JP2000063476A - Rigid polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a foam which has excellent adiabatic properties and suffers no crack within a low or ultra-low temperature range by employing a specific aliphatic polyester polyol in a specific amount in a rigid polyurethane foam using hydrochlorofluorocarbons as a blowing agent. SOLUTION: An aliphatic polyester polyol represented by the formula (wherein (k) is 0 or 1; (l) is 0-5; (m) is 0-5; (n) is 1-8; and (k), (l) and (m) are each not 0 at the same time) constitutes 5-50 wt.% of the total polyol components. As a blowing agent is preferable 1-chloro-1,1-difluoroethane and/or 1-chloro-1,1-difluoromethane. As a polyol employed in combination with the aliphatic polyester polyol of the formula, is preferable a combination of a sucrose-based polyol containing as an essential ingredient a sucrose in an initiator and having an average functionality of 3-7 and a hydroxyl value of 300-500 mg KOH/g with an aromatic polyol having an average functionality of 2-4 and a hydroxyl value of 280-500 mg KOH/g.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rigid polyurethane foam. More specifically, the present invention relates to a rigid polyurethane foam having good strength and dimensional stability without using a specific chlorofluorocarbon as a foaming agent, that is, chlorofluorocarbons, and having excellent heat insulating performance.

[0002]

2. Description of the Related Art Rigid polyurethane foam is widely used as a heat insulating material for refrigerators, frozen warehouses, building materials, etc. and as a spraying application because it has excellent heat insulating performance, dimensional stability and workability. This is 1,1, as a foaming agent when manufacturing rigid polyurethane foam.
The main reason is that chlorofluorocarbons represented by 1-trichloro-1-fluoromethane (hereinafter referred to as CFCs) are used.

[0003]

In recent years, chlorofluorocarbons (CFCs) have been regulated to protect the earth's ozone layer. Since chlorofluorocarbons are stable in the atmosphere, they reach the ozone layer in the sky as they are, and are decomposed by the action of ultraviolet rays, etc., and it is thought that the chlorine radicals generated will destroy the ozone layer. . CFC-1 used as a foaming agent for rigid polyurethane foam is subject to this regulation.
1 is also included. CFC-11 is used for general insulation.
Is contained in the foam in an amount of 7 to 14% by weight.
There is an urgent need to develop a foaming technology using a low ODP (ozone depletion potential) foaming agent that replaces C-11.

As a foaming agent replacing the above CFCs, a foaming agent having a low ODP such as hydrochlorofluorocarbons is promising and has already been used. However, when hydrochlorofluorocarbons are used as the foaming agent, the thermal conductivity as a gas deteriorates as compared with CFC-11, so that the heat insulating performance decreases. Further, cracks may occur in the foam heat insulating material in a low temperature or ultra-low temperature region, and there is a big problem that good heat insulating performance cannot be maintained.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that if an aliphatic polyester polyol is added in an amount of 5 to 50% by weight of all polyol components, a hydrochlorofluorocarbon as a foaming agent. Obtained that good heat insulation performance is obtained even when using a class, and that it is possible to manufacture a rigid polyurethane foam that does not generate cracks in a low temperature or ultra-low temperature region and a heat insulating material using the foam, and The invention was completed.

That is, the present invention relates to a rigid polyurethane foam produced from an organic polyisocyanate, a polyol, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries, and hydrochlorofluorocarbons as a foaming agent,
In particular using 1-chloro-1,1-difluoroethane and / or 1-chloro-1,1-difluoromethane,
Further, the present invention relates to a rigid polyurethane foam characterized in that 5 to 50% by weight of all polyol components is an aliphatic polyester polyol represented by the following general formula (1) [Chemical formula 2].

[0007]

[Chemical 2] (In the formula, k = 0 or 1, 1, m, n are 0 to 5, respectively.
It is an integer of 0-5 and 1-8. Also, k, l, and m are not 0 at the same time. )

That is, the present invention provides the following (1) to (5). (1) A rigid polyurethane foam comprising an organic polyisocyanate, a polyol, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries, wherein hydrochlorofluorocarbons are used as a foaming agent, and 5 to 5 parts of all polyol components are used. 50% by weight of an aliphatic polyester polyol represented by the following general formula (1) [Chemical Formula 3], a rigid polyurethane foam.

[0009]

[Chemical 3] (In the formula, k = 0 or 1, 1, m, n are 0 to 5, respectively.
It is an integer of 0-5 and 1-8. Also, k, l, and m are not 0 at the same time. )

(2) The blowing agent is 1-chloro-1,1-
Difluoroethane and / or 1-chloro-1,1-
The rigid polyurethane foam according to (1), which is difluoromethane.

(3) The blowing agent is 1-chloro-1,1-
The rigid polyurethane foam according to (2), wherein the mixing ratio of difluoroethane and 1-chloro-1,1-difluoromethane is 20:80 to 80:20 (weight ratio).

(4) The polyol has sucrose as an essential component in the (a) initiator and has an average number of functional groups of 3 to 7,
A sucrose-based polyol having a hydroxyl value of 300 to 500 mgKOH / g, and (b) an average number of functional groups of 2 to 4
And the aromatic polyol having a hydroxyl value of 280 to 500 mgKOH / g is used in combination with the aliphatic polyester polyol represented by the general formula (1). The rigid polyurethane foam according to any one of claims.

(5) The sucrose-based polyol (a) is used in an amount of 5 to 70% by weight of the total polyol component, and the aromatic polyol (b) is used in an amount of 5 to 70% by weight of the total polyol component. The rigid polyurethane foam according to (4).

[0014]

The present invention will be described in more detail below. The rigid polyurethane foam of the present invention is obtained by mixing and reacting an organic polyisocyanate, a polyol, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries, and foaming and curing. The aliphatic polyester polyol used in the present invention is a lactone ring-opening polyester polyol represented by the following general formula (1) [Chemical Formula 4].

[0015]

[Chemical 4] (In the formula, k = 0 or 1, 1, m, n are 0 to 5, respectively.
It is an integer of 0-5 and 1-8. Also, k, l, and m are not 0 at the same time. )

The amount used is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, based on the total polyol component. 50% by weight of this compound in all polyol components
If it is added in excess, the compatibility with the hydrochlorofluorocarbons as the foaming agent is likely to decrease because the ester unit is present in the skeleton, and the homogeneity of the resin premix tends to be lost. In addition, the strength of the rigid foam is likely to decrease, and the dimensional stability tends to be adversely affected.

Here, k = 0 in the general formula (1).
In this case, the number of functional groups is 2, and the flexibility at low temperature or ultralow temperature is very excellent, but the strength as a foam body may decrease. In the general formula (1), k = 1
In this case, the number of functional groups is 3, and the flexibility at low temperature can be expressed while maintaining the foam strength, so that it is possible to avoid the generation of cracks in the low temperature or ultra low temperature region.

Therefore, as the aliphatic polyester polyol of the present invention, k = 1 and l = 0 in the general formula (1).
Particularly preferred are compounds of ˜2, m = 0 to 2 and n = 3 to 5. Furthermore, when these compounds are added, the thermal conductivity is also significantly improved.

As the blowing agent used in the present invention, hydrochlorofluorocarbons can be used, and particularly 1-chloro-1,1-difluoroethane and / or 1-chloro-1,1-difluoromethane are preferably used. As.

These may be used alone or in a mixture at an arbitrary ratio, and among them, 1-chloro-
Those in which the mixing ratio of 1,1-difluoroethane: 1-chloro-1,1-difluoromethane is 20:80 to 80:20 (weight ratio) is particularly suitable. As the amount of hydrochlorofluorocarbon used as a foaming agent,
10 to 60 parts by weight is suitable for 100 parts by weight of polyol, and 25 to 45 parts by weight is more suitable.

Further, in the present invention, water may be used in combination as a foaming agent. An appropriate amount of water used is 0.001 to 10 parts by weight based on 100 parts by weight of polyol, and 0.5
.About.5 parts by weight are more suitable.

In the present invention, the polyol used in combination with the aliphatic polyester polyol represented by the general formula (1) is not particularly limited, and all known ones can be used. Specifically, for example, the initiator As the polyol, a polyol having a hydroxyl value of 450 mgKOH / g obtained by adding propylene oxide or the like to a mixture of sucrose / glycerin / tolylenediamine is suitable.

Other than the above, for example, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, pentaerythritol, sorbitol, polyhydric alcohols such as sucrose, aromatic amines such as tolylenediamine, and aliphatic amines such as ethylenediamine and triethanolamine Examples thereof include polyether polyols having a hydroxyl value of 350 to 800 mgKOH / g, which are obtained by addition-polymerizing alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide alone or in a mixed system.

The polyester polyol is not particularly limited and all known ones can be used, but polyester diols and polyesters produced by the condensation reaction of the above polyhydric alcohols and low molecular weight carboxylic acids such as adipic acid and phthalic acid. Triol etc. are mentioned. You may use together these polyether polyol and polyester polyol.

Further preferred in the present invention are uniform stability of resin premix, foam strength,
Considering other foam characteristics, the polyol used in combination with the aliphatic polyester polyol of the general formula (1) is
(A) Sucrose is an essential component in the initiator, the average number of functional groups is 3 to 7, and the hydroxyl value is 300 to 500 mg KOH.
/ G sucrose-based polyol, and (b) the average number of functional groups is 2 to 4, and the hydroxyl value is 280 to 500 m.
Aromatic polyols of gKOH / g are preferred. Further, the amount of the sucrose-based polyol (a) used is 5 to 70% by weight of the total polyol components.
Is particularly preferable when the aromatic polyol (b) is used in an amount of 5 to 70% by weight based on the total polyol component.

The organic polyisocyanate which is a raw material used in the present invention is not particularly limited and all known ones can be used, but the most common one is toluene diisocyanate (hereinafter abbreviated as TDI). In some cases)
And / or diphenylmethane diisocyanate (hereinafter M
It may be abbreviated as DI). Here, as TDI, a mixture of isomers, that is, a 2,4-body 100% product,
2,4-body / 2,6-body = 80/20 and / or 65
/ 35 (each weight ratio) and other mixtures,
A so-called crude TDI containing polyfunctional tar known as TDI-TRC (trade name) manufactured by Mitsui Chemicals, Inc.
Can also be used. Also, as MDI, in addition to pure products containing 4,4'-form as the main component, Mitsui Chemicals Co., Ltd. Cosmonate series (trade name) containing polynuclear substances with three or more nuclei
Polymeric MDI represented by is preferably used.

Further, a prepolymer having an isocyanate group at the molecular end obtained by reacting these organic polyisocyanates with the above-mentioned polyol can also be used as a part or the whole of the isocyanate composition. In addition, it is also possible to use an organic polyisocyanate obtained by partially modifying the above polyisocyanate by means of trimerization, carbodiimidation, amidation or the like.

The catalyst used in the present invention is not particularly limited, but specifically, for example, trimethylaminoethylpiperazine, triethylamine, tripropylamine,
All known catalysts such as amine-based urethane-forming catalysts such as N-methylmorpholine, N-ethylmorpholine, triethylenediamine and tetramethylhexamethylenediamine can be used.

Further, as the trimerization catalyst, specifically,
For example, quaternary ammonium hydroxides; hydroxides of alkaline earth metals, alkoxides and carboxylates,
For example potassium acetate, potassium octanoate and potassium 2-ethylhexanoate; non-basic metal carboxylates,
For example, a known catalyst such as lead octoate can be used. These catalysts may be used alone or as a mixture, and the amount of the catalyst used is appropriately 0.001 to 10.0 parts by weight with respect to 100 parts by weight of the compound having active hydrogen.

The foam stabilizer is not particularly limited, but a conventionally known organosilicon-based surfactant is used. Specifically, for example, L-5420 and L-5421 manufactured by Nippon Unicar Co., Ltd., SH-193 manufactured by Toray Dow Corning Silicone Co., Ltd., and F- manufactured by Shin-Etsu Chemical Co., Ltd. 327, F-345, F-305, etc. (all of which are trade names) are suitable. The amount of these foam stabilizers used is 0.1 to 2 per 100 parts by weight of the total amount of the compound having active hydrogen and the organic polyisocyanate.
0 parts by weight. Other auxiliary agents include flame retardants, plasticizers, stabilizers, coloring agents and the like, and these can be added as necessary.

A method for producing the rigid polyurethane foam of the present invention will be described. To carry out the present invention, first, a predetermined amount of a polyol, a foaming agent, a catalyst and a foam stabilizer is premixed to obtain a resin premix liquid. Next, the resin premix liquid and the organic polyisocyanate are mixed at a high ratio at a high speed and poured into a void or a mold. At this time, the organic polyisocyanate is adjusted so that the equivalent ratio (NCO: H (= isocyanate group: active hydrogen)) of the organic polyisocyanate and the active hydrogen of the resin premix liquid is 0.7: 1 to 5: 1. Adjust the ratio of natto to resin. afterwards,
The rigid polyurethane foam of the present invention is obtained by foaming and curing.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.
The raw materials used in the examples and comparative examples are described below.

Isocyanate-A: manufactured by Mitsui Chemicals, Inc.
(Brand name) Cosmonate M-200 Crude diphenylmethane diisocyanate. NCO%: 31.4

Isocyanate-B: manufactured by Mitsui Chemicals, Inc.
(Brand name) Cosmonate T-1002,4-toluene diisocyanate. NCO%: 48.3

Aliphatic Polyester Polyol 1: Lactone Ring-Opening Polyester Polyol Daicel Chemical Industry Co., Ltd. (trade name) Placcel
205 Aliphatic Polyester Polyol 2: Lactone Ring-Opening Polyester Polyol Daicel Chemical Industries, Ltd. (trade name) Placcel
305

Polyol-1: hydroxyl group value 450 mgKOH / g, viscosity 6,000 CPS obtained by addition-polymerizing propylene oxide to sucrose / glycerin (weight ratio 60/40).
(25 ° C.) polyether polyol. The average number of functional groups is 4.44.

Polyol-2: A polyether polyol obtained by adding propylene oxide to glycerin. Hydroxyl value: 450 mg KOH / g

Polyol-3: A polyether polyol obtained by adding propylene oxide to ethylenediamine. Hydroxyl value: 450 mg KOH / g

Aromatic polyol-4: m-tolylenediamine / triethanolamine (weight ratio 70/30) addition polymerized with propylene oxide / ethylene oxide, hydroxyl value 400 mgKOH / g, viscosity 10,000 CPS.
(25 ° C.) polyether polyol. The average number of functional groups is 3.7. Foam stabilizer: Nippon Unicar Co., Ltd. L-5420

Catalyst 1: Kao Riser N manufactured by Kao Corporation
o. 1 (tetramethylhexamethylenediamine) catalyst 2: Kao Riser No. manufactured by Kao Corporation 3 (pentamethyldiethylenetriamine)

Blowing agent Blowing agent 1: 1-chloro-1,1-difluoromethane Blowing agent 2: 1-chloro-1,1-difluoromethane / 1
-Chloro-1,1-difluoroethane (60/40 mixture)

1-chloro-1,1-difluoromethane:
Daikin Industries, Ltd. (trade name) HCFC-22 1-chloro-1,1-difluoroethane: Daikin Industries, Ltd. (trade name) HCFC-142b

Examples 1 and 2 and Comparative Examples 1 to 3 Mechanical foaming was carried out by adding a predetermined amount of the isocyanate composition to a predetermined amount of the resin liquid having the composition shown in Tables 1-3. The molding conditions are as shown below.・ Foaming machine: Marukaka Kogyo MEG-HK-650 type ・ Foaming pressure: I / R = 110/110 kg / cm ²・ Discharging speed: 500 g / sec ・ Liquid temperature: I / R = 20/20 ° C. ・ Mold temperature : 45 ° C

The following molding was carried out under the above molding conditions.
Wooden free box (size: 200 × 200 × 200m
m) and vertical aluminum panels (size: 400 x 40)
Free foaming and panel molding were performed at 0 × 35 mm). Upon foaming, the equivalent ratio of organic polyisocyanate to total active hydrogen was NCO / H = 1.10.

After foaming, 2 in a thermostatic chamber at 23 ° C. and a humidity of 65%
Various physical properties of the foam left for 4 hours were measured. The thermal conductivity was measured under the following conditions. 1) Sample size: 200 × 200 × 25 mm 2) Measuring device: AUTO-λ manufactured by Eiko Seiki Co., Ltd. Further, the crack test was carried out by holding the panel formed by the above vertical aluminum panel for 12 hours at 70 ° C.
A quenching test was conducted in a freezer set at 50 ° C. to evaluate the presence or absence of cracks.

[0046]

[Table 1] (Note) Explanation of symbols ○: No cracks ×: Cracks occurred

[0047]

[Table 2] (Note) Explanation of symbols ○: No cracks ×: Cracks occurred

[0048]

[Table 3] Table-2. Examples and Comparative Examples when Foaming Agent 1 is used as Foaming Agent (Note) Explanation of symbols ○: No cracks ×: Cracks occurred

[0049]

[Table 4] (Note) Explanation of symbols ○: No cracks ×: Cracks occurred

[0050]

[Table 5] Table-3. Examples and Comparative Examples when Foaming Agent 2 is used as Foaming Agent (Note) Explanation of symbols ○: No cracks ×: Cracks occurred

[0051]

The rigid polyurethane foam using hydrochlorofluorocarbons such as 1-chloro-1,1-difluoroethane and / or 1-chloro-1,1-difluoromethane as a blowing agent has a conventional CF.
There is a problem in that the heat insulation performance is inferior to that of the rigid polyurethane foam using C-11, cracks occur in the low temperature or ultra low temperature region, and good heat insulation performance (heat conductivity) cannot be maintained. According to US Pat. No. 5,867,027, hydrochlorofluorocarbons such as 1-chloro-1,1-difluoroethane and / or 1-chloro-1,1-difluoro are used by using an aliphatic polyester polyol in 5 to 50% by weight of the polyol component. Even when methane is used as a foaming agent, a rigid polyurethane foam having good heat insulation performance (heat conductivity) and capable of maintaining good heat insulation performance without generating cracks even in a low temperature or ultra-low temperature range can be obtained. Further, according to the present invention, it is possible to provide a rigid polyurethane foam having good strength and dimensional stability, and excellent heat insulating performance, without using a specific chlorofluorocarbon having restricted symmetry, that is, chlorofluorocarbons. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 75:04 (72) Inventor Minoru Watanabe 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals, Inc. (72 ) Inventor Hiroshi Fujino 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa F-term within Mitsui Chemicals Co., Ltd. (reference) 4F074 AA81 AD02 BA53 BA57 CA12 CA21 DA07 DA32 4J034 BA03 BA07 DA01 DB03 DB07 DF11 DF16 DF20 DF22 DG02 DG03 DG04 DG05 DG08 DG05 DG08 DG08 DG05 DG08 DG05 DG08 DG08 DG05 DG08 DG08 DG05 DG08 DG08 DG05 DG08 DG05 DG08 DG08 DG05 DG08 DG08 DG05 DG08 DG08 DG05 DG08 DG08 DG08 DG05 DG08 DG05 DG22 DH02 DH06 DH10 HA01 HA07 HB06 HC12 HC26 HC35 HC46 HC61 HC64 HC67 HC71 KA01 KB02 KC02 KC07 KC18 KD02 KD04 KD07 KD12 KE01 KE02 NA02 NA03 NA08 QA02 QB16 QC01 RA15

Claims (5)

[Claims] 1. An organic polyisocyanate, a polyol,
A rigid polyurethane foam comprising a foaming agent, a catalyst, a foam stabilizer and other auxiliaries, wherein hydrochlorofluorocarbons are used as the foaming agent, and 5 to 50% by weight of all polyol components is represented by the following general formula (1). A rigid polyurethane foam characterized by being an aliphatic polyester polyol represented by [Chemical Formula 1]. [Chemical 1] (In the formula, k = 0 or 1, 1, m, n are 0 to 5, respectively.
It is an integer of 0-5 and 1-8. Also, k, l, and m are not 0 at the same time. ) 2. The rigid polyurethane foam according to claim 1, wherein the blowing agent is 1-chloro-1,1-difluoroethane and / or 1-chloro-1,1-difluoromethane. 3. The blowing agent is characterized in that the mixing ratio of 1-chloro-1,1-difluoroethane and 1-chloro-1,1-difluoromethane is 20:80 to 80:20 (weight ratio). The rigid polyurethane foam according to claim 2. 4. A sucrose-based polyol having (a) sucrose as an essential component in an initiator, an average number of functional groups of 3 to 7, and a hydroxyl value of 300 to 500 mgKOH / g, and (b) ) An aromatic polyol having an average number of functional groups of 2 to 4 and a hydroxyl value of 280 to 500 mgKOH / g is used in combination with the aliphatic polyester polyol represented by the general formula (1). The rigid polyurethane foam according to claim 1. 5. The sucrose-based polyol (a) is used in an amount of 5 to 70% by weight of the total polyol component, and the aromatic polyol (b) is used in an amount of 5 to 70% by weight of the total polyol component. The rigid polyurethane foam according to claim 4.