WO2008062792A1

WO2008062792A1 - Method for producing hard polyurethane foam

Info

Publication number: WO2008062792A1
Application number: PCT/JP2007/072466
Authority: WO
Inventors: Teruhiko Yasuda; Hisashi Sato; Hiroshi Wada; Yasuhito Adachi; Katsuhiko Shimizu
Original assignee: Asahi Glass Company, Limited
Priority date: 2006-11-20
Filing date: 2007-11-20
Publication date: 2008-05-29
Also published as: JP2010031064A

Abstract

Disclosed is a method for producing a polymer-dispersed polyol which has excellent storage stability and high compatibility with polyols for hard polyurethane foam, and enables to attain good heat insulation performance when it is formed into a hard polyurethane foam. Specifically disclosed is a method for producing a polymer-dispersed polyol for hard polyurethane foams, wherein a polyol having polymer particles dispersed therein is produced by polymerizing a monomer having a polymerizable unsaturated group in a polyol (X). This method for producing a polymer-dispersed polyol is characterized in that the polyol (X) contains a polyether polyol (Y) having not less than 10% by mass of an oxyethylene group content, and the monomer having a polymerizable unsaturated group contains a fluorine-containing acrylate or a fluorine-containing methacrylate.

Description

Specification

Method for producing rigid polyurethane foam

Technical field

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

Background art

[0002] Rigid foam synthetic resin produced by reacting a polyol component and a polyisocyanate component in the presence of a foaming agent (eg, rigid polyurethane foam, etc .; hereinafter referred to as "hard foam" and! /) It has the power S.)) is widely used as a heat insulating material with closed cells!

As the foaming agent used in the rigid foam, a low-boiling-point hydrocarbon compound or a hydrocarbon compound is mainly used!

[0003] For rigid foams typified by boards and the like, there is a demand for further reduction in foam density in order to reduce the cost by reducing the amount of raw materials used. However, there is a problem that the foam strength decreases and the rigid foam tends to shrink as the density of the foam decreases.

In addition, in the case of blowing agents, considering the burden on the environment, we can reduce the low-boiling Hyde mouth fluorocarbon compounds to increase water, or consider flammability to reduce hydrocarbon compounds. Technologies that increase water or use only water without using a low-boiling Hyde mouth fluorocarbon compound or hydrocarbon compound are being considered!

However, if the foam is reduced in density by water foaming, such as by using a hydrofluoric compound or hydrocarbon compound in combination with water to reduce the density of the foam or foaming with only water, the foam However, the dimensional stability of the foam deteriorates due to the remarkable tendency of shrinkage.

[0004] Measures for the dimensional stability of the foam usually include increasing the density of the foam to increase the foam strength, or making the foam bubbles open. However, measures to increase the density of the foam increase the amount of raw materials used, which increases costs. In addition, the measures to make the foam cells into continuous cells improve the dimensional stability of the foam, but cannot provide sufficient heat insulation performance. That is, in a rigid foam, when water is frequently used as a foaming agent, or foaming is performed only with water, a foam with good foam dimensional stability and sufficient heat insulation performance is desired.

[0005] Conventionally, a method using a fluorine-containing compound such as polytetrafluoroethylene (PTFE) has been proposed as a well-known technique for preventing shrinkage of rigid polyurethane foam and improving dimensional stability ( (See Patent Documents 1 and 2). According to the methods described in Patent Documents 1 and 2, by adding PTFE having a small particle size, dimensional stability is improved by opening fine pores in the foam, and good thermal insulation performance is also obtained.

[0006] Further, a method of blending a polymer-dispersed polyol in a polyol component has been proposed (see Patent Documents 3 and 4).

The “polymer-dispersed polyol” is a polyol in which polymer fine particles are dispersed in a polyol such as a polyether polyol or a polyester polyol.

The polymer-dispersed polyol is conventionally used to improve the hardness of a flexible foam or a semi-rigid foam.

[0007] As a typical example of a method for producing a polymer-dispersed polyol, the following method is known. That is, in a saturated polyol having no polymerizable unsaturated bond, a monomer having a polymerizable unsaturated group is polymerized under the condition that an unsaturated polyol having a polymerizable unsaturated bond is also present in some cases. Thereafter, the unreacted content is removed. As the saturated polyol or the unsaturated polyol, various polyether polyols and polyester polyols are known.

Patent Document 1: European Patent Application Publication No. 0224945

Patent Document 2: Japanese Patent Publication No. 8 503720

Patent Document 3: JP-A-57-25313

Patent Document 4: Japanese Patent Laid-Open No. 11 302340

Disclosure of the invention

Problems to be solved by the invention

[0008] However, for example, fluorine-containing compounds used in the methods described in Patent Documents 1 and 2 generally have poor solubility in organic substances. When added to a polyol compound and stored, the fluorine-containing compound and the polyol compound were separated, and the storage stability was insufficient, and it was found that a rigid polyurethane foam could not be produced stably.

In addition, the polymer-dispersed polyol used in the methods described in Patent Documents 3 and 4 does not have sufficient storage stability when mixed with a polyol for rigid polyurethane foam having a low molecular weight, so that the rigid polyurethane foam can be stably produced. In addition, it was found that it was difficult to achieve both dimensional stability and heat insulation performance when using rigid polyurethane foam.

Yes

The method described in Patent Document 4 aims to achieve both dimensional stability and heat insulation performance, and there is still a little problem with respect to thermal conductivity!

[0009] Therefore, the present invention provides a rigid polyurethane foam having good dimensional stability and sufficient heat insulation performance, and also when storing a mixture of the polymer-dispersed polyol and the rigid polyurethane foam polyol to be used. In this invention, “storage stability” refers to a polymer-dispersed polyol and a polyol for rigid polyurethane foam. Means a property that can maintain the uniformity of the mixture when stored. When the storage stability is poor, it is possible to obtain a rigid polyurethane foam having a stable quality such that the polymer fine particles are separated from the polyol compound, or the polymer-dispersed polyol migrates in the mixture and the composition becomes non-uniform. It becomes difficult.

Means for solving the problem

[0010] The present invention provides a method for producing a rigid polyurethane foam by reacting a polyol component (Z) and a polyisocyanate component in the presence of a foaming agent, a foam stabilizer and a catalyst. (Z) is a method for producing a rigid polyurethane foam having an average hydroxyl value of 200 to 800 mgKOH / g and containing the following polymer-dispersed polyol (A).

However, the polymer-dispersed polyol (A) has a polymerizable unsaturated group in the polyol (X). The polymer fine particles are dispersed in a polyol by polymerizing the monomer, and the polyol (X) contains a polyether polyol, and the monomer having the polymerizable unsaturated group is a fluorine-containing acrylate or fluorine-containing monomer. Includes metatarates.

[0011] In the method for producing a rigid polyurethane foam of the present invention, the fluorine-containing acrylate or fluorine-containing metatalylate is preferably a monomer represented by the following formula (1):

Yes

[0012] [Chemical 1]

R

R ^f — Z—◦— C 1 C = CH ₂ formula (1)

0

In the formula (1), R ^f is a polyfluoroalkyl group having 1 to 18 carbon atoms, R is a hydrogen atom or a methyl group, and Z is a divalent linking group.

[0013] In the method for producing a rigid polyurethane foam of the present invention, it is preferable that the monomer having a polymerizable unsaturated group further contains acrylonitrile or butyl acetate.

In the method for producing a rigid polyurethane foam of the present invention, the polyether polyol preferably has an oxyethylene group content of 10% by mass or more. In the method for producing a rigid polyurethane foam of the present invention, the polyether polyol preferably has a hydroxyl value of 84 mgKOH / g or less! /.

In the method for producing a rigid polyurethane foam of the present invention, the polyether polyol is preferably a polyoxyalkylene polyol obtained by addition-polymerizing propylene oxide and ethylene oxide to a polyhydric alcohol.

In the method for producing a rigid polyurethane foam of the present invention, the ratio of the monomer represented by the formula (1) in the total monomers having the polymerizable unsaturated group is 20 to 100 mass.

% Is preferred.

In the method for producing a rigid polyurethane foam of the present invention, the proportion of the polymer-dispersed polyol (A) in the polyol component (Z) is 0.01% by mass or more, The proportion of the polymer fine particles in the polyol component (Z) is preferably 0.001% by mass or more.

Further, in the method for producing a rigid polyurethane foam of the present invention, it is preferable to use water alone or at least one selected from a hydrofluorocarbon compound and a hydrocarbon compound and water as the foaming agent.

The invention's effect

[0014] According to the method for producing a rigid polyurethane foam of the present invention, a rigid polyurethane foam having good dimensional stability and sufficient heat insulating performance can be obtained. Further, since the storage stability when the mixture of the polymer-dispersed polyol and the polyol for rigid polyurethane foam used is stored is excellent, the rigid polyurethane foam can be produced stably.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] <Method for producing rigid polyurethane foam>

The method for producing a rigid polyurethane foam of the present invention is a method for producing a rigid polyurethane foam by reacting a polyol component (Z) and a polyisocyanate component in the presence of a foaming agent, a foam stabilizer and a catalyst.

Details of each component will be described below.

[0016] [Polyol component (Z)]

The polyol component (Z) in the present invention contains the specific polymer-dispersed polyol (A).

Examples of components other than the polymer-dispersed polyol (A) of the polyol component (Z) include polyols used in the production of ordinary rigid polyurethane foams such as polyether polyols, polyester polyols, and hydrocarbon polymers having a hydroxyl group at the terminal. (Referred to herein as “polyol for rigid polyurethane foam”) can be used.

The polyol for rigid polyurethane foam preferably has an average functional group number of 2-8.

The number of functional groups means the number of functional groups (hydroxyl groups) of a polyol that reacts with the polyisocyanate component. For example, in the case of a polyether polyol, the polyether polyol Equal to the number of active hydrogens in the initiator used in the production of the catalyst.

Specific examples of the polyol for the rigid polyurethane foam include those similar to those exemplified for the polyol (X) described in the polymer dispersion polyol (A) described later.

[0017] The average hydroxyl value of the polyol component (Z) is 200 to 800 mgKOH / g, and 200-700 mgKOH / g force S is preferable to 200 to 600 mgKOH / g force S. The average hydroxyl value S of 200 mgKOH / g or more is preferable because the strength of the obtained rigid polyurethane foam is easy. It is preferable that the average hydroxyl value is 800 mgKOH / g or less because the resulting rigid polyurethane foam is difficult to be brittle.

In the present invention, the average hydroxyl value means the average value of hydroxyl values of all polyol compounds constituting the polyol component (Z).

[0018] (Polymer-dispersed polyol (A))

The polymer-dispersed polyol (A) in the present invention is a polymer fine particle dispersed in a polyol by polymerizing a monomer having a polymerizable unsaturated group in the polyol (X). The polyol (X) The monomer containing a polyether polyol and having a polymerizable unsaturated group contains fluorine-containing acrylate or fluorine-containing metatalylate.

When the polyol component (Z) contains the polymer-dispersed polyol (A), a rigid polyurethane foam having good dimensional stability and sufficient heat insulation performance can be obtained. In addition, the polymer-dispersed polyol (A) is excellent in storage stability when a mixture thereof having high compatibility with the polyol for rigid polyurethane foam is stored, and therefore, a rigid polyurethane foam can be stably produced.

In the present invention, “in the polyol (X)” may be in the polyol (X) alone, or the solvent exemplified in the description of the “method for producing the polymer-dispersed polyol (A)” described later. And a polyol (X).

[0019] 'Polyol (X)

In the polymer-dispersed polyol (A), examples of the polyol (X) include a polyether polyol, a polyester polyol, and a hydrocarbon polymer having a hydroxyl group at the terminal. You can power to use.

However, in the present invention, the polyol (X) contains at least a polyether polyol. By including the polyether polyol, the compatibility between the polyol for rigid polyurethane foam and the polymer-dispersed polyol (A) is increased, and the storage stability is improved.

[0020] As the polyether polyol, for example, those obtained by addition polymerization of cyclic ethers such as alkylene oxides with initiators such as polyhydroxy compounds such as polyhydric alcohols and polyhydric phenols are used. be able to.

Specific examples of initiators include ethylene glycol, diethylene glycol, propylene glycolone, dipropylene glycolanol, neopentyl glycolanol, 3-methyl-1,5-pentanediol, 1,4 butanediol, 1,6-hexanediol. , Water, glycerin, trimethylolpropane, 1,2,6 hexanetriol, pentaerythritol, diglycerin, tetramethylolcyclohexane, methyl dalcoside, sonolebithonole, mannitol, dulcitol, sucrose, triethanolamine, etc. Alcohol: Polyphenols such as bisphenol nore A and phenol-formaldehyde initial condensate; piperazine, aniline, monoethanolamine, diethanolamine, isopropanolamine, aminoethylenoreeta Luramine, ammonia, aminomethylbiperazine, aminoethylpiperazine, ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diphenylenomethanediamine, diethylenetriamine, triethylenetetramine, etc. These amino compounds or their cyclic ether adducts.

The initiators can be used alone or in combination of two or more.

[0021] As the cyclic ether, for example, a 3- to 6-membered cyclic ether compound having one oxygen atom in the ring can be used.

Specific examples of cyclic ethers include ethylene oxide, propylene oxide, isobutylene oxide, 1-buteneoxide, 2-buteneoxide, trimethylethylene oxide, tetramethylethylene oxide, butadiene monooxide, styrene oxide, a-methyl styrene oxide, Epoxychlorohydrin, Epifnoroleorohydrin, Epib mouth mohydrin, Glycid monole, Butinoreglycidinoatenore, Hexinoreglicidinoreatenore, Fuenoreglycidinore Ethenole, 2-chloroethinoreglycidinoleatenore, o-black fenenoreglycidino oleate, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ethenore, cyclohexene oxide, dihydronaphthalenoxide, vinylenocyclo Examples thereof include compounds having a 3-membered cyclic ether group such as xene monooxide (monoepoxide); compounds having a 4- to 6-membered cyclic ether group such as oxetane, tetrahydrofuran, tetrahydropyran and the like.

Among these, a compound having a 3-membered cyclic ether group (monoepoxide) is preferable. An alkylene oxide having 2 to 4 carbon atoms is more preferable. Ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2 —Butenoxide is more preferable, and ethylene oxide and propylene oxide are particularly preferable.

The cyclic ethers can be used alone or in combination of two or more.

When two or more cyclic ethers are used in combination, the cyclic ether is most preferably a combination of propylene oxide and ethylene oxide, preferably an alkylene oxide having 2 to 4 carbon atoms. At that time, the above-described initiator can be subjected to addition polymerization of a mixture of two or more kinds of cyclic ethers or sequential addition polymerization of two or more kinds of cyclic ethers with a force S.

The polyether polyol has an oxyethylene group content in the polyether polyol of preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. It is most preferably 55% by mass or more, and most preferably 60% by mass or more. On the other hand, the oxyethylene group content is preferably 90% by mass or less.

When the oxyethylene group content is 10% by mass or more, a polymer-dispersed polyol (A) in which polymer fine particles are stably dispersed is easily obtained, and storage stability is improved. In particular, when the oxyethylene group content is 60% by mass or more, the storage stability for a longer period (for example, about one month) becomes better.

In the present invention, the “oxyethylene group content” means the ratio of oxethylene groups in the polyol compound. [0023] The polyether polyol has a hydroxyl value of 84 mgK OH / g or less, preferably 67 mg KOH / g or less, more preferably 60 mg KOH / g or less. Is particularly preferred. The lower limit of the hydroxyl value is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, more preferably 20 mgKOH / g or more, particularly preferably 30 mgKOH / g. Most preferably it is. When the hydroxyl value is 84 mgKOH / g or less, it is possible to improve storage stability while having low viscosity, and when it is 5 mgKOH / g or more, storage stability is improved.

When the hydroxyl value of the polyether polyol is 84 mg KOH / g or less, the oxyethylene group content in the polyether polyol is substantially equal to the oxyethylene group content relative to the entire oxyalkylene groups in the polyether polyol.

[0024] The polyether polyol is preferably obtained by addition polymerization of ethylene oxide or ethylene oxide and another cyclic ether using a polyhydric alcohol as an initiator.

As the polyhydric alcohol, for example, glycerin, trimethylolpropane, 1, 2, 6-hexanetriol is preferable!

As other cyclic ethers, for example, propylene oxide, which is preferably propylene oxide, isobutylene oxide, 1-butene oxide, 2-butenoxide, is particularly preferable. Among these, the polyether polyol is composed of a polyhydric alcohol, propylene oxide, Polyoxyalkylene polyols obtained by addition polymerization of ethylene oxide are preferred. When the polyoxyalkylene polyol is used, the polymer-dispersed polyol (A) in which polymer fine particles are more stably dispersed is further easily obtained, and the storage stability is further improved.

[0025] As the polyester polyol, for example, a polyester polyol obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid can be used. Other examples include polycondensation of hydroxycarboxylic acids, polymerization of cyclic esters (latatanes), polyaddition of cyclic ethers to polycarboxylic acid anhydrides, and transesterification of waste polyethylene terephthalate. And polyester polyols obtained by the above.

[0026] As the hydrocarbon polymer having a hydroxyl group at the terminal, for example, polytetramethylene glycol (PTMG) or polybutadiene polyol can be used.

[0027] In the present invention, the polyol (X) contains at least the polyether polyol, and 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 content of the polyether polyol is 50% by mass or more in the polyol (X), preferably S, more preferably 80% by mass or more, and most preferably 100% by mass. When the content is 50% by mass or more, and most preferably 100% by mass, a polymer-dispersed polyol (A) in which polymer fine particles are stably dispersed is easily obtained, and storage stability is improved.

[0028] Monomer having polymerizable unsaturated group

The monomer having a polymerizable unsaturated group in the present invention includes fluorine-containing acrylate or fluorine-containing metatalylate (hereinafter sometimes referred to as “fluorine-containing monomer”).

By including the fluorine-containing monomer, the dispersion stability of the polymer fine particles in the polyol (X) is improved. Further, the compatibility between the polymer-dispersed polyol (A) to be used and the polyol for the rigid polyurethane foam is increased, the storage stability is improved, and the rigid polyurethane foam is easily produced stably. Furthermore, when a rigid polyurethane foam is used, the dimensional stability is improved, and at the same time, good thermal insulation performance is easily obtained.

[0029] In the present invention, suitable fluorine-containing monomers include monomers represented by the above formula (1) because they have high compatibility with the polyol (X).

In the formula (1), R ^f is a polyfluoroalkyl group having 1 to 18 carbon atoms. In R ^f , the number of carbon atoms is 1 to 18; preferably! To 10; more preferably 3 to 8.

R ^f is the total number of hydrogen atoms in which the proportion of fluorine atoms in the alkyl group (the proportion of the number of hydrogen atoms in the alkyl group replaced by fluorine atoms) is preferably 80% or more. It is particularly preferred that it is substituted with an atom. When the number of carbon atoms is 18 or less, foam stability is favorable when foaming in the production of rigid polyurethane foam, which is preferable.

R is a hydrogen atom or a methyl group. That is, the monomer represented by the formula (1) is If R is a hydrogen atom, it becomes attalate, and if R is a methyl group, it becomes metatalylate.

Z is a divalent linking group, and examples thereof include an alkylene group and an arylene group, and an alkylene group is preferable. The alkylene group may be a straight chain or a branched chain, in which an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is particularly preferable.

Specific examples of the monomer represented by the formula (1) are illustrated below.

[0030] [Chemical 2]

CH ₃

C ₆ F ₁₃ — (CH2) ₂ 0— CI = CH ₂ (1 -D

0

C ₆ F ₁₃ — (CHz — 0— — CH = CH ₂ (1 -2)

0

[0031] The fluorine-containing monomer can be used alone or in combination of two or more.

The amount of the fluorine-containing monomer used is preferably 10 to 100% by mass, more preferably 20 to 100% by mass with respect to all monomers having the polymerizable unsaturated group. The proportion of the monomer represented by the formula (1) in the total monomer having a polymerizable unsaturated group is preferably 20 to 100% by mass, and preferably 30 to 100% by mass. More preferably 40-; most preferably 100% by weight.

When the use amount is 10% by mass or more, particularly 20% by mass or more, the rigid polyurethane foam is used. Better heat insulation performance can be obtained.

From the above, the polymer fine particles in the present invention may be a polymer composed of a fluorinated monomer alone or a copolymer of a fluorinated monomer and another monomer having a polymerizable unsaturated group. Among these, the polymer fine particles are preferably a copolymer because the dispersion stability of the polymer fine particles in the polyol (X) is good.

[0032] In the present invention, examples of the monomer having a polymerizable unsaturated group that may be used in combination with the fluorine-containing monomer include a cyano group-containing monomer such as acrylonitrile, methatalonitrile, 2,4 disianobutene 1, styrene, Styrenic monomers such as α-methylstyrene and halogenated styrene; acrylic monomers such as acrylic acid, methacrylic acid or their alkyl esters, acrylamide and methacrylamide; and bull ester monomers such as butyl acetate and vinylene propionate; Isoprene, butadiene and other gen-based monomers; unsaturated fatty acid esters such as maleic acid diesters and itaconic acid diesters; halogenated butyls such as vinyl chloride, bromobromide and fluorinated butyl; vinylidene chloride, vinylidene bromide Such as vinylidene chloride Examples thereof include vinylidene halides; butyl ether monomers such as methyl butyl ether, ethyl vinyl ether, and isopropyl butyl ether; or other olefins, halogenated olefins, macromonomers, and the like. The “macromonomer” refers to a low molecular weight polymer or oligomer having a radically polymerizable unsaturated group at one end.

Among these, acrylonitrile or vinyl acetate is particularly preferable because acrylonitrile, butyl acetate, and styrene have better storage stability for a longer period of time (for example, about 1 month). It is also preferable to use styrene since the bubble breaking effect is high and the dimensional stability is good.

One or two or more monomers other than the fluorine-containing monomer can be used.

[0033] When the fluorine-containing monomer and acrylonitrile are used in combination, the mixing ratio of the fluorine-containing monomer and acrylonitrile is preferably 10:90 to 90:10 by mass ratio 30:70 to 70: More preferably, it is 30. Within this range, long-term storage stability is improved. Moreover, especially when it is set as a rigid polyurethane foam, heat insulation performance improves. When the fluorine-containing monomer and acrylonitrile are used in combination, and a polyether polyol having an oxyethylene group content of 60% by mass or more is used as the polyol (X), the storage stability is particularly excellent, and a rigid polyurethane foam is obtained. In this case, sufficient heat insulation performance can be obtained.

[0034] Further, when the fluorine-containing monomer, acrylonitrile, and styrene are used in combination, the mixing ratio of the fluorine-containing monomer and the other monomer is 10:90 to 90:10 in terms of mass ratio. Preferably, 30: 70-70: 30 is more preferred! /.

Further, the mixing ratio of acrylonitrile and styrene is preferably 0: 100 to; 100: 0 in mass ratio, more preferably 90:10 to 10:90.

With this mixing ratio, the storage stability when the mixture of the polymer-dispersed polyol and the polyol for rigid polyurethane foam used is stored, and the dimensional stability and thermal insulation performance when used as the rigid polyurethane foam are improved. These characteristics are well balanced.

[0035] Furthermore, when the fluorine-containing monomer and the acetic acid butyl monomer are used in combination, the mixing ratio of the fluorine-containing monomer and the other monomers is 30:70 to 70:30 in mass ratio. S, preferably 40: 60-70: 30, better than S! /.

With this mixing ratio, the storage stability when the mixture of the polymer-dispersed polyol according to the present invention and the polyol for the rigid polyurethane foam is stored, and the dimensional stability and the heat insulation performance when the rigid polyurethane foam is obtained. These are all improved, and these characteristics can be obtained with good tolerance.

[0036] [Polyisocyanate component]

The polyisocyanate component in the present invention is not particularly limited, for example, aromatic, alicyclic and aliphatic polyisocyanates having two or more isocyanate groups; two types of the polyisocyanates; Examples thereof include modified polyisocyanates obtained by modifying them. Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate (commonly known as cnolade MDI), xylylene diisocyanate (XDI), isophorone diester. Polyisocyanates such as isocyanate (IPDI) and hexamethylene diisocyanate (HMDI) Repolymer type modified products; isocyanurate modified products, urea modified products, carpositimide modified products, and the like. Of these, TDI, MDI, Crude MD are preferred to their modified forms.

The polyisocyanate component can be used alone or in combination of two or more.

[0037] [Foaming agent]

As the foaming agent in the present invention, water is mainly used. As the blowing agent other than water, for example, it is possible to use a combination of gas, fluorocarbon compound, hydrocarbon compound and general-purpose gas.

Specific examples of the hydrated fluorocarbon compound include 1,1,1,1,2-tetrafluoroethane (HFC—134a), 1,1,1,3,3-pentafluoropropane (HFC—245 fa), 1 , 1, 1, 3, 3, 3-pentafluorobutane (HFC—365mfc), 1, 1, 2, 2-tetrafluoroethyl difluoromethyl ether (HFE—236pc), 1, 1, 2, 2-tetrafluoro-octylmethyl ether (HFE—254 pc), 1, 1, 1, 2, 2, 3, 3-heptafluorov. Methyl pyrmethyl ether (HFE—347 mcc) and the like can be mentioned.

Specific examples of the hydrocarbon compound include butane, normal pentane, isopentane, cyclopentane, hexane, and cyclohexane.

Examples of the general-purpose gas include air, nitrogen, and carbon dioxide gas. Of these, carbon dioxide is preferable. The addition state of the inert gas may be any of a liquid state, a supercritical state, and a subcritical state.

[0038] The foaming agents can be used singly or in combination of two or more.

In the present invention, it is preferable to use water alone or at least one selected from a hydrofluorocarbon compound and a hydrocarbon compound as the blowing agent and water. Thereby, the foaming effect is improved, and the weight of the rigid polyurethane foam can be reduced.

[0039] [Foam stabilizer]

The foam stabilizer in the present invention is not particularly limited, and examples thereof include silicone foam stabilizers. Among them, the heat insulation performance of rigid polyurethane foam is added. Therefore, a silicone type foam stabilizer having a high foam regulating effect capable of reducing the cell diameter is particularly preferred.

One type of foam stabilizer can be used alone, or two or more types can be used in combination.

[0040] [Catalyst]

The catalyst in the present invention is not particularly limited as long as it is a catalyst that promotes the urethanization reaction.

Examples of catalysts that promote the urethanization reaction include triethylenediamine, bis (2-dimethylaminoethinole) ether, N, N, Ν ', N'-tetramethylhexamethylenediamine, etc. Class amines; organometallic compounds such as dibutyltin dilaurate. Further, examples thereof include acetic acid lithium which may be used in combination with a catalyst for promoting the trimerization reaction of isocyanate group, and a metal carboxylate such as potassium 2-ethylhexanoate.

When spray foaming is employed as a method for producing a rigid foam, it is preferable to use an organometallic catalyst such as lead 2-ethylhexanoate in order to complete the reaction in a short time.

[0041] [Other ingredients]

In the present invention, any compounding agent may be used as required! /.

Compounding agents include fillers such as calcium carbonate and barium sulfate; antioxidants such as antioxidants and UV absorbers; flame retardants, plasticizers, colorants, antifungal agents, foam breakers, dispersants, discoloration An inhibitor etc. are mentioned.

[0042] <Method for producing rigid polyurethane foam>

The present invention is a method for producing a rigid polyurethane foam by reacting a polyol component (Ζ) and a polyisocyanate component in the presence of a foaming agent, a foam stabilizer and a catalyst. In production, the polyol component (成分) is prepared in advance, and a mixture of the polyol component (Ζ) and a part or all of the components other than the polyisocyanate component (hereinafter referred to as “polyol system solution”) is prepared. It is preferable to keep it.

The foaming agent may be blended in advance in the polyol system liquid, or may be blended after the polyisocyanate component is mixed in the polyol system liquid. I prefer it. [0043] The polyol component (Z) can be prepared, for example, by mixing the polymer-dispersed polyol (A) and a polyol for a rigid polyurethane foam.

The polymer-dispersed polyol (A) is produced by polymerizing a monomer having a polymerizable unsaturated group in the polyol (X) to produce a polymer-dispersed polyol in which polymer fine particles polymerized with the monomer are dispersed in a polyol. The method is not particularly limited. For example, since the dispersion stability of the polymer fine particles in the polyol (X) is good, a monomer having a polymerizable unsaturated group is polymerized in the polyol (X) in the presence of a solvent as necessary to directly polymerize the polymer. A suitable method is a production method in which fine particles are precipitated to obtain a polymer-dispersed polyol.

[0044] Specific examples of the method for producing the polymer-dispersed polyol (A) include the following methods (1) and (2).

(1) A part of the polyol (X) is charged into a reactor, and a mixture of the remaining polyol (X), a monomer having a polymerizable unsaturated group, a polymerization initiator, etc. is stirred into the reactor. A batch method in which polymerization is performed by gradually feeding.

(2) Polyol (X), a monomer having a polymerizable unsaturated group, a polymerization initiator, and the like are continuously fed into a reactor under stirring to perform polymerization. At the same time, the produced polymer-dispersed polyol is Continuous process that continuously discharges from the reactor.

In the present invention, any of the production methods (1) and (2) can be used.

[0045] In the present invention, the use amount of all the monomers having a polymerizable unsaturated group is not particularly limited, but is an amount such that the concentration of the polymer fine particles in the polymer-dispersed polyol (A) is 50% by mass or less. It is more preferable to be in an amount of 50 to 50% by mass. It is more preferable to be in an amount of 2 to 45% by mass. It is particularly preferable to be in an amount of 5 to 30% by mass. Is most preferred. When the concentration of the polymer fine particles is 50% by mass or less, the polymer-dispersed polyol (A) in which the polymer fine particles are stably dispersed in the polyol (X) is more easily obtained, and the storage stability is further improved. In addition, an appropriate viscosity is obtained, and the liquid stability of the polymer-dispersed polyol (A) is improved.

[0046] In the method for producing the polymer-dispersed polyol (A), as the polymerization initiator, a polymerization initiator that generates a free group and initiates polymerization of a monomer having a polymerizable unsaturated group is usually used. It is done.

Specifically, for example, 2,2-azobismonoisobutyronitrile (hereinafter abbreviated as “AIBN”), 2,2-azobis-2-methylbutyronitrile (hereinafter abbreviated as “AMBN”), 2 1,2-azobis 2,4 dimethylvaleronitrile, benzoyl peroxide, diisopropyl peroxide dicarbonate, acetyl chloride, di-tert butyl peroxide, persulfate and the like. Of these, AIBN and AMBN are preferred.

These polymerization initiators can be used alone or in combination of two or more.

The amount of the polymerization initiator used is 100 in total of polyol (X), all monomers having a polymerizable unsaturated group including a fluorine-containing monomer, and a stabilizer or grafting agent (described later) used as necessary. The amount is preferably 0.01 to 10 parts by mass with respect to parts by mass.

Solvents include, for example, methanol, ethanol, isopropanol, butanol, cyclohexanol, pendinoreanolol, etc .; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, hexene; benzene, toluene Aromatic hydrocarbons such as xylene; ketones such as acetone, methyl ethyl ketone, and acetophenone; esters such as ethyl acetate and butyl acetate; isopropyl ether, tetrahydrofuran, benzyl ethyl ether, acetal, anisole, methyl-tert butyl ether, etc. Ethers: Halogenated hydrocarbons such as chlorobenzene, chlorohonolem, dichloroethane, 1,1,2-trichlorotrifoleoleoethane; Nitro compounds such as nitrobenzene; Acetonitrile, benzonitryl, etc. Tolyl ethers; Torimechiruamin, Toriechiruamin, Toribuchiruamin, amines diphosphorus such Jimechirua; N, N-dimethylformamide, amides such as N-methyl pyrrolidone; dimethyl sulfoxide, sulfur compounds such as sulfolane.

The solvents can be used alone or in combination of two or more. When a solvent is used in the production of the polymer-dispersed polyol (A), the mixing ratio of the solvent and the polyol (X) is preferably 0: 100 to 60:40 by mass ratio. More preferably, it is ˜40: 60. When the mixing ratio is within the range, aggregation of the polymer particles is suppressed, and it becomes easy to obtain a polymer-dispersed polyol (A) in which polymer fine particles are stably dispersed. After the polymerization of the monomer having a polymerizable unsaturated group is completed, the solvent is removed. The method for removing the solvent is usually performed by heating under reduced pressure. It can also be carried out under normal pressure heating or reduced pressure at room temperature. At this time, unreacted monomers are also removed together with the solvent.

[0048] The polymerization reaction of the monomer having a polymerizable unsaturated group in the polyol (X) is performed at a temperature equal to or higher than the decomposition temperature of the polymerization initiator, usually from 80 to 160 ° C, and from 90 to 150 ° C. It is particularly preferable that the reaction be performed at 100 to 130 ° C.

In the present invention, a stabilizer or a grafting agent can be used to improve the dispersion stability of the polymer fine particles in the polymer-dispersed polyol (A). Preferable examples of the stabilizer or grafting agent include compounds having an unsaturated bond in the molecule. Specifically, a high molecular weight polyol or monool obtained by reacting an active hydrogen compound having an unsaturated bond-containing group such as a bur group, a aryl group, or an isopropyl group as an initiator with an alkylene oxide; After reacting the polyol with an unsaturated carboxylic acid such as maleic anhydride, itaconic anhydride, maleic acid, fumaric acid, acrylic acid, methacrylic acid or the like, or an acid anhydride thereof, propylene oxide or ethylene as necessary. High molecular weight polyols or monools obtained by addition of alkylene oxides such as oxides; unsaturated alcohols such as 2-hydroxyethyl acrylate, butene diol, other polyols and polyisocyanates; A reaction product of an unsaturated epoxy compound such as allylic glycidyl ether and a polyol.

These stabilizers or grafting agents preferably have a hydroxyl group and may or may not have a hydroxyl group! /, But preferably have a hydroxyl group. .

The stabilizer or grafting agent can be mixed and blended with the polyol (X), a monomer having a polymerizable unsaturated group, a polymerization initiator, and the like.

[0050] After the completion of the polymerization reaction, the obtained polymer-dispersed polyol (A) is subjected to a decompression treatment on the obtained polymer-dispersed polyol (A) which may be used as a raw material for a rigid polyurethane foam, and has not been subjected to decompression treatment. Of these, the latter is preferred among those that can be used after removal of the reactive monomer.

[0051] In the preparation of the polyol component (Z), the mixing ratio of the polymer-dispersed polyol (A) and the polyol for the rigid polyurethane foam is determined by the polymer-dispersed polymer in the polyol component (Z). The ratio of all (A) is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.9 mass% or more. On the other hand, the proportion of the polymer-dispersed polyol (Α) is preferably 10% by mass or less, and more preferably 7% by mass or less.

In addition, the proportion of the polymer fine particles in the polyol component (Ζ) is 0.001% by mass or more, preferably S, more preferably 0.01% by mass or more, and 0.1% by mass or more. Is more preferable. On the other hand, the proportion of the polymer fine particles is preferably 5% by mass or less, more preferably 1% by mass or less.

When the ratio of the polymer-dispersed polyol (Α) and polymer fine particles in the polyol component (Ζ) is at least the lower limit value, both the dimensional stability and the heat insulation performance are improved when a rigid polyurethane foam is obtained. On the other hand, storage stability improves that it is below an upper limit, and a rigid polyurethane foam can be manufactured stably. In addition, an appropriate viscosity is easily obtained as the polyol component (Ζ), and the liquid stability is improved.

[0052] The amount of water used as a foaming agent is:! To 15 parts by mass is preferably 2 to; 13 parts by mass is more preferably 4 to 100 parts by mass of the polyol component (Ζ); 12 parts by mass is more preferable. If the amount of water used is 1 part by mass or more, it is preferable in terms of reducing the weight of the resulting rigid polyurethane foam. On the other hand, if the amount of water used is 15 parts by mass or less, it is preferable because the miscibility between water and the polyol component (Ζ) becomes better.

When a non-water foaming agent is used in combination, the amount used when using a hydrated fluorocarbon compound other than water is preferably from! To 50 parts by mass with respect to 100 parts by mass of the polyol component (Ζ). More preferred is 20 to 40 parts by mass.

When the hydrocarbon compound is used, the amount used is preferably 1 to 40 parts by mass and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the polyol component (IV).

The amount used when using an inert gas is preferably 1 to 100 parts by mass and more preferably 20 to 20 parts by mass with respect to 100 parts by mass of the polyol component (IV).

[0053] The amount of the foam stabilizer to be used needs to be selected as appropriate, but is preferably from 0 .;

The amount of the catalyst used is preferably 0.;! To 10 parts by mass with respect to 100 parts by mass of the polyol component (Ζ). Good.

[0054] The amount of the polyisocyanate component used is preferably 50 to 300 in terms of the isocyanate index (INDEX).

The isocyanate index (INDEX) is a value expressed by multiplying the ratio of the number of isocyanate groups to the total number of active hydrogens of the polyol component (Z) and other active hydrogen compounds by 100.

In polyurethane formulations that mainly use a urethanization catalyst as the catalyst, the amount of polyisocyanate component used is preferably from 50 to 140, preferably from 60 to 130 force S in terms of isocyanate index.

In polyisocyanurate formulation (urethane-modified polyisocyanurate formulation) that mainly uses a catalyst that promotes the trimerization reaction of isocyanate groups as a catalyst, the amount of polyisocyanate component used is preferably 120 to 300 in terms of isocyanate index. 120-250 is more preferable.

[0055] The method for producing a rigid polyurethane foam in the present invention can be applied to various molding methods. Examples of the molding method include injection, continuous production board, and spray foaming foam. Injection is in a frame of a mold or the like. This is a method in which a rigid polyurethane foam material is injected and foamed. A continuous production board is a laminate in which rigid polyurethane foam is sandwiched between two face materials, and is used as a heat insulating material for architectural purposes. The spray foaming form is a construction in which rigid polyurethane foam is sprayed and applied.

Among these, the method for producing a rigid polyurethane foam of the present invention can be suitably applied to the production of an infused urethane foam, a continuous production board, a spray foam foam, and the like.

[0056] As described above, according to the method for producing a rigid polyurethane foam of the present invention, a rigid polyurethane foam having good dimensional stability and sufficient heat insulating performance can be obtained. Further, since the storage stability when the mixture of the polymer-dispersed polyol and the polyol for the rigid polyurethane foam to be used is stored is excellent, the rigid polyurethane foam can be stably produced. Example

[0057] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. Production Examples 1 to 14 are examples, and Production Example 15 is a comparative example. In addition, test examples;! To 7, 9 to; 15 and 17 to 23 are evaluation results of storage stability of the polymer-dispersed polyols produced in the examples, and test examples 8, 16, and 24 are the results of the present invention. This is an evaluation result of storage stability when PTFE powder is used in place of the polymer dispersed polyol. Production Examples 16 to 30, 34, 35, 38, 39, 42 and 43 are the results of producing rigid urethane foams using the polymer-dispersed polyols produced in the Examples and evaluating the physical properties. 3;! To 33, 36, 37, 40, 41, 44 and 45 (In addition, the results of the evaluation of physical properties by producing this rigid urethane foam using the polymer dispersed polyol of the present invention).

In the following examples, the hydroxyl value was measured according to JIS K1557 (1970 version). The viscosity was measured according to JIS K1557 (1970 version). The polymer fine particle concentration (solid content) was defined as the charged amount of the monomer having a polymerizable unsaturated group as the fine particle concentration (solid content).

«Evaluation of polymer-dispersed polyols>

According to the blending ratios shown in Table 1 and Table 2, polymer dispersion polyols F1 to F15 were produced according to the following production examples;

Table 1 shows the composition at the time of production of the polymer-dispersed polyol, the hydroxyl value (mgKOH / g), the viscosity (mPa's), and the concentration of polymer fine particles (solid content: mass%) of the obtained polymer-dispersed polyols F1 to F15. Each is shown.

In the composition of Table 1 and Table 2, polyols D to G, macromonomers Ml and M2 and monomers having polymerizable unsaturated groups are “g”; polymerization initiator is polyol unsaturated with polyols D to G It is the value of “parts by mass” relative to a total of 100 parts by mass with all monomers having a group.

[0059] (Raw materials used).

'Polyether polyol (Y)

Polyol D: Glycerin is used as an initiator, and ethylene oxide is added to the glycerin. After polymerization, the mixture [PO /

EO = 46. 2 / 53.8 (mass ratio)], polyoxyalkylene polyol in polyol D with a content of oxyethylene group of 65% by mass and a hydroxyl value of 48 mgKOH / g in polyol D Polyol E: Glycerin as initiator The glycerin was added to and polymerized with ethylene oxide,

[PO /

EO = 48. 0 / 52.0 (mass ratio)], polyoxyalkylene polyol with polyol having an oxyethylene group content of 60% by mass and a hydroxyl value of 28 mgKOH / g in polyol E Polyol F: ethylenediamine as an initiator A polyoxyalkylene polyol having an oxyethylene group content of 0% by mass and a hydroxyl value of 760 mgKOH / g in polyol F, obtained by addition polymerization of only PO to the ethylenediamine.

Polyol G: Glycerin was used as an initiator, and PO was added to and polymerized only with PO. The content of oxyethylene group in polyol G was 0% by mass, and the hydroxyl value was 650 mgKOH.

[0061] 'Fluorine-containing monomer

Fluorine-containing monomer (f): A monomer (Asahi Glass Co., Ltd.) represented by the following chemical formula (11) was used.

[0062] [Chemical 3]

(1 -1)

[0063] 'Monomers having other polymerizable unsaturated groups

Acrylonitrile (manufactured by Junsei Kagaku).

Butyl acetate (manufactured by Junsei Kagaku).

• Polymerization initiator 2, 2-azobis-2-methylbutyronitrile (trade name: ABN-E, manufactured by Nippon Hydrazine Industry Co., Ltd .; hereinafter abbreviated as “AMBN”).

[0064] Macromonomer

Macromonomer Ml: Polyol D and tonorene diphenyl diisocyanate (trade name: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-hydroxyethyl methacrylate (manufactured by Seikagaku Co., Ltd.) are used as polyol D / toluene. Charge diphenyldiisocyanate / 2-hydroxyethyl methacrylate = 1/1/1, react at 60 ° C for 1 hour, then react at 80 ° C for 6 hours A macromonomer having a polymerizable unsaturated group having a hydroxyl value of 40 mgKOH / g.

Macromonomer M2: Polyol E and toluene diphenyl diisocyanate (trade name: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 2-hydroxyethyl methacrylate (manufactured by Seikagaku Co., Ltd.) Prepare a molar ratio of enyl diisocyanate / 2-hydroxyethyl methacrylate = 1/1/1, react at 60 ° C for 1 hour, and then react at 80 ° C for 6 hours. A macromonomer having a polymerizable unsaturated group having a hydroxyl value of 21 mgKOH / g obtained in

Production Example 1: Production of polymer-dispersed polyol F1

Charge 70% by weight of polyol D to a 5L pressurized reactor and maintain the remaining 30% by weight of polyol D, acrylonitrile, fluorine-containing monomer (f) and polymerization initiator (AMBN) while maintaining the temperature at 120 ° C. The mixture was fed over 2 hours with stirring, and stirring was continued at the same temperature for about 0.5 hours after the completion of all the feeds. At that time, it was confirmed that the monomer reaction rate measured by the above method was 80% or more, and the reaction was completed. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 8 hours to produce polymer-dispersed polyol F1. The results are shown in Table 1.

[0066] Production Example 2: Production of polymer-dispersed polyol F2

A 5 L pressurized reactor is charged with 70% by weight of polyol D and maintained at 120 ° C, while the remaining 30% by weight of polyol D, acrylonitrile, styrene, fluorine-containing monomer (f), and polymerization initiator ( AMBN) is fed over 1 hour with stirring. After completion of the mixing, stirring was continued for about 0.5 hours at the same temperature. At that time, the reaction was terminated after confirming that the reaction rate of the monomer measured by the above method was 80% or more. Thereafter, the unreacted monomer was removed under reduced pressure at 120 ° C. for 6 hours to produce polymer-dispersed polyol F2. The results are shown in Table 1.

[0067] Production Examples 3 to 7: Production of polymer-dispersed polyols F3 to F7

Polymer-dispersed polyols F3 to F7 were produced in the same manner as in Production Example 1 except that the monomer having a polymerizable unsaturated group shown in Table 1 was used. The results are shown in Table 1.

[0068] Production Example 8: Production of polymer-dispersed polyol F8

In a 5 L pressurized reaction tank, the total amount is 100% by mass, and 090% by mass of polyol is charged, and the remaining 10% by mass of butyl acetate, fluorine-containing monomer (f), and polymerization initiator (120 ° C) The mixture of (AMBN) was fed over 2 hours with stirring, and stirring was continued at the same temperature for about 0.5 hours after the completion of all feeds. At that time, the reaction was terminated after confirming that the monomer reaction rate measured by the above method was 80% or more. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce polymer-dispersed polyol F8. The results are shown in Table 2.

[0069] Production Example 9: Production of polymer-dispersed polyol F9

In a 5L pressurized reaction tank, the total amount is 100% by mass, and 089% by mass of polyol and 1% by mass of the monomer monomer Ml are charged. While maintaining at 120 ° C, the remaining 10% by mass of acetic acid butyl and fluorine-containing The mixture of the monomer (f) and the polymerization initiator (AMBN) was fed over 2 hours with stirring, and stirring was continued for about 0.5 hours at the same temperature after the completion of all feeds. At that time, it was confirmed that the monomer reaction rate measured by the above method was 80% or more, and the reaction was terminated. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce polymer-dispersed polyol F9. The results are shown in Table 2.

[0070] Production Example 10: Production of polymer-dispersed polyol F10

In a 5L pressurized reactor, the total amount is 100% by mass, and 080% by mass of polyol is charged, and the remaining 20% by mass of butyl acetate, fluorine-containing monomer (f) and polymerization initiator are maintained while maintaining at 120 ° C ( The mixture of (AMBN) was fed over 2 hours with stirring, and stirring was continued at the same temperature for about 0.5 hours after the completion of all feeds. At that time, the thing measured by the above method The reaction was completed after confirming that the reaction rate of the monomer was 80% or more. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce polymer-dispersed polyol F10. The results are shown in Table 2.

[0071] Production Examples 11 and 13: Production of polymer-dispersed polyols F11 and 13

As described in Table 2, the polymer composition polyols F11 and F-13 were produced in the same manner as in Production Example 9 by changing the monomer composition having a polyol D and a polymerizable unsaturated group. The results are shown in Table 2.

Production Example 12: Production of polymer-dispersed polyol F12

In a 5 L pressurized reaction tank, the total amount is 100% by mass, and 29.2% by mass of polyol D, 49.8% by mass of Polyol Nore G and 1% by mass of macromonomer Ml are charged to 120 ° C. While maintaining, feed the remaining 20% by mass of the mixture of butyl acetate, fluorine-containing monomer (f) and polymerization initiator (AMBN) over 2 hours with stirring. Stirring was continued for 5 hours. At that time, the reaction was terminated after confirming that the monomer reaction rate measured by the above method was 80% or more. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce polymer-dispersed polyol F12. The results are shown in Table 2.

[0072] Production Example 14: Production of polymer-dispersed polyol F14

In a 5L pressurized reactor, the total amount is 100% by mass, and 079% by mass of polyol and 1% by mass of M2 monomer M2 are charged, and the remaining 20% by mass of acetic acid butyl and fluorine-containing are kept at 120 ° C. The mixture of the monomer (f) and the polymerization initiator (AMBN) was fed over 2 hours with stirring, and stirring was continued for about 0.5 hours at the same temperature after the completion of all feeds. At that time, it was confirmed that the monomer reaction rate measured by the above method was 80% or more, and the reaction was terminated. Thereafter, unreacted monomer was removed under reduced pressure at 120 ° C. for 3 hours to produce polymer-dispersed polyol F14. The results are shown in Table 2.

[0073] Production Example 15: Production of polymer-dispersed polyol F15

After all of polyol D, polyol F, polyol G, acrylonitrile, acetic acid butyl and polymerization initiator (AMBN) are charged into a 5 L pressure reaction tank, the temperature rise is started while stirring, and the reaction liquid is kept at 80 ° C. The reaction was allowed for 10 hours. At that time, measured by the above method The reaction was terminated after confirming that the monomer reaction rate was 80% or more. Thereafter, the unreacted monomer was removed by heating under reduced pressure at 110 ° C. and 20 Pa for 2 hours to produce a polymer-dispersed polyol F15. The results are shown in Table 2.

[table 1]

[Table 2]

Production example Production example Production example Production example Production example Production example Production example Production example

8 9 1 0 1 1 1 2 1 3 1 4 1 5 Polyol D 450 445 400 395 146 395 395 945 Polyol E

Polyol F 900 Polyol G 249 905 Macro monomer M1 5 5 5 5

Macro monomer M2 5

Fluorinated monomer (f) 25 25 50 50 50 40 40

Acrylonitrile 150

Styrene

Vinyl acetate 25 25 50 50 50 60 60 600 Polymerization initiator

2.5 2.5 2.5 2.5 2.5 2.5 2.5 30

(Parts by mass)

Hydroxyl value

46 45 41 41 373 40 40 320

(mgKOH / g)

Viscosity

1810 1930 1750 7120 1950 4060 5400 1500

(mPa-s)

Polymer fine particle concentration

10 10 20 20 20 20 20 20

(Solid content; mass%) '

Name F8 F9 F1 0 F1 1 F1 2 F1 3 F1 4 F1 5

[0076] <Evaluation of storage stability>

Test examples shown in Tables 3 to 5; according to the mixing ratio of! To 24, production examples; polymer dispersed polyols F1 to F14 produced in! To 14 and the following polytetrafluoroethylene (PTFE) powder Polyols A to C, H, and I were added to the mixed polyols to prepare evaluation samples.

Then, the evaluation sample was stored at 23 ° C. for 1 week, the appearance (separated state) of the evaluation sample after storage was visually observed, and the storage stability (1 week) was evaluated according to the following evaluation criteria. Evaluation criteria

◯: A uniform dispersion solution.

X: Polymer fine particles or PTFE powder and polyol were separated.

[0077] (Raw materials used)

Polytetrafluoroethylene (PTFE) powder (trade name: polytetrafluoroethylene resin powder fluon L-173, manufactured by Asahi Glass Co., Ltd.).

[0078] 'Polyol for rigid polyurethane foam

Polioinole A: Tolylenediamine is used as an initiator, E0, P0 and E0 are addition-polymerized in this order to the tolylenediamine, and the hydroxyl value is 350 mgKOH / g. And P〇 Polyether polyol with an EO ratio of 33% by mass with respect to the total.

Polyol B: N- (2-aminoethyl) piperazine was used as an initiator, and only EO was added to the N- (2-aminoethyl) piperazine to polymerize it with a hydroxyl value of 350 mgKOH / g. Etenorepoli-nore.

Polyol C: A polyether polyol having a hydroxyl value of 380 mg KOH / g, in which a mixture of sucrose and glycerin (mass ratio 5: 4) is used as an initiator, and only PO is subjected to addition polymerization.

Polyol H: Polyester polyol having a hydroxyl value of S200 mgKOH / g, obtained by polycondensation of diethylene glycol and terephthalic acid.

Polyol I: The hydroxyl value obtained by adding PO and EO in this order to the Mannich condensation product obtained by reacting nourphenol, formaldehyde and diethanolamine in a molar ratio of 1: 1 to 1.4 to 2.1 is 300 mgKOH. The ratio of EO to the total amount of added PO and EO is 60% by mass.

Polyol J: aniline (1 mol), phenol (0.99 mol), paraformaldehyde (0.64 mol) and diethanolamine (2.2 mol) were reacted to obtain a Mannich compound. Polyetherolene having a hydroxyl value of 540 mg KO H / g, obtained by addition polymerization of only PO to the Mannich compound.

Polyol K: A polyether polyol having a hydroxyl value of 760 mgKOH / g, in which ethylenediamine is used as an initiator and only PO is added to the ethylenediamine to effect polymerization. Polyol L: A polyether polyol having a hydroxyl value of 400 mgKOH / g, in which glycerin is used as an initiator and only PO is added to the glycerin.

[Table 3] Test example Test example Test example Test example Test example Test example Test example Test example

1 2 3 4 5 6 F Polyol A 40 40 40 40 40 40 40 40 Polyol B 20 20 20 20 20 20 20 20 Polyol C 39.7 39.7 39.7 39.7 39.7 39.7 39.7 39.7

F1 0.3

F2 0.3

F3 0.3

F4 0.3

F5 0.3

F6 0.3

F7 0.3

PTFE powder 0.3 Storage stability

○ ○ ○ ○ ○ ○ ○ X (23 ° C, 1 week)

[0080] [Table 4]

[0081] [Table 5]

[0082] From the results shown in Tables 3 to 5, Test Example 1 using polymer-dispersed polyols F1 to F14 1 -7, Test Examples 9-; 15 and Test Examples 17-23 were confirmed to have good storage stability.

On the other hand, Test Example 8, Test Example 16 and Test Example 24 using PTFE powder were confirmed to have poor storage stability.

Therefore, it was confirmed that the polymer monodisperse polyols F1 to F14 produced by the method for producing the polymer-dispersed polyol of the present invention have high compatibility with the polyol for rigid polyurethane foam and excellent storage stability.

[0083] << Evaluation of rigid polyurethane foam >>

In accordance with the mixing ratios of Production Examples 16 to 45 shown in Tables 6 to 10, rigid polyurethane foams were produced by the following production method.

In the composition of Table 6 to Table 10, the unit of the amount of each raw material used is “part by mass”.

[0084] (Raw materials used).

• Polyol component

Polyols A to C and H to L, PTFE powder,

Polyol D, polymer-dispersed polyol F1-F4, F6, F8, F9-F15.

[0085] 'Flame Retardant: Tris (2 black mouth propyl) phosphate (trade name: TMCPP, manufactured by Daihachi Chemical Co., Ltd.)

Yes

• Foaming agent A: Water.

Blowing agent B: Cyclopentane (trade name: Marutsuru FH, manufactured by Maruzen Petrochemical Co., Ltd.)

Foaming agent C: l, 1, 1, 3, 3, pentafluoropropane (HFC—245fa: manufactured by Honeywell)

'Foam stabilizer: Silicone foam stabilizer (trade name: SZ-1671, manufactured by Toray Industries, Inc.). 'Catalyst A: N, N, Ν', Ν, monotetramethylhexamethylenediamine (trade name: TOYOCAT-MR, manufactured by Tosoh Corporation).

• Catalyst B: Triethylenediamine (trade name: TEDA—L33, manufactured by Tosoh Corporation)

• Catalyst C: N, N, N "Tris (dimethylaminopropyl) hexahydro S-triazine (trade name: POLYCAT 41, manufactured by AIR PRODUCTS).

'Catalyst D: Diethylene glycol solution of potassium ethylhexanoate (potassium concentration 15 %, Product name: DABCO K-15, manufactured by AIR PRODUCTS)

• Catalyst E: A mixture of amino alcohols (trade name: TOYOCAT—RX7, manufactured by Tosoh Corporation). 'Catalyst F: N, N-Dimethylcyclohexylamine (trade name: Power Olyzer Ichi · 10, manufactured by Kao Corporation)

• Polyisocyanate: Polymethylene polyphenyl polyisocyanate (crude MDI) (trade name: MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.).

[0086] <Manufacture of rigid polyurethane foam>

In accordance with the compounding ratio shown in Table 6 to Table 10, 100 parts by mass of a polyol component, a foaming agent, a foam stabilizer, a flame retardant, and a catalyst were respectively added to a 1 L poly beaker, and these were mixed well with a stirrer to obtain a polyol system solution. Got.

The amount of polyisocyanate used is 110 or 130 for the isocyanate index (IND EX) when the foaming agent is water only, and 105 for the system using a hydrocarbon compound as the foaming agent. The system using a hyde mouth fluorocarbon compound as the agent was set to 110 as the isocyanate index, and the results were compared. The isocyanate index (INDE X) is a value expressed by multiplying the ratio of the number of isocyanate groups to 100 times the total equivalent of active hydrogens of the polyol composition and other active hydrogen compounds.

The liquid temperature of both the polyol system liquid and the raw material of the polyisocyanate component was kept at 20 ° C., and then stirred and mixed at a rotational speed of 3000 rpm for 5 seconds. After that, it was put into a 200 x 200 x 200 mm high wooden box and subjected to free foaming to produce a rigid polyurethane foam.

Yes

[0087] <Evaluation of rigid polyurethane foam>

In the rigid polyurethane foam obtained in each production example, gel time (second), box free density (unit: kg / m ³ ) as total density, compressive strength (unit: MPa), and high temperature shrinkage (unit: unit) :) and the thermal conductivity at 24 ° C (unit: mW / m * K) was measured as the heat insulation performance. Moreover, the following evaluation was performed as storage stability. The results are shown in Table 3.

[0088] The gel time was measured by inserting a wire into a foam that was in the process of foaming and measuring the time (seconds) until string drawing occurred when the foam was pulled up. 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. The size of the sample piece was 5 cm × 5 cm × 5 cm. The compressive strength was measured in the direction parallel to the gravity direction (重力) and in the vertical direction (top). In Table 3, “〃 + up” represents the compression strength of the compression strength in the parallel direction (垂直) and the compression strength in the vertical direction (up).

[0089] (Evaluation of dimensional stability)

High-temperature shrinkage is measured by a method according to ASTM D 2126-75. When water is the only blowing agent, the high-temperature dimensional stability and wet heat dimensional stability are evaluated, and the blowing agent is a hydrocarbon compound or a hyde mouth fluorocarbon compound. When used together, low temperature dimensional stability was evaluated.

The rigid polyurethane foam of each example was used as a sample, and after curing for 1 hour, a length (Z) 100 mm × width (X) 150 mm × thickness (Y) 75 mm was cut out and used.

High temperature dimensional stability is 70 ° C for the sample piece, wet heat dimensional stability is 70 ° C, relative humidity is 95%, and low temperature dimensional stability is 30 ° C and 0 ° C in each atmosphere for 24 hours or 50 hours. The length (thickness) increased after time storage was expressed as a dimensional change rate (unit:%) with respect to the length (thickness) before storage. In other words, the dimensional change rate was measured for all six directions in three directions (X, Y, and Ζ) under two conditions.

However, in the dimensional change rate, a negative value means shrinkage; a large absolute value means a large dimensional change. The dimensional change was evaluated according to the following evaluation criteria. Evaluation criteria

A: The maximum absolute value among the dimensional change rates in 6 directions was less than 1%.

A: The maximum absolute value among the dimensional change rates in 6 directions was 1% or more and less than 5%. Δ: The maximum absolute value among the dimensional change rates in 6 directions was 5% or more and less than 10%.

X: The maximum absolute value among the dimensional change rates in the 6 directions was 10% or more.

[0090] (Evaluation of thermal insulation)

The thermal conductivity (unit: mW / m'K) was measured in accordance with JIS A1412 using a thermal conductivity measuring device (product name: Auto Lambda HC-074, manufactured by Eiko Seiki Co., Ltd.). The heat insulation was evaluated according to the following evaluation criteria.

Evaluation criteria

When the foaming agent was only water, the following criteria were used.

○: Thermal conductivity was 27 or less.

X: Thermal conductivity was more than 27.

When a hydrocarbon compound was used as a blowing agent, the following criteria were used.

○: Thermal conductivity was 22 or less.

X: Thermal conductivity was over 22.

When using a hyde mouth fluorocarbon compound as a foaming agent, the following criteria were used:

○: Thermal conductivity was 21 or less.

X: Thermal conductivity was more than 21.

(Evaluation of storage stability)

Example of production shown in Table 6 10! ;! After mixing polyol AC and HL according to the blending ratio of ~ 45, F1 F4 F6 F8 F9 F15 PTFE powder and polyol D were added and mixed to prepare 300 g of mixed polyol and put in a glass bottle with a lid It was. Then, store at 23 ° C for 1 week, or at 23 ° C for 1 month, and remove the upper layer liquid lOOg with a syringe from the upper layer of the mixed polyol after storage, and the intermediate layer liquid so that the lower layer liquid lOOg can be removed from the lower layer The mixed polyol of the lower layer solution lOOg was collected from the lower layer.

Next, in <Manufacture of rigid polyurethane foam> in the above <Manufacture of rigid polyurethane foam>, except that 100 parts by mass of the upper layer liquid or 100 parts by mass of the lower layer liquid was used instead of 100 parts by mass of the polyol component, A polyurethane foam was produced. From the characteristics of the obtained rigid polyurethane foam, the storage stability was evaluated based on the following evaluation criteria.

When the storage stability is poor, the polymer-dispersed polyol migrates to the upper layer or lower layer during storage, and the upper and lower compositions of the mixed polyol are different, affecting the properties of rigid polyurethane foams produced using this. Therefore, each of upper layer liquid and lower layer liquid was used. Storage stability can be evaluated by the foamed state of the case or the dimensional change rate of the resulting rigid polyurethane foam.

Evaluation criteria

A: No foaming failure was observed in any of the foamed upper layer liquid and lower layer liquid, and the absolute value of the dimensional change rate of the rigid polyurethane foam was less than 5%.

X: The force at which foaming failure was observed in any of the foamed upper layer liquid and lower layer liquid, or the absolute value of the dimensional change rate of any rigid polyurethane foam was 5% or more.

[Table 6]

[0093] [Table 7]

[0094] [Table 8]

9]

Ten]

As is clear from the results shown in Table 6 to Table 10, when the polymer-dispersed polyol F1 F4 F6 F8 F14 produced by the polymer-dispersed polyol production method of the present invention is used, the storage stability (one week) is excellent. I was able to confirm.

In addition, production examples produced using polymer-dispersed polyol F1 F4 F6 F8 F14 It was confirmed that the rigid polyurethane foams of 16-30, Production Examples 34 to 35, Production Examples 38 to 39, and Production Examples 42 to 43 had good heat insulation performance and dimensional stability.

[0098] In addition, it was confirmed that when the polymer-dispersed polyols F1 to F3, F10, Fl1, and F13 were used, they were further excellent in storage stability (for one month).

Thus, in the method for producing a polymer-dispersed polyol, the content of the oxyethylene group in the polyether polyol (Y) is 60% by mass or more, and acrylonitrile or butyl acetate is included as a monomer having a polymerizable unsaturated group, It was also found that a significant effect of improving storage stability was obtained.

On the other hand, as shown in Production Examples 32, 36, 40 and 44, it was confirmed that when PTFE powder was used, the storage stability (1 week, 1 month) was poor.

It was confirmed that the rigid polyurethane foam of Production Example 31 produced using the fluorine-containing monomer (f) and the polymer dispersion polyol F15 had poor heat insulation performance. It was confirmed that the rigid polyurethane foams of Production Example 33, Production Example 37 and Production Example 41, Production Example 45 produced using Polyol D containing no polymer fine particles had poor dimensional stability.

Industrial applicability

[0100] The polymer-dispersed polyol obtained by the production method of the present invention can be used for production of a rigid polyurethane foam. The polymer-dispersed polyol has good storage stability even when mixed with a polyol having a low molecular weight for rigid polyurethane foam.

Further, by using the polymer-dispersed polyol, it is possible to obtain a rigid polyurethane foam that is reduced in weight and excellent in both heat insulating properties and dimensional stability. Further, the polymer-dispersed polyol can be suitably used for the production of injected urethane foam, continuous production board, spray foamed foam and the like. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2006-312812 filed on November 20, 2006 are hereby incorporated by reference. It is something that is incorporated.

Claims

The scope of the claims

[1] In a method for producing a rigid polyurethane foam by reacting a polyol component (Z) and a polyisocyanate component in the presence of a foaming agent, a foam stabilizer and a catalyst,

The polyol component (Z) has an average hydroxyl value of 200 to 800 mgKOH / g, and contains the following polymer-dispersed polyol (A): A method for producing a rigid polyurethane foam.

However, the polymer-dispersed polyol (A) is obtained by polymerizing a monomer having a polymerizable unsaturated group in the polyol (X) to disperse the polymer fine particles in the polyol. The monomer containing an ether polyol and having the polymerizable unsaturated group contains fluorine-containing acrylate or fluorine-containing metatalylate.

[2] The method for producing a rigid polyurethane foam according to [1], wherein the fluorinated acrylate or fluorinated metatalylate is a monomer represented by the following formula (1).

[Chemical 1

R

R ^f —Z— 0— C— C = CH ₂ formula (1)

0

[3] The method for producing a rigid polyurethane foam according to claim 1 or 2, further comprising monomer power S having a polymerizable unsaturated group, and further acrylonitrile or butyl acetate.

[4] The method for producing a rigid polyurethane foam according to any one of claims 1 to 3, wherein the polyether polyol has an oxyethylene group content of 10% by mass or more.

[5] The polyether polyol has a hydroxyl value of 84 mg KOH / g or less.

The manufacturing method of the rigid polyurethane foam in any one of -4.

[6] The polyether polyol is a polyoxyalkylene polyol obtained by addition polymerization of propylene oxide and ethylene oxide to a polyhydric alcohol.

The manufacturing method of the rigid polyurethane foam in any one of -5.

[7] The rigid polyurethane according to any one of [2] to [6], wherein the ratio of the monomer represented by the formula (1) in all the monomers having a polymerizable unsaturated group is 30 to 100% by mass. Form manufacturing method.

[8] The proportion of the polymer-dispersed polyol (A) in the polyol component (Z) is 0.01% by mass or more, and the proportion of the polymer fine particles in the polyol component (Z) is 0.001 mass. The method for producing a rigid polyurethane foam according to any one of claims 1 to 7, which is not less than 10%.

[9] The method for producing a rigid polyurethane foam according to any one of [1] to [8], wherein water is used alone, or at least one kind selected from a hydrated fluorocarbon compound and a hydrocarbon compound and water. .