JP2003238644A - Composition for rigid polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a rigid polyurethane foam by HFC (hydrofluorocarbon) foaming which does not cause separation in a foaming stock solution even when a large amount of a polyester polyol is compounded and which forms a polyurethane foam highly flame-retardant and not suffering from lowering in self-adhesive properties caused by an increase in brittleness. <P>SOLUTION: The composition for a rigid polyurethane foam comprises (a) an organic polyisocyanate, (b) a polyol, and (c) a blowing agent containing a hydrofluorocarbon, where the polyol (b) is mainly composed of a polyester polyol obtained by reacting an alcohol component mainly composed of a polyhydric alcohol (b-1) bearing only primary hydroxy groups as the hydroxyl groups and bearing an alkyl group in the side chain with a polybasic carboxylic acid (b-3) mainly composed of an aromatic dicarboxylic acid. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a rigid polyurethane foam which is mainly used as a heat insulating material and has excellent flame retardancy, and uses a hydrofluorocarbon (HFC) which does not destroy the ozone layer as a foaming agent. When used, it is a composition for rigid polyurethane foam which does not cause separation of the foaming undiluted solution even if it is blended with a large amount of polyester polyol, and moreover, it is a composition for rigid polyurethane foam capable of satisfying both flame retardancy and brittleness improvement when formed into a foam. Regarding things.

[0002]

2. Description of the Related Art Conventionally, trichlorofluoromethane (CFC-11) or 1,1-dichloro-1-fluoroethane (HCFC-141b) has been used as a foaming agent as a method for producing a rigid polyurethane foam having excellent heat insulating properties. Methods are known. However, from the viewpoint of environmental protection in recent years, the use of CFC-11, which is an ozone depleting substance, has been banned, and HCFC-141b also destroys the ozone layer, albeit slightly, so it is planned to be banned at the end of 2003. . Therefore, as a foaming agent next to HCFC-141b, a hydrofluorocarbon (HFC) that does not destroy the ozone layer, such as HFC-245fa or HF, is used.
Recently, a technique using C-365mfc, HFC-134a, etc. has been proposed (Japanese Patent No. 2901682).
On the other hand, regarding the urethane resin material, a method of producing a urethane foam using a phthalic acid-based polyester polyol as a raw material polyol for a hard polyurethane foam having excellent flame retardancy (Japanese Patent Laid-Open No. 9-31615).
8, JP-A-9-316159, JP-A-2001-2476
45) or a method of producing a urethane foam by using a polyester polyol of phthalic acid and an alkylene oxide of bisphenol A (JP-A-9-328530). However, when HFC is used as a foaming agent and a phthalic acid type polyester polyol which has been conventionally used as a polyol component is blended in order to obtain a highly flame-retardant polyurethane foam, HFC is more polyol than HCFC-141b. Since the solubility of the foaming liquid is extremely low, there is a problem that the foaming stock solution is separated. Further, even if a conventional phthalic acid-based polyester polyol is blended within a range that does not cause the separation of the stock solution, sufficient flame retardancy cannot be achieved. Further, since HCF has a low solubility in isocyanate, the foam formed by the HFC formulation has a low plasticity, which causes a problem that the self-adhesiveness is lowered due to the increase in brittleness. For these problems,
First, as a method for improving the compatibility between the polyester polyol and chlorofluorocarbon, a polyester polyol modified with an oil or a fatty acid (Japanese Patent No. 3197508) has been proposed. However, blending a polyester polyol modified with an oil or a fatty acid causes a problem that the flame retardancy of the foam is lowered. Further, as a method for improving the brittleness of the foam, a method in which a compound having a number of active hydrogen of 0 or 1 is blended in the polyol component in a large amount (Japanese Patent Laid-Open No. 2000-281).
741) has been proposed. When a large amount of a compound having 0 or 1 of active hydrogen is mixed in the polyol component, strength is lowered, dimensional stability is deteriorated, and further, cost is increased.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and is a composition for HFC-foaming rigid polyurethane foam, which causes separation of a foaming stock solution even if a large amount of polyester polyol is blended. It is an object of the present invention to provide a polyurethane foam composition in which the formed polyurethane foam is highly flame-retardant and does not have a problem of a decrease in self-adhesiveness due to an increase in brittleness.

[0004]

[Means for Solving the Problems] As a result of intensive studies by the present inventors, in order to achieve the above object, the composition of the polyester polyol was studied. The present invention has completed the present invention by finding a composition for polyurethane foam in which the formed polyurethane foam is highly flame-retardant and has no problem of deterioration of self-adhesiveness due to increase of brittleness without causing separation of the foaming stock solution. . That is, the present invention provides a composition for a rigid polyurethane foam containing (a) an organic polyisocyanate, (b) a polyol, and (c) a foaming agent containing a hydrofluorocarbon (HFC), wherein the polyol (b) is a hydroxyl group. An alcohol component mainly containing a polyhydric alcohol (b-1) containing only a primary hydroxyl group and an alkyl group in the side chain, and a polyvalent carboxylic acid mainly containing an aromatic dicarboxylic acid (b -3) and a polyester polyol (a) obtained by reacting with 3) as a main component.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The organic polyisocyanate (a) that can be used in the present invention is not particularly limited, and 2,4-tolylene diisocyanate or 2,2
6-tolylene diisocyanate or mixtures thereof, m
-Or p-phenylene diisocyanate, p-xylene diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, diphenylmethane-
4,4'-diisocyanate, 3,3 'dimethyl-diphenylmethane-4,4'-diisocyanate, 3,3'dimethyl-4,4'-biphenylene diisocyanate,
Various derivatives of 3,3 ′ dichloro-4,4 ′ biphenylene diisocyanate, 4,4′-biphenylene diisocyanate or 1,5 naphthalene diisocyanate, crude diphenylmethane diisocyanate (crude MDI) and diphenylmethane diisocyanate can be used. Of these, crude diphenylmethane diisocyanate (crude MDI) is preferably used in terms of safety, cost, and handling (liquid state and excellent handling).

The polyol (b) used in the present invention is an alcohol component mainly containing a polyhydric alcohol (b-1) containing only a primary hydroxyl group as a hydroxyl group and an alkyl group in the side chain. The main component is a polyester polyol (a) obtained by reacting a polycarboxylic acid (b-3) containing an aromatic dicarboxylic acid as a main component, and the polyhydric alcohol (b) is used as an alcohol component. -1) and a polyester polyol (a) obtained by using the other polyhydric alcohol (b-2) in combination are also included.

Contains only primary hydroxyl groups as hydroxyl groups,
And a polyhydric alcohol containing an alkyl group in the side chain (b-1)
As, for example, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-dimethyl-1,4-butanediol, 2,3-dimethyl-1, 4-butanediol, 2-
Methyl-1,5-pentanediol, 3-methyl-1,
5-pentanediol, 2,3-dimethyl-1,5-pentanediol, 3-ethyl-1,5-pentanediol, 2-methyl-1,6-hexanediol, 3-methyl-1,6-hexanediol, 2,3,4-trimethyl-1,5-pentanediol, 3,3-dimethyl-1,
6-hexanediol, 3,3-diethyl-1,5-pentanediol, 3,3-diethyl-1,6-hexanediol and the like can be mentioned, and one kind or two or more kinds may be used in combination. Among these, in order to obtain a highly flame-retardant foam, it is preferable to use a polyhydric alcohol having 4 to 8 carbon atoms. In particular, 2-methyl-1,3-propanediol is preferable because it can provide more excellent flame retardancy.

The other polyhydric alcohol (b-2) mentioned above is a polyhydric alcohol basically containing only a primary hydroxyl group as a hydroxyl group and not having an alkyl group in its side chain. , Aliphatic polyhydric alcohol ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , Bifunctional alcohols such as 1,9-nonanediol, polyfunctional alcohols such as trimethylolpropane and pentaerythritol, and benzene ring-containing hydroxy compounds such as aromatic polyhydric alcohol phenol and bisphenol A and bisphenol S, Or, those derivative compounds and the like, Can be used in combination these one or more. Of these, it is preferable to use polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol from the viewpoint of reducing the viscosity of the polyester polyol. However, primary hydroxyl groups such as 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, dipropylene glycol, polypropylene glycol, glycerin, and sorbitol within a range that does not impair the curability of the rigid polyurethane foam. It is also possible to use a glycol containing a hydroxyl group other than the above.

The content of the polyhydric alcohol (b-1) containing only the primary hydroxyl group and having an alkyl group in the side chain in the polyester polyol (a) depends on the compatibility of the foaming stock solution. From the viewpoint of stabilization, polyvalent carboxylic acid (b-
When 3) is only an aromatic dicarboxylic acid, it is preferably 20 to 70 mol%, more preferably 30 to 50 mol% in the total polyhydric alcohol, and the polyvalent carboxylic acid (b-3) is an aliphatic dicarboxylic acid. When an acid is used in combination, the total polyhydric alcohol is preferably 20 to 100 mol%, more preferably 5%.
It is 0 to 100 mol%.

The polyvalent carboxylic acid (b-3) is mainly an aromatic dicarboxylic acid, and examples thereof include orthophthalic acid and its anhydride, and derivatives such as isophthalic acid, terephthalic acid and dimethylphthalate. It is also possible to use a trifunctional polycarboxylic acid such as an acid together. Further, from the viewpoint of improving the brittleness of the foam and improving the self-adhesiveness, oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid,
Suberic acid, adipic acid, sebacic acid, azelaic acid,
It is preferable to use an aliphatic dicarboxylic acid such as maleic acid together.

As the polyol (b), an ordinary polyol may be used in combination with the above polyester polyol, and various known polyols for hard urethane may be used as the polyol. There are polyether polyols (B) which are typical ones. For example, as the polyether polyol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6 -Hexanetriol, pentaerythritol, sorbitol, sucrose, bisphenol A, novolac and other polyhydric alcohols, benzylic ether derivative compounds obtained by reacting phenols and aldehydes, phenols and aldehydes and amines were reacted Hydroxyl value of 100 to 800 mg KOH / g obtained by addition-polymerizing alkylene oxide to Mannich compound and / or these polyhydroxy compounds
Polyether polyol of. Also, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, ethylenediamine,
A compound having two or more active hydrogens such as diethylenetriamine, triethylenetetramine, and toluenediamine, and / or amines thereof are subjected to addition polymerization with ethylene oxide, propylene oxide, butylene oxide, styrene oxide or the like to obtain a hydroxyl value of 100 to 800 m.
gKOH / g polyether polyol and polytetramethylene glycol can also be used.

From the viewpoint of flame retardancy of the foam, the above-mentioned polyester polyol (a) and polyether polyol (b) are preferably mixed in a ratio of 20 to 90% by weight: 10 to 80% by weight, and 50 ~ 90% by weight: 10
It is more preferable that the mixing ratio is ˜50% by weight.

As the polyol (b) used in the present invention, polyester polyols other than the above-mentioned polyester polyol (a) can be blended within a range not impairing the effects of the present invention, and the average hydroxyl value thereof is preferably 150-.
450 mg KOH / g, more preferably 200-350
It is mgKOH / g. The polyester polyol of the polyol (b) of the present invention can be synthesized by an ordinary known method.

The quantitative ratio of the organic polyisocyanate to the polyol (b) in the present invention, that is, the NCO / OH ratio (molar ratio) is not particularly limited and can be freely selected from 0.8 to 4.0. It can also be converted to isocyanurate with a trimerization catalyst. The ratio is preferably 1.3 to 3.0. Particularly, from the viewpoint of obtaining good flame retardancy, it is preferable to obtain a urethane foam modified with isocyanurate in the presence of a trimerization catalyst.

The blowing agent in the present invention contains HFC, and the HFC in the blowing agent is preferably 10% by weight or more,
More preferably, it contains 50 to 97% by weight.
Examples of such HFC include 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,
3,3-Pentafluoropropane (HFC-245f
a), 1,1,1,2-tetrafluoroethane (HFC
-134a), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), pentafluoroethane (HFC-125), 1,1-difluoroethane (HFC-152a), 1,1 , 1,2,3,3-hexafluoropropane, 1,1,1,4,4,4-hexafluorobutane and the like. Of these 1,1,
1,3,3-Pentafluorobutane (HFC-365m
fc), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,
3,3,3-Heptafluoropropane (HFC-227
ea) is preferably used. Further, in the present invention, another foaming agent can be used in combination within a range that does not impair the effect. Other blowing agents include water (which produces carbon dioxide gas by a urea reaction of water and isocyanate; that is, used as a reactive blowing agent), hydrochlorofluorocarbons such as HCFC-141b, and halogenated methylene chloride. Examples thereof include low boiling point hydrocarbons such as hydrocarbons and pentane. These may be used alone or in combination of two or more. In particular, it is preferable to use water in combination from the viewpoint of cost reduction and improvement of initial foaming. The amount of the foaming agent used to obtain the rigid polyurethane foam of the present invention is
It is preferably 10 to 100% by weight, more preferably 20 to 80% by weight, based on the polyol (b).

In the present invention, it is desirable to add a catalyst to the organic polyisocyanate and the polyol. As such a catalyst, all catalysts usually used for producing polyurethane foam can be used. For example, tertiary amines such as tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, triethylenediamine, tris (dimethylaminopropyl)
Hexahydrotriazine and the like can be mentioned. Further, a quaternary ammonium salt, alkali metal salts such as potassium octylate and potassium acetate, and metal compounds such as lead octylate, lead naphthenate, dibutyltin diacetate and dibutyltin dilaurate can be used. You may use these individually or in mixture of 2 or more types. Also, its amount (total amount when used together)
Is preferably 0.1 to 10% by weight based on the polyol.

It is also preferable to use a foam stabilizer together with the urethane reaction. As such a foam stabilizer, any foaming agent effective for producing a rigid polyurethane foam can be used. For example, a block copolymer of dimethylsiloxane, which is a silicon-based surfactant, and polyether is preferable. The amount thereof is preferably 0.1% with respect to the polyol (b).
It is 1 to 3% by weight.

In the present invention, in addition to the above components, any substance used in polyurethane foam such as flame retardants, plasticizers, fillers, stabilizers, colorants and antioxidants can be used. Particularly, flame retardants include tris (chloroethyl) phosphate and tris (β-chloropropyl) phosphate, which are halogen-containing phosphates, tributylphosphate, tributoxyethylphosphate, triethylphosphate, and arylphosphates, which are alkyl phosphates. Ester cresyl phenyl phosphate, phosphonate diethyl-N, N-bis (2
-Hydroxyethyl) aminomethylphosphonate and the like can be mentioned, and the amount thereof is preferably 5 to 30% by weight based on the polyol (b).

The compounds and additives used in the present invention can be used in a combination of two or more kinds.

The composition for rigid polyurethane foam of the present invention can be produced by a generally known method, but a method for producing rigid polyurethane foam by a thermal airless spray foaming machine or an injection foam molding machine is particularly preferable. Is.

[0021]

EXAMPLES The present invention will now be specifically described with reference to examples, but the invention is not limited thereto. In addition, “part” and “%” in the text are based on weight. The respective raw materials used in the examples are shown below.

(Polyol) Polyol A: A polyester polyol having a hydroxyl value of 250 mgKOH / g, which is synthesized from 2-methyl-1,3-propanediol and phthalic anhydride / terephthalic acid / adipic acid. The molar ratio of phthalic anhydride / terephthalic acid / adipic acid is 3/4/3. Polyol B: 2-methyl-1,3-propanediol
/ Polyester polyol with a hydroxyl value of 250 mgKOH / g synthesized from triethylene glycol and terephthalic acid / isophthalic acid. 2-Methyl-1,3-propanediol / triethylene glycol molar ratio 3/7. Terephthalic acid / isophthalic acid molar ratio 3/7. Polyol C: 2-methyl-1,3-propanediol
/ Triethylene glycol and terephthalic acid / Isophthalic acid
/ Hydroxyl value 250mg KOH / synthesized from adipic acid
g polyester polyol. 2-Methyl-1,3-propanediol / triethylene glycol molar ratio 5 /
5. Molar ratio of terephthalic acid / isophthalic acid / adipic acid 3
/ 4/3. Polyol D: 1,4-butanediol and terephthalic acid
/ Hydroxyl number of 25 synthesized from isophthalic acid / adipic acid
0 mg KOH / g polyester polyol. Molar ratio of terephthalic acid / isophthalic acid / adipic acid 3/4/3. Polyol E: Diethylene glycol and terephthalic acid /
Hydroxyl value 250 mg KOH synthesized from isophthalic acid
/ g polyester polyol. Terephthalic acid / isophthalic acid molar ratio 3/7. Polyol F: 1,2-butanediol and terephthalic acid
/ Hydroxyl value 250mgKO synthesized from isophthalic acid
H / g polyester polyol. Terephthalic acid / isophthalic acid molar ratio 3/7. Polyol G: Polyester polyol having a hydroxyl value of 250 mgKOH / g synthesized from diethylene glycol and orthophthalic acid. Polyol H: Polyether polyol having a hydroxyl value of 500 mgKOH / g obtained by adding propylene oxide to ethylenediamine. Polyol I: Propylene oxide / ethylene oxide added to ethylenediamine, hydroxyl value 450 mg
KOH / g polyether polyol. Propylene oxide / ethylene oxide molar ratio 1/1. Polyol J: Polyether polyol having a hydroxyl value of 600 mgKOH / g obtained by adding propylene oxide to pentaerythritol.

[0023] (Polyisocyanate compound)   Crude MDI (A): Made of Nippon Polyurethane, crude diphenylmethane diisocyanate                         Anate Coronate 1130                         NCO content = 31.6wt%   Crude MDI (B): Made of Nippon Polyurethane, crude diphenylmethane diisocyanate                         Anate Millionate MR-200                         NCO content = 30.8 wt%

Flame retardant: Tri- (β-chloropropyl) phosphate (TMCP) manufactured by Daihachi Chemical Co., Ltd. Foam stabilizer: SH-193 (block copolymer of dimethylsiloxane and polyether) manufactured by Toray Silicon Co., Ltd. Media catalyst A: Tosoh Co., Ltd. triethylenediamine catalyst B: Air Products Co., Ltd. tris (dimethylaminopropyl) hexahydrotriazine catalyst C: Dainippon Ink and Chemicals Co., Ltd. potassium octylate (potassium 15 wt%) catalyst D: Dainippon Ink and Chemicals, Inc. Lead octylate (lead content 20 wt%) Catalyst E: Kao Co., Ltd. Tetramethylhexamethylenediamine foaming agent Foaming agent A: Central Glass Co., Ltd. HFC-245fa
(1,1,1,3,3-pentafluoropropane) Foaming agent B: HFC-365mfc manufactured by Solvay Co., Ltd.
(1,1,1,3,3-pentafluorobutane)

Examples 1 to 6 and Comparative Examples 1 to 8 According to the formulation table shown in Tables 1 and 2, the formulation liquid (A
Solution) and crude MDI (solution B) were prepared. A
The mixing ratio of the liquid / B liquid was determined to be NCO / OH = 1.7 (equivalent ratio). The rigid urethane foam was evaluated by the following tests of compatibility of the foaming stock solution, foam brittleness and flame retardancy. The results are shown in Tables 1 and 2. (Undiluted solution compatibility) After blending the unfoamed undiluted solution (Liquid A: polyol component), the mixture was allowed to stand for 1 day or longer at 10 ± 2 ° C, and then at room temperature (2
After returning to 5 ° C.), the separated state of the stock solution was visually determined. ◎: Compatibility is extremely good (dissolving capacity is marginal) ○: Compatibility is good △ ○: Some separation occurs at low temperature ×: Two-layer separation (brittleness evaluation method) A liquid is weighed in a 30 g cup and determined A large amount of solution B was added and stirred at 3500 rpm for 3 seconds.
Immediately, it was dropped on an aluminum plate having a thickness of 10 mm and foamed free to obtain a hard urethane foam. After 6 minutes, the brittleness of the foamed circular rigid urethane foam was evaluated by touching it with fingers. The evaluation was performed at 20 ° C. for both the aluminum plate and room temperature. ◯: No brittleness Δ: Slightly brittle ×: Brittleness XX: Extremely brittle (flame retardancy evaluation method) Weigh solution A in 120 g cup, add solution B in a predetermined amount, and 3500 rpm for 3 seconds It was stirred. Immediately, it was poured into a wooden box of 240 × 200 × 100 mm for free foaming. After standing for 1 day or more, the core portion of the foam was cut into a size of 40 × 30 × 50 mm, which was used as a test body. For the combustion test, a device for JIS A 9511 combustion test (measurement method B) was used, and 30
The surface of × 40 mm was placed as the lower surface and the mixture was burned for 1 minute to measure the weight retention.

Examples 7 to 10 and Comparative Examples 9 to 11 According to the blending table shown in Table 3, the blended liquid (Liquid A) and the crude M.
Two components of DI (solution B) were prepared. Gasmer FF160 as spray foaming machine of thermal airless mixing type
0 (manufactured by Gasmer Co.) was used, and the mixing ratio of A liquid / B liquid was Vo.
A rigid urethane foam was obtained by pressure-feeding from a main pump at a ratio of 100/100 and spraying it onto a vehicle (a plywood plate or a slate plate). The construction temperature was set to 20 ° C, and the starting temperature was also set to 20 ° C. The preset temperature (hose) of A and B liquids of the foaming machine is 38 ° C, and the air pressure of the air pump is 4 kg.
/ cm2, A and B line pressure is 50 ~ 70kg / cm
It was set to 2. The rigid urethane foam was evaluated by the following tests of compatibility, brittleness, and flame retardancy of the undiluted foaming solution.
The results are shown in Table 3. (Undiluted solution compatibility) It carried out like the said determination method. (Evaluation method for brittleness) One layer (3 to 5 mm) of hard urethane foam was sprayed on a slate plate, and 6 minutes later, the brittleness was evaluated by touching with a finger. The construction temperature is 20 ° C, and the starting temperature is 20 ° C.
Was set and evaluated. (Flame retardancy evaluation method / A) Total thickness 100-120 on the plywood board
mm (5 to 6 layers stacked) was sprayed to obtain a rigid urethane foam. After leaving it for 1 day or more, 40x3 the foam core
It was cut into a size of 0 × 50 mm and used as a test body. For the combustion test, a device of JIS A 9511 combustion test (measurement method B) was used, and 30 × 40 of the test piece was placed on the wire mesh.
The mm surface was placed as the lower surface, the material was burned for 1 minute, and the weight retention rate was measured. (Flame Retardancy Evaluation Method / B) Total thickness 20 mm (2
It was sprayed on (ply layer) to obtain a rigid urethane foam. 1
After being left for more than one day, it was cut out into 99 × 99 mm and subjected to a heat generation test (corn calorie test) of the flame-retardant material according to the Building Standards Method to determine the total heat generation amount for 5 minutes. The test method is good)
The evaluation method of the Japan Building Research Institute was followed.

Examples 11 to 13 and Comparative Examples 12 to 14 According to the formulation table shown in Table 4, two components, a formulation liquid (solution A) and a crude MDI (solution B) at 15 ° C. were prepared. Liquid A / B
The compounding ratio of the liquid was determined to be NCO / OH = 2.5. The rigid urethane foam was evaluated by the following tests of compatibility, brittleness (adhesive strength) and flame retardancy of the undiluted foaming solution. The results are shown in Table 4. (Undiluted solution compatibility) It carried out like the said determination method. (Adhesive strength measuring method) A 0.4 tmm steel plate was placed on the lower surface of a mold of 380 x 380 x 40 tmm, and the temperature was adjusted to 50 ° C. Liquid A and liquid B were stirred for 10 seconds at a determined mixing ratio, adjusted to a molding density of 40 kg / m3, and poured into a mold.
The mold was removed in 5 minutes. After leaving for more than 1 day JIS A 9526
The adhesive strength of the urethane foam / steel plate was measured according to the method for measuring adhesive strength of. (Flame Retardancy Evaluation Method) After leaving the urethane foam prepared by the above adhesive strength measurement method for 1 day or more, the core part of the foam is 4
It was cut into a size of 0 × 30 × 50 mm and used as a test body. The combustion test is a JIS A 9511 combustion test.
Using the device of (Measurement method B), 30 × 4 of the test piece on the wire mesh
The 0 mm surface was placed as the lower surface, the material was burned for 1 minute, and the weight retention was measured.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

[Table 4]

[0032]

According to the present invention, when hydrofluorocarbon (HFC) that does not destroy the ozone layer is used as a foaming agent, even if a large amount of polyester polyol is added, the foaming stock solution does not separate, and a foam is formed. It is possible to provide a composition for a rigid urethane foam that does not sometimes lower the flame retardancy and does not cause the problem of lowering the self-adhesiveness due to an increase in brittleness.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J034 BA03 BA07 BA08 CA04 CC03                       DB04 DB05 DC02 DF01 DF16                       DF21 DG03 DG04 HA01 HA07                       HA11 HB17 HC03 HC12 HC13                       HC64 HC67 KC02 KC17 KD02                       KD12 KE01 KE02 MA16 NA02                       NA08 QA02 QC01 RA06 RA10

Claims (9)

[Claims] 1. A rigid polyurethane foam composition comprising (a) an organic polyisocyanate, (b) a polyol, and (c) a foaming agent containing a hydrofluorocarbon (HFC), wherein the polyol (b) is a hydroxyl group. An alcohol component mainly containing a polyhydric alcohol (b-1) containing only a primary hydroxyl group and an alkyl group in the side chain, and a polyvalent carboxylic acid mainly containing an aromatic dicarboxylic acid (b- 3)
A composition for rigid polyurethane foam, which comprises as a main component a polyester polyol (a) obtained by reacting with. 2. A polyhydric alcohol (b-1) and another polyhydric alcohol (b-2) in which the polyol (b) contains only a primary hydroxyl group as a hydroxyl group and an alkyl group in the side chain. For rigid polyurethane foam, which comprises as a main component a polyester polyol (a) obtained by reacting an alcohol component having a main component with a polycarboxylic acid (b-3) having an aromatic dicarboxylic acid as a main component Composition. 3. The rigid polyurethane foam according to claim 1 or 2, wherein the polyhydric alcohol (b-1) containing only a primary hydroxyl group as a hydroxyl group and having an alkyl group in its side chain has 4 to 8 carbon atoms. Composition. 4. The composition for rigid polyurethane foam according to claim 2 or 3, wherein the other polyhydric alcohol (b-2) contains a polyalkylene glycol containing only primary hydroxyl groups as hydroxyl groups. 5. The polyhydric alcohol (b-1) containing only a primary hydroxyl group as a hydroxyl group and having an alkyl group in a side chain is 20 mol% or more in all polyhydric alcohol components.
The composition for rigid polyurethane foams according to any one of to 4. 6. The composition for rigid polyurethane foam according to claim 1, wherein the polycarboxylic acid (b-3) contains an aliphatic dicarboxylic acid. 7. The composition for rigid polyurethane foam according to claim 1, wherein the polyol (b) contains a polyether polyol (b). 8. The composition for rigid polyurethane foam according to claim 7, wherein the mixing ratio of the polyester polyol (a) and the polyether polyol (b) is 20 to 90% by weight: 10 to 80% by weight. 9. The hydroxyl value of the polyol (b) is 150-4.
It is 50 mgKOH / g, The composition for rigid polyurethane foams in any one of Claims 1-8.