JP2022064565A - Oxyalkylene polymer, curable composition comprising oxyalkylene polymer, and method for producing oxyalkylene polymer - Google Patents

Abstract

To provide an oxyalkylene polymer serving as a raw material of a cured product having excellent strength, a curable composition comprising the oxyalkylene polymer and a method for producing the oxyalkylene polymer.SOLUTION: There is provided an oxyalkylene polymer (A) having more than 0 reactive silicone groups represented by -SiXaR3-a and unsaturated groups in total on average per one terminal group and having the reactive silicone group and urethane bond in the main chain. R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X represents a hydroxy group, a halogen atom or a hydrolyzable group and a represents an integer of 1 to 3, when a is 1, R may be the same or different and when a is 2 or 3, X may be the same or different.SELECTED DRAWING: None

Description

The present invention relates to an oxyalkylene polymer, a curable composition containing an oxyalkylene polymer, and a method for producing an oxyalkylene polymer.

The oxyalkylene polymer having a reactive silicon group is cured by a hydrolysis reaction to form a flexible rubber-like cured product, which is used for sealing materials, adhesives and the like.

Patent Document 1 discloses an oxyalkylene polymer having an average of more than 1.0 reactive silicon groups per terminal group. It is described that the polymer has an average of more than 1.0 reactive silicon groups per terminal group, which makes it a raw material for a cured product having excellent elasticity and strength.

International Publication No. 2013/180203

In adhesive applications, the strength of the cured product is required to be excellent.
The strength of the cured product obtained by using the polymer described in Patent Document 1 as a raw material is not sufficient.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an oxyalkylene polymer as a raw material for a cured product having excellent strength, and a method for producing the oxyalkylene polymer.

The present invention has the following aspects [1] to [15].
[1] A polymer having a reactive silicon group, an unsaturated group and a polyoxyalkylene chain represented by the following formula 1, wherein the total of the reactive silicon group and the unsaturated group is one terminal group. An oxyalkylene polymer (A) having more than 0 on average and having the reactive silicon groups and urethane bonds in the main chain.
-SiX _a R _3-a formula 1
In the above formula 1, R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and a is. It indicates an integer of 1 to 3, and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other.
[2] The main chain contains a residue obtained by removing an isocyanate group from a polyisocyanate, a polyoxyalkylene chain, and a urethane bond connecting the residue and the polyoxyalkylene chain, and the terminal group comprises. The oxyalkylene polymer (A) of [1], which is a terminal group containing an oxygen atom closest to the molecular terminal of the oxyalkylene polymer (A) among the oxygen atoms in the polyoxyalkylene chain.
[3] The oxyalkylene polymer (A) of [1] or [2] having a number average molecular weight of 3,000 to 100,000.
[4] The oxyalkylene polymer (A) according to any one of [1] to [3], which has a molecular weight distribution of 2.0 or less.
[5] The oxyalkylene polymer (A) according to any one of [1] to [4], which has more than 0 reactive silicon groups per terminal group on average.
[6] A curable composition comprising the oxyalkylene polymer (A) according to any one of the above [1] to [5] and a curing catalyst.
[7] The active hydrogen-containing group in the terminal group of the following oxyalkylene polymer (B) and the active hydrogen-containing group in the terminal group of the following oxyalkylene polymer (C) are reacted with a polyisocyanate having a molecular weight of 100 to 20,000. The following oxyalkylene polymer (D) is obtained, and then the unsaturated group present in the terminal group of the oxyalkylene polymer (D) and the unsaturated group present in the main chain are represented by the above formula 1. The method for producing an oxyalkylene polymer (A) according to [5], which comprises reacting with a silylating agent having a reactive silicon group.
Oxyalkylene polymer (B): A polymer having an unsaturated group, an active hydrogen-containing group and a polyoxyalkylene chain, which has one terminal group having more than 0 unsaturated groups on average, and the above-mentioned A polymer having one terminal group having more than 0 and 1.0 or less active hydrogen-containing groups on average.
Oxyalkylene polymer (C): A polymer having an initiator residue having an unsaturated group, an active hydrogen-containing group and a polyoxyalkylene chain, which has the initiator residue in the main chain and said. A polymer having 2 to 4 terminal groups having an average number of active hydrogen-containing groups of more than 0 and 1.0 or less.
Oxyalkylene polymer (D): a main chain having a polyoxyalkylene chain, an unsaturated group present in the main chain, a urethane bond present in the main chain, and a weight having an unsaturated group present in the terminal group. A polymer that is a coalescence and has an average of more than 0 unsaturated groups per terminal group.
[8] The oxyalkylene polymer (B) is an oxyalkylene polymer obtained by subjecting a cyclic ether to a ring-opening addition polymerization reaction with an initiator (b), and the initiator (b) is 1 in one molecule. The method for producing the oxyalkylene polymer (A) according to [7], which is a compound having one or more unsaturated groups and one active hydrogen-containing group in one molecule.
[9] The method for producing an oxyalkylene polymer (A) according to [8], wherein the initiator (b) is a compound represented by the following formula 2.

In the above formula 2, R ¹ is an active hydrogen-containing group, R ² is a hydrogen atom or a methyl group, R ⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. A divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, R ⁶ may contain an oxygen atom or a nitrogen atom, and an oxygen atom or an atom adjacent to the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. A monovalent hydrocarbon group of 20, a hydrogen atom, or a group represented by -R ⁶² -CR ⁶¹ = CH ₂ , R ⁶¹ is a hydrogen atom or a methyl group, and R ⁶² is an oxygen atom or a nitrogen atom. It may be contained, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and the two ^R6s are the same but different. Often, n is an integer from 0 to 10.
[10] The oxyalkylene polymer (C) is an oxyalkylene polymer obtained by subjecting a cyclic ether to a ring-opening addition polymerization reaction with an initiator (c), and the initiator (c) is 1 in one molecule. The oxyalkylene polymer (A) according to any one of [7] to [9], which is a compound having four or more unsaturated groups and having 2 to 4 active hydrogen-containing groups in one molecule. Production method.
[11] The initiator (c) is an initiator (c1) having one or more unsaturated groups in one molecule and two active hydrogen-containing groups in one molecule. 10] Method for producing the oxyalkylene polymer (A).
[12] The method for producing the oxyalkylene polymer (A) according to [11], wherein the initiator (c1) is a compound represented by the following formula 3.

In the above formula 3, R ¹¹¹ is an active hydrogen-containing group, R ¹¹² is a hydrogen atom or a methyl group, R ¹¹⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. It is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, and R ¹¹⁶ may contain an oxygen atom or a nitrogen atom, and an oxygen atom or an atom adjacent to the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. A monovalent hydrocarbon group of 20, a hydrogen atom, or a group represented by -R ¹⁷² -CR ¹⁷¹ = CH ₂ , R ¹⁷¹ is a hydrogen atom or a methyl group, and R ¹⁷² is an oxygen atom or a nitrogen atom. It may be contained, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, a is an integer of 0 to 10, and a plurality of R ^111s . -The groups represented by (CH ₂ ) _a -may be the same or different.
[13] The cyclic ether of [8] to [12], wherein the cyclic ether comprises at least one cyclic ether selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. A method for producing any of the oxyalkylene polymers (A).
[14] The method for producing an oxyalkylene polymer (A) according to any one of [8] to [13], wherein the ring-opening addition polymerization reaction is carried out in the presence of a composite metal cyanide complex catalyst.
[15] The method for producing an oxyalkylene polymer (A) according to any one of [7] to [14], wherein the oxyalkylene polymer (D) has a number average molecular weight of 3,000 to 100,000.

According to the present invention, it is possible to provide an oxyalkylene polymer as a raw material for a cured product having excellent strength, a curable composition containing the oxyalkylene polymer, and a method for producing the oxyalkylene polymer.

The meanings and definitions of the terms in the present specification are as follows.
The numerical range represented by "-" means a numerical range in which the numerical values before and after "-" are the lower limit value and the upper limit value.
The "polymer" means a substance having a number average molecular weight of 1,000 or more.
By "compound" is meant a substance having a number average molecular weight of less than 1,000. The molecular weight of the compound is the number average molecular weight in the gel permeation chromatography (hereinafter referred to as GPC) measurement described later. The molecular weight of a substance having no molecular weight distribution in GPC measurement is the formula weight of the compound.
The "oxyalkylene polymer" means a polymer having a polyoxyalkylene chain formed from a unit based on a cyclic ether.
The "active hydrogen-containing group" is at least one selected from the group consisting of a hydroxyl group bonded to a carbon atom, a carboxy group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, and a sulfanyl group. It is the basis of the seed.
The "active hydrogen" is a hydrogen atom based on the active hydrogen-containing group and a hydrogen atom based on a hydroxyl group of water.
An "initiator" is a compound having an active hydrogen-containing group.
The "initiator residue" is a residue obtained by removing active hydrogen from the initiator.
The "silylating agent" is a compound capable of reacting with an unsaturated group to introduce a reactive silicon group.

The "silylation rate" of an oxyalkylene polymer having a reactive silicon group is the ratio of the number of reactive silicon groups to the total number of reactive silicon groups and unsaturated groups contained in the terminal groups of the polymer.
The number of reactive silicon groups contained in the terminal groups of the polymer can be measured by the internal standard method of ¹ H-NMR.
The number of unsaturated groups contained in the terminal groups of the polymer can be measured by iodine value titration according to JIS K0070: 1992.
The number of hydroxyl groups contained in the terminal group of the polymer can be measured by a titration method (based on JIS K1557: 2007) in which the hydroxyl groups are esterified with a pyridine solution of phthalic anhydride and a sodium hydroxide (NaOH) solution is used.
The number of active hydrogen-containing groups other than hydroxyl groups contained in the terminal groups of the polymer can be measured by the internal standard method of ¹ H-NMR.

The number average molecular weight (hereinafter referred to as “Mn”) and the mass average molecular weight (hereinafter referred to as “Mw”) are polystyrene-equivalent molecular weights obtained by GPC measurement. The molecular weight distribution is a value calculated from Mw and Mn, and is a ratio of Mw to Mn (hereinafter, referred to as “Mw / Mn”).

In the oxyalkylene polymer of the present embodiment (hereinafter referred to as "polymer (A)"), the total of the reactive silicon groups and unsaturated groups represented by the following formula 1 is averaged per one terminal group. More than zero, it has the reactive silicon groups and urethane bonds in the backbone.

<Reactive silicon group>
The reactive silicon group is represented by the following formula 1.
-SiX _a R _3-a formula 1
In the above formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms. R does not contain hydrolytic groups.
Examples of R include a hydrocarbon group, a halohydrocarbon group and a triorganosyloxy group.

As R, an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group and a triorganosyloxy group are preferable. At least one selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a 1-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group and a triphenylsiloxy group. Is more preferable. A methyl group or an ethyl group is preferable from the viewpoint of good curability of the polymer having a reactive silicon group and stability of the curable composition. A 1-chloromethyl group is preferable because the curing rate of the cured product is high. Methyl groups are particularly preferred because they are readily available.

In the above formula 1, X represents a hydroxyl group, a halogen atom or a hydrolyzable group. A hydrolyzable group is a group that can react with water to form a silanol group.
Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group and an alkenyloxy group.
As X, an alkoxy group is preferable because it is mildly hydrolyzable and easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, a siloxane bond is rapidly formed, a crosslinked structure is easily formed in the cured product, and the physical properties of the cured product become better.

In the above equation 1, a represents an integer of 1 to 3. When a is 1, R may be the same or different from each other. When a is 2 or more, X may be the same as or different from each other.
a is preferably 1 or 2, and a is more preferably 2.

Examples of the reactive silicon group represented by the above formula 1 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group and a dimethoxymethylsilyl group. Examples thereof include a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a diisopropoxymethylsilyl group, a chloromethyldimethoxysilyl group and a chloromethyldiethoxysilyl group. From the viewpoint of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group and a diethoxymethylsilyl group are preferable, and a dimethoxymethylsilyl group and a trimethoxysilyl group are more preferable.

<Polymer (A)>
The polymer (A) consists of a main chain and a terminal group. The main chain of the polymer (A) contains a residue obtained by removing the isocyanate group from the polyisocyanate, a polyoxyalkylene chain, and a urethane bond connecting the residue and the polyoxyalkylene chain, and the terminal group is , A terminal group containing an oxygen atom closest to the molecular terminal of the polymer (A) (hereinafter, also referred to as “terminal oxygen atom”) among the oxygen atoms of the polyoxyalkylene chain.
Examples of the cyclic ether include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, and cyclic ethers other than alkylene oxides such as tetrahydrofuran. As the cyclic ether, alkylene oxide is preferable, ethylene oxide and propylene oxide are more preferable, and propylene oxide is particularly preferable.
The polyoxyalkylene chain may be a copolymer chain having two or more kinds of oxyalkylene groups, and in that case, the copolymer chain may be a block copolymer chain or a random copolymer chain.
Examples of the polyoxyalkylene chain contained in the polymer (A) include a polyoxypropylene chain, a polyoxyethylene chain, a poly (oxy-2-ethylethylene) chain, a poly (oxy-1,2-dimethylethylene) chain, and a poly (. Examples thereof include an oxytetramethylene) chain, a poly (oxyethylene / oxypropylene) chain, and a poly (oxypropylene / oxy-2-ethylethylene) chain. As the polyoxyalkylene chain, a polyoxypropylene chain and a poly (oxyethylene / oxypropylene) chain are preferable, and a polyoxypropylene chain is particularly preferable.

The Mn of the polymer (A) is preferably 3,000 to 100,000, more preferably 3,500 to 75,000, and even more preferably 4,000 to 60,000. When Mn is at least the lower limit of the above range, the amount of reactive silicon groups introduced can be suppressed, which is advantageous in terms of manufacturing cost, and when it is at least the upper limit, the viscosity can be suppressed, which is convenient in terms of workability. Tends to be good.
The molecular weight distribution of the polymer (A) is not particularly limited, but is preferably narrow, more preferably 2.0 or less, further preferably 1.5 or less, and particularly preferably 1.4 or less. When the molecular weight distribution is not more than the upper limit value, the stretchable physical properties of the cured product are likely to be improved.
The viscosity of the polymer (A) at 25 ° C. is preferably 0.1 to 100,000 Pa · s, more preferably 0.3 to 10,000 Pa · s, still more preferably 0.4 to 100 Pa · s. If it is within the above range, the workability is better.

The polymer (A) has an average of more than 0 reactive silicon groups and unsaturated groups per terminal group. The average number of the total number of the reactive silicon groups and unsaturated groups in one terminal group of the polymer (A) is preferably 1.2 to 8.0 from the viewpoint of improving the strength of the cured product. More preferably, 1.5 to 3.0 pieces.

The number of terminal groups of the polymer (A) is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6.

The polymer (A) has a urethane bond in the main chain, and the content of the urethane bond with respect to the total amount of the polymer (A) is 0.1 to 10 mass by mass from the viewpoint of improving the strength of the cured product. % Is preferable, and 0.5 to 5% by mass is more preferable.
The position of the urethane bond in the polymer (A) can be clarified by using GPC, NMR or the like after dissociating the urethane bond by the analysis method described in JP-A-2000-227430 or JP-A-2001-141726. .. The urethane bond content with respect to the total amount of the polymer (A) is the isocyanate group contained in the polyisocyanate when the type and amount of the polyisocyanate used in producing the polymer (A) are known. It can be calculated by the following formulas A and B, assuming that all of them form a urethane bond (molecular weight 59).

Urethane bond content (unit: mass%) = W (U) / W (A) × 100 ... Formula A
W (U) = (Mi × 59) + (R (U) × W (P)) ... Equation B
Mi: Total number of moles of isocyanate groups present in the polyisocyanate used to produce the polymer (A) (unit: mol)
R (U): Ratio of urethane bonds to the total amount of polyisocyanate used in the production of the polymer (A) (unit: mass%)
W (P): Mass of polyisocyanate used for producing the polymer (A) (unit: g)
W (A): Total mass of polymer (A) (unit: g)

When two or more kinds of polyisocyanates are used for the production of the polymer (A), W (U) is calculated from the above formula B for each polyisocyanate, and the sum thereof is taken as W (U). Therefore, the content of urethane bonds can be calculated.

The polymer (A) has a reactive silicon group in the backbone. The reactive silicon group in the backbone is bonded to the carbon atom in the backbone via a divalent linking group. The atom constituting the divalent linking group may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom, which is a divalent hydrocarbon group having 1 to 20 carbon atoms or a single bond. Is preferable.
The position of the reactive silicon group in the polymer (A) can be clarified by using GPC, NMR or the like after dissociating the urethane bond by the analysis method described in JP-A-2000-227430 or JP-A-2001-141726. ..
Specifically, when the urethane bond is dissociated, the polymer (A) is composed of a polyoxyalkylene chain containing a terminal group, a polyoxyalkylene chain not containing a terminal group, a molecular chain containing an initiator residue, and a polyisocyanate. It is divided into groups derived from residues excluding isocyanate groups. Since the polyoxyalkylene chain containing a terminal group and the polyoxyalkylene chain not containing a terminal group have different molecular weights in terms of GPC measurement, the position of the silicon group can be specified by preparatively and NMR analysis of each.
The content of the reactive silicon groups present in the main chain of the polymer (A) is preferably 0.5 to 4 on average, and more preferably 0.5 to 2 per molecule.
The content of the reactive silicon group present in the main chain of one molecule of the polymer (A) is determined by dissociating the urethane bond by the analysis method described in JP-A-2000-227430 or JP-A-2001-141726. , Can be calculated by performing the above ¹ H-NMR internal standard method.

The polymer (A) is an oxyalkylene polymer having an average of more than 0 reactive silicon groups per terminal group, and having a urethane bond and a reactive silicon group in the main chain (hereinafter referred to as oxyalkylene polymer). , "Polymer (E)"), having an average of more than 0 unsaturated groups per terminal group, urethane bonds and unsaturated groups in the main chain, said reactivity. An oxyalkylene polymer having no silicon group (hereinafter referred to as “polymer (D)”) can be exemplified.

<Polymer (E)>
The polymer (E) has an average of more than 0 reactive silicon groups per terminal group. The average number of the reactive silicon groups per terminal group of the polymer (E) is preferably 1.2 to 8.0, preferably 1.5 to 3, from the viewpoint of improving the strength of the cured product. .0 is more preferable.
When the polymer (E) has an unsaturated group at the terminal group, the average number of unsaturated groups per terminal group of the polymer (E) is 0. The number is preferably 02 to 1.6, more preferably 0.03 to 1.2.

The polymer (E) includes a polymer represented by the following formula 3-1 (excluding the polymer represented by the following formula 3-2) or a polymer represented by the following formula 3-2. preferable.

R ²⁰ -([ _Au / B _z ] -X) _s -expression 3-1
In the above formula 3-1 X is a monovalent group represented by the following formula 4 or 5, B is a divalent group represented by the following formula 6 or 7, and R ²⁰ has Mn of 100 to 100. It is a residue obtained by removing s isocyanate groups from 20,000 polyisocyanates, and A is-[NHC (= O)-(OR ⁵⁰ ) _t -OC (= O) NH-R ²¹ ]-. Representing a divalent group represented, R ²¹ is a residue obtained by removing two isocyanate groups from a polyisocyanate having Mn of 100 to 20,000, and R ⁵⁰ is an alkylene group having 2 to 4 carbon atoms. Shown, s is an integer of 2 to 4, u is an integer of 0 to 5, z is an integer of 1 to 5, t is an integer of 10 to 900, and a plurality of Xs are the same or different from each other. You may. [A _u / B _z ] indicates that the sequence order of -A- and -B- is arbitrary. (OR ⁵⁰ ) is, for example, a polyoxyalkylene chain formed by ring-opening polymerization of cyclic ether.

X-R ^21- [ _Au / B _z ] -X formula 3-2
In the above formula 3-2, X is a monovalent group represented by the following formula 4 or 5, B is a divalent group represented by the following formula 6 or 7, and R ²¹ has Mn of 100. It is a residue obtained by removing 2 isocyanate groups from ~ 20,000 polyisocyanates, and A is-[NHC (= O)-(OR ⁵⁰ ) _t -OC (= O) NH-R ²¹ ]-. Indicates a divalent group represented by, R ⁵⁰ represents an alkylene group having 2 to 4 carbon atoms, u is an integer of 0 to 5, z is an integer of 1 to 5, and t is an integer of 10 to 900. It is an integer of, and a plurality of Xs may be the same as or different from each other. [A _u / B _z ] indicates that the sequence order of -A- and -B- is arbitrary. (OR ⁵⁰ ) is, for example, a polyoxyalkylene chain formed by ring-opening polymerization of cyclic ether.

u is preferably 0 to 3, more preferably 0 or 1. z is preferably 1 to 3, more preferably 1 or 2. t is preferably 20 to 650, more preferably 30 to 500.

^R20 is, for example, a residue obtained by removing s isocyanate groups from a polyisocyanate having Mn of 100 or more and less than 1,000, or a polyisocyanate having Mn of 1,000 to 20,000 excluding s isocyanate groups. Is a residue. s is preferably 2 to 4, more preferably 2 to 3, and even more preferably 2.
Examples of the polyisocyanate having Mn of 100 or more and less than 1,000 include aromatic polyisocyanate, aralkyl polyisocyanate, aliphatic polydiisocyanate, alicyclic polyisocyanate, and various modified products (having two isocyanate groups) of these polyisocyanates. Denatured product). Two or more kinds of polyisocyanates can be used in combination.
Examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 3,5-tolylene diisocyanate. Examples thereof include p-phenylenediocyanate, 1,5-naphthalenediocyanate, and polymethylene polyphenylene polyisocyanate (crude MDI).
Examples of the aralkyl polyisocyanate include xylylene diisocyanate and tetramethylxylylene diisocyanate.
Examples of the aliphatic polydiisocyanate include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate.
Examples of the alicyclic polydiisocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and the like.
Examples of the polyisocyanate having Mn of 1,000 to 20,000 include an isocyanate-terminated urethane prepolymer obtained by reacting a polyoxyalkylene polyol and a polyisocyanate with an index of more than 100 and an index of 200 or less. The number average molecular weight of the isocyanate-terminated urethane prepolymer can be adjusted by adjusting the index, which is the ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyoxyalkylene polyol, and the index is preferably more than 100 and 120 or less.
As the polyoxyalkylene chain in the polyoxyalkylene polyol, the same as the above-mentioned polymer (A) can be exemplified, and the preferred embodiment is also the same.
The Mn of the polyoxyalkylene polyol used for the isocyanate-terminated urethane prepolymer is preferably 1,000 to 20,000, preferably 200 to 10,000, in that the viscosity of the obtained polymer can be easily adjusted in an appropriate range. More preferred. The Mw / Mn of the polyoxyalkylene polyol is not particularly limited, but is preferably narrow, more preferably 2.0 or less, further preferably 1.5 or less, and particularly preferably 1.4 or less. When the molecular weight distribution is not more than the upper limit value, the stretchable physical properties of the obtained cured product are likely to be improved.
Examples of the polyisocyanate having Mn of 1,000 or more include urethane prepolymers described in paragraphs 0016 to 0030 of International Publication No. 2019-240046 and paragraphs 0125 to 0130 of JP-A-2017-2060602.

R ²¹ is the same as R ²⁰ except that s is 2, and the preferred embodiment is also the same.

前記式４中、Ｒ^１１は酸素原子、硫黄原子、前記式４中の－（ＣＨ_２）_ｍ―と結合する原子が炭素原子である－Ｃ（＝Ｏ）Ｏ－で表される２価の基、又は－Ｎ（Ｒ^１０）－で表される２価の基であり、Ｒ^１０は水素原子又は炭素数１～１０の１価の炭化水素基であり、Ｒ^１２は水素原子又はメチル基であり、Ｒ^１４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^１５は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^１７－ＣＨＲ^１８－ＣＨ_２－^ｒＳｉで表される基であり、Ｒ^１８は水素原子又はメチル基であり、Ｒ^１７は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^５０は前記式３－１、３－２と同様であり、^ｒＳｉは反応性ケイ素基を示し、複数のＲ^１５、Ｒ^５０、^ｒＳｉはそれぞれ互いに同一でも異なってもよく、ｍは０～１０の整数であり、ｑは１０～９００の整数である。

In the above formula 4, R ¹¹ is an oxygen atom, a sulfur atom, and the atom bonded to- (CH ₂ ) _m -in the above formula 4 is a carbon atom-C (= O) O-, which is a divalent atom. A group or a divalent group represented by -N (R ¹⁰ )-, R ¹⁰ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹² is a hydrogen atom or a methyl group. R ¹⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and R ¹⁵ May contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom, which is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or -R ¹⁷ -CHR ¹⁸ -CH. A group represented by ₂ - ^rSi , R ¹⁸ is a hydrogen atom or a methyl group, R ¹⁷ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. It is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, ^R50 is the same as that of the above formulas 3-1 and 3-2, ^rSi is a reactive silicon group, and a plurality of ^R15 , R ⁵⁰ and ^r Si may be the same or different from each other, and m is an integer of 0 to 10 and q is an integer of 10 to 900.

m is preferably 0 to 8, more preferably 1 to 7, and even more preferably 1 to 6.
R ¹⁰ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. The monovalent hydrocarbon group of R ¹⁰ has preferably 1 to 9 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
The carbon number of R ¹⁰ includes the carbon number of the substituent when R ¹⁰ has a substituent having a carbon atom.
As R ¹¹ , a divalent group represented by an oxygen atom or a divalent group represented by —C (= O) O— in which the atom bonded to − (CH ₂ ) _m − in the above formula 4 is a carbon atom is preferable, and an oxygen atom. Is more preferable.

The carbon number of R ¹⁵ includes the carbon number of the substituent when R ¹⁵ has a substituent having a carbon atom.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ¹⁵ include an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group. The alkyl group and alkenyl group may be linear or branched.

As the alkyl group, an alkyl group having 1 to 18 carbon atoms is preferable.
The linear alkyl group includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group and n. Examples thereof include a decyl group, an n-undecyl group, a lauryl group and a stearyl group, and a methyl group and an ethyl group are preferable. The branched alkyl group has a structure in which a hydrogen atom in the linear alkyl group (excluding the hydrogen atom in the terminal carbon) is substituted with an alkyl group. Examples of the alkyl group as the substituent include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group and an n-heptyl. The group can be exemplified, and a methyl group, an ethyl group, and an n-propyl group are preferable.
The alkyl group may be an alkyl group having a cycloalkane structure. Examples of the alkyl group having a cycloalkane structure include a monovalent group in which the methylene group in the linear or branched alkyl group is replaced with a cycloalkylene group. As the cycloalkylene group, a divalent group obtained by removing one hydrogen atom from the cycloalkyl group described later can be exemplified.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group and a cyclodecyl group, and a cyclohexyl group and a cyclopentyl group are preferable. It may have a structure in which a hydrogen atom in a cycloalkyl group is substituted with an alkyl group. The alkyl group as a substituent includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group and an n-heptyl group. Can be exemplified, and a methyl group, an ethyl group, and an n-propyl group are preferable.

Examples of the alkenyl group include those in which the single bond between any one carbon atom of the alkyl group is replaced with a double bond.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, and an anthryl group. It may have a structure in which a hydrogen atom in an aryl group is substituted with an alkyl group. The alkyl group as a substituent includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group and an n-heptyl group. Can be exemplified, and a methyl group, an ethyl group, and an n-propyl group are preferable.

The total number of oxygen atoms and nitrogen atoms in R15 is preferably ⁵ or less, more preferably 3 or less, and even more preferably 1 or less. The atom in R ¹⁵ that is directly bonded to the carbon atom adjacent to R ¹⁴ and R ¹⁵ in the above formula 4 is preferably a carbon atom.

The monovalent hydrocarbon group having ¹ to 20 carbon atoms containing the oxygen atom of R15 has an alkoxy group, a monovalent group in which the hydrogen atom in the alkyl group is replaced with an alkoxy group, and the cycloalkane structure. Examples thereof include monovalent groups in which the hydrogen atom in the alkyl group is substituted with an alkoxy group, and specifically, -OCH ₃ , -O-CH ₂ -CH ₃ , -O- (CH ₂ ) ₂ -CH ₃ , -O- (CH ₂ ) ₃ -CH ₃ , -OCH (CH ₃ ) ₂ , -CH ₂ -O-CH ₃ ,-(CH ₂ ) ₂ -O-CH ₃ ,-(CH ₂ ) ₃ -O -CH ₃ , -CH (CH ₃ ) CH ₂ -O-CH ₃ ,-(CH ₂ ) ₄ -O-CH ₃ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₃ ,-(CH ₂ ) ₅ -O-CH ₃ ,-(CH ₂ ) ₆ -O-CH ₃ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₃ , -CH ₂ -O-CH ₂ -CH ₃ ,-( CH ₂ ) ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ₃ -O-CH ₂ -CH ₃ , -CH (CH ₃ ) CH ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ₄ -O-CH ₂ -CH ₃ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ₅ -O-CH ₂ -CH ₃ ,-(CH ₂ ) _6- Examples thereof include O-CH ₂ -CH ₃ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH ₃ , and the like. In the above example, -C ₆ H _10- means a cyclohexylene group, and so on.

Examples of the monovalent hydrocarbon group having 1 to ²⁰ carbon atoms containing the nitrogen atom of R15 include -CH ₂ -NH-CH ₃ and -CH ₂ -N (CH ₃ ) ₂ .

R ¹⁵ is represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monovalent group represented by -CH ₂ -O-CH ₃ , or -R ¹⁷ -CHR ¹⁸ -CH ₂ - ^r Si. A monovalent group is preferable, a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 1 to 18 carbon atoms, and a monovalent group represented by _−CH2 -O— _CH3 . , Or -R ¹⁷ -CHR ¹⁸ -CH ₂ - ^r Si, monovalent groups are more preferred, hydrogen atoms, linear alkyl groups with 1-18 carbon atoms, or -R ¹⁷ -CHR ¹⁸ -CH. A monovalent group represented by ₂ - ^r Si is more preferable, and a linear alkyl group having 1 to 6 carbon atoms or a monovalent group represented by -R ¹⁷ -CHR ¹⁸ -CH ₂ - ^r Si is preferable. More preferably, a linear alkyl group having 1 to 4 carbon atoms or a monovalent group represented by -R ¹⁷ -CHR ¹⁸ -CH ₂ - ^r Si is particularly preferable, and a methyl group, an ethyl group, a propyl group, or a propyl group, or -R ¹⁷ -CHR ¹⁸ -CH ₂ - ^r A monovalent group represented by Si is particularly preferable.

R ¹⁸ is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms of R ¹⁷ include an alkylene group, a cycloalkylene group, an alkaneylene group and an arylene group. Examples of the alkylene group, cycloalkylene group, ^alkenylene group, and arylene group include a linear alkyl group, a cycloalkyl group, a linear alkenyl group, and a divalent group obtained by removing one hydrogen atom from an aryl group. Can be exemplified. The alkylene group and the alkenylene group may be linear or branched.

R ¹⁷ may have a substituent, and examples of the substituent include alkyl groups having 1 to 10 carbon atoms. The carbon number of R ¹⁷ includes the carbon number of the substituent when R ¹⁷ has a substituent having a carbon atom.

R ¹⁷ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. The total number of oxygen atoms and nitrogen atoms in R ¹⁷ is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less. The atom in R ¹⁷ that directly bonds to the carbon atom adjacent to R ¹⁵ and R ¹⁴ in the above formula 4 is preferably a carbon atom.

As the divalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ¹⁷ , one hydrogen atom is removed from the monovalent hydrocarbon group having 1 to 20 carbon atoms including the oxygen atom exemplified in R ¹⁵ . An example is a divalent group.
As the divalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ¹⁷ , one hydrogen atom is removed from the monovalent hydrocarbon group having 1 to 20 carbon atoms including the nitrogen atom exemplified in R ¹⁵ . An example is a divalent group.

As R ¹⁷ , an alkylene group having 1 to 18 carbon atoms, an alkylene group having 1 to 18 carbon atoms including an oxygen atom, and a cycloalkylene group having 1 to 18 carbon atoms are preferable, and an alkylene group having 1 to 10 carbon atoms or an oxygen atom. An alkylene group having 1 to 10 carbon atoms including the above is more preferable, and an alkylene group having 1 to 6 carbon atoms or an alkylene group having 1 to 6 carbon atoms containing one oxygen atom is further preferable.

The groups represented by -R ¹⁷ -CHR ¹⁸ -CH ₂ - ^r Si are -OCH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -O- (CH ₂ ) ₃ - ^r Si, -O. -(CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -O- (CH ₂ ) ₄ - ^r Si, -O- (CH ₂ ) ₃ -CH (CH ₃ ) -CH ₂ - ^r Si _, -O- (CH ₂ ) ₅ - ^r Si, -O- (CH ₂ ) ₄ -CH (CH ₃ ) -CH ₂ - ^r Si, -O- (CH ₂ ) ₆ - ^r Si, -OC ( CH ₃ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -OC (CH ₃ ) _2- (CH ₂ ) ₂ - ^r Si, -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₃ -- ^r Si,-(CH ₂ ) ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₃ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₃ ^-R Si, -CH (CH ₃ ) CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₃ - ^r Si, -(CH ₂ ) ₄ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) ₃ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₅ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₅ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₆ -O-CH ₂ -CH (CH ₃ )- CH ₂ - ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₃ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₃ - ^r Si, -CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ) ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₄ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) _2- CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) ₄ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -CH (CH 2) CH ₃ ) -CH ₂ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -CH (CH ₃ ) ) -CH ₂ - ^r Si,-(CH ₂ ) ₅ -O- (CH ₂ ) ₄ -- ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH _2- ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₄ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH _2- ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₄ - ^r Si can be exemplified, -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si, -(CH ₂ ) ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₃ - ^r Si are preferable. , -CH ₂ -O- (CH ₂ ) ₃ - ^r Si or-(CH ₂ ) ) ₂ -O- (CH ₂ ) ₃ - ^rSi is more preferable.

R ¹² is the same as R ¹⁸ described above, and the preferred embodiment is also the same.
R ¹⁴ is the same as R ¹⁷ described above, and the preferred embodiment is also the same.
The group represented by -R ¹⁴ -CHR ¹² -CH ₂ - ^r Si is the same as the group represented by -R ¹⁷ -CHR ¹⁸ -CH ₂ - ^r Si described above, and the preferred embodiment is also the same.

q is preferably 10 to 900, more preferably 20 to 650, and even more preferably 30 to 500.

前記式５中、Ｒ^３２は水素原子又はメチル基であり、Ｒ^３４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^３５は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^３７－ＣＨＲ^３８－ＣＨ_２－^ｒＳｉで表される基であり、Ｒ^３８は水素原子又はメチル基であり、Ｒ^３７は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^５０、^ｒＳｉ、ｑは前記式４と同様であり、複数のＲ^５０、^ｒＳｉはそれぞれ互いに同一でも異なってもよい。

In the above formula 5, R ³² is a hydrogen atom or a methyl group, R ³⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. It is a valent hydrocarbon group or a single bond, and ^R35 may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom and is a monovalent hydrocarbon group having 1 to 20 carbon atoms. , A hydrogen atom, or a group represented by -R ³⁷ -CHR ³⁸ -CH ₂ - ^r Si, R ³⁸ is a hydrogen atom or a methyl group, R ³⁷ may contain an oxygen atom or a nitrogen atom, and oxygen. The atom adjacent to the atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and ^R50 , ^rSi , and q are the same as in the above formula 4, and a plurality of Rs are used. ⁵⁰ , ^rSi may be the same as or different from each other.

The carbon number of the divalent hydrocarbon group of R ³⁴ is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less. The carbon number of R ³⁴ includes the carbon number of the substituent when R ³⁴ has a substituent having a carbon atom.

Examples of the divalent hydrocarbon group of R ³⁴ include an alkylene group, a cycloalkylene group, an alkenylene group and an arylene group, and an alkylene group and a cycloalkylene group are preferable, and an alkylene group is more preferable. The alkylene group and the alkenylene group are linear or branched.

Examples of the alkylene group, the cycloalkylene group, the alkenylene group, and the arylene group are the same as those of ^R17 .

The total number of oxygen atoms and nitrogen atoms in R ³⁴ is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less. The atom in R ³⁴ that directly bonds with the nitrogen atom in the formula 5 is preferably a carbon atom.

The groups represented by -R ³⁴ CHR ³² -CH ₂ - ^r Si are -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ). ₃ - ^r Si,-(CH ₂ ) ₂ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ -- ^r Si,-(CH) ₂ ) ₃ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₃ - ^r Si, -CH (CH ₃ ) CH ₂ -O- CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₄ -O-CH ₂ -CH (CH) ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) ₃ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH ₂ ^-R Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₅ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si,- (CH ₂ ) ₅ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₆ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₃ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si, -CH ₂ -C ₆ H ₁₀ -CH _2- O- (CH ₂ ) ₃ - ^r Si, -CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₄ - ^r Si, -(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₃ -O- (CH ₂ ) ₄ - ^r Si, -CH (CH ₃ ) CH ₂ -O -(CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₄ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH 2) ₂ ) ₄ -O- (CH ₂ ) ₄ - ^r Si, -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -C (CH ₃ ) ) ₂ CH ₂ -O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) _5- O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₆ -O- (CH ₂ ) ) ₄ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -C ₆ H ₁₀ -CH _2- O- (CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₄ - ^r Si,-(CH ₂ ) ₅ - ^r Si can be exemplified, and -CH ₂ -O- CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si,-(CH ₂ ) ₂ -O-CH ₂ -CH (CH ₃ ) -CH _2- ^r Si,-(CH ₂ ) ₃ -O-CH ₂ -CH (CH ₃ ) -CH ₂ - ^r Si, -CH ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ) ₃ -O- (CH ₂ ) ₃ - ^r Si,-(CH ₂ ) ₃ - ^r Si is preferred, -CH ₂ -O- (CH ₂ ) ₃ - ^r Si or-(CH ₂ ) ₂ -O- (CH ₂ ) ₃ - ^rSi or-( _CH2 ) ₃ - ^rSi is more preferred.

When R ³⁵ has a substituent having a carbon atom, the carbon number of the substituent is included.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of ^R35 include an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group. The alkyl group and alkenyl group may be linear or branched.
Examples of the alkyl group, the cycloalkyl group, the alkenyl group, and the aryl group are the same as those of ^R15 .

The monovalent hydrocarbon group having 1 to 20 carbon atoms of ^R35 may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. The total number of oxygen atoms and nitrogen atoms in ^R35 is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom include a monovalent group in which a hydrogen atom in an alkyl group is substituted with an alkoxy group, and a hydrogen atom in the alkyl group having a cycloalkane structure. Examples include monovalent groups substituted with alkoxy groups, specifically -CH ₂ -O-CH ₃ ,-(CH ₂ ) ₂ -O-CH ₃ ,-(CH ₂ ) ₃ -O-CH. ₃ , -CH (CH ₃ ) CH ₂ -O-CH ₃ ,-(CH ₂ ) ₄ -O-CH ₃ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₃ ,-(CH ₂ ) _5- O-CH ₃ ,-(CH ₂ ) ₆ -O-CH ₃ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₃ , -CH ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ) ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ₃ -O-CH ₂ -CH ₃ , -CH (CH ₃ ) CH ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) _4- O-CH ₂ -CH ₃ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ₅ -O-CH ₂ -CH ₃ ,-(CH ₂ ) ₆ -O- CH ₂ -CH ₃ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH ₃ , and the like can be mentioned. In the above example, -C ₆ H _10- means a cyclohexylene group, and so on.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms containing a nitrogen atom include -CH ₂ -NH-CH ₃ and -CH ₂ -N (CH ₃ ) ₂ .

R ³⁵ is represented by a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monovalent group represented by -CH ₂ -O-CH ₃ , or -R ³⁷ -CHR ³⁸ -CH ₂ - ^r Si. A monovalent group is preferable, a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 1 to 18 carbon atoms, and a monovalent group represented by _−CH2 -O— _CH3 . , Or -R ³⁷ -CHR ³⁸ -CH ₂ - ^r Si, monovalent groups are more preferred, hydrogen atoms, linear alkyl groups with 1-18 carbon atoms, or -R ³⁷ -CHR ³⁸ -CH. A monovalent group represented by ₂ - ^r Si is more preferable, and a linear alkyl group having 1 to 6 carbon atoms or a monovalent group represented by -R ³⁷ -CHR ³⁸ -CH ₂ - ^r Si is further preferable. Preferably, a linear alkyl group having 1 to 4 carbon atoms or a monovalent group represented by -R ³⁷ -CHR ³⁸ -CH ₂ - ^r Si is particularly preferable, and a methyl group, an ethyl group, a propyl group, or- A monovalent group represented by R ³⁷ -CHR ³⁸ -CH ₂ - ^r Si is particularly preferred.

R ³⁷ is the same as R ³⁴ described above, and the preferred embodiment is also the same.
R ³⁸ is the same as R ³² described above, and the preferred embodiment is also the same.

前記式６中、Ｒ^１３１及びＲ^１４１はそれぞれ独立に酸素原子、硫黄原子、前記式６中の－（ＣＨ_２）_ｖ－又は－（ＣＨ_２）_ｗ－と結合する原子が炭素原子である－Ｃ（＝Ｏ）Ｏ－で表される２価の基、又は－Ｎ（Ｒ^１４０）－で表される２価の基であり、Ｒ^１４０は水素原子又は炭素数１～１０の１価の炭化水素基であり、Ｒ^１３２は水素原子又はメチル基であり、Ｒ^１３４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^１３５は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^１３７－ＣＨＲ^１３８－ＣＨ_２－^ｒＳｉで表される基であり、Ｒ^１３８は水素原子又はメチル基であり、Ｒ^１３７は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^５０は炭素数２～４のアルキレン基を示し、^ｒＳｉは反応性ケイ素基を示し、Ｒ^１３９は、ポリイソシアネートからイソシアネート基を２個除いた残基であり、ｖは０～１０の整数であり、ｗは０～１０の整数であり、ｘは５～５００の整数であり、ｙは５～５００の整数である。複数のＲ^５０は同一でも異なってもよい。
重合体（Ｅ）の１分子中に、式６で表される－Ｂ－が複数存在するとき、複数のＲ^１３１、Ｒ^１３２、Ｒ^１３４、Ｒ^１３５、Ｒ^１３９、Ｒ^１４１、Ｒ^５０、^ｒＳｉはそれぞれ互いに同一でも異なってもよい。

In the above formula 6, R ¹³¹ and R ¹⁴¹ are independent oxygen atoms and sulfur atoms, and the atom bonded to-(CH ₂ ) _v -or-(CH ₂ ) _w -in the above formula 6 is a carbon atom-. It is a divalent group represented by C (= O) O- or a divalent group represented by -N (R ¹⁴⁰ )-, and R ¹⁴⁰ is a hydrogen atom or a monovalent group having 1 to 10 carbon atoms. It is a hydrocarbon group, R ¹³² is a hydrogen atom or a methyl group, R ¹³⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. It is a divalent hydrocarbon group or a single bond, R ¹³⁵ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom, which is a monovalent hydrocarbon having 1 to 20 carbon atoms. A group, a hydrogen atom, or a group represented by -R ¹³⁷ -CHR ¹³⁸ -CH ₂ - ^r Si, R ¹³⁸ may be a hydrogen atom or a methyl group, and R ¹³⁷ may contain an oxygen atom or a nitrogen atom. The atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, R ⁵⁰ indicates an alkylene group having 2 to 4 carbon atoms, and ^r Si is a reaction. Representing a sex silicon group, R ¹³⁹ is a residue obtained by removing two isocyanate groups from polyisocyanate, v is an integer of 0 to 10, w is an integer of 0 to 10, and x is 5 to 500. And y is an atom of 5 to 500. The plurality of R ^50s may be the same or different.
When a plurality of -B- represented by the formula 6 are present in one molecule of the polymer (E), a plurality of R ¹³¹ , R ¹³² , R ¹³⁴ , R ¹³⁵ , R ¹³⁹ , R ¹⁴¹ , R ⁵⁰ , ^r Si may be the same or different from each other.

The monovalent hydrocarbon group of R ¹⁴⁰ has preferably 1 to 9 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
The carbon number of R ¹⁴⁰ includes the carbon number of the substituent when R ¹⁴⁰ has a substituent having a carbon atom.
As R ¹³¹ and R ¹⁴¹ , a divalent group represented by —C (= O) O— in which the oxygen atom or the atom bonded to − (CH ₂ ) _v— in the above formula 6 is a carbon atom is preferable. , Oxygen atom is more preferred.
R ¹³⁹ is the same as that of R ²¹ , and the preferred embodiment is also the same.

v is preferably 0 to 8, more preferably 1 to 7, and even more preferably 1 to 6.
w is preferably 0 to 8, more preferably 1 to 7, and even more preferably 1 to 6.
x is preferably 10 to 900, more preferably 20 to 650, and even more preferably 30 to 500.
y is preferably 10 to 900, more preferably 20 to 650, and even more preferably 30 to 500.
The group represented by -R ¹³⁴ -CHR ¹³² -CH ₂ - ^r Si is the same as the group represented by -R ¹⁴ CHR ¹² -CH ₂ - ^r Si described above, and the preferred embodiment is also the same.
The group represented by -R ¹³⁷ -CHR ¹³⁸ -CH ₂ - ^r Si is the same as the group represented by -R ¹⁴ CHR ¹² -CH ₂ - ^r Si described above, and the preferred embodiment is also the same.

前記式７中、Ｒ^１４２は水素原子又はメチル基であり、Ｒ^１４４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^１４９は、ポリイソシアネートからイソシアネート基を２個除いた残基であり、Ｒ^５０、^ｒＳｉ、ｘ、ｙは前記式６と同様であり、複数のＲ^５０、^ｒＳｉはそれぞれ互いに同一でも異なってもよい。
－Ｒ^１４４ＣＨＲ^１４２－ＣＨ_２－^ｒＳｉで表される基は、上述の－Ｒ^３４ＣＨＲ^３２－ＣＨ_２－^ｒＳｉで表される基と同様であり、好ましい態様も同様である。
Ｒ^１４９は前記Ｒ^２１と同様であり、好ましい態様も同様である。

In the above formula 7, R ¹⁴² is a hydrogen atom or a methyl group, R ¹⁴⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. It is a valent hydrocarbon group or a single bond, R ¹⁴⁹ is a residue obtained by removing two isocyanate groups from polyisocyanate, and R ⁵⁰ , ^r Si, x, y are the same as those in the above formula 6, and a plurality of them. R ⁵⁰ and ^r Si may be the same or different from each other.
The group represented by -R ¹⁴⁴ CHR ¹⁴² -CH ₂ - ^r Si is the same as the group represented by -R ³⁴ CHR ³² -CH ₂ - ^r Si described above, and the preferred embodiment is also the same.
R ¹⁴⁹ is the same as R ²¹ , and the preferred embodiment is also the same.

<Polymer (D)>
The polymer (D) has an average of more than 0 unsaturated groups per terminal group. The average number of unsaturated groups per terminal group of the polymer (D) is preferably 1.2 to 8.0, more preferably 1.5 to 3.0, from the viewpoint of reactivity.
The Mn of the polymer (D) is preferably 3,000 to 100,000, more preferably 3,500 to 75,000, and even more preferably 4,000 to 60,000.

As the polymer (D), X in the formula 3-1 or 3-2 is represented by the following formula 8 or 9, and B in the formula 3-1 or 3-2 is represented by the following formula 10 or 11. The polymer to be obtained is preferable.

前記式８中、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^５０、ｍ、ｑは、前記式４と同様であり、Ｒ^１６は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^６４－ＣＲ^６３＝ＣＨ_２で表される基であり、Ｒ^６３は水素原子又はメチル基であり、Ｒ^６４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、複数のＲ^１６、Ｒ^５０はそれぞれ互いに同一でも異なってもよい。

In the above formula 8, R ¹¹ , R ¹² , R ¹⁴ , R ⁵⁰ , m, and q are the same as those in the above formula 4, and R ¹⁶ may contain an oxygen atom or a nitrogen atom and is adjacent to the oxygen atom or the nitrogen atom. The atom is a carbon atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a group represented by -R ⁶⁴ -CR ⁶³ = CH ₂ , and R ⁶³ is a hydrogen atom or a methyl group. Yes, R ⁶⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and a plurality of R's are present. ¹⁶ and R ⁵⁰ may be the same or different from each other.

The carbon number of R ¹⁶ includes the carbon number of the substituent when R ¹⁶ has a substituent having a carbon atom.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ¹⁶ include an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group. The alkyl group and alkenyl group may be linear or branched.

Examples of the alkyl group, the cycloalkyl group, the alkenyl group, and the aryl group are the same as those of ^R15 including the substituent.

The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ¹⁶ is the same as that of R ¹⁵ , and the preferred embodiment is also the same.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ¹⁶ is the same as that of R ¹⁵ , and the preferred embodiment is also the same.

R ⁶³ is the same as R ¹⁸ , and the preferred embodiment is also the same.
R ⁶⁴ is the same as R ¹⁷ , and the preferred embodiment is also the same.

The groups represented by -R ¹⁴ -CR ¹² = CH ₂ and -R ⁶⁴ -CR ⁶³ = CH ₂ are independently -OCH ₂ -C (CH ₃ ) = CH ₂ and -OCH ₂ -CH = CH, respectively. ₂ , -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -O- (CH ₂ ) ₂ -CH = CH ₂ , -O- (CH ₂ ) ₃ -C (CH ₃ ) = CH _2, -O- (CH ₂ ) ₃ -CH = CH ₂ , -O- (CH ₂ ) ₄ -C (CH ₃ ) = CH ₂ , -O- (CH ₂ ) ₄ -CH = CH ₂ , -OC (CH ₃ ) ₂ -C (CH ₃ ) = CH ₂ , -OC (CH ₃ ) ₂ -CH = CH ₂ , -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH _2- O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ ,-( CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ , -CH (CH ₃ ) CH ₂ -O-CH _2- C (CH ₃ ) = CH ₂ , -CH (CH ₃ ) CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₄ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,- (CH ₂ ) ₄ -O-CH ₂ -CH = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -C (CH ₃ ) ₂ CH _2- O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₅ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₅ -O-CH ₂ -CH = CH ₂ ,-(CH 2) CH ₂ ) ₆ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₆ -O-CH ₂ -CH = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH = CH ₂ , -CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) ) = CH ₂ , -CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -CH = CH ₂ , -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₄ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ) ₄ -O- (CH ₂ ) ₂ -CH = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₅ -O- ( CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -CH = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ) ₂ -CH = CH ₂ can be exemplified, -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ is preferable, -CH ₂ -O-CH ₂ -CH = CH ₂ or-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ is more preferable.

前記式９中、Ｒ^３２、Ｒ^３４、Ｒ^５０、ｑは、前記式５と同様であり、Ｒ^３６は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^７４－ＣＲ^７３＝ＣＨ_２で表される基であり、Ｒ^７３は水素原子又はメチル基であり、Ｒ^７４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、複数のＲ^５０は同一でも異なってもよい。

In the above formula 9, R ³² , R ³⁴ , R ⁵⁰ , and q are the same as those in the above formula 5, R ³⁶ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. A monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a group represented by -R ⁷⁴ -CR ⁷³ = CH ₂ , where R ⁷³ is a hydrogen atom or a methyl group, and R ⁷⁴ is. It may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and a plurality of ^R50s are the same or different. You may.

The groups represented by -R ³⁴ -CR ³² = CH ₂ are -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ , and-. (CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ , -CH (CH ₃ ) CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH (CH ₃ ) CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₄ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₄ -O-CH _2- CH = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O-CH ₂ -CH = CH ₂ ,- (CH ₂ ) ₅ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₅ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₆ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₆ -O-CH ₂ -CH = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O-CH ₂ -CH = CH ₂ , -CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O- (CH ₂ ) _2- CH = CH ₂ ,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O- (CH ₂ ) ₂ -CH = CH ₂ ,- CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH (CH ₃ ) CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH) ₂ ) ₄ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₄ -O- (CH ₂ ) ₂ -CH = C H ₂ , -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -C (CH ₃ ) ₂ CH ₂ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₅ -O- (CH ₂ ) ₂ -CH = CH ₂ ,-(CH) ₂ ) ₆ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₆ -O- (CH ₂ ) ₂ -CH = CH ₂ , -CH ₂ -C ₆ H _10- CH ₂ -O- (CH ₂ ) ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -C ₆ H ₁₀ -CH ₂ -O- (CH ₂ ) ₂ -CH = CH _2, -CH ₂ -CH = CH _2, -(CH ₂ ) ₂ -CH = CH ₂ ,-(CH ₂ ) ₃ -CH = CH ₂ can be exemplified, and -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,- (CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH _2- CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ , -CH ₂ -CH = CH ₂ are preferable. -CH ₂ -O-CH ₂ -CH = CH ₂ or-(CH ₂ ) ₂ -O-CH ₂ -CH = CH ₂ or -CH ₂ -CH = CH ₂ is more preferable.

The carbon number of R ³⁶ includes the carbon number of the substituent when R ³⁶ has a substituent having a carbon atom.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ³⁶ include an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group. The alkyl group and alkenyl group may be linear or branched.

Examples of the alkyl group, cycloalkyl group, alkenyl group, and aryl group are the same as those of ^R35 including the substituent.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ³⁶ is the same as that of R ³⁵ , and the preferred embodiment is also the same.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ³⁶ is the same as that of R ³⁵ , and the preferred embodiment is also the same.

R ⁷³ is the same as R ³² , and the preferred embodiment is also the same.
R ⁷⁴ is the same as R ³⁴ , and so is the preferred embodiment.

前記式１０中、Ｒ^１３１、Ｒ^１３２、Ｒ^１３４、Ｒ^１３９、Ｒ^１４１、Ｒ^５０、ｖ、ｗ、ｘ、ｙは、前記式６と同様であり、Ｒ^１３６は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^１８４－ＣＲ^１８３＝ＣＨ_２で表される基であり、Ｒ^１８３は水素原子又はメチル基であり、Ｒ^１８４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、複数のＲ^５０は同一でも異なってもよい。

In the above formula 10, R ¹³¹ , R ¹³² , R ¹³⁴ , R ¹³⁹ , R ¹⁴¹ , R ⁵⁰ , v, w, x, y are the same as those in the above formula 6, and R ¹³⁶ contains an oxygen atom or a nitrogen atom. However, the atom adjacent to the oxygen atom or the nitrogen atom is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a group represented by ^-R184 - ^CR183 = _CH2 , which is a carbon atom. , R ¹⁸³ is a hydrogen atom or a methyl group, R ¹⁸⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom, which is a divalent hydrocarbon having 1 to 20 carbon atoms. It may be a group or a single bond, and the plurality of ^R50s may be the same or different.

The group represented by —R ¹³⁶ is the same as the group represented by —R ¹⁶ described above, and the preferred embodiment is also the same.
The group represented by -R ¹⁸⁴ -CR ¹⁸³ = CH ₂ is the same as the group represented by -R ¹⁴ CHR ¹² = CH ₂ described above, and the preferred embodiment is also the same.

前記式１１中、Ｒ^１４２、Ｒ^１４４、Ｒ^１４９、Ｒ^５０、ｘ、ｙは前記式７と同様であり、複数のＲ^５０は同一でも異なってもよい。
－Ｒ^１４４ＣＨＲ^１４２＝ＣＨ_２で表される基は、上述の－Ｒ^３４ＣＨＲ^３２＝ＣＨ_２で表される基と同様であり、好ましい態様も同様である。

In the formula 11, R ¹⁴² , R ¹⁴⁴ , R ¹⁴⁹ , R ⁵⁰ , x, and y are the same as those in the formula 7, and the plurality of R ^50s may be the same or different.
The group represented by -R ¹⁴⁴ CHR ¹⁴² = CH ₂ is the same as the group represented by -R ³⁴ CHR ³² = CH ₂ described above, and the preferred embodiment is also the same.

<Manufacturing method of polymer (E)>
The method for producing the oxyalkylene polymer (E) of the present embodiment comprises an active hydrogen-containing group at the terminal group of the following oxyalkylene polymer (B) (hereinafter referred to as "polymer (B)") and the following oxyalkylene. The active hydrogen-containing group at the terminal group of the polymer (C) (hereinafter referred to as "polymer (C)") is reacted with polyisocyanate to obtain the polymer (D), and then the polymer (the polymer (C)). This is a method for producing a polymer (E) by reacting an unsaturated group contained in D) with a silylating agent having a reactive silicon group represented by the above formula 1.
The polymer (B) has one terminal group having an average of more than 0 unsaturated groups and one terminal group having an average of more than 0 and 1.0 or less active hydrogen-containing groups. It is an oxyalkylene polymer.
The polymer (C) has 2 to 4 terminal groups having an initiator residue having an unsaturated group in the main chain and having an average of more than 0 and 1.0 or less active hydrogen-containing groups. It is an oxyalkylene polymer having.
The molecular weight of polyisocyanate is 100 to 20,000.

In the embodiment for producing the polymer (E) represented by the formula 3-1 or 3-2, the polymer (C) mainly contains initiator residues having more than 0 unsaturated groups on average. A diisocyanate having two isocyanates as a polyisocyanate using an oxyalkylene polymer having one in the chain and having two terminal groups having more than 0 and 1.0 or less active hydrogen-containing groups on average. Is used.

<Polymer (B)>
The polymer (B) contains a main chain containing a polyoxyalkylene chain, an oxygen atom at one end of the polyoxyalkylene chain, and a residue of the initiator (b) having one active hydrogen. It is a linear polymer composed of a group and the other terminal group containing an oxygen atom at the other end of the polyoxyalkylene chain. The other terminal group is a hydroxyl group.
Examples of the polyoxyalkylene chain possessed by the polymer (B) are the same as those of the polymer (A).

The hydroxyl group-equivalent molecular weight of the polymer (B) obtained by using the initiator (b) having a hydroxyl group as an active hydrogen-containing group is preferably 2,000 to 35,000, more preferably 2,500 to 17,000. , 3,000 to 10,000 are even more preferred. When the molecular weight converted to hydroxyl groups is at least the lower limit of the above range, the amount of reactive silicon groups introduced can be suppressed in the subsequent reaction, which is advantageous in terms of manufacturing cost, and when it is at least the upper limit, the viscosity is suppressed. , Tends to be convenient in terms of workability.
The Mn of the polymer (B) is preferably 2,200 to 50,000, more preferably 2,500 to 25,000, and even more preferably 3,000 to 15,000. When Mn is at least the lower limit of the above range, the amount of reactive silicon groups introduced can be suppressed in the subsequent reaction, which is advantageous in terms of manufacturing cost, and when it is at least the upper limit, the viscosity is suppressed and the work is performed. It tends to be convenient in terms of sex.
The molecular weight distribution of the polymer (B) is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.4 or less, and particularly preferably 1.2 or less. The molecular weight distribution of the polymer (B) is preferably 1.0 or more. When the molecular weight distribution is not more than the upper limit value, the stretchable physical properties of the cured product are likely to be improved.
The viscosity of the polymer (B) at 25 ° C. is preferably 0.05 to 100,000 Pa · s, more preferably 0.1 to 10,000 Pa · s, still more preferably 0.3 to 100 Pa · s. If it is within the above range, the workability is better.

The polymer (B) has an average of more than 0 unsaturated groups at one end group. The average number of unsaturated groups in one end group of the polymer (B) is preferably 1.2 to 8.0, preferably 1.5 to 3.0, from the viewpoint of improving the strength of the cured product. Is more preferable. The polymer (B) has an average of more than 0 and 1.0 or less active hydrogen-containing groups in the other terminal group. The average number of active hydrogen-containing groups in the other terminal group of the polymer (B) is preferably 0.5 to 1.0, more preferably 1.0, from the viewpoint of reactivity.

As one end group of the polymer (B), an end group containing an initiator residue represented by the following formula 12 or 13 is preferable.

前記式１２中、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１６、ｍは前記式８と同様であり、複数のＲ^１６は互いに同一でも異なってもよい。

In the formula 12, R ¹¹ , R ¹² , R ¹⁴ , R ¹⁶ and m are the same as those in the formula 8, and the plurality of R ¹⁶ may be the same or different from each other.

As the initiator residue represented by the above formula 12, R ¹¹ is an oxygen atom, m is 1 to 3, and R ¹⁴ is -CH ₂ -O-CH ₂ -,-(CH ₂ ) _2- . O-CH ₂ -,-(CH ₂ ) ₃ -A divalent group represented by O-CH _2- , R ¹² is a hydrogen atom or a methyl group, and R ¹⁶ contains an oxygen atom and a nitrogen atom. No alkyl group with 1-2 carbon atoms, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH A monovalent group represented by ₂ or-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ is preferable.

As the initiator residue represented by the above formula 12, R ¹¹ is an oxygen atom, m is 1, and R ¹⁴ is a _divalent group represented by _−CH2 -O—CH2-. , R ¹² is a hydrogen atom or a methyl group, and a plurality of R ¹⁶ are an alkyl group having 1 to 2 carbon atoms containing no oxygen atom and a nitrogen atom, or -CH ₂ -O-CH ₂ -C (CH ₃ ) =. A monovalent group represented by CH ₂ or-(CH ₂ ) -O-CH ₂ -CH = CH ₂ is preferable.

前記式１３中、Ｒ^３２、Ｒ^３４、Ｒ^３６は前記式９と同様である。

In the formula 13, R ³² , R ³⁴ , and R ³⁶ are the same as those in the formula 9.

As the initiator residue represented by the above formula 13, a monovalent group in which R ³² is a hydrogen atom or a methyl group and R ³⁴ is an alkylene group having 1 to 2 carbon atoms and does not contain an oxygen atom or a nitrogen atom. R ³⁶ is an alkyl group having 1 to 2 carbon atoms containing no oxygen atom and nitrogen atom, -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , or-(CH ₂ ) -O-. A monovalent group represented by CH ₂ -CH = CH ₂ is preferable.

(Method for producing polymer (B))
The polymer (B) has a cyclic ether ring-opened and added to the initiator (b) having one or more unsaturated groups in one molecule and one active hydrogen-containing group in one molecule. It is obtained by subjecting it to a polymerization reaction.
Examples of the cyclic ether include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, and cyclic ethers other than alkylene oxides such as tetrahydrofuran. As the cyclic ether, at least one selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide is preferable, ethylene oxide and propylene oxide are more preferable, and propylene oxide is particularly preferable. ..

The number of unsaturated groups in one molecule of the initiator (b) is preferably 2 to 5, preferably 2 to 4, more preferably 2 or 3, and even more preferably 2.
The unsaturated group in the initiator (b) is preferably an unsaturated group at the end of the molecule.

The molecular weight of the initiator (b) is preferably less than 1,000, more preferably 60 or more and less than 900, further preferably 70 to 500, and particularly preferably 70 to 300, from the viewpoint of reactivity with the cyclic ether.

As the initiator (b), a compound represented by the following formula 2 or formula 14 is preferable.

前記式２中、Ｒ^１は活性水素含有基、Ｒ^２は水素原子又はメチル基であり、Ｒ^４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^６は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^６２－ＣＲ^６１＝ＣＨ_２で表される基であり、Ｒ^６１は水素原子又はメチル基であり、Ｒ^６２は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、複数のＲ^６は同一でも異なってもよく、ｎは０～１０の整数である。

In the above formula 2, R ¹ is an active hydrogen-containing group, R ² is a hydrogen atom or a methyl group, R ⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. A divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, R ⁶ may contain an oxygen atom or a nitrogen atom, and an oxygen atom or an atom adjacent to the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. A monovalent hydrocarbon group of 20, a hydrogen atom, or a group represented by -R ⁶² -CR ⁶¹ = CH ₂ , R ⁶¹ is a hydrogen atom or a methyl group, and R ⁶² is an oxygen atom or a nitrogen atom. It may be contained, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and a plurality of R ^6s may be the same or different, and n is It is an integer from 0 to 10.

n is preferably 0 to 8, more preferably 1 to 7, and even more preferably 1 to 6.

R ¹ is an active hydrogen-containing group, and a hydroxyl group, a carboxy group, an amino group, a monovalent functional group obtained by removing a hydrogen atom from a primary amine and a sulfanyl group are preferable, and a hydroxyl group, a carbonyl group or an amino group is more preferable.
^R2 is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
The carbon number of R ⁴ includes the carbon number of the substituent when R ⁴ has a substituent having a carbon atom.
Examples of the divalent hydrocarbon group in ^R4 include an alkylene group, a cycloalkylene group, an alkenylene group and an arylene group. The alkylene group and the alkenylene group may be linear or branched.

Examples of the alkylene group, the cycloalkylene group, the alkenylene group, and the arylene group are the same as those of ^R14 including the substituent.

The divalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ⁴ is the same as that of R ¹⁴ , and the preferred embodiment is also the same.
The divalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ⁴ is the same as that of R ¹⁴ , and the preferred embodiment is also the same.

The group represented by -R ⁴ -CR ² = CH ₂ is the same as the group represented by -R ¹⁴ -CR ¹² = CH ₂ , and the preferred embodiment is also the same.

The carbon number of R ⁶ includes the carbon number of the substituent when R ⁶ has a substituent having a carbon atom.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ⁶ include an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group. The alkyl group and alkenyl group may be linear or branched.

Examples of the alkyl group, the cycloalkyl group, the alkenyl group, and the aryl group are the same as those of ^R16 including the substituent.

The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ⁶ is the same as that of R ¹⁶ , and the preferred embodiment is also the same.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ⁶ is the same as that of R ¹⁶ , and the preferred embodiment is also the same.

R ⁶¹ is the same as R ² , and the preferred embodiment is also the same.
R ⁶² is the same as R ⁴ , and the preferred embodiment is also the same.

The group represented by -R ⁶² -CR ⁶¹ = CH ₂ is the same as the group represented by -R ⁴ -CR ² = CH ₂ , and the preferred embodiment is also the same.

As the initiator (b) represented by the above formula 2, R ¹ is a hydroxyl group, n is 1 to 3, and R ⁴ is -CH ₂ -O-CH ₂ -,-(CH ₂ ) _2- . O-CH ₂ -,-(CH ₂ ) ₃ -A divalent group represented by O-CH _2- , R ² is a hydrogen atom or a methyl group, and R ⁶ contains an oxygen atom and a nitrogen atom. No alkyl group with 1-2 carbon atoms, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH A monovalent group represented by ₂ or-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ is preferable.

In the initiator (b) represented by the above formula 2, R ¹ is a hydroxyl group, n is 1, and R ⁴ is a _divalent group represented by _−CH2 -O—CH2-. , R ² is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 1 to 2 carbon atoms containing no oxygen atom and nitrogen atom, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ Alternatively, a monovalent group represented by-(CH ₂ ) -O-CH ₂ -CH = CH ₂ is preferable.

前記式１４中、Ｒ^２２は水素原子又はメチル基であり、Ｒ^２４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^２６は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^８４－ＣＲ^８３＝ＣＨ_２で表される基であり、Ｒ^８３は水素原子又はメチル基であり、Ｒ^８４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合である。Ｒ^２４の炭素数は、Ｒ^２４が炭素原子を有する置換基を有する場合は、置換基の炭素数を含む。

In the above formula 14, R ²² is a hydrogen atom or a methyl group, R ²⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. It is a valent hydrocarbon group or a single bond, and ^R26 may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom and is a monovalent hydrocarbon group having 1 to 20 carbon atoms. , Hydrogen atom, or a group represented by -R ⁸⁴ -CR ⁸³ = CH ₂ , R ⁸³ is a hydrogen atom or a methyl group, and R ⁸⁴ may contain an oxygen atom or a nitrogen atom, and the oxygen atom or nitrogen may be contained. The atom adjacent to the atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom. The carbon number of R ²⁴ includes the carbon number of the substituent when R ²⁴ has a substituent having a carbon atom.

R ²² is preferably a hydrogen atom. Examples of the divalent hydrocarbon group in R ²⁴ include an alkylene group, a cycloalkylene group, an alkenylene group and an arylene group.

Examples of the alkylene group, the cycloalkylene group, the alkenyl group, and the aryl group are the same as those of ^R34 including the substituent. The alkylene group and the alkenylene group may be linear or branched.

The divalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ²⁴ is independently the same as that of R ³⁴ , and the preferred embodiment is also the same.
The divalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ²⁴ is independently the same as that of R ³⁴ , and the preferred embodiment is also the same.

The carbon number of R ²⁶ includes the carbon number of the substituent when R ²⁶ has a substituent having a carbon atom.
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of ^R26 include an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group. The alkyl group and alkenyl group may be linear or branched.

Examples of the alkyl group, cycloalkyl group, alkenyl group, and aryl group are the same as those of ^R36 including the substituent.

The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of ^R26 is the same as that of ^R36 , and the preferred embodiment is also the same.
The monovalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of ^R26 is the same as that of ^R36 , and the preferred embodiment is also the same.

R ⁸³ is the same as R ²² , and the preferred embodiment is also the same.
R ⁸⁴ is similar to R ²⁴ , and so is the preferred embodiment.

As the initiator (b) represented by the formula 14, a compound in which R ²⁶ is -R ⁸⁴ -CR ⁸³ = CH ₂ is preferable, and a compound in which both R ²⁴ and R ⁸⁴ are methylene groups is more preferable. ..

A conventionally known catalyst can be used as the ring-opening addition polymerization catalyst when the cyclic ether is allowed to undergo the ring-opening addition polymerization reaction with the initiator (b). Examples thereof include a catalyst (a complex obtained by reacting an organic aluminum compound with porphyrin), a composite metal cyanation complex catalyst, and a catalyst composed of a phosphazene compound.

A composite metal cyanide complex catalyst is preferable because the molecular weight distribution of the polymer (B) can be narrowed and a curable composition having a low viscosity can be easily obtained. As the composite metal cyanide complex catalyst, a conventionally known compound can be used, and a known method can also be adopted as a method for producing a polymer using the composite metal cyanide complex. For example, International Publication No. 2003/062301, International Publication No. 2004/067633, JP-A-2004-269767, JP-A-2005-15786, International Publication No. 2013/06582, JP-A-2015-01162 The compounds and production methods disclosed in the publication can be used.

(Manufacturing method of initiator (b))
The initiator (b) contains x-1 active hydrogen-containing groups in a compound having x active hydrogen-containing groups in one molecule (where x is an integer of 3 or more) and unsaturated groups. It can be produced by converting it into a group having. As a method for converting an active hydrogen-containing group into a group having an unsaturated group, a method of reacting an alkali metal hydroxide with a halogenated hydrocarbon having an unsaturated group is preferable.
x is preferably 3 to 6, more preferably 3 to 5, and even more preferably 3 or 4.

Compounds having three or more active hydrogen-containing groups in one molecule include trimethylolpropane, glycerin, butanetriol, pentantriol, hexanetriol, trimethylolethane, benzenetriol, pentaerythritol, sorbitol, and dipentaerythritol. It can be exemplified. Trimethylolpropane, glycerin, pentaerythritol, and sorbitol are preferable because they are easily available.

As a method for converting an active hydrogen-containing group into a group having an unsaturated group, a conventionally known method can be used, and examples thereof include the method proposed in Tokusho 60-231625.

When the active hydrogen-containing group is converted into a group having an unsaturated group, a mixture of compounds in which 1 to x active hydrogen-containing groups are converted into a group having an unsaturated group is obtained. Purification of this mixture by distillation gives the initiator (b) in which x-1 active hydrogen-containing groups are converted to groups having unsaturated groups.

<Polymer (C)>
The polymer (C) was bound to a residue of the initiator (c) having 2 to 4 active hydrogens (hereinafter, also referred to as “initiator residue (c)”) and the initiator residue (c). It is a polymer composed of a main chain containing 2 to 4 polyoxyalkylene chains and 2 to 4 terminal groups containing oxygen atoms at the respective ends of the polyoxyalkylene chain. The terminal group of each polyoxyalkylene chain is a hydroxyl group. The part other than the terminal group is called the main chain.
Examples of the polyoxyalkylene chain contained in the cyclic ether and the polymer (C) are the same as those of the polymer (A).

The hydroxyl group-equivalent molecular weight of the polymer (C) obtained by using the initiator (c) having a hydroxyl group is preferably 2,000 to 35,000, more preferably 2,500 to 17,000, and 3,000 to 3,000. 10,000 is even more preferred. When the molecular weight converted to hydroxyl groups is at least the lower limit of the above range, the amount of reactive silicon groups introduced can be suppressed in the subsequent reaction, which is advantageous in terms of manufacturing cost, and when it is at least the upper limit, the viscosity is suppressed. , Tends to be convenient in terms of workability.
The Mn of the polymer (C) is preferably 2,200 to 50,000, more preferably 2,500 to 25,000, and even more preferably 3,000 to 15,000. When Mn is at least the lower limit of the above range, the amount of reactive silicon groups introduced can be suppressed in the subsequent reaction, which is advantageous in terms of manufacturing cost, and when it is at least the upper limit, the viscosity is suppressed and the work is performed. It tends to be convenient in terms of sex.
The molecular weight distribution of the polymer (C) is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.4 or less, and particularly preferably 1.2 or less. The molecular weight distribution of the polymer (C) is preferably 1.0 or more. When the molecular weight distribution is not more than the upper limit value, the stretchable physical properties of the cured product are likely to be improved.
The viscosity of the polymer (C) at 25 ° C. is preferably 0.05 to 100,000 Pa · s, more preferably 0.1 to 10,000 Pa · s, still more preferably 0.3 to 100 Pa · s. If it is within the above range, the workability is better.

The initiator residue (c) has an unsaturated group. The average number of unsaturated groups in the initiator residue (c) is preferably 1.2 to 8.0, more preferably 1.5 to 3.0, from the viewpoint of improving the strength of the cured product. ..
The polymer (C) has 2 to 4 terminal groups in one molecule. Each terminal group has an average of more than 0 and 1.0 or less active hydrogen-containing groups. The average number of active hydrogen-containing groups in the terminal groups is preferably 0.5 to 1.0, more preferably 1.0, from the viewpoint of reactivity.

The initiator (c) is preferably the initiator (c1) having two active hydrogens. That is, the polymer (C) has a residue of the initiator (c1) (hereinafter, also referred to as “initiator residue (c1)”) and two polyoxys bound to the initiator residue (c1). A polymer (C1) consisting of a main chain containing an alkylene chain and two terminal groups containing an oxygen atom at each end of the polyoxyalkylene chain is preferable.
As the initiator residue (c1), a divalent group represented by the following formula 15 or 16 is preferable.

前記式１５中、Ｒ^１３２、Ｒ^１３４、Ｒ^１３６は前記式１０と同様である。Ｒ^１３０は、前記式１０におけるＲ^１３１及びＲ^１４１と同様であり、２個の－Ｒ^１３０－（ＣＨ_２）_ａ－で表される基は同一でも異なってもよい。ａは０～１０の整数である。
前記式１５で表される開始剤残基としては、Ｒ^１３０が酸素原子であり、ａが１～６であり、Ｒ^１３４が－ＣＨ_２－Ｏ－ＣＨ_２－、－（ＣＨ_２）_２－Ｏ－ＣＨ_２－、－（ＣＨ_２）_３－Ｏ－ＣＨ_２－で表される２価の基であり、Ｒ^１３２が水素原子又はメチル基であり、Ｒ^１３６が酸素原子及び窒素原子を含まない炭素数１～２のアルキル基、又は－ＣＨ_２－Ｏ－ＣＨ_２－Ｃ（ＣＨ_３）＝ＣＨ_２、－（ＣＨ_２）_２－Ｏ－ＣＨ_２－Ｃ（ＣＨ_３）＝ＣＨ_２、－（ＣＨ_２）_３－Ｏ－ＣＨ_２－Ｃ（ＣＨ_３）＝ＣＨ_２、－ＣＨ_２－Ｏ－ＣＨ_２－ＣＨ＝ＣＨ_２、－（ＣＨ_２）_２－Ｏ－ＣＨ_２－ＣＨ＝ＣＨ_２、又は－（ＣＨ_２）_３－Ｏ－ＣＨ_２－ＣＨ＝ＣＨ_２で表される１価の基が好ましい。

In the formula 15, R ¹³² , R ¹³⁴ , and R ¹³⁶ are the same as those in the formula 10. R ¹³⁰ is the same as R ¹³¹ and R ¹⁴¹ in the above formula 10, and the two groups represented by −R ¹³⁰ − (CH ₂ ) _a − may be the same or different. a is an integer from 0 to 10.
As the initiator residue represented by the above formula 15, R ¹³⁰ is an oxygen atom, a is 1 to 6, and R ¹³⁴ is -CH ₂ -O-CH ₂ -,-(CH ₂ ) _2- . It is a divalent group represented by O-CH ₂ -,-(CH ₂ ) ₃ -O-CH _2- , R ¹³² is a hydrogen atom or a methyl group, and R ¹³⁶ contains an oxygen atom and a nitrogen atom. No alkyl group with 1-2 carbon atoms, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH A monovalent group represented by ₂ or-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ is preferable.

As the initiator residue represented by the above formula 15, R ¹³⁰ is an oxygen atom, a is 1, and R ¹³⁴ is a _divalent group represented by _−CH2 -O—CH2-. , R ¹³² is a hydrogen atom or a methyl group, and R ¹³⁶ is an alkyl group having 1 to 2 carbon atoms containing no oxygen atom and a nitrogen atom, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ . Alternatively, a monovalent group represented by-(CH ₂ ) -O-CH ₂ -CH = CH ₂ is preferable.

前記式１６中、Ｒ^１４２、Ｒ^１４４は前記式１１と同様である。
前記式１６で表される開始剤残基としては、Ｒ^１４２が水素原子又はメチル基であり、Ｒ^１４４が－ＣＨ_２－Ｏ－ＣＨ_２－で表される２価の基が好ましい。

In the formula 16, R ¹⁴² and R ¹⁴⁴ are the same as those in the formula 11.
As the initiator residue represented by the above formula 16, a divalent group in which R ¹⁴² is a hydrogen atom or a methyl group and R ¹⁴⁴ is represented by _{−CH2 -} O—CH2- is preferable.

(Method for producing polymer (C))
In the polymer (C), a cyclic ether is opened in the initiator (c) having one or more unsaturated groups in one molecule and having 2 to 4 active hydrogen-containing groups in one molecule. It is obtained by subjecting it to a ring-opening polymerization reaction.
The cyclic ether is the same as the cyclic ether in the method for producing the polymer (B), including preferred embodiments.

The initiator residue (c) has an unsaturated group. The average number of unsaturated groups in the initiator residue (c) is preferably 1.2 to 8.0, more preferably 1.5 to 3.0, from the viewpoint of improving the strength of the cured product. ..
The number of unsaturated groups in one molecule of the initiator (c) is preferably 1 or 2.
The unsaturated group in the initiator (c) is preferably an unsaturated group at the end of the molecule.

The molecular weight of the initiator (c) is preferably less than 1,000, more preferably 60 or more and less than 900, further preferably 70 to 500, and particularly preferably 70 to 300, from the viewpoint of reactivity with the cyclic ether.

The polymer (C1) having an initiator residue represented by the formula 15 or 16 has one or more unsaturated groups in one molecule and has two active hydrogen-containing groups in one molecule. It is obtained by subjecting a cyclic ether to an initiator (c1) having a ring-opening addition polymerization reaction.
As the initiator (c1), a compound represented by the following formula 3 or formula 17 is preferable.

前記式３中、Ｒ^１１１は活性水素含有基、Ｒ^１１２は水素原子又はメチル基であり、Ｒ^１１４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、Ｒ^１１６は酸素原子若しくは窒素原子を含んでもよく、酸素原子若しくは窒素原子と隣接する原子は炭素原子である炭素数１～２０の１価の炭化水素基、水素原子、又は－Ｒ^１７２－ＣＲ^１７１＝ＣＨ_２で表される基であり、Ｒ^１７１は水素原子又はメチル基であり、Ｒ^１７２は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合であり、ａは０～１０の整数であり、複数のＲ^１１１－（ＣＨ_２）_ａ－で表される基は同一でも異なってもよい。

In the above formula 3, R ¹¹¹ is an active hydrogen-containing group, R ¹¹² is a hydrogen atom or a methyl group, R ¹¹⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. It is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, and R ¹¹⁶ may contain an oxygen atom or a nitrogen atom, and an oxygen atom or an atom adjacent to the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. A monovalent hydrocarbon group of 20, a hydrogen atom, or a group represented by -R ¹⁷² -CR ¹⁷¹ = CH ₂ , R ¹⁷¹ is a hydrogen atom or a methyl group, and R ¹⁷² is an oxygen atom or a nitrogen atom. It may be contained, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, a is an integer of 0 to 10, and a plurality of R ^111s . -The groups represented by (CH ₂ ) _a -may be the same or different.

a is preferably 0 to 8, more preferably 1 to 7, and even more preferably 1 to 6.

R ¹¹¹ is an active hydrogen-containing group, and a hydroxyl group, a carboxy group, an amino group, a monovalent functional group obtained by removing a hydrogen atom from a primary amine and a sulfanyl group are preferable, and a hydroxyl group, a carbonyl group or an amino group is more preferable.
R ¹¹² is a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
R ¹¹⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom, which is a divalent hydrocarbon group having 1 to 20 carbon atoms or a single bond. The carbon number of R ¹¹⁴ includes the carbon number of the substituent when R ¹¹⁴ has a substituent having a carbon atom.
Examples of the divalent hydrocarbon group in R ¹¹⁴ include an alkylene group, a cycloalkylene group, an alkenylene group and an arylene group. The alkylene group and the alkenylene group may be linear or branched.

Examples of the alkylene group, the cycloalkylene group, the alkenylene group, and the arylene group are the same as those of ^R64 including the substituent.
The divalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ¹¹⁴ is independently the same as that of R ⁶⁴ , and the preferred embodiment is also the same.
The divalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ¹¹⁴ is independently the same as that of R ⁶⁴ , and the preferred embodiment is also the same.

The group represented by -R ¹¹⁴ -CR ¹¹² = CH ₂ is the same as the group represented by -R ⁶⁴ -CR ⁶³ = CH ₂ , and the preferred embodiment is also the same.

As the initiator (c1) represented by the above formula 3, R ¹¹¹ is a hydroxyl group, a is 2 to 3, and R ¹¹⁴ is -CH ₂ -O-CH ₂ -,-(CH ₂ ) _2- . It is a divalent group represented by O-CH ₂ -,-(CH ₂ ) ₃ -O-CH _2- , R ¹¹² is a hydrogen atom or a methyl group, and R ¹¹⁶ contains an oxygen atom and a nitrogen atom. No alkyl group with 1-2 carbon atoms, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -(CH ₂ ) ₃ -O-CH ₂ -C (CH ₃ ) = CH ₂ , -CH ₂ -O-CH ₂ -CH = CH ₂ ,-(CH ₂ ) ₂ -O-CH ₂ -CH = CH A monovalent group represented by ₂ or-(CH ₂ ) ₃ -O-CH ₂ -CH = CH ₂ is preferable.

As the initiator (c1) represented by the above formula 3, R ¹¹¹ is a hydroxyl group, a is 1, and R ¹¹⁴ is a _divalent group represented by _−CH2 -O—CH2-. , R ¹¹² is a hydrogen atom or a methyl group, and R ¹¹⁶ is an alkyl group having 1 to 2 carbon atoms containing no oxygen atom and a nitrogen atom, or -CH ₂ -O-CH ₂ -C (CH ₃ ) = CH ₂ . Alternatively, a monovalent group represented by-(CH ₂ ) -O-CH ₂ -CH = CH ₂ is preferable.

前記式１７中、Ｒ^１２２は水素原子又はメチル基であり、Ｒ^１２４は酸素原子又は窒素原子を含んでもよく、酸素原子又は窒素原子と隣接する原子は炭素原子である炭素数１～２０の２価の炭化水素基又は単結合である。Ｒ^１２４の炭素数は、Ｒ^１２４が炭素原子を有する置換基を有する場合は、置換基の炭素数を含む。

In the above formula 17, R ¹²² is a hydrogen atom or a methyl group, R ¹²⁴ may contain an oxygen atom or a nitrogen atom, and the atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. It is a valent hydrocarbon group or a single bond. The carbon number of R ¹²⁴ includes the carbon number of the substituent when R ¹²⁴ has a substituent having a carbon atom.

R ¹²² is preferably a hydrogen atom. Examples of the divalent hydrocarbon group in R ¹²⁴ include an alkylene group, a cycloalkylene group, an alkenylene group and an arylene group.

Examples of the alkylene group, the cycloalkylene group, the alkenyl group, and the aryl group are the same as those of ^R34 including the substituent. The alkylene group and the alkenylene group may be linear or branched.

The divalent hydrocarbon group having 1 to 20 carbon atoms containing the oxygen atom of R ¹²⁴ is independently the same as that of R ³⁴ , and the preferred embodiment is also the same.
The divalent hydrocarbon group having 1 to 20 carbon atoms containing the nitrogen atom of R ¹²⁴ is independently the same as that of R ³⁴ , and the preferred embodiment is also the same.

As the initiator (c1) represented by the formula 17, a compound in which R ¹²⁴ is a methylene group is more preferable.

The ring-opening addition polymerization catalyst when the cyclic ether is subjected to the ring-opening addition polymerization reaction with the initiator is the same as the method for producing the polymer (B).

(Manufacturing method of initiator (c))
The initiator (c) having 2 to 4 active hydrogen-containing groups in one molecule is a compound having x active hydrogen-containing groups in one molecule (where x is an integer of 3 or more). It can be produced by converting x-2 to x-4 active hydrogen-containing groups into a group having an unsaturated group.
The initiator (c1) having two active hydrogen-containing groups in one molecule is x in a compound having x active hydrogen-containing groups in one molecule (where x is an integer of 3 or more). -It can be produced by converting two active hydrogen-containing groups into a group having an unsaturated group.
As a method for converting an active hydrogen-containing group into a group having an unsaturated group, a method of reacting an alkali metal hydroxide with a halogenated hydrocarbon having an unsaturated group is preferable.
x is preferably 3 to 6, more preferably 3 to 5, and even more preferably 3 or 4.

The compound having three or more active hydrogen-containing groups in one molecule is the same as the method for producing the polymer (B).
The method for converting an active hydrogen-containing group into a group having an unsaturated group is the same as the method for producing the polymer (B).

When the active hydrogen-containing group is converted into a group having an unsaturated group, a mixture of compounds in which 1 to x active hydrogen-containing groups are converted into a group having an unsaturated group is obtained. When this mixture is purified by distillation, the initiator (c) in which the desired number (x-2, x-3, or x-4) of active hydrogen-containing groups is converted into a group having an unsaturated group is obtained. Obtainable.

(Method for producing polymer (E) from polymer (B) and polymer (C))
The active hydrogen-containing group at the other terminal group of the polymer (B), the active hydrogen-containing group at the terminal group of the polymer (C), and the polyisocyanate are reacted to obtain the oxyalkylene polymer (D).
The oxyalkylene polymer (D) has a main chain having a polyoxyalkylene chain, an unsaturated group present in the main chain, a urethane bond present in the main chain, and an unsaturated group present in a terminal group. It is a polymer and has an average of more than 0 unsaturated groups per terminal group. The unsaturated group in the backbone is derived from the initiator residue (c).

An active hydrogen-containing group at the other terminal group of the polymer (B), an active hydrogen-containing group at the terminal group of the polymer (C), and an active hydrogen-containing group at the terminal group of the following polyoxyalkylene polymer (F). And the polyisocyanate may be reacted to obtain the polymer (D).
The polymer (F) is composed of a polyoxyalkylene chain and a terminal group containing an oxygen atom at the end of the polyoxyalkylene chain, and the terminal group has an active hydrogen-containing group and no unsaturated group. It is an oxyalkylene polymer.

The average number of active hydrogen-containing groups per terminal group of the polymer (F) is preferably 1 to 2 and more preferably 1 from the viewpoint of the viscosity of the polymer to be synthesized.
The number of terminal groups in one molecule of the polymer (F) is preferably 2 to 6, more preferably 2 to 3.

The Mn of the polymer (F) is preferably 2,200 to 100,000, more preferably 2,500 to 50,000, and even more preferably 3,000 to 30,000.
The molecular weight distribution of the polymer (F) is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.4 or less, and particularly preferably 1.2 or less.
The viscosity of the polymer (F) at 25 ° C. is preferably 0.05 to 100,000 Pa · s, more preferably 0.1 to 10,000 Pa · s, still more preferably 0.3 to 100 Pa · s.

The polymer (F) is obtained by subjecting a cyclic ether to a ring-opening addition polymerization reaction with an initiator compound having an active hydrogen-containing group in the molecule.

Initiator compounds include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and low molecular weight poly. Examples thereof include oxypropylene glycol, glycerin, trimethylolpropane, trimethylolethane, low molecular weight polyoxypropylene triol, pentaerythritol, sorbitol, and sucrose.

The conditions of the cyclic ether and the ring-opening addition polymerization reaction are the same as those described in the above-mentioned method for producing the polymer (B).

Examples of the polyisocyanate include the above-mentioned polyisocyanate in which s isocyanate groups are added to ^R20 .

Examples of such a polyisocyanate include the polyisocyanate described in R20, hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexamethylene diisocyanate ( ^H12MDI ). , Xylylene diisocyanate (XDI), dimethylcyclohexane diisocyanate, trizine diisocyanate, naphthalene diisocyanate, pentamethylene diisocyanate, paraphenylenedi isocyanate, lysine diisocyanate, tetramethylximethylene diisocyanate, triphenylmethane triisocyanate, triisocyanate triphenylthiophosphate, dimerate diisocyanate. , Norbornen diisocyanate is preferable, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexamethylene diisocyanate are more preferable, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate are further preferable.

A catalyst may be used for the reaction, and it can be appropriately selected depending on the polyisocyanate used. Examples of catalysts include organic tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and tin 2-ethylhexanoate (tin octylate), iron compounds such as iron acetylacetonate and iron chloride, and octylic acid. Examples thereof include lead compounds such as lead, bismuth compounds such as bismuth octylate, tertiary amine-based catalysts such as triethylamine and triethylenediamine, and preferred examples are organic tin compounds, lead octylate and bismuth octylate.

The reaction temperature and reaction time can be appropriately selected depending on the polyisocyanate used, but the reaction temperature may be 0 to 130 ° C., preferably 20 to 90 ° C., and the reaction time is preferably 0.5 to 24 hours.

The unsaturated group at the terminal group of the polymer (D) is reacted with a silylating agent having a reactive silicon group represented by the above formula 1 to obtain the polymer (E).
As the silylating agent, a compound having both a group capable of reacting with an unsaturated group (for example, a sulfanyl group) and the reactive silicon group, a hydrosilane compound (for example, HSiX _a R _3-a , but X) , R and a are the same as those in the above formula 1). Specifically, for example, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, methyldiisopropoxy. Examples thereof include silane, (α-chloromethyl) dimethoxysilane, and (α-chloromethyl) diethoxysilane. Trimethoxysilane, triethoxysilane, methyldimethoxysilane, and methyldiethoxysilane are preferable, and methyldimethoxysilane or trimethoxysilane is more preferable, from the viewpoint of high activity and good curability.

As a method for reacting the unsaturated group at the terminal group of the polymer (D) with the silylating agent, a conventionally known method can be used. , JP-A-61-197631, JP-A-3-72527, JP-A-8-231707, JP-A-2011-178955, US Pat. No. 3,632,557, and US Pat. No. 4,960,844. ..
The silylation rate is preferably more than 50 mol% and 100 mol% or less, more preferably 55 to 98 mol%, still more preferably 60 to 97 mol%.

[Cursable composition]
The curable composition of the present embodiment contains the polymer (A) and a curing catalyst. The polymer (A) preferably contains the polymer (E). The curable composition is obtained by adding, if necessary, components to the polymer (A) and mixing them.
When the curable composition contains the polymer (E), the content ratio of the polymer (E) to the total mass of the curable composition is preferably 5 to 80% by mass, more preferably 8 to 70% by mass, and 10%. ~ 60% by mass is more preferable. When the content ratio of the polymer (E) is within the above range, the strength and elongation of the cured product are more excellent.
The curable composition of the present embodiment may contain one or more selected from the polymer (B), the polymer (C) and the polymer (D). When the curable composition contains one or more selected from the polymer (B), the polymer (C) and the polymer (D), the polymer (B) and the polymer (B) with respect to the total mass of the curable composition. The total content ratio of C) and the polymer (D) may be 2 to 50% by mass or 5 to 40% by mass.
Examples of the curing catalyst contained in the curable composition of the present embodiment include the curing catalysts described in other components described later. The content of the curing catalyst is preferably 0.01 to 20.0 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (E) and the polymer (D). When it is 0.01 part by mass or more, the curing reaction easily proceeds sufficiently, and when it is 20.0 parts by mass or less, the strength of the cured product is more excellent.

The stress (M50) at 50% elongation, measured by the tensile test shown in the examples below of the cured product obtained from the curable composition of the present embodiment, tends to exceed 0.75 N / mm ² . Furthermore, it tends to be 0.8 N / mm ² or more. If it exceeds 0.75 N / mm ² , good strength can be obtained and it is suitable for adhesive use.

The maximum point cohesive force (Tmax) measured by the tensile test shown in the examples below of the cured product obtained from the curable composition of the present embodiment is likely to be more than 1.25 N / mm ² and further 1 It tends to be .30 N / mm ² or more. When it is 1.25 N / mm ² or more, good strength can be obtained and it is suitable for adhesive use.

The maximum point elongation measured by the tensile test shown in the examples below of the cured product obtained from the curable composition of the present embodiment is likely to be 60% or more, further 100% or more, and particularly 150%. It is easy to become the above. If it is 60% or more, good elongation can be obtained, which is suitable for adhesive use.

[Other ingredients]
The curable composition is an oxyalkylene polymer having a reactive silicon group represented by the above formula 1, which does not correspond to the polymer (E), the polymer (B), the polymer (C), or the polymer (D). , A polymer other than the oxyalkylene polymer having a reactive silicon group represented by the above formula 1, the polymer (B), the polymer (C), and the polymer (D), which is represented by the above formula 1. It may contain a polymer having no reactive silicon group. Examples of the polymer other than the oxyalkylene polymer include vinyl-based polymers such as acrylic acid-based polymers and methacrylic acid-based polymers, saturated hydrocarbon-based polymers, polyester-based polymers, polysulfide-based polymers, and polyamide-based polymers. , Polycarbonate-based polymer, diallyl phthalate-based polymer, and the like.
The curable composition may contain other components. Examples of other components include additives depending on the use of the curable composition, such as fillers, plasticizers, chicosis-imparting agents, antioxidants, ultraviolet absorbers, light stabilizers, dehydrating agents, and adhesive-imparting agents. Examples thereof include agents, amine compounds, oxygen curable compounds, and photocurable compounds.
The curing catalyst and other components are described in International Publication No. 2013/180203, International Publication No. 2014/192842, International Publication No. 2016/002907, JP-A-2014-88481, JP-A-2015-10162, JP-A-2015. Conventionally known substances described in JP-A-2015-105293A, JP-A-2017-039728, JP-A-2017-214541 and the like can be used in combination without limitation.
Two or more kinds of each component may be used in combination.

The curable composition may be a one-component type in which all the compounding components are premixed, sealed and stored, and cured by the humidity in the air after construction, and the main composition containing at least a component having a reactive silicon group and at least A two-component type may be used in which the curing agent composition containing the curing catalyst is stored separately and the curing agent composition and the main agent composition are mixed before use. A one-component curable composition is preferred because it is easy to install.

The one-component curable composition preferably does not contain water. It is preferable to dehydrate and dry the compounding component containing water in advance, or to dehydrate by reducing the pressure during compounding and kneading.
In the two-component curable composition, the curing agent composition may contain water. Although the main ingredient composition is difficult to gel even if it contains a small amount of water, it is preferable to dehydrate and dry the compounding components in advance from the viewpoint of storage stability.
In order to improve storage stability, a dehydrating agent may be added to the one-component curable composition or the two-component main composition.

The curable composition is used as a sealing material (for example, an elastic sealing material for construction, a sealing material for double glazing, a sealing material for rust prevention / waterproofing at the end of glass, a sealing material for the back surface of a solar cell, and a sealing material for buildings. Materials, sealing materials for ships, sealing materials for automobiles, sealing materials for roads), electrical insulating materials (insulating coating materials for electric wires / cables), adhesives, and potting materials are suitable.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following description. Hereinafter, the compound represented by the formula 20 is also referred to as compound 20. The same applies to compounds represented by other formulas.

<Measurement method / evaluation method>
[Molecular weight equivalent to hydroxyl group of polymer]
The molecular weight of the oxyalkylene polymer obtained by polymerizing the alkylene oxide with the initiator having a hydroxyl group (hereinafter referred to as "hydroxyl equivalent molecular weight") is "56100" from the hydroxyl value calculated based on JIS K 1557 (2007). It was calculated based on the formula of / (hydroxyl value of polymer) × number of active hydrogens of initiator.

[Mn and molecular weight distribution]
Mw, Mn and Mw / Mn were determined using HLC-8220GPC (product name of Tosoh Corporation).

[Measurement of average number of unsaturated groups, reactive silicon groups and hydroxyl groups contained in the polymer]
The number of reactive silicon groups contained in the polymer was measured by ¹ H-NMR internal standard method.
The number of unsaturated groups contained in the polymer was measured by iodine value titration according to JIS K0070: 1992.
The number of hydroxyl groups contained in the polymer was measured by a titration method using a sodium hydroxide (NaOH) solution (based on JIS K1557: 2007) after esterifying the hydroxyl groups with a pyridine solution of phthalic anhydride.

[Calculation of urethane bond content with respect to the total amount of polymer]
From the formula A and the formula B, the content of urethane bond with respect to the total amount of the polymer was calculated.

[Tensile test]
The curable composition to be measured was filled in a mold having a thickness of 2 mm, cured at a temperature of 23 ° C. and a humidity of 50% for 3 days, and further cured at a temperature of 50 ° C. and a humidity of 65 ° C. for 4 days. The obtained cured product was punched out with a dumbbell mold to obtain a test piece. A tensile test was performed on this test piece at a tensile speed of 500 mm / min, and the stress (M50, unit: N / mm ² ), maximum point cohesive force (Tmax, unit: N / mm ² ), and maximum point when stretched by 50%. The tensile properties of elongation (unit:%) were measured.

[Production Example 1: Production of compound (a1)]
A flask equipped with a stirrer, a reflux condenser, a thermometer, and two dropping funnels was charged with 1 mol equivalent of trimethylolpropane and heated to 90 ° C. under a nitrogen stream. While stirring at 90 ° C., a 40 mass% sodium hydroxide aqueous solution was simultaneously added dropwise to trimethylolpropane in an equivalent amount of 2 mol and allyl chloride in an equivalent amount of 2 mol to trimethylolpropane using separate dropping funnels. The aqueous sodium hydroxide solution was added dropwise over 2 hours, and the allyl chloride solution was added dropwise over 3 hours. After completion of the reaction, water was added to dissolve the precipitated sodium chloride, and the mixture was allowed to cool. When the organic layer of the solution after the reaction of the two layers consisting of the organic layer and the aqueous layer was separated and analyzed by gas chromatography, it has three allyl groups in one molecule represented by the following formula 18. , The compound 18 having no active hydrogen-containing group, the compound 19 having two allyl groups in one molecule represented by the following formula 19, and having one active hydrogen-containing group, and the compound 19 represented by the following formula 20. Compound 20 having one allyl group and two active hydrogen-containing groups in one molecule was confirmed.

The ratio of the compound 18 to the total peak area of the compound 18, the compound 19 and the compound 20 in the gas chromatography in the organic layer was 5%, the ratio of the compound 19 was 88%, and the ratio of the compound 20 was 7%.

[Production Example 2: Production of compound (a2)]
A flask equipped with a stirrer, a reflux condenser, a thermometer, and two dropping funnels was charged with 1 mol equivalent of pentaerythritol and heated to 90 ° C. under a nitrogen stream. While stirring at 90 ° C., a 40 mass% sodium hydroxide aqueous solution was simultaneously added dropwise to pentaerythritol in an equivalent amount of 3 mol and allyl chloride in an equivalent amount of 3 mol to pentaerythritol using separate dropping funnels. The aqueous sodium hydroxide solution was added dropwise over 2 hours, and the allyl chloride solution was added dropwise over 3 hours. After completion of the reaction, water was added to dissolve the precipitated sodium chloride, and the mixture was allowed to cool. When the organic layer of the solution after the reaction of the two layers consisting of the organic layer and the aqueous layer was separated and analyzed by gas chromatography, it has four allyl groups in one molecule represented by the following formula 21. , The compound 21 having no active hydrogen-containing group, the compound 22 having three allyl groups in one molecule represented by the following formula 22, and having one active hydrogen-containing group, and the compound 22 represented by the following formula 23. Compound 23 having two allyl groups and two active hydrogen-containing groups in one molecule was confirmed.

The ratio of the compound 21 to the total peak area of the compound 21, the compound 22 and the compound 23 in the gas chromatography in the organic layer was 8%, the ratio of the compound 22 was 82%, and the ratio of the compound 23 was 10%.

[Production Example 3: Production of Polymer Mixture (1)]
Using the organic layer (including compounds 18 to 20) obtained in Production Example 1 as an initiator, propylene oxide was polymerized using a TBA-DMC catalyst to obtain an oxypropylene polymer (1B) derived from compound 19. , A mixed solution containing a polymer (1C) derived from compound 20 was obtained.
The polymer (1B) has 2.0 unsaturated groups and 0 hydroxyl groups in one terminal group, and has 0 unsaturated groups and 1.0 hydroxyl group in the other terminal group. The polymer (1C) has 1.0 unsaturated group and 2.0 hydroxyl group in one molecule, and the number of hydroxyl groups in the mixed solution obtained by the above measurement method is unsaturated. The number of groups was distributed to the polymer (1B) and the polymer (1C) according to the ratio of the peak areas of the GPCs of the polymer (1B) and the polymer (1C) contained in the mixed solution.
As a result, the average number of unsaturated groups in one molecule of the polymer (1B) is 2.0, the average number of hydroxyl groups is 1.0, and the number of unsaturated groups in one molecule of the polymer (1C) is 1.0. The average number of groups was 1.0 and the average number of hydroxyl groups was 2.0, confirming that the desired polymer mixture could be produced.
Table 1 shows the hydroxyl group-equivalent molecular weight obtained by the above method from the polymer (1B), the Mn of the polymer (1C), the ratio of the peak area of GPC, and the hydroxyl value of the mixed solution (hereinafter, the same applies).

[Production Example 4: Production of Polymer Mixture (2)]
In Production Example 3, the oxypropylene polymer (2B) derived from compound 19 and the polymer (2C) derived from compound 20 are prepared in the same manner as in Production Example 3 except that the input amount of propylene oxide is changed. A mixed solution containing the mixture was obtained.
The polymer (2B) has 2.0 unsaturated groups and 0 hydroxyl groups in one terminal group, and has 0 unsaturated groups and 1.0 hydroxyl group in the other terminal group. The polymer (2C) has 1.0 unsaturated group and 2.0 hydroxyl group in one molecule, and the number of hydroxyl groups in the mixed solution obtained by the above measurement method is unsaturated. The number of groups was distributed to the polymer (2B) and the polymer (2C) according to the ratio of the peak areas of the GPCs of the polymer (2B) and the polymer (2C) contained in the mixed solution.
As a result, the average number of unsaturated groups in one molecule of the polymer (2B) is 2.0, the average number of hydroxyl groups is 1.0, and the number of unsaturated groups in one molecule of the polymer (2C) is 1.0. The average number of groups was 1.0 and the average number of hydroxyl groups was 2.0, confirming that the desired polymer mixture could be produced.

[Production Example 5: Production of Polymer Mixture (3)]
Using the organic layer (including compounds 21 to 23) obtained in Production Example 2 as an initiator, propylene oxide was polymerized using a TBA-DMC catalyst to obtain an oxypropylene polymer (3B) derived from compound 22. , A mixed solution containing a polymer (3C) derived from compound 23 was obtained.
The polymer (3B) has 3.0 unsaturated groups and 0 hydroxyl groups in one terminal group, and has 0 unsaturated groups and 1.0 hydroxyl groups in the other terminal group. The polymer (3C) has 2.0 unsaturated groups and 2.0 hydroxyl groups in one molecule, and the number of hydroxyl groups in the mixed solution obtained by the above measurement method is unsaturated. The number of groups was distributed to the polymer (3B) and the polymer (3C) according to the ratio of the peak areas of the GPCs of the polymer (3B) and the polymer (3C) contained in the mixed solution.
As a result, the average number of unsaturated groups in one molecule of the polymer (3B) is 3.0, the average number of hydroxyl groups is 1.0, and the number of unsaturated groups in one molecule of the polymer (3C) is 1.0. The average number of groups was 2.0, and the average number of hydroxyl groups was 2.0, confirming that the desired polymer mixture could be produced.

[Production Example 6: Production of Polymer (E1)]
The mixed solution obtained in Production Example 3 was dehydrated under reduced pressure. Then, tin octylate (II) (Nikka octix tin, product name of Nihon Kagaku Sangyo Co., Ltd., the same shall apply hereinafter) was added, and HDI having an index of 100% with respect to the hydroxyl group of the polymer contained in the mixed solution was applied at room temperature. It was added and heated at 85 ° C. for 2 hours. After confirming that there is no residual HDI in the reaction solution by infrared spectroscopy analysis (hereinafter referred to as "IR analysis"), 1% by mass of methanol is added to the total amount of the reaction solution, and the mixture is stirred for 0.5 hours. After that, methanol was removed by degassing under reduced pressure. The reaction solution was analyzed by GPC to confirm that the molecular weight was increased, and it was confirmed that the coupling was surely progressing.
Next, 2% by mass of water was added to the total amount of the obtained reaction solution, the mixture was stirred at 85 ° C. for 0.5 hour, and then water was removed by degassing under reduced pressure. In the presence of the platinum divinyldisiloxane complex, 0.80 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the unsaturated group of the polymer contained in the mixed solution, and the mixture was reacted at 85 ° C. for 3 hours. The unreacted dimethoxymethylsilane was removed under reduced pressure to obtain a polymer (E1) containing the following components (E1-1) and (E1-2).
Component (E1-1): A component derived from a component produced by a coupling reaction between two molecules of the polymer (1B).
Component (E1-2): A component derived from a component produced by a coupling reaction between two molecules of the polymer (1B) and one or more molecules of the polymer (1C).
The ratio of the peak area of Mn and GPC of the components (E1-1) and (E1-2), the number of reactive silicon groups in one molecule, and the concentration of Mn, Mw / Mn and the reactive silicon group of the polymer (E1). , And the urethane bond content are shown in Table 2 (hereinafter, the same applies).

[Production Example 7: Production of Polymer (E2)]
The mixed solution obtained in Production Example 4 was dehydrated under reduced pressure. Then, tin (II) octylate was added, HDI having an index of 100% was added to the hydroxyl group of the polymer contained in the mixed solution at room temperature, and the mixture was heated at 85 ° C. for 2 hours. After confirming that there was no residual HDI in the reaction solution by IR analysis, 1% by mass of methanol was added to the total amount of the reaction solution, the mixture was stirred for 0.5 hours, and then methanol was removed by degassing under reduced pressure. The reaction solution was analyzed by GPC to confirm that the molecular weight was increased, and it was confirmed that the coupling was surely progressing.
Next, 2% by mass of water was added to the total amount of the obtained reaction solution, the mixture was stirred at 85 ° C. for 0.5 hour, and then water was removed by degassing under reduced pressure. In the presence of the platinum divinyldisiloxane complex, 0.80 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the unsaturated group of the polymer contained in the mixed solution, and the mixture was reacted at 85 ° C. for 3 hours. The unreacted dimethoxymethylsilane was removed under reduced pressure to obtain a polymer (E2) containing the following components (E2-1) and (E2-2).
Component (E2-1): A component derived from a component produced by a coupling reaction between two molecules of the polymer (2B).
Component (E2-2): A component derived from a component produced by a coupling reaction between two molecules of the polymer (2B) and one or more molecules of the polymer (2C).

[Production Example 8: Production of Polymer (E3)]
The mixed solution obtained in Production Example 5 was dehydrated under reduced pressure. Then, tin (II) octylate was added, HDI having an index of 100% was added to the hydroxyl group of the polymer contained in the mixed solution at room temperature, and the mixture was heated at 85 ° C. for 2 hours. After confirming that there was no residual HDI in the reaction solution by IR analysis, 1% by mass of methanol was added to the total amount of the reaction solution, the mixture was stirred for 0.5 hours, and then methanol was removed by degassing under reduced pressure. The reaction solution was analyzed by GPC to confirm that the molecular weight was increased, and it was confirmed that the coupling was surely progressing.
Next, 2% by mass of water was added to the total amount of the obtained reaction solution, the mixture was stirred at 85 ° C. for 0.5 hour, and then water was removed by degassing under reduced pressure. In the presence of the platinum divinyldisiloxane complex, 0.80 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the unsaturated group of the polymer contained in the mixed solution, and the mixture was reacted at 85 ° C. for 3 hours. The unreacted dimethoxymethylsilane was removed under reduced pressure to obtain a polymer (E3) containing the following components (E3-1) and (E3-2).
Component (E3-1): A component derived from a component produced by a coupling reaction between two molecules of the polymer (3B).
Component (E3-2): A component derived from a component produced by a coupling reaction between two molecules of the polymer (3B) and one or more molecules of the polymer (3C).

[Production Example 9: Production of Polymer (G1)]
Propylene oxide was polymerized using glycerin as an initiator and a TBA-DMC catalyst to obtain a precursor polymer having a molecular weight in terms of hydroxyl group of 10,000. Then, 1.15 mol equivalents of sodium methoxide in methanol was added to the hydroxyl group of the precursor polymer to alcorate the precursor polymer. Next, methanol was distilled off by heating and reducing pressure, and an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer to introduce an allyloxy group into the terminal group. Next, in the presence of platinum chloride hexahydrate, 0.65 molar equivalent of dimethoxymethylsilane was added as a silylating agent to the converted allyloxy group of the precursor polymer, and the reaction was carried out at 85 ° C. for 3 hours. Then, a linear oxypropylene polymer (G1) in which a reactive silicon group was introduced into the terminal group was obtained. The Mn of the polymer (G1) was 15,000, and the average number of reactive silicon groups per molecule was 2.0.

[Production Example 10: Production of Polymer (G2)]
An oxypropylene polymer having Mn of about 2,000, having two terminal groups and having a hydroxyl group as the terminal group is used as an initiator, and a TBA-DMC catalyst is used as a catalyst to polymerize propylene oxide, which is converted into a hydroxyl group. A precursor polymer having a molecular weight of 12,000 was obtained. Then, 1.0 mol equivalent of a methanol solution of sodium methoxide was added to the hydroxyl group of the precursor polymer to alcorate the precursor polymer. Next, methanol was distilled off by heating and reducing pressure, 1.05 molar equivalent of allyl glycidyl ether was added to the amount of hydroxyl groups of the precursor polymer, and the reaction was carried out at 130 ° C. for 2 hours. Then, 0.28 mol equivalents of sodium methoxide in methanol was added to remove methanol, 1.79 mol equivalents of allyl chloride was added, and after the reaction, unreacted allyl chloride was removed under reduced pressure. An oxypropylene polymer (polymer Q1) having an allyl group introduced into the terminal group was obtained. The average number of allyl groups introduced into one terminal group of the polymer Q1 was 2.0. Next, 0.85 mol equivalent of dimethoxymethylsilane was added as a silylating agent to the allyl group of the polymer Q1 in the presence of the platinum divinyldisiloxane complex, and the mixture was reacted at 85 ° C. for 3 hours before being reacted. The dimethoxymethylsilane of the reaction was removed under reduced pressure to obtain a polymer (polymer (G2)) in which more than 1.0 dimethoxymethylsilyl groups were introduced into one terminal group on average as reactive silicon groups. rice field.

<Other ingredients>
The additives listed in Table 3 are as follows.
Whiten SB: Heavy calcium carbonate, product name of Shiraishi Kogyo Co., Ltd.
CCR: White glossy CCR Colloidal calcium carbonate, product name of Shiraishi Kogyo Co., Ltd.
R-820: Titanium oxide, product name of Ishihara Sangyo Co., Ltd.
Balloon 81GCA: Organic balloon, product name of Matsumoto Oil & Fats Co., Ltd.
Printex30: Carbon Black, Orion Engineered Carbons Product name.
CML35: Calcium oxide, product name of Shiraishi Kogyo Co., Ltd.
DINP: Diisononyl phthalate.
UP-1171: ARUFON UP-1711, Mw3,000 acrylic polymer, Toagosei product name.
S4012: Preminol S4012, a high molecular weight polyol having two hydroxyl groups per molecule and an Mn of 10,000 per hydroxyl group, a product name of AGC Inc.
DINCH: 1,2-Cyclohexanedicarboxylic acid-diisononyl ester.
Polymer Q: Polymer Q synthesized by the method described below.
N-12D: n-dodecane, purity 98.0%, Cactus normal paraffin N-12D, JXTG Energy product.
Sunsocizer EPS: 4,5-Epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl, product name of NEW JAPAN CHEMICAL CO., LTD.
Disparon # 6500: Hydrogenated castor oil-based thixotropic agent, Kusumoto Kaseisha product name.
IRGANOX1135: Hindered phenolic antioxidant, BASF product name.
TINUVIN326: Benzotriazole-based UV absorber, product name of BASF.
TINUVIN765: A hindered amine-based light stabilizer containing a tertiary amine, a product name of BASF.
LA-63P: ADEKA STAB LA-63P, ADEKA product name.
KBM-1003: Vinyl trimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
KBM-403: 3-glycidyloxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
KBM-603: 3- (2-aminoethylamino) propyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
Laurylamine: Reagent, manufactured by Junsei Chemical Co., Ltd.
Farmin CS: Coconut Amine, Kao product name.
DEAPA: 3-diethylaminopropylamine, manufactured by Tokyo Chemical Industry Co., Ltd.
TMP-3TMS: Tritrimethylsilyl form of trimethylolpropane.
Tung oil: Air oxidative curable compound, manufactured by Kimura.
M-309: Aronix M-309, Toagosei product name.
DBTDL: Dibutyl phthalate, manufactured by Tokyo Chemical Industry Co., Ltd.
U-220H: Tin catalyst, product name of Nitto Kaseisha.
TC750: Titanium diisopropoxybis (ethylacetacetate), Organix TC750, Matsumoto Fine Chemical Co., Ltd. Product name.
Neodecanoic acid: manufactured by Strem Chemicals.
Catalyst composition: 4 parts by mass of a mixture of stannoct (stantic octylate, product name of Yoshitomi Pharmaceutical Co., Ltd.) and laurylamine (reagent, manufactured by Genuine Chemical Co., Ltd.) so as to have a mass ratio of 6: 1. Sizer DINP (diisononyl phthalate, product name of Shin Nihon Rika Co., Ltd.) 6 parts by mass, Whiten SB (heavy calcium carbonate, product name of Shiraishi Calcium Industry Co., Ltd.) 15 parts by mass and Glomax LL (baked kaolin, product name of Takehara Chemical Industry Co., Ltd.) ) A composition obtained by mixing 5 parts by mass.

(Synthesis of Polymer Q)
Polyoxypropylene monool (hydroxyl equivalent (molecular weight per hydroxyl group) 2000) obtained by ring-opening addition polymerization of PO to n-butanol was used as an initiator.
Initiator 384 g and PO 594 g are reacted in the presence of 0.05 g of TBA-DMC at 120 ° C. until the pressure of the reaction system does not decrease, and each molecule has one hydroxyl group at the end of the polyoxypropylene chain. A precursor polymer (1') was obtained (Mw8100, Mn6900, Mw / Mn1.10.).
A methanol solution containing 1.05 times mol of sodium methoxide with respect to the hydroxyl group of the precursor polymer (1') is added to the precursor polymer (1') to make it alkoxide, and then heated and depressurized to add methanol. Distilled away. Then, an excess molar equivalent of allyl chloride is added to the hydroxyl group of the precursor polymer (1') to cause a reaction, and the precursor polymer (2') having one allyl group at the end of the polyoxypropylene chain per molecule. Got
Next, in the presence of platinum chloride hexahydrate, 0.85 times the molar equivalent (silylation rate 85 mol%) of methyldimethoxylan was added to the allyl group of the precursor polymer (2'), and 85. The reaction was carried out at ° C. for 3 hours to obtain a polymer Q having a reactive silyl group at one end of the polyoxypropylene chain. The Mn of the polymer Q was 7,000, and the average number of reactive silicon groups per molecule was 0.80.

<Manufacturing of curable composition>
Examples 1 to 3 are examples, and examples 5 and 6 are comparative examples.

(Examples 1 to 6)
The polymer of the formulation (unit: parts by mass) shown in Table 4 and the additive 1 of the formulation shown in Table 3 were mixed to prepare a curable composition. The formulations shown in Table 3 are values (unit: parts by mass) with respect to 100 parts by mass of the polymer.
The cured product of the obtained curable composition was evaluated for M50, Tmax, and maximum point elongation by the above method. The results are shown in Table 4.

In Examples 1 to 3, the values of M50 and Tmax of the cured product were high, and the strength was excellent.

Even when the curable compositions were produced by changing the additives to the additives 2 to 16 in Table 3 in Examples 1 to 3, the values of M50 and Tmax of the cured product were high and the strength was excellent in each of the examples. Was there.

Claims (15)

A polymer having a reactive silicon group, an unsaturated group and a polyoxyalkylene chain represented by the following formula 1, wherein the total of the reactive silicon group and the unsaturated group is averaged per one terminal group. An oxyalkylene polymer (A) having more than 0 and having the reactive silicon group and urethane bond in the main chain.
-SiX _a R _3-a formula 1
In the above formula 1, R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X represents a hydroxyl group, a halogen atom, or a hydrolyzable group, and a is. It indicates an integer of 1 to 3, and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other. The main chain contains a residue obtained by removing an isocyanate group from a polyisocyanate, a polyoxyalkylene chain, and a urethane bond connecting the residue and the polyoxyalkylene chain.
The oxyalkylene polymer according to claim 1, wherein the terminal group is a terminal group containing an oxygen atom closest to the molecular terminal of the oxyalkylene polymer (A) among the oxygen atoms in the polyoxyalkylene chain. (A). The oxyalkylene polymer (A) according to claim 1 or 2, wherein the number average molecular weight is 3,000 to 100,000. The oxyalkylene polymer (A) according to any one of claims 1 to 3, wherein the molecular weight distribution is 2.0 or less. The oxyalkylene polymer (A) according to any one of claims 1 to 4, which has more than 0 reactive silicon groups on average per terminal group. A curable composition comprising the oxyalkylene polymer (A) according to any one of claims 1 to 5 and a curing catalyst. The active hydrogen-containing group in the terminal group of the following oxyalkylene polymer (B) and the active hydrogen-containing group in the terminal group of the following oxyalkylene polymer (C) are reacted with a polyisocyanate having a molecular weight of 100 to 20,000. The following oxyalkylene polymer (D) is obtained, and then the reaction represented by the above formula 1 with the unsaturated group present in the terminal group of the oxyalkylene polymer (D) and the unsaturated group present in the main chain. The method for producing an oxyalkylene polymer (A) according to claim 5, wherein the silylating agent having a sex silicon group is reacted with the silylating agent.
Oxyalkylene polymer (B): A polymer having an unsaturated group, an active hydrogen-containing group and a polyoxyalkylene chain, which has one terminal group having more than 0 unsaturated groups on average, and the above-mentioned A polymer having one terminal group having more than 0 and 1.0 or less active hydrogen-containing groups on average.
Oxyalkylene polymer (C): A polymer having an initiator residue having an unsaturated group, an active hydrogen-containing group and a polyoxyalkylene chain, which has the initiator residue in the main chain and said. A polymer having 2 to 4 terminal groups having an average number of active hydrogen-containing groups of more than 0 and 1.0 or less.
Oxyalkylene polymer (D): a main chain having a polyoxyalkylene chain, an unsaturated group present in the main chain, a urethane bond present in the main chain, and a weight having an unsaturated group present in the terminal group. A polymer that is a coalescence and has an average of more than 0 unsaturated groups per terminal group. The oxyalkylene polymer (B) is an oxyalkylene polymer obtained by subjecting a cyclic ether to a ring-opening addition polymerization reaction with an initiator (b), and the initiator (b) is one or more in one molecule. The method for producing an oxyalkylene polymer (A) according to claim 7, which is a compound having an unsaturated group and having one active hydrogen-containing group in one molecule. The method for producing an oxyalkylene polymer (A) according to claim 8, wherein the initiator (b) is a compound represented by the following formula 2.

In the above formula 2, R ¹ is an active hydrogen-containing group, R ² is a hydrogen atom or a methyl group, R ⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. A divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, R ⁶ may contain an oxygen atom or a nitrogen atom, and an oxygen atom or an atom adjacent to the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. A monovalent hydrocarbon group of 20, a hydrogen atom, or a group represented by -R ⁶² -CR ⁶¹ = CH ₂ , R ⁶¹ is a hydrogen atom or a methyl group, and R ⁶² is an oxygen atom or a nitrogen atom. It may be contained, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, and the two ^R6s are the same but different. Often, n is an integer from 0 to 10. The oxyalkylene polymer (C) is an oxyalkylene polymer obtained by subjecting a cyclic ether to a ring-opening addition polymerization reaction with an initiator (c), and the initiator (c) is one or more in one molecule. The production of the oxyalkylene polymer (A) according to any one of claims 7 to 9, which is a compound having an unsaturated group and having 2 to 4 active hydrogen-containing groups in one molecule. Method. 10. The initiator (c1) is an initiator (c1) having one or more unsaturated groups in one molecule and two active hydrogen-containing groups in one molecule. The method for producing an oxyalkylene polymer (A) according to the above method. The method for producing an oxyalkylene polymer (A) according to claim 11, wherein the initiator (c1) is a compound represented by the following formula 3.

In the above formula 3, R ¹¹¹ is an active hydrogen-containing group, R ¹¹² is a hydrogen atom or a methyl group, R ¹¹⁴ may contain an oxygen atom or a nitrogen atom, and an atom adjacent to the oxygen atom or the nitrogen atom is a carbon atom. It is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, and R ¹¹⁶ may contain an oxygen atom or a nitrogen atom, and an oxygen atom or an atom adjacent to the nitrogen atom is a carbon atom having 1 to 20 carbon atoms. A monovalent hydrocarbon group of 20, a hydrogen atom, or a group represented by -R ¹⁷² -CR ¹⁷¹ = CH ₂ , R ¹⁷¹ is a hydrogen atom or a methyl group, and R ¹⁷² is an oxygen atom or a nitrogen atom. It may be contained, and the atom adjacent to the oxygen atom or the nitrogen atom is a divalent hydrocarbon group or a single bond having 1 to 20 carbon atoms, which is a carbon atom, a is an integer of 0 to 10, and a plurality of R ^111s . -The groups represented by (CH ₂ ) _a -may be the same or different. One of claims 8 to 12, wherein the cyclic ether comprises at least one cyclic ether selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. The method for producing an oxyalkylene polymer (A) according to the above method. The method for producing an oxyalkylene polymer (A) according to any one of claims 8 to 13, wherein the ring-opening addition polymerization reaction is carried out in the presence of a composite metal cyanation complex catalyst. The method for producing an oxyalkylene polymer (A) according to any one of claims 7 to 14, wherein the oxyalkylene polymer (D) has a number average molecular weight of 3,000 to 100,000.