KR101959644B1 - Polyol composition for rigid polyurethane foam and method for preparing rigid polyurethane foam - Google Patents

Abstract

The polyol composition for rigid polyurethane foam of the present invention is a polyol composition for rigid polyurethane foam which contains at least a polyol compound and a foaming agent and is mixed with an isocyanate component containing a polyisocyanate compound to form a hard polyurethane foam by foam- Wherein the blowing agent contains 1-chloro-3,3,3-trifluoropropene and the polyol compound is a polyether polyol having an amino group-containing compound as an initiator and at least one alkylene oxide adduct at the terminal And at least one selected from the group consisting of P1 and a polyether polyol P2 having a mannitol compound as an initiator and having at least one alkylene oxide adduct at the terminal thereof. According to the polyol composition for rigid polyurethane foam of the present invention, even when HFO-1233zd is used as a foaming agent, it is possible to provide a rigid polyurethane foam polyol composition capable of suppressing deterioration of physical properties of a polyurethane foam by suppressing hardening defects, And a method for producing a rigid polyurethane foam.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyol composition for a rigid polyurethane foam and a method for producing the same. More particularly, the present invention relates to a rigid polyurethane foam,

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

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

As the foaming agent, a freon compound such as CFC-11 has been used in the past. However, since the CFC-11 causes destruction of the ozone layer, it is prohibited from use and converted to HCFC-14lb. (HFC-245fa) or HFC-365mfc (Zero-HFC-245fa). However, the HFC-245fa and HFC-365mfc have a problem of a large GWP (global warming coefficient). As a result, development of foaming agents for HFO-1233zd, which has low ozone depletion potential and low global warming potential and is not flammable, is under development.

For example, an attempt has been made to improve the stock storage stability of a polyol composition containing HFO-1233zd because the polyol composition containing HFO-1233zd is poor in stock solution stability (see, for example, Patent Document 1 To 4).

[Patent Document 1] Japanese Patent Application Laid-Open No. 2011-500891 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-500892 [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-500893 [Patent Document 4] JP-A-2013-501844

However, in the conventional technique, the retardation of the reactivity after preservation of the stock solution of the polyol composition containing HFO-1233zd is improved. However, when the polyurethane foam is produced by using the polyol composition, a curing failure is caused and the resulting polyurethane foam shrinks . Even if the catalyst does not cause hardening failure even after mixing with the isocyanate component immediately after the preparation of the polyol premix and foaming, if the premix is stored under the condition of 40 degrees and then mixed with the isocyanate component and foamed, the curing is defective and the polyurethane foam There was a case where this shrinkage occurred. In addition, the condition of 40 degrees assumes the maximum temperature of the inner stock solution when the drum is stored outdoors in summer iron.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a hard polyurethane foam composition which is capable of suppressing the shrinkage of a polyurethane foam, A polyol composition and a process for producing a rigid polyurethane foam.

The polyol composition for rigid polyurethane foam of the present invention is a polyol composition for rigid polyurethane foam which contains at least a polyol compound and a foaming agent and is mixed with an isocyanate component containing a polyisocyanate compound to form a hard polyurethane foam by foam- Wherein the blowing agent contains HFO-1233zd and the polyol compound contains a polyether polyol having an amino group-containing compound as an initiator and at least one alkylene oxide adduct at the terminal.

A method for producing a rigid polyurethane foam according to the present invention is a method for producing a rigid polyurethane foam by mixing an isocyanate component and a polyol composition and foaming and curing the mixture to form a rigid polyurethane foam, wherein the polyol composition comprises the polyol for hard polyurethane foam .

According to the present invention, there is provided a rigid polyurethane foam polyol composition and rigid polyurethane foam production method capable of suppressing shrinkage of a polyurethane foam by suppressing hardening defects and having good stock stability of a stock solution even when HFO-1233zd is used as a foaming agent Can be provided.

≪ Polyol composition for rigid polyurethane foam &

The polyol composition for rigid polyurethane foam of the present embodiment is a polyol composition for rigid polyurethane foam which contains at least a polyol compound and a foaming agent and is mixed with an isocyanate component containing a polyisocyanate compound to form a hard polyurethane foam by foam- The foaming agent contains HFO-1233zd, and the polyol compound contains a polyether polyol having an amino group-containing compound as an initiator and at least one alkylene oxide adduct at the terminal. According to the polyol composition for rigid polyurethane foam of the present embodiment, even when HFO-1233zd is used as the foaming agent, the stability of the stock solution is good and the curing defects can be suppressed, and the shrinkage of the polyurethane foam can be suppressed. The reason for achieving such an effect is not clear, but is considered as follows.

The polyether polyol having an amine group-containing compound as an initiator and at least one alkylene oxide adduct at the terminal thereof has a higher reactivity than a polyether polyol having no structure. When such a polyether polyol is used to produce a foam, the amount of internal heat generated by the foam increases due to its high reactivity. The crosslinking reaction and the trimerization reaction of the isocyanate are likely to proceed by the exothermic reaction and it is considered that the poor curing of the foam due to the poor catalytic activity and the insufficient activity of the catalyst can be suppressed.

[Polyol compound]

The polyol compound contains a polyether polyol having an amino group-containing compound as an initiator and at least one alkylene oxide adduct at the terminal.

 [Polyether polyol]

The polyether polyol is a polyether polyol having an amino group-containing compound as an initiator and having at least one alkylene oxide adduct at the terminal thereof. More specifically, the polyether polyol is a polyether polyol obtained by addition polymerization of an alkylene oxide to the initiator to be.

As the amino group-containing compound, a known amino group-containing compound used as an initiator of the polyether polyol is used. Examples of the amino group-containing compound include 2, 4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'- diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, And alkylenediamines having 2 to 8 carbon atoms such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, diethylenetriamine, and the like. Among these, ethylenediamine, propylenediamine and diethylenetriamine are preferable from the viewpoints of suppression of curing failure and suppression of property deterioration of polyurethane foam, and ethylenediamine is more preferable.

Examples of the alkylene oxide adducts include propylene oxide (PO) adducts, ethylene oxide (EO) adducts, styrene oxide (SO) adducts, and tetrahydrofuran adducts. From the viewpoint of suppressing lowering of the physical properties of the polyurethane foam, an ethylene oxide adduct is preferable.

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

The hydroxyl value of the polyether polyol is preferably from 300 to 1000 mgKOH / g, and more preferably from 400 to 1000 mgKOH / g, from the viewpoints of inhibiting cure failure and suppressing lowering of physical properties of the polyurethane foam.

As a specific example of the polyether polyol, NL-300 (manufactured by Sanyo Chemical Industries, Ltd.) may be used.

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 [Other polyols]

The polyol compound may contain a polyol other than the polyether polyol. As specific examples of the other polyol, a polyol compound having a hydroxyl value of at least 300 to 1000 mg KOH / g selected from aliphatic amine polyol and aromatic amine polyol may be contained.

Examples of the aliphatic amine polyol include an alkylenediamine-based polyol and an alkanolamine-based polyol. The polyol compound is a polyfunctional polyol having a terminal hydroxyl group formed by ring-opening addition of at least one of ethylene oxide and propylene oxide with an alkylene diamine or alkanolamine as an initiator. As the alkylenediamine, known compounds may be used without limitation. Specifically, the use of alkylenediamines having 2 to 8 carbon atoms, such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, diethylenetriamine, etc., is suitable. Of these, use of an alkylenediamine having a small number of carbon atoms is more preferable, and use of a polyol compound having ethylenediamine and propylenediamine as an initiator is particularly preferred. In the alkylenediamine-based polyol, the alkylenediamine as the initiator may be used alone or in combination of two or more. Examples of the alkanolamine include monoethanolamine, diethanolamine and triethanolamine. The number of functional groups of the polyol compound having an alkylene diamine as an initiator is 4, and the number of functional groups of the polyol compound having an alkanolamine as an initiator is 3.

The aromatic amine-based polyol is a polyfunctional polyether polyol having a terminal hydroxyl group obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide with an aromatic diamine as an initiator. As the initiator, known aromatic diamines can be used without limitation. Specific examples thereof include 2, 4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, do. Of these, the use of toluene diamine (2, 4-toluenediamine, 2, 6-toluenediamine or a mixture thereof) is particularly preferred because of the excellent properties of the hard polyurethane foam obtained such as heat insulation and strength.

The content of the polyether polyol is preferably 15% by weight or more, and most preferably 100% by weight, of the polyol compound, from the viewpoints of suppressing the curing failure and suppressing the deterioration of the physical properties of the polyurethane foam.

〔blowing agent〕

The foaming agent contains HFO-1233zd, which has low ozone-depleting ability and global warming potential and is not flammable.

It is preferable that the foaming agent further contains water. By adding water, the vapor pressure of the foaming agent of the polyol composition can be lowered. The content of water 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, per 100 parts by weight of the total amount of the polyol compound.

[Other components]

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 triethylenediamine, N-methylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, Based catalysts such as tributyltin dilaurate, tributyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, and tin octylate can be exemplified as the urethanization reaction catalyst.

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

Examples of the flame retardant include metal compounds such as halogen-containing compounds, organic phosphoric acid esters, antimony trioxide, aluminum hydroxide and the like. When the flame retardant is added in excess, for example, the organic phosphoric acid ester is excessively added, the physical properties of the obtained rigid polyurethane foam will be lowered. Moreover, if the metal compound powder such as antimony trioxide is excessively added, And the like, and the amount thereof to be added is limited to such a range that does not cause such a problem.

Specific examples of the plasticizer include tris (2-chloroethyl) phosphate (CLP, manufactured by Daihachi Chemical Co., Ltd.), tris ( (TMCPP, manufactured by Daihachi Chemical Co., Ltd.), tributoxyethyl phosphate (TBEP, manufactured by Rhodia), tributylphosphate, triethylphosphate, cresylphenylphosphate, dimethylmethylphosphate and the like , And at least one of these can be used. The addition amount of the plasticizer is preferably 5 to 40 parts by weight based on 100 parts by weight of the polyol composition. Exceeding this range may result in insufficient plasticizing effect, deterioration of the physical properties of the foam, and the like.

The polyol composition of the present embodiment can be used for the production of rigid polyurethane foam continuously produced such as a slab stock form and a sandwich panel, rigid polyurethane foam sandwich panel for injection molding, spray foam and the like.

≪ Production 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 by mixing an isocyanate component and the polyol composition and foaming and curing the mixture to form a rigid polyurethane foam.

As the isocyanate component, a liquid MDI is used because of ease of handling, reaction rate, physical properties of the resulting rigid polyurethane foam, low cost, and the like. Examples of the liquid MDI include Crude (MDI) (c-MDI) (44V-10, 44V-20L, etc. manufactured by Sumitomo Bayer Urethane Co., Ltd.), MDI containing uretonimine (Millionate MTL; ) Is used. Of these polyisocyanate compounds, the use of crude (crude) MDI is particularly preferred because of the excellent physical properties such as mechanical strength of the formed rigid polyurethane foam and the low cost.

In addition to the liquid MDI, other isocyanate components may be used in combination. In the technical field of polyurethanes, well-known di- to polyisocyanate compounds are usable without limitation.

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

By such a constitution, it is possible to produce a rigid polyurethane foam in which a large amount of isocyanurate bonds are formed in the resin constituting the rigid polyurethane foam and the flammability is further improved.

The method of producing rigid polyurethane foam of the present embodiment is used for producing hard polyurethane foam continuously produced such as slab stock form and sandwich panel, rigid polyurethane foam sandwich panel for injection molding, spray foam and the like It is possible.

[Example]

Best Mode for Carrying Out the Invention Hereinafter, embodiments and the like showing the construction and effect of the present invention will be described.

<Evaluation method>

[Foam density]

The foam density was obtained according to JIS K 7222.

[Shrinkage of foam]

The mixed mixture of the polyol composition and the isocyanate component was introduced into a mold having a width of 180 mm and a depth of 100 mm, and the foamed foam was cured at room temperature (23 ± 5 ° C) for 10 minutes. Thereafter, the foam was taken out from the mold, followed by curing at room temperature for 30 minutes, and the shrinkage of the foam was confirmed by whether or not the foam top was depressed. When the foam top was depressed, it was determined that a curing failure occurred, and when the foam top was not recessed, no curing failure occurred. In Table 2, when the foam top is recessed, it is indicated by X, and when the foam top is not recessed, it is indicated by.

&Lt; Examples 1 to 9, Comparative Examples 1 to 5 >

[Adjustment of polyol composition]

Table 1 shows the constituent materials of the polyol composition.

ingredient Product Name producer Contents product name Polyol A Kawasaki Kasei Corporation Phthalic acid-based polyester polyol Having a hydroxyl value of 315 mg-KOH / g (polyester polyol) RDK-133 B Daiichi High School Seiyaku Co., Mannich type polyester polyol having hydroxyl value of 360 mg-KOH / g (no EO adduct, Mannich type polyol) DK-3776 C Asahi Garas Co., Ethylenediamine-based polyester polyol having a hydroxyl value of 500 mg-KOH / g (EO adduct free, amine-based polyol) Exenol 500ED D Sanyo Chemical Industries Co., Ltd. Ethylene diamine-based polyester polyol Having a hydroxyl value of 980 mg-KOH / g (EO adduct, amine-based polyol) NE-240 E Sanyo Chemical Industries Co., Ltd. Ethylene diamine-based polyester polyol Having a hydroxyl value of 745 mg-KOH / g (EO adduct, amine-based polyol) NL-300 F Asahi Garas Co., Ethylenediamine-based polyester polyol Having a hydroxyl value of 450 mg-KOH / g (EO adduct, amine-based polyol) Exenol 450ED Flame retardant TMCPP Daihachi Kagaku Corporation Trismonochloropropylphosphate Foaming agent SH-193 Toor Dow Corning Co., Ltd. Silicone surfactant Catalyst A 1-methylimidazole (imidazole-based catalyst) Catalyst B A catalyst obtained by protecting the active site of an amine with 100% of N, N, N ', N', N "-pentamethyldipropylenetriamine (tertiary amine catalyst) with 2-ethylhexanoic acid Catalyst C Cyclohexyldimethylamine (tertiary amine catalyst) Catalyst D N-methylmorpholine (tertiary amine catalyst) HFO-1233zd Hanewell Japan Co., Ltd. 1-chloro-3,3,3, trifluoropropene Polyisocyanate 44V-20L Sumika Bayer Urethane Co., Ltd. The crude diphenylmethane diisocyanate (NCO% = 31.0%)

The polyol compositions of Examples 1 to 9 and Comparative Examples 1 to 5 were prepared by mixing and stirring the components shown in Table 1 in the formulations shown in Table 2 below.

[Preparation of Rigid Polyurethane Foam]

The polyol compositions of Examples 1 to 9 and Comparative Examples 1 to 5 were adjusted to a temperature of 20 占 폚, and an isocyanate component (Sumiru 44V-20L, manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO%: 31%) and an NCO / OH equivalent ratio of 1.70 were mixed and stirred with a laboratory stirrer, followed by foaming and curing to obtain a rigid polyurethane foam. The evaluation results of the hard polyurethane foam are shown in Table 2. In Table 2, the term "initial" refers to a rigid polyurethane foam prepared using the polyol composition immediately after preparation. The term "after storage for 28 days at 40 DEG C" Means a rigid polyurethane foam prepared using a polyol composition.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example
3 Comparative Example 4 Comparative Example 5 Constituent material circulation Polyol A 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Polyol B 35 35 35 35 35 35 35 20 50 50 50 50 35 Polyol C 15 Polyol D 15 15 15 15 Polyol E 15 30 Polyol F 15 50 I am overdue 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Foaming agent 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Catalyst A 6 6 6 6 6 6 6 6 Catalyst B 6 6 Catalyst C 6 6 Catalyst D 6 6 Main blowing agent HFO-1233zd 34 34 34 34 34 34 34 34 34 34 34 34 34 34 Crude foaming agent water 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Early density 22.4 23.6 22.0 23.5 25.5 28.9 24.9 22.7 27.9 31.6 28.5 21.6 26.3 27.5 Shrink O O O O O O O O O x x O O O After being stored at 40 ° C for 28 days density 24.6 24.7 22.1 24.4 26.2 30.1 26.4 23.9 29.8 33.3 29.9 28.2 33.5 32.0 Shrink O O O O O O O O O x x x x x
Curing defects: O is normally foamed, X is defective curing,

From the results shown in Table 2, the polyol compositions according to Examples 1 to 9 are excellent in storage stability even when HFO-1233zd is used as the foaming agent, hard polyurethanes prepared using the polyol compositions according to Examples 1 to 9 as raw materials It can be seen that, even when HFO-1233zd is used as the foaming agent, the foams can suppress the hardening defects and suppress the deterioration of the physical properties.

Claims (4)

A polyol composition for a rigid polyurethane foam comprising at least a polyol compound and a blowing agent, which is mixed with an isocyanate component containing a polyisocyanate compound to form a hard polyurethane foam by foaming and curing,
Wherein the foaming agent contains 1-chloro-3,3,3-trifluoropropene,
Wherein the polyol compound contains a polyether polyol having an amino group-containing compound as an initiator and at least one alkylene oxide adduct at the terminal thereof. The method according to claim 1,
Wherein the content of the polyether polyol in the polyol compound is 15 wt% or more and 100 wt% or less. The method according to claim 1,
Wherein the alkylene oxide adduct is an ethylene oxide adduct. A method for producing a rigid polyurethane foam by mixing an isocyanate component with a polyol composition and foaming and curing the mixture to form a rigid polyurethane foam,
Wherein the polyol composition is the polyol composition for rigid polyurethane foam according to any one of claims 1 to 3. A method for producing a rigid polyurethane foam,