that the mol% (silylation rate) with respect to the allyl group at the end of the entire main chain was a value shown in Tables 1 to 3.

  With respect to 100 parts by mass of the obtained polymer (A), paulownia oil (acid value 3.27 mmol / g) is mixed as a compound (B) in the formulation shown in Tables 1 to 3 to obtain a curable composition (X). Prepared.

[Measurement of sodium content]
The sodium content in the curable composition (X) was measured by the following method. The sodium content is expressed as a mass-based concentration (unit: ppm) with respect to the polymer (A) in the curable composition (X). The results are shown in Tables 1-3.
First, 30 g of the curable composition (X) as a sample was weighed in a platinum dish, burned and incinerated using a gas burner, and then completely incinerated in an electric furnace at 600 ° C. The obtained ashing residue was dissolved in 2 ml of 6N hydrochloric acid, and distilled water was added to make 100 ml. The sodium content of the incineration residue was measured using an atomic absorption photometer (manufactured by Shimadzu Corporation, product name: AA-6200). The quantification of the sodium content was determined from a calibration curve prepared with a metal standard solution.

[Storage stability test of curable composition (X)]
Immediately after preparing the curable composition (X) by mixing the polymer (A) and the compound (B) (paulownia oil), the viscosity of the curable composition (X) is measured by the following viscosity measuring method (1). And pre-storage viscosity (1) (unit · Pa · s).
25 ml of the curable composition (X) immediately after preparation was put into a glass tube, and the inside of the glass tube was replaced with nitrogen, and then allowed to stand and stored for 7 days while maintaining the temperature at 90 ° C. The viscosity after storage for 7 days was measured by the following viscosity measuring method (1), and the viscosity after storage was (1) (unit · Pa · s).
The viscosity increase rate (1) (viscosity increase rate, unit:%) was determined by the following formula (10).
Formula (10): Thickening rate (1) = (viscosity after storage (1) −viscosity before storage (1)) / viscosity before storage (1) × 100
[Viscosity measuring method (1)]
1 mL of a sample was collected and measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE80 type) at a measurement temperature of 25 ° C. and a rotor No. The viscosity was measured under the condition of 4. JS14000 (product name, manufactured by Nippon Grease Co., Ltd.) was used as the calibration standard solution.

As Tables 1-3 show, sodium content in curable composition (X) is 5.0 ppm or less with respect to a polymer (A), and the addition amount of a compound (B) (tung oil) is Examples 1-8, 14-19, and 26-30 which are 8 mass parts or less with respect to 100 mass parts of a polymer (A) have low viscosity increase rate of curable composition (X), and are storage-stable. It was confirmed to be excellent.
On the other hand, in Examples 9 to 11, Examples 20 to 22, and Examples 31 to 35 in which the sodium content in the curable composition (X) exceeds 5.0 ppm, the addition amount of the compound (B) (paulownia oil) is 8 parts by mass. Despite the following, the thickening rate of the curable composition (X) was high, and the storage stability was poor.
In Examples 12, 23, and 24, the sodium content in the curable composition (X) is as low as 5.0 ppm or less, but the addition amount of the compound (B) (paulownia oil) is as large as 10 parts by mass. The thickening rate of thing (X) did not become small enough.
In Examples 13 and 25, although the sodium content in the curable composition (X) is more than 10 ppm, it does not contain the compound (B) (paulownia oil), so the curable composition (X) is stored. Little thickened.

In addition, after the step of introducing an allyl group by reacting the terminal -ONa group of the hydroxyl group-containing polyoxyalkylene polymer with allyl chloride, a purification step of removing by-product salt (sodium chloride) was performed. It was recognized that the sodium content in the curable composition (X) varies depending on the amount of allyl added.
That is, as shown in Tables 1 to 3, when the amount of allyl chloride added is as small as 1.05 molar equivalent to the —ONa group converted from the hydroxyl group of the hydroxyl group-containing polyoxyalkylene polymer, the curable composition ( The sodium content in X) was 10 ppm or more with respect to the polymer (A).
When the addition amount of the allyl chloride is 1.15 molar equivalents or more, the sodium content is 5.0 ppm or less, preferably 4.5 ppm or less, and the addition amount of allyl chloride is 1.25 molar equivalents or more. The sodium content was 2.4 ppm or less.

(Examples 36 to 39)
As shown in Table 4, an additive component was further added to the curable compositions (X) of Examples 1, 6, 11, and 13 to obtain curable compositions (Y). Examples 36 and 37 are examples, and examples 38 and 39 are comparative examples.
That is, simultaneously with adding the compound (B) (Tung oil) to the polymer (A), the additives shown in Table 4 were added, and these were mixed to obtain a curable composition (Y).
The following storage stability test was done about curable composition (Y). The results are shown in Table 4.
Also, the curable composition (Y) is used as a main component composition of a two-component curable composition, mixed with a separately prepared curing agent composition and cured, and the surface stickiness (tack) of the cured product is as follows. It was evaluated with. The results are shown in Table 4.
In addition, since the additive sodium shown in Table 4 is not included, the content of paulownia oil and the sodium content in the curable composition (Y) based on the polymer (A) are the curable composition (X ) Content in each is the same.

The additive components shown in the table are as follows.
[filler]
White gloss CCR (product name): Colloidal calcium carbonate, manufactured by Shiroishi Kogyo Co.
Whiteon SB (product name): Heavy calcium carbonate, manufactured by Shiraishi Calcium Industry Co., Ltd., average particle size 1.78 μm.
Titanium oxide R820 (product name): manufactured by Ishihara Sangyo Co., Ltd.
Balloon 80GCA (product name): Organic balloon, manufactured by Matsumoto Yushi Co., Ltd.
[Plasticizer]
PMLS4012 (product name): high molecular weight polyol, manufactured by Asahi Glass Co., Ltd., molecular weight 5,000 per hydroxyl group (PMLS4012 has two hydroxyl groups in the molecule).
Sansosizer EPS (product name): 4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl manufactured by Shin Nippon Chemical Co., Ltd.
[Thixotropic agent]
Disparon # 305 (product name): Hydrogenated castor oil-based thixotropic agent, manufactured by Enomoto Kasei Co., Ltd.
[Stabilizer]
(Antioxidant) IRGANOX 1135 (product name): hindered phenol antioxidant, manufactured by BASF Corporation.
(Ultraviolet absorber) TINUVIN 326: (Product name): Benzotriazole ultraviolet absorber, manufactured by BASF Corporation.
[Adhesive agent]
KBM-403 (product name): 3-glycidyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

[Curing agent composition]
Curing by mixing 4 parts by mass of the following (a) curing catalyst / co-catalyst mixture, (b) 6 parts by mass of plasticizer, (c) 15 parts by mass of filler, and (d) 5 parts by mass of filler. An agent composition was prepared.
(A) Curing catalyst / co-catalyst mixture: Mass ratio of stannous octylate (manufactured by Yoshitomi Pharmaceutical Co., Ltd., trade name: Stanocto) as a curing catalyst and laurylamine (n-dodecylamine, reagent) as a co-catalyst (Curing catalyst: cocatalyst) A mixture mixed at 6: 1.
(B) Plasticizer: diisononyl phthalate, manufactured by Shin Nippon Rika Co., Ltd., product name: Sansosizer DINP.
(C) Filler: Whiten SB (product name), heavy calcium carbonate, manufactured by Shiraishi Calcium Industry Co., Ltd., average particle size 1.78 μm.
(D) Filler: Glomax LL (product name): calcined kaolin, manufactured by Takehara Chemical Industries, Ltd.

[Storage stability test of curable composition (Y)]
Immediately after preparing the curable composition (Y), the viscosity of the curable composition (Y) was measured by the following viscosity measurement method (2) to obtain a viscosity before storage (2) (unit / Pa · s). .
100 ml of the curable composition (Y) immediately after preparation was placed in a plastic container, and the inside of the plastic container was replaced with nitrogen, and then allowed to stand and stored for 7 days while maintaining the temperature at 70 ° C. The viscosity after storage for 7 days was measured by the following viscosity measuring method (2), and the viscosity after storage was (2) (unit · Pa · s).
Viscosity increase rate (2) (viscosity increase rate, unit:%) was determined by the following formula (20).
Formula (20): Thickening rate (2) = (viscosity after storage (2) −viscosity before storage (2)) / viscosity before storage (2) × 100
[Viscosity measuring method (2)]
20 mL of a sample was collected and measured using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: TV-25 type) at a measurement temperature of 23 ° C. and a rotor No. 7. Viscosity was measured under the condition of 10 rpm.

[Evaluation method of surface tackiness]
Immediately after mixing 10 parts by mass of the curing agent composition with respect to 100 parts by mass of the polymer (A) in the curable composition (Y) (main agent composition), approximately 150 mm in length on the polyethylene terephthalate film. Then, it was constructed in a shape having a width of 50 mm and a thickness of 5 mm. This was cured by curing at 23 ° C. and 50% humidity for 8 hours. The degree of tack (surface stickiness) of the obtained cured product was evaluated by finger touch.
When the finger touched and did not feel stickiness on the surface of the cured product, the stickiness was evaluated as “small”, and when the stickiness was felt, the stickiness was evaluated as “large”.

In Example 36 of Table 4, the sodium content in the curable composition (Y) is 2.1 ppm with respect to the polymer (A), and the addition amount of the compound (B) (paulownia oil) is the polymer (A). ) Of 100 parts by mass is an example of 1.5 parts by mass. In the curable composition (Y) obtained by further adding an additive to the curable composition (X), the viscosity increase rate was low and the storage stability was excellent, and the stickiness of the cured product surface was well suppressed.
In addition,
Example 37 is an example in which the sodium content in the curable composition (Y) is 1.6 ppm and the amount of compound (B) (paulownia oil) added is 6.6 parts by mass. In the curable composition (Y) obtained by further adding an additive to the curable composition (X), the viscosity increase rate was low and the storage stability was excellent, and the stickiness of the cured product surface was well suppressed.

Example 38 is an example in which the sodium content in the curable composition (Y) is 10.0 ppm and the amount of compound (B) (paulownia oil) added is 4.0 parts by mass. In the curable composition (Y), the stickiness on the surface of the cured product was satisfactorily suppressed, but because of the high sodium content, the thickening rate was high and the storage stability was insufficient.
Example 39 is an example in which the sodium content in the curable composition (X) is 10.0 ppm, but no tung oil is added. In the curable composition (Y), the viscosity increase rate was low and the storage stability was good. However, since it did not contain tung oil, the surface of the cured product was very sticky.

Claims (4)

A polymer (A) obtained by introducing a reactive silicon group represented by the following formula (1) into a precursor polymer (A ′) having a functional group capable of introducing a reactive silicon group, a drying oil and its Containing one or more compounds (B) selected from the group consisting of derivatives,
The average number of functional groups of the precursor polymer (A ′) is 2.0 to 3.0, the molecular weight per functional group is 5,000 to 20,000, and the molecular weight distribution is 1.01 to 1.50. , At least a part of the functional group is a hydroxyl group,
Content of the said compound (B) is 0.1-8.0 mass parts with respect to 100 mass parts of the said polymer (A),
Sodium content is more than 0 and 5.0 ppm or less with respect to the said polymer (A), The curable composition characterized by the above-mentioned.
-SiX ¹ ₂ R ¹ (1)
[Wherein, R ¹ represents an optionally substituted monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and X ¹ represents a hydroxyl group or a hydrolyzable group. . Two X ¹ may be the same or different from each other. ]   In the presence of an alkylene oxide ring-opening polymerization catalyst, the precursor polymer (A ′) is subjected to ring-opening addition of alkylene oxide to one or both of an initiator having two hydroxyl groups and an initiator having three hydroxyl groups. The curable composition of Claim 1 which is a hydroxyl-containing polyoxyalkylene polymer obtained.   The curable composition according to claim 2, wherein the alkylene oxide ring-opening polymerization catalyst is a double metal cyanide complex catalyst in which t-butyl alcohol is coordinated as an organic ligand.   The polymer (A) reacts a hydroxyl group of the precursor polymer (A ′) with sodium or a sodium-containing compound, and then reacts with a halogen compound having an unsaturated group to introduce an unsaturated group, The curable composition as described in any one of Claims 1-3 which is a polymer obtained by making the hydrosilane compound which has the said reactive silicon group react with an unsaturated group.