JP3189905B2 - Resin composition for polyurethane foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane foam resin composition having excellent foam-forming properties and excellent flame resistance such as flame resistance and low smoke generation, and further, foam insulation materials such as refrigerators, freezers and building materials. And a resin composition for polyurethane foam.

[0002]

2. Description of the Related Art Rigid polyurethane foams are widely used in heat insulating materials because of their excellent heat insulating properties, water resistance, strength, adhesiveness to face materials and moldability. However, its flame retardancy is inferior to phenolic resin foams, so its use for building materials has been limited.

[0003] On the other hand, phenolic resin foams, although excellent in flame retardancy, are very brittle and have poor adhesiveness to other materials, so their use has been limited. As a supplement to such disadvantages of polyurethane foam and phenolic resin foam, an aromatic ring is introduced into the polyol component,
Various studies have been made on flame-retardant phenol-modified urethane foams cured with polyisocyanates.

For example, a method using a benzylic ether phenol resin as a polyol is disclosed in
JP-A-27039, JP-B-58-69218 and the like can be seen. However, a phenolic-based benzylic ether-based phenol resin is poor in compatibility with a freon, which is a foaming agent for a polyol. It was inferior. In addition, there remain problems such as formalin and phenol odor at the time of molding the foam, and the brittleness of the foam is not sufficiently improved.

When a polyol obtained by adding an alkylene oxide to a novolak phenol resin as disclosed in JP-B-59-11607 is used as a polyol, it is necessary to reduce the amount of the alkylene oxide added to maintain flame retardancy. However, when the viscosity of the polyol increases, the workability deteriorates. On the contrary, when the viscosity of the polyol decreases, the flame retardancy is insufficient.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a resin composition for polyurethane foam which is excellent in polyurethane foam-forming properties and excellent in flame retardancy such as flame resistance and low smoke generation, and a resin for polyurethane foam used for foam insulation. It is intended for compositions.

The present inventors have completed the present research as a result of various studies in view of the above problems.

[0008]

That is, the present invention relates to a polyurethane foam resin composition comprising a polyisocyanate, a benzylic ether resin as a polyol, and a foaming agent. Is substituted with an organic group containing active hydrogen , and the organic group is alkylene oxide, lactone,
Phenolic water
An object of the present invention is to provide a resin composition for a polyurethane foam, which is a group having a hydroxyl group obtained by an addition reaction to an acid group .

(Constitution) The benzylic ether resin of the present invention refers to a phenol or aldehyde which is a salt of zinc, cobalt, manganese, tin, cadmium or lead.
It is obtained by reacting using a catalyst comprising at least one species.

As the phenols, two ortho positions used in the production of conventional phenolic resins are unsubstituted phenols, and any or all of the carbon atoms in the phenol ring of the unsubstituted phenol are substituted. Substituted phenols. Examples of the substituted phenols include alkyl-substituted phenols, aryl-substituted phenols,
There are cycloalkyl-substituted phenols, alkenyl-substituted phenols, alkoxy-substituted phenols, aryloxy-substituted phenols, and halogen-substituted phenols. These substituents have 1 to 26, preferably 1 to 6
Having three carbon atoms.

These phenols include, for example, m-
Cresol, p-cresol, 3,5-xylenol, 3,4-xylenol, 2,3,4-trimethylphenol, 3-ethylphenol, 3,5-dimethylphenol, p-butylphenol, 3,5-dibutylphenol, p- Aminophenol, p-cyclohexylphenol, p-chlorophenol, 3,5-dimethoxyphenol, 3,4,5-trimethoxyphenol, p-
Ethoxyphenol, p-butoxyphenol, 3-methyl-
4-methoxyphenol, p-phenoxyphenol, bisphenol A, bisphenol F, bisphenol S and the like.

[0012] The unsubstituted phenol is phenol. Phenol is most preferred from the viewpoint of flame resistance and low smoke emission. The phenols used in the present invention may be used alone or in combination of two or more.

The aldehydes used in the present invention include aldehydes used for producing conventional phenolic resins, for example, formaldehyde, acetaldehyde, propionzaldehyde, furfurylaldehyde,
And benzaldehyde. The most preferred aldehyde is formaldehyde. The aldehyde may be an aqueous solution type or a low molecular weight polymer such as paraformaldehyde. Finally, a low molecular weight polymer such as paraformaldehyde is more preferable by removing water during the reaction. The aldehydes used in the present invention may be used alone or in combination of two or more.

The molar ratio of aldehydes to phenols used in the present invention is suitably from 0.2: 1 to 3: 1, particularly preferably from 0.5: 1 to 1.5: 1. 0.2: 1
When it is smaller, the binding of phenols by aldehydes is small, a large amount of monol is generated, and the foam becomes brittle. On the other hand, when the ratio is more than 3: 1, unreacted aldehydes increase and the aldehyde odor becomes strong, which is not preferable.

Zinc, calcium, cobalt, and the like as catalysts used in the reaction of the phenols and aldehydes of the present invention.
The salts of manganese, tin, cadmium and lead are one or more divalent metal salts selected from the group consisting of carboxylic acids and naphthenates of these metals. For example, suitable examples include zinc acetate, calcium acetate, cobalt acetate, manganese acetate, tin acetate, cadmium acetate,
Lead acetate, zinc propionate, calcium propionate,
Cobalt propionate, tin propionate, cadmium propionate, lead propionate, zinc octoate, calcium octoate, cobalt octoate, manganese octoate, tin octoate, cadmium octoate, lead octoate, zinc naphthenate, naphthenic acid Examples include calcium, cobalt naphthenate, manganese naphthenate, tin naphthenate, cadmium naphthenate, and lead naphthenate.

The reaction conditions of phenols and aldehydes for obtaining the benzylic ether resin of the present invention are as follows:
Reaction conditions for general benzylic ether synthesis are used. For example, a phenol and an aldehyde are charged into a reaction vessel in the above ratio, and the catalyst is added to the reaction vessel in an amount of 0.1 to 1.0%.
Perform the reaction for at least 0 minutes. In the reaction, the more the amount of catalyst,
The higher the reaction temperature, the faster the reaction. Reaction temperature is 60 ° C
If the temperature is lower, the reaction time becomes remarkably slow.
If it is higher, the contents may gel during the reaction, which is not preferable.

The hydrogen of the phenolic hydroxyl group in the benzylic ether resin of the present invention is referred to as an organic group containing a substituted active hydrogen by ring-opening addition polymerization of at least one selected from alkylene oxides, lactones and lactams. It is an organic group having a hydroxyl group or an amino group at the terminal. The added amount is preferably about 1 to 5 mol.

The alkylene oxide is, for example, ethylene oxide. Propylene oxide, butylene oxide, styrene oxide, epichlorohydrin;
As the lactone, for example, γ-caprolactone, ε
-Caprolactone; As the lactam, γ-caprolactam, ε-caprolactam and the like are used. Particularly preferably, propylene oxide, ethylene oxide,
An alkylene oxide such as butylene oxide is used. These alkylene oxides, lactones, lactams and the like can be obtained by ring-opening addition to a benzylic ether-based resin by a usual method.

The benzylic ether resin polyol thus obtained preferably has a viscosity (Vis, 25 ° C.) of 10
With a hydroxyl value (OHV) of 200 to 80
0.

The polyurethane foam of the present invention comprises, as an essential component, a benzylic ether-based resin in which the hydrogen of a hydroxyl group of a phenolic compound is substituted with an organic group containing active hydrogen, and a polyisocyanate generally used for the polyol. It can be obtained by adding an agent, a catalyst and the like, and molding by a method for producing a usual rigid urethane foam. or,
At the same time, other commonly used polyols, foam stabilizers, flame retardants, fillers, coloring agents, and the like may be used in combination. Usually, in flame-retardant applications, it is preferable to use a flame retardant in combination.

The polyisocyanate used in the present invention is
It is not particularly limited, and 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate or a mixture thereof, m- or p-phenylene diisocyanate, p-xylene diisocyanate, ethylene diisocyanate, tetramethylene-1 , 4-diisocyanate, hexamethylene-1,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'dimethyl-diphenylmethane-4,4'-
Diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,
Various derivatives of 4 'biphenylene diisocyanate, 4,4'-buphenylene diisocyanate or 1,5-naphthalene diisocyanate, crude siphenylmethane diisocyanate and diphenylmethane diisocyanate can be used.

The NCO / OH ratio of the present invention is not particularly limited, and is usually 50/100 to 1000/10.
It can be freely selected up to 0, and can be isocyanurated with a trimerization catalyst. Preferably, 100/100 to 50
0/100 is good.

[Embodiments] Next, embodiments of the present invention will be described, but the present invention is not limited thereto. "Part" in the sentence,
“%” Is based on weight.

Example 1 940 parts of phenol and 150 parts of paraformaldehyde were stirred and mixed with 4.0 parts of zinc acetate as a catalyst for producing benzylic ether, reacted at 110 ° C. for 3 hours, and cooled to 80 ° C. 10-50mmH
g for about 1 hour under reduced pressure to prepare a benzylic ether resin, add 4.0 parts of KOH (potassium hydroxide), add 1742 parts of propylene oxide, neutralize and decatalyze, VIS (25 ° C) = 15,000 cps, OHV = 3
A benzylic ether resin polyol (abbreviated as BE polyol) in which hydrogen of 32 hydroxyl groups was substituted with an organic containing active hydrogen was obtained.

85 parts of BE polyol obtained, trischloroethyl phosphate (flame retardant, abbreviated as TCEP) 1
5 parts, 1 part of silicon SH-193 (foam stabilizer, product of Toray Dow Corning Silicon), 1 part of tetrahexanediamine (catalyst, abbreviated as TMHDA), 33 parts of trichloromonofluoromethane, and after uniform mixing, 20 to 25 ° C In NCO
Crude MDI was added to Index 110, and the mixture was stirred at 2500 rpm for 7 seconds and poured into a wooden box to obtain a urethane foam.

Example 2 470 parts of phenol, 1140 parts of bisphenol A, paraformaldehyde 15
0 parts and 5.3 parts of zinc acetate were stirred and mixed.
After reacting for an hour, the mixture was cooled to 90 ° C., dehydrated under reduced pressure at 10 to 50 mmHg for about 1 hour to prepare a benzylic ether-based phenol resin, and 5.3 parts of KOH was added. Addition, neutralization, decatalysis, Vis (25 ° C.) = 2
A benzylic ether-based resin polyol (BE polyol) having 000 cps and OHV = 351 was obtained. A urethane foam was obtained in the same manner as in Example 1 using the obtained BE polyol.

Example 3 Bisphenol A 2280
Parts, 240 parts of paraformaldehyde, zinc acetate 7.6
Part, bisphenol A PO 6 mol adduct (OHV =
226) 2000 parts were stirred and mixed, reacted at 110 ° C. for 3 hours, cooled to 90 ° C., and dehydrated under reduced pressure at 10 to 50 mmHg for 1 hour to prepare a benzylic ether phenol resin. Add KOH, add 2904 parts of propylene oxide, neutralize and decatalyze,
(25 ° C.) = 10,500 cps, OHV = 303, benzylic ether resin polyol (BE polyol)
I got Using the obtained BE polyol, TMHDA1
Parts to 3 parts of potassium octylate, NCO / OH ratio = NC
A urethane foam was obtained in the same manner as in Example 1, except that O Index 110 was changed to 230.

Example 4 940 parts of phenol, 150 parts of paraformaldehyde and 3 parts of zinc naphthenate were stirred and mixed, reacted at 110 ° C. for 3 hours, cooled to 80 ° C., and heated at 10 to 50 mmHg for about 1 hour. After dehydrating under reduced pressure to adjust the benzylic ether resin, 4.0 parts of KOH was added,
After adding 440 parts of ethylene oxide, neutralizing and decatalyzing, 0.06 parts of tetraisopropyl titanate (catalyst, abbreviated as TiPT) was added, and ε-caprolactone 11 was added.
Add 40 parts, react at 180 ° C., Vis = 50,000,
A benzylic ether resin polyol (BE polyol) having an OHV of 357 was obtained. The obtained polyol 50
Part, bisphenol A PO 6 mol addition polyol (O
HV = 226) A urethane foam was obtained in the same manner as in Example 3 except that 50 parts of the mixture was used as a polyol.

Table 1 shows the formulations of the examples.

[0030]

[Table 1] The number in parentheses indicates the number of moles.

[Comparative Example 1] 940 parts of phenol, 480 parts of paraformaldehyde and 4.26 parts of zinc acetate were stirred and mixed, reacted at 110 ° C for 2 hours, cooled to 80 ° C, and cooled to about 1 at 10 to 50 mmHg. Dehydrate under reduced pressure for hours
(25 ° C.) = 15,000 cps, OHV = 630, a benzylic ether resin was obtained. 85 parts of the obtained benzylic ether resin, 15 parts of flame retardant (TCEP), 1 part of foam stabilizer (silicon SH-193), 0.5 part of TMHDA,
After uniformly mixing 33 parts of trichloromonofluoromethane, 20
Crude MDI was added at ２５25 ° C. with NCOIndex 110, and the mixture was stirred at 2500 rpm for 7 seconds, and then poured into a wooden box to make urethane foam.

Comparative Example 2 940 parts of phenol, 37%
To 324 parts of a formalin aqueous solution, 2.5 parts of a 20% hydrochloric acid aqueous solution was added and mixed as an acid catalyst for novolak formation.
Reaction at 00 ° C for 2 hours, cooling to 90 ° C,
After dehydrating under reduced pressure at 50 mmHg for about 2 hours to prepare a novolak phenol resin, 5.0 parts of KOH was added, 1162 parts of propylenoxide was added, neutralized and decatalyzed.
A novolak-based resin polyol having Vis (25 ° C.) = 500,000 cps and OHV = 305 was obtained. Using the obtained polyol, an attempt was made to form a urethane foam in the same manner as in the examples.

[Comparative Example 3] 940 parts of phenol, 37%
To 405 parts of a formalin aqueous solution, 2.5 parts of a 20% hydrochloric acid aqueous solution was added and mixed as an acid catalyst for novolak formation.
Reaction at 00 ° C for 2 hours, cooling to 90 ° C,
After dehydrating under reduced pressure at 50 mmHg for about 2 hours to prepare a novolak-based phenol resin, 5.0 parts of KOH was added, 2324 parts of propylene oxide was added, neutralized and decatalyzed, and Vis (25 ° C.) = 9,800 cps, OHV = 195
Novolak resin polyol was obtained. Using the obtained polyol, an attempt was made to prepare a urethane foam in the same manner as in Example 1.

Comparative Example 4 Vis (25 ° C.) = 50,000 cp
A urethane foam was obtained in the same manner as in Example 1 except that 85 parts of MDI-based PO polyether having s and OHV = 480 were used as the polyether. Table 2 shows the composition of the comparative example.

[0035]

[Table 2]

<Foam Formability> Judgment was made on the formability and appearance during foam molding. ：: good, ×: bad <Compatibility> Compatibility with Freon was visually observed. ：: Good compatibility, ×: Poor compatibility

[Flame retardancy test] The obtained foam was 6 inch
The sample was cut and sampled to a size of 6 inches x 1 inch, and was set upright. An LPG gas burner flame was applied, and the time until the flame penetrated and the amount of generated smoke were observed.

The test results are shown in Tables 3 and 4.

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

The resin composition for polyurethane foam of the present invention has excellent foam-forming properties, so that the polyurethane foam maintains heat insulation, water resistance, strength, adhesion to face materials and excellent moldability, and has flame resistance. Since it is excellent in flame retardancy such as low smoke emission, it is suitable for rigid polyurethane foam for foam insulation materials such as refrigerators, freezers and building materials.

Claims (1)

(57) [Claims] 1. A polyurethane foam resin composition comprising a polyisocyanate, a benzylic ether resin as a polyol, and a foaming agent, wherein hydrogen of a phenolic hydroxyl group of the benzylic ether resin is substituted with an organic group containing active hydrogen. The organic group
Selected from alkylene oxide, lactone, lactam
Addition reaction of one or more compounds to phenolic hydroxyl groups
A resin composition for a polyurethane foam, which is the obtained group having a hydroxyl group .