JPH04325512A - Polyurethane composition or polyurethane urea composition and roll coated therewith - Google Patents

Abstract

PURPOSE:To provide the title composition which is excellent in durability, chemical resistance, heat resistance, weathering resistance, etc., and can effectively be used as the material of rolls for iron and steel production, papermaking or an office machine or as the material of a belt, a solid tire, a sheet or the like, and to provide a roll coated therewith. CONSTITUTION:A polyurethane or polyurethane urea composition comprising a prepolymer obtained by reacting a hydroxide of a liquid hydroxyisoprene polymer having 2.0 or more hydroxyl groups on the average per molecule with a polyisocyanate compound at 0-150 deg.C for 0.5-50hr and at least one compound selected between a polyol compound having a molecular weight of 500 or below and a polyamine compound having a molecular weight of 500 or below; and a coated roll prepared by coating a metallic surface with the composition.

Description

[Detailed description of the invention]

0001

[Industrial Field of Application] The present invention relates to a polyurethane composition having excellent water resistance, chemical resistance, heat resistance, weather resistance, etc., and a roll coated with the composition, and relates to a roll coated with the same, used for steel, paper manufacturing, etc. It can be effectively used as a material for rolls for office equipment, belts, solid tires, sheets, etc.

0002

[Prior Art and Problems to be Solved by the Invention] Conventionally, thermosetting polyurethane elastomers have been available in a wide range of hardness and elasticity, and have outstanding impact absorption, flexibility, and abrasion resistance. Because of its excellent oil resistance and high tear strength, it is suitable for general materials such as rolls for steel, paper manufacturing, office equipment, belts, solid tires, sheets, plates, round bars, square bars, pipes, square timbers, etc. used in

This thermosetting polyurethane elastomer is a prepolymer made by reacting polyoxypropylene glycol (PPG), polyoxytetramethylene glycol (PTMG), polyester polyol, etc. with an excess of polyisocyanate. (2
-chloroaniline) and other polyamines or polyols.

Among the polyols mentioned above, those using PTMG prepolymers have the best physical properties, but as technology has become more sophisticated in recent years, stricter water resistance, humidity resistance, and chemical resistance are required. There is a growing demand for superior raw materials.

The present inventors attempted to apply a butadiene oligomer containing a hydroxyl group, since it is known as a raw material for obtaining polyurethane with excellent water resistance and chemical resistance. Although the chemical resistance was improved, it was found that there was a major drawback in that the heat resistance and weather resistance were not good.

[0006]

[Means for solving the problem] Therefore, the present inventors
As a result of extensive research to solve these problems, we have found that a prepolymer obtained by reacting a hydrogenated liquid isoprene polymer containing a specific hydroxyl group with a polyisocyanate compound contains a specific polyol compound or polyamine. A polyurethane composition containing a compound is
It has been found that the above-mentioned conventional problems can be solved, and based on this knowledge, the present invention has been completed.

That is, the present invention provides a hydrogenated product (a) of a hydroxyl group-containing liquid isoprene polymer having an average number of hydroxyl groups per molecule of 2.0 or more and a polyisocyanate compound (b).
) with a molecular weight of 50
The present invention provides a polyurethane composition or a polyurethane-urea composition comprising at least one compound selected from 0 or less polyol compounds and polyamine compounds, and a coated roll coated with the composition.

In the present invention, as component (a), 1
A hydride of a hydroxyl group-containing liquid isoprene polymer having an average number of hydroxyl groups per molecule of 2.0 or more is used. The hydrogenated product of the hydroxyl group-containing liquid isoprene polymer can be obtained by hydrogenating the hydroxyl group-containing liquid isoprene polymer using a known method.

The number average molecular weight of the hydroxyl group-containing liquid isoprene polymer is usually 300 to 25,000, preferably 500 to 10,000, and the hydroxyl group content is 0.1
-10 meq/g, preferably 0.3-7 meq/g. Further, structurally, it is preferable that the total of cis-1,4 structure and trans-1,4 structure accounts for 70% or more. The hydroxyl group may be located either at the end of the molecular chain or inside the molecular chain, but it is particularly desirable that the hydroxyl group be located at the end of the molecular chain. Furthermore, two or more types of hydroxyl group-containing liquid isoprene polymers may be used.

[0010] Such a hydroxyl group-containing liquid isoprene polymer can be easily produced by a known method. Specifically, for example, isoprene monomer may be mixed with hydrogen peroxide or an azo compound having a hydroxyl group (e.g., 2,2'-
Azobis[2-methyl-N-(2-hydroxyethyl)
A hydroxyl group-containing liquid polyisoprene can be obtained by radical polymerization using a hydroxyl group-containing peroxide (for example, cyclohexanone peroxide, etc.) as a polymerization initiator.

The amount of polymerization initiator used in this case is, for example, 1.0 g of hydrogen peroxide per 100 g of diene monomer.
~50g is appropriate, and 2,2'-azobis[2-methyl-N-(2-hydroxyeral)-propionamide] or cyclohexanone peroxide is 5.0~10
0g is appropriate. Among these, hydrogen peroxide is preferably used as the polymerization initiator. Although the polymerization can be carried out without a solvent, it is preferable to use a solvent for ease of controlling the reaction. As the solvent, ethanol, isopropanol, n-butanol, etc. are usually used. Reaction temperature is 80-150℃, reaction time is 0.5
~15 hours is appropriate.

[0012] Furthermore, addition polymerizable monomers having 2 to 22 carbon atoms (butene, pentene, styrene, α-methylstyrene, acrylonitrile, acrylic acid and its esters, methacrylic acid, acids and their esters, vinyl chloride, vinyl acetate, acrylamide, etc.), carbon atoms 4 to 22
diene monomers (butadiene, chloroprene, 1,3
-pentadiene, cyclopentadiene, etc.) can also be added.

After the reaction is completed, the solution is distilled under reduced pressure to remove the solvent and obtain a hydroxyl group-containing liquid isoprene polymer.

In the present invention, a hydrogenated product of the hydroxyl group-containing liquid isoprene polymer obtained by further hydrogenating the hydroxyl group-containing liquid isoprene polymer thus obtained is used as component (a). . The hydride of such a hydroxyl group-containing liquid isoprene polymer can be produced by a known method using a homogeneous catalyst, a heterogeneous catalyst, etc.
It can be obtained by hydrogenating the hydroxyl group-containing liquid isoprene polymer produced as described above.

First, when using a homogeneous catalyst, hexane,
Using saturated hydrocarbons such as cyclohexene or aromatic hydrocarbons such as benzene, toluene, and xylene as a solvent,
The hydrogenation reaction is carried out at a reaction temperature of 0° C. and under a hydrogen pressure of from normal pressure to 50 kg/cm 2 . As a homogeneous catalyst, a Ziegler catalyst made of a combination of a transition metal halide and an alkylated product such as aluminum, alkaline earth metal, or alkali metal is used in an amount of about 0.01 to 0.1 mol % per double bond of the polymer. do it. The reaction usually completes in 1 to 24 hours.

On the other hand, when using a heterogeneous catalyst, saturated hydrocarbons such as hexane and cyclohexene, ethers such as diethyl ether, tetrahydrofuran (THF), and dioxane, alcohols such as ethanol and isopropanol, etc., or mixtures thereof. Using the system as a solvent, room temperature ~ 2
At a reaction temperature of 00℃, normal pressure ~ 100kg/cm2
The hydrogenation reaction is carried out under a hydrogen pressure of . As the heterogeneous catalyst, a catalyst such as nickel, cobalt, palladium, platinum, rhodium, or ruthenium may be used alone or supported on a carrier such as silica, diatomaceous earth, alumina, or activated carbon. The amount of catalyst used is 0.05 based on the weight of the polymer.
~10 wt% is appropriate. These catalysts may be used in combination of two or more. In addition, the reaction is usually 1 to 48
Finish in time.

After the reaction is completed, the catalyst is filtered off and the solution is distilled under reduced pressure to remove the solvent and obtain a hydride of a liquid isoprene polymer containing hydroxyl groups.

The hydride of the hydroxyl group-containing liquid isoprene polymer thus obtained has a number average molecular weight of 300.
~25,000, preferably 500-10,000,
It is desirable that the hydroxyl group content is 0.1 to 10 meq/g.

In the present invention, the hydrogenated liquid isoprene polymer containing hydroxyl groups must have an average number of hydroxyl groups per molecule of 2.0 or more. If the average number of hydroxyl groups is less than 2.0, the resultant composition will not only have lower water resistance and chemical resistance, but also significantly poorer heat aging resistance and weather resistance, which is not preferable. The average number of hydroxyl groups per molecule is expressed by the following formula.

[0020]

[Math 1]

The hydrogenation rate of the hydride of the hydroxyl group-containing liquid isoprene polymer is preferably at least 50%, particularly preferably at least 70%. Furthermore, a mixture of hydrides of two or more hydroxyl group-containing liquid isoprene polymers can also be used. In addition, hydrogenation rate,
That is, the hydrogenation rate of unsaturated double bonds in the polymer after the hydrogenation reaction is expressed by the following formula.

[0022]

[Math 2]

Next, in the present invention, a polyisocyanate compound is used as the component (b). This polyisocyanate compound is an organic compound having two or more isocyanate groups in one molecule, and has an isocyanate group reactive with the hydroxyl group of the hydride of the hydroxyl group-containing liquid isoprene polymer.

[0024] As this polyisocyanate compound,
Mention may be made of the usual aromatic, aliphatic and cycloaliphatic ones. Specifically, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MD
I), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, phenylene diisocyanate, naphthalene-1,5-diisocyanate, o-toluidine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl)thiophosphate, isopropylbenzene-2,4 - Aromatic polyisocyanates such as diisocyanates can be mentioned.

[0025] Also, xylylene diisocyanate (XD
I), tetramethylxylylene diisocyanate (TM
Aliphatic-aromatic polyisocyanates (polyisocyanates in which an isocyanate group is bonded to an aromatic ring via an aliphatic hydrocarbon, i.e., polyisocyanates that do not have an isocyanate group directly bonded to an aromatic ring in the molecule) such as isocyanate). Next, hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1
, 8-diisocyanate-4-isocyanate, methyloctane, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and other aliphatic polyisocyanates.

Furthermore, transcyclohexane-1,4
- Alicyclic polyisocyanates such as diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate. .

In addition, cyclized trimers (isocyanurate modified products), biuret modified products of the above polyisocyanate compounds, ethylene glycol, 1,4-butanediol, propylene glycol, dipropylene glycol,
Trimethylolpropane, polyether polyol, polymer polyol, polytetramethylene ether glycol, polyester polyol, acrylic polyol,
Addition reaction products of polyol compounds such as polyalkadiene polyols, hydrides of polyalkadiene polyols, partially saponified ethylene-vinyl acetate copolymers, and castor oil-based polyols with the above-mentioned polyisocyanate compounds can be used.

[0028] These polyisocyanate compounds can also be used as a mixture of two or more types, and furthermore, the isocyanate groups of these polyisocyanate compounds can be replaced with phenols, oximes, imides, mercaptans,
Alcohols, ε-caprolactam, ethyleneimine,
A so-called blocked isocyanate compound blocked with a blocking agent such as α-pyrrolidone, diethyl malonate, sodium bisulfite, or boric acid can also be used.

The prepolymer used in the present invention is a hydride of the above hydroxyl group-containing liquid isoprene polymer (a
) and the polyisocyanate compound (b), specifically the above (a).
) component and (b) component at 0 to 150°C, preferably 2
It can be obtained by reacting at a temperature of 0 to 120°C for 0.1 to 100 hours, preferably 0.5 to 50 hours. At this time, the molar ratio (NCO/OH) of the isocyanate groups (NCO) of the polyisocyanate compound (b) to the hydroxyl groups (OH) of the hydride (a) of the hydroxyl group-containing liquid isoprene polymer is usually 1.7 to 1. It is 5.0.

[0030] In order to obtain the prepolymer,
Various additives as shown below can be added at any appropriate time before, during or after the reaction. At this time, if a compound having a hydroxyl group, an amino group, etc. that reacts with an isocyanate group, such as a polyol compound or a polyamine compound, is blended as an additive, all the hydroxyl groups of the compound having a hydroxyl group (including hydrides) to be blended are (
OH), amino groups of compounds with all amino groups (
molar ratio of isocyanate groups to NH2) (NCO/
OH, NCO/NH2 or NCO/(OH+NH2
) are blended so that the final ratio becomes the above ratio.

That is, in the present invention, during prepolymer synthesis, low molecular weight polyols, polymerizable polyols,
Additives such as polyol compounds such as castor oil polyols and polyamine compounds can be added. Here, the polyol compound is a compound having two or more hydroxyl groups in one molecule, and examples thereof include low molecular weight polyols, polymerized polyols, and castor oil polyols as described above.

First, as the low molecular weight polyol, any of primary polyol, secondary polyol, and tertiary polyol may be used. Specific examples of such low molecular weight polyols include 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, cyclohexanediol, glycerin, N,N-bis-2-hydroxypropylarline, N,N'-bishydroxyisopropyl-2-methylpiperazine, propylene oxide adduct of bisphenol A Mention may be made of low molecular weight polyols containing a hydrogen group bonded to at least one secondary carbon, such as.

Furthermore, as polyols, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,
4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. can also be added. The molecular weight of these polyols usually ranges from 50 to 500.

Next, within the scope of the present invention,
A polymerizable polyol used as a polyurethane raw material can be added at the time of prepolymer synthesis. Specific examples of such polymerizable polyols include polyether polyols and modified products thereof, polytetraethylene ether glycol, THF/alkylene oxide copolymer polyols, epoxy resin-modified polyols, polyester polyols, polydiene polyols, and partially polymerized polyols. Polyols such as polyethylene-vinyl acetate copolymer can be used. The average molecular weight of these polyols is usually 500 to 10,000.

Furthermore, castor oil polyol can also be added during prepolymer synthesis. Examples of castor oil polyols include castor oil, hydrogenated castor oil, castor oil transesterified products, and a mixture of two or more of these polyols can also be used.

In the present invention, further examples of additives that can be added during prepolymer synthesis include polyamine compounds. Here, the polyamine compound is a compound having two or more active hydrogen-containing amino groups in one molecule. Specifically, such polyamine compounds include aliphatic polyamines such as hexamethylene diamine and polyoxypropylene polyamine, 3,3'
-Alicyclic polyamines such as dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dichloro-4,4
'-Diaminodiphenylmethane, 3,5-diethyltoluene-2,4-diamine, 3,5-diethyltoluene-
Examples include aromatic polyamines such as 2,6-diamine.

The above-mentioned polyol compound and polyamine compound may be used in an amount of 100 parts by weight or less, based on 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene polymer.
It can be added at the time of prepolymer synthesis, preferably in a proportion of 50 parts by weight or less.

Next, in the present invention, at least one compound selected from polyol compounds and polyamine compounds having a molecular weight of 500 or less is added to the prepolymer obtained as described above to form a polyurethane composition or a polyurethane-urea composition. get.

[0039] Here, the polyol compound is a compound having two or more hydroxyl groups in one molecule, and it is necessary to use one with a molecular weight of 500 or less. Specifically, a polyol compound with a molecular weight of 500 or less, preferably has a molecular weight of 60-48
0 low molecular weight polyols and castor oil-based polyols. Unless the molecular weight is 500 or less, the object of the present invention cannot be achieved.

[0040] As the low molecular weight polyol, any of primary polyol, secondary polyol, and tertiary polyol may be used. Specific examples of such low molecular weight polyols include 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, cyclohexanediol, glycerin, N,N-bis-2-hydroxypropylaruline, N,N'-bishydroxyisopropyl-2- Mention may be made of low molecular weight polyols containing a hydrogen group bonded to at least one secondary carbon, such as methylpiperazine, propylene oxide adduct of bisphenol A.

Furthermore, as polyols, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,
4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. can also be added. The molecular weight of these polyols is 5
00 or less, usually in the range of 50 to 500.

Furthermore, castor oil polyols having a molecular weight of 500 or less can also be used. Examples of castor oil polyols include castor oil, hydrogenated castor oil, castor oil transesterified products, and a mixture of two or more of these polyols can also be used.

Next, in the present invention, the above molecular weight 50
A polyamine compound can be used instead of a polyol compound of 0 or less. Here, what is a polyamine compound?
It is a compound that has two or more amino groups containing active hydrogen in one molecule. Specifically, such polyamine compounds include aliphatic polyamines such as hexamethylene diamine and polyoxypropylene polyamine;
Alicyclic polyamines such as 3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dichloro-4
, 4'-diaminodiphenylmethane, 3,5-diethyltoluene-2,4-diamine, and 3,5-diethyltoluene-2,6-diamine.

In the present invention, a catalyst may be added to promote the reaction, or inorganic fillers, organic fillers, viscosity modifiers, and other additives may be added depending on the purpose. .

Examples of the catalyst include triethylenediamine, tetramethylguanidine, N,N,N'N
'-Tetramethylhexane 1,6-diamine, N,N,
N'N"N"-pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, 1,2-dimethylimidazole, N-methyl-N'-(2-dimethylamino)-ethylpiperazine, diazabicycloundecene tertiary amines and their carboxylates such as stannath octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptide, dioctyltin thiocarboxy Examples include organometallic compounds such as phenylmercury propionate, phenylmercury propionate, and octenoate.

The amount of such a catalyst added is at most 10 parts by weight per 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene polymer. If the amount added exceeds 10 parts by weight, not only the curing accelerating effect reaches a plateau, but also the risk of local abnormal reaction (gelation) increases, which is not preferable.

[0047] Examples of inorganic fillers include zinc,
Asbestos, alumina, aluminum, kaolin clay, glass bulb, glass flake, glass fiber, carbon (channel black, furnace black, acetylene black, thermal black), carbon fiber, nepheline, cryolite, graphite, silica, wollastonite, diatomaceous earth, zinc oxide, magnesium oxide, zirconium oxide,
Titanium oxide, iron oxide, aluminum hydroxide, magnesium hydroxide, slate powder, zeolite, quartz powder, calcium carbonate, magnesium carbonate, talc, potassium titanate, boron nitride, feldspar powder, copper, nickel, molybdenum disulfide, barium sulfate , whiting, waxite clay, mica, gypsum, etc.

Examples of organic fillers include rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood flour, and natural fibers such as cotton, hemp, wool, and silk.
Synthetic fibers such as nylon, polyester, vinylon, acetate, acrylic, polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate (PC), polyethylene terephthalate (P)
ET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polyvinyl chloride (
Examples include powders or granules of synthetic resins such as PVC), epoxy, and phenol.

The amounts of these inorganic fillers and organic fillers are as follows: hydride 1 of the hydroxyl group-containing liquid isoprene polymer
00 parts by weight, it is 100 parts by weight or less.

[0050] Examples of viscosity modifiers include plasticizers such as dioctyl phthalate, paraffinic, naphthenic, and aromatic process oils, olefin oligomers,
Alkylbenzenes, alkylnaphthalenes, alkyldiphenylethanes, silicone oils, etc. can be used. The amount of these viscosity modifiers to be blended is not particularly limited, but is usually 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene polymer.

Furthermore, as other additives, solvents, tackifier resins, antiaging agents, antioxidants, ultraviolet absorbers, flame retardants, antifoaming agents, antifoaming agents, etc. may be added before, during, or during the reaction. It can also be added at any suitable time later.

The solvent is added to reduce viscosity, and specifically includes hydrocarbon solvents such as n-hexane, cyclohexane, toluene, and xylene, ketone solvents such as methyl ethyl ketone and cyclohexanone, and esters such as butyl acetate. Examples include solvents, ester solvents such as tetrahydrofuran, N,N-diethylformamide, and dimethyl sulfoxide. The amount of the solvent to be blended is not particularly limited, but it is usually 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the hydride of the hydroxyl group-containing liquid isoprene polymer.

[0053] Furthermore, a tackifier resin is used to adjust the adhesive force and adhesion force. Specifically, for example, alkylphenol resins, terpene resins, terpenephenol resins, xylene formaldehyde resins, rosins, hydrogenated rosins, coumaron resins, aliphatic, alicyclic and aromatic petroleum resins, and the like are used.

Furthermore, in order to improve heat resistance and weather resistance, antioxidants such as hindered phenol-based, hindered amine-based, and benzotriazole-based antioxidants, ultraviolet absorbers, etc. are added, and phosphorus compounds, Flame retardants such as halogen compounds and antimony oxide, antifoaming agents such as silicone compounds, and antifoaming agents such as zeolite and quicklime can also be blended.

The polyurethane or polyurethane-urea composition of the present invention may be composed of the prepolymer obtained as described above and at least one compound selected from polyol compounds and polyamine compounds having a molecular weight of 500 or less. Although there is no particular restriction on the preparation method, a general preparation method is shown below. For example, the composition may include a prepolymer as described above and at least one compound selected from a polyol compound and a polyamine compound having a molecular weight of 500 or less at a temperature of 0 to 150°C.
It can be obtained by reacting for 500 minutes.

These components include the hydroxyl group (OH) of the polyol compound and/or the amino group (N
H2), isocyanate groups of the prepolymer (N
CO) is blended so that the molar ratio (NCO/OH, NCO/NH2 or NCO/(OH+NH2)) is 0.5 to 1.5. At this time, when the prepolymer and the polyol compound react, a polyurethane composition containing urethane bonds is obtained. Further, when the prepolymer and the polyamine compound react, a polyurethane-urea composition containing urea bonds and urethane bonds generated during prepolymer synthesis is obtained.

[0057] The composition thus obtained is cast,
By molding and curing using various molding methods such as press molding, centrifugal molding, and coating, various cured products that can be used for the composition of the present invention can be obtained.

[0058]

EXAMPLES Next, the present invention will be explained in detail by examples.

Preparation Example 1 (1) Preparation of liquid polyisoprene having a hydroxyl group at the end of the molecular chain 200 g of isoprene, 40 g of hydrogen peroxide solution with a concentration of 20%, and 100 g of isopropanol were charged into a 1 liter stainless steel pressure-resistant reaction vessel, and the temperature was increased. The reaction was carried out at 120° C. and a maximum pressure of 8 kg/cm 2 for 2 hours. After the reaction was completed, the reaction mixture was placed in a separatory funnel, 600 g of water was added thereto, and the mixture was shaken. After being allowed to stand for 3 hours, the oil layer was separated. From this oil layer, remove the solvent, monomer, and low boiling point components by 2 mm.
Hg was distilled off at 100°C for 2 hours to produce liquid polyisoprene with a hydroxyl group at the end of the molecular chain (yield 66% by weight).
I got it. The number average molecular weight of this product is 2240, the hydroxyl group content is 0.96 meq/g, and the viscosity is 64 poise/g.
The temperature was 30°C and the bromine number was 220g/100g. The average number of hydroxyl groups per molecule at this time is 2.15. In addition, the structural analysis results by 1H-NMR indicate that trans-
57% 1,4-structure, 33% cis-1,4 structure, 1
, 2 structure accounted for 6%, and 3,4 structure accounted for 4%.

(2) Preparation of hydride of liquid polyisoprene having a hydroxyl group at the end of the molecular chain 100 g of the liquid polyisoprene having a hydroxyl group at the end of the molecular chain obtained as in (1) above, containing 5% by weight of ruthenium. 5 g of ruthenium carbon catalyst and 100 g of cyclohexane as a solvent were charged, and a hydrogenation reaction was carried out at 150° C. for 6 hours under a hydrogen pressure of 50 kg/cm 2 G. After the reaction was completed, the catalyst was separated and removed from the reaction solution through a 0.45 μm membrane filter, and then heated at 2 mmHg and 1
The solvent was distilled off at 10°C for 2 hours. As a result, a hydride of liquid polyisoprene having a hydroxyl group at the end of the molecular chain was obtained. The number average molecular weight of this product is 2310, the hydroxyl group content is 0.94 meq/g, and the viscosity is 402
Poise/30°C, bromine number was 1g/100g. The average number of hydroxyl groups per molecule at this time was 2.17.

Preparation Example 2 (1) Preparation of liquid polyisoprene having a hydroxyl group at the end of the molecular chain A 1 liter stainless steel pressure-resistant reaction vessel was charged with 200 g of isoprene, 100 g of hydrogen peroxide solution with a concentration of 30%, and 300 g of isopropanol. The reaction was carried out under the conditions of 115°C, maximum pressure of 7 kg/cm2, and reaction time of 2.5 hours. After the reaction was completed, the reaction mixture was placed in a separatory funnel, 600 g of water was added thereto, and the mixture was shaken. After being allowed to stand for 3 hours, the oil layer was separated. The solvent, monomer, and low-boiling components were distilled off from this oil layer under conditions of 2 mmHg, 100° C., and 2 hours to obtain liquid polyisoprene having a hydroxyl group at the end of the molecular chain (yield: 71% by weight). The number average molecular weight of this product is 1380, and the hydroxyl group content is 1.55 meq/
g, and the viscosity was 46 poise/30°C. 1 at this time
The average number of hydroxyl groups per molecule is 2.14. Also,
The structural analysis results by 1H-NMR show that trans-1,
56% 4-structure, 33% cis-1,4 structure, 1,2
6% had a structure, and 5% had a 3,4 structure.

(2) Preparation of hydride of liquid polyisoprene having a hydroxyl group at the end of the molecular chain 100 g of the liquid polyisoprene having a hydroxyl group at the end of the molecular chain obtained as in (1) above, containing 5% by weight of ruthenium. 5 g of ruthenium carbon catalyst and 100 g of cyclohexane as a solvent were charged, and a hydrogenation reaction was carried out at 150° C. for 6 hours under a hydrogen pressure of 50 kg/cm 2 G. After the reaction was completed, the catalyst was separated and removed from the reaction solution through a 0.45 μm membrane filter, and then heated at 2 mmHg and 1
The solvent was distilled off at 10°C for 2 hours. As a result, a hydride of liquid polyisoprene having a hydroxyl group at the end of the molecular chain was obtained. The number average molecular weight of this product is 1420, the hydroxyl group content is 1.54 meq/g, and the viscosity is 298.
Poise/30°C, bromine number was 1g/100g. The average number of hydroxyl groups per molecule at this time was 2.19.

Preparation Example 3 (1) Preparation of liquid polyisoprene having a hydroxyl group at the end of the molecular chain In a 1 liter glass-lined pressure-resistant reaction vessel, 20
0 ml of n-hexane was charged, and 7.15 g of m-divinylbenzene was added and dissolved. This was cooled to -10°C, and a 2.5M n-hexane solution of n-butyllithium
．． 0 ml was added dropwise over 30 minutes. This contains isoprene 14
9.6 g was added and polymerized at 40° C. for 45 minutes. Then, 176.4 g of ethylene oxide was added to stop the reaction, and the resulting product was poured into 3 liters of methanol. The precipitate was treated at 2 mmHg, 100°C, and for 2 hours to obtain liquid polyisoprene (which has hydroxyl groups in its molecules).
A yield of 96% by weight was obtained. The number average molecular weight of this substance is 3
120, and the hydroxyl group content was 0.61 meq/g. The average number of hydroxyl groups per molecule at this time is 1.9
It is 0.

(2) Preparation of hydride of liquid polyisoprene having hydroxyl groups in the molecule 100 g of liquid polyisoprene having hydroxyl groups in the molecule obtained as in (1) above, ruthenium carbon containing 5% by weight of ruthenium. 5 g of catalyst and 100 g of cyclohexane as a solvent were charged, and a hydrogenation reaction was carried out at 150° C. for 6 hours under a hydrogen pressure of 50 kg/cm 2 G. After the reaction was completed, the catalyst was separated and removed from the reaction solution through a 0.45 μm membrane filter, and then heated at 2 mmHg and 110
The solvent was distilled off at ℃ for 2 hours. As a result, a hydride of liquid polyisoprene having a hydroxyl group in the molecule was obtained. The number average molecular weight of this product was 3210, and the hydroxyl group content was 0.58 meq/g. 1 at this time
The average number of hydroxyl groups per molecule is 1.86.

Production Examples 1 to 11 (Production of Prepolymer) A polyisocyanate compound of the formulation shown in Table 1 was added to a 3-liter separable flask equipped with an oil bath, a stirrer, a thermometer, and an Allene condenser. Add the ingredients except for the following, and stir at 80°C for 1 hour under a reduced pressure of 2 mmHg.
A dehydration operation was performed. Thereafter, a polyisocyanate compound was added, and a reaction was carried out at 80° C. for 3 hours under a nitrogen stream to obtain a prepolymer. After the reaction was completed, the temperature was lowered, and the container was sealed and stored in a nitrogen-sealed container. The isocyanate content of the obtained prepolymer is shown in Table 1.

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[Table 1]

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[Table 2]

[Footnotes to Table 1] *1: Manufactured by Idemitsu Atochem Co., Ltd., trade name Poly bd
R-15HT, OH content = 1.82 meq/g *2: Coronate T- manufactured by Nippon Polyurethane Industry Co., Ltd.
100, NCO content = 48.3 wt% *3: Manufactured by Daicel-Hüls Co., Ltd., NCO content = 37
．． 8wt% *4: Liquid paraffin KP-8*5 manufactured by Idemitsu Kosan Co., Ltd.
: Kyowa Hakko Co., Ltd., 2-ethyl-1,3-hexanediol, OH content = 13.68 meq/g *6: Phase separation was observed in the obtained prepolymer, making it impossible to measure *7: During the reaction The entire system gelled and no prepolymer could be obtained.

Examples 1 to 8 and Comparative Examples 1 to 3 Of the compositions shown in Table 2, the prepolymer was preheated to 90°C, and the other compositions were separately heated to 120°C. The mixture was mixed and stirred for 2 minutes. This is done using a centrifugal molding machine (manufactured by Toho Kikai Kogyo Co., Ltd., ES-300).
) and rotary molded at 100° C. and 800 rpm for 1 hour to obtain a cured product with a thickness of 2 mm. After curing this cured product at 120° C. for 1 hour and further at 25° C. for 168 hours, it was subjected to a hot water resistance test, a chemical resistance test, a heat aging resistance test, and a weather resistance test as described below. The results are shown in Table 2.

1) Hot water resistance test The cured product was punched out into a shape of 20 x 50 x 2 mm, and the rate of weight change was evaluated after immersing it in distilled water at 70°C for 336 hours. The implementation of the test and calculation of the rate of change are based on JIS K 6.
301 Section 12 (immersion test).

2) Chemical resistance test The same cured product as above was immersed in an alkaline aqueous solution prepared by dissolving Ca(OH)2 in distilled water to have a pH of 11, and evaluated in the same manner as the hot water resistance test. .

3) Heat aging resistance test A cured product similar to the above was punched out in the shape of a No. 3 dumbbell specified in JISK 6301, and heated in a gear oven for 12 hours.
A heat aging test was conducted at 0°C for 168 hours. The rate of change in tensile strength and elongation before and after the test was evaluated. Calculation of the rate of change was based on JIS K 6301 Section 12.

4) Weather resistance test An accelerated weather resistance test was carried out under the following conditions.・Testing machine model: Suga Test Instruments Co., Ltd., WEL-6X-L
HP (using WEL xenon lamp) ・Black panel temperature: 60℃ ・Humidity: 60% RH ・Irradiation time: 500 hours ・Irradiation/(irradiation + rain) cycle: 102min/18
min

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[Table 3]

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[Table 4]

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[Table 5]

[Footnotes to Table 2] *1: UNIROYAL Inc.
Co., Ltd., poly(oxytetramethylene) glycol/tolylene diisocyanate prepolymer, trade name: Adiprene L-100, NCO content 4.1 wt%. *2: Manufactured by Ihara Chemical Co., Ltd., trade name: Iharakyuamine MT, amine equivalent: 7.49 meq/g. *3: Manufactured by Nippon Nyukazai Co., Ltd., propylene oxide adduct of bisphenol A, OH content 5.03 meq/g. Number average molecular weight: 400 *4: Cracks were generated on the sheet surface.

Example 9 On the surface of a steel roll with a diameter of 40 mm and a length of 300 mm,
A composition having the same composition as in Example 2 was coated to a thickness of 2 mm, first at 100°C for 5 hours, and then for 1 hour.
It was cured at 20° C. for 1 hour to obtain a coated roll (diameter 44 mm). The two coated rolls were pressed parallel to each other with a pressing pressure of 2 kgf while keeping them in contact with each other, and the same immersion liquid as that used in the chemical resistance test in Example 2 was used (however, the temperature was 44°C). After immersing the lower sides of the cross-sectional circles of both rolls up to 7 mm from the center (up to 15 mm from the lower end of the arc), both rolls were soaked inwardly at 200 rpm for 576 hours while keeping them in contact. After rotation, the coated surface was observed, but no change was observed.

Comparative Example 4 A test was conducted in the same manner as in Example 9, except that a roll coated with a composition having the same composition as that used in Comparative Example 2 was used. Swelling, tackiness, and whitening and devitrification were observed on the coated surface after rotation.

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[Effects of the Invention] The polyurethane composition or polyurethane-urea composition of the present invention is a thermosetting polyurethane elastomer that has excellent (hot) water resistance and chemical resistance, as well as excellent heat aging resistance and weather resistance. be. Therefore, the composition of the present invention can be suitably used as general materials such as rolls for steel, paper manufacturing, and office equipment, as well as various belts, solid tires, sheets, pipes, and the like.

Claims (2)

[Claims] Claim 1: A prepolymer obtained by reacting a hydride (a) of a hydroxyl group-containing liquid isoprene polymer having an average number of hydroxyl groups per molecule of 2.0 or more with a polyisocyanate compound (b), and a molecular weight A polyurethane composition or a polyurethane-urea composition comprising at least one compound selected from 500 or less polyol compounds and polyamine compounds. 2. A coated roll comprising a metal surface coated with the composition of claim 1.