JPH01158024A - Form of poly(urethane) urea amide polymer - Google Patents

Abstract

PURPOSE:To obtain the title foam which is an amorphous polymer, having excellent mechanical strength at high temperatures and well balanced reaction rate, by subjecting a specific polyester polyol derivative and polyisocyanate to polyaddition reaction. CONSTITUTION:The aimed polymer, expressed by the formula [A is polyester polyol residue; B is polyisocyanate residue; n is 2-4; x is 0-(n-1) and obtained by reacting (A) a polyester polyol, etc., prepared by ring opening polymerization of epsilon-caprolactone and having 400-10000 molecular weight with (B) an alkyl aminobenzoate (e.g., alkyl is methyl) to provide a polyester polyol derivative, reacting the resultant polyester polyol with (C) a polyisocyanate (e.g., hexamethylene diisocyanate). A foam is obtained by adding a foaming agent, such as water, to reaction of the above-mentioned polymer with the component (C).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a polyester polyol derivative having at least one terminal amine 7 group represented by the general formula [1] and a polyisocyanate obtained by a polyaddition reaction. (
(urethane) ureamide polymer foam.

(Prior art) Patent application No. 57-199384, which is the applicant's earlier application. Same 5
7-165447. 58-75182. 59-66
599. No. 59-124019 discloses polyether polyol derivatives having an amino group at the end of the molecule, a method for producing the same, a polymer obtained by reacting these polyether polyol derivatives with polyisocyanate, and a method for producing the same. The polyols used as starting materials are all polyether polyols,
Contains no polyester polyol.

In the reaction of a polyester polyol derivative having an amide group and optionally a hydroxyl group at the molecular end and an aromatic amide group in the main chain with a polyisocyanate, a urea group,
Poly(urethane)ureamide polymers containing aromatic amide groups are obtained and have a number of significant advantages compared to the corresponding polyurethanes obtained from polyester polyols and polyisocyanates.

In particular, the poly(urethane) urea amide polymer of the present invention is obtained by a polyaddition reaction between a polyester polyol derivative having an amine 7 group and optionally a hydroxyl group at the terminal end and an aromatic amide group in the main chain and a polyisocyanate. teeth,
It has higher heat resistance and stronger mechanical strength compared to structurally equivalent polyurethanes.

U.S. Patent No. 4,328,322 discloses a polyisocyanate and a para-amino-7 benzoic acid ester of a polyol in which all the terminal hydroxyl groups of the polyol are converted to amino groups by reacting the polyol with para-nitrobenzoic acid chloride and then reducing the nitro group. A polymer obtained by a polyaddition reaction is disclosed. In addition, para-7 mi/benzoic acid amide of a polyamine obtained by reacting the polyamine with para-nitrobenzoic acid chloride or para-nitrobenzoic acid, and then reducing the nitro group to convert all the terminal 7 amine groups into different types of amino groups, and the polyamine Polymers obtained by polyaddition reactions of isocyanates are disclosed.

The present invention produces a poly(urethane) urea amide polymer by a polyaddition reaction between a polyester polyol derivative having an aromatic amide group in the main chain and a polyisocyanate, in which a part or all of the terminals of a polyester polyol are substituted with 7 aromatic amide groups. This is what you get. Therefore, the polymer of the present invention has a completely different chemical structure from the polymer of US Pat. No. 4,328,322.

(Problems to be Solved by the Invention) The object of the present invention is to produce a polyester polyol derivative having a 7-mino group at the end, a hydroxyl group if necessary, and an aromatic amide group in the main chain, and a polyisocyanate. The object of the present invention is to provide a polymer foam made of a poly(urethane)ureamide polymer produced by an addition reaction.

(Means for Solving the Problems) The present invention is based on the general formula [A: n-valent polyester polyol residue obtained by removing the terminal H atom from polyol in the main chain of the molecule 1L400-1000G n: 2≦ Integer X of n≦4: Average value, 0≦≦(n-1) Number of amide 7 adjacent to the carbonyl residue of benzoic acid and/or the carbonyl residue of polybasic acid of polyester polyol B: residue obtained by removing the -NGO group from polyisocyanate]
The molecular weight having a repeating unit represented by is approximately 10,000 to 5
The invention relates to a poly(urethane)ureamide polymer foam made of 0.0000000000 polymer. Furthermore, it relates to a polymer foam made of a polymer obtained by the reaction of the polyester polyol derivative of Mon'ena [1], a fastening agent, and a polyisocyanate.

The polyester polyol derivative of the general formula (Il) used in the present invention is obtained by partially or completely converting the terminal end of a polyester polyol into an aromatic group to contain an aromatic amide group in the main chain. The step reaction completes its production with high yield and does not require purification.

The polyester polyol derivative used in the present invention is
A polyvarnish having a molecular weight of 400 to 10,000 and having a valence of 2 to 4 can be obtained by reacting a chil polyol with an amicyl heptabenzoic 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 polyols include adipic acid, sebacic acid,
Saturated or unsaturated dibasic acids such as terephthalic acid, isophthalic acid, maleic acid, and 7-malic acid; acid anhydrides such as maleic anhydride and 7-thalic anhydride; dialkyl esters such as dimethyl terephthalate; and ethylene glycol and propylene. Polyester polyols are produced by condensation reactions with glycols such as glycol, butylene glycol, diethylene glycol, nopropylene glycol, neopentyl glycol, and 1,6-hexylene glycol. Specific examples include polyethylene adipate polyols, Adipate polyols consisting of one type of acid and one type of glycol such as polybutylene adipate polyol, polyhexylene adipate polyol, polyethylene butylene acbate polyol, polyethylene diethylene adipate polyol, polyhexylene neopentylene adipate polyol One type of acid and many! ! 11
Examples include aromatic polyols such as adipate-based polyols consisting of w1 glyfur, polyethylene adipate tere-7-crate polyols consisting of various acids and one type of glycol, and polyethylene adipate iso-7-thalerate polyols.

Lactone-based polyester polyols are obtained by rWIR polymerization of lactones such as ε-caprolactone and γ-butyrolactone, and polyols with various compositions can be obtained depending on the type of initiator. Initiators include glycols such as ethylene glycol and butylene glycol, polyether polyols such as polyoxypropylene glycol (PPG) and polyoxytetramethylene glycol (PTMG), and condensed polyester polyols such as adipate. However, any of them are suitable for use in the present invention.

Further, polyols having two or more functionalities such as condensed polyester polyols and lactone polyester polyols are also suitable for use in the present invention. For example, condensed polyester polyols include polyester polyols that use glycerin or trinochloride as part of the glycol component, polyester polyols that use polybasic acids such as trimellitic acid as part of the dibasic acid, and lactones. For polyester polyols, glycerin,
Polyester polyols obtained using trinotylolpropane, pentaerythritol, etc. are also suitable for use in the present invention.

Among the above polyester polyols, when the polyester polyol derivatives obtained therefrom are used as raw materials for elastomer synthesis, molecular weights of 2 to 4000
Trivalent polyester polyols are preferred.

In addition, when used as a synthetic raw material for plastics, the molecule fi
Tri- to tetravalent polyester polyols having a valence of 400 to 1,500, such as lactone-based polyester polyols obtained using pentaerythritol as an initiator, are suitable.

The alkyl 7-aminobenzoate used in the present invention may be any of ortho, meta, or para-7benzoic acid, but when the polyester polyol derivative of the present invention is used as a synthetic raw material for elastomers and plastics, the alkyl 7-aminobenzoate Alkyl esters are particularly preferred.

Various types of alkyl groups can be cited as examples of the alkyl group in the alkyl 7-benzoic acid ester, and preferred examples include chain-like groups having 11 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, cyclobutyl, cyclopentyl, and cycloheptyl. Alternatively, cyclic alkyl can be mentioned.

Also suitable are 2-butoxyethyl, 2-ethoxyethyl and the like.

In addition, bis(ami7benzoa>a>alkyl esters) can also be used. 7benzoic acid) ester is preferred.

In the present invention, 0.2 amide-7 benzoic acid alkyl ester is used per mole of the n-valent polyester polyol.
It is preferred to react between 5n and Ion moles, preferably between 0.5n and 21 moles.

The polyester polyol derivative of the present invention can be obtained by dealcoholization without a catalyst or in the presence of a known esterification catalyst, usually by heating to 150 to 250°C while passing an inert gas such as nitrogen gas. . When using a catalyst, it is preferable to use a weakly acidic or weakly basic catalyst that has little effect on the ester bonds in the polyester polyol and is less likely to cause side reactions such as dehydration of hydroxyl groups. Examples include metal oxides, organic titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate, alkaline earth metal salts of weak acids such as calcium acetate, and organic titanium compounds are particularly preferred. The amount of catalyst is usually 11,000 pp or less. In addition, an inert solvent and a coloring inhibitor such as triphenyl phosphate can also be used in the reaction. The reaction may be continued until the distillation of the aliphatic alcohol is completed, and the system is further reduced in pressure to completely distill off the alcohol and, if present, the excess alkyl 7-benzoic acid ester. No particular purification is required.

Note that in the reaction between polyester polyol and 7-minobenzoic acid alkyl ester, it is important to note that ester exchange between the ester bond in the molecular chain of the polyester polyol and the terminal OH group or the NH2 group of the 7-minobenzoic acid alkyl ester occurs. The reaction or amide production reaction proceeds simultaneously.

These two reactions can be carried out by adjusting the reaction temperature, the molar ratio of the polyester polyol and the alkyl 7-benzoic acid ester, the time required for dealcoholization, etc.
It is possible to control.

Therefore, the polyester polyol derivative obtained by the reaction of the polyester polyol of the present invention with the aminobenzoic acid alkyl ester has a molecular weight different from the calculated molecular weight determined from the molecular weight of the charged polyester polyol and the charged amount of the aminobenzoic acid alkyl ester. Therefore, in order to obtain a polyester polyol derivative with a desired molecular weight, attention should be paid to the amount of raw materials charged. The content of 7-mido groups is an important factor to achieve the purpose of the present invention, which is to produce a polymer with higher heat resistance and stronger mechanical strength.

Although the reaction for producing aromatic amide groups has not yet been fully elucidated, it can be inferred as follows.

Formula (1) is a terminal amination reaction, and Formula (2) is a reaction in which an aromatic amide group is produced adjacent to the terminal aminophenyl group.6 Formula (3) is a reaction in which an aromatic amide group is formed in the polyester main chain. Formula 6 (4), which is an insertion reaction, is a reaction in which an aromatic amide group is further inserted into the main chain of a polyester having an aromatic 7-mido group.

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

As a result of '3C-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 found to be greater in the main chain than in the adjacent end. From this result, the following estimation can be made. Since there is a large difference in the number of the two types of ester groups, ie, the difference in the number of terminal amyl-7benzoic acid ester groups and the number of ester groups in the main chain, the probability of reaction occurring in the main chain is naturally greater. It is considered that for this reason, the reaction to generate amide groups in the polyester main chain became predominant.

The polyester polyol derivative obtained by the method of the present invention is an esterified product in which all terminal hydroxyl groups have been converted to amide 7 groups, or a partially esterified product in which some unreacted hydroxyl groups remain, and has an aromatic compound in the main chain. Contains an amide group. The degree of amination (i.e., the esterification rate of terminal hydroxyl groups) and amidation rate can vary over a wide range depending on the application, and on average at least one hydroxyl group of the polyester polyol must be esterified. is required, preferably the amination rate is about 50 to 100%, and the amide group can vary over a range of about 5 to 2000 mol% with respect to the terminal amino group, preferably about 5 to 100 mol%. . When the amide group is in this @ range, the polyester polyol derivative has an appropriate viscosity and excellent moldability.

In the present invention, an example of the polyester polyol derivative of general formula (1) when ethylene activate is used as the raw material polyester is given by the following formula.

However, in the formula, each segment does not indicate the order of bonding (it indicates the ratio; the -NHC, H, CO- groups in the main chain are not blocks (they are bonded randomly, and are bonded to the terminal aminobenzoyl group). There are cases where it is combined and cases where it is not combined.

RI: CH2CR2 R2: CH2CH20H2CH2
Failure of the ≦per≦ theory q: This is an average value indicating the number of structural units contained in one molecule, and is not the number of 0.05≦q≦10 or the number of repetitions.

Positive number determined from Is bimolecular weight, p + r =
Furthermore, an example of the polyester polyol derivative of general formula (1) when a diol obtained by ring-opening polymerization of ε-caprolactone is used as a raw material is similarly given by the following formula.

Rs: C) IzCH2CH2CHzCHtR,:
CH2CH, or alkyl group X such as CH, 2CH2CH2CH, etc.: A value indicating the average valence, and a number of O≦≦1.

5tutv: average value indicating the number of repeating structural units, 0≦5tutV≦-number t: average value indicating the number of structural units contained in one molecule, 0.05≦t≦10 number, R9 It's not the number of returns.

II: A positive number determined from the molecular weight, s + u + v == So The above two examples are examples of when a bifunctional polyester polyol is used, and limit the structure of the polyester polyol derivative of the present invention. No%,%.

The polyisocyanate used in the present invention may be any polyisocyanate known in polyurethane chemistry, for example hexamethylene diisocyanate, isophorone diisocyanate), 4,4'-dicyclohexylmethane diisocyanate), 2,4- ) lylene diisocyanate (2,4-T D I ”), 2,6
- ) lylene diisocyanate (2,6-T DI
), 4,49-diphenylmethane diisocyanate (M
DI), carposiimide-modified MDI.

Polymethylene polyphenyl polyisocyanate (PAP
I), ortho-toluidine diisocyanate (TODI)
, naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), etc., and one type or two or more types can be used.

In the present invention, a poly(urethane) urea amide polymer is produced by a polyaddition reaction between a polyester polyol derivative having an amine 7 group and optionally a hydroxyl group at the terminal and an aromatic amide group in the main chain and a polyisocyanate. ,
This may be carried out in any manner known in polyurethane chemistry. This means that the reaction may be carried out in the presence of an active hydrogen-containing compound capable of reacting with incyanate. Also all additives known in polyurethane chemistry, such as catalysts,
Flame retardants, plasticizers, fillers, blowing agents, anti-aging agents, pigments,
This means that an inert organic solvent or the like may be added.

In the present invention, for example, when producing an elastomer, it is preferable to carry out the production in the presence of a suitable chain extender. Examples of the chain extender include bifunctional to tetrafunctional polyols with a molecular weight of 400 or less and cyamines having 7 primary or secondary terminal amide groups with a molecular fi of 400 or less. Suitable chain extenders include, for example, (a) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, trinotyrolpropane, pentaerythritol, sorbitol, 1,4-cyclohexanediol, 1 .4-Cyclohexane dimetatool, xylylene glycol and other polyols (b) hydralane, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1.4-cyclohexanecyamine, phenylenediamine, xylylenediamine, 2.4-) Lylene diamine, 4.4'-diaminodiphenylmethane, 3.3'-dichloro-4!4'-noaminodiphenylmethane, 1,4-dichloro-3,5-
Cyamines such as diaminobenzene and 1,3-propanediol di-para-aminobenzoate (e) Alkanolamines such as ethanolamine, jetanolamine and triethanolamine (d) Hydroquinone, pyrrolol, 4,4°-isopropylene Examples include polyols with a molecular weight of 400 or less obtained by adding propylene oxide and/or ethylene oxide to lydendiphenol, aniline, and the above polyols, diamines, and alkanolamines in any order. Preferable for enhancing the effect of the invention.

In the present invention, active hydrogen-containing compounds such as known long-chain polyols, polyamines, and aminopolyols that can react with incyanate can be used in combination. Suitable long chain polyols are compounds having a molecular weight exceeding 400 and having at least one hydroxyl group. Particularly suitable long chain polyols include molecular weights of 400 to 10,000.2 to 8.
Polyoxyfulkylene polyols such as polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene oxypropylene podiol, and polyoxytetramethylene polyol, and so-called polymer polyols in which styrene or acrylonitrile is grafted to these polyols, All polyester polyols that can be used as raw materials for the synthesis of the polyester polyol derivative of the present invention are included. In addition, polycarbonate polyols such as polyhexamethylene carbonate polyol, polyolefin polyols such as polybutadiene polyol containing terminal hydroxyl groups, terminal epoxy oligomers containing hydroxyl groups in the side chains, and alkanolamines of these are obtained by ring-opening epoxy groups. Polyols and the like are also suitable.

Suitable long-chain polyamines are compounds having a molecular weight of more than 400 and having at least one amino group. Examples include polyether poly7amines obtained by reacting the terminal hydroxyl group of a polyoxyalkylene polyol with ammonia, etc., and polyether polyamines obtained by reacting a known polyol with ethyleneimine, etc.

A long-chain 7-minoboriol is a compound containing both an amine-7 group and a hydroxyl group in the molecule, and has a molecular weight of over 400. For example, a part of the hydroxyl groups of a polyol can be converted into a 7-minoboriol by the above-mentioned method.
Examples include aminopolyols substituted with mino groups. or,
Polyether polyol derivatives having at least one ami7benzoic acid ester group at the end disclosed in JP-A No. 59-53533 are also preferably used.

In the present invention, in the polyaddition reaction between a polyester polyol derivative having one terminal amino group and a polyisocyanate, the isocyanate index is usually 95.
The same holds true even in the presence of other active hydrogen compounds, which are preferably carried out within the range of 120 to 120. Usually, the polyester polyol derivative is reacted with the molten polyisocyanate at room temperature or around the melting temperature of the polyisocyanate. When using a polyisocyanate that is liquid at room temperature, the reaction system can be at room temperature. When reacting in the presence of a known long-chain active hydrogen-containing compound, chain extender, or blowing agent, these components are preferably mixed and dissolved in the polyester polyol derivative in advance. Another effective method is a prepolymer method in which part or all of the polyester polyol derivative and/or chain extender are reacted in advance with an excess of polyisocyanate to form an isocyanate-terminated prepolymer and then reacted with the remaining polyester polyol derivative and/or chain extender. Part or all of the chain polyol may be reacted in advance with excess polyisocyanate to form an incyanate-terminated prepolymer, which is then reacted with the polyester polyol derivative and chain extender. These prepolymers reduce viscosity and improve processability. 60-80℃ to improve
When using the polymer of the present invention as a foam, it is preferable to use it by heating it to a temperature above 1° or by dissolving it in an inert solvent. The reaction may be carried out in the presence of the agent.

(Effects of the Invention) The polymer obtained by the present invention has many excellent characteristics.

Compared to the corresponding polyester urethane, 1.f
i Excellent mechanical strength. This is especially noticeable at high temperatures.

2. Moderate reactivity.

In the case of a system that does not use a chain extender, the reaction of the polyester polyol derivative of the present invention is moderate, compared to the extremely slow reaction of ordinary polyester polyols.

3. Excellent compatibility.

When using an amine-based chain extender, the apparent reaction becomes extremely fast in the case of ordinary polyester polyols. This is because the chain extender component that reacted first precipitates from the reaction solution due to a large difference in can get.

4. It is immoral.

The polymer obtained by the present invention is of good quality and does not change over time in hardness or the like due to crystallization, unlike polymers obtained from ordinary polyester polyols.

(Example) 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 SOH value 2.02
meq/g] 22,442 g (4.935 eq) was placed in a four-ton flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen gas inlet tube, and water was produced under reduced pressure at 100°C for 1 hour under a nitrogen gas flow. Ethyl para-amino-7 benzoate [manufactured by Gyudon Kagaku Yakuhin Kogyo Co., Ltd., first grade reagent] 570.5 g (
3.46 mole) was added thereto, and the temperature was raised to 88°C.

Next, 1,025 g of tetrabutyl titanate (340 p.
When the mixture was stirred and heated, the reaction system became a homogeneous solution at 110° C., and the walls of the four-tube flask began to be wetted with the produced ethanol. Continue to raise the temperature to 225~
The reaction was carried out in a temperature range of 230°C for 2 hours and 30 minutes, and ethanol was distilled off.

Next, the reaction system was cooled to 138°C, and the pressure of the 6 system was reduced to 7 mmHg under a nitrogen stream, and the temperature was raised to 200°C. A reddish-brown liquid with a viscosity of 11,000 eps was obtained. Yield was 2854g.

When this liquid was analyzed by delpermeation chromatography, no free ethyl para-aminobenzoate was detected. In addition, this liquid was analyzed using the following analysis method.
The production of a polyester polyol derivative having 7 terminal amino groups was confirmed.

That is, the amine value was 0.998 according to titration with perchloric acid in glacial acetic acid (Analytical Chemistry Handbook, Revised 3rd Edition, page 261).
meq/g. In addition, the hydroxyl value measurement method (JIS K
1557), it was 1,277 meq/g.

These measurements are for polyester polyol and para-amic acid 7.
Amine value calculated from the amount of ethyl benzoate charged: 1,213 meq/g, active hydrogen value: 1, 728 m
It did not match eq/g. Actual active hydrogen value 1,2
77IIleq/g, the molecular weight of the polyester polyol derivative having a terminal amino group is 1566, and analysis of this product by del permeation chromatography reveals that the molecular weight distribution is higher than that of the raw material polyester polyol. It was confirmed that there was a shift to the side. Further, I3cm NMR analysis of this product confirmed the presence of an amide group, and the amide group was present in an amount of 20 mol % based on the 7 terminal amide groups.

Further, according to elemental analysis, the nitrogen content was 1.68%, which agreed with the amount of amide (total nitrogen - amine) calculated from this. From these results, the product polyester polyol derivative has 78.2% of the terminal hydroxyl groups converted to amino groups and contains 20 mol% of aromatic amide groups in the molecular chain based on the 7 terminal amide groups. It was a compound. The average structure of the product is estimated to be as follows.

Mso 1566 a + b + c ” 11.2 Example 1 (Addition polymer foam of polyester polyol derivative, chain extender, and MDI) To 100 g of the polyester polyol derivative of Reference Example 1,
1,4-butanediol-(Reagent 1 @) 5.8g,
Pure water 0.3g, triethylenediamine (Toyo Sodako 1L
0.3 g of TEDA) was added and dissolved, and the liquid temperature was adjusted to 47°C. This mixed solution was heated to 50°C with molten aM DI (36,
2 g) was added, mixed vigorously for 10 seconds, and immediately poured into an iron mold with a thickness of 4 mm and 7 taps preheated to 60° C., and foamed. The foam surface became 7 tacky in about 40 seconds. It was demolded in 10 minutes. In this way, density 0.6
A soft sheet-like foam of 0 was obtained. Physical properties were measured after 7 days. The results are shown in Table 1.

Comparative Example 1 In order to compare with the foam of Example 1, in order to match the molecular weight with the polyester polyol derivative used in Example 1 instead of the polyester polyol derivative of Reference Example 1, a foam with a molecular weight of 2000 and about 1000 was used. Polycaprolactone polyols (PCL) of different types were blended and used with an average molecular weight of 311,566.

That is, P CL 200G (manufactured by Daicel Chemical Industries [Bookcell 220J, molecular weight 1959) 74.5. and P.C.
L 1000 (Daicel Chemical Industries “Plaxel 210
A foam was synthesized in exactly the same manner as in Example 1 using a mixed polyol containing 25.5 g of polyol having a liquid temperature of 50°C.

The tack of this foam was 717-1 minute and 20 seconds.

Since the reaction was rather slow, demolding required 20 minutes. In this manner, a soft sheet-like foam having a density of 0.60 was obtained.

This sample showed hardness changes due to crystallization.

That is, the hardness of the sample after 7 days was 4B (JIS A), but the hardness decreased to 36 after heating at 60° C. for 20 minutes. Note that such a change in hardness was not observed in the foam of Example 1. The physical properties of the sample of Comparative Example 1 were measured after crystal removal. The results are shown in Table 1.

Chapter 1 Table (that's all) Patent applicant: Toyo Rubber Industries, Ltd.

Claims (1)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [A: There are ▲ mathematical formulas, chemical formulas, tables, etc. in the main chain with a molecular weight of 400 to 10,000 ▼ The terminal H atom is removed from an n-valent polyester polyol containing groups. n-valent polyester polyol residue obtained by removing n: an integer of 2≦n≦4 x: average value, number of 0≦x≦(n-1) ▲ mathematical formula, chemical formula in the main chain , tables, etc. The -NH- group of the ▼ group forms an amide group adjacent to the carbonyl residue of aminobenzoic acid and/or the carbonyl residue of the polybasic acid of the polyester polyol, and the -CO- group forms an ester group. or B forming an amide group: residue obtained by removing the -NCO group from polyisocyanate]
The molecular weight having a repeating unit represented by is approximately 10,000 to 5
A poly(urethane) ureaamide polymer foam made of 0,000 polymers.