JP2011058009A - Method of producing rigid synthetic resin foam and polyol composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a rigid synthetic resin foam having good surface appearance and exhibiting excellent dimensional stability in production. <P>SOLUTION: The resin is produced by using a hydrofluorocarbon, especially HFC-365mfc, having a boiling point of 30-50°C and serving as a foaming agent, a polyether polyol (X) having the hydroxyl value of 84 mg-KOH/g or less and an oxyethylene group content of 40 mass% or more, an amine polyether polyol (Y) having the hydroxyl value of 250-900 mg-KOH/g and obtained by the addition polymerization of a cyclic ether using a reaction product of the Mannich reaction as an initiator, and a polymer dispersion polyol containing 0.01 mass% or more of stably dispersed polymer particles (P). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a rigid foamed synthetic resin such as rigid polyurethane foam, rigid urethane-modified polyisocyanurate foam, and rigid polyurea foam.

  Production of a foamed synthetic resin by reacting a polyol and a polyisocyanate compound in the presence of a catalyst and a foaming agent is widely performed. Examples of the foamed synthetic resin to be obtained include urethane foams such as polyurethane foam, urethane-modified polyisocyanurate foam, and polyurea foam.

  The urethane foam can be classified into a flexible foam mainly using a low hydroxyl value (high molecular weight) polyol and a rigid foam mainly using a high hydroxyl value (low molecular weight) polyol, depending on the molecular weight of the polyol used. Hereinafter, the rigid foam synthetic resin represents the rigid foam.

  Recently, in order to enhance dimensional stability during the production of rigid foamed synthetic resins, that is, to prevent foam shrinkage, a method of producing a rigid foam by adding a polymer-dispersed polyol to a polyol having a high hydroxyl value is disclosed in Patent Document 1, Patent It is proposed in Document 2.

In the production examples of rigid foam synthetic resins described in the above proposals, water, hydrocarbons, and hydrofluorocarbons are listed as foaming agents that do not cause ozone layer destruction. Among these, when water is used as a blowing agent, carbon dioxide gas is generated by the reaction of water and polyisocyanate, and at the same time, urea bonds are formed, resulting in poor adhesion and high thermal conductivity. is there. Also, hydrocarbons are flammable, so it is not preferable because the production equipment and production environment must be explosion-proof. CF ₃ CH ₂ F (hereinafter referred to as HFC-134a) and CF ₃ CH ₂ CHF ₂ (hereinafter referred to as HFC-245fa), which are cited as hydrofluorocarbons, are preferably nonflammable but have a low boiling point (HFC-134a). -26.5 ° C, HFC-245fa is 15.3 ° C), and there is a problem of poor workability.

  Specific problems when using a low-boiling-point blowing agent are listed below. In the raw material preparation process, when preparing a polyol system in which polyols, catalysts, etc. are premixed, the foaming agent is scattered in an open-type mixing tank, and the pressure-resistant equipment of the tank is required in a closed-type mixing tank. . In addition, when transporting a polyol system, if a conventional drum is used, especially in the summer, the system overflows or the drum swells greatly. When a pressure cylinder is used instead of the drum, There are many problems in operability such as an increase in weight due to a pressure cylinder and recovery of the cylinder.

  Further, at the time of manufacturing the rigid foamed synthetic resin, there is a problem that the foaming agent is difficult to be trapped in the foamed synthetic resin in the initial foaming process, and the appearance of the surface of the foamed synthetic resin such as voids and swelling is likely to occur. Especially in spray construction that sprays on the wall surface, the foaming agent is difficult to be trapped in the foamed synthetic resin immediately after spraying, and the foaming agent escapes between the wall surface and the foamed synthetic resin surface, and the foamed synthetic resin is liable to float and peel off. There are problems such as.

Japanese Unexamined Patent Publication No. 2000-7752 JP 2000-212242 A

  In order to solve the problems described above, the present invention uses a hydrofluorocarbon having a boiling point of 30 to 50 ° C. as a foaming agent, and uses a polymer-dispersed polyol to produce a rigid foam synthetic resin having a good surface appearance. It aims to provide a method.

  The present invention relates to a method for producing a rigid foamed synthetic resin by reacting a polyol and a polyisocyanate in the presence of a foam stabilizer, a catalyst and a foaming agent, and a hydrofluorocarbon having a boiling point of 30 to 50 ° C. And includes the following polyether polyol (X), the following amine-based polyether polyol (Y), and the following polymer fine particles (P) stably dispersed as polyols, and the polymer fine particles (P) are used as all polyols. On the other hand, the present invention provides a method for producing a rigid foam synthetic resin, wherein a polyol containing 0.01% by mass or more is used. The present invention also provides a polyol composition comprising a foam stabilizer, a catalyst, CF3CH2CF2CH3, and the following polyol (V).

Polyol (V): The following polyether polyol (X), the following amine-based polyether polyol (Y), and the following finely dispersed polymer particles (P) stably dispersed, and 0.01% by mass or more of the polymer particles (P) Contains polymer-dispersed polyol. Hereinafter, all polyols are referred to as polyol (V).
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): an amine-based polyether polyol obtained by addition polymerization of a cyclic ether using an amine compound as an initiator, wherein the amine compound is a reaction product obtained by a Mannich reaction. An amine polyether polyol having a hydroxyl value of 250 to 900 mgKOH / g.
Polymer fine particles (P): Polymer fine particles obtained by polymerizing a monomer having a polymerizable unsaturated bond.

  According to the production method of the present invention, it is possible to produce a rigid foam synthetic resin excellent in dimensional stability and the appearance of the foam surface. Further, since the polyol composition of the present invention is excellent in dispersion stability, it can be used without any problem even if the polyol system is left for a long period of time.

[Foaming agent]
In the present invention, a hydrofluorocarbon having a boiling point of 30 to 50 ° C. is used as the foaming agent. Since the blowing agent is hydrofluorocarbon, there is no possibility of destroying the ozone layer. On the other hand, if the boiling point of the foaming agent is lower than 30 ° C., the resulting hard foamed synthetic resin tends to have poor appearance. On the other hand, if the boiling point is higher than 50 ° C., sufficient foaming does not occur, and the physical properties of the obtained rigid foam synthetic resin tend to be poor.

  When a foaming agent having a relatively high boiling point is used in the production of a normal rigid foam synthetic resin, there is a problem that shrinkage easily occurs when foaming is performed in a low temperature environment. In the present invention, the polyol (V) described below is used. By combining them, a hard synthetic foamed resin with little shrinkage and excellent dimensional stability can be obtained.

Among hydrofluorocarbons having a boiling point of 30 to 50 ° C., nonflammable hydrofluorocarbons are more preferable. Nonflammability is preferable because it eliminates the need for explosion-proof management of the production equipment and production environment for rigid foam synthetic resins. Among the nonflammable hydrofluorocarbons, CF ₃ CH ₂ CF ₂ CH ₃ (hereinafter referred to as HFC-365mfc) having a boiling point of 40 ° C. is preferable.

  As the blowing agent, one or more selected from the group consisting of water, a hydrofluorocarbon other than HFC-365mfc, and a hydrocarbon compound having 10 or less carbon atoms can be used in combination with HFC-365mfc. Examples of hydrofluorocarbons other than HFC-365mfc include HFC-134a and HFC-245fa. Examples of the hydrocarbon compound having 10 or less carbon atoms include butane, cyclopentane, n-pentane, cyclohexane, and n-hexane.

  The amount of HFC-365mfc used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the polyol (V). When water as a blowing agent is used in combination with HFC-365mfc, the amount of water used is 10 parts by mass or less with respect to 100 parts by mass of polyol (V) and 100 parts by mass with respect to 100 parts by mass of HFC-365mfc. Part or less is preferred. More preferably, it is 10 parts by mass or less with respect to 100 parts by mass of polyol (V), and 20 parts by mass or less with respect to 100 parts by mass of HFC-365mfc. Moreover, the usage-amount of foaming agents other than water used together with HFC-365mfc is 1-100 mass parts with respect to 100 mass parts of polyols, and 1-200 mass parts with respect to 100 mass parts of HFC-365mfc. preferable. More preferably, it is 1-100 mass parts or less with respect to 100 mass parts of polyol (V), and is 1-100 mass parts or less with respect to 100 mass parts of HFC-365mfc.

[Polyol (V)]
The polyol (V) in the present invention includes a polyether polyol (X), an amine-based polyether polyol (Y), and polymer particles (P) that are stably dispersed, and the polymer particles (P) are 0.01% by mass or more. This is a polymer-dispersed polyol.

  The content of the polyether polyol (X) in the polyol (V) is preferably 0.005% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.2% by mass or more. The content of the amine polyether polyol (Y) in the polyol (V) is preferably 0.003% by mass or more, more preferably 0.03% by mass or more, and particularly preferably 0.1% by mass or more.

  The polymer fine particles (P) are contained in the polyol (V) in an amount of 0.01% by mass or more. When the proportion of the polymer fine particles (P) is less than this, it is difficult to obtain a hard foamed synthetic resin excellent in dimensional stability. The content of the polymer fine particles (P) is preferably 0.05% by mass or more. The content of the polymer fine particles (P) is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 5% by mass or less, and most preferably 2% by mass or less.

  The average hydroxyl value of the polyol (V) is preferably from 100 to 800 mgKOH / g, more preferably from 100 to 750 mgKOH / g. When producing a rigid polyurethane foam as the rigid foamed synthetic resin, the average hydroxyl value of the polyol (V) is preferably from 200 to 800 mgKOH / g, more preferably from 250 to 750 mgKOH / g. When producing a rigid urethane-modified polyisocyanurate foam as the rigid foam synthetic resin, the average hydroxyl value of the polyol (V) is preferably from 100 to 550 mgKOH / g, more preferably from 100 to 450 mgKOH / g.

  The polyol (V) is preferably composed only of the following polymer-dispersed polyol (A), or composed of the polymer-dispersed polyol (A) and another polyol (B) used for producing the rigid foam synthetic resin. More preferably, A) and other polyol (B) used for producing the rigid foam synthetic resin are included.

Polymer-dispersed polyol (A): A polymer-dispersed polyol comprising the following polyol (W) and polymer fine particles (P).
Polyol (W): Polyol including polyether polyol (X), amine-based polyether polyol (Y) and optionally other polyols (Z).

  The mixing ratio of the polymer-dispersed polyol (A) and the other polyol (B) in the polyol (V) is preferably (A) / (B) of 0.1 to 100 / 99.9 to 0 in terms of mass ratio. 3 to 100 / 99.7 to 0 is more preferable, 1 to 50/99 to 50 is more preferable, and 1 to 10/99 to 90 is particularly preferable.

[Polymer-dispersed polyol (A)]
The polymer-dispersed polyol (A) is a polymer-dispersed polyol containing both the polyol (W) and the polymer fine particles (P). The manufacturing method will be described later. The hydroxyl value of the polymer-dispersed polyol (A) is preferably 200 to 800 mgKOH / g, more preferably 200 to 750 mgKOH / g, and particularly preferably 250 to 750 mgKOH / g. The period in which the polymer-dispersed polyol (A) is separated and the polymer fine particles (P) are not settled is preferably at least 1 month, more preferably at least 2 months, and particularly preferably at least 3 months in a stationary state.

[Polyol (W)]
The polyol (W) is a polyol containing a polyether polyol (X), an amine-based polyether polyol (Y), and optionally other polyols (Z). The mixing ratio of the polyether polyol (X), the amine-based polyether polyol (Y) and the other polyol (Z) in the polyol (W) is (X) / (Y) / (Z) in a mass ratio of 5 to 5. 97/3 to 35/0 to 92 are preferable, 10 to 60/5 to 35/10 to 85 are more preferable, and 25 to 50/8 to 25/25 to 67 are particularly preferable.

  The average hydroxyl value of the polyol (W) is preferably 200 to 800 mgKOH / g. When the average hydroxyl value of the polyol (W) is lower than 200 mgKOH / g, the compatibility between the produced polymer-dispersed polyol (A) and the other polyol (B) used for producing a rigid foamed synthetic resin having a high hydroxyl value is Become scarce. Therefore, when used together, there are problems such as separation of polymer fine particles or thickening of the polyol (V), which makes it difficult to use as a raw material for rigid foam synthetic resin. When the average hydroxyl value of the polyol (W) is higher than the above range, it is difficult to obtain a polymer-dispersed polyol (A) in which polymer fine particles (P) are stably dispersed. A more preferable average hydroxyl value of the polyol (W) is 250 to 750 mgKOH / g.

[Polyether polyol (X)]
The polyether polyol (X) in the present invention 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. When the hydroxyl value of the polyether polyol (X) is larger than 84 mgKOH / g, the dispersion stability of the polymer fine particles (P) in the polymer-dispersed polyol (A) is lowered. 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 not particularly limited, but the hydroxyl value is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, particularly preferably 20 mgKOH / g or more, and most preferably 30 mgKOH / g or more. .

  When the oxyethylene group content of the polyether polyol (X) is lower than 40% by mass, the dispersion stability of the polymer fine particles (P) in the polymer-dispersed polyol (A) is lowered. The lower limit of the oxyethylene group content of the polyether polyol (X) is more preferably 50% by mass or more, and particularly preferably 55% by mass or more. The upper limit of the oxyethylene group content of the polyether polyol (X) is not particularly limited, but is preferably about 100% by mass or less, and more preferably 90% by mass or less.

  The content of the polyether polyol (X) in the polyol (W) is preferably 5% by mass to 97% by mass. When the content of the polyether polyol (X) is lower than 5% by mass, the dispersion stability of the polymer fine particles (P) in the polymer-dispersed polyol (A) is lowered. The content of the polyether polyol (X) in the polyol (W) is more preferably 10 to 60% by mass, and particularly preferably 25 to 50% by mass.

  The polyether polyol (X) in the present invention is obtained by addition polymerization using a trihydric or higher polyhydric alcohol as an initiator and using ethylene oxide alone or in combination with ethylene oxide and another cyclic ether. Polyether polyols are preferred. As the trihydric or higher polyhydric alcohol, trihydric alcohols such as glycerin, trimethylolpropane and 1,2,6-hexanetriol are particularly preferable. As other cyclic ether used in combination with ethylene oxide, propylene oxide, isobutylene oxide, 1,2-epoxybutane, 2,3-epoxybutane and the like are preferable, and among these, propylene oxide is particularly preferable.

[Amine-based polyether polyol (Y)]
The amine-based polyether polyol (Y) in the present invention is an amine-based polyether polyol having a hydroxyl value of 250 to 900 mgKOH / g obtained by addition polymerization of a cyclic ether using an amine compound as an initiator. Is an amine polyether polyol having a hydroxyl value of 250 to 900 mgKOH / g, which is a reaction product obtained by a Mannich reaction. The hydroxyl value is preferably from 300 to 800 mgKOH / g, particularly preferably from 350 to 800 mgKOH / g.

  The content of the amine polyether polyol (Y) in the polyol (W) is preferably from 3 to 35% by mass. When the content of the amine-based polyether polyol (Y) is lower than 3% by mass, the dimensional stability of the rigid foam synthetic resin produced using the polymer-dispersed polyol (A) may be poor. When the content of the amine polyether polyol (Y) is higher than 35% by mass, it is difficult to obtain a polymer-dispersed polyol (A) having a low viscosity and good dispersion stability. The content of the amine-based polyether polyol (Y) in the polyol (W) is more preferably 5 to 35% by mass, further preferably 8 to 30% by mass, and most preferably 8 to 25% by mass.

  As the cyclic ether to be subjected to addition polymerization on the amine compound, ethylene oxide, propylene oxide, isobutylene oxide, 1,2-epoxybutane, 2,3-epoxybutane and the like are preferable, and among these, ethylene oxide and propylene oxide are particularly preferable.

[Other polyols (Z)]
The other polyol (Z) is any polyol other than the polyether polyol (X) and the amine polyether polyol (Y). Examples of other polyols (Z) include polyether polyols, polyester 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 content of the other polyol (Z) in the polyol (W) is preferably 0 to 92% by mass, more preferably 10 to 85% by mass, and particularly preferably 25 to 67% by mass.

[Other polyols (B)]
The other polyol (B) is an arbitrary polyol used for producing a rigid foam synthetic resin, which is contained in the polyol (V) together with the polymer-dispersed polyol (A). Examples of other polyols (B) include polyether polyols, polyester polyols, polyhydric alcohols, and hydrocarbon polymers having a hydroxyl group at the terminal. Further, polyether polyols obtained by adding a cyclic ether to a reaction product obtained by reacting phenols, alkanolamines, and aldehydes by Mannich reaction can also be used. Polyether polyol (X) and amine polyether polyol (Y) can also be used.

  Moreover, when manufacturing a rigid urethane modified polyisocyanurate foam, it is preferable to use a polyester polyol as another polyol (B). As the polyester polyol, a polyester polyol obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid is particularly preferable. As the polyvalent carboxylic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid are preferable. The hydroxyl value of the polyester polyol is preferably 100 to 450 mgKOH / g, particularly preferably 100 to 350 mgKOH / g. 10-99.9 mass% is preferable, and, as for the content of the said polyester polyol in polyol (V), 50-99.9 mass% is more preferable.

  Further, when the content of the polyester polyol in the polyol (V) is relatively low at 10 to 50% by mass, (i) a cyclic ether is added to a polyhydric phenol such as bisphenol A or phenol-formaldehyde initial condensate. (Ii) polyether polyols obtained by adding a cyclic ether to a reaction product obtained by reacting phenols, alkanolamines and aldehydes by a Mannich reaction, (iii) It is preferable to use together polyether diols obtained by adding a cyclic ether to diol, etc. as other polyols (B).

  As the other polyol (B), a polyether polyol, polyester polyol, polyhydric alcohol and the like having a relatively low molecular weight can be used in combination as a chain extender and a crosslinking agent. Specifically, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, and glycerin are used.

[Polymer fine particles (P)]
The polymer fine particles (P) in the present invention are polymer fine particles obtained by polymerizing a monomer having a polymerizable unsaturated bond. Specific examples of the monomer having a polymerizable unsaturated bond used in the present invention include nitrile monomers such as acrylonitrile, methacrylonitrile, 2,4-dicyano-1-butene; acrylic acid, methacrylic acid, acrylic acid ester, Acrylic monomers such as methacrylic ester, acrylamide and methacrylamide; styrene monomers such as styrene and α-methylstyrene; vinyl carboxylic acid ester monomers such as vinyl acetate and vinyl propionate; isoprene, butadiene and other diene monomers Unsaturated fatty acid ester monomers such as maleic acid diester and itaconic acid diester; vinyl halide monomers such as vinyl chloride; vinylidene halide monomers such as vinylidene chloride; methyl vinyl ether, ethyl vinyl ether Alkyl vinyl ether monomer such as isopropyl vinyl ether. 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 (P) in the polymer-dispersed polyol (A) is preferably about 1 to 50% by mass, particularly preferably 2 to 45% by mass, and 5 to 40% by mass. % Is most preferred.

[Production method of polymer-dispersed polyol (A)]
Examples of the method for producing the polymer-dispersed polyol (A) in which the polymer fine particles (P) are stably dispersed using the polyol (W) include the following two methods.

  The first method is a method of directly depositing particles by polymerizing a monomer having a polymerizable unsaturated bond in the polyol (W) in the presence of a solvent as necessary. In the second method, if necessary, a monomer having a polymerizable unsaturated bond is polymerized in a solvent in the presence of a grafting agent that stabilizes the particles, and then the particles are precipitated, and then the polyol (W) and the solvent are added. This is a replacement method. In the present invention, either method can be adopted, and the first method is particularly preferable.

  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 (P), 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.

[Polyol composition]
The polyol composition in the present invention contains a foam stabilizer, a catalyst, HFC-365mfc, and polyol (V). The polyol composition is a raw material for producing a rigid foamed synthetic resin by mixing and reacting with a polyisocyanate, and is called a so-called polyol system.

  The polyol (V) is excellent in dispersion stability. The polyol composition is also excellent in dispersion stability. The period during which the polyol composition is separated and the fine polymer particles (P) are not settled is preferably 1 month or longer, more preferably 2 months or longer, and particularly preferably 3 months or longer in the stationary state.

[Method for producing rigid foam synthetic resin]
The present invention uses a hydrofluorocarbon having a boiling point of 30 to 50 ° C. as a foaming agent in a method of producing a rigid foamed synthetic resin by reacting a polyol and a polyisocyanate in the presence of a foam stabilizer, a catalyst and a foaming agent. This is a method for producing a hard foam synthetic resin.

  Examples of polyisocyanates include aromatic, alicyclic, or aliphatic polyisocyanates having an average of two or more isocyanate groups in the molecule. A mixture of two or more of the polyisocyanates or a modified polyisocyanate obtained by modifying the polyisocyanates can also be used. Specifically, polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate (common name: crude MDI), xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate; Examples thereof include a nurate modified body, a urea modified body, and a carbodiimide modified body.

  As a foam stabilizer, what is normally used when manufacturing a hard foam synthetic resin can be used, and a silicone type foam stabilizer, a fluorine type foam stabilizer, etc. are mentioned. As a catalyst, what is normally used when manufacturing a hard foam synthetic resin can be used. An amine-based catalyst such as triethylenediamine, an organometallic compound catalyst such as lead 2-ethylhexanoate and tin (II) 2-ethylhexanoate, and a quaternary ammonium salt catalyst can be used. When producing a rigid urethane-modified polyisocyanurate foam, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-sym-triazine, potassium acetate, potassium 2-ethylhexanoate, quaternary ammonium salt catalyst An isocyanurate-modified catalyst such as

  In addition, chain extenders, crosslinking agents, fillers, stabilizers, colorants, flame retardants, and the like can be arbitrarily used as raw materials for the rigid foam synthetic resin. As the chain extender and the crosslinking agent, alkanolamines such as diethanolamine and triethanolamine; polyamines such as hexamethylenediamine and 4,4'-diaminodiphenylmethane can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these. In the table, AN represents acrylonitrile, St represents styrene, VAc represents vinyl acetate, and MMA represents methyl methacrylate. Numbers without units in the table represent parts by mass.

[Production of polyol]
The polyols used are as follows.
Polyol X1: A polyether polyol obtained by randomly adding propylene oxide and ethylene oxide to glycerin and having a hydroxyl value of 50 mgKOH / g and an oxyethylene group content of 55% by mass.
Polyol X2: A polyether polyol obtained by randomly adding propylene oxide and ethylene oxide to glycerin and having a hydroxyl value of 50 mgKOH / g and an oxyethylene group content of 75% by mass.

Polyol Y1: An amine polyether polyol having a hydroxyl value of 470 mgKOH / g, obtained by adding propylene oxide to a reaction product obtained by subjecting nonylphenol, formaldehyde and diethanolamine to Mannich reaction.
Polyol Y2: An amine polyether polyol having a hydroxyl value of 760 mgKOH / g, obtained by adding propylene oxide to ethylenediamine.
Polyol Y3: An amine polyether polyol having a hydroxyl value of 500 mgKOH / g, obtained by adding propylene oxide to ethylenediamine.

Polyol Y4: An amine polyether polyol having a hydroxyl value of 450 mgKOH / g, obtained by adding propylene oxide to a mixture of sucrose and diethanolamine.
Polyol Y5: An amine polyether polyol having a hydroxyl value of 450 mgKOH / g and an oxyethylene group content of 30%, obtained by adding ethylene oxide and propylene oxide in this order to tolylenediamine. Polyol Y6: an amine polyether polyol having a hydroxyl value of 450 mgKOH / g and an oxyethylene group content of 40%, obtained by adding propylene oxide and ethylene oxide in this order to ethylenediamine.

Polyol Z1: A polyether polyol obtained by randomly adding propylene oxide and ethylene oxide to glycerin and having a hydroxyl value of 50 mgKOH / g and an oxyethylene group content of 25% by mass.
Polyol Z2: A polyether polyol obtained by adding propylene oxide and ethylene oxide to glycerin in this order and having a hydroxyl value of 56 mgKOH / g and an oxyethylene group content of 10% by mass. Polyol Z3: A polyether polyol obtained by adding propylene oxide to glycerin and having a hydroxyl value of 450 mgKOH / g.

Polyol Z4: A polyether polyol obtained by adding propylene oxide to glycerin and having a hydroxyl value of 650 mgKOH / g.
Polyol Z5: A polyether polyol obtained by adding ethylene oxide to bisphenol A and having a hydroxyl value of 280 mgKOH / g.
Polyol Z6: A polyether polyol having a hydroxyl value of 450 mgKOH / g, obtained by adding propylene oxide to a mixture of sucrose and glycerin.
Polyol Z7: Polyester polyol obtained by reacting phthalic acid with diethylene glycol and having a hydroxyl value of 250 mgKOH / g.

(Examples 1 to 6: Production examples of polymer-dispersed polyol)
(Production of polymer-dispersed polyols A1, A2, B1, B2, and B3)
70 mass% of the mixture of polyols shown in Table 1 was charged into a 5 L pressurized reaction vessel, and the mixture of the remaining polyols, the monomer shown in Table 1 and AIBN as an initiator were stirred while maintaining the temperature at 120 ° C. However, it was supplied over 4 hours. After completion of the feeding, stirring was continued at 120 ° C. for about 0.5 hours. In all examples, the monomer conversion was 90% or more. After completion of the reaction, unreacted monomers were removed by heating under reduced pressure at 120 ° C. and 13 Pa for 2 hours to produce a polymer-dispersed polyol.

  Each hydroxyl value (unit: mgKOH / g), viscosity at 25 ° C. (unit: cP) and dispersion stability are shown in Table 1. Polyol B2 produced without using the polyether polyol (X) caused phase separation, a uniform dispersion was not obtained, and the hydroxyl value and viscosity could not be measured.

(Production of polymer-dispersed polyol A3)
After charging all the polyols, monomers, and AIBN as initiators shown in Table 1 into a 5 L pressurized reaction vessel, the temperature was raised with stirring. The reaction was allowed to react for 10 hours while maintaining the temperature at 80 ° C. The monomer reaction rate was 80% or more. After completion of the reaction, the unreacted monomer was removed by heating under reduced pressure at 110 ° C. and 13 Pa for 2 hours to produce a polymer-dispersed polyol. Table 1 shows the hydroxyl value (unit: mgKOH / g), the viscosity at 25 ° C. (unit: cP), and the dispersion stability.

[Manufacture of rigid foam synthetic resin]
(Examples 7 to 29: Production examples of rigid polyurethane foam)
100 parts by weight of polyol, 2 parts by weight of polymer-dispersed polyol (indicated as POP in the table), foaming agent, catalyst, silicone foam stabilizer (Toray Dow Corning Silicone) in the amounts and types shown in Tables 2-3 A polyol composition prepared by mixing 1.5 parts by mass of SH-193) and 10 parts by mass of tris (2-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., hereinafter referred to as TMCPP) as a flame retardant. Manufactured.

  The types of blowing agents used are blowing agent a: HFC-365mfc, blowing agent b: HFC-134a, blowing agent c: HFC-245fa, blowing agent d: cyclopentane, and blowing agent e: n-pentane.

  The type and amount of the catalyst used were as follows: Catalyst f: Triethylenediamine solution (trade name: DABCO 33LV, manufactured by Air Products and Chemicals) parts by mass necessary for the gel time to be 40 seconds during hand foaming, catalyst g: N, N-dimethylcyclohexylamine (trade name: Kaulizer No. 10, manufactured by Kao) is a mass part necessary for the gel time at hand foaming to be 60 seconds.

  To the prepared polyol composition, polymethylene polyphenyl isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., MR-200) as an isocyanate is mixed at a liquid temperature of 20 ° C. so that the isocyanate index is 110, and the length is 200 mm × width 200 mm ×. A rigid polyurethane foam was produced by placing it in a wooden box having a height of 200 mm.

(Examples 30 to 42: Production Examples of Rigid Urethane Modified Polyisocyanurate Foam)
100 parts by weight of polyol, 2 parts by weight of polymer-dispersed polyol, foaming agent, catalyst, silicone foam stabilizer (manufactured by Dow Corning Silicone Co., SH-193) 1.5 of the amounts and types shown in Table 4 A polyol composition was prepared by preparing 20 parts by mass of TMCPP as a flame retardant and 20 parts by mass of a flame retardant.

  The type and amount of the catalyst used were N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-sym-triazine (trade name: Polycat 41, manufactured by Air Products) and potassium 2-ethylhexanoate ( The mixture of potassium 15%, trade name 15%, manufactured by Nippon Kagaku Sangyo Co., Ltd. is the mass part necessary for the gel time during hand foaming to be 40 seconds.

  To the prepared polyol composition, polymethylene polyphenyl isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., MR-200) is used as an isocyanate and mixed at a liquid temperature of 20 ° C. so that the isocyanate index is 200. X The product was placed in a wooden box with a height of 200 mm to produce a rigid urethane-modified polyisocyanurate foam.

[Evaluation of Polyol Composition and Foaming Evaluation 1]
Core density (unit: kg / m 3), low temperature shrinkage (unit:%), storage stability of polyol composition, appearance of foam surface and thermal conductivity (unit: mW / m · K) of the obtained foam Are shown in Tables 2-4.

  The low temperature shrinkage indicates a dimensional change rate in a direction perpendicular to a foaming direction after lapse of 24 hours at −30 ° C. The storage stability of the polyol composition was evaluated by observing the separated state after leaving the polyol composition at 40 ° C. for 2 months. The case where it was stable without separation was marked with ◯, and the case where it was separated was marked with ×.

  The appearance of the foam surface was judged by the size and number of irregularities found on the top surface of the foam. The case where there were no large voids and the like and the appearance was good was marked as ◯, and the case where there were many large voids and the appearance was bad was marked as x. The thermal conductivity was measured according to JIS A-1412.

  In Table 2, Examples 7 to 9 and 11 are Examples, Example 10 is a Reference Example, Examples 12 to 19 are Comparative Examples, and in Table 3, Examples 20 to 22 and 24 to 26 are Examples and Example 23. Are reference examples, Examples 27 to 29 are comparative examples. In Table 4, Examples 30 to 31 and 33 to 36 are Examples, Example 32 is a Reference Example, and Examples 37 to 42 are Comparative Examples.

  As shown in Tables 2 to 4, both the hard polyurethane foam and the hard urethane-modified nurate foam obtained using HFC-365mfc as a foaming agent had a good foam surface appearance with no voids or swelling. It was. In addition, the rigid polyurethane foam and rigid urethane-modified nurate foam produced based on the production method of the present invention have low low temperature shrinkage, both show good dimensional stability, low thermal conductivity, and excellent heat insulation performance. showed that. Further, the polyol composition of the present invention showed good storage stability.

[Foaming evaluation 2]
Next, rigid foams were produced using the compositions of Examples 7 to 11, 20 to 26, and 30 to 36 between the upper and lower surface materials carried by the inverse line belt conveyor. The resin was uniformly dispersed while traversing through a spray nozzle type mixing head, after-curing was performed in the curing zone, and a continuous laminate board was formed. As a result, the continuous laminate board obtained did not show low-temperature shrinkage on the facet or the like, showed good dimensional stability, and had a good appearance with no voids or air accumulation on the surface.

[Foaming evaluation 3]
Next, using the compositions of Examples 7 to 11, 20 to 26, and 30 to 36, injection flow foaming was performed using a high-pressure foaming apparatus in a 2700 × 1000 × 100 mm panel formwork provided with a color steel plate as a face material. It was. The temperature at that time was 20 ° C., and the mold temperature was 35 ° C. The resulting foam did not show low-temperature shrinkage, exhibited good dimensional stability, and had a good appearance with no voids or air accumulation on the surface.

[Foaming evaluation 4]
Next, Examples 7 to 11 were used except that 0.5 parts by mass of a mineral spirit solution of lead 2-ethylhexanoate (concentration 20%, trade name: Nikka Octix Lead 20%, manufactured by Nippon Chemical Industry Co., Ltd.) was used as a catalyst. Using the same polyol composition as 20 to 26 and 30 to 36, using polymethylene polyphenyl isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 1155) as the isocyanate, at a liquid temperature of 35 ° C. and at a room temperature of 5 ° C., foaming by Gasmer Foaming and spraying on the wall surface while spraying using a machine.

  The resulting rigid foam did not show low-temperature shrinkage, showed good dimensional stability, floated between the wall surface and the foamed synthetic resin surface, did not cause peeling, and had a good foam appearance .

Claims (14)

In a method for producing a rigid foam synthetic resin by reacting a polyol and a polyisocyanate in the presence of a foam stabilizer, a catalyst and a foaming agent,
A hydrofluorocarbon having a boiling point of 30 to 50 ° C. is used as a foaming agent, and the following polyether polyol (X), the following amine-based polyether polyol (Y) and the following polymer fine particles that are stably dispersed as a polyol. A method for producing a rigid foam synthetic resin comprising using (P) and a polyol containing 0.01% by mass or more of polymer fine particles (P) based on the total polyol.
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): an amine-based polyether polyol obtained by addition polymerization of a cyclic ether using an amine compound as an initiator, wherein the amine compound is a reaction product obtained by a Mannich reaction. Hydroxyl value 250-900 mgKOH / g amine polyether polyol.
Polymer fine particles (P): Polymer fine particles obtained by polymerizing a monomer having a polymerizable unsaturated bond.   The method for producing a rigid foam synthetic resin according to claim 1, wherein the amine compound is a reaction product obtained by a Mannich reaction between nonylphenol, formaldehyde, and diethanolamine.   The rigid foam synthetic resin according to claim 1 or 2, wherein the cyclic ether is at least one selected from the group consisting of ethylene oxide, propylene oxide, isobutylene oxide, 1,2-epoxybutane, and 2,3-epoxybutane. Manufacturing method.   The manufacturing method of the hard foam synthetic resin as described in any one of Claims 1-3 whose average hydroxyl value of all the polyols is 100-800 mgKOH / g.   The manufacturing method of the hard foam synthetic resin as described in any one of Claims 1-4 in which polyether polyol (X) is contained 0.005 mass% or more in all the polyols.   The manufacturing method of the hard foam synthetic resin as described in any one of Claims 1-5 in which 0.003 mass% or more of amine-type polyether polyol (Y) is contained in all the polyols. Hydrofluorocarbons having a boiling point of 30 to 50 ° C. _is a _{CF 3 CH 2 CF 2 CH 3} , method for producing a rigid foamed synthetic resin according to any one of claims 1-6. As the foaming agent, one or more selected from the group consisting of water, CF ₃ CFH ₂ , CF ₃ CH ₂ CHF ₂ and hydrocarbon compounds having 10 or less carbon atoms are used in combination with CF ₃ CH ₂ CF ₂ CH ₃ The manufacturing method of the hard foam synthetic resin of Claim 7. As a foaming agent used in combination with CF ₃ CH ₂ CF ₂ CH ₃ , water is used, the amount of water used is 10 parts by mass or less based on 100 parts by mass of the total polyol, and CF ₃ CH ₂ CF ₂ CH The manufacturing method of the hard foam synthetic resin of Claim 8 which is 100 mass parts or less with respect to 100 mass parts of _3. FIG. As a blowing agent in combination with _{CF 3 CH 2 CF 2 CH 3} , CF 3 CH 2 CHF 2 using, the amount of the _CF 3 _{CH 2} CHF 2 is from 1 to 100 parts by weight with respect to total polyol 100 parts by weight , and the _and, CF ₃ 1 to 100 parts by weight per 100 parts by weight of CH 2 _CF 2 CH _3, method for producing a rigid foamed synthetic resin according to claim 8 or 9.   The manufacturing method of the hard foam synthetic resin as described in any one of Claims 1-10 which has the process made to foam while spraying.   The manufacturing method of the hard foam synthetic resin of Claim 11 which forms a hard foam synthetic resin on a wall surface.   The method for producing a hard foam synthetic resin according to claim 11, wherein a hard foam synthetic resin is formed between the upper and lower surface materials. A foam stabilizer, a catalyst, a foaming agent, and the following polyol (V), wherein the foaming agent is selected from the group consisting of water, CF ₃ CFH ₂ , CF ₃ CH ₂ CHF ₂ and a hydrocarbon compound having 10 or less carbon atoms. one or more, and a _{CF 3 CH 2 CF 2 CH 3} , polyol compositions.
Polyol (V): The following polyether polyol (X), the following amine-based polyether polyol (Y), and the following finely dispersed polymer particles (P) that are stably dispersed, and 0.01% by mass or more of the polymer particles (P) Contains polymer-dispersed polyol.
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): an amine-based polyether polyol obtained by addition polymerization of a cyclic ether using an amine compound as an initiator, wherein the amine compound is a reaction product obtained by a Mannich reaction. An amine polyether polyol having a hydroxyl value of 250 to 900 mgKOH / g.
Polymer fine particles (P): Polymer fine particles obtained by polymerizing a monomer having a polymerizable unsaturated bond.