JP7053051B2 - Polyol composition for rigid polyurethane foam and method for manufacturing rigid polyurethane foam - Google Patents

Description

The present invention relates to a polyol composition for rigid polyurethane foam and a rigid polyurethane foam containing 1-chloro-3,3,3-trifluoropropene (hereinafter, also referred to as HFO-1233zd) as an essential component as a foaming agent component. Regarding the manufacturing method.

Rigid polyurethane foam is a well-known material as a heat insulating material, a lightweight structural material, and the like. The rigid polyurethane foam is formed by mixing, foaming, and curing a polyol composition containing a polyol compound and a foaming agent as essential components and an isocyanate component.

Freon compounds such as CFC-11 have been used as the effervescent agent in the old days, but since CFC-11 causes destruction of the ozone layer, their use was prohibited, and they were switched to HCFC-141b, and since 2004. Has been switched to HFC-245fa and HFC-365mfc having an ozone depletion potential of zero, but the HFC-245fa and HFC-365mfc have a problem that GWP (global warming potential) is large. Therefore, development as a non-flammable HFO-1233zd foaming agent with a low ozone depletion potential and global warming potential is in progress.

For example, since the polyol composition containing HFO-1233zd has poor stock solution storage stability, attempts have been made to improve the stock solution storage stability of the polyol composition containing HFO-1233zd (for example, Patent Documents 1 to 1 to 1). 4).

Japanese Patent Publication No. 2011-500891 Special Table 2011-500892 Japanese Patent Publication No. 2011-500893 Japanese Patent Publication No. 2013-501844

However, although the conventional technique improves the reactivity delay after storage of the stock solution of the polyol composition containing HFO-1233zd, when a polyurethane foam is produced using the polyol composition, it causes curing failure and is produced. Polyurethane foam could shrink. Further, even if the catalyst is mixed with the isocyanate component immediately after the preparation of the polyol premix and does not cause curing failure even if foamed, when the premix is stored under the condition of 40 ° C. and then mixed with the isocyanate component and foamed, Poor curing may occur and the polyurethane foam may shrink. The condition of 40 ° C. assumes the maximum temperature of the internal undiluted solution when the drum is stored outdoors in the summer.

The present invention has been made in view of the above circumstances, and an object thereof is that even when HFO-1233zd is used as a foaming agent, the stock solution storage stability is good, and the shrinkage of the polyurethane foam can be suppressed by suppressing the curing failure. It is an object of the present invention to provide a polyol composition for rigid polyurethane foam and a method for producing a rigid polyurethane foam.

The polyol composition for rigid polyurethane foam of the present invention contains at least a polyol compound and a foaming agent, is mixed with an isocyanate component containing a polyisocyanate compound, and foamed and cured to form a rigid polyurethane foam. The effervescent agent contains HFO-1233zd, and the polyol compound is a polyether polyol P1 having an amino group-containing compound as an initiator and having at least one alkylene oxide adduct at the end, and a Mannig-based compound. It contains at least one selected from the group consisting of polyether polyols P2 having at least one alkylene oxide adduct at the end.

The method for producing a rigid polyurethane foam of the present invention is a method for producing a rigid polyurethane foam in which an isocyanate component and a polyol composition are mixed, foamed and cured to form a rigid polyurethane foam, wherein the polyol composition is said to be rigid. It is a polyol composition for polyurethane foam.

According to the present invention, a polyol composition for rigid polyurethane foam, which has good stock solution storage stability even when HFO-1233zd is used as a foaming agent, and which can suppress curing failure and shrinkage of polyurethane foam, and rigid polyurethane foam. Production method can be provided.

<Polyol composition for rigid polyurethane foam>
The polyol composition for rigid polyurethane foam of the present embodiment contains at least a polyol compound and a foaming agent, and is mixed with an isocyanate component containing a polyisocyanate compound and foamed and cured to form a rigid polyurethane foam. The effervescent agent contains HFO-1233zd, and the polyol compound is a polyether polyol P1 having an amino group-containing compound as an initiator and having at least one alkylene oxide adduct at the end, and a Mannig-based compound. It contains at least one selected from the group consisting of polyether polyols P2 having a compound as an initiator and having at least one alkylene oxide adduct at the end. According to the polyol composition for rigid polyurethane foam of the present embodiment, even when HFO-1233zd is used as the foaming agent, the stock solution storage stability is good, and the shrinkage of the polyurethane foam can be suppressed by suppressing the curing failure. The reason for this effect is not clear, but it is thought to be as follows.

An amine group-containing compound as an initiator, a polyether polyol having at least one alkylene oxide adduct at the end, and a Mannig-based compound as an initiator, and a polyether polyol having at least one alkylene oxide adduct at the end are those. It has a high reactivity as compared with a polyether polyol having no structure. When a foam is produced using such a polyether polyol, the internal calorific value of the foam increases due to its high reactivity. It is considered that the heat generation facilitates the cross-linking reaction, the triquantization reaction of isocyanate, and the like, and it is possible to suppress the poor curing of the foam due to the deterioration of the catalytic ability and the insufficient activity of the catalyst.

[Polyol compound]
The polyol compound has an amino group-containing compound as an initiator, a polyether polyol P1 having at least one alkylene oxide adduct at the end, and a Mannig-based compound as an initiator, and has at least one alkylene oxide adduct at the end. It contains at least one selected from the group consisting of the polyether polyol P2.

[Polyether Polyol P1]
The polyether polyol P1 is a polyether polyol having an amino group-containing compound as an initiator and at least one alkylene oxide adduct at the end, and more specifically, an alkylene oxide is addition-polymerized to the initiator. The obtained polyether polyol.

As the amino group-containing compound, a known amino group-containing compound used as an initiator for a polyether polyol is used. The amino group-containing compound includes aromatics such as 2,4-toluenediamine, 2,6-toluenediamine, diethyltoludiamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, and naphthalenediamine. Diamines; alkylene diamines having 2 to 8 carbon atoms such as ethylene diamine, propylene diamine, butyrene diamine, hexamethylene diamine, neopentyl diamine, and diethylene triamine can be exemplified. Among these, ethylenediamine, propylenediamine, and diethylenetriamine are preferable, and ethylenediamine is more preferable, from the viewpoint of suppressing curing defects and suppressing deterioration of the physical properties of the polyurethane foam.

Examples of the alkylene oxide adduct include a propylene oxide (PO) adduct, an ethylene oxide (EO) adduct, a styrene oxide (SO) adduct, a tetrahydrofuran adduct, and the like, and from the viewpoint of suppressing curing defects, the physical properties of the polyurethane foam. An ethylene oxide adduct is preferable from the viewpoint of suppressing the decrease in the amount of ethylene oxide.

The average number of functional groups of the polyether polyol P1 is preferably 3 to 6 and more preferably 3 to 4 from the viewpoint of suppressing curing defects and suppressing deterioration of the physical properties of the polyurethane foam.

The hydroxyl value of the polyether polyol P1 is preferably 300 to 1000 mgKOH / g, more preferably 400 to 1000 mgKOH / g, from the viewpoint of suppressing poor curing and suppressing deterioration of the physical properties of the polyurethane foam.

Specific examples of the polyether polyol P1 include NL-300 (manufactured by Sanyo Chemical Industries, Ltd.).

[Polyether Polyol P2]
The polyether polyol P2 is a polyether polyol having a Mannich-based compound as an initiator and having at least one alkylene oxide adduct at the end, and more specifically, a phenol and / or an alkyl substituted derivative thereof, formaldehyde, and a formaldehyde. It is a Mannich-polyether polyol obtained by ring-opening addition polymerization of an alkylene oxide using a Mannich-based compound obtained by the Mannich reaction of alkanolamine as an initiator.

Examples of the alkylene oxide adduct include a propylene oxide (PO) adduct, an ethylene oxide (EO) adduct, a styrene oxide (SO) adduct, a tetrahydrofuran adduct, and the like, and from the viewpoint of suppressing curing defects, the physical properties of the polyurethane foam. An ethylene oxide adduct is preferable from the viewpoint of suppressing the decrease in the amount of ethylene oxide.

The average number of functional groups of the polyether polyol P2 is preferably 2 to 4 from the viewpoint of suppressing curing defects and suppressing deterioration of the physical properties of the polyurethane foam.

The hydroxyl value of the polyether polyol P2 is preferably 250 to 700 mgKOH / g, more preferably 350 to 700 mgKOH / g, from the viewpoint of suppressing poor curing and suppressing deterioration of the physical properties of the polyurethane foam.

Specific examples of the polyether polyol P2 include DK4000 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[Other polyols]
The polyol compound may contain other polyols other than the polyether polyol P1 and the polyether polyol P2. As a specific example of the other polyol, it may contain at least one polyol compound having a hydroxyl value of 300 to 1000 mgKOH / g selected from an aliphatic amine polyol and an aromatic amine polyol.

Examples of the aliphatic amine polyol include an alkylenediamine-based polyol and an alkanolamine-based polyol. These polyol compounds are polyfunctional polyol compounds having terminal hydroxyl groups to which at least one of ethylene oxide and propylene oxide is ring-opened and added with alkylenediamine or alkanolamine as an initiator. As the alkylene diamine, known compounds can be used without limitation. Specifically, it is preferable to use an alkylenediamine having 2 to 8 carbon atoms such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine and diethylenetriamine. Among these, the use of alkylenediamine having a small number of carbon atoms is more preferable, and the use of a polyol compound using ethylenediamine or propylenediamine as an initiator is particularly preferable. In the alkylenediamine-based polyol, the initiator alkylenediamine may be used alone or in combination of two or more. Examples of alkanolamines include monoethanolamine, diethanolamine, and triethanolamine. The number of functional groups of the polyol compound using alkylenediamine as an initiator is 4, and the number of functional groups of the polyol compound using alkanolamine as an initiator is 3.

The aromatic amine-based polyol is a polyfunctional polyether polyol compound having a terminal hydroxyl group to which at least one of ethylene oxide and propylene oxide is ring-opened and added using an aromatic diamine as an initiator. Known aromatic diamines can be used without limitation as the initiator. Specific examples thereof include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, and naphthalenediamine. Among these, the use of toluenediamine (2,4-toluenediamine, 2,6-toluenediamine or a mixture thereof) is particularly preferable in that the obtained rigid polyurethane foam has excellent properties such as heat insulation and strength.

The total content of the polyether polyol P1 and the content of the polyether polyol P2 is preferably 15% by weight or more in the polyol compound from the viewpoint of suppressing curing defects and suppressing deterioration of the physical properties of the polyurethane foam. , 100% by weight is most preferable.

[Effervescent agent]
The foaming agent contains HFO-1233zd, which has a low ozone depletion capacity and a low global warming potential and is not flammable.

The foaming agent preferably further contains water. The addition of water can reduce the vapor pressure of the foaming agent in the polyol composition. The water content is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the total amount of the polyol compound.

The content of the foaming agent is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the polyol compound.

[Other ingredients]
The polyol composition may contain a known catalyst for rigid polyurethane foam, a foam stabilizer, a flame retardant, a compatibilizer, a plasticizer, a colorant, an antioxidant and the like.

Examples of the catalyst include tertiary amines such as triethylenediamine, N-methylmorpholine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, and DBU. Kind, metal-based catalysts such as dibutyltin dilaurate, dibutyltin diacetate, and tin octylate can be exemplified as the urethanization reaction catalyst.

As the defoaming agent, a known defoaming agent for rigid polyurethane foam can be used without limitation. As the defoaming agent, polydimethylsiloxane and a graft copolymer or block copolymer of polydimethylsiloxane and polyalkylene oxide are usually used. As the polyalkylene oxide, polyethylene oxide having an average molecular weight of 5000 to 8000, polypropylene oxide, a random copolymer of ethylene oxide and propylene oxide, or a block copolymer is used.

Examples of the flame retardant include metal compounds such as halogen-containing compounds, organic phosphate esters, antimony trioxide, and aluminum hydroxide. For these flame retardants, for example, excessive addition of organic phosphoric acid ester may deteriorate the physical properties of the obtained rigid polyurethane foam, and excessive addition of metal compound powder such as antimony trioxide may cause foaming behavior of the foam. The addition amount may be limited to a range that does not cause such a problem.

Examples of the plasticizer include a halogenated alkyl ester of phosphoric acid, an alkyl phosphate ester, an aryl phosphoric acid ester, a phosphonic acid ester and the like, and specific examples thereof include tris (2-chloroethyl) phosphate (CLP, manufactured by Daihachi Chemical Co., Ltd.). ), Tris (β-chloropropyl) phosphate (TMCPP, manufactured by Daihachi Kagaku Co., Ltd.), tributoxyethyl phosphate (TBEP, manufactured by Rhodia), tributyl phosphate, triethyl phosphate, cresylphenyl phosphate, dimethylmethylphosphonate, etc. can be exemplified. , One or more of these can be used. The amount of the plasticizer added is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the polyol composition. If it exceeds this range, problems such as insufficient plasticizing effect and deterioration of the physical characteristics of the foam may occur.

The polyol composition of the present embodiment can be used for producing continuously produced rigid polyurethane foams such as slabstock foams and sandwich panels, injection-molded rigid polyurethane foam sandwich panels, spray foams and the like.

<Manufacturing method of rigid polyurethane foam>
The method for producing a rigid polyurethane foam of the present embodiment is a method for producing a rigid polyurethane foam in which an isocyanate component and the polyol composition are mixed, foamed and cured to form a rigid polyurethane foam.

As the isocyanate component, liquid MDI is used because it is easy to handle, the reaction speed is excellent, the physical characteristics of the obtained rigid polyurethane foam are excellent, and the cost is low. As the liquid MDI, crude MDI (c-MDI) (44V-10, 44V-20L, etc. (manufactured by Sumitomo Bayer Urethane Co., Ltd.)), MDI containing uretonimine (millionate MTL; manufactured by Nippon Polyurethane Industry Co., Ltd.), etc. are used. To. Among these polyisocyanate compounds, the use of crude MDI is particularly preferable because it has excellent physical properties such as mechanical strength of the rigid polyurethane foam to be formed and is inexpensive.

In addition to the liquid MDI, other isocyanate components may be used in combination. Di-polyisocyanate compounds well known in the technical field of polyurethane can be used without limitation.

In the method for producing a rigid polyurethane foam, the isocyanate group / active hydrogen group equivalent ratio (NCO index) in the mixture of the polyol composition and the isocyanate component is preferably 0.8 or more, more preferably 0.9 or more.

With such a configuration, a large amount of isocyanurate bonds are formed in the resin constituting the rigid polyurethane foam, and the rigid polyurethane foam having further improved combustion resistance can be produced.

The method for producing a rigid polyurethane foam of the present embodiment can be used for producing a continuously produced rigid polyurethane foam such as a slabstock foam and a sandwich panel, an injection-molded rigid polyurethane foam sandwich panel, and a spray foam.

Hereinafter, examples and the like that specifically show the configuration and effects of the present invention will be described.

<Evaluation method>

[Form density]
The foam density was determined in accordance with JIS K 7222.

[Foam shrinkage]
A mixture of the polyol composition and the isocyanate component was put into a mold having a length and width of 180 mm and a depth of 100 mm, and the foam formed by foaming was cured at room temperature (23 ° C. ± 5 ° C.) for 10 minutes. Then, the foam was taken out from the mold and continuously cured at room temperature for 30 minutes, and shrinkage of the foam was confirmed depending on whether the foam top was depressed. If the foam top is depressed, poor curing has occurred, and if the foam top is not depressed, no poor curing has occurred. In Table 2, when the foam top is depressed, it is indicated by x, and when the foam top is not depressed, it is indicated by ○.

<Examples 1 to 11, Comparative Examples 1 to 5>
[Preparation of polyol composition]
The constituent materials of the polyol composition are shown in Table 1.

The constituent materials shown in Table 1 were mixed and stirred with the formulations shown in Table 2 below to prepare polyol compositions of Examples 1 to 11 and Comparative Examples 1 to 5.

[Manufacturing of rigid polyurethane foam]
The isocyanate components of the polyol compositions of Examples 1 to 11 and Comparative Examples 1 to 5 adjusted to 20 ° C. and then to 20 ° C. (crude diphenylmethane diisocyanate "Sumijour 44V-20L" manufactured by Bayer Urethane Co., Ltd., Sumika). NCO%: 31%) and NCO / OH equivalent ratio were mixed and stirred with a laboratory stirrer at a ratio of 1.70, and foamed and cured to obtain a rigid polyurethane foam. Table 2 shows the evaluation results of the rigid polyurethane foam. In Table 2, "initial" means a rigid polyurethane foam produced using the polyol composition immediately after adjustment, and "after storage at 40 ° C. for 28 days" means a polyol composition stored at 40 ° C. for 28 days after adjustment. It means a rigid polyurethane foam manufactured by using a material.

From the results in Table 2, the polyol compositions according to Examples 1 to 11 have good stock solution storage stability even when HFO-1233zd is used as a foaming agent, and are produced using the polyol compositions according to Examples 1 to 11 as raw materials. It can be seen that the obtained rigid polyurethane foam can suppress poor curing and suppress deterioration of physical properties even when HFO-1233zd is used as a foaming agent.

Claims (2)

A polyol composition for a rigid polyurethane foam containing at least a polyol compound and a foaming agent, which is mixed with an isocyanate component containing a polyisocyanate compound and foamed and cured to form a rigid polyurethane foam.
The foaming agent contains 1-chloro-3,3,3-trifluoropropene and
The polyol compound contains a polyether polyol P1 having an amino group-containing compound (excluding Mannich-based compounds) as an initiator and having at least one ethylene oxide adduct at the end.
The polyol compound contains, in addition to the polyether polyol P1, a polyether polyol P2 having a Mannig-based compound as an initiator and having at least one ethylene oxide adduct at the end .
Polyol composition for rigid polyurethane foam (However, except for those containing polymer particles in the polyol composition in an amount of more than 0% by weight and 30% by weight or less, the content of the polyether polyol P1 is the polyol compound. Excluding those with less than 15% by weight and more than 50% by weight) . A method for producing a rigid polyurethane foam, which comprises mixing an isocyanate component and a polyol composition, foaming and curing to form a rigid polyurethane foam.
A method for producing a rigid polyurethane foam, wherein the polyol composition is the polyol composition for rigid polyurethane foam according to claim 1.