JP2022030316A - Method for producing polyurethane foam - Google Patents

Abstract

To provide a polyurethane foam that is prevented from being peeled from an end of it and a method for producing a polyurethane foam.SOLUTION: A polyurethane foam is made by spraying, reacting and foaming a foamable polyurethane composition containing a polyol, a foamer, a catalyst, and a polyisocyanate. The polyurethane foam has an average thickness of 15 mm or more. In at least one end of it, the thickness at a site of 5 cm from the end is 10 mm or less. There is also provided a method for producing the polyurethane foam.SELECTED DRAWING: None

Description

The present invention relates to polyurethane foam and a method for producing the same.

Polyurethane foam is used as a heat insulating material for buildings such as condominiums and other condominiums, detached houses, various school facilities, and commercial buildings because of its excellent heat insulating properties and adhesiveness. Polyurethane foam is obtained by mixing a polyol composition and polyisocyanate and foaming them.
As a construction method, a method such as mixing a polyol composition and a polyisocyanate, reacting them, foaming them, and spraying them at a construction site is adopted (see, for example, Patent Document 1).

By the way, when the polyurethane foam is sprayed onto a base material, there may be a mixture of parts where heat insulation is required and parts where heat insulation is not required in one base material. In this case, as shown in FIG. 1, the polyurethane foam 1 is formed only at a portion where heat insulation of the base material 2 is required.

Japanese Unexamined Patent Publication No. 2016-145360

As described above, when the polyurethane foam is formed on a part of the base material, there is a problem that the polyurethane foam is peeled off from the terminal E side as shown in FIG.
In view of the above-mentioned problems, it is an object of the present invention to provide a polyurethane foam and a method for producing a polyurethane foam which does not cause peeling from the end.

As a result of diligent studies to solve the above problems, the present inventor has found that the above problems can be solved by providing an inclination as shown in FIG. 3 at the end portion of the polyurethane foam. Was completed. That is, the present invention provides the following [1] to [18].

[1] A polyurethane foam obtained by spraying, reacting and foaming a foamable polyurethane composition containing a polyol, a foaming agent, a catalyst, and a polyisocyanate, having an average thickness of 15 mm or more and at least a part thereof. A polyurethane foam having a thickness of 10 mm or less at an end portion 5 cm from the end portion.
[2] The polyurethane foam according to the above [1], wherein the catalyst contains a trimerization catalyst.
[3] The polyurethane foam according to the above [2], wherein the trimerization catalyst contains a quaternary ammonium salt.
[4] The polyurethane foam according to any one of the above [1] to [3], wherein the catalyst contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin.
[5] The polyurethane foam according to any one of the above [1] to [4], wherein the catalyst contains an imidazole derivative.
[6] The polyurethane foam according to any one of the above [1] to [5], which has an isocyanate index of 200 or more.
[7] The polyurethane foam according to any one of the above [1] to [6], wherein the foaming agent contains a hydrofluoroolefin.
[8] The polyurethane foam according to any one of the above [1] to [7], wherein the foamable polyurethane composition further contains a filler.
[9] The polyurethane foam according to any one of the above [1] to [8], which has a multilayer structure, the lowermost layer extends to the end, and the upper layer has an end on the inner side of the lower layer. ..

[10] A method for producing a polyurethane foam, wherein a foamable polyurethane composition containing a polyol, a foaming agent, a catalyst, and a polyisocyanate is sprayed, reacted, and foamed to form a polyurethane foam, wherein the polyurethane foam has an average thickness. A method for producing a polyurethane foam having a thickness of 15 mm or more and at least a part of the end having a thickness of 5 cm from the end of 10 mm or less.
[11] The method for producing a polyurethane foam according to the above [10], wherein the catalyst contains a trimerization catalyst.
[12] The method for producing a polyurethane foam according to the above [11], wherein the quantification catalyst contains a quaternary ammonium salt.
[13] The method for producing a polyurethane foam according to any one of the above [10] to [12], wherein the catalyst contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin.
[14] The method for producing a polyurethane foam according to any one of the above [10] to [13], wherein the catalyst contains an imidazole derivative.
[15] The method for producing a polyurethane foam according to any one of the above [10] to [14], which has an isocyanate index of 200 or more.
[16] The method for producing a polyurethane foam according to any one of the above [10] to [15], wherein the foaming agent contains a hydrofluoroolefin.
[17] The method for producing a polyurethane foam according to any one of the above [10] to [16], wherein the foamable polyurethane composition further contains a filler.
[18] The polyurethane foam according to any one of the above [10] to [17], which has a multilayer structure, the lowermost layer extends to the end, and the upper layer has an end on the inner side of the lower layer. Manufacturing method.

According to the present invention, it is possible to provide a polyurethane foam and a method for producing a polyurethane foam that does not peel off from the end even when the polyurethane foam is formed on a part of one base material.

It is a conceptual diagram which shows the shape of the end of a polyurethane foam constructed by a usual method. It is a conceptual diagram which shows the state which the polyurethane foam was peeled off. It is a conceptual diagram which shows the polyurethane foam of this invention. It is a conceptual diagram which shows one aspect of the polyurethane foam of this invention. It is a conceptual diagram which shows the other aspect of the polyurethane foam of this invention. It is a conceptual diagram which shows the other aspect of the polyurethane foam of this invention. It is a conceptual diagram which shows the other aspect of the polyurethane foam of this invention. It is a conceptual diagram which shows the aspect of the polyurethane foam which concerns on a comparative example. It is a conceptual diagram which shows the aspect of the polyurethane foam which concerns on a comparative example.

The polyurethane foam of the present invention comprises a foamable polyurethane composition containing a polyol, a foaming agent, a catalyst, and a polyisocyanate, which is sprayed, reacted and foamed. The polyurethane foam is characterized in that the average thickness is 15 mm or more, and at least at a part of the end portion, the thickness of the portion 5 cm from the end portion is 10 mm or less.

[Effervescent polyurethane composition]
The effervescent polyurethane composition of the present invention contains a polyol, a foaming agent, a catalyst, and an isocyanate. Each component in the effervescent polyurethane composition will be described in detail below.

<Polyol>
The effervescent polyurethane composition of the present invention contains a polyol as a raw material for polyurethane foam.
Examples of the polyol used in the present invention include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols. The polyol usually becomes a liquid at normal temperature (23 ° C.) and normal pressure (1 atm).

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.
Examples of the polycarbonate polyol include a polyol obtained by a dealcohol reaction between a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentandiol, hexanediol, octanediol, and nonanediol and ethylene carbonate, propylene carbonate, or the like. And so on.

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolak and the like.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol and the like.
Examples of the aliphatic polyol include alkanediols such as ethylene glycol, propylene glycol, butanediol, pentandiol, and hexanediol.

Examples of the polyester polyol include a polymer obtained by dehydrating and condensing a polybasic acid and a polyhydric alcohol, and a condensate of a hydroxycarboxylic acid and the polyhydric alcohol and the like.
Examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), succinic acid and the like. Examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexaneglycol, neopentyl glycol and the like.
Examples of the hydroxycarboxylic acid include castor oil and reaction products of castor oil and ethylene glycol.

Examples of the polymer polyol include a polymer obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, or the like. , Polybutadiene polyols, or their hydrogenated additives and the like.

As the polyether polymer, for example, at least one kind of alkylene oxide such as ethylene oxide, propylene oxide and tetrahydrofuran is ring-opened in the presence of at least one kind such as a low molecular weight active hydrogen compound having two or more active hydrogens. Examples thereof include a polymer obtained by polymerization. Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol and 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. , Pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives, tetra-octavalent alcohols, ethylenediamine, butylene diamine, etc. Examples of amines and the like.

The polyol used in the present invention is preferably at least one selected from the group consisting of polyester polyols and polyether polyols. Polyester polyols are more preferred from the standpoint of foamability and reactivity. Further, a polyol having two hydroxyl groups is preferable. Of these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferable from the viewpoint of enhancing flame retardancy. Examples of the aromatic polyester polyol include polybasic acids having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), bisphenol A, ethylene glycol, 1,2-propylene glycol and the like. An aromatic polyester polyol obtained by dehydration condensation with the dihydric alcohol of No. 1 is more preferable. By using an aromatic polyester polyol, flame retardancy can be easily improved.

The hydroxyl value of the polyol is preferably 20 to 350 mgKOH / g, more preferably 50 to 300 mgKOH / g, and even more preferably 100 to 250 mgKOH / g. When the hydroxyl value of the polyol is not more than the upper limit, the viscosity of the polyol composition described later tends to decrease, which is preferable from the viewpoint of handleability and the like. On the other hand, when the hydroxyl value of the polyol is at least the above lower limit value, the crosslink density of the polyurethane foam is increased and the strength is increased.
The hydroxyl value of the polyol can be measured according to JIS K 1557-1: 2007.

The content of the polyol in the effervescent polyurethane composition of the present invention is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, still more preferably 15 to 20% by mass. When the content of the polyol is at least the above lower limit value, the polyol and the polyisocyanate are likely to react with each other, which is preferable. On the other hand, when the content of the polyol is not more than the upper limit, the viscosity of the polyol composition does not become too high, which is preferable from the viewpoint of handleability.

<Effervescent agent>
The foaming agent promotes the foaming of the urethane resin. Examples of the foaming agent include water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and other low-boiling hydrocarbons, dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, and the like. Chlorinated aliphatic hydrocarbon compounds such as isobutyl chloride, pentyl chloride and isopentyl chloride, hydrofluoroolefins (hereinafter sometimes referred to as "HFO"), ether compounds such as diisopropyl ether, or mixtures of these compounds, etc. Examples thereof include organic physical foaming agents, nitrogen gas, oxygen gas, argon gas, carbon dioxide gas and other inorganic physical foaming agents.
Among these, it is preferable to contain hydrofluoroolefin (HFO), which has high stability as a foaming agent, is less likely to reduce catalytic activity, and has a low environmental load.

Examples of the HFO which is a suitable foaming agent include fluoroalkenes having about 3 to 6 carbon atoms. Further, the HFO may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms.
Examples of the HFO include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropene such as HFO-1233, and chlorotetrafluoropropene. Will be.
More specifically, 3,3,3-trifluoropropene (HFO-1243zf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3 , 3-Tetrafluoropropene (HFO-1234ze (Z)), 2,3,3,3-Tetrafluoropropene (HFO-1234yf), 1,1,3,3-Tetrafluoropropene, Sis-1,3,3 3,3-tetrafluoropropene (HFO-1234ze (Z)), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), cis-1,2,3,3 3-Pentafluoropropene (HFO-1225ye (Z),), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2,3,3-pentafluoropropene (HFO-) 1225yc), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd (E)), 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz). ) Etc. can be mentioned. Among these, HFO-1233zd (E) is preferable.

The content of the foaming agent is not particularly limited, and is preferably 20 to 70 parts by mass, more preferably 25 to 60 parts by mass, and even more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the polyol. When the content of the foaming agent is at least the above lower limit value, foaming is promoted, foamability is improved, and the density of the obtained polyurethane foam can be reduced. On the other hand, when the content of the foaming agent is not more than the upper limit, it is possible to prevent the foaming from progressing excessively.

The above-mentioned foaming agent may be used alone or in combination of two or more. In the foamable polyurethane composition of the present invention, it is preferable to use the above-mentioned HFO and other foaming agents in combination. For example, HFO may be used in combination with water, oxygen gas, or carbon dioxide gas having excellent handleability. .. In particular, water is preferable from the viewpoint of adjusting the isocyanate index and from the viewpoint of ease of handling.

<Catalyst>
Examples of the catalyst used in the foamable polyurethane composition of the present invention include a resinification catalyst, a trimerization catalyst and the like, and preferably both a resinification catalyst and a trimerization catalyst are used. Examples of the resinification catalyst include a resinified metal catalyst, a resinified amine catalyst, and the like, as described later, and both of them may be used.

<< Metal catalyst (resinized metal catalyst) >>
The catalyst used in the effervescent polyurethane composition of the present invention preferably contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin. This metal catalyst is generally called a resinified metal catalyst. In the present invention, the inclusion of the metal catalyst promotes the reaction between the polyol and the polyisocyanate. Further, if a filler described later is contained in a certain amount or more, the reactivity of the polyurethane foam is hindered and the foamability tends to decrease, but by containing a metal catalyst, the foamability of the polyurethane foam can be easily maintained. The metal catalyst more preferably contains bismuth from the viewpoint of foamability and the like.

The resinized metal catalyst is preferably a metal salt selected from bismuth and tin, and more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. When the carboxylic acid has 5 or more carbon atoms, its stability with respect to a foaming agent, particularly a hydrofluoroolefin, becomes good. The carbon number of the carboxylic acid is preferably 18 or less, more preferably 12 or less, from the viewpoint of catalytic activity and the like. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or may have a branched structure, but it is preferable that the carboxylic acid has a branched structure.
Specific examples of the carboxylic acid include octyl acid, lauryl acid, versatic acid, pentanic acid, acetic acid and the like, and among these, octyl acid is preferable. That is, the transition metal salt is preferably a metal salt of octylic acid. These carboxylic acids may be linear as described above, but may have a branched structure. Examples of the octyl acid having a branched structure include 2-ethylhexanoic acid.
As the metal salt of carboxylic acid, a bismuth salt of carboxylic acid and a tin salt of carboxylic acid are preferable, and a bismuth salt of octyl acid is particularly preferable. Further, the metal salt of the carboxylic acid may be a carboxylate of an alkyl metal. For example, the carboxylic acid tin salt may be a dialkyltin carboxylate or the like, preferably a dioctyltin carboxylate or the like.
Specific examples of the metal salt of the carboxylic acid include bismuth trioctate, dioctyl tin versate, dibutyl tin dilaurate, dioctyl tin dilaurate, tin dioctylate and the like, preferably bismuth trioctate, dioctyl tin versate and more preferably. Bismuth Trioctate.

The content of the metal catalyst in the foamable polyurethane composition is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and 1.5 to 6 parts by mass with respect to 100 parts by mass of the polyol. More preferably, 2 to 5 parts by mass is even more preferable. When the content of the metal catalyst is at least the above lower limit value, the curing reaction speed of the effervescent polyurethane composition is improved and the effervescent property is improved. On the other hand, when the content of the metal catalyst is not more than the upper limit value, the reaction can be easily controlled.

《Imidazole derivative》
The catalyst used in the effervescent polyurethane composition of the present invention preferably contains a resinified amine catalyst, and more preferably contains an imidazole derivative as the resinified amine catalyst.
The imidazole derivative is less susceptible to the influence of hydrofluoroolefins, and makes it easier for the polyol to react with the polyisocyanate while increasing the stability of the polyol composition. Therefore, the effervescent polyurethane composition contains the imidazole derivative in addition to the above-mentioned metal catalyst, so that the reactivity between the polyol and the isocyanate is enhanced, and the effervescent property is further improved.
The imidazole derivative is preferably an imidazole in which the 1-position and the 2-position are independently substituted with an alkyl group having 8 or less carbon atoms, and the alkyl group preferably has 6 or less carbon atoms, and more preferably 4 or less carbon atoms. A suitable specific example of the imidazole derivative is represented by the following general formula (1).

（一般式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に炭素数１～８のアルキル基又は炭素数２～８のアルケニル基を表す。）

(In the general formula (1), R ¹ and R ² independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, respectively.)

R ¹ and R ² in the general formula (1) independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, respectively. The alkyl group and the alkenyl group may be linear or have a branched structure.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, isopentyl group, sec-pentyl group, hexyl group and heptyl. Groups, octyl groups and the like can be mentioned.
Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group and the like.
When the carbon number of the alkyl group or alkenyl group of R ¹ and R ² is at least the above lower limit value, steric hindrance becomes large and it is less likely to be affected by a foaming agent such as a hydrofluoroolefin, which is preferable. On the other hand, when the carbon number of the alkyl group of R ¹ and R ² is not more than the above upper limit value, the steric hindrance does not become extremely large, so that the reaction between the polyol and the polyisocyanate can be rapidly promoted, and the foamability becomes foamy. Will also be good.
From these viewpoints, R ¹ and R ² are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

Examples of the imidazole derivative represented by the general formula (1) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl. Examples thereof include -2-methylimidazole, among which 1,2-dimethylimidazole and 1-isobutyl-2-methyl are used from the viewpoint of improving the activity of the catalyst in the presence of hydrofluoroolefin and promptly advancing the reaction. Imidazole is preferred. Further, 1,2-dimethylimidazole is more preferable from the viewpoint of further enhancing the stability.

The content of the imidazole derivative in the effervescent polyurethane composition is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, still more preferably 2 to 15 parts by mass, based on 100 parts by mass of the polyol. 3 to 10 parts by mass is particularly preferable. When the content of the imidazole derivative is at least the above lower limit value, the formation of urethane bonds is likely to occur, the reaction proceeds rapidly, and the foamability becomes good. On the other hand, when the content of the imidazole derivative is not more than the above upper limit value, the reaction rate can be easily controlled, which is preferable.

《Triquantization catalyst》
The effervescent polyurethane composition of the present invention preferably further contains a trimerization catalyst. The trimerization catalyst is a catalyst that promotes the formation of an isocyanurate ring by reacting an isocyanate group contained in polyisocyanate to trimerize it. The inclusion of the trimerization catalyst has the advantage that the reaction of the unreacted isocyanate group is completed and a good foam is obtained. Examples of the trimerization catalyst include metal catalysts and ammonium salts.
Examples of the metal catalyst used as the trimerization catalyst (trimerization metal catalyst) include potassium organic acid, preferably potassium octylate such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, and the like. It is potassium carboxylate having 2 to 8 carbon atoms such as potassium benzoate.
As the ammonium salt, a tertiary ammonium salt such as triethylammonium salt and triphenylammonium salt, a quaternary ammonium salt such as tetramethylammonium salt, tetraethylammonium salt and tetraphenylammonium salt can be used. Of these, a quaternary ammonium salt is preferable. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of the carboxylic acid in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The saturated fatty acid may have a linear hydrocarbon group or may have a branch, but it is preferable that the saturated fatty acid has a branch. Specific examples of the carboxylic acid include 2-ethylhexanoic acid, 2,2-dimethylpropionic acid, acetic acid, and formic acid, and among these, 2,2-dimethylpropionic acid is preferable. The trimerization catalyst may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable to use a quaternary ammonium salt and a metal catalyst in combination.

The content of the trimerization catalyst in the foamable polyurethane composition is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, still more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the polyol. 4 to 18 parts by mass is even more preferable. When the content of the trimerization catalyst is at least the above lower limit value, there is no big difference in the activity between the resinification and the trimerization, the foaming can be suppressed from being in two stages, and the foaming property is improved. On the other hand, when the content of the quantification catalyst is not more than the above upper limit value, the resinification reaction proceeds to the activity, so that the activity of the quantification can be assisted by the heat of the resinification reaction, and the foaming property becomes good, which is good. A foam can be formed.

<Polyisocyanate>
The effervescent polyurethane composition according to the present invention further contains a polyisocyanate.
Examples of the polyisocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
Examples of the aromatic polyisocyanate include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI). Will be.

Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.

Among these, aromatic polyisocyanates are preferable from the viewpoint of ease of use and availability, and diphenylmethane diisocyanate, polypeptide MDI, or a mixture thereof is more preferable. As the polyisocyanate, one type may be used alone, or two or more types may be mixed and used.
Further, the polyisocyanate may be appropriately blended with a known additive to be blended with the polyisocyanate before being mixed with the polyol composition.

<Isocyanate index>
The isocyanate index of the polyurethane foam of the present invention is not particularly limited, but is preferably 200 or more. When the isocyanate index is at least the lower limit value, the amount of polyisocyanate with respect to the polyol becomes excessive, and isocyanurate bonds are easily generated by the trimericized polyisocyanate, and as a result, the flame retardancy of the polyurethane foam is improved. It is also possible to impart nonflammability. Further, when the above lower limit value or more is set, a polyurethane foam having a sufficient isocyanurate bond, that is, a polyurethane foam having a high level of flame retardancy and heat insulating property, is produced in combination with the combined use of the above-mentioned various catalysts. Easy to manufacture. From these viewpoints, the isocyanate index is more preferably 250 or more, further preferably 300 or more, further preferably 350 or more, and particularly preferably 400 or more.
The isocyanate index is preferably 1,000 or less, more preferably 800 or less, and even more preferably 600 or less. When the isocyanate index is not more than the upper limit value, flame retardancy sufficiently commensurate with the manufacturing cost can be obtained.
In addition, the high isocyanate index may promote peeling from the end of the polyurethane foam, and the polyurethane foam having a high isocyanate index is more likely to exert the effect of the present invention.

The isocyanate index can be calculated by the following method.
Isocyanate index = equivalent number of polyisocyanate ÷ (equivalent number of polyol + equivalent number of water) × 100
Here, each equivalent number can be calculated as follows.
Equivalent number of polyisocyanate = amount of polyisocyanate used (g) x NCO content (mass%) / molecular weight of NCO (mol) x 100
Equivalent number of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol)
OHV is the hydroxyl value (mgKOH / g) of the polyol.
Equivalent number of water = molecular weight of water (g) / molecular weight of water (mol) x number of OH groups of water In each of the above formulas, the molecular weight of NCO is 42 (mol) and the molecular weight of KOH is 56,100 (mmol). ), The molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

<Filler>
The effervescent polyurethane composition of the present invention preferably contains a filler. The filler is contained as a solid component in the effervescent polyurethane composition, and is a component generally present as a granular or powdery component in the effervescent polyurethane composition. In the present invention, by containing a filler, it becomes easy to improve various physical properties such as flame retardancy and mechanical properties of the obtained polyurethane foam.
In addition, the filler may promote peeling from the end of the polyurethane foam, and the polyurethane foam containing the filler is more likely to exhibit the effect of the present invention.

The filler may be a component that is solid at room temperature (23 ° C.) and normal pressure (1 atm) and does not dissolve in the effervescent polyurethane composition. The filler preferably has no hygroscopicity and deliquescent property from the viewpoint of reducing the water absorption rate of the polyurethane foam.
Specifically, as the filler, it is preferable to use a solid flame retardant that is solid at normal temperature (23 ° C.) and normal pressure (1 atm). The solid flame retardant is selected from red phosphorus flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, boric acid-containing flame retardants, antimony-containing flame retardants, chlorine-containing flame retardants, metal hydroxides, needle-like fillers, etc. It is preferably at least one of the above. By using a solid flame retardant as a filler, the flame retardancy of urethane foam is improved. The solid flame retardant may be used alone or in combination of two or more.
Further, as the filler, an inorganic filler other than the solid flame retardant may be used. The inorganic filler other than the solid flame retardant is preferably used in combination with the solid flame retardant from the viewpoint of flame retardancy, but the inorganic filler other than the solid flame retardant may be used alone as the filler. Of course, the solid flame retardant may be used alone.

(Red phosphorus flame retardant)
The red phosphorus-based flame retardant used as a filler may be composed of red phosphorus alone, may be red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or the like, or may be a red phosphorus coated with a resin or a metal. It may be a mixture of hydroxide, metal oxide and the like. The resin coated with red phosphorus or mixed with red phosphorus is not particularly limited, and examples thereof include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. Be done. As the film or the compound to be mixed, a metal hydroxide is preferable from the viewpoint of flame retardancy. As the metal hydroxide, those described later may be appropriately selected and used.

(Phosphate-containing flame retardant)
The phosphate-containing flame retardant is at least selected from various phosphates, metals of the Group IA to IVB of the Periodic Table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Phosphates consisting of salts with one metal or compound can be mentioned. The term "various phosphoric acids" is a concept that includes not only phosphoric acid but also phosphorous acid, hypophosphoric acid and the like.
Examples of the metals of Group IA to Group IVB of the Periodic Table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like. Examples of the aromatic amine include aniline, o-triidin, 2,4,6-trimethylaniline, anicidin, 3- (trifluoromethyl) aniline and the like. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine and the like.

Specific examples of the phosphate-containing flame retardant include monophosphate, polyphosphate and the like. The monophosphate is not particularly limited, but for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, and phosphite. Sodium salts such as monosodium, disodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphite Potassium salts such as potassium, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphate, dilithium phosphate, lithium salts such as lithium hypophosphite, barium dihydrogen phosphate, phosphorus Barium salts such as barium hydrogen phosphate, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium salts such as magnesium hypophosphite, calcium dihydrogen phosphate , Calcium hydrogen phosphate, tricalcium phosphate, calcium salts such as calcium hypophosphite, zinc salts such as zinc phosphate, zinc phosphite, zinc hypophosphite and the like.
Here, the polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate, and the like.
The phosphate-containing flame retardant may be used alone from the above-mentioned ones, or may be used in combination of two or more.

(Brominated flame retardant)
The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure and is solid at room temperature (23 ° C.) and normal pressure (1 atm). Examples include compounds.
Examples of the brominated aromatic ring-containing aromatic compound include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, and ethylenebis (pentabromophenoxy). Examples thereof include monomer-based organic bromine compounds such as pentabromophenyl), ethylene bis (tetrabromophthalimide), and tetrabromobisphenol A.

Further, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer. Specifically, a polycarbonate oligomer produced from brominated bisphenol A as a raw material, a brominated polycarbonate such as a copolymer of this polycarbonate oligomer and bisphenol A, and a diepoxy compound produced by the reaction of brominated bisphenol A with epichlorohydrin. And so on. Furthermore, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, condensates of brominated phenols of brominated polyphenylene ether, brominated bisphenol A and cyanur chloride, uncrosslinked or crosslinked. Examples include brominated polystyrene.
Further, it may be a compound other than a brominated aromatic ring-containing aromatic compound such as hexabromocyclododecane.
These brominated flame retardants may be used alone or in combination of two or more.

(Boron-containing flame retardant)
Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, borate and the like. Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide and the like.
Examples of the borate include alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the Periodic Table, and ammonium borates. Specifically, an alkali metal borate salt such as lithium borate, sodium borate, potassium borate, and cesium borate, an alkaline earth metal salt borate such as magnesium borate, calcium borate, and barium borate, boro Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.
The boron-containing flame retardant may be used alone or in combination of two or more.
The boron-containing flame retardant used in the present invention is preferably borate, more preferably zinc borate.

(Antimony-containing flame retardant)
Examples of the antimony-containing flame retardant include antimony oxide, antimony acid salt, pyroantimony acid salt and the like. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of the antimonate include sodium antimonate, potassium antimonate and the like. Examples of the pyroantimonate include sodium pyroantimonate, potassium pyroantimonate and the like.
The antimony-containing flame retardant may be used alone or in combination of two or more. The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

(Chlorine-containing flame retardant)
Examples of the chlorine-containing flame retardant include those commonly used for polyurethane foam, such as polynaphthalene chloride, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name of "Dechloran Plus". Be done.

(Metal hydroxide)
Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, and copper hydroxide. Examples thereof include vanadium hydroxide and tin hydroxide. The metal hydroxide may be used alone or in combination of two or more. As the metal hydroxide, aluminum hydroxide is preferable.

(Needle-shaped filler)
Examples of the needle-shaped filler include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fiber, carbon fiber, and graphite fiber. , Metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, stainless fiber and the like.
These needle-shaped fillers may be used alone or in combination of two or more.
The range of the aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. The aspect ratio can be obtained by observing the needle-shaped filler with a scanning electron microscope and measuring its length and width.

As the filler, an inorganic filler other than the above-mentioned flame retardant may be used. Such inorganic fillers include alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite. , Calcium sulfate, barium sulfate, calcium silicate, talc, mica, montmorillonite, bentonite, active white clay, imogolite, sericite, glass beads, aluminum nitride, boron nitride, silicon nitride, various metal powders, magnesium sulfate, zirconic acid titanate Lead, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash and the like can be appropriately used. These inorganic fillers may be used alone or in combination of two or more.
These fillers may be used alone or in combination of two or more.

The content of the filler in the foamable polyurethane composition is, for example, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and more preferably 40 parts by mass or more with respect to 100 parts by mass of the polyol. It is more preferably 50 parts by mass or more, and particularly preferably 50 parts by mass or more. By setting the content of the filler to the above lower limit value or more, it becomes easy to impart various performances such as flame retardancy of the polyurethane foam to the polyurethane foam. The content of the filler is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 90 parts by mass or less with respect to 100 parts by mass of the polyol. By setting the content of the filler to these upper limit values or less, it becomes easy to obtain good foamability without lowering the reactivity.

<Phosphate ester>
The foamable polyurethane composition of the present invention may have a flame retardant other than the above-mentioned solid flame retardant. Examples of such a flame retardant include flame retardants that are liquid at normal temperature (23 ° C.) and normal pressure (1 atm), and specific examples thereof include phosphoric acid esters. By using the phosphoric acid ester, it becomes easy to improve the flame retardancy of the urethane foam without lowering the fluidity of the foamable polyurethane composition.

As the phosphoric acid ester, a monophosphate ester, a condensed phosphoric acid ester and the like can be used. The monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. Examples of the monophosphate include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate and tri (2-ethylhexyl) phosphate, halogen-containing phosphate esters such as tris (β-chloropropyl) phosphate, and tributoxyethyl phosphate. Arocyclic-containing phosphoric acid esters such as trialkoxy phosphate, tricredyl phosphate, trixilenyl phosphate, tris (isopropylphenyl) phosphate, cresyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, monoisodecyl phosphate, diisodecyl, etc. Examples thereof include acidic phosphoric acid esters such as phosphate.

Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkylpolyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.
Commercially available products of condensed phosphoric acid ester include, for example, "CR-733S", "CR-741" and "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STUB PFR" and "FP-600" manufactured by ADEKA. And so on.

As the phosphoric acid ester, one of the above-mentioned ones may be used alone, or two or more of them may be used in combination. Among these, monophosphate esters are preferable from the viewpoint of facilitating the appropriate viscosity of the polyol composition and improving the flame retardancy of polyurethane foam, and halogen-containing phosphoric acid esters such as tris (β-chloropropyl) phosphate are preferable. Is more preferable.
The content of the phosphoric acid ester in the foamable polyurethane composition is preferably 5 to 100 parts by mass, more preferably 12 to 90 parts by mass, further preferably 20 to 75 parts by mass, and 30 to 30 to 100 parts by mass with respect to 100 parts by mass of the polyol. 60 parts by mass is even more preferable.

<Foam control agent>
The effervescent polyurethane composition of the present invention may contain a defoaming agent. By containing a foam stabilizer, the foamability of the polyurethane foam can be improved, and for example, foaming can be promoted when reacting with polyisocyanate in a spray spray.
Specific examples of the defoaming agent include a surfactant, more specifically, a polyoxyalkylene defoaming agent such as polyoxyalkylene alkyl ether, and a silicone defoaming agent such as organopolysiloxane. The defoaming agent used in the present invention is not particularly limited, but a silicone defoaming agent is preferable from the viewpoint of foamability. The foam stabilizer may be used alone or in combination of two or more.

The content of the defoaming agent in the foamable polyurethane composition of the present invention is preferably 0.1 to 12 parts by mass, more preferably 1 to 10 parts by mass, and 2 to 8 parts by mass with respect to 100 parts by mass of the polyol. Is more preferable. When the content of the defoaming agent is at least the above lower limit value, the effervescent polyurethane composition is easily foamed, so that a homogeneous polyurethane foam can be obtained. Further, when the content of the defoaming agent is not more than the upper limit value, the balance between the manufacturing cost and the obtained effect is optimized.

<Other ingredients>
The effervescent polyurethane composition may be an antioxidant such as a phenol-based, amine-based or sulfur-based agent, a heat stabilizer, or a metal damage inhibitor (metal inactivating agent), if necessary, as long as the object of the present invention is not impaired. , Antistatic agents, stabilizers, cross-linking agents, lubricants, softeners, pigments, additives such as tackifier resins, tackifiers such as polybutene and petroleum resins, and the like.

<Polyurethane foam shape>
As shown in FIG. 3, the polyurethane foam 1 of the present invention is laminated on the base material 2 and adhered to the base material 2. The base material 2 is a spraying target surface made of a building or the like. The polyurethane foam 1 of the present invention has an inclination at the end of the polyurethane foam, has an average thickness (h2) of 15 mm or more, and is a portion (point) 5 cm (d1) inside (center side) from the end E. The thickness (h1) of M) is 10 mm or less. By having such a terminal shape, peeling from the terminal can be suppressed. The thickness at the point M may be 8 mm or less, or may be 5 mm or less. The lower limit value is not particularly limited, but is preferably 1 mm or more, and more preferably 3 mm or more. The average thickness (h2) of the polyurethane foam may be 15 mm or more, 18 mm or more, or 20 mm or more. The upper limit is not limited and can be appropriately determined depending on the intended use, but may be, for example, 50 mm or less and 30 mm or less.
The average thickness (h2) is the average thickness of the portion of the polyurethane foam excluding the inclined end.
In the conceptual diagram shown in FIG. 3, the inclination is described in a straight line, but the inclination does not have to be linear, and the inclined portion may have irregularities. For example, as shown in FIG. 4, a stepped shape is shown. May be. That is, regardless of the shape, the effect of the present invention is achieved when the thickness of the portion (point M) 5 cm inward from the end E is 10 mm or less.
Here, the end portion refers to all the end portions of the polyurethane foam to be constructed, and refers to the end portions in any shape, not limited to the four sides of the rectangular shape. In the present invention, at least a part of these ends has the above-mentioned inclined structure.

A preferred embodiment of the polyurethane foam of the present invention is the multilayer structure shown in FIG. That is, the lowermost layer (polyurethane foam layer A in FIG. 4) of the laminated polyurethane foam of the present invention extends to the end E, and the upper layer (polyurethane foam layer B) thereof is the lower layer (polyurethane foam layer). There is a terminal M'on the inner side of A). Further, the upper layer (polyurethane foam layer C) has a configuration in which the terminal H'is located on the inner side of the lower layer (polyurethane foam layer B). With such a laminated structure, it becomes easy to control the average thickness (h2) of the polyurethane foam and the thickness (h1) of the point M, and the above-mentioned polyurethane of the present invention having h1 of 10 mm or less and h2 of 15 mm or more. Foam can be easily manufactured.
Although the example of the three layers is shown above, the multilayer structure may be two layers or four or more layers.
Further, the length (d1) from the end E to the point M is 5 cm, but there is no limitation on the length (d2) from the point M to the thickness of the polyurethane foam reaching the average thickness, for example. It may be 1 to 10 cm, preferably 2 to 8 cm, and may be 5 cm, which is the same length as d1.

<Manufacturing method of polyurethane foam>
In the method for producing a polyurethane foam of the present invention, a foamable polyurethane composition is sprayed onto a substrate, reacted and foamed to obtain a polyurethane foam.
Since the foamable urethane resin composition is cured by reacting the polyol with the polyisocyanate, the composition is divided into two or more liquids before using the foamable urethane composition, and the polyol and the polyisocyanate are separated. It is good to prevent it from reacting and hardening. Then, when using the composition, it is advisable to mix each liquid agent divided into two or more. Specifically, it is advisable to divide the polyisocyanate from the polyol composition containing the polyol and mix them before use. Here, the polyol composition contains, in addition to the polyol, components other than the polyisocyanate constituting the effervescent polyurethane composition. Specifically, the polyol composition contains a polyol, a foaming agent, and a catalyst. Further, when a filler, a flame retardant, a defoaming agent, other additives and the like are used, these may also be contained in the polyol composition. However, additives and the like may be appropriately added to the polyisocyanate as needed.

The method for preparing the polyol composition of the present invention is not particularly limited, and for example, each component can be produced by stirring at about 20 to 40 ° C. for about 30 seconds to 20 minutes using a stirrer or the like.
Further, it is preferable that the volume of the polyol composition and the polyisocyanate mixed in the polyol composition are substantially the same. Specifically, the volume ratio of the polyisocyanate to the polyol composition is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

The liquid agent divided into two or more (for example, a polyol composition and a polyisocyanate) may be mixed, and the obtained mixed liquid (foamable polyurethane composition) may be sprayed to react and foam to produce a polyurethane foam. Mixing and spraying of two or more liquids may be performed in a spraying device. The spraying device has a spray gun and the like.
More specifically, it is preferable to collide and mix the polyol composition and the polyisocyanate inside the spraying device, and discharge the mixture (foamable polyurethane composition) from the discharge port of a spray gun or the like toward the base material. .. The mixed liquid discharged from the spraying device may be sprayed at a constant discharge pressure on the base material to be constructed, reacted and foamed to form a polyurethane foam on the base material.

As described above, the polyurethane foam of the present invention has an inclination (including a stepped shape) at the end of the polyurethane foam, has an average thickness (h2) of 15 mm or more, and is 5 cm (d1) inward from the end E. ) The thickness (h1) of the entered portion (point M) is 10 mm or less. Therefore, as long as it is a method capable of producing such a shape, the manufacturing method thereof is not particularly limited.
For example, a method can be used in which the polyurethane foams are laminated by performing spraying a plurality of times to obtain a desired thickness. Specifically, in the range up to the end, for example, a thin polyurethane foam of about 2.5 to 5 mm is formed, and the second and subsequent layers are laminated by shifting inward from the end, so that the end is stepped. Can form an inclined structure. When the inclination is formed by such a multi-layered laminated structure, the number of layers may be two or three or more, and is not particularly limited. From the viewpoint of forming the inclined structure with good control and ensuring work efficiency, the number of layers is preferably about 2 to 5, and more preferably 3 or 4 layers.
Further, the thickness of each layer can be arbitrary, but if it is a thin layer, more lamination is required, and if it is an excessively thick layer, it becomes difficult to form the inclined structure. Therefore, the thickness of one layer is preferably in the range of 0.1 to 10 mm, more preferably in the range of 1 to 8 mm.

Further, it is also possible to adjust the injection amount of the polyurethane composition from the discharge port and increase the irradiation amount from the end to the inside to form a polyurethane foam having an inclination. Further, when laminating the polyurethane foam, it is possible to form the polyurethane foam having an inclination by reducing the spraying area as it moves to the upper layer.
Further, the above-mentioned inclined structure can be formed by forming a polyurethane foam manufactured by a normal construction method as shown in FIG. 1 and cutting it diagonally.

<Use of polyurethane foam>
The use of the polyurethane foam of the present invention is not particularly limited, but since it is excellent in flame retardancy and heat insulating property, it can be suitably used for buildings such as walls, ceilings, roofs and floors of buildings. Specifically, it is preferable to use a wall, ceiling, roof, floor, or the like as a spray target surface (base material) and form polyurethane foam on the base material.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
[Material used]
<Polyform composition>
[Polyol]
-P-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Chemicals, product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)

〔catalyst〕
-Resinylated amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark) -DM70) concentration 65-75% by mass
・ Resinized metal catalyst, bismuth trioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) concentration 55-58% by mass
・ Resinized metal catalyst, dioctyl tin versatate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830) concentration approx. 99% by mass
-Ammonium salt (triquantization catalyst), 2,2-dimethylpropanoic acid tetramethylammonium salt (Air Products, Chemicals, product name: DABCO (registered trademark) TMR7) concentration 45-55% by mass
-Metal catalyst (triquantization catalyst), potassium 2-ethylhexanoate (manufactured by Air Products and Chemicals, product name: DABCO (registered trademark) K-15) concentration 70-80% by mass

[Effervescent agent]
-Hydrofluoroolefin (HFO, manufactured by Honeywell Japan Co., Ltd., product name: Solstice LBA, trans-1-chloro-3,3,3-trifluoropropene)
·water

〔Flame retardants〕
-Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)

[Filler]
・ Wollastonite (SiO ₂・ CaO) (manufactured by Kinsei Matek Co., Ltd., product name: SH-1250)

<Polyisocyanate>
・ 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200)

Example 1
Each component was mixed according to the formulation shown in Table 1 to prepare a polyol composition. The polyol composition and polyisocyanate (MDI) are introduced into a spraying device (GRACO: H-25), and the temperature is adjusted in the device. By spraying the polyurethane composition onto a slate plate having a length of 180 cm, a width of 90 cm, and a thickness of 9 mm using a spray gun (manufactured by Gasmer: D gun), a polyurethane foam is formed up to the end E shown in FIG. Layer A (thickness 5 mm) was applied.
Next, using a polyol composition and polyisocyanate having the same composition, the polyurethane foam was inserted 2 cm inward from the end E so that the thickness of the polyurethane foam at the point M 5 cm inward from the end E was 10 mm. Polyurethane foam layer B (thickness 5 mm) was constructed up to the point M'.
Next, the polyurethane foam layer C (thickness 5 mm) from the end E to the point H'8 cm inward so that the thickness of the polyurethane foam at the point H 10 cm inside from the end E is 15 mm. Was constructed.
That is, the three polyurethane foam layers A, B, and C are sequentially applied, and the average thickness (thickness at the point H) is 15 mm, and the thickness of the portion (point M) 5 cm from the end E is A polyurethane foam having a size of 10 mm was produced.
The temperature of the base material at the time of spraying is set to 0 ° C ± 1 ° C, and the temperature of the isocyanate heater in the spraying device, the heater of the polyol composition, and the heater (hose heater) that heats both before mixing them is set. The temperature was 38 ° C. for each.
The polyurethane foam prepared as described above was cured for 24 hours, and the peeling of the end portion was visually evaluated. The evaluation results are shown in Table 1. The evaluation criteria are as follows.
〇: No peeling ×: With peeling

Example 2
In the first embodiment, the average thickness (point H) is the same as in the first embodiment except that the polyurethane foam layer B (thickness) is applied to the point M'' which is 2 cm further inside than the point M. A polyurethane foam having a thickness of 15 mm and a thickness of a portion (point M) 5 cm from the end E of 5 mm was produced (FIG. 5). Table 1 shows the results of the evaluation in the same manner as in Example 1.

Example 3
In Example 1, the same as in Example 1 except that the polyurethane foam layer D (thickness 5 mm) is further laminated on the polyurethane foam layer C up to the point H "2 cm on the inner side of the point H'. A polyurethane foam having an average thickness (thickness at point H) of 20 mm and a thickness of a portion (point M) 5 cm from the end E of 10 mm was obtained (FIG. 6). The evaluation results are shown in Table 1.

Example 4
In the second embodiment, the same as in the second embodiment except that the polyurethane foam layer D (thickness 5 mm) is further laminated on the polyurethane foam layer C up to the point H "2 cm on the inner side of the point H'. A polyurethane foam having an average thickness (thickness at point H) of 20 mm and a thickness of a portion (point M) 5 cm from the end E of 5 mm was obtained (FIG. 7). The evaluation results are shown in Table 1.

Examples 5, 7, and 9
Polyurethane foam was obtained in the same manner as in Example 2 except that the content of water in the polyol composition was changed to change the isocyanate index in Example 2. Table 1 shows the results of the evaluation in the same manner as in Example 1.

Examples 6, 8 and 10
Polyurethane foam was obtained in the same manner as in Example 3 except that the content of water in the polyol composition was changed to change the isocyanate index in Example 3. Table 1 shows the results of the evaluation in the same manner as in Example 1.

Example 11 and Example 13
In Example 2, a polyurethane foam was obtained in the same manner as in Example 2 except that the composition of the polyol composition was changed as shown in Table 1. Table 1 shows the results of the evaluation in the same manner as in Example 1.

Example 12 and Example 14
In Example 3, a polyurethane foam was obtained in the same manner as in Example 3 except that the composition of the polyol composition was changed as shown in Table 1. Table 1 shows the results of the evaluation in the same manner as in Example 1.

Comparative Example 1
In Example 1, the polyurethane foam layers A, B and C were applied to the end E to obtain a polyurethane foam having an average thickness of 15 mm and a thickness of a portion 5 cm from the end E of 15 mm. Table 1 shows the results of evaluation in the same manner as in Example 1.

Comparative Example 2
In Example 3, the polyurethane foam layer C was applied to the point M', and a polyurethane foam was obtained in the same manner as in Example 3 except that the thickness at the point M was 15 mm (FIG. 8). Table 1 shows the results of the evaluation in the same manner as in Example 1.

Comparative Example 3
In Example 5, the polyurethane foam layer C was applied to the point M', and a polyurethane foam was obtained in the same manner as in Example 5 except that the thickness at the point M was 15 mm (FIG. 9). Table 1 shows the results of the evaluation in the same manner as in Example 1.

Comparative Example 4
In Example 6, the polyurethane foam layer C was applied to the point M', and a polyurethane foam was obtained in the same manner as in Example 6 except that the thickness at the point M was 15 mm (FIG. 8). Table 1 shows the results of the evaluation in the same manner as in Example 1.

Comparative Example 5
Polyurethane foam was obtained in the same manner as in Example 13 except that the polyurethane foam layer C was applied to the point M'in Example 13 and the thickness at the point M was 15 mm (FIG. 9). Table 1 shows the results of the evaluation in the same manner as in Example 1.

Comparative Example 6
Polyurethane foam was obtained in the same manner as in Example 14 except that the polyurethane foam layer C was applied to the point M'in Example 14 and the thickness at the point M was 15 mm (FIG. 8). Table 1 shows the results of the evaluation in the same manner as in Example 1.

As is clear from the results of the above Examples and Comparative Examples, when the thickness of the portion 5 cm from the end of the polyurethane foam having an average thickness of 15 mm or more is 10 mm or less, the polyurethane foam is peeled from the end. An excellent effect was obtained in which

1. 1. Polyurethane foam 2. Base material 11. Polyurethane foam layer A
12. Polyurethane foam layer B
13. Polyurethane foam layer C
14. Polyurethane foam layer D

Claims (18)

A polyurethane foam obtained by spraying, reacting and foaming a foamable polyurethane composition containing a polyol, a foaming agent, a catalyst, and a polyisocyanate, having an average thickness of 15 mm or more, and at least at some ends. , Polyurethane foam having a thickness of 10 mm or less at a portion 5 cm from the end. The polyurethane foam according to claim 1, wherein the catalyst comprises a trimerization catalyst. The polyurethane foam according to claim 2, wherein the trimerization catalyst contains a quaternary ammonium salt. The polyurethane foam according to any one of claims 1 to 3, wherein the catalyst contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin. The polyurethane foam according to any one of claims 1 to 4, wherein the catalyst contains an imidazole derivative. The polyurethane foam according to any one of claims 1 to 5, which has an isocyanate index of 200 or more. The polyurethane foam according to any one of claims 1 to 6, wherein the foaming agent contains a hydrofluoroolefin. The polyurethane foam according to any one of claims 1 to 7, wherein the foamable polyurethane composition further contains a filler. The polyurethane foam according to any one of claims 1 to 8, which has a multi-layer structure, the lowermost layer extending to the end, and the upper layer having an end on the inner side of the lower layer. A method for producing a polyurethane foam by spraying, reacting and foaming a foamable polyurethane composition containing a polyol, a foaming agent, a catalyst, and a polyisocyanate to form a polyurethane foam, wherein the polyurethane foam has an average thickness of 15 mm or more. A method for producing a polyurethane foam, wherein the thickness of a portion 5 cm from the end portion is 10 mm or less at least at the end portion. The method for producing a polyurethane foam according to claim 10, wherein the catalyst comprises a trimerization catalyst. The method for producing a polyurethane foam according to claim 11, wherein the quantification catalyst contains a quaternary ammonium salt. The method for producing a polyurethane foam according to any one of claims 10 to 12, wherein the catalyst contains a metal catalyst containing at least one selected from the group consisting of bismuth and tin. The method for producing a polyurethane foam according to any one of claims 10 to 13, wherein the catalyst contains an imidazole derivative. The method for producing a polyurethane foam according to any one of claims 10 to 14, wherein the isocyanate index is 200 or more. The method for producing a polyurethane foam according to any one of claims 10 to 15, wherein the foaming agent is a hydrofluoroolefin. The method for producing a polyurethane foam according to any one of claims 10 to 16, wherein the foamable polyurethane composition further contains a filler. The method for producing a polyurethane foam according to any one of claims 10 to 17, which has a multi-layer structure, the lowermost layer extends to an end portion, and the upper layer has an end on the inner side of the lower layer.

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