JP2956351B2 - Polyol composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyol composition.

[0002]

BACKGROUND OF THE INVENTION Polyols or polyol compositions form polyurethane resins by reaction with polyisocyanates. This polyurethane resin is widely used as a molding material, a structural adhesive material, and a coating material because it generally has excellent properties of plasticity, abrasion resistance, chemical resistance, and adhesiveness. As a molding resin, it is used to produce a development prototype in a short period of time and at low cost by a casting method under normal pressure or vacuum without raising a mold. The polyurethane resin molded product obtained by this method has a sufficient rigidity and can be used as a shape sample, but has low toughness, so that it is insufficient for evaluation of a structural design or a mounting test.

When such a conventional polyol or polyol composition is used, the Izod impact value increases with an increase in the amount of the high-molecular-weight polyether polyol, but the rigidity is reduced and remarkable deformation tends to occur. ,
If the amount of the polymer polyether polyol introduced is reduced, the rigidity is improved, but the Izod impact value is reduced.

[0004] As a conventional technique, for example, Japanese Patent Application No. Hei.
No. 246039. A conventional polyol composition (which can provide a polyurethane resin having sufficient rigidity and a high Izod impact value) comprises a polyurea-based rubber-like substance having an average particle size of 0.1 to 10 μm and a polyol, and the polyurea-based material based on the total The content of the rubbery substance is 2 to 35% by weight.

In many applications of polyurethane resins, rigidity,
There is a strong demand for the development of a material having improved heat resistance as well as toughness.

[0006]

In the prior art (in order to improve the heat resistance of the polyurethane resin, a low molecular weight polyol is mainly used as the polyol), the dispersion stability of the particles of the polyurea rubber-like substance is poor. There is a drawback that it tends to be difficult to use.

[0007]

Means for Solving the Problems The present invention has an average particle size of 0.1.
In a polyol composition containing a polyurea-based rubbery substance and a polyol having a content of 2 to 35% by weight based on the total, the polyol composition has 2 to 35% by weight of a polyol. 3 hydrogenated bisphenol A di 2-hydroxyalkyl ether (H
A) and cyclohexanedimethanol (CHDM) account for 2 to 30% by weight and 0 to 30% by weight, respectively.

[0008] The polyurea-based rubbery substance in the present invention means a rubbery substance having a urea bond in the main chain.

The composition ratio of the polyurea rubber substance to the total of the polyurea rubber substance and the polyol is within a range of 2% to 35% by weight, preferably 5% to 1%.
By being present within the range of 5% or less, physical properties with a good balance between toughness and rigidity can be provided, and if it is less than 2%, the impact strength becomes insufficient, and if it exceeds 35%, the rigidity becomes insufficient.
Also, the average particle size of the polyurea-based rubbery substance is 0.1 μm or more.
By being present within the range of 0 μm or less, preferably within the range of 0.5 μm or more and 5 μm or less, it is possible to provide physical properties with a balance of toughness and rigidity, and the average particle size is 0.1 μm
If it is less than 10 μm, the impact strength will be insufficient, and if it exceeds 10 μm, the rigidity and impact strength will be insufficient.

As a preferred example of the method for producing the polyol composition of the present invention, a polyol and a polyisocyanate (referred to as polyisocyanate A) are mixed and stirred to partially react, and then the same as the above-mentioned polyisocyanate. Alternatively, a different polyisocyanate (hereinafter, referred to as polyisocyanate B) and a rubber-forming polyamine are added, and a particulate polyurea-based rubber-like substance is formed with stirring.

The amount of polyisocyanate A used is usually 0.5 to 40 mol%, preferably 10 to 30 mol%, with the amount of polyisocyanate groups in polyol being 100 mol%.

This is because a polyurea-based comb-like substance is easily obtained in the range of 0.5 to 40 mol%. And the ratio of partially reacting the polyol and the polyisocyanate A,
Of the isocyanate groups of polyisocyanate A, usually 1
React 0-90%, preferably 20-80% (this is 10-9
This is because in the range of 0%, particles of the polyurea-based rubber-like substance are easily obtained stably). The addition amount of the rubber-forming polyamine and the polyisocyanate B to be subsequently added is usually 60 to 60% of the ratio of the amino group of the rubber-forming polyamine to the total of the unreacted isocyanate group of the polyisocyanate A and the isocyanate group of the polyisocyanate B. 150
Mol%, preferably 70 to 130 mol%. This is because when the amino group is used in the range of 60 to 150 mol%, high rigidity, Izod impact strength and heat resistance can be obtained at the final use stage.

The method for adding the polyisocyanate A is generally preferably a batch addition method.
The method of adding the rubber-forming polyamine may be batch addition or continuous addition in addition to batch addition. Regarding the method of adding the polyol, it is also possible to use a part of the polyol from the beginning of the reaction and add the remaining batchwise or continuously.

The polyol used in the present invention is a compound having two or more alcoholic hydroxy groups, such as a low molecular weight polyol, a polyether polyol, a polyester polyol, and other polyols.

In the present invention, hydrogenated bisphenol A di-2-hydroxyalkyl ether (HA) having an alkyl group having 2 to 3 carbon atoms is an essential component as one component of the polyol, and is used in the polyol composition of the present invention. The proportion of HA in the polyol obtained is 2 to 30% by weight, preferably 5 to 20%.
%. Where the proportion of HA is 2% by weight
If it is less than 30%, heat resistance and impact resistance are insufficient, and if it exceeds 30%, dispersion stability becomes insufficient. HA includes hydrogenated bisphenol A di 2-hydroxyethyl ether and hydrogenated bisphenol A di 2-hydroxypropyl ether,
Each may be used alone or in combination. Examples of commercially available products of HA include, when the alkyl group is ethyl, manufactured by Shin Nippon Rika Co., Ltd., trade name Rica Resin HEO-20, and when the alkyl group is a propyl group, manufactured by Shin Nippon Rika Co., Ltd., trade name: Rica Resin HPO- There are 30. Further, CHDM is used in an amount of 0 to 30% by weight based on the polyol used in the polyol composition of the present invention as a component of the polyol used in the present invention, and heat resistance,
It is preferable to use in the range of 5 to 20% from the balance of impact resistance. Here, if CHDM exceeds 30% by weight, the dispersion stability becomes insufficient.

Other polyols used in the present invention include, for example, ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,2,6-hexanetriol, Glycerin, low molecular weight polyols such as butyl bishydroxyethylamine, polyoxyethylene diol, polyoxypropylene diol, polyoxypropylene triol, polyoxytetramethylene diol,
Polyether polyols such as diols of polyoxyethylene polyoxypropylene block copolymers, diols of polyoxyethylene polyoxypropylene random copolymers, polytetramethylene adipate diol, polydiethylene azelate diol, polyoxytrimethylhexamethylene terephthalate and polyoxypropylene iso- Examples include diols of phthalate, polyester polyols such as polycaprolactone diol, polyoxycarbonyloxyhexamethylenediol, and polytrimethylhexamethylenehexamethylenediurethanediol.

As a part of the polyol used in the present invention, it is preferable to use a polyoxyalkylene polyol having a molecular weight in the range of 160 to 35,000. In this case, the amount of the polyoxyalkylene polyol used is preferably in the range of 20 to 90% by weight in the polyol. This is because the dispersion stability tends to decrease outside this range.

As a part of the polyol used in the present invention, it is preferable to use a polyoxyalkylene polyol having a molecular weight of 3000 or more from the viewpoint of impact strength. In this case, it is possible to obtain a polyurethane resin having an Izod impact strength of 20 kgcm / cm or more.

The polyol used in the present invention includes:
From the viewpoint of heat resistance and impact strength, it is particularly preferable to use a diol and a polyol having three or more hydroxy groups in combination.

The polyisocyanate A and the polyisocyanate B may be the same or different. For example, typical examples include aromatic polyisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate (MDI) and triphenylmethane triisocyanate, meta-xylene diisocyanate, and paraxylene diisocyanate. Alicyclic polyisocyanates such as araliphatic polyisocyanates, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate; aliphatic polyisocyanates such as hexane methylene diisocyanate; Substances that generate isocyanates, such as carbodiimide-modified liquefied M
In addition to carbodiimide compounds such as DI, diisocyanate dimers, for example, toluene diisocyanate dimer, blocked isocyanates, for example, phenol-blocked MDI, the above-mentioned polyisocyanates and polyols or polyamines are also terminated. Of course, prepolymeric polyisocyanates obtained by reacting to have two or more isocyanates can also be used.

As the polyisocyanate A, 2,4-toluene diisocyanate or isophorone diisocyanate, which is a polyisocyanate having an isocyanate group having a different reactivity, is particularly preferred for improving the dispersion stability of the particles of the polyurea rubber-like substance.

The rubber-forming polyamine used in the present invention is the above-mentioned polyisocyanate A and polyisocyanate B
Means a polyamine which forms a polyurea-based rubbery substance having a glass transition temperature of about 0 ° C. or less, for example, a polyoxypropylene-based polyamine or a polyoxytetramethylene-based polyamine. Oxyalkylene-based polyamines, polybutadiene-based polyamines and the like, among which polyoxyalkylene-based polyamines having 2 to 4 carbon atoms in one alkylene unit, particularly polyoxypropylene-based diamine (mainly 60% by weight) % Or more).

Such a polyoxypropylene-based polyamine is commercially available, for example, as Texaco Chemical Co., USA under the trade name Jeffamine ™, or bis (aminopropyl) polypropylene glycol ether manufactured by Koei Chemical Industry Co., Ltd. The molecular weight of the rubber-forming polyamine is usually from 200 to 3
5000, preferably 400-6000 are used.

In the present invention, it is desirable that the polyurea-based rubbery substance is a crosslinked particle, and a small amount of a polyamine mainly composed of diamine and having three or more amino groups in one molecule (for example, 0.02 to 10% by weight of diamine) %). In this case, as the polyamine having three or more amino groups in one molecule, other polyamines such as 1,3,6-trisaminomethylhexane, difluorodiaminetriamine and the like can be used in addition to polyoxyalkylene polyamine. In addition,
To crosslink a polyurea-based rubbery substance, a small amount of a polyisocyanate having three or more isocyanate groups is used without using a polyamine having three or more amino groups in one molecule (for example, 0.03 to 10% by weight based on diisocyanate). There are also methods used.

As a preferred method for producing the polyol composition of the present invention other than the above, a polyisocyanate (referred to as polyisocyanate C) and a rubber-forming polyamine are added to the polyol, and the mixture is stirred. There is a method for forming a polyol composition containing a particulate polyurea-based comb-like substance.

Here, the comb-forming polyamine is usually 50 to 200%, preferably 70 to 170%, based on the isocyanate group of polyisocyanate C.
The amount used is such that it has amino groups corresponding to%. This is because high impact strength can be obtained without impairing high rigidity and heat resistance at the stage of final use when the polyol composition obtained in the range of 50 to 200% is used. In this case, the method of adding the polyisocyanate and the rubber-forming polyamine may be batch addition or continuous addition in addition to batch addition. As a method of adding the polyol, it is also possible to use a part of the polyol from the beginning of the reaction and add the remaining batchwise or continuously.
Here, the polyisocyanate C is the same as that exemplified as the polyisocyanate A and the polyisocyanate B, and the rubber-forming polyamine and the polyol are the same as described above.

In the present invention, the step of partially reacting polyisocyanate A and the step of reacting polyisocyanate B or polyisocyanate C with a comb-forming polyamine are usually carried out at 20 to 160 ° C., preferably 30 to 140 ° C. The reaction can be carried out under atmospheric pressure, under pressure, or even under reduced pressure. In this case, a catalyst may not be used, but a catalyst can be added to promote the reaction. Catalysts are usually organometallic catalysts such as dibutyltin laurate and tin octylate, tertiary amine catalysts such as triethylenediamine (DABCO), and 1,8-diazodicyclohexane.
There are special amine catalysts such as [5,4,0] undecene derivatives. The amount of catalyst used is usually based on the total amount of polyol.
It is 0.001 to 5% by weight, preferably 0.01 to 0.5% by weight.

In the present invention, there is no need to add an organic solvent in producing a polyurea-based rubbery substance. However, it does not prevent the use of organic solvents,
This is convenient when used for paints.

It is not necessary to use all of the polyol used in the present invention prior to producing the polyurea-based rubbery substance, and it is possible to add a part of it later. As a method of post-addition, there is a method of adding a part or all of the remaining amount after the polyurea-based rubber-like substance is formed in the polyol, and a method of adding a part remaining at the stage of final use. The ratio of the polyurea-based rubbery substance in the polyol composition of the present invention is calculated as the ratio of the polyurea-based rubbery substance to the total amount of the polyol and the polyurea-based rubber used in the various cases described above.

In the present invention, the average particle size of the polyurea rubber-like substance is represented by a volume average value. In the present invention, the amount of the polyuria rubber-like substance is determined by mixing a volatile solvent having a property of precipitating the polyuria-based rubber-like substance from the polyol composition containing the polyuria-based rubber-like substance, for example, acetone, and depositing the polyuria-based rubber. The particulate matter is separated by filtration, washed sufficiently with the volatile solvent, and measured by a method for determining the dry weight.

When the polyol composition of the present invention is used, the same polyisocyanate as described above, and if necessary, an aromatic polyamine or the like are further mixed, and the mixture is used for paints, adhesives, impregnations, coatings, and foams. Suitable for use in molding, molding, and especially for casting. Also, so-called RIM
Of course, it is also possible to use it in the form of The polyisocyanate used when the polyol composition of the present invention is used for a polyurethane resin is the same as the polyisocyanate A and the polyisocyanate B described above, and may be an aromatic polyisocyanate, an araliphatic polyisocyanate, or an alicyclic ring. Formula polyisocyanates are particularly preferred. Aromatic polyamines that can be used in such cases include, for example, 3,3'-dichloro-4,4'-diaminodiphenylmethane, tetraethylmethylenedianiline, and the like.

Examples of additives that can be used together with the polyol composition of the present invention include polyurethane resin modifiers (reactive substances such as mercaptoethanol, aminopropanol, dimethylaminopropanol, and epoxy resin having a hydroxyl group), curing accelerators, and emulsifiers. , A surfactant as a foam stabilizer, an additive type flame retardant, a reactive type flame retardant, a reaction retarder, a colorant, a foaming agent, an internal mold release agent, an antioxidant, an antioxidant, a plasticizer, a disinfectant and carbon. Known additives such as black, zinc oxide, calcium oxide, lead oxide, titanium oxide, glass fiber, various whiskers, talc, mica, and other fillers may be used.

There is no particular limitation on the timing of addition of these additives, and they may be added before the production of the polyurea-based rubber material when the polyol composition of the present invention is produced. It can be appropriately added later, or when mixed with a polyisocyanate.

The polyol composition of the present invention can be used for applications other than polyurethane resins, such as a raw material for a saturated or unsaturated polyester resin for reacting with a polybasic acid, and a melamine resin. It can be used as a raw material of curable resin by mixing with amino resin and modifying it, or by esterification with monounsaturated carboxylic acid such as acrylic acid by ultraviolet ray or electron beam. It is effective for imparting impact strength and heat resistance.

The production of a polyurethane resin from the polyol composition of the present invention is usually carried out by mixing and reacting the raw materials using a low-pressure or high-pressure mechanical device, pouring the mixture into a mold, and curing the reaction in the mold. Furthermore, polyurethane can be produced by removing a gas such as dissolved air in the raw material before and after the raw material is mixed (particularly before the raw material is mixed) or air mixed during the mixing by the vacuum method.

Using the polyol composition of the present invention, a non-foamed or foamed polyurethane resin can be produced by a known method such as a one-shot method, a semi-prepolymer method, or a prepolymer method.

[0037]

EXAMPLES Examples of the production of the polyol composition of the present invention and the use of the same as a polyurethane casting are shown below.

In the following description, “parts” means parts by weight unless otherwise specified.

The NCO index means a value obtained by dividing an isocyanate group equivalent by a hydroxyl equivalent (-NCO group / -OH group). When casting test pieces, use liquefied MDI
And 0.05% by weight of DABCO with respect to the total amount of the polyol composition, and a vacuum casting apparatus was used.

The tensile test, the bending test, the Izod impact test, and the thermal deformation temperature test of the test piece cast product are each performed by JI.
SK 7113, JIS K 7203, JIS K 7110 (notch tip radius 0.
25 mm) and JIS K 7207 (load 18.5 kg / cm2).

The particle size of the polyurea-based rubbery substance of the present invention is as follows.
After diluting the diluted solution onto a sample stage of a scanning electron microscope and evaporating the solvent, the rubber particle size of the polyurea-based rubbery substance was measured at a magnification of about 5000 times, and the volume average was measured. The value was determined.

Further, the content of the polyurea-based rubbery substance was determined by diluting the polyol composition with acetone to precipitate the polyurea-based rubbery substance, separating and filtering it, and removing the polyurea-based rubbery substance remaining on the filter paper. After sufficiently washing with acetone, the sample was dried and weighed to calculate the content of the polyurea-based rubbery substance. Example 1 (Experiment Nos. 1 to 6) 5.6 parts of isophorone diisocyanate (polyisocyanate A) and 70 parts of polyoxypropylene triol having a hydroxyl value of 160 were placed in a closed glass container equipped with a heater and a stirrer capable of controlling temperature. Then, 0.004 part of dibutyltin dilaurate was charged, and the mixture was reacted while controlling the reaction temperature at 35 ° C. until the conversion of the isocyanate groups became 54%. 121 parts of polyoxypropylene diamine having a molecular weight of 2,000 and 6.4 parts of polyoxypropylene triamine having a molecular weight of 400 were added to the above reaction solution, and the mixture was stirred and reacted for about 30 minutes while controlling the reaction temperature at 35 ° C.

Next, 119 parts of polyoxypropylene diol having a hydroxyl value of 280 and polyoxypropylene triol having a hydroxyl value of 560 in an amount shown in Table 1 were added, and the temperature was raised to 80 ° C. so that a uniform solution was obtained. For about 5 minutes. Next, 19.5 parts of carbodiimide-modified liquefied MDI (polyisocyanate B) containing 28% of NCO was added, and after stirring for about 30 minutes, 318 parts of dipropylene glycol was heated to 80 ° C. and liquefied hydrogenated bisphenol A di2- Hydroxyethyl ether, the amount of cyclohexane dimethanol liquefied by heating to 80 ° C was added in the amount shown in Table 1 (total amount of polyol is 1060 parts), and the mixture was stirred and mixed to form a polyurea rubber having an average particle size of about 1.4 µm A polyol composition was produced which contained 14% by weight of the substance and the amount of CHDM indicated in Table 2.

The ratio between the polyol composition and the carbodiimide-modified liquefied MDI having an NCO of 28% is such that the NCO index is 1.07.
And the test piece was cast.

[0045]

Table 2 shows the characteristic results of the above test pieces.

[0047]

In the case of Experiment Nos. 5 and 6, when the obtained polyol composition was returned to normal temperature, HA and CHDM were precipitated, and the polyurethane resin obtained from this polyol composition caused poor curing, and a normal molded product was obtained. I couldn't do that.

From the above results, it can be seen that the polyurethane resin obtained from the polyol composition of the present invention containing HA can increase the impact strength and the heat distortion temperature without sacrificing the tensile strength, flexural strength and flexural modulus. And especially
It can be seen that the heat deformation temperature is significantly increased while maintaining a sufficiently high impact strength by using a suitable amount of CHDM. Example 2 (Experiment Nos. 1 to 4) In a closed glass container equipped with a temperature-controllable heater and stirrer, the amount of isophorone diisocyanate (polyisocyanate A) shown in Table 3 and polyoxypropylene having a hydroxyl value of 160 were added. Triol and dibutyltin dilaurate were charged, and the reaction was carried out while controlling the reaction temperature at 35 ° C. until the conversion of the isocyanate groups became about 50%. To the above reaction solution, polyoxypropylene diamine having a molecular weight of 2,000 and polyoxypropylene triamine having a molecular weight of 400 shown in Table 3 were added, and the mixture was stirred and reacted for about 30 minutes while controlling the reaction temperature at 35 ° C. (Experiment No. The proportion of each of the raw materials 2, 3 and 4 was constant as can be seen from Table 3). Next, a hydroxyl value of 280
Of polyoxypropylene diol and 410 parts of polyoxypropylene triol having a hydroxyl value of 560 were added, and the mixture was heated to 80 ° C. and stirred for about 5 minutes to obtain a uniform solution.
Next, carbodiimide-modified liquefied MDI (polyisocyanate B) having an NCO content of 28% as shown in Table 3 was added, and after stirring for about 30 minutes, 318 parts of dipropylene glycol was heated to 80 ° C. to liquefy hydrogenated bisphenol. A 60 parts of di 2-hydroxyethyl ether, 83 parts of cyclohexane dimethanol heated to 80 ° C. and liquefied were added, and the mixture was stirred and mixed to produce a polyol composition containing a polyurea-based rubbery substance described in Table 4. Was.

The ratio of the above polyol composition and carbodiimide-modified liquefied MDI having an NCO of 28% has an NCO index of 1.05.
And the test piece was cast.

[0051]

Table 4 shows the properties of the urethane resin obtained from the above polyol composition.

[0053]

Example 3 A polyoxypropylene diamine having a molecular weight of 2,000 was placed in a closed glass container equipped with a temperature-controllable heater and stirrer.
15 parts, polyoxypropylene triamine having a molecular weight of 400 0.8
Parts, 30 parts of polyoxypropylene diol having a hydroxyl value of 280,
115 parts of polyoxypropylene triol having a hydroxyl value of 560, 50 parts of polyoxypropylene triol having a hydroxyl value of 33, 20 parts of hydrogenated bisphenol A di-2-hydroxyethyl ether,
25 parts of cyclohexanedimethanol and 100 parts of dipropylene glycol were charged, and the mixture was heated to 80 ° C. and stirred for about 10 minutes so as to form a homogeneous solution.

Next, a carbodiimide-modified liquefied MDI containing 28% of NCO in an amount corresponding to about 143% of amino groups to isocyanate groups with respect to amino groups in the homogeneous solution.
(Isocyanate C) 2.1 parts into a glass container, and further stirred at 80 ° C. for about 10 minutes to obtain an average particle size of about 1.4 μm
A polyol composition of 5% by weight of a polyurea-based rubbery material was produced.

A test piece was cast by adjusting the ratio of the above polyol composition and carbodiimide-modified liquefied MDI containing 28% of NCO to an NCO index of 1.07.

The cast product had a tensile strength of 720 kg / cm 2, a bending strength of 810 kg / cm 2, a flexural modulus of 21,000 kg / cm 2, an Izod impact value of 15 kg cm / cm, and a heat deformation temperature of 95 ° C. Example 4 A polyoxypropylene diamine having a molecular weight of 2,000 was placed in a closed glass container equipped with a temperature-controllable heater and a stirrer.
15 parts, polyoxypropylene triamine having a molecular weight of 400 0.8
Parts, 30 parts of polyoxypropylene diol having a hydroxyl value of 280,
115 parts of polyoxypropylene triol having a hydroxyl value of 560, 50 parts of polyoxypropylene triol having a hydroxyl value of 33, hydrogenated bisphenol A di-2-hydroxypropyl ether 20
, 25 parts of cyclohexanedimethanol and 100 parts of dipropylene glycol were added, and the mixture was heated to 80 ° C and stirred for about 10 minutes to obtain a uniform solution.

Next, a carbodiimide-modified liquefied MDI containing 28% of NCO in an amount corresponding to about 143% of amino groups to isocyanate groups with respect to amino groups in the homogeneous solution.
(Isocyanate C) 2.1 parts into a glass container, and further stirred at 80 ° C. for about 10 minutes to obtain an average particle size of about 1.4 μm
A polyol composition of 5% by weight of a polyurea-based rubbery material was produced.

A test piece was cast by adjusting the ratio of the polyol composition to the carbodiimide-modified liquefied MDI containing 28% NCO so as to have an NCO index of 1.07.

The cast product had a tensile strength of 700 kg / cm 2, a bending strength of 800 kg / cm 2, a flexural modulus of 20000 kg / cm 2, an Izod impact value of 15 kg cm / cm, and a heat deformation temperature of 91 ° C.

[0061]

The polyurethane resin obtained from the polyol composition of the present invention has remarkably excellent heat resistance as compared with the polyurethane resin obtained from a polyol composition having an HA content and a CHDM content outside the range of the present invention. In addition, there is an effect that the tensile strength, the bending strength, the bending elastic modulus, and the impact strength have sufficiently large values.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification code FI C08L 75/08 C08L 75/08 (58) Investigated field (Int.Cl. ⁶ , DB name) C08G 18/32 C08K 5/02 C08L 71 / 02,75 / 02,75 / 08

Claims (5)

(57) [Claims] 1. A polyol composition comprising a polyurea-based rubber-like substance having an average particle size of 0.1 μm to 10 μm and a polyol, wherein the content of the polyurea-based rubber-like substance is 2 to 35% by weight based on the total, Hydrogenated bisphenol A di-2-hydroxyalkyl ether having 2 to 3 carbon atoms in the polyol (hereinafter referred to as HA) in the polyol is 2 to 30% by weight,
A polyol composition, wherein cyclohexanedimethanol (referred to as C HDM) accounts for 0 to 30% by weight. 2. Polyol and polyisocyanate (polyisocyanate A) are mixed and stirred to partially react, and then the same or different polyisocyanate as polyisocyanate (polyisocyanate B) and rubber-forming properties. 2. A polyamine-based rubber-like substance in the form of particles is formed by adding a polyamine and stirring the mixture.
The polyol composition as described in the above. 3. The method according to claim 1, wherein a polyisocyanate (referred to as polyisocyanate C) and a rubber-forming polyamine are added to the polyol, and a particulate polyurea rubber-like substance is formed with stirring. A polyol composition. 4. A polyoxyalkylene polyol wherein 20 to 90% by weight of the polyol has 2 to 4 carbon atoms in one alkylene unit and a molecular weight in the range of 160 to 35,000. The polyol composition according to any one of claims 1 to 3. 5. An alkyl group having 2 to 3 carbon atoms having an HA of 5 to 20.
5. The polyol composition according to claim 1, wherein the polyol accounts for 5% to 20% by weight of CHDM.