CN1307230C - Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam - Google Patents

Abstract

The present invention provides a polyol composition for rigid polyurethane foam and a method for producing rigid polyurethane foam while using HFC-245fa as a blowing agent while suppressing its vapor pressure. In the polyol composition for rigid polyurethane foam, the blowing agent component is 1,1,1,3,3-pentafluoropropane (HFC-245fa), and contains diethylene glycol-ethyl ether acetate, and the polyol compound contains A polyol compound with a tertiary amino group, and the nitrogen based on the tertiary amino group is 0.5-9% by weight in the polyol compound. As a blowing agent component, it is preferable to use HFC-365mfc or HFE-254pc together.

Description

Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam

technical field

The present invention relates to a rigid polyurethane foam polyol composition containing 1,1,1,3,3-pentafluoropropane (HFC-245fa) as a necessary main component of a blowing agent and using HFC-245fa as a blowing agent The main component of rigid polyurethane foam manufacturing method.

Background technique

1,1-Dichloro-1-fluoroethane (HCFC-141b), which has a low ozone layer destruction coefficient, is currently used as a foaming agent for rigid polyurethane foam, which is an excellent heat insulating material. Although HCFC-141b has a small ozone depletion coefficient, it is not zero. From the viewpoint of global environmental protection, it was completely abolished at the end of 2003.

As blowing agents to replace HCFC-141b, low-boiling hydrocarbons such as n-pentane and cyclopentane, HFC-245fa or HFC-365mfc, which are chlorine-free low-boiling halogenated hydrocarbon compounds, and global warming HFE-254pc with smaller coefficient.

However, low-boiling hydrocarbons such as n-pentane and cyclopentane are compounds with high flammability, and are used in the production process of polyol compositions containing these compounds as blowing agents and in the production of rigid polyurethane foams using the polyol compositions. In the manufacturing process and the waste treatment process of crushing and disposing of the waste of the rigid polyurethane foam, serious fire prevention measures are required, and it is necessary to renew the equipment in the conventional rigid polyurethane foam manufacturing plant, etc., and the equipment cost Such a huge problem. In addition, rigid polyurethane foam using pentane as a blowing agent has poor flame retardancy compared to conventional products using HCFC-141b as a blowing agent, and is not suitable for use as building materials requiring flame retardancy. It is difficult to use.

HFC-365mfc, according to the Japanese fire protection law, although it is not confirmed as flammable, but according to the German standard, the flash point is confirmed at -27 ℃, and the polyol composition containing it as a blowing agent also has a certain composition according to its composition. It is an example of the first petroleum in the fourth category of hazardous substances stipulated in the Fire Services Act, and has the same problem of inability to handle and store as a polyol composition using HCFC-141b as a blowing agent as a hazardous substance. In addition, HFC-365mfc also has a problem of poor compatibility with the polyol which is the main component of the polyol composition.

HFE-254pc is still a blowing agent in the development stage and has not been fully studied, but as a dangerous substance, it is a substance similar to HFC-365mfc, and has the same problem.

On the other hand, HFC-245fa has no fire hazard and is a blowing agent that does not need to be handled as a hazardous substance, but has a boiling point of 15° C. and a high vapor pressure at room temperature. Therefore, if HFC-245fa is used as a foaming agent, containers such as gasoline tanks or petroleum tanks containing polyol compositions will have problems such as swelling especially in summer and when the plug is opened due to the gas of the foaming agent. The stock solution of the polyol composition is sprayed out or the blowing agent volatilizes and diffuses, thereby reducing its content and failing to obtain a foam with a predetermined density.

Contents of the invention

An object of the present invention is to provide a polyol composition for rigid polyurethane foam and a method for producing rigid polyurethane foam which use HFC-245fa as a foaming agent and whose vapor pressure is suppressed.

The polyol composition for rigid polyurethane foam of the present invention contains at least a polyol compound, a foaming agent, a foam stabilizer, and a catalyst, and can form a hard polyurethane foam by mixing it with an isocyanate component containing an isocyanate compound and foaming and curing it. Quality polyurethane foam, characterized in that,

The first blowing agent, which is the main component of the blowing agent, is 1,1,1,3,3-pentafluoropropane (HFC-245fa), contains diethylene glycol monoethyl ether acetate as a vapor pressure reducing agent, and the above-mentioned HFC-245fa/diethylene glycol monoethyl ether acetate=95/5～60/40 (weight ratio),

The above-mentioned polyol compound includes a polyol compound having a tertiary amino group, and nitrogen based on the above-mentioned tertiary amino group is 0.5 to 9% by weight in the polyol compound.

The object of the present invention can be achieved by making the polyol composition for rigid polyurethane foam having the above-mentioned composition.

That is, by using HFC-245fa as a blowing agent and adding diethylene glycol monoethyl ether (hereinafter, abbreviated as CAc (abbreviation for carbitol acetate)) at the same time, the foaming characteristics or the obtained rigid polyurethane foam were maintained. Physical properties, heat insulation, etc., and can suppress the vapor pressure of HFC-245fa.

When the HFC-245fa/CAc weight ratio exceeds 95/5, the vapor pressure reducing effect cannot be fully exhibited, and the vapor pressure of the polyol composition for rigid polyurethane foams will increase. In addition, when the weight ratio of HFC-245fa/CAc is less than 60/40, the ratio of CAc is too large, and the physical properties of the foam may decrease.

In addition, since polyol compounds containing tertiary amino groups are more compatible with HFC-245fa than other polyol compounds, by using polyol compounds containing tertiary amino groups in combination, a more excellent vapor pressure reduction effect of HFC-245fa can be obtained . By using a polyol compound containing a tertiary amino group in combination, it is also possible to increase the reactivity of the polyol composition, increase the uniformity of the cells of the obtained rigid polyurethane foam, and increase the bonding strength to the surface material at the same time. Effect. When the nitrogen based on the tertiary amino group is less than 0.5 in the polyol compound, the vapor pressure lowering effect, the uniformity of the cells, and the adhesive strength to the surface material cannot be sufficiently improved, and if it exceeds 9% by weight, the obtained rigid polyurethane foam Dimensional stability is reduced.

Nitrogen based on tertiary amino groups is more preferably 1.5 to 8.5% by weight in the polyol compound.

The above-mentioned polyol composition for rigid polyurethane also preferably contains 1,1,1,3,3-pentafluorobutane (HFC-365mfc) as the second blowing agent, and HFC-245fa/HFC-365mfc≥60/40 , (HFC-245fa+HFC-365mfc)/CAc=95/5 to 60/40 (weight ratio).

HFC-365mfc has good compatibility with HFC-245fa, and is a compound with a higher boiling point (40.2°C) than HFC-245fa. Therefore, by using HFC-365mfc in combination, the foaming properties and the obtained rigid polyurethane foam are maintained. Physical properties, heat insulation, etc., can also suppress the vapor pressure of HFC-245fa.

When the weight ratio of HFC-245fa/HFC-365mfc is less than 60/40, the content of HFC-365mfc becomes high, and as a result, the flash point is lowered, and even if the polyol composition is in the fourth category of hazardous substances, it is recognized as In the case of highly flammable petroleum. In addition, if the weight ratio of (HFC-245fa+HFC-365mfc)/CAc exceeds 95/5, the ratio of CAc is too small, and the effect of its addition cannot be fully exerted. If the weight ratio is less than 60/40, the ratio of CAc When the ratio is too large, the physical properties of the foam may decrease.

The (HFC-245fa+HFC-365mfc)/CAc weight ratio is preferably 93/7 to 70/30.

The above-mentioned polyol composition for rigid polyurethane foam also preferably contains tetrafluoromethoxyethane (HFE-254pc) as the 3rd blowing agent, and HFC-245fa/HFE-254pc≥50/50, (HFC-245fa +HFE-254pc)/CAc=95/5 to 60/40 (weight ratio).

By using HFE-254pc which has good compatibility with HFC-245fa and has a higher boiling point than HFC-245fa, the foaming properties and the physical properties and heat insulation properties of the obtained rigid polyurethane foam can be maintained, and HFC-245fa can also be suppressed Vapor pressure, and prevention of global warming is also effective.

When the weight ratio of HFC-245fa/HFE-254pc is less than 50/50, the content of HFE-254pc becomes high, and as a result, the flash point is lowered, and even if the polyol composition is in the fourth category of hazardous substances, it is recognized as In the case of highly flammable petroleum. In addition, if the weight ratio of (HFC-245fs+HFE-254pc)/CAc exceeds 95/5, the ratio of CAc is too small, and the effect of its addition cannot be fully exerted. If the weight ratio is less than 60/40, the ratio of CAc When the ratio is too large, the physical properties of the foam may decrease.

(HFC-245fa+HFE-254pc)/CAc weight ratio is preferably 93/7 to 70/30.

CAc may be pre-mixed with HFC-245fa, and HFC-365mfc or HFE-254pc as a foaming agent composition mixed with polyol compound, and various components may be added separately as long as the result is that they coexist in polyol composition , regardless of the order and form of addition.

It is known that the use of CAc as one component of the polyol composition also improves the adhesive strength between rigid polyurethane foam and surface materials. Although the reason is not clear, when only HFC-245fa, or HFC-245fa and HFC-365mfc or HFE-254pc are used as the blowing agent, the compatibility between the blowing agent and the polyol component is not good, and the mixed When the foaming stock solution composition of the isocyanate component and the polyol composition is in contact with the surface material, etc., the temperature of the contact surface drops, HFC-245fa blooms until the curing reaction starts, and then causes a foaming reaction, and the bubbles of the foam near the interface are disordered, As a result, it is presumed that the adhesiveness with the surface material falls. Since CAc has the effect of improving the compatibility between HFC-245fa and polyol compounds, it is considered to be a substance that improves the adhesive strength between rigid polyurethane foam and surface materials.

In addition, the present invention is a method for producing a rigid polyurethane foam by mixing an isocyanate component and a polyol composition, foaming and curing it to form a rigid polyurethane foam, and is characterized in that, as the polyol composition, the following claims 1 to 1 are used. The polyol composition for rigid polyurethane foam according to any one of 3.

With this production method, rigid polyurethane foam can be produced using the same production equipment as in the case of using HCFC-141b as a blowing agent, without greatly modifying fire prevention measures.

Detailed ways

The polyol composition for rigid polyurethane of the present invention contains at least a polyol compound, a foam stabilizer, and a catalyst in addition to a foaming agent. The polyol compound contains a polyol compound having a tertiary amino group.

The polyol compound is not limited, and known polyol compounds for rigid polyurethane foams can be used. Examples of such polyol compounds include tertiary amino group-containing polyol compounds, aliphatic polyols, aromatic polyols, and the like.

Polyol compounds containing tertiary amino groups use primary or secondary amines as initiators to make epoxides, specifically, propylene oxide (PO), ethylene oxide (EO), phenyl oxirane (SO) A polyfunctional polyol obtained by ring-opening addition polymerization of one or more of tetrahydrofuran and the like.

As the primary or secondary amine initiator of the polyol compound containing tertiary amino group, ammonia, methylamine, ethylamine and other aliphatic primary or secondary monoamines, ethylenediamine, hexamethylene Diamine, N,N'-dimethylethylenediamine and other aliphatic primary or secondary polyamines, aniline, diphenylamine, toluenediamine, diphenylmethanediamine, N-methylaniline and other aromatic primary or secondary monovalent Or polyamines, alkanolamines such as monoethanolamine and diethanolamine.

Aliphatic polyols use polyols as initiators to make epoxides, specifically propylene oxide (PO), ethylene oxide (EO), A polyfunctional oligomer obtained by ring-opening addition polymerization of one or more cyclic ethers such as phenyloxirane (SO) and tetrahydrofuran.

Examples of polyol initiators for aliphatic polyols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and neopentyl glycol. Alcohols, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, polyalcohols such as sorbitol and sucrose, water, etc.

Examples of aromatic polyols include polyol compounds obtained by adding the above-mentioned epoxides to polyfunctional active hydrogen compounds having aromatic rings in the molecule, aromatic polyacids and polyols. Esters of polyol compounds, etc.

As a polyol compound obtained by adding the above-mentioned epoxide to a polyfunctional active hydrogen compound, specifically, hydroquinone, bisphenol A, etc. are ring-opened and added at least one of PO, EO, and SO. The obtained compound.

Specific examples of esters of aromatic polybasic acids and polyhydric alcohols include hydroxyl-terminated ester polyols such as terephthalic acid, phthalic acid, and isophthalic acid, and ethylene glycol, diethylene glycol, and the like.

The above-mentioned polyol compound preferably has a hydroxyl value of 200 to 600 mgKOH/g. Among these polyol compounds, when a polyol compound containing a tertiary amino group or an aliphatic polyol is used, the effect of reducing the viscosity of the polyol composition can be obtained.

The catalyst used in the polyol composition for rigid polyurethane foam of the present invention is not limited, and known catalysts for rigid polyurethane foam can be used. Specifically, examples of the urethanization reaction catalyst include triethylenediamine, N-methyltimorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N ', N'-Tetramethylhexamethylenediamine, DBU and other tertiary amines, dibutyltin dilaurate, dibutyltin diacetate, tin octoate and other metal catalysts.

For the so-called rigid polyurethane foam, the isocyanate group forming the polymer can be only urethane bonds, or urea bonds or isocyanurate bonds.

It is preferable to use a small amount of water as a blowing agent to improve the properties of the resulting rigid polyurethane foam.

In the structure of the polyurethane molecule, it is preferable to use a catalyst that forms an isocyanurate bond that contributes to the improvement of flame retardancy, and examples thereof include potassium acetate and potassium octoate. Among the above-mentioned tertiary amine catalysts, there are substances that promote the isocyanurate ring formation reaction. There is also no problem in using a catalyst that promotes formation of isocyanurate bonds and a catalyst that promotes formation of urethane bonds in combination.

The foam stabilizer is not limited, and known foam stabilizers for rigid polyurethane foams can be used. As foam stabilizers, polydimethylsiloxanes and graft or block copolymers of polydimethylsiloxanes and polyepoxides are generally used. As the polyepoxide, polyethylene oxide, polypropylene oxide, random copolymer or block copolymer of ethylene oxide and propylene oxide having an average molecular weight of 5,000 to 8,000 can be used.

In the polyol composition for rigid polyurethane foam of the present invention, flame retardants, colorants, antioxidants, antiscorch agents and the like known to those skilled in the art may also be used.

Examples of the flame retardant include metal compounds such as halogen-containing compounds, organic phosphates, antimony trioxide, and aluminum hydroxide.

If these flame retardants, such as organic phosphates, are added in excess, the physical properties of the resulting rigid polyurethane foam may sometimes decrease. In addition, if metal compound powder such as antimony trioxide is added in excess, there will be foaming behavior against the foam. Problems such as influence appear, and the amount of addition is limited to a range that does not cause such problems.

In the rigid polyurethane foam of the present invention, a plasticizer is appropriately used if necessary. Such a plasticizer is also preferably a substance that contributes to flame retardancy, and halogenated alkyl esters of phosphoric acid, alkyl phosphoric acid esters or aryl phosphoric acid esters, phosphonic acid esters, and the like can be used. Specifically, phosphoric acid tris(2 -chloroethyl ester) (CLP, manufactured by Daihachi Chemical), tris(β-chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical), tris(butoxyethyl)phosphate (TBXP, manufactured by Daihachi Chemical), One or more of tributyl phosphate, triethyl phosphate, cresyl phenyl phosphate, dimethyl methyl phosphonate, etc. can be used. The amount of the plasticizer added is preferably 5 to 30 parts by weight relative to 100 parts by weight of the polyol component. If it exceeds this range, there will be problems that a sufficient plasticizing effect cannot be obtained, or the physical properties of the generated foam will be lowered.

As a polyisocyanate compound that is mixed with a polyol composition and reacted to form a rigid polyurethane foam, it is used in terms of ease of operation, rapidity of reaction, excellent physical properties of the resulting rigid polyurethane foam, and low cost. Liquid MDI. As the liquid MDI, unrefined (crude) MDI (c-MDI) (44V-10, 44V-20, etc. (manufactured by SumitomoBayer Urethane Co., Ltd.)) and MDI containing ウレトンイミン (MillionateMTL; manufactured by Nippon Polyurethane Industry) can be used. wait. Among these polyisocyanate compounds, it is particularly preferable to use unrefined (crude) MDI from the viewpoint of excellent physical properties such as mechanical strength of the formed rigid polyurethane foam and low cost.

In addition to liquid MDI, other polyisocyanate compounds can also be used together. Such a polyisocyanate compound is not limited, and di- or polyisocyanate compounds known in the technical field of polyurethane can be used.

The polyol composition for rigid polyurethane foam of the present invention can be used for continuous production of rigid polyurethane foam such as slab stock foam, laminated board, injection molded rigid polyurethane foam laminated board, spray foam, etc. (Suprea Form) and other manufacturing.

(Example)

Hereinafter, examples showing the configuration and effects of the present invention will be described.

The constituent materials of the polyol composition are shown in Table 1.

Table 1

Element suppliers content Polyol A Toho Rika Phthalic acid polyester polyol (hydroxyl value = 250) B Mitsui Takeda Chemical Ethylenediamine polyether polyol (hydroxyl value = 760) C Asahi Glass Ethylenediamine polyether polyol (hydroxyl value = 450) D Asahi Glass Bisphenol A polyether polyol (hydroxyl value = 280) Foam stabilizer SH-193 Dow Coring Toray Co., Ltd Silicone Surfactant flame retardant TMCPP Daechi Chemical Industry Phosphate flame retardant Catalyst BELCAT9540 Perron Corporation Potassium octanoate Dabco-33LV Air Products Japan Amine catalyst (triethylenediamine 33% DPG solution) Isocyanate 44V-20 Sumitomo Bayer Urethane Crude MDI (NCO=31.0% by weight)

The composition of the polyol composition and the added amount (parts by weight) of the blowing agent composition are described in Tables 2-4. The addition amount of the foaming agent composition was adjusted so that the density of the rigid polyurethane foam at the time of free foaming became 25 kg/m ³ . The blowing agent composition is a composition in which carbitol acetate (CAc) as an additive for reducing the vapor pressure of the blowing agent is previously added to HFC-245fa, HFC-365mfc, and HFE-254pc as a blowing agent.

Rigid polyurethane foams are produced by usual methods. That is, in the composition described in Table 1, the components other than the isocyanate component and the blowing agent composition were mixed and stirred, and the polyol composition was adjusted, the temperature was adjusted to 20°C, and the temperature was adjusted to 20°C. The polyol component and The isocyanate component is mixed and stirred according to the specified ratio, and it is foamed and cured to obtain a rigid polyurethane foam.

<Evaluation>

(Vapor Pressure Evaluation)

Put 50 g of the stock solution of the polyol composition adjusted to a predetermined mixing ratio into a 100 ml SUS container, make the container completely airtight, freeze and degas it with liquid nitrogen, and then place it in a constant temperature bath at 40°C , to measure the absolute vapor pressure P. The decompression rate is calculated by the following formula. P0 is the vapor pressure of only 245fa (comparative example 2) used as the blowing agent.

Decompression rate (%)=100(P0-P)/P0

(compressive strength)

A cube of 50 mm x 50 mm x 50 mm was cut out from the freely expanded foam in the container, and measured in accordance with JISA9511 (foamed plastic insulation material).

(dimensional stability)

A cube of 100 mm x 100 mm x 100 mm was cut out from the freely expanded foam in the container, and was left to stand in an atmosphere at -30°C for 24 hours to measure the amount of dimensional change. The evaluation results are expressed as a dimensional change rate (Δ%).

(adhesive)

Make free-foaming foam on the kraft paper surface material, and then introduce the surface material bonded to the foam into a 5 cm wide notch from the inside. Then, the end was peeled off, stretched using a spring scale, and the adhesive strength (gf/5cm) was measured.

(bubble stability)

Foam foaming freely in the container was observed visually. The evaluation results were expressed according to the following criteria.

○The pores are uniform and fine, equivalent to HCFC-141b.

△Pore collapse exists, slightly worse than HCFC-141b.

× Poor collapse is severe, which means poor foaming.

<Evaluation result>

The evaluation results are shown in the lower stages of Tables 2-4. The blowing agent composition shown in table 2 is the composition that has mixed HFC-245fa and vapor pressure depressant CAc in advance, and the blowing agent composition shown in table 3 is to have mixed HFC-245fa, HFC-365mfc and The three components of CAc and the blowing agent compositions shown in Table 4 are compositions composed of three components in which HFC-245fa, HFE-254pc, and CAc were mixed in advance. From the results of these tables, by making the blowing agent composition of the present invention, the vapor pressure of the blowing agent is greatly reduced, and the same operation as the conventional polyol composition using HCFC-141b becomes possible, and at the same time, it improves It improves the adhesion with the surface material and the stability of air bubbles. However, regarding the comparative example, the following observations were obtained. Regarding the dimensional stability, the foam using HCFC-141b as a blowing agent was -17.0%, and it was judged based on this.

a) When HFC-245fa/CAc is 55/45, CAc is too much, and as a result, the dimensional stability is lower than the foam using HCFC-141b as the blowing agent (Comparative Example 3).

b) When HFC-245fa/HFC-365mfc is 50/50 (comparative example 4) and HFC-245fa/HFE-254pc is 40/60 (comparative example 7), the addition amount of HFC-365mfc or HFE-254pc is too much , As a result, the dimensional stability is lower than that of a foam using HCFC-141b as a blowing agent.

c) Even if the composition of the foaming agent is within the scope of the present invention, when the nitrogen concentration based on the tertiary amino group in the total amount of the polyol compound is less than 0.5% by weight, the stability of the bubbles decreases, and the bonding strength to the surface material also decreases ( Comparative example 5, 8). If the nitrogen concentration based on the tertiary amino group exceeds 9% by weight, the dimensional stability of the resulting rigid polyurethane foam decreases (Comparative Examples 6, 9).

Table 2

Example Comparative example 1 2 3 1 2 3   Polyol Compounds A 45 45 45 50 50 50 B 45 45 45 40 40 40 C D. 10 10 10 10 10 10 Foaming agent HFC-245fa 50.0 55.0 59.0 50.0 62.0 HFC-365mfc HCFC-141b 46.0 Vapor pressure depressant CAc 5.6 14.3 25.3 - - 50.7 catalyst Perron9540 4.0 4.0 4.0 4.0 4.0 4.0 Dabco-33LV 4.0 4.0 4.0 4.0 4.0 4.0 Flame retardant TMCPP 15 15 15 15 15 15 Foam stabilizer SH-193 2.0 2.0 2.0 2.0 2.0 2.0 Nitrogen in polyol compound (wt%) 4.3 4.3 4.3 3.8 3.8 3.8 [Total amount of HFC]/[CAc] 90/10 80/20 70/30 - 100/0 55/45 Vapor Pressure Evaluation Results Absolute vapor pressure (kPa at 40℃) 186 177 165 203 158 Decompression rate (%) 8 13 19 0 twenty one Foam Evaluation Results Dimensional stability (△%) -1.1 -3.4 -7.4 -17.0 -2.0 -21.3 Compressive strength (kPa) 162 157 156 145 186 139 Adhesive strength (gf/5cm) 1600 1500 1550 1800 400 1500 bubble stability ○～△ ○ ○ ○ × ○

table 3

Example Comparative example 4 5 6 7 B 4 5 6 polyol compound A 60 60 50 45 15 45 73 B 20 20 40 45 85 45 100 C 7 D. 20 20 10 10 10 20 foaming agent HFC-245fa 40.0 49.9 38.0 32.4 43.2 27.5 43.0 43.0 HFC-365mfc 10.0 12.5 16.2 21.6 10.8 27.5 10.8 10.8 HCFC-141b Vapor pressure depressant CAc 5.6 41.6 6.0 6.0 13.5 6.1 13.5 13.5 catalyst Pcrron9540 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 DabCo-33LV 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Flame retardant TMCPP 15 15 15 15 15 15 15 15 Foam stabilizer SH-193 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Nitrogen in polyol compound (wt%) 1.9 1.9 3.8 4.3 8.2 4.3 0.4 10.0 [HFC-245fa]/[HFc-365mfc] 80/20 80/20 70/30 60/40 80/20 50/50 80/20 80/20 [Total amount of HFC]/[CAc] 90/10 60/40 90/10 90/10 80/20 90/10 80/20 80/20 Vapor Pressure Evaluation Results Absolute vapor pressure (kPa at 40℃) 165 134 155 156 158 148 168 159 Decompression rate (%) 18 34 twenty four twenty four twenty one 27 17 twenty one Foam Evaluation Results Dimensional stability (△%) -1.9 -10.9 -7.2 -10.6 -16.3 -20.6 -11.0 -25.6 Compressive strength (kPa) 161 146 179 171 151 137 174 132 Adhesive strength (gf/5cm) 1200 1350 1200 1000 1700 800 500 1750 bubble stability ○ ○ ○ ○ ○ △ × ○

Table 4

Example Comparative example 9 10 11 12 13 14 15 7 8 9 polyol compound A 45 45 45 60 60 50 50 50 73 B 45 45 45 20 20 40 40 40 100 C 7 D. 10 10 10 20 20 10 10 10 20 Foaming agent HPC-245fa 48.6 50.0 40.0 35.0 38.0 30.0 25.0 20.0 40.0 40.0 HFE-254pc 5.4 5.6 10.0 15.0 16.0 20.0 25.0 30.0 10.0 10.0 HCFC-141b Vapor pressure depressant CAc 6.0 23.8 12.0 5.6 23.0 5.6 5.6 5.6 12.0 12.0 catalyst Perron9540 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Dabco-33LV 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Flame retardant TMCPP 15 15 15 15 15 15 15 15 15 15 Foam stabilizer SH-193 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Nitrogen in polyol compound (wt%) 4.3 4.3 4.3 1.9 1.9 3.8 3.8 3.8 0.4 10.0 [HFC-245fa]/[HFE-254pc] 90/10 90/10 80/20 70/30 70/30 60/40 50/50 40/60 80/20 80/20 [HFC-245fa+HFE-254pc]/[CAc] 90/10 70/30 80/20 90/10 70/30 90/10 90/10 90/10 80/20 80/20 Vapor Pressure Evaluation Results Absolute vapor pressure (kPa at 40℃) 178 162 159 167 148 153 147 139 160 158 Decompression rate (%) 13 20 twenty two 18 27 25 28 32 twenty one twenty two Foam Evaluation Results Dimensional stability (△%) -1.5 -2.2 -3.2 -5.4 -10.4 -17.0 -17.0 -22.8 -11.0 -26.3 Compressive strength (kPa) 183 181 180 194 152 178 162 135 170 146 Adhesive strength (gf/5cm) 1200 1500 1300 1100 1300 1000 1000 1200 600 1750 bubble stability ○～△ ○ ○～△ ○～△ ○～△ △ △ △ × ○

Industrial Applicability

As explained above, according to the structure of this invention, the polyol composition for rigid polyurethane foams and the manufacturing method of rigid polyurethane foams which use HFC-245fa as a foaming agent and suppressed the vapor pressure are provided. Therefore, the present invention is industrially significant.

Claims (4)

1. polyol composition for rigid polyurethane foam, it contains polyol compound, whipping agent, surfactant, catalyzer at least, and by mixing with the isocyanate prepolymer composition that contains isocyanate compound, and makes it foamed solidification and form hard polyurethane foams, it is characterized in that

The 1st whipping agent of the main component of above-mentioned whipping agent is 1,1,1,3, and the 3-pentafluoropropane as the vapor pressure lowering agent, contains acetate ethyl carbitol ester, and above-mentioned 1,1,1,3,3-pentafluoropropane/acetate ethyl carbitol ester=95/5～60/40 weight ratio,

Above-mentioned polyol compound comprises the polyol compound with tertiary amine group, and is 0.5～9 weight % in the polyol compound based on the nitrogen of above-mentioned tertiary amine group.

2. according to the polyol composition for rigid polyurethane foam of claim 1 record, it is characterized in that, further contain as 1,1 of the 2nd whipping agent, 1,3, the 3-3-pentafluorobutane, and 1,1,1,3,3-pentafluoropropane/1,1,1,3,3-3-pentafluorobutane 〉=60/40, (1,1,1,3,3-pentafluoropropane+1,1,1,3, the 3-3-pentafluorobutane)/acetate ethyl carbitol ester=95/5～60/40 weight ratio.

3. according to the polyol composition for rigid polyurethane foam of claim 1 record, it is characterized in that, further contain tetrafluoride methyl ethyl ether as the 3rd whipping agent, and 1,1,1,3,3-pentafluoropropane/tetrafluoride methyl ethyl ether 〉=50/50, (1,1,1,3,3-pentafluoropropane+tetrafluoride methyl ethyl ether)/acetate ethyl carbitol ester=95/5～60/40 weight ratio.

4. the manufacture method of a hard polyurethane foams, it mixes isocyanate prepolymer composition with polyhydric alcohol composition, and make it foaming, solidify and become hard polyurethane foams, it is characterized in that, as polyhydric alcohol composition, use the polyol composition for rigid polyurethane foam of each record in the claim 1～3.