JP2500419B2 - Polyol composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyol composition.

[0002]

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

When such a conventional polyol or polyol composition is used for the purpose of improving toughness,
It is known to prepolymerize a high molecular weight polyether polyol with a polyisocyanate and introduce it.

[0004]

In the conventional polyol composition described above, the Izod impact value is increased by increasing the introduction amount of the high molecular weight polyether polyol, but the rigidity is lowered and the deformation is apt to occur significantly. In addition, high molecular weight polyester
If the amount of terpolyol introduced is reduced, the rigidity is improved, but the Izod impact value is lowered.

[0005]

The present invention has an average particle size of 0.1.
A polyol composition comprising a polyacrylate rubber-like substance of 10 μm to 10 μm and a polyol, and the content of the polyacrylate rubber-like substance with respect to the total is 2 to 35% by weight. Is.

The polyacrylate rubber-like substance in the present invention means a glass transition obtained by radical polymerization of a vinyl compound in which the proportion of the polyacrylate compound in the vinyl compound used is 30 to 100% by weight. It means a soft substance with a temperature of 0 ° C or less. here
So, the polyacrylate-based compound has 2 acryloyl groups.
It means a vinyl-based monomer having at least 4
The acrylate compound represents a polyvalent acrylate monomer.
ing. In other words, polyacrylate rubbery substance
Is a polyvalent acrylate monomer of 30 to 100% by weight,
A mixture of vinyl monomers other than 0-70% by weight
Obtained by radical polymerization in a polyol
Polyvalent acrylate-based polymer or other vinyl-based
It means a mixture of polymers.

Polyacrylate type rubber-like substance and polio
The composition ratio of the polyacrylate rubber-like substance to the total amount of the rubber is 2% or more and 35% or less by weight, preferably 5% or more and 15% or less. It can give well-balanced physical properties, and 2
If it is less than%, the impact strength will be insufficient, and if it exceeds 35%, the rigidity will be insufficient. The average particle size of the polyacrylate rubber-like substance is within the range of 0.1 μm to 10 μm, preferably 0.2.
The presence of 5 μm or more and 5 μm or less can provide physical properties with a good balance between toughness and rigidity. When the average particle size is less than 0.1 μm, the impact strength is high, and when it exceeds 10 μm, the rigidity and impact strength are high. Is insufficient.

As a preferred example of the method for producing the polyol composition of the present invention, a polyol polyacrylate compound, particularly a polyol diacrylate compound, is used in a polyol together with a polyol monoacrylate compound, and if necessary, other An example of forming a particulate polyacrylate-based rubber-like substance by mixing and stirring with a vinyl-based compound, adding a radical polymerization initiator, and polymerizing can be given. Where Polio
A polyacrylate compound is a polyvalent polyol
It means a relate monomer.

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

As the polyol used in the present invention,
For example, ethylene glycol, propylene glycol,
Low molecular weight polyols such as dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,2,6-hexanetriol, diglycerin and butylbishydroxyethylamine, polyoxy Ethylene diol, polyoxypropylene diol, polyoxypropylene trio-
, Polyoxytetramethylene diol, polyoxyethylene polyoxypropylene block copolymer diol, and polyoxyethylene polyoxypropylene random copolymer diol such as polyether polyol.
Such as poly (tetramethylene adipate diol), polydiethylene azelate diol, polyoxytrimethylhexamethylene terephthalate, polyoxypropylene isophthalate diol, and polycaprolactone diol. Examples include polyester polyol, polyoxycarbonyloxyhexamethylene diol, and polytrimethylhexamethylene hexamethylene diurethane diol.

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 such 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.

From the viewpoint of impact strength, it is preferable to use polyoxyalkylene polyol having a molecular weight of 3000 or more as a part of the polyol used in the present invention. 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 diol and a polyol having 3 or more hydroxy groups together.

The polyacrylate compound used in the present invention means a compound having two or more acryloyl groups, and a polyol polyacrylate compound ( for example, a polyether polyol polyvalent acrylate monomer
Body , polyester polyol polyvalent acrylate- based unit amount
Body) , a compound obtained by reacting a polyglycidyl ether of a polyol ( for example, a polyether polyol or a polyester polyol ) with acrylic acid or methacrylic acid, and a polyether polyamine ( for example, Jeffarmin manufactured by Texaco Chemical Co., USA ) Isocyanate group-containing acryloyl compound (for example, 2-isocyanate ethyl methacrylate, methacryloyl isocyanate), or epoxy group-containing acryloyl compound (for example, glycidyl methacrylate, N- [4- (2,
There are compounds obtained by reacting 3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide) and compounds such as polybutadiene acrylate. Among them, polyoxyalkylene polyol polyacrylate compounds having a carbon atom number in the range of 2 to 4 in one alkylene unit, particularly polyoxypropylene polyol polyacrylate compound as a main component (usually 25% by weight or more) It is preferable to use it from the viewpoint of dispersion stability. Where polyoxya
What is a ruylene polyol polyacrylate compound?
Oxyalkylene polyol polyvalent acrylate monomer
Means polyoxypropylene polyol polyacrylate
Rate compounds are polyoxypropylene polyols
It means a valent acrylate monomer.

The molecular weight of the polyol polyacrylate compound is usually 300 to 8,000, preferably 100 to 5,000, but it is possible to use a small amount of one having a molecular weight of 300 or less.

[0016] Or CH3 group).

In the present invention, the vinyl compound which can be used together with the polyacrylate compound is a compound having one acryloyl group, such as n-butyldiethylene acrylate, polyoxypropylene monoacrylate, allyl. Oxydipropylene methacrylate,
Hydroxypropyl methacrylic acid and the like and radically polymerizable vinyl compounds other than acryloyl group, such as divinyl sebacate, divinylbenzene, N-vinylpyrrolidone, and styrene are available.

[0018] In the present invention, the rubber-forming polyol Po
Step of polymerizing the re acrylate compound is 20 to 160
C., preferably 30 to 140.degree. C., and can be carried out under atmospheric pressure or under pressure or under reduced pressure. In this case, a catalyst is usually added to accelerate the polymerization reaction.

As the catalyst, a catalyst used in a usual radical polymerization can be used, and examples thereof include an azo compound catalyst such as azobisisobutyronitrile and a peroxide compound catalyst such as benzoyl peroxide. The amount of catalyst used is
0.001 to 5% by weight, preferably 0.01
~ 0.5% by weight.

In the present invention, it is not necessary to add an organic solvent in producing the polyacrylate rubber-like substance. However, it does not prevent the use of the organic solvent and is convenient when it is used for paints.

It is not necessary to use the whole of the polyol used in the present invention prior to the production of the polyacrylate rubber-like substance, and it is possible to add a part thereof afterwards. As a method of post-addition, there is a method of adding a part or all of the remaining amount after the polyacrylate rubber-like substance is formed in the polyol or a method of adding a part remaining at the final use stage. . The proportion of the polyacrylate rubber-like substance in the polyol composition of the present invention is the polyacrylate based on the total amount of the polyols used in the various cases and the total amount of the polyacrylate rubber-like substance. It is calculated as the ratio of rubber-like substances.

In the present invention, the average particle size of the polyacrylate rubber-like substance is represented by a volume average value. Further, in the present invention, the amount of the polyacrylate rubber-like substance is a volatile solvent having a property of precipitating the polyacrylate rubber-like substance from the polyol composition containing the polyacrylate rubber-like substance, for example, acetone. The mixture is mixed, and the precipitated polyacrylate rubber-like substance is separated and filtered, and after sufficiently washing with this volatile solvent, the dry weight thereof is measured.

In use, the polyol composition of the present invention may be mixed with the same polyisocyanate as described above and, if necessary, an aromatic polyamine or the like to prepare a coating composition, an adhesive composition, an impregnating composition, a co-product composition. Suitable for use in coating, foaming, molding, especially casting. Also, so-called RIM
Of course, it is possible to use it in the form of. Typical examples of the polyisocyanate used when the polyol composition of the present invention is used for a polyurethane resin are 2,4-toluene diisocyanate and 2,6-toluene diisocyanate. , Diphenylmethane diisocyanate (MDI), triphenylmethane triisocyanate,
Aromatic polyisocyanate such as p-phenylene diisocyanate, Metaxylene diisocyanate, Aromatic aliphatic polyisocyanate such as paraxylene diisocyanate, Isophorone diisocyanate, Hydrogenated xylene Alicyclic polyisocyanates such as diisocyanate and hydrogenated diphenylmethane diisocyanate, aliphatic polyisocyanates such as hexanemethylene diisocyanate, lysine ester triisocyanate and polyisocyanates in the reaction system. Such as carbodiimide modified liquefied MDI, diisocyanate dimers such as toluene diisocyanate dimers, blocked isocyanates such as phenols. In addition to the above-mentioned MDI, polyisocyanate shown above Doo and polyol - Le or polyamines and the ends of more than two positions isocyanate - prepolymer obtained was reacted as with the door - like polyisocyanate - DOO can of course also be used.

Particularly, aromatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate are preferable. Examples of the aromatic polyamine that can be used in such a case include 3,3'dichloro-4,4'-diaminodiphenylmethane and tetraethylmethylene dianiline.

Examples of additives that can be used with the polyol composition of the present invention include, for example, polyurethane resin modifiers (mercaptoethanol, aminopropanol, dimethylaminopropanol, epoxy resins having a hydroxyl group, etc.). Substances), curing accelerators, emulsifiers, surface active agents as bubble stabilizers, additive flame retardants, reactive flame retardants, reaction retarders, colorants, foaming agents, internal mold release agents, antioxidants, antioxidants Examples include known additives such as plasticizers, bactericides and carbon black, zinc oxide, calcium oxide, lead dioxide, titanium oxide, glass fibers, various whiskers, talc, mica and other fillers.

There is no particular limitation on the timing of addition of these additives, and they may be added before the polyacrylate rubber material is produced during the production of the polyol composition of the present invention.
Further, it can be appropriately added after the preparation of the polyol composition or when it is mixed with the polyisocyanate.

The polyol composition of the present invention can be used for applications other than polyurethane resins, and as such applications, a raw material of a saturated or unsaturated polyester resin for reacting with a polybasic acid, a melamine resin. It can also be used as a raw material for curable resins such as ultraviolet rays and electron beams that can be mixed and modified with amino resins such as acrylic acid and mono-unsaturated carboxylic acids such as acrylic acid. It is effective for imparting high rigidity, impact strength, and heat resistance.

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

The polyurethane composition of the present invention can be used to produce a non-foamed or foamed polyurethane resin by a known method such as a one-shot method, a semi-prepolymer method or a prepolymer method.

[0030]

EXAMPLES The following is a description of the method for producing the polyol composition of the present invention and an example of using it as a polyurethane casting.

In the following description, "part" and% are expressed by weight unless otherwise specified.

The NCO index is a value obtained by dividing the isocyanate group equivalent by the hydroxyl equivalent (-NCO group / -OH group).
Means Liquefied M when casting test pieces
Triethylenediamine (DABCO) 0.05% by weight was added to the total amount of DI and polyol composition, and a vacuum casting device was used.

The tensile test, the bending test, the Izod impact test, and the heat distortion temperature test of the test piece cast product are JI respectively.
S K7113, JIS K7203, JIS K7110 (notch tip radius 0.25m
m), JIS K7207 (load 18.5 kg / cm2).

The particle size of the polyacrylate rubber-like substance of the present invention is the same as that of the polyol composition in isopropyl alcohol.
Dilute it 1000 times, drop the diluted solution on the sample stage of the scanning electron microscope, volatilize the solvent, and measure the rubber particle size of the polyacrylate rubber-like substance at a magnification of about 5000 times. , And the volume average value was obtained. The content of the polyacrylate rubber-like substance is such that the polyol composition is diluted with acetone to precipitate the polyacrylate rubber-like substance, which is separated and filtered, and the polyacrylate remaining on the filter paper is used. The system rubber-like substance was thoroughly washed with acetone, dried and weighed to calculate the content of the polyacrylate rubber-like substance. Example 1 A closed glass container equipped with a temperature-controllable heater and a stirrer was charged with 12 parts of dipropylene glycol and a hydroxyl value of 280.
14 parts of polyoxypropylene diol, 21 parts of polyoxypropylene triol having a hydroxyl value of 560, 3.0 parts of polypropylene glycol dimethacrylate having a molecular weight of 2000,
1.5 parts of polypropylene glycol monomethacrylate having a molecular weight of 800 and 0.15 parts of polypropylene glycol diacrylate having a molecular weight of 400 were added, and the solution temperature was raised to 80 ° C. under a nitrogen atmosphere while mixing and stirring. .

Next, 0.01 part of 2,2'-azobis (2-methylbutyronitrile) was added as a radical polymerization initiator, and 80
The reaction was carried out by stirring for 1 hour in the state of ° C.

Next, the temperature was raised to 110 ° C., stirring was continued at 110 ° C. for 20 minutes, and then the mixture was cooled to room temperature to give a polyacrylate rubber-like substance having an average rubber particle size of 1.0 μm.
A polyol composition containing 0% by weight was obtained.

Next, 0.01% of an antioxidant (trade name IRGANOX1076, manufactured by Nippon Ciba-Gaiki Co., Ltd.) was added to the above polyol composition.
Added in parts.

The above polyol composition was mixed with an amount of NCO 28% carbodiimide-modified liquefied MDI corresponding to an NCO index of 1.05, and a test piece was cast, and the physical properties were measured.

The content of rubber-like substance in the obtained polyurethane resin was 4.7%, tensile strength, bending strength, bending elastic modulus, I
ZOD impact value is 660kg / cm2, 790kg / cm2, 24000kg / c respectively
It was m2 and 8 kgcm / cm. Example 2 Except that 4.5 parts of polypropylene glycol dimethacrylate having a molecular weight of 2000, 2.3 parts of polypropylene glycol monomethacrylate having a molecular weight of 800 and 0.2 part of polypropylene glycol diacrylate having a molecular weight of 400 were used. An experiment was conducted in the same manner as in Example 1. The obtained polyurethane resin has an average rubber particle size of 1.4 μm, a rubber-like substance content of 6.9%, a tensile strength, a bending strength, a bending elastic modulus, and an IZOD impact value of 620 kg / cm2, 770 kg / cm2, and 22000 kg / cm2, respectively. , 1
It was 3 k gcm / cm. Comparative Example 12 parts of dipropylene glycol, 14 parts of polyoxypropylene diol having a hydroxyl value of 280, and 21 parts of polyoxypropylene triol having a hydroxyl value of 560 were mixed, and then carbodiimide was prepared in the same manner as in Example 1. The mixture was mixed with the modified liquefied MDI, and the test point was molded.

Tensile strength of the obtained polyurethane resin,
Flexural strength, flexural modulus, and IZOD impact value are each 770 kg / cm
The values were 2,820 kg / cm2, 27000 kg / cm2, and 2.0 kgcm / cm. Example 3 Polyoxypropylenediol 6 having a hydroxyl value of 280 of Example 1
Polyoxytetramethylenedio with a hydroxyl value of 280
The experiment was carried out in the same manner as in Example 1 except that hydroxyethyl methacrylate was substituted for 0.05 part of polypropylene glycol diacrylate having a molecular weight of 400.

The average rubber particle size was 0.9 μm, and the tensile strength, bending strength, bending elastic modulus, and IZOD impact value of the obtained polyurethane resin were 670 kg / cm 2, 800 kg / cm 2, and 25000 kg / cm 2, respectively.
It was 9.0 kgcm / cm. Example 4 In a closed glass container equipped with a heater and a stirrer capable of controlling temperature, 12 parts of dipropylene glycol and 280 of hydroxyl value were added.
Polyoxypropylene diol of 5 parts, polyoxypropylene triol of hydroxyl value 560 of 17 parts, polyoxypropylene triol of hydroxyl value of 33 of 13 parts, polypropylene glycol dimethacrylate of molecular weight 2000 3.5 parts, 1.7 parts of polypropylene glycol monomethacrylate having a molecular weight of 800, 0.10 parts of polypropylene glycol diacrylate having a molecular weight of 400, and hydroxyethyl methacrylate of 0.
07 parts were charged, and the solution temperature was raised to 80 ° C. under a nitrogen atmosphere while mixing and stirring.

Next, 0.01 part of 2,2'-azobis (2-methylbutyronitrile) was added as a radical polymerization initiator, and 80
The reaction was carried out by stirring for 1 hour in the state of ° C.

Next, the temperature was raised to 110 ° C., stirring was continued at 110 ° C. for 20 minutes, and then the mixture was cooled to room temperature to obtain a polyacrylate rubber-like substance having an average rubber particle size of 1.1 μm.
A polyol composition containing a weight percent was obtained.

Next, 0.01% of an antioxidant (trade name IRGANOX1076, manufactured by Nippon Ciba-Gaiki Co., Ltd.) was added to the above polyol composition.
Added in parts.

The above polyol composition was mixed with a carbodiimide-modified liquefied MDI of NCO 28% in an amount corresponding to an NCO index of 1.05, a test piece was cast, and the physical properties were measured.

The content of rubber-like substance in the obtained polyurethane resin was 5.4%, tensile strength, flexural strength, flexural modulus, I
ZOD impact value is 620kg / cm2, 750kg / cm2, 20000kg / c respectively
The m2 was 13 kgcm / cm.

INDUSTRIAL APPLICABILITY The polyol composition of the present invention has impact resistance without sacrificing rigidity as compared with a polyurethane resin cured product obtained from a polyol containing no polyacrylate rubber-like substance. Has the effect of being extremely excellent.

Claims (3)

(57) [Claims] 1. A polyacrylate rubber-like substance having an average particle size of 0.1 μm to 10 μm and a polyol, and the content of the polyacrylate rubber-like substance with respect to the total is 2
A polyol composition, characterized in that it is ˜35% by weight. 2. The polyacrylate-based rubber-like substance is
Polyols port occupying a vinyl compound in a polyol
Polyol composition according to claim 1, wherein the vinyl compound Li acrylate compound accounts for 30 to 100 wt% is <br/> particulate material is formed by radical polymerization. Wherein the polyol polyacrylate-based compound, a polyalkylene polyol polyacrylate of
A compound, the number of carbon atoms occupying the alkylene unit of 1 pc 2 to 4, and a molecular weight and being in the range of 150 to 5000
The polyol composition according to claim 2, wherein