JP2000281826A - Resin composition for flame-retardant rigid polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for rigid polyurethane foam, capable of producing rigid polyurethane foam having high fire retardancy regardless of containing hydrofluorocarbon having low ozone layer depletion coefficient and readily handling and provide a method for readily producing rigid polyurethane foam having high flame retardancy regardless of containing a hydrofluorocarbon. SOLUTION: This resin composition for rigid polyurethane foam comprises a polyol component containing a foaming agent and a polyhydroxy compound and a polyisocyanate component. In the resin composition, the polyhydroxy compound contains polyesterpolyol having a structure obtained by binding a >=6C diol having ether bond to a dicarboxylic acid by ester bond in an amount of >=10 wt.% based on total amount of polyol component and further, the foaming agent comprises a hydrofluorocarbon having zero ozone layer depletion coefficient and >=5 deg.C boiling point.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a rigid polyurethane foam and a method for producing a rigid polyurethane foam, and more particularly to a rigid polyurethane foam containing a hydrofluorocarbon having a low ozone depletion potential and high flame retardancy. The present invention relates to a resin composition for a rigid polyurethane foam which can be produced and is easily handled, and a method for easily producing a rigid polyurethane foam having high flame retardancy while containing a hydrofluorocarbon.

[0002]

2. Description of the Related Art Rigid polyurethane foams are widely used in homes, frozen warehouses and the like because of their good heat insulating properties and self-adhesiveness. However, chlorofluorocarbons (hereinafter sometimes referred to as “CFC”) such as Freon-11, which have been conventionally used for rigid polyurethane foams,
Due to its chemically stable properties, there has been a problem that CFCs released into the atmosphere reach the stratosphere as they are, where they are decomposed and cause the ozone layer to be destroyed. For this reason, CFCs have been completely abolished, and hydrochlorofluorocarbons containing hydrogen in their molecules (hereinafter sometimes referred to as “HCFCs”) have been used as substitutes for CFCs. These HCFCs also have an ozone layer that is about 1/10 of CFCs. It has a coefficient of destruction and is completely abolished in 2004.

As a substitute for HCFC, a hydrofluorocarbon containing no chlorine in the molecule (hereinafter sometimes referred to as “HFC”) has been proposed. However, since HFC does not have chlorine in the molecule, it is used. The problem that the flame retardancy of the rigid polyurethane foam decreases and the solubility of HFC in the polyol component of the raw material of the rigid polyurethane foam is low. There is a problem that a phenomenon of blowing out (hereinafter, also referred to as "boiling") occurs. In particular, the occurrence of the boiling phenomenon is a serious problem in in-situ foaming in which the raw material of the rigid polyurethane foam is carried to the site in the form of an undiluted solution and mixed and foamed on the site.

[0004] The boiling phenomenon is caused by H
Although closely related to the solubility of FC, HFC shows little solubility, especially for polyester polyols that impart flame retardancy to rigid polyurethane foams. Therefore, when HFC is used, the flame retardant must be increased because the method of increasing the amount of the polyester polyol cannot be used for the purpose of lowering the flame retardancy as described above. It causes a decline. In addition, among the rigid polyurethane foams, the isocyanurate-modified rigid polyurethane foam having a very high flame retardancy that can pass JIS-A-1321 has a large addition amount of the polyester polyol, so that the HFC is separated from the polyol component. The problem was caused by the phenomenon of doing so.

[0005] However, the complete elimination of HCFC is a matter to be determined, and it is certain that in recent years, higher flame retardancy has been demanded from rigid polyurethane foam from the viewpoint of disaster prevention. Therefore, development of a rigid polyurethane foam having high flame retardancy while containing HFC and a resin composition for a rigid polyurethane foam for producing the same have been desired.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above, and is capable of producing a rigid polyurethane foam having high flame retardancy while containing a hydrofluorocarbon having a low ozone layer destruction coefficient. An object of the present invention is to provide a method for easily producing a rigid polyurethane foam having high flame retardancy while containing a resin composition for a rigid polyurethane foam and a hydrofluorocarbon which are easy.

[0007]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the raw material polyol component of a rigid polyurethane foam, and as a result, a polyester polyol which is known to have higher flame retardancy than before. To
As a polyester polyol having a structure in which a diol having 6 or more carbon atoms and having an ether bond and a dicarboxylic acid are ester-bonded, a specific amount of the polyester polyol is blended with the raw material polyol component to obtain an HFC for the raw material polyol component.
It has been found that it is possible to dramatically increase the solubility of polyurethane, and furthermore, there is no occurrence of boiling during production and transportation, and the resulting rigid polyurethane foam has excellent flame retardancy, thereby completing the present invention. That is, the present invention is as follows.

(1) A resin composition for a rigid polyurethane foam, comprising a polyol component containing a foaming agent and a polyhydroxy compound, and a polyisocyanate component,
The polyhydroxy compound has a polyester polyol having a structure in which a diol having 6 or more carbon atoms and having an ether bond and a dicarboxylic acid are bonded by an ester reaction, in a content of 10 to the total amount of the polyol component.
A resin composition for a rigid polyurethane foam, wherein the resin composition further comprises a hydrofluorocarbon having an ozone layer destruction coefficient of 0 and a boiling point of 5 ° C or more.

(2) The diol is HO- (CH ₂ ) _n
The resin composition for a rigid polyurethane foam according to (1), which is a diol represented by —O— (CH ₂ ) _n —OH (n = 3 or more).

(3) When the diol is HO- (C ₂ H
₄ O) _n -H _(n = a diol represented by 3 or more) for rigid polyurethane foams resin composition (1).

(4) The polyester polyol is composed of a decomposition product of polyethylene terephthalate and HO- (CH
_{2) n -O- (CH 2) n -OH} (n = 3 or more) polyol obtained by condensation of a diol represented by (1)
A resin composition for a rigid polyurethane foam.

(5) A method for producing a rigid polyurethane foam, comprising a step of mixing and foaming a polyol component containing a foaming agent and a polyhydroxy compound with a polyisocyanate component, wherein the polyhydroxy compound has 6 or more carbon atoms. And a diol having an ether bond,
A polyester polyol having a structure in which a dicarboxylic acid is bonded by an ester reaction contains 10% by weight or more based on the total amount of the polyol component, and the blowing agent has an ozone layer destruction coefficient of 0 and a boiling point of 5 ° C or more. A method for producing a rigid polyurethane foam, characterized by containing a hydrofluorocarbon as described above.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

(1) Resin composition for rigid polyurethane foam of the present invention The resin composition for rigid polyurethane foam of the present invention comprises a polyol component containing a foaming agent and a polyhydroxy compound, and a polyisocyanate component.

(I) Polyol component In the present invention, the foaming agent contained in the polyol component is:
It contains a hydrofluorocarbon (HFC) having an ozone layer depletion potential of 0 and a boiling point of 5 ° C. or more. Here, the above-mentioned ozone layer depletion coefficient is generally based on the ozone layer depletion rate of trichlorofluoromethane (hereinafter sometimes referred to as “CFC-11”), that is, CFC-
11 is a value calculated as the ratio of the ozone depletion rate of each substance to the ozone depletion rate, assuming that the ozone depletion coefficient of 1 is 1, and the “ozone depletion coefficient” used in this specification is all It was determined by the method. The hydrofluorocarbon used in the present invention has an ozone layer depletion potential of 0 calculated in this manner. The boiling point of the HFC is 5 ° C. or higher, and preferably about 10 ° C. or higher. The upper limit of the boiling point is not particularly limited, but a preferable upper limit is about 50 ° C.

As the HFC having the above properties, specifically, 1,1,1,3,3-pentafluoropropane (hereinafter sometimes referred to as “HFC-245fa”),
1,1,2,2,3,3-hexafluoropropane (hereinafter sometimes referred to as “HFC-236ea”) and the like.

The content of the above HFC in the polyol component is appropriately selected according to the density of the target rigid polyurethane foam and the like. For example, in the case of molding a foamed rigid polyurethane foam in a foamed in-situ polyurethane foam, the total polyol component is 10%.
0 parts by weight and 5 to 50 parts by weight of the above H
FC is preferably contained, and more preferably 15 to
It can be contained at a ratio of 40 parts by weight.

The above-mentioned in-situ foamed rigid polyurethane foam refers to a rigid polyurethane foam produced by transporting a resin composition for a rigid polyurethane foam to a molding site and mechanically or hand foaming the resin composition at the molding site. Spray foaming means that a resin composition for a rigid polyurethane foam is discharged in a mist state by a foaming machine and sprayed directly onto an object to simultaneously perform foam molding of the rigid polyurethane foam and adhesion of the rigid polyurethane foam to the object. A rigid polyurethane foam molding method. In spray foaming in-situ foaming, it is difficult to control the temperature,
As the resin composition for a rigid polyurethane foam to be used, a resin composition having a low viscosity at room temperature and easy to handle is preferable. Therefore, in order to lower the density of the rigid polyurethane foam at the same time as lowering the viscosity of the composition, it is necessary to contain a larger amount of a foaming agent. Become.

In addition to the above-mentioned spray firing, since the density of the obtained rigid polyurethane foam and the amount of HFC contained in the polyol component are inversely proportional,
By determining the density of the rigid polyurethane foam to be produced, the amount of HFC in the polyol component of the resin composition for a rigid polyurethane foam can be determined. For example, in order to produce a rigid polyurethane foam having a density of 18 kg / m ³ , the amount of HFC added to the polyol component is about 40% by weight based on the total amount of the polyol component.

In addition to the above HFC, the above-mentioned foaming agent may be, if necessary, water; 1,1-dichloro-1-fluoroethane,
2,2-dichloro-1,1,1-trifluoroethane (hereinafter referred to as “HCFC-141b”, “HCFC
HCFCs such as -123 ");
1,1,2-tetrafluoroethane (hereinafter referred to as “HFC-
134a ") and one or more of low-boiling HFCs having a boiling point of less than 5 ° C; hydrocarbons such as n-pentane, i-pentane and cyclopentane; May be. The content of the optional component in such a foaming agent can be arbitrarily selected in the range of 0 to 50 parts by weight, preferably in the range of 0 to 20 parts by weight, based on 100 parts by weight of all polyol components. Is selected arbitrarily.

In the present invention, the polyhydroxy compound contained in the polyol component contains a polyester polyol having a structure in which a diol having 6 or more carbon atoms and having an ether bond and a dicarboxylic acid are bonded by an ester reaction.

As the diol having 6 or more carbon atoms and having an ether bond, specifically, HO- (C
_{H 2) n -O- (CH 2} ) diol represented by _n -OH _(n = 3 or _{more), HO- (C 2 H 4} O) n -H (n = 3 or more)
And the like. These may be used alone or in combination of two or more. The above HO-
As the diol represented by (CH ₂ ) _n —O— (CH ₂ ) _n —OH (n = 3 or more), more specifically, n in the formula is 3
, Dibutylene glycol wherein n is 4 and dipentyl glycol wherein n is 5 and the like. N in the above chemical formula preferably ranges from 3 to 5. When n is 6 or more, the flame retardancy may decrease. _{Also, HO- (C 2 H 4 O} ) n -
The diol represented by H (n = 3 or more) is, in other words, polyethylene glycol having a molecular weight of 150 or more (hereinafter, sometimes referred to as “PEG”), and n in the above chemical formula is preferably 3 to 5. Range. When n is 6 or more, the solubility in HFC tends to increase, but the flame retardancy of the obtained rigid polyurethane foam may decrease.

Examples of the dicarboxylic acid forming an ester bond with the diol include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic anhydride, adipic acid, and maleic anhydride.
These are used alone or in combination of two or more.

Further, in the present invention, the polyester
Polyethylene terephthalate as terpolyol
(Hereinafter sometimes referred to as “PET resin”)
And HO- (CH_Two)_n-O- (CH_Two)_n-OH (n = 3 or less
Polyau obtained by condensing the diol represented by
Can be used, which is preferred. HO- (CH
_Two)_n-O- (CH_Two)_n-OH (n = 3 or more)
As the diol, specifically, n = 3 to 5 as described above
Diols, and the preferred range of n is also described above.
The same is true.

In recent years, PET resins, which are resins obtained by polycondensing ethylene glycol with terephthalic acid, are often recycled and used as recycled polyols. Such a recycled polyol is usually produced by decomposing a PET resin with a catalyst and simultaneously adding diethylene glycol. The decomposition products of PET resin used in the present invention and _{HO- (CH 2) n -O- (} CH 2) n -
The polyol obtained by condensing a diol represented by OH (n = 3 or more) is replaced with H in place of the diethylene glycol in the above-mentioned process for producing a recycled polyol.
_{O- (CH 2) n -O- (} CH 2) n -OH (n = 3 or more)
Can be easily produced by taking the same steps as described above except for adding the diol represented by The decomposition product of the PET resin having high solubility in HFC and HO
A polyester polyol obtained by condensing a diol represented by — (CH ₂ ) _n —O— (CH ₂ ) _n —OH (n = 3 or more) is obtained.

Here, the content of the polyester polyol in the polyol component is 10% of the total polyol component.
The amount contained as 0 part by weight is 10 parts by weight or more, and preferably 10 to 40 parts by weight.

The above-mentioned polyhydroxy compound used in the present invention can contain a polyol compound other than the above-mentioned polyester polyol. Specifically, a polyol compound usually used when producing a rigid polyurethane foam is used. There is no particular limitation.
More specifically, amine and formaldehyde are added to glycerin, sucrose, ethylenediamine, etc., and polyether polyol or phenol obtained by addition polymerization of ethylene oxide, propylene oxide, etc., and further ethylene oxide, propylene oxide And polyether polyols such as Mannich-based polyether polyols obtained by addition polymerization of these compounds, and polyester polyols other than those described above. These can be used alone or in combination of two or more.
In this specification, the terms "polyhydroxy compound" and "polyol compound" (hereinafter, also sometimes referred to as "polyol") are used interchangeably.

Further, in addition to the above essential components, the polyol component used in the present invention contains various components contained in a polyol component usually used in the production of a rigid polyurethane foam in an appropriate amount as long as the effects of the present invention are not impaired. can do. Examples of such components include a catalyst, a foam stabilizer, a flame retardant, a foaming aid, a dehydrating agent, a plasticizer, a weathering agent, a dye, and a pigment.

Examples of the catalyst include organometallic compounds such as lead octoate and dibutyltin dilaurate, and amine compounds such as triethylenediamine and tetramethylenediamine, which are usually usable as catalysts in resin compositions for rigid polyurethane foams. Any substance can be used without any particular limitation.
Also, N, N ', N ",-tris (dimethylaminopropyl) hexahydro-S-triazine, potassium acetate, potassium octylate, quaternary ammonium salt of octylic acid and the like can be used as a nullation catalyst.

The foam stabilizer is not particularly limited as long as it can be used as a foam stabilizer for a resin composition for a rigid polyurethane foam, and any substance can be used. it can. Examples of such foam stabilizers include polyoxyalkylene compounds such as polyalkylene alkyl ethers and silicon compounds such as organopolysiloxanes.

Further, as the flame retardant, aluminum hydroxide, phosphates, melamine, red phosphorus, expanded graphite, tris-β-monochloropropyl phosphate, etc., and as foaming aids, HFC-134a, Difluoromethane (hereinafter sometimes referred to as “HCFC-22”) and the like; calcium silicate, calcium carbonate, magnesium sulfate, and synthetic zeolite as dehydrating agents; and DOP (di (2-ethylhexyl) as a plasticizer. ) Phthalate), DOA (di (2-ethylhexyl) adipate), DBP (dibutyl phthalate), etc., as the weathering agent, ultraviolet absorbers, light stabilizers, antioxidants usually used in resin compositions for rigid polyurethane foams And the like compounds similar to the components constituting the above.

(Ii) Polyisocyanate Component The polyisocyanate component constituting the resin composition for a rigid polyurethane foam of the present invention contains a polyisocyanate having two or more isocyanate groups in a molecule. As the polyisocyanate, specifically, polyisocyanates that are usually used in producing a rigid polyurethane foam can be used without any particular limitation, and these can be used alone or in combination of two or more.

As such polyisocyanates, more specifically, aromatic isocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate;
Alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate. These can be used in the present invention in a purified state or in a crude form.

The polyisocyanate component used in the present invention contains, in addition to the above-mentioned polyisocyanate, appropriate amounts of various components contained in the polyisocyanate component usually used for producing a rigid polyurethane foam as long as the effects of the present invention are not impaired. can do. Such components include, for example, flame retardants, foaming aids, dehydrating agents, plasticizers, weathering agents, dyes, pigments, and the like. Specific examples of these various components are the same as those described for the polyol component.

(Iii) Resin composition for rigid polyurethane foam The resin composition for rigid polyurethane foam of the present invention comprises the above-mentioned polyisocyanate component and polyol component. The polyisocyanate component and the polyol component constituting the resin composition for a rigid polyurethane foam of the present invention,
Usually, they are stored separately and mixed at the time of use. When both components are mixed, an intermolecular cross-linking reaction between the polyisocyanate and the polyol is started and the mixture is cured as the reaction proceeds.However, the foaming agent contained in the raw material components generates gas during the mixing reaction, so that bubbles are generated in the hard polyurethane. Is formed.

In the resin composition for a rigid polyurethane foam of the present invention, when the polyisocyanate component and the polyol component are present separately as described above, they are collectively referred to as a resin composition for a rigid polyurethane foam. Further, the category of the resin composition for a rigid polyurethane foam of the present invention also includes a mixture obtained by mixing a polyisocyanate component and a polyol component for the above reaction.

The composition of the resin composition for a rigid polyurethane foam of the present invention is such that the polyol component has the carbon number of 6
A polyester polyol having a structure in which a diol having an ether bond and a dicarboxylic acid are bonded by an ester reaction is contained in an amount of 10% by weight or more based on the total amount of the polyol component, and the ozone layer destruction coefficient is 0 as a foaming agent. Except for containing a hydrofluorocarbon having a boiling point of 5 ° C. or higher, there is no particular limitation as long as the composition can form a rigid polyurethane foam by mixing and foaming the above composition.

Specifically, the composition of the resin composition for a rigid polyurethane foam of the present invention is such that if the above conditions are satisfied, the obtained rigid polyurethane foam is mainly composed of urethane bonds,
The composition may be such that it becomes a rigid polyurethane foam of a type constituted by urea bonds (hereinafter, also sometimes referred to as a "urethane / urea-bonded type rigid polyurethane foam"), or isocyanurate condensation as a main bonding mode. The composition may be an isocyanurate-modified rigid polyurethane foam having a structure in which a urethane bond is partially introduced.

More specifically, when producing a urethane / urea bond type rigid polyurethane foam, the content ratio of the polyol component to the polyisocyanate component of the resin composition for a rigid polyurethane foam of the present invention is determined by the isocyanate index. (The ratio of the polyisocyanate equivalent to the polyol equivalent (NCO / OH) multiplied by 100) is preferably in the range of 95 to 130, more preferably 100 to 120.

When isocyanurate-modified rigid polyurethane foam is produced among the rigid polyurethane foams, the isocyanate index is preferably in the range of 140 to 300 in view of the characteristics of the polymer structure. Preferably, it can be in the range of 150 to 250.

The resin composition for a rigid polyurethane foam of the present invention may further comprise, if necessary, a catalyst, a foam stabilizer, a flame retardant, a foaming aid as described above as components other than the polyol component and the polyisocyanate component. And various components such as a dehydrating agent, a plasticizer, a weathering agent, a dye, and a pigment may be contained in an amount that does not impair the effects of the present invention. These various components may be added to the polyol component or the polyisocyanate component in advance as described above, but can also be added when the polyol component and the polyisocyanate component are mixed.

(2) Production of Rigid Polyurethane Foam In order to produce a rigid polyurethane foam using the above resin composition, the polyol component and the polyisocyanate component constituting the rigid polyurethane foam, and further optionally added components May be mixed and foamed. For the mixed foaming, a device usually used for producing a rigid polyurethane foam, for example, a low-pressure foaming machine, a high-pressure foaming machine, a spray foaming machine or the like can be used without any limitation. In addition, a mixture of the above components (hereinafter sometimes referred to as “foaming stock solution”) is poured into an appropriate mold by a generally used apparatus according to a generally used manufacturing method when manufacturing a rigid polyurethane foam. Molded by spraying or spraying. As a general method for producing such a rigid polyurethane foam, specifically, a slab stock foam production method, a lamination board / panel continuous production method, a multistage press / discontinuous injection foam production method, a mold foam production method, a spray foam Although a production method and the like can be mentioned, the resin composition for a rigid polyurethane foam of the present invention can be applied to any of these methods.

Further, the resin composition for a rigid polyurethane foam of the present invention is applicable to in-situ foaming as defined above. In-situ foaming, which often involves increasing the amount of a foaming agent added to lower the viscosity of the foaming stock solution, particularly in spray foaming, the effect of suppressing the phenomenon of boiling by using the resin composition for a rigid polyurethane foam of the present invention is as follows. Large and particularly useful.

The production conditions such as temperature, pressure and time in each production method can be the same as those usually employed in the production method.

[0045]

EXAMPLES The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.

[0046]

Examples 1 to 6 and Comparative Examples 1 to 6 A resin composition for a rigid polyurethane foam comprising a polyol component, a foaming aid and a polyisocyanate component having the compositions shown in Table 1 was prepared. Similarly, a resin composition for a rigid polyurethane foam of a comparative example having the composition shown in Table 2 was produced. In addition, each component in Table 1 and Table 2 shows the compound demonstrated below, respectively.

Polyol component i) Polyol (OHV in parentheses indicates the amount (mg) of KOH necessary for saponifying 1 g of polyol with KOH) A: Ethylenediamine amine polyetherpolyol (OHV; 750) B : Ethylenediamine / sucrose paste polyetherpolyol (OHV; 470) C: Mannich polyetherpolyol (OHV; 470) D: Phthalic acid + ethylenepolyethylenepolyesterpolyol (OHV; 315) E: Waste PET + ethylenepolyethylenepolyester V ) F: phthalic acid + perfluoropolycarbonate polyester polyol (OHV; 315) G: terephthalic acid + peroxyethylene polyphosphate resin polyol (OHV; 280) H: phthalic acid + polyethylene glycol Lumpur (200) port Riesuteruho ° polyol (OHV; 28
0) I: Waste PET + perfluoropolycarbonate polyester polyol (OHV; 195)

Ii) Catalyst A: 33% solution of triethylenediamine in propylene glycol (Sankyo Air Filter)
B: N, N ', N ",-tris (methylaminopropyl) hexahydro-S-triazine (PC-41, manufactured by Airfloshavan) C: 50% solution of potassium octylate in ethylene glycol Sankyo Airflow Co., Ltd.
DABCO K-15) D: Neoterpene solution of lead octylate (lead concentration 20
%)

Iii) Flame retardant: Tris-β-monochloropropyl phosphate iv) Foam stabilizer: Silicon foam stabilizer (manufactured by Toray Silicone, SH-
193) v) Blowing agent 141b: HCFC-141b (1,1-dichloro-1-fluoroethane) 245fa: HFC-245fa (1,1,1,3,3-pentafluoropropane)

Foaming aid: HFC-134a (1,1,1,2-
Tetrafluoroethane) Polyisocyanate component: Crude diphenylmethane diisocyanate (Nippon Polyurethane Co., Ltd.)

[0051]

[Table 1]

[0052]

[Table 2]

<Evaluation of Resin Composition for Rigid Polyurethane Foam of the Present Invention> Boiling and Separation Test Boiling and separation were confirmed by using the resin compositions for rigid polyurethane foam of Examples and Comparative Examples shown in Tables 1 and 2. After preparing the polyol component (50 parts by weight), the mixture was placed in a beaker and left at room temperature of 20 ° C. for 1 hour. During this time, the case where the foaming agent had separated was judged to be separation, and further separation did not occur. The test was conducted by rapidly stirring to check for boiling. The results are shown in the bottom columns of Tables 1 and 2.

<Evaluation of Rigid Polyurethane Foam Obtained Using Resin Composition of the Present Invention> (1) Production of Rigid Polyurethane Foam Examples 1 to 6 and Comparative Examples 1, 2, 5, and 6 obtained above were prepared. Each component of the resin composition for a rigid polyurethane foam is put into an airless mixing and foaming machine; Gasmer FF-1600 (manufactured by Gasmer), and the pearlite of the sprayed frame is formed under the conditions of a hose length of 30 m, a hose temperature of 32 ° C. and a static pressure of 900 psi. Plate (600 × 300 × 10 mm, temperature; 20
° C). The spraying method at this time is JIS-
This method was based on the method for producing a sample according to A-9526. The rigid polyurethane foam obtained by curing about 20 seconds after spraying was left for one month, then peeled off from the pearlite plate and used for the following physical property measurement.

(2) Measurement of Physical Properties The rigid polyurethane foams obtained using the resin compositions of Examples 1 to 4 and Comparative Examples 1, 2, and 5 were measured for density and flammability according to JIS-A-9526 and JIS-A. It measured according to the method of -9511. Table 3 shows the results. In addition,
The passing value of the combustion test is within 120 seconds of the burning time and within 60 mm of the burning distance.

The rigid polyurethane foams obtained using the resin compositions of Examples 5 and 6 and Comparative Example 6 were also examined for density and flammability. The density was measured in the same manner as described above, and the flammability was measured according to the method described in JIS-A-1321. Table 4 shows the results. In addition, the acceptable value of the flame retardant class 3 is a smoke emission coefficient of 120 or less, a temperature / time area of 350 or less, and a residual flame time of 30 seconds or less.

[0057]

[Table 3]

[0058]

[Table 4]

As is evident from the above results, the use of the resin composition for a rigid polyurethane foam of the present invention, despite the use of HFC having an ozone layer destruction coefficient of 0 and a boiling point of 5 ° C. or more, has a problem in that the boiling point is not so high. No worries about separation, and
A rigid polyurethane foam having high flame retardancy can be produced. Among the rigid polyurethane foams obtained using the resin composition for a rigid polyurethane foam of the present invention, in particular, isocyanurate prepared using the resin composition for a rigid polyurethane foam obtained in Examples 5 and 6 Modified rigid polyurethane foam is JIS-
It can be seen that the material has a very high flame retardancy that can pass A-1321.

[0060]

According to the resin composition for a rigid polyurethane foam of the present invention, a rigid polyurethane foam having high flame retardancy while containing a hydrofluorocarbon having a low ozone layer destruction coefficient can be produced, and a rigid polyurethane foam can be produced. Since there is no occurrence of boiling, separation and the like during the production of, it is easy to handle.

Continued on the front page F-term (reference) 4F074 AA78 AA79 AA80 AA81 BA53 CA12 CC22X CC22Y DA02 DA15 DA18 4J034 CC08 DA01 DF16 DF20 DF22 DF29 DG03 DG04 DG14 HA01 HA07 HC03 HC12 HC17 HC22 HC52 HC64 HC67 HC02 HC73 KB02 NA02 QC01

Claims (5)

[Claims] 1. A resin composition for a rigid polyurethane foam comprising a polyol component containing a foaming agent and a polyhydroxy compound, and a polyisocyanate component, wherein the polyhydroxy compound has 6 or more carbon atoms and has an ether bond. A polyester polyol having a structure in which a diol and a dicarboxylic acid are bonded by an ester reaction, in an amount of 10% by weight or more based on the total amount of the polyol component, and the foaming agent has an ozone layer destruction coefficient of 0 and a boiling point of A resin composition for a rigid polyurethane foam, comprising a hydrofluorocarbon having a temperature of 5 ° C. or higher. 2. The method according to claim 1, wherein the diol is HO— (CH ₂ ) _n —O
_{- (CH 2) n -OH (} n = 3 or more) is a diol represented by claim 1 for rigid polyurethane foams resin composition. 3. The method according to claim 1, wherein the diol is HO— (C ₂ H ₄ O) _n
2. A diol represented by -H (n = 3 or more).
The resin composition for a rigid polyurethane foam according to the above. 4. The polyester polyol is composed of a decomposition product of polyethylene terephthalate and HO— (CH ₂ ) _{n
-O- (CH 2) n -OH (} n = 3 or more) according to claim 1 for rigid polyurethane foams resin composition according to diol represented a polyol obtained by condensation with. 5. A method for producing a rigid polyurethane foam, comprising a step of mixing and foaming a polyol component containing a foaming agent and a polyhydroxy compound and a polyisocyanate component, wherein the polyhydroxy compound has 6 carbon atoms.
A polyester polyol having a structure in which a diol having an ether bond and a dicarboxylic acid are bonded by an ester reaction is contained in an amount of 10% by weight or more based on the total amount of the polyol component, and the foaming agent further comprises an ozone layer. A method for producing a rigid polyurethane foam, comprising a hydrofluorocarbon having a breaking coefficient of 0 and a boiling point of 5 ° C. or higher.