JP2011157469A - Rigid foamed synthetic resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rigid foamed synthetic resin having excellent dimensional stability, giving a rigid foamed synthetic resin having sufficient heat insulation properties, and exhibiting good production stability. <P>SOLUTION: The rigid foamed synthetic resin is obtained when a polyol component (Z) and a polyisocyanate compound are reacted with each other in the presence of a foaming agent, a foam stabilizer and a catalyst. The rigid foamed synthetic resin includes fluorine-treated inorganic particles (F) prepared by treating surfaces of inorganic oxide particles (P) with a fluorine-containing compound (f) having a fluorine-containing alkyl group and/or a fluorine-containing aromatic group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a hard foam synthetic resin and a method for producing the same.

  A rigid foam synthetic resin produced by reacting a polyol compound and a polyisocyanate compound in the presence of a foaming agent or the like (for example, rigid polyurethane foam, rigid nurate foam, etc .; hereinafter sometimes referred to as “hard foam”). Widely used as a heat insulating material having closed cells.

In recent years, foaming agents used in the production of rigid foams have been designed to reduce the low-boiling point hydrofluorocarbon compounds and increase water in consideration of environmental burdens. A technique for reducing and increasing water, or a technique for using only water without using either a hydrofluorocarbon compound or a hydrocarbon compound is being studied.
However, if water is used as the foaming agent, the rigid foam tends to shrink, and thus a technique for improving dimensional stability is required. The problem of shrinkage of rigid foam is particularly noticeable in low density rigid foam.

As a method for improving the dimensional stability of the rigid foam, there is a method in which the bubbles of the rigid foam are made into open cells. However, this method has a problem that the heat insulating performance is impaired.
As a method for improving dimensional stability while maintaining closed cells, a method of blending a polymer-dispersed polyol in a polyol component has been proposed (for example, Patent Documents 1 and 2). The polymer-dispersed polyol here is a polyol in which polymer fine particles are dispersed, obtained by polymerizing a monomer having a polymerizable unsaturated group in the polyol.
In addition, a method for improving dimensional stability while maintaining the closed cell ratio of a rigid foam by using an inorganic layered substance that has been cation-exchanged with organic onium ions (aromatic ammonium ions) has been proposed (for example, patents). Reference 3).

JP 57-25313 A JP-A-11-302340 JP 2006-124689 A

In the method using the polymer-dispersed polyol as described in Patent Documents 1 and 2, it is not easy to produce uniform polymer particles by the method of polymerizing the monomer in the polyol, and the temperature control and stirring speed -It may be necessary to repeat trial and error in optimizing various conditions such as monomer charging speed. For this reason, there is a problem that it is difficult to produce a polymer-dispersed polyol having a stable quality, and a method capable of satisfying both the dimensional stability of the rigid foam and the heat insulating performance without using the polymer-dispersed polyol is desired.
Further, in the method using an inorganic layered substance as described in Patent Document 3, organic onium ions are inserted between the layers and are not chemically fixed, so that the heat resistance is insufficient. Tend to be.
The present invention has been made in view of the above circumstances, a hard foamed synthetic resin having good dimensional stability and sufficient heat insulation performance, having good heat resistance and manufacturing stability, and A manufacturing method thereof is provided.

The present invention is the following [1] to [10].
[1] A rigid foamed synthetic resin obtained by reacting a polyol component (Z) with a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst, comprising inorganic oxide particles (P) A hard foamed synthetic resin comprising fluorine-treated inorganic particles (F) obtained by surface treatment with a fluorine-containing compound (f) having a fluorine alkyl group and / or a fluorine-containing aromatic group.
[2] The hard foam synthetic resin according to [1], wherein the fluorine-containing compound (f) includes a fluorine-containing silane coupling agent (f1) represented by the following formula (1).
(Rf-L) -SiX ¹ _a R ¹ _3-a (1)
(In the formula, Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. L is a divalent having 10 or less carbon atoms. X ¹ represents a hydroxyl group or a hydrolyzable group, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms (hydrolyzable group) which may have a substituent. . excluding) or (Rf-L) - are shown .a If .a represents an integer of 1 to 3 is 2 or 3, two or three of ^{X 1} may be the same or different If .a is 1 or 2, two or three ^{R 1} good .R ¹ be the same or different from each other (Rf-L) - for, ^{R 1} and (Rf-L) - one another They may be the same or different.)

[3] The hard foamed synthetic resin according to [2], wherein the fluorine-containing silane coupling agent (f1) includes a fluorine-containing silane coupling agent (f2) represented by the following formula (2).
_{C n F 2n + 1 - (} CH 2) m -SiX 2 a R 2 3-a ... (2)
(In the formula, n represents an integer of 1 to 10, m represents an integer of 1 to 5. X ² represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom. R ² represents a hydrogen atom or a substituent. 1 represents a monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and a represents an integer of 1 to 3. When a is 2 or 3, 2 Or three X ² may be the same or different from each other, and when a is 1 or 2, two or three R ² may be the same or different from each other.
[4] The hard foamed synthetic resin according to [1] to [3], wherein the inorganic oxide particles (P) are silica particles.
[5] The hardness according to [1] to [4], wherein the compounding amount of the fluorinated inorganic particles (F) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyol component (Z). Foam synthetic resin.
[6] The rigid foamed synthetic resin according to [1] to [5], wherein the polyol component (Z) has an average hydroxyl value of 200 to 800 mgKOH / g.
[7] The hard foamed synthetic resin according to [1] to [6], wherein water is used alone or at least one selected from a hydrofluorocarbon compound and a hydrocarbon compound and water as the foaming agent.
[8] The hard foam synthesis of [1] to [7], wherein only water is used as the foaming agent, and the amount of water used is 1 to 20 parts by mass with respect to 100 parts by mass of the polyol component (Z). resin.

[9] A step of foaming a foamed stock solution composition containing a polyol component (Z), a polyisocyanate compound, a foaming agent, a foam stabilizer, and a catalyst. The foamed stock solution composition contains a fluorine-containing alkyl group and / or A method for producing a rigid foam synthetic resin, comprising fluorine-treated inorganic particles (F) comprising inorganic oxide particles (P) surface-treated with a fluorine-containing compound (f) having a fluorine aromatic group.
[10] The foaming stock solution composition is prepared through a process of mixing a polyol system liquid containing the polyol component (Z) and a liquid containing a polyisocyanate compound, and the polyol system liquid or the polyisocyanate compound is mixed. [9] The method for producing a hard foam synthetic resin according to [9], wherein at least one of the contained liquids contains the fluorinated inorganic particles (F).

The rigid foamed synthetic resin of the present invention has good dimensional stability and sufficient heat insulation performance. Heat resistance and production stability are also good.
According to the method for producing a rigid foamed synthetic resin of the present invention, a rigid foamed synthetic resin having good dimensional stability and sufficient heat insulation performance and heat resistance can be produced stably.

In this invention, a polyol component (Z) means the whole polyol used for reaction with a polyisocyanate compound, and consists of 1 type of polyol or a 2 or more types of polyol mixture. A polyol mixture is preferred.
The value of the hydroxyl value of the polyol in the present invention is a value measured according to JIS K9511.
In this invention, a polyol component (Z) average hydroxyl value means the average value per 1g of polyol of the hydroxyl value of the whole polyol compound which comprises a polyol component (Z).
The average particle diameter of the inorganic oxide particles (P) in the present invention is a value measured according to JIS K1150.
In the present invention, the carbon number of the fluorine-containing alkyl group or fluorine-containing aromatic group is the carbon number of a monovalent group that includes all the carbons to which fluorine atoms are bonded and has the smallest number of carbon atoms.
In the present invention, the foaming stock solution composition means a composition that undergoes a foaming reaction, and is a composition that includes all components used in the reaction.
In the present invention, the polyol system liquid is a liquid to be reacted with the polyisocyanate compound, and in addition to the polyol component (Z), an optional compounding agent such as a foaming agent, a foam stabilizer, a catalyst, a flame retardant and the like is arbitrarily selected. It is a liquid that contains. The polyol system liquid does not contain a polyisocyanate compound.
In the present invention, the liquid containing the polyisocyanate compound may be composed only of the polyisocyanate compound, and optionally contains a compounding agent as necessary as long as it does not react with the polyisocyanate compound during storage. Also good.

<Hard foam synthetic resin>
The rigid foam synthetic resin of the present invention is a rigid foam obtained by reacting a polyol component (Z) and a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst, and is a specific fluorinated inorganic particle. (F) is contained.

[Fluorine-treated inorganic particles (F)]
The fluorine-treated inorganic particles (F) are obtained by surface-treating the inorganic oxide particles (P) with the fluorine-containing compound (f). By including the fluorinated inorganic particles (F) in the rigid foam, the dimensional stability of the rigid foam is improved and at the same time, good heat insulation performance is obtained.
In the present invention, the surface treatment of the inorganic oxide particles (P) with the fluorine-containing compound (f) means that the fluorine-containing compound (f) is partially or entirely on the surface of the inorganic oxide particles (P). It means that it exists. It is preferable that a chemical interaction and / or a chemical bond is generated between the inorganic oxide particles (P) and the fluorine-containing compound (f).
When the fluorine-containing compound (f) is contained in the rigid foam in a state where it exists on the surface of the inorganic oxide particles (P), the foam becomes multi-celled during foaming and the mechanical strength of the resulting rigid foam is improved. . By improving the mechanical strength, it becomes possible to increase the expansion ratio and reduce the weight. Moreover, by becoming a multicell, a cell is stabilized, a closed cell rate improves, and heat insulation performance also improves. Furthermore, since the inorganic oxide particles (P) are surface-treated with the fluorine-containing compound (f), the fluorine-treated inorganic particles (F) can be stably present in the foamed stock solution composition, so that the production stability is good. become.

  The fluorine-treated inorganic particles (F) of the present invention preferably have a fluorine atom content of 0.01 to 40% by mass, more preferably 0.1 to 30% by mass. When it is 0.01% by mass or more, the dimensional stability of the obtained rigid foam is improved, and at the same time, good heat insulation performance is obtained, and when it is 40% by mass or less, the cell array of the hard foam is suppressed, and good heat insulation is achieved. The performance can be maintained.

(Fluorine-containing compound (f))
The fluorine-containing compound (f) in the present invention is a compound having a fluorine-containing alkyl group and / or a fluorine-containing aromatic group. A compound having both a fluorine-containing alkyl group and a fluorine-containing aromatic group in one molecule may be used, but a compound having either a fluorine-containing alkyl group or a fluorine-containing aromatic group in one molecule is preferable.
A fluorine-containing compound (f) may be used individually by 1 type, and may use 2 or more types together.

The fluorine-containing alkyl group in the fluorine-containing compound (f) is a monovalent group in which part or all of the hydrogen atoms of a linear, branched or cyclic alkyl group are substituted with fluorine atoms. As for carbon number of a fluorine-containing alkyl group, 1-20 are preferable. When it is 1 or more, the effect of improving the dimensional stability and heat insulation performance of the rigid foam is exhibited, and when it is 20 or less, cell array can be suppressed. As for this carbon number, 1-10 are more preferable, and 3-8 are more preferable.
The fluorine-containing alkyl group is preferably linear or branched, and more preferably linear, from the viewpoint of dimensional stability and heat insulating performance of the resulting rigid foam.
The fluorine-containing alkyl group is more preferably a perfluoroalkyl group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Particularly preferred is a perfluoroalkyl group in which all of the hydrogen atoms of a linear or branched alkyl group having 3 to 8 carbon atoms are substituted with fluorine atoms.

  The fluorine-containing aromatic group in the fluorine-containing compound (f) is a group in which part or all of the hydrogen atoms of the monovalent hydrocarbon group containing an aromatic ring are substituted with fluorine atoms. As for carbon number of a fluorine-containing aromatic group, 6-14 are preferable. The fluorine-containing aromatic group is preferably a monovalent group in which all of the hydrogen atoms of the phenyl group are substituted with fluorine atoms.

  The fluorine-containing compound (f) of the present invention preferably has a fluorine atom content of 10 to 80% by mass, more preferably 30 to 70% by mass. When it is 10% by mass or more, the dimensional stability of the obtained rigid foam is improved, and at the same time, good heat insulation performance is obtained. When it is 80% by mass or less, the cell array of the hard foam is suppressed, and good heat insulation performance is obtained. Can be maintained.

Examples of the fluorine-containing compound (f) that can cause chemical interaction and / or chemical bond with the inorganic oxide particles (P) when the inorganic oxide particles (P) are surface-treated include fluorine-containing alkyls. A surfactant or a coupling agent having a group and / or a fluorine-containing aromatic group is preferred. A coupling agent (titanium coupling agent, silane coupling agent, etc.) is more preferable in terms of easy surface modification of the inorganic oxide particles (P), and in particular, a silane cup in terms of easier reaction with inorganic oxide particles (P). A ring agent is preferred.
As the silane coupling agent having a fluorine-containing alkyl group and / or a fluorine-containing aromatic group, a fluorine-containing silane coupling agent (f1) represented by the above formula (1) is preferable.
That is, the fluorine-containing compound (f) preferably contains the fluorine-containing silane coupling agent (f1), and the fluorine-containing silane coupling agent (f1) is used as 10 to 80% by mass of the fluorine-containing compound (f). It is preferable. More preferably, it is 20-70 mass%, Most preferably, it is 30-60 mass%.

In the above formula (1), Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. Preferred embodiments are the same as the fluorine-containing alkyl group or fluorine-containing aromatic group in the fluorine-containing compound (f).
In the above formula (1), L represents a divalent linking group having 10 or less carbon atoms. L does not contain a fluorine atom. L is preferably a hydrocarbon group which may contain a linking group such as an ether bond, an ester bond, or an amide bond (hereinafter referred to as an internal linking group). The hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group.
L is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group may be linear or branched, may have the substituent, and may have the internal linking group.
L is particularly preferably —C ₂ H ₄ —, —C ₃ H ₆ —, or —OC ₃ H ₆ —.

In the above formula (1), X ¹ represents a hydroxyl group or a hydrolyzable group. The hydrolyzable group refers to a group that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. The hydrolyzable group is preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom. In particular, an ethoxy group is preferable because it easily reacts uniformly with the inorganic oxide particles (P). When a is 2 or 3, two or three X ¹ may be the same or different from each other.
In the above formula (1), R ¹ is preferably a monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group) which may have a substituent, or (Rf-L)-. The monovalent organic group having 1 to 20 carbon atoms which may have the substituent is more preferably a monovalent organic group having 1 to 5 carbon atoms which may have the substituent. More preferably an ethyl group. When a is 1 or 2, two or three R ¹ may be the same or different from each other. When R ¹ is (Rf-L)-, R ¹ and (Rf-L)-may be the same as or different from each other.
In the above formula (1), a represents an integer of 1 to 3. When a plurality of Rf, L, X ¹ or R ¹ are present in one molecule, they may be the same as or different from each other. a is preferably 3 in terms of reactivity between the inorganic oxide particles (P) and the fluorine-containing silane coupling agent (f1).

Of the fluorine-containing silane coupling agent (f1) represented by the above formula (1), the fluorine-containing silane coupling agent (f2) represented by the above formula (2) is preferable.
The above formula (2) is a linear or branched perfluoroalkyl group having 1 to 10 carbon atoms and L is a linear alkylene group having 1 to 5 carbon atoms in the above formula (1). A group (having no internal linking group), X ¹ is X ² (an alkoxy group having 1 to 5 carbon atoms or a halogen atom), and R ¹ is R ² (having a hydrogen atom or a substituent). Or a monovalent organic group having 1 to 20 carbon atoms).

  Specific examples of the fluorine-containing silane coupling agent represented by the above formula (1) or (2) are shown below, but are not limited thereto. These compounds can be synthesized, for example, by the method described in JP-A-11-189599. It is also available from commercial products.

(Inorganic oxide particles (P))
The inorganic oxide particles (P) are preferably particles made of an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium.
Specific examples include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. Among these, silica particles, alumina particles, zirconia particles, or antimony oxide particles are preferable, and silica particles are particularly preferable in that a lighter rigid foam can be easily obtained.
One kind of inorganic oxide particles (P) may be used alone, or two or more kinds may be used in combination.

  The average particle diameter of the inorganic oxide particles (P) is not particularly limited, but is preferably 5 nm or more from the viewpoint of obtaining good heat insulation performance, and preferably 3,000 nm or less from the viewpoint of suppressing cell array (handling). More preferably, it is 10-2,000 nm, More preferably, it is 20-1,000 nm. In addition, the average particle diameter of this inorganic oxide particle (P) is the value measured based on JISK1150.

The shape of the inorganic oxide particles (P) is not particularly limited. For example, it may be spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or indefinite. Spherical shape is preferable in that uniform modification on the surface is easy.
The inorganic oxide particles (P) are preferably dry powder. Dry powdery inorganic oxide particles (P) can be obtained from commercial products.

[Method for producing fluorinated inorganic particles (F)]
The fluorine-treated inorganic particles (F) can be obtained by surface-treating the inorganic oxide particles (P) with the fluorine-containing compound (f). The surface treatment can be performed by a known method, but is not particularly limited. As a known method, a method of stirring dry powdery inorganic oxide particles (P) and a fluorine-containing compound (f) in a solvent may be mentioned.
Hereinafter, an embodiment in the case of using dry powdered inorganic oxide particles (P) will be described.

  The surface treatment method of the inorganic oxide particles (P) is carried out by dispersing the inorganic oxide particles (P) in the solvent (S), adding the fluorine-containing compound (f), stirring the mixture for a predetermined time, and mixing. A method for obtaining the particles (F) is preferred. The dispersion containing the fluorinated inorganic particles (F) in the solvent (S) thus obtained may be separated into only the fluorinated inorganic particles (F) and contained in the foaming stock solution composition. In this state, the foamed stock solution composition may contain the inorganic oxide particles (P) and the solvent (S). In view of simple operation and elimination of particle aggregation during solvent removal, it is preferable to add a dispersion.

  The amount of the fluorine-containing compound (f) used is appropriately selected depending on the type and average particle diameter of the inorganic oxide particles (P) to be used, the fluorine content of the fluorine-containing compound (f), and the like. The range of 0.1-80 mass parts is preferable with respect to 100 mass parts of inorganic oxide particles (P), and 0.1-50 mass parts is more preferable. The rigid foam obtained when it is 0.1 parts by mass or more has good heat insulating performance, and when it is 100 parts by mass or less, cell array can be suppressed.

The solvent (S) is not particularly limited as long as it can uniformly disperse the inorganic oxide particles (P) and the fluorine-containing compound (f).
When blending into the foaming stock solution composition in a dispersion containing the fluorinated inorganic particles (F) in the solvent (S), the solvent (S) is preferably one that can be easily removed during preparation of the foaming stock solution composition. . Specifically, it is preferable that the volatility of the solvent (S) is so high that the solvent (S) is released into the atmosphere when the liquid to which the fluorinated inorganic particles (F) are added is stirred. Specific examples of the solvent (S) include hydrocarbon solvents such as hexane, benzene and toluene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate, isobutyl acetate and butyl acetate; And fluorine-containing solvents such as fluorocarbon compounds and hydrofluorocarbon compounds.
Examples of the fluorocarbon compound include perfluoroalkane compounds such as perfluoromethane, perfluoroethane, perfluoropropane, and perfluorobutane.
Examples of the hydrofluorocarbon compound include 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoroethane, 1,1,2,2,3-pentafluoropropane, 1,1,1,3. , _{3-pentafluorobutane, C 6 F 13 OCH 3,} C 4 F 9 OCH 3, C 4 F 9 OC 2 H 5, C 3 HF 6 -CH (CH 3) OC 3 HF 6 , and the like.
A solvent (S) can be used individually by 1 type or in combination of 2 or more types.
As the solvent (S), a hydrofluorocarbon compound having 1 to 10 carbon atoms is more preferable in terms of stable dispersion of the inorganic oxide particles (P).
Although the usage-amount of a solvent (S) is not specifically limited, 100-1,000 mass parts is 100 mass parts with respect to 100 mass parts of inorganic oxide particles (P) at the point of the stable dispersion | distribution of inorganic oxide particles (P). Preferably, 300-800 mass parts is more preferable.

[Polyol component (Z)]
The polyol component (Z) is a polyol known as a polyol used in the production of rigid foams such as polyether polyols, polyester polyols, and hydrocarbon polymers having a hydroxyl group at the terminal (in this specification, “for rigid foams”). Polyol ")).
The rigid foam polyol preferably has an average number of functional groups of 2 to 8. The functional group of the polyol means a group (hydroxyl group) that reacts with the polyisocyanate compound. For example, the number of functional groups of the polyether polyol is equal to the number of active hydrogens of the initiator used in producing the polyether polyol. The average number of functional groups in a mixture of two or more polyols having different numbers of functional groups is the average value of the number of functional groups in the entire mixture per molecule of polyol.

The polyether polyol can be obtained, for example, by subjecting a cyclic ether such as alkylene oxide (ethylene oxide, propylene oxide, etc.) to ring-opening addition polymerization to an initiator such as a polyhydroxy compound such as polyhydric alcohol or polyhydric phenol or amines. Things can be used.
Specific examples of the initiator include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,4-butanediol, 1,6-hexanediol, water , Polyglycerols such as glycerin, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, diglycerin, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, dulcitol, sucrose, triethanolamine; bisphenol A, Polyhydric phenol such as phenol-formaldehyde initial condensate; piperazine, aniline, monoethanolamine, diethanolamine, isopropanolamine, aminoethylethanol Amino compounds such as amine, ammonia, aminomethylpiperazine, aminoethylpiperazine, ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenylmethanediamine, diethylenetriamine, triethylenetetramine; or cyclic ether adducts thereof Can be mentioned.

  As the polyester polyol, for example, a polyester polyol obtained by polycondensation of a polyhydric alcohol and a polycarboxylic acid can be used. Other examples include polyester polyols obtained by polycondensation of hydroxycarboxylic acids, polymerization of cyclic esters (lactones), polyaddition of cyclic ethers to polycarboxylic anhydrides, or transesterification of waste polyethylene terephthalate.

  As the hydrocarbon polymer having a hydroxyl group at the terminal, for example, polytetramethylene glycol (PTMG) or polybutadiene polyol can be used.

In the present invention, the polyol component (Z) preferably contains at least a polyether polyol from the viewpoint of improving the compatibility with water, the mechanical strength of the resulting rigid foam, and the bubble appearance. More preferably, 20 to 100% by mass of the polyol component (Z) is a polyether polyol. In addition to the polyether polyol, a polyester polyol, a hydrocarbon polymer having a hydroxyl group at the terminal, or the like may be used in combination.
The average hydroxyl value of the polyol component (Z) is 200 to 800 mgKOH / g, preferably 200 to 700 mgKOH / g, and more preferably 200 to 600 mgKOH / g. When the average hydroxyl value is 200 mgKOH / g or more, it is preferable because the strength of the obtained rigid foam is easily obtained. When the average hydroxyl value is 800 mgKOH / g or less, the resulting rigid foam is less likely to be brittle, which is preferable.

[Polyisocyanate compound]
There is no restriction | limiting in particular as a polyisocyanate compound, A well-known thing can be used suitably as a polyisocyanate compound used when manufacturing a rigid foam.
Examples thereof include aromatic, alicyclic or aliphatic polyisocyanates having two or more isocyanate groups; mixtures of two or more of the polyisocyanates; modified polyisocyanates obtained by modifying them.
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. Polyisocyanates or their prepolymer-type modified products, isocyanurate-modified products, urea-modified products, carbodiimide-modified products, and the like. Of these, TDI, MDI, crude MDI, or modified products thereof are preferred.
A polyisocyanate compound may be used individually by 1 type, and may be used in combination of 2 or more type.

[Foaming agent]
There is no restriction | limiting in particular as a foaming agent, A well-known thing can be used suitably as a foaming agent used when manufacturing a rigid foam. From the viewpoint of reducing the burden on the environment, it is preferable to use water as part or all of the foaming agent. That is, it is preferable to use only water as a foaming agent or to use water and a foaming agent other than water in combination.
As the blowing agent other than water, hydrofluorocarbon compounds, hydrocarbon compounds, and the following general-purpose gases can be used. In particular, at least one selected from a hydrofluorocarbon compound and a hydrocarbon compound is preferable. By using these together with water, the foaming effect is improved, and the rigid foam can be easily reduced in weight.

Examples of the hydrofluorocarbon compound include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3. , 3-pentafluorobutane (HFC-365mfc), 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.
Examples of the hydrocarbon compound include butane, normal pentane, isopentane, cyclopentane, hexane, cyclohexane and the like.
General-purpose gas includes air or inert gas (nitrogen, carbon dioxide). Carbon dioxide gas is particularly preferable. The addition state of the inert gas may be any of a liquid state, a supercritical state, and a subcritical state.
A foaming agent may be used individually by 1 type, and may be used in combination of 2 or more type.

[Foam stabilizer]
There is no restriction | limiting in particular as a foam stabilizer, A well-known thing can be used suitably as a foam stabilizer used when manufacturing a rigid foam. In particular, the silicone-based foam stabilizer has a high foam regulating effect that can reduce the cell diameter, and a small cell diameter is preferable because the heat insulation performance of the rigid foam is easily improved. A foam stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.

[catalyst]
As the catalyst, a catalyst for promoting a urethanization reaction (hereinafter referred to as a urethanization catalyst) and / or a catalyst for promoting a trimerization reaction of an isocyanate group (hereinafter referred to as a trimerization reaction promotion catalyst) is used. These can use a well-known thing suitably.
For example, urethanization catalysts include tertiary amines such as triethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine; and organometallic compounds such as dibutyltin dilaurate. Can be mentioned. Examples of the trimerization reaction promoting catalyst include metal carboxylates such as potassium acetate and potassium 2-ethylhexanoate.

[Other ingredients]
In the present invention, any compounding agent may be used as necessary.
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. These can use a well-known thing suitably as a compounding agent used when manufacturing a rigid foam.

<Method for manufacturing rigid foam>
The rigid foamed synthetic resin of the present invention is the foamed synthetic resin having a step of foaming a foamed stock solution composition comprising a polyol component (Z), a polyisocyanate compound, a foaming agent, a foam stabilizer, and a catalyst. It can manufacture by making a undiluted | stock solution composition contain a fluorinated inorganic particle (F).

A foaming undiluted liquid composition is prepared through a step of mixing a polyol system liquid containing a polyol component (Z) and a liquid containing a polyisocyanate compound, and the polyol system liquid and a liquid containing a polyisocyanate compound are mixed. It is preferable that at least one of the fluorinated inorganic particles (F) is contained in that it is easy to obtain a rigid foam that is lightweight and has good heat insulation performance.
The foaming agent may be blended in advance with the polyol system liquid, or after mixing the polyol system liquid and the liquid containing the polyisocyanate compound, the foaming agent may be blended to form a foaming stock solution composition. In view of improving the compatibility between the foaming agent and the polyol component (Z), the mechanical strength of the resulting rigid foam, and the appearance of the cells, it is preferable to blend the foaming agent in the polyol system liquid in advance.
It is preferable that the fluorine-treated inorganic particles (F) are contained in the polyol system liquid from the viewpoint of obtaining a rigid foam having good heat insulation performance. In this case, the polyol system is prepared by previously mixing the fluorinated inorganic particles (F) with the raw material of the polyol system liquid (polyol component (Z), foaming agent, foam stabilizer, catalyst, or other compounding agent). A liquid may be prepared.

  The blending amount of the fluorine-treated inorganic particles (F) is appropriately selected depending on the coating amount of the fluorine-containing compound (f) on the inorganic oxide particles (P), the average particle diameter of the inorganic oxide particles (P), and the like. The range of 0.01-10 mass parts is preferable with respect to 100 mass parts of a polyol component (Z), 0.1-5 mass parts is more preferable, 0.5-3 mass parts is further more preferable. When the blending amount of the fluorinated inorganic particles (F) is 0.01 parts by mass or more, dimensional stability is likely to be good, and when it is 10 parts by mass or less, cell array is unlikely to occur and the heat insulation performance is likely to be good.

The amount of water used as the blowing agent is preferably 1 to 15 parts by mass, more preferably 2 to 13 parts by mass, and still more preferably 4 to 12 parts by mass with respect to 100 parts by mass of the polyol component (Z). If the usage-amount of water is 1 mass part or more, it is preferable at the point of weight reduction of the rigid foam obtained. On the other hand, if the usage-amount of water is 15 mass parts or less, the mixability of water and a polyol component (Z) tends to become better.
When only water is used as the foaming agent, the amount used is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 4 to 10 parts by mass with respect to 100 parts by mass of the polyol component (Z). preferable.
When using other than water as the foaming agent, the amount used when using a hydrofluorocarbon compound as the other than water is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polyol component (Z). -40 mass parts is more preferable.
1-40 mass parts is preferable with respect to 100 mass parts of a polyol component (Z), and, as for the usage-amount in the case of using a hydrocarbon compound, 10-20 mass parts is more preferable.
1-100 mass parts is preferable with respect to 100 mass parts of a polyol component (Z), and, as for the usage-amount in the case of using air or an inert gas, 1-20 mass parts is more preferable.

Although the usage-amount of a foam stabilizer needs to be selected suitably, 0.1-20 mass parts is preferable with respect to 100 mass parts of a polyol component (Z).
The amount of the catalyst used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyol component (Z).

As for the usage-amount of a polyisocyanate compound, 50-400 are preferable by an isocyanate index (INDEX).
The isocyanate index (INDEX) is a value expressed by multiplying the ratio of the number of isocyanate groups to 100 times the total number of active hydrogens of the polyol component (Z) and other active hydrogen-containing compounds.
In a polyurethane formulation mainly using a urethanization catalyst as the catalyst, the amount of polyisocyanate compound used is preferably 50 to 140, more preferably 60 to 130, in terms of isocyanate index.
Moreover, in the polyisocyanurate formulation (urethane-modified polyisocyanurate formulation) mainly using a trimerization reaction promoting catalyst as a catalyst, the amount of the polyisocyanate compound is preferably 120 to 400, more preferably 120 to 300 in terms of isocyanate index. preferable.

The method for producing a rigid foam of the present invention can be applied to various molding methods.
Examples of the molding method include injection, continuous production board, and spray foaming foam.
The injection is a method of injecting a foaming stock solution composition into a frame such as a mold and foam-curing it. The continuous production board is a method in which the foamed stock solution composition is poured between two continuously supplied face materials and foam-cured, and a board made of a laminate in which a rigid foam is sandwiched between the face materials is obtained. Such a board is suitably used as a heat insulating material in the building field. Spray foaming is a method in which a polyol system liquid and a liquid containing a polyisocyanate compound are mixed and sprayed by a foaming machine.
Among these, the method for producing a rigid foam of the present invention is suitable for producing a continuous production board or a spray foamed foam in that a rigid foam that is stable and lightweight and excellent in heat insulation performance can be easily obtained.

  According to the present invention, as shown in the examples below, water is used as a foaming agent, and even when a low-density rigid foam is produced without using a polymer-dispersed polyol, the dimensional stability is excellent. A rigid foam having good heat insulation performance and heat resistance can be obtained. Further, the fluorinated inorganic particles (F) can be produced by a simple method, and uniform particles can be easily obtained with good reproducibility, so that production stability is also excellent.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples.
Table 1 shows production examples of fluorine-treated inorganic particles (F), Tables 2 and 3 show production examples of rigid foams using fluorine-treated inorganic particles (F), and Table 4 shows comparative examples.

<Production example of fluorine-treated inorganic particles (F)>
[Production Example 1: Production of fluorinated inorganic particles (F1)]
In a 200 mL glass eggplant flask, 10 g of silica fine particles (1) (manufactured by Denki Kagaku Kogyo Co., Ltd., product name: SFP-20M, spherical, average particle size: 330 nm) as inorganic oxide particles (P), and C ₆ F ₁₃ OCH ₃ (manufactured by Asahi Glass Co., Ltd., product name: CT-SOLV100E; hereinafter referred to as solvent (S1)) was added and stirred for 5 minutes with a stirring blade (rotation speed: 100 revolutions / minute). A slurry was obtained. Thereafter, C ₆ F ₁₃ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ (manufactured by Tokyo Chemical Industry Co., Ltd., fluorine atom content: 48 mass% as fluorine-containing silane coupling agent (f2). Hereinafter, fluorine silane (1 )) Was added, and the mixture was further stirred for 1 hour with a stirring blade (rotation speed: 100 revolutions / minute) to obtain a dispersion having a low viscosity. When the dispersion medium of the obtained dispersion liquid was analyzed by nuclear magnetic resonance, it was confirmed that the dispersion medium did not contain fluorine silane (1) (the same applies to the following Production Examples 2 to 9). there were). From this, it is recognized that all of the added fluorine silane (1) is present on the surface of the silica fine particles (1).
Thus, a dispersion liquid in which fluorine-treated inorganic particles (F1) composed of silica fine particles (1) surface-treated with fluorine silane (1) were dispersed in the solvent (S1) was obtained. The fluorine atom content in the fluorine-treated inorganic particles (F1) is shown in Table 1 (the same applies hereinafter).

[Production Examples 2 to 4: Production of fluorinated inorganic particles (F2) to (F4)]
Fluorine comprising silica fine particles (1) surface-treated with fluorine silane (1) in the same manner as in Production Example 1 except that the amount of fluorine silane (1) used in Production Example 1 was changed as shown in Table 1. Dispersions in which the treated inorganic particles (F2) to (F4) were dispersed in the solvent (S1) were obtained.

[Production Example 5: Production of fluorinated inorganic particles (F5)]
In Production Example 1, the inorganic oxide particles (P) were changed to silica fine particles (2) (manufactured by Denki Kagaku Kogyo Co., Ltd., product name: UFP-80, spherical, average particle size: 33 nm), and the use of the solvent (S1) Fluorine comprising silica fine particles (2) surface-treated with fluorine silane (1) in the same manner as in Production Example 1 except that the amount was changed to 60 g and the amount of fluorine silane (1) used was changed to 4.2 ml. A dispersion liquid in which the treated inorganic particles (F5) were dispersed in the solvent (S1) was obtained.

[Production Example 6: Production of fluorinated inorganic particles (F6)]
In Production Example 1, the inorganic oxide particles (P) were changed to silica fine particles (3) (manufactured by Denki Kagaku Kogyo Co., Ltd., product name: SFP-30M, spherical, average particle size: 570 nm), and the use of the solvent (S1) Fluorine comprising silica fine particles (3) surface-treated with fluorine silane (1) in the same manner as in Production Example 1 except that the amount was changed to 70 g and the amount of fluorine silane (1) used was changed to 0.33 ml. A dispersion liquid in which the treated inorganic particles (F6) were dispersed in the solvent (S1) was obtained.

[Production Example 7: Production of fluorinated inorganic particles (F7)]
In Production Example 1, the amount of the solvent (S1) used was changed to 70 g, and the fluorine-containing silane coupling agent (f2) was changed to C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ (manufactured by Kanto Chemical Co., Inc. Silica fine particles (1) surface-treated with fluorine silane (2) in the same manner as in Production Example 1, except that the fluorine atom content is 53 mass%, hereinafter referred to as fluorine silane (2)). A dispersion liquid in which fluorinated inorganic particles (F7) consisting of the above were dispersed in the solvent (S1) was obtained.

[Production Example 8: Production of fluorinated inorganic particles (F8)]
In Production Example 1, the amount of the solvent (S1) used was changed to 70 g, and instead of the fluorine-containing silane coupling agent (f2), (CF ₃ ) ₂ CFOCH ₂ CH ₂ was used as the fluorine-containing silane coupling agent (f1). Except for using 0.43 mL of CH ₂ Si (OCH ₂ CH ₃ ) ₃ (manufactured by Kanto Chemical Co., Inc., fluorine atom content: 35 mass%, hereinafter referred to as fluorine silane (3)), the same as in Production Example 1 A dispersion was obtained in which fluorine-treated inorganic particles (F8) composed of silica fine particles (1) surface-treated with fluorine silane (3) were dispersed in a solvent (S1).

[Production Example 9: Production of fluorinated inorganic particles (F9)]
In Production Example 1, the inorganic oxide particles (P) were changed to 10 g of alumina fine particles (1) (manufactured by Iwatani Corporation, product name: SA-1, spherical, average particle size: 680 nm), and the solvent (S1) It consists of alumina fine particles (1) surface-treated with fluorine silane (1) in the same manner as in Production Example 1, except that the amount used was changed to 70 g and the amount of fluorine silane (1) was changed to 0.14 ml. A dispersion liquid in which the fluorinated inorganic particles (F9) were dispersed in the solvent (S1) was obtained.

<Examples and comparative examples>
A rigid foam was produced by the following method according to the blending ratio shown in Tables 2 to 4 (the unit is “part by mass”). By the following method, the gel time (second), the box free density (unit: kg / m ³ ), and the compressive strength (unit: MPa) were measured as the total density of the rigid foam. High temperature shrinkage (unit:%) and wet heat shrinkage (unit:%) were measured by the following method to evaluate dimensional stability. The thermal conductivity (unit: mW / m · K) at 24 ° C. was measured by the following method to evaluate the heat insulation performance. The results are shown in Tables 2-4.

The raw materials described in the table are as follows. The average hydroxyl value in the mixture of polyols A, B and C is shown in the table.
[Polyol]
Polyol A: A polyether polyol having a hydroxyl value of 350 mgKOH / g, in which N- (2-aminoethyl) piperazine is used as an initiator and only ethylene oxide (hereinafter referred to as EO) is subjected to ring-opening addition polymerization.
Polyol B: Tolylenediamine is used as an initiator, and EO, propylene oxide (hereinafter referred to as PO) and EO are subjected to ring-opening addition polymerization in this order, and the hydroxyl value is 350 mgKOH / g. Polyether polyol having a ratio of EO to 33% by mass based on the total of EO and PO.
Polyol C: A polyether polyol having a hydroxyl value of 380 mgKOH / g, in which a mixture of sucrose and glycerin (mass ratio of 5: 4) is used as an initiator and only PO is subjected to ring-opening addition polymerization.

[Fluorine-treated inorganic particles (F)]
The amount of the dispersion liquid containing the fluorinated inorganic particles (F1) to (F9) obtained in the above Production Examples 1 to 9 having only the fluorinated inorganic particles (F1) to (F9) as shown in the table. Added at.
[Polyisocyanate compound] Polymethylene polyphenyl polyisocyanate (common name: Crude MDI, manufactured by Nippon Polyurethane Industry Co., Ltd., product name: MR-200).
[Flame Retardant] Tris (2-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP).
[Foaming agent] Water.
[Foam stabilizer] Silicone type foam stabilizer (manufactured by Dow Corning Toray, product name: SZ-1671).
[Catalyst] N, N, N ′, N′-Tetramethylhexamethylenediamine (product name: TOYOCAT-MR, manufactured by Tosoh Corporation).
[Unmodified silica (comparative example)]
In the comparative example, the silica fine particles (1) used in Production Example 1 were used as unmodified silica fine particles that were not surface-treated.
[Silane coupling agent (comparative example)]
In the comparative example, the fluorine silane (1) used in Production Example 1 was used as the silane coupling agent.

<Method for manufacturing rigid foam>
In accordance with the blending ratio shown in Tables 2 to 4, a 1 L poly beaker is charged with polyols A to C, fluorine-treated inorganic particles (F), a foaming agent, a foam stabilizer, a flame retardant and a catalyst, and these may be mixed with a stirrer. Mix to prepare a polyol system solution. Separately, a polyisocyanate compound was prepared. The amount of the polyisocyanate compound used was 110 in terms of the isocyanate index (INDEX).
Subsequently, after keeping the liquid temperature of both a polyol system liquid and a polyisocyanate compound at 20 degreeC, these were mixed, and it stirred for 5 second at the rotation speed of 3000 rotation / min. The obtained mixture (foaming concentrate composition) was put into a wooden box having a size of 200 mm in length, 200 mm in width, and 200 mm in height and opened on the upper surface, and was subjected to free foaming to produce a rigid foam. The direction from the top surface to the bottom surface of the wooden box is the height direction.

<Measurement method>
The gel time is measured after the mixing start time of the polyol system liquid and the polyisocyanate compound is set to 0 second, and as the gelation progresses, a thin glass or metal rod is lightly placed on the upper part of the foaming stock solution composition during the reaction. The time until the reaction solution started to draw the yarn when it was quickly pulled out was measured as the gel time (unit: seconds).
The total density (box-free density) was measured from the mass and volume according to JIS K7222 (1998 edition).
The compressive strength was measured according to JIS A9511. After curing the obtained rigid foam for 1 hour, a test piece having a size of 5 cm × 5 cm × 5 cm was cut out from the center and used for measurement. The compressive strength in the parallel direction (//) and perpendicular direction (⊥) to the gravity direction was measured. In the table, “// + ⊥” represents the compression strength obtained by adding the compression strength in the parallel direction (//) and the compression strength in the vertical direction (⊥). The direction of gravity is the height direction of the wooden box.

<Method for evaluating dimensional stability>
High temperature shrinkage and wet heat shrinkage were measured by methods according to ASTM D 2126-75. After curing the obtained rigid foam for 1 hour, a test piece of length (Z) 100 mm × width (X) 150 mm × thickness (Y) 75 mm was cut out from the center and used for measurement. The height direction of the wooden box is the thickness (Y) direction.
The specimen was stored for 24 hours in an atmosphere of 70 ° C. and 0% relative humidity, and in a heat and humidity shrinkage of 70 ° C. and 95% relative humidity, and the increased length (thickness) was stored before storage. It was expressed as a dimensional change rate (unit:%) with respect to the length (thickness). That is, the dimensional change rate was measured for all six directions in each of the three directions (X, Y, Z) under two conditions. In the dimensional change rate, a negative value means shrinkage, and a large absolute value means that a dimensional change is large.
From the measurement result of the dimensional change rate, the dimensional stability was evaluated based on the following evaluation criteria.
(Evaluation criteria)
The maximum absolute value among the dimensional change rates in the 4: 6 direction was less than 1%.
The maximum absolute value among the dimensional change rates in the 3: 6 direction was 1% or more and less than 5%.
2: The maximum absolute value among the dimensional change rates in 6 directions was 5% or more and less than 10%.
The maximum absolute value in the dimensional change rate in the 1: 6 direction was 10% or more.

<Evaluation method of heat insulation performance>
The thermal conductivity (unit: mW / m · K) was measured using a thermal conductivity measuring device (product name: Auto Lambda HC-074, manufactured by Eiko Seiki Co., Ltd.) in accordance with JIS A1412.
From the measurement result of thermal conductivity, the heat insulation performance was evaluated based on the following evaluation criteria.
(Evaluation criteria)
○ (Good): Thermal conductivity was 27 or less.
X (defect): Thermal conductivity was more than 27.
If the thermal conductivity is 27 mW / m · K or less, the rigid foam is judged to have good heat insulation performance.

As shown in the results of Tables 2 to 4, the hard foams of Examples 1 to 14 containing the fluorinated inorganic particles (F1) to (F9) use only water as a foaming agent and have a low density, Excellent heat insulation performance and dimensional stability. Since the high temperature shrinkage rate is small, it also has excellent heat resistance. Compared with the comparative example 1 which does not contain a fluorinated inorganic particle (F), the rigid foams of Examples 1 to 14 have markedly improved dimensional stability, and the thermal conductivity is slightly smaller, but the heat insulation performance is almost the same. It is equivalent.
Above all, from the results of Examples 4 to 7 and Examples 8 to 10 in which the blending amount of the fluorinated inorganic particles (F) was changed, the smaller the blending amount of the fluorinated inorganic particles (F), the lower the thermal conductivity and the heat insulation. There is a tendency for high performance. Moreover, in Examples 4-7, the tendency for dimensional stability to become favorable is seen, so that there are many compounding quantities of a fluorine treatment inorganic particle (F).
On the other hand, in Comparative Examples 2 and 3 containing silica fine particles not subjected to surface treatment instead of the fluorine-treated inorganic particles (F), the thermal conductivity is good, but the dimensional stability is poor. The difference in thermal conductivity between Comparative Example 2 and Comparative Example 3 is considered to be within the error range.
In addition, Comparative Examples 4 to 7 containing no fluorine-treated inorganic particles (F) and containing a fluorine-containing silane coupling agent also have good thermal conductivity but are inferior in dimensional stability.

Claims (10)

A hard foam synthetic resin obtained by reacting a polyol component (Z) with a polyisocyanate compound in the presence of a foaming agent, a foam stabilizer and a catalyst,
Fluorine-treated inorganic particles (F) obtained by surface-treating inorganic oxide particles (P) with a fluorine-containing compound (f) having a fluorine-containing alkyl group and / or a fluorine-containing aromatic group Hard foam synthetic resin. The rigid foam synthetic resin of Claim 1 in which the said fluorine-containing compound (f) contains the fluorine-containing silane coupling agent (f1) represented by the following Formula (1).
(Rf-L) -SiX ¹ _a R ¹ _3-a (1)
(In the formula, Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. L is a divalent having 10 or less carbon atoms. X ¹ represents a hydroxyl group or a hydrolyzable group, R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms (hydrolyzable group) which may have a substituent. . excluding) or (Rf-L) - are shown .a If .a represents an integer of 1 to 3 is 2 or 3, two or three of ^{X 1} may be the same or different If .a is 1 or 2, two or three ^{R 1} good .R ¹ be the same or different from each other (Rf-L) - for, ^{R 1} and (Rf-L) - one another They may be the same or different.) The rigid foam synthetic resin of Claim 2 in which the said fluorine-containing silane coupling agent (f1) contains the fluorine-containing silane coupling agent (f2) represented by the following Formula (2).
_{C n F 2n + 1 - (} CH 2) m -SiX 2 a R 2 3-a ... (2)
(In the formula, n represents an integer of 1 to 10, m represents an integer of 1 to 5. X ² represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom. R ² represents a hydrogen atom or a substituent. 1 represents a monovalent organic group having 1 to 20 carbon atoms (excluding a hydrolyzable group), and a represents an integer of 1 to 3. When a is 2 or 3, 2 Or three X ² may be the same or different from each other, and when a is 1 or 2, two or three R ² may be the same or different from each other.   The hard foam synthetic resin as described in any one of Claims 1-3 whose said inorganic oxide particle (P) is a silica particle.   Hardness as described in any one of Claims 1-4 whose compounding quantity of the said fluorine treatment inorganic particle (F) is 0.01-10 mass parts with respect to 100 mass parts of the said polyol component (Z). Foam synthetic resin.   The rigid foam synthetic resin according to any one of claims 1 to 5, wherein the polyol component (Z) has an average hydroxyl value of 200 to 800 mgKOH / g.   The rigid foam synthetic resin according to any one of claims 1 to 6, wherein water is used as the foaming agent, or only water or at least one selected from a hydrofluorocarbon compound and a hydrocarbon compound and water.   Hard only as described in any one of Claims 1-7 which uses only water as said foaming agent, and the usage-amount of this water is 1-20 mass parts with respect to 100 mass parts of a polyol component (Z). Foam synthetic resin. Foaming a foaming stock solution composition comprising a polyol component (Z), a polyisocyanate compound, a foaming agent, a foam stabilizer and a catalyst;
The foaming stock composition contains fluorine-treated inorganic particles (F) comprising inorganic oxide particles (P) surface-treated with a fluorine-containing compound (f) having a fluorine-containing alkyl group and / or a fluorine-containing aromatic group. A method for producing a hard foam synthetic resin.   The foaming stock composition is prepared through a process of mixing a polyol system liquid containing a polyol component (Z) and a liquid containing a polyisocyanate compound, and the polyol system liquid or a liquid containing a polyisocyanate compound. The method for producing a rigid foam synthetic resin according to claim 9, wherein at least one of the fluorinated inorganic particles (F) is contained.