WO2004060947A1

WO2004060947A1 - Process for the production of synthetic resin foam

Info

Publication number: WO2004060947A1
Application number: PCT/JP2003/016908
Authority: WO
Inventors: Noriaki Shibata; Takashi Shibanuma; Tatsumi Tsuchiya; Yasufu Yamada
Original assignee: Daikin Industries, Ltd.
Priority date: 2002-12-27
Filing date: 2003-12-26
Publication date: 2004-07-22
Also published as: AU2003296147A1; AU2003296147A8; WO2004060947A8

Abstract

A process for the production of synthetic resin foam by reacting a polyol with a polyisocyanate compound in the presence of a blowing agent, characterized in that the blowing agent is a mixture comprising (a) 1,1,1,3,3-pentafluoropropane, (b) 1,1-dimethoxymethane, and (c) at least one compound selected from the group consisting of glycol compounds, fluorine -containing surfactants, and amide compounds.

Description

Specification

Method for producing synthetic resin foam

Technical field '

The present invention relates to a method for producing a synthetic resin foam, a foaming agent and a premix.

Background technology

It is widely practiced to react a polyol and a polyisocyanate compound in the presence of a catalyst and a blowing agent to produce a synthetic resin foam. Examples of the obtained synthetic resin foam include polyurethane and polyisocyanurate.

As a foaming agent used in the production of synthetic resin foams such as the above-mentioned polyurethane foams, trichlorofluoromethane (CFC-11) has been mainly used so far.

In recent years, it has been pointed out that certain chlorofluorocarbons, when released into the atmosphere, destroy the stratospheric ozone layer and, as a result, have serious adverse effects on human ecosystems, including humans. For this reason, the use of chlorofluorocarbon, which has a high risk of destruction of the ozone layer, is restricted by international agreements. CFC-11 above is subject to this usage restriction. From this point, the ozone layer is not destroyed or its danger is low, and it is necessary to develop a new blowing agent.

At present, 1,1-dichloro-11-fluoroethane (HCFC-141b) is used as a substitute for CFC-11 as a chlorofluorocarbon having a small effect on the ozone layer.

However, there is still a risk of destruction of the ozone layer, as this substance also contains chlorine atoms in the molecule.

JP-A-2-29440 and JP-A-2-235982 disclose a method for producing a foam using a fluorinated hydrocarbon that does not contain chlorine and has no risk of destroying the ozone layer. Te, ru. Also, Japanese Patent Application Laid-Open No. 5-239251 discloses 1,1,1,3,3-pentafunolelov. Mouth bread (HFC-245fe) is described as being used as a blowing agent for the production of plastic foam.

HFC-245fa is a non-flammable compound with a boiling point of 15 ° C and is considered to have no risk of ozone layer breakage because it is a fluorinated hydrocarbon containing hydrogen atoms. Furthermore, HFC-245fa has attracted attention as a very promising candidate for a blowing agent to replace HCFC-141b because its boiling point is close to that of CFC-11 and HCFC-141b, and its force is nonflammable. Although the boiling point (15 ° C) of HFC-245fa is within the allowable range, it is slightly lower than that of CFC-11 (boiling point 24 ° C) and HCFC-141b (boiling point 32 ° C). The rapid evaporation makes foam production difficult. In addition, a premix containing HFC-245fa and a polyol, whose solubility in a polyol is not always high, may cause phase separation. In the case where the boiling point of the blowing agent is low, or the solubility in the polyol is low, in the case where the polyol is mixed with the isocyanate compound to produce a foam, poor mixing and residual unreacted components may occur. In addition, coarse bubbles called “voids” are likely to occur, and as a result, the strength and thermal conductivity required for the rigid urethane foam are deteriorated. In addition, HFC-245fa itself or a mixture with a foam material (particularly a premix that is a mixture with a polyol) has a high pressure and a high vapor pressure depending on weather conditions, and is difficult to handle. There is also a problem that the loss of the foaming agent increases in the open system state. In addition, containers that have unprecedented pressure resistance will be required for transportation and storage.

Thus, in order to effectively use HFC ² 4 ⁵ fa as HCFC 141b replacement, its boiling point, the development of techniques for controlling the solubility or the like is desired.

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and a foaming agent which solves or reduces the problems of HFC-245fa while maintaining the performance of HFC-245fa as a foaming agent. A main object of the present invention is to provide a premix containing the foaming agent and a method for producing a synthetic resin foam using the foaming agent.

Disclosure of the invention

As a result of intensive studies, the present inventors have found that the above objects can be achieved by using a foaming agent having a specific composition, and have completed the present invention.

1. In a method for producing a synthetic resin foam by reacting a polyol and a polyisocyanate compound in the presence of a foaming agent, the foaming agent comprises:

(a) l, 1,1,3,3-pentafluoropropane;

(b) 1,1-dimethoxymethane; and

(c) Glycol compound, fluorine-containing surfactant and amide compound power At least one compound selected

A method for producing a synthetic resin foam, which is a mixture containing: 2. The ratio power of 1,1-dimethoxymethane is less than 50% by weight based on the sum of 1,1,1,3,3-pentafluoropropane and 1,1-dimethoxymethane. the method of.

3. having a step of preparing a premix containing a polyol and a foaming agent, wherein the total vapor pressure of the obtained premix is 1,1-dimethoxymethane and glycolide, a fluorine-containing surfactant and A premix containing the same components as the above premix except that it does not contain at least one compound selected from the group consisting of amide compounds, and the 1,1,1,3,3-pentaful The vapor pressure of the premix is the same as the total molar ratio of 1,1,1,3,3-pentafluoropropane and 1,1-dimethoxymethane to the polyol in the premix. 2. The method according to 1 above, wherein the total pressure is 96% or less.

4. Consists of (a) l, 1,1,3,3-pentafluoropropane, (b) l, 1-dimethoxymethane, and (c) glycol compound, fluorine-containing surfactant and amide compound Group power A foaming agent for producing a synthetic resin foam containing at least one compound selected.

5. The proportion of 1,1-dimethoxymethane is 50 weight based on the sum of 1,1,1,3,3-pentafluoropropane and 1,1-dimethoxymethane. /. 5. The blowing agent according to the above item 4, which is less than the above.

6. The blowing agent according to 4 above, which has a boiling point power of 17 to 35 ° C.

7. A premix containing a blowing agent and a polyol, wherein the blowing agent is

(a) l, 1,1,3,3-pentafunololopropane;

(b) 1, 1-dimethoxymethane; and

A premix which is a mixture containing

8. Proportion of 1,1-dimethoxymethane The above-mentioned 7 which is less than 50% by weight based on the sum of 1,1,1,3,3-pentaphnolololopropane and 1,1-dimethoxymethane. Premix as described.

9. Except that the total vapor pressure of the premix does not include 1,1-dimethoxymethane, glycolic compounds, fluorine-containing surfactants, and amide compounds. A premix containing the same components as the premix, wherein the molar ratio of 1,1,1,3,3-pentafunolelopropane to the polyol is 1,1,1 to the polyol of the premix. Total moles of 1,3,3-pentafluoropropane and 1,1-dimethoxymethane 8. The premix according to the above 7, which is 96% or less with respect to the total vapor pressure of the premix having the same ratio.

Hereinafter, the present invention will be described in more detail.

The present invention relates to at least one selected from the group consisting of 1,1,1,3,3-pentafluoropropane, 1,1-dimethoxymethane, a glycol compound, a fluorine-containing surfactant and an amide compound. The present invention relates to a foaming agent for producing a synthetic resin foam containing one kind of compound. The foaming agent of the present invention contains one or more compounds selected from the group consisting of glycol compounds, fluorine-containing surfactants and amide compounds.

Hereinafter, the group power of 1,1,1,3,3-pentafunolene loprononone, 1,1-dimethoxymethane and glyconole compound, a fluorine-containing surfactant and an amide compound, at least one compound power selected. The resulting mixture may be referred to as a "mixed foaming agent".

The present invention provides a premix containing a blowing agent and a polyol, wherein the blowing agent comprises (a) l, 1,1,3,3-pentafluoropropane, (b) l, and 1-dimethoxymethane. (c) The present invention relates to a premix which is a mixture containing a glycol compound, a fluorine-containing surfactant, and at least one compound selected from the group consisting of amide compounds. The premix may contain a foaming catalyst, a stabilizer, a foam stabilizer, a flame retardant, and the like, in addition to the foaming agent and the polyol.

The present invention relates to a method for producing a synthetic resin foam by reacting a polyol and a polyisocyanate compound in the presence of a foaming agent, wherein (a) l, 1, 1, 3 At least one compound selected from the group consisting of 1,3-pentafluoropropane (HFC-245fa), (b) l, 1-dimethoxymethane and (c) glycol compounds, fluorine-containing surfactants and amide compounds The present invention relates to a production method characterized by using a mixture containing: In the production method of the present invention, a foaming agent, a polyol and the like may be mixed in advance to form a premix.

1,1-Dimethoxymethane used in the present invention can itself be a blowing agent. Therefore, the addition amount of the blowing agent of the present invention can be substantially the same as the addition amount when HFC-245fa is used alone as the blowing agent. That is, the ratio of HFC-245fa in the foaming agent can be reduced, and the amount of HFC-245fa scattered in the premixing power can be reduced. Also, when actually foamed, there is no concern that 1,1-dimethoxymethane itself may act as a foaming agent and remain as a condensate in the foam.

* Glycol compound Examples of the glycolic compound used in the present invention include an alkylene glycol such as an ethylene glycol compound, a propylene glycol compound, and a butylene glycol compound. The alkylene glycol generally has an alkylene group having about 2 to 4 carbon atoms, and preferably has an alkylene group having about 2 to 3 carbon atoms.

Examples of the ethylene glycol compound include compounds represented by the following formulas (A) to (C).

Formula (A) C _a H _{2a + 1} 0 (CH ₂ CH ₂₀ ) _b C _c H _{2c + 1}

[Where a, b, and c are independently a = 0, 1, 2, 3, 4, 5, 6, b = l, 2, 3, 4, c = 0, 1, 2, 3, 4 ], Formula (B) C _d H _{2d + 1} CO (OCH ₂ CH ₂ ) _e 0 CO C _f H _{2f + 1}

[Where d, e, and f are independently d = 0, 1, 2, 3, 4, e = l, 2, 3, 4, ^ O, 1, 2, 3, 4],

Formula (C) CiH _{2i + 1} COO (CH ₂ CH ₂₀ ) jC _k H _{2k + 1}

[Where i, j, and k are independently i = 0, 1, 2, 3, 4, j = l, 2, 3, 4, k = 0, 1, 2, 3, 4].

Specific examples of the ethylene glycol compound represented by the formula (A) include, for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol alcohol monoethyl ether, ethylene glycol methyl ether ether, and the like. , Ethylene glycolone monopropynoleate, ethylene glycolone resin propinoleate, ethylene glycolone monobutynoate etheretone, ethylene glycolone resinebutinoleatee nonole, ethylene glycolone glycolate ether, diethylene glycol monoethylene ether Methinole ether, diethylene glycol dimethyl ether, diethylene glycolone monoethynoleate, diethylene glycolone retinole ether, diethylene glycol monopropynole Athenole, diethylene glycolone resin propinoleatenoe, diethyleneglyconelebutinoleatenoatee, diethyleneglyconelorebutinoleatenoatene diethyleneglyconele n-hexyl ether, triethylene glycol monomethinole ethere, triethylene glycol dimethyl ether, triethylene Glycol monoethyl ether, triethylene glycol monoethyl ether, triethylene glycol propyl ether, triethylene glycol dibutyl pill ether, triethylene glycol butyl ether, triethylene glycol dibutyl ether, tetraethylene dalicol, tetraethylene glycol Examples include dimethyl ether ether.

Specific examples of the ethylene glycol compound represented by the formula (B) include, for example, ethylene glycol monoformate, ethylene glycol diformate, and diethylene glycol monoformate. 2003/016908

6, diethylene glycol diformate, triethylene glycol monoformate, triethylene glycol diformate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycolone monoacetate, diethylene glycol diacetate, triethylene glycol monoacetate, triethylene glycol monoacetate Examples include ethylene glycol diacetate, ethylene glycol monopropionate, ethylene glycol dipropionate, diethylene glycol monopropionate, diethylene glycol dipropionate, triethylene glycol monopropionate, and triethylene glycol dipropionate.

Specific examples of the ethylene glycol compound represented by the formula (C) include, for example, ethylene glycol methinoleate enolefonoremate, ethylene glycol enoletin oleatenolefonolemate, and ethylene glycol propinole ethere. Olmate, ethylene glycolone monomethinoleate acetate, ethylene glycolonelet / lethenorea acetate, ethylene glycolone propionoleate acetate, ethylene glycol butyl ether acetate, ethylene glycol methylone etherate propionate, Ethylene glycol olenoate enole propionate, ethylene glycol oleno propyl ate oleno propionate, diethylene glycol oleno methyl enoate oleate, diethylene glycol methino oleate Ruformate, diethylene glycol ethyl monoterformate, diethylene glycol propyl ether formate, diethylene glycol cornolemonoethyl ethereoleate, diethylene glycol propyl ether acetate diethylene glycol olenomethyl ether propionate, diethylene glycol / leetinooleate norepropionate, diethylene glycol propyl Ether propionate, triethylene glycol olenomethyl ether ether phonoremate, triethylene glycol olenoethyl enoate ethereforme triethylene glycol propyl ether formate, triethylene glycol methyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate , Triethylene glycol propyl -Ter acetate, triethylene glycol methyl ether propionate, triethylene glycol ethyl ether propionate, triethylene glycol olenopropionate terpropionate, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, etc. .

Examples of the ethylenedalcol-based compound include a diether compound in which a and c are 1 or more in Formula (A), a diester compound in which d and f are 1 or more in Formula (B), and k and i in Formula (C). Is preferably 1 or more. More specifically, the example For example, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol mono n-butyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol olenoethyl ether acetate, diethylene glycol butyl ether acetate Preferred examples of the compound include diethylene glycol dimethinole ether, diethylene glycol getyl ether, diethylene glycol di-t-butyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.

Examples of the ethylene glycol compound include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monopropyl n-propyl ether, ethylene glycol mono- Hexinoleatenole, diethyleneglyconele monoethynoleatene diethyleneglycol monomethynorateether, diethyleneglyconelemonoisopropylatene, diethyleneglycolonele n-propinoleateneolete, diethyleneglyconele t-ptynoleatele, diethyleneglycolatene -Butyl ether, diethylene glycolone-n-hexinolete, triethyleneglyconelemonoethyl ether, Triethylene glycol monomethyl E one ether such be suitably Yore can Rukoto.

Examples of the propylene glycol compound include propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl butyl ether, tripropylene glycol monomethyl ether tripropylene glycol monobutyl ether, 2-methoxy-1-propanol, tripropylene glycol dimethyl ether, propylene Glycol monomethyl ether acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, tri Compounds such as Russia propylene glycol mono ethyl ether. As the propylene glycol compound, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate. 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate and the like are preferred. Examples of glycolide conjugates include, for example, butylene cholesteric compounds such as butylene glycol diacetate.

As the glycol compound, a compound having high compatibility with HFC-245fa and / or polyol is preferable. For example, after a premix containing HFC-245fa, 1,1-dimethoxymethane, glycol compound, polyol, etc. is shaken for about 10 minutes, phase separation after standing at about 0-25 ° C for about 5 hours Shiny glycol compounds are preferred. Due to the compatibility with HFC-245fa and / or polyol, the compounds having specific names described above can be preferably used.

The glycolic compound having higher compatibility with HFC-245fa and / or polyol reduces the loss (scattering amount) of the blowing agent when the premix containing the polyol and the blowing agent is placed in an open system. be able to. Also, the vapor pressure of the premix can be reduced.

The boiling point of the glycolide conjugate used in the present invention is not particularly limited, but is usually about 85 to 300, preferably 120 to 250. It is about C.

* Fluorine-containing surfactant

As the fluorine-containing surfactant used in the present invention, for example, compounds represented by the following formulas (D) to (F) can be exemplified.

Formula) HO [CH ₂ C (R) (CH ₂ OCH ₂ R ^fa ) CH ₂ 0] _n H

[Where n is 3-30,

R ^fe _{_{is, - (CF 2) a .H}} (a '= l~8) or _{_{- (CF 2) b, F}} (b' indicates = l~8),

R represents H or a lower alkyl group],

_{^{Formula) HOCCH (CH 2 R, b}} ) CH 2 0] m H

[Where m is 3-30,

R ^ib _{_{is, - (CF 2) C .H}} (c '= l~8) or _{_{- (CF 2) d .F (}} d' indicates a = l~8)],

Expression)

[Wherein, R ° represents H or CH ₃ ,

R ¹ represents F-containing alkyl or a substituted product thereof,

R ² represents H or a lower alkyl group, la = l-3, lb = 4-: 15].

In the general formula (D), n is usually about 3 to 30, preferably about 3 to 10. R _{_{is, - (CF 2) a .H}} (a '= l~8) or _{_{- (CF 2) b .F (}} b' indicates a = l~8). a is preferably 1 to 4 b 'is preferably 1 to 4. R represents a hydrogen atom or a lower alkyl group. Lower alkynole denoted by R The carbon number of the group is usually about 1 to 4, preferably about 1 to 2.

As the compound represented by the formula (D), HO [CH ₂ C (CH ₃ ) (CH ₂ OCH ₂ CF ₃ ) CH ₂ 0] ₇ H,

HO [CH ₂ C (CH ₃ ) (CH ₂ OCH ₂ C ₄ F ₈ H) CH ₂ 0] ₆ H is preferred.

In the general formula (E), m is usually about 3 to 30, preferably about 3 to 10. R ^ft represents 5- (CF ₂ ) _C , H (c ′ = l to 8) or − (CF ₂ ) _d .F (d ′ = l to 8). c 'is preferably 1-4. d' is preferably 1-4.

Examples of the compound represented by the general formula (E), HO [CH ( CH 2 C 4 F 9) CH 2 0] 6 H, HO [CH

(CH ₂ C ₂ F ₅ ) CH ₂ 0] ₆ H and the like are preferable.

In the general formula (F), n is usually about 1 to 3, preferably about 1 to 2. m is usually about 410 to 15, preferably about 4 to 10. R ¹ represents F-containing alkyl or a substituted product thereof. The carbon number of the F-containing alkyl represented by R ¹ is generally about 10 to 20, preferably about 12 to 18. The number of fluorine atoms of the F-containing alkyl represented by R ¹ is usually about 10 to 40, preferably about 12 to 34. R ² represents H or a lower alkyl group. The carbon number of the lower alkyl group represented by R ² is usually about 1 to 2.

15 Examples of the compound represented by the general formula (F) include, for example, UNIDYNE DS-401 and DS-403 manufactured by Daikin Industries, Ltd .; and Zonyl FSO and FSN manufactured by DuPont.

As the fluorine-containing surfactant, a compound having high compatibility with HFC-245fa and / or polyol is preferable. For example, after shaking a premix containing HFC-245fa, 1,1-dimethoxymethane, a fluorine-containing surfactant and a polyol for about 10 minutes, and then allowing it to stand at about 0 to 25 ° C for about 520 hours, No phase separation, and fluorine-containing surfactants are preferred. The higher the compatibility with HFC-245fa and / or polyol and the higher the fluorine-containing surfactant, the more the loss of the foaming agent when the premix containing the polyol and the foaming agent is placed in an open system, that is, The scattering amount of the blowing agent can be reduced.

The boiling point of the fluorine-containing surfactant used in the present invention is not particularly limited, but is usually about 25 to 100 ° C, preferably about 120 to 250 ° C.

* Amide compounds

Examples of the amide compound used in the present invention include the compounds represented by the following formulas (G) and (H).

Equation (G) R ^ ONR'R ³ [Wherein, R ¹ represents a hydrogen atom, a lower alkyl group or a phenyl group, and R ² and R ³ are the same or different and represent a hydrogen atom or a lower alkyl group. R ¹ and R ² may form a heterocycle with the carbonyl carbon atom to which R ¹ is bonded and the nitrogen atom to which R ² is bonded. ]

Formula) RR ⁵ NCONR ⁶ R ⁷

[Wherein, RR \ R ⁶ and R ⁷ are the same or different and represent a hydrogen atom or a lower alkyl group. R ⁴ and R ⁶ may form a heterocyclic ring with the nitrogen atom to which R ⁶ is bonded, the nitrogen atom to which R ⁴ is bonded, and a carbonyl carbon. ]

In formula (G), the number of carbon atoms of the lower alkyl group represented by RR ² or is usually about! -2, preferably a methyl group.

R ¹ is a hydrogen atom, a lower alkyl group or a phenyl group, preferably a hydrogen atom or a methyl group.

R ² is a hydrogen atom or a lower alkyl group, preferably a lower alkyl group, particularly preferably a methyl group.

R ³ is a hydrogen atom or a lower alkyl group, preferably a lower alkyl group, and particularly preferably a methyl group.

Further, in the formula (G), R ¹ and R ² may form a heterocyclic ring with the carbonyl carbon atom to which R ¹ is bonded and the nitrogen atom to which is bonded. That is, the compound represented by the formula (G) may be a cyclic amide compound. Examples of the heterocycle include a 5-membered ring. Examples of the amide compound represented by the formula (G) include N, N-dimethylformamide, N, N-dimethylacetamide, Ν, Ν-dimethylpropionamide, Ν-methylformamide, Ν-methylacetamide Ν- Examples of the methylamidopropionamide, Ν-methylbenzamide, etc. Examples of the cyclic amido conjugate represented by the formula (G) include Ν-methylpyrrolidone, etc. Formula (G) As the amide compound represented by, R, R-dimethylformamide, Ν, Ν-dimethylacetamide, Ν, Ν are particularly preferred for compounds in which both R ² and R ³ are lower alkyl go. -Dimethylpropionamide, Ν-methylpyrrolidone and the like are preferred.

In formula (Η), the lower alkyl group represented by R ⁴ , R ⁵ , R ⁶ or R ⁷ usually has about 1 to 2 carbon atoms, and is preferably a methyl group. Further, R ⁴ and R ⁶ may form a heterocycle with the nitrogen atom to which R ⁶ is bonded, the nitrogen atom to which R ⁴ is bonded, and a carbon carbon. That is, the compound of the formula (H) may be a cyclic compound. Examples of the heterocycle include a 5-membered ring.

Examples of the amide compound represented by the formula (H) include, for example, tetramethylurea. Examples of the cyclic conjugate represented by the formula (H) include 1,3-dimethylimidazolidinone.

At least one selected from the group consisting of (a) HFC-245fa and (b) l, 1-dimethoxymethane and (c) glycolide conjugate, a fluorine-containing surfactant and an amide compound in a foaming agent. Can be arbitrarily selected according to the application, the composition of the synthetic resin foam raw material, and the like. For example, at least one selected from the group consisting of (a) HFC-245fa, (: b) l, 1-dimethoxymethane, (c) glycolide, a fluorine-containing surfactant and an amide compound. (D) The total vapor pressure of the premix {(a) + (b) + (c) + (d)} containing the polyol, etc. is (b) 1,1-dimethoxymethane, (c) ) Premix ((a) + (b) + (c) + (d) except that it does not contain at least one compound selected from the group consisting of glyconole compounds, fluorine-containing surfactants and amide compounds. } And a premix containing the same components (ie, [{(a) + (b) + (c) + (d)} — {(b) + (c)} = {(a) + (d)} And (a) the molar ratio of HFC-245fa to the polyol of the premix consisting of only the polyol and (a) HFC_245fa (the number of moles of (a) and the number of moles of (d)). , (C) and (d) in the premix of the present invention comprising the polio. Vapor pressure of the premix which is equal to the total molar ratio of HFC-245fa and 1,1-dimethoxymethane to the total amount of {((a) + (b) moles) Z (d) moles} 100%), the vapor pressure of the premix consisting of «a) + (b) + (c) + (d)} is usually about 96% or less, preferably about 70-94%. Preferably, the composition ratio of each component is set so as to be about 70 to 90%. For comparison of the vapor pressure of the premix, the value at any temperature of about 20 to 40 ° C is usually used, and the value at the same temperature is compared.

A more specific example is described using premix I consisting of (a) to (d) and premix II consisting of (a) and (d) (not including (b) and (c)). I do. Premix I content (mol)

(a) HFC-245fa A

(b) l, 1-Dimethoxymethane B

(c) glycol compound, fluorine-containing surfactant and amide compound C

At least one compound selected

(d) Polyol D

Premix II

(a) HFC-245fa A,

(d) polyol D,

(a) and (d), wherein the molar ratio of HFC-245fa to the polyol (A ′ ZD ′) is HFC-245fa to the polyol of Premix I containing (a) to (d) and 1,1- With respect to the total vapor pressure of premix II (100%), which is the same as the total mole ratio {(A + B) / D} with dimethoxymethane, the premix I containing (a) to (d) above It is preferable to set the composition ratio of each component so that the vapor pressure S is usually about 96% or less, preferably about 70 to 94% or less, more preferably about 70 to 90 ° / o or less. In other words, if the total molar ratio of (a) HFC-245fa and (b) 1,1-dimethoxymethane to (d) polyol in the premix I of the present invention is (A mole + B mole) / D mole For example, the molar ratio (A, / D ') of HFC-245fa to polyol in the premix II to be compared should be the same. However, the types of the components contained in the premix II to be compared are as follows: from the premix I of the present invention, (c) a glycol compound and / or a fluorine-containing surfactant and / or an amide compound and (b) , L Dimethoxymethane is the same except that. Accordingly, when the premix of the present invention contains components such as a foaming catalyst, a stabilizer, a foam stabilizer, and a flame retardant, the premix to be compared also contains the same amount of the components. I do. The vapor pressure ratio was measured based on (a) 100 parts by weight of polyol, (a) HFC-245fa, (b) 1,1-dimethoxymethane, and (c) glycol aldehyde compound and / or fluorine. Total amount of surfactant and / or amide compound contained

1 Use a premix of about 20 to 70 parts by weight.

The boiling point of the premix containing the blowing agent of the present invention, polyol, etc. (the temperature at which the vapor pressure of the premix becomes 1 atm (about O.lMPa)) is usually about 15 ° C or more, preferably about 17 to 35 ° C. And more preferably about 18-30 ° C. The mixing ratio of HFC-245fa, 1,1-dimethoxymethane, dalicol compound, fluorine-containing surfactant, amide compound and the like may be set so that the boiling point of the premix falls within the above range. The vapor pressure of the premix containing the blowing agent and the polyol of the present invention is not particularly limited, but is preferably about 1 atm or less at 17 ° C, more preferably about 1 atm or less at 20 ° C, and still more preferably 24 ° C or less. It is about 1 atmosphere or less. At least one selected from the group consisting of HFC-245fa, 1,1-dimethoxymethane and glycoly conjugate, a fluorine-containing surfactant and an amide compound in such a ratio that the vapor pressure of the premix is in the above range. It is preferable to prepare one compound and mix it with a polyol or the like.

The mixing ratio of HFC-245fa, 1,1-dimethoxymethane, glycolide conjugate and / or fluorine-containing surfactant and / or amide compound in the foaming agent of the present invention depends on the application, the composition of the synthetic resin foam raw material. The ratio can be arbitrarily selected according to the ratio, etc., but the boiling point of the blowing agent (temperature at which the vapor pressure reaches 1 atm (about O.lMPa)) is preferably about 17 to 35 ° C. A ratio of about C is more preferable.

In the foaming agent of the present invention, the total amount of HFC-245fa and 1,1-dimethoxymethane is HFC-245fa, 1,1-dimethoxymethane and a glycol compound and / or a fluorine-containing surfactant and / or an amide-based compound. It is usually about 50% by weight or more, preferably about 65 to 99% by weight, more preferably about 75 to 98% by weight, based on the total amount of the compound.

The mixing ratio of HFC-245fa and 1,1-dimethoxymethane in the blowing agent of the present invention is such that when the total of HFC-245fa and 1,1-dimethoxymethane is 100% by weight, 1,1-dimethoxymethane is Usually about less than 50% by weight, preferably about 9 to 50% by weight, more preferably 13 to 45% by weight. / ₀ , particularly preferably about 16 to 41% by weight.

The total amount of the glyconole compound and / or the fluorine-containing surfactant and / or the amide compound in the foaming agent of the present invention is usually based on 100 parts by weight of the total of HFC-245fa and 1,1-dimethoxymethane. It is about 1 to 49 parts by weight, preferably about 1 to 35 parts by weight, particularly preferably about 2 to 25 parts by weight. .

The blowing agent of the present invention may contain another blowing agent. That is, the mixed foaming agent may be used alone or in combination with another foaming agent. Examples of the foaming agent that can be used in combination include an inert gas such as air, nitrogen, and carbon dioxide; and a low-boiling halogenated hydrocarbon. Examples of low boiling halogenidani hydrocarbons include 1,1,1,2-tetrafluoroethane and 1,1,1,2,3,3,3-hexafluoropropane. The low boiling point halogenated hydrocarbon is not particularly limited, and its boiling point is usually about −30 to 0 ° C. at 1 atm (about 0.1 MPa). Of other blowing agents The amount of addition is not particularly limited as long as the effects of the present invention can be obtained, but the total power of HFC-245fa and 1,1-dimethoxymethane in all the blowing agents is usually about 20% by weight or more, preferably. Is about 40% by weight or more, more preferably about 60 to 95% by weight. These foaming agents are often used by being mixed with a premix at the time of foaming.

The blowing agent of the present invention may contain water. That is, the mixed foaming agent can be used in combination with water. The proportion of water can be added to such an extent that water is less than 20% by weight based on the sum of HFC-245fa, 1,1-dimethoxymethane and water. By setting it in this range, a highly heat-insulating foam can be obtained more reliably.

The foaming agent of the present invention may optionally contain a known decomposition inhibitor. Examples of such a decomposition inhibitor include nitro compounds such as nitrobenzene and nitromethane; aromatic hydrocarbons such as _α -methylstyrene and ρ-isopropenyltoluene; and aliphatic unsaturated hydrocarbons such as isoprene and 2,3-dimethylbutadiene. Hydrogen; epoxy compounds such as 1,2-butylene oxide and epichlorohydrin; phenol compounds such as ρ-t-butyl catechol and 2,6-di-t-butyl-1-p-tarezol; Such acetic acid ester compounds can be exemplified. The mixing ratio of the decomposition inhibitor can be appropriately set according to the type of the inhibitor, etc. Usually, about 0.05 to 5 parts by weight with respect to 100 parts by weight of the total of HFC-245fa and 1,1-dimethoxymethane. is there. The decomposition inhibitor may be previously mixed with the foaming agent used in the present invention, or may be separately added at the time of foaming.

The amount of the foaming agent of the present invention can be appropriately set according to the type of the glycol compound, the fluorine-containing surfactant and the amide compound used. The total of HFC-245fa and 1,1-dimethoxymethane is usually about 1 to 70 parts by weight, preferably about 10 to 60 parts by weight, more preferably about 20 to 55 parts by weight, based on 100 parts by weight of the polyol.

In the production method of the present invention, a polyol and a polyisocyanate conjugate are reacted in the presence of a foaming agent to produce a synthetic resin foam. Examples of the synthetic resin foam obtained by the method of the present invention include a polyurethane foam and a polyisocyanurate foam. Raw materials other than foaming agents such as polyols and polyisocyanate compounds are not particularly limited, and known materials can be used. The following can be exemplified as these.

The polyisocyanate toy is, for example, "Keiji Iwata, polyurethane resin handpouch 71-98 Page, Nikkan Kogyo Shimbun, Inc., any of organic isocyanates such as aliphatic, alicyclic, and aromatic compounds can be used. The most commonly used polyisocyanates include, for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), etc. Can be exemplified. Mainly, a mixture in which the weight ratio of 2,4-TDI / 2,6-TDI is about 80Z20 or about 65/35 is used, and can be suitably used in the present invention. Further, polyphenylpolymethylene polyisocyanate (crude mono-MDI) obtained by phosgenating a condensate of aniline and formaldehyde is also used, and can be suitably used in the present invention.

As the polyol, for example, polyether polyols, polyester polyols and the like described in "Keiji Iwata, Polyurethane Resin Handbook, pp. 99-117, Nikkan Kogyo Shimbun" can be used.

The polyether polyol can be obtained, for example, by reacting an initiator having an active hydrogen atom with an alkylene oxide. As an initiator, for example, ethylene glycol, trimethylolpropane, glycerin, triethanolanolamine, ethylenediamine, methyldanorecodit, tolylenediamine, sorbitol, sucrose, etc. are used, and as an alkylene oxide, ethylene oxide, propylene oxide, or the like is used. Then, those having a functional group number of about 2 to 8 and a hydroxyl value of about 300 to 800 mgKOH / g obtained by reacting both can be suitably used. Examples of polyester polyols include condensed polyester polyols obtained by dehydration condensation of adipic acid and dalicol or toluene, rataton-based polyesters obtained by ring-opening polymerization of force prolactam, polycarbonate diols, aromatic polyester polyols, and the like. Among them, those having a functional group number of about 2 to 4 and a hydroxyl value of about 250 to 500 mgKOH / g can be suitably used.

The mixing ratio of the polyol and the polyisocyanate compound can be determined as appropriate.For each equivalent of the isocyanate group in the polyisocyanate compound, the active hydrogen force in the polyol is usually 1 to 3 equivalents. It mixes so that it may become a degree.

In the production method of the present invention, a catalyst in the reaction between the polyol and the polyisocyanate is used. As such a catalyst, a known catalyst such as a tertiary amine, an organometallic compound, or a mixture thereof can be used. The amount of the catalyst to be added can be appropriately set according to the type of the catalyst, etc., but it is usually from 01 to: LO parts by weight, preferably per 100 parts by weight of the polyol. Is about 0.1 to 5 parts by weight.

Examples of tertiary amines that can be used as a catalyst include monoamines such as triethylamine and dimethylcyclohexylamine; diamines such as tetramethylethylenediamine and tetramethylhexamethylenediamine; triethylenediamine and 1,2- Cyclic amines such as dimethylimidazole; and alcoholamines such as dimethylaminoethanol. Also, Ν, Ν, N ′, N′-tetramethylhexane-1,1,6-diamine can be exemplified as diamines. Examples of the organic metal compound include, for example, starnazotoate, dibutyltin dilaurate, dibutyltin diacetate, and the like.

In the production method of the present invention, additives known in the art (for example, a foam stabilizer) may be used. Examples of the foam stabilizer include silicone-based and fluorine-containing surfactants, and more specifically, surfactants based on polysiloxane-polyalkylene block copolymer, methylpolysiloxane, and the like are used. be able to. Examples of the above-mentioned fluorinated surfactant include perfluoroalkylethylene oxide adduct, perfluoroalkyl sulfonate, perfluoroalkyl group-containing oligomer and the like. The addition amount of the foam stabilizer is usually about 0.1 to 10 parts by weight based on 100 parts by weight of a polyol which can be appropriately set according to the kind of the foam stabilizer.

The production method of the present invention is not particularly limited as long as the foaming agent of the present invention is used in a method of producing a synthetic resin foam by reacting a polyol and a polyisocyanate compound in the presence of a blowing agent. . In the method of the present invention, a foaming agent, a polyol and the like may be mixed in advance to form a premix.

The manufacturing conditions may be in accordance with a conventional method. For example, any apparatus may be used as long as it can uniformly mix the raw materials. More specifically, by using a mixer, a foaming machine, etc., the raw materials such as polyol, polyisocyanate conjugate, foaming agent, catalyst, and other additives are mixed well and molded. The desired foam can be obtained. When the foaming agent and other additives are preliminarily dissolved in the polyol component and used as a premix, a uniform foam can be easily obtained. However, the foaming agent and other additives are not limited to this, but may be added to the polyisocyanate compound in advance. It can also be dissolved.

According to the present invention, a blowing agent having a low vapor pressure can be obtained while maintaining the performance of HFC-245fa as a blowing agent. That is, according to the present invention, the vapor pressure of the premix is HFC-245fa A synthetic resin foam having the same heat insulating properties and mechanical strength as when HFC-245fa is used alone can be obtained, though the level is lower than when HFC-245fa is used alone as a foaming agent. Since the blowing agent of the present invention does not contain chlorine, the ability to destroy the ozone layer is substantially zero. Further, in the present invention, a low-boiling halogenated hydrocarbon having a risk of destruction of the ozone layer may be used, but even in this case, the danger is higher than when the hydrocarbon is used alone. Can be greatly reduced.

Since the foaming agent of the present invention has an appropriate boiling point such that a conventional one can be used as a container for transportation or storage, it is not necessary to use a container having particularly high pressure resistance. Further, even in the case of an open system, loss due to vaporization of the premixing foaming agent can be suppressed.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described more specifically with reference to examples of the present invention. The present invention is not limited to the following embodiments.

In addition, the polyol used in the following Examples is as follows.

Polyol A: Aromatic polyester polyol with hydroxyl value of 300mgKOH / g

Polyol B: Aromatic polyether polyol with hydroxyl value of 440mgKOH / g

Comparative Example 1

A premix was prepared by mixing 100 parts by weight of polyol A and 35 parts by weight of HFC-245fa (0.26 mol AlOOg). The vapor pressure at 30 ° C. of the obtained premix was measured. Table 1 shows the results.

Example:! ~ 3

HFC-245fa, 1,1-dimethoxymethane, and diethylene glycol ethyl ether acetate were mixed at the ratio shown in Table 1 to prepare a foaming agent. A premix was prepared by mixing the obtained blowing agent and 100 parts by weight of polyol A. At this time, the mixing ratio of each mixed blowing agent to the polyol was determined by the total molar amount of HFC-245fa and 1,1-dimethoxymethane in the mixed blowing agent. / Polyol A 100 g).

The vapor pressure at 30 ° C. of the obtained premix was measured. Table 1 shows the results. Mixing ratio in foaming agent (% by weight)

HFC-1, 1-Si, Methoxy "Ethylene Gerlicore Premix Pressure

245fa Simethane tyl ether acetate power (Pa abs.)

Example 1 56 37 7 0.1 18

Example 2 62 26 12 0.1 20

Example 3 64 16 20 0.124

Comparative Example 1 100 0 0 0.153 Example 4

Example 1 A foaming agent was prepared in the same manner as in Example 1 except that in Example 1, ethylene glycol dimethyl ether was used instead of diethylene glycolonoethenolate / rareacetate. Using the obtained blowing agent, a premix was prepared in the same manner as in Example 1, and the vapor pressure of the premix was measured by using the same method as in Example 1.

The vapor pressure of the premix at 30 ° C. was 0.129 MPa, which was 16% lower than the vapor pressure of the premix of Comparative Example 1.

Examples 5 to 7 and Comparative Example 2;

1.5 parts by weight of silicone-based foam stabilizer, 1 part by weight of water, 100 parts by weight of polyol B, N, N, Ν ', N'-tetramethylhexane-1,1,6-diamine as a catalyst rise time A premix was prepared by mixing the required amount for 70 seconds and the blowing agent shown in Table 5 and stirring vigorously. The obtained premix was mixed with 112 parts by weight of crude polymethylene polyphenylisocyanate (manufactured by Nippon Polyurethane Industry, MR-100), and vigorously stirred to foam to obtain a rigid polyurethane foam. The amount of the foaming agent was adjusted such that the core density of the foam was 25 ± lkg _/ in ³ .

Table 2 shows the measurement results of the physical properties of the obtained foam after aging for one week at -20 ° C or room temperature (20 to 25 ° C) one day after foaming. In addition, the evaluation method of the foam conformed to JIS A 9514. Table 2

In addition, the amount of the blowing agent in the table is shown in parts by weight based on 100 parts by weight of the polyol.

As is clear from Table 2, a foam having the same thermal conductivity and compressive strength as Comparative Example 2 was obtained. In addition, a foam having a dimensional change rate, a heat conductivity change rate, and a strength change rate which were substantially the same as those of Comparative Example 2 was obtained.

Thus, by using the mixed foaming agent of the present invention, a polyurethane foam having excellent heat insulating properties or mechanical strength could be obtained.

Claims

The scope of the claims

1. A method for producing a synthetic resin foam by reacting a polyol with a polyisocyanate conjugate in the presence of a foaming agent, wherein the foaming agent comprises:

(a) l, 1,1,3,3-Pentafluoroprono II. N;

(b) l, 1-dimethoxymethane; and

(c) at least one compound selected from the group consisting of glycol compounds, fluorine-containing surfactants and amide compounds

A method for producing a synthetic resin foam, which is a mixture containing:

2. The ratio power of 1,1 dimethoxymethane is less than 50% by weight based on the sum of 1,1,1,3,3-pentafluoropropane and 1,1 dimethoxymethane. The described method.

3. A step of preparing a premix containing a polyol and a foaming agent, wherein the total vapor pressure of the obtained premix is 1,1-dimethoxymethane and a glycol compound, a fluorine-containing surfactant and an amide-based Compound power A premix containing the same components as the above premix except that it does not contain at least one compound selected from the group consisting of 1,1,1,3,3-pentafluoropropane and a polyol. The molar ratio of the premix is the same as the total monole ratio of 1,1,1,3,3-pentafluoropropane and 1,1-dimethoxymethane to the polyol of the premix. The method according to claim 1, which is 96% or less.

4. (a) l, 1,1,1,3,3-pentafluoropropane, (b) l, 1-dimethoxymethane, and (c) glycol compounds, fluorine-containing surfactants and amide compounds A blowing agent for producing a synthetic resin foam, comprising at least one compound selected from the group.

5. Harm of 1,1-dimethoxymethane ij Synthetic strength S, 1,1,1,3,3-pentafunolene 50% weight based on the sum of lopronone and 1,1-dimethoxymethane. 5. The blowing agent according to claim 4, which is less than / ₀ .

6. The blowing agent according to claim 4, having a boiling point of 17 to 35 ° C.

7. A premix comprising a blowing agent and a polyol, wherein the blowing agent is

(a) l, 1,1,1,3,3-pentafluoropropane;

(b) l, 1-dimethoxymethane; and

(c) glycolic compound, fluorine-containing surfactant and amide compound power At least one compound selected

A premix which is a mixture containing

8. Proportion of 1,1-dimethoxymethane 1,1,1,3,3-Pentafenolololoprono II. 8. The premix according to claim 7, which is less than 50% by weight, based on the total of 1,1-dimethoxymethane.

9. The total vapor pressure of the premix does not include at least one compound selected from the group consisting of 1,1-dimethoxymethane and glycolide, a fluorine-containing surfactant and an amide compound. Other than the above, a premix containing the same components as the above premix, and the molar ratio of 1,1,1,3,3-pentafluoropropane to the polyol was 1,1 to the polyol of the premix. The vapor pressure of the premix having the same total molar ratio of 1,1,3,3-pentafluoropropane and 1,1-dimethoxymethane is 96% or less based on the total vapor pressure of the premix. Premix.