KR20000076702A - Liquid phase polymer composition - Google Patents

Abstract

It is an object of the present invention to provide a liquid polymer composition which does not cause foaming in the cured product and has improved curability, coating properties, chipping resistance, storage stability, and the like.

The hydroxyl-containing liquid diene polymer and / or its hydride, and the following general formula (I) as a curing agent

(In formula (I), R ₁ , R ₃ and R ₅ are each H or CH ₂ OX, and R ₂ , R ₄ and R ₆ are each CH ₂ OY. X is hydrogen, methyl group, propyl group and butyl Any one of the groups, and Y is either methyl, propyl or butyl), or the melamine compound, a hydroxyl group-containing liquid diene polymer and / or a hydride thereof and a polyisocyanate compound A liquid polymer composition is provided that contains a blocked polyisocyanate compound after prepolymerization.

Description

Liquid phase polymer composition

The present invention relates to a technique for providing a one-component thermosetting liquid polymer composition, and more particularly, to a hydroxyl group-containing liquid diene-based polymer and / or a hydride thereof, a melamine compound having a melamine structure as a curing agent, or A liquid polymer composition containing a blocked polyisocyanate compound which is blocked by reacting the melamine compound with a hydroxyl group-containing liquid diene polymer and / or its hydride and a polyisocyanate compound and then prepolymerized to form a curable and coating film property. Furthermore, the present invention relates to a novel liquid polymer composition having improved compatibility and the like.

Conventionally, hydroxyl group containing liquid diene type polymer or its hydride is used widely as a polyol material for polyurethanes.

For example, in JP-A-7-5704, a liquid polymer composition composed of a hydride and a polyisocyanate compound of liquid polyisoprene having a hydroxyl group at the branched chain end is proposed.

Such a technique is a method of obtaining a polyurethane rubber by producing a urethane group by reaction of a hydroxyl group-containing liquid diene polymer or a hydroxyl group in a hydride thereof with an isocyanate group in a polyisocyanate compound which is a curing agent. The composition obtained by producing the polyurethane is widely used in paints, adhesives, coating materials, electrical insulation materials and the like.

However, in the composition obtained by producing these polyurethanes, when water is present in the system, an isocyanate group in the curing agent reacts with water to generate a carbon dioxide gas, so that bubbles are generated in the resulting cured product, whereby a good cured product cannot be obtained.

In the case of the thermosetting one-component type, block isocyanates are generally used as a curing agent, but block isocyanates having good compatibility with hydroxyl group-containing liquid diene polymers and their hydrides are limited. Moreover, even if such a hardening | curing agent exists, there exists also a problem that sclerosis | hardenability is bad and the physical property of the coating film obtained further is low.

As a curing system without generation of carbon dioxide gas, liquid polymer compositions using melamine compounds having a specific structure have also been found. However, although it is possible to improve the physical properties of the cured product, it is difficult to improve elongation.

Therefore, the physical properties required for the automotive undercoat material which can utilize the elasticity, vibration damping property, etc. of the hydroxyl group-containing liquid polybutadiene-based polymer and / or its hydride cannot be satisfied. It has a problem that it cannot be applied.

An object of the present invention is to provide a novel liquid polymer composition in which no carbonic acid gas is generated even if water is present in the system, foaming does not occur in the cured product, and the curability and coating film properties are improved.

In addition, an object of the present invention is to provide a novel liquid polymer composition having excellent compatibility and curability, rubber elasticity, and improved elongation, coating resistance, storage stability, and the like as coating film properties.

Furthermore, it is an object of the present invention to provide a novel liquid polymer composition obtained by adding a curing system which can be a thermosetting one-component form.

The present inventors conducted research in order to solve the said conventional problem.

As a result, the liquid polymer composition obtained by using a melamine compound having a specific structure as a curing agent in the hydroxyl group-containing liquid diene polymer and / or its hydride is surprisingly free of foaming in the cured product even if water is present in the system. It has been found that coating properties are improved. Furthermore, it has come to find a curing system that can be a thermoset one-part form.

Further, the present inventors prepolymerized by reacting a melamine compound having a specific structure, and a hydroxyl group-containing liquid diene polymer and / or its hydride with a polyisocyanate compound as a curing agent of the hydroxyl group-containing liquid diene polymer and / or its hydride. Then, it was found that by using the blocked polyisocyanate compound in combination, the compatibility and curability are good, the rubber elasticity is improved, and the elongation, coating resistance, storage stability and the like as the coating film properties are improved.

The present invention has been completed based on this finding.

The present invention according to claim 1 is a hydroxyl group-containing liquid diene polymer and / or a hydride thereof and the following general formula (I) as a curing agent

(However, in formula (I), R ₁ , R ₃ and R ₅ are each H or CH ₂ OX, and R ₂ , R ₄ and R ₆ are each CH ₂ OY, wherein X is hydrogen, methyl group, propyl Any one of a group and a butyl group, Y is any one of a methyl group, a propyl group and a butyl group), or a melamine compound represented by the above general formula (I), a hydroxyl group-containing liquid diene polymer, and / Or a liquid polymer composition containing a blocked polyisocyanate compound blocked by reacting its hydride with a polyisocyanate compound and then prepolymerized.

Next, this invention which concerns on Claim 2 provides the composition of Claim 1 whose hydroxyl group content of a hydroxyl-containing liquid diene type polymer or its hydride is 0.2-10.0 meq / g, and number average molecular weight is 300-10000. .

The present invention according to claim 3 provides a composition according to claim 1 or 2 which is for an undercoat material for a vehicle.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The composition of this invention of Claim 1 is a hydroxyl-containing liquid diene type polymer and / or its hydride, and the melamine compound represented by General formula (I) as a hardening | curing agent, or the melamine compound represented by said General formula (I) And a hydroxyl group-containing liquid diene-based polymer and / or a hydride thereof and a polyisocyanate compound to react with each other to prepolymerize and block the blocked polyisocyanate compound.

In the present invention according to claim 1, a hydroxyl group-containing liquid diene polymer and / or a hydride thereof is used as the first component.

In the present invention, the hydroxyl group-containing liquid diene-based polymer and / or its hydride may be used as it is selected from those known according to the conditions, but may be easily produced by a known method.

First, the hydroxyl group-containing liquid diene polymer may be produced by, for example, radical polymerization of a diene monomer having 4 to 22 carbon atoms using a known polymerization initiator.

Examples of the diene monomer having 4 to 22 carbon atoms include butadiene, isoprene, chloroprene, 1,3-pentadiene, cyclopentadiene and the like, and among these, one type may be used alone, or two or more types may be used in combination. .

Further, as the polymerization initiator, a known hydrogen peroxide (H ₂ O _2), an azo compound having a hydroxyl group (e.g., 2,2'-azobis [2-methyl -N- (2-hydroxyethyl) propionamide]. Or peroxides having a hydroxyl group (for example, cyclohexanone peroxide and the like).

The amount of the polymerization initiator to be used is 1.0 to 50 g, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] relative to 100 g of the diene monomer, for example, when hydrogen peroxide is used. When using, 5.0-100 g and 5.0-100 g are suitable, respectively, when using cyclohexanone peroxide.

The polymerization can be carried out without using a solvent, but for ease of reaction control, a solvent is preferably used. Ethanol, isopropanol, N-butanol and the like are usually used as the solvent. The reaction temperature is suitably 80 to 150 占 폚 and the reaction time is 0.5 to 15 hours.

In addition to the radical polymerization, one or two or more kinds of diene monomers having 4 to 22 carbon atoms are subjected to anionic polymerization using a catalyst such as naphthalenedilithium to prepare an active polymer, and further to react monoepoxy compounds and the like. Also, the target hydroxyl group-containing liquid diene polymer can be obtained.

The anionic polymerization can also be performed without using a solvent, but for the same reason as in the case of radical polymerization, that is, for ease of reaction control, it is preferable to use a solvent. As the solvent in this case, saturated hydrocarbons such as hexane and cyclohexane are preferable. The reaction temperature is preferably 50 to 100 ° C. and the reaction time is 1 to 10 hours.

In addition, it is also possible to mix and use 2 or more types of diene monomers at the time of anionic polymerization, and the following monomer of 50 mo1% or less with respect to a diene monomer can also be added.

As such a monomer, a C2-C22 addition polymerizable monomer, More specifically, butene, pentene, styrene, (alpha) -methylstyrene, acrylonitrile, acrylic acid and its ester, methacrylic acid and its ester And vinyl chloride, vinyl acetate, acrylamide and the like.

After completion of the reaction, if the solution is distilled under reduced pressure, a solvent, an unreacted monomer, and the like are removed to obtain a target hydroxyl group-containing liquid diene polymer.

The number average molecular weight of this hydroxyl-containing liquid diene polymer is 300-10000, Preferably it is 500-5000. The hydroxyl content is 0.2 to 10 meq / g, preferably 0.4 to 7 meq / g.

Therefore, as the hydroxyl group-containing liquid diene polymer, those having a number average molecular weight of 300 to 10000 and a hydroxyl content of 0.2 to 10 meq / g are usually used. Preferably, the number average molecular weight is 500 to 5000 and the hydroxyl content is 0.4 to 7 meq / g is used.

When the number average molecular weight of the hydroxyl group-containing liquid diene polymer is larger than the above range or the hydroxyl group content is less than the above range, the proportion of hydroxyl groups involved in the reaction with the curing agent decreases, so that the crosslinking point decreases and the strength of the cured product of the composition obtained. Becomes insufficient. In addition, when the number average molecular weight is smaller than the above range or the hydroxyl group content is above the above range, the number of crosslinking points generated by the reaction with the curing agent becomes too large, resulting in an inadequate state of weak curing material.

As the microstructure of such a hydroxyl group-containing liquid diene polymer, the ratio of 1,4-cis structure, 1,4-trans structure, 1,2-vinyl structure, or 3,4-vinyl structure is not limited at all, Structured ones can be used. The hydroxyl group may be anywhere in the branched chain terminal or inside the branched chain, but is preferably at the branched chain terminal. Furthermore, two or more hydroxyl group containing liquid diene type polymers can also be used. However, if the liquid diene polymer which does not contain a hydroxyl group is used, the objective of this invention cannot be achieved.

In the present invention, as the first component, a hydroxyl group-containing liquid diene polymer obtained as described above may be used, or a hydride of a hydroxyl group-containing liquid diene polymer obtained by hydrogenation thereof may be used. Mixtures may be used.

The hydride of the hydroxyl group-containing liquid diene polymer may be selected from those known according to the conditions and may be used as it is, but the hydroxyl group-containing liquid diene polymer prepared as described above may be a homogeneous catalyst or a heterogeneous catalyst. It can also manufacture by hydrogenating by the well-known method using etc.

First, when a homogeneous catalyst is used, saturated hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene are used as solvents, under a reaction temperature of room temperature to 150 ° C, and hydrogen pressure of atmospheric pressure to 5 MPa. The hydrogenation reaction is performed. As a homogeneous catalyst, a Zieglar catalyst obtained by combining a transition metal halide with an alkylide such as aluminum, alkaline earth metal or alkali metal may be used in an amount of 0.1 to 0.1 mol% per polymer double bond. The reaction usually ends in 1 to 24 hours.

On the other hand, when using a heterogeneous catalyst or the like, saturated hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane and ethanol And hydrogenation reaction are carried out at a reaction temperature of normal temperature to 200 DEG C and a hydrogen pressure of normal pressure to 10 MPa using alcohols such as isopropanol and 1-butanol, or a mixture thereof as a solvent. As the heterogeneous catalyst, a catalyst such as nickel, cobalt, palladium, platinum, rhodium or ruthenium may be used alone or in a carrier such as silica, diatomaceous earth, alumina or activated carbon. As for the usage-amount of these catalysts, 0.05-10 weight% is suitable with respect to a polymer weight. You may use these catalysts in mixture of 2 or more type. The reaction usually ends in 1 to 48 hours.

After completion of the reaction, the catalyst is filtered off and the solution is distilled off under reduced pressure to remove the solvent to obtain a hydride of the desired hydroxyl group-containing liquid diene polymer.

The number average molecular weight of the hydride of this hydroxyl group containing liquid diene type polymer is 300-10000, Preferably it is 500-5000. The hydroxyl content is 0.2 to 10 meq / g, preferably 0.4 to 7 meq / g. Therefore, as the hydride of the hydroxyl group-containing liquid diene polymer, those having a number average molecular weight of 300 to 10,000 and a hydroxyl group content of 0.2 to 10 meq / g are preferably used. Preferably, the number average molecular weight is 500 to 5000, and the hydroxyl group content is used. 0.4-7 meq / g is used.

When the number average molecular weight of the hydride of the hydroxyl group-containing liquid diene polymer is larger than the above range or the hydroxyl group content is less than the above range, the proportion of hydroxyl groups involved in the reaction with the curing agent decreases, so that the crosslinking point is reduced. The strength of the hardened | cured material of becomes inadequate. In addition, when the number average molecular weight is smaller than the above range or the hydroxyl group content is above the above range, the number of crosslinking points generated by the reaction with the curing agent becomes too large, resulting in an inadequate state of weak curing material.

The hydrogenation rate of the hydride of this hydroxyl group containing liquid diene type polymer is 50% or more, Preferably it is 70% or more. Furthermore, it is also possible to mix and use the hydride of 2 or more types of hydroxyl-containing liquid diene type polymers.

The number of average hydroxyl groups per molecule of the hydride of the hydroxyl group-containing liquid diene polymer is preferably 1.7 or more, and even more preferably 2.0 or more.

In the present invention, it is also possible to use a mixture of at least one hydroxyl group-containing liquid diene polymer and at least one hydride of the hydroxyl group-containing liquid diene polymer.

In the present invention, as the curing agent of the hydroxyl group-containing liquid diene polymer and / or its hydride, that is, as the second component, the melamine compound represented by the general formula (I) is used alone, or the general formula ( Both the melamine compound represented by I), the hydroxyl group-containing liquid diene polymer and / or its hydride, and the polyisocyanate compound are reacted and prepolymerized, and then the blocked polyisocyanate compound is used in combination.

Hereinafter, the case where the melamine compound represented by the said general formula (I) is used independently as a hardening | curing agent is described as 1st aspect of this invention, The melamine compound represented by the said general formula (I), and a hydroxyl-containing liquid diene type The case where both the blocked polyisocyanate compound which is blocked after reacting the polymer and / or its hydride with the polyisocyanate compound and prepolymerized is described as a second aspect of the present invention.

As a hardening | curing agent used in the 1st aspect of this invention, 1 or more types are used in the melamine compound represented by the said General formula (I).

In the general formula (I), R ₁ , R ₃ and R ₅ are each H or CH ₂ OX, and R ₂ , R ₄ and R ₆ are each CH ₂ OY. X is any one of hydrogen, a methyl group, a propyl group, and a butyl group, and Y is any one of a methyl group, a propyl group, and a butyl group.

In addition, in said general formula (I), R <_1> , R <_3> and R <_5> may be same or different, respectively. In addition, R <_2> , R <_4> and R <_6> may be same or different, respectively.

The melamine compound represented by the said general formula (I) has functional groups which participate in reaction, such as a methylol group, an alkyl substituted methylol group, or an imino group. These substituents react with hydroxyl groups in the hydroxyl group-containing liquid diene polymer or its hydride to form a crosslinked structure. Moreover, you may contain the solvent in the hardening | curing agent.

As a preferable melamine compound represented by the said general formula (I), Specifically, hexamethoxy methylol melamine (When X and Y are both methyl groups, ie, all of R <_1> -R <_6> is a methoxy group); Methoxy, butoxymethylolmelamine (ie, when R ₁ , R ₃ and R ₅ are all CH ₃ OCH ₃ , and R ₂ , R ₄ and R ₆ are all CH ₃ OC ₄ H ₉ ); have.

In the first aspect of the present invention, it is necessary to use the melamine compound represented by the general formula (I). For example, simple melamine and the like, in which both of the functional groups bonded to carbon are hydrogen, do not form a crosslinked structure. Inadequate

In addition, R ₁ ~R ₆ is a methoxy group having a carbon number of 5 or more, the alkyl alcohol incidentally generated during the reaction and the molecular weight is unsuitable in that it is difficult to volatilize.

The compounding quantity of the melamine compound represented by the said General formula (I) is 5-200 weight part with respect to 100 weight part of hydroxyl group containing liquid diene type polymers, and / or its hydride, Preferably it is 10-150 weight part. When the compounding quantity of the melamine compound represented by the said General formula (I) is smaller than this, the number of crosslinking points obtained will be small and the physical property of a hardened | cured material will fall. Moreover, even if the compounding quantity of the melamine compound represented by the said General formula (I) is too large, since a reactor remains and a substantial crosslinking is not formed and the physical property of the hardened | cured body obtained is inferior, neither is preferable.

In the first aspect of the present invention, since the melamine compound having the specific structure as described above is used instead of the polyisocyanate compound conventionally used as the curing agent of the hydroxyl group-containing liquid diene polymer and / or its hydride, Reaction does not occur even if moisture exists, and a favorable hardened body can be obtained.

In addition, the melamine compound of the specific structure is capable of forming a thermosetting one-component form with the hydroxyl group-containing liquid diene polymer and / or its hydride, and is considered to have good compatibility with the polymer and / or hydride. The composition can also be useful as an undercoat material for automobiles that can utilize elasticity, vibration damping property, and the like, which are characteristics of the polymer and / or its hydride.

Next, in the second aspect of the present invention, after the prepolymerization by reacting the melamine compound represented by the general formula (I) as described above, the hydroxyl group-containing liquid diene polymer and / or its hydride and polyisocyanate compound Both of the blocked polyisocyanate compounds are used in combination.

The block polyisocyanate compound used in the second aspect of the present invention is prepared by reacting a hydroxyl group-containing liquid diene polymer and / or a terminal hydroxyl group of a hydride thereof with a polyisocyanate compound, and then blocking the free isocyanate group with a blocking agent. Compound.

Examples of the hydroxyl group-containing liquid diene polymer and / or its hydride include the same as those of the hydroxyl group-containing liquid diene polymer and / or its hydride, which may be the same as those described above. You may use it.

In addition, a polyisocyanate compound is an organic compound which has two or more isocyanate groups in 1 molecule, and has a reactive isocyanate group with respect to the hydroxyl group in the said hydroxyl-containing liquid diene type polymer and / or its hydride. As an example of such a polyisocyanate compound, the thing of normal aromatic, aliphatic, and alicyclic can be used. Especially, it is especially preferable that it is a liquid at normal temperature.

Specifically, for example, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate; Mixtures (above, all MDI), tolylene diisocyanate (TDI), carbodiimide modified diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, naphthalene-1,5-diisocyanate, o-toluidine diisocysi Aromatic polyisocyanate, such as annette, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, and isopropylbenzene-2, 4- diisocyanate, etc. are mentioned.

In addition, aliphatic-aromatic polyisocyanates such as xylene diisocyanate (XDI) and tetramethyl xylene diisocyanate (TMXDI) (polyisocyanate in which isocyanate group is directly bonded to aromatic ring via aliphatic hydrocarbon group, that is, isocyanate group directly bonded to aromatic ring group in molecule) The polyisocyanate compound in which isocyanate groups, such as polyisocyanate which does not have), does not directly bond with the carbon which has an unsaturated bond.

Next, hexamethylene diisocyanate (HDI), dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11- undecane triisocyanate, 1,8- diisocyanate-4-isocyanate methyl octane, 1, And aliphatic polyisocyanates such as 3,6-hexamethylene triisocyanate and trimethylhexamethylene diisocyanate.

In addition, transcyclohexane-1,4-diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (hydrogenated MDI), hydrogenated triylene diisocyanate, hydrogenated xylene diisocysi Alicyclic polyisocyanates, such as annette and hydrogenated tetramethyl xylene diisocyanate, are mentioned.

In addition, the ring trimer (isocyanurate modified) biuret modified body of the said polyisocyanate etc. are mentioned.

In addition, these polyisocyanate compounds can also be used in mixture of 2 or more type.

Among these, it is preferable to use MDI, TDI, carbodiimide modified diphenylmethane diisocyanate, and polymethylene polyphenyl isocyanate from a viewpoint of workability and a price as a polyisocyanate compound.

Next, as a blocking agent which blocks an isocyanate group, For example, Phenols, such as a phenol and cresol; Oximes such as methyl ethyl ketone oxime and benzophenone oxime; Alcohols such as methanol and ethanol; lactams such as ε-caprolactam; Imides, such as active methylenes, such as diethylacetyl acetone, malonic acid; Mercaptans; Ethyleneimine; α-pyrrolidone; Sodium hydrogen sulfite; Boric acid etc. are mentioned.

The block polyisocyanate compound used as the curing agent in the second aspect of the present invention is preferably NCO / OH = 2.0 to 10.0, and even more preferably a hydroxyl group-containing liquid diene polymer and / or a terminal hydroxyl group thereof. Preferably, under conditions of 3.0 to 8.0, the polymer is reacted with a polyisocyanate compound to prepolymerize, and then the free isocyanate group is blocked with a blocking agent. The block polyisocyanate compound may be produced by a conventional method.

The compounding quantity of the block polyisocyanate compound as a hardening | curing agent is NCO / OH = 0.2-1.5 (molar ratio) with respect to the hydroxyl group content of the hydroxyl-containing liquid diene type polymer which is a 1st component, and / or its hydride, Preferably it is 0.3-1.4 (molar ratio). More preferably, it is the quantity used as 0.3-1.3 (molar ratio). The remaining hydroxyl groups react with the isocyanate group of the block polyisocyanate compound and the functional groups of the melamine compound. If the blending amount of the block polyisocyanate compound is too small, the resulting urethane group is too small to obtain the effect of increasing the elongation. On the other hand, even if the compounding quantity of a block polyisocyanate compound is too large, unreacted isocyanate group will remain | survive, hard crosslinking will not be formed, sclerosis | hardenability will worsen, and the physical property of the hardened | cured material obtained will be inferior.

The liquid polymer composition of the present invention basically contains the first component and the second component, but in addition, it is a bitumen material or a general agent for imparting performance, viscosity reduction, cost reduction, workability, etc. in various applications. The compounding agent used, for example, a polyol compound, an organic solvent, a viscosity modifier, a filler, a catalyst, etc. can be added.

For example, adding a bitumen substance makes it suitable for the use as an undercoat material for automobiles.

As such a bitumen material, Petroleum asphalt, such as a straight asphalt of various permeability, foamed asphalt, propane (solvent) bitumen asphalt, etc .; Petroleum pitch; Petroleum tar; Coal pitch etc. are mentioned. Among these, petroleum asphalt, especially straight asphalt, is preferable.

Although there is no particular limitation on the amount of the bitumen added, 1000 parts by weight or less is suitable for 100 parts by weight of the hydroxyl group-containing liquid diene-based polymer and / or its hydride, and most preferably 0 to 300 parts by weight. Do.

Next, in this invention, a polyol compound can be added.

A polyol compound is a compound which has two or more hydroxyl groups in 1 molecule, and there exist low molecular weight polyol, high molecular weight polyol, etc.

As the low molecular weight polyol, 1,2-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 2, 5-hexanediol, 2,4-hexanediol, 2-ethyl-1,3-hexanediol, 2,4-diethyl-1,5-pentanediol, cyclohexanediol, glycerin, N, N-bis-2 -Hydroxypropyl aniline, N, N'-bishydroxy-isopropyl-2-methylpiperazine, propylene oxide adduct of bisphenol A, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

As the high molecular weight polyol, polyether polyols and their variants, polytetramethylene ether glycol, tetrahydrofuran / alkylene oxide copolymerized polyols, epoxy resin modified polyols, polyester polyols, partial ester exchanges of trimethylol alkane, partially saponified ethylene- Castor oil-based polyols such as vinyl acetate copolymers, castor oil, hydrogenated castor oil, castor oil ester exchanges, linear or branched long-chain glycols obtained by reducing dimer-acid esters, or hydrides thereof, esters of dimer acids with diols, and the like. Can be mentioned.

Moreover, 2 or more types of said polyols can also be mixed and added.

The addition amount of these polyol compounds is 0-100 weight part with respect to 100 weight part of hydroxyl group containing liquid diene type polymers which are 1st component, and / or its hydride.

In addition, various organic solvents may be added to reduce viscosity and ensure workability. Examples of the organic solvent that can be added include a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a cellosolve solvent, and an ether solvent, and one or more of them can be used.

Examples of the hydrocarbon solvent include toluene, mixed xylene, ortho xylene, paraxylene, acetone, cyclohexane, cyclohexanone, hexane and petroleum mixed solvent.

Methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned as a ketone solvent.

Ethyl acetate, butyl acetate, etc. are mentioned as ester solvent.

Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, butanol, terpinol and the like.

Examples of the cellosolve solvents include methyl cellosolve and ethyl cellosolve.

Ethyl ether, butyl carbitol, etc. are mentioned as an ether solvent.

These solvents are used in the ratio of 500 weight part or less with respect to 100 weight part of hydroxyl group containing liquid diene type polymers which are 1st component, and / or its hydride.

As a viscosity modifier, the following plasticizers, diluents, etc. can be used.

Examples of the plasticizer include dialkyl phthalates such as dioctyl phthalate, diisononyl phthalate, and ditridecyl phthalate, dialkyl adipates such as dioctyl adipate, and alkyl trimellitic acid.

Examples of the diluent include process oils such as paraffinic, naphthenic and aroma, olefin oligomers, alkylbenzenes, alkylnaphthalenes, alkyldiphenylethanes, alkyldiphenyls, silicone oils, liquid paraffins, 1-decene oligomers and paraffinic oligomers. Can be mentioned.

The addition amount of these viscosity modifiers is not particularly limited, but is usually 500 parts by weight or less, preferably 200 parts by weight or less, based on 100 parts by weight of the hydroxyl group-containing liquid diene polymer and / or its hydride.

In addition, the following various inorganic fillers and organic fillers can be used as a filler.

As inorganic fillers, zinc, aluminum, copper, nickel, glass spheres, glass flakes, glass fibers, carbon black (channel black, furnace black, acetylene black, thermal black), carbon fibers, graphite, asbestos, kaolin clay, foliar clay ( agalmatolite clay, talc, nepheline, cryolite, wollastonite, diatomaceous earth, slate powder, chalking, feldspar powder, mica, gypsum, quartz powder, silicate powder, attapulgite , Mica, volcanic ash, vermiculite, silica, alumina, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, molybdenum dioxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zeolite, potassium titanate Boron nitride, boron nitrite, molybdenum disulfide, and the like.

On the other hand, as organic fillers, natural fibers such as rubber powder, cellulose, lignin, chitin, leather powder, palm skin, wood powder, cotton, hemp, wool, and silk, nylon, polyester, vinylon, acetate, acryl and the like Synthetic fibers, further polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polymethyl methacrylate resin, polyvinyl chloride resin, epoxy resin, The powder or granules of synthetic resins, such as a phenol resin, are mentioned.

There are no particular restrictions on the amount of these inorganic fillers and organic fillers added, but they are usually 500 parts by weight or less, preferably 300 parts by weight or less, based on 100 parts by weight of the hydroxyl-containing liquid diene polymer and / or its hydride. .

Moreover, in order to accelerate hardening reaction of the hydroxyl-containing liquid diene type polymer which is a 1st component, and / or its hydride, and the melamine type hardening | curing agent which is a 2nd component, you may add the following catalyst.

Specifically, for example, aromatic sulfonic acid compounds such as paratoluenesulfonic acid, paraxylenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, or these are isopropyl alcohol, isobutanol, ethylene glycol, xylene and the like. What is dissolved in a solvent, further, these aromatic sulfonic acid compounds are blocked by compounds such as amines, epoxies, oximes and the like to be thermally dissociated, and strong acid compounds such as inorganic acids such as hydrochloric acid and sulfuric acid can be used.

Weak acid compounds such as phosphoric acid compounds, ammonium chloride compounds and carboxylic acid compounds can also be used.

Of these, block type and phosphoric acid weak acid catalysts of aromatic sulfonic acid catalysts are preferable.

The amount of these catalysts added is at most 20 parts by weight based on 100 parts by weight of the hydroxyl group-containing liquid diene polymer and / or its hydride. When it exceeds 20 parts by weight, not only the curing accelerator effect reaches a limit point, but also an improper state such as deterioration of compatibility of the composition and layer separation occurs.

Moreover, in order to accelerate hardening reaction of the hydroxyl-containing liquid diene type polymer which is a 1st component and / or its hydride, and the block isocyanate compound which is a 2nd component, it is also possible to add the following urethane curing catalyst.

Specific examples thereof include tertiary amines such as triethylenediamine, tetramethylguanidine and 1,2-dimethylimidazole; It is also possible to use organometallic compounds, such as stannous octoate, dibutyl tin diacetate and dibutyl tin dilaurate.

The amount of these urethane curing catalysts added is 10 parts by weight based on 100 parts by weight of the hydroxyl group-containing liquid diene polymer and / or its hydride as the first component. When it exceeds 10 parts by weight, not only the hardening promoting effect reaches a limit but also the risk of local side reaction (gelling) increases.

In the 2nd aspect of this invention, since a melamine type hardening | curing agent and a block isocyanate compound are used together as a hardening | curing agent, the said 2 types of catalysts may be mixed as a used catalyst.

In the composition for liquid polymers of this invention, it is also possible to add the additive as illustrated below other than the said compounding agent.

For example, anti-aging agents such as hindered phenols, hindered amines, and benzotriazoles can be added to improve the heat resistance and weather resistance. In addition, antifoaming agents such as flame retardants such as phosphorus compounds, halogen compounds and antimony oxides, zeolites such as silicon compounds, natural zeolites or synthetic zeolites, and fine powder silica for thixotropic properties of the composition Thixotropy agents, such as these, can be added. Furthermore, in order to adjust adhesive force and adhesive force, alkylphenol resin, terpene resin, terpene phenol resin, xylene formaldehyde resin, rosin, hydrogenated rosin, coumarone resin, aliphatic, cycloaliphatic, aromatic petroleum resin, etc. It is also possible to add tackifying resin.

It is preferable that the total content of these additives is 20 weight% or less in a composition.

Although the liquid polymer composition of this invention is obtained by mix | blending the said component, More specifically, the hydroxyl-containing liquid diene type polymer which is said 1st component, and / or its hydride, the specific melamine compound as a hardening | curing agent which is a 2nd component, or The melamine compound and the hydroxyl group-containing liquid diene polymer and / or its hydride and the polyisocyanate compound are reacted and prepolymerized, and then mixed with the blocked polyisocyanate compound, and various additives are mixed at the above ratios and painted. It is obtained by kneading using a roll or rollers such as a roll, a mixer such as a Dalton mixer, a planetarium mixer, or various mixing and kneading apparatuses. The kneading time is from 1 minute to 15 hours, and the kneading temperature is from 0 ° C to 100 ° C.

As mentioned above, the target liquid polymer composition can be manufactured.

The liquid polymer composition of the present invention can be used for a wide range of applications such as those described below.

That is, the liquid polymer composition of the present invention can be used in various paints, coating materials, varnish applications, such as for automotive undercoats, precoat metals, and exteriors, and for various adhesives such as thermosetting and water dispersion systems, and for electrical insulating materials. Protective materials, linings or waterproofing materials for buildings and structures, ⑤ textile procedures, ⑥ paints, films, sheets, ⑦ conventional melamine-based paints, alkyd resins, polyurethane rubber, etc. It can be widely used for the use as (iii), the use of (8) paint, ink, etc., (9) various primer uses.

Application to these uses is preferably carried out by application using a coater such as a bar coater or spray coating.

Next, although an Example demonstrates this invention further in detail, the scope of the present invention is not limited to these Examples.

Preparation Example 1

(1) Preparation of hydroxyl-containing liquid isoprene-based polymer

200 g of isoprene, 100 g of hydrogen peroxide solution at 30% concentration and 300 g of isopropanol were placed in a 1 L stainless pressure reactor, and the reaction was carried out under the conditions of a temperature of 115 DEG C, a maximum pressure of 0.9 MPa and a reaction time of 2.5 hours.

After the completion of the reaction, the reaction mixture was placed in a separatory funnel, 600 g of water was added thereto, and the mixture was stirred and heated for 3 hours, after which the oil layer was separated. The solvent, the monomer, and the low boiling point component were distilled off from this oil layer on condition of 2 mmHg, 100 degreeC, and 2 hours, and the hydroxyl terminal liquid isoprene-type polymer (yield 71 weight%) was obtained. The number average molecular weight of this substance was 1340, the hydroxyl content was 1.52 meq / g, and the viscosity was 4.5 Pa.s (30 degreeC). In this case, the average hydroxyl (fn) per molecule is 2.09. The structural analysis results by ¹ H-NMR were 57 mol% of trans-1,4 structure, 30 mol% of cis-1,4 structure, 8 mol% of 1,2-vinyl structure, and 5 mol% of 3,4-vinyl structure.

(2) Preparation of Hydride of Hydroxyl Terminal Liquid Polyisoprene-Based Polymer

10 g of the hydroxyl-terminal liquid polyisoprene-based polymer obtained in the above (1), 5 g of ruthenium carbon catalyst 5 g of ruthenium carbon catalyst, and 100 g of cyclohexane were added as a solvent, and hydrogenated at 150 ° C. under 8 MPa hydrogen pressure for 6 hours. After completion of the reaction, the catalyst was separated and removed from the reaction solution through a 0.45 µm membrane filter, and then the solvent was distilled off under conditions of 2 mmHg, 110 ° C and 2 hours. As a result, the hydride of the hydroxyl terminal terminal liquid polyisoprene-based polymer was obtained.

The number average molecular weight of this substance was 1430, the hydroxyl content was 1.60 meq / g, the viscosity was 31 Pa.s (30 degreeC), and the bromine value was 1g / 100g. At this time, the average number of hydroxyl groups (fn) per molecule was 2.27.

Preparation Example 2 (Preparation of Block Isocyanate Compounds)

100 weight part of hydroxyl-containing liquid polybutadiene and 30 weight part of triylene diisocyanate were put into the fractionation flask, and it reacted at 60-80 degreeC in nitrogen atmosphere, and synthesize | combined the prepolymer which has terminal isocyanate group. Next, 15 parts by weight of methyl ethyl ketooxime was slowly added dropwise to 100 parts by weight of the prepolymer, followed by reaction at 60 to 80 ° C. It diluted with xylene so that it might be 80% of solid content, and the block isocyanate compound was obtained. Content of the effective isocyanate group was 6.2%.

Examples 1-9 and Comparative Examples 1-3

It mix | blended as shown in Table 1, and knead | mixed for 30 minutes at room temperature with the Dalton mixer, and prepared the liquid polymer composition.

The obtained composition was apply | coated with a bar coater so that it might become thickness of 80 micrometers on a cold rolled steel sheet, and it heat-hardened on 140 degreeC and the conditions for 30 minutes in oven, and the hardened | cured material was produced.

The performance of the obtained hardened | cured material was evaluated by the following method. The results are shown in Tables 1a and 1b.

(1) the hardness of the cured product

According to JIS K 5400, the pencil hardness was measured.

(2) hardening state

The hardened state of the obtained hardened | cured material (coating film) was confirmed visually and tactilely, and it evaluated by the presence or absence of foaming or viscosity. When a favorable hardened | cured material (coating film) was obtained, it described as "no problem."

Example One 2 3 4 5 6 Liquid polymer composition Hydroxyl-containing liquid diene polymer / hydride Polybd R-45HT ¹⁾ 100 - - - - - Polybd R-15HT ²⁾ - 100 - - - - Poly ip ³⁾ - - 100 - - - Epol ⁴⁾ - - - 100 - - Preparation Example 1 - - - - 100 - NISSO PB G-2000 ⁵⁾ - - - - - 100 H-3880A ⁶⁾ - - - - - - Hardener Cymel 303 ⁷⁾ 10 10 10 10 10 10 Cymel 254 ⁸⁾ - - - - - - Melamine ⁹⁾ - - - - - - Poly oil 130 ¹⁰⁾ - - - - - - Coronate 2507 ¹¹⁾ - - - - - - catalyst Catalyst 600 ¹²⁾ 0.5 0.5 0.5 0.5 0.5 0.5 Catalyst 296-9 ¹³⁾ - - - - - - DBTDL ¹⁴⁾ - - - - - - evaluation Hardness (pencil hardness) of hardened body 2B-3B HB-B 2B-3B B-2B HB-B HB-B Curing state No problem No problem No problem No problem No problem No problem

Example Comparative example 7 8 9 One 2 3 Liquid polymer composition Hydroxyl-containing liquid diene polymer / hydride Polybd R-45HT ¹⁾ - 100 50 - 100 100 Polybd R-15HT ²⁾ - - - - - - Poly ip ³⁾ - - - - - - Epol ⁴⁾ - - 50 - - - Preparation Example 1 - - - - - - NISSO PB G-2000 ⁵⁾ - - - - - - H-3880A ⁶⁾ 180 - - - - - Hardener Cymel 303 ⁷⁾ 15 - 10 10 - - Cymel 254 ⁸⁾ - 10 - - - - Melamine ⁹⁾ - - - - - 10 Poly oil 130 ¹⁰⁾ - - - 100 - - Coronate 2507 ¹¹⁾ - - - - 31.9 - catalyst Catalyst 600 ¹²⁾ 0.7 - 0.5 0.5 - 0.5 Catalyst 296-9 ¹³⁾ - 0.5 - - - - DBTDL ¹⁴⁾ - - - - 0.5 - evaluation Hardness (pencil hardness) of hardened body HB-B 3B-4B B-2B - 4B-5B Curing state No problem No problem No problem Not cured Viscous Not cured

Footnotes in Tables 1a and lb

1) Hydroxyl-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C

2) Hydroxy group-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 1.82 meq / g, number average molecular weight 1250, viscosity = 14 poise / 30 ° C

3) Hydroxyl-containing liquid C5-based polymer (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl content = 0.83 meq / g, number average molecular weight 2630, viscosity = 73 poise / 30 ° C

4) Hydroxyl group liquid polyolefin (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 0.91 meq / g, number average molecular weight 2700, viscosity = 810 poise / 30 ° C

5) Hydroxyl group liquid polybutadiene (manufactured by Sodatsu Co., Ltd.), hydroxyl content = 0.98 meq / g, number average molecular weight 2000, viscosity = 230 poise / 45 ° C, 1.2-vinyl structure 90%

6) Polybd R-45 HT emulsion, solid content 54%, average particle size 0.54㎛ (produced by Cheil Industries)

7) Hexamethoxymethylol Melamine (manufactured by Mitsui Cytech Co., Ltd.)

8) methoxy, butoxymethylolmelamine (manufactured by Mitsui Cytech Co., Ltd.)

9) Melamine, reagent express (all of R ₁ to R ₆ in formula (I) are hydrogen atoms)

10) Liquid polybutadiene (manufactured by Japan Xeon Co., Ltd.), number average molecular weight 3000, viscosity = 30 poise / 20 ° C, 1,4-cis structure 80%

11) Oxime Block HDI Block Isocyanate (manufactured by Nippon Polyurethane Co., Ltd.), Effective NCO content = 11.6%

12) Aromatic sulfonic acid catalyst, nonvolatile content = 70% (Mitsui Cytech Co., Ltd.)

13) Phosphoric acid weak acid catalyst (manufactured by Mitsui Cytech Co., Ltd.)

14) dibutyl tin dilaurate (manufactured by Kyodo Pharmaceutical Co., Ltd.)

From the results of Tables 1a and 1b, since the compositions of Examples 1 to 9 use a hydroxyl group-containing liquid diene polymer and / or a hydride and a specific melamine compound as a curing agent together, the hardness (penal hardness) and curing state of the cured product It turns out that favorable evaluation is received also about both the performances.

First, the compositions of Examples 1 to 6 are prepared by varying the amount of hydroxyl group-containing liquid diene polymer and / or hydride, respectively.

The same good results as in Example 1 were also obtained in Example 2 using a hydroxyl group-containing liquid polybutadiene having a high hydroxyl group content and a low number average molecular weight compared with the hydroxyl-containing liquid polybutadiene used in Example 1.

Moreover, also when a C5-type polymer (Example 3) was used instead of butadiene, the favorable result similarly to Example 1 was obtained.

Furthermore, even when the hydroxyl group terminal liquid polyolefin with a significantly high viscosity was used (Example 4) compared with the hydroxyl group-containing liquid polybutadiene used in Example 1, good results were obtained in the same manner as in Example 1.

Next, also in the case where the hydride of the hydroxyl group-containing liquid polyisoprene of Example 1 (Example 5) was used, good results were obtained in the same manner as in Example 1.

Moreover, also when the hydroxyl group terminal liquid polybutadiene with a high ratio of 1,2-vinyl structure was used (Example 6), the favorable result similarly to Example 1 was obtained.

Next, Example 7 was made by using a hydroxyl group-containing liquid diene-based polymer emulsion in Example 1 to slightly increase the blending ratio and by increasing the curing agent, but the hardness and curing of the cured product was the same as in Example 1. It turns out that favorable evaluation is received by the state point.

In Example 1, in Example 1, the melamine compound, which is a curing agent, was replaced with other melamine compounds, methoxy and butoxymethylol melamine, and the catalyst was changed to a phosphate-based weakly acidic catalyst. It turns out that favorable evaluation was received by the point of state.

Furthermore, although Example 9 used together the hydroxyl group containing liquid diene type polymer and its hydride, it turns out that favorable evaluation was received by the point of the hardness and hardening state of a hardened | cured material like Example 1.

On the other hand, in Comparative Example 1, liquid polybutadiene containing no hydroxyl group was added instead of the hydroxyl group-containing liquid diene polymer and / or its hydride. However, the hardness of the cured product could not be measured.

Next, Comparative Example 2 uses an oxime block HDI-based block isocyanate and a curing accelerator DBTDL instead of a melamine compound, which is a curing agent. No hardened body could be obtained.

In addition, although the comparative example 3 used melamine whose all R <_1> -R <_6> in general formula (I) is a hydrogen atom as a hardening | curing agent, it did not harden and the hardness of hardened | cured material was not able to be measured.

From the above results, it is possible to obtain a cured body that is sufficiently satisfactory in terms of hardness and cured state of the cured body by blending a hydroxyl group-containing liquid diene polymer and / or its hydride with a specific melamine compound as a curing agent. It became clear.

Example 10

Except adding 0.1 parts by weight of water, it was blended in the same manner as in Example 1 (see Table 2), kneaded for 30 minutes at room temperature with a Dalton mixer, a liquid polymer composition was prepared, and the same operation as in Example 1 was carried out to form a cured product. The performance of the obtained hardened | cured material was evaluated. The results are shown in Table 2.

Comparative Example 4

In Example 10, except having added 31.9 weight part of block isocyanates and 0.5 weight part of DBTDL instead of adding a hardening | curing agent and a catalyst, the hardening body was produced similarly to Example 10, and the performance of the obtained hardened body was evaluated. The results are shown in Table 2.

(Physical Properties of Cured Products When Water Exists in the System) Example 10 Comparative Example 4 Liquid polymer composition Hydroxy-containing liquid diene polymer: Polybd R-45HT ¹⁾ 100 100 Hardener: Cymel 303 ⁷⁾ 10 - Catalyst: Catalyst 600 ¹²⁾ 0.5 - DBTDL ¹⁴⁾ - 0.5 moisture 0.1 0.1 Coronate 2507 ¹¹⁾ - 31.9 Performance evaluation Hardness (pencil hardness) of hardened body 2B-3B Measurement not possible due to poor curing Curing state No problem Big foam, big viscosity

Footnotes in Table 2

1) Hydroxyl-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C

7) Hexamethoxymethylol Melamine (manufactured by Mitsui Cytech Co., Ltd.)

11) Oxime Block HDI Block Isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.), Effective NCO content = 11.6%

12) Aromatic sulfonic acid catalyst, non-volatile content = 70% (Mitsui Cytech Co., Ltd.)

14) dibutyl tin dilaurate (manufactured by Kyodo Pharmaceutical Co., Ltd.)

As apparent from the results of Example 10 in Table 2, even in the presence of water in the system, a good composition was obtained for both the hardness (penal hardness) and the curing state of the cured product.

On the other hand, in the comparative example 4 which used the isocyanate compound instead of the hardening | curing agent of this invention, the hardness (pencil hardness) of the hardened | cured material was unmeasurable, and the hardening state also had foaming and viscosity high.

From this, it turns out that in the composition of this invention, even if there exists water in a system, the favorable hardened | cured material which does not produce foaming and viscosity is obtained.

Examples 11-12

In Example 1, the compounding quantity of a hardening | curing agent and a catalyst was made into 20 weight part and 1.0 weight part, respectively, and it mix | blended like Example 1 except adding a predetermined amount of 40/60 straight asphalt (refer Table 3), and Dalton mixer It knead | mixed for 30 minutes at room temperature, the liquid polymer composition was prepared, it carried out similarly to Example 1, the hardened | cured body was created, and the performance of the hardened body was evaluated. In addition, the performance of the cured product was the same as in Example 1, except that (1) the hardness (pencil hardness) (initial hardness) and (2) the hardened state of the cured product were evaluated for vibration damping properties, Water resistance and storage stability were evaluated. The results are shown in Table 3.

Comparative Examples 5 and 6

In Examples 11-12, except having set it as the compounding like Table 3, it carried out similarly to Examples 11-12, and created the hardened | cured material and evaluated the performance of hardened | cured material. The results are shown in Table 3.

(3) vibration damping

Using the dynamic viscoelasticity measuring apparatus manufactured by Orient Tech, tan-delta value in 23 degreeC was calculated | required on the conditions of a frequency of 11 Hz and a temperature increase rate of 2 degree-C / min. The larger tan δ value indicates better vibration damping.

(4) water resistance

The obtained hardened | cured body was hydrothermally deposited on 80 degreeC and the conditions of 5 days, and the hardness (pencil hardness) of the hardened | cured body before and after a test was evaluated.

(5) storage stability

The obtained liquid polymer composition was left to stand and stored at room temperature for 30 days, and the viscosity before and after storage was measured using the Brookfield viscometer. Viscosity change rate (%) between storages was computed, and the one with the smallest change rate showed good stability.

Performance Evaluation of Compositions Containing Bituminous Materials Example Comparative example 11 12 5 6 Liquid polymer composition Hydroxy-containing liquid diene polymer: Polybd R-45HT ¹⁾ 100 100 100 - Hardener: Cymel 303 ⁷⁾ 20 20 - - Catalyst: Catalyst 602 ¹⁶⁾ 1.0 1.0 - - Polyester Polyol ¹⁵⁾ - - - 100 Coronate 2507 ¹¹⁾ - - 31.9 32.7 DBTDL ¹⁴⁾ - - 0.1 0.1 40/60 straight asphalt ¹⁷⁾ 50 100 50 50 Performance evaluation Hardness of Hardened Material (Initial Hardness) 2B-3B 3B-4B 5B-6B 2B-3B Water resistance (hardness of cured product after 80 days of hot water deposition) 2B-3B 3B-4B 5B-6B Viscosity is not measurable Curing state No problem No problem Viscous No problem Damping 0.65 0.74 0.89 0.76 Storage stability +2.5 +5.4 +13.5 +10.4

[Footnote of Table 3]

1) Hydroxyl-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C

7) Hexamethoxymethylol Melamine (manufactured by Mitsui Cytech Co., Ltd.)

11) Oxime Block HDI Block Isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.), Effective NCO content = 11.6%

14) Dibutyltin dilaurate (manufactured by Kyodo Pharmaceutical Co., Ltd.)

15) Nipporan 3027, hydroxyl content = 0.86 meq / g, viscosity = 11 poise / 75 ° C. (manufactured by Nippon Polyurethane Co., Ltd.)

16) Amine block type of aromatic sulfonic acid catalyst Catalyst 600, nonvolatile content = 47% (Mitsui Cytech Co., Ltd. product)

17) Manufacture of Idemitsukosan Co., Ltd.

Table 3 shows the following things.

In addition to the hydroxyl group-containing liquid diene polymer and the melamine compound, in Example 11 in which asphalt was added, the hardness (pencil hardness) of the cured product before and after the water resistance test did not change at all. In addition, good results were obtained regarding the state of hardening, vibration damping and storage stability.

Example 12 made the addition amount of asphalt into 100 weight part which is 2 times of Example 10, and obtained the hardened | cured material of favorable water resistance and hardening state similarly to Example 11. The storage stability was lower than that of Example 11 but was in an acceptable range.

On the other hand, in Comparative Example 5 in which an isocyanate compound was added instead of a melamine compound as the curing agent, the water resistance was good, but the viscosity was high and the storage stability was also low.

Moreover, in the comparative example 6 using the liquid diene type polymer which does not contain a hydroxyl group, there was no problem regarding the hardening state, but after the water resistance test, large viscosity remained in the hardening | curing agent and water resistance was remarkably low. In addition, the storage stability was inferior.

From this, it is evident that the composition of the present invention is excellent not only in curability but also in water resistance, vibration damping property and storage stability.

Examples 13-21, Reference Example 1, and Comparative Examples 7-9

It mix | blended as Table 4 and knead | mixed for 30 minutes at room temperature with the Dalton mixer, and prepared the liquid polymer composition.

The obtained composition was applied on a cold rolled steel sheet with a bar coater so as to have a thickness of 80 µm, and cured by heating in an oven at 140 ° C. for 30 minutes.

The performance of the obtained hardened | cured material was evaluated by the following method. The results are shown in Tables 4a, 4b and 4c.

(1) compatibility

After removing the filters and preparing the liquid polymer composition, the mixture was left to stand at room temperature for 1 week to confirm the state of the composition. When separation or turbidity was seen, it was referred to as compatibility "poor" and when there was no separation and turbidity, it was called "good".

(2) Physical properties of hardened body

In accordance with JIS K 6251, the elongation and tensile strength at the time of cutting were measured.

(3) chipping resistance

A cured product having a thickness of 500 µm was prepared on the electrodeposition coating plate, and the hexagon nut was dropped at a height of 3 m through the cylinder. In addition, the hardening body was set at the angle of 30 degrees with respect to the fall direction of a nut, and showed the nut total weight when a base was exposed.

(4) hardened state

The hardening state of the obtained hardened | cured material (coating film) was confirmed by visual and touch, and it evaluated by the presence or absence of foaming and viscosity. When a favorable hardened | cured material (coating film) was obtained, it described as "there is no problem."

Example 13 14 15 16 17 Liquid polymer composition Hydroxyl-containing liquid diene polymer / hydride Polybd R-45HT ¹⁾ 100 - - - - Polybd R-15HT ²⁾ - 100 - - - Poly ip ³⁾ - - 100 - - Epol ⁴⁾ - - - 100 - Preparation Example 1 - - - - 100 filling Clay ⁵⁾ 200 200 200 200 200 MT-100 ⁶⁾ 50 50 50 50 50 NS-100 ⁷⁾ - - - - - solvent Ifsol 150 ⁸⁾ 30 30 30 30 30 Hardener Preparation Example 2 30 30 30 30 30 Coronate 2507 ⁹⁾ - - - - - Coronate 2516 ¹⁰⁾ - - - - - Cymel 303 ¹¹⁾ 20 20 20 20 10 Cymel 254 ¹²⁾ - - - - - catalyst Catalyst 600 ¹³⁾ 0.5 0.5 0.5 0.5 0.5 Catalyst 296-9 ¹⁴⁾ - - - - - DBTDL ¹⁵⁾ 1.5 1.5 1.5 1.5 1.5 Performance evaluation Compatibility Good Good Good Good Good Physical properties of the cured product Elongation at Cutting (%) 100 100 130 120 120 Tensile Strength (Mpa) 2.0 1.9 1.5 1.6 1.5 Chipping resistance (Nut weight: kg) 33 30 26 27 26 Curing state No problem No problem No problem No problem No problem

Example 18 19 20 21 Liquid polymer composition Hydroxyl-containing liquid diene polymer / hydride Polybd R-45HT ¹⁾ 100 100 100 100 Polybd R-15HT ²⁾ - - - - Poly ip ³⁾ - - - - Epol ⁴⁾ - - - - Preparation Example 1 - - - - filling Clay ⁵⁾ 200 100 200 200 MT-100 ⁶⁾ 50 - - 50 NS-100 ⁷⁾ - - 50 - solvent Ifsol 150 ⁸⁾ 30 30 30 30 Hardener Preparation Example 2 80 30 30 30 Coronate 2507 ⁹⁾ - - - - Coronate 2516 ¹⁰⁾ - - - - Cymel 303 ¹¹⁾ 20 20 20 - Cymel 254 ¹²⁾ - - - 20 catalyst Catalyst 600 ¹³⁾ 0.7 0.5 0.5 Catalyst 296-9 ¹⁴⁾ - - - 0.5 DBTDL ¹⁵⁾ 3.0 1.5 1.5 1.5 Performance evaluation Compatibility Good Good Good Good Physical properties of the cured product Elongation at Cutting (%) 150 120 100 110 Tensile Strength (Mpa) 1.3 1.6 2.1 1.8 Chipping resistance (Nut weight: kg) 28 28 32 27 Curing state No problem No problem No problem No problem

Reference Example Comparative example One 7 8 9 Liquid polymer composition Hydroxyl-containing liquid diene polymer / hydride Polybd R-45HT ¹⁾ 100 100 100 100 Polybd R-15HT ²⁾ - - - - Poly ip ³⁾ - - - - Epol ⁴⁾ - - - - Preparation Example 1 - - - - filling Clay ⁵⁾ 200 100 200 200 MT-100 ⁶⁾ 50 50 50 50 NS-100 ⁷⁾ - - - - solvent Ifsol 150 ⁸⁾ 30 30 30 30 Hardener Preparation Example 2 60 - - Coronate 2507 ⁹⁾ - - 32 - Coronate 2516 ¹⁰⁾ - - - 27 Cymel 303 ¹¹⁾ 20 - - 20 Cymel 254 ¹²⁾ - - - - catalyst Catalyst 600 ¹³⁾ 0.5 - - 0.5 Catalyst 296-9 ¹⁴⁾ - - - - DBTDL ¹⁵⁾ - 1.5 1.0 1.0 Performance evaluation Compatibility Good Good Good Bad Physical properties of the cured product Elongation at Cutting (%) 40 250 Not measurable - Tensile Strength (Mpa) 3.0 0.7 Not measurable - Chipping resistance (Nut weight: kg) 15 13 Not measurable - Curing state No problem Viscous Viscous -

Footnotes in Table 4

1) Hydroxyl-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C

2) Hydroxyl-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl content = 1.82 meq / g, number average molecular weight 1250, viscosity = 14 poise / 30 ° C

3) Hydroxyl-containing liquid C5-based polymer (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl content = 0.83 meq / g, number average molecular weight 2630, viscosity = 73 poise / 30 ° C

4) Hydroxyl group liquid polyolefin (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 0.91 meq / g, number average molecular weight 2700, viscosity = 810 poise / 30 ° C

5) OA kaolin clay (manufactured by Maruo Calcium Co., Ltd.)

6) Hard Calcium Carbonate (manufactured by Maruo Calcium Co., Ltd.)

7) Heavy calcium carbonate (manufactured by Maruo Calcium Co., Ltd.)

8) High boiling point solvent (manufactured by Idemitsu Petrochemical Co., Ltd.)

9) Oxime Block HDI Block Isocyanate (manufactured by Nippon Polyurethane Co., Ltd.), Effective NCO content = 11.6%

10) Oxime Block HDI Block Isocyanate (manufactured by Nippon Polyurethane Co., Ltd.), Effective NCO content = 13.5%

11) Hexamethoxymethylol melamine (manufactured by Mitsui Cytech Co., Ltd.)

12) methoxy, butoxymethylol melamine (manufactured by Mitsui Cytech Co., Ltd.)

13) aromatic sulfonic acid catalyst, non-volatile content = 70% (Mitsui Cytech Co., Ltd.)

14) Phosphoric acid weak acid catalyst (manufactured by Mitsui Cytech Co., Ltd.)

15) Dibutyl tin dilaurate (manufactured by Kyodo Pharmaceutical Co., Ltd.)

Tables 4a, 4b, and 4c show the following things.

According to the comparative example 7, even if the block isocyanate of this invention is used, when this and a melamine compound are not used together, it will be inferior in the physical property of a hardened | cured material.

Next, according to the comparative example 8, when the block isocyanate of this invention is not used and this and a melamine compound are not used together, viscosity is large and a favorable hardened body cannot be obtained.

Moreover, according to the comparative example 9, even when a block isocyanate and a melamine compound are used together, when the block isocyanate of this invention is not used as a block isocyanate, it will become incompatible.

In addition, as shown in Reference Example 1, in the case of melamine compound alone, the compatibility is good and the curing state is no problem, but the physical properties of the cured product are inferior.

On the other hand, according to Examples 13-21, when using the block isocyanate and melamine compound of this invention together, any of compatibility, the physical property of hardened | cured material, chipping resistance, and a hardened state becomes favorable.

Examples 22-23 and Comparative Example 10

It mix | blended as Table 5 and knead | mixed for 30 minutes at room temperature with the Dalton mixer, and prepared the liquid polymer composition.

The obtained composition was apply | coated with a bar coater on the cold rolled steel sheet so that it might become thickness of 80 micrometers, and it heat-hardened on 140 degreeC and the conditions for 30 minutes in oven, and the hardened body was produced.

The performance of the obtained hardened | cured material was evaluated by the following method. The results are shown in Table 5. In addition, the physical property and hardening state of the hardened | cured material were evaluated like Table 4a, 4b, and 4c. Storage stability was evaluated by the following method.

Storage stability

The obtained liquid polymer composition was left to stand at room temperature for 30 days, the viscosity was measured by the Brookfield viscometer, and it was represented by the viscosity change rate (%). The smaller the change rate, the better the storage stability.

Example Comparative example 22 23 10 Liquid polymer composition Hydroxyl-containing liquid diene polymer / hydride Polybd R-45HT ¹⁾ 100 100 100 filling Clay ⁵⁾ 200 100 200 MT-100 ⁶⁾ 50 - 50 solvent Ifsol 150 ⁸⁾ 30 30 30 Hardener Preparation Example 2 30 30 - Coronate 2507 ⁹⁾ - - 32 Cymel 303 ¹¹⁾ 20 20 - catalyst Catalyst 602 ¹⁶⁾ 1.5 1.0 - DBTDL ¹⁵⁾ 1.5 1.5 1.0 Physical properties of the cured product Elongation at Cutting (%) 110 130 Not measurable Tensile Strength (Mpa) 0.4 0.3 Not measurable Curing state No problem No problem Viscous Storage stability +5.0 +8.5 +15.0

Footnotes in Table 5

1) Hydroxyl-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C

5) OA kaolin clay (manufactured by Maruo Calcium Co., Ltd.)

6) Hard Calcium Carbonate (manufactured by Maruo Calcium Co., Ltd.)

8) High boiling point solvent (manufactured by Idemitsu Petrochemical Co., Ltd.)

9) Oxime Block HDI Block Isocyanate (manufactured by Nippon Polyurethane Co., Ltd.), Effective NCO content = 11.6%

11) Hexamethoxymethylol melamine (manufactured by Mitsui Cytech Co., Ltd.)

15) dibutyl tin dilaurate (made by Kyodo Pharmaceutical Co., Ltd.)

16) Amine block type of aromatic sulfonic acid catalyst Catalyst 600, nonvolatile content = 47% (Mitsui Cytech Co., Ltd. product)

Table 5 shows the following things.

According to the comparative example 10, when the block isocyanate of this invention is not used and this and a melamine compound are not used together, viscosity is large and a favorable hardened | cured material is not obtained and it is inferior also in storage stability.

On the other hand, according to Examples 22-23, when the block isocyanate and melamine compound of this invention are used together, all the physical properties, hardening state, and storage stability of a hardened | cured material become favorable.

According to the first aspect of the present invention, there is provided a curing system capable of becoming a thermosetting one-liquid type, so that carbon dioxide gas is not generated even when moisture is present in the system, and foaming does not occur in the resulting cured product, In addition, a liquid polymer composition with improved coating properties can be obtained.

That is, the composition according to the first aspect of the present invention uses a melamine compound having a specific structure that is highly compatible with the polymer as a curing agent for the thermosetting one-component type of the hydroxyl group-containing liquid diene-based polymer. One composition can be obtained. And since it hardens | cures with the melamine compound of such a specific structure, it is excellent in sclerosis | hardenability of the hardened | cured body obtained. Moreover, since the obtained hardened | cured material is excellent also in water resistance, it has the characteristic calculated | required as a coating material.

Moreover, since the composition in the 1st aspect of this invention uses the melamine compound of a specific structure as a hardening | curing agent, even when moisture exists in a system, a functional group does not react and produces | generates a carbon dioxide gas, and therefore a hardened body No foaming occurs in the Therefore, the liquid polymer composition in which curability and coating-film property were improved can be provided.

Moreover, according to the 2nd aspect of this invention, the liquid polymer composition which is favorable in compatibility and sclerosis | hardenability, and improved rubber elongation, coating property, storage stability, etc. as a coating film property can be obtained.

Therefore, the composition of the present invention can be widely and effectively used for various applications as described above, including various paints, coating materials and varnish applications such as undercoat for vehicles, precoat metals, and exteriors.

Claims (3)

Hydroxyl group-containing liquid diene polymer and / or hydride thereof, melamine compound represented by the following general formula (I) as a curing agent, or melamine compound represented by the following general formula (I), hydroxyl group-containing liquid diene polymer and / Or a liquid polymer composition containing a blocked polyisocyanate compound blocked by reacting the hydride with the polyisocyanate compound and prepolymerizing the same. One (However, in formula (I), R ₁ , R ₃ and R ₅ are each H or CH ₂ OX, and R ₂ , R ₄ and R ₆ are each CH ₂ OY, wherein X is hydrogen, methyl group, propyl Any one of a group and a butyl group, and Y is one of a methyl group, a propyl group and a butyl group.) The composition according to claim 1, wherein the hydroxyl group-containing liquid diene polymer or its hydride has a hydroxyl group content of 0.2 to 10.0 meq / g and a number average molecular weight of 300 to 10,000. The composition according to claim 1 or 2, which is for an undercoat material for a vehicle.