JP4349095B2 - Flexible polyurethane foam for frame lamination - Google Patents

Description

  The present invention relates to a flexible polyurethane foam for frame lamination which is preferably used for adhesion to a skin material in a vehicle seat, and in particular, has low fogging and low pollution using a non-halogen type organic phosphorus flame retardant. The present invention relates to a flexible polyurethane foam for frame lamination, which has a small compression residual strain and is excellent in frame laminating properties, foam stability, and flame retardancy.

  Polyurethane foam for cushioning materials for vehicle seats, child seats, sofas, mattresses, beds, etc., vehicle interior materials, clothing pads, helmet interior materials, heat insulation or cold insulation cushioning materials for beverages, flooring cushioning materials, etc. In many cases, a frame laminating method is employed for bonding the main body to a skin material such as cloth or leather. The frame laminating method is a method in which the surface of the flexible polyurethane foam for frame lamination is heated and melted with a flame, etc., and the skin material is pasted and cured and integrated using the heat-fusibility, making the skin material easy It is widely used in various fields because it can be adhered to the surface and the texture of the skin material is not impaired. For example, in a vehicle seat, the soft polyurethane foam main body and the skin material are bonded via the frame lamination soft polyurethane foam sheet.

  Not only the flexible polyurethane foam for frame lamination used in such a frame laminating method, but usually a flame retardant is blended in the polyurethane foam raw material in order to impart flame retardancy.

  Conventionally, as a flame retardant to be blended in a polyurethane foam raw material, a halogen-containing (halogen type) organic phosphorus flame retardant such as trischloroethyl phosphate, trischloropropyl phosphate, or a condensate thereof is generally known. . However, these halogen-type organophosphorus flame retardants are used, for example, when a polyurethane foam containing the organophosphorus flame retardant is used as a vehicle seat, particularly when the interior temperature rises in summer or the like. Or the halogen released from the flame retardant is diffused into the passenger compartment, fogging the glass (fogging), and in some cases, the flame retardant is emitted, the flame retardancy is lowered, the foam is discolored or deteriorated was there. Furthermore, when the foam is incinerated at a low temperature, there is a concern about the generation of dioxins.

  Therefore, in recent years, an organic phosphorus flame retardant containing no halogen (non-halogen type) has been used instead of the halogen type organic phosphorus flame retardant.

JP 2001-151919 discloses a reactive non-halogen type organic phosphorus flame retardant having a hydroxyl group at the end as a non-halogen type organic phosphorus flame retardant, and an oligomer type non-reactive non-halogen type organic phosphorus flame retardant. There has been proposed a flexible polyurethane foam for frame lamination using a combination.
JP 2001-151919 A

  However, when a reactive non-halogen type organophosphorus flame retardant is blended, there is a problem that the compression residual strain (sagging property) of the resulting polyurethane foam is remarkably deteriorated. This compressive residual strain tends to be further worsened when used in combination with the polyol component of the raw material of polyurethane foam for frame lamination, and the product that is compounded by frame laminating with skin materials such as cloth and leather collapses under its own weight. There was a problem that it could not be restored. Furthermore, due to the reactive flame retardant, the foaming stability is very poor, and there is a drawback that the foam tends to be solitary (a lot of independent pores, not continuous pores).

  In Japanese Patent Laid-Open No. 2001-151919, in order to alleviate the problems caused by this reactive flame retardant, the combined use with an oligomer-type non-reactive flame retardant is proposed, but the combined use of this Japanese Patent Laid-Open No. 2001-151919 is proposed. In the example, the amount of each flame retardant added is limited, and sufficient flame retardancy cannot be obtained. In addition, the non-reactive non-halogen type organophosphorus flame retardant does not contribute to the improvement of the heat-fusibility at the time of frame lamination, and thus has a drawback that the skin material used is also restricted.

  The present invention solves the above-mentioned conventional problems, and is a low-fogging and low-contamination flexible polyurethane foam for flame lamination using a non-halogen type organic phosphorus flame retardant. Another object of the present invention is to provide a flexible polyurethane foam for frame lamination having excellent foam stability and flame retardancy.

  The flexible polyurethane foam for frame lamination of the present invention is a flexible polyurethane foam for frame lamination obtained by foaming a polyurethane foam raw material containing a non-halogen type organic phosphorus flame retardant as a flame retardant, wherein the organic phosphorus flame retardant is: It comprises a non-oligomeric organic phosphorus flame retardant containing no hydroxyl group and an oligomeric organic phosphorus flame retardant having a phosphorus content of 10% by weight or more and having at least three phosphate ester units.

  As non-halogen type organophosphorus flame retardant, non-reactive non-oligomeric organophosphorus flame retardant containing no hydroxyl group and the above specific oligomeric organophosphorus flame retardant are used together with good compression residual strain and foaming It is possible to obtain a flexible polyurethane foam for flame-retardant flame lamination which has stability and also has excellent fusion properties (frame laminating properties).

  That is, in the present invention, since the non-reactive non-oligomeric organophosphate flame retardant is used, the problems of compressive residual strain and foam stability due to the use of the reactive non-oligomeric organophosphate flame retardant are solved. Is done. In addition, the specific oligomeric organic phosphoric acid flame retardant used in combination with the non-oligomeric organic phosphoric acid flame retardant sufficiently contributes to the fusibility, so that the flexible polyurethane foam for frame lamination has excellent frame laminating properties. It can be.

  In the present invention, the content of the non-oligomeric organophosphorous flame retardant in the flame retardant is 25 to 95% by weight, the content of the oligomeric organophosphorous flame retardant is 75 to 5% by weight, It is preferable that substantially only non-oligomeric organophosphorus flame retardant and oligomeric organophosphorus flame retardant are included.

  Moreover, as an oligomeric organophosphorus flame retardant, what is represented by the following general formula [I] is preferable.

（上記一般式［Ｉ］中、ｎは数平均に基づいて２〜２０の範囲であり、Ｒはアルキル基又はヒドロキシアルキル基を表し、Ｒ’はアルキレン基を表す。なお、一分子中に複数存在するＲは同一であっても異なるものであっても良いが、好ましくはＲは同一である。）

(In the general formula [I], n is in the range of 2 to 20 based on the number average, R represents an alkyl group or a hydroxyalkyl group, and R ′ represents an alkylene group. The Rs present may be the same or different, but preferably R are the same.)

  In the above general formula [I], R is preferably an ethyl group, and R 'is preferably an ethylene group.

  Such an organophosphorus flame retardant is preferably contained in an amount of 2 to 35 parts by weight with respect to 100 parts by weight of the polyol component in the polyurethane foam raw material.

  According to the present invention, a low-fogging and low-contamination flexible polyurethane foam for flame lamination using a non-halogen type organophosphorus flame retardant has a low compression residual strain, frame laminating properties, foam stability, and difficulty. A flexible polyurethane foam for flame lamination having excellent flammability is provided.

  Hereinafter, embodiments of the flexible polyurethane foam for frame lamination of the present invention will be described in detail.

  First, the non-oligomeric organophosphorus flame retardant and oligomeric organophosphorus flame retardant used in the present invention will be described.

  As the non-oligomeric organophosphorous flame retardant, a phosphoric acid ester represented by the following general formula [II] is preferable.

（上記一般式［II］中、Ｒ”は炭素数１〜５個のアルキル基、又はアリール基を表し、一分子中に複数存在するＲ”は同一であっても異なるものであっても良いが、好ましくはＲ”は同一である。）

(In the general formula [II], R ″ represents an alkyl group having 1 to 5 carbon atoms or an aryl group, and a plurality of R ″ present in one molecule may be the same or different. But preferably R ″ is the same.)

  Such non-oligomeric organophosphorous flame retardants include triphenyl phosphate (“TPP”); propylated or butylated TPP (“PTPP” and “BTPP”, respectively); triethyl phosphate (“TEP”); And tributyl phosphate ("TBP"). The non-oligomeric organophosphorous flame retardant is not necessarily a monomer as long as it is non-oligomeric, and may be a dimer, trimer, tetramer, or a mixture thereof. Preferred are dimers, trimers or mixtures thereof, with dimers being most preferred. An example of such a dimer includes resorcinol diphosphate (“RDP”).

  The non-oligomeric organophosphorus flame retardant may be a non-oligomeric one in which one of the —OR ″ groups in the general formula [II] is replaced by a —R ″ group. Examples of the oligomeric organophosphorous flame retardant include dimethylmethylphosphonate.

  On the other hand, the oligomeric organophosphorus flame retardant has a phosphorus content of 10% by weight or more and has at least three phosphate ester units. Here, “oligomeric” means “monomer” and “dimer”. Except for an oligomer that may contain a small amount of trimer or tetramer. This oligomeric organophosphorous flame retardant, for example, reacts phosphorus pentoxide with a selected trialkyl phosphate (eg triethyl phosphate) to form a polyphosphate ester containing a P—O—P bond. It can be prepared by reacting with an epoxide (eg ethylene oxide) to form the desired product.

  A preferred oligomeric organophosphorous flame retardant in the present invention is represented by the following general formula [I].

（上記一般式［Ｉ］中、ｎは数平均に基づいて２〜２０の範囲であり、Ｒはアルキル基又はヒドロキシアルキル基を表し、Ｒ’はアルキレン基を表す。なお、一分子中に複数存在するＲは同一であっても異なるものであっても良いが、好ましくはＲは同一である。）

(In the general formula [I], n is in the range of 2 to 20 based on the number average, R represents an alkyl group or a hydroxyalkyl group, and R ′ represents an alkylene group. The Rs present may be the same or different, but preferably R are the same.)

  In the above general formula [I], n is more preferably in the range of 2-10. R represents an alkyl group having 1 to 24 carbon atoms, particularly an alkyl group having 2 to 10 carbon atoms, especially an alkyl group having 2 to 4 carbon atoms, or a hydroxyl group having 1 to 10 carbon atoms and 1 to 10 hydroxyl groups. An alkyl group, particularly a hydroxyalkyl group having 2 to 10 carbon atoms and 1 to 4 hydroxy groups, particularly a hydroxyalkyl group having 2 to 4 carbon atoms, is preferred, and R ′ is 1 to 24 carbon atoms, In particular, an alkylene group having 2 to 10 carbon atoms, particularly 2 to 4 carbon atoms is preferable.

  A particularly preferred oligomeric organophosphorus flame retardant is represented by the formula [I], wherein R is an ethyl group, R ′ is an ethylene group, has a hydroxy functional group of about 30 mg-KOH / g or less, It has an acid value of not more than 5 mg-KOH / g and a phosphorus content in the range of about 15-25% by weight. In the following, such an oligomeric organophosphorous flame retardant may be referred to as “PEEOP” (or “poly (ethylethyleneoxy) phosphate”).

  As the oligomeric organophosphorus flame retardant, in the above general formula [I], one of the right-side terminal —OR groups or the —OR group of the repeating unit in parentheses is substituted with an —R group. May be included.

  The flexible polyurethane foam for flame lamination of the present invention is a polyol component, an isocyanate component, a foaming agent, except that such a non-oligomeric organophosphorous flame retardant and an oligomeric organophosphorus flame retardant are used in combination as a flame retardant. It can be produced according to a conventional method by reacting a urethane foam raw material such as a catalyst, and the production method is not particularly limited, and various methods such as a one-shot method and a prepolymer method can be adopted.

  In the present invention, in order to produce a flexible polyurethane foam for flame lamination excellent in heat-fusibility, it is preferable to use 10 parts by weight or more of ester-modified polyether polyol as a polyurethane foam raw material in 100 parts by weight of all polyol components. . As the ester-modified polyether polyol, glycerin / propylene oxide / phthalic anhydride / propylene oxide adduct is preferable, and those having a functional group number f of 2 to 8 and a molecular weight Mw of 500 to 6000 are suitable. In addition, in the above adduct, maleic acid or the like may be added instead of phthalic anhydride.

  In the present invention, only such ester-modified polyether polyol may be used as the polyol component, but other polyols may be used in combination. In this case, as other polyols, polyether polyols and polyester polyols having a molecular weight of about 1000 to 5000 can be used.

  Polyisocyanates include toluene diisocyanate (TDI) or pure and crude types, diphenylmethane diisocyanate (MDI) or modified MDI, xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), and these. The isocyanate prepolymer type, carbodiimide-modified type and the like are mainly used. Furthermore, a mixture of crude MDI and TDI can be used, and the isocyanate index of the polyurethane foam raw material is usually about 80 to 120.

  As the catalyst, a metal catalyst such as stannous octoate is mainly used, but an amine catalyst may be used in combination. The blending amount of the catalyst is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the polyol component, and particularly 0 to 1 part by weight of the tin catalyst and 0.1 to 4.0 parts by weight of the amine catalyst. Are preferably used.

  Moreover, as a foaming agent, water is normally used and it is preferable that the compounding quantity shall be 0.5-6.0 weight part with respect to 100 weight part of polyol components.

  In addition, as a urethane foam raw material, a foam stabilizer, various additives, etc. can be mix | blended other than said various components as needed. Other additives include flame retardants, colorants, ultraviolet absorbers, and the like that are usually used in the production of urethane foam. The blending amount of these additives and the like may be set to such an extent that the heat-fusibility and other characteristics of the obtained flexible polyurethane foam for frame lamination are not impaired.

Flame lamination for flexible polyurethane foams of the present invention is generally a density 18 kg / ^{m 3} or more, and preferably from 20 to 50 kg / ^{m 3.}

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

In addition, the polyurethane foam raw material used in the following is as follows.
Polyol 1: Polyoxyalkylene polyol (manufactured by Mitsui Takeda Chemical Co., Ltd., average functional group number 3, hydroxyl value 56 mg-KOH / g, oxypropylene content of oxyalkylene moiety is 100% by weight)
Polyol 2: Polyoxyalkylene polyester block copolymer polyol (Mitsui Takeda Chemical Co., Ltd. average number of functional groups 3, hydroxyl value 56 mg-KOH / g)
Isocyanate: Toluene diisocyanate (Mitsui Takeda Chemical Co., Ltd. 2,4-isomer 80%, 2,6-isomer 20%)
Foaming aid: Methylene chloride Catalyst: Triethylenediamine "Caorizer No31" (manufactured by Kao Corporation)
Foam stabilizer: Siloxane / oxyalkylene block copolymer “SRX-298” (made by Toray Dow Corning Silicone)
Tin catalyst: Tin octylate "STANOCTO" (manufactured by Yoshitomi Pharmaceutical Co., Ltd.)
Foaming agent: water (ion exchange water)
Flame retardant A: Non-oligomeric organophosphorus flame retardant and oligomeric organophosphorus flame retardant “PNX” (manufactured by Akzo Nobel Co., Ltd.)
Flame Retardant B: Reactive non-halogen type oligomeric organophosphorous flame retardant “Dieguard 580” (manufactured by Daihachi Chemical Industry Co., Ltd.) (hydroxyl value 130 mg-KOH / g, phosphorus content 18% by weight, molecular weight 860)
Flame retardant C: Reactive non-halogen type oligomeric organophosphorous flame retardant “Diagard 610” (manufactured by Daihachi Chemical Industry Co., Ltd.) (hydroxyl value 130 mg-KOH / g, phosphorus content 18% by weight, molecular weight 860)
Flame retardant D: Reactive non-halogen type oligomeric organophosphorous flame retardant “ECOFIN110” (manufactured by Netzah Chemical Industry)
Flame retardant E: Halogen type condensed phosphate "UF500" (manufactured by Daihachi Chemical Industry Co., Ltd.)

Example 1, Comparative Examples 1-5
A flexible polyurethane foam for frame lamination was produced by the one-shot method according to a conventional method with the polyurethane foam raw material composition and isocyanate index shown in Table 1.

  The obtained flexible polyurethane foam for frame lamination was measured for density, hardness and compressive residual strain according to JIS K6400, and the following characteristic evaluation test was conducted. The results are shown in Table 1.

  Frame laminating property: After bonding the fabric and polyurethane foam by frame laminating method, punching out to 25mm width, fixing the end of the fabric surface with a jig, peeling polyurethane foam at a constant speed, peeling over 300g / 25mm width The case of strength was determined as “good”, the case of less than 200 g / 25 mm width was determined as “No”, and the case where it was not adhered to the fabric was determined as “impossible”.

  MVSS (Motor Beagle Safety Standard) 302 Flame Retardancy Test: Those with a maximum burning rate of 80 mm / min or less were accepted, and those with a maximum burning rate of 81 mm / min or less were rejected.

  Fogging property: Put a test piece (thickness 10 mm × diameter 80 mm) in a 1 liter glass bottle, cover with a glass plate, heat at 80 ° C. for 3 hours, leave it for 1 hour, and then measure the reflectance of the glass plate To do. Divide the value by the reflectance before the test and multiply by 100 to obtain the haze value. The haze value is 85% or more and less than 90%. The haze value is 90% or more. Was marked with x.

Discoloration resistance: According to the heat discoloration test method for frame laminate products, the following procedure was used.
a. Using a spectrophotometer, the fabric is measured, and the b value (b ₀ ) of the Lab system and the b ^* value (b ^* ₀ ) of the L ^* a ^* b ^* system are obtained.
b. Two polyurethane foams of 50 × 50 mm and 5 mm thickness obtained by laminating the fabrics by frame lamination are combined so that the fabrics are on the outside, and 10 places are fixed with staples to obtain test pieces.
c. The thermostat (oven) is set to a predetermined temperature (110 ° C.) in advance.
d. The test piece is put in a beaker, the upper part of the beaker is sealed with aluminum foil, this is put in a thermostatic bath, and is heated for a predetermined time (192 hours).
e. After heating, the test piece is taken out and measured again with a spectrophotometer to obtain the b value (b ₁ ) and b ^* value (b ^* ₁ ) of the fabric.
f. B value before the test from the b value after the test _{(b 1) (b 0)} the pulling together seek [Delta] b, a ^{b *} value after the test ^(b _{* 1)} before test from the ^{b *} value ^(b _{* 0)} The pull Δb ^* is determined.
g. If the Δb value is 1.0 or less and the Δb ^* value is 1.6 or less, the result is excellent (（), the Δb value is in the range of 1.0 to 3.0, and the Δb ^* value is 1.6 to 4.8. The one in the range is judged as good (Δ), and the one out of both is judged as defective (x).

  From Table 1, it can be seen that according to the present invention, a flexible polyurethane foam for frame lamination having a small compressive residual strain and excellent frame laminating property, flame retardancy, and discoloration resistance can be obtained.

  The flexible polyurethane foam for frame lamination according to the present invention is a cushioning material for vehicle seats, child seats, sofas, mattresses, beds, etc., vehicle interior materials, clothing pads, helmet interior materials, beverages, etc. It is useful for adhesion of skin materials such as cloth and leather by a frame laminating method such as cushioning material for flooring.

Claims (5)

As a flame retardant, a flexible polyurethane foam for frame lamination obtained by foaming a polyurethane foam raw material containing a non-halogen type organophosphorus flame retardant,
The organophosphorus flame retardant includes a non-oligomeric organophosphorus flame retardant containing no hydroxyl group and an oligomeric organophosphorus flame retardant having a phosphorus content of 10% by weight or more and having at least three phosphate ester units. A flexible polyurethane foam for frame lamination.   In Claim 1, the content of the non-oligomeric organophosphorous flame retardant in the flame retardant is 25 to 95 wt%, and the content of the oligomeric organophosphorous flame retardant is 75 to 5 wt%. Characteristic flexible polyurethane foam for frame lamination. The flexible polyurethane foam for flame lamination according to claim 1 or 2, wherein the oligomeric organophosphorous flame retardant is represented by the following general formula [I].

(In the general formula [I], n is in the range of 2 to 20 based on the number average, R represents an alkyl group or a hydroxyalkyl group, and R ′ represents an alkylene group. The Rs present may be the same or different.)   The flexible polyurethane foam for flame lamination according to claim 3, wherein, in the general formula [I], R is an ethyl group and R 'is an ethylene group. In any one of claims 1 to 4, with respect to 100 parts by weight of the polyol component of the polyurethane foam in the raw material, a flexible polyurethane frame lamination which comprises the 2 to 35 parts by weight of an organic phosphorus-based flame retardant Form.