JP2006124621A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for treating metal-containing impurities of curing reaction inhibitors in the curing composition which is cured by a hydrosilylation reaction, and to provide a curable composition obtained by the method. <P>SOLUTION: This curable composition comprises (A) an unsaturated group-containing polyether containing a composite metal cyanide complex and/or its residual compound, (B) ascorbic acid and/or its derivative, (C) a compound containing at least two hydrosilyl groups in the molecule, and (D) a hydrosilylation catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable composition that is cured by a hydrosilylation reaction and a method for producing a cured product.

Conventionally, various types of curable compositions that are cured to produce a rubbery substance have been developed. Among them, a polymer having one or more alkenyl groups in one molecule by using a curing agent having two or more hydrosilyl groups in one molecule has a relatively long pot life at around room temperature. And has characteristics such as rapid curing by heating or excellent deep-part curability. As an example of such a curable composition, a curable composition using a polymer having a polyether having an alkenyl group as a main chain has been devised and used for adhesives, electrical / electronic material parts, and the like. . (For example, see Patent Document 1)
Examples of the method for synthesizing the polyether polymer having an alkenyl group used in the curable composition include ring-opening polymerization of alkylene oxide using an alkali metal catalyst, a metal porphyrin catalyst, a complex metal cyanide complex catalyst, or the like. Among them, the method using a double metal cyanide complex can obtain a polymer having a number average molecular weight of 8000 or more and a narrow molecular weight distribution, and a curable resin obtained by using this. The composition is useful in that flexibility can be imparted to the cured product, low viscosity of the composition, and good workability can be obtained.
JP-A-6-297469

  The present invention was made by finding that a composite metal cyanide complex or its residual compound becomes a reaction inhibitor during a hydrosilylation reaction in a curable composition cured by a hydrosilylation reaction. It aims at providing the processing method of the containing metal impurity (double metal cyanide complex or its residue compound) which is an inhibitor, and the curable composition obtained by it.

As a result of intensive studies on the above problems, the present inventor has achieved the above-described problem by the following method. That is, the present invention
(1)
Unsaturated group-containing polytel (A) containing double metal cyanide complex and / or its residue compound (A), ascorbic acid and / or its derivative (B), compound containing at least two hydrosilyl groups in the molecule (C) A curable composition containing a hydrosilylation catalyst (D),
(2)
After mixing the unsaturated group-containing polyter (A) having a polyether main chain obtained by polymerization using a double metal cyanide complex as a catalyst and ascorbic acid and / or its derivative (B) at 20 to 150 ° C., molecules A method for producing a cured product in which a compound (C) containing at least two hydrosilyl groups and a hydrosilylation catalyst (D) are added and cured by a hydrosilylation reaction,
(3)
The curable composition according to (1), wherein the hydrosilylation catalyst (D) is a platinum complex catalyst,
(4)
The method for producing a cured product according to (2), wherein the hydrosilylation catalyst (D) is a platinum complex catalyst,
(5)
Curability according to (1) or (3), wherein the amount of peroxide in the polyether before addition of ascorbic acid and / or its derivative (B) determined by iodine-thiosulfate titration is 30 ppm or less. Composition.
(6)
Hardened | cured material as described in (2) or (4) whose amount of peroxide in polyether before adding ascorbic acid and / or its derivative (B) calculated | required by the iodine- thiosulfate titration is 30 ppm or less Manufacturing method.
About.

  In addition, the amount of peroxide was determined by CHEMetrics. Inc. Model HP-10B by iodine-thiosulfate titration described in RM Johnson and IWSiddiqi, The Determination Of Organic Peroxides, Pergamon Press, London, 1970 Chp. 3. Done using a kit. The present invention is effective even when the peroxide amount is 30 ppm or less, and even if it is 20 ppm or less or 10 ppm or less, the effect can be sufficiently exerted.

  The present invention provides a curable composition that is cured by a hydrosilylation reaction, and the curing reaction can be carried out without any problem by simply performing a treatment without removing the metal from the metal impurity-containing polyether polymer. Since the process proceeds, the metal impurity treatment process can be simplified.

  The present invention will be described in detail below. The main chain structure of the polyether (A) used in the present invention may be a polymer having a structure represented by —RO— as a repeating unit. , R may be a divalent organic group having 1 to 20 carbon atoms containing one or more selected from the group consisting of hydrogen, oxygen, and nitrogen as constituent atoms. Moreover, the homopolymer in which all the repeating units are the same may be sufficient, and the copolymer containing a 2 or more types of repeating unit may be sufficient. Further, the main chain may have a branched structure.

Specific examples of the repeating unit represented by —RO— include, for example, —CH ₂ CH ₂ O—, —CH (CH ₃ ) CH ₂ O—, —CH (C ₂ H ₅ ) CH ₂ O—, —C (CH ₃ ) ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ CH ₂ O— and the like can be mentioned.

  In order to obtain the component (A) of the present invention, alkylene oxides (specifically, ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α-methylstyrene) Oxide); and alkyl or allyl or aryl glycidyl ethers (specifically, 2 to 12 carbon atoms such as methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, etc.) Substituted or unsubstituted epoxy compounds) having ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, water Divalent bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, etc. A polyether obtained by ring-opening polymerization in the presence of a composite metal cyanide catalyst using an alcohol or a polyhydric alcohol and various oligomers having a hydroxyl group as an initiator can be used.

Examples of the composite metal cyanide complex catalyst include Zn ₃ [Fe (CN) ₆ ] ₂ , Zn ₃ [Co (CN) ₆ ] ₂ , Fe [Fe (CN) ₆ ], Fe [Co (CN) ₆ ] and the like. Is mentioned. More preferably, Zn ₃ [Co (CN) ₆ ] ₂ (that is, zinc hexacyanocobaltate complex) is used as a catalyst skeleton and a structure in which an organic ligand is coordinated.

  Such a catalyst can be produced, for example, by coordinating an organic ligand with a reaction product obtained by reacting a metal halide salt with an alkali metal cyanometalate in water. As the metal of the metal halide salt, Zn (II) or Fe (II) is preferable, and Zn (II) is particularly preferable. Zinc chloride is particularly preferred as the metal halide salt. As a metal constituting the cyanometalate of the alkali metal cyanometalate, Co (III) or Fe (III) is preferable, and Co (III) is particularly preferable. As the alkali metal cyanometalate, potassium hexacyanocobaltate is preferable. As an organic ligand, alcohol and / or ether are preferable. tert-butyl alcohol, ethanol, sec-butyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-pentyl alcohol, isopentyl alcohol, isopropyl alcohol and other alcohols, and ethylene glycol dimethyl ether (hereinafter, glyme), diglyme One or more selected from ethers such as (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), dioxane, and polyether having a number average molecular weight of 150 to 5,000 are preferred. Of these, tert-butyl alcohol and / or glyme are particularly preferable.

As a method of obtaining the component (A) by introducing an unsaturated group into a polyether polymer having a hydroxyl group, the hydroxyl group of the polyether polymer is converted to -OM group (M is Na or K) by metal oxidation of the hydroxyl group. And a method of producing a polyether having an unsaturated group by reacting with an organic halogen compound represented by the general formula (1).
^{_{H 2 C = C (R 2}} ) -R 1 -Y or ^{H (R 2) C = CH} -R 1 -Y (1)
(In the formula, R ¹ is a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of hydrogen, oxygen and nitrogen as a constituent atom, R ² is hydrogen, or 10 carbon atoms. The following hydrocarbon groups, Y is a halogen atom.)
As this organic halogen compound, allyl chloride and methallyl chloride are most preferable.

  An antioxidant can be added to a polyether having a hydroxyl group or a polyether having an unsaturated group in order to suppress oxidative degradation of the polyether. Antioxidants include phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2, 2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol) ), Tetrakis {methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate} methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Butane or the like can be used.

  Ascorbic acid or a derivative thereof (B) used in the present invention is L-ascorbic acid; isoascorbic acid which is a structural isomer thereof; ester derivatives thereof (specifically, L-ascorbyl palmitate, stearic acid L Ascorbyl, 2-ethylhexanoic acid L-ascorbyl, isoascorbyl palmitate, isoascorbyl stearate, or isoethylcortyl 2-ethylhexanoate; their phosphate ester derivatives (specifically, L-ascorbic acid monophosphate) Esters, L-ascorbic acid diphosphates, L-ascorbic acid triphosphates, isoascorbic acid monophosphates, isoascorbic acid diphosphates, or isoascorbic acid triphosphates; L-ascorbic acid-2-glucoside or isoascorbic acid-2-glucoside); and alkali metal salts thereof such as sodium and potassium, alkaline earth metal salts such as magnesium, calcium and barium, and many such as aluminum Although various metal salts, such as a valent metal salt, etc. are mentioned, L-ascorbic acid, isoascorbic acid, or its metal salt is more preferable.

  The above-mentioned ascorbic acid or a derivative thereof may be added immediately before the curing reaction, or added in advance to a polyether having an unsaturated group, but is added in advance to a polyether having an unsaturated group. The method is good.

  Examples of the addition method include a method of adding by dissolving in a solvent, a method of adding as a solid, a method of adding by dissolving in water, etc. The most preferable effect when used by dissolving in methanol or ethanol Is obtained. The amount of ascorbic acid or its derivative added varies depending on the amount of catalyst residue in the polymer. However, if the amount added is large, the polymer is unfavorably colored, and if it is too small, it will affect the hydrosilylation in the subsequent step. Is more preferable, and a range of 20 to 700 ppm is more preferable.

  After adding ascorbic acid or a derivative thereof to a polyether having an unsaturated group, the compound (C) containing at least two hydrosilyl groups in the molecule and the hydrosilylation catalyst (D) may be added and cured. Although it is good, it usually contains 20 to 150 ° C., preferably 40 to 120 ° C., and after mixing and stirring for 0 to 5 hours, more preferably 0.5 to 2 hours, the molecule contains at least two hydrosilyl groups. The compound (C) and the hydrosilylation catalyst (D) are preferably added and cured.

  The compound containing at least two hydrosilyl groups in one molecule as component (C) in the present invention can be used without particular limitation as long as it has a hydrosilyl group, but the number average molecular weight is 400 to 3000. The thing of 500-1000 is more preferable. If the number average molecular weight is less than 400, it will volatilize at the time of heat curing and a sufficient cured product cannot be obtained, and if it exceeds 3000, a sufficient curing rate cannot be obtained. Examples of such compounds include organohydrogenpolysiloxanes modified with organic groups from the standpoint of availability of raw materials and compatibility with the component (A). Moreover, these (C) components preferably have good compatibility with the (A) component. In particular, when the viscosity of the whole system is low, use of a material having low compatibility may cause phase separation and cause poor curing. Specifically showing the structure of such an organohydrogenpolysiloxane, for example,

（式中、２≦ｂ＋ｃ≦５０、１≦ｂ≦３、０≦ｃである。Ｒ³は、主鎖の炭素数が２〜２０の炭化水素基で１個以上のフェニル基を含有してもよい）、

(In the formula, 2 ≦ b + c ≦ 50, 1 ≦ b ≦ 3, 0 ≦ c. R ³ is a hydrocarbon group having 2 to 20 carbon atoms in the main chain and containing one or more phenyl groups. )

（式中、０≦ｄ＋ｅ≦５０、０≦ｄ≦１、０≦ｅである。Ｒ³は、主鎖の炭素数が２〜２０の炭化水素基で１個以上のフェニル基を含有してもよい）、又は、

(In the formula, 0 ≦ d + e ≦ 50, 0 ≦ d ≦ 1, 0 ≦ e. R ³ is a hydrocarbon group having 2 to 20 carbon atoms in the main chain and containing one or more phenyl groups. Or)

（式中、３≦ｆ＋ｇ≦２０、１≦ｆ≦３、０≦ｇ＜１８である。Ｒ³は、主鎖の炭素数が２〜２０の炭化水素基で１個以上のフェニル基を含有してもよい）などで示される鎖状又は環状のもの等が挙げられる。

(In the formula, 3 ≦ f + g ≦ 20, 1 ≦ f ≦ 3, 0 ≦ g <18. R ³ is a hydrocarbon group having 2 to 20 carbon atoms in the main chain and containing one or more phenyl groups. Or a chain-like or cyclic group represented by

  Specific examples of the component (C) having a relatively good compatibility with the component (A) or relatively good dispersion stability and curing speed include the following.

（式中、１≦ｋ≦３、０≦ｌ≦８であり、Ｒ⁴は炭素数８以上の炭化水素基である。）
（Ｃ）成分のより具体的な例としては、メチルハイドロジェンポリシロキサンを、（Ａ）成分との相溶性確保と、ＳｉＨ量の調整のために、α−オレフィン、スチレン、α−メチルスチレン、アリルアルキルエーテル、アリルアルキルエステル、アリルフェニルエーテル、アリルフェニルエステル等により変性した化合物が例示され、一例として、以下の構造があげられる。

(In the formula, 1 ≦ k ≦ 3, 0 ≦ l ≦ 8, and R ⁴ is a hydrocarbon group having 8 or more carbon atoms.)
As a more specific example of the component (C), methyl hydrogen polysiloxane is used for the purpose of ensuring compatibility with the component (A) and adjusting the amount of SiH, α-olefin, styrene, α-methylstyrene, Examples include compounds modified with allyl alkyl ethers, allyl alkyl esters, allyl phenyl ethers, allyl phenyl esters, and the like, and examples include the following structures.

但し、１≦ｐ≦３、１≦ｑ≦８である。

However, 1 ≦ p ≦ 3 and 1 ≦ q ≦ 8.

It does not specifically limit as a hydrosilylation catalyst which is (D) component of this invention, Arbitrary things can be used. For example, solid platinum supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, carbon black; platinum-vinylsiloxane complex {for example, Ptn (ViMe ₂ SiOSiMe ₂ Vi) n , Pt [(MeViSiO) ₄ ] m}; platinum-phosphine complex {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer)}, Pt (acac) 2, and the platinum-hydrocarbon complex described in the specifications of Ashby et al., US Pat. Nos. 3,159,601 and 3,159,662, and Lamoreaux et al., US Pat. The platinum alcoholate catalyst described in the specification of 20972 is also mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt (acac) _{2 and the} like are preferable. Among these, platinum complex catalysts such as platinum-olefin complexes, platinum-vinylsiloxane complexes, and Pt (acac) ₂ are particularly preferable. Although there is no restriction | limiting in particular as a usage-amount of a catalyst, It is good to use in the range of 10 ^<-8 > ^-10 < ^-1 > mol with respect to ¹ mol of alkenyl groups in (A) component. Preferably, it is used in the range of 10 ⁻⁶ to 10 ⁻² mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas may be generated to cause the cured product to foam. Therefore, it is better not to use more than 10 ⁻¹ mol.

  If the components (A), (B), (C), and (D) of the present invention are mixed and heated, a uniform cured product excellent in deep part curability can be obtained without causing a phenomenon such as foaming. Although there is no restriction | limiting in particular about hardening conditions, Generally 0-200 degreeC, More preferably, it is good to harden | cure at 30-150 degreeC for 5 second-4 hours. In particular, at a high temperature of 80 to 150 ° C., a material that cures in a short time of about 5 seconds to 1 hour can be obtained.

  In addition to the essential four components (A), (B), (C), and (D), the curable composition of the present invention includes a solvent, an adhesion improver, and a pot life extension depending on the purpose of use. An agent, a plasticizer, an anti-sagging agent, a filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a pigment, a foaming agent, an extender, and the like can be appropriately added.

  Specific applications of the cured product obtained from the present curable composition include sealing materials, adhesives, pressure-sensitive adhesives, elastic adhesives, paints, waterproof coatings, foams, sealants for electronic and electrical parts, potting Examples thereof include agents, films, gaskets, various molding materials, and dental impression materials.

  In order to further clarify the present invention, specific examples will be described below, but the present invention is not limited thereto.

(Production Example 1)
Ring-opening polymerization of propylene oxide was carried out with a zinc hexacyanocobaltate glyme complex catalyst using polypropylene glycol having a number average molecular weight of 3000 as an initiator to obtain a hydroxyl group-terminated polyether polymer having a number average molecular weight of 12,000. Subsequently, 1.2 times equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyether polymer to distill off the methanol, and 1.5 times equivalent of allyl chloride was added to the hydroxyl group. The terminal hydroxyl group was converted to an allyl group to obtain an unsaturated group-containing polyether (a) containing metal impurities. The metal content in the unsaturated group-containing polyether (a) was 26 ppm Zn and 9.2 ppm Co as measured by IPC emission spectroscopic analysis.

(Production Example 2)
To 100 g of the unsaturated group-containing polyether (a) obtained in Production Example 1, 300 g of hexane and 300 g of water are added and stirred for 20 minutes. After allowing the mixture to stand, the hexane phase was taken out, and hexane was devolatilized under reduced pressure to obtain an unsaturated group-containing polyether (b) containing metal impurities. The amount of metal in the unsaturated group-containing polyether (b) was 4.1 ppm Zn and 1.1 ppm Co.

(Production Example 3)
A polyoxypropylene polymer having a number average molecular weight of 3000 polymerized using caustic alkali as a catalyst was reacted with dichloromethane in the presence of alkali to obtain a hydroxyl group-terminated polyether polymer having a number average molecular weight of 9000 by molecular chain extension reaction. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyether polymer to distill off the methanol, and 1.5-fold equivalent of allyl chloride was added to remove the terminal hydroxyl group. Conversion to an allyl group gave an unsaturated group-containing polyether. The same operation as in Production Example 2 was performed on the obtained unsaturated group-containing polyether to obtain an unsaturated group-containing polyether (c). The unsaturated group-containing polyether (c) does not contain Zn or Co.

(Production Example 4)
In the presence of a platinum catalyst, 0.5 equivalent of α-methylstyrene of the total amount of hydrosilyl groups was added to methylhydrogen silicone having an average of 5 repeating units represented by (—Si—O—), Compound (d) having an average of 2.5 hydrosilyl groups was obtained. The Si—H group content of this compound was 3.2 mmol / g.

(Examples 1-2)
1 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant in the polymer (a) obtained in Production Example 1 or the polymer (b) obtained in Production Example 2 and 5% of ascorbic acid The amount of methanol solution shown in Table 1 was added and dissolved. Further, a xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3% by weight as platinum) was mixed at a platinum atom / alkenyl group molar ratio of 5 × 10 ⁻⁴ equivalents. Was added and stirred well. To this, the compound (d) having a hydrosilyl group was added so that the hydrosilyl group / alkenyl group had a molar ratio of 1.1.

  A small amount of the obtained curable composition was scooped with a toothpick and dropped on a hot plate heated to 120 ° C., and the time (curing time) until gel formation was measured while slowly stirring. The results are shown in Table 1.

(Examples 3 to 4)
The amount shown in Table 1 for the unsaturated group-containing polyether (a) obtained in Production Example 1 or the unsaturated group-containing polyether (b) obtained in Production Example 2 and a 5% methanol solution of ascorbic acid The mixture was added and stirred at 90 ° C. for 30 minutes. Thereafter, the mixture was cooled to room temperature, and 1 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) was added and dissolved as an antioxidant. Further, a xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3% by weight as platinum) was mixed at a platinum atom / alkenyl group molar ratio of 5 × 10 ⁻⁴ equivalents. Was added and stirred well. Here, the compound (d) having a hydrosilyl group was added so that the hydrosilyl group / alkenyl group had a molar ratio of 1.1.

  A small amount of the obtained curable composition was scooped with a toothpick and dropped on a hot plate heated to 120 ° C., and the time until the gel was formed (curing time) was measured while slowly stirring. The results are shown in Table 1.

(Comparative Examples 1-2)
Irganox 1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant was added to the unsaturated group-containing polyether (a) obtained in Production Example 1 or the unsaturated group-containing polyether (b) obtained in Production Example 2. 1 part) was added and dissolved. Further, a xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3% by weight as platinum) was mixed at a platinum atom / alkenyl group molar ratio of 5 × 10 ⁻⁴ equivalents. Was added and stirred well. To this, the compound (d) having a hydrosilyl group was added so that the hydrosilyl group / alkenyl group had a molar ratio of 1.1.

  A small amount of the obtained curable composition was scooped with a toothpick and dropped on a hot plate heated to 120 ° C., and the time (curing time) until gel formation was measured while slowly stirring. The results are shown in Table 1.

(Reference Example 1)
To the unsaturated group-containing polyether (c) obtained in Production Example 3, a 5% methanol solution of ascorbic acid was added in the amount shown in Table 1, and the mixture was stirred at 90 ° C. for 30 minutes. After cooling to room temperature, 1 part of an antioxidant and Irganox 1010 (manufactured by Ciba Specialty Chemicals) were added and dissolved. Further, a xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3% by weight as platinum) was mixed at a platinum atom / alkenyl group molar ratio of 5 × 10 ⁻⁴ equivalents. Was added and stirred well. To this, the compound (d) having a hydrosilyl group was added so that the hydrosilyl group / alkenyl group had a molar ratio of 1.1.

  A small amount of the obtained curable composition was scooped with a toothpick and dropped on a hot plate heated to 120 ° C., and the time until the gel was formed (curing time) was measured while slowly stirring. The results are shown in Table 1.

(Reference Example 2)
To the unsaturated group-containing polyether (c) obtained in Production Example 3, 1 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) was added and dissolved as an antioxidant. Further, a xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3% by weight as platinum) was mixed at a platinum atom / alkenyl group molar ratio of 5 × 10 ⁻⁴ equivalents. Was added and stirred well. To this, the compound (d) having a hydrosilyl group was added so that the hydrosilyl group / alkenyl group had a molar ratio of 1.1.

  A small amount of the obtained curable composition was scooped with a toothpick and dropped on a hot plate heated to 120 ° C., and the time until the gel was formed (curing time) was measured while slowly stirring. The results are shown in Table 1.

表１より、アスコルビン酸を添加し処理した不飽和基含有ポリエーテルを用いると（実施例１〜４）、添加処理しない場合（比較例１、２）と比較して、硬化時間が速くなることがわかる。

From Table 1, when the unsaturated group containing polyether which added and processed ascorbic acid is used (Examples 1-4), compared with the case where addition processing is not carried out (comparative examples 1 and 2), hardening time becomes quick. I understand.

Claims (6)

  Unsaturated group-containing polytel (A) containing double metal cyanide complex and / or its residue compound (A), ascorbic acid and / or its derivative (B), compound containing at least two hydrosilyl groups in the molecule (C) A curable composition containing a hydrosilylation catalyst (D).   After mixing the unsaturated group-containing polyter (A) having a polyether main chain obtained by polymerization using a double metal cyanide complex as a catalyst and ascorbic acid and / or its derivative (B) at 20 to 150 ° C., molecules A method for producing a cured product, wherein a compound (C) containing at least two hydrosilyl groups and a hydrosilylation catalyst (D) are added and cured by a hydrosilylation reaction.   The curable composition according to claim 1, wherein the hydrosilylation catalyst (D) is a platinum complex catalyst.   The method for producing a cured product according to claim 2, wherein the hydrosilylation catalyst (D) is a platinum complex catalyst.   The curable composition according to claim 1 or 3, wherein the amount of peroxide in the polyether before addition of ascorbic acid and / or its derivative (B) determined by iodine-thiosulfate titration is 30 ppm or less. .   The production of the cured product according to claim 2 or 4, wherein the amount of peroxide in the polyether before addition of ascorbic acid and / or its derivative (B) determined by iodine-thiosulfate titration is 30 ppm or less. Method.