TW201321426A - Method for producing rigid foam synthetic resin - Google Patents

Abstract

Provided is a method for producing a rigid foam synthetic resin, whereby it is possible to produce a lighter rigid foam while achieving good storage stability of a polyol system liquid and suppressing shrinkage deformation. A method for producing a rigid foam synthetic resin by reacting a polyether polyol (P) and a polyisocyanate compound (Y) in the presence of a foaming agent, a flame retardant, a foam stabilizer and a catalyst, wherein the method is characterized in that the polyether polyol (P) contains a polyether polyol (A) which has a random polymer chain of oxyethylene groups and oxypropylene groups, has a hydroxyl group number of 2 to 8, has a hydroxyl group value of 10 to 100 mg KOH/g and has an oxyethylene group content of 20 to 60 mass%, and a polyether polyol (B) which has a hydroxyl group number of 3 to 8 and has a hydroxyl group value of 200 to 700 mg KOH/g.

Description

Method for producing rigid foamed synthetic resin Field of invention

The present invention relates to a method for producing a rigid foamed synthetic resin.

Background of the invention

In the presence of a foaming agent or the like, a polyol and a polyisocyanate compound are reacted to produce a rigid foamed synthetic resin such as a rigid polyurethane foaming material or a rigid polytrimeric isocyanate foaming material (hereinafter sometimes referred to as It has been widely used in, for example, construction and building materials. In such applications, in addition to the desired heat insulating properties, flame retardancy, and the like, it is also desired to reduce the weight and increase the dimensional stability, so that a rigid foamed material of continuous cells is used. In the production of the rigid foamed material of the continuous cells, the foaming agent is often used for foaming to achieve further weight reduction, but shrinkage of the foamed material due to insufficient bubble chamber strength is likely to occur.

Further, it is conventionally known that a low-boiling fluorine-containing compound mainly used as a foaming agent has a problem of promoting global warming once it is present in the atmosphere. Therefore, a technique of using water as a foaming agent to reduce the amount of fluorine-containing compound used has been proposed.

However, once water is used as a foaming agent, the component having low hydrophilicity in the raw material is difficult to dissolve. Therefore, in a blended liquid (hereinafter also referred to as a polyol-based liquid) in which a polyol, a foaming agent, a catalyst, or the like is mixed, the problem of deterioration in storage stability or a problem of mixing of a polyol-based liquid and a polyisocyanate liquid is likely to occur. question. Poor mixing, when foaming, the bubble size and distribution of the foamed material are likely to be uneven, the bubble chamber becomes thick, and a large amount of independent bubbles or shrinkage or collapse of the foamed material is likely to occur.

Therefore, in particular, in the method using water as a foaming agent, it is more difficult to further reduce the weight of the rigid foamed foam material by increasing the amount of the foaming agent used.

Thus, a method for achieving weight reduction from polyols is proposed. For example, it is proposed to produce a mixture of (A) a polyoxyalkylene polyether polyol having a number average molecular weight of 2000 to 9000 and (B) a polyoxyalkylene polyether polyol having a number average molecular weight of 250 to 750. It is connected to the air bubbles and is lightweight (Patent Document 1). Further, in the same manner, in order to spray-form a continuous bubble polyurethane foam material so as not to cause dripping, it is proposed to use (A) a hydroxyl value of 30 to 70 mgKOH/g in a polyoxyalkylene chain. a mixture of a polyether polyol having an oxygen-extended ethyl group content of 50 to 90% by mass and a terminal hydroxyl group having a first-stage rate of 20 to 50% and (B) a polyether polyol having a hydroxyl value of 300 to 800 mgKOH/g. (Patent Document 2).

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2002-293868

Patent Document 2: Japanese Laid-Open Patent Publication No. 2011-57893

Summary of invention

However, it has been found that the above polyol mixture is especially in a polyol molecule. The polyol mixture containing a plurality of oxygen-extended ethyl polyols tends to have a poor appearance of the foamed material, and the foamed material may shrink as occasion demands. Moreover, when it is stored as a polyol liquid containing a foaming agent, etc., it is not sufficient in storage stability. Accordingly, an object of the present invention is to provide a method for producing a rigid foamed synthetic resin which can obtain a good stability of a polyol liquid and which can suppress shrinkage deformation and which can produce a relatively lightweight continuous cell rigid foam.

The present invention is the invention of the following [1] to [12].

[1] A method for producing a rigid foamed synthetic resin produced by reacting a polyether polyol (P) with a polyisocyanate compound (Y) in the presence of a foaming agent, a flame retardant, a foam stabilizer, and a catalyst The rigid foamed synthetic resin is characterized in that the polyether polyol (P) contains at least the following polyether polyol (A) and polyether polyol (B), and the foaming agent contains water; polyether polyol (A): a random polymeric chain having an oxygen-extended ethyl group and an oxygen-extended propyl group, and having a hydroxyl group number of 2 to 8, a hydroxyl value of 10 to 100 mgKOH/g, and an oxygen-extended ethyl group content of 20 to 60% by mass. Polyether polyol; polyether polyol (B): a polyether polyol having a hydroxyl number of 3 to 8 and a hydroxyl value of 200 to 700 mgKOH/g.

[2] The method for producing a rigid foamed synthetic resin according to [1], wherein the content of the polyether polyol (B) is from 1 to 50% by mass based on the polyether polyol (P).

[3] The method for producing a rigid foamed synthetic resin according to [1] or [2] wherein the polyether polyol (A) is subjected to ring-opening addition of propylene oxide to an initiator (S1). A polyether polyol prepared by subjecting a mixture of propylene oxide and ethylene oxide to ring-opening addition.

[4] The method for producing a rigid foamed synthetic resin according to [3], wherein the ring-opening addition amount of the mixture of the propylene oxide and the ethylene oxide is relative to the total amount of the alkylene oxide which has been subjected to ring-opening addition 40 to 90% by mass.

[5] The method for producing a rigid foamed synthetic resin according to [3] or [4], wherein the amount of ethylene oxide relative to the mixture is 30 to 90 by mass in the mixture of propylene oxide and ethylene oxide. %.

[6] The method for producing a rigid foamed synthetic resin according to any one of [1] to [5] wherein the water is used in an amount of 15 to 60 by mass based on 100 parts by mass of the polyether polyol (P). Share.

[7] The method for producing a rigid foamed synthetic resin according to any one of [1] to [6] wherein the polyether polyol (B) is a polyoxypropylene propylene polyol.

[8] The method for producing a rigid foamed synthetic resin according to any one of [1] to [7] wherein the polyether polyol (P) further contains 1 to 20 with respect to the polyether polyol (P). % by mass of the following polyether polyol (C); polyether polyol (C): a random polymeric chain having a polyoxyethylene group at the end and having no oxygen-extended ethyl group and an oxygen-extended propyl group, and having a hydroxyl group number of 2~ 8 and a polyether polyol having a hydroxyl value of 20 mgKOH/g or more and less than 200 mgKOH/g.

[9] The method for producing a rigid foamed synthetic resin according to any one of [1] to [8] wherein the flame retardant is used in an amount of 10 to 100 based on 100 parts by mass of the polyether polyol (P). Parts by mass.

[10] The method for producing a rigid foamed synthetic resin according to any one of [1] to [9] wherein the polyisocyanate compound (Y) is used in an amount of isocyanate The number is 10~100.

[11] The method for producing a rigid foamed synthetic resin according to any one of [1] to [10] wherein the hard foamed synthetic resin has a core density of 5 to 12 kg/m ³ .

[12] The method for producing a rigid foamed synthetic resin according to any one of [1] to [11], wherein the hard foamed synthetic resin is produced by a spray method.

According to the method for producing a rigid foamed synthetic resin of the present invention, a storage stability of a polyol liquid can be obtained, and at the same time, shrinkage deformation can be suppressed and a relatively rigid foamed synthetic resin can be produced.

Form for implementing the invention

The method for producing a rigid foamed material of the present invention is a method of reacting a polyether polyol (P) with a polyisocyanate compound (Y) in the presence of a foaming agent, a flame retardant, a foam stabilizer and a catalyst.

[Polyether polyol (P)]

In the present invention, the polyether polyol (P) contains at least a mixture of the following polyether polyol (A) and polyether polyol (B). However, in the following, only the polyether polyol is referred to as "polyol".

Polyether polyol (A): a random polymeric chain having an oxygen-extended ethyl group and an oxygen-extended propyl group, and having a hydroxyl number of 2 to 8, a hydroxyl value of 10 to 100 mgKOH/g, and an oxygen-extended ethyl group content of 20 ~60% by mass of polyether polyol.

Polyether polyol (B): a polyether polyol having a hydroxyl number of 3 to 8 and a hydroxyl value of 200 to 700 mgKOH/g.

[Polyether polyol (A)]

The polyether polyol (A) has a hydroxyl number of 2 to 8. The polyether polyol (A) having the hydroxyl group number can be obtained by subjecting an alkylene oxide to a ring-opening addition of an initiator (S1) having 2 to 8 functional groups. The number of functional groups is preferably from 2 to 6, and particularly preferably from 2 to 4. The number of functional groups of the initiator in the present invention represents the number of active hydrogen atoms of the initiator. When the number of functional groups of the initiator (S1) is at least the lower limit of the above range, the strength of the obtained rigid foamed material is easily improved, and if it is at most the upper limit of the above range, the polyether polyol (A) The viscosity does not become too high, and it is easy to ensure the compatibility of the polyether polyol (P) and the polyol liquid.

As the initiator (S1), water, a polyol or an amine compound can be used.

Specific examples of the polyhydric alcohols include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, diethylene glycol, diglycerin, pentaerythritol, sorbitol, and sucrose.

Examples of the amine compound include aliphatic amines, alicyclic amines, and aromatic amines. Examples of the aliphatic amines include alkylamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; and alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. Aminoethyl hexahydropyridinium Wait. Examples of the aromatic amines include diamine toluene and a Mannich reaction product. The reaction product of the Mannich reaction product is a phenol, an alkanolamine, or an aldehyde, and examples thereof include a reaction product of indophenol, monoethanolamine, and formaldehyde.

The initiator (S1) may be used alone or in combination of two or more.

It is better in storage stability, preferably water or polyols, especially It is preferably at least one selected from the group consisting of water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, diglycerin, pentaerythritol, sorbitol, and sucrose.

The polyether polyol (A) has a random polymeric chain of an oxygen-extended ethyl group and an oxygen-extended propyl group. Hereinafter, unless otherwise specified, the random polymeric chain represents a random polymeric chain of an oxygen-extended ethyl group and an oxygen-extended propyl group. The random polymer chain of an oxygen-extended ethyl group and an oxygen-extended propyl group is an oxygen-exane formed by ring-opening addition of a mixture of ethylene oxide (hereinafter also referred to as EO) and propylene oxide (hereinafter also referred to as PO). chain. However, it may contain an oxygen-extended alkyl group other than an oxygen-extended ethyl group and an oxygen-extended propyl group, and the alkylene oxide which forms the oxygen-extended alkyl group may be 1,2-butylene oxide or 2,3-epoxy. Butane and styrene oxide.

The polyether polyol (A) may also contain a polyoxyalkylene moiety other than the random polymeric chain in its polyoxyalkylene chain. For example, the residue of the initiator (S1) may have a polyoxyethylene chain or a polyoxyalkylene propyl chain between the random chain, and may also have a polyoxyethylidene chain or poly on the terminal side of the random chain. Oxygen extended propyl chain.

As a method for producing the polyether polyol (A), it is preferred to directly open-loop addition of a mixture of PO and EO to the initiator (S1), and to open-loop addition of the initiator (S1) to PO. A method of ring-opening addition of a mixture of PO and EO, a ring-opening addition of PO to the initiator (S1), a ring-opening addition of a mixture of PO and EO, and further ring-opening addition of EO to make the terminal an oxygen-extended ethyl group ( Further, even if the terminal hydroxyl group is a first-order hydroxyl group, and the initiator (S1) is directly subjected to ring-opening addition of a mixture of PO and EO, a method of ring-opening addition of EO to make the terminal an oxygen-extended ethyl group or the like is obtained.

Directly open-loop addition of the initiator (S1) to the mixture of PO and EO The method and the method of ring-opening addition PO of the initiator (S1) followed by ring-opening addition of a mixture of PO and EO are easy to obtain the effect of suppressing shrinkage, which is preferable.

After the ring-opening addition of PO to the initiator (S1), the ring-opening addition of a mixture of PO and EO, and further ring-opening addition of EO to make the terminal an oxygen-extended ethyl group, has the effect of suppressing shrinkage and can also be improved. It is ideal because it is reactive.

In the polyether polyol (A), the ring-opening addition amount of the mixture of EO and PO is preferably 40 to 90% by mass, and is 45 to 85 mass, based on the total amount of the alkylene oxide which has been subjected to ring-opening addition. % is better. It is preferable that the effect of suppressing shrinkage is 40% by mass or more, that is, 90% by mass or less, and good storage stability can be obtained.

In the mixture of EO and PO which has been subjected to ring-opening addition, the EO content is preferably from 30 to 90% by mass, and preferably from 50 to 70% by mass, based on the mixture of EO and PO. When the content is 30% by mass or more, the dimensional stability of the obtained foamed material is good, and when it is 90% by mass or less, the storage stability is excellent.

When the polyether polyol (A) has an oxygen-extended propyl group other than the random chain (the oxygen-extended propyl group such as a polyoxypropyl group formed by PO directly added to the initiator (S1)), The oxygen-extension ratio other than the random chain is preferably 70% by mass or less based on the total of the oxygen-extended propyl groups in the polyether polyol (A), more preferably 60% by mass or less, and 50% by mass. % or less is especially good. When the amount of the oxygen-extended propyl group is within the above range, the storage stability of a good polyol-based liquid can be easily obtained.

When the polyether polyol (A) has an oxygen-extended ethyl chain in addition to the random chain (the oxygen-extended ethyl group at the end of the polyoxyalkylene chain at the end of the sealing), the oxygen-extended ethyl group other than the random chain The amount is 20% by mass or less based on the polyether polyol (A). Preferably, it is preferably 15% by mass or less, and more preferably 10% by mass or less. When the amount of the oxygen-extended ethyl group is within the above range, the activity of the polyether polyol (A) does not become too high, and it is difficult to cause shrinkage of the foamed material due to excessive formation of the closed cells. Here, the content ratio of the oxygen-extended ethyl group in the polyether polyol (A) is a mass ratio of ethylene oxide to the total mass of the initiator (S1) and the total alkylene oxide to which the ring-opening is added. .

The content of the oxygen-extended ethyl group in the polyether polyol (A) is from 20 to 60% by mass. The content of the oxygen-extended ethyl group is preferably 25 to 60% by mass, more preferably 25 to 50% by mass, and particularly preferably 25 to 45% by mass. When the ratio of the oxygen-extended ethyl group is at least the lower limit of the above range, it is easy to obtain a storage stability of a good polyol-based liquid, and if it is at most the upper limit of the above range, the polyether polyol (A) The activity does not become too high. When the activity of the polyol is too high, it is easy to form a large number of independent bubbles, and thus it is easy to cause shrinkage of the foam.

The polyether polyol (A) has a hydroxyl value of from 10 to 100 mgKOH/g. It is preferably 20 to 80 mgKOH/g, more preferably 20 to 70 mgKOH/g, and particularly preferably 25 to 70 mgKOH/g. When the hydroxyl value is at least the lower limit of the above range, the viscosity of the polyether polyol (A) does not become too high, which is preferable, and when it is at most the upper limit of the above range, the resinization reaction rate is Since it is moderate, the gas generated in the urethanization reaction can be sealed into the bubble chamber constituting the foamed material before being released to the outside of the foamed material, so that it is easy to reduce the weight of the rigid foamed material.

[Polyether polyol (B)]

Polyether polyol (B) has a hydroxyl number of 3-8 and a hydroxyl value of 200~ 700 mg KOH/g of polyether polyol. The number of hydroxyl groups of 3 to 8 can be obtained by using only one type or a combination of two or more types of polyether polyols (A) in order to make the total number of functional groups as the initiator (S2) 3 to 8. The initiator (S1) exemplified is obtained as an initiator (S2).

The polyether polyol (B) is preferably a polyoxypropylene propylene polyol. In this case, the rigid foam material tends to become continuous bubbles and it is easy to prevent shrinkage of the foam material. Further, the polyether polyol (B) has a hydroxyl value of from 200 to 700 mgKOH/g. It is preferably 300 to 650 mgKOH/g, and more preferably 300 to 600 mgKOH/g. When the hydroxyl value is at least the lower limit of the above range, the obtained rigid foamed material is likely to be a continuous bubble, so that it is easy to prevent shrinkage of the foamed material; if it is below the upper limit of the above range, the polyether polyol (B) ) The viscosity does not become too high, so it is ideal.

In addition to the above polyether polyols (A) and (B), the polyether polyol (P) may further contain an active hydrogen-containing compound other than the polyether polyol (C) and a polyol thereof Compound (D). The following is explained in order.

[Polyether polyol (C)]

The polyether polyol (C) has a polyoxyethylidene group and a random polymeric chain having no oxygen-extended ethyl group and an oxygen-extended propyl group, the hydroxyl group number is 2-8, and the hydroxyl value is 20 mgKOH/g or more and less than 200 mgKOH. / g of polyether polyol. In other words, the polyether polyol (C) is obtained by ring-opening addition of an alkylene oxide such as PO and EO to an initiator (S3) having 2 to 8 functional groups, and is a polyether polyol having no random polymerization chain. And it is a polyether polyol having an oxygen-extended ethyl group at the end. The initiator (S3) together with the ideal aspect is the same as the initiator (S1) in the polyether polyol (A).

The polyether polyol (C) is preferably a ring-opening addition PO to the initiator (S3), respectively. Polyether polyol derived from EO. The oxygen-extended ethyl group may also exist outside the terminal portion. That is, in the manufacturing method having the process of opening-ring addition PO after EO ring-opening addition and finally opening-ring addition to form an end portion, there is an oxygen extension B formed by the open-loop addition of the former EO. The base chain is also available.

As the polyether polyol (C), a polyether polyol obtained by subjecting the initiator (S3) to ring-opening addition of PO and EO, respectively, is preferred.

By using a polyether polyol (C) having an oxygen-extended ethyl group at the molecular end, the appearance of the foamed material can be made more beautiful. In the alkylene oxide which is subjected to ring-opening addition of the initiator (S3), the ratio of ethylene oxide is preferably 5 to 60% by mass, preferably 7 to 50% by mass, more preferably 9 to 40% by mass. When the ratio of the ethylene oxide is at least the lower limit of the above range, it is easy to sufficiently obtain the effect of suppressing the thickening of the bubble chamber by using the polyether polyol (C). Moreover, when it is below the upper limit of the above range, the activity of the polyether polyol (A) does not become too high and it is difficult to cause shrinkage of the foamed material.

The polyether polyol (C) has a hydroxyl value of 20 mgKOH/g or more and less than 200 mgKOH/g. It is preferably 25 to 180 mgKOH/g, and more preferably 30 to 160 mgKOH/g. When the hydroxyl value is at least the lower limit of the above range, the viscosity of the polyether polyol (C) is not excessively high, which is preferable, and if it is at most the upper limit of the above range, the obtained rigid foam is obtained. The material tends to be continuous bubbles, and thus it is easy to prevent the foam from shrinking.

[Method for Producing Polyether Polyols (A), (B), and (C)]

The reaction of the initiator (S1), (S2) or (S3) ring-opening addition alkylene oxide is preferably carried out in the presence of a catalyst.

As the catalyst, selected from the group consisting of complex metal cyanide complexes At least one of the group consisting of a chemical agent, a Lewis acid catalyst, and an alkali metal catalyst is preferred, and only one type is preferable. The use of the above catalyst makes it easy to uniformly add an alkylene oxide to the initiator.

As the composite metal cyanide complex catalyst, a composite metal cyanide complex catalyst having an organic ligand coordinated to zinc hexacyanocobaltate is preferred. The organic ligand may, for example, be a tertiary butanol, a tertiary pentanol, an ethylene glycol monotributyl ether, a combination of a tertiary butanol and an ethylene glycol monotributyl ether.

The Lewis acid catalyst may, for example, be a BF3 complex, ginseng (pentafluorophenyl)borane or ginseng (pentafluorophenyl)aluminum.

The alkali metal catalyst may, for example, be an alkali metal compound such as cesium hydroxide, potassium hydroxide or sodium hydroxide. Especially potassium hydroxide is preferred.

As the catalyst used in the polyether polyol (A), (B) or (C) used in the present invention, potassium hydroxide is most preferably used.

[Ideal state of polyether polyols (A), (B) and (C)]

As the polyether polyol (A) of the present invention, a polyether polyol (A1) and a polyether polyol (A2) are preferred, and the polyether polyol (A1) is in the presence of a potassium hydroxide catalyst, and the number of functional groups is The initiator of 2~8 (S1) is subjected to ring-opening addition of PO, and is randomly added to form a mixture of PO and EO, and the hydroxyl value is 10 to 100 mgKOH/g; the polyether polyol (A2) is In the presence of a potassium hydroxide catalyst, the initiator (S1) having a functional group number of 2 to 8 is subjected to ring-opening addition of PO, followed by ring-opening addition of a mixture of PO and EO, and sealing with EO, and the hydroxyl value is 10 to 100 mgKOH/ g.

As the polyether polyol (B) of the present invention, polyoxyl propyl polyol (B1) is preferred, the polyoxy-extension propyl polyol (B1) is obtained by adding a PO to the initiator (S2) having a functional group of 3 to 8 in the presence of a potassium hydroxide catalyst, and having a hydroxyl value. It is 200 to 700 mgKOH/g.

The polyether polyol (C) of the present invention is preferably a polyether polyol (C1) which is an initiator having a functional group number of 2 to 8 in the presence of a potassium hydroxide catalyst ( S3) After ring-opening addition of PO, the EO of 5 to 60% by mass of the total alkylene oxide to be added to the initiator (S3) is subjected to ring-opening addition, and the hydroxyl value is 20 to 200 mgKOH/g.

[Content ratio of each polyether polyol in the polyether polyol (P)]

The content of the polyether polyol (A) in the polyether polyol (P) is preferably 40 to 90% by mass, more preferably 55 to 85% by mass, and 60 to 80% by mass based on the polyether polyol (P). % is especially good. When the ratio of the polyether polyol (A) is at least the lower limit of the above range, even if the polyol-based liquid contains a large amount of water, a good stability of the polyol liquid can be obtained, and it can be easily obtained at the same time. The effect of suppressing shrinkage deformation while producing a lightweight hard foam material. If it is below the upper limit of the above range, it is difficult to cause shrinkage or collapse due to insufficient bubble chamber strength.

The content of the polyether polyol (B) is preferably from 1 to 50% by mass, more preferably from 15 to 50% by mass, even more preferably from 20 to 50% by mass, based on the polyether polyol (P). When the ratio of the polyether polyol (B) is at least the lower limit of the above range, it is easy to obtain a storage stability of a good polyol liquid, and it is easy to suppress shrinkage deformation of the foam. If it is below the upper limit of the above range, the bubble chamber is difficult to be thick.

When the polyether polyol (C) is also used, the content thereof is 1 to 20% by mass, preferably 3 to 15% by mass, and 5 to 10% by weight based on the polyether polyol (P). The quality % is especially good. When the ratio of the polyether polyol (C) is at least the lower limit of the above range, the effect of suppressing the thickening of the bubble chamber can be easily obtained. Further, when the ratio of the polyether polyol (C) is at most the upper limit of the above range, shrinkage or collapse due to insufficient bubble strength is less likely to occur. That is, the ideal ratio when the polyether polyol (P) contains the polyether polyol (A), the polyether polyol (B), and the polyether polyol (C) is a polyether polyol (A): a polyether polyol (B): The polyether polyol (C) is 40 to 90% by mass: 9 to 59% by mass: 1 to 20% by mass. The reason for each of the upper limit value and the lower limit value is the same as described above.

[Active hydrogen-containing compound (D)]

The polyether polyol (P) may contain, in addition to the above polyether polyols (A), (B) and (C), a compound containing an active hydrogen atom other than the polyol thereof in a range not inhibiting the object of the present invention. Active hydrogen compound (D). Examples of the active hydrogen-containing compound (D) include other polyhydric alcohols and polyphenols which are not contained in the polyether polyol (A), the polyether polyol (B), and the polyether polyol (C). Aminated polyols.

Examples of the other polyhydric alcohols include polyether polyols, polyester polyols, and polycarbonate polyols.

Examples of the polyphenols include non-condensed compounds such as bisphenol A and resorcin; and a resol-type initial condensate in which a phenol is condensed and bonded with an excess of formaldehyde in the presence of a base catalyst; A benzyl type initial condensate which is reacted with a non-aqueous system when the phenolic type initial condensate is dissolved; and a phenolic initial condensate which reacts an excess phenol with formaldehyde in the presence of an acid catalyst. The number average molecular weight of the initial condensates is preferably from about 200 to 10,000. In the above, examples of the phenols include phenol and cresol. Bisphenol A and resorcinol. Further, examples of the formaldehyde include formaldehyde water and polyoxymethylene.

Examples of the aminated polyols include polyether triamine (manufactured by Huntsman Co., Ltd., trade name: JEFFAMINE T-5000), and the like, which is obtained by subjecting glycerin to ring-opening addition PO to amination, and the number is obtained. The average molecular weight is 5,000 and the amination rate is 95%.

The ratio of the active hydrogen-containing compound (D) in 100% by mass of the polyether polyol (P) is preferably 0 to 10% by mass.

[Polyisocyanate compound (Y)]

The polyisocyanate compound (Y) of the present invention is not particularly limited, but is a polyisocyanate such as an aromatic, alicyclic or aliphatic having two or more isocyanate groups; and a mixture of two or more kinds of the polyisocyanate; It is preferred to modify the modified polyisocyanate or the like.

Specific examples include, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (general: crude MDI), ditolyl diisocyanate. (XDI), isophorone diisocyanate (IPDI), polyisocyanate such as hexamethylene diisocyanate (HDI) or these prepolymer type modified substances, cyanuric acid modified substances, urea modified substances and carbodiimide modified Quality and so on. Among them, TDI, MDI, crude MDI or these modified substances are preferred. It is particularly desirable from the viewpoint of convenience in handling of crude MDI and ease of handling. The polyisocyanate compound (Y) may be used singly or in combination of two or more kinds.

The polyisocyanate compound (Y) is used in an amount of 100 times the number of isocyanate groups in terms of the total number of active hydrogen atoms contained in components other than the polyisocyanate compound (Y) (generally expressed in 100 times) The value is called the isocyanate index), preferably 10 to 100. It is preferably 20 to 80, and preferably 30 to 70. When the isocyanate index is at least the lower limit of the above range, it is likely to become continuous bubbles and it is easy to suppress shrinkage. When it is below the upper limit of the above range, it is easy to reduce the weight. In addition, the components other than the polyisocyanate compound (Y) are a polyhydric alcohol such as a polyether polyol, a water of a foaming agent, and an active hydrogen-containing compound thereof when an active hydrogen-containing compound having a hydroxyl group or an amine group is contained. .

When the rigid foam material is produced by a spray method, the polyisocyanate compound (Y) and the polyether polyol (P) are preferably used in a volume ratio of about 1:1.

[foaming agent]

In the present invention, the blowing agent contains water. The water is not particularly limited as long as it does not impair the properties of the obtained rigid foam material, and distilled water, ion-exchanged water or the like can be used. In addition to water, it is also possible to use hydrocarbons, hydrofluorocarbons (also known as HFC compounds), dichloromethane, other halogenated hydrocarbons or mixtures thereof. Examples of the hydrocarbon compound include butane, n-pentane, isopentane, cyclopentane, hexane, and cyclohexane. Among them, n-pentane, isopentane and cyclopentane are preferred.

Examples of the HFC compound include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 1,1. 1,3,3-pentafluorobutane (HFC-365mfc) and the like.

For the foaming agent to be used in combination with water, hydrocarbons and HFC compounds are preferred. In the case of hydrocarbons used in combination with water, cyclopentane, isopentane, n-pentane or a mixture thereof is preferred, and in combination with water, HFC-134a, HFC- 245fa, HFC-365mfc or the Mixtures such as are preferred. From the viewpoint of the environment, it is preferred to use only water as the foaming agent.

The present invention is particularly suitable for a system in which a foaming agent is frequently used for weight reduction, and is also suitable for a system in which water is used as a foaming agent.

Specifically, in the case of using water alone as a foaming agent or water and a foaming agent other than one or more, water is used in an amount of 100 parts by mass relative to the polyether polyol (P) (water) It is not considered to be a polyol calculation. The following is the same) in 15 to 60 parts by mass. It is preferably 15 to 50 parts by mass, and more preferably 20 to 50 parts by mass. When the amount of water used is at least the lower limit of the above range, the obtained rigid foamed material can be easily reduced in weight, and if it is at most the upper limit of the above range, water and polyether polyol (P) are easily obtained. Good mix. When the foaming agent other than the above water is used in combination with water, the amount of the foaming agent other than water is preferably 5 to 30 parts by mass based on 100 parts by mass of the polyether polyol (P), and is 7 to 7 parts by mass. 15 parts by mass is preferred.

[Flame retardant]

A flame retardant will be used in the present invention. In the case of a flame retardant, a phosphorus-based flame retardant is preferred, and in the case of a compound, tricresyl phosphate (TCP), triethyl phosphate (TEP), and stilbene (β-chloroethyl) phosphate (TCEP) And ginseng (β-chloropropyl) phosphate (TCPP), etc. are preferred.

The flame retardant is preferably used in an amount of 10 to 100 parts by mass, preferably 30 to 80 parts by mass, and more preferably 40 to 70 parts by mass, per 100 parts by mass of the polyether polyol (P). When the amount of the flame retardant used is at least the lower limit of the above range, the flame retardancy of the foamed material can be favorably improved. When it is at most the upper limit of the above range, the storage stability of a good polyol liquid is easily obtained.

The flame retardant may be used alone or in combination of two or more.

[catalyst]

The catalyst used in the present invention is not particularly limited as long as it is a urethanation catalyst which can promote the urethanization reaction. For example, N,N,N',N",N"-pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, triamethylenediamine, and N,N,N' , an amine-based catalyst such as N'-tetramethylhexamethylenediamine; a reactive amine-based catalyst such as N,N,N'-trimethylamineethylethanolamine; and an organometallic catalyst such as dibutyltin dilaurate . Further, a catalyst for promoting the tertiary polymerization of an isocyanate group may be used in combination, and examples thereof include metal carboxylates such as potassium acetate and potassium 2-ethylhexanoate. The amount of the urethanization catalyst used is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the polyether polyol (P). Further, the amount of the catalyst for promoting the tri-polymerization reaction is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the polyether polyol (P).

In terms of the catalyst, it is preferred to use only an amine catalyst or a reactive amine catalyst without using a metal catalyst from the viewpoint of environmental pollution.

[stabilizer]

In the present invention, a foam stabilizer is used in order to form a good bubble. The foam stabilizer may, for example, be an oxygen-based foam stabilizer or a fluorine-containing compound foam stabilizer. In general, in addition to the antimony-based foam stabilizer used in the production of the urethane foaming material, a cerium-oxygen foam stabilizer used in the production of a highly permeable soft urethane foam material can also be used. . The amount of the foam stabilizer to be used may be appropriately selected, and it is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the polyether polyol (P).

[Other blending agents]

In the present invention, in addition to the above polyether polyol (P), polyisocyanate compound (Y), a foaming agent, a flame retardant, a foam stabilizer, and a catalyst, any blending agent may be used. The blending agent may, for example, be a filler such as calcium carbonate or barium sulfate; an anti-aging agent such as an antioxidant or a UV absorber; a plasticizer, a colorant, an antifungal agent, a defoaming agent, a dispersing agent, and discoloration prevention. Agents, etc.

[Method for Producing Rigid Foamed Synthetic Resin]

The method for producing the rigid foam material is not particularly limited, and the present invention is particularly suitable for a method for producing a rigid foam material by a spray method.

The spray method prepares a solution (polyol-based liquid) containing a polyether polyol (P), a foaming agent, a flame retardant, a foam stabilizer, a catalyst, and a blending agent according to requirements, and the polyol liquid and the solution are prepared. The polyisocyanate liquid of the polyisocyanate compound (Y) is mixed and sprayed onto the construction surface, and the mixture is foamed and hardened on the construction surface to form a rigid foam material.

The spray method is a method of directly producing a rigid foam material at a construction site, and has the advantages of being able to suppress the construction cost and allowing seamless construction even with a construction surface having irregularities. Therefore, the spray method is often used in construction of a heat insulating material composed of a hard foam material such as a wall or a roof in a construction site. For specific construction examples, heat insulating materials such as buildings, commercial buildings, and prefabricated refrigerated warehouses may be mentioned.

As for the spray method, various methods are known, and in particular, an airless spray method in which a polyol component is mixed with a polyisocyanate component and sprayed by a mixing head is preferred.

The rigid foamed material of the continuous bubble is inherently lighter than the rigid foamed material of the closed cell. Light weight means that the density of the rigid foam material is low, that is, the value measured as the core density is low. The present invention is suitable for a method of producing a relatively lightweight continuous cell rigid foamed material as compared to conventional continuous cell rigid foamed materials. Specifically, the core foam density of the rigid foamed material obtained by the production method of the present invention is preferably 5 to 12 kg/m ³ . It is preferably 7 to 12 kg/m ^{3 and more} preferably 8 to 12 kg/m ³ . When the core density is 5 kg/m ³ or more, shrinkage deformation is less likely to occur; if the core density is 12 kg/m ³ or less, the desired weight reduction can be achieved.

The core density of the rigid foamed material in the present invention is a value measured in accordance with the measurement method of JIS K7222.

The rigid foamed material obtained by the production method of the present invention is easy to be lightweight and blended with a flame retardant, and thus is particularly suitable for use in construction and building materials.

Further, the rigid foamed material obtained by a method of forming by a spray method or a method of forming by injection into a predetermined mold is suitable for an automobile interior member, and is particularly suitable for use between a ceiling member, a door trim, and a door frame.

According to the present invention, even in the case where a large amount of the foaming agent is used, an ultra-lightweight rigid foamed material having no shrinkage deformation (that is, a continuous-cell rigid foamed material having a core density of 12 kg/m ³ or less) can be produced. Ideally, an ultra-lightweight rigid foam material having no shrinkage deformation and no thickening of the bubble chamber can be produced.

Further, in the method using water as a foaming agent, even when a large amount of water is used, storage stability of a good polyol liquid can be obtained, and a polyether polyol (P) and a polyisocyanate compound can also be obtained. (Y) An ultra-lightweight rigid foam material which is excellent in mixing and has no shrinkage deformation. It is desirable to manufacture an ultra-lightweight rigid foamed material which can obtain a good storage stability of a polyol liquid using a large amount of water, and which has no shrinkage deformation and no thickened cavity. For example, as shown in the examples below, it is possible to suitably produce 24.5 parts by mass of water relative to 100 parts by mass of the polyether polyol (P) while obtaining a good storage stability of the polyol liquid, and the core density has exceeded A rigid foamed material which is reduced in weight to about 10 kg/m ³ .

Further, the polyol-based liquid of the method of the present invention has good storage stability, and even if a large amount of the flame retardant is blended, the ultra-lightweight rigid foam material can be favorably produced, which is suitable for the spray method.

However, when a rigid foam material is produced by a flat foaming method or an injection method, the mixing ratio of the polyol liquid and the polyisocyanate liquid can be freely determined. However, in the spray method, the mixing ratio is usually expressed by volume ratio. It is a limit of about 1:1.

Moreover, since the spray method is mainly used for construction purposes, flame retardancy is required. In the spray method in which the polyol liquid and the polyisocyanate liquid are mixed at a volume ratio of 1:1, since the structural formula of cyanuric acid (structural formula which can form a trimer) is difficult to increase the flame retardancy, it is necessary to add a large amount. Flame retardant. Further, when a polyhydric alcohol (A) is used as a polyhydric alcohol containing no aromatic ring or N atom, it is difficult to ensure sufficient flame retardancy of the obtained rigid foamed material, and therefore it is necessary to add a large amount of a flame retardant. Especially in the system using a large amount of water, once a large amount of the flame retardant is blended, there is a concern that the compatibility is lowered. A decrease in compatibility may cause shrinkage and collapse of the foam material or a thickening of the bubble chamber.

In contrast, the method for producing a rigid foamed material of the present invention can produce a super lightweight which can obtain a good storage stability of a polyol liquid without shrinkage deformation even if a large amount of water is blended and a large amount of a flame retardant is blended. Hard foaming material. The ideal system can produce a part with good flame retardancy and no shrinkage deformation and no thickening of the bubble chamber. Ultra lightweight hard foam.

For example, as described in the examples below, a rigid foamed material can be favorably produced by a spray method using 24.5 parts by mass of water and 50 parts by mass of a flame retardant with respect to 100 parts by mass of the polyether polyol (P). The storage stability of a good polyol liquid is still obtained, and the core density has been ultra-lightweight to a level of about 10 kg/m ³ .

Example

The invention will be specifically illustrated by the following examples, but the invention is not limited by the examples. Hereinafter, the hydroxyl value is measured in accordance with JIS K1557 (1970 version).

The materials used in the examples and comparative examples are as follows.

[Polyether polyol (A)]

Polyether polyol (A-1): using glycerol as an initiator and ring-opening addition of 1658 g of PO in the presence of a potassium hydroxide catalyst, ring-opening addition of 1750 g of a mixture of PO and EO (PO/EO) The mass ratio = 40/60) gave a polyether polyol having a hydroxyl number of 3 and a hydroxyl value of 45 mgKOH/g. The mixture ratio of PO to EO was 47% by mass based on the total amount of PO and EO of the ring-opening addition. The EO ratio was 30% by mass based on the total amount of EO and PO which had been subjected to ring-opening addition.

Polyether polyol (A-2): using glycerol as an initiator and ring-opening addition of 1866 g of PO in the presence of a potassium hydroxide catalyst, followed by ring-opening addition of 2702 g of a mixture of PO and EO (PO/ The EO mass ratio = 40/60) gave a polyether polyol having a hydroxyl number of 3 and a hydroxyl value of 36 mgKOH/g. The mixture ratio of PO to EO was 58% by mass based on the total amount of PO and EO in which the ring-opening addition was added. The EO ratio is 35 compared to the combined EO and PO of the open loop addition. quality%.

Polyether polyol (A-3): using glycerol as an initiator and ring-opening addition of 1318 g of PO in the presence of a potassium hydroxide catalyst, followed by ring-opening addition of 3290 g of a mixture of PO and EO (PO/ EO mass ratio = 50/50), and capping with EO176g to obtain a polyether polyol having a hydroxyl group of 3 and a hydroxyl value of 36 mgKOH/g. The mixture ratio of PO to EO was 70% by mass based on the total amount of PO and EO which had been subjected to ring-opening addition, and the EO ratio in the mixture of PO and EO was 34% by mass. The EO ratio was 35 mass% with respect to the total amount of EO and PO which had been subjected to ring-opening addition, and the closed EO ratio was 4 mass%.

[Polyether polyol (B)]

Polyether polyol (B-1): a mixture of sucrose (functional group number 8) and glycerol (functional group number 3) is used as an initiator, and only a ring-opening addition PO is carried out in the presence of a potassium hydroxide catalyst to obtain a hydroxyl group. A polyether polyol having a number of 4.7 and a hydroxyl value of 450 mgKOH/g.

Polyether polyol (B-2): using a mixture of sorbitol (functional group number 6) and glycerol as an initiator, and only ring-opening addition of PO in the presence of a potassium hydroxide catalyst to obtain a hydroxyl group of 3.5 and A polyether polyol having a hydroxyl value of 550 mgKOH/g.

Polyether polyol (B-3): using a mixture of sucrose and glycerol as an initiator, and only ring-opening addition of PO in the presence of a potassium hydroxide catalyst to obtain a hydroxyl group of 4.3 and a hydroxyl value of 375 mgKOH/g. Polyether polyol.

Polyether polyol (B-4): using neopentyl alcohol (functional group number 4) as an initiator, and only ring-opening addition of PO in the presence of a potassium hydroxide catalyst to obtain a hydroxyl group A polyether polyol having a number of 4 and a hydroxyl value of 410 mgKOH/g.

Polyether polyol (B-5): using sorbitol as an initiator and only ring-opening addition of PO in the presence of a potassium hydroxide catalyst to obtain a polyether polyol having a hydroxyl number of 6 and a hydroxyl value of 500 mgKOH/g. .

[Polyether polyol (C)]

Polyether polyol (C-1): using glycerol as an initiator, ring-opening addition of 913 g of PO in the presence of a potassium hydroxide catalyst, followed by ring-opening addition of 495 g of EO to obtain a hydroxyl group of 3 and A polyether polyol having a hydroxyl value of 112 mgKOH/g. In the total amount of EO and PO which have been subjected to ring-opening addition, the EO ratio accounts for 33% by mass.

Polyether polyol (C-2): using glycerol as an initiator, and ring-opening addition of 2518 g of PO in the presence of a potassium hydroxide catalyst, followed by ring-opening addition of 390 g of EO to obtain a hydroxyl group of 3 And a polyether polyol having a hydroxyl value of 56 mgKOH/g. In the total amount of EO and PO which have been added to the ring, the EO ratio accounts for 13% by mass.

Polyether polyol (C-3): using glycerol as an initiator, and ring-opening addition of 4108 g of PO in the presence of a potassium hydroxide catalyst, followed by ring-opening addition of 800 g of EO to obtain a hydroxyl group of 3 And a polyether polyol having a hydroxyl value of 34 mgKOH/g. In the total amount of EO and PO which have been added to the ring, the EO ratio accounts for 16% by mass.

[Compared polyether polyol (E)]

Polyether polyol (E-1): using glycerol as an initiator, and ring-opening addition of PO in the presence of a potassium hydroxide catalyst, ring-opening addition of a mixture of PO and EO to obtain a hydroxyl group of 3 and A polyether polyol having a hydroxyl value of 44 mg KOH/g. In the total amount of EO and PO which have been added to the ring, the EO ratio accounts for 12% by mass.

Polyether polyol (E-2): using glycerol as an initiator, and ring-opening addition of a mixture of PO and EO in the presence of a potassium hydroxide catalyst to obtain a hydroxyl group of 3 and a hydroxyl value of 45 mgKOH/g. Polyether polyol. In the total amount of EO and PO which have been added to the ring, the EO ratio accounts for 67% by mass.

Flame Retardant A: ginseng (β-chloropropyl) phosphate (trade name: manufactured by FYLOLPCFICL-IPJAPAN Co., Ltd.).

Blowing agent A: water.

Foam stabilizer A: 矽 oxygen-based foam stabilizer (trade name: SF2938F, manufactured by TORAY Dow Corning Co., Ltd.).

Catalyst A: Reactive amine catalyst (trade name: POLYCAT 52, manufactured by Air Products Japan Co., Ltd.).

Catalyst B: a reactive amine-based catalyst (trade name: TOYOCAT-RX7, manufactured by Tosoh Corporation).

Polyisocyanate compound (Y-1): crude MDI, trade name: CORONATE 1130, viscosity (25 ° C): 120 mPa. s, NCO content: 31.2% (manufactured by Japan Polyurethane Industrial Co., Ltd.).

[Examples 1 to 25, Comparative Examples 1 to 6] [Box type free foaming test]

The polyol liquid, the foaming agent, the foam stabilizer, the catalyst and the flame retardant are mixed under the blending shown in the table to prepare a polyol liquid. The liquid temperature of the obtained polyol liquid and the polyisocyanate compound (Y-1) was respectively kept at 15 ° C, and a stirring device for a disc type stirring blade for a ball disc manufactured by Hitachi, Ltd. was placed, and the like The mixture was stirred for 3 seconds at 3,000 rotations per minute to prepare a mixed solution. Thereafter, the mixed solution was filled in a wooden mold equipped with a polyethylene release bag and having a length of 150 mm × a width of 150 mm × a height of 150 mm to be foamed, thereby producing an ultra-lightweight hard having a box core density of about 10 kg/m ³ . Foaming material.

In the table, the numerical unit indicating the amount of blending is part by mass. However, the amount of polyisocyanate used is expressed by the isocyanate index (INDEX).

The reactivity in the above box-type free foaming, the density of the obtained rigid foamed material, the shrinkage, the appearance of the foamed material, and the storage stability of the polyol-based liquid were evaluated by the following methods. The evaluation results are shown in Table 1, Table 2 and Tables 4-6. In the table, "polyol" means "polyether polyol".

(reactive)

The mixing start time of the polyol liquid and the polyisocyanate compound is 0 seconds, and the time until the start of bubbling of the mixed solution is the milk thick time (seconds), the time when the mixed liquid starts to foam and the foam material rises and stops is Rise time (seconds).

(box core density)

The core portion of the self-made hard polyurethane foam material was cut into cubes having a cube of 100 mm on one side, and the density was measured in accordance with JIS K7222. Density measurements were not made for those with larger shrinkage deformation.

(non-shrinking)

In the box type free foaming, after the foaming material due to foaming was stopped from rising, it was allowed to stand at 20 ° C for 30 minutes and the appearance state was observed. The evaluation was performed on the basis of the following criteria.

○ (good): no deformation; good.

△ (may): Partial deformation due to shrinkage.

× (not available): collapsed due to shrinkage; bad.

(appearance of foamed material)

The surface of the rigid foamed material obtained by box-type free foaming is the surface of the entire surface with respect to the foaming direction (the height direction of the box) as the lower side (the bottom surface side of the wooden box mold). Further, a surface of a 100 mm cube was cut out from the core portion of the hard foam material as a core portion surface.

The surface of the entire face and the core portion was visually observed for the presence or absence of a non-uniform cavity portion (the portion where the bubble chamber became thick), and was evaluated on the basis of the following criteria.

◎ (excellent): the portion where the bubble chamber is thickened; the bubble chamber is fine and uniform.

○ (good): the part where the bubble chamber is thick; the bubble chamber is uniform.

△ (may): Some of the bubble chambers become thicker.

× (not available): The bubble chamber becomes thick as a whole;

(Storage stability of polyol liquid)

The polyol liquid prepared in the box free foaming was stored at 20 ° C for one month, and then visually observed and evaluated on the following basis.

○ (good): no turbidity, separation, precipitation, solidification and transparency.

× (not available): One or more of turbidity, separation, precipitation, and solidification may occur.

[spray construction test]

The results of the spray application test are shown in Tables 2 and 3.

The polyol, the foaming agent, the foam stabilizer, the catalyst, and the flame retardant were mixed in the same manner as in the box type free foaming of each of the above examples to prepare a polyol liquid.

The liquid polyol and the polyisocyanate compound (Y-1) were sprayed to a hypothetical wall surface by a spray foaming machine at a liquid temperature of 40 ° C, a room temperature of 20 ° C and a volume ratio of 1:1. 600mm × 600mm × 5mm flexible plate (substrate) for construction, by this method Create a rigid foam material. The spray foaming machine was a MODEL N-1600 UE-HYD foaming machine manufactured by NUE Co., Ltd., which was connected with a D gun manufactured by GUSMER. The spray was applied to a lower spray layer having a thickness of 1 mm, and two layers of spray were applied so as to have a thickness of 25 to 30 mm, and a total of three layers were laminated.

The core density, shrinkage, adhesion, flame retardancy and thermal conductivity in spray application were evaluated by the following methods.

(core density)

According to JIS K7220, a rectangular parallelepiped of 200 mm × 200 mm × 25 mm was cut out from the core portion on the next day of the spray application, and the density was measured.

(non-shrinking)

In the above spray application, after the foaming material due to foaming was stopped from rising, it was allowed to stand at 20 ° C for 30 minutes, and the appearance state was observed. Those who are not deformed are regarded as ○ (good) and those who have shrinkage deformation are regarded as × (bad).

(adhesive)

The end portion of the foamed material to be applied was cut, and the feeling of touch when the foamed material was peeled off from the substrate was confirmed, and evaluated based on the following criteria.

○ (good): The foamed material remained on the substrate and was firmly adhered to, and the foamed material was hardly peeled off;

× (not possible): The foamed material does not remain on the substrate, and can be easily peeled off from the foamed material;

(combustion test (flame retardancy))

The hard foaming material obtained was subjected to a self-extinguishing test in accordance with Test Method B of JIS-A-9511, and the burning time (unit: second) and the burning length (unit: mm) were measured. The smaller the burning length and the shorter the burning time, the better the flame retardancy.

(Thermal conductivity)

The thermal conductivity (unit: mW/m.K) was measured in accordance with JIS A1412 using a thermal conductivity measuring device (product name: AUTO Λ HC-074 type, manufactured by Hidehiro Seiki Co., Ltd.).

Table 1 shows Examples 1 to 5. As shown in the results of Table 1, in Examples 1 to 5 in which the polyether polyol (P) contained the polyether polyol (A) in the range of 50 to 70% by mass, no observation was observed in all the foam materials. shrink. Further, the appearance of the foamed material was good and the storage stability of the polyol-based liquid was also good. Example 4 is an example in which a polyether polyol (C) is used in addition to the polyether polyols (A) and (B). No shrinkage of the foamed material was observed. Further, the appearance of the foamed material was good and the storage stability of the polyol-based liquid was also good.

Table 3 shows an example in which a polyol-based liquid and a polyisocyanate compound which were blended with the same raw materials as in Examples 2 to 5 of Table 1 were subjected to a spray application test. In the spray application tests of Examples 2 to 5, no shrinkage of the foamed material was observed, and hard hair having excellent adhesion and flame retardancy was obtained even at a low density. Bubble material.

Table 2 shows the results of the box type free foaming test and the spray application test (parts) of Examples 6 to 11. In these examples, a polyether polyol (A-2) having a hydroxyl value of 36 mgKOH/g was used. As shown in Table 2, the polyether polyol (A) was in the range of 50% by mass to 80% by mass, and no shrinkage was observed in all of the foamed materials. Further, the appearance of the foamed material was good and the storage stability of the polyol-based liquid was also good.

Table 3 shows the spray construction test results of Examples 7, 9, and 10 of Table 2 for comparison. As shown in Table 3, prepared in Examples 7, 9, and 10. Compared with Examples 2 to 5, the hard foaming material had a lower core density at the time of spray foaming. This reason is considered to be due to an increase in the molecular weight of the polyether polyol (A).

Table 4 shows Examples 12 to 21, and Table 5 shows Examples 22 to 25. In these examples, as the polyether polyol (B), a polyol obtained by ring-opening addition of PO to an initiator such as sorbitol or pentaerythritol in the presence of a potassium hydroxide catalyst (B-) is used. 1, 2, 3, 4, 5). As shown in the results of Table 4, in Examples 12 to 19 containing 60% by mass or 80% by mass of the polyether polyol (A), no shrinkage was observed in all of the foamed materials. Further, the appearance of the foamed material was good and the storage stability of the polyol-based liquid was also good. Examples 20 and 21 are examples in which a polyether polyol (C) is used in addition to the polyether polyols (A) and (B). No shrinkage of the foamed material was observed in these examples. Further, the appearance of the foamed material was good and the storage stability of the polyol-based liquid was also good.

In Examples 22 and 23 of Table 5, a polyol (A-3) whose terminal has been first-staged was used. Compared with other examples, it can be seen that the milk thickening time is short and the reaction is fast. Further, as shown in Examples 24 and 25, even when two or more types of polyether polyols (B) were used in combination, a good foamed material was obtained, and the storage stability of the polyol-based liquid was also good.

Table 6 shows Comparative Examples 1 to 6. Comparative Examples 1~3 use polyether An example in which a polyhydric alcohol (E-1) is substituted by a polyhydric alcohol (E-1) having a random chain of an oxygen-extended ethyl group and an oxygen-extended propyl group, and an initiator The content ratio of EO in the ring-opening addition alkylene oxide is as small as 12% by mass. In these examples, the polyol liquid has poor storage stability and the box core density is also slightly higher. ratio In the examples 4 to 6, the polyether polyol (E-2) is used, and the polyether polyol (E-2) is a content ratio of EO in the alkylene oxide which is subjected to ring-opening addition of the initiator in Patent Document 2 Within the range of the record and up to 67% by mass. In these examples, the core density is high, and the foamed material is observed to shrink and has a poor appearance. This is considered to be because the activity of the polyether polyol (E-2) is too high, and the resinization reaction is too fast, so that the expansion ratio becomes insufficient and the shrinkage or core density becomes high. Further, due to the influence of the crystallinity of the polyoxyalkylene chain, the bubble chamber becomes thick, and the appearance of the foamed material is deteriorated.

Industrial availability

As described above, in the production method of the present invention, it is possible to produce a rigid foamed material which is excellent in storage stability when stored in a polyol-based liquid and which has no shrinkage deformation and is light in weight. The rigid foam material is suitable for construction, building materials use and interior components of automobiles, and is particularly suitable for being disposed between a roof panel, a door trim and a door frame.

Japanese Patent Application No. 2011-231725, filed on Oct. 21, 2011, and the Japanese Patent Application No. 2012-022766, filed on Feb. 6, 2012, The entire contents of the abstract are incorporated herein by reference.

Claims (12)

A method for producing a rigid foamed synthetic resin by reacting a polyether polyol (P) with a polyisocyanate compound (Y) in the presence of a foaming agent, a flame retardant, a foam stabilizer and a catalyst to produce a rigid foam The synthetic resin is characterized in that the polyether polyol (P) contains at least the following polyether polyol (A) and polyether polyol (B), and the foaming agent contains water; polyether polyol (A) : a random polymeric chain having an oxygen-extended ethyl group and an oxygen-extended propyl group, and having a hydroxyl number of 2 to 8, a hydroxyl value of 10 to 100 mgKOH/g, and an oxygen-extended ethyl group content of 20 to 60% by mass; Polyol (B): the number of hydroxyl groups is 3 to 8 and the hydroxyl value is 200 to 700 mgKOH/g. The method for producing a rigid foamed synthetic resin according to the first aspect of the invention, wherein the content of the polyether polyol (B) is from 1 to 50% by mass based on the polyether polyol (P). The method for producing a rigid foamed synthetic resin according to claim 1 or 2, wherein the polyether polyol (A) is subjected to ring-opening addition of propylene oxide to an initiator (S1), followed by propylene oxide and A mixture of ethylene oxide is prepared by ring-opening addition. The method for producing a rigid foamed synthetic resin according to claim 3, wherein the ring-opening addition amount of the mixture of the propylene oxide and the ethylene oxide is relative to the total amount of the alkylene oxide which has been subjected to ring-opening addition 40 to 90% by mass. A method for producing a rigid foamed synthetic resin according to claim 3 or 4, wherein the epoxy propylene oxide and ethylene oxide are mixed, epoxy The amount of ethane relative to the mixture is from 30 to 90% by mass. The method for producing a rigid foamed synthetic resin according to any one of claims 1 to 5, wherein the water is used in an amount of 15 to 60 parts by mass based on 100 parts by mass of the polyether polyol (P). The method for producing a rigid foamed synthetic resin according to any one of claims 1 to 6, wherein the polyether polyol (B) is a polyoxypropylene propylene polyol. The method for producing a rigid foamed synthetic resin according to any one of claims 1 to 7, wherein the polyether polyol (P) further contains 1 to 20% by mass based on the polyether polyol (P). The following polyether polyol (C); polyether polyol (C): a random polymeric chain having a polyoxyalkylene group at the end and having no oxygen-extended ethyl group and an oxygen-extended propyl group, and having a hydroxyl number of 2 to 8 and The hydroxyl value is 20 mgKOH/g or more and less than 200 mgKOH/g. The method for producing a rigid foamed synthetic resin according to any one of claims 1 to 8, wherein the flame retardant is used in an amount of 10 to 100 parts by mass based on 100 parts by mass of the polyether polyol (P). . The method for producing a rigid foamed synthetic resin according to any one of claims 1 to 9, wherein the polyisocyanate compound (Y) is used in an amount of from 10 to 100 in terms of an isocyanate index. The method for producing a rigid foamed synthetic resin according to any one of claims 1 to 10, wherein the hard foamed synthetic resin has a core density of 5 to 12 kg/m ³ . The method for producing a rigid foamed synthetic resin according to any one of claims 1 to 11, wherein the hard foamed synthetic resin is produced by a spray method.