JPS60155220A - Friction and abrasion-resistant polyurethane - Google Patents

Abstract

PURPOSE:A polyurethane having a high heat distortion temperature (>=about 100 deg.C) and excellent friction and abrasion resistances, prepared by reaction curing of a composition comprising a specified mixed polyol, a polyisocyanate and an oil component. CONSTITUTION:A mixed polyol comprising 50-90pts.wt. aromatic amine-based polyoxyalkylene glcyol of an OH value of 200-700 and 50-10pts.wt. polyol of an OH value of 50-1,830 (water conten <=about 0.05%) is mixed with a polyisocyanate (e.g., 4,4'-diphenylmethane diisocyanate) and about 1-15pts.wt. alipphatic oil component (e.g., turpentine oil) and/or aromatic oil component (e.g., naphthenic process oil) per 100pts.wt. formed polyurethane resin, and the resulting mixture is poured into a desired mold and cured at about 50-120 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new polyurethane, and particularly to a polyurethane that has a high heat distortion temperature and excellent friction and abrasion resistance.

Rigid polyurethane is broadly classified into non-foamed molded products and foamed molded products, and foamed molded products are further classified into high-foamed molded products and low-foamed molded products depending on the foaming rate. The non-foamed molded products and the low-foamed molded products are used as ennealing resins for various equipment parts, automobile parts, and the like.

Conventional rigid polyurethanes are composed of one or more polyfunctional aliphatic or aromatic polyol monomers, polyoxyalkylene polyols, especially polyoxypropylene polyols, or polyfunctional aliphatic or aromatic polyester polyols. A polyol component consisting of a mixture and a polyincyanate component consisting of one or more mixtures of aliphatic or aromatic polyinsyanate or polyinthiocyanate are cured and molded in the presence of a catalyst, a blowing agent, etc.

However, these polyurethane molded products generally have poor heat resistance, and when heat distortion temperature (measured according to ^STM D-648) is taken as a measure for evaluating heat resistance, conventional polyurethane molded products have a temperature of 70 to 70 at most. 90°C
is the limit, and it was difficult to exceed 90°C with practical strength. On the other hand, heat resistance can be improved by introducing an incyanurate group obtained by trimerizing incyanate, but at the same time, the resulting molded product becomes extremely brittle and cannot be put into practical use.

Also, as an engineering resin, P (load kI?/c
It is said that it is preferable for the sliding member to have a Pv value, which is the product of m2) and (velocity+n/min), of 800 or more. However, the current rigid polyurethane made of polyol and polyisocyanate has a PV value of 400.
It has a deficiency α that can only be used under conditions of low speed and low load. Generally improves friction and wear resistance.
Molybdenum disulfide and graphite are used to strengthen rigid polyurethanes, but these compounds do not have a significant effect on rigid polyurethanes, but rather reduce the heat distortion temperature, tensile strength, bending strength and impact resistance.

Therefore, in order to improve friction resistance and wear resistance, we tried adding various silicone resins, fluorine oligomers, titanium coupling agents, silane coupling agents, encapsulated oil, etc., but none of them resulted in foaming or fit resistance. It was found that properties such as impact resistance, tensile strength, and bending strength deteriorated. Furthermore, fiber reinforcement had only a negative effect.

The object of the present invention is to have high thermal stability, friction resistance,
Our goal is to provide polyurethane with excellent wear resistance.
In particular, the object of the present invention is to provide a new polyurethane that has a high heat distortion temperature of at least 100° C., which could not be achieved with conventional rigid polyurethanes, and has practical strength, especially its impact resistance.

Another object of the present invention is to provide a polyurethane with friction and wear resistance that can be used at low speeds and high loads, high speeds and low loads, and high speeds and high loads.

The present invention relates to a polyurethane obtained by the reaction of a polyol component having at least a difunctional hydroxyl group and an at least difunctional polyisocyanate component, wherein the polyol component is an aromatic amine-based polyoxyalkylene having a hydroxyl value of 200 to 700. 50 to 90 parts by weight of polyol and 10 to 50 parts of polyol with a hydroxyl value of 50 to 1830
A friction resistant product characterized in that a mixed polyol consisting of parts by weight is used, and an aliphatic or aromatic oil component is added to the polyol component and/or polyisocyanate component.
i (relating to abrasive polyurethane)

The polyurethane of the present invention can be used in various fields, but in particular, various industrial parts that require heat resistance, friction resistance, and wear resistance, such as WJ! It is useful as parts of e-materials and ground coverings thereof.

In the present invention, an aromatic amine-based polyoxyalkylene polyol having a hydroxyl value of 200 to 700 and a hydroxyl value of 50 to 18 are used.
A mixed polyol consisting of 30 conventional polyols is used.

the above-mentioned at least bifunctional hydroxyl value 200 to 700,
Preferably, the aromatic amine-based polyoxyalkylene polyol having a molecular weight of 300 to 500 is prepared by known methods such as aromatic monoamines such as aniline (or 2,4- and 2,8-)
Lylene diamine (TDA) and so-called crude 1 sip^, 4
, 4'-Diami7cyphenylmethane and polymethylene polyphenylene polyamine obtained by condensation of aniline and formalin, ortho- or meta- or ha-paraphenylene diamine, meta- or para-xylylene diamine, and other aromatic diamines and aromatic polyamines. It is a polyol obtained by adding one or more types of fullylene oxide such as propylene oxide and ethylene oxide to one or more species, and substantially no free primary or secondary amine remains.

In order to lower the viscosity and improve the processability of the above-mentioned aromatic amine-based polyol, in addition to the aromatic amines, the following aliphatic glycols and the like can be used as co-initiators in the synthesis stage. For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, chrycerin, trimethylolpropane,
Multifunctional Ji? such as glucose, sorbitol, and sucrose? Examples include aliphatic amines such as aliphatic glycols, ethanolamine, jetanolamine, triethanolamine, and ethylenediamine, and aliphatic alkafuramines. It is preferable to use

Specific examples of polyols having a hydroxyl value of 50 to 1,830 include the following polyols.

(,) An aromatic polyol having a hydroxyl value of 50 to 850 and having at least difunctional hydroxyl groups.

(a) Hydroxyl group obtained by adding alkylene oxide such as propylene oxide or ethylene oxide to a monocyclic or polycyclic aromatic compound having at least two hydroxyl groups such as hydroquinone, pyrogallol, and 4,4'-isopropylidenephenol. Polyols with a valence of 250 to 600 (ro) Hepthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and other aromatic polybasic acids, propylene oxide,
A polyol with a hydroxyl value of 300 to 500 obtained by adding an alkylene oxide such as ethylene oxide, (c) meta-xylylene glycol, para-xylylene glycol (d), an aromatic dicarboxylic acid such as 7-talic acid, isophthalic acid, terephthalic acid, or Anhydrides or lower alcohol esters thereof, and/or aliphatic dicarboxylic acids such as adipic acid and succinic acid are used as acid components, and aliphatic polyols such as ethylene glycol, 1,4-butylene glycol, and trimethylolpropane, 1, 4-cyclohexanediol, 1,4-cyclohexane dimetatool, β, β, β゛, β°-tetramethyl-2,4,8,
10-tetraoxaspiro(5,5)-undecane-3
, 9-jethanol, or the above (
A polyester polyester with a hydroxyl value of 50 to 450 containing the polyols of (a), (b), and (c) as polyol components When these aromatic polyols of (a) are used together, the amount should not exceed 50% by weight based on the total polyol. , and preferably has an average hydroxyl value of 200 to 500 ν1° (1)) A polyfunctional aliphatic glycol having a hydroxyl value of 800 to 1830.

For example, ethylene glycol, diethylene glycol, propylene gellicol, dipropylene glycol, glycerin, triethanolamine, etc. may be mentioned, and they are used together in an amount of 10% by weight or less based on the total polyol.

(c) A polyfunctional aliphatic polyol having a hydroxyl value of 300 to 800.

For example, one or more of sucrose, sorbitol, glucose, hentaerythritol, trimethylolpropane, glycerin, ethylenediamine, jetanolamine, water, etc., and one or more of fullylene oxides such as propylene oxide, ethylene oxide, etc. It is preferable to use the added polyol in an amount of 40% by weight or less based on the total polyol.

The polyols listed above are particularly preferred,
It is possible to use polyols other than these with a hydroxyl value of 50 to 1,830.

In the present invention, a mixed polyol consisting of 50 to 90 parts by weight of the aromatic amine-based polyoxyalkylene polyol described in 1. and 10 to 50 parts by weight of a conventional polyol is used.

Then, the average hydroxyl value of the mixed polyol component was set to 2 (
10-700. When the value is preferably 300 to 500, the impact strength of the polyurethane obtained is surprisingly contrary to expectations, and it has been found that a synergistic effect can be obtained by increasing the impact strength without substantially reducing the high IIDT. That is, the impact strength of the polyurethane using the above two types of polyol components in combination is superior to the impact strength of each polyurethane when the above two types of polyol components are used alone.

Although the reason for this has not yet been fully elucidated, the impact strength of conventional hard polyurethanes tends to decrease when the IIDT is increased, and it is extremely difficult to increase both HDT and impact strength. Considering this, the above effects of the present invention are surprising.

In addition, in the present invention, it has been found that by using an aromatic amine-based polyol and a normal polyol in combination, not only high HDT and impact strength can be obtained, but also processability, moldability, etc. can be effectively improved. . The improvement in processability mentioned here is due to the introduction of the aromatic amine-based polyol, which lowers the viscosity of the polyol liquid, and also improves the so-called compatibility, which allows the polyol liquid and polyisocyanate-1 liquid to mix well even at room temperature. Moreover, since the chemical reaction proceeds due to the moderate autocatalytic action of the aromatic tertiary amine, no catalyst is intentionally required. Therefore, since there is no need to add a catalyst to the polyol liquid, the storage stability of the polyol liquid can be improved.

Furthermore, improvement in moldability includes increasing the strength of the polyurethane molded product upon demolding due to the introduction of a primary network using at least a bifunctional aromatic amine-based polyol.

These polyols need to have a moisture content of 0.05% or less, preferably 0.02% or less before reacting with incyanates. Polyisocyanates should also be sufficiently degassed in advance (If this is neglected, unnecessary foaming will occur during the curing reaction.

However, this is of course not the case when obtaining a foam.

As the polyisocyanate component of the present invention, various at least difunctional aliphatic, alicyclic, and aromatic polyisocyanates known in the field of polyurethane production can be used, but aromatic polyisocyanates are particularly preferably used. Ru. For example, 4,4'-diphenylmethane incyanate (MDI) and carposiimide-modified MDI
(e.g. Nippon Polyurethane Co., Ltd. MTL), polymethylene polyphenylisocyanate (PAPI), polymeric polyisocyanate (e.g. Bayer Urethane 4)
4v), 2,4- and 2,6-tolylene diisocyanate (TDT), ortho-toluidine diisocyanate (T
ODI), Na7 ethylene diisocyanate) (Null)
, quinrylene diisocyanate) (XDI), etc. are preferably used.

The polyol component and the polyisocyanate component can be reacted by either the one-shot method or the prepolymer method. The reaction between polyol and polyisocyanate preferably has an isocyanate index of 100 to 18.
0, particularly preferably in the range of 105 to 160; outside this range, heat resistance decreases regardless of whether the isocyanate index becomes small or large. Although the cause of this is not clear, it is presumed that it is due to a decrease in the substantial molecular weight of the polymer. In order to lower the coefficient of friction, the incyanate index is preferably 100 to 115.

In the present invention, in order to improve the friction and abrasion resistance of polyurethane, an aliphatic or aromatic oil component is added to the polyol component and/or polyisocyanate component described in 1. Fatty oil release also includes alicyclic oil release. The above-mentioned fat release oil is preferably a lubricating oil specified by JIS, and specific examples thereof include turbine oil, gear oil, machine oil, bearing oil, refrigeration machine oil, and lubricating oil for internal combustion engines. In addition, as the aromatic oil, for example, a petroleum-based softener called extengu oil or process oil is used, and various softeners such as paraffin-based process oil, naphthenic process oil, and aromatic process oil are used. can be used.

In the present invention, the above fatty oil or aromatic oil is used alone or as a mixture, and its rsovc [viscosity grade, C3t (IIIIII12/S), 40°C] is 68
~io.

is preferable, and 100 to 680 is particularly preferable. In this range, a bleed phenomenon in which the oil oozes out onto the surface of the polyurethane occurs, and this bleed phenomenon produces a grease effect and improves friction and abrasion resistance.

In the present invention, the amount of the oil component added is 1
It is preferably 1 to 15 parts by weight, and 2 to 1 parts by weight per 00 parts by weight.
Particularly preferred is 0 parts by weight. Within this range, friction resistance and abrasion resistance can be improved without reducing the tensile strength, bending strength, impact strength, etc. of the polyurethane obtained.

By adding the oil component in this way, the polyurethane of the present invention has better resistance than polyacetal resin, monomer cast nylon resin, and high density polyethylene tel11t)! #Abrasion, tI' Torque by imparting abrasion properties.

However, bleeding of oil components onto the surface may adversely affect the appearance of the product and impair its commercial value. To solve this drawback, fat-free oil and solid lubricants such as molybdenum disulfide, graphite, and carbon were added to the urethane resin after kneading, but even if the fat-free oil and solid lubricant were the same, the fat-free urethane resin Bleed to the surface could not be prevented.

As a result of further intensive research, it was found that in the present invention, it is more preferable to use an oil component and an inorganic compound powder capable of retaining the oil component in combination.

Inorganic compounds used here include, for example, metal hydroxides such as calcium hydroxide, zinc hydroxide, and aluminum hydroxide, metal sulfates such as barium sulfate, and metal sulfites such as barium sulfate and sulfite. One or more metal halides such as sulfites, sodium chloride, and potassium chloride can be used. If the particle size of the inorganic compound powder is large, wetting by the oil component will be insufficient, and it will become scattered in the polyurethane resin, causing a local decrease in physical properties and adversely affecting the resin surface due to secondary heating, so the particle size should be 50μ or less. is preferred.

Further, in the present invention, the mixing ratio of the oil component and the inorganic compound powder is preferably 2 to 6 ha by weight, and more preferably 3 to 5/1. Kneading the oil component and inorganic compound powder is
It is preferable to knead equal amounts of both in a normal weight ratio using a ball mill or the like, and dilute with a desired amount of oil component before use.

Adding an oil component and an inorganic compound powder as an oil carrier to polyurethane resin does not lower the heat distortion temperature, but
Impact strength, tensile strength and bending strength are slightly reduced.

Therefore, we improved impact strength, tensile strength and bending strength,
As a result of further intensive research in order to solve the oil bleed phenomenon, it has become possible to solve the above problems by using a polymer polyol together with the oil component in the present invention.

In the present invention, the polymer polyol is a polyether polyol graft-polymerized with a monomer having a vinyl group, and preferably has a hydroxyl value in the range of about 56 to 200. As a specific example, a representative example of a commercially available product is POP manufactured by Mitsui Nisso: '11/28.3
2/30.34/45.36/28.40745 and the like. The amount of the polymer polyol added is preferably 2 to 30 parts by weight, and the most desirable range is 6 to 20 parts by weight, based on 100 parts by weight of the polyol component. Further, the polymer polyol is preferably added to the polyol component and/or the polyisocyanate component in a state mixed with the oil component.

Incidentally, it is also possible to suppress the bleeding phenomenon of the oil component to the surface by using a mixture of the oil component, the polymer polyol, and the Matsuki compound powder as an oil carrier.

Although a catalyst is not particularly required for producing the polyurethane of the present invention, known catalysts such as tertiary amines such as triethylene diamine and organometallic compounds such as dibutyltin dilaurate can also be used. However, incyanate trimerization catalysts that produce isocyanurate rings are not preferred. Incidentally, it is also possible to prepare an inorganic filler-containing polyurethane by preliminarily mixing an amorphous filler with a polyol or polyisocyanate. Graphite, silicon carbide, aluminum oxide,
Examples include molybdenum disulfide, which has a hardness and a molding yield of 11δ.
It is effective in improving friction coefficient, friction coefficient, wear resistance, etc. In the present invention, it is also possible to form a foam by using water, a halogenated hydrocarbon such as trichloroethane, or an organic blowing agent such as azobisisobutyronitrile.

In the present invention, the curing reaction can be carried out, for example, as follows. First, the liquid temperature of the compound is set to room temperature to 120°C, and the temperature of the casting mold is set to 50 to 120°C, and the mixture is cast and cured.
Type IIL. Although the cured molded product of the present invention has a higher 11rlT than conventional polyurethane molded products as it is, properties such as impact strength can be improved by further heat-treating at a temperature of 140 to 180°C. .

The heat treatment can be performed in an inert gas atmosphere such as air or nitrogen.

The present invention will be explained below with reference to reference examples and examples.

Reference Example 1 2.4-) For 1 mole of lylene diamine (TDA), 5.6 moles of propylene oxide, 2 moles of ethylene oxide
．． TDA with a valency of 08 and 400 obtained by addition reaction of 6 moles
Base polyol (Narita Pharmaceutical Co., Ltd. rG R-30J) 7
5g and polyether triol (propylene oxide added to glycerin) (manufactured by Asahi Denka Kogyo ``G400j, 0
100 g of a mixed polyol consisting of 25 g of octavalent 400) was heated to 100° C. and dehydrated under reduced pressure. In addition, carposiimide-modified MDI (Japan Polyurethane Co., Ltd., [Millionate M
T1. J, NCO content 28.8%) 109g 8
It was heated to 0°C and dehydrated under reduced pressure. Both were stirred in a beaker for 40 seconds using a propeller-type stirring oven, and then defoamed in a vacuum desiccator for 1 minute. Immediately bring this mixture to 90°C.
The cured product was poured into a prefabricated glass mold with inner dimensions of 130+nmXnmX13O6mm heated to 100°C, and reacted for 30 minutes in an air constant temperature bath at 100°C, and then the cured product was taken out from the mold. During this time, no bubbles were observed. Then 160℃
Heat treatment was performed for 2 hours in an air constant temperature bath to obtain a non-foamed, tough, rigid polyurethane.

The heat distortion temperature of the obtained polyurethane is ^STM, D64
8 is the load of 18.6 kg/am", the bending elastic modulus is S1°8, D790 is Izod), the impact value is STM, and D256 is the notched condition, and the friction coefficient is Toyo Baldwin Co., Ltd. Using a friction tester manufactured by
It was measured under the conditions of dry state, 20+a/Iain, and 50 kg/cm2.

Heat deformation temperature 108℃ Flexural modulus 26600 kg/c + n 2 Izot impact value 4.3 kg-cto/c1n friction coefficient
μ=0.400 PV value 200 Reference Example 2 85 g of TI′1^ base polyol used in Reference Example 1 and sucrose-based polyol [Mitsui Nisso C Co., Ltd.] l! ! , [S
u-450LAJ, 100 g of mixed polyol consisting of 08 valence 450115 g and carposiimide modified Ml)T
(r millione) HTl, J, NCO content 2868%
) Illg, and in the same manner as in Reference Example 1 except that a non-foamed, tough, rigid polyurethane was obtained.

Heat deformation temperature 113°C Flexural modulus 25800kg/cm2 Izot impact value 3.8kg-cm/Cm Friction coefficient
μ=0.450 PV value 150 Examples 1 to 3 In the same manner as in Reference Example 1, TDA base polyol 300
g and polyether triol [G 400J 100g
400 g of mixed polyol was heated to 100° C. and dehydrated under reduced pressure. Also, carposiimide modified MDI (436g
) was heated to 80°C and dehydrated under reduced pressure. Meanwhile, put Na2S in a mortar.
Take 20g of O4 and 20g of lubricating oil (Maruzen Sekiyu [150
BJ, 15OVG 530) was added and kneaded well.

Next, in a beaker, mix polyol in the proportions listed in Table 1,
” 5g of kneading oil (Na2SO<+ side oil) and lubricating oil Sg (Example 1), 7.5g (Example 2), and 10g (Example 3) were added, and on top of that, carposiimide-modified MDI
Adding the required amount, the same operation as in Reference Example 1 was carried out to obtain a non-foamed, tough, rigid polyurethane.

Example 4 A hard polyurethane was obtained in the same manner as in Example 2 except that no kneading oil was used. The results are shown in Table 1.

Table 11 Examples 5 to 7 340 g of the TD octahedral polyol used in Reference Example 2 and 60 g of a sucrose-based polyol were added, heated to 100° C., and dehydrated in vacuum. Also, carposiimide modified Ml) T467
g was heated to 80°C and dehydrated under vacuum. Meanwhile, 85 g of lubricating oil (manufactured by Maruzen Oil Co., Ltd., r150BJ) and polymer polyol (
Manufactured by Mitsui Nisso, [POP 40/45J, hydroxyl value 110
) was added thereto, heated to 60° C., and dehydrated under vacuum.

These were weighed into a beaker in the proportions shown in Table 2, and the lubricating oil and polymer polyol were stirred well just before being added. Other processing operations were conducted in the same manner as in Reference Example 2 to obtain a non-foamed, tough, rigid polyurethane.

Example 8 A rigid polyurethane was obtained in the same manner as in Example 5 except that no polymer polyol was used. The results are shown in Table 2.

Table 2 Examples 9 to 11 20g of Zn(Off)2 was placed in a mortar and thoroughly kneaded with 20g of lubricating oil (Maruzen Oil Co., Ltd., r150BJ). Take 5 g of this kneading oil in a beaker, and add 7.5 g (Example 9), 10 g (Example 10), and 12 g of the above lubricating oil to each beaker.
．． Polymer polyol (manufactured by Mitsui Nisso, [PO
P 40/45J), 7.5 g (Example 9), 10 g (
Example 10), 12.5B (Example 11) were added and stirred well, and in addition, 298 g of TDA base polyol and a hexafunctional polyol (manufactured by Mitsui Nisso, [+1s700sJ
, OH value 460) 52g as mixed polyol, 1
It was vacuum dehydrated at 00°C and a predetermined amount was added to a beaker. Other places Fl! The operation was the same as in Reference Example 1 to obtain a non-foamed, tough, rigid polyurethane. The results are shown in Table 3.

Table 3 (Note 1) Slight oil oozes from the surface.

(Note 2) Content of polymer polyol in polyol (Note 3) Content of oil component in urethane resin (more than) Patent applicant: Toyo Rubber Industries, Ltd. Representative Patent Attorney 1) Iwao Mura

Claims (3)

[Claims] (1) A polyurethane obtained by the reaction of a polyol component having at least a difunctional hydroxyl group and an at least difunctional polyisocyanate component, wherein the polyol component is an aromatic amine-based polyoxyalkylene having a hydroxyl value of 200 to 700. A mixed polyol consisting of 50 to 90 parts by weight of polyol and 10 to 50 parts by weight of polyol with a hydroxyl value of 50 to 1830 is used, and an aliphatic or aromatic oil component is added to the polyol component and/or polyisocyanate component. Friction resistant, characterized by
Abrasion resistant polyurethane. (2) Use 1 to 15 parts by weight of the oil component per 100 parts by weight of the polyurethane resin, and further use the inorganic compound powder in such a range that the weight ratio of the oil component to the inorganic compound powder is 2 to 6/1. The polyurethane resin according to claim 1. (3) The polyurethane according to claim 1 or 2, further comprising 2 to 30 parts by weight of a polymer polyol based on 100 parts by weight of the polyol component.