JP5877626B2 - Flexible polyurethane foam for frame lamination - Google Patents

Description

  The present invention relates to a cushioning composite material in which a cushioning material is bonded to a skin material, such as a cushioning skin material or ceiling material of an automobile seat, an upper material of a sofa of a furniture, or an upper material of a bed. The present invention relates to a flexible polyurethane foam excellent in frame laminating properties, which is preferably used in the above.

Cushioning composites formed by laminating flexible polyurethane foam and other sheet-like materials such as fabrics and leathers are cushioning, have a good feel, and have a sense of volume. Widely used.
As a method of manufacturing such a cushioning composite material, conventionally, a skin material and a cushioning material are pasted without using an adhesive by utilizing the heat melting property and tackiness of a flexible polyurethane foam as a cushioning material. A frame laminating method is used. In addition, the flexible polyurethane foam applicable to the frame laminating method can be used as long as only the surface layer of the flexible polyurethane foam is appropriately melted by a flame and has a characteristic of instantly and firmly adhering when bonded to the skin material. Well, for example, those using a polyester ether polyol (Patent Document 1), containing an organic phosphorus compound (Patent Document 2), containing a low molecular weight polyol (Patent Document 3), etc. A flexible polyurethane foam is known.

Japanese Patent Publication No. 48-10078 JP 61-174217 A JP 2003-252946 A

However, when frame laminating with a flexible polyurethane foam using the polyester ether polyol of Patent Document 1, although the foam has excellent heat melting properties, the peel strength immediately after the skin material and the foam are bonded together (hereinafter referred to as initial (It may be indicated as peel strength) is weak, so that deviation occurs, wrinkles are easily generated, the appearance is impaired, and the manufacturing process becomes complicated.
Further, in Patent Document 2, an organophosphorus compound is added to a polyol in order to increase the peel strength. However, depending on the organophosphorus compound, a volatile organic compound is likely to be generated due to thermal decomposition. Or a discoloration of the skin material, or a sufficient peel strength could not be obtained depending on the skin material or backing cloth.
Furthermore, Patent Document 3 uses a polyol in which a low molecular weight polyol is added as a cross-linking agent to a polyoxyalkylene ether polyol to give an initial peel strength. There were few problems such as few heat decomposable adhesive residues and poor initial peel strength depending on the type of fabric.

  Therefore, the present invention solves the above-mentioned problem, and is a flexible polyurethane foam for a frame laminate comprising a polyol and a polyisocyanate, which has excellent peel strength from the skin material, has no discoloration, and has an appearance. It is an object of the present invention to provide a flexible polyurethane foam for frame lamination which can obtain a good cushioning composite material.

  The present invention solves the above-mentioned problems, and as a result of studying to improve frame laminating properties using a polyol and a polyisocyanate, a low molecular weight phosphorus-containing polyol and a low molecular weight polyol It has been found that not only the initial peel strength but also the final peel strength can be imparted with good frame laminate properties by the combination, leading to the invention.

  The flexible polyurethane foam for frame laminate of the present invention has an average molecular weight of 2000 to 4000, a hydroxyl value of 30 to 110 KOH · mg / g, a high molecular weight polyol (A) having an average functional group number of 2 to 4, an average molecular weight of 200 to 700, Low molecular weight polyol (B) having a hydroxyl value of 150 to 1200 KOH · mg / g, average functional group number of 2 to 3, and low average molecular weight of 200 to 300, hydroxyl value of 400 to 500 KOH · mg / g, average functional group number of 2 to 3 A flexible polyurethane foam raw material containing a phosphorus-containing polyol (C) having a molecular weight is foamed.

Thus, when a polyol obtained by adding the low molecular weight polyol (B) and the low molecular weight phosphorus-containing polyol (C) to the high molecular weight polyol (A) is used, not only the initial peel strength but also the final peel It becomes a flexible polyurethane foam having a frame laminating property with excellent strength.
The phosphorus-containing polyol of the present invention is a polyol containing phosphorus in a molecule through a chemical bond.

  Further, when the total amount of the polyol is 100 parts by weight, 0.1 to 5 parts by weight of the polyol (B) and 0.1 to 5 parts by weight of the phosphorus-containing polyol (C) are added. If so, a flexible polyurethane foam having a good foamed state can be obtained, and the cushioning property and the feel will be excellent.

  In addition, when the phosphorus-containing polyol (D) having an average molecular weight of 400 to 1200, a hydroxyl value of 100 to 200 KOH · mg / g, and an average number of functional groups of 2 to 3 is 100 parts by weight of the polyol, If it is a flexible polyurethane foam added by 0.1 to 3 parts by weight, the hardness will be lower than that of a foam made of a polyol containing no phosphorus-containing polyol (D), and it will be excellent in frame laminating properties. Become.

  In addition, when the total amount of the polyol is 100 parts by weight, if the flame retardant is added in an amount of 5 to 30 parts by weight, the flame-retardant softness for the frame laminate is excellent without impairing the foamability of the urethane foam. A polyurethane foam is obtained.

The present invention uses a flexible polyurethane foam raw material containing a high molecular weight polyol (A), a low molecular weight polyol (B) and a low molecular weight phosphorus-containing polyol (C). It is possible to obtain a flexible polyurethane foam for frame laminating that has excellent peel strength.
In particular, when applying the frame laminating method, the initial peel strength is too weak, and it is possible to suppress the occurrence of defects such as deviation from the skin material and wrinkles during the manufacturing process. Can be suitably used.

  Further, if a phosphorus-containing polyol (D) different from the low-molecular weight phosphorus-containing polyol (C) is added, the hardness of the foam can be lowered as compared with the case where it is not added, so that the frame laminating property is further improved. .

  Moreover, if a specific amount of a flame retardant is added, a flexible polyurethane foam for frame lamination that is excellent in flame retardancy can be obtained without impairing the frame lamination property.

Hereinafter, the present invention will be described in detail.
The flexible polyurethane foam for frame lamination of the present invention is formed by foaming a flexible polyurethane foam raw material containing a polyol, polyisocyanate, catalyst, foaming agent, and foam stabilizer, and the polyol is a high molecular weight polyol (A ), A low molecular weight polyol (B), and a low molecular weight phosphorus-containing polyol (C).
In addition, all the average molecular weights in this invention show a number average molecular weight.

In the present invention, as the high molecular weight polyol (A), those having an average molecular weight of 2000 to 4000, a hydroxyl value of 30 to 110 KOH · mg / g, and an average number of functional groups of 2 to 4 can be used.
Specifically, polyoxyalkylene ether polyols which are addition compounds starting from ethylene oxide and propylene oxide, or ethylene oxide and propylene oxide, saturated fatty acid polycarboxylic acids such as succinic acid and adipic acid, and polyoxyalkylene polyols General-purpose polyols used for forming a flexible polyurethane foam having a frame laminating property, such as a polyester ether polyol obtained by condensing the above.
In particular, it is a polyoxyalkylene ether polyol, and a propylene oxide adduct is selected from the group of polyols alone, or a mixture of two or more is used as a moldability when urethane foam is foamed. Therefore, it is preferable.

Further, as the low molecular weight polyol (B), a polyol having an average molecular weight of 200 to 700, a hydroxyl value of 150 to 1200 KOH · mg / g, and an average number of functional groups of 2 to 3 can be used.
Such a low molecular weight polyol (B) can reduce the regularity of the polymer skeleton of the flexible polyurethane foam and increase its heat melting property, and is particularly effective for improving the final peel strength. is there.
Specifically, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, and the above polyol compound and at least one alkylene oxide such as propylene oxide or ethylene oxide Can be selected from addition compounds.
In particular, it is preferable to use one kind selected from the group of polyols which are propylene oxide adducts, or a mixture of two or more kinds, because the moldability at the time of foaming urethane foam is improved.

The phosphorus-containing polyol (C) used in the present invention may be a low-molecular weight phosphorus-containing polyol having an average molecular weight of 200 to 300, a hydroxyl value of 400 to 500 KOH · mg / g, and an average number of functional groups of 2 to 3.
Such a phosphorus-containing polyol (C) is remarkably effective for improving the initial peel strength, and also has the property of improving the flame retardancy of the resulting flexible polyurethane foam. In addition, since it has an active hydrogen group in the molecule, it reacts with isocyanate during foam formation and is incorporated into the polyol skeleton to improve the thermal meltability of the foam and suppress volatilization even at a low molecular weight. Therefore, it is less likely to cause discoloration or a decrease in peel strength.
Specifically, tris (ethylene glycol) phosphate, tris (propylene glycol) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethanephosphonate (FYROL (trademark registration) -6 manufactured by Akzo Japan), And diisopropyl-N, N-bis (2-hydroxyethyl) aminomethanephosphonate (FYROL (registered trademark) -7 manufactured by Akzo Japan).

  As described above, the polyol forming the flexible polyurethane foam of the present invention comprises a high molecular weight polyol (A), a low molecular weight polyol (B), and a low molecular weight phosphorus-containing polyol (C). To do.

The addition amount of the polyol (B) and the phosphorus-containing polyol (C) is 0.1 to 5 parts by weight of the polyol (B) and 0 of the phosphorus-containing polyol (C) when the total amount of the polyol is 100 parts by weight. 0.1 to 5 parts by weight is preferable because a flexible polyurethane foam having a good foamed state can be obtained, and the cushioning property and feel can be excellent. In particular, if the amount of the phosphorus-containing polyol (C) added is less than 0.1 parts by weight, the content of phosphorus contributing to the initial peel strength is too small and the peel strength tends to be inferior, and 5 parts by weight If added in excess, the peel strength is excellent, but the cushioning property tends to be impaired.
In addition, if the phosphorus content in the polyol is 0.01% by weight or more, the effect of sufficiently improving the initial peel hardness can be exhibited.

  In addition, as described above, the polyol (B) and the phosphorus-containing polyol (C) are incorporated into the polyol skeleton during foam formation, thereby reducing the regularity of the polyol skeleton and improving the heat melting property. Have Therefore, in the present invention, the combined amount of the polyol (B) and the phosphorus-containing polyol (C) is 0.5 to 10 parts by weight when the total amount of the polyol is 100 parts by weight. Thus, if it is less than 0.5 parts by weight, the thermal meltability of the foam tends to be low, and the peel strength with the skin material tends to be inferior. The amount of bubbles becomes excessive, tends to shrink, tends to cause inconveniences such as low foaming stability, and further tends to have a long time to adhere and cure with the skin material due to too good heat meltability. is there.

Further, a phosphorus-containing polyol (D) having an average molecular weight of 400 to 1200, a hydroxyl value of 100 to 200 KOH · mg / g, and an average number of functional groups of 2 to 3 may be added to the polyol of the present invention.
Since this phosphorus-containing polyol (D) has a higher molecular weight than the above-mentioned phosphorus-containing polyol (C), compared to a flexible polyurethane foam made of a polyol to which this is not added, the foam added is The hardness is reduced, and the frame laminating property is further improved.
As the phosphorus-containing polyol (D) having such an effect, a phosphoric ester, a phosphonic ester, a phosphinic ester, a phosphorous ester of a polyether polyol starting from an alkylene oxide such as ethylene oxide or propylene oxide, And condensates thereof, such as “OP-550” manufactured by Clariant.

  Further, the addition amount of the phosphorus-containing polyol (D) is preferably 0.1 to 3 parts by weight when the total amount of polyol is 100 parts by weight. If the addition amount is less than 0.1 weight, it is difficult to obtain the effect of reducing the hardness of the foam. If the addition amount exceeds 3 parts by weight, the foam is too soft and the thickness of the foam to be melted during frame lamination (melting allowance) ) Becomes thick, and the peel strength may decrease.

Furthermore, even when phosphorus-containing polyol (D) is added, when the total amount of polyols (B), (C) and (D) other than polyol (A) is 100 parts by weight of the total amount of polyol 0.5 to 10 parts by weight is preferable for forming a good foam.
In particular, when the combined amount of the phosphorus-containing polyol (C) and the phosphorus-containing polyol (D) is 0.2 parts by weight to 8 parts by weight when the total amount of the polyol is 100 parts by weight, the initial peel strength is improved. The effect of the contributing phosphorus is sufficiently exhibited, which is more preferable. If it is less than 0.2 parts by weight, the content of phosphorus contributing to the initial peel strength may not be sufficient, and if added over 8 parts by weight, the peel strength is excellent, but the cushioning property tends to be impaired. It is in.
Even in this case, if the phosphorus content in the polyol is 0.01% by weight or more, the effect of sufficiently improving the initial peel strength can be exhibited.

Next, as the polyisocyanate, a polyisocyanate used as a raw material for producing a general flexible polyurethane foam can be used as it is. Specific examples include tolylene diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, xylene diisocyanate, hydrogenated polymethylene polyphenylene polyisocyanate, and isophorone diisocyanate. A mixture of seeds or more can be used.
Moreover, if a polyisocyanate is 105-125 by an isocyanate index, a favorable flexible polyurethane foam will be formed.

  As a catalyst, all the catalysts used for manufacture of a normal flexible polyurethane foam can be used. For example, organotin compounds (such as stannic dibutyl lalarate and stannous octylate) and tertiary amines (such as triethylenediamine, bisdimethylaminoethyl ether, pentamethyldiethylenetriamine, and N-alkylmorpholines) For example, n-methylmorpholine and n-ethylmorpholine). The catalyst is generally used in an addition amount of 0.05 to 2% based on the total weight of polyisocyanate and polyol.

  The blowing agent may be composed of at least one selected from water and low-boiling halogenated hydrocarbons such as trichlorofluoromethane, dichlorofluoromethane, and methylene chloride. The blowing agent is generally used in an addition amount of 10% or less based on the total weight of the polyisocyanate and the polyol.

  As the foam stabilizer, for example, at least one siloxane compound such as polyalkylsiloxane or polyalkylsiloxane-polyoxyalkyl block copolymer can be used. The foam stabilizer is generally used in an amount of 0.3 to 2% based on the total weight of the polyisocyanate and the polyol.

You may add a flame retardant further to the flexible polyurethane foam raw material of this invention as needed. Examples of the flame retardant include conventionally known flame retardants such as tris (2-chloroethyl) phosphate and tris (chloroethyl) phosphate, organic powders such as melamine cyanurate, melamine polyphosphate, and ammonium polyphosphate, and metal oxides. Inorganic powders can be used.
In particular, as the flame retardant, it is preferable to use a halogen-containing type condensed phosphorus flame retardant. The amount of the flame retardant is appropriately adjusted depending on the desired degree of flame retardancy. When it is 5 parts by weight, 5 to 30 parts by weight is preferable in that flame retardancy can be imparted without impairing the foamability of the urethane foam. Moreover, in this invention, since phosphorus-containing polyol (C) and / or phosphorus-containing polyol (D) are added, the addition amount of the flame retardant to add can also be reduced rather than the normally required amount.

  As other auxiliaries, colorants such as pigments and dyes, plasticizers, and other inorganic weight agents may be used. Further, the amount added is appropriately set so as not to impair the frame laminating property.

The flexible polyurethane foam of the present invention is produced by mixing the above-described polyol, polyisocyanate, catalyst, foaming agent and foam stabilizer, foaming and curing.
Then, the cushioned composite material can be obtained by cutting the obtained foam into a sheet and pasting the skin material on the surface of the sheet by the frame laminating method.
As the skin material, for example, nylon fabric, polyester fabric, polyurethane fabric, etc. can be used. Furthermore, for example, a non-woven fabric or a mesh fabric can be bonded to the surface other than the skin material as a back fabric.

Hereinafter, the present invention will be described specifically by way of examples.
A flexible polyurethane foam was produced using raw materials in which the components shown in Tables 1 and 2 were blended in the proportions shown in Tables 1 and 2.
In addition, the ratio of each component of the foam raw material in Tables 1 and 2 is expressed in parts by mass except for the isocyanate index, and each raw material is expressed in parts by weight when the total amount of polyol is 100 parts by weight. .

The raw materials in Table 1 and Table 2 are as follows.
Polyol (A1): Glycerin-based propylene oxide adduct Average molecular weight 3000, Hydroxyl value 56.1 KOHmg / g, Average functional group number 3
Polyol (A2): Polyester polyol Average molecular weight 2500, hydroxyl value 72 KOH · mg / g, average functional group number 3.2
(Hitachi Chemical Polymer Co., Ltd., trade name “Tesrack 2458”)
Polyol (B): glycerin-based propylene oxide adduct average molecular weight 400, hydroxyl value 420 KOH · mg / g, average number of functional groups 3
(Asahi Glass Co., Ltd., trade name "EL-430")
Phosphorus-containing polyol (C): diethyl-N, N-bis (2-hydroxyethyl) aminomethanephosphonate Average molecular weight 255, hydroxyl value 440 KOH · mg / g, average number of functional groups 2
(Product name “FYROL (registered trademark) -6” manufactured by Akzo Japan Co., Ltd.)
Phosphorus-containing polyol (D): polyether polyol phosphate ester average molecular weight 863, hydroxyl value 130 KOH · mg / g, average number of functional groups 2
(Clariant, trade name “OP-550”)
Flame retardant Daihachi Chemical Co., Ltd., trade name "CR-504L"
Foam stabilizer manufactured by Shin-Etsu Chemical Co., Ltd., trade name “F-258”
Blowing agent water, methylene chloride

  The obtained flexible polyurethane foam was subjected to the following measurements and evaluations. The results are shown in Tables 3 and 4.

(1) Foam physical properties In accordance with JIS K 6400, foam density, hardness, tensile strength, elongation, and compressive residual strain were measured.

(2) Foam properties Suitable for polymerization and excellent cushioning properties: ○
Cushion is slightly inferior: △
Polymerization has progressed too much, resulting in closed cells and shrinkage: ×

(3) Frame laminating properties Each flexible polyurethane foam is sliced to a thickness of 6 mm, passed through a burner frame at a speed of 20 to 30 m / min, and the surface is melted. And crimped. The peel strength was measured after 1 hour and 24 hours after pressure bonding. In the measurement, it was cut into a width of 25 mm and a length of 150 mm and measured according to JIS L 1066. Among them, Table 2 shows the measurement results of the peel strength in the vertical direction (winding direction).
The peel strength after 1 hour of pressure bonding is shown as the initial peel strength, and the peel strength after 24 hours of pressure bonding is shown as the final peel strength.

  From Tables 3 and 4, when the frame is laminated using the flexible polyurethane foam of Example 1, the flexible polyurethane foams of Comparative Examples 1 to 5 that do not contain all the polyols (A), (B), and (C) are used. Compared with the case where it had, initial peeling strength and the final peeling strength were also large. Further, in Examples 3 and 4 in which a specific amount of the phosphorus-containing polyol (D) was added, the foam hardness was lower than in Example 1 and the frame laminating property was improved.

  Further, in Example 2, when a specific amount of the addition type phosphorus-based flame retardant was added, a flexible polyurethane foam having a good foamed state and excellent frame laminating property was obtained.

  INDUSTRIAL APPLICABILITY The present invention provides a flexible polyurethane foam having excellent frame laminating properties, and can be used as a cushioning material for a cushioning composite material bonded to a skin material such as an automobile interior material or furniture.

Claims (4)

Average molecular weight 2000 to 4000, hydroxyl value 30 to 110 KOH · mg / g, high molecular weight polyol (A) having an average functional group number 2 to 4, average molecular weight 200 to 700, hydroxyl value 150 to 1200 KOH · mg / g, average A low molecular weight polyol (B) having 2 to 3 functional groups, and a low molecular weight phosphorus-containing polyol (C) having an average molecular weight of 200 to 300, a hydroxyl value of 400 to 500 KOH · mg / g, and an average functional group of 2 to 3 Ri name by foaming a polyurethane foam raw material,
The flexible polyurethane foam for a frame laminate , wherein the phosphorus-containing polyol is a polyol containing phosphorus in a molecule through a chemical bond .   When the total amount of the polyol is 100 parts by weight, 0.1 to 5 parts by weight of the polyol (B) and 0.1 to 5 parts by weight of the phosphorus-containing polyol (C) are added. The flexible polyurethane foam for frame lamination according to claim 1.   When the polyol contains a phosphorus-containing polyol (D) having an average molecular weight of 400 to 1200, a hydroxyl value of 100 to 200 KOH · mg / g, and an average functional group number of 2 to 3, the total amount of the polyol is 100 parts by weight. The flexible polyurethane foam for frame lamination according to claim 1 or 2, wherein 1 to 3 parts by weight are added.   The flexible polyurethane foam for frame laminate according to any one of claims 1 to 3, wherein a flame retardant is blended in an amount of 5 to 30 parts by weight when the total amount of the polyol is 100 parts by weight.