JPS6092317A - Cellular polyurethane elastomer composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in elastic recovery and durability and suitable for a vibration-proof material, comprising a specified polyhydroxyl compound, an organic diisocyanate, a blowing agent, a foam stabilizer, and an extender. CONSTITUTION:The following components (A)-(E) are mixed together so that the equivalent ratio of the isocyanato groups in the resulting urethane prepolymer to the total amount of the active hydrogen atoms in components A, C, and E (NCO/OH+NH2) may fall within the range of 1:0.9-1.1, and when the total of the active hydrogen atoms forming the expandable mixture, A+C+E, is 1.0, the equivalent ratio of the active hydrogen atoms in component A may fall within the range of 0.05-0.08, that in component E may fall within the range of 0.2-0.5, and that in component C may fall within the range of 0.32-0.75: (A) an aliphatic polyesterpolyol, MW of 1,000-3,000, as a polyhydroxyl compound, (B) diphenylmethane diisocyanate as an organic organic diisocyanate, (C) water as a blowing agent, (D) a foam stabilizer at least 50wt% of which comprises a sulfate or sulfonate group-containing surfactant, and (E) an aromatic diamine as a chain extender.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cellular polyurethane disstomer compositions. Specifically, the present invention relates to a composition that provides a cellular polyurethane nidistomer suitable for use in vibration damping materials and the like with excellent elastic recovery and durability. More specifically, the present invention relates to a composition that provides a cellular polyurethane elastomer that is particularly applicable as a vibration damping material for automobiles used under severe natural conditions such as rain, snowfall, intense heat, and extreme cold.

Conventionally, naphthalene diisocyanate has been mainly used as an isocyanate component in automobile vibration damping materials due to the excellent properties of urethane obtained from the isocyanate component. In some cases, the composition consists of a chain extender, a reaction accelerator, and a colorant as main ingredients. However, 1,5-naphthalene diincyanate has drawbacks such as being very expensive, having poor stability and being difficult to handle. The present inventors conducted extensive research to improve the drawbacks of naphthalene diincyanate-based vibration damping materials and arrived at the present invention.

That is, the present invention provides polyhydroxy compound fAl, organic diisocyanate (B), foaming agent (C1, foam stabilizer tDl,
In a cellular polyurethane elastomer composition comprising at least a chain extender fEl, the polyhydroxy compound is an aliphatic polyester polyol with a molecular weight of 1000 to 3000, the blowing agent fcl is an organic diisocyanate (Bl casiphenylmethane diisocyanate), and the blowing agent fcl is water. At least 50% by weight of the foam stabilizer FD+ is a surfactant having either a acid ester base or a sulfone base, and at least one of the chain extenders (El is an aromatic diamine, and (Al + (C1+) (Al + (C1 + The equivalent ratio of active hydrogen forming the mixture is fAl + fcI + fEl-0,1
whereas polyhydroxy compound fAl is 005-008,
Chain extender fEl is 0, 2-0.5, blowing agent 1cI is 03
The present invention provides a cellular polyurethane elastomer composition having the following characteristics.

Commonly used are aliphatic dibasic acids, such as succinic acid, geltaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, cepatic acid, dodecanedicarboxylic acid and aliphatic glycols, such as ethylene glycol, diethylene glycol, furopylene gelicol, futilengelic acid. Although it can be obtained by a condensation reaction with recall, pentyl glycol, or hexane glycol, adipic acid ester is preferred from the economic point of view. Polyesters obtained by open-wall polymerization of lactones can also be used. These polyester polyols can be prepared by a condensation reaction by mixing two or more types of glycols, or by mixing two or more types of polyesters that are different in type and/or have different molecular weights.

The molecular weight of the polyester polyol of the present invention is from 1000 to
Must be 3000.

If the molecular weight is less than 1,000, the repeated compression fatigue resistance as a vibration isolating material will be poor, especially at low temperatures, and if the molecular weight exceeds 3,000, the compressive stress as a vibration isolating material will decrease and it will not be suitable for practical use.

The organic diisocyanate (B1 is diphenylmethane diisocyanate) used in the present invention. Diphenylmethane diisocyanate is generally 4,4'-diphenylmethane diisocyanate, but contains up to 10% of 2,4'-diphenylmethane diisocyanate. You may do so.

The blowing agent used in the present invention [C1 is water. The water neck is not particularly limited. Generally, the density is 03-0.817
A water jar is used that is appropriate for the amount of carbon dioxide gas generated by the reaction with the isocyanate group, which is suitable for obtaining a male vibration damping material.

One of the foam stabilizers used in the present invention is at least 50% of the foam stabilizer used in the present invention.
It is a surfactant having either a sulfate ester base or a sulfonate base by weight. Examples of surfactants having a sulfate ester base or a sulfonate group include alkyl sulfates, olefin sulfates, alkylbenzenesulfonic acids, alkylnaphthalenesulfonic acids, oleamide sulfonic acids, dialkylsulfosuccinic acids, and sulfated castor 6- Cover with lithium, potassium, sodium, ammonium salts, etc. of oil. A surfactant having either a sulfate ester base or a sulfonate base has 5.01 Jti! A foam stabilizer having l: less than 1 has poor formability into a vibration damping material and is inferior in practicality.

As a foam stabilizer that can be used in combination with the surfactant having either a image acid ester base or a sulfonic acid group according to the present invention, a typical foam stabilizer is preferably a polyether-modified dimethylpolysiloxane represented by the following structural formula. mentioned, -rl-
There is a +15 notification for Toray Silicone 5RX-2740 (Toray Silicone 1IJJ product).

CH, CH, R' CH.

A: There are no particular restrictions on the amount of foam stabilizer used, but in general, it is preferable to use a foam stabilizer of 0.1 to 6 weight relative to the total weight. It has the disadvantage of high water absorption.

At least one of the chain extenders fEl used in the present invention is an aromatic diamine. As aromatic diamine, 3
, 3'-dichloro-4,4'-diamino-diphenyl-methane, trimethylene glycol di-P-aminobenzoate (Ihara Chemical Industry ■ trade name Iharacuamine CUA-4), 4,4'-diaminodiphenylmethane, 1. Examples include 5-naphthalenediamine, 1,4-phenylenediamine, polymethluidine-diamine, xylylenediamine, tolylenediamine, polymethylene:polyphenylpolyamine, etc., but 3,3'-dichloro-, which has low reactivity in terms of processing, 4,4'-diaminodiphenylmethane and trimethylene glycol-di-P-aminobenzoate are preferred. When these aromatic cyanogens are not contained, the vibration damping material obtained therefrom has a disadvantage that the repeated compression fatigue resistance is significantly poor. Examples of chain extenders that can be used in combination as the chain extender of the present invention include glycols such as ethylene glycol, glopylene glycol, and butylene glycol, and polymethylene polyphenyl polyamine.

In the present invention, the equivalent ratio of active hydrogen to incyanate group is 1.
0.9 to 1.1. Active hydrogen is polyhydroxy compound IAI, foaming agent + CI water, or foam stabilizer f
If Dl contains a compound having active hydrogen, its foam stabilizer and chain extender (attributable to 8), and the isocyanate group is attributable to diphenylmethane diisocyanate, which is an organic diisocyanate IB+. Equivalent of incyanate group to active hydrogen. If the ratio is lower than 0.9, the molecular weight of the obtained nidistomer will not be sufficiently reduced, resulting in poor durability.-If the ratio is higher than 1.1, the obtained vibration damping material will have a particularly poor quality. It has the disadvantage of poor cyclic compression fatigue resistance at low temperatures.

The present invention provides a polyhydroxy compound FAI and a chain extender fEI.
The equivalent ratio is 1:1 to 5. However, if the equivalence ratio is lower than 1:1, sufficient rebound resilience as a vibration damping material cannot be obtained, and if it is higher than -1:1:5, there is a drawback that the repeated compression fatigue resistance, especially at low temperatures, is poor.

In the cellular polyurethane elastomer composition comprising at least the polyhydroxy compound IAI of the present invention, Yamazakura diisocyanate (B), a foaming agent (C1, a foam stabilizer (D), and a chain extender IEI), the polyhydroxy compound fAI has a molecular weight of 1000 to 6000. an aliphatic polyester polyol, an organic diisocyanate (Bl is diphenylmethane diincyanate, a blowing agent tel is water, a foam stabilizer (at least 50% by weight of DI is sulfuric acid varnish 1
0- A surfactant that supports either a methyl base or a sulfonic acid group, at least one type of chain extender fEl is an aromatic diamine, and the equivalent ratio of active hydrogen to incyanate group is 1. 0.9 to 1.1, and the equivalent ratio of the polyhydroxy compound (A) to chain extension 4J (El) is 1 to 1 to 5. If necessary, an incyanate group reaction accelerator or retardant may be added, and antioxidants, ultraviolet absorbers, continuous water decomposition inhibitors, colorants, etc. may also be added.

The cellular polyurethane disstomer of the present invention is produced by a conventional one-shot method or a prepolymer method, but it is produced by a polyhydroxy compound fAI and an organic diisocyanate (B
) is preferably reacted with the prepolymer method. All or all of the foam stabilizer iDl and/or the chain extender fEl,
Portions of either can be mixed at any stage of prepolymer production.

The vibration damping material obtained by the composition of the present invention consists of a component heated to 70 to 90C and a component heated to 25 to 45C (foaming agent,
The ingredients (foam stabilizer, chain extender) are mixed for 5 to 10 seconds using a commonly used stirring mixer, and poured into a mold whose inner surface is coated with a mold release agent and heated to 50 to 100C. Usually, the first reaction is aged at 110C for 115 minutes, and then demolded, and further in a heated atmosphere at room temperature or preferably at 90 to 150C, 5 to 2
4 hours, particularly preferably 100-110C, 10-20C
It is obtained by secondary reaction ripening for hours.

The composition of the present invention is preferably used as a vibration damping material for foam molded products, especially automobiles, and its cream time is 3.
Rise time 1 for 5 to 60 seconds (200g of meat)
It is 20 to 180 seconds. In addition to this, Ichikawa is very particular about products that require compression durability.

The present invention will be described in detail below with reference to Examples, but all "parts" in the text are based on diphthongs.

Example 1 Ethylene glycol (EG) and butylene glycol (EG)
-# Esthetics of (B G ) and adipic acid, M molecule -ji2000, OH value 55.6, acid value 0.5) 7
5.67 parts (0,07567 parts IA-) in vacuum degree 5H
After degassing and dehydrating for 30 minutes at 125C under 1, 24.33 parts (0,19
A urethane prepolymer (NCO 1i840) was added and reacted for 30 hours at 8DC in a nitrogen stream to produce a urethane prepolymer (NCO 1i840).

Next, the blowing agent was 3,3'-dichloro-4,4'-diaminodiphenylmethane (hereinafter abbreviated as MOCA) 1.5
1 part (0,0113 equivalents), ethylene glycol (EG
ester of diethylene glycol (referred to as DEC) and succinic acid (molecular weight 2000, OH value 55.5
, acid value, 6) 13-5.65 parts (0,0056.5 equivalents) at 110C to 12
After melting in a heating bath at 5C, 0.88 parts of water (0,0978
It was produced by adding and mixing 088 parts of low sulfated oil, and 0005 parts of citric acid.

Urethane prepolymer 10 manufactured previously and adjusted to 70C
1DOO of 8.925 parts of blowing agent adjusted to 0 parts and 55C
After stirring at a high speed of rpm for 5 to 10 seconds, the mixture was poured into a mold heated to 80C.

After aging at 110C for 15 minutes, demolding and further aging at 110C for 1
The molded product obtained by aging for 5 hours was tested for dynamic properties and static properties, and the results are shown in Table 1 along with the formulation.

Examples 2 to 6 Molded articles were obtained in the same manner as in Example 1 except that the blending ratio of the blowing agent mixture shown in Table 1 was changed, and the properties thereof are shown in Table 1.

14- Comparative Example 1 EG/BG adipate ester 2000 (OHV56.
5. Acid value 0.5 > 75.671 vacuum level 5 m
After degassing and dehydration under Hf at 125C for 30 minutes, 4,4
24.33 parts of '-diphenylmethane diisocyanate was added, and the mixture was reacted for 30 hours at 8 DC in a cumulative air flow to produce a urethane prepolymer (NCO @ 840).

Next, the blowing agent was mixed with 1.02 parts of water and 1.02 parts of low-grade (M-based oil).
1 part, and 0.005 part of citric acid.

Urethane prepolymer 1 manufactured previously and adjusted to 70C
00 parts and 2.045 parts of blowing agent adjusted to 35C to 110 parts
After stirring at a high speed of 0 Orp for 5 to 10 seconds, the mixture was poured into a mold preheated to 80C.

After aging at 110C for 15 minutes, the mold was demolded and further aged at 110C for 15 hours.The static and dynamic properties of the resulting molded product are shown in comparison with the examples shown in Table 1.

Comparative Example 2 EG/B G adipate ester (molecular weight -2000,
OH value 55.6, acid value 0.5) 75.67 parts in vacuum degree 5
After degassing and dehydrating for 60 minutes at 125C under ++aH7, 4.
4'-diphenyl-methane-diisocyanate 24.3
Three parts were added and reacted for 30 hours at 80C in a nitrogen gas stream.
A urethane prepolymer (NCO 1-840) was produced.

Next, the blowing agents were 1.51 parts of 3,3'-dichloro-4,4'-diaminodiphenylmethane, EG/DEG Nisdel succinate (molecular weight 2000, OH value 55.5, acid value 0).
．． 6) After heating and melting 5.65 parts at 110C to 125C, 0.88 parts of water, 0.88 parts of low-value oxidized oil, and 1 and 105 parts of citric acid were added and mixed to produce the product.

100 parts of the urethane prepolymer prepared previously and adjusted to 70 GK:iM and 8.925 parts of a blowing agent adjusted to 35C,
After stirring at a high speed of 11,000 rpm for 5 to 10 seconds, the mixture was poured into a mold preheated to 80C.

Table 1 compares the static and dynamic properties of the molded product obtained by aging at 110C for 15 minutes, demolding, and further aging at 110C for 15 hours, and the molded product obtained from the example. It was shown to.

Comparative Example 3 A molded article was obtained in the same manner as in Comparative Example 1 using the formulation shown in Table 1, and its static and dynamic properties are shown in Table 1.

Example 7 EG/BG adipate (molecule [2000, OH
Value: 55.6, acid value: 0.5) 75.67 parts, degree of vacuum: 5
After degassing and dehydration for 125C'''c5D under mHf, 4.4'-diphenyl-methane diincyanate)24.
A urethane prepolymer (NCO 840) was produced by adding 33 parts of the mixture and reacting for 50 hours at 80C in a nitrogen stream.

Next, the blowing agents were 3.53 parts of trimethylene glycol-di-P-aminobenzoate (Ihara Chemical Industries product Iharacuamine CU-A-4), EG/DEG succinate ester 2000 (OR value 56.5, acid value 0.6)5
．． After melting 65 parts at 125 to 135C, add 0.76 parts of water, 0.76 parts of low sulfated oil, 0.0
05 parts were mixed and produced.

Urethane polymer 100 manufactured previously and adjusted to 70CK
9,175 parts of a blowing agent adjusted to 4DC and 11,000r
After stirring at high speed for 5 to 10 seconds, the mixture was poured into a mold preheated to 80C.

After aging at 110C for 15 minutes, the mold was removed, and further aged at 110C for 1
The molded product obtained by aging for 5 hours was tested for static and dynamic properties, and the results are shown in Table 2.

Examples 8 to 12 Molded products were produced in the same manner as in Example 7 except that the blending ratios of the prepolymer and blowing agent mixture shown in Table 2 were changed, and their static and dynamic properties were as shown in Table 2. Indicated.

Comparative Example 4 EG/BG adipate ester 2000 (OH value 55.
6. After degassing and dehydrating 79.18 parts of acid value 0.5 at 125C for 30 minutes under a vacuum degree of 5m HIt, 20.82 parts of 1,5-naphthalene diisocyanate) was added, and the mixture was heated to 120 parts in a N gas stream. The reaction was carried out at ~125C for 25 minutes to produce a urethane prepolymer (NCO 840).

Next, the blowing agents were 1.02 parts of water and 1.02 parts of low-sulfated oil.
1 part, and 0.005 part of citric acid.

Urethane prepolymer 1 manufactured previously and adjusted to 70CK
00 parts and 2.045 parts of blowing agent adjusted to 35 rK to 110 parts
After stirring for 5 to 10 seconds using a high-speed stirrer at 0Orp, the mixture was poured into a mold preheated to 80C.

After aging at 110C for 15 minutes, the mold was removed, and further aged at 110C for 1
The static and dynamic properties of the molded product obtained after aging for 5 hours are shown in Table 2 in comparison with the examples.

Comparative Example 5 EG/BG adipate ester (molecular weight 2000, OH
Value 55.6, acid value 0.5) 75.67 parts, Jlc emptyness 5
After dehydration with no degassing for 30 minutes at 125C under iua Hf, 4.4'-diphenyl-methane diisocyanate 24.
33 parts of urethane prepolymer (NGO
840) was produced.

Next, the blowing agent was trimethylene glycol-di-p-7 minopenzoate (Iharacuamine CU-A-4) 1
．． 76 parts, 5.65 parts of EG/D EG succinic acid ester (Molecular weight 2000, OH value 56.5, acid value 0.6) ff After heating and melting at 125-165C, water 0.8
8 parts, 0.88 parts of low sulfated oil, and 0.005 parts of citric acid were added and mixed.

Urethane prepolymer 1 manufactured previously and adjusted to 70CK
00 parts and 9175 parts of blowing agent adjusted by 40CK to 100O
After stirring at high rpm for 5 to 10 seconds, the mixture was poured into a mold preheated to 80C.

After aging at 110C for 15 minutes, demolding and further aging at 110C for 1
Table 2 shows the static properties and dynamic customization of the molded product obtained by aging for 5 hours.

22- Comparative Example 6 A molded article was obtained in the same manner as Comparative Example 5 except that the blending ratio of the blasting agent mixture shown in Table 2 was changed, and its static and dynamic properties are shown in Table 2.

Incidentally, the static characteristics and dynamic characteristics were measured as follows.

(1) Static properties Density, tensile strength, elongation, tear strength, rebound resilience, compression set are JIS-6301 (7111 sulfur rubber test method),
Hardness is 5RIR-0101 (Japan Rubber Association standard)
It was fixed at 1.

(2) Dynamic properties The test sample was compressed by applying a load of 600 Kjl, and then the load was removed. This is counted as one time, and the compression speed is 160.
A compression test was repeatedly performed using C8M, and the number of times until cracks appeared in the sample was measured.

The spring constant is 1 according to JIS-6385 (vibration-proof rubber test method).

Attorney: Patent Attorney Takam Winning Procedural Amendment (spontaneous) dated April 1980, Mr. Aio Wakasugi, Commissioner of the Patent Office1, Indication of the case, Patent Application No. 201215 of 19812, Name of the invention: Cellular polyurethane elastomer Fa product 6, relationship with the amended person case Patent applicant 65-58 Sakashita 3-chome, Itabashi-ku, Tokyo 174 (28
B) Kawamura, Representative of Dainippon Ink & Chemicals Co., Ltd.
Kuni Shigeru 4゜ Agent Address: 6, Dainippon Ink & Chemicals Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Contents of Amendment (1) The scope of claims in the specification will be corrected as shown in Attachment 1. .

(2) The equivalent ratio of 1 to 0.9 to 1 as stated in page 4, line 5 of
．． 1," is equivalent to "(NCO,/(OH+N
H, ) ) is 0.9 to 1.1 to 1,'' he corrected.

(3) Page 4, line 6 cD r(A)+(C)+(E)
= o, 1J tr(A)+(c)+(E)== 1
．． Correct O.J.

(4) On page 9, line 15, "molecular weight does not decrease sufficiently" is corrected to "molecular weight does not increase sufficiently."

(5) "30 hours" in the following part of the specification is corrected to "3.0 hours".

Page 13, line 9, page 15, line 6, page 16, line 7, page 19, line 6, page 22, line 1.

(6) Table 1 on page 18 of the same page is corrected as shown in Attachment-2.

(7) Table 2 on page 24 of the same page is corrected as shown in Attachment-3.

(Above) 2- (Attachment-1) S59.4. Submitted patent claims (after correction) 1. A cellular polyurethane comprising at least a polyhydroxyl compound (A), an organic diisocyanate (B), a blowing agent (C), a foam stabilizer (D), and a chain extender (E). In the elastomer composition, the polyhydroxyl compound (A)
is an aliphatic polyester polyol with a molecular weight of 1000 to 3000, the organic diisocyanate (B) is diphenylmethane diincyanate, and at least 50% by weight of the blowing agent (C1 is water, foam stabilizer) is a sulfuric ester base. , a sulfonic acid group, at least one of the chain elongation groups is an aromatic diamine, and the total amount of active hydrogen of (A)-He) Equivalence ratio (NC
'/(on+NH2)) is 1.0 to 0.9 to 1.1, and the equivalent ratio of active hydrogen forming the blowing agent mixture is:
CI-HE = 1.0, polyhydroxyl compound (A) is 0.05-0.08, chain extender (E)
A cellular polyurethane elastomer composition, characterized in that the polyurethane elastomer has a polyurethane elastomer of 082 to 05 and a blowing agent (C) of 0.32 to 0.75.

Claims (1)

[Claims] t Polyhydroxy compound, organic diisocyanate (B), foaming agent (CI, foam stabilizer (D), chain extender 1B+
In a cellular polyurethane elastomer composition comprising at least
000 to 6,000 aliphatic polyester polyol, an organic diisocyanate (B1 is diphenylmethane diincyanate, a blowing agent (C1 is water, at least 50% of the foam stabilizer TDI, and at least 50% of the foam stabilizer TDI is an image acid ester base, at least one of the chain extenders fEl is an aromatic diamine, and (Al + (C1+ The equivalent ratio of the inocyanate group of the urethane prepolymer obtained by reacting TBI with TBI is 1.
The equivalent ratio of active hydrogen forming the blowing agent mixture is (4)+(C1+ (El= o
, 1, whereas the polyhydroxyl compound [AI is 0.0
5-piece, chain extender IEI 0.2-0.5, before foaming C)
A cellular polyurethane disstomer composition, characterized in that the