JP2538458B2 - Poly (urethane) urea amide polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a poly (urethane) ureaamide polymer obtained by a polyaddition reaction of a polyester polyol derivative having at least one terminal amino group represented by Chemical formula 1 with a polyisocyanate.

[0002]

2. Description of the Related Art Japanese Patent Application No. 57-19938, which is a prior application of the present applicant.
4, Same 57-165447, Same 58-75182, Same 59-66599, Same 59-1
24019 shows a polyether polyol derivative having an amino group at the molecular end, a method for producing the same, a polymer produced by reacting the polyether polyol derivative with a polyisocyanate, and a method for producing the polymer. The polyols used as starting materials in these inventions are all polyether polyols, and do not include polyester polyols.

In the reaction of a polyester polyol derivative having an amino group and, if necessary, a hydroxyl group at the molecular end and an aromatic amide group in the main chain with polyisocyanate, a polyamine containing a urea group or an aromatic amide group is used. (Urethane) urea amide polymers are obtained and have many significant advantages compared to polyurethanes obtained from the corresponding polyester polyols and polyisocyanates.

Particularly, a poly (urethane) ureaamide obtained by a polyaddition reaction of a polyester polyol derivative having an amino group at the terminal and a hydroxyl group as required and having an aromatic amide group in the main chain of the present invention and polyisocyanate. The polymer, compared to the structurally equivalent polyurethane,
It has higher heat resistance and stronger mechanical strength.

In US Pat. No. 4,328,322, a para-aminobenzoic acid ester of a polyol in which all the terminal hydroxyl groups of the polyol are converted into amino groups by reacting the polyol with para-nitrobenzoic acid chloride and then reducing the nitro group, and a polyisocyanate Polymers obtained by addition reactions are disclosed. Also, polyamine was reacted with para-nitrobenzoic acid chloride or para-nitrobenzoic acid, and then the nitro group was reduced to convert all the terminal amino groups of the polyamine into amino groups of different species. Polyaddition of para-aminobenzoic acid amide with polyisocyanate Polymers obtained by the reaction are disclosed.

According to the present invention, a poly (urethane) ureaamide is obtained by a polyaddition reaction of a polyester polyol derivative having an aromatic amide group in the main chain with a part or all of the terminals of the polyester polyol substituted with an aromatic amino group. A polymer is obtained. Therefore, the polymers of the present invention are quite different in chemical structure from the polymers of US Pat. No. 4,328,322.

[0007]

The object of the present invention is to carry out a polyaddition reaction between a polyester polyol derivative having an amino group at the terminal and, if necessary, a hydroxyl group and an aromatic amide group in the main chain, and a polyisocyanate. To provide a polymer composed of a poly (urethane) ureaamide polymer.

[0008]

The present invention provides a polyester polyol derivative of Chemical formula 1

[0009]

[Chemical 1]

[A: n-valent polyester polyol residue obtained by removing a terminal H atom from an n-valent polyester polyol containing a group represented by Chemical formula 2 in the main chain having a molecular weight of 400 to 10,000

[0011]

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N: integer of 2≤n≤4 x: average value and number of 0≤x≤ (n-1)

The -NH- group of the group represented by Chemical formula 2 in the main chain is adjacent to a carbonyl residue of aminobenzoic acid and / or a carbonyl residue of a polybasic acid of polyester polyol to form an amide group, CO- group forms an ester group or an amide group]

[0014]

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And polyisocyanate of isocyanate
The present invention relates to a poly (urethane) ureaamide polymer comprising a polymer having a repeating unit represented by Chemical formula 3 obtained by a reaction having an index in the range of 95 to 120 .

[0016]

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[B: Residue obtained by removing -NCO group from polyisocyanate]

Further, it relates to a polymer comprising a polymer obtained by reacting the polyester polyol derivative of Chemical formula 1, a chain extender and a polyisocyanate.

The polyester polyol derivative of the chemical formula 1 used in the present invention is obtained by partially or completely aromatic aminating the polyester polyol to have an aromatic amide group in the main chain, and substantially 1 The reaction of the stage completes its preparation and yields high and does not require purification.

The polyester polyol derivative used in the present invention can be obtained by reacting a divalent to tetravalent polyester polyol having a molecular weight of 400 to 10,000 with an aminobenzoic acid alkyl ester.

The polyester polyol used in the present invention may be either a condensed polyester polyol or a lactone polyester polyol obtained by a known method. Condensed polyester polyol is adipic acid,
Sebacic acid, terephthalic acid, isophthalic acid, maleic acid, saturated or unsaturated dibasic acids such as fumaric acid, maleic anhydride, acid anhydrides such as phthalic anhydride, dialkyl esters such as dimethyl terephthalate and ethylene glycol, A polyester polyol obtained by a condensation reaction with glycols such as propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, and 1,6-hexylene glycol, and specific examples include polyethylene adipate polyol and poly Butylene adipate polyol,
An adipate-based polyol consisting of one kind of acid such as polyhexylene adipate polyol and one kind of glycol,
An adipate-based polyol comprising one kind of acid and many kinds of glycols such as polyethylene butylene adipate polyol, polyethylene diethylene adipate polyol, and polyhexylene neopentylene adipate polyol,
Examples thereof include aromatic polyols such as polyethylene adipate terephthalate polyol and polyethylene adipate isophthalate polyol, which are composed of various kinds of acids and one kind of glycol.

The lactone polyester polyol is ε-
It can be obtained by ring-opening polymerization of lactones such as caprolactone and γ-butyrolactone, but polyols having various compositions can be obtained depending on the type of initiator. As the initiator, glycols such as ethylene glycol and butylene glycol, polyether polyols such as polyoxypropylene glycol (PPG) and polyoxytetramethylene glycol (PTMG), and condensation type polyester polyols such as adipate are selected. However, both are suitable for use in the present invention.

Bifunctional or higher functional polyols such as condensed polyester polyols and lactone polyester polyols are also suitable for use in the present invention. For example, in a condensed polyester polyol, a polyester polyol using glycerin or trimethylolpropane as a part of a glycol component, or a polyester polyol using a polybasic acid such as trimellitic acid as a part of a dibasic acid, or a lactone polyester polyol is used. As an initiator of ring-opening polymerization,
Polyester polyols obtained by using glycerin, trimethylolpropane, pentaerythritol, etc. are also suitable for use in the present invention.

When the polyester polyol derivative obtained from the above polyester polyols is used as a raw material for synthesizing an elastomer, a divalent or trivalent polyester polyol having a molecular weight of 1000 to 4000 is preferable.

When used as a synthetic raw material for plastics, a trivalent to tetravalent polyester polyol having a molecular weight of 400 to 1500, for example, a lactone type polyester polyol obtained by using pentaerythritol as an initiator is suitable.

The aminobenzoic acid alkyl ester used in the present invention may be any of ortho, meta or para-aminobenzoic acid alkyl ester. When the polyesterpolyol derivative of the present invention is used as a synthetic raw material for elastomers and plastics, paraaminobenzoic acid is used. Alkyl esters are particularly preferred.

As the alkyl group of the aminobenzoic acid alkyl ester, various groups can be exemplified, and preferable examples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl, cyclobutyl, cyclopentyl, cycloheptyl and the like having 1 to 8 carbon atoms. Chain-like or cyclic alkyl may be mentioned. Further, 2-butoxyethyl, 2-ethoxyethyl and the like are also suitable.

Further, bis (aminobenzoic acid) alkyl esters can also be used. 2 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, heptylene glycol
Bis (aminobenzoic acid) esters such as glycols of -8 are preferred.

In the present invention, it is suitable to react 0.25n to 10nmol, preferably 0.5n to 2nmol of the aminobenzoic acid alkyl ester with 1 mol of the n-valent polyester polyol.

The polyester polyol derivative of the present invention is obtained by carrying out dealcoholization by usually heating to 150 to 250 ° C. in the presence of a catalyst or a known esterification catalyst while passing an inert gas such as nitrogen gas. To be When a catalyst is used, it is preferable to use a weakly acidic or weakly basic catalyst that has little influence on the ester bond in the polyester polyol and is less likely to cause side reactions such as dehydration reaction of hydroxyl groups, for example, antimony trioxide, lead monoxide, etc. And organic titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate, alkaline earth metal salts of weak acids such as calcium acetate, and the like, and organic titanium compounds are particularly preferable. The catalyst amount is usually 1000 ppm or less. Further, for the reaction, an inert solvent or a color preventing agent such as triphenyl phosphate can be used. The reaction is continued until the distillation of the aliphatic alcohol is completed, and the system is further depressurized to completely distill off the alcohol and excess aminobenzoic acid alkyl ester, if present. No purification is necessary.

The point to be noted in the reaction between the polyester polyol and the aminobenzoic acid alkyl ester is that the ester bond between the ester bond in the molecular chain of the polyester polyol and the terminal OH group or the NH ₂ group of the aminobenzoic acid alkyl ester is used. That is, the exchange reaction or the amide formation reaction proceeds at the same time.

These two reactions can be controlled by adjusting the reaction temperature, the molar ratio of the polyester polyol to the aminobenzoic acid alkyl ester, and the time required for dealcoholization. Therefore, the polyester polyol derivative obtained by the reaction of the polyester polyol of the present invention with the aminobenzoic acid alkyl ester is different from the molecular weight of the charged polyester polyol and the calculated molecular weight obtained from the charged amount of the aminobenzoic acid alkyl ester. Since a compound having a molecular weight is obtained, in order to obtain a polyester polyol derivative having a desired molecular weight, it is necessary to pay attention to the charged amount of raw materials. The content of amide groups is an important factor for achieving the object of the present invention to produce a polymer having higher heat resistance and higher mechanical strength.

Although the reaction for forming an aromatic amide group has not been fully clarified yet, it can be inferred as follows.

[0034]

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(1) is a reaction for terminal amination, and (2) is a reaction for forming an aromatic amide group adjacent to a terminal aminophenyl group. (3) is a reaction in which an aromatic amide group is inserted into the polyester main chain. (4) is a reaction in which an aromatic amide group is further inserted into the polyester main chain having an aromatic amide group.

The aromatic amide group in the above polyester polyol derivative can be quantitatively confirmed by NMR analysis and nitrogen element analysis.

As a result of ¹³ C-NMR analysis, the number of amide groups in the polyester polyol derivative of the present invention when an aliphatic polyester polyol was used as a starting material was higher in the main chain than in the adjacent ends. From this result, the following can be estimated. Since the difference in the number of two kinds of ester groups, that is, the difference in the number of terminal aminobenzoic acid ester groups and the number of ester groups in the main chain is large, the probability that a reaction can occur is naturally greater in the main chain. Therefore, it is considered that the amide group formation reaction in the polyester main chain became dominant.

The polyester polyol derivative obtained by the present invention is an esterified product in which all the terminal hydroxyl groups are converted into amino groups or a partially esterified product in which some unreacted hydroxyl groups remain, and the aromatic amide is present in the main chain. Contains a group. The amination ratio (that is, the esterification ratio of the terminal hydroxyl group) and the degree of the amidation ratio can be varied over a wide range depending on the application, and at least one hydroxyl group of the polyester polyol is esterified on average. Is required, and the amination ratio is preferably about 50 to 100%, and the amide group can be changed over a range of about 5 to 2000 mol% with respect to the terminal amino group, but about 5 to 100 mol% is preferable. .
When the amide group is within this range, the viscosity of the polyester polyol derivative is appropriate and the moldability is excellent.

An example of the polyester polyol derivative of Chemical formula 1 when ethylene adipate is used as the raw material polyester in the present invention is given by the following formula. However where each of each segment represents the ratio does not indicate the order of binding, -NHC ₆ H ₄ CO- groups in the main chain is linked to a random rather than block, when attached to the terminal amino benzoyl group And may not be combined.

[0040]

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R ₁ : CH ₂ CH ₂ R ₂ : CH ₂ CH ₂ CH ₂ CH ₂ x: a value showing the average valence, 0 ≦ x ≦ 1 p, r: the number of repeating structural units Is the average value shown,
Number of ≦ p, r ≦ m q: Average value showing the number of structural units contained in one molecule, not the number of 0.05 ≦ q ≦ 10, not the number of repetitions. m: positive number determined from molecular weight, p + r = m

An example of the polyester polyol derivative of Chemical formula 1 when a diol obtained by ring-opening polymerization of ε-caprolactone is used as a raw material is also given by Chemical formula 6.

[0043]

[Chemical 6]

R ₃ : CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ R ₄ : CH ₂ CH ₂ or an alkyl group such as CH ₂ CH ₂ CH ₂ CH ₂ x: a value showing the average valence, 0 ≦ Number of x ≦ 1 s, u, v: average value indicating the number of repeating structural units,
Number of 0 ≦ s, u, v ≦ m t: Average value showing the number of structural units contained in one molecule, not the number of 0.05 ≦ t ≦ 10, not the number of repetitions. m: positive number determined from molecular weight, s + u + v = m

The above two examples are examples of using a bifunctional polyester polyol, and do not limit the structure of the polyester polyol derivative of the present invention.

The polyisocyanate used in the present invention may be any polyisocyanate known in polyurethane chemistry, such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4 '.
-Dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI), carbodiimide modified MDI, polymethylene polyphenyl polyisocyanate (PAPI), orthotoluidine diisocyanate (TODI), naphthylene diisocyanate (ND)
I), xylylene diisocyanate (XDI) and the like, and one kind or two or more kinds can be used.

In the present invention, a poly (urethane) ureaamide polymer is obtained by a polyaddition reaction between a polyester polyol derivative having an amino group at the terminal and optionally a hydroxyl group and an aromatic amide group in the main chain, and polyisocyanate. Manufacture may be carried out by any method known in polyurethane chemistry. That is, it means that the reaction can be carried out in the presence of an active hydrogen-containing compound capable of reacting with isocyanate. It also means that any additives known in polyurethane chemistry may be added, such as catalysts, flame retardants, plasticizers, fillers, blowing agents, anti-aging agents, pigments, inert organic solvents and the like.

The poly (urethane) ureaamide polymer obtained in the present invention has a JIS A hardness of generally 30 to 99,
Especially in the range of 50 to 95, and the tensile strength is generally 10 at 70 ° C.
~ 120 kg / cm ² , especially about 10-60 kg / cm ² .

In the present invention, for example, the elastomer is preferably produced in the presence of a suitable chain extender. As the chain extender, for example, 2 to 4 having a molecular weight of 400 or less
Examples thereof include functional polyols and diamines having a molecular weight of 400 or less and a primary or secondary terminal amino group. Examples of suitable chain extenders include (a) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol. Le, sorbitol,
Polyols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and xylylene glycol (b) Hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,4-cyclohexane Diamine, phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 1,4-dichloro −3,5-Diaminobenzene, 1,3
-Diamines such as propanediol diparaaminobenzoate (c) alkanolamines such as ethanolamine, dieanolamine, and triethanolamine (d) hydroquinone, pyrogallol, 4,4'-isopropylidene diphenol , Aniline and the above-mentioned polyols, diamines, alkanolamines, and propylene oxide and / or ethylene oxide obtained by adding propylene oxide and / or ethylene oxide in any order. Are preferable for enhancing the effect of the present invention. When a chain extender is also used in this way, the tensile strength of the resulting poly (urethane) ureaamide polymer is 6 at 120 ° C.
It is improved to 0 to 230 kg / cm ² , especially 60 to 140 kg / cm ² .

In the present invention, active hydrogen-containing compounds such as known long-chain polyols, polyamines and aminopolyols which can react with isocyanate can be used in combination.
Suitable long chain polyols are compounds having at least one hydroxyl group having a molecular weight of more than 400. Particularly suitable long chain polyols have a molecular weight of 400 to 10000, 2 to
Polyoxyalkylene polyols such as octavalent polyoxyethylene polyols, polyoxypropylene polyols, polyoxyethyleneoxypropylene polyols, polyoxytetramethylene polyols, etc., and so-called polymer polyols obtained by grafting styrene or acrylonitrile thereto, the present invention All the polyester polyols that can be used as the raw material for synthesizing the polyester polyol derivative of are mentioned. Further, polycarbonate polyols such as polyhexamethylene carbonate polyols, polyolefin polyols such as polybutadiene polyols having terminal hydroxyl groups, terminal epoxy oligomers having hydroxyl groups in the side chains, and polyols obtained by ring-opening epoxy groups with these alkanolamines and the like. Are also suitable.

Suitable long chain polyamines have a molecular weight of 400
Is a compound having at least one or more amino groups. For example, polyether polyamines obtained by reacting the terminal hydroxyl group of polyoxyalkylene polyol with ammonia or the like, and polyether polyamines obtained by reacting a known polyol with ethyleneimine or the like can be mentioned.

A long-chain aminopolyol has a molecular weight of 40.
It is a compound containing both an amino group and a hydroxyl group exceeding 0 in the molecule, and examples thereof include an aminopolyol in which a part of the hydroxyl groups of the polyol is substituted with an amino group by the above method. Further, the polyether polyol derivative having at least one aminobenzoic acid ester group at the terminal disclosed in JP-A-59-53533 is also preferably used.

In the present invention, the polyaddition reaction between the polyester polyol derivative having at least one terminal amino group and the polyisocyanate is usually preferably carried out in the isocyanate index in the range of 95 to 120. The same is true in the presence of other active hydrogen compounds. Usually, the polyester polyol derivative is reacted with the molten polyisocyanate at room temperature or around the melting temperature of the polyisocyanate. When a polyisocyanate which is liquid at room temperature is used, the reaction system can be brought to room temperature. When the reaction is carried out in the presence of a known long-chain active hydrogen-containing compound, a chain extender or a foaming agent, these components are preferably mixed and dissolved in the polyester polyol derivative in advance. A prepolymer method in which a part or all of the polyester polyol derivative is preliminarily reacted with an excess polyisocyanate to react as an isocyanate-terminated prepolymer with the rest of the polyester polyol derivative and / or the chain extender is also an effective method. Alternatively, a part or all of the known long-chain polyol may be previously reacted with an excess of polyisocyanate to form an isocyanate-terminated prepolymer, and then the polyester polyol derivative and the chain extender may be reacted. These prepolymers have a viscosity of 60 to 60% to improve processability.
It is recommended to heat it to 80 ℃ or higher or dissolve it in an inert solvent before use.

When the polymer of the present invention is cast into an elastomer, the mold temperature is usually preferably heated to 50 to 100 ° C.

[0055]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples, Examples and Comparative Examples.

Reference Example 1 (Synthesis of Polyester Polyol Derivative) Lactone-based polyester polyol [Plaxel-21
0, manufactured by Daicel Corporation, MW 990, OH value 2.02meq / g] 2
442 g (4.935 eq) was placed in a 4-necked flask equipped with a stir bar, a cooling tube, a thermometer, and a nitrogen gas introducing tube, and dehydrated under reduced pressure at 100 ° C. for 1 hour under a nitrogen gas stream. Next, 570.5 g (3.46 mole) of ethyl para-aminobenzoate (manufactured by Hanai Chemical Co., Ltd., first-grade reagent) was added, and the temperature was raised to 88 ° C.

Next, 1.025 g of tetrabutyl titanate (3
40 ppm) was added and the temperature was raised with stirring, the reaction system became a uniform solution at 110 ° C., and the wall surface of the 4-necked flask began to get wet with ethanol. Continue to raise the temperature to 225-230 ℃
The reaction was carried out for 2 hours and 30 minutes in the temperature range described above, and ethanol was distilled off. Then, the reaction system was cooled to 138 ° C., and then the pressure was reduced to 7 mmHg under a nitrogen gas stream. The temperature of the system was raised to 200 ° C., unreacted ethyl paraaminobenzoate was distilled off for 3 hours, and a reddish brown liquid having a viscosity at 30 ° C. of 11000 cps was obtained. The yield was 2854 g.

When this liquid was analyzed by gel permeation chromatography, no free ethyl paraaminobenzoate was detected. Further, the formation of a polyester polyol derivative having a terminal amino group was confirmed by using the following analytical method for this liquid.

That is, the amine value was determined by titration with perchloric acid in glacial acetic acid (Analytical Chemistry Handbook, Rev. 3rd edition, page 261)
It was 0.998 meq / g. Further, a hydroxyl value measuring method (JIS) capable of measuring the total amount of hydroxyl groups and amino groups (active hydrogen group value)
According to K1557), it was 1.277 meq / g. These measured values are calculated based on the charged amounts of polyester polyol and ethyl paraaminobenzoate.
It did not agree with q / g and active hydrogen group value of 1.728 meq / g. From the measured active hydrogen group value of 1.277 meq / g, the molecular weight of the polyester polyol derivative having a terminal amino group is 1566. Also, when this product is analyzed by gel permeation chromatography, it is compared with the raw material polyester polyol. It was confirmed that the molecular weight distribution was shifted to the polymer side. The ¹³ C-NMR analysis of this product confirmed the presence of an amide group, and the amide group was present in 20 mol% with respect to the terminal amino group. In addition, nitrogen was 1.68% by elemental analysis, which was in agreement with the amount of amide calculated from this (total nitrogen-amine). From these results, the product polyester polyol derivative is
% Was converted into an amino group and contained 20 mol% of an aromatic amide group in the molecular chain with respect to the terminal amino group. The average structure of the product is estimated to be:

[0060]

[Chemical 7]

Example 1 (Polyaddition Polymer of Polyester Polyol Derivative and MDI) Polyester Polyol Derivative 100 Obtained in Reference Example 1
Weigh g in a 300 ml polypropylene cup and heat to 50 ° C. 16.4 g of 4,4'-diphenylmethane diisocyanate [pure MDI, "Millionate MT" manufactured by Nippon Polyurethane Industry Co., Ltd.] melted at 50 ° C was added, and the mixture was mixed with a propeller-type stirrer at 30
Mix for seconds. Then degas in a vacuum desiccator and
It was poured into an iron mold preheated to 0 ° C. The mold was placed in an oven at 110 ° C. and cured. The tack free time was 11 minutes. After 2 hours, the cured product was removed from the mold and subsequently post-cured at 110 ° C. for 16 hours. The 2 mm thick sheet thus obtained was a transparent, soft but strong elastomer. After curing for 7 days at room temperature, J
Physical properties were measured according to IS K6301 (hereinafter, the same), and the results are shown in Table 1.

Comparative Example 1 A polymer of the corresponding polyester polyol and MDI was synthesized for comparison with the polymer of Example 1. In order to match the molecular weight with the polyester polyol derivative used in Example 1, two kinds of polycaprolactone polyol (PCL) having a molecular weight of about 2000 and about 1000 were blended and used as an average molecular weight of 1566. PCL2000 (Daicel Chemical Industries "Plaxel 220", molecular weight 1959) 74.5g and PCL1
000 ("Placcel 210" manufactured by Daicel Chemical Industries, molecular weight 9
88) Mixed polyol with a liquid temperature of 50 ℃ blended with 25.5 g 10
A polymer was synthesized in the same manner as in Example 1 using 0 g and 50.degree. C. molten MDI (16.76 g). The reaction was slow to cure and tacky even after 1 hour. After 2 hours, I tried to remove the mold, but it was too soft to remove, so I left it in the mold 11
The mold was demolded after continuing the curing at 0 ° C. for 16 hours to cool the mold. The sheet thus obtained was a transparent and soft elastomer. However, this sample is 3 at room temperature.
After 4 days it becomes opaque and after 7 days the hardness is 86 (JI
S A) has been reached. When this sample was heated at 50-60 ° C for 20 minutes, it became clear again and softened. When the hardness was measured after 1 hour at room temperature, it was found to be 56. This phenomenon is considered to be due to crystallization of the polyester component in the elastomer.

No change in hardness due to such crystallization was observed in the elastomer of Example 1. Comparative Example 1
The physical properties of the sample (1) were measured after crystallization. The results are shown in Table 1.

[0064]

[Table 1]

Example 2 (Polyaddition Polymer of Polyester Polyol Derivative and TDI) 100 g of the polyester polyol derivative of Reference Example 1 heated to 50 ° C. and 2,4′-tolylene diisocyanate [2,4- A polymer was synthesized in the same manner as in Example 1 using 11.67 g of TDI, “Coronate T-100” manufactured by Nippon Polyurethane Industry Co., Ltd. The tack free time was about 1 hour. After 4 hours, it was demolded and subsequently post-cured at 110 ° C. for 16 hours. In this way, a transparent, soft but strong elastomer was obtained. Table 2 shows the results.

Comparative Example 2 A polymer of the corresponding polyester polyol and TDI was synthesized for comparison with the polymer of Example 2. The polyol used was the same as the mixed polyol used in Comparative Example 1. 100 g of this mixed polyol (50 ° C) and 2,4-TDI (2
A polymer was synthesized in the same manner as in Example 1 using 11.67 g (5 ° C.). This reaction cures extremely slowly and is difficult to demold, so continue curing at 110 ° C for 20 hours in the mold.
The mold was cooled and then demolded. The sample thus obtained showed significant crystallization. That is, this sample was transparent and very soft immediately after demolding, but
It turned white and hard after a day. Hardness is 7 days after 94 (JIS
A) has been reached. When this sample was heated at 50 ° C. for 20 minutes, it became transparent again and the hardness decreased to 15 (JIS A). It is considered that this is due to crystallization of the polyester component in the elastomer.

The sample of Example 2 did not show such a change in hardness. The physical properties of the sample of Comparative Example 2 were measured after crystallization. Table 2 shows the results.

[0068]

[Table 2]

(Note) Measurement cannot be performed due to softening deformation

Example 3 (Polyaddition Polymer of Polyester Polyol Derivative, Chain Extender and MDI) 100 g of the polyester polyol derivative of Reference Example 1 was added with 3,3′-
Dichloro-4,4'-diaminodiphenylmethane (Ihara Chemical Industry "Kyuamine MT") 8.5 g was dissolved, and the mixed solution 108.5 g and the melted MDI (25.
A polymer was synthesized in the same manner as in Example 1 using 1 g). However, the mixing time was 20 seconds, defoaming was performed for 1 minute, and the mixture was immediately cast. The reaction was tack free in 4 minutes.
The mold was removed in 30 minutes, and subsequently post-cured at 110 ° C. for 16 hours. Thus, a semitransparent tough sheet-like elastomer was obtained. The physical properties are shown in Table 3.

Comparative Example 3 A polymer was synthesized using the corresponding polyester polyol for comparison with the polymer of Example 3. That is, Comparative Example 1
100 g of the mixed polyol used in Example 3,3'-dichloro-4,4 '
-Dissolve 8.5 g of diaminodiphenylmethane and set the liquid temperature to 5
Mixture of 108.5g at 0 ℃ and molten MDI at 50 ℃ (25.1g)
Was used. When operated in the same manner as in Example 3, the reaction was too fast and the reaction solution whitened and thickened in 1 minute and 10 seconds during the defoaming step, and casting could not be performed. Therefore, it became possible to cast by shortening the mixing time to 15 seconds and the defoaming process to 45 seconds. After all 1 minute
The reaction solution became white in 10 seconds and became tack-free in 2 minutes and 15 seconds. Demolding was difficult in 30 minutes because the cured product was brittle despite the rapid solidification reaction, and required 1 hour and 30 minutes. Then, post cure was performed at 110 ° C. for 16 hours. Thus, a cloudy white hard elastomer was obtained.

This sample showed a change in hardness due to crystallization. That is, the hardness of the sample is 96 (JIS
A) was reached, but the hardness decreased to 77 by heating at 60 ° C. for 20 minutes. The sample of Example 3 did not show such a change in hardness. Physical properties were measured after crystallization. The results are shown in Table 3.

[0073]

[Table 3]

(Note) When the sample is sandwiched between pneumatic fixing tools,
It was destroyed by compression and could not be measured.

Example 4 (Polyaddition Polymer of Polyester Polyol Derivative, Chain Extender and TDI) 100 g of polyester polyol derivative of Reference Example 3 was added with 3,3 '
-Dichloro-4,4'-diaminodiphenyl methane 17.0g was dissolved and the liquid temperature was adjusted to 50 ° C.
A polymer was synthesized in the same manner as in Example 3 using 2,4-TDI (23.3 g). The reaction was tack free in 9 minutes. It was demolded in 30 minutes, and subsequently post-cured at 110 ° C. for 16 hours. Thus, a transparent and tough sheet-like elastomer was obtained. The physical properties are shown in Table 4.

Comparative Example 4 A polymer was synthesized using the corresponding polyester polyol for comparison with the polymer of Example 4. That is, Comparative Example 1
In 100 g of the mixed polyol used in 3, 3,3'-dichloro-4,
17.0 g of 4'-diaminodiphenyl methane was dissolved and 117.0 g of a mixed liquid having a liquid temperature of 50 ° C and 2,4-TDI (23.3
g) was used. When operated in the same manner as in Example 3, the reaction was extremely fast, and the reaction solution became white and casting could not be performed in about 40 seconds during the defoaming step. Therefore, the liquid temperature of the above mixed liquid was lowered to 44 ° C., the mixing time was shortened to 15 seconds, and the mixture was immediately cast without defoaming. The reaction solution turned white and solidified in about 40 seconds. Demolding was difficult in 40 minutes because the cured product was brittle despite the rapid solidification reaction, and cracking occurred in about 2 hours when the curing was continued, so demolding was performed. It is considered that the cracks occurred because the gel strength was insufficient with respect to curing shrinkage. Then, post cure was performed at 110 ° C. for 16 hours. In this way, a cloudy white hard sheet-like elastomer was obtained.

This sample showed a change in hardness due to crystallization. That is, the hardness of the sample is 97 (JIS
A), but when heated at 60 ° C. for 20 minutes, the hardness decreased to 82. The sample of Example 4 had no such change in hardness. The physical properties of the sample of the comparative example were measured after removing the crystal. The results are shown in Table 4.

[0078]

[Table 4]

(Note) When the sample is sandwiched between pneumatic fixing tools,
It was destroyed by compression and could not be measured.

[0080]

The polymer obtained according to the present invention has many excellent characteristics.

Compared with the corresponding polyester type urethane, Excellent mechanical strength. Especially at high temperatures. 2. Reactivity is moderate. In the case of a system that does not use a chain extender, the reaction of ordinary polyester polyol is extremely slow, whereas the reaction of the polyester polyol derivative of the present invention is moderate. 3. Excellent compatibility. When an amine-based chain extender is used, the apparent reaction becomes extremely fast in the case of a normal polyester polyol. This is because the compatibility of the reaction system is low,
This is because the chain extender component previously reacted is precipitated from the reaction solution due to the fact that there is too much difference in the reaction rate between the polyol and the chain extender. In the present invention, the compatibility is excellent and the reaction rates are well balanced, so that an appropriate reaction rate can be obtained. 4. It is amorphous. The polymer obtained according to the present invention is amorphous, and does not change with time such as hardness due to crystallization unlike polymers obtained from ordinary polyester polyols.

Claims (4)

(57) [Claims] 1. A polyester polyol derivative of Chemical Formula 1 [A: n-valent polyester polyol residue obtained by removing a terminal H atom from an n-valent polyester polyol having a group represented by Chemical formula 2 in the main chain having a molecular weight of 400 to 10000] n: integer of 2≤n≤4 x: number of 0≤x≤ (n-1), which is an average value, and the -NH- group of the group represented by Chemical formula 3 in the main chain is a carbonyl residue of aminobenzoic acid. Group and / or adjacent to the carbonyl residue of the polybasic acid of the polyester polyol to form an amide group, and the —CO— group forms an ester group or an amide group. And the isocyanate index of polyisocyanate
Poly (urethane) composed of a polymer having a repeating unit represented by Chemical formula 4 obtained by a reaction in the range of 95 to 120
Urea amide polymer. Embedded image [B: Residue obtained by removing -NCO group from polyisocyanate] 2. The polymer according to claim 1, which is obtained by reacting with a polyisocyanate in the presence of a chain extender having a molecular weight of 400 or less. 3. The polymer according to claim 1, which is obtained by reacting with a polyisocyanate in the presence of a long-chain polyol having a molecular weight of more than 400, a long-chain polyamine and / or a long-chain aminopolyol. 4. JIS A hardness of 30 to 99 , tensile strength (70
4. The polymer according to claim 1, having a temperature of 10 to 120 kg / cm ² .