JPH02232218A - Polyurethane foam - Google Patents

Abstract

PURPOSE:To obtain a polyurethane foam improved in mechanical properties, weldability, high-frequency weldability, etc., by reacting a polyhydroxy compound comprising a specified polyester polyol and polyoxyalkylene glycol with a polyisocyanate. CONSTITUTION:An alcohol component (i) comprising a polyalcohol having a side chain, a low-MW polyhydroxy compound, and/or a polyoxyalkylene glycol of an MW of 300-2500 is esterified with an acid component (ii) comprising an aliphatic, aromatic or alicyclic dicarboxylic acid to obtain a polyester polyol (a) of an MW of 300-3000, having a main chain comprising at least one kind of component (i). A polyhydroxy compound (A) comprising component (a) and a polyoxyalkylene glycol (b) of an MW of 500-5000 in an amount to give a mixing ratio of component (a) to component (b) of (1-50)/(99-50) is reacted with an organic polyisocyanate (B) in the presence of a catalyst, a blowing agent, a foam stabilizer, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to polyurethane 7 ohm which has excellent stability of raw polyol liquid, mechanical properties of foam, and excellent heat fusion and high frequency fusion properties. It is.

(Prior Art and its Problems) Conventionally, various attempts have been made to impart heat-adhesive properties to flexible polyurethane foams. For example, a method using phosphorus-containing polyether/polyol (% Kosho 48-
37600), frame lamination. A method of attaching phosphoric acid to at least one of the urethane foam or the base material before coating (Japanese Patent Publication No. 47-6519), or a method of attaching phosphoric acid to at least one of the urethane foam or the base material, or a method of attaching phosphoric acid to at least one of the urethane foam or the base material, or a method of attaching phosphoric acid to at least one of the urethane foam or the base material (Japanese Patent Publication No. 47-6519), or a method of attaching phosphoric acid to at least one of the urethane foam or the base material, or a method of attaching phosphoric acid to at least one of the urethane foam or the base material. Method using urethane foam made of organic phosphorus compound (q!! Publication No. 46-303
No. 09), flexible urethane foam using hydroxyl-terminated urethane polyol (JP-A-61-78816), flexible foam using I-lyester polyether polyol whose alcohol component is W compound with 7-rukylene oxide of an aromatic dihydroxy compound Polyurethane foam (Japanese Unexamined Patent Publication No. 73717/1983) is known. However, such foam has low polyol stability, (I1
) Mechanical properties of foam, qID heat fusion properties and high frequency fusion properties (depending on the type of adherend, it has no adhesive strength at all)
However, it was not perfect as there were still some problems.

(The invention is about to come!!M) However, in view of the existence of various drawbacks of the prior art as described above, the present inventors have conducted intensive research to eliminate all of these drawbacks (2) As a result, the present invention has been developed. (Means for solving the problem) That is, the present invention provides polyester polyol (I) and polyol pieces using one or more polyhydric alcohols having side chains in the main chain. A polyurethane foam characterized by the combination of a polyester polyol (.1) with a polyhydric alcohol having a side chain and a linear low-molecular polyhydroxy compound and/or a molecule t.
To provide a polyurethane foam characterized in that it is an I-lyester polyol containing 300 to 2,500 polyoxydialkylene glycol as an alcohol component, and further, the polyester polyol (I) has a molecular weight of 7,300 to 3,000. It is.

(Structure) The 2-rester polyol (I) of the present invention contains a polyhydric alcohol having all side chains, a low-molecular polyhydroxy compound and/or a polyoxyalkylene glycol having a molecular weight of 300 to 2500 as alcohol components, and a dicarboxylic acid (fatty It is obtained by an esterification reaction using an aromatic group (aromatic group, alicyclic group) as an acid component.

The 1-bar chain low molecular weight polyhydroxy compound of the present invention is preferably a compound that does not have a side chain (alkyl group) in the main chain, has 2 to 4 functional groups, and has a molecular weight of 60 to 300,
For example, ezalene glycol, 1.3-f robylene glycol, miqueterene glycol, 1,4-butylene glycol A., L5-amyl glycol, 1,6-hexamethylene glycol, bishydroxye} xybenzene. Or glycols such as p-xylene glycol, glycerin, . Polyfunctional polyhydroxy compounds such as hexanetriol, triethanolamine, pentaerythritol, and ethylenediamine can be used.

In the present invention, polyester polyol is used.
A polyhydric alcohol having at least one side in total is a compound having an alkyl group as a side chain, and preferably has 1 to 34 carbon atoms in the side chain, for example, 1. 2-
'7'' robylene glycol, zo1 .2-glopylene glycol, 1.2-7'' tyrene glycol, 1.3
-1-terene glycol, 2,3-pterene glycol,
2.2-dimethyl-X. 3-7'0 pandiol, 3-
Methyl-1,5-pentanol, 3-methyl-1.
3.5-Pentanetriol% 2,2.4-trimethyl-X. ．． 3--S tannediol, 2.1-ethyl-1
．． 3-hexanediol, 2,2-dimethe-3-hydroxyglobyl-2,2-dimethe-3-hydroxypronomate, neobentyl glycol. 2-N-2-ethyl 1.3-f
3-Ethyl 1.5-entanediol, 3-globyl-1.5pentanediol, 2.2-diethyl-1
．． 3-zolopanool, 3-octyl-1.54-tanediol, 2-edyl-1,3-hexanediol, 3
- myristyl-1,5-pentanediol, 3-stearyl-1,5-pentanediol, 3-7enyl-X.
5--<ntandiol, 3-(4-nonylphenyl)
-1.5-4 entanediol, 3,3-bis(4-nonylphenyl)-1.5 --e entanediol% 1,
2-bis(hydroxymethyl)cyclode,・tan,
1.3-bis(hydrooxyethyl)cyclobutane, 1
．． 3-bis(hydroxymethyl)citalobentane, 1.
4-bis(hydroxymethyl)cyclohexane, 1.4
-bis(hydroxyethyl)cyclohexane, 1.4-
Bis(hydroxyprobyl)cyclohexane, 1.4-
Bis(hydroxyethyl)cyclohegtane, 1,4-bis(hydroxymethoxy)cyclohexane, 1,4-bis(hydroxyethoxy)cyclohexane, 2,2-bis(4'-hydroxymethoxycyclohexyl)zolono ξ to 2,2-bis (4'-Hydroxyethoxycyclohexyl) f mouth) 4 7 s } 'J / ? Examples include Rollpronodan.

The aliphatic dicharge/acid of the present invention has 3 to 1 carbon atoms.
4 are preferred, such as malo/acid, succinic acid, glutaric acid, adivic acid, pimelic acid, schelic acid, azelaic acid, sebacic acid, 1.9-nonamethylene dicarboxylic acid, 1.10-fcamethylene dicarboxylic acid, 1.10-fcamethylene dicarboxylic acid, etc. acid, 1.11
-unr-camethylene dicarboxylic acid, 1,12-do-camethylene dicarboxylic acid, and the like. Examples of aromatic dicarboxylic acids include orthophthalic acid, inphthalic acid,
Tere-7thalic acid, naphthalene dicarboxylic acid, andhracene dicarboxylic acid, and phenanthenedicarponic acid, but of course their anhydrides or various derivatives can also be used, and two or more of these can be used. It may also be used as a mixture.

In order to split the polyester ether polyol or polyester polyol using the raw materials listed above, conventionally known esterification techniques using vacuum and/or catalysts can be employed,
One of the most representative books is ``Glycols and radicals under normal pressure?'' A method of reacting with phosphoric acids, a method of esterification under vacuum, or a method of esterification in the presence of an inert solvent such as toluene, and then azeotropically distilling the condensed water and the solvent to expel the water from the reaction system. There are methods to remove it.

Although it is of course possible to carry out the reaction in a system without a catalyst, inorganic or organic acids; Li. NasK
．． Rh, Ca. Bmu*Sr*Zn*Al*
T1,V,Cr*Mn,F@eCo,
Nl, Cu, Zr*Pd*Sne
Metal chlorides, oxides, hydroxides such as Sb or pb or fatty acid salts such as acetic acid, oxalic acid, octylic acid, lauric acid or naphthenic acid; sodium menalate, sodium ethylate, aluminum triisopropoxide , alcoholates such as isoglobil detanate or n-pter titanate; heptenolates such as sodium phenolate; or other organometallic compounds of metals such as AL, 'l'i, Zll, Sn*Zr or pb. Preferably, all catalysts commonly used for esterification and transesterification are used, such as.

In this case, the amount of the catalyst used is suitably within the range of 0.00001 to about 511 parts by weight, preferably 0.001 to 2 parts by weight, based on the total amount of the raw materials for preparing the polyester diol. The reaction temperature at this time is usually
It is in the range of 100 to 250°C.

The molecular weight of the polyester polyol (I) of the present invention is preferably in the range of 300 to 3,000, particularly preferably in the range of 500 to 2,000.

If the molecular weight of the polyester polyol is less than 300, the foaming stability during foam production will be poor and the mechanical properties of the foam will be poor. On the other hand, if the molecular weight of the polyester polyol is greater than 3,000, it will have poor compatibility with other polyoxyalkylene glycols and the like, resulting in poor stability of the polyol stock solution.

The mixing ratio of the I-rester polyol (I) of the present invention and the polyoxyalkylene glycol mixture is not particularly limited, but is preferably in the range of 1/99 to 50/50.

The polyoxyallene glycol of the present invention (I0 is a low-molecular polyhydroxy compound having a functional group number of 2 to 4). oxide, shrimp chlorohydrin (alone or in combination).The molecular weight is preferably 500 to 50.
00, more preferably 700-4500.

Also, molecular weight 300 to 250 used as an alcohol component.
Although it can be obtained in the same manner as No. 0 I-lyoxyalkylene dalicolmo, it needs to have a molecular weight of about 300 to 2,500 in order to be used as the alcohol component of polyester polyol. More preferably molecular weight 350-220
It is 0. If it is less than 300, it is difficult to distinguish it from ordinary glycol, and if it is more than 2,500, the esterification reaction takes time and it is difficult to use it as a real alcohol component.

The mixing ratio of the polyester polyol (I) of the present invention to polyoxyalkylene glycol (m is preferably 1
．． / 9 9 to 50/50.

The above-mentioned 4 +7 used as a percentage in carrying out the present invention
A mixture of ester-liol (I) and polyoxyalkylene glycol (ON) 1. As mentioned above, it is a heat-melting material with excellent stability and excellent foam properties, heat-melting properties, and mold resistance. Since the adhesive flexible urethane foam is to be obtained, the above-mentioned specific components should be exclusively used, but if necessary, the number of functional groups may be 2 to 8. ,, Molecule It 500 ~ 7000 (D, $ 17) Adivic acid-based polyesters such as diether polymers such as oxytetramethylene glycol, zari, ethylene oxide, polybutylene azisheet, etc. Polyols, lactone-based polyesters, and specific polyester polyols (I
) and polyoxyalkylene glycol ().

The polyisocyanates that can be used in the present invention include 11, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture thereof, and m-moshi (ij: p-7-enylene diisocyanate). N゜anethane, p~xylene diisocyanate, eblene diisocyanate, tetramethylene-1
, 4-diisocyanate, hexamethylene-1,fl-
Di-isocyanate, diphenylmethane-4.4'-
Diisocyanate, 3.3'-dimenal-diphenylmethane-4.4' monoisocyanate, 3.3'-dimethy/I/-4.4'-biphenylene diisocyanate, 3
．． 3'-dichlor-4.4'-bife. :? Len Cuisocyane}. There are various derivatives of 414'-1-phenylene diisocyanate or 1,5-naphthalene diisocyanate, crude diph,nylmethane diisocyanate, and diphenylmethane diisocyanate.

More ingredients? A conventionally known method such as a one-piece method can be used. The urethane foam of the present invention may be produced by a cutting method, a graypolymer method, or the like. What is the polymer method and polyhydroquine compound? All lysocyanate is pre-treated.
In this method, a pre-volatile polymer is obtained, and then a polyhydroxy compound is reacted with gold in the presence of a blowing agent, a catalyst, a foam stabilizer, and other additives. ?
/The method uses a catalyst and a blowing agent. K organic in the presence of foam stabilizers and other additives? Polyurethane foams can be produced by these methods by combining a reisosibnate and a polyhydroxy compound.

Here, as polyisoanate, the following items can be used.

The catalyst used in the present invention may be one that is commonly used in the production of polyurethane foam, such as organotin compound catalysts and amine catalysts. Examples of the tin compound catalyst include stannath octoate, stannath oleate, dibutyltin dilaurate, dibutyltin di~2
- Ether xoate, dibutyltin diacetate, etc.

In the present invention, the foam stabilizer used may be a general silicone foam stabilizer for producing polyurethane foam.

Sixth, in the present invention, water (which produces a carbonate bath by reaction with an organic isocyanate) is mainly used as a blowing agent, but if necessary, monofluorotrichloromethane or Methylene chain mouth. Low boiling organic compounds such as lide and air can also be used.

In addition to the above-mentioned ingredients, fillers, antistatic agents, coloring agents, flame release agents, etc. may be added depending on the performance required for the foam, as long as they do not deviate from the purpose of the present invention. .

(Effects) The polyurethane foam of the present invention is preferably used as a flexible polyurethane foam because it has excellent polyol stability and mechanical properties, as well as excellent heat fusion and high frequency fusion properties. be done.

It can be used for vehicle seats, interior materials, chairs, cushions, etc. as it has excellent thermal and high frequency fusion properties with textiles, cloth, non-woven fabrics, etc. for interior materials, chairs, etc. It is used in fields that require cushioning properties such as cushioning.

Next, examples of the present invention will be described, but the present invention is not limited thereto. In the text, "part" and "chi" are based on weight.

Example 1 3-methyl-1.5 --{513 parts of ntanediol,
A polyester polyol having an average molecular weight of 985 was obtained from 487 parts of adipic acid.

20 parts of the above polyester polyol K average molecule [300
A mixture of 80 parts tl of polyoxypropylene triol and 0.1 parts of triethylene diamine
4. part with water. O II K dissolved, silicon L-
Add 1.0 part of 540 (Nippon Unica fM), 0.25 part of Stanus Octoate, and further add 49.6 parts of TDI-80 (NGO index 105), stir vigorously, and pour into a suitable mold to make flexible polyurethane foam [). I got it.

Example 2 257 parts of 3-methyl-1,5-intanediol, 293 parts of dipropylene glycol, and 450 parts of adipic acid!
A polyester polyol having a F average molecular weight of 810 was obtained.

30 parts of the above polyester polyol K average molecule [300
A mixture of 70 parts of polyoxypropylene triol of 0.0 and 0.0% was foamed as a polyol in the same manner as in Example I to obtain a flexible polyurethane foam (I13).

Example 3 A polyester polyol having an average molecular weight of 1,205 was obtained from 457 parts of 3-methyl-L5--tantanediol, 102 parts of trimethylolgulonone, and 441 parts of adivic acid.

20 parts of the above polyester polyol has an average molecular weight of 300.
A mixture of 80 parts of polyoxyderovylene triol of 0.0% and 80 parts of polyoxyderovylene triol was used as the total polyol and foamed in the same manner as in Example 1 to obtain a flexible polyurethane foam (Iff).

Example 4 A polyester polyol having an average molecular weight of 995 was obtained from 266 parts of 3-methyl-1,5-pentanediol, 234 parts of neointyl glycol, and 500 parts of adivic acid.

The above polyester polyol l 5 parts K average molecular weight 300
A mixture of 85 parts of polyoxypropylene triol of 0.0% and 85 parts of polyoxypropylene triol was used as a polyol and foamed in the same manner as in Example 1 to obtain a flexible polyurethane foam CF/).

Example 5 287 parts of 3-methyl-1.5--e tanediol,
Polyoxyglobylene diol 3 with average molecular weight iooo
70 parts, average molecular weight 2550 from 343 parts of anhydrous 7tal R
A polyester polyol was obtained.

40 parts of the above polyester polyol K average molecule [300
A mixture of 60 parts fc of polyoxypropylene triol of 0.0 and 60 parts fc was used as a polyol and foamed in the same manner as in Example 1 to obtain a flexible polyurethane foam [■].

Comparative Example 1 97 parts of 4-lioxyglopylene triol with an average molecular weight of 3000 obtained by adding globylene oxide to glycerin and kijun oxy with a Suishun group value of 330 obtained by adding propylene oxide to 100% phosphoric acid. rLiz
A flexible polyurethane foam [■] was obtained by foaming in the same manner as in Example 1 except that 3 parts of phosphoric acid was mixed and used.

Comparative Example 2 A commercially available 85% phosphoric acid fi! :20fl/m
A flexible polyurethane foam [■] was obtained. Comparative Example 3 Propylene glycol K as a polyol 2250 parts of polyoxyderobylene glycol with an average molecular weight of 1500 to which propylene oxide was added, 500 parts of phthalic anhydride, 2.5 parts of triethylamine, 2 parts of propylene oxide
50 parts were charged into a pressure-resistant reaction vessel and reacted at 80 to 120°C. After the reaction is complete, remove unreacted glopylene oxide and low-boiling compounds under reduced pressure. Hydroxyl value: 55, acid value: 042
50 parts of polyester ether polyol of 0.0, 48 parts of polyoxyderobylene triol with an average molecular weight of t3000 obtained by adding zolobylene oxide to glycerin, and 2lI'f of propoxylated phosphoric acid used in the comparative example:
A flexible urethane foam [■] was obtained by foaming in the same manner as in Example 1 except for mixing and using.

Comparative Example 4 501 parts of dide I″I♂lene glycol, 4 parts of phthalic anhydride
A polyester polyol having an average molecular weight of 3500 was obtained from 99 parts.

An average amount of 300 parts per 10 parts of the above polyester polyol
A mixture of 90 parts of polyoxyderovylene triol of 0.0 and 0.0% was used as a polyol and foamed in the same manner as in Example 1 to obtain a flexible urethane foam (UK).

Comparative Example 5 Esderboliol with an average molecular weight of 4050 was obtained from 468% of 3-methyl-1.5 to pentanediol and 532 parts of adivic acid.

30 parts of the above polyester polyol has an average molecular weight of 300.
A mixture of 70 parts of polyoxypropylene triol of No. 0 was used as a polyol and foamed in the same manner as in Example 1 to obtain flexible polyurethane foam [X].

Comparative Example 6 A polyester polyol having an average molecular weight of 295 was obtained from 185 parts of 3-methyl-1.5-pentanediol, 95 parts of ethylene glycol, and 220 parts of 'adibic acid.

Average molecular weight: 30 parts to 30 parts of the above polyester polyol
00c! A mixture of 75 parts of J polyoxyglobylene triol was mixed with polyol [2] and foamed in the same manner as in Example 1 to obtain flexible urethane foam [X'3].

Example 6 560 parts of diglobylene glycol, 440 parts of adivic acid, and a polyester polyol with an average molecular weight of 900 Lv.
It was 8.

? An average molecular weight of 300 is added to 20 parts of the polyester polyol.
A mixture of 80 parts of polyoxyglopyrene triol (T-4) was foamed in the same manner as in Example 1 to obtain flexible urethane foam. Example 7 Neotynyl glycol 486 parts, butynic acid 514 parts
A polyester polyol having a percent average molecular weight of 850 was obtained from the sample.

25 parts of the above polyester polyol has an average molecular weight of 300.
A soft urethane foam [■] was obtained by foaming a mixture of 75 parts of polyoxypropylene triol of -0 as a polyol by the method of Example 1 and Mall.

[Heat fusion method]

The flexible polyurethane foam obtained above (I3 ~ [Knowledge]) was sliced into 15 mm thick pieces, and
Cut to size m. Melt the entire surface of these Sandel 7 ohms with a gas burner set to a constant flame,
Immediately fuse it onto the specified fabric under constant pressure. 24 hour broadcast M. Then take a test piece of 120w x 25 cod and JISL-
Peel strength 'jk was measured based on 1066-1963.

The measurement results are shown in Table 1.

／ ／−′−／ ・One 2／′ ／゛′ ／ ／′ ／ ／ [High frequency welding method] Using a high frequency welding device (self-excited oscillation type, output 3 kW) manufactured by No4 Kogyo Co., Ltd., The time required for high turbidity welding to fuse 7 ohms together is 1-1 when two sheets of foam T sampled to a thickness of 10 m are stacked and 7 ohms are fused together under the following conditions K! lIIJ was determined and high frequency fusion properties were evaluated. The results are shown in Table 2.

*Condition 1 Tuning dial = 80, Pressure: 3k9/cfn2, Cooling time = 4 seconds *Condition-2 Tuning dial = 50, Pressure: 3 Yu/piece, Cooling time: 4 seconds Table 2 [Stability of raw polyol liquid Sex test method〕1 0 0
oe beaker K Examples 1 to 7 and comparative examples 1.3.4.
Add the raw material polyol 30.9 from Step 5 and add 100% relative humidity.
It was stored for 4 weeks at 50°C and changes in appearance over time were measured. The results are shown in Table 3.

11!3 table

Claims (1)

[Claims] 1. A polyurethane foam characterized in that a polyester polyol (I) containing one or more polyhydric alcohols having a side chain in its main chain and a polyoxyalkylene glycol (II) are used in combination. 2. Polyester polyol (I) has a molecular weight of 300
3,000. The polyurethane foam of claim 1, wherein the polyurethane foam has a polyurethane foam of 3. A claim characterized in that the polyester polyol (I) contains a polyhydric alcohol having a side chain, a linear low-molecular-weight polyhydroxy compound, and/or a polyoxyalkylene glycol having a molecular weight of 300 to 2,500 as alcohol components. 1 and 2 polyurethane foam.