JPS6279218A - Production of flame-retardant polyurethane foam - Google Patents

Abstract

PURPOSE:To obtain the titled foam having excellent laminating property, flame- retardancy and heat-resistance and especially, excellent age stability, by using a flame-laminatable polyol in combination with specific amounts of specific flame-retardant, crosslinking agent and amine catalyst. CONSTITUTION:The objective foam can be produced by compounding (A) a flame-laminatable polyol, (B) 5-40pts.(wt.) of an aromatic phosphate compound (e.g. triphenyl phosphate) as a flame-retardant, (C) <=5pts. of a diol having a molecular weight of <=1,000 (e.g. diethylene glycol) as a crosslinking agent, (D) <=3pts. of a nitrogen-containing compound having active hydrogen group (e.g. dimethylaminoethanol) as an amine catalyst, (E) an organic polyisocyanate, (F) a foaming agent and (G) a foam stabilizer, etc., and foaming and polymerizing the mixture.

Description

[Detailed Description of the Invention] (Field of Industrial Application) This invention is applicable to cushioning materials such as cushioning skin materials and ceiling materials for automobile seats, upholstery materials for furniture sofas, and bed top and spread materials. This invention relates to a method for producing a flame-retardant flexible polyurethane foam that can be frame-laminated with a skin material, as a cushioning composite material laminated with a skin material such as cloth or leather.

(Prior technology) In recent years, flexible polyurethane foam and other sheet-like materials such as fabric and leather have been bonded together to create cushioning materials, and are widely used in automobile interior materials and furniture as surface materials with a good feel and bulk. has been done.

Bonding methods include using adhesives, and bonding the surface of the flexible polyurethane foam to lII contact fabric using a high-frequency welder or flame. The lamination method (frame lamination) does not require a drying process and is an efficient method with fast adhesion speed, so it is widely used as an industrially established method for laminating flexible polyurethane foam and other sheet materials. It is.

On the other hand, in the United States, urethane laminate materials used as automobile interior materials are required to have da properties that comply with MVSS-302, and flexible polyurethane foam has been converted into four-combustion foam, and various laminate materials with flame retardant foam have been developed. has been done.

For example, polyester-based urethane foam is made into a four-flame material using halogenated phosphate esters as a fumigant, and polyether polyol is used as a 7-ohm flame lamination property to improve flame lamination characteristics.Reactive type as a fumigant Some use phosphorus- or halogen-containing compounds.

(While the invention is intended to solve the problem, however) any of these monolayer forms,
It has been discovered that the fabric and foam of laminate materials have the disadvantage of discoloration or deterioration over a long period of time,
When an accelerated heating test was conducted at a temperature of about 7 hours, the fabric discolored.
In particular, in the case of interior materials for self-driving cars, there was a problem with ohmic deterioration and heat resistance and stability over time. Afterwards, they were often left in the hot sun for long periods in sealed caps with the windows closed, so there was a desire to produce soft polylanthanum foam with excellent heat resistance and stability over time. In addition, since the above-mentioned white automobile interior materials are required to have flame retardancy that complies with MVSS-302, it has been desired to develop a foam material that is even more immersive.

In view of these requirements, the present invention enables frame lamination, has flame retardant properties that comply with MVEIS-302, and prevents discoloration and deterioration of laminated materials even under the above-mentioned fixed-line injection, which is practically effective. The purpose is to provide a flexible polyurethane foam with good heat resistance.

(Means for solving the problem) By the way, the above-mentioned deterioration phenomenon of the female retardant foam for laminates is thought to be mainly affected by the halogen compounds used as the retardant, and recently, tria has been used as a retardant. A combustible foam using only a reel phosphate compound has also been proposed (Terakai Sho 60-11283).
No. 6) and (Japanese Unexamined Patent Publication No. 60-123539), but the current situation is that nothing satisfactory has been obtained yet.

Therefore, the present inventors used 5 to 4 parts of an aromatic phosphoric acid ester compound as a fuel agent, diols of a specific molecular weight as a crosslinking agent, and as an amine catalyst,
If a nitrogen-containing compound containing an active hydrogen group (3 parts by weight or less) is combined with a specific flame-laminable polyol and foam polymerized with an organic polyisocyanate, the resulting product will have excellent laminating properties, flammability, and heat resistance. They have newly discovered that a flexible polyurethane foam with particularly good stability over time can be produced, and have completed the present invention.

That is, the present invention provides the following steps when manufacturing a flexible polyurethane foam by foaming polymerizing an organic polyisocyanate and a polyol in the presence of a blowing agent, a catalyst, a foam stabilizer, and a silkworm additive. 2) 1 part by weight of 5 to 40 aromatic phosphoric acid ester compounds as an auxiliary combustion agent for 100 parts by weight of the above polyol; 3) As a crosslinking agent, 1 part by weight of an aromatic phosphoric acid ester compound having a molecular weight of 1000 or less; 5 parts by weight or less of diols; and 4) 3 parts by weight or less of a nitrogen-containing compound having an active hydrogen group as an amine catalyst. be.

In this case, as the polyol that can be flame laminated, a polyfunctional polyester ether polyol or the like can be used, preferably a di- or tri-functional polyester ether polyol.

This oak polyester ether polyol is, for example, as disclosed in Japanese Patent Publication No. 48-100'78, etc.
The flexible polyurethane foam produced using this product is one that is easily melted by heat and has flame lamination properties, such as general (where R is an aliphatic or aromatic polycarboxylic acid residue). , A represents a ring-opened residue of a compound having a cyclic ether group, t is a number larger than 1 on average, and m is O or 1). It is a polyol with a blocked structure.

In the present invention, even if this polyester ether polyol is not used alone, it can be used in combination with other commonly used polyether polyols to provide flame lamination characteristics exceeding a certain standard. The polypropylene glycol adduct with a functional group of 2 to 4 used in combination is a polypropylene glycol with a molecular weight of about 11,000 to 6,000, which is used for general flexible polyurethane foam, and changes the mechanical properties and cushioning properties of the foam as desired. In addition, since this pigeon polyol is inexpensive, the overall cost of the polyol can also be reduced.

The combined ratio of polyfunctional polyester ether polyol and polyoxypropylene polyol is '70 to 10.
Weight 4: Can be arbitrarily selected within the range of 30 to 90 parts by weight.

The ratio of this combination depends on the desired physical properties of the polyurethane foam to be used, but if the polyester ether polyol exceeds 70 parts by weight, the viscosity of the polyol will be high and it will be difficult to handle, and the compressive residual strain of the returned foam will increase. This increases the size and makes it less practical as a cushioning material. Furthermore, if the number is less than the prize, the desired frame lamination characteristics will not reach a certain standard, and the object of the present invention will not be achieved.

In the production of the frame-laminable flexible polyurethane foam of the present invention, an organic polyisocyanate component and a polyol component based on the above-mentioned specific combination are foam-polymerized in the presence of a blowing agent, foaming agent, etc.
It is unique in that it contains specific additives in order to impart flame lamination properties, heat resistance and fanning properties.

That is, in the present invention, as described above, a polyol that can be flame laminated is used, an aromatic phosphoric acid ester compound is used as a smoke retardant, diols with a molecular weight of 1000 or less are used as a crosslinking agent, and nitrogen-containing nitrogen containing active hydrogen groups are used as an amine catalyst. It contains a compound in combination.

In this case, the aromatic phosphoric acid ester compound as a fumigant not only achieves a single combustion of 7 ohms, but also has the property of improving heat resistance performance. Usable aromatic phosphate ester compounds include triphenyl phosphate, tricresyl phosphate, octyldiphenyl phosphate, cresyl diphenyl phosphate, tricylenyl phosphate, and the like.

The content of this aromatic phosphate ester compound varies depending on the content of the additives used in the pond, but it may be 5 to 40 parts,
Preferably it is 10 to 30 parts by weight. If it is less than 5 parts by weight, the smoldering performance will be poor and undesirable, and the
This is because if the weight part is exceeded, no improvement in flammability performance is observed, and the physical properties of the obtained foam, especially the elongation rate, are deteriorated, which is not only undesirable, but also increases costs. .

Diols with a molecular weight of 1000 or less that are contained as crosslinking agents have the effect of changing the molecular arrangement by changing the structure of the molecular skeleton of the foam (polymer), and as a result, improving the flame lamination characteristics. be. The aromatic phosphoric acid ester compound in the foam can control the heat resistance of 7 ohms (polymer) to a temperature close to the temperature at which the flame retardant effect can be optically diluted when heated. It is useful for optimizing

Examples of the diols of this dawn include ethylene glycol, diethylene glycol, fluorene gelicol, fluorene gelicol, neopentyl glycol, l' diethylene glycol, positive ethylene glycols, polyglobylene glycol, and bisphenol A. The content in this case depends on the use of the aromatic phosphate ester compound, but it is preferable to add 5 parts by weight or less. If it exceeds 5 parts by weight, the number of closed cells in the foam increases. or the catalytic range becomes significantly narrower.
51 Destroyed due to lack of stability.

Examples of the amine catalyst that can be used in the present invention include nitrogen-containing compounds having active hydrogen groups. Conventionally used amine catalysts with high sublimation properties discolor laminated materials such as PVC leather and cause metal corrosion at high temperatures.

This is because the nitrogen-containing gold compound having an active hydrogen group reacts with free polyisocyanate during 7-ohm foaming, so that the amine catalyst does not sublimate even if the foam is exposed to high temperatures.

Examples of nitrogen-containing compounds having an active hydrogen group that can be conveniently used in the present invention include dimethylaminoethanol, dimethylaminoethoxyethanol, NN NN N'-)limethylaminoethylethanolamine, N,N.

N'-trimethylaminopropylethanolamine, 1
, 3-bis(N,N-dimethylamine-2-propatool, N, N, N', N#tetramethylN"-(2-
hydroxy)ethyltriethylenediamine, N1N1N
ISN#-Tetramethyl-NJI (2-hydroxypropyltriethylenediamine, N,N-bis(3-dimethylaminopropyl)aminoethanol, NXN-his(3-dimethylaminopropyl)amino-2-propanol, N- Examples include methyl-N'(2- and droxyethyl)piperazine, N-methyl-N'-(2-hydroxypropyl)piperazine, N-(2-hydroxyethyl)morpholine, and 3-(dimethylamino)propylamine carbonate. It will be done.

If the amount of the amine catalyst having active hydrogen groups exceeds 3 parts by weight, the amount of heat generated during foaming of 7 ohm urethane may increase, the foam may become scorched, and stability may be poor when foaming 7 ohm foam. This is not preferable because the elongation of the foam becomes low, resulting in a decrease in strength.

Note that other components in the present invention, that is, organic polyisocyanate and foam stabilizer, may be those commonly used for producing flexible polyurethane foam, and may also include commonly used dyes, pigments, plasticizers, and foaming agents. It is also possible to add additives, fillers, etc.

In addition, in the lamination process of the present invention, when laminating the flexible polyurethane foam, there is no particular restriction on the order in which each component is blended, and all the components may be blended at the same time or may be blended in stages. It's okay.

In this way, in the method of mowing flexible polyurethane foam that can be laminated according to the present invention, aromatic phosphoric acid is used as a fan agent instead of the conventional combination of a halogen compound and a phosphoric acid ester compound as a fan agent. An ester compound is used alone, and a molecular weight of 10 is added to it as a crosslinking agent.
00 or less diols and a nitrogen-containing compound having an active hydrogen group as an amine catalyst,
In addition, by incorporating such additives into a specific polyol, a flexible polyurethane foam having excellent lamination properties that meets the specifications of IAVSS-302 can be produced.

(Example) The present invention will be explained in more detail below using Examples and Comparative Examples.

Flexible polyurethane foam was manufactured based on the formulation shown in Table-1.

A combustion test was conducted on the obtained flexible polyurethane foam, and the test results are shown in the table as #11.

In addition, each flexible polyurethane foam has a thickness of 11
The surface was melted at a flame temperature of about 900°C, and flame lamination was performed by overlapping and pressing polyester/polyamide 80/20 fabric with a basis weight of 470 r/m'' and nonwoven fabric to form a fabric/foam/ A non-woven laminate material was obtained. This material was also subjected to a quasi-flammability test and a heat resistance test, and the results are also listed in the table. Each test method was in accordance with the following.

Density: J Engineering 5K-6401 Flexible polyurethane foam flammability test: MVSS-
Smoking performance test of 302-item laminate material: MVSS-Heat resistance performance test of 302-item laminate material; Place 4 samples with J corners stapled (Max company cutting), seal, and heat at 100℃.
After heating for 200 hours, visual observations such as discoloration of the skin material and degree of rust on the stapler were made.

(Note) 1: Polyol A is a polyester ether polyol with functional group a3, and hydroxyl group WJ5F2 = polyol B is a glycerin-based propylene oxide adduct 3: U-OAT2'i'90 is a polyester ether polyol with functional group a3. An amine catalyst with active hydrogen groups.

4: DAPCO 33LV is Sankyo Air Products (Amine Catalyst from Tosha Raku) 5: F-258 is a silicone foam stabilizer manufactured by Shin-Etsu Chemical Co., Ltd. 6: Each number in the formulation is parts by weight.

(Effects of the Invention) As is clear from the above results, the effects obtained by the present invention are as follows.

(1) Flexible polyurethane foam itself has MYS
A combustion performance that passes the standard of Section S-302 can be obtained.

(→ Flexible polyurethane foam can be laminated well with fabrics, etc.)

(3) The obtained laminate material has smoldering performance that meets the standards of MVSS-302.

(4) Laminated materials are heat resistant and stable over time.

(5) It is a good laminated material with no noticeable thermal discoloration or deterioration of the fabric or foam.

In addition, there is no corrosion of all four types such as staplers.

Since the polyoxypropylene polyol having the above-mentioned 11D characteristics is used in combination with an inexpensive polyoxypropylene polyol as a component, it has the advantage of reducing costs.

Further, since the smoldering performance is synergistically improved by a combination of specific additives without using flame retardants, which are halogen-based compounds, the amount of the flame retardant can be reduced.

Claims (2)

[Claims] (1) When manufacturing a flexible polyurethane foam by foaming polymerizing an organic polyisocyanate and a polyol in the presence of a blowing agent, catalyst, foam stabilizer, and other additives, 1) A polyol that can be flame laminated as a polyol component. 2) 5 to 40 parts by weight of an aromatic phosphoric acid ester compound as a flame retardant based on 100 parts by weight of the above polyol; 3) Diols with a molecular weight of 1000 or less as a crosslinking agent 5
and 4) 3 parts by weight or less of a nitrogen-containing compound having an active hydrogen group as an amine catalyst. (2) The manufacturing method according to claim 1, wherein the polyol for frame lamination is a di- or tri-functional polyester ether polyol.