JPH09296160A - Polyurethane foam for sealing material and door for air conditioning apparatus using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane foam for a sealing material excellent in ozone-deterioration resistance, accordingly capable of keeping practical air permeability as a sealing material, resistant to hydrolysis and little in initial loss of tensile strength, and to provide a door for an air-conditioning apparatus using the polyurethane foam. SOLUTION: This polyurethane foam is produced by adding 3-12 pts.wt. of an antiozonant such as an aromatic secondary amine compound of a diphenylamine, etc., to a raw material for a polyurethane foam such as a polyisocyanate and a polyol. Further, a door for an air conditioning apparatus of a vehicle is produced by using a sealing material consisting of the polyurethane foam. As the polyol, a polyol which is used for producing a soft polyurethane foam can be usually used. However, it is preferably to concomitantly use specific amounts of a polyetherpolyol and a polyesterpolyol or to use a polyesterpolyetherpolyol containing polyester parts and polyether parts at the same time in a molecule.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent ozone deterioration resistance, maintains a practical air permeability even after being exposed to ozone for a long time, and has a mechanical property after being exposed to a high temperature and high humidity atmosphere for a long time. The present invention relates to a polyurethane foam for a sealing material (hereinafter referred to as a sealing material foam) having excellent performance with a small decrease in strength, and an air conditioner door using the sealing material foam as a sealing material. The foam for a sealing material of the present invention can be used as a sealing material for a door used in an air conditioner for a vehicle and a toner sealing material for various printers, facsimiles, copiers and the like.

[0002]

2. Description of the Related Art Air sealing materials are used, for example, in doors for air conditioners provided in various air ducts of vehicles and the like. This air sealing material seals a flow path switching valve of a duct for introducing air of an appropriate temperature, humidity, etc. into a vehicle cabin for air conditioning and ventilation. Further, the toner sealing material is used as a sealing material for a toner container of, for example, a laser printer or a copying machine. The ink toner filling container is sealed by this toner sealing material so that the toner, which is fine powder, does not leak out.

Polyurethane foam using polyester polyol (hereinafter referred to as ester foam).
Is flexible and has low breathability. In addition, since it has a small compression set and excellent durability, it has been widely used as various sealing materials. Further, in the use of the sealing material as described above, it is necessary to have excellent ozone deterioration resistance and the like. In addition, the ester foam is also very excellent in this respect as compared with a polyurethane foam using a polyether polyol (hereinafter referred to as an ether foam).

However, in the case of both the air seal material and the toner seal material, even if the ester foam is used, the cell membrane is destroyed and the air permeability is greatly increased during long-term exposure to a slight amount of ozone in the atmosphere. However, there is a problem that it does not function as a sealing material. In addition, the ester-based foam also has a problem of deterioration due to hydrolysis of an ester bond due to the polyester polyol which is the main raw material.

Ester foams or ether foams have hitherto been used as sealing materials for vehicle air conditioner doors. Although this ester-based foam has excellent initial sealing properties, it hydrolyzes and becomes brittle in a few years in the actual vehicle use environment. In extreme cases, it may disintegrate into powder when touched, and as a result, there is a problem that the sealing property is greatly reduced. To address this hydrolysis problem, ether foams have also begun to be used in recent years. It has been confirmed that this ether foam has a life three times or more longer than that of the ester foam with respect to hydrolysis, but there is a problem that it is more likely to be deteriorated by ozone than the ester foam.

[0006] Further, since the assumed environment of use of a door for an air conditioner of a vehicle is severe, recently, the air seal material used is also required to have long-term durability such as a 10-year warranty. Is increasing. Therefore, hydrolysis of ester foams or ozone deterioration of ether foams has become a more serious problem.

Further, in recent years, in copying machines and the like, finer toner particles have been promoted along with the definition of images and the colorization of images. Therefore, as a resin component for converting the colorant into a toner, a strong acidic or alkaline resin is often used instead of the conventional neutral one. Due to such changes in the pH of the resin, the hydrolysis of the ester foam is accelerated, and the number of cases where the ester foam does not function sufficiently as a sealing material in a relatively short period of time is increasing.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above problems by incorporating an appropriate amount of an ozone deterioration inhibitor such as a specific amine-based additive into a raw material of a foam for a sealing material. . As a result, ozone deterioration (in the present invention, the degree of deterioration is evaluated by the air permeability after exposure to ozone. Note that suppression of ozone deterioration is hereinafter also referred to as ozone deterioration resistance). , And hydrolysis (in the present invention, the difficulty of hydrolysis is evaluated by the retention of the tensile strength after exposure to a humid heat atmosphere. In addition, the fact that hydrolysis is suppressed is hereinafter referred to as resistance to wet heat aging. It is an object of the present invention to provide a foam for a sealing material having excellent performance in which all of the above are suppressed to a low level, and an air conditioner door using the foam for a sealing material.

Further, in the present invention, a specific polyester polyether polyol is used as the polyol, or a normal polyester polyol or polyether polyol is used in combination therewith, and the above-mentioned specific amine compound or the like is prevented from ozone deterioration. It is an object of the present invention to provide a foam for a sealing material, which also has excellent performance, and a door for an air conditioner using the foam for a sealing material by blending the agent.

[0010]

The foam for a sealing material of the first invention is a polyurethane foam obtained by reacting and curing a foamable composition containing a polyisocyanate, a polyol, and an antiozonant. Is 100 parts by weight, the aromatic secondary amine compound is 1 to 25 parts by weight. The second invention is characterized in that an aromatic secondary amine compound is used as the ozone deterioration inhibitor.

As the above-mentioned "polyisocyanate", those generally used for the production of flexible polyurethane foam can be used without any particular limitation. For example, TDI, MDI and a mixture of TDI and MDI, or M
A modified product such as DI or TDI can be used.

As the above-mentioned "polyol", those which are usually used for the production of flexible polyurethane foam can be used without any particular limitation. For example, in addition to polyester polyol, polyether polyol, etc., polycarbonate polyol, polydiene-based polyol, etc. can be used. These polyols may be used alone or in combination of two or more.

The polyol used as described above is not specified. However, in the present invention, it is necessary to suppress ozone deterioration and hydrolysis of the obtained “foam for sealing material”. Therefore, it is preferable to use a polyester polyol having poor resistance to moisture and heat aging, and a polyether polyol having poor resistance to ozone deterioration, although the foam does not hydrolyze, although the resulting foam has excellent resistance to ozone deterioration. The amount ratio is not particularly limited, but when the total amount of the polyol is 100 parts by weight, the polyether polyol is preferably 60 parts by weight or more, particularly preferably 70 parts by weight or more.

As the polyol, the "polyester polyether polyol" of the third invention is preferable.
This polyol has a polyester portion and a polyether portion in its molecule. Therefore, the ozone deterioration resistance of the obtained foam is considerably improved as compared with the ether foam. Further, the resistance to moist heat aging is improved to the same degree as that of ether foam.

However, this polyester polyether polyol alone is not particularly sufficient in ozone deterioration resistance. Therefore, in the present invention, a specific amount of an ozone deterioration inhibitor such as an aromatic secondary amine compound is added to the foamable composition. This makes it possible to obtain a foam for a sealing material having both excellent ozone deterioration resistance and wet heat aging resistance, without using a polyester polyol or a polyether polyol together.

When the above-mentioned polyester polyether polyol and polyester polyol are used together as the polyol, 15 to 60 parts by weight, and particularly 20 to 50 parts by weight of the polyester polyol are used when the total amount of the polyol is 100 parts by weight. It is preferable to set it as a part. When used in combination with a polyether polyol, the polyether polyol is added in an amount of 50 to 80 parts by weight, particularly 60 to 75 parts by weight.
It is preferable to use parts by weight.

Further, when the above-mentioned three types of polyols are used in combination, the polyester polyol is 15 to 30 parts by weight, the polyester polyether polyol is 25 to 45 parts by weight, and the total amount of the polyols is 100 parts by weight.
The amount of polyether polyol is preferably about 30 to 50 parts by weight. In this case, it is more preferable to add a large amount of polyether polyol as compared with the polyester polyol. Incidentally, the polyester polyether polyol is often provided as a mixture with the polyether polyol, and it is necessary to take this point into consideration when setting the amount ratio of the polyol.

The above-mentioned "ozone deterioration inhibitor" is the second
It is particularly preferable to use the above-mentioned “aromatic secondary amine compound” (hereinafter referred to as secondary amine compound) as in the invention. The secondary amine compound includes phenyl-
1-naphthylamine, alkylated diphenylamine,
N, N'-diphenyl-p-phenylenediamine, p-
(P-toluenesulfonylamide) diphenylamine,
4,4 ′-(α, α-dimethylbenzyl) diphenylamine, mixed diallyl-p-phenylenediamine, octylated diphenylamine, and the like. Also, poly (2,2,4-trimethyl-1,2-dihydroquinoline), 6-ethoxy-1,2-dihydro-2,2,4-
Amine-ketone compounds such as trimethylquinoline can also be used.

These secondary amine compounds are used as antiaging agents for rubber and the like. But,
It is not known that these compounds have an action of suppressing ozone deterioration of the polyurethane foam. When used as an anti-aging agent for rubber, the compounding amount is usually several hundred to several thousand ppm relative to rubber, at most 50 parts.
It is about 00 ppm.

On the other hand, in the present invention, 1 is added to the polyol.
It is mixed in a large amount such as not less than 3 parts by weight, particularly not less than 3 parts by weight, more preferably not less than 5 parts by weight. Even when this is converted into the blending amount with respect to the foam, the amount is 7000 ppm or more, particularly 2 parts by weight, and more preferably 3.5 parts by weight or more. As described above, in the present invention, the secondary amine compound is not only known for its action and effect, but is also used in a large amount, far exceeding the conventional usual compounding amount.

The above secondary amine compounds may be used alone or in combination of two or more. If the compounding amount of this compound is less than 1 part by weight, the ozone deterioration resistance is not improved to a practically sufficient degree. On the other hand, if the blending amount exceeds 25 parts by weight, it is difficult to react and cure the foamable composition, and a normal foam cannot be obtained.

The blending amount of the secondary amine compound is preferably in the range of "3 to 12 parts by weight" as in the fourth invention. With this blending amount, JIS L 1096 after 400 hours of exposure according to the JIS K 6301 ozone deterioration test
The air permeability of the foam measured in accordance with
m ² / sec (the range of the blending amount and the air permeability is the area [A] in FIG. 3), and a foam for a sealing material having practically sufficient performance can be obtained. At the same time, reaction and curing are easy, and there is no problem in operation.

When the amount of the secondary amine compound is in the range of 8 to 12 parts by weight, the reaction and curing are similarly easy, and the air permeability after exposure to ozone is 5 to 10 cc / cm ² / sec. The range of the amount and the air permeability is the area [B] in FIG. 3), and a polyurethane foam for a sealing material having excellent performance can be obtained. Further, depending on the kind of the secondary amine compound, even if the compounding amount is as small as 3 to 7 parts by weight,
Air permeability after exposure to ozone is 3.5 to 6.5 cc / cm ² /
Second (The range of this blending amount and air permeability is [C] in FIG.
Area. ) And a foam for a sealing material having very excellent performance can be obtained. In addition, when such a small amount is blended, the operability of reaction and curing is further improved, which is particularly preferable.

Further, in the foam for a sealing material of the present invention,
As in the fifth aspect of the invention, after the temperature is adjusted to 80 ° C. and the relative humidity is 95% and the atmosphere is adjusted to 1600 hours, the JI
“Tensile strength retention” measured according to SK6301
Is usually "70% or more". This excellent resistance to wet heat aging is similarly achieved even with a polyol other than the polyester polyether polyol, which has a remarkable effect of improving this performance.

Further, the resistance to moisture and heat aging is not affected by the kind of ozone deterioration inhibitor such as a secondary amine compound and the compounding amount thereof, and a foam for a sealing material having an excellent performance can be obtained. This high retention of tensile strength even in this harsh acceleration test confirms that the foam for a sealing material of the present invention is extremely resistant to hydrolysis.

The air conditioner door of the sixth invention is an air conditioner door comprising a substrate and a sealing material layer formed on at least one surface of the substrate, wherein the sealing material layer is the first to fifth inventions. The sealant foam according to any one of 1. The sealing material layer may be formed on one of the both surfaces of the substrate, but is usually formed on both the front and back surfaces of the substrate.

The air conditioner door 1 used in the vehicle air conditioner 2 generally has a shaft 1 as shown in FIG.
1, the substrate 12 and the sealing material layer 13.
The sealing material layer 13 is formed by adhering to the substrate 12, but may be directly foamed on the substrate 12. Then, as shown in FIG. 5, it has an action of opening / closing or switching the air passages in the cases 9 and 16 of the vehicle air conditioner 2. This air passage is closed by pressing the sealing material layer 13 against the inner peripheral edges of the openings of the cases 9 and 16 as shown in FIG. 6, for example. However, when a part of the cell membrane is destroyed due to ozone deterioration or oxidative deterioration due to oxidant in the exhaust gas, the air permeability of the sealing material layer becomes large, and the amount of air passing through the flow path of FIG. Increase, and the sealing property deteriorates. On the other hand, when the sealing material layer 13 pressed against the inner peripheral edges of the openings of the cases 9 and 16 is deteriorated by ozone or the like and a part of the surface is missing, or when the compressive strain of the sealing material layer 13 is not sufficiently recovered. Is
The amount of air that passes through the flow paths of FIGS. 6 and B increases, and the sealing performance of the air conditioner door 1 deteriorates.

In the air conditioner door of the sixth aspect of the present invention, the use of polyurethane foam for a sealing material containing an ozone deterioration inhibitor such as a secondary amine compound as the sealing material layer suppresses the deterioration of sealing performance. To be Also,
By using a polyether polyol and a polyester polyol in a specific amount ratio together, or by using a polyester polyether polyol having both an ether bond and an ester bond in the molecule, it is possible to more surely suppress the deterioration of the sealing property. You can Further, these polyether polyols, polyester polyols and polyester polyether polyols may be used in combination. Further, the foam for a sealing material used for the door for an air conditioner of the sixth invention is not only used as a sealing material for a door, but is also interposed between the case and the duct of the air conditioner, and the joint portion thereof is It can also be used as a sealing material.

In the present invention, in addition to the above-mentioned various components, a foaming agent, a catalyst, a foam stabilizer and the like are added to the foamable composition. Water is mainly used as the foaming agent, but dichloromethane or the like can be used together for the purpose of suppressing heat generation. As the catalyst, usually, an amine catalyst, particularly a tertiary amine, and an organic tin compound such as stannasoctoate, dibutyltin diacetate, dibutyltin dilaurate are used in combination. As the foam stabilizer, a general-purpose block copolymer of dimethylpolysiloxane and polyether is used. In addition, a colorant, a filler, and the like can be blended as necessary.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Tables 1 to 5 (comparative examples) and Tables 6 to 1
1 (Example) and the secondary amine compound (in the case of Tables 6 to 11) or other various antioxidants or plasticizers (in the case of Tables 1 to 5), the following polyisocyanate, catalyst and preparation. Using a foamable composition consisting of a foaming agent,
A flexible slab foam was manufactured according to a conventional method. Table 1
Numerical values of secondary amine compounds and other various anti-aging agents, etc. represent the parts by weight when the total amount of the polyol is 100 parts by weight.

(1) Polyisocyanate; 41.5 parts by weight of trade name "TDI80" manufactured by Nippon Polyurethane Co., Ltd. was used. (2) Catalyst: 0.3 parts by weight of an amine-based catalyst manufactured by Nippon Emulsifier Co., Ltd., a trade name "LV33", and stanna octoate (SO) manufactured by Johoku Chemical Co., Ltd. were used. (3) Foam stabilizer; other than Comparative Example 1, trade name "SH193" manufactured by Toray Dow Corning Co., Ltd.
The product name "L532" manufactured by Nippon Unicar Co., Ltd. was used. The compounding amount is 1.5 parts by weight in each case.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

[Table 5]

[0037]

[Table 6]

[0038]

[Table 7]

[0039]

[Table 8]

[0040]

[Table 9]

[0041]

[Table 10]

[0042]

[Table 11]

The polyols listed in Tables 1-11 above, 2
Details of the primary amine compound and various antiaging agents are as follows. (1) Polyol Product name “GP3000” (manufactured by Sanyo Kasei Co., Ltd.): propylene oxide-based polyether polyol,
Hydroxyl value (OHV); 56 Product name "3P56B" (manufactured by Takeda Pharmaceutical Co., Ltd.):
75/25 of the product name "PPG1500" (manufactured by the same company, polyether polyol) and a polyester polyether polyol obtained by adding 10 moles of phthalic acid and propylene glycol to each other and the product name "PPG3000" (manufactured by the company, polyether polyol) (Weight ratio) quantity mixture, OHV; 56

Trade name "N2200" (manufactured by Nippon Polyurethane Co., Ltd.): Polyester polyol obtained by condensing adipic acid with diethylene glycol (DEG) and trimethylolpropane, OHV; 60 Trade name "Teslac 2458" (Hitachi Chemical Polymer Co., Ltd.) Manufactured): polyester polyol obtained by condensing dimer acid and DEG, OHV; 70

Product name "Kurapol P2010" (manufactured by Kuraray Co., Ltd.): Polyester polyol obtained by condensation of methylpentanediol and adipic acid, OHV; 56 Product name "Kurapol L2010" (manufactured by Kuraray Co., Ltd.): Methylvalerolactone Polyester polyol by ring-opening polymerization, OHV; 56 Product name "Placcel 220" (manufactured by Daicel Chemical Industries, Ltd.): Polyester polyol by ring-opening polymerization of caprolactone, OHV; 56

(2) Secondary Amine Compound In the following secondary amine compounds and other antiaging agents, all those with "Nocrac" in the trade name are manufactured by Ouchi Shinko Chemical Co., Ltd. Product name "Nocrac 224"; Poly (2,2,4-trimethyl-1,2-dihydroquinoline) Product name "Nocrac AW"; 6-Ethoxy-1,2-
Dihydro-2,2,4-trimethylquinoline

Trade name "Nocrac AD"; Octylated diphenylamine Trade name "Nocrac ODA"; Alkylated diphenylamine Trade name "Nocrac CD"; 4,4 '-(α, α-dimethylbenzyl) diphenylamine Trade name "Nocrac DP" N, N'-diphenyl-
p-phenylenediamine

(3) Hindered Phenol Antiaging Agent Product Name "Nocrac 200" 2,6-Di-t-butylmethylphenol Product Name "Nocrac NS6";2,2'-methylenebis (4-methyl-6-) t-Butylphenol) Trade name “Irganox 1010” (manufactured by Ciba Geigy); Tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane

(4) Imidazole Antiaging Agent Product Name "Nocrac MMB"; 2-Mercaptomethylbenzimidazole Product Name "Nocrac MBZ"; Zinc salt of 2-mercaptobenzimidazole

(5) Phosphorous acid ester anti-aging agent (both manufactured by Johoku Chemical Co., Ltd.) trade name "JP360"; triphenyl phosphite trade name "JP351"; tris (nonylphenyl) phosphite trade name " JP650 "; Tris (2,4-di-t-butylphenyl) phosphite Product name" JPP13 "; Bis (tridecyl) pentaerythritol diphosphite

(6) Plasticizer, hydrocarbon DOP; dioctyl phthalate DOA; dioctyl adipate Trade name "Hisol SAS-LH"; (manufactured by Nippon Petrochemical Co., Ltd.), liquid petroleum liquid paraffin

Specimens were cut out from the obtained soft slab foam, and the density and tensile strength were measured according to JIS K6301. Further, a test piece for the ozone deterioration test and a sheet having a thickness of 10 mm for the wet heat aging test in some Examples and Comparative Examples were cut out and subjected to the respective tests. In the ozone deterioration test, 50 and 10 after the start of exposure.
The air permeability was measured every 0, 200 and 400 hours.
Furthermore, in the moist heat aging test, 300, 60
Tensile strength was measured every 0, 900, 1200 and 1600 hours. The results are also shown in Tables 1 to 11.

The results of Comparative Examples 1 and 2 in Table 1 clearly show the superiority and inferiority of the ester foam and the ether foam. Further, according to the results of Comparative Example 3, when the polyester polyether polyol is used, the moisture heat aging resistance of the obtained foam is improved to the same degree as that of the ether foam, but the ozone deterioration resistance is not sufficiently improved. I understand. This is also clear from the comparison between ●, ▲ and ■ in FIG. 1 and the result of the tensile strength retention rate in FIG.

In Comparative Examples 4 to 44 of Tables 1 to 5, various polyester-polyol polyols were used to prepare various hindered phenol-based, imidazole-based and phosphite-based antioxidants, plasticizers and hydrocarbons. It is compounded in the range of 1 to 20 parts by weight. However, the air permeability after exposure to ozone for 400 hours is 200 cc / cm ^{2 in} many cases.
/ Sec or more. Further, depending on the kind of compounded compound, the air permeability becomes 200 cc / cm ² / sec or more after exposure for 200 hours and further for 100 hours. Thus, it can be seen that these antioxidants and the like have no effect of improving the ozone deterioration resistance.

On the other hand, in Examples 1 to 35 of Tables 6 to 9, the above polyester polyether polyol was used,
Various secondary amine compounds are blended in the range of 1 to 25 parts by weight. According to the results, except for the case of Nocrac ODA (alkylated diphenylamine) of Examples 18 to 23, the ozone resistance is considerably improved with 1 part by weight of the compound, but it is still a foam for a sealing material. Turns out it's not enough.

However, in the case of blending 5 parts by weight, the air permeability after exposure to ozone is 20 c regardless of the kind of the secondary amine compound.
It was found to be c / cm ² / sec or less, indicating that the foam has sufficient performance as a foam for a sealing material. Further, the air permeability further decreases with an increase in the blending amount. For example, in the case of blending 10 parts by weight, the air permeability becomes 5.4 to 8.9 cc / cm ² / sec, which is a particular problem in the operability of foam production. It can be seen that a foam for a sealing material having a very good ozone deterioration resistance is obtained. Such a correlation between the blending amount of the secondary amine and the ozone deterioration resistance is also clear from the results of ◯, Δ, □ and ◇ in FIG.

Further, the correlation between the kind and amount of the secondary amine compound as described above and the effect of improving the ozone deterioration resistance is clear from FIG. In particular, Table 7-
It can be seen that the Nocrac ODA used in Examples 18 to 23 of No. 8 has an extremely high effect as compared with other secondary amine compounds.

When Nocrac ODA was used, even with 1 part by weight, the air permeability after ozone exposure was 14.2 cc /
cm ² / sec, which is an excellent result over the case where 5 parts by weight of another secondary amine compound is blended. And with 5 parts by weight, the air permeability is 4.5 cc / cm ² / sec,
With 10 parts by weight, the air permeability is 2.0 cc / cm.
² / sec. Therefore, this secondary amine compound can be compounded in a smaller amount than other compounds. Therefore, the operability is further improved, and the foam can be manufactured more easily.

In the examples using only the polyester polyether polyol "3P56B" as the polyol, the retention of tensile strength after exposure to a high temperature and high humidity atmosphere for 1600 hours was 75% in all examples. % Or more, and it can be seen that a foam having excellent resistance to moist heat aging is obtained. When polyester polyester polyol or polyether polyol is used in combination with polyester polyol, the retention rate may be as low as about 50% depending on the combination. However, even when the polyol is also used in this way, the retention rate of 80% or more is obtained in many examples, and it can be seen that a foam for a sealing material having excellent performance can be obtained.

Further, polyester polyol 75% by weight
And a polyether polyol 25% by weight are used, and a foam in which a secondary amine compound is compounded (Form 1) and a foam in which only a polyether polyol is compounded with a secondary amine compound (Form 2) are compounded. 50pp at 40 ℃ for non-foam (Form 3)
Exposure to m of ozone was performed to examine changes in air permeability. As a result, with foam 1, even after 430 hours, the air permeability was about 1.3 times higher than the initial air permeability. On the other hand, with foam 3, after the lapse of 170 hours with respect to the initial air permeability, 3.
It is obvious that the air permeability is rapidly increased to 44 times after the elapse of 2 times and 280 hours, and the ether foam is inferior in ozone deterioration resistance. However, in the foam 2 in which a secondary amine compound was blended with this ether foam, the initial air permeability was 1.9 times after 170 hours, 2.6 times after 280 hours, and 4.8 after 430 hours. It was double. Thus, the remarkable effect of the secondary amine compound was confirmed also in the foam using only the polyether polyol.

[0061]

According to the first aspect of the invention, 1 to 25 parts by weight of a specific secondary amine compound is blended with the raw material of the foam for a sealing material. This makes it possible to obtain a foam for a sealing material, which has both excellent ozone deterioration resistance of the ester foam and excellent wet heat aging resistance of the ether foam. Also,
In the second invention, by using the polyester polyether polyol, it is possible to obtain the above-mentioned foam for a sealing material, which does not require blending of the polyester polyol or the polyether polyol. Further, in the sixth invention, by using the foam for a sealing material having the excellent sealing properties of the first and second inventions, it is possible to obtain a door for an air conditioner particularly excellent in ozone deterioration resistance.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between ozone exposure time and air permeability after ozone exposure when the type of polyol and the blending amount of a secondary amine compound are changed.

FIG. 2 is a graph showing the relationship between wet heat exposure time and tensile strength when the type of polyol and its combination are changed.

FIG. 3 is a graph showing the relationship between the blending amount of various secondary amine compounds and the air permeability after exposure to ozone for 400 hours. In this figure, specific regions [A], [B] and [C] of the blending amount of the secondary amine compound and the air permeability are also shown.

FIG. 4 is a perspective view of a door for an air conditioner.

FIG. 5 is a schematic cross-sectional view of a vehicle air conditioner.

FIG. 6 is a cross-sectional view showing a state where the air conditioner door is pressed against the inner peripheral edge of the opening of the case of the vehicle air conditioner.

[Explanation of symbols]

1; Air conditioner door, 11; Rotating shaft, 12; Substrate,
13; Seal material layer, 2; Air conditioner for vehicle, 3; Blower unit, 4; Cooler unit, 5; Heater unit, 6; Blower case, 7; Fan, 8; Blower motor, 9; Inside / outside air switching box, 10 An inside air inlet, 11; an outside air inlet, 12; an inside / outside air switching door, 13; a heat exchanger for cooling, 14; a cooler case, 15; a heat exchanger for heating, 1
6; heater case, 17; air mix door, 18, 1
9, 20; outlet switching door, 21; hot water piping, 22, 2
3, 24; outlet, 25; detour.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 4, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0027

[Correction method] Change

[Correction contents]

The air conditioner door 1 used in the vehicle air conditioner 2 generally has a shaft 1 as shown in FIG.
1, the substrate 12 and the sealing material layer 13.
The sealing material layer 13 is formed by adhering to the substrate 12, but may be directly foamed on the substrate 12. Then, as shown in FIG. 5, it has an action of opening / closing or switching the air passages in the cases 9 and 16 of the vehicle air conditioner 2. Closure of the air passage, for example case as shown in FIG. 6
The sealing material layer 13 is pressed against the inner peripheral edge of the opening 34 . However, when a part of the cell membrane is destroyed due to ozone deterioration or oxidative deterioration due to oxidant in the exhaust gas, the air permeability of the sealing material layer becomes large, and the amount of air passing through the flow path of FIG. Increase, and the sealing property deteriorates. On the other hand, when the sealing material layer 13 pressed against the inner peripheral edge of the opening of the case 34 is deteriorated by ozone or the like and part of the surface is missing, or the sealing material layer 1
If the compression strain of No. 3 is not sufficiently recovered, the amount of air passing through the flow path of FIG. 6B increases, and the sealing property of the air conditioner door 1 deteriorates.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction contents]

[0061]

According to the first aspect of the invention, the raw material of the foam for the sealing material is used.
In the second invention, a specific amount of antiozonant is added to the material
Is a specific secondary amine compound as this ozone deterioration inhibitor.
Use things . This makes it possible to obtain a foam for a sealing material, which has both excellent ozone deterioration resistance of the ester foam and excellent wet heat aging resistance of the ether foam. Further, in the third invention, by using the polyester polyether polyol, it is possible to obtain the foam for a sealing material having the excellent performance described above, without the need of blending the polyester polyol or the polyether polyol. Further, in the sixth invention, by using the foam for a sealing material having the excellent sealing properties of the first, second and third inventions, it is possible to obtain a door for an air conditioner which is particularly excellent in ozone deterioration resistance.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] Figure 2

[Correction method] Change

[Correction contents]

FIG. 2 is a graph showing the relationship between wet heat exposure time and tensile strength retention when the type of polyol and its combination are changed.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] Explanation of sign

[Correction method] Change

[Correction contents]

[Explanation of Codes] 1; Door for air conditioner, 11; Rotating shaft, 12; Substrate,
13; Seal material layer, 2; Air conditioner for vehicle, 3; Blower unit, 31 ; Blower case, 32 ; Fan, 3
3 ; Blower motor, 34 ; Inside / outside air switching box, 35 ; Inside air introducing port, 36 ; Outside air introducing port, 37 ; Inside / outside air switching door, 4;
Cooler unit, 41 ; Cooling heat exchanger, 42 ; Cooler case, 5; Heater unit, 51 ; Heating heat exchanger,
52 ; Heater case, 53; Hot water piping, 6 ; Air mix door, 71 , 72 , 73 ; Air outlet switching door, 81 , 8
2, 83 ; outlet, 9 ; detour.

[Procedure Amendment 5]

[Document name to be amended] Drawing

[Correction target item name] Fig. 5

[Correction method] Change

[Correction contents]

[Figure 5]

[Procedure correction 6]

[Document name to be amended] Drawing

[Correction target item name] Fig. 6

[Correction method] Change

[Correction contents]

FIG. 6

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inoue Masao Yasue 3- 1-36 Imaikecho, Anjo City, Aichi Prefecture Inoac Corporation Anjo Office (72) Inventor Masahiro Ito 1-1, Showacho, Kariya City, Aichi Prefecture Address In stock company DENSO (72) Inventor Masashi Shimizu No. 1 Cha Sen Sakashita, Hitotsuki-machi, Kariya city, Aichi Shimizu Industry Co., Ltd.

Claims (6)

[Claims] 1. A polyurethane foam obtained by reacting and curing a foamable composition containing a polyisocyanate, a polyol, and an antiozonant, wherein the antiozonant is the ozone degradant when the amount of the polyol is 100 parts by weight. Is 1 to 25 parts by weight, and is a polyurethane foam for a sealing material. 2. The polyurethane foam for a sealing material according to claim 1, wherein the antiozonant is an aromatic secondary amine compound. 3. At least a part of the polyol is a polyester polyether polyol.
Polyurethane foam for the sealing material described. 4. The antiozonant is 3 to 12 parts by weight, and has an air permeability of 5 to 20 cc / cm ² / sec measured by JIS L 1096 after being exposed for 400 hours according to the ozone deterioration test of JIS K6301. The polyurethane foam for a sealing material according to any one of claims 1 to 3, which is 5. JIS K after the temperature of 80 ° C. and the relative humidity of 95% are exposed to a controlled atmosphere for 1600 hours.
The polyurethane foam for a sealing material according to any one of claims 1 to 4, wherein a retention rate of tensile strength measured according to 6301 is 70% or more. Retention rate = (tensile strength after exposure to the above atmosphere / tensile strength before exposure to the above atmosphere) × 100 (%) 6. A door for an air conditioner comprising a substrate and a sealing material layer formed on at least one surface of the substrate, wherein the sealing material layer is any one of claims 1 to 5.
7. A door for an air conditioner, which is made of the polyurethane foam for a sealing material according to the item.