JP2012056987A - Method of manufacturing polymer-dispersed polyol and method of manufacturing rigid foamed synthetic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a polymer-dispersed polyol that is low odorous and exhibits good storage-stability-enhancing effects of polyol system liquid and good dimensional-stability-enhancing effects of a rigid foamed synthetic resin.SOLUTION: The method for manufacturing a polymer-dispersed polyol comprises polymerizing, in a polyol X, a monomer M bearing a polymerizable unsaturated group, where the polyol X comprises a polyether polyol Y having a hydroxy value of 5-84 mgKOH/g and an oxyethylene group content of 40-100 mass%, and an amine-based polyol Z of a hydroxy value of 250-900 mgKOH/g obtained by addition-polymerizing a cyclic ether onto an amine compound, where (Y+Z) accounts for at least 80 mass% of X; the mass ratio, Y:Z, is 85:15 to 97:3; an average hydroxy value of X is 20-180 mgKOH/g; and M comprises an ethylenic double bond-containing nitrile and at least one selected from among an ethylenic double bond-containing carboxylic acid and a derivative thereof and a carboxylic acid vinyl ester.

Description

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

It is widely practiced to react a polyol compound and a polyisocyanate compound in the presence of a foaming agent to produce a rigid foam synthetic resin (hereinafter also referred to as a rigid foam) such as a rigid polyurethane foam and a rigid polyisocyanurate foam. It has been broken. By the way, the use of chlorofluorocarbons (so-called CFC compounds such as CCl ₃ F) and hydrochlorofluorocarbons (so-called HCFC compounds such as CCl ₂ FCH ₃ ) conventionally used as blowing agents is prohibited from the viewpoint of environmental protection. .

  Alternative foaming agents include hydrocarbon compounds such as hydrofluorocarbon (hereinafter also referred to as HFC compound), hydrofluoroether (hereinafter also referred to as HFE compound), and cyclopentane. Moreover, since water produces | generates a carbon dioxide gas by reacting with a polyisocyanate compound, using the said foaming agent and water together, or using water alone as a foaming agent is performed. In addition, an inert gas such as air, nitrogen or carbon dioxide is also used as a foaming agent.

The rigid foam obtained by using the above HFC compound, HFE compound, hydrocarbon compound, water, inert gas, etc., has a shrinkage of the foam as compared with the rigid foam obtained by using a conventional CFC compound or HCFC compound. Due to this, dimensional stability is poor.
Therefore, in order to prevent foam shrinkage, a method has been proposed in which a polymer-dispersed polyol is used as part of the polyol used in the production of rigid polyurethane foam.
The polymer-dispersed polyol refers to a dispersion system in which polymer particles as a dispersoid are stably dispersed in a base polyol such as polyether polyol or polyester polyol as a dispersion medium.

  For example, Patent Documents 1 and 2 below disclose a polymer-dispersed polyol obtained by polymerizing a monomer having a polymerizable unsaturated group in a base polyol, wherein the base polyol has a hydroxyl value of 84 mgKOH / g or less and is oxy 5% by weight or more of a polyether polyol having an ethylene group content of 40% by weight or more, and 3% by weight of an amine-based polyol having a hydroxyl value of 250 to 900 mgKOH / g obtained by ring-opening addition polymerization of a cyclic ether to an amine compound A polymer-dispersed polyol, which is a polyol mixture having an average hydroxyl value of 200 to 800 mgKOH / g, is described. Moreover, it is described that the monomer which has a polymerizable unsaturated group contains the mixture whose weight ratio of ethylenically unsaturated nitrile: carboxylic acid vinyl ester is 75: 25-5: 95.

JP-A-11-302340 Japanese Unexamined Patent Publication No. 2000-7752

However, the polymer-dispersed polyols described in Patent Documents 1 and 2 have a strong odor and may cause discomfort to workers who handle the polymer-dispersed polyols.
In addition, the greater the amount of the polymer-dispersed polyol contained in the rigid foam polyol system liquid, the more easily the uniform dispersibility in the polyol system liquid is impaired. The smaller the amount of polymer particles contained in the polyol system liquid, the easier it is to improve the mechanical properties of the rigid foam. Accordingly, it is desirable that the effect of improving the dimensional stability of the rigid foam by the polymer-dispersed polyol is good, and the desired effect can be obtained without containing a large amount of polymer particles.

  The present invention has been made in view of the above circumstances, can reduce the odor of the polymer-dispersed polyol, has an excellent effect of improving the storage stability of the polyol system liquid, and improves the dimensional stability of the rigid foam by containing polymer particles. It is an object of the present invention to provide a method for producing a polymer-dispersed polyol and a method for producing a rigid foam using the polymer-dispersed polyol obtained by the production method.

The present invention includes the following [1] to [10].
[1] A method for producing a polymer-dispersed polyol by polymerizing a monomer (M) having a polymerizable unsaturated group in a polyol (X), wherein the polyol (X) is the following polyether polyol (Y) And the following amine-based polyol (Z), the total of the polyether polyol (Y) and the amine-based polyol (Z) is 80% by mass or more of the polyol (X), and the polyether polyol (Y) And the mass ratio (Y) :( Z) of the amine-based polyol (Z) is 85:15 to 97: 3, the average hydroxyl value of the polyol (X) is 20 to 180 mgKOH / g, M) is selected from the group consisting of ethylenic double bond-containing nitriles, ethylenic double bond-containing carboxylic acids and derivatives, and carboxylic acid vinyl esters. Characterized in that it comprises at least one and that method for producing a polymer-dispersed polyol.
Polyetherol (Y): One or more polyether polyols having a hydroxyl value of 5 to 84 mgKOH / g and an oxyethylene group content of 40 to 100% by mass.
Amine-based polyol (Z): One or more amine-based polyols obtained by ring-opening addition polymerization of a cyclic ether to an amine compound and having a hydroxyl value of 250 to 900 mgKOH / g.
[2] The monomer (M) having a polymerizable unsaturated group contains an ethylenic double bond-containing nitrile and a carboxylic acid vinyl ester, and the total of both is 80% by mass or more of the monomer (M). [1] A method for producing a polymer-dispersed polyol according to [1].
[3] The polymer according to [2], wherein the ethylenic double bond-containing nitrile is acrylonitrile, the carboxylic acid vinyl ester is vinyl acetate, and a mass ratio of acrylonitrile: vinyl acetate is 75:25 to 5:95. A method for producing a dispersed polyol.

[4] A method for producing a rigid foamed synthetic resin by reacting a polyol composition (P) and a polyisocyanate compound (I) in the presence of a foaming agent, a foaming agent and a catalyst, the polyol composition ( A process for producing a rigid foam synthetic resin, wherein P) comprises a polymer-dispersed polyol obtained by the process of [1] to [3].
[5] The method for producing a rigid foam synthetic resin according to [4], wherein the polyol composition (P) has an average hydroxyl value of 100 to 800 mgKOH / g and an average functional group number of 2 to 10.
[6] The method for producing a rigid foam synthetic resin according to [4] or [5], wherein the polymer particle content in the polyol composition (P) is 0.01 to 8% by mass.
[7] The method for producing a rigid foamed synthetic resin according to [4] to [6], wherein the polyol composition (P) contains Mannich polyol.
[8] The method for producing a hard foam synthetic resin according to [4] to [7], wherein the foaming agent contains water.
[9] The method for producing a hard foam synthetic resin according to [4] to [8], wherein the foaming agent is only water.
[10] The method for producing a rigid foamed synthetic resin according to [8] or [9], wherein the amount of water used is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyol composition (P).

According to the method for producing a polymer-dispersed polyol of the present invention, it has a low odor, has an excellent effect of improving the storage stability of a polyol system liquid, and has an excellent effect of improving the dimensional stability of a rigid foam by containing polymer particles. The resulting polymer-dispersed polyol is obtained.
According to the method for producing a rigid foam synthetic resin of the present invention, a rigid foam having good dimensional stability can be produced using a low-odor polymer-dispersed polyol and a polyol system solution having good storage stability.

The “polyol system liquid” in the present invention is a liquid to be reacted with a polyisocyanate compound, and is a liquid containing a compounding agent as required in addition to a polyol, such as a foaming agent, a foam stabilizer, a catalyst, and a flame retardant. is there.
The “foaming stock solution composition” in the present invention is a liquid obtained by mixing a polyol system liquid, a polyisocyanate compound, and optionally the remaining components.
The “Mannich condensation product” generally means a compound obtained by a condensation reaction of an aromatic compound such as aniline or phenol, an aldehyde, and an amine. In the present invention, Mannich condensation products obtained by reacting phenols, aldehydes, and alkanolamines are used.
The “Mannich polyol” in the present invention is a polyether polyol obtained by adding a cyclic ether such as alkylene oxide using a Mannich condensation product as an initiator.
The hydroxyl value of the polyol in this specification is a value measured according to JIS K1557 (2007 edition).

<Polymer-dispersed polyol and method for producing the same>
The polymer-dispersed polyol of the present invention is a polymer-dispersed polyol obtained by polymerizing a monomer (M) having a polymerizable unsaturated group in polyol (X) which is a base polyol. The polyol (X) contains a polyether polyol (Y) and an amine-based polyol (Z).
[Polyether polyol (Y)]
The polyether polyol (Y) in the present invention comprises at least one polyether polyol having a hydroxyl value of 5 to 84 mgKOH / g and an oxyethylene group content of 40 to 100% by mass. Preferably only one polyether polyol is present.
The polyether polyol (Y) is preferably a polyether polyol obtained by ring-opening addition polymerization of a cyclic ether using a catalyst as an initiator. 2-8 are preferable, as for the average functional group number of polyether polyol (Y), 3-6 are more preferable, and 3-4 are especially preferable. When the average number of functional groups is less than or equal to the upper limit of the above range, good dispersion stability of the polymer particles in the polymer-dispersed polyol can be easily obtained, and the viscosity of the polymer-dispersed polyol becomes low and easy to handle.

As an initiator for the polyether polyol (Y), a compound having active hydrogen is preferable, and a polyhydric alcohol or a polyhydric phenol is more preferable. In addition, an amine compound is not used as an initiator of polyether polyol (Y).
Examples of the polyhydric alcohol include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-butanediol, and 1,6-hexanediol. Trihydric alcohols such as glycerin, trimethylolpropane and 1,2,6-hexanetriol; tetrahydric alcohols such as pentaerythritol, diglycerin, tetramethylolcyclohexane and methylglucoside; hexavalents such as sorbitol, mannitol and dulcitol Alcohol; octavalent alcohols such as sucrose are listed.
Examples of the polyhydric phenol include bisphenol compounds such as bisphenol A; phenol-formaldehyde initial condensates.

The catalyst used for the production of the polyether polyol (Y) is preferably at least one selected from the group consisting of a double metal cyanide complex catalyst, a Lewis acid catalyst, and an alkali metal catalyst, and more preferably only one. When the catalyst is used, it is easy to uniformly add the cyclic ether to the initiator.
As the double metal cyanide complex catalyst, a double metal cyanide complex catalyst in which an organic ligand is coordinated to zinc hexacyanocobaltate is preferable. Examples of the organic ligand include tert-butanol, tert-pentyl alcohol, ethylene glycol mono-tert-butyl ether, a combination of tert-butanol and ethylene glycol mono-tert-butyl ether, and the like.
Examples of the Lewis acid catalyst include BF ₃ complex, tris (pentafluorophenyl) borane, and tris (pentafluorophenyl) aluminum.
Examples of the alkali metal catalyst include alkali metal compounds such as cesium hydroxide, potassium hydroxide, and sodium hydroxide. In particular, potassium hydroxide is preferred.
As the catalyst used for the production of the polyether polyol (Y) in the present invention, potassium hydroxide is most preferably used.

As the cyclic ether used for the production of the polyether polyol (Y), it is preferable to use ethylene oxide alone or to use ethylene oxide and one or more other cyclic ethers in combination. As another cyclic ether used in combination with ethylene oxide, propylene oxide, isobutylene oxide, 1-butylene oxide, or 2-butylene oxide is preferable, and propylene oxide is particularly preferable.
In addition, when using ethylene oxide and another cyclic ether together, block polymerization may be sufficient and random copolymerization may be sufficient, but random copolymerization is preferable at the point which normal temperature liquid polyether polyol (Y) is easy to be obtained. In the case of block polymerization, it is preferable to add in the order of ethylene oxide, other cyclic ether, and ethylene oxide, or in the order of other cyclic ether and ethylene oxide.

  The oxyethylene group content of the polyether polyol (Y) needs to be 40% by mass or more. When the oxyethylene group content is 40% by mass or more, the dispersion stability of the polymer particles in the polymer-dispersed polyol becomes good. In addition, the compatibility between the polyol for rigid foam having a high hydroxyl value and the polymer-dispersed polyol of the present invention is improved. The oxyethylene group content is preferably 50% by mass or more, and more preferably 55% by mass or more. The upper limit of the oxyethylene group content is 100% by mass, preferably 90% by mass or less. The oxyethylene group is a group introduced when the cyclic ether that undergoes ring-opening addition polymerization to the initiator is ethylene oxide. The oxyethylene group content of the polyether polyol (Y) is the mass proportion of oxyethylene groups in the total mass of the polyether polyol (Y).

  The hydroxyl value of the polyether polyol (Y) is 84 mgKOH / g or less. The hydroxyl value is preferably 67 mgKOH / g or less, particularly preferably 60 mgKOH / g or less. When the amount is not more than the above upper limit, the dispersion stability of the polymer particles in the polymer-dispersed polyol becomes good. The lower limit of the hydroxyl value is 5 mgKOH / g or more. 8 mgKOH / g or more is preferable, and 20 mgKOH / g or more is particularly preferable. When it is at least the above lower limit, the viscosity of the polymer-dispersed polyol becomes low and easy to handle.

[Amine-based polyol (Z)]
The amine-based polyol (Z) in the present invention comprises at least one polyether polyol having a hydroxyl value of 250 to 900 mgKOH / g, obtained by ring-opening addition polymerization of a cyclic ether to an amine compound as an initiator. Preferably only one polyether polyol is present.
The hydroxyl value is preferably from 300 to 800 mgKOH / g, particularly preferably from 350 to 800 mgKOH / g. Within the above range, good dispersion stability of the polymer particles in the polymer-dispersed polyol can be easily obtained, and the viscosity of the polymer-dispersed polyol is hardly increased.

  2-6 are preferable, as for the average functional group number of amine-type polyol (Z), 3-6 are more preferable, and 3-4 are especially preferable. Within the above range, good dispersion stability of the polymer particles in the polymer-dispersed polyol can be easily obtained, and the viscosity of the polymer-dispersed polyol is hardly increased.

  Examples of amine compounds as initiators include aliphatic amine compounds such as ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine, diethanolamine, and isopropanolamine; N-aminomethylpiperazine, N- (2- Saturated cyclic amine compounds such as aminoethyl) piperazine; aromatic amine compounds such as aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine (not including Mannich condensation products). From the viewpoint of dispersion stability of the polymer particles, an aliphatic amine compound or a saturated cyclic amine compound is preferable.

  The amine compound which is an initiator of the amine-based polyol (Z) has active hydrogen and can directly perform ring-opening addition polymerization with a cyclic ether. However, a catalyst is used in the case of ring-opening addition polymerization of a cyclic ether having an active hydrogen number greater than that of the initiator. As the catalyst, an alkali metal catalyst is preferable because it can easily add the cyclic ether to the initiator uniformly. Specific examples of the alkali metal catalyst include alkali metal compounds such as cesium hydroxide, potassium hydroxide, and sodium hydroxide. In particular, potassium hydroxide is preferred.

As the cyclic ether used for the production of the amine-based polyol (Z), it is preferable to use one or more members selected from the group consisting of ethylene oxide, propylene oxide, isobutylene oxide, 1-butylene oxide and 2-butylene oxide. It is preferable to use propylene oxide alone or to use ethylene oxide and propylene oxide together, and more preferably to use propylene oxide alone. When ethylene oxide and another cyclic ether are used in combination, either block polymerization or random copolymerization may be used, but block polymerization is preferred because the viscosity of the amine-based polyol (Z) tends to be moderately low. In the case of block polymerization, it is preferable to add in the order of ethylene oxide, other cyclic ether, and ethylene oxide, or in the order of other cyclic ether and ethylene oxide.
If the oxyethylene group content of the amine polyol (Z) is high, the viscosity of the polyol (X) tends to decrease and the handling may be easy, but the chromaticity of the amine polyol (Z) increases and odor Therefore, the oxyethylene group content is preferably 30% by mass or less. It is particularly preferable that the cyclic ether used for the production of the amine-based polyol (Z) is only propylene oxide.

[Other polyols]
The polyol (X) can contain other polyols that do not fall under either the polyether polyol (Y) or the amine-based polyol (Z) as long as the effects of the present invention are not impaired. Examples thereof include polyether polyols and polyester polyols having a hydroxyl value of 84 mgKOH / g or less equivalent to that of the polyether polyol (Y) and an oxyethylene group content of less than 40% by mass. As the other polyol, one or more known base polyols for the polymer-dispersed polyol can be used.

[Polyol (X)]
The polyol (X) in the present invention is a base polyol of a polymer-dispersed polyol.
Polyol (X) is a polyol mixture containing polyether polyol (Y) and amine-based polyol (Z). Other polyols may be included as long as the effects of the present invention are not impaired.
The average hydroxyl value of polyol (X) is 20 to 180 mgKOH / g. 40-160 mgKOH / g is preferable, and 75-150 mgKOH / g is particularly preferable. When the average hydroxyl value is less than or equal to the upper limit of the above range, good dispersion stability of the polymer particles in the polymer-dispersed polyol can be obtained, and odor can be easily reduced. When it is at least the lower limit of the above range, good compatibility between the polyol for a rigid foam having a high hydroxyl value and the polymer-dispersed polyol is easily obtained.

The proportion of the total of the polyether polyol (Y) and the amine polyol (Z) in the polyol (X) is 80% by mass or more, preferably 90% by mass or more, and particularly preferably 100% by mass. That is, the polyol (X) is particularly preferably a polyol mixture composed of a polyether polyol (Y) and an amine-based polyol (Z).
The mass ratio (Y) :( Z) of the polyether polyol (Y) and the amine polyol (Z) is 85:15 to 97: 3. 87:13 to 96: 4 is preferable, and 90:10 to 95: 5 is particularly preferable.
When the main component of the polyol (X) is a mixture of the polyether polyol (Y) and the amine-based polyol (Z), and the proportion of the polyether polyol (Y) is not less than the lower limit of the above range, the polymer dispersion Good dispersion stability of the polymer particles in the polyol is obtained, good compatibility between the rigid foam polyol and the polymer dispersed polyol is easily obtained, and the odor of the polymer dispersed polyol is easily reduced. When the proportion of the amine polyol (Z) is not less than the lower limit of the above range in the total of the polyether polyol (Y) and the amine polyol (Z), a good dimensional stability improving effect of the rigid foam can be obtained. .

Regarding the compatibility between the polymer-dispersed polyol and the polyol for rigid foam, generally, the higher the molecular weight (low hydroxyl value) of the base polyol of the polymer-dispersed polyol, the higher the compatibility with the polyol for rigid foam. Tend to get worse. In the present invention, since the polyol (X) which is the base polyol contains a large amount of polyether polyol (Y) containing 40% by mass or more of oxyethylene groups, although the average hydroxyl value of the polyol (X) is low, It is considered that good compatibility with a polyol for rigid foam having a high hydroxyl value is obtained.
Regarding the good dispersion stability of the polymer particles, when the monomer having a polymerizable unsaturated group is polymerized in the base polyol, the base polyol has a high molecular weight (low hydroxyl value). It is considered that the particles are less likely to agglomerate during the process of growing the particles by the polymerization reaction.
If the compatibility between the polymer-dispersed polyol and the polyol for the rigid foam is good and the dispersion stability of the polymer particles is good, the storage stability of the polymer system liquid is good.

The odor reduction is considered as follows. When the base polyol of the polymer-dispersed polyol has a low molecular weight (high hydroxyl value), the precipitation timing of polymerized polymer particles is advanced, and the reactivity of the monomer during polymerization tends to be low. In the present invention, since the polyol (X) contains a large amount of the polyether polyol (Y) having a high molecular weight (low hydroxyl value), the reactivity of the monomer (M) during polymerization is hardly inhibited, and the monomer concentration in the reaction solution Is likely to decrease. For this reason, it is presumed that the interaction between the residual monomer and the polyol (X), which is the base polymer, hardly occurs during and after the polymerization, and the odor resulting from the interaction is reduced.
For improving the dimensional stability of the rigid foam, it is presumed that the amine-based polyol (Z) contributes to the surface modification of the polymer particles. Specifically, the surface of the polymer particle is modified by the transesterification reaction of the amine-based polyol (Z) with the polymer particle and hydrogen bond, or a part of the polymer particle surface, and the polymer particle in the rigid foam. It is presumed that the foam shrinkage-suppressing effect is sufficiently exhibited.

[Monomer having polymerizable unsaturated group (M)]
The monomer (M) having a polymerizable unsaturated group contains an ethylenic double bond-containing nitrile, and is further selected from the group consisting of ethylenic double bond-containing carboxylic acids and derivatives thereof, and carboxylic acid vinyl esters. Includes more than species. When these are used as essential monomers, it is easy to obtain a good dimensional stability improvement effect of the rigid foam.
Other monomers having a polymerizable unsaturated group that do not fall under any of these may be included within a range not impairing the effects of the present invention. The proportion of the total of the ethylenic double bond-containing nitrile, the ethylenic double bond-containing carboxylic acid and its derivative, and the carboxylic acid vinyl ester in the monomer (M) is preferably 80% by mass or more, and 90% by mass or more. More preferred is 100% by mass. When the total is equal to or more than the above lower limit, good compatibility between the polymer-dispersed polyol and the rigid foam polyol is easily obtained.
The mass ratio of [ethylenic double bond-containing nitrile]: [one kind selected from the group consisting of ethylenic double bond-containing carboxylic acids and derivatives thereof and carboxylic acid vinyl esters] is 75:25 to 5: 95 is preferable, 50:50 to 10:90 is more preferable, and 40:60 to 15:85 is particularly preferable.
When the content ratio of the ethylenic double bond-containing nitrile is larger than the lower limit value of the above range, it is easy to obtain a polymer-dispersed polyol having a good effect of improving the dimensional stability of the rigid foam. Is low, and it is easy to obtain a polymer-dispersed polyol having good dispersibility of polymer particles.

It is preferable that the monomer (M) contains at least an ethylenic double bond-containing nitrile and a carboxylic acid vinyl ester, and the total of both is 80% by mass or more of the entire monomer (M). More preferably, it is 90 mass% or more, and 100 mass% is especially preferable.
In this case, the mass ratio of ethylenic double bond-containing nitrile: carboxylic acid vinyl ester is preferably 75:25 to 5:95, more preferably 50:50 to 10:90, and 40:60 to 15:85. Is particularly preferred.

The ethylenic double bond-containing nitrile may be used alone or in combination of two or more. Specific examples include acrylonitrile and methacrylonitrile. Acrylonitrile is particularly preferred.
The ethylenic double bond-containing carboxylic acid and its derivative may be used alone or in combination of two or more. Specific examples of the ethylenic double bond-containing carboxylic acid include acrylic acid and methacrylic acid. Specific examples of the ethylenic double bond-containing carboxylic acid derivative include acrylic acid alkyl ester, methacrylic acid alkyl ester, acrylamide. And acrylic monomers such as methacrylamide. In addition, in this invention, what corresponds to an ethylenic double bond containing nitrile shall not be contained in ethylenic double bond containing carboxylic acid and its derivative (s).
The carboxylic acid vinyl ester may be used alone or in combination of two or more. Monocarboxylic acid vinyl ester is preferable, and a compound represented by the following general formula (I) is more preferable. R in the formula represents an alkyl group having 1 to 3 carbon atoms.
CH ₂ = CHOCOR (I)
Examples of the compound represented by the general formula (I) include vinyl acetate and vinyl propionate. Vinyl acetate is particularly preferred.

  Examples of other monomers having a polymerizable unsaturated group include styrene monomers such as styrene, α-methylstyrene and halogenated styrene; diene monomers such as isoprene and butadiene; vinyl halides such as vinyl chloride and vinyl bromide; And vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene fluoride; and alkyl vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, and isopropyl vinyl ether.

  In particular, the monomer (M) contains acrylonitrile and vinyl acetate so that the total of both is 80% by mass or more of the entire monomer (M), and the mass ratio of acrylonitrile: vinyl acetate is 75:25 to 5:95. It is preferable. The mass ratio is more preferably 50:50 to 10:90, and particularly preferably 40:60 to 15:85.

[Method for producing polymer-dispersed polyol]
The method for producing a polymer-dispersed polyol of the present invention includes a step of polymerizing a monomer (M) having a polymerizable unsaturated group in the polyol (X).
Any of a known batch method, semi-batch method, and continuous method can be used. In any method, the polymerization reaction is preferably performed at a temperature equal to or higher than the decomposition temperature of the polymerization initiator, usually 50 to 150 ° C, more preferably 80 to 150 ° C, and particularly preferably 100 to 130 ° C.
The batch method is a method in which the reactor is charged with the total amount of polyol (X), the total amount of monomer (M), and the total amount of polymerization initiator, and then the temperature rise is started to carry out the reaction. It is preferable at the point which is excellent in the dispersion stability of a polymer particle.
In the batch method, the polymerization reaction is preferably carried out at a temperature equal to or higher than the decomposition temperature of the polymerization initiator, usually 50 to 120 ° C, more preferably 55 to 110 ° C, and particularly preferably 60 to 100 ° C.
In the semi-batch method, a part of the polyol (X) is charged into a reactor, and while stirring, a mixture of the remaining polyol (X), monomer (M), polymerization initiator, etc. is gradually fed into the reactor for polymerization. It is a method to do.
In the continuous method, a mixture of polyol (X), monomer (M), polymerization initiator and the like is continuously fed to the reactor with stirring, and at the same time, the produced polymer composition is continuously discharged from the reactor. It is.

  Although the usage-amount of a monomer (M) is not specifically limited, It is preferable that it is the quantity from which the density | concentration of the polymer particle in the polymer dispersion polyol finally obtained becomes 1-50 mass%, 2-45 mass% is more preferable, 5-40 mass% is especially preferable.

  As the polymerization initiator used for the polymerization of the monomer (M), a polymerization initiator of a type that generates a free radical and starts polymerization, that is, a free radical polymerization initiator is preferably used. Specific examples include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethyl). Valeronitrile), dimethyl = 2,2′-azobis (2-methylpropionate), benzoyl peroxide, diisopropyl peroxydicarbonate, acetyl peroxide, t-butyl peroxide, persulfate and the like. In particular, AIBN, AMBN, 2,2′-azobis (2,4-dimethylvaleronitrile), and dimethyl = 2,2′-azobis (2-methylpropionate) are preferable.

In general, the higher the polymer concentration in the reaction solution, the more likely the particles are agglomerated in the process of growing the particles during monomer polymerization, and an aggregate is more likely to be generated. In order to prevent this, the polymer-dispersed polyol can be produced in the presence of a solvent as required.
Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, cyclohexanol and benzyl alcohol; aliphatic hydrocarbons such as pentane, hexane, cyclohexane and hexene; aromatic hydrocarbons such as benzene, toluene and xylene; acetone Ketones such as methyl ethyl ketone and acetophenone; esters such as ethyl acetate and butyl acetate; ethers such as isopropyl ether, tetrahydrofuran, benzyl ethyl ether, 1,1-diethoxyethane, acetal, anisole, and methyl-t-butyl ether; Halogenated hydrocarbons such as chlorobenzene, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichlorotrifluoroethane; nitration of nitrobenzene and the like Nitriles such as acetonitrile and benzonitrile; amines such as trimethylamine, triethylamine, tributylamine and N, N-dimethylaniline; amides such as N, N-dimethylformamide and N-methylpyrrolidone; dimethyl sulfoxide, sulfolane and the like And sulfur compounds.
These solvents may be used alone or in combination of two or more. It is preferable that the solvent is removed after the polymerization of the monomer (M) is completed. Solvent removal is usually carried out by heating under reduced pressure, but can also be carried out under normal pressure heating or under reduced pressure at room temperature. At this time, unreacted monomers are also removed together with the solvent.

By such a production method, a polymer-dispersed polyol in which polymer particles are stably dispersed is obtained. In order to further improve the dispersion stability of the polymer particles, a polymerizable compound having a polyether chain or a polyester chain and having a double bond in the molecule can be used as a stabilizer or a grafting agent.
Specific examples of such stabilizers or grafting agents include a high molecular weight obtained by reacting a cyclic ether with an active hydrogen compound having a double bond-containing group such as a vinyl group, an allyl group, or an isopropenyl group as an initiator. A polyether polyol or a polyether monool; an unsaturated carboxylic acid such as maleic anhydride, itaconic anhydride, maleic acid, fumaric acid, acrylic acid, methacrylic acid or the acid anhydride thereof; And a high molecular weight polyol or monool obtained by adding a cyclic ether if necessary; unsaturated group-containing alcohols such as 2-hydroxyethyl acrylate and butenediol, other polyols and polyisocyanates; A reaction product containing unsaturated groups such as allyl glycidyl ether Carboxymethyl compound and a reaction product of a polyol; and the like. These compounds preferably have a hydroxyl group but are not limited thereto.

  The average hydroxyl value of the polymer-dispersed polyol is preferably 20 to 180 mgKOH / g, more preferably 40 to 120 mgKOH / g, and particularly preferably 50 to 110 mgKOH / g. The average hydroxyl value of the polymer-dispersed polyol is usually lower than the average hydroxyl value of the polyol (X) used as the base polyol.

According to the present invention, it is possible to produce a polymer-dispersed polyol that is excellent in dispersion stability of polymer particles and that does not cause separation, for example, in a stationary state for 1 month or longer, preferably 2 months or longer.
The reason why the polymer-dispersed polyol of the present invention is excellent in dispersion stability in this way can be presumed to be because the size of the polymer particles obtained by polymerizing the monomer (M) is fine and uniform.
In the polymer-dispersed polyol obtained in the present invention, since the polymer obtained by polymerizing the monomer (M) has high affinity for the polyol (X), a part of the polymer is dissolved in the polyol (X). It may be.

<Rigid foam synthetic resin and its manufacturing method>
The manufacturing method of the hard foam synthetic resin of this invention has the process of making a polyol composition (P) and polyisocyanate compound (I) react in presence of a foaming agent, a foam making agent, and a catalyst. The polyol composition (P) contains a polymer-dispersed polyol obtained by the production method of the present invention.
The polymer-dispersed polyol can be used alone as a raw material for rigid polyurethane foam. That is, 100% by mass of the polyol composition (P) can be used as a polymer-dispersed polyol, but a mixture of a polymer-dispersed polyol and a rigid foam polyol that does not contain polymer particles is used as the polyol composition (P). It is preferable to do.
In the present specification, a polyol other than the polymer-dispersed polyol in the polyol composition (P) is referred to as a rigid foam polyol.

[Polyol for rigid foam]
The polyol for rigid foam of the present invention is appropriately selected according to the physical properties of the rigid foam to be obtained. Examples thereof include polyether polyols, polyester polyols, polymers in which the main chain is composed of a hydrocarbon polymer and a hydroxyl group is introduced into the terminal portion (hereinafter referred to as a hydrocarbon polymer having a hydroxyl group at the terminal). The rigid foam polyol may be one kind of polyol or two or more kinds.
In particular, it is preferable to use only polyether polyol as the rigid foam polyol, or to use polyester polyol in combination with polyether polyol as the main component.

(Polyether polyol)
Examples of the polyether polyol include polyether polyols obtained by adding cyclic ethers such as alkylene oxides to initiators such as polyhydroxy compounds and amine compounds such as polyhydric alcohols and polyhydric phenols.
Specific examples of the polyhydroxy compound as the initiator include the compounds described above as the initiator of the polyether polyol (Y). Specific examples of the amine compound include Mannich condensation products in addition to the aliphatic amine compound, saturated cyclic amine compound, and aromatic amine compound described above as the initiator of the amine-based polyol (Z).

As the cyclic ether, a 3- to 6-membered cyclic ether compound having one oxygen atom in the ring can be used, and specific examples include the following compounds.
Ethylene oxide, propylene oxide, isobutylene oxide, 1-butylene oxide, 2-butylene oxide, trimethylethylene oxide, tetramethylethylene oxide, butadiene monooxide, styrene oxide, α-methylstyrene oxide, epichlorohydrin, epifluorohydrin, epibromo Hydrin, glycidol, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, 2-chloroethyl glycidyl ether, o-chlorophenyl glycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, cyclohexene oxide, dihydronaphthalene oxide, 3 , 4-Epoxy-1-vinylcyclohexane or other 3-membered cyclic ether group Compound; oxetane, tetrahydrofuran, a compound having a 4-6 membered cyclic ether group such as tetrahydropyran.

  Preferably, it is a compound (monoepoxide) having one 3-membered cyclic ether group, and particularly preferred cyclic ethers are ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, which are alkylene oxides having 2 to 4 carbon atoms, -Butene oxide. The most preferred cyclic ether is propylene oxide or a combination of propylene oxide and ethylene oxide. Two or more cyclic ethers to be added to the initiator can be used in combination. In that case, they may be mixed and subjected to an addition reaction, or may be subjected to an addition reaction sequentially.

(Mannich polyol)
As a polyether polyol, a polyether polyol obtained by adding a cyclic ether to a reaction product (also referred to as a Mannich condensation product) obtained by reacting a phenol, an alkanolamine, and an aldehyde with a Mannich reaction (in this specification, a Mannich polyol) It is preferable to use.

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

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

  The alkanolamines are at least one selected from the group consisting of monoethanolamine, diethanolamine and 1-amino-2-propanol. Of these, diethanolamine is preferable in that a low-viscosity Mannich polyol is easily obtained.

The Mannich condensation product used as an initiator is a reaction product obtained by reacting the above phenols, aldehydes, and alkanolamines (hereinafter sometimes referred to as Mannich condensation reaction). The reaction product includes unreacted substances remaining after the reaction. The Mannich condensation reaction can be carried out by a known method.
In the raw material used for the Mannich condensation reaction, the ratio of aldehydes to 1 mol of phenols is preferably 0.3 mol or more and 3 mol or less. When the ratio of the aldehydes is 0.3 mol or more, good dimensional stability of the rigid foam is easily obtained. When the amount is 3 mol or less, it becomes easy to obtain a low-viscosity Mannich polyol. Further, from the viewpoint that the viscosity of Mannich polyol tends to be lower, it is preferably 0.3 mol or more and less than 0.9 mol, and more preferably 0.9 mol or more and 1.5 mol or less from the viewpoint of the strength of the obtained rigid foam. .
In the raw material used for the Mannich condensation reaction, the ratio of alkanolamines to 1 mol of aldehydes is preferably 0.7 mol or more and 12 mol or less. When the ratio of the alkanolamines is 0.7 mol or more, a rigid foam having good strength can be easily obtained. When the amount is 12 mol or less, a favorable flame-retardant rigid foam is easily obtained. Moreover, from the flame retardance point of the rigid foam obtained, 0.7 mol or more and 5 mol or less are preferable. From the point of obtaining a low-viscosity Mannich polyol, 0.7 mol or more and 5 mol or less are preferable, and 0.7 mol or more and 3.5 mol or less are more preferable.

Mannich polyol is obtained by ring-opening addition polymerization of alkylene oxide by a known method using a reaction product obtained by Mannich condensation reaction as an initiator.
The addition amount of alkylene oxide added to the initiator is preferably 2 to 30 mol, particularly preferably 4 to 20 mol, relative to 1 mol of phenols used in the Mannich condensation reaction. When the added amount of alkylene oxide is not less than the lower limit of the above range, the hydroxyl value and viscosity of the produced Mannich polyol tend to be low. It is easy to suppress shrinkage | contraction of a rigid foam as the addition amount of alkylene oxide is below the upper limit of the said range.

The alkylene oxide that undergoes ring-opening addition polymerization to the Mannich condensation product that is an initiator is preferably one or more selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. The alkylene oxide preferably contains ethylene oxide, more preferably ethylene oxide alone or a combination of ethylene oxide and propylene oxide.
When the total alkylene oxide used in the ring-opening addition polymerization reaction is 100% by mass, the ethylene oxide ratio is preferably 10 to 100% by mass, more preferably 20 to 100% by mass. When it is at least the lower limit of the above range, the viscosity of the Mannich polyol tends to be low, which is preferable for reducing the viscosity of the polyol composition (P) and the viscosity of the polyol system liquid.
Ethylene oxide also contributes to the improvement of the hydrophilicity of Mannich polyols. When the Mannich polyol has high hydrophilicity, the compatibility with water and the solubility of the polyol in a polyol system liquid containing water as a foaming agent are improved.
In addition, as a Mannich polyol, when using in combination of several types of polyol, the ratio of this ethylene oxide is a value as the whole Mannich polyol.

The hydroxyl value of Mannich polyol is 100 to 800 mgKOH / g, more preferably 200 to 550 mgKOH / g, and particularly preferably 250 to 450 mgKOH / g.
When a plurality of types of polyols are used in combination as the Mannich polyol, the hydroxyl value of each Mannich polyol may be within the above range.
It is preferable that the hydroxyl value of Mannich polyol is not less than the lower limit of the above range because the strength of the resulting rigid foam can be easily secured and good dimensional stability can be easily obtained. On the other hand, when the hydroxyl value is less than or equal to the upper limit, the amount of alkylene oxide-derived oxyalkylene chains present in the Mannich polyol increases, and the viscosity of the Mannich polyol tends to decrease. Moreover, the brittleness of the rigid foam to be produced is suppressed, and the adhesiveness is likely to appear.

(Polyester polyol)
Examples of the polyester polyol include a polyester polyol obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. In addition, there are polycondensation of hydroxycarboxylic acid, polymerization of cyclic ester (lactone), polyaddition of cyclic ether to polycarboxylic acid anhydride, polyester polyol obtained by transesterification of waste polyethylene terephthalate, and the like.

Also, a relatively low molecular weight hydroxy compound generally called a chain extender or a crosslinking agent can be used as a part of the polyol composition (P). For example, polyhydric alcohols, alkanolamines, saccharides, polyhydric phenols, or the like, or low molecular weight polyether polyols obtained by adding a small amount of alkylene oxide thereto, low molecular weight polyester polyols, or the like can be used.
Preferably, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol and glycerin, alkanolamines such as diethanolamine and triethanolamine, and polyether polyols having a hydroxyl value of 300 mgKOH / g or more are chain extenders. Used as a crosslinking agent.
Moreover, amine compounds, such as a monoamine and a polyamine, can also be used together with a polyol composition (P). Preferably, hexamethylenediamine, diaminodiphenylmethane, etc. are used.

The rigid foam polyol preferably contains at least one member selected from the group consisting of polyether polyols and Mannich polyols, which use an aromatic amine compound (not including the Mannich condensation product) as an initiator, in terms of improving reaction activity. In particular, when Mannich polyol is included, it is more preferable because flexibility is easily obtained in the rigid foam.
Moreover, when the polyol for rigid foam contains a polyether polyol and / or Mannich polyol that uses the aromatic amine compound as an initiator, the polyol is selected from the group consisting of a polyester polyol and a polyether polyol that uses a bisphenol compound as an initiator. One or more types are preferably used in combination in terms of improving the flame retardancy of the rigid foam.
As the bisphenol compound, one or more selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxybiphenyl, and 2,2′-bis (4-hydroxyphenyl) hexafluoropropane are used. It is preferable. More preferred are bisphenol A, bisphenol F, and bisphenol S.

[Polyol composition (P)]
The polyol composition (P) in the present invention consists of a polymer-dispersed polyol alone or a polymer-dispersed polyol and a rigid foam polyol. When only the polymer-dispersed polyol is used, the dispersion of the polymer particles tends to be more stable.
The average hydroxyl value of the polyol composition (P) is preferably 100 to 800 mgKOH / g, particularly preferably 150 to 500 mgKOH / g. When the average hydroxyl value is not less than the lower limit of the above range, a flexible rigid foam is easily obtained, and when it is not more than the upper limit of the above range, brittleness of the obtained rigid foam is likely to be suppressed.
2-10 are preferable and, as for the average functional group number of a polyol composition (P), 2-6 are especially preferable. If the average number of functional groups is not less than the lower limit of the above range, a rigid foam having an appropriate compressive strength can be easily obtained, and if it is not more than the upper limit of the above range, a low viscosity polyol can be easily obtained.
In the polyol composition (P), the content of polymer particles derived from the polymer-dispersed polyol is preferably 0.01% by mass or more. When the ratio of the polymer particles is less than this, it is difficult to obtain a sufficient dimensional stability improvement effect of the rigid foam. 0.05 mass% or more is more preferable. The upper limit is preferably 8% by mass or less, and more preferably 6% by mass or less. More preferably, it is 5 mass% or less, Most preferably, it is less than 2 mass%. When the content of the polymer particles is 8% by mass or less, the brittleness of the obtained rigid foam is easily suppressed.

[Polyol compositions (P1) to (P4)]
Preferable compositions of the polyol composition (P) include, for example, the following polyol compositions (P1) to (P4).
0.05 to 10% by weight of polymer-dispersed polyol, preferably 0.1 to 6% by weight, 20 to 80% by weight of Mannich polyol, preferably 30 to 70% by weight, and 20 to 80% by weight of polyester polyol, Preferably the polyol composition (P1) which consists of 30-70 mass%. This polyol composition (P1) is particularly preferable in terms of suppressing shrinkage of the obtained rigid foam. The polyol composition (P1) is suitable for a continuous board molding method or a spray method, and particularly suitable for a spray method using water alone or water and an HFC compound as a foaming agent.
Polyether using 0.05 to 8% by mass of polymer-dispersed polyol, preferably 0.1 to 6% by mass, 20 to 80% by mass of Mannich polyol, preferably 30 to 70% by mass, and a bisphenol compound as an initiator A polyol composition (P2) comprising 20 to 80% by mass, preferably 30 to 70% by mass of the polyol. This polyol composition (P2) is particularly preferable in terms of suppressing shrinkage of the obtained rigid foam and workability. The polyol composition (P2) is suitable for a continuous board molding method or a spray method, and particularly suitable for a spray method using only water as a foaming agent.

0.1 to 10% by mass of polymer-dispersed polyol, preferably 1 to 8% by mass, 5 to 40% by mass of polyether polyol having a saturated cyclic amine compound as an initiator, preferably 10 to 30% by mass, 10 to 60% by mass, preferably 20 to 50% by mass of a polyether polyol having an aromatic amine compound (not including a Mannich condensation product) as an initiator, and an average number of functional groups having a polyhydric alcohol as an initiator is 3 to 6%. A polyol composition (P3) comprising 10 to 60% by mass, preferably 20 to 50% by mass of the polyether polyol. This polyol composition (P3) is preferable in that good fluidity is obtained particularly when a rigid foam is molded. The polyol composition (P3) is suitable for a continuous board molding method or a spray method, and particularly suitable for a continuous board molding method using only water as a foaming agent.
0.1 to 10% by weight of polymer-dispersed polyol, preferably 1 to 8% by weight, 20 to 60% by weight of polyether polyol with an aliphatic amine compound as an initiator, preferably 30 to 50% by weight, and aromatic 10 to 50% by weight, preferably 20 to 40% by weight of a polyether polyol using an aliphatic amine compound (not including a Mannich condensation product) as an initiator, and 5 to 30% by weight, preferably 5 to 20% by weight of a Mannich polyol % And a polyol composition (P4) comprising 5 to 40% by mass, preferably 10 to 30% by mass of the polyester polyol. This polyol composition (P4) is preferable in that good fluidity is obtained and a rigid foam excellent in heat insulation performance can be obtained particularly when molding a rigid foam. The polyol composition (P4) is suitable for a continuous board molding method or a spray method, and particularly suitable for a board method in which water and a hydrocarbon compound are used in combination as a foaming agent.

[Polyisocyanate Compound (I)]
Examples of the polyisocyanate compound (I) include aromatic, alicyclic, and aliphatic polyisocyanates having two or more isocyanate groups; mixtures of two or more of the above polyisocyanates; Polyisocyanate etc. are mentioned.
Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI). And the like, or prepolymer-type modified products, isocyanurate-modified products, urea-modified products, carbodiimide-modified products, and the like. Of these, crude MDI or a modified product thereof is preferred, and a modified product of crude MDI is particularly preferred.

  The viscosity of the polyisocyanate compound (I) at 25 ° C. is preferably 50 to 300 mPa · s, particularly preferably 100 to 300 mPa · s. If it is this range, shrinkage | contraction will hardly generate | occur | produce in the rigid foam obtained.

The use amount of the polyisocyanate compound (I) is expressed by 100 times the number of isocyanate groups with respect to the total number of active hydrogens in the polyol composition (P) and other active hydrogen compounds (hereinafter, the numerical value expressed by 100 times this). Is referred to as “isocyanate index”), preferably 100 to 300, particularly preferably 100 to 200.
In the case of a urethane formulation mainly using a urethanization catalyst as a catalyst, the amount of the polyisocyanate compound (I) used is preferably 100 to 170, particularly preferably 100 to 150, in terms of the isocyanate index.
In the case of an isocyanurate prescription mainly using a trimerization reaction accelerating catalyst that promotes a trimerization reaction of an isocyanate group as a catalyst, the amount of the polyisocyanate compound (I) used is preferably 100 to 300, preferably 100 to 250 in terms of the isocyanate index. Is particularly preferred.

[Foaming agent]
As the foaming agent, water, hydrocarbon compounds, HFC compounds, methylene chloride, and other halogenated hydrocarbons are preferable. Two or more foaming agents may be used in combination.
Examples of the hydrocarbon compound include butane, normal pentane, isopentane, cyclopentane, hexane, cyclohexane and the like. Of these, normal pentane, isopentane, and cyclopentane are preferable.
Examples of HFC compounds include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3. , 3-pentafluorobutane (HFC-365mfc) and the like.
Among these, it is preferable to use water alone or to use water and one or more other foaming agents in combination. As the blowing agent used in combination with water, hydrocarbon compounds and HFC compounds are preferable. As the hydrocarbon compound used in combination with water, cyclopentane, isopentane, normal pentane or a mixture thereof is particularly preferable. As the HFC compound used in combination with water, HFC-134a, HFC-245fa, HFC-365mfc or these Mixtures are preferred. In consideration of the environment, it is more preferable to use only water as the foaming agent.
The amount of water used as the foaming agent is preferably 0.1 to 10 parts by weight, and preferably 1.0 to 10 parts by weight with respect to 100 parts by weight of the polyol composition (P) (water is not calculated as a polyol; the same applies hereinafter). Part by mass is particularly preferred.
When using a hydrocarbon compound together with water, the usage-amount is 5-40 mass parts with respect to 100 mass parts of a polyol composition (P), and 10-30 mass parts is more preferable.
When the HFC compound is used in combination with water, the amount used is preferably 5 to 50 parts by weight, particularly preferably 10 to 40 parts by weight, based on 100 parts by weight of the polyol composition (P).

[Foaming agent]
Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. In the present invention, it is preferable to use a silicone foam stabilizer in order to form good bubbles.
[catalyst]
As a catalyst, a well-known catalyst can be used suitably in manufacture of a rigid polyurethane foam. Amine-based catalysts such as tertiary amines and organometallic compounds such as organotin compounds are suitable.
[Other additives]
Furthermore, stabilizers, colorants, fillers, flame retardants, and other additives may be used.

The density of the rigid foamed synthetic resin of the present invention is preferably from 10 to 50 kg / ^{m 3,} more preferably ^{15~40kg / m 3, 20~35kg / m} 3 is especially preferred. When the density is in the above range, it is lightweight and therefore easy to convey.
The density of hard foam synthetic resin which is molded by spraying in the present invention (foam core density) is preferably from 10 to 50 kg / ^{m 3,} more preferably 15~45kg / ^{m 3,} particularly preferably 20~40kg / ^{m 3} . When the density is in the above range, the amount of raw material used during construction can be reduced because of light weight.
The density of hard foam synthetic resin which is molded by a continuous board forming process (panel core density) is preferably from 10 to 50 kg / ^{m 3,} more preferably ^{15~45kg / m 3, 20~40kg / m} 3 is especially preferred. When the density is in the above range, it is lightweight and therefore easy to convey.

[Method for producing rigid foam synthetic resin]
The rigid foam synthetic resin of the present invention can be preferably produced by the following method.
A polyol composition (P) is prepared in advance, and a polyol system liquid is prepared by mixing the polyol composition (P) and a part or all of components other than the polyisocyanate compound (I). Thereafter, a method in which the polyol system liquid, the polyisocyanate compound (I) and the remaining components are mixed to form a foamed stock solution composition and cured while foaming is preferred.
The foaming agent may be blended in advance in the polyol system liquid, or may be blended after mixing the polyol system liquid and the polyisocyanate compound (I). Preferably, it mix | blends beforehand with a polyol system liquid.
The foam stabilizer and the catalyst may be contained in either the polyol system liquid or the liquid containing the polyisocyanate compound (I). From the standpoint of problems such as separation of the polyol system liquid, that is, stable performance, the polyol system liquid is preferably contained.

The method for producing a rigid foam synthetic resin of the present invention can be applied to various molding methods.
Examples of the molding method include an injection method, a continuous board molding method, and a spray method.
The injection method is a method in which a rigid foam material is injected into a frame such as a mold and foamed. The continuous board molding method is a method of manufacturing a laminate in which a rigid foam is sandwiched between two face materials by supplying a foam material between two face materials and foaming. It is used for the manufacture of heat insulation materials. The spray method is a method in which a rigid foam is sprayed and applied.
In particular, by using the polyol composition (P) containing the polymer-dispersed polyol of the present invention, the continuous board molding method can easily reduce the weight of the rigid foam, and the spray method can suppress the shrinkage of the rigid foam after construction. Easy to do well.

According to the method for producing a rigid foam synthetic resin of the present invention, a rigid foam having good dimensional stability can be produced using a low-odor polymer-dispersed polyol.
In addition, the dispersion stability of the polymer particles in the polymer-dispersed polyol is good, the compatibility between the polymer-dispersed polyol and the polyol for the rigid foam is good, and the storage stability of the polyol system liquid is excellent.
Furthermore, as shown in the examples described later, the effect of improving the dimensional stability of the rigid foam by adding the polymer-dispersed polyol is high, and the amount of the polymer-dispersed polyol added to obtain the desired effect is reduced. Can do. When there is little addition amount of polymer dispersion polyol,
The uniform dispersibility in the polyol composition (P) is improved, which is preferable in terms of improving the physical properties of the rigid foam.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. Below, the unit of the numerical value of the mixing | blending shown to the table | surface is a mass part. The amount of polyisocyanate used is represented by the isocyanate index (INDEX).

<Production example of polymer-dispersed polyol>
The raw materials shown in Table 1 were used. The details are as follows. The abbreviation AN represents acrylonitrile, St represents styrene, VAc represents vinyl acetate, PO represents propylene oxide, EO represents ethylene oxide, and EO group content represents oxyethylene group content. AMBN represents 2,2-azobis-2-methylbutyronitrile and is a polymerization initiator.

[Polyol (X)]
Polyol (X) was prepared by using the following polyol. Table 1 shows the average hydroxyl value (unit: mg KOH / g) of the polyol (X).
Polyol Y-1 (example of polyether polyol (Y)): hydroxyl group value obtained by randomly adding PO and EO in the presence of potassium hydroxide catalyst using glycerin as an initiator, 50 mg KOH / g, EO group A polyether polyol having a content of 70% by mass.
Polyol Z-1 (example of amine polyol (Z)): A polyether polyol having a hydroxyl value of 760 mgKOH / g obtained by adding only PO with ethylenediamine as an initiator.
Polyol A-1: A polyether polyol having a hydroxyl value of 50 mgKOH / g and an EO group content of 25% by mass obtained by randomly adding PO and EO in the presence of a potassium hydroxide catalyst using glycerol as an initiator.
Polyol B-1: A polyether polyol having a hydroxyl value of 650 mg KOH / g obtained by adding only PO in the presence of a potassium hydroxide catalyst using glycerol as an initiator.

[Examples 1 to 16: Production of polymer-dispersed polyol]
Examples 1 to 7 are examples, and examples 8 to 16 are comparative examples.
After all of the polyol, monomer and AMBN shown in Table 1 were charged in a 5 L pressurized reaction vessel, the temperature was raised while stirring, and the reaction was continued for 10 hours while maintaining the reaction solution at 80 ° C. In all examples, the monomer conversion was 80% or more. After completion of the reaction, the polymer-reacted polyol was produced by removing the unreacted monomer by heating and degassing at 110 ° C. and −0.10 MPa (gauge pressure) for 2 hours.

The average hydroxyl value (unit: mg KOH / g), polymer particle content (unit: mass%), viscosity at 25 ° C. (unit: mPa · s), odor, and dispersion stability of the polymer-dispersed polyol produced in each example The evaluation results are shown in Table 1.
The average hydroxyl value of the polymer-dispersed polyol was measured according to JIS K 1557-1: 2007, and the viscosity was measured according to JIS K 1557-5: 2007.
The polymer particle content (polymer concentration) contained in the polymer-dispersed polyol was measured by the following method.
5 ± 0.01 g (α1) of polymer-dispersed polyol was placed in a centrifuge tube, and 25 g of methanol was added. The polymer particles in the polymer-dispersed polyol were dispersed by stirring well, and the centrifuge tube was capped. The centrifuge tube was rotated at 12,000 rpm for 30 minutes in a centrifuge. After the centrifuge stopped, the centrifuge tube was taken out and the supernatant was discarded. Using a vacuum dryer, drying was performed at 40 ° C. and a gauge pressure of −0.10 MPa for 1 hour, and the polymer mass (α2) was measured. The solid in the polymer was pulverized and the polymer mass (α3) was measured again. Using a vacuum dryer once again, it is dried at 40 ° C. and a gauge pressure of −0.10 MPa for 2 hours, and the polymer mass (α4) is measured. Then, polymer particle content was computed with the following formula.
Polymer particle content (%) = (α2 × α4) × 100 / (α1 × α3)
The odor was evaluated by a human sensory test. A case where the odor was intense was evaluated as x (impossible), a case where there was no or very little odor was evaluated as ◯ (good), and a case where neither could be said was evaluated as △ (possible).
Evaluation of dispersion stability was observed after the produced polymer-dispersed polyol was allowed to stand in an environment of 40 ° C. and stored for 3 months, and the polymer particles were not dispersed or aggregated and were in a uniform dispersed state. Good).

As shown in Table 1, the polymer-dispersed polyols obtained in Examples 1 to 7 had very low odor and were stable dispersions after storage for 3 months. The polymer-dispersed polyols obtained in Examples 1 to 7 are designated as POP1 to 7, respectively.
Example 8 is a comparative example in which a polymer-dispersed polyol was produced by replacing polyol Y-1 which is a polyether polyol (Y) with polyol A-1 having a low EO group content. When the particles settled or aggregated vigorously, the entire polymer-dispersed polyol coagulated or separated into layers, and a uniform dispersion could not be obtained, and the average hydroxyl value and viscosity could not be measured. .
Examples 9 and 10 are comparative examples in which the amine-based polyol (Z) is less than the range of the mass ratio of (Y) :( Z) in the present invention. The dispersion had a very low odor and was stable after storage for 3 months. The polymer-dispersed polyols obtained in Examples 9 and 10 are designated as POP8 and 9, respectively.

  Examples 11 to 13 are comparative examples in which the polyether polyol (Y) is less than the range of the mass ratio of (Y) :( Z) in the present invention. It had a strong odor and was a problem. The polymer-dispersed polyols obtained in Examples 11 to 13 are designated POP10 to 12, respectively.

Example 14 is a comparative example in which the monomer (M) does not contain an ethylenic double bond-containing nitrile, and Examples 15 and 16 do not contain any of carboxylic acid vinyl ester, ethylenic double bond-containing carboxylic acid and derivatives thereof. It is a comparative example.
In any of Examples 14 to 16, the dispersion had a very low odor and was stable even after storage for 3 months. The polymer-dispersed polyols obtained in Examples 14 to 16 are designated as POP13 to 15, respectively.

<Production example of rigid foam synthetic resin>
The raw materials used are as follows.
[Polyester polyol]
Polyol C-1: An aromatic polyester polyol having a hydroxyl value of 200 mgKOH / g, obtained by polycondensation of diethylene glycol and terephthalic acid. (Brand name: PHANTOL SV-165, manufactured by Hitachi Chemical Co., Ltd.).
Polyol C-2: An aromatic polyester polyol having a hydroxyl value of 245 mgKOH / g. (Product name: TEROL 563, manufactured by Oxide).
Polyol C-3: An aromatic polyester polyol having a hydroxyl value of 250 mgKOH / g. (Product name: TEROL 693, manufactured by Oxide).

[Mannich polyol]
Polyol D-1: Ring opening of PO and EO in this order using a reaction product obtained by reacting 1.5 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol A polyether polyol having a hydroxyl value of 300 mgKOH / g obtained by addition polymerization. The amount of alkylene oxide added is 15.4 moles per mole of nonylphenol. The ratio of EO to the total amount of added PO and EO is 58% by mass. The viscosity at 25 ° C. (hereinafter the same) is 1,000 mPa · s.
Polyol D-2: EO, PO, and EO were added in this order using a reaction product obtained by reacting 0.75 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol. A polyether polyol having a hydroxyl value of 300 mgKOH / g obtained by ring-opening addition polymerization. The amount of alkylene oxide added is 16.7 moles per mole of nonylphenol. The ratio of EO to the total amount of added PO and EO is 75% by mass. The viscosity at 25 ° C. is 470 mPa · s.

Polyol D-3: Ring-opening addition polymerization of PO and EO in this order using a reaction product obtained by reacting 1 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol A polyether polyol having a hydroxyl value of 300 mgKOH / g obtained by the process. The amount of alkylene oxide added is 16.4 moles per mole of nonylphenol. The ratio of EO to the total amount of added PO and EO is 55% by mass. The viscosity is 640 mPa · s.
Polyol D-4: Ring opening of PO and EO in this order with the reaction product obtained by reacting 1.3 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol A polyether polyol having a hydroxyl value of 300 mgKOH / g obtained by addition polymerization. The amount of alkylene oxide added is 15.8 moles per mole of nonylphenol. The ratio of EO to the total amount of added PO and EO is 55% by mass. The viscosity is 800 mPa · s.

[Other polyether polyols]
Polyol E-1: A polyether polyol having a hydroxyl value of 270 mgKOH / g, in which bisphenol A is used as an initiator and only EO is subjected to ring-opening addition polymerization. The viscosity at 25 ° C. is 11,000 mPa · s.
Polyol E-2: A polyether polyol having a hydroxyl value of 150 mgKOH / g, in which bisphenol A is used as an initiator and only EO is subjected to ring-opening addition polymerization. The viscosity at 25 ° C. is 1,200 mPa · s.
Polyol F: A polyether polyol having a hydroxyl value of 350 mgKOH / g, in which N- (2-aminoethyl) piperazine is used as an initiator and only EO is subjected to ring-opening addition polymerization. The viscosity at 25 ° C. is 700 mPa · s.
Polyol G: Tolylenediamine was used as an initiator, and EO, PO and EO were subjected to ring-opening addition polymerization in this order, the hydroxyl value was 350 mgKOH / g, and the total of EO and PO A polyether polyol having an EO ratio of 33% by mass. The viscosity at 25 ° C. is 7,000 mPa · s.
Polyol H: A polyether polyol having a hydroxyl value of 380 mgKOH / g, in which a mixture of sucrose and glycerin (mass ratio of 5: 4) is used as an initiator, and only PO is subjected to ring-opening addition polymerization. The viscosity at 25 ° C. is 2,300 mPa · s.
Polyol I: Polyether polyol having a hydroxyl value of 760 KOH / g, obtained by ring-opening addition polymerization of only PO in the initiator, using ethylenediamine as the initiator. The viscosity at 25 ° C. is 45,000 mPa · s.

[Polymer particle content]
The polymer particle content (unit: mass%) contained in the polyol composition was calculated from the polymer particle content (unit: mass%) in the polymer-dispersed polyol used and the mass of the polymer composition (P).
In addition, since the same result is obtained even if it measures by the following method similarly to the polymer particle content contained in the polymer-dispersed polyol, it may be measured by the following method.
5 ± 0.01 g (α1 ′) of the polyol composition (P) was placed in a centrifuge tube, and 25 g of methanol was added. The polymer particles in the polyol composition (P) were dispersed by stirring well, and the centrifuge tube was capped. The centrifuge tube was rotated at 12,000 rpm for 30 minutes in a centrifuge. After the centrifuge stopped, the centrifuge tube was taken out and the supernatant was discarded. Using a vacuum dryer, drying was performed at 40 ° C. and a gauge pressure of −0.10 MPa for 1 hour, and the polymer mass (α2 ′) was measured. The solid in the polymer was pulverized and the polymer mass (α3 ′) was measured again. Using a vacuum dryer once again, it is dried at 40 ° C. and a gauge pressure of −0.10 MPa for 2 hours, and the polymer mass (α4 ′) is measured. Then, polymer particle content was computed with the following formula.
Polymer particle content (%) = (α2 ′ × α4 ′) × 100 / (α1 ′ × α3 ′)

[Foaming agent]
-Foaming agent A: distilled water.
-Foaming agent B: cyclopentane.
-Foaming agent C: 245fa and 365mfc mixed at a mass ratio of 70:30.
[Flame retardants]
Trischloropropyl phosphate (product name: Pyrol PCF, manufactured by Spresta Japan).
[Foam stabilizer]
-Silicone type foam stabilizer (trade name: SH-193, manufactured by Toray Dow Corning, Silicone).

[catalyst]
Catalyst A: Reactive foaming catalyst (70% by mass D of bis (2-dimethylaminoethyl) ether)
PG (dipropylene glycol) solution, trade name: TOYOCAT RX7, manufactured by Tosoh Corporation)
.
Catalyst B: resinification catalyst (N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-S-triazine, trade name: Polycat 41, manufactured by Air Products).
Catalyst C: Mixture of quaternary ammonium salt and ethylene glycol (trade name: TOYOCA
T TRX, manufactured by Tosoh Corporation).
Catalyst D: Resinification catalyst (N, N, N ′, N ′,-tetramethylhexanediamine product name: TOYOCAT MR, manufactured by Tosoh Corporation)
Catalyst E: Octylate of 1,8-diazabicyclo (5,4,0) -undecene-7 (trade name: U-CAT SA 102, manufactured by San Apro).
Catalyst F: Resin catalyst (Triethylenediamine trade name: TEDA-L33, manufactured by Tosoh Corporation).
Catalyst G: Trimerization catalyst (potassium octylate, trade name: PACCAT 15G, manufactured by Nippon Chemical Industry Co., Ltd.)

[Polyisocyanate compound]
Polyisocyanate-1: polymeric MDI (mixture of MDI and crude MDI), trade name: Coronate 1130, manufactured by Nippon Polyurethane Industry Co., Ltd., viscosity at 25 ° C .: 130 mPa · s, isocyanate group content: 31% by mass.
Polyisocyanate-2: polymeric MDI (mixture of MDI and crude MDI), trade name: Millionate MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd., viscosity at 25 ° C .: 200 mPa · s, isocyanate group content: 31% by mass).
Polyisocyanate-3: Polymeric MDI (mixture of MDI and Crude MDI), trade name: Sumidur 44V20, manufactured by Sumika Bayer Polyurethanes, viscosity at 25 ° C .: 200 mPa · s, isocyanate group content: 31% by mass).

The following method was used for evaluation.
(Reactivity)
In simple foaming, cream time / rise time was measured. In box-free foaming, cream time / gel time / tack free time were measured.
[Cream time]
The mixing start time of the polyol system liquid and the polyisocyanate compound was measured as 0 second, and the time until the foaming stock solution composition started to foam was measured as cream time (seconds).
[Rise time]
The mixing start time of the polyol system liquid and the polyisocyanate compound was set to 0 second, and the time when the foaming stock solution composition started to foam and the rise of the foam stopped was measured as the rise time (seconds).
[Geltime]
The mixing start time of the polyol system liquid and the polyisocyanate compound is set to 0 seconds. As the gelation progresses, a thin glass or metal rod is slightly added to the upper part of the foaming stock solution composition during foaming. After that, the time until the foamed undiluted composition began to draw the yarn when it was quickly pulled out was measured as the gel time (seconds).
[Tack Free Time]
The mixing start time of the polyol system liquid and the polyisocyanate compound was set to 0 second, and the time from the end of foaming to the absence of stickiness in the foam was measured as a tack-free time (seconds).

(Density (cup-free density, BOX core density, foam core density, panel core density))
In the rigid foam obtained by simple foaming and box-free foaming, the density of a test piece obtained by cutting out the vicinity of the center of the rigid foam into a 10 cm square was measured by a method according to JIS A9526.
In the rigid foam obtained by spray foaming, a test piece obtained by cutting out the vicinity of the center of the rigid foam into 70 mm × 100 mm × 100 mm was measured by a method based on JIS A9526.
In the rigid foam obtained by panel foaming, a test piece obtained by cutting out the vicinity of the center of the rigid foam into 25 mm × 200 mm × 200 mm was measured by a method based on JIS A9526.
(Compressive strength)
The compressive strength was measured according to JIS A9511. The size of the sample piece was 50 mm × 50 mm × 50 mm. The compressive strength in the direction parallel to and perpendicular to the direction of gravity was measured.

(Dimensional change rate (high temperature, wet heat, low temperature))
The high temperature shrinkage is measured by a method according to ASTM D 2126-75. When the foaming agent is only water, the high temperature dimensional stability and wet heat dimensional stability are evaluated. The foaming agent is used in combination with a hydrocarbon compound or an HFC compound. In the case, the low temperature dimensional stability was evaluated.
The hard foams of each example were used, and after curing for 1 hour, a test piece was cut out in the width (X) × length (Y) × height (Z) in the dimensions shown in the table.
High temperature dimensional stability was stored for 24 hours in an atmosphere at 70 ° C., wet heat dimensional stability at 70 ° C. and 95% relative humidity, and low temperature dimensional stability at −30 ° C., and increased length (thickness). ) Was expressed as a dimensional change rate (unit:%) with respect to the length (thickness) before storage. That is, the dimensional change rate was measured for all six directions in each of the three directions (X, Y, Z) under two conditions. Note that the measurement was performed in three directions under low temperature conditions.
In the dimensional change rate, a negative value means shrinkage, and a large absolute value means that a dimensional change is large.
Evaluation of the appearance shrinkage was based on the following evaluation criteria based on the dimensional change rate (unit%) in all three directions under each condition.
[Evaluation criteria]
○ (Good): The maximum absolute value among the dimensional change rates in all three directions was less than 3%.
Δ (possible): The maximum absolute value among the dimensional change rates in all three directions was 3% or more and less than 10%.
X (impossible): The maximum absolute value among the dimensional change rates in all three directions was 10% or more.
(Thermal conductivity)
The thermal conductivity (unit: mW / m · K) was measured using a thermal conductivity measuring device (product name: Auto Lambda HC-074, manufactured by Eiko Seiki Co., Ltd.) in accordance with JIS A1412.

(Examples 21 to 37, 41 to 53, 61 to 65: simple foaming / liquid temperature 10 ° C.)
With the formulations shown in Tables 2 to 6, rigid foams were produced by simple foaming, and the items shown in the tables were evaluated.
Examples 21 to 37 in Tables 2 and 3 are examples, and are blends using the polyol composition (P1) and using only water as a blowing agent. Both are particularly suitable for the spray method.
Examples 41 to 53 in Tables 4 and 5 are comparative examples.
Examples 61 to 65 in Table 6 are examples, and are blends using the polyol composition (P2) and using only water as a blowing agent. Both are particularly suitable for the spray method.
In other words, the polyol component, foaming agent, foam stabilizer, flame retardant and catalyst were mixed well with a stirrer in the formulation shown in the table to obtain a polyol system liquid. After stirring and mixing the polyol system liquid and the polyisocyanate compound (liquid temperature: 10 ° C.), foaming was performed in a 1 L polyethylene descup to produce a rigid foam.

(Examples 71-75, 81-84: Box-free foaming / liquid temperature 20 ° C.)
With the formulations shown in Tables 7 and 8, rigid foams were produced by box-free foaming, and the items shown in the tables were evaluated.
Examples 71 to 74 in Table 7 are examples, and are blends using the polyol composition (P3) and using only water as a blowing agent. Both are particularly suitable for the continuous board molding method. Example 75 is a comparative example.
Examples 81 to 83 in Table 8 are examples, which are blended using the polyol composition (P4) and water and a hydrocarbon compound as a foaming agent. Both are particularly suitable for the continuous board molding method. Example 84 is a comparative example.
That is, the polyol system liquid and polyisocyanate prepared in the same manner as in the examples of Tables 2 to 6 were stirred and mixed (liquid temperature 20 ° C.), then placed in a 200 mm × 200 mm × 200 mm wooden box, foamed and hardened A foam was produced.

(Examples 91-94: Box-free foaming / liquid temperature 15 ° C.)
A rigid foam was produced by box-free foaming with the formulation shown in Table 9, and the items shown in the table were evaluated.
Examples 91 to 93 in Table 9 are examples, and are blends using the polyol composition (P1) and water and an HFC compound as a foaming agent. Both are particularly suitable for the spray method. Example 94 is a comparative example.
That is, in the examples of Tables 7 and 8, a rigid foam was produced by foaming in a wooden box in the same manner except that the liquid temperature after stirring and mixing the polyol system liquid and the polyisocyanate was changed to 15 ° C.

From the results of Tables 2 to 9, in Examples 21 to 37, 61 to 65, 71 to 74, 81 to 83, 91 to 93 using the polymer-dispersed polyols (POP1 to POP7) according to the present invention, good dimensional stability A rigid foam having was obtained. In particular, in Examples 34 to 37 in Table 3 and Examples 61 to 65 in Table 6, the dimensional stability of the obtained rigid foam was good despite the small amount of the polymer-dispersed polyol added. According to the knowledge of the present inventor, the first example of actually producing a rigid foam with a polymer-dispersed polyol addition amount of 1 part or less and a polymer particle content in the polyol composition (P) of 0.15% by mass or less is the first. . By making the polymer particle content in the polyol composition (P) 0.15% by mass or less, the mechanical properties of the obtained rigid foam can be further improved, which is preferable. From the above results, the present invention is not only able to obtain a polymer-dispersed polyol having a low odor, an excellent effect of improving the storage stability of the polymer system liquid, and an excellent effect of improving the dimensional stability of the hard foamed synthetic resin. There is an effect that the content of the polymer particles in the composition (P) can be reduced to 0.01 to 0.15% by mass. The mechanical properties of the resulting rigid foam can be improved.
On the other hand, the rigid foams obtained in Examples 41, 75, 84 and 94 to which no polymer-dispersed polyol was added have large shrinkage.
In Examples 42 to 53 using the polymer-dispersed polyol (POP 8 to 15) of the comparative example, the shrinkage was large when the addition amount of the polymer-dispersed polyol was 3 parts by mass, and even when the amount was increased to 6 parts by mass, it was not sufficiently improved.

(Spray construction test)
In Examples 23, 27, 33, 41, 91 to 94, the foaming evaluation was carried out using a spray foaming machine (trade name: FF-1600) manufactured by Gasmer Co., and a liquid temperature of 40 ° C. and a room temperature of 20 ° C. A rigid foam was produced by foaming and reacting under.
The base material to be used was a flexible plate having a length of 600 mm, a width of 600 mm, and a thickness of 5 mm. For the spraying, after a lower spray layer having a thickness of 1 mm was applied, two layers were applied so that the thickness of one layer was 25 to 30 mm, and a total of three layers were laminated.
Evaluation was made of adhesion, workability, moldability, mixability, density of the obtained rigid foam (foam core density), thermal conductivity, compressive strength, and dimensional stability in spray application. Evaluation of adhesiveness, workability, formability, and mixability was performed by the following methods. The evaluation results are shown in Tables 10 and 11.

[Adhesiveness]
The edge of the applied foam was cut, and the feeling of peeling the substrate and the foam was confirmed, and evaluated according to the following criteria.
○ (Good): Foam remains on the base material, making it hard to peel off the foam.
X (impossible): The foam does not remain on the substrate, and the foam easily peels off.
[Spray workability]
The spread of the spray mist was visually confirmed and evaluated in the following three stages.
○ (Good): A state where the mist opens sufficiently wide and smooth spraying is possible.
Δ (possible): The mist opening is slightly insufficient, and smooth spraying is somewhat difficult.
X (impossible): The state where mist opening is insufficient and smooth spraying is difficult.
[Moldability (state inside the foam)]
The end of the applied foam was cut, the state of the cross section was confirmed, and the following criteria were evaluated.
○ (good): There is no coloring or cracking due to scorch or the like, or cell non-uniformity inside the foam.
X (impossible): The foam has coloring or cracking due to scorch or the like, and / or there is a defective portion such as cell non-uniformity.
[Mixability]
The appearance of the foam immediately after spraying was observed, and the cell size and hue uniformity were visually confirmed. The evaluation was based on the following criteria, and a three-level evaluation was performed.
○ (Good): Cell size and hue are uniform and there are no mixed spots.
Δ (possible): A state in which any one of the cell size is not uniform, the hue is not uniform, or the presence of mixed spots is confirmed.
X (impossible): a state in which two or more of cell size non-uniformity, hue non-uniformity, or presence of mixed spots are confirmed.

As shown in Tables 10 and 11, in Examples 23, 27, 33, and 91 to 93 using the polymer-dispersed polyol (POP2 to 4) according to the present invention, the adhesiveness, workability, formability, and mixing properties are excellent. A rigid foam having good dimensional stability was obtained.
On the other hand, in Examples 41 and 94 in which the polymer-dispersed polyol was not added, the adhesiveness, workability, moldability, and mixing properties were good, but the resulting rigid foam had a large shrinkage.

(Panel molding test)
In Examples 72 to 75 and 81 to 84, foaming was evaluated using a metal mold having a thickness of 50 mm, a length of 400 mm, and a width of 400 mm under the condition of a metal mold having a surface temperature of 40 ° C. To produce a rigid foam.
The density (panel core density), compressive strength, dimensional stability, and thermal conductivity of the rigid foam obtained by panel molding were evaluated. The evaluation results are shown in Tables 12 and 13.

As shown in Tables 12 and 13, in Examples 72 to 74 and 81 to 83 using the polymer-dispersed polyol (POP 2 to 4) according to the present invention, rigid foams having good dimensional stability were obtained.
On the other hand, in Examples 75 and 84 in which the polymer-dispersed polyol was not added, the obtained rigid foam had a large shrinkage.

(Evaluation of storage stability)
In Examples 21, 23, 26, 30 to 33, 44, 46, and 48, after the polyol system liquid used for evaluation of dimensional stability was stored at 40 ° C. for 2 weeks, a rigid foam was similarly produced, and the above-mentioned High temperature dimensional stability was evaluated. The evaluation criteria are the same as described above. The results are shown in Tables 14 and 15.

As shown in Tables 10 and 11, the polymer system liquid used in Examples 21, 23, 26 and 30 to 33 using the polymer-dispersed polyol (POP1 to 7) according to the present invention has good dimensional stability after storage. A rigid foam having properties was obtained. That is, the storage stability of the polyol system liquid was good.
In contrast, in the polymer system liquids used in Examples 44, 46, and 48 using the polymer-dispersed polyol (POP10-12) of the comparative example, the dimensional stability of the rigid foam produced using the polyol system liquid after storage. Decreased. That is, the storage stability of the polyol system liquid was insufficient.

Claims (10)

A method for producing a polymer-dispersed polyol by polymerizing a monomer (M) having a polymerizable unsaturated group in a polyol (X),
The polyol (X) includes the following polyether polyol (Y) and the following amine-based polyol (Z), and the total of the polyether polyol (Y) and the amine-based polyol (Z) is the polyol (X). 80 mass% or more, and the mass ratio (Y) :( Z) of the polyether polyol (Y) and the amine polyol (Z) is 85:15 to 97: 3,
The average hydroxyl value of the polyol (X) is 20 to 180 mgKOH / g,
The monomer (M) includes an ethylenic double bond-containing nitrile, and at least one selected from the group consisting of an ethylenic double bond-containing carboxylic acid and a derivative thereof, and a carboxylic acid vinyl ester. A method for producing a polymer-dispersed polyol.
Polyetherol (Y): One or more polyether polyols having a hydroxyl value of 5 to 84 mgKOH / g and an oxyethylene group content of 40 to 100% by mass.
Amine-based polyol (Z): One or more amine-based polyols obtained by ring-opening addition polymerization of a cyclic ether to an amine compound and having a hydroxyl value of 250 to 900 mgKOH / g.   The monomer (M) having the polymerizable unsaturated group contains an ethylenic double bond-containing nitrile and a carboxylic acid vinyl ester, and the total of both is 80% by mass or more of the monomer (M). A process for producing a polymer-dispersed polyol as described in 1.   The polymer dispersion according to claim 2, wherein the ethylenic double bond-containing nitrile is acrylonitrile, the carboxylic acid vinyl ester is vinyl acetate, and the mass ratio of acrylonitrile: vinyl acetate is 75:25 to 5:95. Production method of polyol. A method for producing a rigid foam synthetic resin by reacting a polyol composition (P) and a polyisocyanate compound (I) in the presence of a foaming agent, a foaming agent and a catalyst,
The manufacturing method of hard foam synthetic resin in which this polyol composition (P) contains the polymer dispersion polyol obtained by the manufacturing method as described in any one of Claims 1-3.   The manufacturing method of the hard foam synthetic resin of Claim 4 whose average hydroxyl value of the said polyol composition (P) is 100-800 mgKOH / g, and whose average functional group number is 2-10.   The manufacturing method of the hard foam synthetic resin of Claim 4 or 5 whose polymer particle content in the said polyol composition (P) is 0.01-8 mass%.   The manufacturing method of the hard foam synthetic resin as described in any one of Claims 4-6 in which a polyol composition (P) contains a Mannich polyol.   The manufacturing method of the hard foam synthetic resin as described in any one of Claims 4-7 with which the said foaming agent contains water.   The manufacturing method of the hard foam synthetic resin as described in any one of Claims 4-8 whose said foaming agent is only water.   The manufacturing method of the hard foam synthetic resin of Claim 8 or 9 whose usage-amount of the said water is 0.1-10 mass parts with respect to 100 mass parts of a polyol composition (P).