JP2003252946A - Method for producing polyurethane foam for flame lamination and polyurethane foam for flame lamination - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyurethane foam for frame lamination excellent in initial adhesion, and to provide a polyurethane foam for frame lamination provided with sufficient repulsive elasticity. <P>SOLUTION: The method for producing the polyurethane foam comprises foaming a foamable raw material comprising a polyoxyalkylene ether polyol of EO/PO addition product having an average molecular weight of 1,500 to 5,000, and 2 to 4 functional groups, a polyisocyanate such as TDI and a crosslinking agent of an EO addition product having a hydoxy value of 300 to 700 and 2 to 6 functional groups. In this case, a formulating amount of the crosslinking agent is 1 to 12 pts.mass to 100 pts.mass of the polyoxyalkylene ether polyol, giving a foam further excellent in adhesive force. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyurethane foam for frame lamination and a polyurethane foam for frame lamination. More specifically, the present invention relates to a method for producing a polyurethane foam for frame lamination having excellent initial adhesion and a polyurethane foam for frame lamination having sufficient impact resilience.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a polyurethane foam for frame lamination, a foam raw material containing a polyether polyester polyol and an organic phosphorus compound having active hydrogen is foamed and cured to obtain a polyurethane foam ( Japanese Examined Japanese Patent Publication No. 46-30309
Gazette), a polyether polyester polyol,
A method for obtaining a polyurethane foam having low impact resilience by foaming and curing a foam raw material containing a polyol having a hydroxyl value of 200 to 300 and a phosphorus-containing compound (JP-A-9-
No. 151234), a foam raw material containing a polyoxyalkylene ether polyol and tolylene diisocyanate having a 2,4 isomer ratio of 84% or more is foamed and cured to obtain a polyurethane foam (JP-A-4-266919). Gazette) etc. are known.

[0003]

However, when a polyurethane foam is produced by using the above-mentioned special polyether polyester polyol or special isocyanate, the number of manufacturing steps is increased and becomes complicated. Further, when an organic phosphorus compound is contained, it may function as a plasticizer, and the physical properties such as compressive strain and hardness of the foam may be lowered. Further, depending on the skin material used, sufficient adhesive strength, particularly initial adhesive strength, may not be obtained. Further, the special polyether polyester polyol and the special isocyanate are expensive and disadvantageous in terms of cost. The present invention is to solve the above problems, using a general-purpose polyol and a general-purpose polyisocyanate, a method for producing a polyurethane foam for frame lamination having excellent initial adhesion, and for frame lamination having sufficient impact resilience. It is intended to provide a polyurethane foam.

[0004]

[Means for Solving the Problems] As a result of studying the improvement of frame lamination property by using a general-purpose polyoxyalkylene ether polyol and a general-purpose polyisocyanate, a foam raw material containing a specific cross-linking agent is foam-cured. It has been found that by doing so, the melting start temperature of the obtained foam is lowered, the difference from the decomposition temperature is increased, and good flame lamination properties can be imparted, as compared with the case where this crosslinking agent is not used. The present invention has been made based on such findings.

The method for producing a polyurethane foam for frame lamination according to the present invention has a polyoxyalkylene ether polyol, tolylene diisocyanate, a hydroxyl value of 300 to 700, and a functional group number of 2 to 6.
A foam raw material containing a cross-linking agent comprising a polyol other than the above polyoxyalkylene ether polyol is foamed. In the production method of the present invention, the blending amount of the cross-linking agent is 1 to 12 parts by mass when the polyoxyalkylene ether polyol is 100 parts by mass, which is a method for producing a polyurethane foam for frame lamination. it can. In addition, the cross-linking agent has a number of functional groups of 2 to 3 and can be a method for producing a polyurethane foam for frame lamination, which is an ethylene oxide (EO) adduct. Further, the above polyoxyalkylene ether polyol can be used as a method for producing a polyurethane foam for frame lamination, which has an average molecular weight of 1500 to 5000, a functional group number of 2 to 4, and is an ethylene oxide / propylene oxide adduct. Also,
The polyisocyanate can be used in a method for producing a polyurethane foam for frame lamination, which is tolylene diisocyanate. Another method for producing a polyurethane foam for frame lamination of the present invention is,
Average molecular weight 2000-4000, hydroxyl value 30-8
0, the number of functional groups is 2 or 3, and a polyoxyalkylene ether polyol which is an ethylene oxide / propylene oxide adduct, tolylene diisocyanate, an average molecular weight of 200 to 1000, and a hydroxyl value of 30.
It is characterized in that a foam raw material containing 0 to 700, a functional group number of 2 or 3, and a crosslinking agent composed of a polyol which is an EO adduct is foamed. The polyurethane foam for frame lamination of the present invention is manufactured by the above manufacturing method, and has a rebound resilience of 20 to 50%.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The above-mentioned "polyoxyalkylene ether polyol" is not particularly limited, but the starting material for obtaining the polyol is chain-extended with ethylene oxide (EO), propylene oxide (PO), or ethylene oxide and propylene oxide. (Hereinafter, referred to as “EO adduct,” “PO adduct,” “EO / PO adduct” in this order) and the like. Examples thereof include general-purpose polyols such as polyoxyethylene ether polyol, polyoxypropylene ether polyol, and polyoxyethylene / oxypropylene ether polyol (having oxyethylene units and oxypropylene units as oxyalkylene units). These may be used alone or in combination of two or more.

The polyoxyalkylene ether polyol has an average molecular weight of 1500 to 5000 (more preferably 2000 to 4000, still more preferably 2500 to 5,000).
3500) is preferred. Within this range,
Appropriate hardness and impact resilience can be imparted to the molded product after laminating. Furthermore, the polyoxyalkylene ether polyol has 2 to 4 functional groups (the number of OH groups).
(More preferably 2 or 3, and still more preferably 3). Within this range, the foam can be molded satisfactorily and stably, and the foam can be mass-produced. Further, the polyoxyalkylene ether polyol preferably has a hydroxyl value of 30 to 80 (more preferably 40 to 70, further preferably 50 to 60). Within this range, the foam can be made continuous and has excellent cushioning properties. Further, the polyoxyalkylene ether polyol is preferably an EO adduct, a PO adduct and an EO / PO adduct, and more preferably an EO / PO adduct such as a polyoxyethylene / oxypropylene ether polyol.

In the present invention, the polyoxyalkylene ether polyol has an average molecular weight of 1500 to 500.
0, the number of functional groups is 2 to 4, and the EO / PO adduct is preferable. The average molecular weight is 2000-4.
000, the number of functional groups is 2 to 3, and an EO / PO adduct is more preferable. Furthermore, the average molecular weight is 25
00-3500, having 3 functional groups, and EO / PO
An adduct is particularly preferable.

The above-mentioned "polyisocyanate" includes tolylene diisocyanate (TDI), crude TDI, 4,
4'-diphenylmethane diisocyanate (MDI),
Besides crude MDI, 1,6-hexamethylene diisocyanate (HDI), crude HDI, 1,5-naphthalene diisocyanate, paraphenylene diisocyanate, 2,2
4-trimethylhexamethylene diisocyanate, 2,
4,4-trimethylhexamethylene diisocyanate,
4,4'-dicyclohexylmethane diisocyanate,
Various aromatic and aliphatic compounds such as m-xylene diisocyanate, hexamethylene diisocyanate, hydrogenated MDI and isophorone diisocyanate can be used. Especially, it is preferable to use TDI.
These may be used alone or in combination of two or more.

The above-mentioned "crosslinking agent" is a polyol excluding the above polyoxyalkylene ether polyol, that is, a polyol having a larger hydroxyl value and a smaller average molecular weight than this polyoxyalkylene ether polyol. That is,
In the foam after synthesis, the molecular chain between the cross-linking points is short. The hydroxyl value of this crosslinking agent is 300 to 700.
(Preferably 400 to 650, more preferably 500 to
650). If the hydroxyl value is less than 300, the meltability of the foam will be impaired, and the skin material cannot be bonded during frame lamination. On the other hand, when the hydroxyl value exceeds 700, the degree of cross-linking of the foam becomes high and the cushioning property is impaired, and it is not possible to obtain a good foam suitable for applications such as vehicle seats. The number of functional groups (the number of OH groups) of this crosslinking agent is 2 to 6 (preferably 2 or 3). When the number of functional groups is more than 6, the viscosity of the foam raw material becomes too high, which makes it difficult to produce the foam. Further, the average molecular weight of the crosslinking agent is 100 to 1200.
(More preferably 200 to 1000, further preferably 2
50 to 800) is preferable. Within this range, good frame lamination properties are guaranteed. Generally, when the number of functional groups is the same and the molecular weight of the crosslinking agent is small, the hydroxyl value is high. In the present invention, the crosslinking agent preferably has a large number of functional groups and a small average molecular weight. Therefore, the hydroxyl value is preferably high within the above range.

Further, as the crosslinking agent, an EO adduct,
PO adducts can be used. In particular, the EO adduct is preferable because it has high polarity and can improve the adhesive strength. As for the EO adduct and the PO adduct, the description on the polyoxyalkylene ether polyol can be applied. As such a cross-linking agent, trade name "PP200" (PO adduct, number of functional groups: 2, hydroxyl value: 561, average molecular weight: 200, manufactured by Sanyo Chemical Industry Co., Ltd.), trade name "PEG200" (EO adduct) , Number of functional groups: 2, hydroxyl value: 561, average molecular weight: 200, manufactured by Sanyo Chemical Industry Co., Ltd.), product name “Dabco2035”
(EO adduct, number of functional groups: 3, hydroxyl value: 620, average molecular weight: 271, manufactured by Sankyo Air Products Co., Ltd.), trade name "SU464" (PO adduct, number of functional groups: 6, hydroxyl value: 449, average molecular weight) : 750, manufactured by Mitsui Takeda Chemical Co., Ltd., and trade name “MN300” (PO adduct, number of functional groups: 3, hydroxyl value: 547, average molecular weight: 3)
08, manufactured by Mitsui Takeda Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more. In the present invention, the cross-linking agent preferably has 2 to 3 functional groups and is an EO adduct.

The blending amount of the cross-linking agent is 100 parts by mass of the polyoxyalkylene ether polyol.
It is preferably 1 to 12 parts by mass (more preferably 2 to 10 parts by mass, further preferably 3 to 6 parts by mass). If the blending amount is less than 1 part by mass, the melting start temperature of the foam cannot be sufficiently lowered, and flame lamination processing may not be possible. On the other hand, when the blending amount exceeds 12 parts by mass, a foam having excellent frame lamination properties and adhesive strength can be obtained, but the compression strain tends to increase.

The combination of polyoxyalkylene ether polyol, polyisocyanate and crosslinking agent has an average molecular weight of 2000 to 4000, a hydroxyl value of 30 to 80, a functional group number of 2 or 3, and EO / P.
O-adduct polyoxyalkylene ether polyol, tolylene diisocyanate, and an average molecular weight of 20
A combination with a crosslinking agent composed of a polyol having 0 to 1000, a hydroxyl value of 300 to 700, a functional group number of 2 or 3, and an EO adduct is preferable. The amount of the cross-linking agent is 1 to 12 parts by mass (more preferably 2 to 10 parts by mass, further preferably 3 to 6 parts by mass) when the polyoxyalkylene ether polyol is 100 parts by mass.
It is preferable that

In addition to the above-mentioned polyoxyalkylene ether polyol, polyisocyanate and crosslinking agent, a catalyst, a foaming agent, an auxiliary agent and the like can be blended in the above "foam raw material". Examples of the catalyst include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate and other organotin compounds, zinc octylate and other organozinc compounds, nickel acetylacetoate, nickel diacetylacetoate and other organonickel compounds, and iron acetyl. A metal catalyst such as an organic iron compound such as acetoate, an alkali metal or alkaline earth metal alkoxide such as sodium acetate, or a phenoxide can be used. Furthermore, triethylamine, triethylenediamine,
N-methylmorpholine dimethylaminomethylphenol, imidazole, 1,8-diazabicyclo [5,4,4]
[0] A tertiary amine-based catalyst such as undecene can be used. Further, organic acid salts and the like can also be used. These may be blended alone or in a mixture of two or more kinds.

Water is often used as the blowing agent. In addition, for example, halogen-substituted aliphatic hydrocarbons (trichloromonofluoromethane, dichlorodifluoromethane, methylene dichloride, etc.) can be used. These may be blended alone, or 2
You may mix and mix 2 or more types.

As the auxiliary agent, for example, a surfactant and an addition type phosphoric acid ester flame retardant can be used.
As the surfactant, for example, silicone oil (polysiloxane-polyoxyalkylene copolymer) or the like is used. Further, as the addition-type phosphate ester-based flame retardant, for example, trischloroethyl phosphate, trischloropropyl phosphate, tris β-chloropropyl phosphate, tetrakis 2-chloroethyl ethylene diphosphate and the like can be used. . These may be blended alone or in a mixture of two or more kinds. It should be noted that the foam raw material may be appropriately blended with raw materials generally used for blending urethane such as an ultraviolet absorber, an antioxidant, an organic and inorganic filler, a colorant and the like.

The polyurethane foam obtained by the production method of the present invention has a rebound resilience of 20 to 50% (preferably 25 to 50) measured in the same manner as in the following examples.
%). Furthermore, this polyurethane foam has a density of 20 to 40 kg / m ³ (preferably 25 to 35 kg / m ³⁾ measured in the same manner as in the following examples.
³ ). The polyurethane foam may have a compressive strain rate of 20% or less (preferably 10% or less) measured in the same manner as in the following examples. Furthermore, the respective ranges of the impact resilience, the density, and the compressive strain rate may be combined with each other. In particular, the polyurethane foam obtained by the production method of the present invention can be a flexible slab polyurethane foam. The foamed sheet obtained by processing this foam is suitable for cushions used in vehicles and the like.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples. (1) Raw materials used (A) Polyoxyalkylene ether polyol Polyoxyethylene / oxypropylene ether polyol (EO / PO adduct, number of functional groups: 3, hydroxyl value: 5
6.1) (B) Polyisocyanate Tolylene diisocyanate (2,4-TDI and 2,6
-TDI is a ratio of 80:20), trade name "TDI-80", Nippon Polyurethane Industry Co., Ltd. (C) crosslinking agent PP200 (PO adduct, number of functional groups: 2, hydroxyl value:
561, average molecular weight: 200), trade name "PP20
0 ", PP400 manufactured by Sanyo Kasei Co., Ltd. (PO adduct, number of functional groups: 2, hydroxyl value:
281, average molecular weight: 400), trade name "PP40
0 ", PP1000 manufactured by Sanyo Kasei Co., Ltd. (PO adduct, number of functional groups: 2, hydroxyl value: 112, average molecular weight: 1000), trade name" PP1 "
000 ”, PEG200 manufactured by Sanyo Chemical Industries, Ltd. (EO adduct, number of functional groups: 2, hydroxyl value: 561, average molecular weight: 200), trade name“ PEG2
00 ”, Sanyo Kasei Co., Ltd. Dabco2035 (EO adduct, number of functional groups: 3, hydroxyl value: 620, average molecular weight: 271), trade name“ Da
bco2035 ", SU464 manufactured by Sankyo Air Products Co., Ltd. (PO adduct, number of functional groups: 6, hydroxyl value:
449, average molecular weight: 750), trade name “SU46
4 ”, MN300 manufactured by Mitsui Takeda Chemical Co., Ltd. (PO adduct, number of functional groups: 3, hydroxyl value:
547, average molecular weight: 308), trade name “MN30
0 ”, Mitsui Takeda Chemical Co., Ltd. (D) foaming agent water; ion-exchanged water (E) auxiliary agent surfactant; silicone foam stabilizer (trade name“ L-520 ”,
Nippon Unicar Co., Ltd. (F) Catalyst Metal catalyst; stanna octoate (trade name: "MRH
-110 ", manufactured by Johoku Chemical Co., Ltd. Amine catalyst: 33% triethylenediamine / dipropylene glycol (trade name:" Dabco 33LV ", manufactured by Sankyo Air Products Co., Ltd.)

(2) Production of Polyurethane Foam (Examples 1 to 7 and Comparative Examples 1 to 3) Each component other than polyisocyanate was stirred at a predetermined ratio shown in Table 1 using a hand mixer, and then a predetermined isocyanate was obtained. According to the index, the mixture was mixed with polyisocyanate in a predetermined ratio, and the mixture was put into a foam box and foamed and cured. Each of the polyurethane foams thus obtained was allowed to stand at room temperature for 1 day. The proportions of the respective components of the foam raw material in Table 1 are all expressed in parts by mass except for the isocyanate index, and the respective components are expressed in parts by mass relative to 100 parts by mass of the polyoxyalkylene ether polyol.

[0020]

[Table 1]

(3) Performance Test The polyurethane foams of Examples 1 to 7 and Comparative Examples 1 to 3 obtained in (2) above were subjected to a performance test by the following method. Physical property test Density (kg /
m ³ ), impact resilience (%), and compressive strain rate (%) were measured according to JIS K6401. The respective results are also shown in Table 1. Using each polyurethane foam, the melting start temperature and the decomposition temperature of the foam were determined by thermogravimetric analysis (TG-DTA).
("SSC-5200" manufactured by Seiko Instruments Inc.)
Was used). The results are also shown in Table 1.
The larger the difference between the melting start temperature and the decomposition temperature, the better the flame lamination property. Heat fusion test From each polyurethane foam, foam piece (length: 20
0mm, width: 50mm, thickness: 10mm),
Each foam piece was passed over a flame of LP gas adjusted to a width of 100 mm and a height of 70 mm at a speed of 8 m / min to melt the surface, and then a nylon nonwoven fabric was superposed on the surface and passed through a roll for pressure bonding. did. After pressure bonding, the initial peel strength was measured to be 50 mm in width and 150 mm in length, and the final peel strength was measured to be 25 mm in width and 150 mm in length, and the initial peel strength and the final peel strength were measured by the following methods. The respective results are also shown in Table 1. (Measurement of Initial Peel Strength) The initial peel strength was measured according to JIS L1066 after peeling the nylon nonwoven fabric for 2 minutes. (Measurement of Final Peel Strength) The final peel strength is JIS L1066, which is the peel strength 24 hours after pressure bonding of a nylon nonwoven fabric.
It was measured according to. In Table 1, "*" means that the peeling in the peeling test was not interface peeling but material destruction.

(3) Effects of Examples According to Table 1, Comparative Example 1 in which no cross-linking agent was used and claims of the present invention (hydroxyl value of cross-linking agent: 300 to 70) were used.
Crosslinking agent having a hydroxyl value lower than that of 0) (hydroxyl value: 112)
In Comparative Example 3 in which No. 1 was used, there were no problems in density, impact resilience, and compressive strain rate, but these had a high melting start temperature and a difference from the decomposition temperature of 90 ° C. It could not be fused and had poor frame lamination properties. Further, in Comparative Example 2 using a crosslinking agent (hydroxyl value: 281) having a hydroxyl value lower than the claims of the present invention (hydroxyl value of crosslinking agent: 300 to 700), the density, repulsion elastic modulus and compressive strain rate were measured. Although there was no problem, the melting start temperature was high, the difference from the decomposition temperature was not so large as 101 ° C., and although the frame lamination process could be performed, the initial peel strength was 0.1.
N / 50 mm, final peel strength was 1.0 N / 25 mm, initial adhesiveness was low, and strong adhesion was not possible.

On the other hand, in Examples 1 to 6, the density,
There was no problem in the impact resilience and the compressive strain rate, the melting start temperature was as low as 105 to 130 ° C., and the difference from the decomposition temperature was sufficiently large at 113 to 142 ° C., and frame lamination processing could be performed easily. Furthermore, the initial peel strength is 0.7 to 2.0 N / 50 mm, and the final peel strength is 2.
It was 0 to 4.7 N / 25 mm, which was excellent in initial adhesiveness and could be firmly bonded. In addition, Example 1,
In Nos. 3 to 6, in the final peeling test, not interfacial peeling but material destruction, and strong adhesiveness was obtained. In Example 7, the compressive strain rate was 15.6%, and Examples 1 to 1
Although it was larger than that of No. 6, there was no problem in density and impact resilience, the melting start temperature was as low as 95 ° C, and the difference from the decomposition temperature was 155 ° C, which was the largest in the examples, making frame lamination processing easy. I was able to give it. Furthermore, the initial peel strength was 3.9 N / 50 mm, and the final peel strength was 5.0 N / 25 mm (material destruction), which was excellent in initial adhesiveness and could be firmly bonded. Also,
Those using the crosslinking agent of the EO adduct (Examples 1, 3, 6, and 7) were superior in initial peel strength and final peel strength.

[0024]

According to the manufacturing method of the present invention, without using a special polyol and a special isocyanate,
By using a general-purpose polyol and a general-purpose polyisocyanate, and a specific cross-linking agent, it is possible to produce a polyurethane foam for frame lamination having excellent initial adhesion. Further, as a result, a polyurethane foam for frame lamination having sufficient impact resilience can be easily manufactured. Furthermore, by setting the compounding amount of the cross-linking agent to a specific amount or using a cross-linking agent having a specific composition, it is possible to produce a polyurethane foam for frame lamination having more excellent adhesive strength.
According to another production method of the present invention, a polyurethane foam for frame lamination having sufficient impact resilience, excellent initial adhesiveness, and excellent adhesive strength can be produced.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J034 BA07 DA01 DB03 DB07 DC50                       DG03 DG04 DG09 HA01 HA06                       HA07 HC03 HC12 HC13 HC17                       HC22 HC46 HC52 HC61 HC63                       HC64 HC67 HC71 HC73 KA01                       KC08 KC17 KC35 KD02 KD04                       NA02 NA03 NA05 QA02 QB14                       QC01 RA12

Claims (7)

[Claims] 1. A polyoxyalkylene ether polyol, a polyisocyanate, and a hydroxyl value of 300 to 70.
A method of producing a polyurethane foam for frame lamination, which comprises foaming a foam raw material containing 0, a functional group number of 2 to 6, and a cross-linking agent comprising a polyol other than the above polyoxyalkylene ether polyol. 2. The method for producing a polyurethane foam for frame lamination according to claim 1, wherein the blending amount of the cross-linking agent is 1 to 12 parts by mass when the polyoxyalkylene ether polyol is 100 parts by mass. 3. The method for producing a polyurethane foam for frame lamination according to claim 1 or 2, wherein the crosslinking agent has 2 or 3 functional groups and is an ethylene oxide adduct. 4. The polyoxyalkylene ether polyol according to claim 1, wherein the polyoxyalkylene ether polyol has an average molecular weight of 1500 to 5000, a functional group number of 2 to 4, and is an ethylene oxide / propylene oxide adduct. A method for producing the polyurethane foam for frame lamination described. 5. The method for producing a polyurethane foam for frame lamination according to claim 1, wherein the polyisocyanate is tolylene diisocyanate. 6. A polyoxyalkylene ether polyol having an average molecular weight of 2000 to 4000, a hydroxyl value of 30 to 80, a functional group number of 2 or 3, and an ethylene oxide / propylene oxide adduct, and tolylene diisocyanate, Average molecular weight of 200 to 1000,
A method for producing a polyurethane foam for frame lamination, which comprises foaming a foam raw material containing a cross-linking agent having a hydroxyl value of 300 to 700, a functional group number of 2 or 3, and a polyol which is an EO adduct. 7. A polyurethane foam for frame lamination, which is manufactured by the manufacturing method according to any one of claims 1 to 6 and has a rebound resilience of 20 to 50%.