JPH0676471B2 - Method for manufacturing laminated foam - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a laminate, and in particular, a flexible polyurethane foam having excellent heat fusion property is produced by using a polyol containing a specific low molecular weight polyol, and then the flexible polyurethane foam is produced. The present invention relates to a method for producing a laminated foam by laminating and integrating the same with a fabric base material by heat fusion.

The flexible polyurethane foam is usually obtained by reacting a polyether polyol having a hydroxyl value of about 40 to 70, especially about 50 to 60 with a polyisocyanate compound in the presence of a catalyst and a blowing agent. Woven fabric as the application of this flexible polyurethane foam,
In some cases, a non-woven fabric or a sheet that is laminated and integrated with another fabric base material by heat fusion is used for clothing or the like. The heat fusion includes a method of heating the surface of the flexible polyurethane foam by flame or hot air, which is called flame lamination, and a method of laminating it on a substrate, and a high frequency fusion method, and the former is particularly common.
However, the usual flexible polyurethane foam has a very low fusion force, and the above-mentioned flexible polyurethane foam for heat fusion is produced by using a polyol obtained by modifying an ordinary polyether polyol or a specific additive. For example, Japanese Patent Publication Sho 46
-28425 discloses a modified polyether polyol obtained by ester-modifying the end of a polyether polyol, and JP-B-49-13880 discloses a urethane-modified polyether polyol modified by reacting an isocyanate compound. It is described as being suitable as a raw material for flexible polyurethane foam. Further, a method of improving heat fusion property by using a phosphorus compound in combination is also known, and in addition to the above Japanese Patent Publication No. 48-13880, for example, Japanese Patent Publication Nos. 46-30309 and 48-37600. Have been described.

However, the method using the above-mentioned specific modified polyether polyol has a demerit due to the need for modification, and it is considered to be extremely advantageous technically and economically if an unmodified polyether polyol can be used. To be The present inventor has studied a method for producing a flexible polyurethane foam having high heat fusion property by using an ordinary polyether polyol. As a result, they have found that a flexible polyurethane foam having a high heat fusion property can be produced by a method in which a small amount of a specific low molecular weight polyol is used in combination. This low molecular weight polyol can also be used in combination with the modified polyether polyol to further improve its heat fusion property. This low molecular weight polyol is composed of a polyhydric alcohol- (ε-caprolactone) adduct or a polyhydric phenol- (alkylene oxide) adduct, and its hydroxyl value is 150 to 600, preferably about 250 to 600. The present inventor obtains a flexible polyurethane foam having excellent heat-sealing property by using a mixed polyol of a high-molecular weight polyol consisting of the unmodified or modified polyether-based polyol and the above specific low-molecular weight polyol. At the same time, it was found that when a small amount of phosphorus compound is used together with this specific mixed polyol, more excellent heat fusion property is exhibited.

The present invention produces a flexible polyurethane foam having excellent heat fusion characteristics, which is characterized by the combined use of the above specific low molecular weight polyol, and then the flexible polyurethane foam is laminated and integrated with a fabric base material by heat fusion to obtain a laminated foam. Which is the following invention.

A polyol and a polyisocyanate compound are reacted in the presence of a catalyst, a foaming agent, an additive such as a foam stabilizer to produce a flexible polyurethane foam having excellent heat fusion properties, and then the flexible polyurethane foam is used as a fabric substrate. In the method for producing a laminated foam by laminating and integrating by heat fusion,
A high molecular weight polyol consisting of a polyether polyol having a hydroxyl value of 30 to 70 as a polyol or a modified product thereof.
A mixed polyol containing 70 to 98% by weight and 2 to 30% by weight of a low molecular weight polyol having a hydroxyl value of 150 to 600 consisting of a polyhydric alcohol- (ε-caprolactone) adduct or a polyhydric phenol- (alkylene oxide) adduct. Is used and 0.01 to 5% by weight of an organic phosphorus compound based on the mixed polyol is used as an additive.

As the polyether polyol in the present invention, a polyether polyol obtained by adding a monoepoxide, particularly an alkylene oxide, to a polyfunctional initiator is suitable. The most preferred alkylene oxide is propylene oxide alone or a combination of propylene oxide and ethylene oxide. In some cases, a small amount of propylene oxide such as butylene oxide or styrene oxide and a monoepoxide other than ethylene oxide can be used together with them. The proportion of ethylene oxide units, that is, oxyethylene groups, in the polyether polyol is preferably at most about 35% by weight, particularly preferably about 20% by weight or less. This oxyethylene group may be inside or at the end of the polyether chain, and may be bonded to other oxyalkylene groups or the like in a random or block form. A polyfunctional initiator is a compound having two or more active hydrogen atoms of a functional group having an active hydrogen atom to which a monoepoxide such as a hydroxyl group, a carboxylic acid group and an amino group can bond, and examples thereof include polyhydric alcohols and polyfunctional alcohols. There are polyhydric phenols, alkanolamines, mono- or polyamines, etc., and polyhydric alcohols are most preferable.
Two or more of these polyfunctional initiators can be used in combination.
It is suitable that the number of functions of the polyfunctional initiator is about 2 to 8, and particularly preferably about 2.5 to 6.0 on average. Particularly preferred polyfunctional initiators are glycerin, trimethylolpropane, pentaerythritol, diglycerin, sorbitol, sucrose, and other polyhydric alcohols having 3 to 8 valences, alone or in combination, or with them, ethylene glycol, diethylene glycol, Propylene glycol, dipropylene glycol and other 2
It is a combination with a polyhydric alcohol. The most preferred polyfunctional initiator is glycerin or a combination of glycerin with other polyhydric alcohols. The polyether-based polyol in the present invention may also be a mixture of at least two types of polyether-based polyols produced separately. The average hydroxyl value of the polyether type polyol in the present invention needs to be 30 to 70, and more preferably about 35 to 60. The average number of hydroxyl groups per molecule is preferably about 2-8, and more preferably about 2.5-6.0.

As described above, the main polyol in the present invention may also be a modified product of the above polyether polyol.
For example, as described in the above-mentioned known examples, an ester-modified polyether-based polyol or polyether obtained by reacting a polyether-based polyol with a polycarboxylic acid or its anhydride and then adding a small amount of alkylene oxide or the like. A urethane-modified polyether-based polyol obtained by modifying a system-based polyol with a polyisocyanate compound can be used. It is necessary that the hydroxyl value of the modified polyether polyol is within the range of the present invention as a result of modification. For example, a polyether polyol having a hydroxyl value of more than 70 can be used, and a modified polyether polyol having a hydroxyl value of 30 to 70 as a result of modification can be used. The modified polyether-based polyol can be used in the form of a mixture with the unmodified polyether-based polyol. For example, a mixture of an unmodified one obtained by modifying a part of an unmodified polyether polyol and a modified one can be used. Needless to say, in these, the average hydroxyl value is required to be 30 to 70.

The specific low-molecular weight (that is, high hydroxyl value) polyol in the present invention comprises a polyhydric alcohol- (ε-caprolactone) adduct or a polyhydric phenol- (alkylene oxide) adduct. The former is a polyol obtained by adding one or more molecules of ε-caprolactone to a polyhydric alcohol, which is obtained by adding other lactone or alkylene oxide together with ε-caprolactone (hereinafter referred to as a modified product). Good. Suitable polyhydric alcohols are ethylene glycol, diethylene glycol, dipropylene glycol, 1.4-butanediol, glycerin, trimethylolpropane, diglycerin, pentaerythritol, and other polyhydric alcohols having 2 to 8 valences, particularly about 2 to 4 valences. Of course, at least two of these may be used in combination. The adduct of ε-caprolactone is defined by the hydroxyl value described below. As modified products, polyhydric alcohols and γ-caprolactone together with γ-
Ε is added to polyhydric alcohols and adducts obtained by adding other lactones such as butyrolactone or sequentially.
-Addition products obtained by adding a small amount of alkylene oxide after adding caprolactone. The polyhydric phenol- (alkylene oxide) adduct is a polyhydric phenol with at least 1 per phenolic hydroxyl group.
It is a polyol obtained by adding a molecular alkylene oxide. Examples of the polyphenols include bisphenol A (that is, 2.2-bis (4-hydroxyphenyl) propane) and bisphenol F (that is, bis (4-
Hydroxyphenyl) methane), bis-phenol S
(Ie, bis (4-hydroxyphenyl) sulfone),
There are novolak (that is, phenol-formaldehyde initial condensate), tetrabromobisphenol A, tetrachlorobisphenol A, resorcin, and the like, and these can be used in combination. The most preferred polyhydric phenol is bisphenol A. Suitable alkylene oxides are propylene oxide, ethylene oxide, and combinations thereof, with propylene oxide being particularly preferred. The amount of alkylene oxide added is defined by the hydroxyl value described below. Further, as a modified product, a product obtained by adding another monoepoxide together with an alkylene oxide can be used.

The hydroxyl value of each of the above two types of low molecular weight polyols is 15
Must be in the range 0-600, especially about 250-6
It is preferably in the range of 00. These low molecular weight polyols can be used in combination, and a small amount of other low molecular weight (a hydroxyl value of 150 or more) that does not exceed the majority of each.
You may use together with a polyol. However, it is preferred to use substantially only one of the above two low molecular weight polyols or a combination thereof. The more preferred hydroxyl number of the low molecular weight polyol is about 250-600. From a general tendency, the softer the polyurethane resin foam obtained, the higher the heat fusion property as the hydroxyl value of the low molecular weight polyol is relatively high.

The mixing ratio of the high molecular weight polyol and the low molecular weight polyol is 70 to 98% by weight of the former and 2 to 30% by weight of the latter. A particularly preferred range is about 80 to 97% by weight of the former and about 3 to 20% by weight of the latter. If the proportion of the low molecular weight polyol is too high, the physical properties of the resulting flexible polyurethane foam will be unfavorably affected. This is because the flexible polyurethane foam with good physical properties is obtained by using a polyol having an average hydroxyl value of about 100 or less as a raw material, and if the ratio of the low molecular weight polyol is too high, the average hydroxyl value of all polyols will be too high. .

The flexible polyurethane foam can be obtained by reacting the above-mentioned mixed polyol and polyisocyanate compound as main raw materials in the presence of additives such as a catalyst and a foaming agent. As the polyisocyanate compound, one kind or two or more kinds of aromatic, alicyclic or aliphatic polyisocyanate compounds can be used, and preferably aromatic polyisocyanate compounds are used. When a non-yellowing flexible polyurethane foam is desired, an aromatic polyisocyanate compound in which an isocyanate group is not directly bonded to an aromatic nucleus (for example, a xylylene diisocyanate compound) or an alicyclic or aliphatic polyisocyanate compound is used. used. These polyisocyanate compounds may be prepolymer-type modified products, trimerized products, dimerized products, carbodiimide modified products, and other modified polyisocyanate compounds. A preferred polyisocyanate compound is tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, a mixture thereof, or a mixture with another polyisocyanate compound containing them as a main component. The amount of the polyisocyanate compound used is appropriately about 0.9 to 1.3 equivalents, and particularly preferably about 0.95 to 1.20 equivalents, relative to 1 equivalent of the mixed polyol.

The compounds that are usually essential as additives are catalysts, blowing agents, and foam stabilizers. Typical catalysts are organometallic compounds such as organotin compounds and tertiary amine compounds, and in many cases, these are used in combination. Typical blowing agents are water and trichlorofluoromethane, dichlorodifluoromethane, methylene chloride, and other low-boiling halogenated hydrocarbon-based blowing agents.What is water and low-boiling halogenated hydrocarbon-based blowing agents? Often used together.
As the foam stabilizer, polydimethylsiloxane, polydimethylsiloxane-polyoxyalkylene block copolymer, and other silicon-based foam stabilizers are used, but fluorine-based surfactants and other surfactants may also be used. is there. Other additives include, for example, colorants, fillers, flame retardants, stabilizers (eg antioxidants, light stabilizers,
UV absorbers, etc.), etc. can be optionally used.

In the present invention, an organic phosphorus compound is used as an additive for improving the heat fusion property. It has been found that the use of the organophosphorus compound further synergistically enhances the effect of improving the heat fusion property by using the low molecular weight polyol. The organic phosphorus compound does not necessarily have a functional group capable of reacting with an isocyanate group. Rather, the presence of hydroxyl functional groups is unnecessary. Phosphoric acid ester, phosphorous acid ester, and other phosphoric acid ester are suitable as the preferable organic phosphorus compound, and phosphoric acid type alkyl or aryl ester is most effective. The amount used is preferably 0.01 to 5% by weight, more preferably about 0.1 to 2% by weight, based on the mixed polyol.

The flexible polyurethane foam is produced by the one-shot method, the quasi-prepolymer method, the prepolymer method or the like using the above raw materials, and the one-shot method is most suitable. A slab molding method is suitable as the molding method, but the molding method is not limited to this. The obtained foam block is usually formed into a foam sheet having an appropriate thickness by slicing and the like, and then heat-bonded to a base material such as a cloth, but the method is not limited to this method. As a heat fusion method, a method of melting the surface of the flexible polyurethane foam with a flame or hot air and immediately laminating it with the base material and integrating it is suitable. The flexible polyurethane foam of the present invention has high heat fusion (peeling resistance), and an excellent laminated foam can be obtained.

The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples and Comparative Examples Production of Flexible Polyurethane Foam 100 parts by weight of the following high molecular weight polyol alone (comparative example) or a mixed polyol of the following high molecular weight polyol and the following low molecular weight polyol, 4.0 parts by weight of water, triethylenediamine solution (trade name) "Dabco 33LV") 0.3 part by weight, silicone type foam stabilizer (Brand name "L-520": sold by Nippon Unicar Co., Ltd.)
About 1.0 part by weight, 5.0 parts by weight of trichlorofluoromethane, stanas octoate (hereinafter referred to as STO, the amount used is shown in Table 1), and optionally 1 part by weight of trioctyl phosphate (hereinafter referred to as TOP) to a mixture, 1.05 equivalents of T-80 (which means a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate in a weight ratio of 80/20, hereinafter the same) are mixed to produce a flexible polyurethane foam by a one-shot method. did. The composition of the polyol, the presence or absence of TOP, the amount of STO used, and the physical properties of the obtained flexible polyurethane foam are shown in Tables 1 and 2 below.

Heat fusion test A sheet having a width of 150 mm and a thickness of 10 mm was cut out from the flexible polyurethane foam block manufactured as described above. The surface of this sheet was heated and melted with a flame, and a nylon cloth was laminated with a roll.

After allowing the laminate to stand under constant pressure for 1 day, a test piece having a width of 25 mm was cut out and subjected to an Instron meter to measure the peel strength.

Physical property test: ILD [25%], BR (semi-elastic modulus), elongation, and tear strength were measured according to ASTM D3574.

High molecular weight polyol: The high molecular weight polyols used in Examples and Comparative Examples are the following polyols A to D.

Polyol A: Polyoxypropylene triol having a hydroxyl value of about 56 obtained by adding propylene oxide to glycerin.

Polyol C: Polyurethane A A urethane-modified polyether polyol having a hydroxyl value of about 42, obtained by reacting about 1 molecule of T-80 per 2 molecules of Polyol A.

Polyol D: Ester-modified polyether polyol having a hydroxyl value of about 56, which is obtained by reacting 1 mol of polyoxypropylenetriol having a hydroxyl value of about 76 with 3 mol of phthalic anhydride and further adding 3 mol of propylene oxide.

Low molecular weight polyol: The low molecular weight polyols used in Examples and Comparative Examples are as follows.

Polyol E: A trimethylolpropane- (ε-caprolactone) adduct having a hydroxyl value of about 540.

Polyol H: 1.4-butanediol with a hydroxyl value of about 367
(Ε-caprolactone) adduct.

Polyol J: Bisphenol A- (propylene oxide) adduct having a hydroxyl value of about 326.

Polyol P: A trimethylolpropane- (propylene oxide) adduct having a hydroxyl value of about 400.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-80426 (JP, A) JP-A-59-20318 (JP, A) JP-A-51-139898 (JP, A) JP-B-46- 30309 (JP, B1) JP48-37600 (JP, B1) JP49-13880 (JP, B1)

Claims (2)

[Claims] 1. A polyol and a polyisocyanate compound are reacted in the presence of an additive such as a catalyst, a foaming agent and a foam stabilizer to produce a flexible polyurethane foam having excellent heat fusion properties, and then the flexible polyurethane foam is prepared. In the method for producing a laminated foam by laminating and integrating with a fabric base material by heat fusion, a polyol having a hydroxyl value of 30 to 70 as a polyol and a high molecular weight polyol consisting of a modified product of 70 to 98% by weight and a polyvalent polyol A mixed polyol containing 2 to 30% by weight of a low molecular weight polyol having a hydroxyl value of 150 to 600, which comprises an alcohol- (ε-caprolactone) adduct or a polyhydric phenols- (alkylene oxide) adduct, and is mixed as an additive. 0 for polyol.
A method for producing a laminated foam, which comprises using 01 to 5% by weight of an organic phosphorus compound. 2. The hydroxyl value of the low molecular weight polyol is 250 to 600.
The method of claim 1 wherein: