JP4956897B2 - Flexible polyurethane foam for frame lamination, cushion material with skin material, and method for producing the same - Google Patents

Description

The present invention relates to a flexible polyurethane foam for frame lamination, a cushion material with a skin material, and a method for producing the same .

The soft polyurethane foam for frame lamination is melted by blowing it with a flame, the skin material such as cloth is pasted by using the heat-fusibility of the flexible polyurethane foam, and the skin is made by “frame lamination”. It can be laminated and integrated with the material. Therefore, the flexible polyurethane foam for frame lamination is used as a base material for cushion materials with various skin materials such as automobile seats, interior materials, bedding, and flooring cushioning materials.
In this frame lamination, the heat-fusibility between the flexible polyurethane foam and the skin material is very important. In particular, it has good peel strength at the time of initial heat-sealing, that is, excellent in initial heat-fusibility. It is hoped that.

In addition, the flexible polyurethane foam is required to be light, that is, to have a low density. Therefore, for the purpose of reducing the density, methylene chloride is used as a foaming agent. However, when a large amount of methylene chloride is used, there is a problem that the foamed state of the resulting foam is poor and cracks are likely to occur.
In order to satisfy both the initial heat-fusibility of flexible polyurethane foam and the good foamed state of the foam, it is known that the performance of the raw material polymer polyol is a major factor, and much development has been made in the past. ing. The polymer polyol refers to a polymer in which fine polymer particles having an ethylenically unsaturated bond are stably dispersed in a polyol.

  In Patent Document 1, an ethylenically unsaturated monomer is polymerized in a polyether polyol, a compound having a polymerizable ethylenically unsaturated bond, and an unsaturated polyol which is a reaction product with an isocyanate compound or a polyol containing the same. A polymer polyol produced in this manner and a flexible polyurethane foam using the same are proposed. When the polymer polyol is used, a foam having a relatively good foamed state can be obtained even with methylene chloride foaming. However, when the foam is used for frame lamination, the initial heat with the skin material by frame lamination is obtained. The fusing property was insufficient.

  Patent Document 2 discloses a technique for controlling the glass transition point of a polymer component in a polymer polyol by using an amine as a chain transfer agent during production of the polymer polyol, and a flame-retardant soft material using the obtained polymer polyol. Polyurethane foam has been proposed. When the polymer polyol was used, the heat-fusibility of the flexible polyurethane foam by methylene chloride foaming was not bad, but the foamed state of the foam obtained was bad, and cracks and the like were likely to occur.

In Patent Document 3, dodecyl mercaptan is used as a chain transfer agent, a polymer having an ethylenically unsaturated bond capable of terminal polymerization as a stabilizer, a number average molecular weight of 6000 to 100,000, and the number of hydroxyl groups per molecule is A polymer polyol having a good dispersion stability obtained by using a polymer of 1.0 or less has been proposed. However, when the polymer polyol was used, the foamed state of the methylene chloride foam was poor.
Thus, with the polymer polyol obtained in the prior art, it has been difficult to achieve both the initial heat-fusibility of the flexible polyurethane foam and the good foamed state of the foam in methylene chloride foaming.
Japanese Patent Publication No.59-5608 JP 07-138330 A JP 05-247109 A

The present invention relates to a flexible polyurethane foam for flame lamination having good initial heat-fusibility and particularly good foaming even in methylene chloride foaming, a cushion material with a skin material using the flexible polyurethane foam, and its production Provide a method.

The process for producing the polymer polyol (I) (hereinafter referred to as “polymer polyol of the present invention”) used in the production of the flexible polyurethane foam for flame lamination according to the present invention comprises an ethylenically unsaturated monomer (M) comprising acrylonitrile and / or styrene. ) In the presence of the stabilizer (B) and the chain transfer agent (C) in the polyol (A), in the method for producing a polymer polyol; the stabilizer (B) has a hydroxyl value of 10 to 190 mgKOH / g Polyol (b1), an isocyanate compound (b2), and a compound (b3) having a polymerizable ethylenically unsaturated bond and a hydroxyl group, and the average number of hydroxyl groups per molecule is 1.5 or more The stabilizer (B) is added to the polyol (A), an ethylenically unsaturated monomer. (M) and stabilizer (B) are used in a total amount (100% by mass) of 2.5% by mass or more; the chain transfer agent (C) is used as polyol (A), ethylenically unsaturated monomer (M) and stable characterized by using 0.1 to 1 parts by weight per 100 parts by weight of agent (B).

  The polyol (A) is preferably a polyol having a hydroxyl value of 10 to 190 mgKOH / g and an oxyethylene group content of 0 to 30% by mass in the polyol (A) (100% by mass).

In the method for producing a polymer polyol of the present invention, the ethylenically unsaturated monomer (M) is added to the polyol (A) in the presence of a stabilizer (B), a chain transfer agent (C), and an antioxidant (D). ), At least one of the antioxidants (D) is a hindered phenol antioxidant, and the phenolic hydroxyl group content is 10% by mass or less in one molecule (100% by mass). preferable.
Moreover, in the manufacturing method of the polymer polyol of this invention, the said chain transfer agent (C) is 0 with respect to a total of 100 mass parts of a polyol (A), an ethylenically unsaturated monomer (M), and a stabilizer (B). It is preferable to use 1 to 1 part by mass.

The polymer polyol of the present invention is obtained by the method for producing a polymer polyol of the present invention.
It is preferable that the polymer outflow temperature measured by the following method of the polymer component formed by polymerizing the ethylenically unsaturated monomer (M) contained in the polymer polyol is 100 to 170 ° C.
(Polymer outflow temperature measurement method)
The polymer component was taken out from the polymer polyol by centrifugation, washed with methanol, and dried. Then, the obtained polymer component was put into a die having an inner diameter of 1 mm and a length of 1 mm, and attached to a flow tester tester. A method in which a temperature is increased at a rate of 3 ° C. per minute under a load, and the temperature when the polymer flows out of the die is measured.

  In the polymer polyol of the present invention, the content of the polymer component is preferably 20 to 60% by mass in the polymer polyol (100% by mass).

The flexible polyurethane foam for frame lamination of the present invention is obtained by reacting a polyol component containing the polymer polyol of the present invention and an isocyanate component in the presence of a foaming agent, a urethanization catalyst, and a foam stabilizer. It is.
As the foaming agent , it is preferable to use water or water and methylene chloride.

The flexible polyurethane foam of the present invention is obtained by heat-sealing the flexible polyurethane foam and the skin material by the following method, and after 2 minutes from the heat-sealing, performs a 180 degree peeling test described in JIS K6854 (1994 version), The average peel strength obtained in the test is preferably 0.98 N / 25.4 mm or more.
(Heat fusion method)
Immediately after delivering a 10 mm thick flexible polyurethane foam at a rate of 500 mm / min, applying an open flame to the flexible polyurethane foam with a gas burner to melt the surface layer portion of about 1 mm thick, A method of heat-sealing flexible polyurethane foam and skin material by stacking materials.

The method for producing a cushion material with a skin material of the present invention is characterized in that the surface of the flexible polyurethane foam for frame lamination of the present invention is melted and the skin material is heat-sealed to the melted surface.
The skin material is preferably any of Tetron, Knit, Double Russell, Woven, Moquette and Tricot.
The cushion material with a skin material of the present invention is obtained by the method for producing a cushion material with a skin material of the present invention.
The cushion material with a skin material of the present invention is preferably any one of an automobile seat, an interior material, a bedding, and a flooring cushioning material.

According to the polymer polyol of the present invention, it is possible to obtain a flexible polyurethane foam having good initial heat-fusibility and a good foamed state even in methylene chloride foaming.
According to the method for producing a polymer polyol of the present invention, it is possible to produce a polymer polyol for obtaining a flexible polyurethane foam having a good initial heat-fusibility and a good foamed state even in methylene chloride foaming.
The flexible polyurethane foam of the present invention has good initial heat-fusibility, and the foamed state of the foam is particularly good even in methylene chloride foaming.

<Polymer polyol>
The polymer polyol of the present invention is obtained by polymerizing at least one ethylenically unsaturated monomer (M) in the polyol (A) in the presence of the stabilizer (B) and the chain transfer agent (C). It is.

The polymer polyol of the present invention preferably has a polymer effluent temperature of 100 to 170 ° C. measured by the following method of the polymer component obtained by polymerizing the ethylenically unsaturated monomer (M) contained in the polymer polyol. .
(Polymer outflow temperature measurement method)
The polymer component was taken out from the polymer polyol by centrifugation, washed with methanol and dried, and then the obtained polymer component was put into a die having an inner diameter of 1 mm and a length of 1 mm, and a flow tester tester (Shimadzu Corporation) A method of measuring the temperature at which the polymer flows out from the die by attaching a load of 980 N, increasing the temperature at a rate of 3 ° C. per minute, and attaching to a CFT-500D).

When the polymer outflow temperature is 100 ° C. or higher, the foamed state of methylene chloride foaming is good, and the foam does not crack. If the polymer outflow temperature is 170 ° C. or lower, the peel strength in heat fusion between the flexible polyurethane foam and the skin material will be good.
Moreover, 20-60 mass% is preferable in polymer polyol (100 mass%), and, as for content of a polymer component, 30-50 mass% is especially preferable. If content of a polymer component is 20 mass% or more, the hardness of the foam obtained will become enough. When the content of the polymer component is 60% by mass or less, the viscosity of the polymer polyol becomes appropriate and easy to handle.

Hereinafter, each raw material of the polymer polyol of the present invention will be described.
<Ethylenically unsaturated monomer (M)>
The ethylenically unsaturated monomer (M) has at least one polymerizable ethylenically unsaturated bond. Examples of the ethylenically unsaturated monomer (M) include (meth) acrylic aryl esters such as acrylonitrile, methacrylonitrile, (meth) acrylic acid, phenyl (meth) acrylate, and methyl (meth) acrylate ( Examples include (meth) acrylic acid alkyl esters, acrylamide, styrene, methyl styrene, phenyl styrene, chlorostyrene, butadiene, 1,4-pentadiene, and vinyl acetate. Here, (meth) acrylic acid refers to acrylic acid or methacrylic acid, and other compounds also conform to this. An ethylenically unsaturated monomer (M) is used individually by 1 type or in mixture of 2 or more types. As the ethylenically unsaturated monomer (M), the combined use of acrylonitrile and styrene is preferable from the viewpoint of the stability as a polymer polyol and the properties of the foam obtained by using the polymer polyol. In this case, the ratio (mass ratio) of acrylonitrile / styrene is preferably 0/100 to 70/30, particularly preferably 10/90 to 50/50.

  The amount of the ethylenically unsaturated monomer (M) used is preferably 20 to 60% by mass in the total (100% by mass) of the polyol (A), the ethylenically unsaturated monomer (M) and the stabilizer (B), 30 ˜50 mass% is particularly preferred. When the amount of the ethylenically unsaturated monomer (M) used is 20% by mass or more, the hardness of the obtained flexible polyurethane foam is sufficient. When the amount of the ethylenically unsaturated monomer (M) used is 60% by mass or less, the viscosity of the polymer polyol becomes appropriate and easy to handle.

<Polyol (A)>
The polyol (A) is preferably a polyoxyalkylene polyol obtained by subjecting an alkylene oxide to ring-opening addition polymerization to an initiator in the presence of a ring-opening addition polymerization catalyst.
Examples of the initiator include polyhydric alcohols, amines, phenols, and alkylene oxide adducts thereof. As the initiator, compounds having 2 to 8 active hydrogen atoms in the molecule are preferable, and polyhydric alcohols are particularly preferable.

  Examples of polyhydric alcohols include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol; trivalents such as glycerin, trimethylolpropane, trimethylolethane, and hexanetriol. Examples include alcohols; tetravalent alcohols such as pentaerythritol, methylene glycoside, and diglycerin; pentavalent or higher alcohols such as saccharides such as sorbitol, mannitol, and sucrose.

Examples of amines include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and isopropanolamine; heterocyclic amines such as N- (2-aminoethyl) piperazine and N-aminomethylpiperazine; ethylenediamine and propylenediamine And aliphatic amines such as hexamethylenediamine; aromatic amines such as tolylenediamine and diaminodiphenylmethane.
Examples of phenols include bisphenol A and resorcinol.
An initiator may be used individually by 1 type and may use 2 or more types together.

Examples of the ring-opening addition polymerization catalyst include alkali metal compound catalysts and double metal cyanide complex catalysts.
Examples of the alkali metal compound catalyst include alkali metals such as sodium and potassium; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium propoxide, potassium methoxide, potassium ethoxide and potassium propoxide; sodium hydroxide and hydroxide Examples thereof include hydroxides such as potassium and cesium hydroxide; carbonates such as sodium carbonate and potassium carbonate.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, styrene oxide, and the like. An alkylene oxide may be used individually by 1 type, and may use 2 or more types together. As the alkylene oxide, propylene oxide alone or a combination of propylene oxide and ethylene oxide is preferable. When propylene oxide and ethylene oxide are used in combination, propylene oxide and ethylene oxide may be reacted sequentially to form a block copolymer, or a mixture of propylene oxide and ethylene oxide may be reacted to form a random copolymer.

  The hydroxyl value of the polyol (A) is preferably 10 to 190 mgKOH / g, more preferably 14 to 70 mgKOH / g, and particularly preferably 28 to 70 mgKOH / g. By setting the hydroxyl value of the polyol (A) to 190 mgKOH / g or less, the resulting flexible polyurethane foam becomes moderately soft. By setting the hydroxyl value of the polyol (A) to 10 mgKOH / g or more, the foamed state of the foam is improved and the production of the flexible polyurethane foam is facilitated. In the present invention, the hydroxyl value of the polyol is obtained by measurement according to JIS K1557 (1970 edition).

The polyol (A) is preferably obtained by ring-opening addition polymerization of a mixture of propylene oxide and ethylene oxide as an initiator. Furthermore, the terminal may have an oxyethylene block chain.
0-30 mass% is preferable in a polyol (A) (100 mass%), and, as for oxyethylene group content of a polyol (A), 5-20 mass% is especially preferable. By setting the oxyethylene group content of the polyol (A) to 30% by mass or less, the obtained flexible polyurethane foam has an appropriate closed cell ratio, which facilitates the production of the flexible polyurethane foam.

<Stabilizer (B)>
The stabilizer (B) is a reaction product of a polyol (b1) having a hydroxyl value of 10 to 190 mgKOH / g, an isocyanate compound (b2), and a compound (b3) having a polymerizable ethylenically unsaturated bond and a hydroxyl group. Yes, it is a compound having an average number of hydroxyl groups per molecule of 1.5 or more.

(Polyol (b1))
The polyol (b1) is preferably a polyoxyalkylene polyol, like the polyol (A).
The hydroxyl value of the polyol (b1) is 10 to 190 mgKOH / g, preferably 14 to 56 mgKOH / g. By setting the hydroxyl value of the polyol (b1) to 190 mgKOH / g or less, the dispersion stability of the resulting stabilizer (B) and the polyol (A) becomes good, and as a result, the stability as the resulting polymer polyol is good. It becomes. By setting the hydroxyl value of the polyol (b1) to 10 mgKOH / g or more, the foamed state of the foam in methylene chloride foaming becomes good. The hydroxyl value of the polyol (b1) is preferably lower than the hydroxyl value of the polyol (A) in order to satisfy the dispersion stability of the polymer component in the obtained polymer polyol. In addition, the hydroxyl value of a polyol (b1) can be determined by the method similar to a polyol (A).

The polyol (b1) preferably has an oxyethylene group at the terminal, obtained by subjecting propylene oxide to ring-opening addition polymerization to an initiator and then ring-opening addition polymerization of ethylene oxide.
0-15 mass% is preferable in a polyol (b1) (100 mass%), and, as for the oxyethylene group content of a polyol (b1), 5-10 mass% is especially preferable. By setting the oxyethylene group content of the polyol (b1) to 15% by mass or less, the dispersion stability of the resulting stabilizer (B) and the polyol (A) is improved, and as a result, the stability as the resulting polymer polyol is improved. Property is improved.

(Isocyanate compound (b2))
As the isocyanate compound (b2), 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), crude tolylene diisocyanate (crude TDI), 4,4 '-Diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), isomers of diphenylmethane diisocyanate Diisocyanates such as mixtures (MDI), polymethylene polyphenyl isocyanate (crude MDI), toluidine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, these diiso Carbodiimide-modified products of Aneto, biuret modified products, dimers, trimers, or the like of these prepolymers may be mentioned. An isocyanate compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. Of these, 2,4-TDI, 2,6-TDI, crude TDI, and mixtures thereof are preferred because the viscosity of the resulting stabilizer (B) is low. Particularly preferred are 80/20 mass mixture of 2,4-TDI / 2,6-TDI (80 / 20-TDI) or 65/35 mass ratio (65 / 35-TDI).

(Compound (b3))
Examples of the compound (b3) having a polymerizable ethylenically unsaturated bond and a hydroxyl group include (1) unsaturated alcohols such as allyl alcohol, 2-buten-1-ol, and 3-buten-2-ol; ) Unsaturated carboxylic acids such as acrylic acid, methacrylic acid and itaconic acid; (3) esters of unsaturated carboxylic acids such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate and polyhydric alcohols.

(Production of stabilizer (B))
The stabilizer (B) is obtained by mixing the polyol (b1), the isocyanate compound (b2), and the compound (b3), and heating and reacting them.
The mixing ratio of the polyol (b1), the isocyanate compound (b2), and the compound (b3) is prepared so that the average number of hydroxyl groups per molecule of the resulting stabilizer (B) is 1.5 or more. By setting the average number of hydroxyl groups per molecule of the stabilizer (B) to 1.5 or more, a good foam foam state can be obtained even when methylene chloride is used as the foaming agent. The average number of hydroxyl groups per molecule of the stabilizer (B) is preferably 5 or less, and more preferably 3 or less.
The reaction temperature is preferably 50 ° C to 120 ° C, particularly preferably 70 ° C to 90 ° C.
After completion of the reaction, the obtained stabilizer (B) may be used as it is as a raw material for the polymer polyol, but it is preferably used after removing unreacted substances, decomposition products and the like by subjecting to a reduced pressure treatment.

  The usage-amount of a stabilizer (B) is 2.5 mass% or more in the sum total (100 mass%) of a polyol (A), an ethylenically unsaturated monomer (M), and a stabilizer (B), 2.5 -10.0 mass% is preferable. When the amount of the stabilizer (B) used is 2.5% by mass or more, a good foam foam state can be obtained when methylene chloride is used as the foaming agent.

<Chain transfer agent (C)>
As the chain transfer agent (C), an alkyl mercaptan is preferable because the reaction can be stably controlled. Examples of the alkyl mercaptan include dodecyl mercaptan and mercaptoethanol.
The amount of the chain transfer agent (C) used is 0.01 to 1 part by mass with respect to 100 parts by mass in total of the polyol (A), the ethylenically unsaturated monomer (M), and the stabilizer (B). 0.1 to 0.5 parts by mass is preferable, and 0.2 to 0.8 parts by mass is particularly preferable. By making the usage-amount of a chain transfer agent (C) 0.01 mass part or more, the heat-fusion property of the flexible polyurethane foam obtained becomes favorable. A flexible polyurethane foam can be stably manufactured by making the usage-amount of a chain transfer agent (C) into 1 mass part or less. Moreover, the polymer outflow temperature of the polymer component in a polymer polyol mentioned later can be optimized to 100-170 degreeC by making the usage-amount of a chain transfer agent (C) into 0.1-1.0 mass part.

<Antioxidant (D)>
In the production of the polymer polyol, the antioxidant (D) may be used, and it is particularly preferable to use the antioxidant (D). At least one of the antioxidants (D) is a hindered phenol antioxidant.
The hindered phenol-based antioxidant has a phenolic hydroxyl group content of 0.1 to 10% by mass, preferably 1 to 7% by mass, per molecule (100% by mass). By setting the phenolic hydroxyl group content to 10% by mass or less, volatilization of the hindered phenolic antioxidant from the obtained flexible polyurethane foam is suppressed, and discoloration of the skin material is suppressed.

Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert). -Butyl-4-hydroxyphenyl) propionate, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene bis [3- (3,5-di- -Tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.
Examples of commercially available hindered phenol-based antioxidants include hindered phenol type IRGANOX 245, IRGANOX 259, IRGANOX 1010, and IRGANOX 1035 manufactured by Ciba Specialty Chemicals.

  As the antioxidant (D), a hindered phenol-based antioxidant may be used alone or in combination with other antioxidants. Other antioxidants include phosphorus stabilizers, sulfur stabilizers, hindered amine stabilizers, and the like. Examples of the hindered amine stabilizer include 4,4'-dicumyldiphenylamine, 4,4'-octyldiphenylamine, and the like. Examples of commercially available hindered amine stabilizers include nonflex DCD and nonflex OD-R manufactured by Seiko Chemical Co., Ltd.

As antioxidant (D), combined use with a hindered phenolic antioxidant and a hindered amine stabilizer is preferable.
When using antioxidant (D), the usage-amount is 0.01-5 mass with respect to a total of 100 mass parts of a polyol (A), an ethylenically unsaturated monomer (M), and a stabilizer (B). Part is preferable, and 0.1 to 0.5 part by mass is particularly preferable.

<Polymerization initiator>
In the production of the polymer polyol, a polymerization initiator for polymerizing the ethylenically unsaturated monomer (M) may be used.
Examples of the polymerization initiator include peroxides such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, di-tert-butyl peroxide; azobis (isobutyronitrile), azobis (2 -Azo compounds such as methylbutyronitrile) and peroxides such as persulfate, persuccinic acid, and di-isopropylperoxy dicarbonate. As the polymerization initiator, an azo compound is preferable.
The amount of the polymerization initiator used is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the polyol (A), the ethylenically unsaturated monomer (M) and the stabilizer (B). 2 parts by mass is particularly preferred.

A solvent may be used in the production of the polymer polyol.
Examples of the solvent include aliphatic ethers such as diisopropyl ether, methyl-tert-butyl ether and ethyl-tert-butyl ether; alcohols such as methanol, ethanol and isopropyl alcohol; hydrocarbons such as hexane, toluene and xylene. .
The amount of the solvent used is preferably 1 to 50 parts by mass, particularly preferably 5 to 45 parts by mass, with respect to 100 parts by mass in total of the polyol (A), the ethylenically unsaturated monomer (M) and the stabilizer (B). .

<Method for producing polymer polyol>
The polymer polyol of the present invention comprises an ethylenically unsaturated monomer (M), a stabilizer (B) a chain transfer agent (C), an antioxidant (D), if necessary, a polymerization initiator and a solvent in the presence of a polyol. Produced by polymerizing in (A).
The polymerization of the ethylenically unsaturated monomer (M) may be carried out batchwise or continuously. The polymerization temperature is determined according to the kind of the polymerization initiator, and is preferably equal to or higher than the decomposition temperature of the polymerization initiator, more preferably 60 to 200 ° C, and still more preferably 90 to 160 ° C. In addition, the polymerization reaction may be performed in a pressurized system or a normal pressure system.
After completion of the polymerization reaction, the obtained polymer polyol can be used as a raw material for the flexible polyurethane foam as it is, but it should be used after removing the unreacted monomer, the decomposition product of the polymerization initiator, the chain transfer agent, etc. by reducing the pressure. Is preferred.

<Soft polyurethane foam>
The flexible polyurethane foam of the present invention is obtained by reacting a polyol component containing the polymer polyol of the present invention and an isocyanate component in the presence of a foaming agent, a urethanization catalyst, a foam stabilizer, and, if necessary, other auxiliary agents. It is what was done.

The flexible polyurethane foam of the present invention is obtained by heat-sealing the flexible polyurethane foam and the skin material by the following method, and after 2 minutes from the heat-sealing, performs a 180 degree peeling test described in JIS K6854 (1994 version), It is preferable that the average value (3 samples) of the peel strength obtained in the test is 0.98 N / 25.4 mm or more. If the average value of peel strength is 0.98 N / 25.4 mm or more, the flexible polyurethane foam and the skin material are not easily peeled off. Although an upper limit is not specifically limited, 10 N / 25.4mm or less is preferable.
(Heat fusion method)
Immediately after delivering a 10 mm thick flexible polyurethane foam at a rate of 500 mm / min, applying an open flame to the flexible polyurethane foam with a gas burner to melt the surface layer portion of about 1 mm thick, The materials are stacked and the flexible polyurethane foam and the skin material are heat-sealed.

Hereinafter, each raw material of the flexible polyurethane foam of the present invention will be described.
<Polyol component>
The polyol component contains the polymer polyol of the present invention. The polyol component may contain other polyols other than the polymer polyol of the present invention. Examples of other polyols include the same polyoxyalkylene polyols and polyester polyols as the polyol (A) used in producing the polymer polyol. The other polyol is preferably a polyoxyalkylene polyol, preferably a polyoxyalkylene polyol having a hydroxyl value of 10 to 190 mgKOH / g, particularly 14 to 70 mgKOH / g.
10-100 mass% is preferable, as for the ratio of the polymer polyol in a polyol component (100 mass%), 50-100 mass% is more preferable, and 60-90 mass% is especially preferable.

<Isocyanate component>
As an isocyanate component, the thing similar to what was illustrated by the isocyanate compound (b2) can be used. An isocyanate compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. As the isocyanate component, a mixture of 80/20 mass ratio (80 / 20-TDI) of 2,4-TDI, 2,6-TDI and 2,4-TDI / 2,6-TDI is particularly preferable.

  The amount of the isocyanate component used is preferably 80 to 130, expressed as 100 times the number of isocyanate groups relative to the number of active hydrogen atoms in the active hydrogen atom-containing compound (usually, the numerical value expressed as 100 times is referred to as the isocyanate index). 90-120 are more preferable. The “active hydrogen atom-containing compound” in the present invention is a polyol component, water, and a crosslinking agent described later.

<Foaming agent>
As a blowing agent, water, 2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, methylene chloride, trichlorotrifluoroethane, dibromotetrafluoroethane, trichloroethane, pentane , N-hexane and the like. A foaming agent may be used individually by 1 type, and may mix and use 2 or more types. As the foaming agent, water, methylene chloride, or a combination thereof is preferable. When producing a low-density flexible polyurethane foam, it is preferable to use methylene chloride or water and methylene chloride as the blowing agent.
As for the usage-amount of a foaming agent, 0.5-15 mass parts is preferable with respect to 100 mass parts of polyol components, 1-10 mass parts is more preferable, and 1-5 mass parts is especially preferable. 1-15 mass parts is preferable with respect to 100 mass parts of polyol components, and, as for a methylene chloride, 1-10 mass parts is especially preferable.

<Urethane catalyst>
Examples of the urethanization catalyst include amine-based catalysts and organometallic catalysts.
Examples of amine catalysts include triethylamine, tripropylamine, polyisopropanolamine, tributylamine, trioctylamine, hexamethyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, diethylenetriamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N'-tetramethylbutanediamine, N, N, N', N'-tetra Methyl-1,3-butanediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis [2- (N, N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N , N-dimethylcyclohexylamine, N, N, N ′, N′-pentamethyldiethylenetri Mines, triethylenediamine, formate or other salts of triethylenediamine, oxyalkylene adducts of amino groups of primary or secondary amines, azacyclic compounds such as N, N-dialkylpiperazines, various N, N ′ , N ″ -trialkylaminoalkylhexahydrotriazines and the like.

Organometallic catalysts include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate Etc.
A urethanization catalyst may be used individually by 1 type, and may mix and use 2 or more types.
The amount of the urethanization catalyst used is preferably 0.0001 to 10 parts by mass with respect to 100 parts by mass of the active hydrogen atom-containing compound.

<Foam stabilizer>
As the foam stabilizer, a silicone surfactant (silicone foam stabilizer) is preferable. Examples of the silicone surfactant include L-520, L-532, L-540, L-544, L-550, L-3550, L-5305, L-3600, manufactured by Nippon Unicar Co., Ltd. L-3601, L-5305, L-5307, L-5309, L-5710, L-5720, L-5740M, L-6202, etc .; SH-190, SH- manufactured by Toray Dow Corning Silicone Co., Ltd. 194, SH-200, SPX-253, SRX-274C, SF-2961, SF-2962, SPX-280A, SPX-294A, etc .; Shin-Etsu Chemical Co., Ltd. F-114, F-121, F-122 F-220, F-230, F-258, F-260B, F-317, F-341, F-601, F-606, X-20-200, X-20-201, etc .; Shiba Silicone Co., Ltd. of TFA-4200, TFA-4202 and the like; Goldschmidt Corp. B-4113, and the like.
As for the usage-amount of a foam stabilizer, 0.1-5 mass parts is preferable with respect to 100 mass parts of active hydrogen atom containing compounds.

<Other auxiliaries>
In this invention, a crosslinking agent, another stabilizer, a filler, a coloring agent, a flame retardant, etc. can be used as needed.

(Crosslinking agent)
As a crosslinking agent, a low molecular weight polyhydroxy compound or a polyamine is preferable.
As the low molecular weight polyhydroxy compound, a hydroxy compound having a hydroxyl value of 280 mgKOH / g or more is preferable. Ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene Examples include glycol, monoethanolamine, diethanolamine, triethanolamine, N-alkyldiethanolamine, bisphenol A, trimethylolpropane, pentaerythritol, sucrose, and a small amount of these alkylene oxide adducts. In addition, a small amount of an alkylene oxide adduct of the following polyamine is also included.
Examples of the polyamine include aliphatic amines, alicyclic amines, heterocyclic polyamines, aromatic amines and the like, and compounds having a molecular weight of 400 or less are preferable.
A crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
30 mass parts or less are preferable with respect to 100 mass parts of polyol components, and, as for the usage-amount of a crosslinking agent, 20 mass parts or less are especially preferable.

<Method for producing flexible polyurethane foam>
As a molding method of flexible polyurethane foam, a method of injecting a raw material mixture into a conveyor using a low pressure foaming machine or a high pressure foaming machine (general slab foaming device); a method of injecting a raw material mixture directly into a mold (reaction injection) Molding method); a method of injecting a raw material mixture into an open mold and sealing it.

As the high-pressure foaming machine, a normal type in which two liquids are mixed is preferable. One of the two liquids is a polyisocyanate compound, and the other liquid is a mixture of all raw materials other than the isocyanate compound. In some cases, a urethanization catalyst, a foam breaker (usually dispersed or dissolved in a part of the polyol component), liquid carbon dioxide gas, etc. may be used as separate liquids, and a total of 3 liquid material mixtures may be injected. .
Also, a mixture of a polyol component, a crosslinking agent, a foam breaker, etc .; a mixture of a polyisocyanate compound, a foaming agent (water, etc.), an amine catalyst, a foam stabilizer, a metal catalyst (eg, a tin catalyst), etc. And may be foamed.

<Soft polyurethane foam for frame lamination>
The flexible polyurethane foam of the present invention is used for “frame lamination” in which the surface is melted by applying a flame, and a skin material such as a cloth is attached by using the heat-fusibility of the flexible polyurethane foam, and is cured and integrated. It is suitable as a flexible polyurethane foam for frame lamination.
Examples of the skin material include those used in conventional frame lamination, such as Tetron (registered trademark) , knit, double raschel, woven fabric, moquette, tricot and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by the following example. In addition, "part" in an Example and a comparative example is a mass part.

[Production Example 1]
Obtained by ring-opening addition polymerization of propylene oxide and then ethylene oxide using glycerin as an initiator and a potassium hydroxide catalyst, and having an oxyethylene group at the terminal, the terminal oxyethylene group content is 8.7% by mass 1 mol of polyoxypropyleneoxyethylenetriol (polyol (b1-1)) having a hydroxyl value of 26 mgKOH / g and 1 mol of 2-hydroxyethyl methacrylate (2-HEMA) were charged into a reactor, and toluene diisocyanate (80 / 1 mol of 20-TDI) and triethylamine (an amount corresponding to 0.153 parts by mass with respect to 100 parts by mass of polyol (b1-1)) were added and stirred at 80 ° C. for reaction. Thereafter, a reduced pressure treatment was performed at 80 ° C. to remove unreacted compounds such as 2-HEMA. The average number of hydroxyl groups per molecule of the obtained compound (referred to as stabilizer B1) was 2.0.

[Production Example 2]
The same operation as in Production Example 1 was carried out with 1 mol of 2-HEMA and 1.7 mol of toluene diisocyanate per 1 mol of polyol (b1-1). The average number of hydroxyl groups per molecule of the obtained compound (referred to as stabilizer B2) was 0.6.

[Example 1, Comparative Examples 1 to 4]
In the formulation shown in Table 1, the reactor is charged with polyol A1 and antioxidants D1 to D3, to which acrylonitrile, styrene, stabilizers B1 to B2, polymerization initiator, chain transfer agent C1 and aliphatic ether solvent. While the mixture was additionally charged, the mixture was stirred at a reaction temperature of 105 ° C. to carry out a polymerization reaction. The obtained reaction product was subjected to a reduced pressure treatment at 115 ° C. to remove unreacted monomers and solvent, thereby obtaining a polymer polyol. The obtained polymer polyol was measured for hydroxyl value, viscosity, number average molecular weight, unreacted monomer remaining amount, and polymer outflow temperature. The results are shown in Table 1.

(material)
Polyol A1: obtained by random ring-opening addition polymerization of propylene oxide and ethylene oxide using glycerin as an initiator and a potassium hydroxide catalyst, and having a hydroxyl value of 56 mgKOH / g having an oxyethylene group content of 7% by mass Polyoxypropylene oxyethylene triol.
Polymerization initiator: Azobis (2-methylbutyronitrile).
Chain transfer agent C1: n-dodecyl mercaptan.
Antioxidant D1: Pentaerystol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals, trade name “IRGANOX1010”, 1 molecule (100 mass) %) Phenolic hydroxyl group content in 5.8% by mass).
Antioxidant D2: 2,6-di-tert-butyl-4-methylphenol (BHT) (phenolic hydroxyl group content in one molecule (100% by mass) 7.7% by mass).
Antioxidant D3: 4,4′-dicumyldiphenylamine (manufactured by Seiko Chemical Co., Ltd., hindered amine stabilizer, trade name “Nonflex DCD”).

<Evaluation>
(Hydroxyl value, viscosity)
The hydroxyl value and viscosity were measured by a method based on JIS K1557 (1970 edition).
(Number average molecular weight)
The number average molecular weight was determined in terms of polystyrene by gel permeation chromatography.
(Remaining unreacted monomer)
The remaining amount of the unreacted monomer after the pressure reduction treatment was measured with GC-14A manufactured by Shimadzu Corporation under a constant condition of 150 ° C.
(Polymer outflow temperature)
The polymer component was taken out from the polymer polyol by centrifugation, washed with methanol, and dried. The obtained polymer component was put into a die having an inner diameter of 1 mm and a length of 1 mm, and attached to a flow tester tester (manufactured by Shimadzu Corporation: CFT-500D). The temperature when the polymer flows out from the die was measured.

[Examples 2 and 3, Comparative Examples 5 to 12]
In the formulations shown in Tables 2 and 3, the polymer polyols obtained in Example 1, Comparative Examples 1 to 4, Polyol A2, Foaming agents 1 and 2, Urethane catalysts 1 to 4, Silicone foam stabilizers 1 to 1 2. Flame retardant was mixed and then adjusted to 25 ° C. Next, an isocyanate component was added so as to have an isocyanate index shown in Table 2, and after stirring for 5 seconds, the mixture was poured into a 300 mm × 300 mm × 300 mm wooden box containing a polyethylene bag to produce a flexible polyurethane foam.

(material)
Polyol A2: A polyoxypropylene polyol having an average number of functional groups of 3 and a hydroxyl value of 56 mgKOH / g.
Urethane catalyst 1: Diethylene glycol solution of triethylenediamine (trade name “TEDA-L33” manufactured by Tosoh Corporation).
Urethane catalyst 2: Dipropylene glycol solution of bis-[(2-dimethylamino) ethyl] ether (trade name “TOYOCAT-ET” manufactured by Tosoh Corporation).
Urethane catalyst 3: N-methylmorpholine (trade name “TOYOCAT-NEM” manufactured by Tosoh Corporation).
Urethane catalyst 4: stannous octylate (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name “STANOCTO”).
Silicone-based foam stabilizer 1: product name “SZ-1142” manufactured by Nippon Unicar Co., Ltd.
Silicone-based foam stabilizer 2: Nippon Unicar Co., Ltd., trade name “L-580”.
Flame retardant: Product name “CR-504” manufactured by Daihachi Chemical Industry Co., Ltd.
Foaming agent 1: water.
Foaming agent 2: methylene chloride.
Isocyanate component: 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate 80/20 mass ratio mixture, NCO group content 48.3 mass% (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name “Coronate T-80 ").

<Evaluation>
Density (kg / m ³ ), 25% hardness (ILD) (N / 314 cm ² ), rebound resilience (%), tear strength (N / cm), tensile strength (kPa), elongation (%), dry The thermal compression residual strain (%) was measured and evaluated by a method based on JIS K6400 (1997 edition).

(Thermal fusion test: peel strength)
Immediately after sending out a soft polyurethane foam having a thickness of 10 mm at a rate of 500 mm / min and igniting the soft polyurethane foam with a gas burner to melt a surface layer portion having a thickness of 1 mm, a skin material is applied to the flexible polyurethane foam. (Tricot having a thickness of about 0.2 mm) was stacked, and the flexible polyurethane foam and the skin material were heat-sealed.
Two minutes after the heat fusion, the peel strength (N / 25.4 mm) was measured according to the 180 degree peel test described in JIS K6854 (1994 edition). The measurement was performed on three samples, and the average value of peel strength was obtained.

(Scorch property)
After foaming, the discoloration inside the foam was visually observed to evaluate the scorch property. Those with good scorch properties were marked with ○.
(Foging test)
A flexible polyurethane foam cut to a thickness of 10 mm and a diameter of 80 mm was placed in a wide-mouthed bottle, and the mouth of the bottle was covered with a glass plate that had been polished transparently. After heating at 110 ° C. for 3 hours, the amount (mg) of deposits on the glass plate was measured.

(Foam state of foam)
For foam stability in methylene chloride foaming, the foamed state of the foam after foaming was visually evaluated. Those that can be stably foamed are indicated by ○, and those that cause cracks in the foam are indicated by ×.

  As shown in Tables 2 and 3, for the flexible polyurethane foams using the polymer polyols of Comparative Examples 1, 3, and 4, the initial heat-fusibility is satisfied, but the foamed state of the foam by methylene chloride foaming is It was bad. Moreover, about the flexible polyurethane foam using the polymer polyol of the comparative example 2, although the foaming state of the foam by methylene chloride foaming was favorable, heat-fusibility was inadequate. With respect to the flexible polyurethane foam using the polymer polyol of Example 1, good results were obtained for both initial heat-fusibility and foam stability.

Flexible polyurethane foam for the frame lamination of the present invention, kill automotive interior parts, furniture, such as the bedding in use.

Claims (12)

A flexible polyurethane foam for flame lamination obtained by reacting a polyol component containing the following polymer polyol (I) with an isocyanate component in the presence of a foaming agent, a urethanization catalyst, and a foam stabilizer.
[Polymer polyol (I)]
A polymer polyol obtained by polymerizing an ethylenically unsaturated monomer (M) composed of acrylonitrile and / or styrene in a polyol (A) in the presence of a stabilizer (B) and a chain transfer agent (C);
As the stabilizer (B), a reaction product of a polyol (b1) having a hydroxyl value of 10 to 190 mgKOH / g, an isocyanate compound (b2), and a compound (b3) having a polymerizable ethylenically unsaturated bond and a hydroxyl group. And a compound having an average number of hydroxyl groups per molecule of 1.5 or more,
The stabilizer (B) is used in an amount of 2.5% by mass or more in the total (100% by mass) of the polyol (A), the ethylenically unsaturated monomer (M) and the stabilizer (B),
The chain transfer agent (C) is obtained by using 0.1 to 1 part by mass with respect to 100 parts by mass in total of the polyol (A), the ethylenically unsaturated monomer (M), and the stabilizer (B). A polymer polyol. The polymer polyol (I) is a polymer component formed by polymerizing the ethylenically unsaturated monomer (M) contained in the polymer polyol, and the polymer outflow temperature measured by the following method is 100 to 170 ° C. The flexible polyurethane foam for flame lamination according to claim 1 .
(Polymer outflow temperature measurement method)
The polymer component was taken out from the polymer polyol by centrifugation, washed with methanol, and dried. Then, the obtained polymer component was put into a die having an inner diameter of 1 mm and a length of 1 mm, and attached to a flow tester tester. A method in which a temperature is increased at a rate of 3 ° C. per minute under a load, and the temperature when the polymer flows out of the die is measured. The flexible polyurethane foam and the skin material are heat-sealed by the following method, and after 2 minutes from the heat-sealing, the 180 degree peel test described in JIS K6854 (1994 version) is performed, and the peel strength obtained by the test is obtained. The flexible polyurethane foam for flame lamination according to claim 1 or 2 , wherein an average value of is 0.98 N / 25.4 mm or more.
(Heat fusion method)
Immediately after delivering a 10 mm thick flexible polyurethane foam at a rate of 500 mm / min, applying an open flame to the flexible polyurethane foam with a gas burner to melt the surface layer portion of about 1 mm thick, A method of heat-sealing flexible polyurethane foam and skin material by stacking materials. The flexible polyurethane foam for flame lamination according to any one of claims 1 to 3, wherein the polyol (A) is a polyoxyalkylene polyol. The polyol (A) is a hydroxyl value is 10~190mgKOH / g, an oxyethylene group content of a polyol is 0-30 wt% in the polyol (A) (100 mass%), according to claim 1-4 A flexible polyurethane foam for flame lamination according to any one of the above. The polymer polyol (I) polymerizes the ethylenically unsaturated monomer (M) in the polyol (A) in the presence of a stabilizer (B), a chain transfer agent (C), and an antioxidant (D). A polymer polyol obtained by
At least one of antioxidant (D) is a hindered phenolic antioxidant, and phenolic hydroxyl group content is 10 mass% or less in 1 molecule (100 mass%), Any of Claims 1-5 A flexible polyurethane foam for flame lamination according to claim 1.   The polymer polyol (I) contains 20 to 60% by mass of a polymer component obtained by polymerizing the ethylenically unsaturated monomer (M), and is soft for flame lamination according to any one of claims 1 to 6. Polyurethane foam.   The flexible polyurethane foam for flame lamination according to any one of claims 1 to 7, wherein water or water and methylene chloride is used as the foaming agent. The manufacturing method of the cushioning material with a skin material which fuse | melts the surface of the flexible polyurethane foam for flame lamination as described in any one of Claims 1-8 , and heat-seal | wears a skin material to this fuse | melted surface. The method for producing a cushioning material with a skin material according to claim 9 , wherein the skin material is any one of Tetron (registered trademark) , knit, double raschel, woven fabric, moquette and tricot. A cushion material with a skin material obtained by the production method according to claim 9 or 10 . The cushion material with a skin material according to claim 11 , which is any one of an automobile seat, an interior material, a bedding, and a cushioning material for flooring.