JP5314167B2 - Rigid polyurethane foam panel and manufacturing method thereof - Google Patents

Description

  The present invention uses a foaming stock solution composition containing a polyol compound, a polyol composition containing water as a foaming agent, and a polyisocyanate component as raw materials, and a rigid polyurethane foam panel having low density and excellent heat insulation performance, and It relates to the manufacturing method.

  Conventionally, glass wool has been widely used as a heat insulating material for buildings such as detached houses. Glass wool is not necessarily sufficient in its heat insulation performance, but it is considered that it is a reason why it is widely used because it is inexpensive. On the other hand, hard polyurethane foam panels are superior in heat insulation performance to glass wool, but are not as widely used as glass wool because of their high price.

As a method for reducing the price of the rigid polyurethane foam panel, it is conceivable to reduce the density while maintaining the heat insulation performance of the foam panel. In the following Patent Document 1, a polyol composition consisting of a polyoxyalkylene polyether polyol having a number average molecular weight of 2000 to 9000 and a polyoxyalkylene polyether polyol having a number average molecular weight of 250 to 750 is used as a raw material. It describes that a low density rigid polyurethane foam having a core density of 2 kg / m ³ or more and 20 kg / m ³ or less is produced. However, when the polyol composition described in this document is used as a raw material, there is a limit to reducing the density of the foam in consideration of cell roughness (foam appearance failure), brittleness (fogging of the foam), and the like. Moreover, since the rigid polyurethane foam described in this literature assumes the spraying use, it is important that it is a low restoration rate, and it is inferior to the softness | flexibility of foam.

In the following Patent Document 2, a polyether polyol having an average functional group number of 2.5 to 4 and a hydroxyl value of 200 to 300 mgKOH / g, a polyether polyol having an average functional group number of 4 to 6 and a hydroxyl value of 400 to 900 mgKOH / g, and an average functionality Low density whose core density is 5 kg / m ³ or more and 14 kg / m ³ or less by continuous slab foaming using a polyether polyol having a group number of 2.5 to 3.5 and a hydroxyl value of 20 to 60 mg KOH / g and a polyol composition as a raw material. The point of producing a density rigid polyurethane foam is described. However, even in the rigid polyurethane foam described in this document, there is a limit to reducing the density of the foam in consideration of cell roughness (foam appearance failure), brittleness (foaming of the foam), and the like.

  In the following Patent Document 3, (a) a polyoxyalkylene polyol having a functional group number of 2 to 3.5, a hydroxyl value of 28 to 90 mgKOH / g and a polyoxyethylene unit content of 5% by weight or less, (b) a functional group number of 3 to 3 6 and a polyoxyalkylene polyol having a hydroxyl value of 150 to 500 mgKOH / g, and (c) a mixture of a polyol having 2 to 3 functional groups and a hydroxyl value of 450 to 840 mgKOH / g, and 100 parts by weight of the mixture of the above polyols And a process for producing an open-celled rigid polyurethane foam using 6 to 12 parts by weight of water as a blowing agent. However, in such a manufacturing method, the lower limit of the foam density is determined from the viewpoint of foam strength, and there is a limit to reducing the density of the foam.

  By the way, when reducing the density of rigid polyurethane foam panels, it is important to reduce the closed cell ratio of the foam cells and increase the ratio of open cells. However, the invention described in the above-mentioned patent document merely focuses on the composition of the polyol composition. For example, in the shape of a low density rigid polyurethane foam panel, the manufacturing process, etc., the heat insulation of the foam is improved. It was not devised.

JP 2002-293868 A Japanese Patent No. 4079254 Japanese Patent Laid-Open No. 06-25375

  The present invention has been made in view of the above circumstances, and its object is to provide a rigid polyurethane foam panel having a low density and excellent heat insulation performance and useful as a heat insulating material for buildings such as detached houses and the like. It is in providing the manufacturing method.

  In order to solve the above-mentioned problems, the present inventors have eagerly studied the blending of the polyol composition as a raw material, and set the thickness direction of the rigid polyurethane foam panel and the foaming direction of the cells substantially perpendicularly, thereby insulating the heat insulating material. As a result, it was found that the heat insulation performance can be improved most efficiently. The present invention has been accomplished based on the above findings, and is configured as follows.

  The above object can be achieved by the present invention as described below. That is, the rigid polyurethane foam panel according to the present invention is a rigid polyurethane foam panel obtained by mixing and reacting a polyol composition and a polyol composition containing water as a foaming agent and a polyisocyanate component. The compound has an average functional group number of 2 to 4, a weight average molecular weight of 3000 to 8000, a polyether polyol (A) which is a polymer of alkylene oxide, and a short glycol (B) having a molecular weight of less than 250, The water content is 20 to 100 parts by weight with respect to 100 parts by weight of the polyol compound, and the thickness direction of the rigid polyurethane foam panel and the foaming direction of the cells in the foam are substantially perpendicular. And

  The polyol composition contains 20 to 100 parts by weight of water as a blowing agent. For this reason, when such a polyol composition is used as a raw material, a low-density rigid polyurethane foam panel can be produced.

  By the way, when only a high molecular weight polyether polyol is contained as a polyol compound and the blending amount of water in the polyol composition is increased, the resin strength becomes insufficient at the foaming stage of the foam, and the foaming gas in the foam Many omissions occur and foam shrinkage tends to occur. As a result, the density of the foam tends to be insufficient. However, since the polyol composition contains the high-molecular-weight polyether polyol (A) and the short glycol (B) having a molecular weight of less than 250, the speed of thickening (resinization speed) is high at the early stage of foam foaming. Become. Thereby, the restoration rate of the foam is increased due to the high molecular weight polyether polyol (A), and the resin strength is increased from the early stage of foam foaming due to the low molecular weight short glycol (B). As a result, a rigid polyurethane foam panel having low density and excellent flexibility can be produced.

  Further, since the polyol composition contains the high molecular weight polyether polyol (A) and the low molecular weight short glycol (B), the cell diameter of the foam is reduced even if the density of the foam is reduced. As a result, foam cell roughness (foam appearance defect) can be prevented, and foam brittleness can be suppressed and brittleness can be reduced.

  As described above, the rigid polyurethane foam panel according to the present invention has a low density, the cells in the foam are individually substantially elliptical, the plurality of cells communicate with each other, the open cell ratio is high, and the foaming direction is constant. Have In such a rigid polyurethane foam panel, since the thickness direction and the foaming direction of the cells in the foam are substantially perpendicular, the heat transfer in the thickness direction can be suppressed. Therefore, when a hard polyurethane foam panel is disposed in a building such as a detached house, the heat insulation performance in the thickness direction is particularly enhanced.

  The rigid polyurethane foam panel preferably contains 10 to 80 parts by weight of the polyether polyol (A) and 10 to 60 parts by weight of the short glycol (B) in 100 parts by weight of the polyol compound. According to such a configuration, it is possible to increase the foam recovery rate and reduce the foam cell diameter while increasing the resin strength of the foam. As a result, the brittleness and flexibility can be further improved in a balanced manner while reducing the density of the rigid polyurethane foam panel.

  In the rigid polyurethane foam panel, the polyol compound may further contain an average functional group number of 2 to 4, a weight average molecular weight of 3000 to 5000, and a polyether polyol (C) that is a polymer of propylene oxide. preferable. When the high molecular weight polyether polyol (C), which is a propylene oxide polymer, is contained as the polyol compound, the cell membrane of the foam is broken at the end of the foaming stage of the foam, and an open-celled rigid polyurethane foam panel tends to be formed. As a result, the density of the foam can be reduced more reliably while suppressing shrinkage of the foam.

  The manufacturing method of the rigid polyurethane foam panel which concerns on this invention manufactures the rigid polyurethane foam panel obtained from the foaming stock solution composition containing the polyol composition containing the polyol compound and the water which is a foaming agent, and a polyisocyanate component as a raw material. A method having a longitudinal direction, a width direction, and a thickness direction with respect to a mold having a side surface extending in the longitudinal direction and the thickness direction as a bottom surface, an injection step of injecting the foamed stock solution composition; A reaction step of reacting the foamed stock solution composition, wherein the polyol compound has an average functional group number of 2 to 4 and a weight average molecular weight of 3000 to 8000, and is a polyether polyol (A ) And a short glycol (B) having a molecular weight of less than 250. With respect to the polyol compound 100 parts by weight, characterized by containing the water 20 to 100 parts by weight. According to such a manufacturing method, the rigid polyurethane foam panel excellent in the heat insulation performance in the thickness direction can be efficiently manufactured because the thickness direction of the rigid polyurethane foam panel and the foaming direction of the cells in the foam are substantially perpendicular. .

  In the method for producing a rigid polyurethane foam panel, the polyether polyol (A) is contained in 10 to 80 parts by weight and the short glycol (B) is contained in 10 to 60 parts by weight in 100 parts by weight of the polyol compound. preferable.

  In the method for producing a rigid polyurethane foam panel, the polyol compound further has an average number of functional groups of 2 to 4, a weight average molecular weight of 3000 to 5000, and a polyether polyol (C) which is a propylene oxide polymer. It is preferable to contain.

It is a figure which shows an example of the manufacturing method of the rigid polyurethane foam panel of this invention . It is a figure which shows an example of the manufacturing method of the conventional rigid polyurethane foam panel.

  The polyol composition used as the raw material of the rigid polyurethane foam panel according to the present invention is a polyether polyol having an average functional group number of 2 to 4 and a weight average molecular weight of 3000 to 8000 as a polyol compound and a polymer of alkylene oxide. (A) and short glycol (B) whose molecular weight is less than 250 are contained.

  The polyether polyol (A) is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of alkylene oxide to an initiator having 2 to 4 active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexane. Diols, neopentyl glycol, cyclohexylene glycol, glycols such as cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, aliphatic amines (eg, ethylenediamine, propylenediamine, butylenediamine) , Alkylene diamines such as hexamethylene diamine and neopentyl diamine, alkanol amines such as monoethanolamine and diethanolamine), aromatic amines (for example, 2, -Toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, etc.), each of which is used alone. However, it is preferable to use an aliphatic alcohol as the initiator, more preferably a triol, more preferably glycerin, and the polyether polyol (A) may be used in combination. The average functional group number is 2 to 4, more preferably 2.5 to 3.5, and the polyether polyol (A) more preferably has a weight average molecular weight of 3000 to 5000.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and cyclohexene oxide. Among these, it is preferable to use ethylene oxide and propylene oxide in combination to cause ring-opening addition polymerization to the initiator. At that time, the ratio of ethylene oxide ((ethylene oxide) / (ethylene oxide + propylene oxide)) is preferably 5% to 30%.

  The hydroxyl value of the polyether polyol (A) is preferably 20 to 100 mgKOH / g, and more preferably 30 to 60 mgKOH / g. When the hydroxyl value is less than 20 mg KOH / g, the viscosity ratio of the polyol composition to the polyisocyanate component increases, leading to poor stirring during mixing. On the other hand, when it exceeds 100 mgKOH / g, it becomes difficult to impart appropriate toughness to the obtained polyurethane foam. The hydroxyl value is a value measured according to JIS K1557-1: 2007.

Short glycol (B) having a molecular weight of less than 250 includes, for example, ethylene glycol (molecular weight 62), propylene glycol (molecular weight 76), diethylene glycol (molecular weight 106), dipropylene glycol (molecular weight 134), 1,4-butanediol (molecular weight). 90), 1,3-butane diol (molecular weight 90), 1,6-hexanediol (molecular weight 118), preparative polypropylene glycol (molecular weight 192), and the like. Among these, in order to increase the resin strength of the foam more reliably, diethylene glycol, dipropylene glycol is preferred, diethylene glycol is particularly preferred. The molecular weight of the short glycol (B) is preferably 62 to 200 mgKOH / g, and more preferably 90 to 150 mgKOH / g.

  In the polyol composition for rigid polyurethane foam according to the present invention, as the polyol compound, polyether polyol (C) which has an average number of functional groups of 2 to 4 and a weight average molecular weight of 3000 to 5000 and is a propylene oxide polymer. It is preferable to contain. The polyether polyol (C) is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of propylene oxide alone to an initiator having 2 to 4 active hydrogen atoms. Examples of the initiator include the aliphatic polyhydric alcohols, aliphatic amines, and aromatic amines described above, and are not particularly limited. As the initiator, glycerol is particularly preferable.

  In the polyol composition used as a raw material in the present invention, in order to produce a rigid polyurethane foam panel having a low density and excellent heat insulating performance, 10 to 80 weight parts of polyether polyol (A) in 100 weight parts of the polyol compound. It is preferable to contain 10 to 60 parts by weight of the short glycol (B), 15 to 70 parts by weight of the polyether polyol (A), and 10 to 50 parts by weight of the short glycol (B). Is more preferable. When the polyether polyol (C) is contained, the polyether polyol (A) is contained in an amount of 10 to 30 parts by weight, the short glycol (B) is contained in an amount of 10 to 60 parts by weight, and the polyether polyol (C) 30. ~ 70 parts by weight, preferably 15 to 25 parts by weight of polyether polyol (A), 10 to 50 parts by weight of short glycol (B), and 40 to 60 parts by weight of polyether polyol (C) It is more preferable to contain part.

  Water is added to the polyol composition as a foaming agent. The foaming agent is preferably water alone, and the blending amount thereof is 20 to 100 parts by weight with respect to 100 parts by weight of the polyol compound, more preferably 30 to 90 parts by weight, and further preferably 40 to 80 parts by weight. Part. Thus, the density of a polyurethane foam panel can be reduced by blending a large amount of water.

The core density of the rigid polyurethane foam panel according to the present invention is preferably 20 kg / m ³ or less, more preferably 15 kg / m ³ or less, and further preferably 12 kg / m ³ or less. Such foam density can be set within the above range by adjusting the amount of water as a foaming agent to 20 to 100 parts by weight (vs. 100 parts by weight of polyol compound), for example. Here, the foam density is a value measured according to JIS K7222.

  Usually, a flame retardant, a catalyst, and a foam stabilizer are further blended in the polyol composition. Moreover, you may further mix | blend various additives mix | blended with the polyol composition for rigid polyurethane foams, such as a coloring agent and antioxidant.

  Examples of the flame retardant include metal compounds such as organophosphates, halogen-containing compounds, and aluminum hydroxide. Particularly, organophosphates are preferable because they have an effect of reducing the viscosity of the polyol composition. Examples of the organic phosphate ester include halogenated alkyl ester of phosphoric acid, alkyl phosphate ester, aryl phosphate ester, and phosphonate ester. Specific examples include tris (chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical), tributoxyethyl phosphate (TBEP), tributyl phosphate, triethyl phosphate, trimethyl phosphate, cresyl phenyl phosphate, and the like. It is preferable that the compounding quantity of a flame retardant is 10-50 weight part with respect to 100 weight part of polyol compounds, More preferably, it is 15-40 weight part. In particular, when the flame retardant is contained in an amount of 20 parts by weight or more with respect to 100 parts by weight of the polyol compound in addition to the polyether polyol (A) and the short glycol (B) in the polyol composition, the brittleness of the foam is prevented. This is preferable.

  Although it will not specifically limit if it is a catalyst which accelerates | stimulates a urethanation reaction, Preferably it is using the reactive amine catalyst which can react with the isocyanate group of a polyisocyanate component. Examples of such reactive amine catalysts include N, N-dimethylethanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanolamine, N, N, N ′, N ′. -Tetramethyl-2-hydroxypropylenediamine, N-hydroxyethylmorpholine, N-methyl-N-hydroxyethylpiperazine, N, N-dimethylpropylenediamine and the like.

  In addition, a normal tertiary amine catalyst can also be used, and as such a tertiary amine catalyst, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′— Examples include tetramethylhexamethylenediamine, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine, diazabicycloundecene, N, N-dimethylcyclohexylamine, triethylenediamine, and N-methylmorpholine.

  The compounding amount of the catalyst is preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight with respect to 100 parts by weight of the polyol compound.

  As the foam stabilizer, among the known foam stabilizers for rigid polyurethane foam, for example, a graft copolymer of polyoxyalkylene glycol and polydimethylsiloxane, which is a polymer of ethylene oxide or propylene oxide, can be mentioned, Silicone foam stabilizers having an oxyethylene group content of 70 to 100 mol% in polyoxyalkylene are preferably used. Specifically, SH-193, SF-2937F, SF-2938F (manufactured by Toray Dow Corning Silicone) , B-8465, B-8467, B-8441 (Evonik Degussa Japan), L-6900 (Momentive) and the like. The blending amount of the foam stabilizer is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polyol compound.

  Various polyisocyanate compounds such as aromatic, alicyclic and aliphatic polyisocyanates having two or more isocyanate groups are used as the polyisocyanate component which is mixed and reacted with the polyol composition to form a rigid polyurethane foam panel. be able to. Preferably, liquid diphenylmethane diisocyanate (MDI) is used because it is easy to handle, fast in reaction, excellent in physical properties of the resulting polyurethane foam, and low in cost. As liquid MDI, Crude MDI (c-MDI) (44V-10, 44V-20, etc. (manufactured by Sumika Bayer Urethane Co., Ltd.), Millionate MR-200 (Nippon Polyurethane Industry)), Murenate-containing MDI (Millionate MTL; Nippon Polyurethane) Industrial)). In addition to liquid MDI, other polyisocyanate compounds may be used in combination. As the polyisocyanate compound to be used in combination, a polyisocyanate compound known in the technical field of polyurethane can be used without limitation.

  In the rigid polyurethane foam panel according to the present invention, the thickness direction of the rigid polyurethane foam panel and the foaming direction of the cells in the foam are substantially perpendicular, and the heat insulation performance in the thickness direction is excellent. In the present invention, “substantially vertical” specifically means 90 ° ± 15 °, and particularly 90 ° ± 10 °. The “foaming direction of the cells in the foam” means the major axis direction when each cell shape is regarded as an ellipse. In particular, the center part in the width direction (from the width direction center to both sides, the width direction length). The direction when measured in a portion of about 10%).

The rigid polyurethane foam panel according to the present invention has the following production method:
A method for producing a rigid polyurethane foam panel obtained from a raw material foam composition containing a polyol composition, a polyol composition containing water as a foaming agent, and a polyisocyanate component, the longitudinal direction, the width direction and the thickness direction. An injection step of injecting the foamed stock solution composition with a side surface extending in the longitudinal direction and the thickness direction as a bottom surface, and a reaction step of reacting the foamed stock solution composition after the injection step. The polyol compound has an average functional group number of 2 to 4, a weight average molecular weight of 3000 to 8000, a polyether polyol (A) which is a polymer of alkylene oxide, and a short glycol (B And 20 parts of the water with respect to 100 parts by weight of the polyol compound. Method for producing a rigid polyurethane foam panels containing 100 parts by weight, can be prepared by.

  In the conventional method for producing a rigid polyurethane foam panel, as shown in FIG. 2, the polyol composition and the polyisocyanate component are mixed from the mixing head 1 onto the surface material 3 while the surface material 3 is unwound and supplied from the raw fabric. The foaming stock solution composition to be contained is injected (injection step). After the injection step, the foamed stock solution composition is reacted while the foamed stock solution composition is covered with another surface material (back surface material) 4 (reaction step). As a result, a rigid polyurethane foam panel having a foaming direction parallel to the thickness direction is obtained. In particular, in a low-density rigid polyurethane foam panel, each cell has open cells, so that heat transfer is large in the foaming direction and the heat insulation performance tends to decrease. For this reason, in the manufacturing method of the conventional rigid polyurethane foam panel, there existed a tendency for the heat insulation performance in the thickness direction to deteriorate.

  On the other hand, in the method for manufacturing a rigid polyurethane foam panel according to the present invention, for example, as shown in FIG. 1, a side surface extending in the longitudinal direction a and the thickness direction c with respect to the mold 2 having the longitudinal direction a, the width direction b, and the thickness direction c. Is the bottom surface X, and a foaming stock solution composition containing a polyol composition and a polyisocyanate component is injected from the mixing head 1 (injection step). After the injection, the foamed stock solution composition reacts and forms a foam while foaming (swelling) in the width direction b (reaction process). As a result, a rigid polyurethane foam panel in which the foaming direction (width direction b) and the thickness direction c are substantially perpendicular is obtained. In the reaction step, the mold may be heated as a whole or locally as necessary.

  In the said manufacturing method, it is preferable that the isocyanate index (NCO Index) at the time of mixing and making a polyol composition and a polyisocyanate component react is 30-100, More preferably, it is 40-70. By setting the isocyanate index within the above range, it is possible to prevent the deterioration of brittleness even when the density of the foam is reduced. Here, the isocyanate index is the percentage equivalent of the isocyanate group of the polyisocyanate component to all active hydrogen groups contained in the polyol composition (calculated using water as a blowing agent as a bifunctional active hydrogen compound). (Equivalent ratio of isocyanate groups to 100 equivalents of active hydrogen groups).

  The rigid polyurethane foam panel obtained by the production method preferably has a closed cell ratio of 15% or less, more preferably 0 to 10%. By increasing the communication rate in this way, it is possible to ensure excellent dimensional stability as a rigid polyurethane foam. Here, the closed cell ratio is a value measured according to ASTM D2856.

  The rigid polyurethane foam panel obtained by the production method preferably has a thermal conductivity λ of λ ≦ 0.04 W / m · K. In this case, even a rigid polyurethane foam having a reduced density can exhibit sufficient heat insulation performance. Here, the thermal conductivity is a value measured in accordance with JIS A1412-2.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

(Preparation of polyol composition)
A polyol composition was prepared with the formulation described in Table 1 below. The details of each component in Table 1 are as follows.

(1) Polyol compound Polyether polyol (A) -1; polyether polyol obtained by addition polymerization of ethylene oxide and propylene oxide using the trade name “Exenol-820” (manufactured by Asahi Glass Co., Ltd.) and glycerol as an initiator. Weight average molecular weight 4900, hydroxyl value (OHV) = 34 mgKOH / g)
Polyether polyol (A) -2; trade name “Excenol-230” (manufactured by Asahi Glass Co., Ltd.), polyether polyol obtained by addition polymerization of ethylene oxide and propylene oxide with glycerol as an initiator (weight average molecular weight 3000, Hydroxyl value (OHV) = 56 mgKOH / g)
Polyether polyol (A) -3; trade name “Exenol-851” (manufactured by Asahi Glass Co., Ltd.), polyether polyol obtained by addition polymerization of ethylene oxide and propylene oxide using glycerol as an initiator (weight average molecular weight 7000, Hydroxyl value (OHV) = 25 mgKOH / g)
Short glycol (B) -1; diethylene glycol (DEG) (molecular weight 106, hydroxyl value (OHV) = 1058 mg KOH / g, manufactured by Nacalai Tesque)
Polyether polyol (C); trade name “T-3000S” (manufactured by Mitsui Chemicals), polyether polyol obtained by addition polymerization of only propylene oxide using glycerol as an initiator (weight average molecular weight 3000, hydroxyl value = 56mgKOH / g)

(2) Flame retardant: Trade name “TMCPP” (Daihachi Chemical Co., Ltd.)
(3) Foam stabilizer Foam stabilizer-1; silicone-based nonionic surfactant, trade name “SF-2938F” (manufactured by Toray Dow Corning Silicone)
(4) Catalyst Catalyst-1; Tertiary amine catalyst, trade name “TOYOCAT-ET” (manufactured by Tosoh Corporation)
Catalyst-2; N, N-dimethylaminoethoxyethanol, trade name “Kao No. 26” (manufactured by Kao Corporation)

(Panel evaluation)
Example 1-2
Using a polyol composition and a polyisocyanate component (c-MDI (“Sumijoule 44V-10” manufactured by Sumika Bayer Urethane Co., Ltd., NCO%: 31%) adjusted with the formulation shown in Table 1), an isocyanate index (NCO Index) 1 is mixed on the bottom surface X of the mold (longitudinal direction a length 1820 mm, width direction b length 400 mm, thickness direction c length 100 mm) shown in FIG. Injected from. Thereafter, the foamed stock solution composition was reacted to produce a rigid polyurethane foam panel having substantially the same shape as the space in the mold, and the thickness direction of the panel and the foaming direction of the cells in the foam being substantially perpendicular (90 °). . The results are shown in Table 1.

Comparative Example 1
Instead of the polyol composition used in Example 1, a rigid polyurethane foam panel was produced in the same manner as in Example 1 except that the polyol composition described in Table 1 was used. The thickness direction of the panel and the foaming direction of the cells in the foam were the same as in Example 1 (substantially vertical (90 °)). The results are shown in Table 1.

Comparative Example 2
Using a polyol composition and a polyisocyanate component (c-MDI (“Sumijoule 44V-10” manufactured by Sumika Bayer Urethane Co., Ltd., NCO%: 31%) adjusted with the formulation shown in Table 1), an isocyanate index (NCO Index) Is injected from the mixing head 1 onto the surface material 3 shown in FIG. Thereafter, the foamed stock solution composition is reacted and cut in the width direction, thereby having the same shape as the rigid polyurethane foam panel of Example 1, and the thickness direction of the panel and the foaming direction of the cells in the foam are substantially parallel ( A rigid polyurethane foam panel that is 0-30 ° was produced. The results are shown in Table 1.

[Weight average molecular weight]
The weight average molecular weight was measured by GPC (gel permeation chromatography) and converted by standard polystyrene.
GPC device: manufactured by Shimadzu Corporation, LC-10A
Column: Polymer Laboratories, (PLgel, 5 μm, 500 Å), (PLgel, 5 μm, 100 及 び), and (PLgel, 5 μm, 50 Å) are connected and used. Flow rate: 1.0 ml / min
Concentration: 1.0 g / l
Injection volume: 40 μl
Column temperature: 40 ° C
Eluent: Tetrahydrofuran

[Form density]
The foam density was determined according to JIS K 7222.

[Thermal conductivity]
Based on JIS A9526 (Blowing rigid urethane foam for thermal insulation of buildings), it conforms to JIS A1412-2 (Measurement method of thermal resistance and thermal conductivity of thermal insulation materials-Part 2: Heat flow meter method) (HFM method). The thermal conductivity in the thickness direction of the panel was measured.

[Form appearance]
The appearance of the core portion of the rigid polyurethane foam after production was visually evaluated. The case where the cell diameter of the foam was fine and the foamed state was particularly good and the brittleness was very small was marked with “◯”, and the foam cell diameter was coarse, the foamed state was poor and the brittleness was marked with “x”.

  From the results in Table 1, it can be seen that the rigid polyurethane foam panel of Example 1-2 has a low density, low brittleness, and excellent heat insulation performance in the thickness direction. On the other hand, the rigid polyurethane foam panel of Comparative Example 1 contracted due to a large amount of foaming gas loss in the foam. Furthermore, cell roughening occurred and brittleness was great. Moreover, the heat insulation performance deteriorated in the thickness direction. Moreover, although the rigid polyurethane foam panel of the comparative example 2 was manufactured by using the same polyol composition as a raw material, the heat insulation performance in the thickness direction was worse than that of the first example.

  Next, a 5 cm square foam sample was produced from the rigid polyurethane foam produced using the polyol composition according to Example 1 as a raw material. It was compressed until it became 90% shape (perpendicular to the foaming direction) (compressed 10%), and its restoration rate was measured. The results were restored to 99.0% shape in the T direction and 98.2% shape in the W direction. Therefore, it can be seen that the rigid polyurethane foam panel according to the present invention has a high restoration rate and excellent flexibility.

Claims (4)

A rigid polyurethane foam panel obtained by mixing and reacting a polyol composition and a polyol composition containing water as a blowing agent and a polyisocyanate component,
The polyol compound has an average functional group number of 2 to 4, a weight average molecular weight of 3000 to 8000, a polyether polyol (A) which is a polymer of alkylene oxide, and a short glycol (B) having a molecular weight of less than 250 And containing
20 to 100 parts by weight of the water is contained with respect to 100 parts by weight of the polyol compound,
A rigid polyurethane foam panel, wherein a thickness direction of the rigid polyurethane foam panel and a foaming direction of cells in the foam are substantially perpendicular.   The rigid polyurethane foam panel according to claim 1, comprising 10 to 80 parts by weight of the polyether polyol (A) and 10 to 60 parts by weight of the short glycol (B) in 100 parts by weight of the polyol compound. A method for producing a rigid polyurethane foam panel obtained by using as a raw material a foam stock solution composition comprising a polyol compound, a polyol composition containing water as a foaming agent, and a polyisocyanate component,
An injection step of injecting the foaming stock solution composition with a side surface extending in the longitudinal direction and the thickness direction as a bottom surface for a mold having a longitudinal direction, a width direction, and a thickness direction;
A reaction step of reacting the foaming stock solution composition after the injection step,
The polyol compound has an average functional group number of 2 to 4, a weight average molecular weight of 3000 to 8000, a polyether polyol (A) which is a polymer of alkylene oxide, and a short glycol (B) having a molecular weight of less than 250 And containing
The manufacturing method of the rigid polyurethane foam panel characterized by containing 20-100 weight part of said water with respect to 100 weight part of said polyol compounds. The rigid polyurethane foam panel according to claim 3 , wherein 10 to 80 parts by weight of the polyether polyol (A) and 10 to 60 parts by weight of the short glycol (B) are contained in 100 parts by weight of the polyol compound. Method.

Images