JP2011241255A - Method for producing polyether polyol and method for producing rigid foamed synthetic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyether polyol, which suppresses the viscosity of polyol system liquid low, has excellent miscibility between a polyol system liquid and an isocyanate compound and forms a rigid foamed synthetic resin having improved strength and dimensional stability and excellent flame retardancy and thermal insulation properties in spite of having low density.SOLUTION: The method for producing a polyether polyol (A) includes reacting a phenol with an aldehyde and an alkanolamine and adding an alkylene oxide to the obtained reaction product. The use amount of the aldehyde to 1 mol of the phenol is ≥0.9 mol and <1.35 mol and the use amount of the alkanolamine is ≥2.1 mols and ≤10.5 mols.

Description

  The present invention relates to a method for producing a polyether polyol, and a method for producing a rigid foam synthetic resin using a polyether polyol obtained by the production method.

  An active hydrogen compound such as a polyol and a polyisocyanate compound are reacted in the presence of a foam stabilizer, a catalyst, and a foaming agent to form a rigid polyurethane foam or a rigid polyisocyanurate foam (hereinafter collectively referred to as a rigid foam synthetic resin). .) Is widely done. Rigid foamed synthetic resin is suitably used as a heat insulating material for various devices or buildings because it has a high degree of freedom in molding and excellent heat insulation. In the heat insulating material, it is desirable that the heat conductivity is lower and the heat insulating property is higher.

These rigid foam synthetic resins are manufactured using molding methods such as spraying, continuous board molding, and injection.
For example, a spray method is often employed when manufacturing a rigid foam synthetic resin as a heat insulating material or the like in a construction site or the like. The spray method is, for example, a polyol system liquid containing a polyol and a foaming agent and the like, and a polyisocyanate compound that is pumped and reacted while spraying from a spray gun onto a wall surface that is a construction target. It is the method of making it foam and making it a heat insulating material etc. The advantage of the spray method is that a heat insulating material having a desired thickness can be constructed regardless of the shape of the wall surface or the like to be constructed. Moreover, according to the multi-layer spraying method among the spray methods, it is possible to form a thick heat insulating layer by laminating the hard foam synthetic resin by spraying twice or more.

In general, rigid foamed synthetic resins are required to be further reduced in density while maintaining good heat insulating properties for cost reduction by reducing the amount of raw materials used or ease of conveyance by weight reduction. However, there is a problem that the strength decreases and shrinks easily with a decrease in density, that is, the dimensional stability decreases. It is necessary to develop a hard foam synthetic resin that is excellent in strength and dimensional stability even at low density.
In addition, the hard foamed synthetic resin also needs flame retardancy from the viewpoint of fire resistance as a building material. In particular, when the spray method is employed, flame retardancy is required from the viewpoint of preventing fire accidents caused by welding sparks at the construction site.

  In the production of rigid foam synthetic resins, hydrofluorocarbons (for example, HFC-245fa, HFC-365mfc, etc .; hereinafter referred to as HFCs) are mainly used as foaming agents. However, considering the environmental load, it is desirable to reduce the use of the HFCs. Therefore, in order to reduce the amount of HFCs used and make up for it, a technique using water as a blowing agent has been studied. However, since the amount of water used in HFCs and water necessary to obtain the same foaming density is extremely small, the use of water instead of HFCs reduces the solvent effect of HFCs. And the viscosity of a polyol system liquid increases, and there exists a problem which a moldability and workability deteriorate. In addition, as the water content in the polyol system liquid increases, there is also a problem that the miscibility between the polyol system liquid and the highly hydrophobic polyisocyanate compound deteriorates, and molding defects are likely to occur. In particular, the above-mentioned problems when using water as a foaming agent are prominently shown by the spray method, and at the same time as lowering the density of hard foamed synthetic resins that have been required for many years and improving heat insulation and flame retardancy, It is strongly desired to solve these problems.

On the other hand, polyether polyols produced using a reaction product (Mannich condensation product) obtained by subjecting phenols, aldehydes and alkanolamines to a Mannich condensation reaction have high strength and high flame retardancy. It is evaluated for its ease.
The following Patent Documents 1 to 5 describe Mannich polyols using Mannich condensation products.
Patent Document 1 describes a method of using Mannich polyol in a method of producing a rigid polyurethane foam using water as a foaming agent. In the reaction of phenols, aldehydes, and alkanolamines to obtain a Mannich condensation product, the molar ratio of phenols: aldehydes: alkanolamines is 1: 1: 1 to 1: 2.2: 2. A range of .2 is stated, but the molar ratios used in the examples are 1: 1.5: 2.0 and 1: 2.0: 2.0.
In Patent Document 2, 1-2 mol of an amine compound is mixed per 1 mol of phenols, and 1.25 to 1.75 mol of formaldehyde is added to 1 mol of the phenols to add a highly functional Mannich. A Mannich polyol is described in which a condensate is produced and an alkylene oxide is added thereto.

Patent Document 3 relates to a method for producing a rigid foamed synthetic resin using water as a foaming agent, and describes a low-viscosity Mannich polyol produced using a Mannich condensation product. The Mannich condensate is a Mannich condensate having a high number of functional groups produced by condensation with alkylphenol: diethanolamine: formaldehyde = 1: 2.5 to 4: 1.5 to 2.
Patent Document 4 relates to a method for producing a Mannich polyol in which a phenolic compound is reacted with formaldehyde and an alkanolamine to form a Mannich condensation product, and the Mannich condensation product is at least partially dehydrated and then alkoxylated. It is usually used in a ratio of 1 mol of formaldehyde to 0.75 to 1.5 mol of alkanolamine, and a molar ratio of phenolic compound: formaldehyde of 1: 0.9 to 1: 3.5 is advantageously used. However, the ratio of phenolic compound: formaldehyde: alkanolamine used in the examples is 1: 2.0: 2.0.
Patent Document 5 relates to a method for producing a polyether polyol by adding propylene oxide and / or butylene oxide (without using ethylene oxide) to a reaction product obtained by reacting phenols, aldehydes and alkanolamines. It is described that the use ratio of aldehydes is 1.35 to 3.0 moles per mole of phenols, and the use ratio of alkanolamines is 1.1 to 3.0 per mole of aldehydes. ing. The ratio of phenols: aldehydes: alkanolamines used in the examples is 1: 1.4-2: 1.8-2.4.

Japanese translation of PCT publication No. 2002-524630 JP 2004-10812 A Japanese Patent Laid-Open No. 08-301820 Japanese Patent Laid-Open No. 03-121113 Japanese Patent Laid-Open No. 11-189645

However, the conventional Mannich polyol tends to have a high viscosity, and the viscosity of the polyol system solution tends to be high. When the polyol system liquid has a high viscosity, poor mixing of the polyol system liquid and the isocyanate compound raw material occurs during foaming, and workability tends to deteriorate.
The present invention has been made in view of the above circumstances, and can suppress the viscosity of the polyol system liquid to a low level, obtain a good mixing property between the polyol system liquid and the isocyanate compound, and have low strength and strength and dimensional stability. It aims at providing the manufacturing method of polyether polyol which can form the hard foaming synthetic resin which is favorable and excellent in a flame retardance and heat insulation, and the manufacturing method of hard foaming synthetic resin using this polyether polyol.

The present invention includes the following [1] to [10].
[1] A method for producing a polyether polyol (A) by reacting the following phenols, the following aldehydes and the following alkanolamines, and then adding an alkylene oxide to the obtained reaction product. The use ratio of the aldehydes is 0.9 mol or more and less than 1.35 mol, and the use ratio of the alkanolamines is 2.1 mol or more and 10.5 mol or less with respect to 1 mol of the class. A method for producing a polyether polyol (A).
Phenols: One or more selected from the group consisting of phenol and phenol derivatives having a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol.
Aldehydes: One or more selected from the group consisting of formaldehyde and acetaldehyde.
Alkanolamines: One or more selected from the group consisting of monoethanolamine, diethanolamine and 1-amino-2-propanol.

[2] The phenol derivative has a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, and one or more of the other hydrogen atoms bonded to the aromatic ring have 1 to 15 carbon atoms. The method for producing a polyether polyol (A) according to [1], which is an alkylphenol substituted with an alkyl group.
[3] The method for producing a polyether polyol (A) according to [1] or [2], wherein the alkylene oxide is one or more selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide.
[4] The method for producing a polyether polyol (A) according to [1] to [3], wherein the polyether polyol (A) has a hydroxyl value of 200 to 800 mgKOH / g.

[5] A method for producing a rigid foamed synthetic resin by reacting a polyol composition (P) and a polyisocyanate compound (I) in the presence of a foaming agent, a foam stabilizer and a catalyst, the polyol composition ( P) contains the polyether polyol (A) obtained by the manufacturing method of [1]-[4], The manufacturing method of the hard foam synthetic resin characterized by the above-mentioned.
[6] The method for producing a rigid foam synthetic resin according to [5], wherein the content of the polyether polyol (A) in the polyol composition (P) is 20 to 100% by mass.
[7] The method for producing a hard foam synthetic resin according to [5] or [6], wherein water is used alone as the foaming agent.
[8] The method for producing a rigid foam synthetic resin according to [5] to [7], wherein the polyol composition (P) includes a polymer-dispersed polyol (W).
[9] The method for producing a rigid foam synthetic resin according to [8], wherein the polymer-dispersed polyol (W) has a hydroxyl value of 100 to 800 mgKOH / g.
[10] The method for producing a rigid foamed synthetic resin according to [5] to [9], using a spray method.

In the polyether polyol (A) obtained by the production method of the present invention, the viscosity of the polyol system liquid containing the polyether polyol (A) is suppressed to be low, and good mixing properties between the polyol system liquid and the isocyanate compound can be obtained. Moreover, by producing a rigid foamed synthetic resin using the polyether polyol (A), the rigid foamed synthetic resin has low strength and good strength and dimensional stability, and is excellent in flame retardancy and heat insulation. Is obtained.
Therefore, even when water is used instead of HFC as the foaming agent, the viscosity of the polyol system liquid can be kept low. It can also be preferably applied to the spray method, and a good hard foam synthetic resin can be formed.
According to the method for producing a rigid foam synthetic resin of the present invention, the viscosity of the polyol system liquid is low, the mixing property between the polyol system liquid and the isocyanate compound is good, and good moldability and workability are obtained. A rigid foamed synthetic resin that is excellent in strength and dimensional stability and excellent in flame retardancy and heat insulation is obtained despite its density. A good rigid foamed synthetic resin can also be formed by spraying.

The “polyol system liquid” in the present invention is a liquid to be reacted with a polyisocyanate compound, and is a liquid containing a compounding agent as required, such as a foaming agent, a foam stabilizer, a catalyst, etc. in addition to a polyol.
The “rigid foam synthetic resin” in the present invention is a general term for rigid polyurethane foam and rigid polyisocyanurate foam. Hereinafter, it may be called a rigid foam.
The “polymer-dispersed polyol” in the present invention is obtained by polymerizing a monomer having a polymerizable unsaturated bond in a base polyol (W ′) such as a polyether polyol or a polyester polyol to form polymer particles. The polyol (W) in which the polymer particles are dispersed in the base polyol (W ′).
The “Mannich condensation product” in the present invention is a compound obtained by reacting phenols, aldehydes, and alkanolamines.
The “Mannic polyol” in the present invention is a compound obtained by adding an alkylene oxide to a Mannich condensation product.

<Method for producing polyether polyol (A)>
In the production method of the polyether polyol (A) of the present invention (hereinafter referred to as “polyol (A)”), phenols, aldehydes and alkanolamines are first reacted (hereinafter also referred to as Mannich condensation reaction). To obtain a reaction product containing a Mannich condensation product. The reaction product includes unreacted substances remaining after the reaction.

The phenol is at least one selected from the group consisting of phenol and a phenol derivative having a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol. That is, it suffices to have a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, which may be phenol or a phenol derivative. One type of phenol may be used, or two or more types may be used in combination.
The phenol derivative has a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, and one or more of the other hydrogen atoms bonded to the aromatic ring are alkyl groups having 1 to 15 carbon atoms. Substituted alkylphenols are preferred. The substitution position of the alkyl group in the alkylphenol may be any of the ortho, meta, and para positions. In one molecule of alkylphenol, the number of hydrogen atoms substituted with an alkyl group is 1 to 4, preferably 1 to 2, and most preferably 1.
The number of carbon atoms of the alkyl group in the alkylphenol is preferably 1-10. As the alkylphenol, nonylphenol and cresol are preferably used. Nonylphenol is particularly preferable in terms of improving the compatibility between the polyol (A) and the polyisocyanate compound (I) and improving the cell appearance.

  As aldehydes, one or a mixture of formaldehyde and acetaldehyde is used. Among these, formaldehyde is preferable in terms of improving the adhesiveness of the rigid foam. Formaldehyde may be used in any form, and can be used as a formalin aqueous solution, a methanol solution, or paraformaldehyde. When used as paraformaldehyde, paraformaldehyde may be heated to form formaldehyde, and the formaldehyde may be used in the reaction of this step. The amount used is calculated as the number of moles in terms of formaldehyde.

  The alkanolamines are at least one selected from the group consisting of monoethanolamine, diethanolamine and 1-amino-2-propanol. Of these, diethanolamine is more preferable for achieving a balance between improving the strength of the rigid foam obtained and reducing the viscosity of the polyol (A).

  In the present invention, the raw material is used in an amount of 0.9 to 1.35 mol, preferably 0.98 to 1.30 mol, with respect to 1 mol of phenols, More preferably, it is more than 1.25 mol. If it is 0.9 mol or more and less than 1.35 mol, the polyol (A) has a low viscosity, and the rigid foam obtained using this has good dimensional stability and better heat insulation.

  The use ratio of alkanolamines is 2.1 to 10.5 mol, preferably 2.5 to 10 mol, relative to 1 mol of phenols. If it is the range of 2.1-10.5 mol, the viscosity of a polyol system liquid will be easy to be suppressed low, the mixability of a polyol system liquid and polyisocyanate compound (I), and the dimensional stability of the rigid foam obtained, This is preferable in that the flame retardancy tends to be good.

In the present invention, setting the proportion of aldehydes to be in the above range contributes to lowering the viscosity of the polyol (A). The reason is considered as follows. In the following, description will be made using alkylphenol having an alkyl group R at the para position as an example of phenols, formaldehyde as an example of aldehydes, and diethanolamine as an example of alkanolamines, but the same applies to other compounds.
That is, when the phenols, aldehydes, and alkanolamines are reacted, if the aldehydes are 0.9 mol or more and less than 1.35 mols per mol of the phenols, the resulting reaction product is represented by the following formula: Phenols as represented by the following formula (iii), containing many Mannich condensation products having a structure in which phenols: aldehydes are reacted at 1: 1 (molar ratio) as represented by (i) : Mannich condensation product having a structure in which aldehydes are reacted at 1: 2 (molar ratio) and polynuclear compound represented by formula (iv) are low in content and unreacted as represented by formula (ii) This alkylphenol is hardly contained.
Compared with the compound represented by the following formula (iii) or (iv), the compound represented by the formula (i) can suppress the viscosity of the Mannich polyol low. When such a compound is present in a relatively large amount, the polyol (A) is reduced in viscosity.

Further, since there is almost no unreacted phenol represented by the formula (ii), a decrease in the average number of functional groups of Mannich polyol (polyol (A)) can be suppressed, and a decrease in strength of the rigid foam can be suppressed. Thereby, the dimensional stability of the rigid foam can be improved.
Furthermore, since the Mannich condensation product represented by the formula (i) has a lower molecular weight than the compound represented by the formula (iii) or (iv), the Mannich polyol (polyol (A )) Contributes to the improvement of the compatibility with the isocyanate compound and water, and contributes to the refinement of the cells of the resulting rigid foam. When the cells of the rigid foam are miniaturized, heat transfer due to radiation is suppressed and the thermal conductivity is lowered.

The ratio of alkanolamines used affects the viscosity of Mannich polyol (polyol (A)) and the flame retardancy of the rigid foam. That is, if the proportion of alkanolamines used is high and unreacted alkanolamines are contained in the reaction product (Mannich condensation product), Mannich polyol (polyol (A)) is produced using the reaction product as an initiator. In this case, a polyol in which alkylene oxide is added to unreacted alkanolamines is produced. Such a polyol contributes to a reduction in viscosity. However, as the amount increases, the content ratio of Mannich polyol having an aromatic ring is relatively low, so that the flame retardancy is likely to decrease.
In the present invention, the use ratio of the aldehydes is in the above range, and the use ratio of the alkanolamines is in the above range, thereby reducing the low viscosity of the polyol (A)) without reducing the flame retardancy of the rigid foam. Can be achieved.

The Mannich condensation reaction in the present invention can be carried out by a known method. Phenols, aldehydes and alkanolamines are mixed and reacted by heating at a temperature of 50 to 150 ° C., preferably 80 to 130 ° C. As the mixing method, methods (1) to (3) are conceivable.
(1) Phenols, aldehydes and alkanolamines are mixed simultaneously.
(2) Mix aldehydes with a mixture of phenols and alkanolamines.
(3) A phenol is mixed with a mixture of aldehydes and alkanolamines.
(2) is most preferable in terms of low production of polynuclear bodies, and then (3) is preferable.
Since water is generated by the Mannich condensation reaction, and when a formalin aqueous solution is used, water is present in the reaction product. Therefore, it is preferable to remove water from the reaction product by an appropriate method. For example, the internal pressure of the reactor is lowered to 1,330 to 66,500 Pa at 100 to 150 ° C. and dehydrated under reduced pressure, so that the residual water content is about 1% by mass. The step of removing water can be performed before or after the step of adding alkylene oxide, and is preferably performed before the step of adding alkylene oxide.

In the production of the polyether polyol (A) of the present invention, the reaction product obtained by the Mannich condensation reaction is used as an initiator (S1), and an alkylene oxide is added thereto to obtain the polyol (A).
The addition amount of alkylene oxide added to the initiator (S1) is preferably 2 to 30 mol, more preferably 4 to 20 mol, relative to 1 mol of the phenols used in the Mannich condensation reaction. When the added amount of alkylene oxide is not less than the lower limit of the above range, the hydroxyl value and viscosity of the resulting polyol (A) tend to be low. When the added amount of alkylene oxide is not more than the upper limit of the above range, when the resulting polyol (A) is used for producing a rigid foam, it is easy to suppress the shrinkage of the rigid foam.

The alkylene oxide (sometimes described as AO) that undergoes ring-opening addition polymerization to the initiator (S1) is ethylene oxide (sometimes described as EO) or propylene oxide (sometimes described as PO). And one or more selected from the group consisting of butylene oxide are preferred. Of these, EO and / or PO are more preferably used, and EO and PO are more preferably used.
When PO and EO are used in combination, any polymerization method of block polymerization and random polymerization may be used, and furthermore, both block polymerization and random polymerization may be combined. In the case of block polymerization, the order in which AO is subjected to ring-opening addition polymerization is preferably added in the order of PO and EO, or EO is added first, and PO and EO are added in this order. By ring-opening addition polymerization in this order, most of the hydroxyl groups of the polyol (A) become primary hydroxyl groups, and the reactivity between the polyol (A) and the polyisocyanate compound (I) increases. As a result, the appearance of the resulting rigid foam tends to be favorable, which is preferable. It is also effective in improving the adhesiveness of the resulting rigid foam.

In the AO to be subjected to ring-opening addition polymerization to the initiator (S1), the ratio of the total of EO and PO (EO + PO) / AO is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and 100% by mass. % Is most preferred. Within this range, the polyol viscosity tends to be low, and the strength of the rigid foam is easily secured.
Moreover, 50-100 mass% is preferable and, as for the ratio EO / (EO + PO) of EO with respect to the total amount of EO and PO, 50-80 mass% is more preferable. Within this range, it is easy to ensure the strength of the rigid foam while keeping the viscosity of the polyol low. In particular, when the terminal is an oxyethylene group derived from ethylene oxide, the terminal hydroxyl group becomes a primary hydroxyl group, and good activity can be obtained.
When a plurality of types of polyol (A) are used in combination as the polyol (A), the value of (EO + PO) / AO or the value of EO / (EO + PO) is the value of the entire polyol (A). .

The hydroxyl value of the polyol (A) is preferably 200 to 800 mgKOH / g, more preferably 200 to 550 mgKOH / g, and further preferably 250 to 450 mgKOH / g.
As a polyol (A), when using in combination of multiple types of polyol (A), the hydroxyl value of each polyol (A) should just be in said range, respectively.
When the hydroxyl value of the polyol (A) is not more than the upper limit of the above range, the amount of alkylene oxide-derived oxyalkylene chains present in the polyol (A) increases, and the viscosity of the polyol (A) tends to decrease. Moreover, the brittleness of the manufactured rigid foam is reduced, and the adhesiveness is likely to be obtained. On the other hand, it is preferable for the hydroxyl value to be equal to or higher than the lower limit of the above range because the strength of the resulting rigid foam is easily secured and the dimensional stability is improved.

  According to the method for producing a polyol (A) of the present invention, a polyol (A) having a viscosity at 25 ° C. of 800 mPa · s or less, preferably 650 mPa · s or less can be obtained. The lower limit of the viscosity is not particularly limited, but is preferably 200 mPa · s or more and more preferably 300 mPa · s or more from the viewpoint of securing the strength of the rigid foam.

<Method for producing rigid foam synthetic resin>
The method for producing a rigid foamed synthetic resin of the present invention includes a reaction / foaming step in which a polyol composition (P) and a polyisocyanate compound (I) are reacted in the presence of a foaming agent, a foam stabilizer and a catalyst.
[Polyol composition (P)]
The polyol composition (P) (hereinafter sometimes simply referred to as the composition (P)) contains the polyol (A). 20-100 mass% is preferable, as for content of the polyol (A) in a composition (P), 30-99 mass% is more preferable, and 30-80 mass% is more preferable. Within this range, preferred strength, heat resistance and flame retardancy are obtained in the resulting rigid foam, and foam cracking is suppressed. In addition, in the spray method, from the point of showing good activity, the occurrence of lateral flow when spraying on the wall surface is suppressed, and the adhesiveness between foam layers when multi-layer spraying is also improved, so that good workability is obtained. It is done.

[Polyol (C)]
The composition (P) is further obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol, and a polyester polyol (C) having a hydroxyl value of 100 to 400 mgKOH / g (hereinafter sometimes referred to as polyol (C)). ) May be included.
At least one of the polycarboxylic acid and polyhydric alcohol to be polycondensed is preferably an aromatic compound having an aromatic ring.
As polyvalent carboxylic acid, dicarboxylic acid or its anhydride is preferable. Examples of the dicarboxylic acid having an aromatic ring include phthalic acids such as phthalic anhydride. Examples of the dicarboxylic acid having no aromatic ring include maleic acid, fumaric acid, and adipic acid.
As the polyhydric alcohol, a diol is preferable. Examples of the diol having an aromatic ring include a diol obtained by adding ethylene oxide to bisphenol A. Examples of the diol having no aromatic ring include ethylene glycol, diethylene glycol, and polyethylene glycol.

The hydroxyl value of the polyol (C) is 100 to 500 mgKOH / g, preferably 100 to 400 mgKOH / g, and more preferably 100 to 350 mgKOH / g.
As a polyol (C), when using combining multiple types of polyester polyol, the hydroxyl value of each polyester polyol should just be in said range, respectively.
When the hydroxyl value of the polyol (C) is less than or equal to the upper limit of the above range, the resulting rigid foam is less brittle and easily exhibits adhesiveness. Moreover, since the viscosity of a polyol (C) becomes easy to fall, the mixability in a composition (P) improves and is preferable. Furthermore, in the spray method, the isocyanate index when the construction is performed using the polyol system liquid and the polyisocyanate compound (I) at a predetermined volume ratio can be set high. On the other hand, when the hydroxyl value of the polyol (C) is not less than the lower limit of the above range, the resulting rigid foam is difficult to shrink. That is, if it is in the said range, the adhesive strength of a rigid foam, especially the initial adhesive strength can be made high, maintaining the mixing property of a raw material favorable.
When the composition (P) contains the polyol (C), the content is preferably 1 to 80% by mass, more preferably 1 to 70% by mass, and more preferably 20 to 70% by mass of the entire composition (P). Further preferred. If it is in the said range, the strength improvement effect of a rigid foam and the adhesive improvement effect will fully be acquired.

[Polymer-dispersed polyol (W)]
It is preferable to contain polymer particles in the composition (P). The polymer particles are preferably dispersed in the composition (P). Specifically, a polymer-dispersed polyol (W) in which polymer particles are dispersed in a base polyol (W ′) is prepared, The polymer-dispersed polyol (W) is preferably contained in the composition (P).
One type of polymer-dispersed polyol (W) may be used, or two or more types may be used in combination.
The polymer particles preferably have an outer diameter of 10 μm or less. The outer diameter of the polymer particles is measured with a Nikkiso Co., Ltd. Microtrac Ultra Fine Particle Size Analyzer UPA-EX150.
The content of the polymer particles in the entire composition (P) is preferably 0.002 to 10% by mass, more preferably 0.02 to 10% by mass, and particularly preferably 0.5 to 7% by mass. Within the above range, the shrinkage of the rigid foam obtained while maintaining the heat insulating performance can be effectively suppressed.

The hydroxyl value of the polymer-dispersed polyol (W) is preferably from 100 to 800 mgKOH / g, more preferably from 150 to 800 mgKOH / g. The hydroxyl value of the polymer-dispersed polyol (W) in the present specification is a value obtained by measuring the hydroxyl value of a polyol in which polymer particles are dispersed in the base polyol (W ′).
When the hydroxyl value of the polymer-dispersed polyol (W) is not less than the lower limit of the above range, the compatibility with other polyols is good, and when it is not more than the upper limit of the above range, the dispersion stability of the polymer particles is good. It is.

The polymer-dispersed polyol (W) is produced by a method in which a polymer particle is precipitated by polymerizing a monomer having a polymerizable unsaturated bond in the base polyol (W ′) in the presence of a solvent as necessary.
As the monomer having a polymerizable unsaturated bond used for forming the polymer particles, a monomer having one polymerizable unsaturated bond is usually used, but is not limited thereto.
Specific examples of the monomer include cyano group-containing monomers such as acrylonitrile, methacrylonitrile, and 2,4-dicyanobutene-1, styrene monomers such as styrene, α-methylstyrene, and halogenated styrene; acrylic acid, methacrylic acid, or Acrylic monomers such as alkyl esters, acrylamide and methacrylamide; vinyl ester monomers such as vinyl acetate and vinyl propionate; isoprene, butadiene and other diene monomers; unsaturated fatty acids such as maleic acid diester and itaconic acid diester Esters; vinyl halides such as vinyl chloride, vinyl bromide, vinyl fluoride; vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene fluoride; methyl vinyl ether, ethyl vinyl ether, isopropyl Vinyl ether monomers such as vinyl ether; and other than the above olefin, there is a halogenated olefin.
A combination of 20 to 90% by mass of acrylonitrile and 10 to 80% by mass of other monomers is preferred, and styrene, alkyl acrylate ester, alkyl methacrylate ester and vinyl acetate are preferred as other monomers. Two or more of these other monomers may be used in combination.

In addition to the monomers listed above, fluorine-containing acrylate or fluorine-containing methacrylate (hereinafter sometimes referred to as “fluorine-containing monomer”) is used as a part or all of the monomer having a polymerizable unsaturated group. It is also preferable. By using the fluorine-containing monomer, the dispersion stability of the polymer particles in the base polyol (W ′) becomes better. In addition, the compatibility between the polymer-dispersed polyol (W) and other polyols is enhanced, and it can be expected to improve the dimensional stability and heat insulation performance of the rigid foam.
As a suitable thing of a fluorine-containing monomer, the monomer represented by following formula (1) is mentioned.

In Formula (1), ^Rf is a C1-C18 polyfluoroalkyl group. In ^Rf , carbon number is 1-18, 1-10 are preferable and 3-8 are more preferable.
R ^f is preferably such that the ratio of fluorine atoms in the alkyl group (the ratio of the number of hydrogen atoms in the alkyl group replaced by fluorine atoms) is 80% or more, and all the hydrogen atoms are replaced by fluorine atoms. It is particularly preferable. When the number of carbon atoms is 18 or less, the foam stability is favorable during foaming in the production of rigid foam, which is preferable.
R is a hydrogen atom or a methyl group.
Z is a divalent linking group containing no fluorine atom, preferably a hydrocarbon group, such as an alkylene group or an arylene group, and more preferably an alkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, particularly preferably an alkylene group having 1 to 5 carbon atoms, and may be linear or branched. In Formula (1), Z and R ^f are separated so that the number of carbon atoms in R ^f is small.
Specific examples of the monomer represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-3).

The said fluorine-containing monomer can be used individually by 1 type or in combination of 2 or more types.
When using a fluorine-containing monomer, the usage-amount is preferable 10-100 mass% with respect to all the monomers which have a polymerizable unsaturated group, and 30-80 mass% is more preferable.
In particular, when the monomer represented by the formula (1) is used, it is preferably 20 to 100% by mass, more preferably 30 to 60% by mass, and more preferably 40 to 60% by mass in all monomers having a polymerizable unsaturated group. Is most preferred.
When the proportion of the monomer represented by the formula (1) is 20% by mass or more, particularly 30% by mass or more, good heat insulating performance is easily obtained when a rigid foam is obtained.

  When a fluorine-containing monomer is used, a macromonomer may be used in combination with the monomer having a polymerizable unsaturated bond listed above. The “macromonomer” refers to a low molecular weight polymer or oligomer having a radical polymerizable unsaturated group at one end.

The total amount of the monomers having a polymerizable unsaturated bond used for forming the polymer particles is not particularly limited, but the content of the polymer particles in the polymer-dispersed polyol (W) is preferably about 1 to 50% by mass, more preferably Is preferably 2 to 45% by mass, more preferably 10 to 30% by mass.
For the polymerization of the monomer having a polymerizable unsaturated bond, a polymerization initiator of a type that initiates polymerization by generating a free radical is suitably used. Specific examples of the polymerization initiator include 2,2′-azobis-isobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile (AMBN), 2,2′-azobis-2,4. -Dimethylvaleronitrile, benzoyl peroxide, diisopropyl peroxydicarbonate, acetyl peroxide, di-tert-butyl peroxide, persulfate and the like. In particular, AMBN is preferable.

Examples of the base polyol (W ′) include polyether polyol, polyester polyol, and a hydrocarbon polymer having a hydroxyl group at the terminal. In particular, it is preferable to use only a polyether polyol or to use a small amount of a polyester polyol or a hydrocarbon-based polymer having a hydroxyl group at the terminal as a main component.
Examples of the polyether polyol include polyether polyols obtained by adding cyclic ethers such as alkylene oxides to initiators such as polyhydroxy compounds such as polyhydric alcohols and polyhydric phenols and amines. The polyether polyol used as the base polyol (W ′) may be the same as the polyol (A). The polyester polyol used as the base polyol (W ′) may be the same as the polyol (C).

It is preferable that 5 mass% or more of the base polyol (W ′) is the following polyether polyol (X). The polyether polyol (X) is one having a hydroxyl value of 84 mgKOH / g or less and an oxyethylene group content of 40% by mass or more based on the entire polyether polyol (X).
The polyether polyol (X) is preferably obtained by using a polyhydric alcohol as an initiator and adding ethylene oxide or ethylene oxide and another cyclic ether.
As the polyhydric alcohol, glycerin, trimethylolpropane, 1,2,6-hexanetriol and the like are preferable. As other cyclic ethers, propylene oxide, isobutylene oxide, 1-butene oxide and 2-butene oxide are preferable, and propylene oxide is particularly preferable.
In the polyether polyol (X), when the hydroxyl value is 84 mgKOH / g or less, a polymer-dispersed polyol (W) in which polymer particles are stably dispersed is easily obtained. The hydroxyl value of the polyether polyol (X) is preferably 67 mgKOH / g or less, particularly preferably 60 mgKOH / g or less. The lower limit of the hydroxyl value of the polyether polyol (X) is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, particularly preferably 20 mgKOH / g or more, and 30 mgKOH / g or more from the viewpoint of dispersion stability of the polymer particles. Is most preferred.

In the polyether polyol (X), when the oxyethylene group content with respect to the entire polyether polyol (X) is 40% by mass or more, the dispersion of the polymer particles in the polymer-dispersed polyol (W) is easily stabilized. The oxyethylene group content is more preferably 50% by mass or more, and further preferably 55% by mass or more. The upper limit of the oxyethylene group content may be about 100% by mass, that is, polyether polyol (X) in which only EO is added to the initiator. From the viewpoint of dispersion stability of the polymer particles, the oxyethylene group content is more preferably 90% by mass or less.
When the content of the polyether polyol (X) in the base polyol (W ′) is 5% by mass or more, a polymer-dispersed polyol (W) with good dispersibility is easily obtained. As for content of this polyether polyol (X), 10 mass% or more is more preferable. The upper limit of the content of the polyether polyol (X) is not particularly limited, but it is preferable to set the hydroxyl value of the entire polymer-dispersed polyol (W) so as to fall within the above preferable range.

The base polyol (W ′) is a mixture of 5 to 90% by mass of the polyether polyol (X) and 10 to 95% by mass of the polyol (Z) having a hydroxyl value of 400 to 850 mgKOH / g. Preferably, it is a mixture of 30 to 80% by mass of the polyether polyol (X) and 20 to 70% by mass of the polyol (Z).
The hydroxyl value of the polyol (Z) is more preferably 400 to 800 mgKOH / g.

  As the polyether polyol (Z), those having a hydroxyl value in the above range among the polyether polyols contained in the base polyol (W ′) can be used. Among them, those obtained by adding propylene oxide using polyhydric alcohols or amines as initiators are preferable.

  When the polymer-dispersed polyol (W) is contained in the composition (P), the content is set so that the content of the polymer particles in the entire composition (P) is within the above-described preferable range. For example, the content of the polymer-dispersed polyol (W) in the entire composition (P) is preferably in the range of 0.01 to 20% by mass, and more preferably 0.1 to 20% by mass.

[Other polyols (D)]
You may make the composition (P) contain the other polyol (D) which does not belong to any of a polyol (A), a polyol (C), or a polymer dispersion | distribution polyol (W).
Examples of the polyol (D) include polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polyol. The hydroxyl value of the polyol (D) is preferably 10 to 600 mgKOH / g. As a polyol (D), when using combining multiple types of polyol, the hydroxyl value of each polyol should just be in said range, respectively.
25 mass% or less is preferable and, as for content of the polyol (D) in the whole composition (P), 20 mass% or less is more preferable.

The hydroxyl value of the composition (P) as a whole is preferably from 100 to 450 mgKOH / g, more preferably from 150 to 350 mgKOH / g. If the hydroxyl value of the composition (P) is in the above range, the strength of the resulting rigid foam is sufficiently high, which is preferable.
Composition (P) comprises polyol (A) and can optionally comprise polyols (C), (W), and / or (D). The composition (P) may further contain a component having a thinning action.

[Polyisocyanate Compound (I)]
Examples of the polyisocyanate compound (I) include aromatic, alicyclic, and aliphatic polyisocyanates having two or more isocyanate groups; modified polyisocyanates obtained by modifying these.
Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI). And polyisocyanates such as these, or prepolymer-modified products thereof, isocyanurates, urea-modified products, and carbodiimide-modified products. Of these, crude MDI or a modified product thereof is preferred, and a modified product of crude MDI is particularly preferred. The polyisocyanate compound (I) may be used alone or in combination of two or more.

Usually, the polyisocyanate compound (I) is a liquid. The viscosity of the polyisocyanate compound (I) at 25 ° C. is preferably 50 to 450 mPa · s. Within this viscosity range, the resulting rigid foam is unlikely to shrink. Moreover, the workability | operativity at the time of spray molding by a spray method becomes favorable, and the external appearance of the rigid foam obtained can be kept favorable.
The amount of polyisocyanate compound (I) used is represented by 100 times the number of isocyanate groups relative to the total number of active hydrogens in the composition (P) and other active hydrogen compounds present in the reaction system (hereinafter referred to as this A value represented by 100 times is referred to as “isocyanate index”), and 50 to 300 are preferable.
In particular, in the case of a urethane formulation mainly using a urethanization catalyst as a catalyst, the amount of the polyisocyanate compound (I) used is preferably 50 to 170, more preferably 70 to 150, in terms of the isocyanate index.
In the case of an isocyanurate formulation mainly using a catalyst that promotes a trimerization reaction of an isocyanate group as a catalyst, the amount of polyisocyanate compound (I) used is preferably 100 to 350, more preferably 100 to 300, in terms of the isocyanate index. Preferably, 100 to 180 is more preferable.

[catalyst]
The catalyst is preferably a tertiary amine as a urethanization catalyst, and a metal salt and / or a quaternary ammonium salt excluding a tin salt, a lead salt and a mercury salt as a trimerization promoting catalyst. In the case of an isocyanurate formulation, the combined use of a urethanization catalyst and a trimerization reaction promoting catalyst is preferable, and it is more preferable to use a tertiary amine in combination with the metal salt and / or the quaternary ammonium salt.

  As the tertiary amine, for example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ″, N ″ — Pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N-methyl-N- And tertiary amine compounds such as (N, N-dimethylaminoethyl) ethanolamine. Of these, bis (2-dimethylaminoethyl) ether is preferred from the viewpoint that the odor generated during foaming is small.

  As the metal salt excluding the tin salt, lead salt and mercury salt, carboxylic acid metal salts such as potassium acetate, potassium 2-ethylhexanoate and bismuth 2-ethylhexanoate are preferable. In the spray method, potassium 2-ethylhexanoate is preferable from the viewpoint of low cost and excellent catalytic activity.

Examples of the quaternary ammonium salt include tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; tetramethylammonium 2-ethylhexanoate, 2-hydroxy Tetraalkylammonium organic acid salts such as propyltrimethylammonium formate and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate; tertiary amines such as N, N, N ′, N′-tetramethylethylenediamine and carbonic acid diesters And quaternary ammonium compounds obtained by reacting 2-ethylhexanoic acid with an anion exchange reaction.
As for the usage-amount of a catalyst, it is preferable that the total amount of a catalyst is 0.1-20 mass parts with respect to 100 mass parts of a composition (P).
Also, by adjusting the amount of catalyst used, the time from the start of mixing the composition (P) with the polyisocyanate compound (I), the foaming agent, and the foam stabilizer until the reaction starts visually (cream time) The time (rise time) until foaming is completed can be adjusted.

[Foaming agent]
A known foaming agent can be used, but it is preferable to use water as part or all of the foaming agent from the viewpoint of reducing environmental burden, and it is more preferable to use water alone as the entire foaming agent. .
When water is used as part of the blowing agent, it is preferable to use a combination of water and air or an inert gas (carbon dioxide, nitrogen, etc.). Further, a fluorine-containing compound or hydrocarbon compound having a low boiling point may be used in combination.
Examples of the low boiling point fluorine-containing compound include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1. , 3,3-pentafluorobutane (HFC-365mfc), 1,1,2,2-tetrafluoroethyl difluoromethyl ether (HFE-236pc), 1,1,2,2-tetrafluoroethyl methyl ether (HFE- 254 pc), 1,1,1,2,2,3,3-heptafluoropropyl methyl ether (HFE-347mcc) and the like. Of these, HFC-134a, HFC-245fa, and HFC-365mfc are preferred.
Examples of the hydrocarbon compound include butane, normal pentane, isopentane, cyclopentane, hexane, and cyclohexane.
When using foaming agents other than water, it may be used individually by 1 type and may use 2 or more types together.

The amount of water used as the foaming agent is preferably 0.5 to 10 parts by mass, particularly preferably 0.5 to 7 parts by mass with respect to 100 parts by mass of the composition (P).
Moreover, 0-60 mass parts is preferable with respect to 100 mass parts of a composition (P), and, as for the usage-amount of the low boiling point fluorine-containing compound as a foaming agent, 5-45 mass parts is more preferable. The amount of pentane (normal pentane, isopentane, and / or cyclopentane) used as a foaming agent is preferably 0.5 to 40 parts by mass, and 0.5 to 30 parts by mass with respect to 100 parts by mass of the composition (P). Is more preferable.

[Foam stabilizer]
In the present invention, a foam stabilizer is used to form good bubbles. Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. These can use a commercial item. Although the usage-amount of a foam stabilizer can be selected suitably, 0.1-10 mass parts is preferable with respect to 100 mass parts of a composition (P).

[Other ingredients]
In this invention, arbitrary compounding agents can be used in addition to the above-described composition (P), polyisocyanate compound (I), catalyst, foaming agent, and foam stabilizer. Compounding agents include fillers such as calcium carbonate and barium sulfate; anti-aging agents such as antioxidants and UV absorbers; flame retardants, plasticizers, colorants, anti-fungal agents, foam breakers, dispersants, discoloration prevention Agents and the like.

[Reaction and foaming process]
The reaction / foaming step is preferably a method in which a polyol system liquid containing the composition (P) and the foaming agent and a liquid containing the polyisocyanate compound (I) are prepared, and these are mixed and reacted. The foam stabilizer and the catalyst may be contained in either the polyol system liquid or the liquid containing the polyisocyanate compound (I). From the standpoint of problems such as separation of the polyol system liquid, that is, stable performance, it is preferable to contain a foam stabilizer and a catalyst in the polyol system liquid.

According to the present invention, the viscosity of the polyol (A) can be lowered, and thereby the viscosity of the composition (P) can be lowered. Therefore, a low viscosity polyol system liquid can be obtained. For example, a polyol system liquid having a viscosity at 25 ° C. of 500 mPa · s or less, preferably 450 mPa · s or less can be obtained.
The lower limit of the viscosity of the polyol system liquid is not particularly limited, but is preferably 100 mPa · s or more and more preferably 150 mPa · s or more from the viewpoint of the strength of the resulting foam.
By reducing the viscosity of the polyol system liquid, it is possible to improve the miscibility with the polyisocyanate compound (I) and the smoothness when a rigid foam is formed by a spray method.
Especially when using the spray method, the viscosity difference between the liquid containing the polyisocyanate compound (I) and the polyol system liquid should be as small as possible in order to prevent clogging of the spray gun as a mixing device or abnormal fluctuation of the mixing ratio. Is preferred. Since the viscosity at 25 ° C. of the liquid containing the polyisocyanate compound (I) is 50 to 450 mPa · s, the viscosity of the polyol system liquid at 25 ° C. is more preferably 50 to 450 mPa · s.

[Construction method]
The method for producing a rigid foam of the present invention is suitable for a construction method in which the polyol system liquid has a low viscosity, and is particularly suitable for a spray method.
In the spray method, first, a polyol system liquid containing a composition (P), a foaming agent, a foam stabilizer, a catalyst, and other compounding agents as required is prepared, and the polyol system liquid and the polyisocyanate compound (I) are included. This is a foaming method in which a liquid is reacted while sprayed on a construction surface.
Since the spray method can directly manufacture a hard foam at a construction site, it has advantages such as being able to control the construction cost, being able to perform construction on an uneven construction surface without a gap, and being able to form a multilayer hard foam. Therefore, the spray method is suitable for construction, construction, and residential use, and is often suitably employed when constructing a hard foam heat insulating material on a wall, ceiling or the like at a construction site. Specific construction examples include heat insulating materials for condominiums, office buildings, prefabricated refrigerated warehouses, and the like. In particular, the production method of the present invention is suitable for the construction of heat insulating materials such as condominiums and office buildings.
Various methods are known as the spray method, and an airless spray method in which a polyol system liquid and a liquid containing the polyisocyanate compound (I) are mixed with a mixing head and foamed is particularly preferable. The temperature of the mixed solution at the mixing head is preferably 30 to 50 ° C. If the temperature of the mixed solution is too high, the foaming reaction tends to proceed rapidly, and the balance with the resinification reaction tends to be lost. As a result, the foaming stress becomes dominant, and problems such as peeling from the substrate surface tend to occur.

  Moreover, the manufacturing method of this invention is applicable also to methods other than the spray method. For example, a continuous board molding method or an injection method can be used. In particular, in the molding method that is injected into a sash part such as a bay window, the low viscosity of the polyol system liquid can provide good workability and workability, and can produce a rigid foam with excellent strength and dimensional stability. .

<Rigid foam>
Rigid foam Density (core density) produced by the production method of the present invention is a value obtained by the measuring method conforming to JIS A 9526, preferably 15~60kg / ^{m 3,} preferably from 20 to 50 kg / ^{m 3.} The rigid foam density (core density) can be adjusted by the amount of the foaming agent, and can be reduced by using a large amount of foaming agent. When water is used as the blowing agent, the polyol system solution and the isocyanate compound (I) are mixed at a volume ratio of 1: 1 in the spray method, or in the spray method. In many cases, there is a limit to the preferred amount of water used.
In the present invention, by using the polyol (A), it is possible to form a rigid foam having excellent strength and dimensional stability as well as excellent moldability and workability within the above range of the rigid foam density (core density).

According to the present invention, a low-viscosity polyol (A) can be obtained, and by using this, a low-viscosity polyol composition (P) can be obtained. As a result, an increase in the viscosity of the polyol system liquid when water is used as the foaming agent can be suppressed, and good workability and workability can be obtained. Moreover, since the difference in viscosity between the polyol system liquid and the liquid containing the polyisocyanate compound (I) can be reduced, the mixing property of the two is improved, and a rigid foam excellent in strength, dimensional stability, and heat insulation can be obtained. Especially in the spray method, the mist state in the spray method becomes fine due to the reduced viscosity of the polyol system solution, and the so-called mist pattern becomes wide-angle, facilitating uniform spraying and good surface smoothness. become.
In addition, since there are almost no unreacted phenols in the reaction product of the Mannich condensation reaction, the average functional group number of the Mannich polyol (polyol (A)) obtained using the reaction product as an initiator is not decreased. The strength of the rigid foam can be increased. In the reaction product, the content of the Mannich condensation product having a structure in which phenols: aldehydes are reacted at 1: 1 (molar ratio) as represented by the above formula (i) is relatively high. Therefore, the thermal insulation of the rigid foam is likely to be improved.
Furthermore, the polyol (A) having a Mannich condensation product as an initiator contributes to the improvement of the flame retardancy of the rigid foam. Particularly in the spray method, it is preferable that the hard foam has high flame retardance from the viewpoint of fire accidents caused by welding sparks at construction sites and fire resistance as a building material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In Tables 3 and 4, Examples 1 to 7 are examples, and Examples 8 to 10 are comparative examples. The raw materials used are as follows.

[Flame retardants]
Trischloropropyl phosphate (manufactured by Spresta Japan, trade name: Pyrol PCF).
[Foam stabilizer]
Silicone type foam stabilizer (trade name: SH-193, manufactured by Toray Dow Corning Silicone).
[catalyst]
Catalyst A: Reactive foaming catalyst (70 mass% DPG (dipropylene glycol) solution of bis (2-dimethylaminoethyl) ether, trade name: TOYOCAT RX7, manufactured by Tosoh Corporation).
Catalyst B: amine-based foaming catalyst (trade name: TOYOCAT TT, manufactured by Tosoh Corporation).
Catalyst C: A mixture of a quaternary ammonium salt and ethylene glycol (trade name: TOYOCATTRX, manufactured by Tosoh Corporation).
[Polyisocyanate Compound (I)]
Polymeric MDI (mixture of MDI and crude MDI), trade name: Coronate 1130, manufactured by Nippon Polyurethane Industry Co., Ltd., viscosity at 25 ° C .: 130 mPa · s, isocyanate group content: 31% by mass).

<Polyol (A)>
As the polyol (A) containing the Mannich condensation product, polyols A1 to A5 shown in Table 1 below were produced. Polyols A3 to A5 are comparative polyols.
[Polyol A1]
Using a reaction product obtained by reacting 1 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol, a hydroxyl value of 300 mgKOH / OH obtained by ring-opening addition polymerization of PO and EO in this order was used. g polyether polyol. The amount of alkylene oxide added is 16.4 moles per mole of nonylphenol. The ratio of EO to the total amount of added PO and EO is 55% by mass. The viscosity at 25 ° C. (hereinafter the same) is 640 mPa · s.
[Polyols A2 to A5]
Polyols A2 to A5 were produced in the same manner as polyol A1 with the formulation shown in Table 1.

<Polyol (C)>
[Polyol C1]
A polyester polyol having a hydroxyl value of 315 mgKOH / g, obtained by polycondensation of diethylene glycol and phthalic anhydride.

<Polymer-dispersed polyol (W)>
As the polymer-dispersed polyol (W), polymer-dispersed polyols W1 to W6 produced by the method of the following production example with the formulation shown in Table 2 below were used. The unit of the blending ratio in Table 2 is “mass%”.
[Monomer having polymerizable unsaturated bond]
Examples of the monomer having a polymerizable unsaturated bond for forming polymer particles include acrylonitrile (AN), vinyl acetate (Vac), methyl methacrylate (MMA), and polyfluoroalkyl represented by the formula (1-1). Methacrylate (FMA) was used.

Moreover, the following 2 types were used as a macromonomer.
Macromonomer M1: The following polyol E, tolylene diisocyanate (trade name: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-hydroxyethyl methacrylate (manufactured by Junsei Chemical Co., Ltd.), polyol E / tolylene diisocyanate / 2- Hydroxyethyl methacrylate = 1/1/1 molar ratio was prepared, reacted at 60 ° C for 1 hour, and further reacted at 80 ° C for 6 hours, resulting in a polymerizable non-polymerizable group having a hydroxyl value of 40 mgKOH / g. Macromonomer having a saturated group.
Macromonomer M2: The following polyol F, tolylene diisocyanate (trade name: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-hydroxyethyl methacrylate (manufactured by Junsei Chemical Co., Ltd.), polyol F / tolylene diisocyanate / 2- Hydroxyethyl methacrylate = 1/1/1 molar ratio was prepared, reacted at 60 ° C for 1 hour, and further reacted at 80 ° C for 6 hours, resulting in a polymerizable non-polymerizable property having a hydroxyl value of 21 mgKOH / g. Macromonomer having a saturated group.
Polyol E: Using glycerin as an initiator, EO is ring-opening addition polymerized to the glycerin, and then a mixture of PO and EO [PO / EO = 46.2 / 53.8 (mass ratio)] is opened. Polyoxyalkylene polyol having an oxyethylene group content of 65% by mass and a hydroxyl value of 48 mgKOH / g in polyol D, obtained by addition polymerization.
Polyol F: glycerin was used as an initiator, and after ring-opening addition polymerization of EO, the mixture of PO and EO [PO / EO = 48.0 / 52.0 (mass ratio)] was opened. An addition-polymerized polyoxyalkylene polyol having an oxyethylene group content of 60% by mass and a hydroxyl value of 28 mgKOH / g in polyol T.

[Base polyol (W ')]
As the base polyol (W ′), a mixture of the following polyols X1, Z1, and Z2 was used.
(Polyol X1)
A polyether polyol having a hydroxyl value of 50 mgKOH / g, obtained by randomly adding PO and EO using glycerin as an initiator. The ratio of EO to the total amount of PO and EO added is 70% by mass. The content of oxyethylene groups in the entire polyol X1 is 68% by mass.
(Polyol Z1)
A polyether polyol having a hydroxyl value of 650 mgKOH / g, obtained by ring-opening addition polymerization of PO using glycerin as an initiator.
(Polyol Z2)
A polyether polyol obtained by ring-opening addition polymerization of PO using ethylenediamine as an initiator and having a hydroxyl value of 760 mgKOH / g.

[Production Example 1: Production of polymer-dispersed polyol (W1)]
After charging all the base polyol (W ′), monomer, and AMBN as a polymerization initiator in the 5 L pressure reaction tank with the formulation shown in Table 2, the temperature was increased while stirring, and the reaction solution was heated to 80 ° C. The reaction was continued for 10 hours. The monomer reaction rate was 80% or more. After completion of the reaction, the unreacted monomer was removed by heating and degassing at 110 ° C. and 20 Pa for 2 hours to obtain a polymer-dispersed polyol W1.
The hydroxyl value of the obtained polymer-dispersed polyol W1, the viscosity at 25 ° C., and the content of polymer particles in W1 are shown in Table 1 (the same applies hereinafter).

[Production Examples 2, 3: Production of polymer-dispersed polyol (W2), (W3)]
Into a 5 L pressure reaction tank, 70% by mass of the mixture of the base polyol (W ′) shown in Table 2 was charged, and the mixture of the remaining base polyol (W ′), monomer and AMBN was kept at 120 ° C. The mixture was fed over 2 hours with stirring, and stirring was continued for about 0.5 hour at the same temperature after the completion of all feeding. In any of Production Examples 2 and 3, the monomer reaction rate was 80% or more. After the completion of the reaction, unreacted monomers were removed by heating under reduced pressure at 120 ° C. and 20 Pa for 2 hours to obtain polymer-dispersed polyols W2 and W3.

[Production Examples 4 to 6: Production of polymer-dispersed polyol (W4), (W5), and (W6)]
In a 5 L pressurized reaction vessel, polyol X1, polyol Z1, and macromonomer were charged with the formulation shown in Table 2, and the mixture of monomer and polymerization initiator (AMBN) was stirred for 2 hours while maintaining at 120 ° C. After completion of the entire feed, stirring was continued for about 0.5 hours at the same temperature. Thereafter, unreacted monomers were removed under reduced pressure at 120 ° C. for 3 hours to obtain polymer-dispersed polyols W4 to W6.

[Viscosity of polyol and polyol system liquid]
The viscosity of the polyol and the polyol system liquid was measured at a measurement temperature of 25 ° C. according to JIS K 1557-5.

<Example 1 to Example 10: Production of rigid foam>
A rigid foam was produced using the polyol system liquid prepared with the formulation shown in Table 3 and the polyisocyanate compound (I), and evaluated by the following methods. The unit of the blending ratio shown in Table 3 is “parts by mass”.
In the polyol system liquid, a catalyst, a foam stabilizer, and a flame retardant are added to a composition (P) composed of a mixture of polyols (A), (C), a polymer-dispersed polyol (W), and water as a blowing agent. Prepared by mixing. Only water was used as the blowing agent. Table 3 shows the hydroxyl value (unit: mgKOH / g) of the entire composition (P) and the viscosity (unit: mPa · s) at 25 ° C. of the polyol system liquid.
Moreover, the usage-amount of the polyol system liquid and polyisocyanate compound (I) used for manufacture of a rigid foam was set to 1/1 by the body ratio. Table 3 shows the amount of polyisocyanate compound (I) used (unit: parts by mass) and the isocyanate index.

<Spray construction test>
The polyol system liquid and the polyisocyanate compound (I) were subjected to conditions of discharge pressure of 70 to 85 kg / m ² , liquid temperature of 40 ° C., and room temperature of 20 ° C. using a spray foaming machine (trade name: FF-1600) manufactured by Gasmer. A rigid foam was produced by foaming and reacting under.
The base material to be used was a flexible plate having a length of 600 mm, a width of 600 mm, and a thickness of 5 mm. For the spraying, after a lower spray layer having a thickness of 1 mm was applied, two layers were applied so that the thickness of one layer was 25 to 30 mm, and a total of three layers were laminated.
The following methods evaluated the workability in a spray construction, a moldability, a mixability, the density of the obtained rigid foam, compressive strength, dimensional stability, thermal conductivity, and a flame retardance. The evaluation results are shown in Table 4.

Evaluation method [spray pattern (sprayability)]
The extent of spread of the spray mist was visually confirmed and evaluated in the following three stages.
3: A state where the opening of the mist is sufficiently wide and smooth spraying is possible.
2: Slightly insufficient opening of the mist and a state where smooth spraying is somewhat difficult.
1: Opening of the mist is insufficient and smooth spraying is difficult.
[State inside foam (formability)]
The end of the applied foam was cut, the state of the cross section was confirmed, and the following criteria were evaluated.
X (defect): The foam has coloring or cracking due to a scorch or the like, or there is a defect portion such as cell non-uniformity.
○ (good): There is no coloring or cracking due to scorch or the like, or cell non-uniformity inside the foam.
[Mixability]
The foam immediately after spraying was observed, and the uniformity of the cell and hue was visually confirmed. Evaluation was made into three-stage evaluation as follows.
3: The cells are uniform, there are no mixed spots, and the hue is uniform.
2: A state where the cells are not uniform or one of the mixed spots is confirmed.
1: Cells are non-uniform, mixed spots are confirmed, and hue is non-uniform.

[Compressive strength / density]
The compressive strength and density of the rigid foam were measured by a method according to JIS A 9526.
[Dimensional change rate (dimensional stability at high temperature)]
The foam cut into a 100 mm × 100 mm × 40 mm rectangular parallelepiped was held in an environment of 70 ° C., and the dimensional change rate in the direction perpendicular to the foaming direction was measured after 24 hours.
[Thermal conductivity]
The thermal conductivity (unit: W / m · K) is based on JIS A 1412-2, and the average temperature is measured using a thermal conductivity measuring device (product name: Auto Lambda HC-074, manufactured by Eiko Seiki Co., Ltd.). Measured at 20 ° C.

[Flame retardance test]
As a flame retardant test, the sample obtained in the spray application test including a flexible plate was cut to a thickness of 20 mm, and a heat generation test using a cone calorimeter based on ISO5660 was performed.
As shown in Table 4, as a result, HRR indicates the maximum heat generation rate and THR indicates the total heat generation amount. In ISO 5660, in a 5-minute test that is a standard for flame retardant materials, when HRR continues 200 kW / m ² or more for 10 s or more, THR is 8 MJ / m ² or more, or cracks that penetrate to the back side that are harmful to fire prevention And if there is a hole, it is rejected. Cracks and penetrations were evaluated by visual appearance, and those having no cracks and / or penetrations were evaluated as ◯ (defect), and those having cracks and / or penetrations were evaluated as x (defects).

<Simple foaming test>
The polyol system liquid and the polyisocyanate compound were adjusted to 10 ° C., quickly put into a polyethylene cup, stirred at 3,000 rpm for 3 seconds, and foamed in a 2 L cup.
The reactivity and core density of the rigid foam were evaluated by the following methods. The evaluation results are shown in Table 4.
(Evaluation methods)
[Reactivity (Cream Time / Rise Time)]
The mixing start time of the polyol system liquid and the polyisocyanate compound is 0 second, the time until the liquid mixture starts to foam is the cream time (seconds), the time when the liquid mixture begins to foam and the rise of the foam stops is the rise time (Seconds).
[Core density]
The core portion of the obtained rigid foam was cut into a cube of 50 mm long × 50 mm wide × 50 mm thick, and the density (unit: kg / m ³ ) was calculated from the mass and volume.

As shown in the results of Tables 3 and 4, in Examples 1 to 7, the viscosity of the polyol system liquid is low despite the fact that the foaming agent is only water, and the mixability, workability, and moldability in the spray method are low. Was good. Moreover, the obtained rigid foam had good compressive strength and dimensional stability while having a low density, and was excellent in flame retardancy and heat insulation. In addition, good foam with low density could be formed by simple foaming.
On the other hand, in Examples 9 and 10, since the initiator (S1) of the polyol (A) was obtained by reacting 1.5 mol and 2.2 mol of the aldehyde with respect to 1 mol of the phenol, The viscosity of (A) and the viscosity of the polyol system liquid were relatively high. Since the spray pattern deteriorated, smooth spraying was somewhat difficult, and the miscibility with the polyisocyanate compound (I) was slightly inferior. Further, in the obtained rigid foam, a non-uniform portion of cells was observed inside, and a decrease in compressive strength and a deterioration in dimensional stability were observed. Furthermore, about thermal conductivity, it became a result a little worse compared with Examples 1-7.
In Example 8, the initiator (S1) of the polyol (A) is obtained by reacting 2.0 mol of alkanolamines with respect to 1 mol of phenols. Compared to Example 7 using the polyol (A2) obtained from the initiator (S1) obtained by reacting 2.1 mol or more of alkanolamine with 1 mol of phenol, the viscosity of the polyol (A) and the polyol system The viscosity of the liquid becomes relatively high, and the miscibility with the polyisocyanate compound (I) is inferior, and the sprayability is not good. Further, in the obtained rigid foam, a non-uniform portion of cells was observed inside, and a decrease in compressive strength and a deterioration in dimensional stability were observed. The thermal conductivity was also slightly deteriorated.

Claims (10)

A method for producing a polyether polyol (A) by reacting the following phenols, the following aldehydes and the following alkanolamines, and then adding an alkylene oxide to the obtained reaction product,
The usage rate of the aldehydes is 0.9 mol or more and less than 1.35 mol and the usage rate of the alkanolamines is 2.1 mol or more and 10.5 mol or less with respect to 1 mol of the phenols. The manufacturing method of the polyether polyol (A) characterized by the above-mentioned.
Phenols: One or more selected from the group consisting of phenol and phenol derivatives having a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol.
Aldehydes: One or more selected from the group consisting of formaldehyde and acetaldehyde.
Alkanolamines: One or more selected from the group consisting of monoethanolamine, diethanolamine and 1-amino-2-propanol.   The phenol derivative has a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, and one or more other hydrogen atoms bonded to the aromatic ring are alkyl groups having 1 to 15 carbon atoms. The manufacturing method of the polyether polyol (A) of Claim 1 which is the substituted alkylphenol.   The method for producing a polyether polyol (A) according to claim 1 or 2, wherein the alkylene oxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide.   The manufacturing method of the polyether polyol (A) as described in any one of Claims 1-3 whose hydroxyl value of the said polyether polyol (A) is 200-800 mgKOH / g. A method for producing a rigid foam synthetic resin by reacting a polyol composition (P) and a polyisocyanate compound (I) in the presence of a foaming agent, a foam stabilizer and a catalyst,
The said polyol composition (P) contains the polyether polyol (A) obtained by the manufacturing method as described in any one of Claims 1-4, The manufacturing method of the hard foam synthetic resin characterized by the above-mentioned.   The manufacturing method of the hard foam synthetic resin of Claim 5 whose content of the polyether polyol (A) in the said polyol composition (P) is 20-100 mass%.   The manufacturing method of the hard foam synthetic resin of Claim 5 or 6 which uses water independently as the said foaming agent.   The manufacturing method of the hard foam synthetic resin as described in any one of Claims 5-7 in which the said polyol composition (P) contains a polymer dispersion | distribution polyol (W).   The method for producing a rigid foam synthetic resin according to claim 8, wherein the polymer-dispersed polyol (W) has a hydroxyl value of 100 to 800 mgKOH / g.   The manufacturing method of the hard foam synthetic resin as described in any one of Claims 5-9 using a spray method.