WO2012105657A1

WO2012105657A1 - Process for production of hard foam synthetic resin

Info

Publication number: WO2012105657A1
Application number: PCT/JP2012/052420
Authority: WO
Inventors: 勝彦清水; 茂夫波田野; 孝之佐々木
Original assignee: 旭硝子株式会社
Priority date: 2011-02-02
Filing date: 2012-02-02
Publication date: 2012-08-09
Also published as: JPWO2012105657A1; JP5664669B2

Abstract

A hard foam having good properties can be produced by reacting a polyol composition with a polyisocyanate compound in the presence of a foaming agent, a foam control agent and a catalyst, wherein a hydrofluoroolefin is used as the foaming agent. The foaming agent comprises a hydrofluoroolefin (I) represented by the formula: R¹CH=CHR² (wherein R¹ represents a perfluoroalkyl group having 1-6 carbon atoms, and R² represents a perfluoroalkyl group having 1-6 carbon atoms or a halogen atom). The polyol composition to be used is any one of three types of compositions [i.e., a polyol composition (Pa), a polyol composition (Pb) and a polyol composition (Pc)], each containing polymer particles.

Description

Manufacturing method of rigid foam synthetic resin

The present invention relates to a method for producing a rigid foam synthetic resin.

Rigid foam synthetic resin such as rigid polyurethane foam, rigid urethane modified polyisocyanurate foam or rigid polyurea foam by reacting active hydrogen compound such as polyol with polyisocyanate compound in the presence of foam stabilizer, catalyst and foaming agent ( Hereinafter, the production of rigid foams is generally performed.

With respect to the blowing agent, conventionally used chlorinated fluorinated carbon compounds (chlorofluorocarbon compounds, so-called CFCs such as CCl ₃ F) and chlorinated fluorinated hydrocarbon compounds (hydrochlorofluorocarbon compounds, CCl ₂ FCH ₃ etc.) Since the use of so-called HCFCs is restricted from the viewpoint of environmental protection (protection of the ozone layer), a foaming agent that replaces these has been demanded.

As a solution to the above problem, hydrofluorinated hydrocarbon compounds (hydrofluorocarbons (HFCs) such as CHF ₂ CH ₂ CF ₃ and CH ₃ CF ₂ CH ₂ CF ₃ ) are used. However, the HFCs have zero ozone layer depletion potential (ODP), but have a high global warming potential (GWP), and therefore there is a need for further alternative blowing agents. Hydrofluoroolefins (HFOs) have been proposed as one of the candidate substances.

Patent Documents 1 to 4 listed below describe hydrofluoroolefins as blowing agents that do not destroy the ozone layer even when released into the atmosphere.
That is, Patent Document 1 describes cis-1,1,1,4,4,4-hexafluoro-2-butene, and Patent Document 2 describes R ^F CH═CHR ^F ′ (R ^F , R ^F ′ is a perfluoroalkyl group) or a brominated hydrofluoroolefin. Patent Document 3 describes hydrochlorofluoroolefin, and Patent Document 4 describes the use of trans-1,1,1,3-tetrafluoropropene as a part of the foaming agent.

In Patent Document 1, cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336) is used as a foaming agent, and an aromatic amine-based polyol is used as a polyol. The resulting rigid foam is described. Patent Document 2 uses HFO-1438mzz or HFO-1336mmz as a foaming agent and foams in a closed mold using a general sucrose / glycerin polyol as a polyol (hereinafter also referred to as a casting method). The resulting rigid foam is described. Patent Document 3 describes a rigid foam obtained by free rise using HFO-1233zd or HFO-1234ze and using a nonylphenol-based Mannich polyol as part of the polyol. Patent Document 4 describes a rigid foam using HFO1234ze as a foaming agent.

Japanese Patent Laid-Open No. 5-179043 Special table 2009-513815 gazette US Patent Application Publication No. 2010/0105788 US Patent Application Publication No. 2009/0253820

However, in Patent Documents 1 to 4, there has been little study on the combination of a hydrofluoroolefin (which may be referred to as HFO hereinafter), which is a foaming agent, and a polyol. Not obtained. In particular, no consideration has been given to reducing the weight of foams required in recent years.

The present invention has been made in view of the above circumstances, and the present invention A uses a hydrofluoroolefin as a foaming agent to obtain a rigid foam having good characteristics, particularly dimensional stability even when reduced in weight. With the goal.
Another object of the present invention is to obtain a rigid foam having good characteristics by using HFO as a foaming agent, particularly by using an injection method.
The object of the present invention B is to obtain a rigid foam produced by a continuous board method having good characteristics by using hydrofluoroolefins as a foaming agent, particularly a rigid foam having good dimensional stability even when the weight is reduced. And

The present invention C has been made in view of the above circumstances, and an object thereof is to obtain a rigid foam having good characteristics by using hydrofluoroolefins as a foaming agent. The object is to obtain a rigid foam with good properties using HFO as a blowing agent, in particular using a spray method.

The present invention A includes the following [1] to [9].
[1] A method for producing a rigid foamed synthetic resin by reacting a polyol composition (Pa) with a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst,
The polyol composition (Pa) contains 30 to 70% by mass of the following polyol (Aa) and 0.002 to 30% by mass of polymer particles, and the polyol composition (Pa) has an average number of hydroxyl groups of 2 to 8, Hydrofluoroolefins (I) having a value of 100 to 800 mg KOH / g and the blowing agent represented by the following formula (I)
R ¹ CH═CHR ² (I)
(Wherein R ¹ is a perfluoroalkyl group having 1 to 6 carbon atoms and R ² is a perfluoroalkyl group having 1 to 6 carbon atoms or a halogen atom). Production method.
Polyol (Aa): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aromatic amine having 4 to 12 active hydrogen atoms as an initiator, and containing ethylene oxide in the total amount of the alkylene oxide A polyether polyol having an amount of 0 to 60% by mass and a hydroxyl value of 100 to 800 mgKOH / g.

[2] The method for producing a rigid foam synthetic resin according to [1], wherein the polymer particles are polymer particles obtained by polymerizing a monomer having a polymerizable unsaturated group.
[3] The method for producing a rigid foam synthetic resin in [1] or [2], wherein the polyol composition (Pa) contains 1 to 50% by mass of the following polyol (Ba).
Polyol (Ba): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using a polyhydric alcohol having 5 to 12 active hydrogen atoms as an initiator, and containing ethylene oxide in the total amount of the alkylene oxide A polyether polyol having an amount of 0 to 20% by mass and a hydroxyl value of 100 to 800 mgKOH / g.
[4] The method for producing a rigid foam synthetic resin according to [1] to [3], wherein the polyol composition (Pa) contains 10 to 40% by mass of the following polyol (Ca).
Polyol (Ca): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aliphatic amine having 2 to 4 active hydrogen atoms as an initiator, and containing ethylene oxide in the total amount of the alkylene oxide A polyether polyol having an amount of 0 to 50% by mass and a hydroxyl value of 100 to 800 mgKOH / g.
[5] The method for producing a rigid foam synthetic resin according to [1] to [4], wherein the polyol composition (Pa) contains 10 to 60% by mass of the following polyol (Da).
Polyol (Da): Polyester polyol produced by polycondensation of a monomer mixture containing an aromatic compound and having an average hydroxyl number of 2 to 3 and a hydroxyl value of 100 to 500 mgKOH / g.
[6] The polymer particles are polymer particles derived from a polymer-dispersed polyol (Wa), and the polyol composition (Pa) contains 0.01 to 50% by mass of the polymer-dispersed polyol (Wa). 5] The method for producing a hard foam synthetic resin.

[7] The method for producing a rigid foamed synthetic resin according to [1] to [6], wherein the hydrofluoroolefin (I) contains Z—CF ₃ CH═CHCF ₃ .
[8] The method for producing a rigid foam synthetic resin according to [1] to [6], wherein the hydrofluoroolefin (I) contains E-CF ₃ CH═CHCl.
[9] The method for producing a rigid foam synthetic resin according to [1] to [8], wherein the production method is a casting method.

The gist of invention B is the following [1] to [7].
[1] A method for producing a rigid foam synthetic resin by reacting and foaming a polyol composition (Pb) and a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst by a continuous board molding method. ,
The polyol composition (Pb) contains 5 to 99.998 mass of the following polyol (Ab) and 0.002 to 30 mass% of polymer particles, and the polyol composition (Pb) has an average number of hydroxyl groups of 2 to 8, Hydrofluoroolefins (I) having a hydroxyl value of 100 to 800 mg KOH / g and the blowing agent represented by the following formula (I)
R ¹ CH═CHR ² (I)
(Wherein R ¹ is a perfluoroalkyl group having 1 to 6 carbon atoms and R ² is a perfluoroalkyl group having 1 to 6 carbon atoms or a halogen atom). Production method.
Polyol (Ab): Polyol obtained by ring-opening addition polymerization of alkylene oxide using a Mannich condensation product obtained by reacting phenols and / or aromatic amines, aldehydes and alkanolamines as an initiator. Ether polyol.

[2] The method for producing a rigid foam synthetic resin according to [1], wherein the polymer particles are polymer fine particles obtained by polymerizing a monomer having a polymerizable unsaturated group.
[3] The method for producing a rigid foam synthetic resin according to [1] or [2], wherein the polyol composition (Pb) contains 20 to 70% by mass of the following polyol (Bb).
Polyol (Bb): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aliphatic amine as an initiator.
[4] The method for producing a rigid foam synthetic resin according to [1] to [3], wherein the polyol composition (Pb) contains 20 to 60% by mass of the following polyol (C).
Polyol (C): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aromatic amine (excluding Mannich condensation product) as an initiator.
[5] The rigid foamed synthetic resin according to [1] to [4], wherein the polymer particles are polymer particles derived from a polymer-dispersed polyol (Wb), and the polyol composition (Pb) contains the polymer-dispersed polyol (Wb). Manufacturing method.

[6] The method for producing a rigid foamed synthetic resin according to [1] to [5], wherein the hydrofluoroolefin (I) comprises Z—CF ₃ CH═CHCF ₃ .
[7] The method for producing a rigid foam synthetic resin according to [1] to [6], wherein the hydrofluoroolefin (I) contains E—CF ₃ CH═CHCl.

The gist of the present invention C is the following [1] to [9].
[1] A method for producing a rigid foamed synthetic resin by reacting a polyol composition (Pc) with a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst,
The polyol composition (Pc) contains 20 to 99.998 mass% of the following polyol (Ac) and 0.002 to 30 mass% of polymer particles, and the polyol composition (Pc) has an average number of hydroxyl groups of 2 to 8, Hydrofluoroolefins (I) having an average hydroxyl value of 100 to 800 mgKOH / g and the blowing agent represented by the following formula (I)
R ¹ CH═CHR ² (I)
(Wherein R ¹ is a perfluoroalkyl group having 1 to 6 carbon atoms and R ² is a perfluoroalkyl group having 1 to 6 carbon atoms or a halogen atom). Production method.
Polyol (Ac): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using a Mannich condensation product obtained by reacting phenols, aldehydes and alkanolamines as an initiator.

[2] The method for producing a rigid foam synthetic resin according to [1], wherein the polymer particles are polymer particles obtained by polymerizing a monomer having a polymerizable unsaturated group.
[3] The method for producing a rigid foam synthetic resin according to [1] or [2], wherein the polyol composition (Pc) contains the following polyol (Bc) in an amount of more than 0% by mass and 70% by mass or less.
Polyol (Bc): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an amine compound (excluding the Mannich condensation product) as an initiator.
[4] The method for producing a rigid foam synthetic resin according to [1] to [3], wherein the polyol composition (Pc) contains the following polyol (Cc) in an amount of more than 0% by mass and 40% by mass or less.
Polyol (Cc): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using a polyhydric alcohol having 2 to 6 active hydrogen atoms as an initiator.
[5] The method for producing a hard foam synthetic resin according to [1] to [4], wherein the polyol composition (Pc) contains the following polyol (Dc) in an amount of more than 0% by mass and 70% by mass or less.
Polyol (Dc): Polyester polyol produced by polycondensation of a monomer mixture containing an aromatic compound.
[6] The rigid foam synthetic resin according to [1] to [4], wherein the polymer particles are polyol particles derived from a polymer-dispersed polyol (Wc), and the polyol composition (P) includes the polymer-dispersed polyol (W). Manufacturing method.

[7] The method for producing a rigid foamed synthetic resin according to [1] to [6], wherein the hydrofluoroolefin (I) contains Z—CF ₃ CH═CHCF ₃ .
[8] The method for producing a rigid foam synthetic resin according to [1] to [6], wherein the hydrofluoroolefin (I) contains E-CF ₃ CH═CHCl.
[9] The method for producing a hard foam synthetic resin according to any one of [1] to [8], wherein a spray method is used.

According to the present invention A, B, and C, it is possible to produce a rigid foam having good characteristics, particularly dimensional stability even when the weight is reduced, using hydrofluoroolefins as a foaming agent. In particular, it is possible to produce a rigid foam having good characteristics in the injection method.

It is a perspective view which shows the metal mold | die used for manufacture of the panel foam in the Example.

<Description of Invention A>
The “polyol composition (Pa)” in the present specification is a mixture of all polyols (including polymer-dispersed polyols) used for the reaction with the polyisocyanate compound.
In the present specification, the “polyol system liquid” is a liquid to be reacted with a polyisocyanate compound. In addition to the polyol composition (Pa), a blending agent as necessary, such as a foaming agent, a foam stabilizer, a catalyst and the like. Contains liquid.
In the present specification, 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.
The “polymer-dispersed polyol” in the present invention A is obtained by polymerizing a monomer having a polymerizable unsaturated bond in a base polyol (Wa ′) such as a polyether polyol or a polyester polyol to form polymer particles. It is a polyol (Wa) in which the polymer particles are dispersed in the base polyol (Wa ').

[Polyol (Aa)]
The polyol composition (Pa) in the present invention A contains a polyol (Aa).
The polyol (Aa) is a polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aromatic amine as an initiator. As the polyol (Aa), only one type may be used, or two or more types may be used in combination.

An aromatic amine as an initiator is an amine having an aromatic ring having 4 to 12 active hydrogen atoms. Specific examples thereof include phenylenediamine, tolylenediamine, diaminodiphenylmethane, and Mannich condensate.
The Mannich condensation product is preferably a compound obtained by reacting phenols such as phenol and nonylphenol; aldehydes such as formaldehyde; and alkanolamines such as monoethanolamine and diethanolamine. The molecular weight of the Mannich condensation product is preferably about 200 to 10,000.
Of these initiators, tolylenediamine is particularly preferable because low thermal conductivity is obtained. As tolylenediamine, o-tolylenediamine and m-tolylenediamine are preferable.

As the alkylene oxide used in the production of the polyol (Aa), it is preferable to use ethylene oxide (hereinafter also referred to as EO) and / or propylene oxide (hereinafter also referred to as PO). In addition, butylene oxide, isobutylene oxide, styrene oxide or the like may be used in combination. When using EO and / or PO, any of the following methods may be used. (1) A method of ring-opening addition polymerization of EO alone. (2) A method of ring-opening addition polymerization of PO alone. (3) A method of ring-opening addition polymerization of a mixture of PO and EO. (4) A method of ring-opening addition polymerization by arbitrarily combining the above methods (1) to (3).
In order to impart good physical properties to the rigid foam, it is preferable to use a combination of (1) and (2) or a method of (2). When combining (1) and (2), it is more preferable to perform ring-opening addition polymerization in the order of (1)-(2)-(1).
The ethylene oxide content (total EO content) in the total amount of alkylene oxide used in the production of the polyol (Aa) is preferably 0 to 60% by mass, more preferably 0 to 45% by mass, and particularly preferably 0 to 30% by mass. preferable. When it is at most the upper limit of the above range, the moldability is good because it has an appropriate reactivity.
By reacting the alkylene oxide with the active hydrogen atom of the initiator, the alkylene oxide undergoes ring-opening addition to produce a polyol having an oxyalkylene group. Hydroxyalkyl group is formed by ring-opening addition of one molecule of alkylene oxide to active hydrogen atom, and alkylene oxide is ring-opening addition to the hydroxyl group, and this reaction is repeated to form a chain of oxyalkylene groups. To do. When the alkylene oxide is EO, the oxyethylene group is linked, and when the alkylene oxide is PO, the oxypropylene group is linked.
When ring-opening addition polymerization is carried out in the order of (1)-(2)-(1) above, the amount of EO (terminal EO content) to be subjected to ring-opening addition polymerization after the addition of EO and PO in this order is determined by the polyol ( It is preferably 1 to 40% by weight, more preferably 1 to 30% by weight, particularly preferably 1 to 20% by weight, based on the total amount of alkylene oxide used for the production of Aa). The viscosity of polyol (Aa) does not become too high as it is below the upper limit of the said range, and the reactivity of polyol (Aa) improves that it is more than a lower limit. In the polyol (Aa) obtained by performing ring-opening addition polymerization in the order of (1)-(2)-(1), an oxyethylene group is linked to the initiator, followed by an oxypropylene group, A polyol in which oxyethylene groups are chained.

The number of hydroxyl groups of the polyol (Aa) is 4 to 12, preferably 4 to 10, and particularly preferably 4 to 8. When the number of hydroxyl groups of the polyol (Aa) is not less than the lower limit of the above range, the shrinkage of the rigid foam is easily suppressed, and when it is not more than the upper limit, the viscosity becomes an appropriate range and handling is easy.
The hydroxyl value of the polyol (Aa) is 100 to 800 mgKOH / g, preferably 200 to 600 mgKOH / g, particularly preferably 300 to 500 mgKOH / g. When the hydroxyl value of the polyol (Aa) is not less than the lower limit of the above range, the compression strength of the rigid foam is improved, the closed cell ratio is improved, and the thermal conductivity is improved. The brittleness of a rigid foam is suppressed as it is below the upper limit of the said range.
The content of the polyol (Aa) in the polyol composition (Pa) is 30 to 70% by mass, preferably 30 to 60% by mass, particularly preferably 30 to 50% by mass. When the content of the polyol (Aa) is not less than the lower limit of the above range, the closed cell rate is improved and good thermal conductivity is obtained. When the viscosity is not more than the upper limit of the above range, the viscosity of the polyol system liquid does not become too high and handling is easy.
In particular, in the case of the casting method, when the content of the polyol (Aa) is not more than the upper limit of the above range, cell roughening is unlikely to occur.

[Polyol (Ba)]
The polyol (Ba) is a polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using a polyhydric alcohol having 5 to 12 active hydrogen atoms as an initiator.
The polyol composition (Pa) preferably contains a polyol (Ba) in addition to the polyol (Aa). The polyol (Ba) contributes to an improvement in the compressive strength of the rigid foam and good dimensional stability. Moreover, it can also prevent that the viscosity of a polyol composition (Pa) becomes high too much by using a polyol (Ba) other than a polyol (Aa).
As the polyol (Ba), only one type may be used, or two or more types may be used in combination.

Saccharides are preferably used as polyhydric alcohols having 5 to 12 active hydrogen atoms, which are initiators. Specific examples of the saccharide include fructose, sorbitol, sucrose and the like. Of these, sorbitol or sucrose is preferred.
Examples of the alkylene oxide used for the production of the polyol (Ba) include ethylene oxide, propylene oxide, butylene oxide and the like. It is preferable that at least propylene oxide or butylene oxide is contained, and at least propylene oxide is particularly preferably contained.
The alkylene oxide used for the production of the polyol (Ba) is preferably propylene oxide alone or a combination of ethylene oxide and propylene oxide. When used in combination, ethylene oxide and propylene oxide may be reacted after being mixed or sequentially.
The ethylene oxide content (total EO content) in the total amount of alkylene oxide used in the production of the polyol (Ba) is 0 to 20% by mass, preferably 0 to 10% by mass, and 0% by mass, ie, PO alone. Particularly preferred. When the ethylene oxide content is not more than the upper limit of the above range, the reactivity can be easily controlled.

The number of hydroxyl groups in the polyol (Ba) is 5 to 12, preferably 5 to 10, and particularly preferably 5 to 8. When the number of hydroxyl groups of the polyol (Ba) is not less than the lower limit of the above range, the shrinkage of the rigid foam is easily suppressed, and when it is not more than the upper limit, the viscosity becomes an appropriate range and handling is easy.
The hydroxyl value of the polyol (Ba) is 100 to 800 mgKOH / g, preferably 200 to 600 mgKOH / g, particularly preferably 300 to 500 mgKOH / g. When the hydroxyl value of the polyol (Ba) is not less than the lower limit of the above range, the shrinkage of the rigid foam can be suppressed and the dimensional stability becomes good. The brittleness of a rigid polyurethane foam can be suppressed as it is below the upper limit of the said range.
The content of the polyol (Ba) in the polyol composition (Pa) is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and particularly preferably 5 to 45% by mass. When the content of the polyol (Ba) is not less than the lower limit of the above range, the compressive strength of the rigid foam is improved, shrinkage is suppressed, and good dimensional stability is easily obtained. When the amount is not more than the upper limit of the above range, it is easy to ensure good curing characteristics (curing properties) when molding a rigid foam.

[Polyol (Ca)]
The polyol (Ca) is a polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aliphatic amine as an initiator.
The polyol composition (Pa) preferably contains a polyol (Ca) in addition to the polyol (Aa). The polyol (Ca) contributes to improvement of moldability and reactivity. Moreover, it can also prevent that the viscosity of a polyol composition (Pa) becomes high too much by using a polyol (Ca) other than a polyol (Aa).
A polyol (Ca) may use only 1 type and may use 2 or more types together.

An aliphatic amine as an initiator is an aliphatic amine having 2 to 4 active hydrogen atoms. Specific examples include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as ethylenediamine, propylenediamine and 1,6-hexanediamine. Of these, ethylenediamine, monoethanolamine or diethanolamine is preferred.
Examples of the alkylene oxide used for the production of the polyol (Ca) include ethylene oxide, propylene oxide, butylene oxide and the like. Use of propylene oxide alone or a combination of ethylene oxide and propylene oxide is preferred. When used in combination, ethylene oxide and propylene oxide may be reacted after being mixed or sequentially.
The ethylene oxide content (total EO content) in the total amount of alkylene oxide used in the production of the polyol (Ca) is 0 to 50% by mass, preferably 0 to 48% by mass, more preferably 0 to 45% by mass. 0 mass%, that is, PO alone is particularly preferred. When the content of ethylene oxide is not more than the upper limit of the above range, the reactivity during foaming can be easily controlled, and good moldability can be secured.

The number of hydroxyl groups in the polyol (Ca) is 2-4. When the number of hydroxyl groups of the polyol (Ca) is less than or equal to the upper limit of the above range, the viscosity is in an appropriate range and handling is easy.
The hydroxyl value of the polyol (Ca) is 100 to 800 mgKOH / g, preferably 200 to 600 mgKOH / g, particularly preferably 300 to 500 mgKOH / g. When the hydroxyl value of the polyol (Ca) is not less than the lower limit of the above range, the compression strength of the rigid polyurethane foam is improved, shrinkage is suppressed, and good dimensional stability is obtained. When it is below the upper limit of the above range, the viscosity does not become too high and handling is easy.
The content of the polyol (Ca) in the polyol composition (P) is preferably 10 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 10 to 25% by mass. When the content of the polyol (Ca) is not less than the lower limit of the above range, the curing property becomes good, and the workability at the time of demolding is easily improved. It is easy to control the reactivity at the time of foaming as it is below the upper limit of the said range.

[Polyol (Da)]
The polyol (Da) is a polyester polyol produced by polycondensation of a monomer mixture containing an aromatic compound.
A polyol composition (Pa) may contain a polyol (Da) as needed. The polyol (Da) contributes to the improvement of flame retardancy.
As the polyol (Da), only one type may be used, or two or more types may be used in combination.

The monomer mixture used for the production of the polyol (Da) preferably contains a dicarboxylic acid compound and a polyhydric alcohol, and one or both of the dicarboxylic acid compound and the polyhydric alcohol contain a compound having an aromatic ring.
In particular, the polyol (Da) preferably contains an aromatic polyester polyol obtained by polycondensation reaction between a dicarboxylic acid having an aromatic ring and a polyhydric alcohol not having an aromatic ring.
Examples of the dicarboxylic acid having an aromatic ring include terephthalic acid, isophthalic acid, and orthophthalic acid. Terephthalic acid is more preferable in terms of improving heat resistance.
Examples of the polyhydric alcohol having no aromatic ring include ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol, dipropylene glycol (DPG), 1,4-butanediol, 1,6-hexanediol (1,6 -HD), diol compounds such as neopentyl glycol; and triol compounds such as glycerin and trimethylolpropane. Ethylene glycol or diethylene glycol is more preferable, and diethylene glycol is particularly preferable in that the viscosity of the polyol (Da) can be lowered and a good flame retardancy improving effect can be easily obtained.

The average number of hydroxyl groups of the polyol (Da) is 2 to 3, and is preferably 2. When the average number of hydroxyl groups is 3 or less, the viscosity can be kept low and the handling is easy.
The hydroxyl value of the polyol (Da) is 100 to 500 mgKOH / g, preferably 150 to 350 mgKOH / g, particularly preferably 180 to 300 mgKOH / g. When the hydroxyl value of the polyol (Da) is not less than the lower limit of the above range, the shrinkage of the rigid foam is easily suppressed, and when it is not more than the upper limit of the above range, the brittleness of the rigid foam is suppressed and good physical properties are easily obtained. .
The content of the polyol (Da) in the polyol composition (Pa) is preferably 10 to 60% by mass, more preferably 10 to 50% by mass, and particularly preferably 10 to 40% by mass. If the content of the polyol (Da) is not less than the lower limit of the above range, the effect of improving flame retardancy can be sufficiently obtained. When the amount is not more than the upper limit of the above range, the shrinkage of the rigid foam is suppressed, and good dimensional stability is easily obtained.

[Polymer-dispersed polyol (Wa)]
The polyol composition (Pa) contains polymer particles. Specifically, it is preferable to prepare a polymer-dispersed polyol (Wa) in which polymer particles are dispersed in a base polyol (Wa '), and to contain the polymer-dispersed polyol (Wa) in the polyol composition (Pa). .
The presence of polymer particles in the polyol composition (Pa) can suppress the shrinkage of the rigid foam and improve the dimensional stability. This effect is particularly useful when producing a lower density rigid urethane foam. The polymer-dispersed polyol (Wa) may be one type or a combination of two or more types.

The content of the polymer particles in the entire polyol composition (Pa) is preferably 0.002 to 30% by mass, more preferably 0.02 to 20% by mass, and particularly preferably 0.5 to 10% by mass. Within the above range, shrinkage of the obtained rigid foam can be effectively suppressed while maintaining heat insulation performance. Moreover, the storage stability at normal temperature and the storage stability at high temperature are good.
The average hydroxyl value of the polymer-dispersed polyol (Wa) is preferably 100 to 800 mgKOH / g, more preferably 150 to 800 mgKOH / g. The average hydroxyl value of the polymer-dispersed polyol (Wa) in the present specification is a value obtained by measuring the average hydroxyl value of a polyol in which polymer particles are dispersed in the base polyol (Wa '). It becomes lower than the average hydroxyl value of the base polyol (Wa ').
When the average hydroxyl value of the polymer-dispersed polyol (Wa) is at least the lower limit of the above range, the compatibility with other polyols is good, and when it is below the upper limit of the above range, the dispersion stability of the polymer particles is It is good.

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

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

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

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

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

The total amount of monomers having a polymerizable unsaturated bond used for forming the polymer particles is not particularly limited, but the content of the polymer particles in the polymer-dispersed polyol (Wa) is 1 to 50% by mass, more preferably The amount is preferably 2 to 45% by mass, particularly preferably 10 to 30% by mass.

For polymerization of a monomer having a polymerizable unsaturated bond, a polymerization initiator that generates a free radical and starts polymerization is suitably used. Specific examples of the polymerization initiator include 2,2′-azobis-isobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile (AMBN), 2,2′-azobis-2, Examples include 4-dimethylvaleronitrile, benzoyl peroxide, diisopropyl peroxydicarbonate, acetyl peroxide, di-tert-butyl peroxide, persulfate, and the like. In particular, AMBN is preferable.

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

It is preferable that 5 mass% or more of the base polyol (Wa ′) is the following polyether polyol (X). The polyether polyol (X) is one having a hydroxyl value of 84 mgKOH / g or less and an oxyethylene group content of 40% by mass or more based on the entire polyether polyol (X).
The polyether polyol (X) is preferably obtained by using a polyhydric alcohol as an initiator and adding ethylene oxide or ethylene oxide and another cyclic ether.
As the polyhydric alcohol, glycerin, trimethylolpropane, 1,2,6-hexanetriol and the like are preferable. As other cyclic ethers, propylene oxide, isobutylene oxide, 1-butene oxide and 2-butene oxide are preferable, and propylene oxide is particularly preferable.

In the polyether polyol (X), the upper limit of the hydroxyl value is preferably 84 mgKOH / g or less, preferably 67 mgKOH / g or less, particularly preferably 60 mgKOH / g or less. When it is the above upper limit, a polymer-dispersed polyol (Wa) in which polymer particles are stably dispersed is easily obtained. The lower limit of the hydroxyl value is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, further preferably 20 mgKOH / g or more, and particularly preferably 30 mgKOH / g or more. When it is the above lower limit, the dispersion stability of the polymer particles becomes good.

In polyether polyol (X), the minimum of oxyethylene group content with respect to the whole polyether polyol (X) is 40 mass% or more, 50 mass% or more is more preferable, and 55 mass% or more is especially preferable. When it is the lower limit, the dispersion of polymer particles in the polymer-dispersed polyol (Wa) is likely to be stable. The upper limit of the oxyethylene group content may be 100% by mass, that is, polyether polyol (X) in which only ethylene oxide is added to the initiator. From the viewpoint of dispersion stability of the polymer particles, the oxyethylene group content is more preferably 90% by mass or less.
The lower limit of the content of the polyether polyol (X) in the base polyol (Wa ′) is preferably 5% by mass or more, and particularly preferably 10% by mass or more. When it is the above lower limit, a polymer-dispersed polyol (Wa) having good dispersibility is easily obtained. The upper limit of the content of the polyether polyol (X) is not particularly limited, but it is preferable to set the hydroxyl value of the entire polymer-dispersed polyol (Wa) within the above-mentioned preferable range.

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

As the polyether polyol (Y), those having a hydroxyl value in the above range among the polyether polyols mentioned as the base polyol (Wa ') can be used. Among them, those obtained by adding propylene oxide using polyhydric alcohols or amines as initiators are preferable. The polyether polyol (Y) may be one type or a combination of two or more types.

When the polymer-dispersed polyol (Wa) is contained in the polyol composition (Pa), the content is set so that the content of the polymer particles in the entire polyol composition (Pa) is in the above-described preferable range. For example, the content of the polymer-dispersed polyol (Wa) in the entire polyol composition (Pa) is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass, and particularly preferably 0.1 to 20% by mass. .

[Other polyols (Ea)]
The polyol composition (Pa) contains other polyol (Ea) that does not belong to any of the polyol (Aa), polyol (Ba), polyol (Ca), polyol (Da), or polymer-dispersed polyol (Wa). You may let them.
Examples of the other polyol (Ea) include polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polyol. The hydroxyl value of the polyol (Ea) is preferably 5 to 1,000 mgKOH / g, more preferably 10 to 800 mgKOH / g, and particularly preferably 20 to 700 mgKOH / g.
The content of the polyol (Ea) in the polyol composition (Pa) is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

<Polyol composition (Pa)>
The polyol composition (Pa) preferably contains a polyol (Aa) and polymer particles, and further contains one or more selected from polyol (Ba), polyol (Ca), and polyol (Da). Optionally, other polyol (Ea) may be contained. The polymer particles are preferably derived from a polymer-dispersed polyol (Wa).
The average number of hydroxyl groups as a whole of the polyol composition (Pa) is 2 to 8, preferably 2.5 to 7.5. When the average number of hydroxyl groups is not less than the lower limit of the above range, the compression strength of the rigid foam is improved and shrinkage can be suppressed, so that the dimensional stability is good. Viscous behavior is suppressed, and fluidity and moldability are improved.
The average hydroxyl value of the entire polyol composition (Pa) is 100 to 800 mgKOH / g, preferably 200 to 700 mgKOH / g, particularly preferably 300 to 600 mgKOH / g. When the average hydroxyl value is not less than the lower limit of the above range, the shrinkage of the rigid foam is suppressed and the dimensional stability becomes good, and when it is not more than the upper limit, the brittleness of the rigid foam is suppressed.

In the present invention A, all of the polyol composition (Pa) may be polyol (Aa) and polymer particles.
Preferred combinations of the polyol composition (Pa) are shown below.
(Combination 3)
30 to 50% by mass of polyol (Aa), 5 to 45% by mass of polyol (Ba), 10 to 20% by mass of polyol (Ca), and polymer-dispersed polyol (Wa), containing polymer particles The amount is 0.01 to 20% by mass.
(Combination 4)
30 to 50% by weight of polyol (Aa), 5 to 45% by weight of polyol (Ba), 10 to 30% by weight of polyol (Ca), 10 to 60% by weight of polyol (Da), polymer dispersion It consists of polyol (Wa), and the content of polymer particles is 0.01 to 20% by mass.

<Polyisocyanate compound>
Examples of the polyisocyanate compound include aromatic, alicyclic, and aliphatic polyisocyanates having two or more isocyanate groups; modified polyisocyanates obtained by modifying these.
Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), and the like. These polyisocyanates or their prepolymer-type modified products, isocyanurates, urea-modified products, carbodiimide-modified products, and the like. Among these, crude MDI or a modified product thereof is preferable, and a modified product of crude MDI is particularly preferable. The polyisocyanate compound may be used alone or in combination of two or more.

The amount of polyisocyanate compound used is represented by 100 times the number of isocyanate groups relative to the total number of active hydrogen atoms in the polyol composition (Pa) and other active hydrogen compounds present in the polyol system liquid (hereinafter referred to as this A numerical value expressed by 100 times is referred to as “isocyanate index (INDEX)”, preferably 50 to 400.
In particular, in the case of a urethane formulation mainly using a urethanization catalyst as a catalyst, the amount of polyisocyanate compound used is preferably 50 to 170, particularly preferably 70 to 150 in terms of the isocyanate index.
In the case of an isocyanurate formulation mainly using a catalyst that promotes a trimerization reaction of an isocyanate group as a catalyst, the amount of the polyisocyanate compound used is preferably 110 to 400, more preferably 150 to 350 in terms of the isocyanate index. ~ 300 is particularly preferred.

<Foaming agent>
In the present invention A, at least one hydrofluoroolefin (I) represented by the above formula (I) is used as the foaming agent. That is, the foaming agent contains at least hydrofluoroolefins (I).
The melting point of the foaming agent is preferably 10 ° C. or less, particularly preferably 0 ° C. or less. The boiling point of the foaming agent is preferably 15 to 80 ° C., particularly preferably 15 to 60 ° C. When the boiling point is not less than the lower limit of the above range, handling is easy. When it is not more than the upper limit of the above range, the foaming efficiency is good.

In the above formula (), R ¹ is a C 1-6 perfluoroalkyl group, and R ² is a C 1-6 perfluoroalkyl group or a halogen atom.
R ¹ and R ² may be a cis form (hereinafter sometimes referred to as Z-) in which double bonds are present on the same side, and a trans form (hereinafter referred to as E-) present on the opposite side. May also be). In particular, when R ² is a perfluoroalkyl group, a cis type (Z-) is preferable from the viewpoint of ease of handling since the boiling point is in the normal temperature range. When R ² is a halogen atom, the trans type (E-) is preferable in terms of low ODP and GWP and low environmental impact.
Hydrofluoroolefins (I) can be produced by a known method, and can also be obtained from commercial products.

The halogen atom as R ² is preferably any one of fluorine (F), chlorine (Cl), and bromine (Br), and chlorine (Cl) is particularly preferable from the viewpoint of economical advantage.
When the carbon number of the perfluoroalkyl group as R ¹ and R ² is 6 or less, the boiling point becomes an appropriate region, the foaming efficiency is good, and handling is easy. The carbon number is preferably 1 to 5, and particularly preferably 1 to 4.
Specific examples of the perfluoroalkyl group include CF ₃ , C ₂ F _5, CF ₂ CF ₂ CF ₃ , CF (CF ₃ ) ₂ , CF ₂ CF ₂ CF ₂ CF ₃ , CF (CF ₃ ) CF ₂ CF ₃ CF ₂ CF (CF ₃ ) ₂ , C (CF ₃ ) ₃ , CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ CF ₂ CF (CF ₃ ) ₂ , C (CF ₃ ) ₂ C ₂ F ₅ , CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , CF (CF ₃ ) CF ₂ CF ₂ C ₂ F ₅ , C (CF ₃ ) ₂ CF ₂ C ₂ F _{5, and the} like can be given.
Among these, CF ₃ and C ₂ F ₅ are particularly preferable in terms of cost.

Preferred examples of hydrofluoroolefins (I) that are liquid at room temperature include Z—CF ₃ CH═CHCF ₃ (Z-1,1,1,4,4,4-hexafluoro-2-butene, HFO-1336mzz in the document), E-CF ₃ CH═CHCl (E-1-chloro-3,3,3-trifluoro-propene, also referred to herein as HCFO-1233zd). E-CF ₃ CH═CHCF ₃ (E-1,1,1,4,4,4-hexafluoro-2-butene), Z—CF ₃ CH═CHCl (Z-1-chloro-3,3, 3-trifluoro-propene) and the like.
Of these, the foaming agent preferably contains at least HFO-1336mzz or HCFO-1233zd, which is easy to handle and particularly preferable in terms of cost.

Moreover, you may use well-known foaming agents other than hydrofluoro olefins (I) as a foaming agent in the range which does not impair the effect of this invention A.
Known foaming agents include water. The amount of the known blowing agent used is preferably 1 to 25 parts by mass with respect to 100 parts by mass of the polyol composition (Pa). The amount of water used as a known blowing agent is preferably 0 to 25 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol composition (Pa). .
In the present invention A, the main component of the foaming agent is preferably hydrofluoroolefins (I), and specifically 50 to 100% by mass of the total foaming agent is preferably hydrofluoroolefins (I). .
The amount of the hydrofluoroolefins (I) used as the blowing agent is preferably 1 to 100 parts by weight, more preferably 3 to 80 parts by weight, with respect to 100 parts by weight of the polyol composition (Pa). Part is particularly preferred.
When hydrofluorocarbons (HFCs) are used in combination with the hydrofluoroolefins (I) in addition to the hydrofluoroolefins (I), the amount of HFCs used is 0 to 50 masses per 100 mass parts of the polyol composition (Pa). Part, preferably 0.01 to 50 parts by weight, more preferably 1 to 40 parts by weight, and particularly preferably 1 to 20 parts by weight.

<Catalyst>
As the catalyst, a urethanization catalyst that promotes a urethanization reaction and / or a trimerization reaction promotion catalyst that promotes a trimerization reaction of an isocyanate group is used. A tertiary amine is preferred as the urethanization catalyst. As the trimerization promoting catalyst, tin salts, lead salts, metal salts excluding mercury salts, and / or quaternary ammonium salts are preferable. In the case of an isocyanurate formulation, the combined use of a urethanization catalyst and a trimerization reaction promoting catalyst is preferable, and it is more preferable to use a tertiary amine in combination with the metal salt and / or the quaternary ammonium salt.

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

As the metal salt excluding the tin salt, lead salt, and mercury salt, carboxylic acid metal salts such as potassium acetate, potassium 2-ethylhexanoate and bismuth 2-ethylhexanoate are preferable.
Examples of the quaternary ammonium salt include tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; tetramethylammonium 2-ethylhexanoate, 2-hydroxy Tetraalkylammonium organic acid salts such as propyltrimethylammonium formate and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate; tertiary amines such as N, N, N ′, N′-tetramethylethylenediamine and carbonic acid diesters And a quaternary ammonium compound obtained by reacting 2-ethylhexanoic acid with an anion exchange reaction.
The amount of the catalyst used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyol composition (Pa).
By adjusting the amount of catalyst used, the time from the start of mixing the polyol composition (Pa) with the polyisocyanate compound, the foaming agent and the foam stabilizer until the reaction starts visually (cream time), after the reaction starts It is possible to adjust the time (foam time) until foaming progresses and shows resination behavior (gel time) and the time until foaming ends (rise time).

<Foam stabilizer>
In the present invention A, a foam stabilizer is used to form good bubbles. Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. These can use a commercial item. The amount of the foam stabilizer used can be appropriately selected, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyol composition (Pa).

<Other ingredients>
In the present invention A, in addition to the above-described polyol composition (Pa), polyisocyanate compound, catalyst, foaming agent, and foam stabilizer, known compounding agents can be used. Compounding agents include fillers such as calcium carbonate and barium sulfate; anti-aging agents such as antioxidants and UV absorbers; flame retardants, plasticizers, colorants, anti-fungal agents, foam breakers, dispersants, discoloration prevention Agents and the like. The amount of other compounding agents can be appropriately selected, but is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyol composition (Pa).

<Method for manufacturing rigid foam>
The method for producing a rigid foam of the present invention A is a method for producing a rigid foamed synthetic resin by reacting a polyol composition (Pa) with a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst.
In particular, when the present invention A is applied to a so-called injection method in which a rigid foam raw material is injected into a frame such as a mold and foamed, it is preferable in that the effect that cell roughening hardly occurs even near the injection point is obtained. .

The injection method can be performed, for example, by a method using a high pressure foaming device or a low pressure foaming device. When a high pressure foaming device or a low pressure foaming device is used, the above foaming agent is blended into a polyol system liquid, injected into various molds, and then foamed and cured to produce a rigid foam. The foaming agent may be blended in advance in the polyol system liquid, or may be blended when foaming with a foaming apparatus. Here, blending in the raw material system in advance means blending only in the polyol system liquid, or blending in both the polyol system liquid and the polyisocyanate compound.
Articles that can be manufactured using the injection method include refrigeration equipment such as electric refrigerators, panels for freezing / refrigerated vehicles, and the like.

The present invention A can also be applied to the production of rigid foams by a continuous board molding method or a spray method.
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. It is used for the manufacture of heat insulating materials.
The spray method is a method in which a rigid foam is sprayed and applied. The spray method is roughly classified into an air spray method and an airless spray method. Of these, the airless spray method in which the blended liquid is mixed with a mixing head and foamed is particularly preferable. As an article which can be manufactured using a spray method, a heat insulating material for architectural use can be cited.

According to the present invention A, a rigid foam having good characteristics can be obtained by using the hydrofluoroolefins (I) as a foaming agent.
Specifically, for rigid foams, it is desirable that the polyol system liquid has good storage stability, good moldability, and good dimensional stability even when the density is reduced. . According to the present invention A, it is possible to obtain a rigid foam in which all of these characteristics are good. Further, according to the present invention A, the high temperature storage stability of the polyol system liquid is improved.
Further, by combining the polyol (Aa) and polymer particles with the hydrofluoroolefins (I), a rigid foam having good dimensional stability and low thermal conductivity, that is, good heat insulation performance can be obtained.

<Description of Invention B>
The “polyol composition (Pb)” in the present invention B is a mixture of all the polyols (including polymer-dispersed polyols) used for the reaction with the polyisocyanate compound.
The “polyol system liquid” in the present invention B is a liquid to be reacted with the polyisocyanate compound, and in addition to the polyol composition (Pb), a blending agent as necessary, such as a foaming agent, a foam stabilizer, a catalyst and the like. Contains liquid.
The “foaming stock solution composition” in the present invention B is a liquid obtained by mixing a polyol system liquid, a polyisocyanate compound, and optionally the remaining components.
The “Mannich condensation product” in the present invention B is generally a condensation reaction of aromatic compounds such as aromatic amines and phenols, aldehydes, and amines (hereinafter sometimes referred to as Mannich condensation reaction). Means the compound obtained.
The “polymer dispersed polyol” in the present invention B is obtained by polymerizing a monomer having a polymerizable unsaturated bond in a base polyol (Wb ′) such as a polyether polyol or a polyester polyol to form polymer particles. It is a polyol (Wb) in which the polymer particles are dispersed in the base polyol (Wb ′).

[Polyol (Ab)]
The polyol composition (Pb) in the present invention B contains a polyol (Ab).
The polyol (Ab) is obtained by ring-opening addition polymerization of alkylene oxide using a Mannich condensation product obtained by reacting phenols and / or aromatic amines, aldehydes, and alkanolamines as an initiator. Polyether polyol (Mannich polyol). The Mannich polyol contributes to the improvement of flame retardancy.

The phenol is at least one selected from the group consisting of phenol and a phenol derivative having a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol. That is, it suffices to have a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, which may be phenol or a phenol derivative. One type of phenol may be used, or two or more types may be used in combination.
The phenol derivative has a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, and at least one of the other hydrogen atoms bonded to the aromatic ring is an alkyl group having 1 to 15 carbon atoms. Substituted alkylphenols are preferred. The substitution position of the alkyl group in the alkylphenol may be any of the ortho, meta, and para positions. In one molecule of alkylphenol, the number of hydrogen atoms substituted with an alkyl group is 1 to 4, preferably 1 to 2, and particularly preferably 1.

The carbon number of the alkyl group in the alkylphenol is preferably 1-10. As the alkylphenol, nonylphenol and cresol are preferably used. Nonylphenol is particularly preferable in terms of improving the compatibility between the polyol (Ab) and the polyisocyanate compound and improving the cell appearance.

Examples of aromatic amines include aniline, phenylenediamine, tolylenediamine, and diaminodiphenylmethane. Among these, aniline is preferred from the viewpoints of liquidity at room temperature and easy handling, the viscosity of Mannich polyol does not become too high, and cost.

As the 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. Specifically, it 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 subjecting the above-mentioned phenols and / or aromatic amines, aldehydes, and alkanolamines to a 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 the total of phenols and aromatic amines is preferably 0.3 mol or more and 3 mol or less. When the ratio of the aldehydes is at least the lower limit of the above range, good dimensional stability of the rigid foam can be easily obtained. If it is not more than the upper limit, 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 resulting 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 at least the lower limit of the above range, a rigid foam having good strength can be easily obtained. When the amount is not more than the upper limit value, 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, it is preferably from 0.7 mol to 5 mol, particularly preferably from 0.7 mol to 3.5 mol.

The alkylene oxide used for the production of Mannich polyol is preferably at least one selected from the group consisting of ethylene oxide (hereinafter also referred to as EO), propylene oxide (hereinafter also referred to as PO), and butylene oxide.
When using EO and / or PO, any of the following methods may be used.
(1) A method of ring-opening addition polymerization of EO alone.
(2) A method of ring-opening addition polymerization of PO alone.
(3) A method of ring-opening addition polymerization of a mixture of PO and EO.
(4) A method of ring-opening addition polymerization by arbitrarily combining the above methods (1) to (3).

By reacting the alkylene oxide with the active hydrogen atom of the initiator, the alkylene oxide undergoes ring-opening addition to produce a polyol having an oxyalkylene group. Hydroxyalkyl group is formed by ring-opening addition of one molecule of alkylene oxide to active hydrogen atom, and alkylene oxide is ring-opening addition to the hydroxyl group, and this reaction is repeated to form a chain of oxyalkylene groups. To do. When the alkylene oxide is EO, the oxyethylene group is linked, and when the alkylene oxide is PO, the oxypropylene group is linked.
The addition amount of alkylene oxide added to the initiator is preferably 2 to 30 mol, particularly preferably 4 to 20 mol, based on 1 mol of the total of phenols and aromatic amines 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 it is below the upper limit of the said range.

The hydroxyl value of the polyol (Ab) is preferably from 100 to 800 mgKOH / g, more preferably from 200 to 700 mgKOH / g, particularly preferably from 250 to 650 mgKOH / g.
It is preferable that the hydroxyl value of the polyol (Ab) 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 amount is not more than the upper limit of the above range, the amount of the alkylene oxide-derived oxyalkylene chain present in the Mannich polyol increases, and the viscosity of the Mannich polyol tends to decrease. Moreover, the brittleness of the manufactured rigid foam is suppressed, the adhesiveness with the base material is easily obtained, and the compressive strength is improved.

The content of the polyol (Ab) in the polyol composition (Pb) is 5 to 100% by mass, preferably 5 to 80% by mass, more preferably 5 to 60% by mass, and particularly preferably 5 to 50% by mass. When the content of the polyol (Ab) is not less than the lower limit of the above range, a rigid foam having good adhesion and flame retardancy can be obtained. When it is at most the upper limit of the above range, the viscosity of the polyol system liquid does not become too high and handling is easy.

[Polyol (Bb)]
The polyol (Bb) is a polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aliphatic amine as an initiator.
The polyol composition (Pb) preferably contains a polyol (Bb) in addition to the polyol (Ab). The polyol (Bb) contributes to lowering the viscosity and improving the reactivity of the polyol system liquid. As the polyol (Bb), only one type may be used, or two or more types may be used in combination.

The aliphatic amine as the initiator is preferably an aliphatic amine having 2 to 4 active hydrogen atoms. Specific examples include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as ethylenediamine, propylenediamine and 1,6-hexanediamine. Of these, ethylenediamine is preferred.
Examples of the alkylene oxide used for producing the polyol (Bb) include ethylene oxide, propylene oxide, butylene oxide and the like. It is preferable that at least propylene oxide or butylene oxide is contained, and at least propylene oxide is particularly preferably contained.

Specifically, the use of propylene oxide alone or the combined use of ethylene oxide and propylene oxide is preferable. When used in combination, ethylene oxide and propylene oxide may be reacted after being mixed or sequentially.
When ethylene oxide is used, the content of ethylene oxide (hereinafter also referred to as total ethylene oxide content or total EO content) in the total amount of alkylene oxide used in the production of polyol (Bb) is preferably 5 to 55% by mass, 10 to 50% by mass is more preferable, and 15 to 45% by mass is particularly preferable. When the total EO content is not less than the lower limit of the above range, the polyol does not have too high a viscosity and is easy to handle. When the amount is not more than the upper limit of the above range, the reaction does not become too fast and the foaming reaction is easily controlled.
In this specification, when ring-opening addition polymerization of different alkylene oxides such as when ethylene oxide is ring-opening addition polymerization after propylene oxide ring-opening addition polymerization, out of the total amount of alkylene oxide. The ratio of ethylene oxide finally subjected to ring-opening addition polymerization is also referred to as terminal EO content (unit: mass%).

The number of hydroxyl groups in the polyol (Bb) is preferably 2-4. When it is at least the lower limit of the above range, the strength of the rigid foam is improved and shrinkage is suppressed. When it is at most the upper limit of the above range, the viscosity of the polyol does not become too high and handling is easy, and the fluidity during molding is also good.
The hydroxyl value of the polyol (Bb) is preferably from 300 to 1,000 mgKOH / g, more preferably from 350 to 900 mgKOH / g, particularly preferably from 400 to 800 mgKOH / g. When the hydroxyl value of the polyol (Bb) is not less than the lower limit of the above range, the reaction with the polyisocyanate compound is promoted, and the curing property at the time of molding is improved. When the amount is not more than the upper limit of the above range, the brittleness of the rigid foam is suppressed, and the strength of the rigid foam becomes good.

The content of the polyol (Bb) in the polyol composition (Pb) is preferably 20 to 70% by mass, more preferably 25 to 65% by mass, and particularly preferably 30 to 60% by mass. When the content of the polyol (Bb) is not less than the lower limit of the above range, the compatibility between the polyol composition (Pb) and the hydrofluoroolefins (I) is improved, and separation of the polyol system liquid is suppressed. The Further, the curing property at the time of molding is also good. Separation of a polyol system liquid is suppressed as it is below the upper limit of the said range.

[Polyol (Cb)]
The polyol (Cb) is a polyether polyol obtained by ring-opening addition polymerization of an alkylene oxide using an aromatic amine (excluding a Mannich condensation product) as an initiator. As the polyol (Cb), only one type may be used, or two or more types may be used in combination.

As the aromatic amine as the initiator, amines having an aromatic ring having 4 to 12 active hydrogen atoms are preferably used. Specific examples thereof include phenylenediamine, tolylenediamine, diaminodiphenylmethane and the like.
Of these initiators, tolylenediamine is particularly preferred because of its low thermal conductivity. Tolylenediamine may be o-tolylenediamine or m-tolylenediamine.

Examples of the alkylene oxide used for the production of the polyol (Cb) include ethylene oxide, propylene oxide, butylene oxide and the like. It is preferable to contain at least ethylene oxide, and the combined use of ethylene oxide and propylene oxide is preferable. Ethylene oxide and propylene oxide may be reacted after mixing or sequentially.
The ethylene oxide content (total EO content) in the total amount of alkylene oxide used in the production of the polyol (Cb) is preferably 0 to 60% by mass, more preferably 0 to 45% by mass, and particularly preferably 0 to 30% by mass. preferable. If the total EO content is less than or equal to the upper limit of the above range, the moldability is good because of the appropriate reactivity.

The number of hydroxyl groups in the polyol (Cb) is preferably 4 to 12, more preferably 4 to 10, and particularly preferably 4 to 8. When it is at least the lower limit of the above range, the strength of the rigid foam becomes good and the shrinkage of the rigid foam is suppressed. When it is at most the upper limit of the above range, the fluidity during foaming and molding will be good.
The hydroxyl value of the polyol (Cb) is preferably 100 to 800 mgKOH / g, more preferably 200 to 600 mgKOH / g, and particularly preferably 300 to 500 mgKOH / g. When the hydroxyl value of the polyol (Cb) is not less than the lower limit of the above range, the closed cell rate of the rigid foam is improved and good thermal conductivity is obtained. If it is not more than the upper limit of the above range, the brittleness of the rigid foam is suppressed and the strength of the rigid foam is improved.

The content of the polyol (Cb) in the polyol composition (Pb) is preferably 20 to 60% by mass, more preferably 30 to 55% by mass, and particularly preferably 30 to 50% by mass. Thermal conductivity becomes favorable in content of a polyol (Cb) being more than the lower limit of the said range. When the amount is not more than the upper limit of the above range, an increase in the viscosity of the polyol system liquid is suppressed, handling is easy, and fluidity during foaming / molding of the rigid foam is improved.

[Polymer-dispersed polyol (Wb)]
The polyol composition (Pb) contains polymer particles. Specifically, it is preferable to prepare a polymer-dispersed polyol (Wb) in which polymer particles are dispersed in the base polyol (Wb ′), and to contain the polymer-dispersed polyol (Wb) in the polyol composition (Pb). .
The presence of polymer particles in the polyol composition (Pb) can suppress the shrinkage of the rigid foam and improve the dimensional stability. This effect is particularly useful in producing lower density rigid foams. The polymer-dispersed polyol (Wb) may be one type or a combination of two or more types.

The content of the polymer particles in the entire polyol composition (Pb) is preferably 0.002 to 30% by mass, more preferably 0.02 to 20% by mass, and particularly preferably 0.5 to 10% by mass. Within the above range, shrinkage of the obtained rigid foam can be effectively suppressed while maintaining heat insulation performance. Moreover, the storage stability at normal temperature and the storage stability at high temperature are good.
The polymer-dispersed polyol (Wb) in the present invention C is the same as the polymer-dispersed polyol (Wa) in the present invention A including preferred embodiments.
The base polyol (Wb ′) in the production of the polymer-dispersed polyol (Wb) in the present invention C is the same as the base polyol (Wa ′) in the present invention A, including preferred embodiments. The base polyol (Wb ′) may be the same as any of the polyols (Ab) to (Cb).

[Other polyols (Eb)]
The polyol composition (Pb) may contain other polyol (Eb) that does not belong to any of the polyol (Ab), the polyol (Bb), the polyol (Cb), or the polymer-dispersed polyol (Wb).
Examples of the other polyol (Eb) include polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polyol. The hydroxyl value of the polyol (Eb) is preferably 200 to 800 mgKOH / g, more preferably 200 to 600 mgKOH / g, and particularly preferably 200 to 500 mgKOH / g.
The content of the polyol (Eb) in the polyol composition (Pb) is preferably 80% by mass or less, more preferably 50% by mass or less, further preferably 25% by mass or less, and particularly preferably 20% by mass or less.

<Polyol composition (Pb)>
The polyol composition (Pb) preferably contains a polyol (Ab) and polymer particles, and further contains one or more selected from polyol (Bb) and polyol (Cb). Optionally, other polyol (Eb) may be included. The polymer particles are preferably derived from a polymer-dispersed polyol (Wb).
The average number of hydroxyl groups as a whole of the polyol composition (Pb) is 2 to 8, preferably 2.5 to 7.5. When the average number of hydroxyl groups is within the above range, the compression strength of the rigid foam is improved and shrinkage can be suppressed, so that the dimensional stability is good.
The average hydroxyl value of the polyol composition (Pb) as a whole is 100 to 800 mgKOH / g, preferably 200 to 700 mgKOH / g, particularly preferably 200 to 600 mgKOH / g. When the average hydroxyl value is in the above range, rapid thickening behavior during foaming and molding is suppressed, and fluidity and moldability are improved.

In the present invention B, all of the polyol composition (Pb) may be polyol (Ab) and polymer particles.
Preferred combinations in the case of producing a rigid polyurethane foam with the urethane formulation described below are shown below.
(Combination 2) The polyol composition (Pb) comprises 5 to 80 mass% of the polyol (Ab), 20 to 70 mass% of the polyol (Bb), 10 to 60 mass% of the polyol (Cb), and the polyol (Eb ) And a polyol (Wb), and the content of polymer particles is 0.002 to 10% by mass.

(Combination 3)
The polyol composition (Pb)
5 to 60 mass of the polyol (Ab);
20 to 65% by mass of the polyol (Bb),
20 to 55% by mass of the polyol (Cb);
0 to 25% by mass of the polyol (Eb);
A polyol (Wb),
The polymer particle content is 0.01 to 10% by mass.
(Combination 4)
The polyol composition (Pb)
5 to 50 mass of the polyol (Ab);
20 to 60% by mass of the polyol (Bb),
20 to 50% by mass of the polyol (Cb);
0 to 25% by mass of the polyol (Eb);
A polyol (Wb),
The polymer particle content is 0.01 to 7% by mass.

Preferred combinations for producing a rigid polyisocyanurate foam with the isocyanurate formulation described below are shown below.
(Combination 5) The polyol composition (Pb) comprises 20 to 100% by mass of the polyol (Ab) and 0 to 80% by mass of the polyol (Eb). (Combination 6) The polyol composition (Pb) is composed of 20 to 100% by mass of the polyol (Ab), 0 to 80% by mass of the polyol (Eb), and the polyol (Wb). 0.01 to 7% by mass.

<Polyisocyanate compound>
The polyisocyanate compound in the present invention B is the same as the polyisocyanate compound in the present invention A including preferred embodiments.
In the present invention B, in the case of an isocyanurate formulation mainly using a catalyst that promotes the trimerization reaction of isocyanate groups as a catalyst, the amount of polyisocyanate compound used is preferably 100 to 350, preferably 100 to 300 in terms of the isocyanate index. Particularly preferred.

<Foaming agent>
The foaming agent in the present invention B is the same as the foaming agent in the present invention A including preferred embodiments.
The hydrofluoroolefins represented by formula (I) are the same as the hydrofluoroolefins represented by formula (I) in Invention A, including preferred embodiments.
<Catalyst>
The catalyst in the present invention B is the same as the catalyst in the present invention A including preferred embodiments.
<Foam stabilizer>
The foam stabilizer in the present invention B is the same as the foam stabilizer in the present invention A including preferred embodiments.
<Other ingredients>
Other compounding agents in the present invention B are the same as other compounding agents in the present invention A, including preferred embodiments.

<The manufacturing method of the rigid foam of this invention B>
The manufacturing method of the rigid foam of the present invention B is a rigid foam synthesis by reacting and foaming a polyol composition (Pb) and a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst by a continuous board molding method. This is a method for producing a resin.
The continuous board molding method is to produce a laminate in which a rigid foam is sandwiched between these face materials by supplying the foamed stock solution composition between two continuously supplied face materials and foaming. This method is used for manufacturing a heat insulating material for architectural use. Rigid foam as a building material needs flame retardance from the viewpoint of fire resistance. In order to obtain a good moldability in the continuous board molding method, a fluidity capable of satisfactorily pouring the foaming stock solution composition is required.

In the present invention B, since the polyol composition (Pb) contains Mannich polyol in particular, high flame retardancy is easily obtained. Further, when the present invention B is applied to the continuous board molding method, the fluidity and the curing property are good, so that the moldability is excellent.
Representative examples of the face material include kraft paper, vinyl chloride film and sheet, iron plate, slate plate, gypsum plate and the like.
Typical examples of the use of the rigid foam obtained by the continuous board molding method include a heat insulating material for buildings, a heat insulating material for refrigeration equipment such as a vending machine, and the like.

The present invention B can also be applied to the production of rigid foams by spraying or pouring.
The spray method is a method in which a rigid foam is sprayed and applied. The spray method is roughly classified into an air spray method and an airless spray method. Of these, the airless spray method in which the blended liquid is mixed with a mixing head and foamed is particularly preferable. As a specific spray method, the method in Invention C can be used.
The injection method is a method in which a rigid foam material is injected into a frame such as a mold and foamed. As a specific injection method, the method in Invention A can be used.

According to the present invention B, a rigid foam having good characteristics can be obtained by using the hydrofluoroolefins (I) as the foaming agent.
Specifically, for rigid foams, it is desirable that the polyol system liquid has good storage stability, good moldability, and good dimensional stability even when the density is reduced. . According to the present invention B, it is possible to obtain a rigid foam in which all of these characteristics are good.
Further, by combining the polyol (Ab) and polymer particles with the hydrofluoroolefins (I), a rigid foam having good dimensional stability and low thermal conductivity, that is, having good heat insulation performance can be obtained. Moreover, according to the present invention B, the high-temperature storage stability of the polyol system liquid is improved.

<Description of Invention C>
The “polyol composition (Pc)” in the present invention C is a mixture of all polyols (including polymer-dispersed polyols) used for the reaction with the polyisocyanate compound.
The “polyol system liquid” in the present invention C is a liquid to be reacted with the polyisocyanate compound, and in addition to the polyol composition (Pc), a blending agent as necessary, such as a foaming agent, a foam stabilizer, a catalyst and the like. Contains liquid.
The “Mannich condensation product” in the present invention C is generally obtained by subjecting an aromatic compound such as aniline or phenols, an aldehyde, and an amine to a condensation reaction (hereinafter sometimes referred to as a Mannich condensation reaction). Means a compound.
The “polymer-dispersed polyol” in the present invention C is obtained by polymerizing a monomer having a polymerizable unsaturated bond in a base polyol (Wc ′) such as a polyether polyol or a polyester polyol to form polymer particles. It is a polyol (Wc) in which the polymer particles are dispersed in the base polyol (Wc ′).

[Polyol (Ac)]
The polyol composition (Pc) in the present invention C contains a polyol (Ac).
Polyol (Ac) is a polyether polyol (Mannich polyol) obtained by ring-opening addition polymerization of alkylene oxide using a Mannich condensation product obtained by reacting phenols, aldehydes and alkanolamines as an initiator. . The Mannich polyol contributes to the improvement of flame retardancy.

The phenol is at least one selected from the group consisting of phenol and a phenol derivative having a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol. That is, it suffices to have a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, which may be phenol or a phenol derivative. One type of phenol may be used, or two or more types may be used in combination.

The phenol derivative has a hydrogen atom in at least one ortho position with respect to the hydroxyl group of phenol, and at least one of the other hydrogen atoms bonded to the aromatic ring is an alkyl group having 1 to 15 carbon atoms. Substituted alkylphenols are preferred. The substitution position of the alkyl group in the alkylphenol may be any of the ortho, meta, and para positions. In one molecule of alkylphenol, the number of hydrogen atoms substituted with an alkyl group is 1 to 4, preferably 1 to 2, and 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 polyol (Ac) and the polyisocyanate compound and improving the cell appearance.

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 subjecting the above phenols, aldehydes, and alkanolamines to a 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 at least the lower limit of the above range, good dimensional stability of the rigid foam can be easily obtained. If it is not more than the upper limit, 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 resulting 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 at least the lower limit of the above range, a rigid foam with good strength can be easily obtained. When the amount is not more than the upper limit, a good flame-retardant rigid foam can be easily obtained. Moreover, from the flame-retardant 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, it is preferably from 0.7 mol to 5 mol, particularly preferably from 0.7 mol to 3.5 mol.

The alkylene oxide used for the production of Mannich polyol is preferably at least one selected from the group consisting of ethylene oxide (hereinafter also referred to as EO), propylene oxide (hereinafter also referred to as PO), 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 using EO and / or PO, any of the following methods may be used.
(1) A method of ring-opening addition polymerization of EO alone.
(2) A method of ring-opening addition polymerization of PO alone.
(3) A method of ring-opening addition polymerization of a mixture of PO and EO.
(4) A method of ring-opening addition polymerization by arbitrarily combining the above methods (1) to (3).

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 the phenols used in the Mannich condensation reaction. When the added amount of alkylene oxide is not less than the lower limit of the above range, the hydroxyl value and viscosity of the produced Mannich polyol tend to be low. It is easy to suppress shrinkage | contraction of a rigid foam as it is below the upper limit of the said range.
The ethylene oxide content (hereinafter also referred to as total ethylene oxide content or total EO content) in the total amount of alkylene oxide used in the ring-opening addition polymerization reaction is preferably 10 to 100% by mass, and 20 to 100% by mass Is particularly preferred. When the viscosity is not less than the lower limit of the above range, the Mannich polyol viscosity tends to be low, which is preferable for reducing the viscosity of the polyol composition (Pc) and the polyol system solution.
When a plurality of Mannich polyols are used in combination as a polyol (Ac), the total EO content is a value of the entire polyol (Ac).

By reacting an alkylene oxide with the active hydrogen atom of the initiator, the alkylene oxide undergoes ring-opening addition to produce a polyol having an oxyalkylene group. Hydroxyalkyl group is formed by ring-opening addition of one molecule of alkylene oxide to active hydrogen atom, and alkylene oxide is ring-opening addition to the hydroxyl group, and this reaction is repeated to form a chain of oxyalkylene groups. To do.

The hydroxyl value of the polyol (Ac) is preferably from 100 to 800 mgKOH / g, more preferably from 200 to 550 mgKOH / g, particularly preferably from 250 to 450 mgKOH / g.
It is preferable for the hydroxyl value of the polyol (Ac) to be equal to or greater than the lower limit of the above range since 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 amount is not more than the upper limit of the above range, the amount of the alkylene oxide-derived oxyalkylene chain present in the Mannich polyol increases, and the viscosity of the Mannich polyol tends to decrease. Further, the brittleness of the manufactured rigid foam is suppressed, and the adhesiveness is likely to be obtained.

The content of the polyol (Ac) in the polyol composition (Pc) is 20 to 100% by mass, preferably 20 to 70% by mass, more preferably 25 to 60% by mass, further preferably 30 to 60% by mass, 30 to 50% by mass is particularly preferable. When the content of the polyol (Ac) is not less than the lower limit of the above range, a rigid foam having good adhesion and flame retardancy can be obtained. When the viscosity is not more than the upper limit of the above range, the viscosity of the polyol system liquid does not become too high and handling is easy.

[Polyol (Bc)]
The polyol (Bc) is a polyether polyol obtained by subjecting an alkylene oxide to ring-opening addition polymerization using an amine compound (excluding a Mannich condensation product) as an initiator. The polyol (Bc) contributes to the effect of increasing the initial activity of the urethanization reaction. As the polyol (Bc), only one type may be used, or two or more types may be used in combination.
The number of active hydrogen atoms of the amine compound as an initiator is preferably 2 to 6, more preferably 3 to 6, and particularly preferably 3 to 4.

Examples of amine compounds that are initiators include aliphatic amine compounds such as alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.) and alkylamines (ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine). Saturated aromatic amine compounds such as N-aminomethylpiperazine and N- (2-aminoethyl) piperazine; aromatic amine compounds such as aniline, tolylenediamine, xylylenediamine, and diphenylmethanediamine (not including Mannich condensation products) Can be mentioned. From the viewpoint of the effect of increasing the initial activity of the urethanization reaction, an aliphatic amine compound or a saturated cyclic amine compound is preferred.

Examples of alkylene oxide used in the production of polyol (Bc) include ethylene oxide, propylene oxide, butylene oxide and the like. Use of propylene oxide alone or a combination of ethylene oxide and propylene oxide is preferred. When used in combination, ethylene oxide and propylene oxide may be reacted after being mixed or sequentially.

The number of hydroxyl groups in the polyol (Bc) is preferably 2 to 6, more preferably 3 to 6, and particularly preferably 3 to 4. When it is at least the lower limit of the above range, shrinkage of the rigid foam is suppressed, and when it is at most the upper limit, the viscosity is in an appropriate range and handling is easy.
The hydroxyl value of the polyol (Bc) is preferably 100 to 800 mgKOH / g, more preferably 200 to 600 mgKOH / g, and particularly preferably 300 to 500 mgKOH / g. When the hydroxyl value of the polyol (Bc) is not less than the lower limit of the above range, the strength of the rigid foam is improved, shrinkage is suppressed, and the dimensional stability is improved. When it is below the upper limit of the above range, the viscosity does not become too high and handling is easy.

In the present invention C, the polyol (Bc) is not essential, but when the polyol (Bc) is used, the content of the polyol (Bc) in the polyol composition (Pc) is preferably more than 0% by mass and 70% by mass or less. 1 to 40% by mass is more preferable, 3 to 35% by mass is further preferable, and 3 to 30% by mass is particularly preferable. When the content of the polyol (Bc) is not less than the lower limit of the above range, the shrinkage of the rigid foam is suppressed, and good dimensional stability is easily obtained. When it is at most the upper limit of the above range, it is easy to ensure good curing characteristics (curing properties) during molding of the rigid foam.

[Polyol (Cc)]
The polyol (Cc) is a polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using a polyhydric alcohol having 2 to 8 active hydrogen atoms as an initiator. By using polyol (Cc) in addition to polyol (Ac), it is possible to prevent the viscosity of the polyol composition (Pc) from becoming too high.
As the polyol (Cc), only one type may be used, or two or more types may be used in combination.

Examples of the polyhydric alcohol that is an initiator include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,6- Dihydric alcohols such as hexanediol; trihydric alcohols such as glycerin, trimethylolpropane, 1,2,6-hexanetriol; tetrahydric alcohols such as pentaerythritol, diglycerin, tetramethylolcyclohexane, methylglucoside; sorbitol, mannitol, Hexavalent alcohols such as dulcitol; octavalent alcohols such as sucrose.
Of these, glycerin is preferred in terms of a good balance between dimensional stability and viscosity.

Examples of the alkylene oxide used for the production of the polyol (Cc) include ethylene oxide, propylene oxide, butylene oxide and the like. Use of propylene oxide alone or a combination of ethylene oxide and propylene oxide is preferred. When used in combination, ethylene oxide and propylene oxide may be reacted after being mixed or sequentially.
When ethylene oxide is used in combination with the production of the polyol (Cc), the ethylene oxide content (total EO content) in the total amount of alkylene oxide is more than 0% by mass, preferably 50% by mass or less, more preferably 5 to 40% by mass. Preferably, 10 to 20% by mass is particularly preferable. When the ethylene oxide content is at least the lower limit of the above range, the reactivity is good, and when it is at most the upper limit of the above range, the brittleness of the resulting rigid foam is suppressed.

The number of hydroxyl groups in the polyol (Cc) is 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 4. When it is at least the lower limit of the above range, the shrinkage of the rigid foam is suppressed and the dimensional stability is improved. When it is at most the upper limit, the viscosity does not become too high and handling is easy.
The hydroxyl value of the polyol (Cc) is preferably from 100 to 800 mgKOH / g, more preferably from 200 to 700 mgKOH / g, particularly preferably from 300 to 600 mgKOH / g. When the hydroxyl value of the polyol (Cc) is not less than the lower limit of the above range, the strength of the rigid foam becomes good and shrinkage is suppressed. When the viscosity is not more than the upper limit of the above range, the viscosity is not excessively high and handling is easy, and the mixing property between the polyisocyanate and the compound is improved.

In the invention C, the polyol (Cc) is not essential, but when the polyol (Cc) is used, the content of the polyol (Cc) in the polyol composition (Pc) is preferably more than 0% by mass and 40% by mass or less. 1 to 35% by mass is more preferable, and 3 to 30% by mass is particularly preferable. When the content of the polyol (Cc) is not less than the lower limit of the above range, the polyol system liquid can be reduced in viscosity, and good moldability is easily obtained. When the amount is not more than the upper limit of the above range, good compressive strength of the rigid foam is easily obtained.

[Polyol (Dc)]
The polyol (Dc) is a polyester polyol produced by polycondensation of a monomer mixture containing an aromatic compound.
The polyol composition (Pc) may contain a polyol (Dc) as necessary. The polyol (Dc) contributes to the improvement of flame retardancy.
As the polyol (Dc), only one type may be used, or two or more types may be used in combination.

The monomer mixture used for producing the polyol (Dc) preferably contains a dicarboxylic acid compound and a polyhydric alcohol, and one or both of the dicarboxylic acid compound and the polyhydric alcohol contain a compound having an aromatic ring.
In particular, the polyol (Dc) preferably contains an aromatic polyester polyol obtained by polycondensation reaction between a dicarboxylic acid having an aromatic ring and a polyhydric alcohol not having an aromatic ring.
Examples of the dicarboxylic acid having an aromatic ring include terephthalic acid, isophthalic acid, and orthophthalic acid. Terephthalic acid is more preferable in terms of improving heat resistance.
Examples of the polyhydric alcohol having no aromatic ring include ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol, dipropylene glycol (DPG), 1,4-butanediol, 1,6-hexanediol (1,6 -HD), diol compounds such as neopentyl glycol; and triol compounds such as glycerin and trimethylolpropane. Ethylene glycol or diethylene glycol is more preferable, and diethylene glycol is particularly preferable in that the viscosity of the polyol (Dc) can be lowered and a good flame retardancy improving effect can be easily obtained.

The average number of hydroxyl groups in the polyol (Dc) is preferably 2 to 3, and 2 is particularly preferable. When the average number of hydroxyl groups is 3 or less, the viscosity can be kept low and the handling is easy.
The hydroxyl value of the polyol (Dc) is preferably 100 to 500 mgKOH / g, more preferably 150 to 350 mgKOH / g, and particularly preferably 180 to 300 mgKOH / g. When the hydroxyl value of the polyol (Dc) is not less than the lower limit of the above range, the shrinkage of the rigid foam is easily suppressed, and when it is not more than the upper limit of the above range, the brittleness of the rigid foam is suppressed and good physical properties are easily obtained. .
In the invention C, the polyol (Dc) is not essential, but when the polyol (Dc) is used, the content of the polyol (Dc) in the polyol composition (Pc) is preferably more than 0% by mass and 70% by mass or less. 10 to 65% by mass is more preferable, and 30 to 60% by mass is particularly preferable. When the content of the polyol (Dc) is not less than the lower limit of the above range, an effect of reducing the viscosity of the polyol system liquid is easily obtained. When the amount is not more than the upper limit of the above range, shrinkage of the rigid foam is easily suppressed.

[Polymer-dispersed polyol (Wc)]
The polyol composition (Pc) contains polymer particles. Specifically, it is preferable to prepare a polymer-dispersed polyol (Wc) in which polymer particles are dispersed in the base polyol (Wc ′), and to contain the polymer-dispersed polyol (Wc) in the polyol composition (Pc). .
The presence of polymer particles in the polyol composition (Pc) can suppress the shrinkage of the rigid foam and improve the dimensional stability. This effect is particularly useful in producing lower density rigid foams. The polymer-dispersed polyol (Wc) may be one type or a combination of two or more types.

The content of the polymer particles in the entire polyol composition (Pc) is preferably 0.002 to 30% by mass, more preferably 0.02 to 20% by mass, and particularly preferably 0.02 to 10% by mass. Within the above range, shrinkage of the obtained rigid foam can be effectively suppressed while maintaining heat insulation performance. Moreover, the storage stability at normal temperature and the storage stability at high temperature are good.
The polymer-dispersed polyol (Wc) in the present invention C is the same as the polymer-dispersed polyol (Wa) in the present invention A including preferred embodiments.
The base polyol (Wc ′) in the production of the polymer-dispersed polyol (Wc) in the present invention C is the same as the base polyol (Wa ′) in the present invention A including preferred embodiments. The base polyol (Wc ′) may be the same as any of the polyols (Ac) to (Cc).

[Other polyols (Ec)]
The polyol composition (Pc) contains other polyol (Ec) that does not belong to any of the polyol (Ac), polyol (Bc), polyol (Cc), polyol (Dc), or polymer-dispersed polyol (Wc). You may let them.
Examples of the other polyol (Ec) include polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polyol. The hydroxyl value of the polyol (Ec) is preferably 5 to 1,000 mgKOH / g, more preferably 10 to 800 mgKOH / g, and particularly preferably 20 to 700 mgKOH / g.
The content of the polyol (Ec) in the polyol composition (Pc) is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

<Polyol composition (Pc)>
The polyol composition (Pc) preferably contains a polyol (Ac) and polymer particles, and further contains one or more selected from polyol (Bc), polyol (Cc), and polyol (Dc). Optionally, other polyols (Ec) may be included. The polymer particles are preferably derived from a polymer-dispersed polyol (Wc). The average number of hydroxyl groups as a whole of the polyol composition (Pc) is 2 to 8, preferably 2.5 to 7.5. When the average number of hydroxyl groups is not less than the lower limit of the above range, shrinkage of the rigid foam is suppressed and dimensional stability is improved. When it is at most the upper limit value, the viscosity of the polyol system liquid becomes moderate and the moldability becomes good.
The average hydroxyl value of the whole polyol composition (Pc) is 100 to 800 mgKOH / g, preferably 150 to 700, more preferably 200 to 600. When the average hydroxyl value is at least the lower limit of the above range, the shrinkage of the rigid foam is suppressed and the dimensional stability is improved. The brittleness of a rigid foam is suppressed as it is below an upper limit.

In the present invention C, the polyol composition (Pc) may be all polyol (Ac) and polymer particles.
A more preferable composition of the polyol composition (Pc) is as follows.
Preferred combinations for producing a rigid polyisocyanurate foam with the isocyanurate formulation described below are shown below.
(Combination 1) The polyol composition (Pc) comprises 30 to 50% by mass of the polyol (A), 1 to 30% by mass of the polyol (Bc), 30 to 70% by mass of the polyol (Dc), Wc), and the polymer particle content is 0.02 to 7% by mass.
(Combination 2) The polyol composition (Pc) comprises 30 to 50% by mass of the polyol (Ac), 1 to 30% by mass of the polyol (Bc), 1 to 30% by mass of the polyol (Cc), It is composed of 10 to 60% by mass of Dc) and polyol (Wc), and the content of polymer particles is 0.02 to 7% by mass.

Preferred combinations in the case of producing a rigid polyurethane foam with the urethane formulation described below are shown below.
(Combination 5) The polyol composition (Pc) comprises 30 to 70% by mass of the polyol (Ac), 10 to 50% by mass of the polyol (Bc), 5 to 30% by mass of the polyol (Cc), Wc), and the polymer particle content is 0.02 to 7% by mass.
(Combination 7) The polyol composition (Pc) comprises 30 to 60% by mass of the polyol (Ac), 10 to 60% by mass of the polyol (Bc), 5 to 20% by mass of the polyol (Cc), Wc), and the polymer particle content is 0.02 to 7% by mass.

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

The amount of polyisocyanate compound used is represented by 100 times the number of isocyanate groups relative to the total number of active hydrogen atoms of the polyol composition (Pc) and other active hydrogen compounds present in the polyol system liquid (hereinafter referred to as this A numerical value expressed by 100 times is referred to as “isocyanate index (INDEX)”, preferably 50 to 400.
In particular, in the case of a urethane formulation mainly using a urethanization catalyst as a catalyst, the amount of polyisocyanate compound used is preferably 50 to 170, particularly preferably 70 to 150 in terms of the isocyanate index.
In the case of an isocyanurate formulation mainly using a catalyst that promotes a trimerization reaction of an isocyanate group as a catalyst, the amount of the polyisocyanate compound used is preferably 100 to 350, more preferably 100 to 300, in terms of the isocyanate index. Is particularly preferred.

<Foaming agent>
The foaming agent in the present invention C is the same as the foaming agent in the present invention A including preferred embodiments.
The hydrofluoroolefins represented by the formula (I) are the same as the hydrofluoroolefins represented by the formula (I) described above including preferred embodiments.
<Catalyst>
The catalyst in the present invention C is the same as the catalyst in the present invention A including preferred embodiments.

<Foam stabilizer>
The foam stabilizer in the present invention C is the same as the foam stabilizer in the present invention A including preferred embodiments.
In the present invention C, a foam stabilizer is used to form good bubbles. Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. These can use a commercial item. The amount of the foam stabilizer used can be appropriately selected, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyol composition (Pc).

<Other ingredients>
The other compounding agents in Invention C are the same as the other compounding agents in Invention A, including preferred embodiments.
In the present invention C, a known compounding agent can be used in addition to the polyol composition (Pc), polyisocyanate compound, catalyst, foaming agent, and foam stabilizer described above. Compounding agents include fillers such as calcium carbonate and barium sulfate; anti-aging agents such as antioxidants and UV absorbers; flame retardants, plasticizers, colorants, anti-fungal agents, foam breakers, dispersants, discoloration prevention Agents and the like. The amount of other compounding agents can be appropriately selected, but is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyol composition (Pc).

<Method for producing rigid foam of invention C>
The method for producing a rigid foam of the present invention C is a method for producing a rigid foam synthetic resin by reacting a polyol composition (Pc) with a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst.
In particular, a spray method in which a rigid foam is sprayed and applied can be suitably used. In the spray method, for example, a polyol system liquid and a polyisocyanate compound are each sent by a pump, reacted while sprayed from a spray gun onto a substrate such as a wall surface to be constructed, and foamed on the substrate to insulate. It is a method of using a material or the like. The spray method is roughly classified into an air spray method and an airless spray method. Of these, the airless spray method in which the blended liquid is mixed with a mixing head and foamed is particularly preferable.
For example, a spray method is often used in construction sites. Such a rigid foam as a building material needs flame retardancy from the viewpoint of fire resistance. In particular, when the spray method is employed, flame retardancy is required from the viewpoint of preventing fire accidents caused by welding sparks at the construction site.

In the invention C, in particular, since the polyol composition (Pc) contains Mannich polyol, high flame retardancy is easily obtained. Further, when the present invention C is applied to a spray method, a hard synthetic foamed resin can be obtained by a spray method having good dimensional stability and good flame retardancy.
In the spray method, it is preferable that the polyol system liquid and the polyisocyanate compound are sprayed on the base material and then cured at a high speed so that the liquid does not flow. For example, the rise time is preferably 8 to 25 seconds, particularly preferably 10 to 20 seconds.
Examples of the substrate include plywood, plywood, slate board, gypsum board and the like.
Examples of the articles that can be manufactured using the spray method include residential dew-preventing heat insulating materials, refrigerated warehouse heat insulating materials, and the like.

The present invention C is also applicable to the production of rigid foams by a continuous board molding method or an injection method.
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. It is used for the manufacture of heat insulating materials. The injection method is a method in which a rigid foam material is injected into a frame such as a mold and foamed.

According to the present invention C, a rigid foam having good characteristics can be obtained using the hydrofluoroolefins (I) as the foaming agent.
Specifically, for rigid foams, it is desirable that the polyol system liquid has good storage stability, good moldability, and good dimensional stability even when the density is reduced. . According to the present invention C, it is possible to obtain a rigid foam having all of these characteristics good.
Further, by combining the polyol (Ac) and polymer particles with the hydrofluoroolefins (I), a rigid foam having good dimensional stability and low thermal conductivity (that is, good heat insulation performance) can be obtained. Further, according to the present invention C, the high temperature storage stability of the polyol system liquid is improved.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
<Examples of Invention A>
The hydroxyl value of the polyol is a value measured according to JIS K 1557 (1970 edition).
The raw materials used in the following examples of the present invention A are as follows.
[Polyol (Aa)]
Polyol Aa1: obtained by ring-opening addition polymerization of EO to m-tolylenediamine, followed by ring-opening addition polymerization of alkylene oxide in the order of PO and EO in the presence of a potassium hydroxide catalyst, the water base value being 450 mgKOH / g Polyether polyol. Of the total of EO and PO, the E content (total EO content) is 25% by mass. The EO content at the end is 3% by mass.

Polyol Aa2: obtained by ring-opening addition polymerization of EO to m-tolylenediamine, followed by ring-opening addition polymerization of alkylene oxide in the order of PO and EO in the presence of a potassium hydroxide catalyst, having a hydroxyl value of 350 mgKOH / g Polyether polyol. Of the total of EO and PO, the EO content (total EO content) is 25% by mass. The EO content at the end is 11% by mass.
Polyol Aa3: A polyether polyol having a hydroxyl value of 350 mgKOH / obtained by ring-opening addition polymerization of only PO as an alkylene oxide to m-tolylenediamine.
Polyol Aa4: hydroxyl value obtained by ring-opening addition polymerization of only PO as alkylene oxide to a Mannich condensation product obtained by condensing nonylphenol, diethanolamine and formaldehyde at a ratio of 1 mol / 2.2 mol / 1.5 mol 470 mg KOH / g, polyether polyol having an average number of functional groups of 4.

[Polyol (Ba)]
Polyol Ba1: A polyether polyol having a hydroxyl value of 500 mgKOH / g, obtained by ring-opening addition polymerization of only PO as an alkylene oxide to sorbitol.
Polyol Ba2: A polyether polyol having a hydroxyl value of 385 mgKOH / g, obtained by ring-opening addition polymerization of only PO as an alkylene oxide to sorbitol.
Polyol Ba3: A polyether polyol having a hydroxyl value of 450 mgKOH / g, obtained by subjecting a mixture of sucrose and glycerin (mass ratio 2: 1) to ring-opening addition polymerization of only PO as an alkylene oxide.

[Polyol (Ca)]
Polyol Ca1: A polyether polyol having a hydroxyl value of 760 mgKOH / g obtained by ring-opening addition polymerization of only PO as an alkylene oxide to ethylenediamine.
Polyol Ca2: A polyether polyol having a hydroxyl value of 500 mgKOH / g, obtained by ring-opening addition polymerization of only PO as an alkylene oxide to monoethanolamine.
Polyol Ca3: A polyether polyol having a hydroxyl value of 450 mgKOH / g, obtained by ring-opening addition polymerization of PO as an alkylene oxide to ethylenediamine, followed by ring-opening polymerization of EO in the presence of a potassium hydroxide catalyst. Of the total of EO and PO, the EO content (total EO content) is 41% by mass.

[Polyol (Da)]
Polyol Da1: Polyester polyol obtained by polycondensation of diethylene glycol and terephthalic acid and having an average hydroxyl number of 2 and a hydroxyl value of 250 mgKOH / g (product name: Terol 563, manufactured by Oxide).
[Other polyols (Ea)]
Polyol Ea1: A polyether polyol having a hydroxyl value of 56 mgKOH / g, obtained by ring-opening addition polymerization of PO as alkylene oxide to glycerin and ring-opening addition polymerization of EO in the presence of a potassium hydroxide catalyst. Of the total of EO and PO, the EO content (total EO content) is 13% by mass.

Polyol Ea2: A polyether polyol having a hydroxyl value of 56 mgKOH / g obtained by ring-opening addition polymerization of PO as alkylene oxide to glycerin and ring-opening addition polymerization of EO in the presence of a potassium hydroxide catalyst. Of the total of EO and PO, the EO content (total EO content) is 20% by mass.
Polyol Ea3: A polyether polyol having a hydroxyl value of 410 mgKOH / g, obtained by subjecting pentaerythritol to ring-opening addition polymerization of only PO as an alkylene oxide.
Polyol Ea4: A polyether polyol having a hydroxyl value of 450 mgKOH / obtained by ring-opening addition polymerization of only PO as an alkylene oxide to dipropylene glycol.

[Polymer-dispersed polyol (Wa)]
As the polymer-dispersed polyol (Wa), polymer-dispersed polyols Wa1 to Wa6 produced by the method of the following production example with the composition shown in Table 1 below were used. The unit of the blending ratio in Table 1 is “part by mass”.
[Monomer having a polymerizable unsaturated bond]
Examples of the monomer having a polymerizable unsaturated bond for forming polymer particles include acrylonitrile (AN), vinyl acetate (Vac), methyl methacrylate (MMA), and polyfluoroalkyl methacrylate represented by the formula (1-1). (FMA) was used.

[Macromonomer]
The following two types were used as macromonomers.
Macromonomer M1: Polyol G / tolylene diisocyanate / 2-polyol G, tolylene diisocyanate (trade name: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-hydroxyethyl methacrylate (made by Junsei Kagaku Co.) Hydroxyethyl methacrylate = 1/1/1 molar ratio was prepared, reacted at 60 ° C for 1 hour, and further reacted at 80 ° C for 6 hours, resulting in a polymerizable non-polymerizable polymer having a hydroxyl value of 40 mgKOH / g. Macromonomer having a saturated group.

Macromonomer M2: Polyol F, Tolylene Diisocyanate (trade name: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-hydroxyethyl methacrylate (Pure Chemical Co., Ltd.) Hydroxyethyl methacrylate = 1/1/1 molar ratio was prepared, reacted at 60 ° C for 1 hour, and further reacted at 80 ° C for 6 hours, resulting in a polymerization resistance of 21 mgKOH / g. Macromonomer having a saturated group.
Polyol G: Glycerol is used as an initiator, and EO is subjected to ring-opening addition polymerization to the glycerol, and then a mixture of PO and EO [PO / EO = 46.2 / 53.8 (mass ratio)] is opened. A polyoxyalkylene polyol having an oxyethylene group content of 65% by mass and a hydroxyl value of 48 mgKOH / g in the polyol G, subjected to cycloaddition polymerization.
Polyol F: Glycerol is used as an initiator, and after ring-opening addition polymerization of EO, the mixture of PO and EO [PO / EO = 48.0 / 52.0 (mass ratio)] is opened. A polyoxyalkylene polyol having a content of oxyethylene group in polyol F of 60% by mass and a hydroxyl value of 28 mgKOH / g, which is subjected to cycloaddition polymerization.

[Polyisocyanate compound]
Polyisocyanate compound 1: Polymethylene polyphenylene polyisocyanate (crude MDI) (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Millionate MR-200).
[Foaming agent]
Foaming agent 1: E-1-chloro-3,3,3-trifluoro-propene.
Foaming agent 2: Z-1,1,1,4,4,4-hexafluoro-2-butene.
Foaming agent 3: water.
[Flame retardants]
Flame retardant 1: Tris (β-chloropropyl) phosphate (manufactured by Spresta Japan, product name: Pyrol PCF).
[catalyst]
Catalyst 1: Pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT DT).
Catalyst 2: N, N, N ′, N′-tetramethylhexamethylenediamine (manufactured by Tosoh Corporation, product name: TOYOCAT MR).
Urethane catalyst 1: Mixture of catalyst 1 / catalyst 1/3 (mass ratio).
[Foam stabilizer]
Foam stabilizer 1: Silicone foam stabilizer (manufactured by Dow Corning Toray, product name: SH-193).

<Production Example 1>
In a 5 L pressurized reaction vessel, 300 parts by mass of the following polyether polyol (X1), 150 parts by mass of the following polyether polyol (Y1), 300 parts by mass of the following polyether polyol (Y2), 50 parts by mass of acrylonitrile, acetic acid After charging 200 parts by mass of vinyl and 10 parts by mass of 2,2-azobis-2-methylbutyronitrile (AMBN) as a polymerization initiator, heating was started while stirring, and the reaction solution was brought to 80 ° C. The reaction was allowed to proceed for 10 hours. The monomer reaction rate was 80% or more. After completion of the reaction, the unreacted monomer was removed by heating under reduced pressure at 110 ° C. and minus 0.10 MPa (gauge pressure) for 2 hours to obtain a polymer-dispersed polyol (polyol Wa1). The hydroxyl value of the obtained polymer-dispersed polyol Wa1, the viscosity at 25 ° C., and the content of polymer particles in Wa1 are shown in Table 1 (the same applies hereinafter).

<Production Examples 2 and 3: Production of polymer-dispersed polyol (Wa2) and (Wa3)>
Into a 5 L pressurized reaction vessel, 70% by mass of the mixture of the base polyol (Wa ′) shown in Table 1 was charged, and while maintaining at 120 ° C., polymerization of the remaining mixture of the base polyol (Wa ′), the monomer and the start The mixture with the agent (AMBN) was fed over 2 hours with stirring, and stirring was continued for about 0.5 hours at the same temperature after completion of all the feeds. In any of Production Examples 2 and 3, the monomer reaction rate was 80% or more. After completion of the reaction, unreacted monomers were removed by heating under reduced pressure at 120 ° C. and 20 Pa for 2 hours to obtain polymer-dispersed polyols Wa2 and Wa3.

<Production Examples 4 to 6: Production of polymer-dispersed polyol (Wa4), (Wa5), (Wa6)>
In a 5 L pressurized reaction vessel, polyol X1, polyol Y1, and macromonomer were charged with the formulation shown in Table 1, and the mixture of monomer and polymerization initiator (AMBN) was stirred for 2 hours while maintaining at 120 ° C. After completion of the entire feed, stirring was continued for about 0.5 hours at the same temperature. Thereafter, unreacted monomers were removed under reduced pressure at 120 ° C. for 3 hours to obtain polymer-dispersed polyols Wa4, Wa5 and Wa6.

Polyether polyol (X1): Polyol having a hydroxyl value of 50 mgKOH / g and an oxyethylene group content of 70% by mass obtained by randomly adding PO and EO in the presence of a potassium hydroxide catalyst using glycerol as an initiator. Ether polyol.
Polyether polyol (Y1): A polyether polyol having a hydroxyl value of 760 mgKOH / g, obtained by adding only PO with ethylenediamine as an initiator.
Polyether polyol (Y2): A polyether polyol having a hydroxyl value of 650 mgKOH / g, obtained by adding only PO in the presence of a potassium hydroxide catalyst using glycerol as an initiator.
The average hydroxyl value of the polymer-dispersed polyol was measured according to JIS K1557-1: 2007.

<Examples 1 to 50>
Examples 19, 21, 23, 25, 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, 49 are examples, Examples 1-18, 20, 22, 24, 26, 28 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50 are comparative examples.
Rigid foams are produced with the formulations shown in Tables 2, 3, 4, and 5. The unit of the numerical values of the formulations shown in the table is parts by mass. However, the compounding amount of the polyisocyanate compound is represented by an isocyanate index (INDEX). The table shows the average number of hydroxyl groups and the average hydroxyl value in the whole polyol composition (Pa).
First, each polyol, urethanization catalyst, foam stabilizer, mixed foaming agent, and a predetermined amount of water are mixed to prepare a polyol system liquid. The blending amount of the urethanization catalyst was set to an amount that would make the gel time 100 seconds. The liquid temperatures of the polyol system liquid and the polyisocyanate compound are adjusted to 20 ° C., respectively.

[Manufacture of free foaming foam]
The polyisocyanate compound prepared in the above procedure was charged into the polyol system solution, and using a stirrer equipped with a disc-shaped stirrer blade on a drilling machine manufactured by Hitachi, Ltd., at a rotational speed of 3,000 revolutions per minute. A foaming stock solution composition is prepared by stirring and mixing for 5 seconds. The foamed stock solution composition immediately after preparation is quickly put into a 200 mm long, horizontal, and height wooden box equipped with a polyethylene release bag to obtain a free foaming foam. The box-free density of the obtained free foaming foam is measured by the following method. In the middle of foaming, the reactivity (cream time, gel time, tack free time) is measured by the following method. The results are shown in Tables 3 and 4.

[Manufacture of panel forms]
A state in which an organic mold release agent is applied to an aluminum mold having a length of 400 mm, a width of 800 mm, and a thickness of 40 mm, the temperature of which is adjusted to 40.degree. And immediately after mixing the polyol system liquid and the polyisocyanate compound. The input amount is set to an amount that is 15% overfilled with respect to the mold volume. After charging, the foamed foam is closed and sealed, held for 10 minutes, and taken out of the mold to produce a panel foam.
The panel total density (unit: kg / m ³ ) of the obtained panel foam is measured by the following method. Each characteristic is evaluated by the following method. The results are shown in Tables 3 and 4.

<Evaluation method of free foaming foam>
[Box-free density]
The density (unit: kg / m ³ ) is measured by a method in accordance with JIS A 9511 for a test piece obtained by cutting the vicinity of the center of the foam obtained by free foaming into a 100 mm square.
[Reactivity]
The mixing start time of the polyol system liquid and the polyisocyanate compound is set to 0 second, and the cream time, gel time, and tack-free time are measured.
Cream time (seconds): Time until the mixed liquid of the polyol system liquid and the polyisocyanate compound starts to foam.
Gel time (seconds): As the gelation progresses, after a thin glass or metal rod is lightly inserted on top of the foaming stock solution composition during foaming, the time it takes for the foaming stock composition to start drawing the yarn when it is quickly pulled out .
Tack-free time (seconds): Time until foaming ends and there is no stickiness in the foam.

<Panel form evaluation method>
[Total panel density]
The total panel density (unit: kg / m ³ ) is measured for the whole obtained panel foam by a method according to JIS A 9511.
[Formability]
(1) Presence or absence of shrinkage after demolding: The obtained panel foam is allowed to stand at 20 ° C. for 30 hours, and then the appearance is observed. Evaluation is based on the following criteria.
○ (good): No deformation. Good.
Δ (possible): Partial deformation occurs due to shrinkage.
X (impossible): The whole is crushed by shrinkage. Bad.
(2) Cell appearance: Of the surface of the obtained panel foam, the surface on the lower side (the bottom surface side of the mold) with respect to the foaming direction (the thickness direction of the mold) is the surface of the skin part. The surface of the test piece cut out from the core part of the panel foam with dimensions of horizontal (x) 100 mm, vertical (y) 100 mm, and height (z) 25 mm is taken as the surface of the core part.
With respect to the respective surfaces of the skin part and the core part, the presence / absence of a non-uniform cell portion (portion where the cell is rough) is visually observed and evaluated according to the following criteria.
A (Excellent): There is no portion where the cell is rough. The cells are fine and uniform.
○ (good): There is no portion where the cell is rough. The cells are uniform.
Δ (possible): The cell is partially rough.
X (impossible): The cell is rough as a whole. Bad.

[Dimensional stability]
Dimensional stability is measured by a method according to ASTM D 2126-75. After removing the panel foam from the mold, it was cured for 30 hours in an atmosphere at an ambient temperature of 25 ° C. and a relative humidity of 50%, and then, from the core of the panel foam, horizontal (x) 100 mm, vertical (y) 100 mm, height (Z) Each test of high temperature dimensional stability, low temperature dimensional stability, and wet heat dimensional stability is performed using a sample cut out with a size of 25 mm as a test piece.
The curing conditions are as follows.
High temperature dimensional stability: The specimen is stored in a thermostat at 70 ° C. for 24 hours.
Low temperature dimensional stability: Specimens are stored in a constant temperature bath at -30 ° C for 24 hours.
Humid heat dimensional stability: Specimens are stored for 24 hours in a thermostatic chamber at 70 ° C. in an atmosphere with a relative humidity of 95%.
After the storage under the above-mentioned conditions, the ratio of the changed dimension to the dimension before storage in the three directions x, y, and z of the test piece is expressed as a dimensional change rate (unit:%).
In the dimensional change rate, a negative value means shrinkage, and a large absolute value means that a dimensional change is large.

[Compressive strength]
The compressive strength of the panel foam was measured according to JIS A 9511. As for the size of the sample piece, the length (x) and the width (y) are cut out to 50 mm each, and the height direction (z) is kept at 40 mm which is the thickness of the panel foam without cutting out the surface skin layer. Measure the compressive strength.
[Thermal conductivity]
The thermal conductivity (unit: W / m · K) of the panel foam is based on JIS A 9511, and is averaged using a thermal conductivity measuring device (product name: Auto-Lambda HC-074, manufactured by Eiko Seiki Co., Ltd.). Measurement was performed at a temperature of 24 ° C.

[Room temperature storage stability]
After the polyol system liquid is stored at 20 ° C. for 1 month, the state of the liquid is visually observed. Evaluation is based on the following criteria.
○ (good): No turbidity, separation, precipitation or solidification occurs, and it is transparent. Good.
X (impossible): One or more of turbidity, separation, precipitation, and solidification occurs. Bad.
[High temperature storage stability]
After storing the polyol system liquid at 40 ° C. for one month, the state of the liquid is visually observed. Evaluation is based on the following criteria.
○ (good): No turbidity, separation, precipitation or solidification occurs, and it is transparent. Good.
X (impossible): One or more of turbidity, separation, precipitation, and solidification occurs. Bad.
XX (more impossible): Two or more of turbidity, separation, precipitation and solidification occur. More bad.

From the results of Table 6, Examples 1 to 18 in which the polyol composition does not contain polymer particles have poor storage stability at high temperatures of the polyol system.
From the results of Table 7, the rigid foams of Examples 19 and 21 of the present invention have good dimensional stability and moldability even when the box-free density is reduced and reduced in weight compared to Examples 20 and 22, and the polyol system Stability is good and storage stability at high temperature is also good. In Examples 23 and 25 using polyester polyol (polyol (Da)), which has a stronger tendency to shrink than polyether polyols, foam shrinkage is suppressed as compared with Examples 24 and 26, and moldability, dimensional stability, Compressive strength, thermal conductivity and the storage stability of the polyol system are all improved.

From the results of Tables 8 and 9, Examples 27, 29, 31, 33, 35, 37, 39, 41, 43, 45, 47, and 49 using the polyol composition of the present invention do not use polyol (Aa). Compared with Comparative Examples 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, the moldability, dimensional stability, compressive strength, thermal conductivity and polyol system The room temperature storage stability is good, and the high temperature storage stability is also good.

<Examples of Invention B>
The hydroxyl value of the polyol is a value measured according to JIS K 1557 (1970 edition). Each raw material used in the following examples is as follows.
[Polyol (Ab)]
Polyol Ab1: PO is subjected to ring-opening addition polymerization using a reaction product obtained by reacting 1.5 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol, followed by hydroxylation. A polyether polyol having a hydroxyl value of 300 mgKOH / g, obtained by ring-opening addition polymerization of EO in the presence of a potassium catalyst. The amount of alkylene oxide added is 15.4 moles per mole of nonylphenol. The ratio of EO to the total amount of PO and EO added (total EO content) is 58% by mass.
Polyol Ab2: PO is ring-opening addition polymerized with the reaction product obtained by reacting 2.2 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol, and then hydroxylated. A polyether polyol having a hydroxyl value of 430 mgKOH / g, obtained by ring-opening addition polymerization of EO in the presence of a potassium catalyst. The addition amount of alkylene oxide is 6.3 mol per 1 mol of nonylphenol. The ratio of EO to the total amount of added PO and EO (total EO content) is 23% by mass.

Polyol Ab3: Obtained by ring-opening addition polymerization of PO alone 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 470 mg KOH / g. The amount of alkylene oxide added is 5.5 moles per mole of nonylphenol.
Polyol Ab4: obtained by subjecting 1 mol of aniline to 1 mol of phenol, 0.6 mol of formaldehyde and 2.2 mol of diethanolamine, and using PO as the initiator for ring-opening addition polymerization. A polyether polyol having a hydroxyl value of 540 mgKOH / g. The amount of alkylene oxide added is 6.9 moles per mole of aniline.
Polyol Ab5: obtained by subjecting 1 mol of nonylphenol to 1.5 mol of formaldehyde and 2.2 mol of diethanolamine as an initiator and subjecting only EO to ring-opening addition polymerization A polyether polyol having a hydroxyl value of 580 mg KOH / g. The addition amount of alkylene oxide is 2.6 mol per 1 mol of nonylphenol.

[Polyol (Bb)]
Polyol Bb1: A polyether polyol having a hydroxyl value of 450 mgKOH / g, obtained by subjecting PO to ring-opening addition polymerization to ethylenediamine and then subjecting EO to ring-opening addition polymerization in the presence of a potassium hydroxide catalyst. Of the total of EO and PO, the EO content (total EO content) is 41% by mass.
Polyol Bb2: A polyether polyol having a hydroxyl value of 760 mgKOH / g, obtained by ring-opening addition polymerization of only PO as an alkylene oxide to ethylenediamine.
Polyol Bb3: A polyether polyol having a hydroxyl value of 500 mgKOH / g, obtained by ring-opening addition polymerization of only PO as an alkylene oxide to monoethanolamine.

[Polyol (Cb)]
Polyol Cb1: obtained by ring-opening addition polymerization of EO to m-tolylenediamine, followed by ring-opening addition polymerization of alkylene oxide in the order of PO and EO in the presence of a potassium hydroxide catalyst, having a hydroxyl value of 450 mgKOH / g Polyether polyol. Of the total of EO and PO, the EO content (total EO content) is 25% by mass. The EO content at the end is 3% by mass.
Polyol Cb2: obtained by ring-opening addition polymerization of EO to m-tolylenediamine, followed by ring-opening addition polymerization of alkylene oxide in the order of PO and EO in the presence of a potassium hydroxide catalyst, having a hydroxyl value of 350 mgKOH / g Polyether polyol. Of the total of EO and PO, the EO content (total EO content) is 25% by mass. The EO content at the end is 11% by mass.
Polyol Cb3: A polyether polyol having a hydroxyl value of 350 mgKOH / obtained by ring-opening addition polymerization of only PO as an alkylene oxide to m-tolylenediamine.

[Other polyols (Eb)]
Polyol Eb1: Polyester polyol having a hydroxyl value of 250 mgKOH / g, obtained by polycondensation of diethylene glycol and terephthalic acid (product name: Terol 563, manufactured by Oxide).

[Polymer-dispersed polyol (Wb)]
Polyol Wb1: A polymer-dispersed polyol having an average hydroxyl value of 320 mgKOH / g obtained in Production Example 1 below.
As the polymer-dispersed polyol (Wb), polymer-dispersed polyols Wb1 to W6 produced by the method of the following production example with the composition shown in Table 1 below were used. The unit of the blending ratio in Table 1 is “part by mass”. [Monomer having a polymerizable unsaturated bond]
Examples of the monomer having a polymerizable unsaturated bond for forming polymer particles include acrylonitrile (AN), vinyl acetate (Vac), methyl methacrylate (MMA), and polyfluoroalkyl methacrylate represented by the formula (1-1). (FMA) was used.

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

[Base polyol (Wb ′)]
As the base polyol (Wb ′), the following polyols X1, Z1, and Z2 were used.
(Polyol X1)
A polyether polyol having a hydroxyl value of 50 mgKOH / g, obtained by random ring-opening addition polymerization of EO and PO using glycerin as an initiator. The ratio of EO to the total amount of PO and EO added is 70% by mass. The content of EO groups in the entire polyol X1 is 68% by mass. (Polyol Y1)
A polyether polyol having a hydroxyl value of 650 mgKOH / g, obtained by ring-opening addition polymerization of PO using glycerol as an initiator. (Polyol Y2)
A polyether polyol obtained by ring-opening addition polymerization of PO using ethylenediamine as an initiator and having a hydroxyl value of 760 mgKOH / g.

[Production Example 1: Production of polymer-dispersed polyol (Wb1)]
After charging all the base polyol (Wb ′), monomer, and AMBN as a polymerization initiator in the 5 L pressure reaction tank with the formulation shown in Table 1, the temperature was increased while stirring, and the reaction solution was heated to 80 ° C. The reaction was continued for 10 hours. The monomer reaction rate was 80% or more. After completion of the reaction, the unreacted monomer was removed by heating under reduced pressure at 110 ° C. and 20 Pa for 2 hours to obtain a polymer-dispersed polyol Wb1.
The hydroxyl value of the obtained polymer-dispersed polyol Wb1, the viscosity at 25 ° C., and the content of the polymer particles in Wb1 are shown in Table 1 (the same applies hereinafter).

[Production Examples 2, 3: Production of polymer-dispersed polyol (Wb2), (Wb3)]
Into a 5 L pressurized reaction vessel, 70% by mass of the mixture of base polyol (Wb ′) shown in Table 1 was charged and maintained at 120 ° C., while the remaining mixture of base polyol (Wb ′), monomer and polymerization were started. The mixture with the agent (AMBN) was fed over 2 hours with stirring, and stirring was continued for about 0.5 hours at the same temperature after completion of all the feeds. In any of Production Examples 2 and 3, the monomer reaction rate was 80% or more. After completion of the reaction, unreacted monomers were removed by heating under reduced pressure at 120 ° C. and 20 Pa for 2 hours to obtain polymer-dispersed polyols Wb2 and Wb3.

[Production Examples 4 to 6: Production of polymer-dispersed polyol (Wb4), (Wb5), (Wb6)]
In a 5 L pressurized reaction vessel, polyol X, polyol Y1, and macromonomer were charged with the formulation shown in Table 1, and the mixture of monomer and polymerization initiator (AMBN) was stirred for 2 hours while maintaining at 120 ° C. After completion of the entire feed, stirring was continued for about 0.5 hours at the same temperature. Thereafter, unreacted monomers were removed under reduced pressure at 120 ° C. for 3 hours to obtain polymer-dispersed polyols Wb4, Wb5 and Wb6. The average hydroxyl value of the polymer-dispersed polyol was measured according to JIS K1557-1: 2007.

[Polyisocyanate compound]
Polyisocyanate compound 1: Polymethylene polyphenylene polyisocyanate (crude MDI) (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Millionate MR-200). [Foaming agent]
Foaming agent 1: E-1-chloro-3,3,3-trifluoro-propene.
Foaming agent 2: Z-1,1,1,4,4,4-hexafluoro-2-butene.
Foaming agent 3: water.
[Flame retardants]
Flame retardant 1: Tris (β-chloropropyl) phosphate (manufactured by Spresta Japan, product name: Pyrol PCF).
[catalyst]
Catalyst 1: Pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT DT).
Catalyst 2: N, N, N ′, N′-tetramethylhexamethylenediamine (manufactured by Tosoh Corporation, product name: TOYOCAT MR).
Catalyst 3: Potassium octylate (manufactured by Nippon Chemical Industry Co., Ltd., product name: PACCAT 15G).
Urethane catalyst 1: Mixture of catalyst 1 / catalyst 1/3 (mass ratio).
[Foam stabilizer]
Foam stabilizer 1: Silicone foam stabilizer (manufactured by Dow Corning Toray, product name: SH-193).

<Examples 1 to 16, 21 to 34>
Free-foam foam and panel foam samples were prepared with the formulations shown in Tables 2, 3, 6 and 7. Tables 2 and 3 are blends of polyurethane foam (urethane formulation), and Tables 6 and 7 are blends of polyisocyanurate foam (isocyanurate formulation). Examples 3 to 4, 11 to 24, 33 to 34, 37 to 38, and 41 to 57 are Examples, and Examples 1 to 2, 5 to 10, 25 to 32, 35 to 36, 39 to 40, and 58 to 59 are compared. It is an example.
The unit of the numerical values of the formulations shown in the table is parts by mass. However, the compounding amount of the polyisocyanate compound is represented by an isocyanate index (INDEX). The table shows the average number of hydroxyl groups and the average hydroxyl value in the whole polyol composition (Pb). In the following, the foaming direction is the thickness direction.

[Preparation of foaming stock composition]
Of the blends in each example, a predetermined amount of each component excluding the polyisocyanate compound is weighed into a plastic container, and stirred and mixed at 3,000 rpm for 30 seconds using a mixer with a stirring blade, to obtain a polyol system solution. Was prepared. The liquid temperature of the polyol system liquid is kept at 25 ° C.
Separately, a predetermined amount of the polyisocyanate compound is weighed into a plastic container, and the liquid temperature is kept at 20 ° C.
The polyisocyanate compound is charged into the polyol system solution, and stirred and mixed at 3,000 rpm for 5 seconds using a mixer to prepare a foaming stock solution composition.

[Manufacture of free foaming foam]
Immediately after preparing the foaming stock solution composition prepared by the above procedure, it was immediately put into a wooden box of 20 cm in length, width and height to obtain a free foaming foam. The box-free density of the obtained free foaming foam is measured by the following method. In the middle of foaming, the reactivity (cream time, gel time, tack free time) is measured by the following method.

[Manufacture of panel forms]
FIG. 1 is a perspective view of a mold 1 used for manufacturing a panel foam. The mold 1 includes an aluminum lower mold 2 and an upper lid 3.
The lower mold 2 is a rectangular parallelepiped having a length in the longitudinal direction (X) of 800 mm, a length in the lateral direction (Y) of 400 mm, and a length in the thickness direction (t) of 40 mm in the thickness direction (t). The upper opening 4 is formed by removing the vertical upper surface, and the side opening 5 is formed by removing one side surface perpendicular to the longitudinal direction (X). That is, the lower mold 2 includes a bottom surface 2a, two side surfaces 2c perpendicular to the horizontal direction (Y), and one side surface 2b perpendicular to the vertical direction (X).
The upper lid 3 has a plate shape that closes the upper opening 4 of the lower mold 2, and is hinged to the upper end of one side surface 2 c perpendicular to the lateral direction (Y) of the lower mold 2.

In the manufacture of the panel foam, the temperature of the mold 1 is adjusted to 60 ° C. in advance, and after the foaming stock solution composition is prepared by the above procedure, it is immediately charged into the charging position 6 in the lower mold 2. The amount to be charged is an amount (just pack) in which the mold volume (800 mm × 400 mm × 40 mm) is just filled after foaming. The charging position 6 is a central portion in the horizontal direction (Y) of the bottom surface 2a in the vicinity of the side surface 2b perpendicular to the vertical direction (X). The foaming stock solution composition charged to the charging position 6 flows along the vertical direction (X) toward the side opening 5 on the bottom surface 2a. Immediately after the entire amount is charged, the upper lid 3 is closed and foamed to produce a panel foam. The mixing start time of the polyol system liquid and the polyisocyanate compound is set to 0 second, and after 10 minutes, the upper lid 3 is opened and the product (panel foam) is taken out.

<Evaluation method of free foaming foam>
[Reactivity]
The mixing start time of the polyol system liquid and the polyisocyanate compound is set to 0 second, and the cream time, gel time, and tack-free time are measured.
Cream time (seconds): Time until the mixed liquid of the polyol system liquid and the polyisocyanate compound starts to foam.
Gel time (seconds): As the gelation progresses, after a thin glass or metal rod is lightly inserted on top of the foaming stock solution composition during foaming, the time it takes for the foaming stock composition to start drawing the yarn when it is quickly pulled out .
Tack-free time (seconds): Time until foaming ends and there is no stickiness in the foam.
[Box-free density]
The density (unit: kg / m ³ ) is measured by a method in accordance with JIS A 9526 for a test piece obtained by cutting the vicinity of the center of the foam obtained by free foaming into a 10 cm square.

<Panel form evaluation method>
[Panel core density]
The density (unit: kg / m ³ ) is measured for a test piece cut out to a length of 10 cm and a thickness of 2.5 cm excluding the skin portion from the center portion of the panel foam produced as described above.
[Formability]
The following items are observed on the panel form to evaluate the moldability.
(1) Presence / absence of edge shrinkage: Observe the appearance of the foam at the edge of the side opening 5 (hereinafter referred to as the flow edge) out of both ends in the longitudinal direction (X) of the panel foam. Evaluate with.
○ (good): There is no deformation (shrinkage) near the flow end. Good.
Δ (possible): The flow end part is partially deformed by contraction.
X (impossible): The flow end portion contracted greatly due to contraction. Bad.
(2) Cell appearance: Evaluate the cell state of the surface on the lower side (the bottom surface 2a side of the lower mold 2) with respect to the foaming direction (thickness direction (t)) of the surface of the center part of the obtained panel foam To do. The presence or absence of non-uniform cell portions (portion where the cells are rough) is visually observed and evaluated according to the following criteria.
A (Excellent): There is no portion where the cell is rough. The cells are fine and uniform.
○ (good): There is no portion where the cell is rough. The cells are uniform.
Δ (possible): The cell is partially rough.
X (impossible): The cell is rough as a whole. Bad.

[Dimensional stability]
Two conditions of 70 ° C. high temperature dimensional stability and −30 ° C. low temperature dimensional stability are evaluated by a method according to ASTM D 2126-75.
That is, a test piece obtained by cutting a panel foam produced as described above into a length of 10 cm, a width of 15 cm, and a thickness of 2.5 cm from a center portion has a high temperature dimensional stability of 70 ° C. and a low temperature dimensional stability of − Store in an atmosphere of 30 ° C. for 24 hours, and increase the length (thickness) in the longitudinal (X) direction, lateral (Y) direction, and thickness (t) direction to the length (thickness) before storage. Dimensional change rate (unit:%). In the dimensional change rate, a negative value means shrinkage; a large absolute value means a large dimensional change.

[Compressive strength]
About the test piece cut out from the center part of the panel form manufactured as mentioned above to length (X) 40mm, width (Y) 40mm, thickness (t) 40mm, longitudinal (X) direction according to JIS A9511 The compressive strength in the transverse (Y) direction and the thickness (t) direction is measured.
[Thermal conductivity]
In accordance with JIS A 1412, measurement is performed at an average temperature of 20 ° C. using a thermal conductivity measuring device (manufactured by Eiko Seiki Co., Ltd., product name: Auto Lambda HC-074 type).
[Flame retardance]
The foam combustibility was evaluated by a method based on the JIS A 9511B method. That is, a panel foam core part is cut into a length of 150 mm, a width of 50 mm, and a thickness of 13 mm, a flame is applied to one end of the foam with a Bunsen burner, and a combustion time (second) and a combustion distance (mm) are measured.

[Room temperature storage stability]
After the polyol system liquid is stored at 20 ° C. for 1 month, the state of the liquid is visually observed. Evaluation is based on the following criteria.
○ (Good): No turbidity, separation, precipitation, or solidification occurs, and it is transparent.
X (impossible): One or more of turbidity, separation, precipitation, and solidification occurs.
XX (more impossible): Two or more of turbidity, separation, precipitation and solidification occur. More bad.
[High temperature storage stability]
After storing the polyol system liquid at 40 ° C. for one month, the state of the liquid is visually observed. Evaluation is based on the following criteria.
○ (good): No turbidity, separation, precipitation or solidification occurs, and it is transparent. Good.
X (impossible): One or more of turbidity, separation, precipitation, and solidification occurs. Bad.
XX (more impossible): Two or more of turbidity, separation, precipitation and solidification occur. More bad.

From the results of Table 4-1, Table 4-2 and Table 5, in the evaluation by urethane formulation, Examples 3 to 4 and 11 to 24 containing polyol (Ab) and polymer particles are panels having good moldability and physical properties. A form can be obtained. The polyol system solution has good room temperature storage stability and high temperature storage stability. On the other hand, the foams obtained in Examples 1-2, 5-10, and 25-30, which do not contain polyol (Ab) and / or polymer particles, are insufficient in the high-temperature storage stability of the polyol system liquid.

From the results of Tables 8 and 9, in the evaluation of the isocyanurate formulation, Examples 33 to 34, 37 to 38 and 41 to 57 containing polyol (Ab) and polymer particles are panel foams having good moldability and physical properties. Obtainable. On the other hand, the foams obtained in Examples 31 to 32, 35 to 36, 39 to 40, and 58 to 59 containing no polyol (Ab) and / or polymer particles are insufficient in the high temperature storage stability of the polyol system liquid. is there.

<Examples of Invention C>
(Example 3)
Hereinafter, the present invention C will be described in more detail using examples, but the present invention C is not limited to these examples. The hydroxyl value of the polyol is a value measured according to JIS K 1557 (1970 edition).
The raw materials used in the following examples are as follows.
[Polyol (Ac)]
Polyol Ac1: PO is subjected to ring-opening addition polymerization using a reaction product obtained by reacting 1.5 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol, and then potassium hydroxide. A polyether polyol having a hydroxyl value of 300 mgKOH / g, obtained by ring-opening addition polymerization of EO in the presence of a catalyst. 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.

Polyol Ac2: EO was subjected to ring-opening addition polymerization using a reaction product obtained by reacting 0.75 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol, and then potassium hydroxide. A polyether polyol having a hydroxyl value of 300 mgKOH / g, obtained by ring-opening addition polymerization of PO and EO in this order in the presence of a catalyst. The amount of alkylene oxide added is 18.0 moles per mole of nonylphenol. The ratio of EO to the total amount of added PO and EO is 75% by mass.
Polyol Ac3: PO is subjected to ring-opening addition polymerization using a reaction product obtained by reacting 2.2 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol, and then potassium hydroxide. A polyether polyol having a hydroxyl value of 430 mgKOH / g, obtained by ring-opening addition polymerization of EO in the presence of a catalyst. The addition amount of alkylene oxide is 6.3 mol per 1 mol of nonylphenol. The ratio of EO to the total amount of added PO and EO is 23% by mass.
Polyol Ac4: Obtained by ring-opening addition polymerization of PO alone 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 470 mg KOH / g. The amount of alkylene oxide added is 5.5 moles per mole of nonylphenol.

[Polyol (Bc)]
Polyol Bc1: A polyether polyol having a hydroxyl value of 760 mgKOH / g, obtained by ring-opening addition polymerization of only PO with ethylenediamine.
Polyol Bc2: A polyether polyol having a hydroxyl value of 500 mgKOH / g, obtained by ring-opening addition polymerization of PO alone with monoethanolamine.
[Polyol (Cc)]
Polyol Cc1: A polyether polyol having a hydroxyl value of 56 mgKOH / g obtained by ring-opening addition polymerization of PO to glycerin and then ring-opening addition polymerization of EO in the presence of a potassium hydroxide catalyst. Of the total of EO and PO, the EO content is 13% by mass.
Polyol Cc2: A polyether polyol having a hydroxyl value of 56 mgKOH / g obtained by ring-opening addition polymerization of PO to glycerin and then ring-opening addition polymerization of EO in the presence of a potassium hydroxide catalyst. Of the total of EO and PO, the EO content is 20% by mass.
Polyol Cc3: A polyether polyol having a hydroxyl value of 400 mgKOH / g, obtained by ring-opening addition polymerization of only PO with glycerin.

[Polyol (Dc)]
Polyol Dc1: Polyester polyol obtained by polycondensation of diethylene glycol and terephthalic acid and having an average hydroxyl number of 2 and a hydroxyl value of 250 mgKOH / g (product name: Terol 563, manufactured by Oxide).
[Other polyols (Ec)]
Polyol Ec1: 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 in the presence of a potassium hydroxide catalyst.

[Polymer-dispersed polyol (Wc)]
As the polymer-dispersed polyol (Wc), polymer-dispersed polyols Wc1 to Wc6 having the composition shown in the following Table 1 and produced by the method of the following production examples were used. The unit of the blending ratio in Table 1 is “part by mass”.
(Monomer having a polymerizable unsaturated bond)
Examples of the monomer having a polymerizable unsaturated bond for forming polymer particles include acrylonitrile (AN), vinyl acetate (Vac), methyl methacrylate (MMA), and polyfluoroalkyl methacrylate represented by the formula (1-1). (FMA) was used.

(Macromonomer)
The following two types were used as macromonomers.
Macromonomer M1: Polyol G / tolylene diisocyanate / 2-polyol G, tolylene diisocyanate (trade name: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-hydroxyethyl methacrylate (made by Junsei Kagaku Co.) Hydroxyethyl methacrylate = 1/1/1 molar ratio was prepared, reacted at 60 ° C for 1 hour, and further reacted at 80 ° C for 6 hours, resulting in a polymerizable non-polymerizable polymer having a hydroxyl value of 40 mgKOH / g. Macromonomer having a saturated group.

[Polyisocyanate compound]
Polyisocyanate compound 1: polymethylene polyphenylene polyisocyanate (crude MDI) (product name: Coronate 1130, manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate group content: 31% by mass).
Polyisocyanate compound 2: polymethylene polyphenylene polyisocyanate (crude MDI), (product name: Millionate MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanate group content: 31% by mass) [foaming agent]
Foaming agent 1: E-1-chloro-3,3,3-trifluoro-propene.
Foaming agent 2: Z-1,1,1,4,4,4-hexafluoro-2-butene.
Foaming agent 3: water.

[catalyst]
Catalyst 1: Urethane catalyst (1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, product name: Polycat 41, manufactured by Air Products).
Catalyst 2: A mixture of a quaternary ammonium salt and ethylene glycol (product name: TOYOCAT TRX, manufactured by Tosoh Corporation).
Catalyst 3: Urethane catalyst (N, N, N ′, N ′,-tetramethylhexamethylenediamine, product name: TOYOCAT MR, manufactured by Tosoh Corporation).
Catalyst 4: Urethane catalyst (triethylenediamine, product name: TEDA-L33, manufactured by Tosoh Corporation).
Catalyst 5: Trimerization reaction promoting catalyst (potassium octylate, product name: PACCAT 15G, manufactured by Nippon Chemical Industry Co., Ltd.).
[Foam stabilizer]
Foam stabilizer 1: Silicone foam stabilizer (product name: SH-193, manufactured by Toray Dow Corning).
[Flame retardants]
Flame retardant 1: Tris (β-chloropropyl) phosphate (Product name: Pyrol PCF, manufactured by Spresta Japan).

<Production Example 1: Production of polymer-dispersed polyol (Wc1)>
In a 5 L pressurized reaction vessel, 300 parts by mass of the following polyether polyol (X1), 150 parts by mass of the following polyether polyol (Y1), 300 parts by mass of the following polyether polyol (Y2), 50 parts by mass of acrylonitrile, acetic acid After charging 200 parts by mass of vinyl and 10 parts by mass of 2,2-azobis-2-methylbutyronitrile (AMBN) as a polymerization initiator, heating was started while stirring, and the reaction solution was brought to 80 ° C. The reaction was allowed to proceed for 10 hours. The monomer reaction rate was 80% or more. After completion of the reaction, unreacted monomer was removed by heating under reduced pressure at 110 ° C. and minus 0.10 MPa (gauge pressure) for 2 hours to obtain a polymer-dispersed polyol (polyol Wc1).
The hydroxyl value of the obtained polymer-dispersed polyol Wc1, the viscosity at 25 ° C., and the content of polymer particles in Wc1 are shown in Table 1 (the same applies hereinafter).

<Production Examples 2, 3: Production of polymer-dispersed polyol (Wc2), (Wc3)>
Into a 5 L pressure reaction tank, 70% by mass of the mixture of the base polyol (Wc ′) shown in Table 1 was charged, and while maintaining at 120 ° C., the remaining mixture of the base polyol (Wc ′), the monomer and the polymerization were started. The mixture with the agent (AMBN) was fed over 2 hours with stirring, and stirring was continued for about 0.5 hours at the same temperature after completion of all the feeds. In any of Production Examples 2 and 3, the monomer reaction rate was 80% or more. After completion of the reaction, unreacted monomers were removed by heating under reduced pressure at 120 ° C. and 20 Pa for 2 hours to obtain polymer-dispersed polyols Wc2 and Wc3.

<Production Examples 4 to 6: Production of polymer-dispersed polyol (Wc4), (Wc5), (Wc6)>
In a 5 L pressurized reaction vessel, polyol X1, polyol Y1, and macromonomer were charged with the formulation shown in Table 1, and the mixture of monomer and polymerization initiator (AMBN) was stirred for 2 hours while maintaining at 120 ° C. After completion of the entire feed, stirring was continued for about 0.5 hours at the same temperature. Thereafter, unreacted monomers were removed under reduced pressure at 120 ° C. for 3 hours to obtain polymer-dispersed polyols Wc4, Wc5 and Wc6.

<Examples 1 to 52: Production and evaluation of rigid foam>
Examples 1-2, Examples 5-6, 9-24, 27-28, 31-46, 49-50 are Examples, Examples 3-4, 7-8, 21-22, 25-26, 47-48, Reference numerals 51 to 52 are comparative examples. Examples 1 to 24 are blends of polyisocyanurate foams (isocyanurate formulations), and Examples 25 to 52 are blends of polyurethane foams (urethane formulations).
Rigid foams were produced with the formulations shown in Tables 2-6. The unit of the numerical values of the formulations shown in the table is parts by mass. The compounding quantity of a polyisocyanate compound uses the same volume as a polyol system liquid. As the polyisocyanate compound, polyisocyanate compound 1 is used in Examples 1 to 24, and polyisocyanate compound 2 is used in Examples 25 to 52. The table shows the average number of hydroxyl groups and the average hydroxyl value in the whole polyol composition (Pc).
First, a polyol system liquid was prepared by mixing predetermined amounts of each polyol, catalyst, foam stabilizer, mixed foaming agent and foaming agent 4 (water). The liquid temperatures of the polyol system liquid and the polyisocyanate compound are adjusted to 10 ° C., respectively.

[Simple foaming test]
The polyol system solution and the polyisocyanate compound prepared in the above procedure were quickly put into a polyethylene cup each with the same volume, stirred at 3,000 rpm for 3 seconds, and foamed in a 2 L cup. Get foamed foam. The core density of the obtained simple foamed foam is measured by the following method. Further, during the foaming, the reactivity (cream time, rise time) is measured by the following method. The results are shown in Tables 4-6.

[Spray construction test]
Using a spray foaming machine (product name: FF-1600) manufactured by Gasmer, the polyol system liquid and the polyisocyanate compound prepared by the above procedure were discharged at a pressure of 70 to 85 kg / m ² , a liquid temperature of 40 ° C., and a room temperature. A rigid foam (spray construction foam) is produced by spraying, foaming, and reacting on a base material at 20 ° C. The polyol system liquid and the polyisocyanate compound are adjusted to have the same volume.
As the substrate, a flexible plate having a length of 600 mm, a width of 600 mm, and a thickness of 5 mm is used. In the spraying, after a lower spray layer having a thickness of 1 mm is applied, two layers are applied so that the thickness of one layer is 25 to 30 mm, and a total of three layers are laminated.
Each characteristic is evaluated by the following method. The results are shown in Tables 4-6.

<Evaluation method of simple foaming foam>
[Core density]
The center part of the obtained simple foamed foam is cut into a 10 cm square, and the core density (kg / m ³ ) of the simple foamed foam is measured by a method based on JIS A 9511.
[Reactivity]
The mixing start time of the polyol system liquid and the polyisocyanate compound is 0 second, the time until the liquid mixture starts to foam is the cream time (seconds), the time when the liquid mixture begins to foam and the rise of the foam stops is the rise time (Seconds).

<Evaluation method of spray construction form>
[density]
The density of the sprayed foam is measured by a method according to JIS K 9511.
[Moldability (state inside the foam)]
Cut the end of the spray construction form, check the cross-section and evaluate it according to the following criteria.
X (defect): The foam has coloring or cracking due to a scorch or the like, or there are defective portions such as non-uniform cells.
○ (good): There is no coloring or cracking due to scorch or the like, or cell nonuniformity inside the foam.

[Dimensional change rate]
A sample cut into a 100 mm × 100 mm × 40 mm rectangular parallelepiped from the core part of the spray construction foam is used as a test piece, and the high temperature dimensional change rate and the low temperature dimensional change rate are measured. After storage under the following conditions, the length increased in the direction perpendicular to the foaming direction of the test piece is defined as a dimensional change rate (%) with respect to the length before storage. In the dimensional change rate, a negative value means shrinkage, and a large absolute value means that a dimensional change is large.
The measurement is performed under the following conditions.
High temperature dimensional change rate: Measured after storing the test piece in a thermostat at 70 ° C. for 24 hours.
Low temperature dimensional change rate: Measured after storing the test piece in a thermostatic bath at −30 ° C. for 24 hours.
[Compressive strength]
The compressive strength of the spray construction foam is measured by a method according to JIS K 7220. Measure in the direction parallel to the spraying direction.

[Thermal conductivity]
The thermal conductivity (unit: W / m · K) of the sprayed foam conforms to JIS A 1412-2, and uses a thermal conductivity measuring device (Product name: Auto-Lambda HC-074, manufactured by Eihiro Seiki Co., Ltd.) The average temperature was 20 ° C. The lower the thermal conductivity, the better the heat insulation performance.
[Combustion test]
The spray construction foam including the flexible plate is cut to a thickness of 20 mm, and a test using a cone calorimeter based on ISO 5660 is performed.
In ISO 5660, when the maximum heat release rate (HRR) is 200 kW / m ² or more for 10 seconds or longer in the 5-minute test that is the standard for flame retardant materials, and the total heat generation amount (THR) is 8 MJ / m ² or more. Or if there are cracks and holes penetrating to the back side, which is harmful to fire prevention. Cracks and penetrations are evaluated by visual appearance, and those having no cracks and / or penetrations are evaluated as “good” (good), and the determination is acceptable. For those with cracks and / or penetrations, the appearance evaluation is x (defect), and the judgment is rejected.

From the results of Tables 7 and 8, Examples 1-2 and Examples 5-6, 9-24, which contain polyol (Ac) and polymer particles, have good moldability in the spray application test even if the core density is lowered and the weight is reduced. And a polyisocyanurate spray foam having physical properties can be obtained. Moreover, the storage stability at normal temperature and the storage stability at high temperature of the polyol system liquid are also good. On the other hand, the rigid foams obtained in Examples 3 to 4 containing no polyol (Ac) and polymer particles are insufficient in moldability, dimensional stability, compressive strength and flame retardancy. Also, the storage stability of the polyol system liquid at normal temperature is insufficient. Examples 7 to 8 containing no polymer particles are insufficient in the high-temperature storage stability of the polyol system liquid.
From the results of Tables 9, 10 and 11, in Examples 23 to 24, 27 to 46 and 49 to 50 containing polyol (Ac) and polymer particles, it is possible to obtain a polyurethane spray foam having good thermal conductivity and physical properties. The polyol system solution also has good storage stability at normal temperature and storage stability at high temperature. On the other hand, Examples 51 and 52 containing no polyol (Ac) and polymer particles are insufficient in moldability, dimensional stability, compressive strength and thermal conductivity. Further, the storage stability at normal temperature and the storage stability at high temperature of the polyol system liquid are insufficient. Examples 25, 26, 29, 30, 47, and 48 that do not contain polymer particles have insufficient high-temperature storage stability. Japanese Patent Application No. 2011-021030 filed on Feb. 2, 2011, 2011 Japanese Patent Application No. 2011-021031 filed on Feb. 2 and Japanese Patent Application No. 2011-021032 filed on Feb. 2, 2011, the contents of claims, drawings and abstracts It is incorporated herein as a disclosure of the specification of the present invention.

1 Mold 2 Lower mold 3 Upper lid 4 Upper opening 5 Side opening 6 Input position of foaming stock solution composition

Claims

A method for producing a rigid foamed synthetic resin by reacting a polyol composition (Pa) with a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst,
The polyol composition (Pa) contains 30 to 70% by mass of the following polyol (Aa) and 0.002 to 30% by mass of polymer particles, and the polyol composition (Pa) has an average number of hydroxyl groups of 2 to 8, Hydrofluoroolefins (I) having a value of 100 to 800 mg KOH / g and the blowing agent represented by the following formula (I)
R 1 CH═CHR 2 (I)
(Wherein R 1 is a perfluoroalkyl group having 1 to 6 carbon atoms and R 2 is a perfluoroalkyl group having 1 to 6 carbon atoms or a halogen atom). Production method.
Polyol (Aa): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aromatic amine having 4 to 12 active hydrogen atoms as an initiator, and containing ethylene oxide in the total amount of the alkylene oxide A polyether polyol having an amount of 0 to 60% by mass and a hydroxyl value of 100 to 800 mgKOH / g.
The method for producing a rigid foam synthetic resin according to claim 1, wherein the polymer particles are polymer particles obtained by polymerizing a monomer having a polymerizable unsaturated group.
The method for producing a rigid foam synthetic resin according to claim 1 or 2, wherein the polyol composition (Pa) contains 1 to 50 mass% of the following polyol (Ba).
Polyol (Ba): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using a polyhydric alcohol having 5 to 12 active hydrogen atoms as an initiator, and containing ethylene oxide in the total amount of the alkylene oxide A polyether polyol having an amount of 0 to 20% by mass and a hydroxyl value of 100 to 800 mgKOH / g.
The method for producing a rigid foam synthetic resin according to any one of claims 1 to 3, wherein the polyol composition (Pa) contains 10 to 40% by mass of the following polyol (Ca).
Polyol (Ca): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aliphatic amine having 2 to 4 active hydrogen atoms as an initiator, and containing ethylene oxide in the total amount of the alkylene oxide A polyether polyol having an amount of 0 to 50% by mass and a hydroxyl value of 100 to 800 mgKOH / g.
The method for producing a rigid foam synthetic resin according to any one of claims 1 to 4, wherein the polyol composition (Pa) contains 10 to 60 mass% of the following polyol (Da).
Polyol (Da): Polyester polyol produced by polycondensation of a monomer mixture containing an aromatic compound and having an average hydroxyl number of 2 to 3 and a hydroxyl value of 100 to 500 mgKOH / g.
The polymer particles are polymer particles derived from a polymer-dispersed polyol (Wa),
The method for producing a rigid foam synthetic resin according to any one of claims 1 to 5, wherein the polyol composition (Pa) contains 0.01 to 50% by mass of the polymer-dispersed polyol (Wa).
The method for producing a rigid foam synthetic resin according to any one of claims 1 to 5, wherein the hydrofluoroolefin (I) contains Z-CF 3 CH = CHCF 3 .
The method for producing a rigid foam synthetic resin according to any one of claims 1 to 5, wherein the hydrofluoroolefins (I) include E-CF 3 CH = CHCl.
The method for producing a rigid foam synthetic resin according to any one of claims 1 to 8, wherein the production method is an injection method.
A method for producing a rigid foam synthetic resin by reacting and foaming a polyol composition (Pb) and a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst by a continuous board molding method,
The polyol composition (Pb) contains 5 to 99.998 mass% of the following polyol (Ab) and 0.002 to 30 mass% of polymer particles, and the polyol composition (Pb) has an average number of hydroxyl groups of 2 to 8, Hydrofluoroolefins (I) having an average hydroxyl value of 100 to 800 mgKOH / g and the blowing agent represented by the following formula (I)
R 1 CH═CHR 2 (I)
(Wherein R 1 is a perfluoroalkyl group having 1 to 6 carbon atoms and R 2 is a perfluoroalkyl group having 1 to 6 carbon atoms or a halogen atom). Production method.
Polyol (Ab): Polyol obtained by ring-opening addition polymerization of alkylene oxide using a Mannich condensation product obtained by reacting phenols and / or aromatic amines, aldehydes and alkanolamines as an initiator. Ether polyol.
The method for producing a rigid foam synthetic resin according to claim 10, wherein the polymer particles are polymer particles obtained by polymerizing a monomer having a polymerizable unsaturated group.
The method for producing a rigid foam synthetic resin according to claim 10 or 11, wherein the polyol composition (Pb) contains 20 to 70 mass% of the following polyol (Bb).
Polyol (Bb): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aliphatic amine as an initiator.
The method for producing a rigid foam synthetic resin according to any one of claims 10 to 12, wherein the polyol composition (Pb) contains 20 to 60 mass% of the following polyol (Cb).
Polyol (Cb): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an aromatic amine (excluding the Mannich condensation product) as an initiator.
The polymer particles are polymer particles derived from a polymer-dispersed polyol (Wb),
The method for producing a rigid foam synthetic resin according to any one of claims 10 to 13, wherein the polyol composition (Pb) contains 0.01 to 50% by mass of the polymer-dispersed polyol (Wb).
The method for producing a rigid foam synthetic resin according to any one of claims 10 to 14, wherein the hydrofluoroolefin (I) contains Z-CF 3 CH = CHCF 3 .
The method for producing a rigid foam synthetic resin according to any one of claims 10 to 14, wherein the hydrofluoroolefin (I) contains E-CF 3 CH = CHCl.
A method for producing a rigid foam synthetic resin by reacting a polyol composition (Pc) and a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst,
The polyol composition (Pc) contains 20 to 99.998 mass% of the following polyol (Ac) and 0.002 to 30 mass% of polymer particles, and the polyol composition (Pc) has an average number of hydroxyl groups of 2 to 8, Hydrofluoroolefins (I) having an average hydroxyl value of 100 to 800 mgKOH / g and the blowing agent represented by the following formula (I)
R 1 CH═CHR 2 (I)
(Wherein R 1 is a perfluoroalkyl group having 1 to 6 carbon atoms and R 2 is a perfluoroalkyl group having 1 to 6 carbon atoms or a halogen atom). Production method.
Polyol (Ac): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using a Mannich condensation product obtained by reacting phenols, aldehydes and alkanolamines as an initiator.
The method for producing a rigid foam synthetic resin according to claim 17, wherein the polymer particles are polymer particles obtained by polymerizing a monomer having a polymerizable unsaturated group.
The manufacturing method of the hard foam synthetic resin of Claim 17 or 18 in which the said polyol composition (Pc) contains the following polyol (Bc) more than 0 mass% and 70 mass% or less.
Polyol (Bc): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using an amine compound (excluding the Mannich condensation product) as an initiator.
The method for producing a rigid foam synthetic resin according to any one of claims 17 to 19, wherein the polyol composition (Pc) contains the following polyol (Cc) in an amount of more than 0% by mass and 40% by mass or less.
Polyol (Cc): A polyether polyol obtained by ring-opening addition polymerization of alkylene oxide using a polyhydric alcohol having 2 to 6 active hydrogen atoms as an initiator.
The method for producing a rigid foam synthetic resin according to any one of claims 17 to 20, wherein the polyol composition (Pc) contains the following polyol (Dc) in an amount of more than 0% by mass and 70% by mass or less.
Polyol (Dc): Polyester polyol produced by polycondensation of a monomer mixture containing an aromatic compound.
The rigid foam according to any one of claims 17 to 21, wherein the polymer particles are polymer particles derived from a polymer-dispersed polyol (Wc), and the polyol composition (Pc) contains the polymer-dispersed polyol (Wc). A method for producing a synthetic resin.
The method for producing a rigid foam synthetic resin according to any one of claims 17 to 22, wherein the hydrofluoroolefin (I) contains Z-CF 3 CH = CHCF 3 .
The method for producing a rigid foam synthetic resin according to any one of claims 17 to 23, wherein the hydrofluoroolefin (I) contains E-CF 3 CH = CHCl.
The method for producing a rigid foam synthetic resin according to any one of claims 17 to 24, wherein a spray method is used.