JP2002220430A - Method for producing rigid synthetic resin foam and polyol composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a rigid synthetic resin foam which has good surface appearance and excellent dimensional stability upon manufacture. SOLUTION: The resin is produced by using a hydrofluorocarbon having a boiling point of 30-50 deg.C, especially HFC-365mfc as a foaming agent, a polyether polyol (X) having the hydroxyl value of 84 mgKOH/g or less and an oxyethylene group content of 40 mass% or more, an amine polyether polyol (Y) having the value of 250-900 mgKOH/g which is obtained by the addition polymerization of a cyclic ether using an amine compound as an initiator and a polymer dispersion polyol in which a polymer particulate of 0.01 mass% or more is stably dispersed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art It has been widely practiced to react a polyol with a polyisocyanate compound in the presence of a catalyst and a foaming agent to produce a foamed synthetic resin. Examples of the obtained foamed synthetic resin 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 polyol having a low hydroxyl value (high molecular weight) and a rigid foam mainly using a polyol having a high hydroxyl value (low molecular weight) depending on the molecular weight of the polyol used. . Hereinafter, the rigid foam synthetic resin refers to the rigid foam.

In recent years, a method for producing a rigid foam by adding a polymer-dispersed polyol to a polyol having a high hydroxyl value has been proposed in order to enhance dimensional stability in producing a rigid foamed synthetic resin, that is, to prevent foam shrinkage. 2000
-7752 and JP-A-2000-212242.

[0005] In the production examples of the rigid foamed synthetic resin described in the above proposal, water, hydrocarbons and hydrofluorocarbons are mentioned as foaming agents which do not cause destruction of the ozone layer. When water is used as the blowing agent,
The reaction between water and the polyisocyanate generates carbon dioxide gas and at the same time generates a urea bond, causing problems such as poor adhesion and high thermal conductivity. Since hydrocarbons are flammable, it is necessary to make the production facilities and production environment compatible with explosion-proof, which is not preferable. Further, CF ₃ CH ₂ F (hereinafter referred to as HF) which is mentioned as a hydrofluorocarbon
C-134a), CF ₃ CH ₂ CHF ₂ (hereinafter HF)
C-245fa) is nonflammable and preferred, but has a low boiling point (HFC-134a is -26.5 ° C, HFC-2
45fa is 15.3 ° C.), and there is a problem of poor workability.

Specific problems when using a low-boiling blowing agent are listed below. In the raw material preparation process, when preparing a polyol system in which the polyol, catalyst, etc. are premixed,
In an open type mixing tank, the foaming agent is scattered, and in a closed type mixing tank, it is necessary to cope with pressure-resistant equipment of the tank. Also, in the transport of the polyol system, when using a conventionally used drum, especially in summer, the system overflows or the drum swells greatly, and when a pressure-resistant cylinder is used instead of the drum, In addition, there are many operability problems such as an increase in weight due to a pressure cylinder and collection of the cylinder.

In the production of a hard foamed synthetic resin, the foaming agent is hardly trapped in the foamed synthetic resin in the initial stage of foaming, and the appearance of the foamed synthetic resin such as voids and blisters tends to be poor. is there. In particular, when spraying on the wall surface, the foaming agent is hardly 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 likely to float and peel off. There are problems such as.

[0008]

SUMMARY OF THE INVENTION In order to solve the problems described above, the present invention uses a hydrofluorocarbon having a boiling point of 30 to 50.degree. C. as a blowing agent and a polymer-dispersed polyol. An object of the present invention is to provide a method for producing a rigid foam synthetic resin having an appearance.

[0009]

SUMMARY OF THE INVENTION 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. Using a hydrofluorocarbon at 30 to 50 ° C., and as a polyol,
Polymer fine particles (P) comprising the following polyether polyol (X), the following amine-based polyether polyol (Y), and the following finely dispersed polymer particles (P)
Of a rigid foamed synthetic resin, characterized by using a polyol containing 0.01% by mass or more of the total polyol. Further, the present invention provides a polyol composition comprising a foam stabilizer, a catalyst, CF ₃ CH ₂ CF ₂ CH ₃ , and the following polyol (V).

Polyol (V): contains the following polyether polyol (X), the following amine-based polyether polyol (Y), and the following finely dispersed polymer particles (P), and contains 0.01% of polymer particles (P). mass%
A polymer-dispersed polyol containing the above. Hereinafter, all polyols are referred to as polyol (V). Polyether polyol (X): hydroxyl value is 84 mgK
OH / g or less and a polyether polyol having an oxyethylene group content of 40% by mass or more. Amine-based polyether polyol (Y): obtained by addition polymerization of a cyclic ether using an amine compound as an initiator,
An amine-based 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.

[0011]

DETAILED DESCRIPTION OF THE INVENTION [Blowing agent] In the present invention, a hydrofluorocarbon having a boiling point of 30 to 50 ° C is used as a blowing agent. Since the blowing agent is hydrofluorocarbon, there is no possibility of destroying the ozone layer. 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., foaming does not occur sufficiently, and the physical properties of the obtained hard foamed synthetic resin tend to be poor.

When a foaming agent having a relatively high boiling point is used in the production of an ordinary rigid foamed synthetic resin, there is a problem that shrinkage easily occurs when foaming is performed in a low-temperature environment. By combining with V), a hard synthetic foamed resin with little shrinkage and excellent dimensional stability can be obtained.

Among the hydrofluorocarbons having a boiling point of 30 to 50 ° C., nonflammable hydrofluorocarbons are more preferable. Incombustibility is preferable because it is not necessary to perform explosion-proof management of the production equipment and production environment of the hard foamed synthetic resin. Among the non-flammable hydrofluorocarbons, CF ₃ CH ₂ CF ₂ CH ₃ (hereinafter H) having a boiling point of 40 ° C.
FC-365mfc).

As a foaming agent, water, HFC-365mf
one or two selected from the group consisting of hydrofluorocarbons other than c and hydrocarbon compounds having 10 or less carbon atoms
More than one species can be used in combination with HFC-365mfc. Hydrofluorocarbons other than HFC-365mfc include HFC-134a, HFC-245fa, and the like. 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 polyol (V). In addition, water as a foaming agent is converted to HFC-365mfc.
When used in combination with water, the amount of water used is polyol (V) 1
100 parts by mass or less, and HFC-
The amount is preferably 100 parts by mass or less based on 100 parts by mass of 365 mfc. More preferably, it is 10 parts by mass or less based on 100 parts by mass of the polyol (V), and HFC-365m
20 parts by mass or less based on 100 parts by mass of fc. The amount of the foaming agent other than water used in combination with HFC-365mfc is 1 to 1 with respect to 100 parts by mass of the polyols.
00 parts by mass, and preferably 1 to 200 parts by mass with respect to 100 parts by mass of HFC-365mfc. More preferably, it is 1 to 100 parts by mass or less based on 100 parts by mass of the polyol (V), and 1 to 100 parts by mass or less based on 100 parts by mass of HFC-365mfc.

[Polyol (V)] The polyol (V) in the present invention contains a polyether polyol (X), an amine-based polyether polyol (Y), and finely dispersed polymer particles (P). It is a polymer-dispersed polyol containing 0.01% by mass or more of P).

The content of the polyether polyol (X) in the polyol (V) is preferably at least 0.005% by mass, more preferably at least 0.05% by mass, particularly preferably at least 0.2% by mass. The content of the amine-based polyether polyol (Y) in the polyol (V) is 0.1%.
It is preferably at least 003% by mass, more preferably at least 0.03% by mass, particularly preferably at least 0.1% by mass.

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 foam synthetic resin having excellent 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 100
~ 800mgKOH / g, preferably 100 ~ 750m
gKOH / g is more preferred. When a rigid polyurethane foam is produced as a rigid foam synthetic resin, the average hydroxyl value of the polyol (V) is 200 to 800 mgKOH / g.
Is preferable, and 250 to 750 mgKOH / g is more preferable. When a rigid urethane-modified polyisocyanurate foam is produced as a rigid foam synthetic resin, the average hydroxyl value of the polyol (V) is 100 to 550 mgKOH /
g is preferable, and 100 to 450 mgKOH / g is more preferable.

The polyol (V) is preferably composed of only the following polymer-dispersed polyol (A) or the polymer-dispersed polyol (A) and another polyol (B) used for producing a rigid foam synthetic resin. It is more preferable to include both the dispersed polyol (A) and another polyol (B) used for producing a rigid foam synthetic resin.

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

The mixing ratio of the polymer-dispersed polyol (A) to the other polyol (B) in the polyol (V) is such that (A) / (B) is 0.1 to 100/99.
9 to 0 are preferable, 0.3 to 100 / 99.7 to 0 are more preferable, 1 to 50/99 to 50 are more preferable,
1 to 10/99 to 90 are particularly preferred.

[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 from 200 to 800 mgKOH / g, more preferably from 200 to 750 mgKOH / g, particularly preferably from 250 to 750 mgKOH / g. The period during which the polymer-dispersed polyol (A) is separated and the polymer fine particles (P) do not settle is preferably 1 month or more, more preferably 2 months or more, and particularly preferably 3 months or more in a standing state.

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

The average hydroxyl value of the polyol (W) is 200
~ 800 mgKOH / g is preferred. Polyol (W)
When the average hydroxyl value of is less than 200 mgKOH / g,
The compatibility between the produced polymer-dispersed polyol (A) and another polyol (B) used for producing a rigid foamed synthetic resin having a high hydroxyl value becomes poor. Therefore, when used in combination, 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 a rigid foamed 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 the polymer fine particles (P) are stably dispersed. The more preferred average hydroxyl value of the polyol (W) is 2
It is 50 to 750 mgKOH / g.

[Polyether polyol (X)] The polyether polyol (X) in the present invention has a hydroxyl value of 8
It is a polyether polyol having an oxyethylene group content of 4 mgKOH / g or less and 40% by mass or more. Polyether polyol (X) has a hydroxyl value of 84 mg KO
When it is larger than H / g, the dispersion stability of the polymer fine particles (P) in the polymer-dispersed polyol (A) is reduced.
The hydroxyl value of the polyether polyol (X) is 67 mgK
OH / g or less is preferable, and 60 mgKOH / g or less is particularly preferable. Although the lower limit of the hydroxyl value of the polyether polyol (X) is not particularly limited, the hydroxyl value is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more,
20 mgKOH / g or more is particularly preferable, and 30 mgKO
H / g or more is most preferable.

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) decreases. 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, more preferably 90% by mass or less.

The content of the polyether polyol (X) in the polyol (W) is preferably from 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) decreases. The content of the polyether polyol (X) in the polyol (W) is 1
0-60 mass% is more preferable, and 25-50 mass% is especially preferable.

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

[Amine-based polyether polyol (Y)] The amine-based polyether polyol (Y) in the present invention is obtained by addition polymerization of a cyclic ether using an amine compound as an initiator, and has a hydroxyl value of 250 to 900 mg.
It is an amine-based polyether polyol having a KOH / g. The hydroxyl value of the amine-based polyether polyol (Y) is preferably from 300 to 800 mgKOH / g.
Particularly preferred is -800 mg KOH / g.

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

The amine compound used as the initiator is preferably an aliphatic amine compound or a saturated cyclic amine compound. Examples of the aliphatic amine compound include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine. Examples of the saturated cyclic amine compound include N-aminomethylpiperazine, N- (2-aminoethyl) piperazine, and the like.

The cyclic ether to be addition-polymerized to the amine compound is ethylene oxide, propylene oxide, isobutylene oxide, 1,2-epoxybutane,
2,3-epoxybutane and the like are preferred, and among them, ethylene oxide and propylene oxide are particularly preferred.

[Other polyol (Z)] The other polyol (Z) is any polyol other than the polyether polyol (X) and the amine-based polyether polyol (Y). Examples of other polyols (Z) include polyether polyols, polyester polyols, polyhydric alcohols, and hydrocarbon polymers having a hydroxyl group at a terminal.

The hydroxyl value of the other polyol (Z) is as follows:
200 to 1000 mgKOH / g is preferable, and 400 to
850 mg KOH / g is particularly preferred. The content of the other polyol (Z) in the polyol (W) is from 0 to 9
2 mass% is preferable, 10-85 mass% is more preferable, and 25-67 mass% is especially preferable.

[Other polyols (B)] The other polyols (B) are any polyols used in the production of rigid foamed synthetic resins, which are contained in the polyol (V) together with the polymer-dispersed polyol (A). Examples of other polyols (B) include polyether polyols, polyester polyols, polyhydric alcohols, hydrocarbon polymers having a hydroxyl group at the terminal, and the like. Further, a polyether polyol or the like obtained by adding a cyclic ether to a reaction product obtained by reacting a phenol, an alkanolamine and an aldehyde by a Mannich reaction can also be used. Polyether polyol (X) and amine-based polyether polyol (Y) can also be used.

When a rigid urethane-modified polyisocyanurate foam is produced, it is preferable to use a polyester polyol as the other polyol (B). As the polyester polyol, a polyester polyol obtained by polycondensation of a polyhydric alcohol and a polycarboxylic acid is particularly preferable. As the polycarboxylic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid are preferable. The hydroxyl value of the polyester polyol is 100 to 450 mgKOH / g.
Is preferable, and 100 to 350 mgKOH / g is particularly preferable. The content of the polyester polyol in the polyol (V) is preferably from 10 to 99.9% by mass,
9.9% by mass is more preferred.

When the content of the polyester polyol in the polyol (V) is relatively low, such as 10 to 50% by mass, (i) a cyclic phenol such as bisphenol A or a phenol-formaldehyde precondensate is further added to the cyclic polyol. Polyether polyols obtained by adding an ether, (ii) polyether polyols obtained by adding a cyclic ether to a reaction product obtained by reacting a phenol, an alkanolamine and an aldehyde by a Mannich reaction , (Iii) a polyether diol obtained by adding a cyclic ether to a diol, and the like, are preferably used in combination as the other polyol (B).

Other polyols (B) include:
Polyether polyols, polyester polyols, polyhydric alcohols, and the like having relatively low molecular weights can also be used as chain extenders and crosslinking agents. Specifically, ethylene glycol,
Polyhydric alcohols such as propylene glycol, 1,4-butanediol, and glycerin are used.

[Polymer Fine Particle (P)] The polymer fine particle (P) in the present invention is a polymer fine particle 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, and 2,4-dicyano-1-butene; acrylic acid, methacrylic acid, acrylate, Acrylic monomers such as methacrylic acid ester, acrylamide, and methacrylamide; styrene monomers such as styrene and α-methylstyrene; carboxylic acid vinyl ester monomers such as vinyl acetate and vinyl propionate; isoprene, butadiene, and other diene monomers An unsaturated fatty acid ester monomer such as maleic acid diester and itaconic acid diester; a vinyl halide monomer such as vinyl chloride; a vinylidene halide monomer such as vinylidene chloride; methyl vinyl ether, ethyl vinyl ether Alkyl vinyl ether monomer such as isopropyl vinyl ether. These monomers may be used in combination of two or more kinds.

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,
Alternatively, a combination of a nitrile-based monomer and a vinyl carboxylate-based monomer is preferable for obtaining a polymer-dispersed polyol having 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, more preferably 85 to 60/60.
15-40 is most preferred. In the case of a combination of acrylonitrile and vinyl acetate, the ratio is preferably acrylonitrile / vinyl acetate in a mass ratio of 50 to 10/50 to 90, and most preferably 40 to 15/60 to 85.

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,
-45 mass% is particularly preferred, and 5-40 mass% is most preferred.

[Production Method of Polymer-Dispersed Polyol (A)] Using the polyol (W), polymer fine particles (P)
The method for producing the polymer-dispersed polyol (A) in which is dispersed stably includes the following two methods.

The first method is a method in which a monomer having a polymerizable unsaturated bond is polymerized in a polyol (W) in the presence of a solvent, if necessary, to directly precipitate particles. In the second method, a monomer having a polymerizable unsaturated bond is polymerized in a solvent in the presence of a grafting agent for stabilizing the particles, if necessary, to precipitate the particles, and then the polyol (W)
And replacing the solvent. 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, diisopropylperoxydicarbonate, acetyl peroxide, tert-butyl peroxide,
Persulfate and the like. In particular, AIBN, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-
Azobis (methyl 2-methylpropionate) is preferred.

To improve the dispersion stability of the fine polymer 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,
High molecular weight polyol or monool obtained by addition polymerization of alkylene oxide; unsaturated carboxylic acid or unsaturated carboxylic acid such as maleic anhydride, itaconic anhydride, maleic acid, fumaric acid, acrylic acid, methacrylic acid, etc. A high-molecular-weight polyol or monool obtained by reacting an acid anhydride and then adding an alkylene oxide as necessary; and an alcohol having an unsaturated bond in the molecule such as 2-hydroxyethyl acrylate or butenediol. A reaction product of another polyol with a polyisocyanate; a reaction product of an epoxy compound having an unsaturated bond such as allyl glycidyl ether in a molecule with a polyol; These compounds preferably have a hydroxyl group, but are not limited thereto.

[Polyol Composition] The polyol composition of the present invention comprises 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 a so-called polyol system.

The polyol (V) has excellent dispersion stability. The polyol composition is also excellent in dispersion stability.
The polyol composition is separated and polymer fine particles (P)
The period during which no sedimentation occurs is preferably 1 month or more, more preferably 2 months or more, and particularly preferably 3 months or more in a stationary state.

[Production Method of Hard Foam Synthetic Resin] The present invention relates to a method of 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. Boiling point 30-50
A method for producing a rigid foamed synthetic resin, characterized by using a hydrofluorocarbon having a temperature of ° C.

Examples of the polyisocyanate include aromatic, alicyclic and aliphatic polyisocyanates having an average of two or more isocyanate groups in the molecule. Further, a mixture of two or more of the above-mentioned polyisocyanates or a modified polyisocyanate obtained by modifying the above-mentioned polyisocyanate can also be used. Specifically, polyisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate (commonly called crude MDI), xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate; prepolymer-modified polyisocyanate compounds; Nurate modified form, urea modified form, carbodiimide modified form and the like can be mentioned.

As the foam stabilizer, those usually used for producing a rigid foam synthetic resin can be used, and examples thereof include a silicone foam stabilizer and a fluorine foam stabilizer. As a catalyst,
What is usually used when manufacturing a rigid foam synthetic resin can be used. Amine catalysts such as triethylenediamine, 2
-Lead ethylhexanoate, tin 2-ethylhexanoate (I
Organometallic compound catalysts such as I) and quaternary ammonium salt catalysts can be used. When producing a rigid urethane-modified polyisocyanurate foam, N, N ', N "-
Tris (dimethylaminopropyl) hexahydro-sy
Isocyanurate-modified catalysts such as m-triazine, potassium acetate, potassium 2-ethylhexanoate, and quaternary ammonium salt catalysts can be used.

In addition, as a raw material of the hard foamed synthetic resin, a chain extender, a crosslinking agent, a filler, a stabilizer, a colorant, a flame retardant, and the like can be arbitrarily used. As chain extenders and crosslinking agents,
Alkanolamines such as diethanolamine and triethanolamine; polyamines such as hexamethylenediamine and 4,4'-diaminodiphenylmethane can be used.

[0055]

EXAMPLES The present invention will now be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the table, AN represents acrylonitrile, St represents styrene, VAc represents vinyl acetate, and MMA represents methyl methacrylate. The numbers without units in the table represent parts by mass.

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

Polyol Y1: an amine-based 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 a Mannich reaction. Polyol Y2: a hydroxyl value obtained by adding propylene oxide to ethylenediamine and having a hydroxyl value of 760 mgKOH /
g of an amine-based polyether polyol. Polyol Y3: A hydroxyl value obtained by adding propylene oxide to ethylenediamine and having a hydroxyl value of 500 mgKOH /
g of an amine-based polyether polyol.

Polyol Y4: 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: 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-based 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 having a hydroxyl value of 50 mg KOH / g and an oxyethylene group content of 25% by mass, obtained by randomly adding propylene oxide and ethylene oxide to glycerin. Polyol Z2: a polyether polyol having a hydroxyl value of 56 mgKOH / g and an oxyethylene group content of 10% by mass, obtained by adding propylene oxide and ethylene oxide in this order to glycerin. Polyol Z3: a polyether polyol having a hydroxyl value of 450 mgKOH / g, obtained by adding propylene oxide to glycerin.

Polyol Z4: A hydroxyl value obtained by adding propylene oxide to glycerin and having a hydroxyl value of 650 mgK
OH / g polyether polyol. Polyol Z5: Bisphenol A obtained by adding ethylene oxide, having a hydroxyl value of 280 mgKOH / g
Polyether polyol. 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: a polyester polyol having a hydroxyl value of 250 mgKOH / g, obtained by reacting phthalic acid and diethylene glycol.

(Examples 1 to 6: Production Examples of Polymer-Dispersed Polyol) (Polymer-dispersed polyols A1, A2, B1, B2, B)
Production of 3) 70% by mass of the mixture of polyols shown in Table 1 was charged into a 5 L pressurized reaction vessel, and the mixture of remaining polyols, monomers shown in Table 1, and AIBN as an initiator were maintained at 120 ° C. 4 while stirring the mixture
Supplied over time. After the supply is completed,
Stirring was continued for hours. In all cases, the conversion of the monomers was greater than 90%. 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. The polyol B2 produced without using the polyether polyol (X) was phase-separated, a uniform dispersion was not obtained, and the hydroxyl value and viscosity could not be measured.

(Production of Polymer-Dispersed Polyol A3) 5
After all the polyol, monomer and AIBN as an initiator shown in Table 1 were charged into the L pressure reaction tank, the temperature was raised while stirring. The reaction was performed for 10 hours while maintaining the reaction solution at 80 ° C. The conversion of the monomer was 80% or more. After completion of the reaction, unreacted monomers were removed by heating under reduced pressure at 110 ° C. and 13 Pa for 2 hours to remove polymer, thereby producing a polymer-dispersed polyol. Hydroxyl value (unit: mgKOH / g),
Table 1 shows the viscosity (unit: cP) at 25 ° C. and the dispersion stability.

[Production of Rigid Foam Synthetic Resin] (Examples 7 to 29: Production Examples of Rigid Polyurethane Foam) 100 parts by mass of a polyol in the amounts and types shown in Tables 2 and 3 and a polymer-dispersed polyol (POP in the table) Expressed as
2 parts by weight, foaming agent, catalyst, silicone foam stabilizer (Toray
1.5 parts by mass of Dow Corning Silicone, SH-193) and tris (2-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., hereinafter TMC) as a flame retardant
10 parts by weight of PP) to prepare a polyol composition.

The type of foaming agent used was foaming agent a: HF
C-365mfc, foaming agent b: HFC-134a, foaming agent c: HFC-245fa, foaming agent d: cyclopentane, foaming agent e: n-pentane.

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

To the prepared polyol composition, polymethylene polyphenyl isocyanate (MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used as an isocyanate at a liquid temperature of 2 so that the isocyanate index was 110.
Mix at 0 ° C, length 200mm x width 200mm x height 20
It was placed in a 0 mm wooden box to produce a rigid polyurethane foam.

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

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 solution (potassium 15%, trade name Pcat 15G, manufactured by Nippon Chemical Industry Co., Ltd.) ) Is a mass part necessary for the gel time at the time of hand foaming to be 40 seconds.

For the prepared polyol composition, polymethylene polyphenyl isocyanate (MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used as the isocyanate so that the isocyanate index became 200.
The mixture was mixed at a liquid temperature of 20 ° C., and put into a wooden box of 200 mm × 200 mm × 200 mm in height 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 the polyol composition, appearance of foam surface, and thermal conductivity (unit: mW / m · K) are shown in Tables 2 to 4.

The low-temperature shrinkage indicates a dimensional change rate in the direction perpendicular to the foaming direction after 24 hours at -30 ° C. The storage stability of the polyol composition depends on the polyol composition.
Evaluation was made by observing the state of separation after standing at 2 ° C. for 2 months.場合 indicates stable without separation, and X indicates separation.

The appearance of the foam surface was judged by the size and number of irregularities seen on the surface of the foam upper surface. The case where there was no large void or the like and the appearance was good was evaluated as ○, and the case where there were many large voids or the like and the appearance was poor was evaluated as x. Thermal conductivity is JI
Measured according to SA-1412.

In Table 2, Examples 7 to 11 are Examples and Example 1
2 to 19 are comparative examples. In Table 3, Examples 20 to 26 are Examples, and Examples 27 to 29 are Comparative Examples.
6 is an Example, and Examples 37 to 42 are Comparative Examples.

As shown in Tables 2 to 4, H was used as a foaming agent.
Both the rigid polyurethane foam and the rigid urethane-modified nurate foam obtained by using FC-365mfc had a good foam surface appearance without voids and blisters. Further, the rigid polyurethane foam and the rigid urethane-modified nurate foam produced according to the production method of the present invention have a low degree of low-temperature shrinkage, show good dimensional stability, and have low thermal conductivity, and excellent heat insulating performance. showed that. Further, the polyol composition of the present invention showed good storage stability.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[Evaluation 2 of Foaming] Next, Example 7 was placed between the upper and lower surface materials conveyed by the inverse line belt conveyor.
Rigid foams were manufactured using compositions of ~ 11, 20-26, 30-36. The resin was uniformly dispersed while traversing through a spray nozzle type mixing head, after-cured in a cure zone, and a continuous laminate board was formed. As a result, the obtained continuous laminate board did not show low-temperature shrinkage on the small face and the like, showed good dimensional stability, and had a good appearance with no voids or air pockets on the surface.

[Evaluation 3 of Foaming] Next, Examples 7 to 11, 20 to 2
6, using a high-pressure foaming apparatus, injection flow foaming was performed in a 2700 × 1000 × 100 mm panel form provided with a color steel plate as a face material. The temperature at that time was 20 ° C, and the mold temperature was 35 ° C. The resulting foam did not show low-temperature shrinkage, showed good dimensional stability, and had a good appearance with no voids or air pockets on the surface.

[Evaluation of Foaming 4] Next, a mineral spirit solution of lead 2-ethylhexanoate (concentration: 20%,
Examples 7 to 11 and 20 except that 0.5 parts by mass of trade name: Nikka Octic Lead 20%, manufactured by Nippon Chemical Industry Co., Ltd.) was used.
To 26, 30 to 36, using polymethylene polyphenyl isocyanate (Coronate 115, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate.
Using 5), foaming was carried out at a liquid temperature of 35 ° C. and a room temperature of 5 ° C. while spraying using a foaming machine manufactured by Gasmer Co., Ltd. and sprayed on the wall surface.

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

[0084]

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

Continued on the front page F term (reference) 4F074 AA80 BA34 BA53 BA86 BA95 BC05 CA25 CC22X DA07 DA15 4J034 BA07 CA04 CA05 CB03 CB07 CC02 CC03 DA01 DB03 DB07 DF03 DF22 DG02 DG03 DG04 DG05 DG14 D12Q15 D14 DQ23 HA01 HA06 HA07 HB06 HB07 HB09 HC12 HC17 HC22 HC35 HC46 HC52 HC61 HC63 HC64 HC67 HC71 HC73 KA01 KB03 KB05 KC02 KC17 KC18 KD02 KD12 MA22 NA02 NA03 NA06 NA08 NA09 QA02 QB13 QB16 QC01

Claims (7)

[Claims] 1. 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, wherein a hydrofluorocarbon having a boiling point of 30 to 50 ° C. is used as the foaming agent. And containing, as a polyol, the following polyether polyol (X), the following amine-based polyether polyol (Y), and the following finely dispersed polymer particles (P), wherein the polymer fine particles (P) are all polyols A method for producing a rigid foamed synthetic resin, comprising using a polyol containing 0.01% by mass or more of the polyol. Polyether polyol (X): hydroxyl value is 84 mgK
OH / g or less and a polyether polyol having an oxyethylene group content of 40% by mass or more. Amine-based polyether polyol (Y): obtained by addition polymerization of a cyclic ether using an amine compound as an initiator,
An amine-based 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. 2. The average hydroxyl value of all polyols is 100-8.
The method for producing a rigid foamed synthetic resin according to claim 1, wherein the amount is 00 mgKOH / g. 3. The method for producing a rigid foamed synthetic resin according to claim 1, wherein the polyether polyol (X) is contained in all the polyols in an amount of 0.005% by mass or more. 4. The method for producing a rigid foam synthetic resin according to claim 1, wherein the amine-based polyether polyol (Y) is contained in all the polyols in an amount of 0.003% by mass or more. 5. The hydrofluorocarbon having a boiling point of 30 to 50 ° C. is CF ₃ CH ₂ CF ₂ CH ₃ .
5. The method for producing a rigid foam synthetic resin according to 2, 3, or 4. 6. A foaming agent comprising water, CF ₃ CFH ₂ , CF ₃
One or more selected from the group consisting of CH ₂ CHF ₂ and having 10 or less of the hydrocarbon compound carbons, CF ₃ C
In combination with H ₂ CF ₂ CH _3, method for producing a rigid foamed synthetic resin according to claim 5. 7. A polyol composition comprising a foam stabilizer, a catalyst, CF ₃ CH ₂ CF ₂ CH ₃ , and the following polyol (V). Polyol (V): The following polyether polyol (X), the following amine-based polyether polyol (Y), and the following polymer fine particles (P) that are stably dispersed, and the polymer fine particles (P) are 0.01% by mass or more. Containing polymer-dispersed polyol. Polyether polyol (X): hydroxyl value is 84 mgK
OH / g or less and a polyether polyol having an oxyethylene group content of 40% by mass or more. Amine-based polyether polyol (Y): obtained by addition polymerization of a cyclic ether using an amine compound as an initiator,
An amine-based 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.