JP5267423B2 - Manufacturing method of rigid foam synthetic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing lightweight rigid foam having excellent adhesivity and dimensional stability by using water as a foaming agent. <P>SOLUTION: The method for producing the rigid foam comprises reacting a polyol compound with a polyisocyanate compound together with water, etc., wherein a polyol mixture which contains a polyoxyethylene polyol produced by subjecting only ethylene oxide to ring-opening addition polymerization by using at least one kind selected from the group consisting of aliphatic amines and alicyclic amines as an initiator and having a hydroxyl value of 150-800 mgKOH/g and in which polymer fine particles are stably dispersed is used as the polyol compound, and water is used as the foaming agent. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a rigid foam synthetic resin. More specifically, the present invention relates to a method for producing a rigid foamed synthetic resin such as a rigid polyurethane foam characterized by using a relatively large amount of water as a foaming agent.

  It is widely performed to produce a rigid foamed synthetic resin (hereinafter referred to as a rigid foam) such as a rigid polyurethane foam and a rigid polyisocyanurate foam by reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent or the like. ing. Here, various compounds are known as a foaming agent for producing a rigid foam. Previously, low-boiling fluorine-containing compounds have been mainly used. However, considering the burden on the environment, it is desirable to reduce the use of fluorine-containing compounds. Therefore, in order to reduce the amount of use, techniques for using a large amount of water as a blowing agent have been studied. When a large amount of water is used, a relatively lightweight rigid foam can be obtained at low cost.

  However, when a rigid foam is produced using a large amount of water, the compatibility between the polyol compound and water is generally not so high, and therefore water tends to be sufficiently dispersed and difficult to dissolve in the polyol compound. As a result, the reaction between water and the polyisocyanate compound does not proceed sufficiently, and as a result, it is difficult to reduce the density of the rigid foam produced. In particular, when producing a rigid foam in a low temperature environment, it is difficult to control the density of the rigid foam low. Specifically, particularly when manufacturing a rigid foam by spray foaming at a construction site in winter, temperature control is difficult, and the density of the manufactured rigid foam cannot be controlled low. Further, when the density of the rigid foam is lowered by using a large amount of water, there arises a problem that the obtained rigid foam tends to shrink.

  In addition, the low compatibility between water and the polyol compound results in a decrease in compatibility and miscibility between the polyisocyanate compound and the mixed liquid (polyol system liquid) of the polyol compound, water, and other additives. . As a result, it is difficult to form fine bubbles uniformly during the production of the rigid foam, and cell roughness and striped patterns are likely to appear in the obtained rigid foam.

  In addition, rigid foams produced using a large amount of water increase the proportion of urea bonds formed by the reaction of water and polyisocyanate compounds, making the resulting foams brittle, thus reducing the adhesiveness of the rigid foams. There is a problem of doing.

  Among these problems, a polyoxyalkylene polyol produced using piperazines such as 1- (2-aminoethyl) piperazine as an initiator is used as a method for producing a lightweight rigid foam using a large amount of water. Has been proposed (see, for example, Patent Documents 1 and 2).

  In addition to the polyoxyalkylene polyol produced by using the piperazine as an initiator, a polymer-dispersed polyol in which polymer fine particles are stably dispersed is used to solve the problem that the obtained rigid foam tends to shrink. (See, for example, Patent Documents 3 and 4).

JP-A-6-87943 JP-A-8-100044 JP 2000-226427 A JP 2000-256434 A

  However, the techniques proposed in Patent Documents 1 and 2 do not sufficiently solve the problem that the obtained rigid foam tends to shrink. In addition, the techniques proposed in Patent Documents 3 and 4 have a feature that the hard foam obtained by using a relatively large amount of water is difficult to shrink, but the rigid foam is lightened (low density). Improvements are desired in terms of adhesiveness.

  That is, the present invention solves the above problems, uses water as a foaming agent, produces a lightweight, excellent adhesive, hardly shrinkable rigid foam with good mechanical properties, and stable storage of raw materials. It aims at providing the manufacturing method of the rigid foam excellent in property.

In the method for producing a rigid foam synthetic resin by reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst, the following polyether polyol (X) and the following polyether polyol (X) are used as the polyol compound. a polymer-dispersed polyol obtained by the method of precipitating directly particle monomer is polymerized with a polymerizable unsaturated bond in the polyol mixture containing an amine-based polyether polyol (Y), and a following polyol (a), a hydroxyl group There is provided a method for producing a rigid foam synthetic resin, characterized in that a polyol mixture having a value of 100 to 700 mg KOH / g and polymer fine particles is stably dispersed and water is used as a foaming agent. However, the polyether polyol (X) is a polyether polyol having a hydroxyl value of 84 mgKOH / g or less and an oxyethylene group content of 40% by mass or more. The amine-based polyether polyol (Y) is a polyether polyol having a hydroxyl value of 250 to 900 mgKOH / g, obtained by ring-opening addition polymerization of alkylene oxide using an aliphatic amine or alicyclic amine as an initiator. Polyol (A) is an initiator such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, and aminoethylethanolamine. A polyoxyethylene polyol having a hydroxyl value of 150 to 800 mgKOH / g, produced by ring-opening addition polymerization of only ethylene oxide using at least one selected from the group consisting of

Here, the polyol mixture preferably contains the following polyol (BA) and / or polyol (BB). However, the polyol (BA) is a polyoxyalkylene polyol having a hydroxyl value of 100 to 700 mgKOH / g, produced by ring-opening addition polymerization of alkylene oxide using an aromatic compound as an initiator. The polyol (BB) is a polyester polyol having a hydroxyl value of 100 to 700 mgKOH / g, produced by polycondensation of a monomer containing an aromatic compound. Here, it is preferable to use at least one selected from the group consisting of a Mannich condensation product, diaminotoluene and bisphenol A as an initiator for the polyol (BA) .
As the monomer having a polymerizable unsaturated bond, a combination of acrylonitrile and styrene having a mass ratio of acrylonitrile / styrene of 90 to 40 / 10-60, or a mass ratio of acrylonitrile / vinyl acetate of 50 to 10/50 to 90 It is preferred to use some combination of acrylonitrile and vinyl acetate.
It is preferable that the ratio of a polyol (A) is 15-80 mass% among the said polyol mixtures.
The amount of water used as the blowing agent is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polyol compound.
When the polyol compound and the polyisocyanate compound are reacted in the presence of a foaming agent, a foam stabilizer and a catalyst, a polyol system liquid containing the polyol compound, the foaming agent, the foam stabilizer and the catalyst is sprayed with the polyisocyanate compound. It is preferable to carry out spray foaming while reacting.

  According to the present invention, water can be used as a foaming agent, and it has become possible to produce a rigid foam that is lightweight, excellent in adhesiveness, hardly contracted, has a good appearance, and has good mechanical properties. Moreover, it is excellent also in the storage stability of a raw material.

  In the method for producing a rigid foam of the present invention, a rigid foam synthetic resin is produced by reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst. The details will be described below.

(Polyol compound)
In the present invention, the polyol (A) is produced by ring-opening addition polymerization of only ethylene oxide using at least one selected from the group consisting of aliphatic amines and alicyclic amines as an initiator and having a hydroxyl value of 150. It is a polyoxyethylene polyol which is ˜800 mg KOH / g. By using this polyol (A), the dissolution stability of water and the polyol compound is improved, the reactivity of water and the polyisocyanate compound is also improved, and an effect such that a lower density rigid foam can be produced is obtained. It is done.

The initiator used for the production of the polyol (A) is at least one selected from the group consisting of aliphatic amines and alicyclic amines. Here, as the initiator, an alicyclic amine is more preferable. Examples of the aliphatic amine include alkylamines and alkanolamines. Examples of alkylamines include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetraamine. Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, and aminoethylethanolamine. Examples of the alicyclic amines include piperidines, piperazines, pyrrolidines, etc., piperazines are particularly preferred, and piperazines substituted with aminoalkyl groups are most preferred. Piperazine has a high effect as a catalyst for promoting the urethane bond formation reaction, and by using it as an initiator of the polyol (A), an effect of increasing the reactivity at the time of producing the rigid foam can be obtained. Examples of piperidines include 1- (2-aminoethyl) piperidine. Examples of piperazines include piperazine, N-aminomethylpiperazine, 1- (2-aminoethyl) piperazine and the like. Examples of pyrrolidines include 1- (2-aminoethyl) pyrrolidine.
In the present invention, as an initiator of the polyol (A), ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, and aminoethyl At least one selected from the group consisting of ethanolamine is used.

  Moreover, as an alkylene oxide used for manufacture of a polyol (A), only ethylene oxide is used. By using only ethylene oxide, the affinity between the polyol (A) and water is improved, and the dissolution stability of water and polyol is improved. Further, by using only ethylene oxide, the hydroxyl group of the polyol (A) becomes a primary hydroxyl group, the reactivity of the polyol (A) is increased, and the adhesiveness is improved.

  The hydroxyl value of the polyol (A) is 150 to 800 mgKOH / g, preferably 250 to 700 mgKOH / g. When the hydroxyl value of the polyol (A) is within the above range, the compatibility between the polyol compound and water can be secured, the reactivity of the polyol compound can be increased, and the adhesiveness of the rigid foam can be easily secured, which is preferable. Moreover, 2-8 are preferable and, as for the average functional group number of a polyol (A), 2-6 are more preferable. Here, the average number of functional groups means the average number of active hydrogen atoms in the initiator.

  In the polyol mixture used in the present invention, the proportion of the polyol (A) is preferably 5 to 95% by mass, and more preferably 15 to 80% by mass. If the proportion of the polyol (A) is less than 5% by mass, the adhesive property of the rigid foam tends to deteriorate, such being undesirable. Moreover, when the ratio of a polyol (A) exceeds 85 mass%, it becomes difficult to obtain the strength of a rigid foam, which is not preferable.

  In the present invention, the polyol mixture preferably contains a polyol (BA) and / or a polyol (BB). By using this polyol (BA) and / or polyol (BB), flame resistance can be imparted to the resulting rigid foam.

  In the present invention, the polyol (BA) is a polyoxyalkylene polyol having a hydroxyl value of 100 to 700 mgKOH / g, produced by ring-opening addition polymerization of alkylene oxide using an aromatic compound as an initiator.

  As an initiator used for the production of the polyol (BA), an aromatic compound is used, but it is preferable to use at least one selected from the group consisting of a Mannich condensation product, diaminotoluene and bisphenol A. Here, the aromatic compound means a compound having an aromatic ring. Here, the aromatic ring may be a ring composed of only carbon atoms or a ring containing atoms (heteroatoms) other than carbon atoms such as nitrogen atoms. Examples of the ring consisting of only carbon atoms include a benzene ring and a naphthalene ring. Examples of the ring containing an atom other than a carbon atom include a pyridine ring. However, the presence or absence of a heteroatom in these rings is not considered.

  The aromatic compound may be a condensed compound or a non-condensed compound. Condensation compounds include Mannich condensation products, which are reaction products of phenols, alkanolamines and aldehydes, resol-type initial condensates obtained by condensation-bonding phenols with excess formaldehydes in the presence of an alkali catalyst. Examples include a benzylic type initial condensate reacted in a non-aqueous system when synthesizing a type initial condensate, a novolak type initial condensate obtained by reacting excess phenols with formaldehyde in the presence of an acid catalyst, and the like. The molecular weight of these initial condensates is preferably about 200 to 10,000. In the above, examples of phenols include phenol, nonylphenol, cresol, bisphenol A, resorcinol, and examples of aldehydes include formalin and paraformaldehyde. Examples of non-condensable compounds include polyphenols such as bisphenol A and resorcinol, diaminotoluene, diethyldiaminotoluene, diaminodiphenylmethane, and the like.

  Examples of the alkylene oxide used for producing the polyol (BA) include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, and styrene oxide. Of these, propylene oxide and ethylene oxide are preferred.

  The hydroxyl value of the polyol (BA) is 100 to 700 mgKOH / g, preferably 200 to 600 mgKOH / g. When the hydroxyl value of the polyol (BA) is within the above range, it is preferable because sufficient flame retardancy can be imparted while maintaining the mixing property of the polyol compound. Moreover, 2-8 are preferable and, as for the average functional group number of a polyol (BA), 2-6 are more preferable.

  In the present invention, the polyol (BB) is a polyester polyol having a hydroxyl value of 100 to 700 mgKOH / g produced by polycondensation of a monomer containing an aromatic compound. That is, as a monomer used for producing this polyol (BB), a diol having an aromatic ring or a dicarboxylic acid having an aromatic ring is used. Examples of the diol having an aromatic ring include a diol obtained by adding ethylene oxide to bisphenol A. Examples of the dicarboxylic acid having an aromatic ring include phthalic acids such as terephthalic acid. The hydroxyl value of the polyol (BB) is 100 to 700 mgKOH / g, preferably 200 to 600 mgKOH / g. When the hydroxyl value of the polyol (BA) is within the above range, it is preferable because sufficient flame retardancy can be imparted while maintaining the mixing property of the polyol compound.

  7-90 mass% is preferable and, as for the ratio of the sum total of a polyol (BA) and a polyol (BB) among the polyol mixtures used for this invention, 20-70 mass% is more preferable. If the total ratio of the polyol (BA) and the polyol (BB) is within the above range, an appropriate flame retardancy can be imparted to the obtained rigid foam, and other mechanical properties and the like are not impaired. Moreover, there is no restriction | limiting in particular in the ratio of a polyol (BA) and a polyol (BB).

  In the present invention, a polyol mixture in which polymer fine particles are stably dispersed is used as the polyol compound. The polyol mixture in which the polymer fine particles are stably dispersed may be produced by stably dispersing the polymer fine particles in the polyol mixture, or may be produced by mixing the polyol in which the polymer fine particles are stably dispersed with the polyol (A) or the like. May be. However, the latter is particularly preferable because the polymer fine particles in the polyol mixture have high stability and the production of the polyol mixture according to the present invention is easy. A polyol in which polymer fine particles are stably dispersed is hereinafter referred to as a polymer-dispersed polyol. In the present invention, a polymer-dispersed polyol suitable for mixing with the polyol (A) or the like is hereinafter referred to as a polymer-dispersed polyol (W).

  In the present invention, the polymer-dispersed polyol (W) is a polyether polyol (X) described later, an amine polyether polyol (Y) described later, and optionally other (polyether polyol (X), amine polyether polyol (Y). It is a polyol containing polyol (Z) other than). The mixing ratio of the polyether polyol (X), the amine-based polyether polyol (Y) and the other polyol (Z) in the polymer-dispersed polyol (W) is (X) / (Y) / (Z) by mass ratio. 5 to 97/3 to 35/0 to 92 is preferable, 10 to 60/5 to 35/10 to 85 is more preferable, and 25 to 50/8 to 25/25 to 67 is particularly preferable. The average hydroxyl value of the polymer-dispersed polyol (W) is preferably 200 to 800 mgKOH / g, more preferably 250 to 750 mgKOH / g. When the mixing ratio in the polymer-dispersed polyol (W) and the average hydroxyl value of the polymer-dispersed polyol (W) are in the above ranges, it is preferable that the polymer fine particles are easily dispersed stably.

  The polyether polyol (X) is a polyether polyol having a hydroxyl value of 84 mgKOH / g or less and an oxyethylene group content of 40% by mass or more. The hydroxyl value of the polyether polyol (X) is 84 mgKOH / g or less, preferably 5 to 84 mgKOH / g, particularly preferably 30 to 60 mgKOH / g. Moreover, as an initiator used for manufacture of polyether polyol (X), a polyhydric alcohol more than trivalence is preferable. Specific examples thereof include glycerin, trimethylolpropane, and 1,2,6-hexanetriol. As the alkylene oxide used in the production of the polyether polyol (X), ethylene oxide alone or a combination of alkylene oxide having 3 or more carbon atoms such as propylene oxide and ethylene oxide is preferable. Here, the content of the oxyethylene group derived from ethylene oxide in the polyether polyol (X) is 40% by mass or more, preferably 50 to 90% by mass.

The amine-based polyether polyol (Y) is a polyether polyol having a hydroxyl value of 250 to 900 mgKOH / g, obtained by ring-opening addition polymerization of alkylene oxide using an amine compound described later as an initiator. However, among the polyol (A) and polyol (BA) described above, the hydroxyl value may fall within the above range. The hydroxyl value of the amine polyether polyol (Y) is 250 to 900 mgKOH / g, preferably 300 to 800 mgKOH / g, particularly preferably 350 to 800 mgKOH / g. As also amine compound initiator used in the production of amine based polyether polyol (Y), aliphatic amines or alicyclic amine is preferred. Aliphatic amines include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine and the like. Examples of the alicyclic amine include 1- (2-aminoethyl) piperazine. Moreover, as an alkylene oxide used for manufacture of amine polyether polyol (Y), ethylene oxide, propylene oxide, etc. are preferable.

  Said other polyol (Z) is arbitrary polyols other than polyether polyol (X) and amine polyether polyol (Y). That is, when the polyol (V) is a polyol other than the aforementioned polyol (A), polyol (BA), polyol (BB), polyether polyol (X), or amine polyether polyol (Y), the polyol (Z ) Consists of one or more polyols selected from the group consisting of polyol (BA ′), polyol (BB) and polyol (V). However, the polyol (BA ′) is a polyether polyol other than the polyol (Y) in the polyol (BA). Examples of other polyols (V) include polyether polyols, polyester polyols, polycarbonate polyols, polyhydric alcohols, and hydrocarbon polymers having a hydroxyl group at the terminal. The hydroxyl value of the other polyol (Z) is preferably 200 to 1000 mgKOH / g, particularly preferably 400 to 850 mgKOH / g.

  The polymer fine particles in the present invention are preferably polymer fine particles obtained by polymerizing a monomer having a polymerizable unsaturated bond. Specific examples of the monomer having a polymerizable unsaturated bond include nitrile monomers such as acrylonitrile, methacrylonitrile, 2,4-dicyano-1-butene; acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, Acrylic monomers such as acrylamide and methacrylamide; Styrene monomers such as styrene and α-methylstyrene; Vinyl ester monomers such as vinyl acetate and vinyl propionate; Isoprene, butadiene and other diene monomers; Maleic acid diesters Unsaturated fatty acid ester monomers such as itaconic acid diesters; vinyl halide monomers such as vinyl chloride; vinylidene halide monomers such as vinylidene chloride; methyl vinyl ether, ethyl vinyl ether, isopropyl Alkyl vinyl ether monomers such as vinyl ether and the like. Two or more of these monomers may be used in combination.

  As a combination of monomers having a polymerizable unsaturated bond, a combination of 5 to 90% by mass of a nitrile monomer and 10 to 95% by mass of another monomer is preferable. A combination of a nitrile monomer and a styrene monomer, or a combination of a nitrile monomer and a carboxylic acid vinyl ester monomer is preferable in order to obtain a polymer-dispersed polyol having a low viscosity and good dispersion stability. As the combination of the monomers, a combination of acrylonitrile and styrene and a combination of acrylonitrile and vinyl acetate are particularly preferable, and a combination of acrylonitrile and vinyl acetate is particularly preferable because of good dispersion stability.

  In the case of a combination of acrylonitrile and styrene, the ratio of acrylonitrile / styrene is preferably 90 to 40/10 to 60, and most preferably 85 to 60/15 to 40 in terms of mass ratio. In the case of a combination of acrylonitrile and vinyl acetate, the ratio of acrylonitrile / vinyl acetate is preferably 50 to 10/50 to 90, and most preferably 40 to 15/60 to 85 in terms of mass ratio.

  The amount of the monomer used is not particularly limited, but the concentration of the polymer fine particles in the polymer-dispersed polyol (W) is preferably about 1 to 50% by mass, particularly preferably 2 to 45% by mass, and most preferably 5 to 40% by mass. preferable.

  Examples of the method for producing the polymer-dispersed polyol (W) include the following two methods. The first method is a monomer having a polymerizable unsaturated bond in a mixture of polyether polyol (X), amine-based polyether polyol (Y) and other polyol (Z) in the presence of a solvent as necessary. In which particles are directly deposited. In the second method, a polyether polyol (X) is prepared by polymerizing a monomer having a polymerizable unsaturated bond in a solvent in the presence of a grafting agent that stabilizes the particles as necessary, and precipitating the particles. In this method, the solvent is replaced with a mixture of amine-based polyether polyol (Y) and other polyol (Z). In the present invention, either method can be adopted, but the first method is particularly preferable in that the stability of the polymer fine particles is good.

  For polymerization of a monomer having a polymerizable unsaturated bond, radical polymerization is usually employed. As polymerization initiators for radical polymerization, 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (methyl 2-methylpropionate), benzoyl peroxide, diisopropyl peroxydicarbonate, acetyl peroxide, tert-butyl peroxide, persulfate and the like. In particular, AIBN, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (methyl 2-methylpropionate) are preferable. .

  In order to improve the dispersion stability of the polymer fine particles, a grafting agent can be used. As the grafting agent, a compound having a polyether chain or a polyester chain and having a polymerizable unsaturated bond in the molecule can be used.

  As the grafting agent, an active hydrogen compound having an unsaturated bond in the molecule is used as an initiator, and a high molecular weight polyol or monool obtained by addition polymerization of alkylene oxide; a polyether polyol with maleic anhydride, After reacting with unsaturated carboxylic acid or unsaturated carboxylic acid anhydride such as itaconic anhydride, maleic acid, fumaric acid, acrylic acid, methacrylic acid, etc., high molecular weight obtained by adding alkylene oxide as required Polyol or monool; reaction product of alcohol having unsaturated bond such as 2-hydroxyethyl acrylate and butenediol with other polyol and polyisocyanate; epoxy having unsaturated bond such as allyl glycidyl ether in the molecule Examples include a reaction product of a compound and a polyol. These compounds preferably have a hydroxyl group but are not limited thereto.

  In the present invention, as the polyol compound, a polyol mixture containing the above-described polyol (A), having a hydroxyl value of 100 to 700 mgKOH / g, and in which polymer fine particles are stably dispersed is used. Here, the hydroxyl value of the polyol mixture is 100 to 700 mgKOH / g, but preferably 150 to 600 mgKOH / g. When the hydroxyl value is within this range, a rigid foam having good physical properties can be obtained. Moreover, as a density | concentration of a polymer fine particle, 0.05-3 mass% is preferable among a polyol mixture, and 0.2-1 mass% is more preferable. When the concentration of the polymer fine particles is in the above range, shrinkage of the obtained rigid foam can be effectively suppressed. That is, when the polymer dispersed polyol (W) having a polymer fine particle concentration of 25% by mass is mixed to obtain a polyol mixture, the ratio of the polymer dispersed polyol (W) is preferably 0.2 to 12% by mass. 0.8 to 4% by mass is more preferable.

  As the above polyol mixture, the polyol (BA) and / or the polyol (BB) described above may be mixed in addition to the polyol (A) and, optionally, the polymer-dispersed polyol (W), and other active hydrogen-containing compounds. May be used in combination. Here, other active hydrogen-containing compounds include polyols, polyhydric phenols, and polyamines. The polyols that may be used in combination here are any polyols other than polyol (A), polyol (BA), polyol (BB), and polymer-dispersed polyol (W), such as polyether polyol (X), amine-based It consists of 1 or more types chosen from the group which consists of polyether polyol (Y ') and polyol (V). However, the amine polyether polyol (Y ′) is an amine polyether polyol other than the polyol (A) and the polyol (BA) in the amine polyether polyol (Y).

  Examples of the polyhydric phenols that may be used in combination include compounds having a phenolic hydroxyl group among the initiators used in the production of the polyol (BA) described above, specifically, Mannich condensation products, resol type initial condensations. Products, benzylic type initial condensates, novolak type initial condensates, bisphenol A, resorcinol and the like. Polyamines that may be used in combination include aliphatic amines, alicyclic amines used as initiators for the production of polyol (A), and aromatic amines used as initiators for the production of polyol (BA). Is mentioned. Examples of the aromatic amines include diaminotoluene, diethyldiaminotoluene, diaminodiphenylmethane, and the like.

(Foaming agent)
In the present invention, water is used as the foaming agent. As the blowing agent, a low boiling point hydrocarbon compound, a low boiling point fluorine-containing compound, and an inert gas can be used in combination. The amount of water used as the foaming agent is preferably 1 to 15 parts by mass, particularly preferably 2 to 13 parts by mass with respect to 100 parts by mass of the polyol compound. When the amount of water used is less than 1 part by mass, the obtained rigid foam is not preferred because it is difficult to lighten. Moreover, when there is much usage-amount exceeding 15 mass parts, the miscibility of water and a polyol compound tends to deteriorate, and it is not preferable. From the viewpoint of low environmental load, it is preferable to use only water as the foaming agent.

  Examples of the low-boiling hydrocarbon compound include butane, pentane, hexane, and cyclohexane. 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-254pc), 1,1,1,2,2,3,3-heptafluoropropyl methyl ether (HFE-347mcc) and the like. Examples of the inert gas include air, nitrogen, carbon dioxide gas and the like.

(Polyisocyanate compound)
In the present invention, the polyisocyanate compound is not particularly limited, but aromatic, alicyclic and aliphatic polyisocyanates having two or more isocyanate groups; mixtures of two or more of the above polyisocyanates; And modified polyisocyanates obtained by modifying. Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), and the like. These polyisocyanates or their prepolymer-modified products, nurate-modified products, urea-modified products, carbodiimide-modified products, and the like. Of these, TDI, MDI, crude MDI, or modified products thereof are preferred.

  The amount of the polyisocyanate compound used is represented by 100 times the number of isocyanate groups with respect to the total number of active hydrogens of the polyol compound and other active hydrogen compounds (usually, the value represented by 100 times is referred to as the isocyanate index), 300 is preferred. Here, in the urethane prescription which mainly uses a urethanization catalyst as a catalyst, the usage-amount of a polyisocyanate compound is an isocyanate index | exponent, 50-140 are preferable and 60-130 are more preferable. Moreover, in the isocyanurate prescription which mainly uses the catalyst which accelerates | stimulates the trimerization reaction of an isocyanate group as a catalyst, the usage-amount of a polyisocyanate compound is an isocyanate index, 120-300 are preferable and 150-250 are more preferable.

(catalyst)
The catalyst used in the present invention is not particularly limited as long as it is a catalyst that promotes the urethanization reaction. Examples thereof include tertiary amines such as triethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine; and organometallic compounds such as dibutyltin dilaurate. Moreover, you may use together the catalyst which accelerates | stimulates the trimerization reaction of an isocyanate group, and carboxylic acid metal salts, such as potassium acetate and potassium 2-ethylhexanoate, etc. are mentioned. When spray foaming is adopted as a method for producing a rigid foam, it is preferable to use an organometallic catalyst such as lead 2-ethylhexanoate in order to complete the reaction in a short time. As for the usage-amount of a catalyst, 0.1-10 mass parts is preferable with respect to 100 mass parts of polyol compounds.

(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. Although the usage-amount of a foam stabilizer may be selected suitably, 0.1-10 mass parts is preferable with respect to 100 mass parts of polyol compounds.

(Other ingredients)
In the present invention, any compounding agent can be used in addition to the above-described polyol compound, polyisocyanate compound, foaming agent, catalyst, 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.

(Foaming device)
As a manufacturing method of the rigid foam of the present invention, normal hand foaming or a foaming apparatus may be used. As the foaming apparatus, either a high pressure foaming apparatus or a low pressure foaming apparatus can be used. The reaction conditions may be appropriately selected, but the reaction temperature is preferably 0 to 50 ° C, more preferably 15 to 45 ° C.

  As a method for producing the rigid foam of the present invention, spray foaming is particularly preferable. This is because high reactivity can be obtained by using the polyol (A). Various methods for producing by spray foaming are known. Of these, airless spray foaming is preferred, in which the compounded liquid is mixed and foamed by a mixing head. Here, spray foaming is a foaming method in which a polyol system solution and a polyisocyanate compound are reacted while sprayed, and the reaction is completed in a short time by selecting a catalyst or the like. Spray foaming is often employed when constructing hard foam insulation on walls, ceilings, etc. at construction sites. Spray foaming has advantages such as manufacturing rigid foams directly at the construction site, thus reducing the construction cost, and being able to construct even on uneven construction surfaces. Specific construction examples include heat insulating materials for condominiums, office buildings, prefabricated refrigerated warehouses, etc. In recent years, they are also being used as heat insulating materials for highly airtight detached houses.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Of the following examples, Examples 1 and 2 are examples of producing polymer-dispersed polyols, Examples 3 to 33 are examples of producing rigid polyurethane foams, and Examples 34 to 63 are examples of producing rigid urethane-modified polyisocyanurate foams. . However, Examples 3, 11 , 17 , 34 , 42 , 48 are Examples, Examples 4-10 , 12-16 , 18-22 , 35-41 , 43-47 , 49-53 are Reference Examples , Examples 23- 33 and Examples 54 to 63 represent comparative examples. Moreover, the unit of the numerical value of the part which showed prescription in the table | surface is a mass part. The raw materials used in Examples , Reference Examples and Comparative Examples are as shown in each table, and the details are as follows. As abbreviations in the table, AN represents acrylonitrile, ST represents styrene, and VA represents vinyl acetate.

(Polyol compound)
Polyol A1: Polyoxyethylene polyol having a hydroxyl value of 350 mgKOH / g, obtained by reacting only ethylene oxide as an alkylene oxide using ethylenediamine as an initiator.
Polyol A2: A polyoxyethylene polyol having a hydroxyl value of 350 mgKOH / g, obtained by reacting only ethylene oxide as alkylene oxide using 1- (2-aminoethylpiperazine) as an initiator.
Polyol BA1: A polyoxyethylene polyol having a hydroxyl value of 280 mgKOH / g, obtained by reacting only ethylene oxide as an alkylene oxide using bisphenol A as an initiator.
Polyol BA2: Polyoxyethylene having a hydroxyl value of 350 mgKOH / g and a proportion of oxyethylene groups of 25% by mass, obtained by mixing and reacting ethylene oxide and propylene oxide as alkylene oxide using diaminotoluene as an initiator Polyoxypropylene polyol.
Polyol BB1: Polyoxyethylene polyol having a hydroxyl value of 250 mgKOH / g, obtained by polycondensation of diethylene glycol and terephthalic acid.
Polyol X1: Polyoxyethylene poly having a hydroxyl value of 50 mgKOH / g and a proportion of oxyethylene groups of 55% by mass, obtained by mixing and reacting ethylene oxide and propylene oxide as alkylene oxide using glycerin as an initiator. Oxypropylene polyol.
Polyol Y1: Polyoxypropylene polyol having a hydroxyl value of 760 mgKOH / g, obtained by reacting only propylene oxide as an alkylene oxide using ethylenediamine as an initiator.
Polyol Y2: A polyoxypropylene polyol having a hydroxyl value of 350 mgKOH / g, obtained by reacting only propylene oxide as an alkylene oxide using ethylenediamine as an initiator.
Polyol Y3: Polyoxypropylene polyol having a hydroxyl value of 500 mgKOH / g, obtained by reacting only propylene oxide as alkylene oxide using ethylenediamine as an initiator.
Polyol Y4: A polyoxypropylene polyol having a hydroxyl value of 350 mgKOH / g, obtained by reacting only propylene oxide as alkylene oxide using 1- (2-aminoethylpiperazine) as an initiator.
Polyol Z1: Polystyrene having a hydroxyl value of 300 mgKOH / g, obtained by reacting only propylene oxide as alkylene oxide using a mixture of sucrose and glycerin as the initiator (mixing ratio is 1.5: 1 by mass). Oxypropylene polyol.
Polyol Z2: A polyoxypropylene polyol having a hydroxyl value of 650 mgKOH / g, obtained by reacting only propylene oxide as an alkylene oxide using glycerin as an initiator.

(Foaming agent)
Blowing agent 1: HFC-245fa.
Foaming agent 2: HFC-365mfc.
Blowing agent 3: HFC-134a.
Foaming agent 4: cyclopentane.

(Example 1)
The polyols shown in Table 1 were mixed and used. 70% by mass of this polyol mixture was charged into a 5 L pressure reactor and heated to 120 ° C. While maintaining the temperature, the remainder of the polyol mixture, and the mixture of monomers and AIBN shown in Table 1 were added over 4 hours under stirring. After completion of the addition, the mixture was stirred for 30 minutes while maintaining the temperature. The monomer reaction rate was 92%. After completion of the reaction, unreacted monomers were removed over 2 hours at a temperature of 120 ° C. and a pressure of 50 Pa. Thus, polyol W1 was obtained. The hydroxyl value of the polyol W1 was 325 mgKOH / g, and the viscosity at 25 ° C. was 4000 mPa · s.

(Example 2)
The polyols shown in Table 1 were mixed and used. This polyol mixture, a monomer shown in Table 1, and a mixture of AIBN were charged into a 5 L pressure reactor. The temperature was raised to 80 ° C. with stirring. The mixture was stirred for 10 hours while maintaining the temperature. The monomer reaction rate was 85%. After completion of the reaction, unreacted monomers were removed over 2 hours at a temperature of 110 ° C. and a pressure of 50 Pa. Thus, polyol W2 was obtained. The hydroxyl value of polyol W2 was 330 mgKOH / g, and the viscosity at 25 ° C. was 1500 mPa · s.

(Examples 3-33)
The polyols shown in Tables 2 to 4 were mixed and used. The foaming agents shown in Tables 2 to 4 were used. The following foaming agent, catalyst, foam stabilizer and flame retardant were added to and mixed with the polyol mixture and the foaming agent to obtain a polyol composition. As the catalyst, N, N-dimethylcyclohexylamine (trade name: Kaulizer No. 10, manufactured by Kao Corporation) was used. The amount used was such that the gel time was 25 seconds. As the foam stabilizer, 1.5 parts by mass of a silicone foam stabilizer (trade name: SH-193, manufactured by Toray Dow Corning Silicone) was used. As the flame retardant, 10 parts by mass of tris (2-chloropropyl) phosphate (trade name: TMCPP, manufactured by Daihachi Chemical Co., Ltd.) was used. As the polyisocyanate compound, polymethylene polyphenyl polyisocyanate (trade name: MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used. The amount of polyisocyanate compound used was set to 110 in terms of isocyanate index.

  The polyol composition and the polyisocyanate compound were mixed at a liquid temperature of 20 ° C., and placed in a wooden box having a length of 200 mm × width of 200 mm × height of 200 mm to produce a rigid polyurethane foam by foaming.

(Examples 34 to 63)
The polyols shown in Tables 5 to 7 were mixed and used. Further, the foaming agents shown in Tables 5 to 7 were used. The following foaming agent, catalyst, foam stabilizer and flame retardant were added to and mixed with the polyol mixture and the foaming agent to obtain a polyol composition. As the catalyst, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-S-triazine (trade name: Polycat 41, manufactured by Air Products) and diethylene glycol solution of potassium 2-ethylhexanoate (potassium concentration) 15%, trade name: PACCAT 15G, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was used at a ratio of 2 parts by mass to 3 parts by mass, and the amount used was such that the gel time was 25 seconds. As a foaming agent, 1.5 parts by mass of SH-193 was used, as a flame retardant, 20 parts by mass of TMCPP, and as a polyisocyanate compound, polymethylene polyphenyl polyisocyanate (trade name: MR-200, Nippon Polyurethane Industry Co., Ltd. The polyisocyanate compound was used in an amount of 200 in terms of isocyanate index. .

  The polyol composition and the polyisocyanate compound were mixed at a liquid temperature of 20 ° C., and placed in a wooden box having a length of 200 mm × width of 200 mm × height of 200 mm to foam and produce a rigid urethane-modified polyisocyanurate foam.

(Evaluation)
The obtained rigid foam was evaluated for core density (unit: kg / m ³ ), low temperature shrinkage (unit:%), high temperature shrinkage (unit:%), initial adhesion and cell appearance. The low temperature shrinkage is -30 ° C, the dimensional change rate in the direction perpendicular to the foaming direction after 24 hours, and the high temperature shrinkage is 70 ° C, the dimensional change rate in the direction perpendicular to the foaming direction after 48 hours. Indicates. Regarding the initial adhesiveness, the laminate paper was spread in a box before foaming, foamed, the foam was removed after 30 minutes of stirring, and the adhesiveness when the laminate paper was peeled off was evaluated as good ○ and bad ×. As for the cell appearance, the produced foam was cut, and the internal cell state and the rough state of the bottom surface of the foam were evaluated as ○: good, ×: poor.

  As shown in Tables 2 to 7, each of the rigid foams produced by the method for producing a rigid foam of the present invention had a low density and exhibited good initial adhesiveness, cell appearance, and dimensional stability.

(Evaluation 2)
Next, to the polyol compositions used in Examples 3 to 10, 17 to 22, 34 to 41, and 48 to 53, a mineral spirit solution of lead 2-ethylhexanoate (lead concentration: 20%, trade name: Nikka Octix) 1.0 part by mass of 20% lead (manufactured by Nippon Chemical Industry Co., Ltd.) was further added and mixed. This liquid and C-1155 as a polyisocyanate compound were sprayed onto the wall surface by spray foaming using a gasmer foaming machine at a liquid temperature of 35 ° C. and a room temperature of 10 ° C.

The resulting foam showed a good foaming process even though it was manufactured at room temperature of 10 ° C. and a low temperature assuming winter, and the density of the resulting rigid foam was a core density of 31 kg / m ³ or less. It was sufficiently low and showed good cell appearance, initial adhesion, and self-extinguishing properties.

  For the rigid foams of Examples 34 to 41 and Examples 48 to 53, which are production examples of rigid urethane-modified polyisocyanurate foam, the core portion is cut out to a thickness of 15 mm, and a corn calorimeter (manufactured by Toyo Seiki Seisakusho) is used. The combustion test according to ISO5600Part1 was conducted. As a result, it was found that the prescribed flame retardancy was satisfied.

  The manufacturing method of the rigid foam which is lightweight and excellent in adhesiveness based on this invention is suitable for construction of the rigid foam by spray foaming constructed | assembled at a construction site.

Claims (7)

In a method for producing a rigid foam synthetic resin by reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst,
Polymer dispersion obtained by polymerizing a monomer having a polymerizable unsaturated bond in a polyol mixture containing the following polyether polyol (X) and the following amine-based polyether polyol (Y) as a polyol compound and directly depositing particles A method for producing a hard foam synthetic resin, comprising using a polyol mixture containing a polyol and the following polyol (A), having a hydroxyl value of 100 to 700 mgKOH / g, and using water as a foaming agent.
Polyether polyol (X): A polyether polyol having a hydroxyl value of 84 mgKOH / g or less and an oxyethylene group content of 40% by mass or more.
Amine-based polyether polyol (Y): A polyether polyol having a hydroxyl value of 250 to 900 mgKOH / g, obtained by ring-opening addition polymerization of alkylene oxide using an aliphatic amine or alicyclic amine as an initiator.
Polyol (A): As an initiator, composed of ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, monoethanolamine, diethanolamine, triethanolamine, 1-amino-2-propanol, and aminoethylethanolamine A polyoxyethylene polyol having a hydroxyl value of 150 to 800 mgKOH / g, produced by ring-opening addition polymerization of only ethylene oxide using at least one selected from the group. The method for producing a rigid foam synthetic resin according to claim 1, wherein the polyol mixture contains the following polyol (BA) and / or polyol (BB).
Polyol (BA): A polyoxyalkylene polyol having a hydroxyl value of 100 to 700 mgKOH / g, produced by ring-opening addition polymerization of alkylene oxide using an aromatic compound as an initiator.
Polyol (BB): Polyester polyol produced by polycondensation of a monomer containing an aromatic compound and having a hydroxyl value of 100 to 700 mgKOH / g.   The manufacturing method of the hard foam synthetic resin of Claim 2 using at least 1 sort (s) chosen from the group which consists of a Mannich condensation product, diaminotoluene, and bisphenol A as an initiator of the said polyol (BA). As the monomer having a polymerizable unsaturated bond, a combination of acrylonitrile and styrene having a mass ratio of acrylonitrile / styrene of 90 to 40 / 10-60, or a mass ratio of acrylonitrile / vinyl acetate of 50 to 10/50 to 90 The manufacturing method of the hard foam synthetic resin as described in any one of Claims 1-3 using the combination of a certain acrylonitrile and vinyl acetate. The manufacturing method of the hard foam synthetic resin as described in any one of Claims 1-4 whose ratio of a polyol (A) is 15-80 mass% among the said polyol mixtures. The manufacturing method of the hard foam synthetic resin as described in any one of Claims 1-5 whose usage-amount of the water as said foaming agent is 1-15 mass parts with respect to 100 mass parts of said polyol compounds. When the polyol compound and the polyisocyanate compound are reacted in the presence of a foaming agent, a foam stabilizer and a catalyst,
The rigid foam synthetic resin according to any one of claims 1 to 6 , wherein spray foaming is performed by reacting a polyol system liquid containing a polyol compound, a foaming agent, a foam stabilizer and a catalyst and a polyisocyanate compound while spraying. Manufacturing method.