JP2012111904A - Two-component type polysulfide-based sealing material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-component type polysulfide-based sealing material composition, which suppresses foaming when the composition is cured, and which can improve strength of the obtained cured product.SOLUTION: The composition comprises: a first liquid containing, in one molecule, a polysulfide polyether polymer having a polysulfide bond and one or more thiol groups at a terminal; and a second liquid containing a urethane prepolymer containing an isocyanate group at a terminal and a compound having at least one oxazolidine ring.

Description

  The present invention relates to a two-component polysulfide sealant composition.

  Conventionally, a two-component curable polysulfide-based sealing material composition containing a polysulfide block polymer having a thiol group at both ends and a polyether block segment reacts with a thiol group and an isocyanate group in the presence of an amine catalyst. Thus, a thiourethane bond is formed and cured to obtain a sealing material.

  As a method for producing a two-component curable polysulfide-based sealing material composition, for example, polysulfide-containing block copolymer is prepared by reacting polysulfide polymer having thiol groups at both ends with hydroxyethyl methacrylate (HEMA) or hydroxyethyl acrylate (HEA). A method for obtaining a merger has been proposed (for example, Patent Document 1).

JP-A-7-196753

  However, when curing with a two-component curable polysulfide-based sealant composition, moisture present in the environmental atmosphere during construction or moisture contained in the adherend reacts with the isocyanate groups of the urethane prepolymer to produce carbonic acid. There is a problem that by generating gas, foaming occurs when the two-component curable polysulfide-based sealing material composition is cured. Therefore, many pores are observed in the obtained sealing material, and the aesthetic appearance is impaired.

  When the isocyanate group of the urethane prepolymer reacts with water and is consumed, the sulfide group at the terminal of the polysulfide block polymer becomes unreacted. Thereby, since the reaction rate of the thiourethane bond by the thiol group of a polysulfide block polymer and the isocyanate group of a urethane prepolymer falls, there exists a problem that the intensity | strength of the hardened | cured material obtained by hardening a polysulfide polymer falls. .

  In view of the above problems, an object of the present invention is to provide a two-component polysulfide-based sealing material composition capable of suppressing foaming during curing and improving the strength of the resulting cured product. .

That is, this invention is (1)-(4) shown next.
(1) A first liquid containing a polysulfide polyether polymer containing a polysulfide bond and containing one or more thiol groups at one end in one molecule, a urethane prepolymer containing an isocyanate group at the end, and at least one oxazolidine And a second liquid containing a ring-containing compound. A two-component polysulfide-based sealant composition comprising:
(2) The two-component polysulfide-based sealing material composition according to (1), wherein the polysulfide polyether polymer includes a sulfide group and a polypropylene oxide group.
(3) The two-component polysulfide-based sealing material composition according to the above (1) or (2), wherein the compound having an oxazolidine ring has a hydroxyl group in the molecule.
(4) The compound having the oxazolidine ring is 3- (2-hydroxyethyl) -2- (1-methylbuthyl) oxazolidine or 2-phenyl-3- (2-hydroxyethyl) oxazolidine according to (3) above. Two-component polysulfide sealant composition.

  ADVANTAGE OF THE INVENTION According to this invention, while suppressing the foaming at the time of hardening, the two-component polysulfide type sealing material composition which makes it possible to improve the intensity | strength of the hardened | cured material obtained can be provided.

  The present invention will be described in detail below. The present invention is not limited by the following modes for carrying out the invention (hereinafter referred to as embodiments). In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the following embodiments can be appropriately combined.

  The two-component polysulfide sealant composition according to this embodiment will be described. The two-component polysulfide-based sealant composition according to the present embodiment includes a first liquid containing a polysulfide polyether polymer containing a polysulfide bond in one molecule and containing one or more thiol (SH) groups at the end, A two-component polysulfide-based sealing material composition comprising a urethane prepolymer containing an isocyanate group at a terminal and a second liquid containing a compound having at least one oxazolidine ring. Hereinafter, the two-component polysulfide-based sealant composition according to this embodiment may be referred to as “the sealant composition of this embodiment”.

<First liquid>
The first liquid contains a polysulfide polyether polymer containing a polysulfide bond in one molecule and containing one or more thiol (SH) groups (mercapto group-containing groups) at the terminals. The first liquid is obtained by reacting a polysulfide polymer having two or more thiol groups in one molecule with a polyether polymer having a thiol group at the terminal. In the present embodiment, the first liquid may be referred to as the main agent.

[Polysulfide polyether polymer]
The polysulfide polyether polymer contained in the first liquid has a polysulfide bond in one molecule and one or more thiol groups at the terminal. Polysulfide polyether polymer having one or more thiol group at the end, in the main chain, - (R-Sx) - having a structural unit represented by (R is _{C 2 H 4 OCH 2 OC 2} H 4 or Represents an alkylene group having 1 to 12 carbon atoms, and x represents an integer of 2 to 5. The polysulfide polyether polymer may be, for example, a diblock polymer or a triblock polymer.

  In the polysulfide polyether polymer, the structural unit represented by-(R-Sx)-preferably forms all (100% by mass) of the main chain, even if it contains other structural units. It is preferable to form 5 mass% or more and 95 mass% or less.

  The number average molecular weight of the polysulfide polyether polymer is usually preferably from 300 to 200,000, more preferably from 500 to 50,000. Further, from the viewpoint of improving the followability of the joint, which is a function as a sealing material, low modulus and high elongation are desirable, preferably from 1000 to 10,000, and more preferably from 3000 to 5000. The production method of the polysulfide polymer is not particularly limited, and examples thereof include conventionally known methods.

As a polysulfide polyether polymer, a polyether unit represented by-(R1O) n- (R1 is an alkyl group having 2 to 4 carbon atoms, and n is an integer of 6 to 200) in the main chain. _{If, -C 2 H 4 OCH 2 OC} 2 H 4 Sx- and _{-CH 2 CH (OH) CH 2} Sx- (x is 1 to 5 which is an integer.) and a polysulfide units represented by and polysulfide polyether polymers having terminal to _{-C 2 H 4 OCH 2 OC 2} H 4 SH and / or _-CH 2 CH (OH) thiol groups represented by _CH 2 SH are preferably exemplified. Specific examples of such a polysulfide polyether polymer include trade name “thiocol LP-282” (manufactured by Toray Fine Chemical Co., Ltd.). The sealing material composition according to the present embodiment may include two or more kinds of polysulfide polymers.

  The mixing ratio of the polysulfide polymer and the thiol group-containing polyether polymer is 95/5 to 5/95, preferably 90/10 to 10/90, in mass ratio.

  The reaction conditions of the polysulfide polymer and the thiol-containing polyether polymer are 10 to 100 ° C., preferably 20 to 80 ° C., and may be stirred for 1 to 60 minutes.

  Polysulfide polymers can be used alone or in combination of two or more.

(Polysulfide polymer)
The polysulfide polymer used when producing the polysulfide polyether polymer will be described below. The polysulfide polymer contains a polysulfide bond in one molecule and contains two or more thiol (SH) groups at the terminal.

A preferred specific example of the polysulfide polymer is represented by the following general formula (1).
HS- (A-Sx) m-ASH (1)
(In the formula, A is an oxyalkylene group, x is an integer of 1 to 5, and m is an integer of 1 to 50.)

In the above formula (1), examples of the oxyalkylene group represented by A include —CH ₂ OCH ₂ —, —C ₂ H ₄ OC ₂ H ₄ —, —C ₂ H ₄ OCH ₂ OC ₂ H ₄ —, — C ₃ H ₆ OC ₃ H ₆ —, —C ₄ H ₈ OC ₄ H ₈ — and the like can be mentioned. x is preferably 1, 2 or 3, and m is preferably an integer of 6 or more and 40 or less. The polysulfide polymer represented by the above formula (1) has fluidity at normal temperature, and its molecular weight (mass average molecular weight) is usually 100 or more and 200,000 or less. Specific examples of such a polysulfide polymer include trade names “thiocol LP-32”, “thiocol LP-55” (manufactured by Toray Fine Chemical Co., Ltd.), and trade names “THIOPLAST polymer” (manufactured by AKZO NOBEL). .

(Thiol group-containing polyether polymer)
The thiol group-containing polyether polymer can be synthesized using, for example, a known method described in Japanese Patent Publication No. 47-48279. That is, after adding an epihalohydrin such as epichlorohydrin or epibromohydrin to a polyalkylene glycol such as polypropylene glycol or polyethylene glycol, an alkali hydroxide such as sodium hydroxide or potassium hydroxide (MSH, where M is an alkali metal) ), An alkali metal sulfide (M ₂ Sx, where x represents an integer of 1 to 5), a polyether polymer having a thiol group at the terminal can be obtained. The main chain of the polymer thus obtained partially contains polysulfide bonds and is suitable as the polyether polymer containing the thiol group of this embodiment.

[Metal catalyst]
In the sealing material composition of the present embodiment, the first liquid may contain a metal catalyst. The metal catalyst contained in the first liquid is not particularly limited. Examples of the metal catalyst include organic carboxylic acid metal salts and inorganic carboxylic acid metal salts. Of these, organic carboxylic acid metal salts are preferred from the viewpoints of excellent compatibility and foaming resistance, an appropriate pot life, and excellent curability.

  The organic carboxylic acid metal salt is not particularly limited as long as it is a salt formed from an organic carboxylic acid and a metal.

  Examples of the organic carboxylic acid used to form the organic carboxylic acid metal salt include 2-ethylhexylic acid and neodecanoic acid. Of these, bismuth of either one or both of 2-ethylhexylic acid and neodecanoic acid is excellent from the viewpoints of excellent compatibility and foaming resistance, an appropriate working time, and excellent curability. A salt is preferred.

  Examples of the metal used to form the organic carboxylic acid metal salt include bismuth, tin, zinc, zirconium, cobalt, vanadium, aluminum, barium, and titanium (titanium). Among these, bismuth is preferable from the viewpoints of being excellent in compatibility and foam resistance, capable of setting the pot life to an appropriate length, and excellent in curability.

  The metal catalysts can be used alone or in combination of two or more.

  The amount of the metal catalyst is excellent from the viewpoint of compatibility and foaming resistance, the pot life can be set to an appropriate length, and from the viewpoint of excellent curability, 0.01 mass% or more in the total amount of the sealing material composition 3 It is preferably 0.0% by mass or less, and more preferably 0.05% by mass or more and 0.15% by mass or less.

  The sealing material composition of the present embodiment contains a metal catalyst such as an organic carboxylic acid metal salt, for example, with respect to the polysulfide polyether polymer. You can get time. Further, by adding an organic acid (free carboxylic acid) to a metal catalyst (particularly an organic carboxylic acid metal salt), a bond based on a urethane bond and a part of a urea bond can be formed. Thereby, compared with the case where an amine catalyst is used, the stable performance and physical property can be obtained.

[Polyoxyalkylene polyol]
In the sealing material composition of the present embodiment, it is preferable that the first liquid further contains a polyoxyalkylene polyol from the viewpoint of being excellent in compatibility and foam resistance and excellent in strength and elongation of the cured product.

  The polyoxyalkylene polyol has a main chain having an oxyalkylene group as a repeating unit, and has two or more hydroxy groups.

  Examples of the oxyalkylene group include those having 4 to 400 carbon atoms. Of these, an oxyethylene group and an oxypropylene group are preferred from the viewpoints of excellent foam resistance in a state having compatibility and pot life and excellent curability.

  The polyoxyalkylene polyol is preferably polyoxypropylene triol from the viewpoints of excellent foam resistance in a state having compatibility and pot life and excellent water resistance of cured properties.

  The number average molecular weight of the polyoxyalkylene polyol is preferably 300 or more and 200,000 or less from the viewpoint that it is excellent in foaming resistance in a state having compatibility and pot life and excellent in water resistance of cured properties. More preferably, it is 50000 or less.

  A polyoxyalkylene polyol can be used individually or in combination of 2 types or more, respectively.

  The content of the polyoxyalkylene polyol is greater than 0% by mass and less than or equal to 50.0% by mass in the total amount of the first liquid from the viewpoint of being excellent in compatibility and foam resistance and excellent in water resistance of cured properties. Preferably it is 5.0 mass% or more and 30.0 mass% or less.

[Organic acid]
In the sealing material composition of the present embodiment, it is preferable that the first liquid further contains an organic acid from the viewpoint of excellent foam resistance and a good balance between pot life and curability.

  The organic acid is not particularly limited as long as it is a hydrocarbon compound having one or more carboxylic acids. Examples thereof include those having 3 to 20 carbon atoms other than the carbon atoms possessed by the carboxylic acid. Of these, octylic acid, 2-ethylhexylic acid, and neodecanoic acid are preferred from the viewpoint of superior foam resistance and a good balance between pot life and curability.

  The organic acids can be used alone or in combination of two or more.

  The content of the organic acid is 0.01% by mass or more and 3.00% by mass or less in the total amount of the first liquid from the viewpoint of excellent compatibility and foaming resistance, and excellent balance between pot life and curability. Is preferably 0.1% by mass or more and 1.0% by mass or less.

<Second liquid>
The second liquid contains a urethane prepolymer containing an isocyanate group at the terminal and a compound having at least one oxazolidine ring. In this embodiment, the urethane prepolymer containing the second liquid or oxazolidine may be referred to as a curing agent. A compound having an oxazolidine ring may be referred to as an oxazolidine compound.

(Urethane prepolymer)
The urethane prepolymer will be described below. In the sealing material composition of the present embodiment, the urethane prepolymer contained in the second liquid is not particularly limited. For example, a conventionally well-known thing is mentioned. Specifically, for example, a reaction product obtained by reacting a polyisocyanate compound and a polyol compound so that an isocyanate group (NCO group) is excessive with respect to a hydroxy group (OH group) can be mentioned. . The urethane prepolymer preferably contains 0.5% by mass or more and 5% by mass or less of isocyanate groups at the molecular ends.

The polyisocyanate compound used when producing the urethane prepolymer is not particularly limited as long as it has two or more isocyanate groups in the molecule. Examples of the polyisocyanate compound include TDI (for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI)), MDI (for example, 4,4 '-Diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), Aromatic polyisocyanates such as tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; hexamethylene diisocyanate Aliphatic polyisocyanates such as (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanate methyl) cyclohexane ( H ₆ XDI), alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate (H ₁₂ MDI); these carbodiimide-modified polyisocyanates; and these isocyanurate-modified polyisocyanates. Among these, the urethane prepolymer obtained has a low viscosity, is easy to handle, is excellent in compatibility, foam resistance, and is excellent in curability, particularly tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Xylylene diisocyanate (XDI) and hexamethylene diisocyanate (HDI) are preferred.

  A polyisocyanate compound can be used individually or in combination of 2 types or more, respectively.

  The polyol compound used when producing the urethane prepolymer is not particularly limited as long as it has two or more hydroxy groups. Examples of the polyol compound include polyoxyalkylene polyol; polyester polyol; polymer polyol; polycarbonate polyol; polybutadiene polyol; hydrogenated polybutadiene polyol; acrylic polyol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, and pentane. Examples thereof include low molecular weight polyols such as diol and hexanediol. Of these, polyoxyalkylene polyols are preferred from the viewpoints of better compatibility and foam resistance, and excellent strength and elongation of the cured product.

  Examples of the polyoxyalkylene polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, Polyol obtained by adding at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and polyoxytetramethylene oxide to at least one selected from the group consisting of 1,4-butanediol and pentaerythritol Etc. Specifically, polyoxyethylene diol, polyoxyethylene triol, polyoxypropylene diol, and polyoxypropylene triol are preferably exemplified.

  A polyol compound can be used individually or in combination of 2 types or more, respectively. The polyol compound is preferably a polyoxyalkylene polyol, more preferably a polyoxypropylene diol or a polyoxypropylene triol, from the viewpoints of excellent compatibility and foam resistance, and excellent cured product strength and elongation. .

  The number average molecular weight of the polyol compound is preferably 400 or more and 10,000 or less, and more preferably 400 or more and 8000 or less, from the viewpoints of excellent compatibility and foam resistance and excellent strength and elongation of the cured product.

  The polyol compound used when preparing the urethane prepolymer is a polyoxy compound used when preparing a polysulfide polyether polymer from the viewpoint of excellent compatibility and foam resistance, and excellent strength and elongation of the cured product. The same as the alkylene polyol is preferred.

  In the present embodiment, the combination of the polyisocyanate compound and the polyol compound in producing the urethane prepolymer is selected from the group consisting of tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), and diphenylmethane diisocyanate (MDI). A combination of at least one selected from the above and polyoxypropylene diol and / or polyoxypropylene triol is preferably exemplified.

  The amount of the polyisocyanate compound and the polyol compound in producing the urethane prepolymer is such that the equivalent ratio of the isocyanate group to the hydrosyl group (isocyanate group (NCO group) / hydrosyl group (OH group)) is 1.2 or more. 0.5 or less is preferable, and 1.5 or more and 2.0 or less is more preferable. When the equivalence ratio is within such a range, the viscosity of the obtained urethane prepolymer becomes appropriate, and the remaining amount of the unreacted polyisocyanate compound in the urethane prepolymer can be reduced.

  The production method of the urethane prepolymer is not particularly limited. For example, the urethane prepolymer is produced by heating and stirring the polyol compound having the above equivalent ratio (NCO group / OH group) and the polyisocyanate compound at 50 ° C. or higher and 130 ° C. or lower. Can do. Moreover, if necessary, for example, a urethanization catalyst such as an organic tin compound, organic bismuth, or amine can be used.

  A urethane prepolymer can be used individually or in combination of 2 types or more, respectively.

  The amount of urethane prepolymer is equivalent ratio of isocyanate group of urethane prepolymer in second liquid to thiol group of polysulfide polyether polymer contained in first liquid (isocyanate group (NCO group)) / thiol group. (SH group)) is preferably 0.7 or more and 1.3 or less from the viewpoint of excellent properties of the cured product and excellent foam resistance, and more preferably 0.85 or more and 1.15 or less. preferable.

  Even when the first liquid further contains a polyoxyalkylene polyol, the denominator of the equivalent ratio (NCO group / SH group) is the amount of the thiol group that the polysulfide polyether polymer has and the hydroxy group that the polyoxyalkylene polyol has. Is the total amount.

  As described above, the second liquid contains the following compound having at least one oxazolidine ring. In this case, the denominator is the total amount of the thiol group of the polysulfide polyether polymer and the amino group generated from the compound having an oxazolidine ring.

  When the first liquid further contains a polyoxyalkylene polyol and the second liquid further contains a compound having at least one oxazolidine ring shown below, the denominator of the above equivalent ratio is the thiol group possessed by the polysulfide polyether polymer. And the hydroxy group of the polyoxyalkylene polyol and the total amount of amino groups produced from the compound having an oxazolidine ring.

(Compound having oxazolidine ring)
The second liquid can further contain a compound having at least one oxazolidine ring. The oxazolidine compound is not particularly limited as long as it is a hydrocarbon compound having one or more oxazolidine rings. In the present embodiment, a compound having at least one oxazolidine ring may be hereinafter referred to as “oxazolidine compound”. When the second liquid further contains an oxazolidine compound, the pot life can be set to an appropriate length and the suppression of foaming can be improved.

  In addition to the oxazolidine ring, the oxazolidine compound can have, for example, an active hydrogen group such as a hydroxy group, an amino group, or a thiol group.

（上記式（２）中、Ｒ⁵はアルキレン基であり、Ｒ⁶は炭化水素基であり、Ｘ（活性水素基）はヒドロキシ基、アミノ基、チオール基である。） Examples of the oxazolidine compound containing an active hydrogen group include those represented by the following formula (2).

(In the above formula (2), R ⁵ is an alkylene group, R ⁶ is a hydrocarbon group, and X (active hydrogen group) is a hydroxy group, an amino group, or a thiol group.)

  The alkylene group preferably has 1 to 5 carbon atoms from the viewpoint of excellent compatibility. Specific examples include a methylene group, an ethylene group, a trimethylene group, and a propylene group.

The hydrocarbon group as R ⁶ is not particularly limited. For example, what combined any 1 or more of these, such as an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, is mentioned.

  The oxazolidine compound preferably has one or more hydroxy groups in the molecule from the viewpoint that the pot life can be set to an appropriate length and is excellent in storage stability and foam suppression.

  When the oxazolidine compound has one or more hydroxy groups in the molecule, the oxazolidine compound can be introduced into the urethane prepolymer when producing the urethane prepolymer, and the oxazolidine ring is excellent in foaming resistance and storage stability. Excellent. Moreover, the oxazolidine compound which has 1 or more of hydroxyl groups in a molecule | numerator can react with a urethane prepolymer in a 2nd liquid, is excellent in foaming resistance, and is excellent in storage stability.

  Examples of the oxazolidine compound having a hydroxy group include 2-isopropyl-3- (2-hydroxyethyl) oxazolidine, 3- (2-hydroxyethyl) -2- (1-methylbutyl) oxazolidine, 2-phenyl-3- ( 2-hydroxyethyl) oxazolidine, 2- (p-methoxyphenyl) -3- (2-hydroxyethyl) oxazolidine, 2- (2-methylbutyl) -3- (2-hydroxyethyl) -5-methyloxazolidine, the following formula (3) The compound represented by Formula (4) is mentioned.

（上記式（３）、式（４）中、ｎは０以上２以下の整数を表し、Ｒ¹は、ヒドロキシ基または炭素数１以上１２以下の分岐していてもよいアルキル基もしくはアルコキシ基であり、ｎが２の場合のＲ¹は、それぞれ同一であっても異なっていてもよい。Ｒ²は、炭素数１以上６以下の分岐していてもよいヒドロキシ基を有するアルキル基である。Ｒ³およびＲ⁴は、それぞれ独立に、水素原子、炭素数１以上６以下の分岐していてもよいアルキル基またはフェニル基である。）

(In the above formulas (3) and (4), n represents an integer of 0 or more and 2 or less, and R ¹ is a hydroxy group or an alkyl group or alkoxy group having 1 to 12 carbon atoms which may be branched. Yes, R ¹ when n is 2 may be the same or different from each other, and R ² is an alkyl group having a hydroxy group having 1 to 6 carbon atoms which may be branched. R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, which may be branched, or a phenyl group.)

  Specifically, preferred examples of the compound represented by the above formula (3) include a compound represented by the following formula (5). Preferable examples of the compound represented by the above formula (4) include compounds represented by the following formulas (6) and (7).

  The oxazolidine compound having one or more hydroxy groups is superior in foaming resistance and excellent in storage stability from the viewpoint of 3- (2-hydroxyethyl) -2- (1-methylbutyl) oxazolidine and / or 2-phenyl- 3- (2-Hydroxyethyl) oxazolidine is preferred.

  The oxazolidine compounds can be used alone or in combination of two or more.

  The oxazolidine compound may react with the urethane prepolymer, for example, during production or storage.

  The amount of the oxazolidine compound is preferably 0.01% by mass or more and 3.00% by mass or less in the total amount of the sealing material composition from the viewpoint of excellent foam resistance and excellent storage stability, and 0.05% by mass. % To 1.00% by mass is more preferable.

  The sealing material composition of this embodiment can contain an additive in the range which does not impair the objective of this invention as needed. Examples of additives include plasticizers, fillers (for example, calcium carbonate, surface-treated calcium carbonate, resin hollow bodies), curing catalysts, thixotropic agents, silane coupling agents, pigments, dyes, anti-aging agents. , Antioxidants, antistatic agents, flame retardants, drying oils, adhesion-imparting agents, dispersants, dehydrating agents, ultraviolet absorbers, solvents and the like.

  The method for producing the sealing material composition of the present embodiment is not particularly limited. For example, a first liquid having a polymer compound containing a polysulfide bond and containing one or more thiol (SH) groups at one end, a urethane prepolymer containing an isocyanate group at one end, and at least one oxazolidine in one molecule The second liquid containing a ring-containing compound can be prepared separately by a method in which the second liquid is sufficiently mixed under a nitrogen gas atmosphere. The sealing material composition of the present embodiment can also be stored by filling the prepared first liquid and second liquid in containers replaced with nitrogen gas or the like. The sealing material composition of the present embodiment can be used by thoroughly mixing and using the first liquid and the second liquid.

  As a use of the sealing material composition of this embodiment, a sealing material and an adhesive agent are mentioned, for example. Examples of the adherend to which the sealing material composition of the present embodiment can be applied include mortar, concrete, metal, painted plate, plastic, and rubber. The method for applying the sealing material composition of the present embodiment to an adherend is not particularly limited. For example, a conventionally well-known thing is mentioned.

Thus, according to the sealing material composition of the present embodiment, the following effects can be obtained.
1. Since the first liquid is a polymer having a polysulfide bond in the main chain skeleton, it is possible to maintain the effect of suppressing peripheral contamination such as heat resistance, self-adhesion, weather resistance, and joints of polysulfide.
2. Since the second liquid contains a urethane prepolymer containing an isocyanate group at the terminal and a compound having at least one oxazolidine ring, the moisture content of the adherend and the isocyanate group of the urethane prepolymer during construction Can react to suppress foaming caused by the generation of carbon dioxide gas. Thereby, the fall of the aesthetics of the external appearance of hardened | cured material and the fall of hardened | cured material strength can be prevented. Further, at the surface of the sealing material composition and the adherend interface at the time of construction, the ring-opening speed of oxazolidine increases, and a urea bond with oxazolidine is formed. As a result, the oxazolidine of the second liquid reacts before the moisture present in the environment atmosphere at the time of construction and the moisture contained in the adherend, so that the moisture and urethane pre- A by-product reaction of reacting with the isocyanate group of the polymer to generate carbon dioxide gas can be suppressed, and a cured product according to the original structural design can be obtained. Therefore, a thiourethane bond with a high reaction rate between the sulfide group at the end of the polysulfide block polymer and the isocyanate is secured, and the cured product is improved in weather resistance because it is less susceptible to UV degradation, thermal degradation, hydrolysis degradation, etc. Can be obtained.
3. Since the 2nd liquid contains the compound which has an oxazolidine ring, the addition amount of the tertiary amine in a base material can be reduced. Thereby, the disulfide bond by reaction acceleration | stimulation of a tertiary amine can be suppressed during storage, it can suppress that a viscosity raises, and storage stability can be improved.
4). When the second liquid further contains an oxazolidine compound, the oxazolidine ring in the component of the curing agent comes into contact with moisture in the system by mixing the first liquid and the second liquid stored in a sealed container. The ring-opening generates a functional group (amino group) that reacts with isocyanate, and the reaction is accelerated. When the water in the system reacts with isocyanate, carbon dioxide gas is generated or the curing catalyst is deactivated. Therefore, when water reacts with isocyanate and generates carbon dioxide, a large number of pores are generated on the surface of the obtained sealing material, which may impair the appearance. In particular, when it is applied to an adherend containing a large amount of water such as mortar, physical properties are likely to be deteriorated near the interface, which may cause poor adhesion. Further, when the curing catalyst is deactivated, foaming is likely to occur because the reaction between isocyanate and water proceeds more than the reaction between isocyanate and polyol. When the second liquid contains the oxazolidine compound, the oxazolidine ring in the component of the second liquid (curing agent) is brought into contact with moisture in the system by mixing the first liquid and the second liquid, and the ring is opened. Since a functional group (amino group) that reacts with isocyanate can be generated and the reaction can be promoted, it is possible to suppress the generation of carbon dioxide gas due to the reaction of moisture in the system with isocyanate.
5. When the second liquid further contains an oxazolidine compound, it becomes less susceptible to moisture, and the influence of moisture absorption during storage can be reduced, so that it becomes a sealing material composition having excellent storage stability. Since the oxazolidine compound is promoted to react with moisture in the air, the surface curability is particularly improved, so that the internal curing rate can be slowed and the pot life can be secured.

  Below, an Example is shown and the sealing material composition of this invention is demonstrated concretely. However, the present invention is not limited to these.

<Adjustment of the first liquid (main agent)>
Each component shown in the following Table 1 was blended in the ratio (parts by mass) shown in the same table to prepare a first liquid (main agent).

The details of each component in Table 1 are as follows.
Polysulfide polyether polymer: number average molecular weight 1100 (trade name “thiocol LP-282”, manufactured by Toray Fine Chemical Co., Ltd.) Also, the number average molecular weight of the polysulfide polyether polymer is N, N-dimethylformamide (DMF) as a solvent. It is expressed in terms of polystyrene by gel permeation chromatography (GPC).
Polyoxyalkylene polyol: Polyoxypropylene triol having a number average molecular weight of 3000 (trade name “EXCENOL-3030”, manufactured by Asahi Glass Urethane Co., Ltd.)
・ Plasticizer: Diisononyl phthalate (trade name “DINP”, manufactured by J Plus Co., Ltd.)
Metal catalyst 1: Bismuth salt of organic carboxylate (trade name “Pucat 10”, manufactured by Nippon Chemical Industry Co., Ltd.)
Metal catalyst 2: Organic carboxylic acid zinc salt (trade name “Nikka Octix Zinc 8% EH”, manufactured by Nippon Chemical Industry Co., Ltd.)
・ Organic acid: Organic carboxylic acid (trade name "Octylic acid", manufactured by Kyowa Hakko)
・ Phenolic antioxidant (trade name “AO-30”, manufactured by ADEKA CORPORATION)
・ Thioether-based antioxidant (trade name “AO-412S”, manufactured by ADEKA CORPORATION)
・ Anhydrous gypsum (trade name “D-1”, manufactured by Noritake Company Limited)
-Resin hollow body: Organic balloon (trade name “MFL100L”, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)
・ Calcium carbonate 1: Surface-treated light calcium carbonate (trade name “MS-700”, manufactured by Maruo Calcium Co., Ltd.)
・ Calcium carbonate 2: Surface treated light calcium carbonate (trade name “N-350”, manufactured by Maruo Calcium Co., Ltd.)
・ Calcium carbonate 3: Calcium bicarbonate (trade name “Super SS”, manufactured by Maruo Calcium Co., Ltd.)

<Adjustment of second liquid (curing agent)>
The components shown in Table 2 below were blended in the proportions (parts by mass) shown in the same table, and reacted for 24 hours at 80 ° C. to prepare the second liquid (curing agents 1 and 2). Table 2 also shows NCO groups / OH groups (ratio of isocyanate group equivalents to total OH group equivalents in the second liquid) and final NCO% (ratio of unreacted NCO in the second liquid).

The details of each component in Table 2 are as follows.
Polyoxyalkylene polyol 1: polyoxypropylene triol having a number average molecular weight of 1000 (trade name “EXCENOL-1000”, manufactured by Asahi Glass Urethane Co., Ltd.)
Polyoxyalkylene polyol 2: Polyoxypropylene diol having a number average molecular weight of 2000 (trade name “EXCENOL-2020”, manufactured by Asahi Glass Urethane Co., Ltd.)
・ Plasticizer: Diisononyl adipate (trade name “DINA”, manufactured by J Plus Co., Ltd.)
Polyisocyanate: xylene diisocyanate (trade name “Takenate 500”, manufactured by Mitsui Chemicals Polyurethanes, Inc.)
・ Oxazolidine compound: 3- (2-hydroxyethyl) -2- (1-methylbuthyl) oxazolidine (trade name “PHO”, manufactured by Yokohama Rubber Co., Ltd.)

<Evaluation>
The sealing material composition obtained as described below was evaluated for compatibility, heat resistance, hydrolyzability, tensile adhesiveness, and weather resistance by the following methods. The evaluation results are shown in Table 3.

(Compatibility)
The compatibility is evaluated by mixing the first liquid and the second liquid under the conditions of 20 ° C. and 50% RH (relative humidity) to form a mixture (sealing material composition), and the first liquid and the second liquid The appearance of the mixture after mixing, the appearance of the cured product after curing the mixture, and the cured state of the cured product were visually observed. The test results of the appearance of the mixture after mixing the first liquid and the second liquid, the appearance of the cured product, and the cured state of the cured product were evaluated as follows. The test results are shown in Table 1. In Table 1, o and x indicate the following states, respectively. If the appearance of the mixture after mixing and the appearance of the cured product after curing were transparent (clear), it was judged that the compatibility was excellent. Moreover, if the cured state of the cured product was uniformly cured without unevenness, it was judged that the compatibility was excellent.
(Appearance of mixture after mixing, appearance of cured product)
○: Appearance of the mixture after mixing and the appearance of the cured product after the transparent were clear (clear) ×: Appeared slightly cloudy (cured state of the cured product)
○: The cured product is uniformly cured without unevenness ×: Unevenly cured with unevenness

(Heat-resistant)
Evaluation of heat resistance was carried out by leaving a cured product obtained by mixing the first liquid and the second liquid under the conditions of 20 ° C. and 50% RH (relative humidity) in a high temperature atmosphere at 120 ° C. for 7 days. The state of the cured product was observed by visual observation and finger touch. The test results were evaluated as follows. The test results are shown in Table 1. In Table 1, o and x indicate the following states, respectively. From the surface state of the cured product and the touch feeling with a finger, it was judged that the cured product was excellent in heat resistance if there was no abnormality after the curing.
(Evaluation criteria)
○: The surface of the cured product and the touch feeling with the finger were recognized as normal with no change after curing. ×: The surface of the cured product was soft and sticky.

(Hydrolyzable)
The hydrolyzability was evaluated by leaving the cured product obtained by mixing the first and second solutions under the conditions of 20 ° C. and 50% RH (relative humidity) in an autoclave at 120 ° C. for 24 hours. The state of the cured product was observed by visual observation and finger touch. The test results were evaluated as follows. The test results are shown in Table 1. In Table 1, o and x indicate the following states, respectively. From the surface state of the cured product and the touch feeling with a finger, it was judged that the product was excellent in hydrolyzability if there was no change after curing and no abnormality.
(Evaluation criteria)
○: The surface of the cured product and the touch feeling with the finger were recognized as normal with no change after curing. ×: The surface of the cured product was soft and sticky.

(Tensile adhesion)
Tensile adhesion was evaluated by using a cured product after standard curing of the sealing material composition and a cured product obtained by immersing the obtained cured product in water (after immersion), respectively. An adhesion test was performed. The tensile adhesiveness test was performed according to “5.20 Tensile adhesiveness test” defined in “Testing method of sealing material for building” of JIS A1439: 2004. The test was conducted under conditions of 23 ° C. and 50% relative humidity. Aluminum was used for the adherend, and the shape of the test body was shown in FIG. 14B 2 shown in JIS A1439. For the standard curing, curing curing was performed under the conditions of Table 3 in JIS A1439 (multi-component form, 23 ° C., 50% RH × 7 days (pre-curing) + 50 ° C. × 7 days (post-curing)). The obtained cured product was immersed in water at an underwater temperature of 20 ° C. for 7 days. Tests of maximum tensile stress (Tmax), elongation at maximum load (Emax) and fracture state of cured product after standard curing of sealant composition, and Tmax, Emax and fracture state of cured product after immersion in water The results are shown in Table 1. The fracture state was evaluated by the ratio of cohesive fracture (CF). Regarding the cured product immersed in water after standard curing, when the Tmax of the cured product is 0.4 N / mm ² or more, when the Emax of the cured product is 400% or more, the fracture state is CF of 75% or more. In this case, it was judged that the tensile adhesiveness was good.

(Weather resistance (accelerated weather resistance test))
Each obtained sealing material composition was apply | coated to plate glass by 3 mm thickness, and the test body was obtained. The specimen was placed in an atmosphere of 20 ° C. and 65% RH for 7 days, and then left on a metal weatherometer for 300 hours to evaluate the weather resistance. The test results were evaluated as follows. The test results are shown in Table 1. In Table 1, o and x indicate the following states, respectively. If there was no abnormality in appearance, it was judged that the weather resistance was good.
(Evaluation criteria)
○: When there is no abnormality in appearance ×: When hair cracks are occurring

<Preparation of sealing material composition>
Using the components shown in Table 1 and Table 2 in the amounts (parts by mass) shown in the same table, a sealing material composition containing the first liquid and the second liquid was produced.

  As is clear from the results shown in Table 3, in Comparative Example 1, it was confirmed that the polysulfide polymer and the second liquid were not compatible and the appearance and curability were inferior. In Comparative Example 2, it was confirmed that the tensile adhesiveness and weather resistance were inferior. On the other hand, in Examples 1 and 2 for confirming the compatibility, the compatibility is good (particularly, the compatibility between the first liquid containing the polysulfide polymer and the second liquid containing the urethane prepolymer). In Examples 3 to 4 in which a filler and the like were blended, tensile strength and weather resistance were confirmed to be good.

  Therefore, when the oxazolidine compound is not included in the second liquid (curing agent), it can be said that the polysulfide polymer and the second liquid are incompatible and inferior in curability. Further, when the second liquid does not contain an oxazolidine compound, it can be said that the tensile adhesiveness and the weather resistance are inferior. On the other hand, it can be said that the compatibility, tensile adhesiveness, and weather resistance are all excellent by including the oxazolidine compound in the second liquid.

  As described above, the two-component polysulfide-based sealing material composition according to the present invention suppresses foaming due to the generation of carbon dioxide gas and is useful for improving the strength of a cured product. In particular, the two-component curable polysulfide-based sealing material Suitable for use in.

Claims (4)

A first liquid containing a polysulfide polyether polymer containing a polysulfide bond in one molecule and having one or more thiol groups at its ends;
A second liquid comprising a urethane prepolymer containing an isocyanate group at a terminal and a compound having at least one oxazolidine ring;
A two-component polysulfide-based sealant composition comprising:   The two-component polysulfide-based sealing material composition according to claim 1, wherein the polysulfide polyether polymer contains a sulfide group and a polypropylene oxide group.   The two-component polysulfide-based sealing material composition according to claim 1 or 2, wherein the compound having an oxazolidine ring has a hydroxyl group in the molecule. The compound having an oxazolidine ring is 3- (2-hydroxyethyl) -2- (1-methylbuthyl) oxazolidine, or 2-phenyl-3- (2-hydroxyethyl) oxazolidine
The two-component polysulfide-based sealant composition according to claim 3.