JP4609179B2 - Manufacturing method of rigid foam synthetic resin - Google Patents

Description

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

It is widely performed to produce a rigid foamed synthetic resin (hereinafter referred to as a rigid foam) such as a rigid polyurethane foam and a rigid polyisocyanurate foam by reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent or the like. ing.
By the way, the use of chlorofluorocarbons (so-called CFC compounds such as CCl ₃ F) and hydrochlorofluorocarbons (so-called HCFC compounds such as CCl ₂ FCH ₃ ) conventionally used as foaming agents has been regulated in recent years from the viewpoint of environmental protection. ing.

Examples of foaming agents that can replace these regulated foaming agents include hydrocarbon compounds such as hydrofluorocarbons (hereinafter also referred to as HFC compounds), hydrofluoroethers (hereinafter also referred to as HFE compounds), and cyclopentane.
Moreover, since water produces | generates a carbon dioxide gas by reacting with a polyisocyanate compound, using the said foaming agent and water together, or using water alone as a foaming agent is performed.
In addition, an inert gas such as air, nitrogen or carbon dioxide is also used as a foaming agent.
An inert gas is also directly added in a liquefied state, a supercritical state, or a subcritical state. Since the HFC compound has a high global warming potential, when using the HFC compound as a foaming agent, a technique of using water as a foaming agent in order to reduce the amount of use has been studied.

The foamed synthetic resin obtained by using the above HFC compound, HFE compound, hydrocarbon compound, water, inert gas, etc., that is, using a foaming agent other than CFC compound or HCFC compound, is a conventional CFC compound as a foaming agent. Compared with foamed synthetic resin obtained using HCFC or HCFC compound, physical properties are deteriorated. In particular, deterioration of dimensional stability due to foam shrinkage is remarkable.
On the other hand, foam shrinkage can be suppressed by increasing the density of the foamed synthetic resin, but on the other hand, there is a problem that the manufacturing cost increases.

  Patent Document 1 below discloses a method for producing a rigid polyurethane foam by adding a polymer-dispersed polyol to a high hydroxyl group polyol in order to prevent foam shrinkage. The polymer-dispersed polyol refers to a dispersion system in which fine polymer particles as a dispersoid are stably dispersed in a base polyol such as polyether polyol or polyester polyol as a dispersion medium. The polymer-dispersed polyol has heretofore been used as a raw material for a flexible or semi-rigid polyurethane foam to improve the properties of the polyurethane foam. In the technique described in Patent Document 1 below, a rigid polyurethane foam having good dimensional stability can be obtained by adding a polymer-dispersed polyol to a polyol having a high hydroxyl value. The polymer fine particles in the polymer-dispersed polyol have some action. It is thought that it is exerting.

  A method for producing such a polymer-dispersed polyol includes a polymerizable unsaturated bond in a saturated polyol having no polymerizable unsaturated bond and, optionally, an unsaturated polyol having a polymerizable unsaturated bond is also present. There is known a method of polymerizing a monomer having, and then removing unreacted components. Various polyether polyols and polyester polyols are known as the polyol constituting the polymer-dispersed polyol.

  The conventional polymer-dispersed polyol is a polymer-dispersed polyol having a low hydroxyl value (50 mg KOH / g or less) used as a raw material for a flexible or semi-rigid polyurethane foam. Therefore, even when such a conventional polymer-dispersed polyol is mixed with a polyol for a rigid polyurethane foam having a high hydroxyl value, the compatibility is poor. End up. Or the mixture of polyols is thickened. Therefore, it has been difficult to use a conventional polymer-dispersed polyol having a low hydroxyl value as a raw material for rigid polyurethane foam.

  In general, when a polymer-dispersed polyol is synthesized by polymerizing a monomer having a polymerizable unsaturated bond in the polyol, the higher the hydroxyl value of the polyol (the lower the molecular weight of the polyol), the less the particle stabilizing action by the polyol. . For this reason, agglomeration of particles in the process of particle growth during polymerization is very likely to occur and an aggregate is generated.

In the following Patent Documents 2, 3, and 4, a proposal using a polymer-dispersed polyol having a high hydroxyl value is made, but even these methods are not sufficient in dispersion stability of polymer fine particles.
Further, polymer-dispersed polyols in which the stability of polymer fine particles is improved are described in, for example, Patent Documents 5, 6, 7 and the like.
JP 57-25313 A JP-A-2-240125 Japanese Examined Patent Publication No. 6-62797 Japanese Patent Publication No. 7-80986 Japanese Patent Laid-Open No. 11-060651 Japanese Patent Laid-Open No. 11-106447 JP-A-11-302340

Regarding Patent Documents 1 to 4, not only the dispersion stability of the polymer fine particles is not sufficient, but also a sufficient improvement effect is not seen with respect to foam shrinkage.
With respect to Patent Documents 5 to 7, an improvement effect can be obtained in any of dispersion stability and foam shrinkage improvement. However, when one or more selected from the group consisting of water, hydrocarbon compounds, HFC compounds, HFE compounds, and inert gases are selected as the blowing agent, conventional CFC compounds and HCFC compounds are used. Compared with the case, the deterioration of dimensional stability due to foam shrinkage is remarkable. In addition, when water is used as a foaming agent, foam shrinkage becomes significant particularly when the amount of water used is large. Foam shrinkage becomes more prominent when water is used alone or when water and carbon dioxide are used in combination. Thus, when water or carbon dioxide gas is selected as the foaming agent, the foam shrinkage becomes most noticeable because the carbon dioxide gas easily penetrates the cell membrane of the rigid foam, and as a result, the internal pressure in the cell decreases. It is thought that it is easy.
On the other hand, for the purpose of cost reduction, it is required to reduce the weight of the foam. For this purpose, further improvement is required for improvement of foam shrinkage.

  Regarding Patent Documents 6 and 7, there is a new problem of odor of polymer-dispersed polyol. The problem of odor is often pointed out as an inconvenience in a method such as a spray method in which the foam raw material is a mist and scattered in the space. Moreover, since the spray method is a field where cost reduction is severe, it is the field where foam weight reduction is most demanded. Therefore, the demand for improvement with respect to foam shrinkage is the most severe field.

  The present invention has been made in view of the above circumstances, improves the dispersion stability of a polymer-dispersed polyol, and uses foam, a water, a hydrocarbon compound, an HFC compound, an HFE compound, or an inert gas as a foam. Provided is a method for producing a rigid foamed synthetic resin that is capable of obtaining a rigid foam that hardly shrinks and can be reduced in weight.

In order to solve the above-mentioned problems, the method for producing a rigid foam synthetic resin according to the present invention comprises reacting a polyol composition (V) and a polyisocyanate compound in the presence of a foam stabilizer, a catalyst, and a foaming agent to produce a rigid foam synthesis. In the method for producing a resin, 0.1% by mass or more of the polyol composition (V) is a polymer-dispersed polyol (Z) in which polymer fine particles are dispersed in a base polyol (W), and the polymer fine particles are at least one selected from the group consisting of acrylic acid alkyl esters and methacrylic acid alkyl esters, see contains at least one selected from the group consisting of polymerizable unsaturated bond-containing nitrile, the alkyl acrylate and alkyl methacrylate At least one selected from the group consisting of esters, or the above-mentioned polymerizable unsaturated bond At least one not one selected from the group consisting of tolyl, a polymer fine particles obtained by the content of other monomers is polymerized the monomer is less than 20 wt%, or the foaming agent is water alone, Or it consists of water and a carbon dioxide gas, It is characterized by the above-mentioned.

The polymer fine particles are preferably polymer fine particles obtained by polymerizing a monomer (M) containing an alkyl methacrylate and at least one selected from the group consisting of polymerizable unsaturated bond-containing nitriles.
The alkyl methacrylate is preferably methyl methacrylate.
The base polyol (W) has an average hydroxyl value of 200 to 800 mgKOH / g, and 5% by mass or more of the base polyol (W) has a hydroxyl value of 84 mgKOH / g or less and an oxyethylene group content of 40. It is preferable that it is polyether polyol (X) of the mass% or more.
It is preferable that the usage-amount of the water as said foaming agent is 1-20 mass parts with respect to 100 mass parts of polyol compositions (V) .
It can be reacted and foamed by spraying.

  According to the present invention, a polymer-dispersed polyol having good dispersion stability and excellent storage stability can be obtained, and a rigid foam with little foam shrinkage can be produced using it.

<Polyol>
Polyols used in the present invention include polyether polyols, polyester polyols, hydrocarbon-based polymers having a hydroxyl group at the end, in particular, consisting of only polyether polyols, or polyester polyols and carbonized having hydroxyl groups at the ends. It is preferable to use a hydrogen polymer or the like together.

-Polyether polyol In this invention, polyether polyol is a polyol obtained by ring-opening addition of cyclic ether to an initiator. Examples of the initiator include polyhydroxy compounds such as polyhydric alcohols and polyhydric phenols, amines, and the like. Examples of the cyclic ether include alkylene oxide and tetrahydrofuran.

-Initiator Examples of the initiator include the following compounds and their cyclic ether adducts, and mixtures of two or more thereof. That is, water, polyhydric alcohols, polyhydric phenols, and amines can be mentioned.
Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,6-hexanediol, and glycerin. , Trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, diglycerin, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, dulcitol, and sucrose (sucrose). Examples of the polyhydric phenols include bisphenol A and a phenol-formaldehyde initial condensate. Examples of the amines include ammonia; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and N- (2-aminoethyl) ethanolamine; ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, and triethylene. Aliphatic amines such as tetramine; Alicyclic amines such as piperazine, N-aminomethylpiperazine, N- (2-aminoethyl) piperazine; Mannich reaction obtained by reacting phenols with formaldehyde and alkanolamines Aromatic amines such as condensates, aniline, tolylenediamine, xylylenediamine and diphenylmethanediamine can be exemplified.

-Cyclic ether As cyclic ether added to an initiator, there are 3-6 membered cyclic ether compounds which have one oxygen atom in a ring, and the following compounds are specifically mentioned. Ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylethylene oxide, butadiene monooxide, styrene oxide, α-methylstyrene oxide, epichlorohydrin, epifluorohydrin, epibromo Has a three-membered cyclic ether group such as hydrin, glycidol, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, 2-chloroethyl glycidyl ether, o-chlorophenyl glycidyl ether, cyclohexene oxide, dihydronaphthalene oxide, vinylcyclohexene monoxide Compound: Compound having 4- to 7-membered cyclic ether group such as oxetane, tetrahydrofuran, tetrahydropyran, etc. Compound.
Of these, a compound having one 3-membered cyclic ether group (monoepoxide) is preferable, and ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, and 2-butene oxide, which are alkylene oxides having 2 to 4 carbon atoms, are particularly preferable.
These cyclic ethers can be used in combination of two or more, and when used in combination, they can be mixed (randomly) reacted or sequentially reacted. Particularly preferred cyclic ethers are alkylene oxides having 2 to 4 carbon atoms, particularly propylene oxide alone, ethylene oxide alone, or a combination of propylene oxide and ethylene oxide. Moreover, you may use together cyclic esters, such as (epsilon) -caprolactone and a lactide.

-Polyester polyol As a polyester polyol, there exists a polyester polyol obtained by polycondensation of a polyhydric alcohol and polyhydric carboxylic acid, for example. In addition, there are polycondensation of hydroxycarboxylic acids, polymerization of cyclic esters (lactones, lactides), polyaddition of cyclic ethers to polycarboxylic anhydrides, polyester polyols by transesterification of waste polyethylene terephthalate, and the like.

-Hydrocarbon polymer having a hydroxyl group at the end As a hydrocarbon polymer having a hydroxyl group at the end, for example, an acrylic polyol having a hydroxyl group introduced into an acrylic copolymer, butadiene alone is polymerized, or butadiene and other monomers are used. There are liquid polybutadiene polyols having a hydroxyl group at the terminal obtained by copolymerization.

<Polyol composition (V)>
The polyol composition (V) used as a raw material for producing the rigid foam synthetic resin contains 0.1% by mass or more of the polymer-dispersed polyol (Z) shown below.
The polymer-dispersed polyol (Z) is obtained by stably dispersing polymer fine particles in the base polyol (W). The polymer fine particles are formed by polymerizing a monomer having a polymerizable unsaturated bond (hereinafter referred to as monomer (M)).

<Polymer-dispersed polyol (Z)>
The average hydroxyl value of the base polyol (W) used in the production of the polymer-dispersed polyol (Z) is preferably from 200 to 800 mgKOH / g, particularly preferably from 250 to 750 mgKOH / g. When the average hydroxyl value of the base polyol (W) is lower than this range, the produced polymer-dispersed polyol (Z) has poor compatibility with other polyols (E) used in the production of the rigid polyurethane foam. When used in combination with the polyol (E), the polyol (polymer fine particles) separates or thickens, making it difficult to use as a raw material for rigid polyurethane foam. When the average hydroxyl value of the base polyol (W) used for the production of the polymer-dispersed polyol (Z) is high, it is difficult to obtain a polymer-dispersed polyol in which polymer fine particles are stably dispersed.

<Base polyol (W)>
The base polyol (W) is a polyol mixture composed of two or more polyols having different hydroxyl values. It is preferable that 5 mass% or more of the base polyol (W) is the following polyether polyol (X).
By setting the ratio of the polyether polyol (X) in the base polyol (W) to 5% by mass or more, a polymer-dispersed polyol (Z) having good dispersibility (storage stability) can be easily obtained. The ratio is particularly preferably 10% by mass or more. The upper limit of the ratio is preferably 50% by mass or less, and particularly preferably 45% by mass or less.
That is, the base polyol (W) is preferably a mixture of polyether polyol (X) 5 to 50% by mass and polyol (Y) 50 to 95% by mass. However, the polyol (Y) is a polyol other than the polyether polyol (X) constituting the base polyol (W). The base polyol (W) is particularly preferably a mixture of polyether polyol (X) 10 to 45 mass% and polyol (Y) 55 to 90 mass%.

<Polyether polyol (X)>
The polyether polyol (X) in the present invention is a polyether polyol having a hydroxyl value of 84 mgKOH / g or less and an oxyethylene group content of 40% by mass or more.
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 alcohols, triols such as glycerin, trimethylolpropane and 1,2,6-hexanetriol are particularly preferable. As other cyclic ethers, propylene oxide, isobutylene oxide, 1-butene oxide and 2-butene oxide are preferable, and propylene oxide is particularly preferable. That is, the polyether polyol (X) is preferably a polyether polyol obtained by ring-opening addition of ethylene oxide alone or ethylene oxide and propylene oxide to a triol.
The hydroxyl value of the polyether polyol (X) is 84 mgKOH / g or less, preferably 67 mgKOH / g or less, more preferably 60 mgKOH / g or less. The lower limit of the hydroxyl value of the polyether polyol (X) is preferably 5 mgKOH / g or more, and more preferably 8 mgKOH / g or more.

  In polyether polyol (X), oxyethylene group content is 40 mass% or more. However, in the present invention, the oxyethylene group content of the polyether polyol is the ratio of oxyethylene groups derived from ethylene oxide in the polyether polyol molecule, specifically, the ratio of ethylene oxide in the polyol molecule including the initiator ( (Mass%). When the oxyethylene group content is lower than this, it is difficult to obtain a polymer-dispersed polyol in which polymer fine particles are stably dispersed. 50 mass% or more is preferable and, as for oxyethylene group content in polyether polyol (X), 55 mass% or more is especially preferable. The upper limit of the oxyethylene group content is preferably about 100% by mass, more preferably 90% by mass.

<Polyol (Y)>
The polyol (Y) is a polyol other than the polyether polyol (X) constituting the base polyol (W). The polyol (Y) may be used alone or in combination of two or more. Here, the polyol (Y) preferably has no nitrogen atom, because of the stability of the polymer-dispersed polyol (Z). When the polyol (Y) has a nitrogen atom, the viscosity of the polymer-dispersed polyol (Z) may increase. The polyol (Y) is preferably a polyether polyol. In particular, the polyol (Y) is preferably a polyether polyol obtained by ring-opening addition of a cyclic ether using a polyhydric alcohol having no nitrogen atom as an initiator. The cyclic ether for producing the polyol (Y) is preferably propylene oxide alone or a combination of ethylene oxide and propylene oxide. The hydroxyl value of the polyol (Y) is preferably 400 to 850 mgKOH / g, and more preferably 400 to 750 mgKOH / g.

<Monomer (M)>
The monomer (M) used in the present invention includes at least one selected from the group consisting of polymerizable unsaturated bond-containing nitriles and at least one selected from the group consisting of alkyl acrylates and alkyl methacrylates. Is included. Mass ratio of polymerizable unsaturated bond-containing nitrile and methacrylic acid alkyl ester and / or acrylic acid alkyl ester (polymerizable unsaturated bond-containing nitrile: total of methacrylic acid alkyl ester and acrylic acid alkyl ester) is 95: 5 to 5:95 is preferable, 80:20 to 40:60 is more preferable, and 60:40 to 46:54 is most preferable. In particular, when the mass ratio is 60:40 to 45:55, the odor during the production of the rigid foam is sufficiently suppressed, the produced rigid foam has excellent dimensional stability, and the viscosity of the polymer-dispersed polyol (Z). Furthermore, it has an excellent characteristic that it is low and easy to handle.
Examples of the polymerizable unsaturated bond-containing nitrile include acrylonitrile, methacrylonitrile, 1,4-dicyano-2-butene, 2,4-dicyano-1-butene and the like. Of these, acrylonitrile is preferred because of the good stability of the polymer fine particles. As the alkyl methacrylate, methyl methacrylate and ethyl methacrylate are preferable, and as the alkyl acrylate, methyl acrylate and ethyl acrylate are preferable.
In the present invention, the monomer (M) is particularly preferably a combination of acrylonitrile and methyl methacrylate.

As the monomer (M), other monomers other than the polymerizable unsaturated bond-containing nitrile, acrylic acid alkyl ester, or methacrylic acid alkyl ester may be used in combination.
As the other monomer, a monomer having one polymerizable unsaturated bond can be used, but is not limited thereto. Specific examples include styrene monomers such as styrene, α-methylstyrene, and halogenated styrene; acrylic monomers (other than alkyl esters) such as acrylic acid, acrylamide, and methacrylamide; vinyl acetate, vinyl propionate, and the like. Vinyl ester monomers; isoprene, butadiene, other diene monomers; unsaturated fatty acid ester monomers such as maleic acid diester and itaconic acid diester; vinyl halide monomers such as vinyl chloride, vinyl bromide and vinyl fluoride; Vinylidene halide monomers such as vinylidene, vinylidene bromide, vinylidene fluoride; vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether; and other olefins, halogenated Olefin, and the like.

The amount of the monomer (M) used is not particularly limited, but is preferably an amount such that the polymer concentration (content of polymer fine particles) in the finally obtained polymer-dispersed polyol (Z) is 1 to 50% by mass, 2-45 mass% is especially preferable, and 10-30 mass% is the most preferable.
When the monomer (M) selected from the polymerizable unsaturated bond-containing nitrile, alkyl acrylate ester and alkyl methacrylate ester and the other monomer are used in combination, the amount of the other monomer used is the total amount of the monomer (M). It is preferable to set it as 50 mass% or less among usage-amount, and 20 mass% or less is more preferable. It is preferable that the amount of the monomer causing odor such as vinyl acetate is small, and it is preferable not to use it.

For the polymerization of the monomer (M), a polymerization initiator of a type that generates a free radical and starts polymerization is usually used. Specifically, for example, 2,2-azobis-isobutyronitrile (AIBN), 2,2-azobis-2-methylbutyronitrile (AMBN), 2,2-azobis-2,4-dimethylvaleronitrile, benzoyl Examples include peroxide, diisopropyl peroxydicarbonate, acetyl peroxide, di-tert-butyl peroxide, persulfate and the like. Of these, AIBN and AMBN are particularly preferable.
The polymerization reaction is performed at a temperature equal to or higher than the decomposition temperature of the polymerization initiator, usually 80 to 160 ° C, preferably 90 to 150 ° C, particularly preferably 100 to 130 ° C.

<Method for producing polymer-dispersed polyol (Z)>
There are two methods for producing the polymer-dispersed polyol (Z) using the base polyol (W), for example. In the first method, if necessary, the monomer (M) having a polymerizable unsaturated bond is polymerized in the base polyol (W) in the presence of a solvent and a grafting agent to directly deposit particles in the base polyol (W). Is the method. In the second method, if necessary, the monomer (M) having a polymerizable unsaturated bond is polymerized in a solvent in the presence of a grafting agent that stabilizes the particles, and then the particles are precipitated, and then the base polyol (W) And a solvent are substituted to obtain a stable dispersion. In the present invention, either method can be adopted, and the first method is particularly preferable.

  When the polymer-dispersed polyol (Z) is produced by the first method, (a) a part of the base polyol (W) is charged into the reactor, and the remaining base polyol (W) and monomers are added to the reactor under stirring. (M), a batch method in which polymerization is carried out by gradually feeding a mixture of polymerization initiators, and (a) a mixture of base polyol (W), monomer (M), polymerization initiator, etc. is continuously added to the reactor with stirring. There is a continuous method in which the polymer-dispersed polyol composition produced at the same time is continuously discharged from the reactor, and the present invention can be produced by either method.

In general, the higher the polymer concentration, the more likely the particles are agglomerated in the process of growing the particles during polymerization of the monomer (M), resulting in the formation of aggregates. In order to prevent this, in the first method, it is preferable to produce the polymer-dispersed polyol (Z) in the presence of a solvent.
Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, cyclohexanol and benzyl alcohol; aliphatic hydrocarbons such as pentane, hexane, cyclohexane and hexene; aromatic hydrocarbons such as benzene, toluene and xylene. Ketones such as acetone, methyl ethyl ketone, and acetophenone; esters such as ethyl acetate and butyl acetate; ethers such as isopropyl ether, tetrahydrofuran, benzyl ethyl ether, acetal, anisole, and methyl-tert-butyl ether; chlorobenzene, chloroform, dichloroethane, Halogenated hydrocarbons such as 1,1,2-trichlorotrifluoroethane; nitro compounds such as nitrobenzene; nitriles such as acetonitrile and benzonitrile S; trimethylamine, triethylamine, tributylamine, amines dimethylaniline; N, N'-dimethylformamide, amides such as N- methyl pyrrolidone; dimethyl sulfoxide, sulfur compounds such as sulfolane and the like.
In the present invention, these solvents can be used alone or in combination. After the polymerization of the monomer (M) having a polymerizable unsaturated bond is completed, the solvent is removed. Solvent removal is usually performed by heating under reduced pressure. However, it can also be carried out under normal pressure heating or reduced pressure at room temperature. At this time, unreacted monomers are also removed together with the solvent.

  Although the polymer-dispersed polyol (Z) in which polymer fine particles are stably dispersed can be obtained by the production method as described above, a stable dispersion may be difficult to obtain depending on the monomer (M) used. Furthermore, a stabilizer or a grafting agent can be used to improve the dispersion stability of the particles.

  As the stabilizer or grafting agent, a polyether compound having a polymerizable unsaturated bond in the molecule is preferable. High molecular weight polyether polyol or monool obtained by reacting an alkylene oxide with an active hydrogen compound having an unsaturated bond-containing group such as vinyl group, allyl group or isopropyl group as an initiator; maleic anhydride to polyether polyol It is obtained by reacting unsaturated carboxylic acid such as itaconic anhydride, maleic acid, fumaric acid, acrylic acid, methacrylic acid or the like or an acid anhydride thereof, and then adding alkylene oxide such as propylene oxide or ethylene oxide as necessary. High molecular weight polyether polyols or monools; reaction products of unsaturated alcohols such as 2-hydroxyethyl acrylate and butenediol with polyether polyols and polyisocyanate compounds; unsaturated epoxy compounds such as allyl glycidyl ether with polyether poly Reaction product between Lumpur; and the like. These compounds preferably have a hydroxyl group but are not limited thereto.

<Characteristics of polymer-dispersed polyol (Z)>
The hydroxyl value of the polymer-dispersed polyol (Z) is preferably 200 to 800 mgKOH / g, more preferably 200 to 750 mgKOH / g, and particularly preferably 250 to 750 mgKOH / g. The hydroxyl value of the polymer-dispersed polyol (Z) is usually lower than that of the base polyol (W) used as the base.

  The polymer-dispersed polyol (Z) obtained as described above can realize dispersion stability (storage stability) that does not cause separation in a stationary state for 1 month or longer, particularly 2 months or longer, more preferably 3 months or longer. The reason why the polymer-dispersed polyol (Z) is excellent in dispersion stability in this way can be presumed that the size of the polymer fine particles is fine and uniform. The size (average particle diameter) of the polymer fine particles is preferably 0.3 μm or less.

<Composition of polyol composition (V)>
When the rigid polyurethane foam is produced by reacting the polyol composition (V) and the polyisocyanate compound in the presence of a foam stabilizer, a catalyst and a foaming agent, 0.1% by mass or more of the polyol composition (V) is the above. The polymer-dispersed polyol (Z). In the polyol composition (V), 0.8% by mass or more is preferably the polymer-dispersed polyol (Z), and 1.0% by mass or more is particularly preferably the polymer-dispersed polyol (Z).
The polymer-dispersed polyol (Z) can be used alone as a raw material for the rigid polyurethane foam. That is, 100% by mass of the polyol composition (V) may be the polymer-dispersed polyol (Z), but it is a raw material that is used by mixing with the polyol (E) that is usually used as a raw material for rigid polyurethane foam. This is preferable because of its relatively low viscosity and high operability during production. For example, when the polymer-dispersed polyol (Z) having a polymer fine particle content of 25% by mass is used, the proportion of the polymer-dispersed polyol (Z) in the polyol composition (V) is 0.1 to 30% by mass. Preferably, 1-10 mass% is more preferable.
The average hydroxyl value of the polyol composition (V) is preferably 250 to 800 mgKOH / g, particularly preferably 300 to 750 mgKOH / g.

  Further, the proportion (content) of the polymer fine particles in the polyol composition (V) is preferably 0.01% by mass or more with respect to the total mass of the polyol composition (V). When the ratio of the polymer fine particles is smaller than this, it is difficult to obtain a rigid polyurethane foam excellent in low and high temperature dimensional stability. The proportion of the polymer fine particles is preferably 0.01 to 10% by mass, more preferably 0.1 to 3% by mass with respect to the total mass of the polyol composition (V).

  In the polyol composition (V), a polyol other than the polymer-dispersed polyol (Z) is referred to as a polyol (E). As this polyol (E), the above-mentioned polyether polyol, polyester polyol, hydrocarbon polymer having a hydroxyl group at the terminal, or the like can be used. These may use only 1 type or may use 2 or more types together. Further, the same polyol as that used in the base polyol (W) may be used. Here, the polyol (E) is preferably a polyether polyol alone or a combination of a polyether polyol and a polyester polyol. Moreover, it is preferable to use the polyether polyol which has a nitrogen atom in a molecule | numerator as a part of polyol (E). In particular, amine-based polyether polyols obtained by using the amines described in the section of the polyether polyol initiator as initiators are preferred. In addition, it is preferable to use a polyether polyol obtained by using an alicyclic amine as an initiator as the amine-based polyether polyol because fast curing properties are obtained.

As a more specific example of the composition of the polyol composition (V) (100 parts by mass as a whole of the polyol composition (V)), a rigid foam is produced by a spray method using only water as a foaming agent. (1) 1 to 10 parts by mass of polymer dispersed polyol (Z) having a polymer fine particle content of 20 to 30% by mass, (2) 50 to 80 parts by mass of (2a) polyester polyol as polyol (E), (2b) The composition of 10 to 40 parts by mass of amine-based polyether, (2c) 0 to 10 parts by mass of polyether polyol having no nitrogen atom, flame retardancy, relatively fast curing properties, adhesiveness, This is preferable in terms of dimensional stability and the like.
The hydroxyl value of the polyol (E) is preferably 250 to 800 mgKOH / g, more preferably 300 to 750 mgKOH / g.

<Foaming agent>
In the present invention, one or more selected from the group consisting of water, hydrocarbon compounds having 2 to 8 carbon atoms, hydrofluorocarbon, hydrofluoroether, and inert gas are used in combination as the foaming agent.

  The hydrocarbon compound preferably has 4 to 6 carbon atoms, and examples include butane, pentane, hexane, and cyclopentane. These can be used alone or in combination of two or more. As the usage-amount of these hydrocarbon compounds used as a foaming agent, 5-40 mass parts is preferable with respect to 100 mass parts of polyols, and 5-20 mass parts is more preferable.

  The hydrofluorocarbon preferably has 1 to 8 carbon atoms, particularly preferably 2 to 4 carbon atoms. Examples include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3. , 3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and the like. Of these, HFC-245fa alone, HFC-245fa and HFC-365mfc, HFC-134a and HFC-245fa, HFC-134a and HFC-365mfc, and HFC-134a and HFC- The combined use of 245fa and HFC-365mfc is preferred. The amount of these hydrofluorocarbons used is preferably such that the total amount of hydrofluorocarbons is 5 to 100 parts by mass with respect to 100 parts by mass of polyol, and more preferably 5 to 75 parts by mass. When using 2 or more types of hydrofluorocarbon together, the usage-amount of each hydrofluorocarbon has preferable 0.1-70 mass parts with respect to 100 mass parts of polyol, respectively.

The hydrofluoroether preferably has 2 to 8 carbon atoms, particularly preferably 2 to 4 carbon atoms. Examples thereof include 1,1,2,2-tetrafluoroethyl difluoromethyl ether (HFE-236pc), 1,1,2, , 2-tetrafluoroethyl methyl ether (HFE-254pc), 1,1,1,2,2,3,3-heptafluoropropyl methyl ether (HFE-347mcc) and the like.
The amount of the hydrofluoroether used is preferably such that the total amount of hydrofluoroether is 1 to 100 parts by mass with respect to 100 parts by mass of the polyol, more preferably 5 to 75 parts by mass. When using 2 or more types of hydrofluoro ether together, the usage-amount of each hydrofluoro ether has preferable 0.1-70 mass parts with respect to 100 mass parts of polyol, respectively.

The hydrocarbon compound having 2 to 8 carbon atoms, hydrofluorocarbon, and hydrofluoroether can be used without water, but is preferably used in combination with water.
Examples of the inert gas include air, nitrogen, carbon dioxide gas and the like. Of these, carbon dioxide is preferred. The addition state of the inert gas may be a liquid state, a supercritical state, or a subcritical state. The inert gas can be used without water, but is preferably used in combination with water. As for the usage-amount of an inert gas, 1-100 mass parts is preferable with respect to 100 mass parts of polyols.

In the present invention, it is particularly preferable to use water alone or a combination of water and an inert gas as the foaming agent. The inert gas used in combination with water is more preferably carbon dioxide. When water is used alone as a foaming agent or when water and an inert gas are used in combination, it is preferable to use the specific polyol composition (V) in the present invention because the dimensional stability is good.
When using water as a foaming agent, the usage-amount is 1-20 mass parts with respect to 100 mass parts of polyol compositions (V), and 2-10 mass parts is especially preferable. When the amount of water used is less than 1 part by mass, the obtained rigid foam is not preferred because it is difficult to lighten. Moreover, when there is much usage-amount exceeding 20 mass parts, the miscibility with water and a polyol composition (V) tends to worsen, and is unpreferable.

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

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

<Catalyst>
The catalyst used in the present invention is not particularly limited as long as it is a catalyst that promotes the urethanization reaction. Examples thereof include tertiary amines such as triethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine; and organometallic compounds such as dibutyltin dilaurate. These may be used alone or in combination of two or more.
A catalyst for promoting the trimerization reaction of an isocyanate group may be used in combination. Examples of the carboxylic acid metal salt such as potassium acetate and potassium 2-ethylhexanoate, and quaternary ammoniums and triazines as amine catalysts. . These may be used alone or in combination of two or more.

  When a spray method (hereinafter sometimes referred to as spray foaming) is adopted as a method for producing a rigid foam, an organic metal catalyst such as lead 2-ethylhexanoate is used in combination in order to complete the reaction in a short time. May be. As for the usage-amount of this organometallic catalyst, 0.1-10 mass parts is preferable with respect to 100 mass parts of polyol compositions (V).

<Foam stabilizer>
In the present invention, a foam stabilizer is used to form good bubbles. Examples of the foam stabilizer include silicone foam stabilizers and fluorine-containing compound foam stabilizers. Although the usage-amount of a foam stabilizer may be selected suitably, 0.1-10 mass parts is preferable with respect to 100 mass parts of polyol compositions (V).

<Other ingredients>
In this invention, arbitrary compounding agents can be used besides the polyol composition (V), the polyisocyanate compound, the foaming agent, the catalyst, and the foam stabilizer. Compounding agents include fillers such as calcium carbonate and barium sulfate; anti-aging agents such as antioxidants and UV absorbers; flame retardants, plasticizers, colorants, anti-fungal agents, foam breakers, dispersants, discoloration prevention Agents and the like.

<Method for manufacturing rigid foam>
In the present invention, the method for producing the rigid foam may be a method using a foaming device, or a method using normal hand foaming without using a foaming device. As the foaming apparatus, either a high pressure foaming apparatus or a low pressure foaming apparatus can be used. The reaction conditions may be appropriately selected, but the reaction temperature is preferably 0 to 50 ° C, more preferably 15 to 45 ° C.
Although the manufacturing method of the rigid foam of this invention is not necessarily limited, spray foaming is especially preferable. This is because in spray foaming, demands for weight reduction and odor improvement are particularly strong, and the improvement effect of the present invention is particularly great. Various methods for producing by spray foaming are known. Of these, airless spray foaming is preferred, in which the compounded liquid is mixed with a mixing head and foamed. Here, spray foaming is a foaming method in which a polyol composition containing a polyol composition (V) and a polyisocyanate compound are reacted while sprayed, and the reaction is completed in a short time by selecting a catalyst or the like. To do. Formulations other than the polyisocyanate compound can be contained in the polyol composition.
Spray foaming is often employed when constructing hard foam insulation on walls, ceilings, etc. at construction sites. Spray foaming has advantages such as manufacturing rigid foams directly at the construction site, thus reducing the construction cost, and being able to construct even on uneven construction surfaces. Specific construction examples include heat insulating materials for condominiums, office buildings, prefabricated refrigerated warehouses, etc. In recent years, they are also being used as heat insulating materials for highly airtight detached houses.

<Characteristics of rigid foam>
The rigid foam produced according to the present invention is characterized in that even if it is lightweight, there is almost no shrinkage of the foam and excellent dimensional stability. The density of the rigid foam produced according to the present invention is preferably 15 to 40 kg / m ^{3 and} particularly preferably 18 to ³⁰ kg / m ³ in terms of core density. With these lightweight rigid foams, the method for producing rigid foams of the present invention is characteristically effective (particularly dimensional stability).

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. Of the following examples, Examples 1 to 12 are production examples of polymer-dispersed polyol (Examples 1 to 4 are production examples corresponding to Comparative Examples, and Examples 5 to 12 are production examples corresponding to Examples). Examples 13 to 44 are examples in which dispersion stability and odor were evaluated when a polymer-dispersed polyol and another polyol were blended (Examples 13 to 19 were production examples corresponding to Comparative Examples, and Examples 20 to 44 were equivalent to Examples. Production example). Examples 45-95 are production examples of rigid polyurethane foam. Examples 96-144 are production examples of rigid urethane-modified polyisocyanurate foams.
Of these rigid foam production examples, Examples 45-48, Examples 62-65, Examples 80-82, Examples 96-97, Examples 112-113 and Examples 129-130 are comparative examples, and Examples 49-61. and examples 98 to 111, it is an example. Examples 66-79, Examples 83-95, Examples 114-128 and Examples 131-144 are reference examples.

  The unit of the numerical value of the part representing the prescription in the table is part by mass. The raw materials used in Examples and Comparative Examples are as shown in each table, and the details are as follows. As abbreviations, AN is acrylonitrile, ST is styrene, Vac is vinyl acetate, MMA is methyl methacrylate, EMA is ethyl methacrylate, MA is methyl acrylate, PO is propylene oxide, EO is ethylene oxide, and EO group content is oxy. Each ethylene group content is represented. AMBN represents 2,2-azobis-2-methylbutyronitrile and is a polymerization initiator.

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

(Base polyol (W))
As the base polyol (W), a mixture of the following polyols X1 and Y1, or a mixture of X1, Y1, and Y2 was used.
Polyol X1: Polyether polyol having a hydroxyl value of 50 mg KOH / g and an EO group content of 70% by mass obtained by randomly adding PO and EO to glycerin Polyol Y1: Obtained by adding only PO to glycerin A polyether polyol having a hydroxyl value of 650 mg KOH / g.
Polyol Y2: A polyether polyol having a hydroxyl value of 760 mgKOH / g obtained by adding only PO to ethylenediamine.

(Other polyol (E))
The other polyol (E) used when the polymer-dispersed polyol (Z) and the other polyol (E) are blended is as follows.
Polyol E1: A polyether polyol having a hydroxyl value of 380 mg KOH / g, obtained by adding only PO to a mixture of sucrose and glycerin (mass ratio 5: 4).
Polyol E2: A polyether polyol having a hydroxyl value of 350 mgKOH / g and an EO group content of 25% by mass, obtained by adding EO, PO, and EO to tolylenediamine in this order.
Polyol E3: A polyether polyol having a hydroxyl value of 350 mgKOH / g, obtained by adding EO to N- (2-aminoethyl) piperazine.
Polyol E4: Polyether polyol having a hydroxyl value of 400 mgKOH / g, obtained by adding PO to pentaerythritol.
Polyol E5: A polyether polyol obtained by adding PO to monoethanolamine and having a hydroxyl value of 350 mgKOH / g.
Polyol E6: hydroxyl value obtained by adding PO and EO in this order to a Mannich condensation product obtained by reacting nonylphenol, formaldehyde and diethanolamine in a molar ratio of 1.0 to 1.4 to 2.1 A polyether polyol having 450 mg KOH / g and an EO group content of 30% by mass.
Polyol E7: Polyester polyol having a hydroxyl value of 250 mgKOH / g, obtained by polycondensation of diethylene glycol and terephthalic acid.
Polyol E8: A polyether polyol having a hydroxyl value of 500 mgKOH / g obtained by adding only PO to ethylenediamine.
Polyol E9: A polyether polyol having a hydroxyl value of 450 mgKOH / g and an EO group content of 41% by mass obtained by adding PO and EO to ethylenediamine in this order.
Polyol E10: A hydroxyl value obtained by adding PO and EO in this order to a Mannich condensation product obtained by reacting nonylphenol, formaldehyde and diethanolamine in a molar ratio of 1 to 1.4 to 2.1 is 300 mgKOH / g, a polyether polyol having an EO group content of 60% by mass.

(Examples 1-4: Production Example of Polymer Dispersed Polyol)
After all of the polyol, monomer and AMBN shown in Table 1 were charged in a 5 L pressurized reaction vessel, the temperature was raised while stirring, and the reaction was continued for 10 hours while maintaining the reaction solution at 80 ° C. In all examples, the monomer conversion was 80% or more. After the completion of the reaction, the unreacted monomer was removed by heating under reduced pressure at 110 ° C. and 20 Pa for 2 hours to produce a polymer-dispersed polyol.
The polymer-dispersed polyols obtained in these examples do not correspond to the polymer-dispersed polyol (Z) in the present invention because they do not contain methacrylic acid alkyl ester or acrylic acid alkyl ester as monomers.

(Examples 5 to 12: Production examples of polymer-dispersed polyol (Z))
70 mass% of the polyol mixture shown in Table 1 is charged into a 5 L pressure reaction tank, and the remaining polyol mixture and the monomer and AMBN mixture shown in Table 1 are fed over 2 hours while stirring at 120 ° C. Then, stirring was continued for about 0.5 hours at the same temperature after completion of all the feeds. After the completion of the reaction, the unreacted monomer was removed by heating under reduced pressure at 120 ° C. and 20 Pa for 2 hours to produce a polymer-dispersed polyol (Z).

Table 1 shows the hydroxyl value (unit: mgKOH / g), viscosity at 25 ° C. (unit: mPa · s), and odor evaluation of the polymer-dispersed polyols produced in each example. As for odors, evaluation was made with “X” indicating that the odor was intense, and “◯” indicating that there was no or very little odor (hereinafter the same). In addition, Table 1 shows the dispersion stability of the produced polymer-dispersed polyol itself. Dispersion stability was evaluated under two conditions of 25 ° C. condition for 3 months and 70 ° C. condition for 1 month, respectively. If any of separation, precipitation, and solidification occurred, x was evaluated.
Moreover, the measurement result of the particle size of the polymer fine particle in a polymer dispersion polyol is shown. The average particle size 1 (unit: μm) is a value measured with a microtrack particle size distribution measuring device (laser diffraction scattering type particle size distribution measuring device FRA-9220; manufactured by Nikkiso Co., Ltd.) using methanol as a dispersion solvent. . Average particle size 2 (unit: μm) is a polymer-dispersed polyol diluted with methanol (dilution rate: 50 to 400 times), observed using a scanning electron microscope (SEMEDX3 type N; manufactured by Hitachi, Ltd.) It is a value obtained by performing image analysis (image analysis software; WinRoof ver. 3.6) using a computer.
An electron micrograph of the fine particles in the polymer-dispersed polyol obtained in Example 7 is shown in FIG.

In the following tables, the polymer-dispersed polyols produced in Examples 1 to 12 are represented as follows in order.
Examples 1-4: Polyols NZ1 to NZ4.
Examples 5-12: Polyols Z1-Z8.

(Examples 13 to 44, storage stability, odor evaluation example)
The polymer-dispersed polyols (NZ1 to NZ4 and Z1 to Z8) and other polyols were blended and mixed in the ratios shown in Tables 2 and 3, and the dispersion stability and odor of the resulting polyol mixtures were evaluated. Dispersion stability was evaluated under two conditions of 25 ° C. condition for 3 months and 70 ° C. condition for 1 month, respectively. If any of separation, precipitation, and solidification occurred, x was evaluated.
The polyol mixture obtained in Examples 20 to 44 corresponds to the polyol composition (V) in the present invention.

(Examples 45-95: Production examples of rigid polyurethane foam)
In the formulations shown in Tables 4 to 9, a polyol mixture (a mixture of a polymer-dispersed polyol and another polyol) and a foaming agent were used. The water in the table corresponds to the foaming agent (hereinafter the same).
A polyol composition was prepared by adding and mixing a polyol mixture, a foaming agent, and the following catalyst, foam stabilizer and flame retardant.
As the catalyst, N, N, N ′, N′-tetramethylhexanediamine (trade name: TOYOCAT MR, manufactured by Tosoh Corporation) was used. The amount used was such that the gel time was 25 seconds.
As the foam stabilizer, 2 parts by mass of a silicone foam stabilizer (trade name: SZ-1646, manufactured by Nippon Unicar Co., Ltd.) was used. As the flame retardant, 10 parts by mass of tris (2-chloropropyl) phosphate (trade name: TMCPP, manufactured by Daihachi Chemical Co., Ltd.) was used.
The prepared polyol composition and polyisocyanate compound were mixed at a liquid temperature of 20 ° C., and placed in a wooden box having a length of 200 mm × width of 200 mm × height of 200 mm, and a rigid polyurethane foam was foamed and produced.
As the polyisocyanate compound, polymethylene polyphenyl polyisocyanate (trade name: MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used. The amount of polyisocyanate compound used was set to 110 in terms of isocyanate index.

(Physical property evaluation of rigid foam)
The core density (unit: kg / m ³ ) and the high temperature and high humidity shrinkage (unit:%) of the rigid foam (rigid polyurethane foam) obtained in each of Examples 45 to 95 were evaluated. The results are shown in Tables 4-9. The high temperature and high humidity shrinkage indicates a dimensional change rate in a direction perpendicular to the foaming direction after elapse of 24 hours at 70 ° C./95%.
As shown in Tables 4 to 9, the rigid foams produced by the rigid foam production method of the present invention (Examples 49 to 61, Examples 66 to 79, and Examples 83 to 95) all have a low density and are good. Dimensional stability was demonstrated.

(Examples 96 to 144: Production example of rigid urethane-modified polyisocyanurate foam)
In the formulations shown in Tables 10 to 15, a polyol mixture (a mixture of a polymer-dispersed polyol and a polyol) and a foaming agent were used. A polyol composition was prepared by adding and mixing a polyol mixture, a foaming agent, and the following catalyst, foam stabilizer and flame retardant.
As examples of the catalyst, ethylene glycol solution of 1,2-dimethylimidazole (trade name: Toyocat DM-70, manufactured by Tosoh Corporation), which is an amine catalyst in Examples 96 to 111, trade name: Toyocat TT (manufactured by Tosoh Corporation), grade 4 A mixture obtained by mixing Toyocat TRX (manufactured by Tosoh Corp.) at a mass ratio of 3/1/3 as an ammonium catalyst was used in such an amount that the gel time was 20 seconds.
In Examples 112 to 144, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-S-triazine (trade name: Polycat 41, manufactured by Air Products) and diethylene glycol solution of potassium 2-ethylhexanoate ( Potassium concentration 15%, trade name: PACCAT 15G, manufactured by Nippon Kagaku Sangyo Co., Ltd.) was used at a mass ratio of 2/3 and the amount used was such that the gel time was 20 seconds.
As the foam stabilizer, 1.5 parts by mass of SH-193 was used. As the flame retardant, 20 parts by mass of TMCPP was used.
The prepared polyol composition and polyisocyanate compound were mixed at a liquid temperature of 20 ° C., and placed in a wooden box having a length of 200 mm × width of 200 mm × height of 200 mm, and a rigid urethane-modified polyisocyanurate foam was foamed and produced.
As the polyisocyanate compound, polymethylene polyphenyl polyisocyanate (trade name: C-1130, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used. The amount of polyisocyanate compound used was set to 160 in terms of isocyanate index.

(Physical property evaluation of rigid foam)
About the rigid foam (rigid urethane-modified polyisocyanurate foam) obtained in each of Examples 96 to 144, the core density (unit: kg / m ³ ) and the high temperature and high humidity shrinkage (unit: %). The results are shown in Tables 10-15.
As shown in Tables 10 to 15, the rigid foams (Examples 98 to 111, Examples 114 to 128, and Examples 131 to 144) manufactured by the method for manufacturing a rigid foam of the present invention are low in density and good. Dimensional stability was demonstrated.

(Example 1 of rigid foam production by spray method)
Next, to the polyol compositions prepared in Examples 49 to 61, Examples 66 to 79, and Examples 114 to 128, a mineral spirit solution of lead 2-ethylhexanoate as an organometallic catalyst (lead concentration: 20%, trade name: Nikkaoku) 1.0 part by mass of 20% Chicks lead (manufactured by Nippon Chemical Industry Co., Ltd.) was further added.
In addition, a mineral spirit solution of lead 2-ethylhexanoate as an organometallic catalyst was added to the polyol compositions prepared in Examples 98 to 111 (lead concentration: 20%, trade name: Nikka Octix Lead 20%, manufactured by Nippon Chemical Industry Co., Ltd.) Was further added in an amount of 3.0 parts by mass.
Using the liquid obtained in each case and polymethylene polyphenyl polyisocyanate (trade name: C-1155, manufactured by Nippon Polyurethane Industry Co., Ltd.) as the polyisocyanate compound, foaming by Gasmer Co., Ltd. at a liquid temperature of 35 ° C. and a room temperature of 10 ° C. We sprayed the wall surface by spray foaming using a machine.
As a result, the foam obtained had a good foaming process even though it was produced at a room temperature of 10 ° C. and a low temperature assuming winter, and the density of the obtained rigid foam was a core density of 29 kg / m ³ or less. It was sufficiently low and showed good cell appearance, initial adhesion, and self-extinguishing properties.

  Furthermore, using the polyol compositions prepared in Examples 98 to 111 and Examples 114 to 128, which are production examples of rigid urethane-modified polyisocyanurate foam, the core portion of the rigid foam obtained by spray foaming is thickened. It cut out to 15 mm, and when the combustion test based on ISO5600Part1 was implemented with the cone calorimeter (made by Toyo Seiki Seisakusho), it turned out that predetermined flame-retardant performance is satisfied.

(Example 2 of rigid foam production by spray method)
In this example, carbon dioxide gas in a supercritical state was further used as the foaming agent.
That is, to the polyol composition used in Examples 49 to 61, a mineral spirit solution of lead 2-ethylhexanoate as an organometallic catalyst (lead concentration: 20%, trade name: Nikka Octix Lead 20%, manufactured by Nippon Chemical Industry Co., Ltd.) ) Was further added in an amount of 1.0 part by mass.
Further, a mineral spirit solution of lead 2-ethylhexanoate as an organometallic catalyst was added to the polyol composition used in Examples 98 to 111 (lead concentration: 20%, trade name: Nikka Octix Lead 20%, manufactured by Nippon Chemical Industry Co., Ltd.) Was further added in an amount of 3.0 parts by mass.
While using C-1155 as a polyisocyanate compound and the liquid obtained in each, 2 mass% carbon dioxide gas was used in a supercritical state at a liquid temperature of 40 ° C. and a pressure of 70 kg / cm ² with respect to 100 mass% of polyol. Then, spraying was performed on the wall surface at a room temperature of 10 ° C. by spray foaming using a gasmer foaming machine.
The resulting foam showed a good foaming process even though it was manufactured at room temperature of 10 ° C. and a low temperature assuming winter, and the density of the rigid foam obtained was a core density of 28 kg / m ³ or less. It was sufficiently low and showed good cell appearance, initial adhesion, and self-extinguishing properties.

  Furthermore, using the polyol composition prepared in Examples 98 to 111, which are production examples of rigid urethane-modified polyisocyanurate foam, for the rigid foam obtained by spray foaming, the core portion is cut out to a thickness of 15 mm, When the combustion test based on ISO5600Part1 was implemented with the cone calorimeter (made by Toyo Seiki Seisakusho), it turned out that predetermined flame-retardant performance is satisfied.

  According to the method for producing a rigid foam synthetic resin of the present invention, a rigid foam that hardly undergoes foam shrinkage and can be reduced in weight can be obtained. In particular, the production method of the present invention has little foam shrinkage even when a relatively large amount of water is used as a foaming agent, has no odor during foam production, and is easy to handle during production.

It is an electron micrograph of the polymer fine particle in the polymer dispersion | distribution polyol obtained by the manufacture example concerning this invention.

Claims (6)

In a method for producing a rigid foam synthetic resin by reacting a polyol composition (V) and a polyisocyanate compound in the presence of a foam stabilizer, a catalyst and a foaming agent,
0.1% by mass or more of the polyol composition (V) is the polymer-dispersed polyol (Z) in which polymer fine particles are dispersed in the base polyol (W),
The polymer particles, see contains at least one selected from at least one and, the group consisting of polymerizable unsaturated bond-containing nitrile selected from the group consisting of acrylic acid alkyl esters and methacrylic acid alkyl esters,
The content of the other monomer is not at least one selected from the group consisting of the alkyl acrylate ester and the alkyl methacrylate ester, or at least one selected from the group consisting of the polymerizable unsaturated bond-containing nitrile. Polymer fine particles obtained by polymerizing the monomer (M) that is 20% by mass or less ,
The method for producing a hard foam synthetic resin, wherein the foaming agent is water only or water and carbon dioxide gas. The polymer fine particles are polymer fine particles obtained by polymerizing a monomer (M) containing an alkyl methacrylate and at least one selected from the group consisting of polymerizable unsaturated bond-containing nitriles. Manufacturing method of hard foam synthetic resin. The method for producing a rigid foam synthetic resin according to claim 2, wherein the alkyl methacrylate is methyl methacrylate. The average hydroxyl value of the base polyol (W) is 200 to 800 mgKOH / g, and 5% by mass or more of the base polyol (W) has a hydroxyl value of 84 mgKOH / g or less and an oxyethylene group content of 40 mass. The method for producing a rigid foam synthetic resin according to any one of claims 1 to 3 , wherein the polyether polyol (X) is at least%. The amount of water used as the foaming agent is 1 to 20 parts by mass with respect to 100 parts by mass of the polyol composition (V), of the rigid foam synthetic resin according to any one of claims 1 to 4. Production method. The method for producing a rigid foam synthetic resin according to any one of claims 1 to 5 , wherein the foam is reacted and foamed by a spray method.

Images