JP2000178337A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition which exhibits high adhesiveness even to glass or a polyolefin material without the aid of a primer by adding a polyisocyanate to a polymer comprising polymer units derived from a cyclic olefin monomer, polymer units derived from a linear olefin monomer, and polymer units derived from another monomer and having a specified hydroxy value. SOLUTION: A polymer having a hydroxy of 2 or above and represented by the formula and a polyisocyanate having at least two isocyanate groups on the average are used. In the formula, P is a polymer unit derived from a cyclic olefin monomer; Q is a polymer unit derived from a cyclic olefin monomer; and R is polymer unit derived from another monomer and being bondable to P and/or Q. P, Q, and R may be arranged in any order. The respective units may be arranged in a random, block, or gradient manner. p, q, and r have values satisfying the relationships: p+q+r=100; 1<=p<=100; 0<=q<=99; and 0<=r<=99.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cured composition, which is used as a sealing material or an adhesive.
Automotive field, construction engineering field, electric and electronic field, textile field,
The present invention relates to a curable composition applicable to the medical field, resin product field, and the like.

[0002]

2. Description of the Related Art Conventionally, the fields of automobiles, construction and civil engineering,
A wide variety of materials are used in electrical and electronic fields, textile fields, medical fields, resin products fields, etc.When these are used in combination, adhesion and sealing between the materials are performed, and each application and use Various adhesive and sealing materials have been developed and used according to the conditions.

[0003] In recent years, plastic materials, particularly polyolefin-based materials such as polyethylene and polypropylene, are preferably used from the viewpoints of weight reduction, cost reduction, and improvement in recyclability. However, this polyolefin-based material and other materials, for example, glass are preferred. It is difficult to adhere to both at the same time, and there are frequent cases where it is necessary to take measures such as surface treatment, use of primer, etc.In particular, these materials have strong adhesion, and in addition, adhere to other materials There is a strong demand for the development of a material that has high strength, high weather resistance, high heat resistance, low moisture permeability, fast curing properties, and various properties of good mechanical properties.

Polyolefin polyols, for example, polyols obtained by hydrogenating a polyhydroxydiene-based polyol as disclosed in JP-A-63-130616, contain polar groups such as esters and ethers in the main chain. Polyurethane elastomers containing this as a main component are excellent in electrical insulation, low moisture permeability, and hydrolysis resistance, but are insufficient in adhesion to polyolefin materials. Hydrogenated polybutadiene and polyisobutylene polymers containing hydrolyzable silicon as disclosed in, for example, JP-A-1-198673 also use a special primer to improve the adhesion to glass. However, the adhesive strength to the polyolefin-based material is insufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention has various properties such as high weather resistance, low moisture permeability, and good mechanical properties without the use of a primer, having a strong adhesion to glass and polyolefin materials. It is an object to provide a satisfactory cured composition. Another object is to provide a curable composition suitable as a sealing material or a material for an adhesive.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific polymer and polyisocyanate. That is, the first of the present invention is a curable composition containing the following components (A) and (B). (A) A resin having a hydroxyl value of 2 or more and comprising at least one polymer represented by the following composition formula (1).

[-(P) p-,-(Q) q-,-(R) r-] (1) [P, Q and R represent polymer units constituting a polymer main chain, and P is cyclic It is a polymer unit composed of one or more monomer units selected from olefin-based monomer units. Q represents a polymer unit composed of one or more monomer units selected from linear olefinic monomers, and R represents P and / or other monomer units capable of binding to Q. Represents one or more polymer units. R may be bonded to any of P, Q and R units. P, Q, and R may be arranged in any order, and the units may be arranged randomly, in blocks, or arranged in a gradient. p, q, and r are monomer units P,
It represents the mole% of each of Q and R based on the whole polymer.
The number average molecular weight of the polymer in terms of standard polystyrene is 1,0.
The range is from 00 to 500,000. Also, P, Q, R
In the side chain of the polymer composed of, a hydrogen atom or hydrogen, oxygen, nitrogen, sulfur, phosphorus, silicon, halogen (F,
Cl, Br, I) a functional group containing at least one element selected from the group consisting of a functional group or an organic residue having a functional group, a C1-C20 alkyl group, a C2-C20 unsaturated aliphatic hydrocarbon group, and a C5- C20 aryl group, C3 to
A cycloalkyl group of C20, a cyclodienyl group of C4 to C20, or a 5- to 10-membered ring, to which a group selected from a heterocyclic group containing at least one nitrogen, oxygen or sulfur as a hetero atom is bonded; Is also good.

[0008] p, q, and r satisfy the following relationship. p + q + r = 100, 1 ≦ p ≦ 100, 0 ≦ q ≦ 99,
0 ≦ r ≦ 99] (B) A polyisocyanate having an average of two or more isocyanate groups per molecule. A second aspect of the present invention is the curable composition according to claim 1, which comprises (C) a curing catalyst.

A third aspect of the present invention is the curable composition according to any one of the first and second aspects, wherein p is 3 or more. A fourth aspect of the present invention is the curable composition according to any one of the first to third aspects of the present invention, wherein the cyclic olefin-based monomer is cyclohexene and / or cyclohexane, or a derivative unit thereof.

A fifth aspect of the invention is a sealing material containing the curable composition according to any one of the first to fourth aspects of the invention. A sixth aspect of the present invention is an adhesive material containing the curable composition according to any one of the first to fourth aspects of the invention. Hereinafter, the present invention will be described in more detail.

The curable composition of the present invention comprises a resin (A) having a hydroxyl value of at least 2 and comprising at least one polymer represented by the formula (1) and an isocyanate group (B). By combining and curing a polyisocyanate having an average of two or more, weather resistance, heat resistance,
It can be a material having low moisture permeability, fast curing properties, and various properties of good mechanical properties. In particular, the curing of hydroxyl group and isocyanate can be controlled by the coexistence of an appropriate catalyst.For example, curing proceeds easily even under severe conditions such as room temperature or lower. In addition to excellent properties such as excellent heat resistance and good curability, the urethane bond generated by curing is effective in expressing weather resistance, heat resistance, good mechanical properties, adhesion to various materials, etc. Having a cyclic olefin-based monomer unit contained in the resin, without impairing the function of high adhesion to a polyolefin-based material, without taking measures such as surface treatment which is the object of the present invention. A material that simultaneously adheres the same material to other materials and has the characteristics of high weather resistance, high heat resistance, low moisture permeability, fast curing, and good mechanical properties. It is those that have found the door.

In the present invention, it is essential that the resin comprising at least one kind of the polymer having at least two hydroxyl groups as the component (A) contains a cyclic olefin monomer unit P. Here, the cyclic olefin-based monomer unit refers to a unit having a structure in which carbon atoms are cyclically bonded,
The cyclic carbon atom is a hydrogen atom, or hydrogen (H), oxygen (O), nitrogen (N), sulfur (S), phosphorus (P), silicon (Si), halogen (F, Cl, Br, I). A functional group containing at least one element selected from the group consisting of: an organic residue having a functional group; a C1 to C20 alkyl group;
2 to C20 unsaturated aliphatic hydrocarbon group, C5 to C20 aryl group, C3 to C20 cycloalkyl group, C4 to C20
A cyclodienyl group of 20 or a 5- to 10-membered ring to which a heterocyclic group containing at least one nitrogen, oxygen or sulfur as a hetero atom is bonded. Specifically, derivative units such as cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cyclooctane, and cyclooctene can be exemplified. In particular, cyclohexane and cyclohexene units are thermally stable and can be suitably used. These units are obtained by polymerizing a cyclic olefin, a cyclic conjugated diene, for example, cyclohexene, 1,3-cyclohexadiene or a derivative thereof. , 3-cyclohexadiene or a derivative thereof can be suitably obtained by anionic polymerization. For example, when 1,3-cyclohexadiene is used as a monomer, a 1,2- or 1,4-bonded cyclohexene unit is formed, and this is converted to 1,2- or 1,4 by a method such as hydrogenation. −
A linked cyclohexane unit can be obtained.

The preferred content of the above-mentioned cyclic olefin-based monomer unit is at least 1 mol%, more preferably at least 3 mol%, of the total number of moles of the total monomer including other copolymerized monomer units. . Below this, the adhesion to inorganic materials such as polyolefin-based materials and glass is insufficient. Also,
The chain olefin monomer unit Q optionally introduced into the resin comprising at least one polymer having at least two hydroxyl groups used in the present invention is not particularly limited, but may be an aliphatic unsaturated hydrocarbon or When an unsaturated bond is present in the unit formed by polymerizing the derivative or the polymerized unit formed, it is preferably a group generated by an addition reaction such as hydrogenation. By way of example, an ethylethylene group generated by polymerizing 1-butene is one example of a chain olefin-based monomer unit. Further, for example, a vinylethylene group, a 2-butenylene group generated when 1,3-butadiene is polymerized, and an ethylethylene group and a butylene group generated by hydrogenating these are also examples of the chain olefin monomer unit. is there. Examples of the above unsaturated hydrocarbons include ethylene, propylene, butenes, 1,3-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, pentenes,
Examples include 1,3-pentadiene, hexenes, 1,3-hexadiene and the like and derivatives thereof.

Further, the above-mentioned P and / or Q to be introduced into the resin comprising at least one polymer having at least two hydroxyl groups used in the present invention, if necessary.
One or two or more monomer units R selected from monomer units copolymerizable with a monomer unit that combines with a monomer that forms a P or Q polymerization unit. Any unit may be used as long as it is a unit generated by. Examples of such monomers include vinyl aromatic monomers such as styrene, α-methylstyrene, divinylbenzene, diisopropenylbenzene, (meth) acrylic acid, methyl (meth) acrylate, (Meth) acrylic acid monomers such as hydroxyethyl, unsaturated nitriles such as (meth) acrylonitrile, unsaturated ketones such as methyl vinyl ketone, unsaturated amides such as acrylamide and diacetone acrylamide, ethylene oxide; Examples include cyclic ethers such as propylene oxide and tetrahydrofuran, cyclic lactones, cyclic lactams, and cyclic siloxanes. One of these monomers may be used alone, or two or more of these monomers may be used in combination.

When the polymer according to the present invention contains two or more types of polymer units, the type of copolymerization can be selected as necessary. For example, block copolymerization such as diblock, triblock, multiblock, and radial block, graft copolymerization, taper copolymerization, random copolymerization, and alternating copolymerization can be mentioned. Among these, the block copolymer is a particularly preferable form because even when the proportion of the cyclic monomer unit is small, properties such as adhesiveness are sufficiently exhibited.

The number average molecular weight of the polymer having at least two hydroxyl groups (A) of the present invention is from 1,000 to 2
It is preferably 00,000. Examples of the production of the polymer according to the present invention include methods such as radical polymerization, anionic polymerization, and cationic polymerization. When the polymer according to the present invention contains two or more types of polymer units, a method of simultaneously polymerizing each monomer, partially polymerizing the monomers first, sequentially, adding other monomers A method of copolymerizing, a method of polymerizing each monomer separately, introducing a reactive functional group at that time, and then bonding each polymer to form a copolymer, or Although a method of combining these is mentioned, by appropriately selecting a production method in consideration of the reactivity of the monomer,
A copolymer can be designed.

The most preferred polymerization method for the cyclic conjugated diene, particularly 1,3-cyclohexadiene, which is particularly preferably used for obtaining the cyclic olefin-based polymer unit essential for the resin according to the present invention, is described in the Periodic Table IA. A complex compound is formed by reacting an organometallic compound containing a metal of the group III with an organic compound capable of forming a complex with the organometallic compound (hereinafter, referred to as a complexing agent). This is a method in which polymerization is carried out to obtain a cyclic conjugated diene-based polymer having an arbitrary molecular weight and a high-molecular structure, and if necessary, hydrogenated.

I can be used as the organometallic compound
The group A metal is lithium, sodium, potassium, rubidium, cesium, and francium, and lithium is a particularly preferred group IA metal. These Group IA metals may be one kind or, if necessary, a mixture of two or more kinds. The organolithium compound suitably used for the polymerization catalyst is a compound containing one or more lithium atoms that binds to an organic molecule or an organic polymer containing at least one carbon atom.
The organic molecule is a C1-C20 alkyl group, C2-
C20 unsaturated aliphatic hydrocarbon group, C5-C20 aryl group, C3-C20 cycloalkyl group, C4-C2
0 is a cyclodienyl group.

As the organic lithium compound used for the polymerization catalyst, methyl lithium, ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, n-hexyllithium, allyllithium, cyclohexyllithium, phenyllithium, hexamethylenedilithium, cyclopentadienyllithium, indenyllithium, butadienyldilithium, isoprenyldilithium or the like, or polybutadienyllithium, polyisolithium Conventionally known oligomeric or polymeric organic lithiums containing a lithium atom in a part of the polymer chain, such as prenyllithium and polystyryllithium, can be exemplified. Preferred organic lithium compounds include methyllithium, ethyllithium,
Examples thereof include n-butyllithium and cyclohexyllithium. In particular, n-butyllithium can be exemplified as the most preferred organic lithium compound that can be industrially employed.

The organometallic compound containing a Group IA metal employed in the polymerization catalyst may be one kind or, if necessary, a mixture of two or more kinds. As the organic compound (complexing agent) capable of forming a complex with an organometallic compound containing a Group IA metal, amines, ethers, and thioethers are preferable, and one of these complexing agents may be used if necessary. Mixtures of more than one species may be used.

Particularly preferred complexing agents include amines which have high complexing ability and are widely used industrially. Among them, tertiary (tertiary) amines are most preferable. Specific examples of the tertiary amine compound include trimethylamine, triethylamine, N, N-dimethylaniline, N, N, N ′, N′-tetramethyldiaminomethane,
N, N, N ', N'-tetramethylethylenediamine,
N, N, N ', N'-tetramethyl-1,3-propanediamine, tetramethyldiethylenetriamine, 1,8-
Examples thereof include diazabicyclo [5,4,0] undecene-7, diazabicyclo [2,2,2] octane, and 4,4′-bipyridyl. The most preferred tertiary amine compound is 1,1 in the polycyclohexadiene chain. 2 / 1,4
Tetramethylethylenediamine (TMEDA) can be used to control the microstructure of the polymer, including the ratio.

The method for preparing the polymerization catalyst comprising the organometallic compound and the complexing agent is not particularly limited, and any conventionally known technique can be employed if necessary. For example,
A method in which an organic metal compound is dissolved in an organic solvent under a dry inert gas atmosphere, and a solution of amines is added thereto.For example, an amine is dissolved in an organic solvent under a dry inert gas atmosphere, and the organic metal compound is added thereto. A method of adding a solution of the compound can be exemplified. Alternatively, an organic metal is dissolved in an organic solvent under an inert gas atmosphere, a solution of an amine is added thereto, and the solution is kept for a certain period of time. Then, the monomer is added without isolating the polymerization catalyst (complex). It is also possible to carry out the polymerization.

The temperature of the reaction between the organometallic compound and the amine is generally carried out in the range of -100 to 100 ° C. Helium, nitrogen and argon are preferred as the dry inert gas. When preparing the polymerization catalyst, the compounding ratio of the constituent organometallic compound and the complexing agent is determined by mixing the complexing agent with M1mo.
l, when the organometallic compound is M2 mol, M1 / M2
= 30/1 to 1/30, and most preferably M1 / M2 = 20/1 to 1/20, in order to obtain a polymer with high yield.

The type of polymerization is not particularly limited, and for example, methods such as gas phase polymerization, bulk polymerization, and solution polymerization can be employed. The polymerization reaction process is not particularly limited, and for example, any of a batch system, a semi-batch system, and a continuous system may be used. In the case of solution polymerization, the solvent used for the polymerization is not particularly limited as long as it has a very low reactivity with the polymerization catalyst and has a capability of dissolving the monomer and the polymer, and n-butane, n-pentane, n -Hexane, n-
Aliphatic hydrocarbons such as heptane, iso-octane, cyclopentane, methylcyclopentane, cyclohexane, cyclohexane, methylcyclohexane, cycloheptane, decalin, benzene, toluene, xylene, ethylbenzene Examples include aromatic hydrocarbons, ethers such as diethyl ether and tetrahydrofuran. These polymerization solvents may be one kind or a mixture of two or more kinds.

The amount of the polymerization catalyst synthesized from the above-mentioned organometallic compound and complexing agent can be variously varied depending on the purpose, and thus cannot be particularly limited. 0.00000 as metal atom
It is carried out in the range of 1 mol to 0.1 mol. The polymerization can be carried out at a temperature of -100 to 150C, most preferably 0 to 100C. Further, from an industrial point of view, it is advantageous to carry out the polymerization at a temperature in the range of room temperature to 90 ° C. What is necessary is just to perform, and it does not specifically limit.

The time required for the polymerization reaction varies depending on the purpose and polymerization conditions and cannot be particularly limited. However, it is usually within 48 hours, particularly preferably 1 to 10 hours. Is done. The polymerization atmosphere is desirably an inert gas atmosphere of dry nitrogen, argon, helium, or the like. In the polymerization method in the present reaction, prior to polymerization, a part or all of the catalyst components are preliminarily reacted or aged to synthesize a complex compound serving as a polymerization catalyst in advance. This is the preferred method to obtain.

As the polymerization terminator, water, alcohol, polyhydric alcohol, phenol and the like can be used. The addition amount of the terminator is generally 0.001 to 1 with respect to the polymer.
The polymer represented by the formula (1) used in the curable composition of the present invention needs to have a hydroxyl group equivalent to 2 or more in hydroxyl value. is there. If the number of hydroxyl groups is less than 2, it is not preferred because the effect of crosslinking produced by reacting with the isocyanate group is not only small, but also swells and dissolves in a solvent or the like. The upper limit of the hydroxyl value does not need to be particularly set, but is preferably 2 to 80 because problems such as shortening of the pot life when a resin having an extremely high hydroxyl value and polyisocyanate are mixed occur. A more preferable range of the hydroxyl value is 2 to 50.

As a method for introducing a hydroxyl group or an organic residue having a hydroxyl group into the polymer represented by the formula (1) used in the curable resin of the present invention, any known method may be used. For example, (a) a method in which polymerization is carried out using a monomer having a hydroxyl group as a monomer for producing a polymer unit of P, Q, and R of the formula (1); (b) P, Q, and R of the formula (1) A method of performing a chemical reaction after polymerization using a monomer having a functional group capable of generating a hydroxyl group by a chemical reaction as a monomer that produces a monomer unit of (c) reacting with a polymerization terminal For example, a method of reacting a monomer capable of generating a hydroxyl group at the end of the polymerization may be used.
In particular, the method (c) is a method in which a hydroxyl group can be introduced into the terminal of the polymer. For example, after polymerization is performed by living anionic polymerization, ketones such as formaldehyde, acetaldehyde, and acetone, ethylene oxide, propylene oxide, By reacting a cyclic ether such as oxetane, tetrahydrofuran, or tetrahydropyran at the end of the polymerization and deactivating the polymerization terminal with a compound having active hydrogen such as alcohol or water, a hydroxyl group can be introduced to the polymerization terminal.

The side chains of the P, Q, and R polymer units constituting the polymer having at least one hydroxyl group used in the present invention have a hydrogen atom or hydrogen (H), oxygen (O), nitrogen (N ), Sulfur (S), phosphorus (P), silicon (Si), a functional group containing at least one element selected from halogens (F, Cl, Br, I), or an organic residue having a functional group, or C1-C20 alkyl group, C2-C20 unsaturated aliphatic hydrocarbon group, C5-C20
20 aryl groups, C3-C20 cycloalkyl groups,
A C4-C20 cyclodienyl group or a 5- to 10-membered ring, to which a group selected from a heterocyclic group containing at least one nitrogen, oxygen or sulfur as a hetero atom may be bonded, Alternatively, any known method can be used to introduce an organic residue having a functional group. For example, (a) a method in which polymerization is carried out using a monomer having a desired functional group as a monomer for forming a polymer unit of P, Q, and R in the above formula (1) (b) P in the above formula (1) A method in which a monomer having a group capable of generating a desired functional group by a chemical reaction is polymerized as a monomer for producing a polymer unit of, Q and R, and then subjected to a chemical reaction; For example, a method of reacting a monomer capable of producing a desired functional group by reacting the terminal with the terminal at the end of the polymerization may be used.

A hydroxyl group or an organic residue having a hydroxyl group,
Alternatively, hydrogen (H), oxygen (O), nitrogen (N), sulfur (S), phosphorus (P), silicon (Si), halogen (F, C
Preferred methods for introducing a functional group containing at least one element selected from l, Br, I) or an organic residue having a functional group include, for example, a cyclic conjugated diene monomer and / or an aliphatic conjugated diene. This is a method in which a reaction reagent having a desired functional group is added to a polymer obtained by polymerizing a system monomer by a conventionally known reaction, for example, an alkylation reaction, a halogenation reaction, an oxidation reaction, and water. The reaction can be carried out by appropriately using a summation reaction, an epoxidation reaction or the like.

When the polymer according to the present invention is obtained by anionic polymerization, the polymerization is usually carried out using a polymerization terminator such as water, alcohol, polyhydric alcohol, phenol or the like. The addition amount of the terminator is 0.001 to 1 with respect to the polymer.
Used in the range of 0 wt%. When the polymer according to the present invention is obtained by polymerizing a cyclic conjugated diene-based monomer and / or an aliphatic conjugated diene-based monomer, a double bond remains in the polymer. Depending on the conditions, the remaining double bonds may be attacked by, for example, oxygen during use, causing cross-linking or decomposition to cause deterioration in physical properties.If necessary, double bonds in the polymer may be reduced. is there. One of the methods is a method in which a reaction reagent having the above-described functional group is used to add the compound by a conventionally known reaction. Another preferable method is a method in which hydrogenation is performed to form a saturated bond. The hydrogenation reaction is carried out under a hydrogen atmosphere in the presence of a polymer and a hydrogenation catalyst. A conventionally known method can be adopted as the reaction format.
For example, any of a batch system, a semi-batch system, a continuous system, and a combination thereof can be adopted. As the hydrogenation reaction catalyst, any of conventionally known homogeneous catalysts and heterogeneous catalysts can be used, and the type and amount thereof are not particularly limited as long as a certain degree of hydrogenation is satisfied.

The preferable hydrogenation rate is 80% or more, more preferably 90% or more, and further preferably 95% or more. Industrially particularly preferable metals contained in the hydrogenation catalyst include titanium, cobalt, nickel, ruthenium, rhodium, palladium and the like. These metals are ethers, amines, thiols, phosphines, carbonyls, olefins,
It may be used as a homogeneous catalyst in combination with an organic compound (ligand) having a functional group such as a diene, or supported on a carrier such as activated carbon, alumina, barium sulfate, silica, titania, zeolite, or cross-linked polystyrene. It may be used as a heterogeneous catalyst. From an industrial point of view, particularly preferred are heterogeneous catalysts from which the hydrogenation catalyst can be recovered.

Preferred solvents used in the hydrogenation reaction include aliphatic hydrocarbons such as n-butane, n-pentane, n-hexane and n-heptane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and the like. Examples include alicyclic hydrocarbons such as cycloheptane and decalin, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and ethers such as diethyl ether and tetrahydrofuran. These hydrogenation reaction solvents may be one kind or a mixture of two or more kinds.

The temperature of the hydrogenation reaction is usually from 0 to 300 ° C.
And particularly preferably from 30 to 200 ° C.
The pressure of the hydrogenation reaction is generally 1~250kgf / cm ^2, particularly preferably 5~150kgf / cm ²
It is. The time required for the hydrogenation reaction is not particularly limited because it is related to the concentration of the polymer solution, the temperature and the pressure of the reaction system, but it can be generally carried out in the range of 5 minutes to 240 hours.

The polyisocyanate having an average of two or more isocyanate groups used in the present invention includes aliphatic, alicyclic and aromatic diisocyanates. In the field where weather resistance is required, aliphatic or aliphatic diisocyanates are used. It is preferred to use cyclic diisocyanates. The aliphatic diisocyanate preferably has 4 to 30 carbon atoms, and the alicyclic diisocyanate preferably has 8 to 30 carbon atoms. For example, tetramethylene-1,4-diisocyanate, pentamethylene-1,5- Diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene-1,6-diisocyanate, lysine diisocyanate, isophorone diisocyanate,
Examples thereof include 1,3-bis (isocyanatomethyl) -cyclohexane and 4,4'-dicyclohexylmethane diisocyanate. Among them, hexamethylene diisocyanate (hereinafter referred to as HMDI) and isophorone diisocyanate (hereinafter referred to as IPDI) are preferred from the viewpoint of weather resistance and industrial availability. On the other hand, examples of aromatic diisocyanates include toluene diisocyanate,
And diphenylmethane diisocyanate.

Since the above diisocyanates have a vapor pressure even at room temperature and are toxic, these diisocyanates are oligomerized by buret bond, urea bond, isocyanurate bond, urethane bond, allophanate bond, uretdione bond or the like, or a combination thereof. Those that have been used are preferably used. In addition, polyfunctional isocyanates such as polymeric diphenylmethane diisocyanate can also be used.

Further, these polyisocyanates are previously reacted with a part of a resin represented by the formula (1) and comprising at least one polymer having at least one hydroxyl group to form an isocyanate prepolymer.
For example, the compatibility between the resin and the isocyanate may be improved. In some cases, it is also possible to use a blocked polyisocyanate obtained by blocking the above isocyanate with a phenol compound, an oxime compound, an active methylene compound, or the like, and use the composition as a one-part composition.

The number average molecular weight of the polyisocyanate is 4
It is preferably from 100 to 100,000. The amount of the polyisocyanate used is NCO / OH = 0.1 to 10 in the molar ratio of the hydroxyl group (OH) contained in the resin of the formula (1) to the isocyanate group (NCO) in the polyisocyanate.
Preferably 0.2 to 5, more preferably 0.3 to 3.
3 range.

In the curable composition of the present invention, it is also advantageous to add a curing catalyst which promotes curing by a resin containing the polymer of the formula (1) and a polyisocyanate having an average of two or more isocyanate groups. is there. The catalyst is not particularly limited as long as it promotes a known urethane-forming reaction. Examples thereof include organic, inorganic salts and organometallic compounds of metals such as dibutyltin dilaurate, stannous octylate and lead octylate, and organic amines such as triethylamine and diazabicycloundecene. The amount to be used should be determined in consideration of the balance between pot life and curability, depending on the catalyst used and curing conditions. Usually, 1 to 50 to the total weight of the resin containing the polymer of the formula (1) and the polyisocyanate having two or more isocyanate groups on average.
Used in the range of 000 ppm.

Various fillers can be added to the composition of the present invention. Examples of fillers include general-purpose fillers such as silica, silicate compounds, carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, talc, titanium oxide, zinc oxide, bentonite, and glass fiber carbon fiber. To select as appropriate. For example, in the case of a sealing material, calcium carbonate, carbon black, silica, titanium oxide, zinc oxide, magnesium oxide, magnesium hydroxide, talc and the like are suitably used.

In the composition of the present invention, a plasticizer may be mixed and used for adjusting the hardness and improving workability. Examples of the plasticizer include paraffinic, naphthenic, and aromatic mineral oils, synthetic oils such as alkylbenzene and alkylnaphthalene, esters such as dioctyl phthalate and dibutyl phthalate, and tricresyl phosphate, which are often used in the rubber industry. Phosphoric esters,
Epoxy plasticizers such as epoxidized soybean oil, chlorinated paraffins and the like can be mentioned, and one or more of these can be used in combination.

The amount of the plasticizer to be added is usually 10 parts per 100 parts by weight of the total of the resin containing the polymer of the formula (1) and the polyisocyanate having two or more isocyanate groups on average.
To 300 parts by weight, more preferably 20 to 150 parts by weight. The composition of the present invention may be blended with a photocuring component for improving the tackiness of the surface, an adhesive imparting agent, and the like, for example, to improve various physical properties as a sealing material or an adhesive material. It is.

The composition of the present invention may contain, in addition to the above components, a stabilizer generally used in the urethane industry and the rubber industry.

[0044]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, the measuring method of various physical properties was performed as follows. (1) Molecular weight and molecular weight distribution A sample was dissolved in 1,2,4-trichlorobenzene,
It was measured by the PC (gel permeation chromatography) method and expressed as a standard polystyrene equivalent value. (2) Approximately 3 g of the resin was precisely weighed (Yg
2 g in 100 mL as an acetylation reagent
Pyridine / decalin mixture containing 5% acetic anhydride (5
(0 wt / 50 wt) 5 mL is accurately taken with a whole pipette, added to the sample, and heated at 140 ° C. for 24 hours with stirring.

After air cooling, 2 mL of distilled water is added by a whole pipette, and the mixture is further heated and stirred for 15 minutes. Using phenolphthalein as an indicator, titrate with a 1 / 10N KOH ethanol solution (factor is F2) (titer CmL). The above acetylating reagent 5 was placed in a 50 mL eggplant flask.
mL accurately with a whole pipette.
Add mL with a whole pipette and heat and stir for an additional 15 minutes. Using phenolphthalein as an indicator,
Titrate with 10N KOH ethanol solution (titration D
mL).

The hydroxyl value is determined by the following equation. Hydroxyl value = (D−C) × F2 × 5.61 / Y (3) Number of Isocyanate Groups per Molecule Samples 2-3 in a dry 200 mL Erlenmeyer flask
g is precisely weighed (Wg), and 20 mL of dry toluene is added to dissolve the sample.

20 mL of a 2N solution of di-n-butylamine in toluene is precisely added to the sample with a whole pipette. Plug the flask and stir at room temperature for 15 minutes.
Add 0 mL of isopropanol and add bromothymol green as indicator.

Titrate with 1N hydrochloric acid for volumetric analysis (factor is F1) (AmL). Perform the same operation without a sample, and use it as a blank test (the titer is BmL). The number of isocyanate groups is determined from the following equation.

NCO content = (BA) × F1 × 42 /
(W × 1000) × 100 (4) Breaking Elongation and Breaking Situation A glass plate (5 m thick) was formed so as to have the structure shown in FIG.
m) or a polypropylene plate (thickness 5 mm, Mitsubishi Chemical Noblen MH8) and a Teflon casting frame (thickness 12 m
m) is prepared. Note that no primer is used for any of them. The Teflon casting frame can be removed in at least two parts after the composition is cured. Center space (12 mm x 50 mm, thickness 12 mm) composed of one glass plate or polypropylene plate and Teflon casting frame
And the same glass plate or polypropylene plate is overlaid. Cured and cured for 14 days at 20 ° C. After curing, remove the Teflon casting frame,
A cured product for evaluation formed between a glass plate or a polypropylene plate is obtained.

After the glass plate or the polypropylene plate was sandwiched between the chucks of the tensile tester and pulled in the direction perpendicular to the glass plate or the polypropylene plate, the breaking strength and elongation of the cured product and the state of the fracture were examined.

[0051]

[Production Example 1] <Preparation of polymerization catalyst> 1 Msec-butyllithium (hereinafter s-BuLi) in a dry argon atmosphere
Triethylamine (hereinafter TE)
A) is calculated by converting s-BuLi / TEA = 1/1 (mol / mo)
l). Further, m-diisopropenylbenzene (hereinafter, m-DIPB) was added to this solution with s-BuL.
i / TEA / m-DIPB = 2/2/1 (mol / mo
1 / mol). After the addition, the mixture was stirred at room temperature for 24 hours.

<Production of Hydroxyl Group-Containing Resin> The inside of a 5 L autoclave dried according to a conventional method was replaced with dry argon. 1200 g of cyclohexane, 116 g of the polymerization catalyst solution prepared by the above method (125 mmol in terms of Li atom)
1) 19 g of tetramethylethylenediamine was injected into the autoclave. Liquid temperature in autoclave is 40 ℃
, 180 g of 1,3-cyclohexadiene was added, and the mixture was stirred for 30 minutes. Then, 1280 g of a 33 wt% cyclohexane solution of butadiene was added, and the mixture was further stirred for 30 minutes.

Thereafter, 8 g of a 50% by weight solution of methanol in cyclohexane was added to stop the reaction. Thereafter, the polymer was separated with a large amount of methanol, washed with methanol, and then washed with methanol.
Vacuum dried at 0 ° C. This polymer was dissolved again in cyclohexane to form a 20 wt% solution. 2.5 kg of this polymer solution was placed in a 5 L autoclave, and 5
90 g of carbon black carrying% Pd was dispersed therein. After replacing the gas phase in the autoclave with hydrogen, a hydrogen pressure of 4
The reaction was carried out at 5 kg / cm2-G and 100 ° C. for 2 hours. Thereafter, the temperature was lowered, and the Pd-supporting carbon black was separated by filtration. The obtained polymer solution was separated with a large amount of methanol, further washed with methanol, and dried under vacuum. When the obtained polymer A was measured by NMR, it was found that 95% of the unsaturated unsaturated hydrocarbon bonds contained in the polymer before hydrogenation were contained.
Had been hydrogenated. The number average molecular weight (Mn) in terms of styrene by GPC was 12,000, and the ratio of number average molecular weight / weight average molecular weight (Mn / Mw) was 1.17.

[0054]

Preparation Example 2 To the polymer A obtained in Preparation Example 1, 0.2% by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 5% by weight of hydroxyethyl acrylate were added. Maximum temperature 250 in twin screw extruder
The mixture was melted at a residence time of about 15 minutes at ℃. The obtained polymer B had a hydroxyl value of 16.1.

[0055]

Production Example 3 <Preparation of polymerization catalyst> 1 Msec-butyllithium (hereinafter s-BuLi) in a dry argon atmosphere
Triethylamine (hereinafter TE)
A) is calculated by converting s-BuLi / TEA = 1/1 (mol / mo)
l). Further, m-diisopropenylbenzene (hereinafter, m-DIPB) was added to this solution with s-BuL.
i / TEA / m-DIPB = 2/2/1 (mol / mo
1 / mol). After the addition, the mixture was stirred at room temperature for 24 hours.

<Production of Hydroxyl Group-Containing Resin> The inside of a 5 L autoclave dried according to a conventional method was replaced with dry argon. 1200 g of cyclohexane, 116 g of the polymerization catalyst solution prepared by the above method (125 mmol in terms of Li atom)
1) 19 g of tetramethylethylenediamine was injected into the autoclave. Liquid temperature in autoclave is 40 ℃
After adding 60 g of 1,3-cyclohexadiene and stirring for 30 minutes, 1640 g of a 33 wt% solution of butadiene in cyclohexane was added and further stirred for 30 minutes.

Thereafter, 30 wt.
24.5 g of a 50% by weight cyclohexane solution of methanol was further added, and the reaction was stopped. Thereafter, the polymer was separated with a large amount of methanol, washed with methanol, and dried at 50 ° C. in vacuo.

This polymer was dissolved again in cyclohexane to obtain a 20 wt% solution. This polymer solution 2.5
The kg was put in a 5 L autoclave, and 125 g of 5% Pd-supported carbon black was dispersed at the same time. After replacing the gas phase in the autoclave with hydrogen, a hydrogen pressure of 45 kg
/ Cm ² -G at 100 ° C. for ² hours. Thereafter, the temperature was lowered, and the Pd-supporting carbon black was separated by filtration. The obtained polymer solution was separated with a large amount of methanol, further washed with methanol, and dried under vacuum. NMR measurement of the obtained polymer C revealed that 99% of the unsaturated unsaturated hydrocarbon bonds contained in the polymer before hydrogenation were hydrogenated. The number average molecular weight (Mn) in terms of styrene by GPC was 12,000, and the ratio of number average molecular weight / weight average molecular weight (Mn / Mw) was 1.17. The hydroxyl value of the polymer was 9.3.

[0059]

[Production Example 4] In the same manner as in Production Example 3, except that 232 g of the polymerization catalyst solution (250 mmol in terms of Li atom), 38 g of tetramethylethylenediamine, and 49 g of a 30 wt% propylene oxide cyclohexane solution were used in the production of the hydroxyl group-containing resin. Hydrogenated polymer D is converted to N
As measured by MR, 99% of the unsaturated unsaturated hydrocarbon bonds contained in the polymer before hydrogenation were hydrogenated. The number average molecular weight (Mn) in terms of styrene by GPC was 6000, and the ratio of number average molecular weight / weight average molecular weight (Mn / Mw) was 1.19. The hydroxyl value of the polymer was 18.6.

[0060]

[Comparative Production Example 1] In the production of a hydroxyl group-containing resin,
Without using 3-cyclohexadiene, butadiene 33
A hydrogenated polymer E was prepared in the same manner as in Production Example 3 except that 1820 g of a wt% cyclohexane solution was added.
As measured by MR, 99% of the unsaturated unsaturated hydrocarbon bonds contained in the polymer before hydrogenation were hydrogenated. The number average molecular weight (Mn) in terms of styrene by GPC was 12,000, and the ratio of number average molecular weight / weight average molecular weight (Mn / Mw) was 1.18. The hydroxyl value of the polymer was 9.3.

[0061]

Example 1 50 parts of polymer B was kneaded with 50 parts of process oil PW32 manufactured by Idemitsu Kosan Co., Ltd., and as a polyisocyanate, duranate T manufactured by Asahi Kasei Kogyo Co., Ltd., which is a nulated oligomer of hexamethylene diisocyanate
3.4 parts of PA-100 and 0.05 part of dibutyltin dilaurate as a curing catalyst were kneaded. Using this kneaded material, the strength at break and elongation of the cured product and the state of the fracture were examined.

Both the glass plate and the polypropylene plate undergo cohesive failure, and their breaking strength and elongation are 4.5 for glass, respectively.
Kg / cm ² , 250%, 2.2K for polypropylene
g / cm ² , 180%.

[0063]

Comparative Example 1 A kneaded product was prepared and cast in the same manner as in Example 1 except that polymer A was used instead of polymer B.
After curing, the resin did not cure at all and the resin flowed.

[0064]

Example 2 Polymer C was used instead of Polymer B,
Casting and curing were performed in the same manner as in Example 1 except that the amount of duranate TPA-100 was changed to 2.0 parts, to obtain a cured product adhered to glass and a polypropylene plate. This was subjected to a breaking strength and elongation test in the same manner as in Example 1. As a result, both glass and polypropylene cohesively fractured, and the breaking strength and elongation of glass were 2.3 kg / c, respectively.
m ² , 380%, 1.7 kg / cm for polypropylene
² , 290%.

[0065]

Example 3 Polymer D was used instead of Polymer B,
A cured product was cast and cured in the same manner as in Example 1 except that the amount of duranate TPA-100 was changed to 4.0 parts to obtain a cured product adhered to glass and a polypropylene plate. When this was subjected to a breaking strength and elongation test in the same manner as in Example 1, both the glass and the polypropylene cohesively fractured, and the breaking strength and the elongation were 3.0 Kg / c for glass, respectively.
m ² , 300%, 2.0 kg / cm for polypropylene
² , 300%.

[0066]

Comparative Example 2 Polymer E was used instead of Polymer B,
Casting and curing were performed in the same manner as in Example 1 except that the amount of duranate TPA-100 was changed to 2.0 parts, to obtain a cured product adhered to glass and a polypropylene plate. When this was subjected to a breaking strength / elongation test in the same manner as in Example 1, both the glass and the polypropylene were interfacially broken, and the breaking strength and elongation were 0.8 kg / c for glass, respectively.
m ² , 60%, 0.6 kg / c for polypropylene
m ² , 50%.

[0067]

According to the present invention, it has weather resistance, heat resistance, low moisture permeability, fast curing properties, and various properties of good mechanical properties, and cures even under relatively low temperature conditions, but has excellent processing properties such as pot life. . Further, since it has adhesiveness to glass and polyolefin-based materials, it is possible to bond polyolefin-based materials and other materials to other materials without taking measures such as surface treatment.

Particularly, it is suitable as a sealing material and a material for an adhesive.

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a view schematically showing a configuration at the time of preparing a sample for evaluating the breaking elongation at break and the breaking state of the curable composition of the present invention.

[Explanation of symbols]

 1 Glass plate (or polypropylene plate) 2 Curable composition 3 Teflon casting frame

Continued on front page F term (reference) 4H017 AA04 AA31 AB06 AB07 AB18 AC16 AE03 AE05 4J034 BA03 DA01 DB04 DB07 DC07 DC12 DC35 DC37 DC42 DD01 DD05 DD06 DD07 DD08 DD09 DD11 DP03 DP04 DP06 DP12 DP13 DP18 DP19 DP20 DQ14 DQ15 DQ16 GA HA01 HA02 HA07 HA11 HB05 HB07 HB08 HB09 HC03 HC17 HC22 HC46 HC52 HC61 HC67 HC71 HC73 KA01 KB02 KC17 KC18 KD12 KE02 QA05 QA07 RA02 RA08 RA10 RA12 RA14 RA19 4J040 EF181 EF251 GA02 GA03 GA04 GA05 GA13 GA02 GA05 NA16 NA19

Claims (6)

[Claims] 1. A curable composition containing the following components (A) and (B). (A) A resin having a hydroxyl value of 2 or more and comprising at least one polymer represented by the following composition formula (1). [-(P) p-,-(Q) q-,-(R) r-] (1) [P, Q, and R each represent a polymer unit constituting a polymer main chain, and P represents a cyclic olefin-based unit. It is a polymer unit composed of one or more monomer units selected from monomer units. Q represents a polymer unit composed of one or more monomer units selected from linear olefinic monomers, and R represents P and / or other monomer units capable of binding to Q. Represents one or more polymer units. R may be bonded to any of P, Q and R units. P, Q, and R may be arranged in any order, and the units may be arranged randomly, in blocks, or arranged in a gradient. p, q, and r are monomer units P,
It represents the mole% of each of Q and R based on the whole polymer.
The number average molecular weight of the polymer in terms of standard polystyrene is 1,0.
The range is from 00 to 500,000. Also, P, Q, R
In the side chain of the polymer composed of, a hydrogen atom or hydrogen (H), oxygen (O), nitrogen (N), sulfur (S), phosphorus (P), silicon (Si), halogen (F, Cl, Br,
A functional group containing at least one element selected from I) or an organic residue having a functional group, or C1-C
20 alkyl groups, C2-C20 unsaturated aliphatic hydrocarbon groups, C5-C20 aryl groups, C3-C20 cycloalkyl groups, C4-C20 cyclodienyl groups, or 5- to 10-membered rings, A group selected from a heterocyclic group containing one nitrogen, oxygen or sulfur as a hetero atom may be bonded. p, q, and r satisfy the following relationship. p + q + r = 100, 1 ≦ p ≦ 100, 0 ≦ q ≦ 99,
0 ≦ r ≦ 99] (B) A polyisocyanate having an average of two or more isocyanate groups per molecule. 2. The curable composition according to claim 1, further comprising (C) a curing catalyst. 3. The curable composition according to claim 1, wherein p is 3 or more. 4. The curable composition according to claim 1, wherein the cyclic olefin monomer is cyclohexene and / or cyclohexane, or a derivative unit thereof. 5. A sealing material containing the curable composition according to claim 1. 6. An adhesive material containing the curable composition according to claim 1.