JP2001031827A - Liquid polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid polymer composition not generating carbon dioxide even when moisture exists in a system and therefore not causing bubbles in a cured product, improved in hardenability and physical properties of coating film and useful for an undercoating material for vehicles by employing a melamine compound having a specific structure as a curing agent. SOLUTION: This composition comprises (A) a hydroxyl group-containing liquid diene-based polymer and/or its hydride and (B) a melamine compound expressed by the formula (wherein R1, R3 and R5 are each H or CH2OX; R2, R4 and R6 are each CH2OY; X is H, methyl, propyl or the like; and Y is methyl, propyl or butyl) or a block polyisocyanate compound obtained by reacting the above melamine compound and the component A with a polyisocyanate compound and then by the block copolymerization of the resultant prepolymer as a curing agent. The content of hydroxyl group of the component A preferably is 0.2-10.0 meq/g and the number average molecular weight of the component A preferably is 300-10,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technology for providing a one-pack type thermosetting liquid polymer composition, and more particularly to a hydroxyl group-containing liquid diene polymer and / or a hydrogenated product thereof, and a melamine structure as a curing agent. Or a liquid containing a blocked polyisocyanate compound obtained by reacting a melamine compound with a hydroxyl group-containing liquid diene polymer and / or a hydride thereof and a polyisocyanate compound to form a prepolymer and then blocking the melamine compound. The present invention relates to a novel liquid polymer composition having improved curability, coating film properties, and compatibility.

[0002]

2. Description of the Related Art Conventionally, liquid hydroxyl-containing diene polymers or hydrides thereof have been widely used as polyol materials for polyurethane. For example, Tokuho 7-5704
In Japanese Patent Application Laid-Open Publication No. H11-146, a liquid polymer composition comprising a hydride of a liquid polyisoprene having a hydroxyl group at a molecular chain terminal and a polyisocyanate compound is proposed. These techniques are a method of producing a urethane group by reacting a hydroxyl group in a hydroxyl group-containing liquid diene polymer or a hydride thereof with an isocyanate group in a polyisocyanate compound as a curing agent, thereby obtaining a polyurethane rubber. It is. The composition capable of forming the polyurethane is widely applied to paints, adhesives, coating materials, electric insulating materials and the like.

[0003] However, in the composition capable of forming polyurethane, when moisture is present in the system, isocyanate groups in the curing agent react with water to generate carbon dioxide gas, so that bubbles are generated in the obtained cured product. And a good cured product cannot be obtained.

In the case of a thermosetting one-pack type, a blocked isocyanate is generally often used as a curing agent. However, blocked isocyanates having good compatibility with a hydroxyl group-containing liquid diene polymer and its hydride are limited. I have. Further, even if such a curing agent is present, there are problems that the curability is poor and that the physical properties of the obtained coating film are low.

As a curing system that does not generate carbon dioxide, a liquid polymer composition using a melamine compound having a specific structure has been found, but even if the physical properties of the cured product can be improved, It is difficult to improve elongation.

[0006] For this reason, the required physical properties cannot be satisfied even in the use of an undercoat material for automobiles utilizing the elasticity and vibration damping properties of a hydroxyl group-containing liquid polybutadiene polymer and / or a hydride thereof. There was a problem that it could not be applied to

[0007]

SUMMARY OF THE INVENTION The present invention does not generate carbon dioxide gas even when moisture is present in the system, so that no foaming occurs in the cured product, and the curability and physical properties of the coating film are improved. It is an object of the present invention to provide a novel liquid polymer composition.

Further, the present invention provides a novel liquid polymer composition which has good compatibility and curability, has rubber elasticity, and has improved properties such as elongation in coating film properties, chipping resistance and storage stability. The purpose is to provide.

Another object of the present invention is to provide a novel liquid polymer composition which can provide a curing system which can be a thermosetting one-part type.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these conventional problems. as a result,
Surprisingly, a liquid polymer composition obtained by using a melamine compound having a specific structure as a curing agent for a hydroxyl group-containing liquid diene polymer and / or a hydride thereof,
Even if water is present in the system, foaming does not occur in the cured body, and
It has been found that curability and physical properties of a coating film are improved. Furthermore, they have found a curing system that can be a thermosetting one-pack type.

Further, the present inventors have proposed as a curing agent for a hydroxyl group-containing liquid diene polymer and / or a hydride thereof.
Using a combination of a melamine compound having a specific structure and a hydroxyl group-containing liquid diene polymer and / or a hydride thereof, and a blocked polyisocyanate compound which is prepolymerized by reacting with a polyisocyanate compound and then blocked. Have good compatibility and curability, have rubber elasticity, and improve elongation, chipping resistance, storage stability and the like in physical properties of a coating film. The present invention has been completed based on these findings.

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

Embedded image (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. Here, X is , Hydrogen, a methyl group, a propyl group or a butyl group, and Y is any one of a methyl group, a propyl group and a butyl group), or the above-mentioned general formula (I) A liquid polymer comprising a melamine compound represented by the formula (I) and a hydroxyl group-containing liquid diene polymer and / or a hydride thereof and a polyisocyanate compound, which are prepolymerized and then blocked to form a blocked polyisocyanate compound. It provides a composition.

Next, according to the present invention, 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. 2. The method according to claim 1, wherein
It provides a composition as described.

According to a third aspect of the present invention, there is provided the composition according to the first or second aspect, which is used for an undercoat material for vehicles.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The composition of the present invention according to claim 1 comprises a hydroxyl group-containing liquid diene polymer and / or a hydride thereof, and a melamine compound represented by the general formula (I) alone as a curing agent;
Or a melamine compound represented by the general formula (I);
It contains both a hydroxyl group-containing liquid diene polymer and / or a hydrogenated product thereof and a blocked polyisocyanate compound which is prepolymerized by reaction with a polyisocyanate compound and then blocked.

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

In the present invention, the hydroxyl group-containing liquid diene polymer and / or its hydride may be selected from known ones which meet the conditions, and may be used as they are, but by a known method. It can be easily manufactured.

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

The diene monomer having 4 to 22 carbon atoms includes butadiene, isoprene, chloroprene,
3-pentadiene, cyclopentadiene and the like,
One of these can be used alone, or two or more can be used in combination.

Known polymerization initiators include hydrogen peroxide (H ₂ O ₂ ) and azo compounds having a hydroxyl group (for example,
2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]) and the like, or a peroxide having a hydroxyl group (for example, cyclohexanone peroxide and the like). The amount of the polymerization initiator used is
For example, when hydrogen peroxide is used, 1.0 to 50 g, and when 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] is used, 100 g of the diene monomer is used. 5.0 to 100 g, and 5.0 to 100 g when cyclohexanone peroxide is used.
100 g are each suitable.

The polymerization can be carried out without solvent,
It is preferable to use a solvent because the reaction can be easily controlled. Solvents include ethanol, isopropanol, N
-Butanol and the like are usually used. Reaction temperature is 80-1
At 50 ° C., the reaction time is suitably 0.5 to 15 hours.

In addition to the above radical polymerization, one or two or more of diene monomers having 4 to 22 carbon atoms are anion-polymerized using a catalyst such as naphthalenedilithium to produce a living polymer. The desired hydroxyl-containing liquid diene polymer can also be obtained by reacting a compound or the like. This anionic polymerization can also be carried out without a solvent, but it is preferable to use a solvent from the same viewpoint as in the case of radical polymerization, that is, because of easy control of the reaction. As the solvent at that time, a saturated hydrocarbon such as hexane and cyclohexane is preferable. The reaction temperature is 50-100 ° C, and the reaction time is 1
10 hours is appropriate.

At the time of anionic polymerization, two or more diene monomers may be used as a mixture, or the following monomer may be added in a proportion of 50 mol% or less based on the diene monomer. Examples of such a monomer include an addition polymerizable monomer having 2 to 22 carbon atoms, more specifically, for example, butene, pentene, styrene, α-methylstyrene, acrylonitrile, acrylic acid and its ester, methacrylic acid and its ester, Examples thereof include vinyl chloride, vinyl acetate, and acrylamide.

After the completion of the reaction, the solution is distilled under reduced pressure to remove the solvent, unreacted monomers and the like, thereby obtaining the desired hydroxyl group-containing liquid diene polymer.

The hydroxyl group-containing liquid diene polymer has a number average molecular weight of 300 to 10,000, preferably 500 to 10,000.
5000. The hydroxyl group content is 0.2 to 10 m
eq / g, preferably 0.4 to 7 meq / g. Therefore, as a hydroxyl group-containing liquid diene polymer, usually,
Those having a number average molecular weight of 300 to 10000 and a hydroxyl group content of 0.2 to 10 meq / g are preferably used, and preferably have a number average molecular weight of 500 to 5000 and a hydroxyl group content of 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 when the hydroxyl group content is below the above range, the proportion of hydroxyl groups involved in the reaction with the curing agent decreases, so that the crosslinking point is reduced. And the strength of the cured product obtained from the composition becomes insufficient. When the number average molecular weight is smaller than the above range or when the hydroxyl group content is more than this range, the number of crosslinking points generated by the reaction with the curing agent becomes too large, resulting in a problem that the cured product becomes brittle.

The fine structure of such a hydroxyl group-containing liquid diene polymer is as follows: 1,4-cis structure, 1,4-trans structure, 1,2-vinyl structure or 3,4-vinyl structure. It is not limited at all, and those having various fine structures can be used. The hydroxyl group may be at either the terminal of the molecular chain or inside the molecular chain, but is preferably at the terminal of the molecular chain. Furthermore, it is also possible to use two or more types of hydroxyl group-containing liquid diene polymers. Note that the object of the present invention cannot be achieved even if a liquid diene polymer containing no hydroxyl group is used.

In the present invention, the hydroxyl group-containing liquid diene polymer thus obtained may be used as the first component, or the hydroxyl group-containing liquid diene polymer obtained by further hydrogenating the polymer may be used. A hydride of a system polymer may be used, or a mixture of both may be used.

The hydride of such a hydroxyl group-containing liquid diene polymer may be selected from known ones which meet the conditions, and may be used as it is, but the hydroxyl group-containing liquid diene polymer prepared as described above may be used as it is. The polymer can be produced by hydrogenating a system polymer by a known method using a homogeneous catalyst, a heterogeneous catalyst, or the like.

First, when a homogeneous catalyst is used, a saturated hydrocarbon such as hexane or cyclohexane or an aromatic hydrocarbon such as benzene, toluene or xylene is used as a solvent at a reaction temperature of normal temperature to 150 ° C. and normal pressure to normal pressure. The hydrogenation reaction is performed under a hydrogen pressure of 5 MPa. As a homogeneous catalyst,
A Ziegler catalyst or the like formed by a combination of a transition metal halide and an alkylated product such as aluminum, alkaline earth metal or alkali metal is applied to the double bond of the polymer.
What is necessary is just to use about 0.01-0.1 mol%. The reaction is usually completed in 1 to 24 hours.

On the other hand, when a heterogeneous catalyst or the like is used,
Saturated hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane; ethanol, isopropanol;
The hydrogenation reaction is carried out at a reaction temperature of normal temperature to 200 ° C. under a hydrogen pressure of normal pressure to 10 MPa using alcohols such as butanol or the like or a mixed system thereof as a solvent. As the heterogeneous catalyst, a catalyst such as nickel, cobalt, palladium, platinum, rhodium, ruthenium, or the like may be used alone, or may be supported on a carrier such as silica, diatomaceous earth, alumina, or activated carbon. The amount of these catalysts used is
0.05 to 10% by weight based on the weight of the polymer is appropriate. These catalysts may be used as a mixture of two or more kinds. The reaction is usually completed in 1 to 48 hours.

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

The number average molecular weight of the hydride of the hydroxyl group-containing liquid diene polymer is from 300 to 10,000, preferably from 500 to 5,000. Further, the hydroxyl group content is 0.1.
2 to 10 meq / g, preferably 0.4 to 7 meq / g
It is. Therefore, as a hydride of a hydroxyl group-containing liquid diene polymer, the number average molecular weight is usually 300 to 1000.
0, having a hydroxyl group content of 0.2 to 10 meq / g, and preferably having a number average molecular weight of 500 to 50.
The one having a hydroxyl group content of 0.4 to 7 meq / g is used. If 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 below the above range, the proportion of hydroxyl groups involved in the reaction with the curing agent is reduced, and the crosslinking point is reduced. And
The strength of the cured product of the composition obtained is insufficient. Also,
When the number average molecular weight is smaller than the above range or the hydroxyl group content is more than this range, the number of crosslinking points generated by the reaction with the curing agent becomes too large, and a problem that a brittle cured product occurs

The hydrogenation rate of the hydride of the hydroxyl group-containing liquid diene polymer is 50% or more, preferably 70% or more. Furthermore, it is also possible to use a mixture of two or more hydrides of a hydroxyl group-containing liquid diene polymer.

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

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

In the present invention, the melamine compound represented by the general formula (I) may be used alone as a curing agent for the hydroxyl-containing liquid diene polymer and / or its hydride, that is, as the second component, Alternatively, both a melamine compound represented by the general formula (I), a hydroxyl group-containing liquid diene polymer and / or a hydride thereof, and a polyisocyanate compound are reacted to form a prepolymer to form a blocked polyisocyanate compound. To be used together.

Hereinafter, the case where the melamine compound represented by the general formula (I) is used alone as a curing agent will be described as a first embodiment of the present invention, and the melamine compound represented by the general formula (I) and a hydroxyl group A second embodiment of the present invention describes a case in which both a containing liquid diene polymer and / or a hydride thereof are reacted with a polyisocyanate compound, prepolymerized, and then blocked, and a blocked polyisocyanate compound is used in combination.

As the curing agent used in the first embodiment of the present invention, at least one of the melamine compounds represented by the general formula (I) is used. Formula (I)
, R ₁ , R ₃ and R ₅ are each H or CH ₂ O
X, and R ₂ , R ₄ and R ₆ are each CH ₂ OY. Here, 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 the general formula (I), R ₁ , R ₃ and R ₅ may be the same or different. Also,
R ₂ , R ₄ and R ₆ may be the same or different.

The melamine compound represented by the general formula (I) has a functional group involved in the reaction, such as a methylol group, an alkyl-substituted methylol group or an imino group. These substituents form a crosslinked structure by reacting with a hydroxyl group in a hydroxyl group-containing liquid diene polymer or a hydride thereof. Note that a solvent may be contained in the curing agent.

As the melamine compound represented by the above general formula (I), specifically, hexamethoxymethylol melamine (X and Y are both methyl groups, ie, all of R _{1 to} R ₆ are methoxy groups) in the case of);
Methoxy, butoxymethylolmelamine (ie, R
₁ , R ₃ and R ₅ are all CH ₃ OCH ₃ , and R ₂ ,
R ₄ and R ₆ are both CH ₃ OC ₄ H ₉ ).

In the first embodiment of the present invention, it is necessary to use a melamine compound represented by the above general formula (I). For example, a melamine compound in which both of the carbon-bonded functional groups are hydrogen has a crosslinked structure. Is not suitable because it does not form Further, when R _{1 to} R ₆ are methoxy groups having 5 or more carbon atoms, alkyl alcohol by-produced during the reaction has a high molecular weight, which is disadvantageous in that it is difficult to volatilize.

The compounding amount of the melamine compound represented by the above general formula (I) is based on the amount of the hydroxyl group-containing liquid diene polymer and / or
Alternatively, the amount is 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of the hydride. If the blending amount of the melamine compound represented by the general formula (I) is less than this, the number of obtained crosslinking points is small and the physical properties of the cured product are inferior. Also, if the blending amount of the melamine compound represented by the general formula (I) is too large, the reactive group becomes excessive, substantial cross-linking is not formed, and the physical properties of the obtained cured product are deteriorated. Neither is preferred.

In the first embodiment of the present invention, a melamine having a specific structure as described above is used as a curing agent for a hydroxyl group-containing liquid diene polymer and / or a hydride thereof in place of the conventionally used polyisocyanate compound. Since a compound is used, even if water is present in the system, it does not react, and a good cured product can be obtained.

The melamine compound having the above specific structure is
It is possible to form a thermosetting one-pack type with the hydroxyl group-containing liquid diene polymer and / or its hydride, and has good compatibility with the polymer and / or hydride. The composition can be a useful composition for use in undercoat materials for automobiles, which makes use of the properties of the coalesced and / or hydride thereof, such as elasticity and vibration damping properties.

Next, in a second embodiment of the present invention, a melamine compound represented by the above general formula (I), a hydroxyl group-containing liquid diene polymer and / or a hydrogenated product thereof and a polyisocyanate compound are used. Both a blocked polyisocyanate compound which has been reacted and prepolymerized and then blocked is used in combination.

The blocked polyisocyanate compound used in the second embodiment of the present invention is obtained by reacting a terminal hydroxyl group of a hydroxyl group-containing liquid diene polymer and / or a hydride thereof with a polyisocyanate compound, and then blocking a free isocyanate group. A compound that is blocked by an agent.

Here, as the hydroxyl group-containing liquid diene polymer and / or its hydride, those similar to the hydroxyl group-containing liquid diene polymer and / or its hydride shown as the first component can be mentioned. The same one may be used, or a different one may be used.

The polyisocyanate compound is
An organic compound having two or more isocyanate groups in a molecule, the compound having a reactive isocyanate group for a hydroxyl group in the hydroxyl group-containing liquid diene polymer and / or a hydride thereof. Examples of such polyisocyanate compounds include ordinary aromatic, aliphatic, and alicyclic compounds. Among them, those which are liquid at room temperature are particularly preferable.

Specifically, for example, 4,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, a mixture of 4,4′-diphenylmethane diisocyanate and 2,2′-diphenylmethane diisocyanate (all MDI), Tolylene diisocyanate (TDI), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, naphthalene-1,5-diisocyanate, o-toluidine diisocyanate, triphenylmethane triisocyanate,
Tris (isocyanatephenyl) thiophosphate,
Aromatic polyisocyanates such as isopropylbenzene-2,4-diisocyanate and the like can be mentioned.

Further, xylylene diisocyanate (XD
I), tetramethylxylylene diisocyanate (TM
XDI) or other aliphatic-aromatic polyisocyanate (a polyisocyanate in which an isocyanate group is directly bonded to an aromatic ring via an aliphatic hydrocarbon group, that is, a polyisocyanate having an isocyanate group directly bonded to an aromatic ring group in the molecule). And polyisocyanates in which the isocyanate group is not directly bonded to carbon having an unsaturated bond.

Next, hexamethylene diisocyanate (HDI), dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate,
6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane,
Examples thereof include aliphatic polyisocyanates such as 1,3,6-hexamethylene triisocyanate and trimethylhexamethylene diisocyanate.

Further, transcyclohexane-1,4
-Diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MD
I) and alicyclic polyisocyanates such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated tetramethyl xylylene diisocyanate.

In addition, cyclized trimers (modified isocyanurates) and modified burettes of the above-mentioned polyisocyanates can also be mentioned.

These polyisocyanate compounds can be used as a mixture of two or more kinds. Among these, as the polyisocyanate compound, it is preferable to use MDI, TDI, carbodiimide-modified diphenylmethane diisocyanate and polymethylene polyphenylisocyanate in terms of workability and cost.

Examples of the blocking agent for blocking the isocyanate group include phenols such as phenol and cresol; oximes such as methyl ethyl ketone oxime and benzophenone oxime; alcohols such as methanol and ethanol; lactams such as ε-caprolactam. Other examples include active methylenes such as diethyl acetylacetone malonate and the like; imides; mercaptans; ethylene imine; α-pyrrolidone; sodium bisulfite; boric acid and the like.

In the second embodiment of the present invention, the blocked polyisocyanate compound used as a curing agent may have a terminal hydroxyl group of a hydroxyl group-containing liquid diene polymer and / or a hydride thereof as described above, preferably NCO / OH = 2. 0
After reacting with a polyisocyanate compound to form a prepolymer under a condition of from 10.0 to 10.0, more preferably from 3.0 to 8.0, free isocyanate groups are blocked by a blocking agent. The preparation of the blocked polyisocyanate compound may be performed by a conventional method.

The amount of the blocked polyisocyanate compound used as the curing agent is NCO / OH = 0.2 to 1 with respect to the hydroxyl group content of the first component, ie, the hydroxyl group-containing liquid diene polymer and / or its hydride. 0.5 (molar ratio), preferably 0.3 to 1.4 (molar ratio), more preferably 0.5 to 0.5 (molar ratio).
The amount is 3 to 1.3 (molar ratio). The remaining hydroxyl groups that have reacted with the isocyanate groups of the blocked polyisocyanate compound will react with the functional groups of the melamine compound. If the amount of the blocked polyisocyanate compound is too small, the amount of urethane groups generated is too small to obtain the effect of increasing elongation. On the other hand, if the blending amount of the blocked polyisocyanate compound is too large, unreacted isocyanate groups become excessive, substantial cross-linking is not formed, curability is deteriorated, and physical properties of the obtained cured product are poor.

The liquid polymer composition of the present invention basically comprises the above-mentioned first component and second component. In order to reduce costs and ensure workability, bituminous substances and commonly used compounding agents such as polyol compounds, organic solvents, viscosity modifiers, fillers, and catalysts can be added.

For example, by adding a bituminous substance,
It is suitable for use as an undercoat material for automobiles. Examples of such bituminous substances include petroleum asphalts such as straight asphalt, blown asphalt and propane (solvent) deasphalted asphalt having various penetration degrees; petroleum pitch; petroleum tar; Of these, petroleum asphalt, particularly straight asphalt, is preferred. The amount of the bituminous substance to be added is not particularly limited, but may be 1 to 100 parts by weight of the first component, that is, the hydroxyl group-containing liquid diene polymer and / or its hydride.
000 parts by weight or less is appropriate, and most preferably 0 to 300 parts by weight.

Next, in the present invention, a polyol compound can be added. The polyol compound is 1
A compound having two or more hydroxyl groups in a molecule, such as a low-molecular-weight polyol and a high-molecular-weight polyol.

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-hydroxypropylaniline, 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.

Examples of high molecular weight polyols include polyether polyols and their variants, polytetramethylene ether glycol, tetrahydrofuran / alkylene oxide copolymerized polyols, epoxy resin-modified polyols, polyester polyols, partial transesterification products of trimethylolalkane, Ethylene-vinyl acetate copolymer, castor oil or hydrogenated castor oil, castor oil-based polyols such as castor oil transesterified product, obtained by reducing dimer acid ester, linear or long-chain glycol of molecular chain or the like. Examples include hydrides and esterified products of dimer acid and diol.

Further, two or more of the above polyols may be mixed and added. The amount of the polyol compound to be added is 0 to 100 parts by weight with respect to 100 parts by weight of the first component, that is, the hydroxyl group-containing liquid diene polymer and / or its hydride.

Further, various organic solvents can be added to reduce viscosity and ensure workability. Organic solvents that can be added include hydrocarbon solvents, ketone solvents,
Examples include ester solvents, alcohol solvents, cellosolve solvents, and ether solvents, and at least one of them can be used.

Here, examples of the hydrocarbon-based solvent include toluene, mixed xylene, ortho-xylene, para-xylene, acetone, cyclohexane, cyclohexanone, hexane, and petroleum-based mixed solvents. Examples of the ketone solvent include methyl ethyl ketone and methyl isobutyl ketone. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, butanol, terpinol and the like. Examples of the cellosolve-based solvent include methyl cellosolve, ethyl cellosolve and the like. Examples of the ether solvent include ethyl ether and butyl carbitol.

These solvents are used in an amount of 500 parts by weight or less based on 100 parts by weight of the first component, ie, the hydroxyl group-containing liquid diene polymer and / or its hydride.

As the viscosity modifier, the following plasticizers and diluents 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 acids. Diluents include process oils such as paraffin, naphthene, and aroma, olefin oligomers, alkylbenzene, alkylnaphthalene, alkyldiphenylethane, alkyldiphenyl,
Examples include silicone oil, liquid paraffin, 1-decene oligomer, and paraffin-based oligomer.

The amount of the viscosity modifier is not particularly limited, but is usually 500 parts by weight or less based on 100 parts by weight of the first component, ie, the hydroxyl group-containing liquid diene polymer and / or its hydride. , Preferably 200 parts by weight or less.

The following various inorganic fillers and organic fillers can be used as the filler. Inorganic fillers include 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, and wax. Stone clay, talc, nepheline, cryolite, wollastonite, diatomaceous earth, slate powder, whiting, feldspar powder, mica, gypsum, quartz powder, fine silica, attapulgite, sericite, 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, nitriding C arsenide, boron nitrite, mention may be made of molybdenum disulfide.

On the other hand, organic fillers include natural fibers such as rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood powder, cotton, hemp, wool, silk, nylon, and the like.
Synthetic fibers such as polyester, vinylon, acetate, and acrylic, as well as polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polymethyl methacrylate resin, polyvinyl chloride resin, and epoxy resin And powders or granules of synthetic resins such as phenol resins.

The amount of the inorganic filler and the organic filler is not particularly limited, but is usually 500 parts by weight based on 100 parts by weight of the first component, the hydroxyl group-containing liquid diene polymer and / or its hydride. It is at most 300 parts by weight, preferably at most 300 parts by weight.

Further, in order to accelerate a curing reaction between the first component, a hydroxyl group-containing liquid diene polymer and / or a hydride thereof, and a second component, a melamine curing agent, the following catalyst is used. Can be added. Specifically, for example, aromatic sulfonic acid compounds such as paratoluenesulfonic acid, paraxylenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, or isopropyl alcohol, isobutanol, ethylene Dissolved in solvents such as glycol, xylene, etc., and further blocked these aromatic sulfonic acid compounds with compounds such as amines, epoxies, oximes, etc. to make them thermally dissociable, mineral acids such as hydrochloric acid and sulfuric acid, etc. Such strongly acidic compounds can be used. Further, a phosphoric acid compound, an ammonium chloride compound,
It is also possible to use weakly acidic compounds such as carboxylic acid compounds. Among these, a block type aromatic sulfonic acid catalyst and a weakly acidic phosphoric acid catalyst are preferred.

The amount of the catalyst to be added is up to 20 parts by weight based on 100 parts by weight of the first component, that is, the hydroxyl group-containing liquid diene polymer and / or its hydride. In addition, 2
If the amount exceeds 0 parts by weight, not only does the curing acceleration effect level off, but also the compatibility of the composition deteriorates, causing problems such as layer separation.

Further, in order to accelerate the curing reaction between the hydroxyl-containing liquid diene polymer as the first component and / or its hydride and the blocked isocyanate compound as the second component, the following urethane curing agent is used. A catalyst can be added.

Specifically, for example, tertiary amines such as triethylenediamine, tetramethylguanidine, and 1,2-dimethylimidazole; and organic metal compounds such as stannasoctoate, dibutyltin diacetate, and dibutyltin dilaurate can be used. .

The amount of the urethane curing catalyst added is up to 10 parts by weight based on 100 parts by weight of the first component, that is, the hydroxyl group-containing liquid diene polymer and / or its hydride. When the amount exceeds 10 parts by weight, the effect of accelerating curing hardens, and the risk of local abnormal reaction (gelation) increases.

In the second embodiment of the present invention, since a melamine-based curing agent and a blocked isocyanate compound are used in combination as the curing agent, the catalyst used is a mixture of the above two catalysts.

In the composition for a liquid polymer of the present invention,
In addition to the above-mentioned compounding agents, the following additives can be further added. For example, an antioxidant such as a hindered phenol type, a hindered amine type, or a benzotriazole type can be added to improve heat resistance and weather resistance. In addition, flame retardants such as phosphorus compounds, halogen compounds and antimony oxide; antifoaming agents such as silicone compounds, zeolites such as natural zeolites and synthetic zeolites; and thixotropic properties such as finely divided silica for providing thixotropic properties of the composition. An imparting agent can be added. Furthermore, for the adjustment of adhesive strength and adhesive strength, alkylphenol resin,
A tackifying resin such as a terpene resin, a terpene phenol resin, a xylene formaldehyde resin, a rosin, a hydrogenated rosin, a cumarone resin, an aliphatic / alicyclic / aromatic petroleum resin can be added. The total content of these additives is preferably 20% by weight or less in the composition.

The liquid polymer composition of the present invention can be obtained by blending the above components. More specifically, the first component, that is, the hydroxyl group-containing liquid diene polymer and / or its hydride, A specific melamine compound as a curing agent as a second component, or a reaction between a melamine compound, a hydroxyl group-containing liquid diene polymer and / or a hydride thereof, and a polyisocyanate compound to form a prepolymer, followed by blocking. A mixture with the blocked polyisocyanate compound, and further various additives are mixed in the above ratio,
It is obtained by kneading using rolls and rollers such as paint rolls, mixers such as Dalton mixer and planetarium mixer, or various mixing / kneading devices. The kneading time is 1 minute to 15 hours, and the kneading temperature is 0 ° C to 100 ° C.

Thus, the desired liquid polymer composition can be produced. The liquid polymer composition of the present invention can be applied to a wide range of applications as described below. That is, the liquid polymer composition of the present invention is used for undercoats for vehicles, for precoated metals, various paints and coating materials for exteriors, varnish applications, thermosetting systems,
Various adhesive applications such as water dispersion systems, electrical insulation materials applications,
Protective materials for buildings and structures, lining materials or waterproof materials,
Fiber sizing agents, paints, films, sheets, existing melamine-based paints, alkyd resins, polyurethane rubbers, etc. as modifiers for the protection of daily necessities and miscellaneous goods, paints, inks, various primers Can be widely used for applications. Application to these uses may be performed by application using a coater such as a bar coater or spray application.

[0082]

Next, the present invention will be described in more detail with reference to Examples, but it goes without saying that the scope of the present invention is not limited to these Examples.

Production Example 1 (1) Preparation of Hydroxyl-Containing Liquid Isoprene-Based Polymer In a 1 L stainless steel pressure-resistant reaction vessel, isoprene 200 was added.
g, 30 g of hydrogen peroxide solution having a concentration of 30%, and 300 g of isopropanol were charged at a temperature of 115 ° C. and a maximum pressure of 0.1 g.
The reaction was performed under the conditions of 9 MPa and a reaction time of 2.5 hours.
After the reaction is completed, the reaction mixture is placed in a separating funnel, and 600 g
Of water was added, shaken, and allowed to stand for 3 hours, after which the oil layer was separated. 2 m of solvent, monomer and low boiling point component from this oil layer
Distillation was conducted under the conditions of mHg, 100 ° C. and 2 hours to obtain a hydroxyl-terminated liquid isoprene-based polymer (yield: 71% by weight). It had a number average molecular weight of 1340, a hydroxyl group content of 1.52 meq / g, and a viscosity of 4.5 Pa · s (30 ° C.).
Met. At this time, the average hydroxyl group per molecule (f
n) is 2.09. The results of structural analysis by ¹ H-NMR show that the trans-1,4 structure is 57 mol% and the cis-
30 mol% of 1,4 structure, 8 mol% of 1,2-vinyl structure,
The 3,4-vinyl structure was 5 mol%.

(2) Preparation of hydride of hydroxyl group-terminated liquid polyisoprene polymer 100 g of hydroxyl group-terminated liquid polyisoprene polymer obtained in (1) above, 5 g of a ruthenium carbon catalyst having a ruthenium content of 5% by weight and a solvent Cyclohexane 100
g and a hydrogenation reaction was carried out at 150 ° C. for 6 hours under a hydrogen pressure of 8 MPa. 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 the conditions of 2 mmHg, 110 ° C. and 2 hours. As a result, a hydride of a hydroxyl group-terminated liquid polyisoprene polymer was obtained. This had a number average molecular weight of 1,430, a hydroxyl group content of 1.60 meq / g, a viscosity of 31 Pa · s (30 ° C.), and a bromine value of 1 g / 100 g. At this time, the average number of hydroxyl groups per molecule (fn)
Is 2.27.

Production Example 2 (Preparation of Blocked Isocyanate Compound) Hydroxyl-containing liquid polybutadiene 1 was placed in a separable flask.
Then, 100 parts by weight and 30 parts by weight of tolylene diisocyanate were charged and reacted at 60 to 80 ° C. in a nitrogen atmosphere to synthesize a prepolymer having a terminal isocyanate group. Next, 15 parts by weight of methyl ethyl ketoxime was gradually dropped into 100 parts by weight of the prepolymer with a dropping funnel, and the reaction was carried out at 60 to 80 ° C. The mixture was diluted with xylene to a solid content of 80% to obtain a blocked isocyanate compound. The content of effective isocyanate groups is
6.2%.

Examples 1 to 9 and Comparative Examples 1 to 3 The compositions shown in Table 1 were used at room temperature with a Dalton mixer.
The mixture was kneaded for 0 minutes to prepare a 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 was then placed in an oven at 140 ° C. and 30 ° C.
The composition was cured by heating under the conditions of minutes. The performance of the obtained cured product was evaluated by the following method. The results are shown in Table 1.

(1) Hardness of cured product Pencil hardness was measured according to JIS K5400.

(2) Cured State The cured state of the obtained cured product (coating film) was confirmed visually and by finger touch, and evaluated by the presence or absence of foaming or tack. When a good cured product (coating film) was obtained, it was described as "no problem".

[0089]

[Table 1] Table 1 [Part 1]

[0090]

[Table 2] Table 1 [Part 2]

[Footnotes to Table 1] 1) Hydroxy group-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C. 2) A hydroxyl group-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 group-containing liquid C5 polymer (Idemitsu Petrochemical) (Manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 0.83 meq / g, number average molecular weight 2630, viscosity = 73 poise / 30 ° C. 4); hydroxyl group content = 0.91 meq / G, number average molecular weight 2700, viscosity = 810 poise / 30 ° C. 5); hydroxyl-terminated liquid polybutadiene (manufactured by Nippon Soda Co., Ltd.), hydroxyl group content = 0.98 meq / G, number average molecular weight 2000, viscosity = 230 poise / 45 ° C., 1,2
-90% vinyl structure 6); Polybd R-45HT emulsion, solid content 54%, average particle size 0.54 µm (Daiichi Kogyo Seiyaku Co., Ltd.) 7); Hexamethoxymethylol melamine (Mitsui Cytec Co., Ltd.) 8); methoxy, butoxymethylol melamine (manufactured by Mitsui Cytec Co., Ltd.) 9); melamine, reagent grade (R _{1 to} R ₆ in the general formula (I))
Are all hydrogen atoms) 10); Liquid polybutadiene (manufactured by Nippon Zeon Co., Ltd.),
Number average molecular weight 3000, viscosity = 30 poise / 20 ° C.,
1,4-cis structure 80% 11); oxime block HDI-based blocked isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.), effective NCO content = 11.6% 12); aromatic sulfonic acid catalyst, nonvolatile content = 70% ( 13); Phosphoric acid-based weakly acidic catalyst (Mitsui Cytec Co., Ltd.)
14); dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd.)

From the results in Table 1, it is clear that the compositions of Examples 1 to 9 were cured by the use of the hydroxyl group-containing liquid diene polymer and / or hydride and the specific melamine compound as a curing agent. It can be seen that the performance of both the body hardness (pencil hardness) and the cured state has been evaluated well.

First, the compositions of Examples 1 to 6 were prepared by changing the amount of the hydroxyl group-containing liquid diene polymer and / or hydride used. As compared with the hydroxyl group-containing liquid polybutadiene used in Example 1, Example 2 using a hydroxyl group-containing liquid polybutadiene having a higher hydroxyl group content and a lower number average molecular weight also gave good results as in Example 1. Also, when a C5 polymer (Example 3) was used instead of butadiene, good results were obtained as in Example 1. Furthermore, when a hydroxyl-terminated liquid polyolefin having a significantly higher viscosity than that of the hydroxyl-containing liquid polybutadiene used in Example 1 is used (Example 4).
Also, as in Example 1, good results were obtained. next,
In the case of using the hydride of the hydroxyl group-containing liquid polyisoprene of Production Example 1 (Example 5), good results were obtained as in Example 1. Also in the case of using a hydroxyl-terminated liquid polybutadiene having a high 1,2-vinyl structure ratio (Example 6), good results were obtained as in Example 1.

Next, in Example 7, a liquid diene polymer emulsion containing a hydroxyl group was used in Example 1 with a slightly higher blending ratio and an increased amount of a curing agent. It can be seen that, similarly to Example 1, the cured product was evaluated well in terms of hardness and cured state. Example 8 differs from Example 1 in that the melamine compound as the curing agent was changed to other melamine compounds, methoxy and butoxymethylol melamine, and the catalyst was changed to a phosphoric acid weakly acidic catalyst. Similarly to the above, it can be seen that the cured product was evaluated well in terms of hardness and cured state. Further, in Example 9, a combination of a hydroxyl group-containing liquid diene polymer and a hydride thereof was used.
Similarly to the above, it can be seen that the cured product was evaluated well in terms of hardness and cured state.

On the other hand, in Comparative Example 1, instead of adding the hydroxyl group-containing liquid diene polymer and / or its hydride,
The liquid polybutadiene containing no hydroxyl group was added, but did not cure, and the hardness of the cured product could not be measured. Next, in Comparative Example 2, an oxime block HDI-based blocked isocyanate and DBTDL as a curing accelerator were used instead of the melamine compound as a curing agent, but the hardness (pencil hardness) of the cured product was used. Is 4B-
5B, which was insufficient, the appearance was large and the tack was large, and a satisfactory cured product could not be obtained. Comparative Example 3 uses melamine in which all of R _{1 to} R ₆ in the general formula (I) are hydrogen atoms as a curing agent, but does not cure and measures the hardness of the cured body. Could not.

From the above results, by mixing the hydroxyl group-containing liquid diene polymer and / or its hydride and a specific melamine compound as a curing agent as in the present invention, the hardness and the cured state of the cured product can be improved. It is clear that a cured product sufficiently satisfactory in point can be obtained.

Example 10 The same composition as in Example 1 except that 0.1 part by weight of water was further added (see Table 2), and the mixture was kneaded with a Dalton mixer at room temperature for 30 minutes to obtain a liquid polymer composition. Prepare things,
Further, a cured product was prepared in the same manner as in Example 1, and the performance of the obtained cured product was evaluated. The results are shown in Table 2.

Comparative Example 4 The procedure of Example 10 was repeated, except that no curing agent and no catalyst were added, but instead 31.9 parts by weight of blocked isocyanate and D
A cured product was prepared in the same manner as in Example 10 except that 0.5 parts by weight of BTDL was added, and the performance of the obtained cured product was evaluated. The results are shown in Table 2.

[0099]

Table 3 (Physical properties of cured product when water is present in the system)

[Footnotes to Table 2] 1); Hydroxy group-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C. 7) Hexamethoxymethylol melamine (manufactured by Mitsui Cytec Co., Ltd.) 11); oxime block HDI-based blocked isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.), effective NCO content = 11.6% 12); aromatic sulfonic acid catalyst, nonvolatile Min = 70% (manufactured by Mitsui Cytec Co., Ltd.) 14); dibutyltin dilaurate (manufactured by Kyodo Chemical Co., Ltd.)

As is clear from the results of Example 10 in Table 2, even when moisture was present in the system, a good composition was obtained in both the hardness (pencil hardness) and the cured state of the cured product. .
On the other hand, in Comparative Example 4 in which an isocyanate compound was used instead of the curing agent of the present invention, the hardness (pencil hardness) of the cured product could not be measured, and the cured state was large in foaming and tack. From this, in the composition of the present invention,
It can be seen that even if water is present in the system, no foaming or tack is generated, and a good cured product can be obtained.

Examples 11 to 12 In Example 1, the amounts of the curing agent and the catalyst were changed to 2
Kneading at room temperature for 30 minutes with a Dalton mixer in the same formulation as in Example 1 except that 0 and 1.0 parts by weight and a predetermined amount of 40/60 straight asphalt were added. Then, a liquid polymer composition was prepared, and a cured product was prepared in the same manner as in Example 1, and the performance of the cured product was evaluated. The performance of the cured product was the same as in Example 1, (1) Hardness (pencil hardness) of cured product (initial hardness)
And (2) In addition to evaluating the cured state,
The water resistance and storage stability were evaluated. The results are shown in Table 3.

Comparative Examples 5 and 6 Cured products were prepared in the same manner as in Examples 11 to 12, except that the formulations shown in Table 3 were used, and the performance of the cured products was evaluated. The results are shown in Table 3.

(3) Vibration Suppression Using a dynamic viscoelasticity measuring device manufactured by Orientec Co., Ltd.
Under the conditions of a frequency of 11 Hz and a heating rate of 2 ° C./min, 2
The tan δ value at 3 ° C. was determined. A larger tan δ value indicates better vibration damping property.

(4) Water Resistance The obtained cured product was immersed in hot water at 80 ° C. for 5 days, and the hardness (pencil hardness) of the cured product before and after the test was evaluated.

(5) Storage stability The obtained liquid polymer composition was stored at room temperature for 30 days, and the viscosity before and after storage was measured using a B-type viscometer. The rate of change in viscosity (%) during storage is calculated, and the smaller the rate of change, the better the stability.

[0107]

Table 4 (Performance evaluation of compositions containing bituminous substances)

[Footnotes to Table 3] 1) Hydroxy group-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C. 7) Hexamethoxymethylol melamine (manufactured by Mitsui Cytec Co., Ltd.) 11); oxime block HDI-based blocked isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.), effective NCO content = 11.6% 14); dibutyltin dilaurate (Kyodo Chemical ( 15); Nipporan 3027, hydroxyl group content = 0.86 m
eq / g, viscosity = 11 poise / 75 ° C. (manufactured by Nippon Polyurethane Industry Co., Ltd.) 16); Amine block type of aromatic sulfonic acid catalyst catalyst 600, nonvolatile content = 47% (manufactured by Mitsui Cytec Co., Ltd.) 17 ); Idemitsu Kosan Co., Ltd.

Table 3 shows the following. In Example 11 in which asphalt was added in addition to the hydroxyl group-containing liquid diene polymer and the melamine compound, the hardness (pencil hardness) of the cured product before and after the water resistance test was not changed at all. Good results were also obtained for the cured state, vibration damping properties and storage stability.

In Example 12, the amount of asphalt added was twice that of Example 10 to 100 parts by weight. As in Example 11, a cured product having good water resistance and a cured state was obtained. . Although the storage stability was inferior to that of Example 11, it was acceptable.

On the other hand, in Comparative Example 5, in which an isocyanate compound was added instead of a melamine compound as a curing agent, water resistance was good, but tackiness was large and storage stability was poor. In Comparative Example 6 using a liquid diene polymer containing no hydroxyl group, although there was no problem with the cured state, a large tack remained in the curing agent after the water resistance test, and the water resistance was extremely low. In addition, storage stability was poor. From this, it became clear that the composition of the present invention was excellent not only in curability but also in water resistance, vibration damping properties and storage stability.

Examples 13 to 21, Reference Example 1 and Comparative Example 7
-9 In the formulation shown in Table 4, 3
The mixture was kneaded for 0 minutes to prepare a 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 was then placed in an oven at 140 ° C. and 30 ° C.
The composition was cured by heating under the conditions of minutes. The performance of the obtained cured product was evaluated by the following method. The results are shown in Table 4.

(1) Compatibility After preparing a liquid polymer composition excluding fillers, the composition was allowed to stand at room temperature for one week to confirm the state of the composition. When separation or turbidity was observed, the compatibility was determined to be “poor”, and when there was no separation or turbidity, the compatibility was determined to be “good”.

(2) Physical Properties of Cured Body According to JIS K6251, elongation at break and tensile strength were measured.

(3) Chipping resistance A cured product having a thickness of 500 μm was prepared on an electrodeposition coated plate, and a hexagon nut was dropped from a height of 3 m through a cylinder. The cured product was placed at an angle of 30 degrees with respect to the direction in which the nut fell, and the total weight of the nut when the substrate was exposed was represented.

(4) Cured State The cured state of the obtained cured product (coating film) was visually and visually confirmed and evaluated by the presence or absence of foaming or tack. When a good cured product (coating film) was obtained, it was described as "no problem".

[0117]

[Table 5] Table 4 [Part 1]

[0118]

Table 6 [Part 2]

[0119]

[Table 7] Table 4 [Part 3]

[Footnotes to Table 4] 1) Hydroxy group-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C. 2) A hydroxyl group-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 group-containing liquid C5 polymer (Idemitsu Petrochemical) (Manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 0.83 meq / g, number average molecular weight 2630, viscosity = 73 poise / 30 ° C. 4); hydroxyl group content = 0.91 meq / G, number average molecular weight 2700, viscosity = 810 poise / 30 ° C. 5); OA kaolin clay (Maruo Calcium Co., Ltd.)
6); Light calcium carbonate (Maruo Calcium Co., Ltd.)
7); Heavy calcium carbonate (Maruo Calcium Co., Ltd.)
8); High boiling point solvent (manufactured by Idemitsu Petrochemical Co., Ltd.) 9); Oxime block HDI-based blocked isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.), effective NCO content = 11.6% 10); Oxime block MDI Block isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.), effective NCO content = 13.5% 11); hexamethoxymethylol melamine (manufactured by Mitsui Cytec Co., Ltd.) 12); methoxy, butoxymethylol melamine (Mitsui Cytec Co., Ltd.) 13); Aromatic sulfonic acid catalyst, non-volatile content = 70% (manufactured by Mitsui Cytec Co., Ltd.) 14); Phosphoric acid weakly acidic catalyst (Mitsui Cytec Co., Ltd.)
15); dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd.)

Table 4 shows the following. According to Comparative Example 7, even if the blocked isocyanate of the present invention was used, if this was not used in combination with the melamine compound, the physical properties of the cured product would be poor. Next, according to Comparative Example 8, when the blocked isocyanate of the present invention was not used and this was not used in combination with the melamine compound, the tackiness was large and a good cured product could not be obtained. Further, according to Comparative Example 9, even when the block isocyanate and the melamine compound were used in combination,
If the blocked isocyanate of the present invention is not used as the blocked isocyanate, the compatibility will be poor. In addition, as shown in Reference Example 1, when only a melamine compound is used, the compatibility is good and the cured state is not a problem, but the physical properties of the cured product are inferior.

On the other hand, according to Examples 13 to 21, when the blocked isocyanate of the present invention and the melamine compound were used in combination, the compatibility, the physical properties of the cured product, the chipping resistance, and the cured state were reduced. Will also be excellent.

Examples 22 to 23 and Comparative Example 10 With the composition shown in Table 5, the mixture was mixed at room temperature with a Dalton mixer at room temperature.
The mixture was kneaded for 0 minutes to prepare a 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 was then placed in an oven at 140 ° C. and 30 ° C.
The composition was cured by heating under the conditions of minutes. The performance of the obtained cured product was evaluated by the following method. The results are shown in Table 5. The physical properties and cured state of the cured product were evaluated in the same manner as in Table 4. The storage stability was evaluated by the following method.

Storage stability The obtained liquid polymer composition was allowed to stand at room temperature for 30 days.
The viscosity was measured with a type viscometer and expressed as a viscosity change rate (%).
The smaller the rate of change, the better the storage stability.

[0125]

[Table 8] Table 5

[Footnotes to Table 5] 1) Hydroxy group-containing liquid polybutadiene (manufactured by Idemitsu Petrochemical Co., Ltd.), hydroxyl group content = 0.84 meq / g, number average molecular weight 2590, viscosity = 51 poise / 30 ° C. 5) OA kaolin clay (Maruo Calcium Co., Ltd.)
6); Light calcium carbonate (Maruo Calcium Co., Ltd.)
8); high boiling point solvent (manufactured by Idemitsu Petrochemical Co., Ltd.) 9); oxime block HDI-based blocked isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.), effective NCO content = 11.6% 11); hexamethoxymethylol Melamine (manufactured by Mitsui Cytec Co., Ltd.) 15); Dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd.) 16); Amine block type of aromatic sulfonic acid catalyst catalyst 600, nonvolatile content = 47% (Mitsui Cytec Co., Ltd.) Made)

Table 5 shows the following. According to Comparative Example 10, when the blocked isocyanate of the present invention was not used, and when this and the melamine compound were not used in combination, the tackiness was large, a good cured product was not obtained, and the storage stability was poor. Become.

On the other hand, according to Examples 22 to 23, when the blocked isocyanate of the present invention was used in combination with the melamine compound, the cured product was excellent in all of the physical properties, the cured state, and the storage stability. It will be.

[0129]

According to the first aspect of the present invention, there is provided a curing system which can be a thermosetting one-pack type, and does not generate carbon dioxide gas even when moisture is present in the system. A liquid polymer composition in which foaming does not occur in the obtained cured product and curability and physical properties of the coating film are improved can be obtained.

That is, the composition according to the first embodiment of the present invention is used as a thermosetting one-pack type curing agent for a hydroxyl group-containing liquid diene polymer and has a specific structure of a melamine-based polymer having high compatibility with the polymer. Since a compound is used, a uniform composition is obtained. And since it is cured with a melamine compound having a specific structure in this way, the obtained cured product is:
Excellent curability. Further, the obtained cured product is excellent in water resistance, and thus has characteristics required as a paint.

Further, since the composition according to the first embodiment of the present invention uses a melamine compound having a specific structure as a curing agent, even when moisture is present in the system, the functional group reacts to form a carbonate. No gas is generated, and there is no risk of foaming in the cured product. Accordingly, a liquid polymer composition having improved curability and coating film properties is provided.

Further, according to the second aspect of the present invention, the compatibility and the curability are good, the rubber has elasticity, and the elongation, the chipping resistance, the storage stability and the like of the coating film are improved. A liquid polymer composition is obtained.

Therefore, the composition of the present invention can be widely and effectively used in various applications as described above, including various paints, coating materials and varnishes for undercoats for vehicles, for pre-coated metals and exteriors. Is done.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 75/04 C08L 75/04 C09D 109/00 C09D 109/00 147/00 147/00 175/04 175 / 04 F-term (reference) 4J002 BL01W BL02W CK02X EU186 FD010 FD030 FD14X FD146 GH01 4J034 BA03 BA08 CA03 CA04 CA05 CC03 CC08 CC26 CC33 CC35 CC61 CC62 CC65 DC12 DC34 DC37 DC50 DD08 DG01 DP02 DP19 GA02 GA05 GA06 HC13 HC03 HC22 HC23 HC52 HC54 HC64 HC65 HC67 HD03 HD04 HD05 HD06 HD07 HD12 HD13 HD15 4J038 DG101 DG221 DG302 MA14 PA07 PB07 PC02

Claims (3)

[Claims] 1. A hydroxyl group-containing liquid diene polymer and / or a hydride thereof, and a curing agent represented by the following general formula (I): ## STR1 ## (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. Here, X is , Hydrogen, a methyl group, a propyl group or a butyl group, and Y is any one of a methyl group, a propyl group and a butyl group), or the above-mentioned general formula (I) A liquid polymer comprising a melamine compound represented by formula (I), a hydroxyl group-containing liquid diene polymer and / or a hydrogenated product thereof, and a blocked polyisocyanate compound which is prepolymerized and then blocked. Composition. 2. 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. A composition as described. 3. The composition according to claim 1, which is used for an undercoat material for vehicles.