WO2008001784A1

WO2008001784A1 - Method for producing curable polymer exhibiting excellent curability

Info

Publication number: WO2008001784A1
Application number: PCT/JP2007/062824
Authority: WO
Inventors: Tatsuhiro Futami; Yuuji Kimura; Hideaki Tanaka; Genichirou Enna
Original assignee: Asahi Glass Company, Limited
Priority date: 2006-06-30
Filing date: 2007-06-26
Publication date: 2008-01-03
Also published as: JP5556013B2; JPWO2008001784A1

Abstract

Disclosed is a method for producing a curable polymer whose cured product is excellent in hardness. Also disclosed is a curable composition. Specifically disclosed is a method for producing a curable polymer, which is characterized in that when a polymer (pP) having a polyoxyalkylene chain and a hydroxy group and a compound (U) having an alkoxysilyl group and an isocyanate group are urethanized, the polymer (pP) is urethanized while controlling the moisture content thereof to be 150 ppm or less, thereby producing an alkoxysilyl group-containing oxyalkylene polymer (P) having a urethane bond. Also specifically disclosed is a curable composition containing the thus-produced curable polymer.

Description

Specification

Method for producing curable polymer exhibiting excellent curability

Technical field

TECHNICAL FIELD [0001] The present invention relates to a method for producing a curable polymer that exhibits excellent curability and can obtain a cured product having excellent hardness, and a curable composition containing the curable polymer. Background art

[0002] A polymer having a hydrolyzable silicone group at the end of a polyoxyalkylene chain (also referred to as a modified silicone polymer) is a powerful curable composition that is cured by moisture to form a cured product having excellent rubber elasticity. To do. For this reason, the curable composition is widely used as an adhesive, a coating agent, and a sealing material. Among them, a curable composition comprising a polymer having a methyldimethoxysilyl group at the end of a polyoxyalkylene chain is widely accepted as a sealing material in the market due to its excellent elongation property (see Patent Document 1). ).

[0003] Further, a curable composition containing a polymer having a polyoxyalkylene chain and a trialkoxysilyl group has a fast curing speed and a high crosslink density, so that it can be used as a fast-curing adhesive and a coating material. As useful (see Patent Document 2).

The curable composition includes a trialkoxy bonded to a polyoxyalkylene chain and an end of the polyoxyalkylene chain via a —OCH CH CH— group or one SCH CH CH— group.

2 2 2 2 2 2

A specific polymer having a silyl group, a specific polymer having a polyoxyalkylene chain and a trialkoxysilyl group bonded to the end of the polyoxyalkylene chain via a urethane bond, or a compound having an amino group and an alkoxysilyl group The curable composition containing is known (refer patent document 3 and patent document 4).

[0004] In addition, these curable compositions can be used for adhesives, coating agents, sealing materials, and other applications, and in the same applications, the hardness of the cured product (hereinafter referred to as the type and location of the substrate). , Called hardness).

A specific polymer having a polyoxyalkylene chain and a trialkoxysilyl group bonded to the polyoxyalkylene chain end via a urethane bond usually contains a compound having an isocyanate group and a trialkoxysilyl group, and a hydroxy group at the chain end. Polyoxyalkyl having It can be produced by reacting with the hydroxyl group at the chain end of the len chain. At this time, if a compound such as water is mixed during the production, the isocyanate group reacts with moisture and does not react with the hydroxyl group at the chain end of the polyoxyalkylene chain.

[0005] In order to prevent such a side reaction, a specific polymer having a polyoxyalkylene chain and a trialkoxysilyl group bonded to the end of the polyoxyalkylene chain via a urethane bond is usually used. After the step of removing moisture by dehydrating polyoxyalkylene having a hydroxy group at the first chain end, etc., the reaction between the isocyanate group and the compound having a trialkoxysilyl group is performed. However, even when dehydrated in this manner, there is a problem in that a polymer may be produced in which the hardness of the cured product of the curable composition is lowered.

[0006] Patent Document 1: Japanese Patent Laid-Open No. 03-072527

Patent Document 2: Japanese Patent Laid-Open No. 03 047825

Patent Document 3: Japanese Patent Laid-Open No. 10-245482

Patent Document 4: JP-A-11 124509

Disclosure of the invention

Problems to be solved by the invention

[0007] The present invention increases the hardness of a cured product of a curable composition containing a specific polymer having a polyoxyalkylene chain and an alkoxysilyl group bonded to the end of the polyoxyalkylene chain via a urethane bond. An object of the present invention is to provide a method for producing a curable polymer, and a curable composition containing the curable polymer.

Means for solving the problem

[0008] As a result of diligent investigations on various production conditions, the present inventors have produced a curable polymer that exhibits high hardness and hardness without lowering the hardness of the cured product of the curable composition. The method has been found and the present invention has been completed.

That is, the present invention has the following gist.

(1) When the polymer (pP) having a polyoxyalkylene chain and a hydroxy group and the compound (U) having an alkoxysilyl group and an isocyanate group represented by the following formula (1) are subjected to a urethanization reaction, The polymer (pP) was urethanated with a water content of 150 _PP m or less. A method for producing a curable polymer, comprising producing an alkoxysilyl group-containing oxyalkylene polymer (P) having a urethane bond.

(X ^1- ) (R—) Si-Q ^u -NCO (1)

a b

(In the formula, each X ¹ is independently an alkoxyl group having 1 to 6 carbon atoms, R is an alkyl group having 6 to 6 carbon atoms, a is 2 or 3, and b is 0 or 1, a + b is 3, and Q ^U is a divalent organic group having carbon number:! -20.

(2) The method for producing a curable polymer according to the above (1), wherein the polymer (pP) has a water content of 120 ppm or less and undergoes a urethane reaction.

(3) The ratio of the total number of isocyanate groups of the compound (U) to the total number of hydroxy groups of the polymer (pP) (isocyanate group Z hydroxy group) is 0.8 to: 1.05 above (1) or ( The method for producing a curable polymer as described in 2).

(4) The polymer (pP) obtained by ring-opening polymerization of an alkylene oxide on a compound having an active hydrogen atom in the presence of a double metal cyanide complex catalyst having an organic ligand (pPl ) The method for producing a curable polymer according to any one of the above (1) to (3)

(5) Peroxide value of the polymer (pP) POV (content of peroxide group generated by oxidation of a polyoxyalkylene chain) 1 Any one of the above (1) to (4) which is 170 ppm or less A method for producing a curable polymer.

(6) The method for producing a curable polymer according to (1) to (5) above, wherein the urethanization reaction is performed in the presence of an antioxidant.

(7) A curable composition comprising a curable polymer produced by the production method described in (1) to (6) above.

(8) A cured product obtained by curing the curable composition according to (7).

The invention's effect

The curable composition containing the curable polymer obtained by the method for producing a curable polymer of the present invention has excellent curability, and can increase the hardness of the cured product of the curable composition. That is, the curable composition of the present invention can increase the hardness by increasing the crosslink density of the resin, can improve the tensile strength useful in the adhesive field, and improve the adhesiveness. You can make it S. Further, the tensile strength useful as a sealing material can be improved, the elastic modulus can be increased, and the weather resistance can be improved. The curable composition of the present invention is useful as an adhesive or a sealing material used for various applications.

BEST MODE FOR CARRYING OUT THE INVENTION

In the present specification, the number average molecular weight is denoted by Mn, the weight average molecular weight is denoted by Mw, and the molecular weight distribution is denoted by MwZMn. In addition, ppm, the unit of substance content, means mass ppm.

[0012] The polymer (pP) used in the production method of the present invention is a polymer having a polyoxyalkylene chain and a hydroxyl group.

The polyoxyalkylene chain in the polymer (pP) is preferably composed of an oxyalkylene polymer unit formed by ring-opening polymerization of an alkylene oxide having 2 to 6 carbon atoms. Ethylene oxide, propylene oxide, Formed by ring-opening polymerization of propylene oxide, more preferably composed of polymerized units of oxyalkylene formed by ring-opening polymerization of one or more alkylene oxides selected from the group consisting of butylene oxide and hexylene oxide force It is particularly preferred to consist of polymerized oxyalkylene units. When the polyoxyalkylene chain is composed of two or more types of oxyalkylene polymer units, the arrangement of the two or more types of oxyalkylene polymer units may be block or random.

[0013] The hydroxy group is preferably located at the end of the polyoxyalkylene chain.

Mnf or per hydroxy group of the polymer _{(P P),} 1000~18000 force S, and particularly preferably 3000 to 15 000.

The polymer (pP) is a polymer (pPl) obtained by ring-opening polymerization of an alkylene oxide to a compound having an active hydrogen atom in the presence of a double metal cyanide complex catalyst having an organic ligand. Is preferred. Hereinafter, a double metal cyanide complex having an organic ligand is also referred to as a DMC complex, and a double metal cyanide complex catalyst having an organic ligand is also referred to as a DMC catalyst.

[0014] The DMC complex as a DMC catalyst used in the present invention has a skeleton of a cyanide complex of a composite metal composed of a combination of zinc and cobalt or a combination of zinc and iron. I like it. In particular, those having zinc hexocyanobaltate as a skeleton or those having zinc hexocyano iron as a skeleton are preferred.

The organic ligand in the DMC complex is preferably an ether ligand or an alcohol ligand. Specific examples of the ether ligand include ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), and triethylene glycol dimethyl ether. Specific examples of alcohol-based ligands include ter t-butinoreanoreconole, n_butinoleanoreconole, sec-butinoreanoreconole, iso-butinoreanoreconole, tert-pentenoreanorecole Nole, iso-pentenoreanoreconole, ethylene glycol mono-tert-butyl ether.

In the present invention, the compound having an active hydrogen atom is a compound having 1 to 6 hydroxy groups, which is preferably a compound having a hydroxy group or an amino group, which is preferably an organic compound having an active hydrogen atom. Further preferred are compounds having 1 to 4 preferred hydroxy groups.

Specific examples of the organic compound having an active hydrogen atom include ethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene glycol, and jetylene. Alcohols such as glycol, triethylene glycol, aryl alcohol, methallyl alcohol, glycerin, trimethylol methane, trimethylol propane, pentaerythritol; polyoxypropylene monool, polyoxypropylene diol, polyoxypropylene triol, polyoxy Examples thereof include polymeric alcohols selected from the group consisting of ethylene monool, polyoxyethylene diol, and polyoxyethylene triol. The Mn (number average molecular weight) per hydroxyl group of the polymer-like alcohol is preferably 300 to 2000, more preferably 400 to 1900.

[0017] As the compound having an active hydrogen atom, one kind may be used, or two or more kinds may be used. When a compound having two or more kinds of active hydrogen atoms is used, it is preferable to use a polymer alcohol having two hydroxy groups and a polymer alcohol having three hydroxy groups.

The polymerization temperature at the time of polymerizing the polymer (pPl) may be appropriately selected, but usually 80 to 15: 0 ° C is preferred. 100 to 140 ° C is more preferred.

In the present invention, one kind of polymer (pP) may be used, or two or more kinds of polymers (pP) may be used.

[0018] The compound (U) used in the present invention is a compound having an alkoxysilyl group and an isocyanate group, and is a compound represented by the following formula (1).

(X ^1- ) (R-) Si-Q ^u -NCO (1)

a b

[0019] X ¹ in the formula (1) is particularly preferably a methoxy group, preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, or a hexenoreoxy group. Two or three X ¹ in the formula (1) may be the same group or different groups, but are preferably the same group. R is particularly preferably a methyl group, preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group. a is 2 or 3, with 3 being preferred.

Q ^u in [0020] Equation (1) is a divalent organic group having 1 to 20 carbon atoms.

The divalent organic group is particularly preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 14 carbon atoms.

A particularly preferable divalent organic group is a trimethylene group or a methylene group.

[0021] Specific examples of the compound (U) include 1-isocyanate methyltrimethoxysilane, 2-isocyanate trimethylsilane, 3-isocyanate propyltrimethoxysilane, 3-

1_isocyanate methinoret triethoxysilane, 2_isocyanate ethinoretriethoxysilane, 3_isocyanate propyltriethoxysilane, 3_isocyanate butyltriethoxysilane, 3_isocyanate pentyltri Examples include ethoxysilane, 1_isocyanate probitrimethoxysilane, 1_isocyanate methyldimethoxymethylsilane, 1_isocyanate propyltriethoxysilane. Of these, 3_isocyanatepropyltrimethoxysilane or 1-isocyanatemethyldimethoxymethylsilane is preferred. In the present invention, when the polymer (pP) and the compound (U) are subjected to a urethanization reaction, the water content of the polymer (pP) is reduced to 150 ppm or less for the urethanation reaction. Thereby, the hardness of the hardened | cured material of the obtained curable composition can be made high.

The water content of the polymer _(P P) is preferably not more than 120 ppm, particularly preferably at most LOOppm.

In addition, since compound (U) has an isocyanate group, it is managed so that moisture does not enter.

In the urethanization reaction system, a polymer (pP) and a compound (U) are present, and usually a small amount of a urethanization catalyst is present. This urethanization reaction is preferably performed under conditions where moisture does not enter.

In addition, other compounds such as a solvent may be added to the urethanization reaction system. In that case, it is preferable to reduce the water content in the compound. Les, preferably within the range.

The measurement of the amount of water is not particularly limited as long as a minute amount of water can be evaluated, and the measurement by the coulometric titration method, which is preferable to the volumetric titration method, is more preferable. In addition, the anolyte used in the coulometric titration method is not particularly limited as long as the sample is dissolved satisfactorily. A methanol solvent product is preferred, which contains black mouth form as a solvent. It is more preferable because it is dissolved.

In the present invention, in the urethane reaction, the peroxide value (hereinafter referred to as POV) of the polymer (pP) is preferably 170 ppm or less, preferably 60 ppm or less. More preferably, it is 3 ppm or less. Here, the POV of the polymer (pP) indicates the content of peroxide groups generated by oxidation of the polyoxyalkylene chain of the polymer (pP). If the POV of the polymer (pP) exceeds 170 ppm, the urethanization reaction may be delayed, or a cured product that does not exhibit sufficient hardness may be obtained when attempting to cure as a curable composition.

In the present invention, it is preferable to contain an antioxidant when the urethane reaction is carried out. Addition of an antioxidant prevents PV increase during the reaction and oxidation of the polyoxyalkylene chain, preventing side reactions in the urethanization reaction and reactions such as acids. Generation of the inhibiting factor can be prevented, and it becomes easy to produce a polymer that provides a cured product exhibiting sufficient hardness.

Antioxidants are not particularly limited, and are capable of using various antioxidants. Hindered phenolic antioxidants or hindered phenolic antioxidants that are preferred are hindered amine antioxidants. Particularly preferred. Specific examples of preferred antioxidants include, for example, 2,6-di_tert_butyl_4_methylphenol, pentaerythritol tetrakis [3- (3,5_di-tert-butyl_4-hydroxyphenyl) propionate ] (Manufactured by Chinoku 'Specialty' Chemicals, trade name “IRGAN〇X1010”), 6 _Methylheptyl 1 3 _ (3,5-di-tert-butyl _4-hydroxyphenol) propionate (Chinoku. Specialty Chemicals, trade name “IRGAN〇X1135”), Octadecyl _ 3_ (3, 5 _di-tert-butyl _4-hydroxyphenyl) propionate (Ciba 'Specialty' Chemicals, trade name “IRGAN”) O X1076 ”). The antioxidant may be used alone or in combination of two or more. The amount of the antioxidant added is 0.001 to 100 parts by mass of the polymer (pP): ! Parts by mass are preferred 0. 01-0. 1 part by mass is particularly preferred.

In the present invention, it is preferable to use a catalyst for the urethane reaction of the polymer (pP) and the compound (U). Examples of the catalyst include organic tin compounds (dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, etc.), metal catalysts such as bismuth compounds, and base catalysts such as organic amines. In addition, when the polymer (pP) is produced using a DMC catalyst, if the DMC catalyst is present, the urethanization reaction can be performed without adding any other catalyst. . In that case, since a tin catalyst or the like is not added, the storage stability of the final product is good, which is preferable. In particular, after synthesizing a polymer (pP) using a DMC catalyst, the water content of the polymer is urethanated at 150 _PP m or less, so that it can be obtained not only with good storage stability. Further, the hardness of the cured product of the curable composition can be further increased.

[0024] In the present invention, the DMC complex used as a catalyst in the urethane-like reaction is in an activated state so that the polymer (pP) and the compound (U) can undergo a urethanation reaction. Examples of the activated DMC catalyst include, for example, a DMC complex obtained by ring-opening polymerization of an alkylene oxide to a compound having an active hydrogen atom in the presence of a DMC complex, or a DMC complex in a similar state. Is mentioned. In this case, the DMC complex may be the one immediately after the initiation of the ring-opening polymerization reaction of the alkylene oxide, or may be in the middle of the ring-opening polymerization reaction, or the ring-opening polymerization reaction. Even after the end.

[0025] In the present invention, the polymer (pP) contained in the polymer (pPl) obtained by ring-opening polymerization of alkylene oxide with a compound having an active hydrogen atom in the presence of a DMC catalyst is produced. If the polymer (pPl) and the compound (U) are urethanated using the DMC catalyst used for purification without purification, the urethanation reaction proceeds efficiently. The polymer (pPl) containing the DMC catalyst used to produce the polymer (pPl) can be used alone or in combination of two or more.

[0026] When two or more of the polymers (pPl) containing the DMC catalyst used to produce the polymer (pPl) are used in combination, the amount of the DMC catalyst contained can be adjusted.

In the present invention, the amount of catalyst used in the urethanization reaction of the polymer (pP) and the compound (U) is preferably 5 to 500 ppm force S, more preferably 10 to 200 ppm force S based on the polymer (pP). , 20 ~: OOppm is particularly preferred. If the amount exceeds 500 ppm, the long-term storage stability of the polymer itself will decrease, and if it is less than 5 ppm, the urethane reaction will not proceed easily.

When a DMC catalyst is used as a catalyst for the urethanization reaction, the amount of DMC catalyst used may be an amount that allows the urethanation reaction, but it is 5 to 500 ppm in terms of metal amount with respect to the mass of the polymer (pP) Force S preferred, 5 to 200 ppm force S preferred, 8 to:! OOppm force S more preferred, 10 to 80 ppm force S Particularly preferred.

In the present invention, the ratio of the total number of isocyanate groups of the compound (U) to the total number of hydroxy groups of the polymer (pP) in the urethane reaction (isocyanate group Z hydroxy group) is from 0.8 to: 1 .05 force S preferred, 0.85 ~: 1. 0 particularly preferred, _{0 in} this range, the rapid curability and storage stability of the curable composition containing the polymer (P) are remarkable. There is an effect to improve. The reason for this is not necessarily clear, but in this range, even if hydroxy groups remain in the obtained polymer (P), since there are few hydroxy groups, the hydroxyl group in the polymer (P) The number of alcohol exchange reactions is small, so the storage stability of the polymer is low. Qualitative properties and fast curability of the polymer after storage can be maintained. In addition, since side reactions (allophanate reaction, isocyanurate reaction, etc.) in the urethanization reaction are suppressed, it is considered that the curable composition, which is difficult to produce side reaction products, is difficult to thicken.

[0028] Refractive degree ί or 20-200. C force, 50 ~: 150. C-powered girls, 50-: 120. Preferred for C force S. Further, the urethanization reaction is more preferably performed in a nitrogen gas atmosphere, which is preferably performed in an inert gas atmosphere.

[0029] According to the method for producing a curable polymer of the present invention, an alkoxysilyl group-containing oxyalkylene polymer (P) having a urethane bond can be produced. This polymer (P) is a polymer having curability and having the following formula (2) and a polyoxyalkylene chain.

(X ^1- ) (R-) Si-Q ^u -NHCOO- (2)

a b

The polymer (P) obtained by the urethanization reaction can be obtained without separating or removing the urethanization catalyst to obtain the curable composition of the present invention.

That is, the curable composition of the present invention is a curable composition containing the polymer (P) obtained by the above production method.

The curable composition of the present invention can contain a curing catalyst when cured.

The strong curing catalyst is not particularly limited as long as it is a compound that acts as a catalyst for the crosslinking reaction by hydrolysis reaction of the alkoxysilyl group of the polymer. Specific examples of the curing catalyst include organotin compounds, organometallic compounds containing metals other than tin, metallic organic alkoxides, complexes containing metals other than tin, organic amines, and other catalysts.

[0031] Specific examples of the organic tin compound include dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, (n-C H) Sn (OCOCH = CHCOOCH),

4 9 2 3 2

(n-C H) Sn (OC ○ CH = CHCO〇 (n_C H)), (n-C H) Sn (〇COCH

4 9 2 4 9 2 8 17 2

= CHCOOCH), (n-C H) Sn (〇C〇CH = CHCO〇 (n_C H)), (n-C

3 2 8 17 2 4 9 2 8

Organotin carboxylates such as H) Sn (OCOCH = CHCOO (iso-C H)); (n_C H) Sn (SCH COO), (n— CH) Sn (SCH COO), (n— CH) Sn (SCH

4 9 2 2 8 17 2 2 8 17 2 2

CH COO), (n-C H) Sn (SCH COOCH CH OCOCH S), (n— C H) S

2 8 17 2 2 2 2 2 4 9 2 n (SCH COO (iso-C H)), (n-C H) Sn (SCH COO (iso— C H)), (

2 8 17 2 8 17 2 2 8 17 2 n-C H) Sn (SCH COO (n_C H)), (n-C H) SnS, (C H) Sn (SC

8 17 2 2 8 17 2 4 9 2 8 17 2

Organotin compounds containing sulfur atoms such as H 2 COOC H);

2 8 17 2

[0032] Organic stanoxide compounds such as (n-C H) SnO and (n-C H) SnO;

4 9 2 8 17 2

Reaction product obtained by reacting sid with estenole (ethenoresilicate, dimethyl maleate, cetinole maleate, dioctyl maleate, dimethyl phthalate, jetyl phthalate, dioctyl phthalate, etc.); (nC H) Sn (acac), (nC H) Sn (acac), (n

4 9 2 2 8 17 2 2

-C H) Sn (OC H) (acac), (n-C H) Sn (etac), (n-C H) Sn (etac)

4 9 2 8 17 4 9 2 2 8 17 2 2

, (N-C H) Sn (OC H) (etac), organotins such as bis (acetylacetonate) tin

4 9 2 8 17

Compound chelate; reaction product obtained by reacting organotin compound chelate with alkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc.); (n — CH) (CH COO) SnOSn ( OCOCH) (nC H), (nC H) (CH 0) SnO

4 9 2 3 3 4 9 2 4 9 2 3

Organotin compounds having SnOSn bonds such as Sn (OCH) (n-C H);

3 4 9 2

Examples include divalent sulphate salts such as tin norehexanoate, tin n-octylate, tin naphthenate and tin stearate. However, acac represents a acetylacetonate ligand, and etac represents an ethylacetoacetate ligand (the same applies hereinafter).

[0033] Specific examples of organometallic compounds containing metals other than tin include calcium carboxylate, zirconium carboxylate, iron carboxylate, vanadium carboxylate, bismuth tris 2-ethylhexoate, and other bismuth carboxylates and lead carboxylates. , Titanium carboxylate and nickel carboxylate.

[0034] Specific examples of the organometallic alkoxide, tetraisopropyl titanate, Tetorapuchi Norechitaneto, tetramethyl titanate, titanium alkoxides such as tetra (Kishiruchitaneto to 2_ Echiru); aluminum isopropylate, mono - _sec _ butoxy aluminum Jie Aluminum alkoxides such as so-propylate; Zirconium alkoxides such as zirconium n-propylate, zirconium _n-butyrate; titanium tetraacetyl acetonate, titanium ethinoreacetoacetate, titanium oxytylene glycolate, titanium latate And titanium alkoxides.

[0035] Specific examples of the complex containing a metal other than tin include aluminum chelates such as aluminum trisacetylacetonate, aluminum trisethylacetate acetate, and diisopropoxyaluminum ethyl acetate acetate; Zirconium chelates such as cetyl acetate, zirconium bisacetyl acetate, zirconium acetyl acetate bisacetate, and zirconium acetate.

[0036] Specific examples of organic amines include aliphatic monoamines such as butyramine, hexylamine, octylamine, decenoreamine, laurylamine; aliphatic diamines such as ethylenediamine, hexanediamine; triethylamine, diethylenetriamine, triethylenetetramine, teto Aliphatic polyamines such as raethylenepentamine; heterocyclic amines such as piperidine and piperazine; aromatic amines such as metaphenylenediamine; monoethanolamine, diethanolamine, triethanolamine, etc. Alkanolamines: various modified amines used for curing epoxy resins.

[0037] Specific examples of other compounds include phosphoric acid, p-toluenesulfonic acid, and phthalic acid.

The curing catalyst is preferably an organic tin hydrate compound from the viewpoint of handleability. From the viewpoint of fast curing, (n- C H) Sn (acac), (n— C H) Sn (acac), (n— C H)

4 9 2 2 8 17 2 2 4 9 2

Sn (OC H) (acac), (n— C H) Sn (etac), or (n— C H) Sn (etac)

8 17 4 9 2 2 8 17 2 2 is particularly preferred.

[0038] It is also possible to appropriately select a curing catalyst to control the curing rate of the curable composition. For example, the curing rate of the curable composition of the present invention can be decreased by selecting a catalyst having low activity as the curing catalyst.

Specific examples of the low activity catalyst include specific organotin compounds containing a sulfur atom in the ligand (trade name UL-29, manufactured by Crompton Co., Ltd., and trade name Neostan U-860, manufactured by Nitto Kasei Co., Ltd.). It is done.

[0039] The curable composition of the present invention may contain one or more curing catalysts or two or more curing catalysts. When two or more kinds of curing catalysts are contained, the curable composition of the present invention is excellent in curability, and therefore preferably contains an organic tin compound and an organic amine. The curable composition of the present invention preferably contains 0.00 :! to 10 parts by mass of the curing catalyst with respect to 100 parts by mass of the polymer (P). In this case, there is an effect that the curing speed is high, foaming during curing is suppressed, and the durability of the cured product is excellent.

[0040] The curable composition of the present invention further includes one or more additives selected from the group consisting of a filler, a plasticizer, an adhesiveness imparting agent, a solvent, a dehydrating agent, a thixotropic agent, an antiaging agent, and a pigment. An agent may be included.

Specific examples of the filler in the present invention include calcium carbonate, calcium carbonate, silica, anhydrous key acid, carbon black, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, bentonite, ferric oxide, zinc oxide, charcoal. , Pulp, cotton chips, my strength, crushed rice flour, and rice husk flour. The filler may be a fine hollow body (silica balloon, shirasu balloon, glass balloon, resin balloon, etc.) which may be a fine powder. The curable composition of the present invention may contain one or more fillers and may contain two or more fillers.

[0041] The calcium carbonate is preferably calcium carbonate surface-treated with a fatty acid or a resin acid. Calcium carbonate is either colloidal calcium carbonate with an average particle size of 1 / im or less, light calcium carbonate with an average particle size of 1 to 3 μm, or heavy carbonated lucium with an average particle size:! To 20 μm. preferable.

The curable composition of the present invention particularly preferably contains 50 to 250 parts by mass, preferably 1000 parts by mass or less of the filler, with respect to 100 parts by mass of the polymer (P).

[0042] The plasticizer in the present invention includes phthalate esters such as dioctyl phthalate, dibutyl phthalate, and butyryl phthalate; dioctyl adipate, bis (2-methylnonyl) succinate, dibutyl sebacate, butyl oleate Aliphatic carboxylic acid esters such as pentaerythritol ester, etc .; Phosphate esters such as trioctyl phosphate and tricresyl phosphate; Epoxidized soybean oil, 4,5_Epoxyhexahydrophthalate dioctyl, Epoxy stearin Epoxy plasticizers such as acid benzil; Chlorine paraffins; Polyester plasticizers obtained by reacting dibasic acids with dihydric alcohols; Polyether plastics such as polyoxypropylene glycol 1J; Styrene plasticizers such as monomethylstyrene and polystyrene Polybutadiene, butadiene one Atari Roni Turin Les Examples thereof include polymer plasticizers such as copolymers, polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, and epoxy polybutadiene.

[0043] The curable composition of the present invention preferably contains 1000 parts by mass or less of the plasticizer with respect to 100 parts by mass of the polymer (P).

Specific examples of the adhesion-imparting agent in the present invention include organic silane cups such as a silane having a (meth) ataryloxy group, a silane having an amino group, a silane having an epoxy group, and a silane having a carboxynole group. Ring agent; isopropyl tri (N aminoethylamino) organometallic coupling agent; epoxy resin.

[0044] Specific examples of the silane having a (meth) attayloxy group include 3-methacryloyl acryloyloxypropyl methyldimethoxysilane.

Specific examples of the silane having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3 aminopropyltri Methoxysilane, N— (2 aminoethyl) 3 aminopropylmethyldimethoxysilane, N— (2 aminoethyl) 3 aminopropyltriethoxysilane, 3 Ureidopropyltriethoxysilane, N— (N-Buylbenzyl 2-silane Is mentioned.

[0045] Specific examples of the silane having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropyltriethoxysilane.

Specific examples of carboxyl group-containing silanes include: 2_carboxyethyltriethoxysilane, 2_carboxyethylphenylbis (2-methoxyethoxy) silane, N_ (N-force carboxymethyl 2-aminoethyl) _ 3-Aminopropyltrimethoxysilane and the like.

[0046] Alternatively, a reaction product obtained by reacting two or more silane coupling agents may be used as an adhesion-imparting agent. As the reactant, it has a silane having an amino group and an epoxy group. A reaction product obtained by reacting silane, a reaction product obtained by reacting a silane having an amino group and a silane having a (meth) taroyloxy group, a silane having an epoxy group and a silane having a mercapto group are reacted. And reaction products of silanes having different mercapto groups.

[0047] Specific examples of the epoxy resin include bisphenol A-diglycidyl ether type epoxy resin, bisphenol F-diglycidyl ether type epoxy resin, tetrabromobisphenol A-glycidyl ether type epoxy resin, novolac type epoxy resin. , Hydrogenated Bisphenol A type epoxy resin, Bisphenol A-propylene oxide adduct glycidyl ether type epoxy resin, 4-Glycidyloxybenzoic acid glycidyl, Phthalic acid diglycidyl, Tetrahydrophthalic acid diglycidyl, Hexahydrophthalic acid diglycidyl , Diglycidyl ester epoxy resin, m-aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, N, N-diglycidyl aniline, N, N-diglycidyl o-Toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohol (glycerin etc.), hydantoin type epoxy resin, unsaturated polymer (petroleum resin etc.) epoxy resin It is done.

[0048] When the curable composition of the present invention contains the silane coupling agent, it preferably contains more than 0 to 30 parts by mass of the silane coupling agent with respect to 100 parts by mass of the polymer (P). . When the curable composition of this invention contains the said epoxy resin, it is preferable that 100 mass parts or less of an epoxy resin is included with respect to 100 mass parts of a polymer (P).

[0049] Specific examples of the solvent in the present invention include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, ester alcohols, ketanololeconore, etherenorenorenorenore. , Ketone ester, ketone ester, and esterol. When alcohol is used, the storage stability of the curable composition is improved. The alcohol is particularly preferably methanol, ethanol, isopropanol, isopentyl alcohol or methanol or ethanol, more preferably hexyl alcohol, which is preferably an alkyl alcohol having 1 to 10 carbon atoms.

[0050] When the curable composition of the present invention contains a solvent, it is dissolved in 100 parts by mass of the polymer (P). It is preferable to contain 500 parts by mass or less of the agent.

Specific examples of the dehydrating agent in the present invention include trialkyl orthoformate such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate; trimethyl orthoacetate, triethyl orthoacetate, orthoacetic acid And trialkyl orthoacetate such as tripropyl and tributyl orthoacetate.

[0051] When the curable composition of the present invention contains a dehydrating agent, it preferably contains 0.00 :! to 30 parts by mass of the dehydrating agent with respect to 100 parts by mass of the polymer (P).

Specific examples of the thixotropic agent in the present invention include hydrogenated castor oil and fatty acid amide.

[0052] Specific examples of the antioxidant in the present invention include antioxidants for polyurethane resins, ultraviolet absorbers, and light stabilizers. Specific examples of anti-aging agents include hindered amines, benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, hindered phenols, phosphorus, or sulfur. It is done.

Specific examples of the pigment in the present invention include inorganic pigments such as iron oxide, chromium oxide and titanium oxide; organic pigments such as phthalocyanine blue and phthalocyanine green.

[0053] The method for producing the curable composition of the present invention is not particularly limited. For example, 100 parts by mass of a polymer), the curing catalyst, the filler, the adhesiveness-imparting agent, the solvent, the desorbing agent. Water solution, the thixotropic agent, the anti-aging agent, the pigment and the like. ) (Hereinafter referred to as other components), the order of blending the other components is not particularly limited, but after mixing the polymer (P) and other components other than the curing catalyst, the curing catalyst Les, which is preferable to mix.

[0054] The curing method of the curable composition of the present invention is not particularly limited, and the curable composition of the present invention and other desired components are mixed and stored, and are used in the air when used. Curing of the curable composition with moisture The curing method of the one-component curable composition, or the two-component curable composition in which the curable composition of the present invention and the desired other components are mixed and cured as needed It is preferred to use a method of curing the product.

[0055] The curable composition of the present invention is capable of forming a cured product having high curability and good mechanical properties. The curable composition of the present invention is a cured composition for coating and sealing. It is useful as a building sealant, waterproofing material, adhesive, or coating agent, and particularly useful as an adhesive.

[0056] As a preferred mode of use of the adhesive comprising the curable composition of the present invention, the curable composition of the present invention and other desired components are blended and stored, and are used in the air when used. Examples thereof include a one-component curable adhesive that cures the adhesive by moisture, or a two-component curable adhesive that is mixed and cured when the curable composition of the present invention and other desired components are used.

Example

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited thereto. The ratio of the total amount of isocyanate groups of the compound (U) to the total amount of hydroxy groups of the polymer (pP) is represented by NCO / It is called OH. The total amount of hydroxy groups in the polymer (pP) was calculated from the hydroxyl value (mgK0H / g) measured according to JIS K1557 6.4.

Molecular weight and molecular weight distribution were measured by gel permeation chromatography (standard: polystyrene).

For the moisture content measurement, a coulometric titration moisture meter (CA-06 type / Ver 5.0) manufactured by Mitsubishi Kasei Co., Ltd. (currently Dai Instruments Inc.) was used. Aquamicron AS (manufactured by API Corporation) was used as the anolyte, and Aquamicron CXU (manufactured by API Corporation) was used as the catholyte. The amount of sample collected at the time of measurement was adjusted according to the water content of the sample, and an appropriate amount was used in the range of 0.1 lg to 10 g. The measurement was performed 5 times, and the average value of 3 points excluding the maximum and minimum values was taken as the measurement value.

For POV measurement, 10 g of a sample was weighed in a 300 mL iodine flask, and 50 mL of isopropyl alcohol was added to dissolve the sample. Potassium iodide (lg) was added, and 2 mL of a mixture of acetic acid and water mass ratio to 1 was added. The iodine flask was stoppered and sealed with isopropyl alcohol. The mixture was heated at 100 ° C for 20 minutes to react peroxide and potassium iodide to liberate iodine. The peroxide value was measured by titration with sodium thiosulfate (200N).

The hardness is measured by measuring the hardness of the resulting cured product with a hardness meter (DD2-C2 type, manufactured by Kobunshi Keiki Co., Ltd.) It measured using. The hardness was measured at 5 points, and the average value of 3 points excluding the maximum and minimum values was used.

The reaction time was defined as the time (hr) from when the raw material was charged into the reactor until the completion of the reaction could be confirmed.

[Example 1]

[1] Production of polymer (P-1)

In the presence of 960 mg of zinc hexanocobaltate whose ligand is glyme, 4500 g of propylene oxide was ring-opened and polymerized with 300 g of polyoxypropylene diol (Mnl000) to produce polyoxyanoloxy diethanolol (Mnl 6000 Thus, a hydroxyl value of 7.4) (polymer (ρΡ_1)) was obtained. 3000g of this polymer (pP_l) with 500ppm of pylated hydroxytoluene (2,6-di_tert_butyl_4_methylphenol, hereinafter abbreviated as BHT) as an antioxidant is added to the pressure reactor. (Internal volume: 5L), and dehydrating under reduced pressure until the water content became 112ppm with force S, keeping the internal temperature at 110 ° C. The POV of the polymer (pP 1) measured at this stage is shown in Table 1. The catalyst amount of the remaining composite metal cyanide complex was 21.5 ppm for zinc and 9.2 ppm for Konoletoka.

[0059] Next, the inside of the reactor was replaced with nitrogen gas, and while maintaining the internal temperature at 50 ° C, γ-isocyanate propyltrimethoxysilane (I 匕) was adjusted so that NCO / OH became 0 · 97. 82.8 g of a compound (U-1), purity 95%) was added, and the mixture was heated to 80 ° C and stirred while maintaining at 80 ° C. Analysis was performed with a Flier-transform infrared spectrophotometer, and the reaction was continued until the completion of the reaction between the hydroxy group and the isocyanate group could be confirmed. As a result of analyzing the contents of the reactor, it was found that a polymer (Mn = 16000, Mw / Mn = l.3) (polymer (P_l)) having urethane bonds, polyoxypropylene chains, and trimethoxysilyl groups was formed. confirmed. A polymer having a trimethoxysilyl group at the end of the polyoxypropylene chain was obtained.

[0060] [2] Production of curable composition and cured product

30 g of the polymer (P_l) obtained in [1] above, 20 g of dioctino phthalate, 0.15 g of ion-exchanged water, 10 g of heavy calcium carbonate (Whiteon SB: manufactured by Shiroishi Calcium Co., Ltd.), organotin catalyst Medium (No918: manufactured by Sansha Co., Ltd.) 0.75 g was mixed well to obtain a curable composition. Next, it was put into a stainless steel mold, defoamed with a nitrogen stream, and then cured at 100 ° C for 30 minutes. A 9 mm cured body (C1) was obtained.

[0061] [Example 2]

[1] Production of polymer (P-2)

A polymer (P-2) was obtained in the same manner as in Example 1 except that dehydration under reduced pressure was performed until the water content became 71 ppm. As a result of analyzing the contents of the reactor, it was confirmed that a polymer having a urethane bond, a polyoxypropylene chain, and a trimethoxysilyl group (Mn = 18000, MwZMn = 1.5) (polymer (P_2)) was formed. .

[2] Production of curable composition and cured product

A curable composition and a cured product (C-12) were obtained in the same manner as in Example 1 except that the polymer (P-2) obtained in [1] was used.

[Example 3]

[1] Production of polymer (P-3)

A polymer (P-3) was obtained in the same manner as in Example 1 except that it was dehydrated under reduced pressure until the water content became 22 ppm. As a result of analysis of the reactor contents, formation of a polymer (Mn = 19000, Mw / Mn = l. 4) (polymer (P-3)) with urethane bonds, polyoxypropylene chains, and trimethoxysilyl groups It was confirmed.

[2] Production of curable composition and cured product

A curable composition and a cured product (C3) were obtained in the same manner as in Example 1 except that the polymer (P-3) obtained in [1] was used.

[0063] [Example 4]

[1] Production of polymer (P— 4)

A polymer (P-4) was obtained in the same manner as in Example 1 except that dehydration under reduced pressure was performed until the water content became 9 ppm. As a result of analysis of the contents of the reactor, the polymer (Mn = 18000, Mw / Mn = l. 4) (polymer (P_4)) having urethane bonds and polyoxypropylene chains and trimethoxysilyl groups was obtained. Confirmed generation.

[2] Production of curable composition and cured product

A curable composition and a cured product (C-14) were obtained in the same manner as in Example 1 except that the polymer (P-4) obtained in [1] was used. [0064] [Comparative Example 1]

[1] Production of polymer (P-5)

A polymer (P-5) was obtained in the same manner as in Example 1 except that it was dehydrated under reduced pressure until the water content reached 195 ppm. As a result of analyzing the reactor contents, it was found that a polymer having a urethane bond, a polyoxypropylene chain, and a trimethoxysilyl group (Mn = 17000, Mw / Mn = l. 4) (polymer (P_5)) was formed. confirmed.

[2] Production of curable composition and cured product

A curable composition and a cured product (C-15) were obtained in the same manner as in Example 1 except that the polymer (P-5) obtained in [1] was used.

Examples:! To 4 and the production conditions of the polymers in Comparative Example 1 and the hardness of the obtained cured products are shown in Table 1.

[0065] [Table 1]

[0066] In Examples 1 to 4 where the polymers (P— :!) to (P-4) prepared with a water content of 150 ppm or less were used, the cured product obtained was compared with Comparative Example 1. It can be seen that the hardness value is remarkably high, and that it exhibits excellent hardness. Furthermore, it is understood that the moisture content is preferably 120 ppm or less, and particularly preferably ρρρm or less.

On the other hand, as shown in Comparative Example 1, when a cured product was prepared using a polymer (P-5) produced with a water content exceeding 150 ppm, a cured product with extremely low hardness was obtained. This indicates that the isocyanate group of isocyanatopropyltrimethoxysilane reacts with moisture in the reaction system and deactivates, and the trimethoxysilyl group is not sufficiently introduced into the polyoxyalkylene polymer.

[0067] [Example 5]

[1] Production of polymer (P-6) A polymer (P-6) was obtained in the same manner as in Example 1 except that dehydration under reduced pressure was performed until the water content became 12 ppm. As a result of analyzing the contents of the reactor, it was found that a polymer having a urethane bond, a polyoxypropylene chain, and a trimethoxysilyl group (Mn = 18000, Mw / Mn = l.3) (polymer (P_6)) was formed. confirmed.

[2] Production of curable composition and cured product

A curable composition and a cured product (C-16) were obtained in the same manner as in Example 1 except that the polymer (P-6) obtained in [1] was used.

[Example 6]

[1] Production of polymer (P-7)

A polymer (P_7) was obtained in the same manner as in Example 1 except that BHT was changed to lOOOOppm of IRGANOX 1076 (manufactured by Ciba 'Specialty' Chemicals) and dehydrated under reduced pressure until the water content became 31 ppm. As a result of analyzing the contents of the reactor, a polymer having a urethane bond, a polyoxypropylene chain, and a trimethoxysilyl group (Mn = 18000, Mw / Mn = l.5) (Polymer (P-7)) Confirmed the generation of.

[2] Production of curable composition and cured product

A curable composition and a cured product (C7) were obtained in the same manner as in Example 1 except that the polymer (P-7) obtained in [1] was used.

[0069] [Example 7]

[1] Production of polymer (P-8)

A polymer (P_8) was obtained in the same manner as in Example 1 except that BHT was changed to lOOOppm of IRGAN ○ X1135 (manufactured by Ciba 'Specialty' Chemicals) and dehydrated under reduced pressure until the water content became 26 ppm. As a result of analyzing the contents of the reactor, a polymer having a urethane bond, a polyoxypropylene chain, and a trimethoxysilyl group (Mn = 19000, Mw / Mn = l.4) (Polymer (P-8)) Confirmed the generation of.

[2] Production of curable composition and cured product

A curable composition and a cured product (C-18) were obtained in the same manner as in Example 1 except that the polymer (P-8) obtained in [1] was used.

[0070] [Example 8] [1] Production of polymer (P-9)

A polymer (P_9) was obtained in the same manner as in Example 1 except that BHT was changed to 1 OOOppm of IRGANOX 1010 (manufactured by Ciba Specialty Chemicals) and dehydrated under reduced pressure until the water content became 42 ppm. As a result of analyzing the contents of the reactor, a polymer having urethane bonds, polyoxypropylene chains, and trimethoxysilyl groups (Mn = 19000, Mw / Mn = l. 4) (Polymer (P-9)) Confirmed the generation of.

[2] Production of curable composition and cured product

A curable composition and a cured product (C-9) were obtained in the same manner as in Example 1 except that the polymer (P-9) obtained in [1] was used.

[0071] [Example 9]

[1] Production of polymer (P-10)

A polymer (P-10) was obtained in the same manner as in Example 1 except that no BHT was added and dehydration was performed under reduced pressure until the water content became 20 _PP m. As a result of analyzing the contents of the reactor, it was found that a polymer having a urethane bond, a polyoxypropylene chain, and a trimethoxysilyl group (Mn = 17000, Mw / Mn = l.5) (polymer (P-10)) Confirmed generation.

[2] Production of curable composition and cured product

A curable composition and a cured product (C10) were obtained in the same manner as in Example 1 except that the polymer (P-10) obtained in [1] was used.

[0072] [Example 10]

[1] Production of polymer (P-11)

A polymer (P-11) was obtained in the same manner as in Example 1 except that BHT was not added and dehydration was performed under reduced pressure until the water content became 21 ppm. As a result of analysis of the reactor contents, formation of a polymer (Mn = 17000, Mw / Mn = l.5) (polymer (P_11)) with urethane bonds, polyoxypropylene chains, and trimethoxysilyl groups It was confirmed.

[2] Production of curable composition and cured product

A curable composition and a cured product (C-11) were obtained in the same manner as in Example 1, except that the polymer (P-11) obtained in [1] was used.

Examples 5 to: Table 2 shows the production conditions of the polymer in 10 and the hardness of the obtained cured product. Show.

[0073] [Table 2]

In the table, Irl076 means IRGANOX1076, Irll35 means IRGANOX1135, and IrlOlO means IRGANOX1010.

[0074] In Examples 5 to 10 using polymers (P-6) to (P-11) produced with a water content of lOOppm or less and a POV of 170 ppm or less, it was obtained as compared with Comparative Example 1 It can be seen that the hardness value of the cured product is remarkably high, and exhibits excellent hardness. In particular, in Examples 5 to 9 where polymers (P-6) to (P-10) produced with a POV of 60 ppm or less were used, the hardness values of the obtained cured products were higher. It can be seen that it exhibits excellent hardness. In particular, in Examples 5 to 8 using the polymers (P-6) to (P-9) produced with a POV of 3 ppm or less, the hardness value of the obtained cured product was further increased. It can be seen that it exhibits excellent hardness. It can also be seen that when the POV is produced at 3 ppm or less, the polymer can be produced in a short time with a short reaction time between the hydroxy group and the isocyanate group.

Industrial applicability

[0075] The curable composition of the present invention is a curable composition capable of forming a cured product having excellent hardness. The curable composition of the present invention comprises a sealing material (elastic sealant for building, sealant for double-glazed glass, etc.), sealant (anti-glazing at the edge of glass, waterproof sealant, solar cell backside seal It is useful as an adhesive used in the fields of electrical insulation materials (insulation coatings for electric wires and cables). The curable composition of the present invention can also be used as an adhesive, a coating material, a film material, a gasket material, and a casting material. In addition, the Japanese patent application 2006-18001, filed on June 30, 2006 To incorporate.

Claims

The scope of the claims

[1] polyoxyalkylene chain and a polymer having a hydroxy group and _(P P), upon a compound having an alkoxysilyl group and Isoshianeto group express by the following formula (1) and (U), is allowed to urethanization reaction, Production of a curable polymer, characterized in that an alkoxysilyl group-containing oxyalkylene polymer (P) having a urethane bond is produced by urethanizing the polymer (pP) with a water content of 150 ppm or less. Method.

(X ^1- ) (R—) Si-Q ^u -NCO (1)

a b

(In the formula, each X ¹ is independently an alkoxyl group having from 6 to 6 carbon atoms, and R is a carbon number.

:! To 6 alkyl groups, a is 2 or 3, b is 0 or 1, a + b is 3

Q ^U is a divalent organic group having 20 to 20 carbon atoms. )

[2] The method for producing a curable polymer according to [1], wherein the polymer (pP) has a water content of 120 ppm or less and undergoes a urethane reaction.

[3] The ratio of the total number of isocyanate groups of the compound (U) to the total number of hydroxy groups of the polymer (pP) (isocyanate groups / hydroxy groups) is 0.8 to 1.05. The manufacturing method of curable polymer of description.

[4] The polymer (pP) is present in the presence of a double metal cyanide complex catalyst having an organic ligand.

4. The method for producing a curable polymer according to any one of claims 1 to 3, which is a polymer (pPl) obtained by ring-opening polymerization of an alkylene oxide to a compound having an active hydrogen atom.

[5] The polymer (pP) has a peroxide value POV (content of peroxide group generated by oxidation of a polyoxyalkylene chain) of 170 _PP m or less. A method for producing the curable polymer as described.

[6] The method for producing a curable polymer according to any one of [1] to [5], wherein the urethanization reaction is performed in the presence of an antioxidant.

[7] Claim: A curable composition comprising the curable polymer produced by the production method according to any one of! To 6.

[8] A cured product obtained by curing the curable composition according to claim 7.