KR101224777B1 - Material set of forming polyurethane resin coating film formed on substrate - Google Patents

Abstract

Provided is a polyurethane resin coating material set formed on a substrate that is excellent in film strength. Polyurethane resin coating material set consists of polyol obtained by reaction of polycarbonate polyol and polycaprolactone polyol, and isocyanate group terminal prepolymer obtained by reaction of polytetramethylene glycol and polyisocyanate, and polycaprolactone polyol The ratio of the polycarbonate polyol to the mass ratio is 65/35 or more. In addition, the polyurethane resin coating material set further contains a fine metal organometallic catalyst for curing reaction and a curing reaction inhibitor at room temperature.

Description

Polyurethane resin coating material set formed on base material {MATERIAL SET OF FORMING POLYURETHANE RESIN COATING FILM FORMED ON SUBSTRATE}

The present invention relates to, for example, a solvent-free polyurethane resin coating material formed on a substrate to be coated.

Background Art [0002] Polyurethane resins are used in various fields such as electronic and electrical materials, automobiles and railway vehicle materials, and civil engineering and building materials.

In the field of use of such a polyurethane resin, for example, there is a paint. Polyurethane resin paints are widely used in the fields of construction, civil constructions, and vehicles, and have excellent paint appearance, good coating performance, and excellent durability.

Polyurethane resin paints are often used together with organic solvents, but in this case, improvement of environmental problems, work safety problems, etc. is a major problem.

In order to solve this problem, the aqueous system and solvent-freeization of resin to be used are examined variously (for example, refer patent document 1).

However, with regard to the water-based formation of electrons, problems such as lack of uniformity of the coated surface, large energy and time required for drying, and lack of water resistance, hydrolysis resistance, etc. in terms of physical properties, etc. It is.

On the other hand, with regard to the latter solvent-free, the above-mentioned problems caused by the aqueous system are relatively small. However, when the resin solution becomes highly viscous with the solvent-free, the coating becomes impossible, and conversely, the resin solution in order to enable the coating. When the viscosity of the resin is lowered, there is a problem that the strength and durability are insufficient in terms of physical properties.

Japanese Patent Publication No. 2008-303250

This invention is made | formed in view of the said subject, and an object of this invention is to provide the polyurethane resin film material set formed on the base material which is excellent in the strength of a film under solvent-free conditions.

The polyurethane resin coating material set formed on the base material concerning this invention is an isocyanate group terminal obtained by reaction of the polyol obtained by reaction of a polycarbonate polyol and a polycaprolactone polyol, and polytetramethylene glycol and polyisocyanate. It is composed of a prepolymer, characterized in that the ratio of polycarbonate polyol to polycaprolactone polyol is 65/35 or more by mass ratio.

The polyurethane resin coating material set formed on the substrate according to the present invention is preferably characterized in that both the polyol and the isocyanate group terminal prepolymer are liquid at room temperature.

Moreover, the polyurethane resin film material set formed on the base material concerning this invention, Preferably, the said polyol further contains the organometallic catalyst for hardening reaction of a fine powder, and a hardening reaction inhibitor at normal temperature, Characterized in that made.

Moreover, the polyurethane resin film material set formed on the base material concerning this invention, Preferably, the said polyol is obtained by reaction of a polycarbonate polyol, a polycaprolactone polyol, and an aliphatic glycol, It is characterized by the above-mentioned. do.

Moreover, the polyurethane resin film material set formed on the base material concerning this invention, Preferably, the said polycarbonate polyol is obtained by reaction of 1, 6- hexanediol and dialkyl carbonate, It is characterized by the above-mentioned. do.

Moreover, the polyurethane resin film material set formed on the base material concerning this invention, Preferably, the said polyisocyanate is aliphatic diisocyanate, It is characterized by the above-mentioned.

Moreover, the polyurethane resin film material set formed on the base material concerning this invention, Preferably, the said aliphatic diisocyanate is hexamethylene diisocyanate, It is characterized by the above-mentioned.

The polyurethane resin coating material set formed on the base material concerning this invention is an isocyanate group terminal obtained by reaction of the polyol obtained by reaction of a polycarbonate polyol and a polycaprolactone polyol, and polytetramethylene glycol and polyisocyanate. Since it consists of a prepolymer and the ratio of the polycarbonate polyol with respect to a polycaprolactone polyol is 65/35 or more by mass ratio, the polyurethane resin film formed on a base material is excellent in strength.

Embodiment of this invention is described below.

The polyurethane resin film material set (hereinafter, may only be referred to as a polyurethane resin film material set) formed on the substrate according to the present embodiment is, for example, a paint, which is a coating film on a substrate to be coated. Used to form However, it is needless to say that the present invention can be used to form a polyurethane resin film on another substrate as long as the effect of the present invention is obtained.

The polyurethane resin film material set which concerns on the 1st example of this embodiment demonstrated below manages a polyol and an isocyanate group terminal prepolymer separately, and mix | blends with a catalyst for hardening at the time of film formation, and is used. Thereby, it is excellent in the storage stability at the time of long-term storage until a polyol and an isocyanate group terminal prepolymer are used. Moreover, the polyurethane resin film material set which concerns on the 2nd example of this embodiment further mix | blends and uses a fine powder-type organometallic catalyst for hardening reaction and a hardening reaction inhibitor in a polyol at normal temperature. Thereby, the handleability at the time of use of a polyurethane resin film material set is excellent.

The polyurethane resin coating material set which concerns on the 1st example and the 2nd example of this embodiment is a non-solventized coating material which does not contain the organic solvent which may cause an environmental problem etc. in all.

First, the polyurethane resin film material set formed on the base material which concerns on the 1st example of this embodiment is demonstrated.

The polyurethane resin coating material set formed on the substrate according to the first example is an isocyanate obtained by a reaction of a polyol obtained by the reaction of a polycarbonate polyol and a polycaprolactone polyol, and a polytetramethylene glycol and a polyisocyanate. It consists of group terminal prepolymers, and the ratio of the polycarbonate polyol to the polycaprolactone polyol (polycarbonate polyol / polycaprolactone polyol) is 65/35 or more by mass ratio.

Either one or both of a polyol and an isocyanate group terminal prepolymer may be solid at normal temperature. However, from the viewpoint of handling when storing or transporting, or when heat-melting treatment is unnecessary when mixing and curing curing both during the film formation, both the polyol and the isocyanate group terminal prepolymer are liquid at room temperature. desirable.

The polycarbonate polyol, which is one of the raw materials of the polyol, is not particularly limited in kind, and for example, the dehydrochlorination reaction between the short-chain polyol and the phosgene or a low-molecular carbonate such as a short-chain polyol and a dialkyl carbonate, an alkylene carbonate or a diaryl carbonate. It is obtained suitably by transesterification condensation reaction of the like.

Examples of this short-chain polyol include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, and 3-methyl -1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 3-methyl-1, 5-pentanediol, dimethylolheptane, diethylene glycol, dipropylene Glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-1, 4-diol, cyclohexane-1, 4-dimethanol, dimer diol, glycerin, trimethylolpropane, ethylene oxide or propylene of bisphenol A The molecular weight less than 500 is mentioned, such as an oxide adduct.

Dialkyl carbonate, diethyl carbonate, etc. are mentioned as dialkyl carbonate, As alkylene carbonate, ethylene carbonate, propylene carbonate, etc. are mentioned, Diphenyl carbonate etc. are mentioned as diaryl carbonate.

These can all be used individually or in mixture of 2 or more types.

However, from the viewpoint of further increasing the mechanical strength of the resulting polyurethane resin film, a polycarbonate polyol using a linear aliphatic glycol that contributes to mechanical strength by crystallization is preferable, and in particular, 1, 6-hexanediol and dialkyl carbonate It is preferable that it is obtained by reaction.

The polycaprolactone polyol, which is another raw material of the polyol, is, for example, any one or both of ε-caprolactone and alkyl-substituted ε-caprolactone, using the short-chain polyol used in the above-described polycarbonate as an initiator. What is obtained by ring-opening addition can be used.

From the viewpoint of facilitating molecular weight adjustment of the polyol and obtaining high storage stability, the polyol is preferably one obtained by blending more aliphatic glycols and transesterification reaction with the polycarbonate polyol and polycaprolactone polyol.

Examples of the aliphatic glycols include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, and 3-methyl- 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octane diol, 1, 9-nonanediol, 3-methyl-1, 5-pentanediol, dimethylolheptane, diethylene glycol, dipropylene glycol And neopentyl glycol. From the viewpoint of increasing the mechanical strength of the resulting polyurethane resin film, the aliphatic glycol preferably has a molecular weight of 200 or less, and most preferably 1, 6-hexanediol.

As for the compounding ratio of a polyol raw material, the ratio (polycarbonate polyol / polycaprolactone polyol) of the polycarbonate polyol with respect to a polycaprolactone polyol is 65/35 or more by mass ratio. The upper limit of the ratio is not particularly limited, and the polycarbonate polyol may be almost 100%, but is preferably 75% or less (75/25 as the ratio) from the viewpoint of handling as a liquid at normal temperature. Moreover, when aliphatic glycol is further used as a polyol raw material, the compounding ratio counts aliphatic glycol as the number in a polycarbonate polyol [(polycarbonate polyol + aliphatic glycol) / polycaprolactone polyol].

Although the molecular weight does not specifically limit the polytetramethylene glycol which is one of the raw materials of an isocyanate group terminal prepolymer, From a viewpoint of the external appearance of the polyurethane resin film obtained, it is preferable that number average molecular weight is 500 or more.

The polyisocyanate which is another raw material of an isocyanate group terminal prepolymer does not specifically limit a kind, For example, 2, 4-tolylene diisocyanate (it abbreviates as 2, 4-TDI hereafter), 2, 6-TDI , 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as 4, 4'-MDI), 2, 4'-MDI, 2, 2'-MDI, 1, 5-naphthylene diisocyanate, 1, 4-naphthylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethyl xylene diisocyanate, 4, 4'-diphenyl Ether diisocyanate, 2-nitrodiphenyl-4, 4'-diisocyanate, 2, 2'-diphenylpropane-4, 4'-diisocyanate, 3, 3'-dimethyldiphenylmethane-4, 4'- Diisocyanate, 4, 4'-diphenylpropanediisocyanate, 3, 3'-dimethoxydiphenyl-4, 4 ' Aromatic diisocyanates such as diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), 2-methyl-1, 5-pentane diisocyanate, 3-methyl-1, 5-pentane diisocyanate , Aliphatic diisocyanates such as lysine diisocyanate, isophorone diisocyanate (hereinafter abbreviated as IPDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate (hereinafter abbreviated as H ₁₂ MDI), hydrogenated xylene Alicyclic diisocyanates such as diisocyanate (hereinafter abbreviated as H ₆ XDI), hydrogenated tetramethylxylene diisocyanate, cyclohexyl diisocyanate, mixtures of two or more thereof, and adduct modified bodies of these organic diisocyanates , Burette modified, uredion modified, uretimine modified, isocyanurate modified, carbo And a diimide modified product. In the example of this embodiment, an aliphatic diisocyanate and an alicyclic diisocyanate are preferable from a viewpoint of the ease of mix | blending with the polyol at the time of polyurethane coating manufacture, the external appearance of a polyurethane resin film obtained, and mechanical strength, and especially hexa Methylene diisocyanate (HDI) is most preferred.

Isocyanate group terminal prepolymer has an isocyanate content of 4-12 mass%, and it is preferable that content of unreacted polyisocyanate is 1 mass% or less.

Although the compounding ratio of a polyol and an isocyanate group terminal prepolymer at the time of forming a film is not specifically limited, It is a preferable example to mix | blend so that the isocyanate group in an isocyanate group terminal prepolymer may be 0.90-1.10 with respect to 1 mol of hydroxyl groups in a polyol.

Next, the polyurethane resin film material set formed on the base material which concerns on the 2nd example of this embodiment is demonstrated.

As for the polyurethane resin film material set formed on the base material which concerns on a 2nd example, the polyol of the polyurethane resin film material set formed on the base material which concerns on the said embodiment is used for hardening reaction of fine powder form at normal temperature. It further contains an organometallic catalyst and a curing reaction inhibitor.

Thereby, the state which disperse | distributed the organometallic catalyst for hardening reactions in a polyol is hold | maintained, Comprising: When forming a polyurethane resin film on a base material, compared with the case of adding the organometallic catalyst for normal hardening reactions, what is called a housework The extension of the time can be achieved, and the delay of the curing time can be prevented. Hereinafter, this will be described in detail.

The organometallic catalyst is not particularly limited as long as it is an organometallic compound that brings about the catalytic action of the curing reaction at predetermined curing temperature conditions. For example, Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Of malate compounds, oxide compounds, ester compounds, mercaptide compounds and chelate compounds containing metals such as Fe, Ti, Cu, Co, Ni, In, Ca, Y, Ce, Sr, Mo, and La One or a mixture thereof can be employed. Among these, it is more preferable to use a fine powdery organic tin compound at normal temperature.

Examples of the organotin compound include dibutyltin distearate, dibutyltin maleate polymer, dibutyltin bis (alkyl maleate) salt, bis (dibutyltin maleate alkyl ester) maleate, dibutyltin s, o Mercaptocarboxylic acid polymer, dioctyl tin distearate, dioctyl tin maleate polymer, dioctyl tin bis (maleic acid alkyl ester) salt, bis (dioctyl tin maleic acid alkyl ester) maleate, dioctyl tin s and o-mercaptocarboxylate polymers, dioctyl tin dioctoate, dioctyl tin oxide, and the like, and among these, ordinary temperature solids can be employed.

The particle diameter of the organometallic catalyst is preferably 70 μm or less, and more preferably 50 μm or less.

The amount of the organometallic catalyst added to the polyol is preferably in the range of 50 to 2000 ppm with respect to the total amount of the polyol and isocyanate group terminal prepolymer to be used as the polyurethane resin coating material set, and more preferably 80 to 1500 ppm It should be in the range of. In addition, in order to prepare a desired reactivity, in addition to the said organometallic catalyst, a tertiary amine catalyst may be added.

The curing reaction inhibitor may include at least one or a mixture of phosphoric acid, phosphorous acid, acidic phosphate ester, and acidic phosphate ester, and from the viewpoint of achieving both a long pot life and a short curing time, it is very suitably 1 to 18 acidic phosphate esters and mixtures thereof can be employed. Examples of the acidic phosphate ester include ethyl phosphate, diethyl phosphate, isopropyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) acid phosphate, isodecyl acid phosphate, lauryl acid phosphate and tri Decyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, stearyl acid phosphate, and the like.

The amount of the curing reaction inhibitor added to the polyol is preferably in the range of 25 to 1000 mass ppm with respect to the total amount of the polyol and isocyanate group terminal prepolymer used as the polyurethane resin coating material set, more preferably 40 It is set as the range of -750 ppm, More preferably, it is set as the range of 50-600 ppm.

Next, about the formation method of the polyurethane resin film formed on a base material using the polyurethane resin film material set formed on the base material concerning the 1st example or 2nd example of the said embodiment, The method of forming a coating film on a base material using a polyurethane resin as a coating material is outlined, for example.

First, the polyurethane resin coating material set etc. which concern on this embodiment etc. are mixed at room temperature, and a coating material (raw material) solution is prepared. At this time, for example, with respect to 1 mol of hydroxyl groups in a polyol, each amount of a polyol and an isocyanate group terminal prepolymer is adjusted so that the isocyanate group in a isocyanate group terminal prepolymer may be 0.90-1.10, and the 1st example of this embodiment In the case, a curing catalyst is added in the ratio of 0.001-0.5 mass part with respect to 100 mass parts of liquid mixture of a polyol and an isocyanate group terminal prepolymer. Moreover, when a coating material (raw material) is solid at normal temperature, it heats at a suitable temperature until it liquefies.

Next, a liquid coating material is applied onto a substrate such as a metal plate, and then dried and cured.

Here, in the case of the polyurethane resin film material set which concerns on the 2nd example of this embodiment, the hardening catalyst to add uses the above-mentioned organometallic catalyst and uses a hardening reaction inhibitor together, In the case of the polyurethane resin film material set which concerns on the 1st example of embodiment, the catalyst for hardening is not specifically limited, For example, triethylamine, triethylenediamine, N-methylimidazole, Amines such as N-ethylmorpholine, 1,8-diazabicyclo-5, 4, 0-undecene-7 (DBU), Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Fe, Ti Maleate compounds, oxide compounds, ester compounds, mercaptide compounds and chelate compounds containing metals such as Cu, Co, Ni, In, Ca, Y, Ce, Sr, Mo, La, and the like, specifically potassium acetate, N-octoate, dibutyl tin dilaurate, dioctyl tin dilaurate (DOTDL), etc. Groups can be used very suitable for metal objects.

The polyurethane resin film material set etc. formed on the base material which concerns on this embodiment demonstrated above are excellent in the strength of the polyurethane resin film formed on a base material. In addition, the strength of a polyurethane resin film can be evaluated as TB (tensile strength), EB (extension), and TR (tear strength) as mentioned later, for example.

The polyurethane resin film material set etc. formed on the base material concerning this embodiment can be used suitably as a resin film formed on a coating material and other base materials. In addition, the present invention can also be applied to adhesives, synthetic leathers, plastic films, and the like.

<Examples>

The present invention will be further described with reference to Examples and Comparative Examples. In addition, this invention is not limited to the Example demonstrated below.

(Preparation Example of Polyol)

The polyol, which is one of the polyurethane resin coating material sets, is blended with raw materials under each of the conditions shown in Table 1, and stirred at 190 ° C. for 24 hours while bubbling nitrogen gas in a 2 liter separable flask. It obtained by performing transesterification (60 rpm).

In Table 1 and each following table | surfaces, the unit of the quantity of each component to mix | blend is all a mass part. In addition, the unit of hydroxyl value is mgKOH / g.

Each polyol raw material shown by the symbol in Table 1 is the following.

○ 1, 6-HD: 1, 6-hexanediol

PCD-HG-1000: Polycarbonate diol with a number average molecular weight of 1000 obtained from the deethanol reaction of 1, 6-hexanediol and diethyl carbonate

PCD-HG-2000: Polycarbonate diol with a number average molecular weight of 2000 obtained from the deethanol reaction of 1, 6-hexanediol and diethyl carbonate

PCD-HG-5000: Polycarbonate diol with a number average molecular weight of 5000 obtained from the deethanol reaction of 1, 6-hexanediol and diethyl carbonate

○ PCL-210: A bifunctional polycaprolactone diol having a number average molecular weight of 1000 obtained by ring-opening addition of? -Caprolactone to 1,4-butanediol. Initiator is ethylene glycol

○ PCL-220: A bifunctional polycaprolactone diol having a number average molecular weight of 2000 obtained by ring-opening addition of epsilon -caprolactone to 1,4-butanediol. Initiator is ethylene glycol

○ PCL-320: trifunctional polycaprolactone diol having a number average molecular weight of 2000 obtained by ring-opening addition of? -Caprolactone to 1,4-butanediol. Initiator is trimethylolpropane

(Preparation example of polyisocyanate)

Polyisocyanate which is one material of a polyurethane resin film material set mix | blended raw materials on each condition of Table 2, and made it urethane-react at 80 degreeC for 4 hours, carrying out nitrogen gas bubbling in a separable flask. Then, thin film distillation was performed at 140 degreeC and 0.3 Torr, and it was obtained by removing unreacted HDI.

Each polyisocyanate raw material shown by the symbol in Table 2 is the following.

○ HDI: hexamethylene diisocyanate

PTG-250: Polytetramethylene glycol (polypropylene glycol) with a number average molecular weight of 250

PTG-650: polytetramethylene glycol having a number average molecular weight of 650

○ PTG-1000: polytetramethylene glycol having a number average molecular weight of 1000

○ PTG-2000: polytetramethylene glycol with a number average molecular weight of 2000

PPG-600: Polypropylene glycol having a number average molecular weight of 600

PPG-1000: Polypropylene glycol having a number average molecular weight of 1000

In Table 2, isocyanate species C-HX are as follows.

○ C-HX: Coronate HX (coronate is a registered trademark of Japan Polyurethane Industry Co., Ltd.). Isocyanurate modified polyisocyanate of hexamethylene diisocyanate. Isocyanate content = 21.0%. Viscosity (25 ° C) 2500 mPas

(Examples 1-12 and Comparative Examples 1-6)

A polyol and a polyisocyanate are mix | blended on each condition of Tables 3-5, 0.01 mass part of dioctyl tin dilaurate (DOTDL) is added with respect to 100 mass parts of mixtures of a polyol and an isocyanate group terminal prepolymer as a catalyst for hardening, A polyurethane film (film) was prepared and evaluated. In addition, about a polyol being a room temperature solid and solidifying by compounding, after heat-melting, the catalyst for hardening was added, the polyurethane film (film) was prepared, and the evaluation was performed.

(Characteristic evaluation)

The liquid immediately after mixing the polyol and isocyanate of each condition of Examples 1-12 and Comparative Examples 1-6 was flowed on the release paper, and cast so that it might become a film of 100 micrometers in thickness and 300 mm x 300 mm of planar dimensions with a bar coater. cast), and cured at 120 ° C. for 10 minutes to obtain a polyurethane film (film). Using the polyurethane film as a sample, the following evaluation items were evaluated.

○ TB (strength at break)

TB was evaluated based on JISK6251. The unit of TB value is MPa.

In addition, depending on the use, the TB value was considered to be 20 or more, and was divided into Examples and Comparative Examples with this value as a boundary.

○ EB (height at break)

EB was evaluated based on JISK6251. The unit of the EB value is%.

In addition, depending on the use, the EB value was considered to be 300 or more, and it divided into the Example and the comparative example based on this value.

○ TR (tear strength)

TR was evaluated based on JISK6252. The unit of TR value is kN / m.

In addition, depending on the use, in consideration of the fact that TR value is 30 or more, it distinguished between the Example and the comparative example based on this value.

(Example 13)

1000 g of OH-5, 2 g of an organometallic catalyst (NW-96), and 1 g of a curing reaction inhibitor (JP-508) were put into a 2 liter separable flask, and the mixture was stirred at 25 ° C for 30 minutes. As a result, JP-508 was uniformly mixed with the polyol to obtain a polyol premix (hereinafter, referred to as OH-10) in which NW-96 was dispersed in the polyol. In addition, NW-96 uses KS-1010A-1 (di-n-octyl tin maleate polymer: manufactured by Co-Pharma Co., Ltd.), which is an organic tin compound catalyst, and PN-250 (manufactured by ADEKA, Inc.), which is an adipic ester plasticizer. It is a dispersion processed product obtained by mix | blending in the same mass ratio, and kneading until three particle diameters of KS-1010-A become a maximum of 30 micrometers, and JP-508 is an acidic phosphoric acid ester manufactured by Johoku Chemical Industry Co., Ltd. : A mixture of mono (2-ethylhexyl acid phosphate) and bis (2-ethylhexyl acid phosphate).

NCO-1 and OH-10, each temperature controlled at 25 ° C, were mixed for 30 seconds in a 25 ° C atmosphere. The state immediately after mixing was a state in which the organometallic component was dispersed. 400 g of this mixed solution was placed in a 500 cc glass sample bottle, which was left still in a 25 ° C. atmosphere to maintain fluidity even after 5 hours from mixing. The liquid 5 hours after mixing was flowed on the release paper, it cast with the bar coater so that it might become a film of 100 micrometers in thickness, and a planar dimension of 300 mm x 300 mm, and it hardened | cured at 150 degreeC for 3 minutes, and obtained the polyurethane film. As for the obtained polyurethane film, TB was 50 MPa, EB was 600%, and TR was 80 kN / m.

On the other hand, the liquid immediately after mixing was flowed on the release paper, it cast with the bar coater so that it might become a film with a thickness of 100 micrometers, and a planar dimension of 300 mm x 300 mm, and it hardened | cured at 150 degreeC for 3 minutes, and obtained the polyurethane film. As for the obtained polyurethane film, TB was 50 MPa, EB was 600%, and TR was 80 kN / m.

(Example 14)

1000 g of OH-5, 0.2 g of DOTDL (dioctyltin dilaurate, room temperature solid) and 0.1 g of JP-508 were respectively added to a two-liter separable flask, and stirred at 25 ° C. for 30 minutes, and the DOTDL and JP A polyol premix (hereinafter referred to as OH-11) in which -508 became homogeneous with the polyol was obtained.

NCO-1 and OH-11 which were each temperature-controlled at 25 degreeC were mixed for 30 second in 25 degreeC atmosphere. The state immediately after mixing was uniform. 400 g of this mixed solution was placed in a 500 cc glass sample bottle, which was left still under a 25 ° C atmosphere. The 30 minutes elapsed from the mixing resulted in no fluidity, and no liquid emerged even when the glass bottle was inverted.

On the other hand, the liquid immediately after mixing was flowed on the release paper, it cast with the bar coater so that it might become a film with a thickness of 100 micrometers, and a planar dimension of 300 mm x 300 mm, and it hardened | cured at 150 degreeC for 3 minutes, and obtained the polyurethane film. As for the obtained polyurethane film, TB was 50 MPa, EB was 600%, and TR was 80 kN / m.

Claims (7)

It consists of the polyol obtained by reaction of a polycarbonate polyol and a polycaprolactone polyol, and the isocyanate group terminal prepolymer obtained by reaction of a polytetramethylene glycol and a polyisocyanate,
A polyurethane resin coating material set formed on a substrate, wherein the ratio of polycarbonate polyol to polycaprolactone polyol is 65/35 or more by mass ratio. The method of claim 1,
A polyurethane resin coating material set formed on a substrate, wherein both the polyol and the isocyanate group terminal prepolymer are liquid at room temperature. The method of claim 2,
The polyol is a polyurethane resin coating material set formed on a substrate, characterized by further comprising an organic metal catalyst for a curing reaction and a curing reaction inhibitor at room temperature. 4. The method according to any one of claims 1 to 3,
A set of polyurethane resin coating materials formed on a substrate, wherein the polyol is obtained by a reaction of a polycarbonate polyol, a polycaprolactone polyol, and an aliphatic glycol. 5. The method of claim 4,
The polycarbonate polyol is a polyurethane resin film material set formed on a substrate, characterized in that the polycarbonate polyol is obtained by the reaction of 1, 6- hexanediol and dialkyl carbonate. 4. The method according to any one of claims 1 to 3,
A polyurethane resin film material set formed on a substrate, wherein the polyisocyanate is an aliphatic diisocyanate. The method according to claim 6,
The polyurethane resin coating material set formed on the substrate, wherein the aliphatic diisocyanate is hexamethylene diisocyanate.