JP3902143B2 - Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam - Google Patents

Description

ポリオール組成物の組成並びに発泡剤組成物の添加量（重量部）は、表２〜４に記載した。発泡剤組成物の添加量は、フリー発泡時の硬質ポリウレタンフォームの密度が２５ｋｇ／ｍ³ となるように調整した。発泡剤組成物は、発泡剤であるＨＦＣ−２４５ｆａ，ＨＦＣ−３６５ｍｆｃ，ＨＦＥ−２５４ｐｃに発泡剤の蒸気圧を低下させる添加剤であるカルビトールアセテート（ＣＡｃ）を予め添加したものである。
【００５０】
硬質ポリウレタンフォームは、常法により作製した。即ち表１に記載の組成において、イソシアネート成分を除く成分と発泡剤組成物を混合撹拌してポリオール組成物を調整し、２０℃に温度調整し、次いで２０℃に温度調整したポリオール成分とイソシアネート成分を所定比率で混合撹拌し、発泡硬化させて硬質ポリウレタンフォームを得た。
【００５１】
＜評価＞
（蒸気圧評価）
所定配合比率にて調整したポリオール組成物原液を１００ｍｌ容量のＳＵＳ製容器に５０ｇ仕込み、容器を完全に密閉状態にして液体窒素により凍結脱気後、４０℃の恒温槽に静置し、絶対蒸気圧Ｐを測定した。減圧率は以下の式により計算した。Ｐ₀ は、発泡剤が２４５ｆａのみ（比較例２）の蒸気圧である。減圧率（％）＝１００（Ｐ₀ −Ｐ）／Ｐ₀
（圧縮強度）
容器中にて自由発泡させたフォームから５０ｍｍ×５０ｍｍ×５０ｍｍの立方体を切り出し、ＪＩＳ Ａ ９５１１（発泡プラスチック保温材）に準拠して測定した。
（寸法安定性）
容器中にて自由発泡させたフォームから１００ｍｍ×１００ｍｍ×１００ｍｍの立方体を切り出し、−３０℃の雰囲気下に２４時間放置して寸法変化量を測定した。評価結果は寸法変化率（Δ％）として表示した。
（接着性）
クラフト紙面材の上に自由発泡させたフォームを作成し、フォームと接着している面材を裏面から幅５ｃｍの切欠きを入れ端部を引き剥がし、バネ秤を使用して引っ張り、接着強度（ｇｆ／５ｃｍ）を測定した。
（気泡安定性）
容器中にて自由発泡させたフォームを目視にて観察した。評価結果を以下の基準により表示した。
○：セルが均一で細かく、ＨＣＦＣ−１４１ｂ発泡品と同等である。
△：セル荒れがあり、ＨＣＦＣ−１４１ｂ発泡品よりやや劣る。
×：セル荒れがひどく、発泡不良である。
【００５２】
＜評価結果＞
評価結果は、表２〜４の下段に示した。表２に示した発泡剤組成物は、ＨＦＣ−２４５ｆａと蒸気圧低下剤であるＣＡｃとを予め混合した組成物であり、表３に示した発泡剤組成物は、ＨＦＣ−２４５ｆａ、ＨＦＣ−３６５ｍｆｃ及びＣＡｃの３成分、表４に示した発泡剤組成物は、ＨＦＣ−２４５ｆａ、ＨＦＥ−２５４ｐｃ及びＣＡｃを予め混合した３成分からなる組成物である。これらの表の結果から、本発明の発泡剤組成物とすることにより、発泡剤の蒸気圧が大きく低下し、従来のＨＣＦＣ−１４１ｂを使用したポリオール組成物と同等の取扱いが可能になると共に、面材との接着性、気泡安定性も改善されたものとなった。ただし、比較例については、以下の知見が得られた。寸法安定性については、ＨＣＦＣ−１４１ｂを発泡剤として使用したフォームが−１７．０％であり、これを基準として判断した。
ａ）ＨＦＣ−２４５ｆａ／ＣＡｃが５５／４５の場合には、ＣＡｃが多すぎる結果、寸法安定性がＨＣＦＣ−１４１ｂを発泡剤として使用したフォームより低下している（比較例３）。
【００５３】
ｂ）ＨＦＣ−２４５ｆａ／ＨＦＣ−３６５ｍｆｃが５０／５０の場合（比較例４）、ＨＦＣ−２４５ｆａ／ＨＦＥ−２５４ｐｃが４０／６０の場合（比較例７）は、ＨＦＣ−３６５ｍｆｃ又はＨＦＥ−２５４ｐｃの添加量が多すぎる結果、寸法安定性がＨＣＦＣ−１４１ｂを発泡剤として使用したフォームより低下している。
【００５４】
ｃ）発泡剤組成が本発明の範囲内であっても、ポリオール化合物全量中の第３級アミノ基に基づく窒素濃度が０．５ｗｔ％未満の場合は、気泡安定性が低下し、面材との接着強度も低下する（比較例５、８）。第３級アミノ基に基づく窒素濃度濃度が９ｗｔ％を超えると、得られる硬質ポリウレタンフォームの寸法安定性が低下する（比較例６、９）。
【００５５】
【表２】

【表３】

【表４】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rigid polyurethane foam polyol composition containing 1,1,1,3,3-pentafluoropropane (HFC-245fa) as an essential component of a blowing agent as a blowing agent component, and HFC-245fa as a blowing agent. The present invention relates to a method for producing a rigid polyurethane foam used as a main component.
[0002]
[Prior art]
Currently, 1,1-dichloro-1-fluoroethane (HCFC-141b) having a small ozone layer depletion coefficient is used as a foaming agent for rigid polyurethane foam, which is an excellent heat insulating material. HCFC-141b has a small ozone depletion coefficient but is not zero, and it has been decided that it will be completely abolished at the end of 2003 from the viewpoint of protecting the global environment.
[0003]
As blowing agents to replace HCFC-141b, there are currently low-boiling hydrocarbons such as n-pentane or cyclopentane, HFC-245fa to HFC-365mfc which are low-boiling halogenated hydrocarbon compounds not containing chlorine, and global warming potential HFE-254pc with a smaller is studied.
[0004]
[Problems to be solved by the invention]
However, low boiling point hydrocarbons such as n-pentane or cyclopentane are highly flammable compounds, a process for producing a polyol composition containing these compounds as a foaming agent, and a rigid polyurethane foam using the polyol composition Strict fire prevention measures are required in the manufacturing process and waste processing process of pulverizing the waste of the rigid polyurethane foam, and it is necessary to update the equipment in the conventional rigid polyurethane foam manufacturing factory, etc. There is a problem that the equipment cost becomes very high. In addition, the flame retardancy of rigid polyurethane foam using pentane as a foaming agent is inferior to that using conventional HCFC-141b as a foaming agent, and it can be used as it is for building materials that require flame retardancy. It is difficult to do.
[0005]
Although HFC-365mfc has not been confirmed to be flammable according to the standards of the Japanese Fire Service Act, the flash point is confirmed at -27 ° C. in the German standard, and the polyol composition containing this as a blowing agent is: Depending on the composition, there is an example that falls under the dangerous goods class 4 and 1 petroleum defined in the Fire Service Law, and the problem is that the polyol composition using HCFC-141b as a blowing agent and handling and storage equivalent to dangerous goods cannot be performed. Have HFC-365mfc also has a problem that the compatibility with the polyol compound which is the main component of the polyol composition is poor.
[0006]
HFE-254pc is a foaming agent at the development stage and has not been studied sufficiently, but as a dangerous substance, it is close to HFC-365mfc and has the same problem.
[0007]
On the other hand, HFC-245fa is a foaming agent that has no danger of ignition and does not need to be handled as a hazardous material, but has a boiling point of 15 ° C. and a high vapor pressure at room temperature. Therefore, when HFC-245fa is used as a foaming agent, a container such as a drum can or a petroleum can containing the polyol composition swells particularly in summer, and the polyol composition undiluted solution blows out by evaporation of the foaming agent at the time of opening, A foaming agent volatilizes, the content reduces, and the problem that the foam of a predetermined density cannot be obtained arises.
[0008]
The objective of this invention is providing the manufacturing method of the polyol composition for rigid polyurethane foams which suppressed the vapor pressure, and the rigid polyurethane foam, using HFC-245fa as a foaming agent.
[0009]
[Means for Solving the Problems]
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 is mixed with an isocyanate component containing a polyisocyanate compound to be foam-cured to form a rigid polyurethane foam. A polyol composition for rigid polyurethane foam,
The first foaming agent as the main component of the foaming agent is 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 1,1,1,3,3-penta as the second foaming agent. It contains fluorobutane (HFC-365mfc), and contains diethylene glycol monoethyl ether acetate as a vapor pressure reducing agent. (HFC-245fa + HFC-365mfc) / diethylene glycol monoethyl ether acetate = 93/7 to 60/40 (weight ratio) And
The polyol compound includes a polyol compound containing a tertiary amino group, and nitrogen based on the tertiary amino group is 0.5 to 9% by weight in the polyol compound.
[0011]
When the HFC-245fa / CAc weight ratio exceeds 95/5, the effect of reducing the vapor pressure is not sufficiently exhibited, and the vapor pressure of the polyol composition for rigid polyurethane foam increases. Further, when the HFC-245fa / CAc weight ratio is less than 60/40, the CAc ratio becomes too high, and the physical properties of the foam may be deteriorated.
[0012]
In addition, since the polyol compound containing a tertiary amino group is more compatible with HFC-245fa than other polyol compounds, the combined use of a tertiary amino group-containing polyol compound further improves the HFC- A vapor pressure lowering effect of 245fa is obtained. The combined use of a tertiary amino group-containing polyol compound further increases the reaction activity of the polyol composition, increases the uniformity of bubbles in the resulting rigid polyurethane foam, and increases the adhesive strength with the face material. Can also be obtained. When the nitrogen based on the tertiary amino group is less than 0.5 in the polyol compound, the effect of lowering the vapor pressure, the uniformity of the bubbles, and the adhesive strength with the face material are not sufficiently improved. The dimensional stability of the rigid polyurethane foam is reduced.
[0013]
The nitrogen based on the tertiary amino group is more preferably 1.5 to 8.5% by weight in the polyol compound.
[0015]
HFC-365mfc is a compound with good compatibility with HFC-245fa and a higher boiling point (40.2 ° C.) than HFC-245fa. By using HFC-365mfc together, foaming characteristics and rigid polyurethane foam obtained The vapor pressure of HFC-245fa can be further suppressed while maintaining the physical properties, heat insulation properties, and the like.
[0016]
When the weight ratio of HFC-245fa / HFC-365mfc is less than 60/40, the content of HFC-365mfc is increased, resulting in a decrease in flash point, and the polyol composition is a flammable substance among the 4th hazardous materials. There are cases where it is certified as a high-quality oil. Further, when the weight ratio of (HFC-245fa + HFC-365mfc) / CAc exceeds 95/5, the ratio of CAc becomes too small to sufficiently exert the effect of addition, and when the weight ratio is less than 60/40, In some cases, the ratio becomes too high and the physical properties of the foam deteriorate.
[0018]
Another polyol composition for rigid polyurethane foams of the present invention contains at least a polyol compound, a foaming agent, a foam stabilizer, and a catalyst, and is mixed with an isocyanate component containing a polyisocyanate compound to be foam-cured to form a rigid polyurethane foam. A polyol composition for rigid polyurethane foam to be formed,
The primary foaming agent of the foaming agent is 1,1,1,3,3-pentafluoropropane (HFC-245fa), and tetrafluoromethoxyethane (HFE-254pc) is used as the third foaming agent. And HFC-245fa / HFE-254pc ≧ 50/50 , containing diethylene glycol monoethyl ether acetate as a vapor pressure reducing agent , (HFC-245fa + HFE-254pc) / diethylene glycol monoethyl ether acetate = 93 / 7-60 / 40 (weight ratio) ,
The polyol compound includes a polyol compound containing a tertiary amino group, and nitrogen based on the tertiary amino group is 0.5 to 9% by weight in the polyol compound.
[0019]
Good compatibility with HFC-245fa, and combined use of HFE-254pc, which has a higher boiling point than HFC-245fa, further maintains HFC-, while maintaining foaming properties, physical properties of the resulting rigid polyurethane foam, heat insulation properties, etc. The vapor pressure of 245fa can be suppressed and is effective in preventing global warming.
[0020]
When the weight ratio of HFC-245fa / HFE-254pc is less than 50/50, the content of HFE-254pc increases, resulting in a decrease in flash point, and the polyol composition is a flammable substance among the 4th hazardous materials. May be recognized as high-grade oil. Further, when the weight ratio of (HFC-245fa + HFE-254pc) / CAc exceeds 95/5, the ratio of CAc becomes too small to sufficiently exert the effect of addition, and when the weight ratio is less than 60/40, In some cases, the ratio becomes too high and the physical properties of the foam deteriorate.
[0022]
CAc may be premixed with HFC-245fa and HFC-365mfc or HFE-254pc and mixed with the polyol compound as a blowing agent composition, and the individual components may be added and mixed separately. If it coexists in a polyol composition, the addition order and form will not ask | require.
[0023]
By using CAc as one component of the polyol composition, it has been found that the adhesive strength between the rigid polyurethane foam and the face material is also improved. The reason for this is not clear, but when HFC-245fa alone or HFC-245fa and HFC-365mfc or HFE-254pc is used as the blowing agent, the compatibility between the blowing agent and the polyol component is not good. When the foaming stock composition in which the component and the polyol composition are mixed comes into contact with the face material or the like, the temperature at the contact surface decreases, and HFC-245fa blooms before the curing reaction starts, after which the foaming reaction occurs. It is estimated that the foam cell near the interface is roughened, and as a result, the adhesion with the face material is lowered. CAc is considered to improve the adhesive strength between the hard polyurethane foam and the face material because it has an effect of improving the compatibility between HFC-245fa and the polyol compound.
[0024]
Another aspect of the present invention is a method for producing a rigid polyurethane foam in which an isocyanate component and a polyol composition are mixed and foamed and cured to obtain a rigid polyurethane foam, wherein the rigid composition according to claim 1 or 2 is used as the polyol composition. A polyol composition for polyurethane foam is used.
[0025]
By this manufacturing method, it is possible to manufacture a rigid polyurethane foam by using the same manufacturing apparatus as that used when HCFC-141b is used as a foaming agent without significant modification for fire prevention measures.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
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 the foaming agent. The polyol compound contains a tertiary amino group-containing polyol compound.
[0027]
As the polyol compound, known polyol compounds for rigid polyurethane foam can be used without limitation. Examples of such polyol compounds include tertiary amino group-containing polyol compounds, aliphatic polyols, and aromatic polyols.
[0028]
The tertiary amino group-containing polyol compound is an alkylene oxide using a primary or secondary amine as an initiator, specifically, propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran or the like. It is a polyfunctional polyol compound obtained by ring-opening addition polymerization of one or more kinds.
[0029]
Examples of the primary or secondary amine initiator that is an initiator of the tertiary amino group-containing polyol compound include aliphatic primary and secondary monoamines such as ammonia, methylamine, and ethylamine, ethylenediamine, and hexamethylene. Aliphatic primary to secondary polyamines such as diamine, N, N′-dimethylethylenediamine, aromatic primary to secondary mono to aniline, diphenylamine, toluenediamine, diphenylmethanediamine, N-methylaniline, etc. Illustrative are alkanolamines such as polyamines, monoethanolamine and diethanolamine.
[0030]
The aliphatic polyol is an aliphatic or alicyclic polyfunctional active hydrogen compound as a polyol initiator, alkylene oxide, specifically propylene oxide (PO), ethylene oxide (EO), styrene oxide (SO), tetrahydrofuran, etc. It is a polyfunctional oligomer obtained by ring-opening addition polymerization of one or more cyclic ethers.
[0031]
As polyol initiators for aliphatic polyols, glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin And the like, trifunctional alcohols such as pentaerythritol, polyfunctional alcohols such as sorbitol and sucrose, water and the like.
[0032]
Aromatic polyols include polyol compounds obtained by the above-described method of adding an alkylene oxide to a polyfunctional active hydrogen compound having an aromatic ring in the molecule, polyol compounds that are esters of aromatic polycarboxylic acids and polyhydric alcohols, and the like. Illustrated.
[0033]
Specific examples of the polyol compound obtained by adding the above-described alkylene oxide to a polyfunctional active hydrogen compound include compounds obtained by ring-opening addition of at least one of PO, EO, and SO to hydroquinone, bisphenol A, and the like. The
[0034]
Specific examples of the ester of an aromatic polycarboxylic acid and a polyhydric alcohol include ester polyols having a hydroxyl group terminal between terephthalic acid, phthalic acid, isophthalic acid and the like and ethylene glycol, diethylene glycol and the like.
[0035]
The polyol compound preferably has a hydroxyl value of 200 to 600 mgKOH / g. Among these polyol compounds, when a tertiary amino group-containing polyol compound or an aliphatic polyol is used, an effect of reducing the viscosity of the polyol composition can be obtained.
[0036]
As a catalyst used for the polyol composition for rigid polyurethane foams of this invention, the well-known catalyst for rigid polyurethane foams can be used without limitation. Specifically, tertiary amines such as triethylenediamine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine and DBU Metal catalysts such as dibutyltin dilaurate, dibutyltin diacetate and tin octylate are exemplified as the urethanization reaction catalyst.
[0037]
In the rigid polyurethane foam, the isocyanate group forming the polymer may be only a urethane bond, or a urea bond or an isocyanurate bond may be present.
[0038]
It is a preferred embodiment to improve the properties of rigid polyurethane foam obtained using a small amount of water as a blowing agent.
[0039]
The use of a catalyst that forms an isocyanurate bond that contributes to improvement in flame retardancy in the structure of the polyurethane molecule is also preferred, and examples thereof include potassium acetate and potassium octylate. Some of the above-mentioned tertiary amine catalysts also promote the isocyanurate ring formation reaction. A catalyst that promotes the formation of isocyanurate bonds and a catalyst that promotes the formation of urethane bonds may be used in combination.
[0040]
As the foam stabilizer, a known foam stabilizer for rigid polyurethane foam can be used without limitation. As the foam stabilizer, polydimethylsiloxane and a graft copolymer or block copolymer of polydimethylsiloxane and polyalkylene oxide are usually used. As the polyalkylene oxide, polyethylene oxide having a mean molecular weight of 5000 to 8000, polypropylene oxide, random copolymer or block copolymer of ethylene oxide and propylene oxide is used.
[0041]
For the polyol composition for rigid polyurethane foam of the present invention, flame retardants, colorants, antioxidants, scorch inhibitors and the like well known to those skilled in the art can be used.
[0042]
Examples of the flame retardant include metal compounds such as halogen-containing compounds, organophosphates, antimony trioxide, and aluminum hydroxide.
[0043]
When these flame retardants are added, for example, excessive amounts of organophosphates, the physical properties of the resulting rigid polyurethane foam may deteriorate, and when excessive addition of metal compound powders such as antimony trioxide is added, foam foaming behavior The amount of addition is limited to a range that does not cause such a problem.
[0044]
In the rigid polyurethane foam of the present invention, it is preferable to use a plasticizer as necessary. Such a plasticizer is also preferably one that contributes to flame retardancy. Halogenated alkyl esters of phosphoric acid, alkyl phosphate esters, aryl phosphate esters, phosphonate esters, and the like can be used. 2-chloroethyl) phosphate (CLP, manufactured by Daihachi Chemical), tris (β-chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical), tributoxyethyl phosphate (TBXP, manufactured by Daihachi Chemical), tributyl phosphate, triethyl phosphate, Examples include cresyl phenyl phosphate and dimethyl methyl phosphonate, and one or more of these can be used. The addition amount of the plasticizer is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polyol component. If this range is exceeded, problems such as insufficient plasticizing effect and a decrease in physical properties of the foam may occur.
[0045]
The polyisocyanate compound that forms a rigid polyurethane foam by mixing and reacting with the polyol composition is easy to handle, fast in reaction, excellent in the physical properties of the resulting rigid polyurethane foam, and low in cost. For this reason, liquid MDI is used. As liquid MDI, crude (crude) MDI (c-MDI) (44V-10, 44V-20, etc. (manufactured by Sumitomo Bayer Urethane Co., Ltd.)), uretonimine-containing MDI (Millionate MTL; manufactured by Nippon Polyurethane Industry Co., Ltd.), etc. are used. . Among these polyisocyanate compounds, the use of crude (crude) MDI is particularly preferable in that the physical properties such as mechanical strength of the formed rigid polyurethane foam are excellent and the cost is low.
[0046]
In addition to liquid MDI, other polyisocyanate compounds may be used in combination. As such polyisocyanate compounds, di- or polyisocyanate compounds well known in the technical field of polyurethane can be used without limitation.
[0047]
The polyol composition for rigid polyurethane foams of the present invention can be used for producing continuously produced rigid polyurethane foams such as slabstock foams and sandwich panels, rigid polyurethane foam sandwich panels to be injection-molded, and spray foams.
[0048]
【Example】
Examples and the like specifically showing the configuration and effects of the present invention will be described below.
The constituent materials of the polyol composition are shown in Table 1.
[0049]
[Table 1]

The composition of the polyol composition and the addition amount (parts by weight) of the blowing agent composition are shown in Tables 2 to 4. The amount of the foaming agent composition added was adjusted so that the density of the rigid polyurethane foam at the time of free foaming was 25 kg / m ³ . The foaming agent composition is obtained by adding carbitol acetate (CAc), which is an additive for reducing the vapor pressure of the foaming agent, to HFC-245fa, HFC-365mfc, and HFE-254pc, which are foaming agents.
[0050]
The rigid polyurethane foam was produced by a conventional method. That is, in the composition shown in Table 1, a polyol composition was prepared by mixing and stirring the component excluding the isocyanate component and the foaming agent composition, adjusting the temperature to 20 ° C, and then adjusting the temperature to 20 ° C. Were mixed and stirred at a predetermined ratio, and foamed and cured to obtain a rigid polyurethane foam.
[0051]
<Evaluation>
(Vapor pressure evaluation)
Prepare 50g of a 100ml SUS container with the polyol composition adjusted at the specified mixing ratio, freeze and deaerate the container completely with liquid nitrogen, and leave it in a constant temperature bath at 40 ° C. The pressure P was measured. The decompression rate was calculated by the following formula. P ₀ is the vapor pressure of the foaming agent only 245fa (Comparative Example 2). Decompression rate (%) = 100 (P ₀ −P) / P ₀
(Compressive strength)
A 50 mm × 50 mm × 50 mm cube was cut out from the foam that was freely foamed in a container, and measured according to JIS A 9511 (foamed plastic heat insulating material).
(Dimensional stability)
A 100 mm × 100 mm × 100 mm cube was cut out from the foam that was freely foamed in a container, and allowed to stand in an atmosphere of −30 ° C. for 24 hours, and the amount of dimensional change was measured. The evaluation result was expressed as a dimensional change rate (Δ%).
(Adhesiveness)
Create a foam that is foamed freely on top of the kraft paper surface, and make a notch with a width of 5cm from the back side of the surface material that is bonded to the foam. gf / 5 cm).
(Bubble stability)
The foam foamed freely in the container was visually observed. The evaluation results were displayed according to the following criteria.
(Circle): A cell is uniform and fine, and is equivalent to a HCFC-141b foamed product.
(Triangle | delta): There exists cell roughening and it is inferior to HCFC-141b foaming goods a little.
X: Cell roughening is severe and foaming is poor.
[0052]
<Evaluation results>
The evaluation results are shown in the lower part of Tables 2 to 4. The blowing agent composition shown in Table 2 is a composition in which HFC-245fa and CAc which is a vapor pressure reducing agent are mixed in advance, and the blowing agent compositions shown in Table 3 are HFC-245fa and HFC-365mfc. And the three components of CAc, the blowing agent composition shown in Table 4, is a composition composed of three components in which HFC-245fa, HFE-254pc and CAc are mixed in advance. From the results of these tables, by making the foaming agent composition of the present invention, the vapor pressure of the foaming agent is greatly reduced, and the same handling as the polyol composition using the conventional HCFC-141b is possible, Adhesion with the face material and bubble stability were also improved. However, the following knowledge was acquired about the comparative example. Regarding the dimensional stability, the foam using HCFC-141b as a foaming agent was −17.0%, and this was judged based on this.
a) When HFC-245fa / CAc is 55/45, too much CAc results in lower dimensional stability than foam using HCFC-141b as a blowing agent (Comparative Example 3).
[0053]
b) When HFC-245fa / HFC-365mfc is 50/50 (Comparative Example 4), when HFC-245fa / HFE-254pc is 40/60 (Comparative Example 7), addition of HFC-365mfc or HFE-254pc As a result of the amount being too high, the dimensional stability is lower than the foam using HCFC-141b as the blowing agent.
[0054]
c) Even when the foaming agent composition 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 wt%, the bubble stability is reduced, and the face material and The adhesive strength also decreases (Comparative Examples 5 and 8). When the nitrogen concentration based on the tertiary amino group exceeds 9 wt%, the dimensional stability of the obtained rigid polyurethane foam is lowered (Comparative Examples 6 and 9).
[0055]
[Table 2]

[Table 3]

[Table 4]

Claims (3)

A polyol composition for a rigid polyurethane foam comprising at least a polyol compound, a foaming agent, a foam stabilizer, a catalyst, mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam,
The first foaming agent as the main component of the foaming agent is 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 1,1,1,3,3-penta as the second foaming agent. Containing fluorobutane (HFC-365mfc), HFC-245fa / HFC-365mfc ≧ 60/40 , containing diethylene glycol monoethyl ether acetate as a vapor pressure reducing agent, (HFC-245fa + HFC-365mfc) / diethylene glycol monoacetate Ethyl ether = 93/7 to 60/40 (weight ratio) ,
The polyol compound includes a polyol compound containing a tertiary amino group, and nitrogen based on the tertiary amino group is 0.5 to 9% by weight in the polyol compound. Composition. A polyol composition for a rigid polyurethane foam comprising at least a polyol compound, a foaming agent, a foam stabilizer, a catalyst, mixed with an isocyanate component containing a polyisocyanate compound and foam-cured to form a rigid polyurethane foam,
The primary foaming agent of the foaming agent is 1,1,1,3,3-pentafluoropropane (HFC-245fa), and tetrafluoromethoxyethane (HFE-254pc) is used as the third foaming agent. And HFC-245fa / HFE-254pc ≧ 50/50 , containing diethylene glycol monoethyl ether acetate as a vapor pressure reducing agent , (HFC-245fa + HFE-254pc) / diethylene glycol monoethyl ether acetate = 93 / 7-60 / 40 (weight ratio) ,
The polyol compound includes a polyol compound containing a tertiary amino group, and nitrogen based on the tertiary amino group is 0.5 to 9% by weight in the polyol compound. Composition. It is a manufacturing method of the rigid polyurethane foam which mixes an isocyanate component and a polyol composition, and makes it foam and harden | cure to make a rigid polyurethane foam, Comprising: The polyol composition for rigid polyurethane foams of Claim 1 or 2 as a polyol composition A method for producing a rigid polyurethane foam, characterized in that