JP2595658B2 - Foam laminate - Google Patents

Description

The present invention relates to a heat insulating material for building structures, hot and cold water pipes, bathtub tanks, etc., and a floor base material for heat insulating and maintaining airtightness of railway vehicles and the like. The present invention relates to a composite foam laminate of a hard urethane resin foam and a phenol resin foam that can be suitably used.

2. Description of the Related Art As is well known, a rigid urethane resin foam (hereinafter, referred to as a rigid urethane foam) is used as an in-situ spray foaming construction, and is also manufactured as a laminate pod. And so on.

However, although this rigid urethane foam has low thermal conductivity and excellent heat insulation, it may easily ignite and cause a fire only by contact with a small fire source such as a welding spark. There is a problem in point.

On the other hand, a phenol resin foam (hereinafter referred to as phenol foam) is suitably used as a laminate board or the like. However, although this phenol foam is excellent in fire resistance, it has a drawback that heat insulation is considerably inferior to that of rigid urethane foam.

For this reason, development of a foam having excellent heat insulation and high fire resistance is desired.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a foam laminate having an excellent heat insulating effect, high fire resistance, and which can be widely used as various heat insulating materials.

Means and Action for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, by integrally foaming a rigid urethane foam and a phenol foam, the heat conductivity is reduced and the heat insulating property is reduced. It is possible to obtain a foam laminate that is excellent, has high fire resistance, and has good adhesion to various face materials, concrete skeleton, etc. This foam laminate is formed by bonding on various face materials, concrete skeleton. It has been found that it can be widely used as a heat insulating material or a floor base material. In particular, in this case, the conventional phenol foam required a long time for foam curing and was relatively difficult to be spray-foamed in place, but as a phenol foam raw material, a low-molecular-weight resole type phenol resin having a number average molecular weight of less than 200 was used. By using a resole type phenol resin mixture in which a high molecular weight resole type phenol resin having an average molecular weight of 200 or more is mixed at a weight ratio of 5/95 to 80/20, foaming and hardening can be performed in a short time, and on-site spray foaming can be achieved. The present invention has been found to be easy and can be integrally foamed with good adhesiveness on hard urethane foam which has been similarly spray-foamed and cured.

Therefore, the present invention is a foam laminate obtained by integrally foaming a rigid urethane foam and a phenol foam, wherein the phenol resin foam is a low molecular weight resol type phenol resin having a number average molecular weight of less than 200 as a resol type phenol resin. Resol-based resin foam obtained from a foam raw material containing a resole-type phenolic resin mixture in which a high-molecular-weight resole-type phenolic resin having a number average molecular weight of 200 or more and a weight ratio of 5/95 to 80/20 are mixed. The present invention provides a foam laminate.

 Hereinafter, the present invention will be described in more detail.

The type of the rigid urethane foam (hard urethane resin foam) used in the laminate of the present invention is not particularly limited, and is usually a polyol compound and an isocyanate compound, as well as a catalyst, a foaming agent, a foam stabilizer, a flame retardant and the like. Various hard urethane foams obtained from the above hard urethane foam raw materials can be used.

Here, the chemical structure of the polyol compound is not particularly limited, but it is preferable to use a compound having two or more hydroxyl groups at one terminal per molecule alone or as a mixture of two or more kinds. Specific examples include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, hexanetriol, pentaerythritol, trimethylolpropane, diethanolamine, triethanolami, methylglycoside, sorbitol, and soucrose. Alkylene oxide adducts of polyhydric alcohols such as polyamines; alkylene oxide adducts of polyamines such as aromatic amines such as ammonia, ethylene diamine, diethylene triamine and tolylene diamine; A phosphorus-containing polyol such as an acid alkylene oxide adduct; a phenol alkylene oxide adduct represented by bisphenol A; a novolak resin having a phenolic hydroxyl group, an intermediate alkylene oxide adduct of a resole resin, and the like. Can be.

Next, as the isocyanate compound, for example, 2
・ 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, 1,5-naphthalenediisocyanate, polymethylene polyphenylene polyisocyanate, etc. In particular, crude diphenylmethane-4.4'-diisoyanate can be suitably used.

The compounding ratio of the polyol compound and the isocyanate compound can be a normal compounding ratio, and both compounds may be compounded so that the index value representing the ratio between the polyol compound and the isocyanate compound becomes 95 to 115. Although it is preferable, the amount of the isocyanate compound may be excessive, and may be blended so that the index value is larger than the above range.

Further, as the catalyst, for example, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N'-tetramethylethylenediamine, 1,4-diazacyclo- (2.2)
.2) -octane, N-methyl-N'-dimethylaminoethylpiperazine, N, N-dimethylbenzylamine, bis-
(N, N-diethylaminoethyl) -adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N'
Amine catalysts such as tetramethyl-1,3-butanediamine, N, N-dimethyl-β-phenylethylamine, 1,2-diethylimidazole, 2-methylimidazole, tin acetate,
Organotin-based catalysts such as divalent tin such as tin octenoate and tin laurate, and tetravalent tin such as butyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate; Further, one or more of potassium acetate, lead acetate, and other organometallic compound catalysts can be used as necessary.

Further, as the foaming agent, for example, water (carbon dioxide), trichloromonofluoromethane, methylene dichloride, pentane, air and the like are not limited, but the foam stabilizer is not necessarily limited to the copolymer of ethylene oxide and propylene oxide. Polydimethylsiloxane-based foam stabilizers are preferably used. Examples of flame retardants include tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2.3-dibromopropyl) phosphate, and the like. Phosphorus-containing flame retardants such as tris (1.3-dichloroisopropyl) phosphate, melamine powder, and the like can be used. In addition,
As the raw material of the rigid urethane foam, there may be no problem in mixing an optional component other than the above components.

The amount of the catalyst, the blowing agent, the foam stabilizer, the flame retardant, and the optional components is not particularly limited, and can be appropriately adjusted according to the purpose of use.

The method for producing a rigid urethane foam from the above-mentioned rigid urethane foam raw material can be the same as a general foam production method.For example, a catalyst, a foaming agent, a foam stabilizer, a flame retardant are added to a polyol compound. A foam can be obtained by employing a method such as mixing and stirring the polyol component and the isocyanate compound.

Next, the phenol foam (phenol resin foam) used in the present invention is obtained by weighting a low molecular weight resol type phenol resin having a number average molecular weight of less than 200 and a high molecular weight resol type phenol resin having a number average molecular weight of 200 or more as a resol type phenol resin. A resol-based phenolic foam obtained by mixing and using at a ratio of 5/95 to 80/20 and using a foam raw material containing a foaming agent, a curing agent, etc. It is short and has excellent adhesiveness.

That is, when a high-molecular-weight resol-type phenol resin is used as a resol-based phenol foam raw material, although the adhesiveness of the obtained foam is greatly improved, the active methylol group concentration is reduced and the foam hardening time is extremely long. Number average molecular weight of 20 as resol type phenol resin
By combining a low molecular weight resin of less than 0 and a high molecular weight resin having a number average molecular weight of 200 or more, and mixing and using both resins in the above-described specific ratio, the high molecular weight resin is used for the adhesiveness of the foam. In addition to acting as a relatively independent factor, the low-molecular-weight resin exhibits a curing promoter effect, has excellent adhesion to various face materials, concrete frames, etc., and foams and hardens in a short time. As a result, it is possible to obtain a highly practical resol-based phenol foam that can be effectively used in on-site spray foaming.

In this case, the resole type phenol resin is phenol,
A liquid phenolic resin rich in methyl groups such as phenol formaldehyde resin, phenol furfural resin, cresol formaldehyde resin, cresol furfural resin obtained by reacting cresol, etc. with formaldehyde, furfural, etc. in the presence of an alkaline catalyst. In the present invention, various resol-type phenolic resins can be used as long as they are suitable for the field and purpose of phenolic resin synthesis, and one kind may be used alone, or two or more kinds may be used in combination. You may.

Of the various resol-type phenolic resins, phenol formaldehyde resin is particularly frequently used because of its high reaction rate between phenol and formaldehyde, and its economical advantage of shortening the synthesis time. Formaldehyde resins are preferably used.

The viscosity of the resol-type phenol resin is not particularly limited, but is preferably about 2000 to 20000 centipoise (cp).

Here, as the resole type phenol resin, as described above, a low molecular weight resole type phenol resin and a high molecular weight resole type phenol resin are used in combination, and as the low molecular weight resin, the number average molecular weight is used. A resol type phenol resin having a number average molecular weight of 200 or more, preferably 250 or more and 450 or less is used as the high molecular weight resin. In this case, the low molecular weight resin and the high molecular weight resin are in a weight ratio of 5/95 to 80.
/ 20, preferably 10/90 to 60/40.

Next, the foaming agent is not particularly limited as long as it is generally used as a phenol foam raw material. For example, chlorinated hydrocarbons such as chloroform and methylene chloride,
Trichlorofluoromethane, 1,1,2-trichloro-1,2,2-
Trifluoroethane, monochlorodifluoromethane, dichlorodifluoromethane, 1,1-dichloro-12,2,2-tetrafluoroethane, 1,2-dichloro-1,1,2,2-tetrafluoroethane, 1,1, 1-trichloro-2,2,2-trifluoroethane, 1,2-difluoroethane, 1,1,2,2-tetrachloro-1,2-difluoroethane, 1,1,1,2-tetrachloro-
One or more kinds of chlorine-fluorinated hydrocarbon compounds such as 2,2-difluoroethane can be used in a usual blending amount.

As the curing agent, a mineral acid or an organic acid generally used as a curing agent in phenol resin polymerization can be suitably used, and specifically, a mineral acid such as sulfuric acid, hydrochloric acid, phosphoric acid, or p-toluene. Organic acids such as sulfonic acid, xylene sulfonic acid and phenol sulfonic acid are exemplified. The amount of the curing agent is not particularly limited, and may be a normal amount.

In addition, as the foam stabilizer, for example, polysiloxane compounds, castor oil ethylene oxide adducts, polyoxyethylene sorbitan fatty acid esters, and the like are used.

It should be noted that, as a phenol foam raw material, it is possible to mix other optional components within a range that does not hinder the purpose of the present invention.
No problem.

When producing a resol-based phenol foam from the above-mentioned phenol foam raw material, the same method as that of a normal phenol foam can be employed. For example, a foaming agent and a foam stabilizer together with a mixture of both high-molecular weight and low-molecular-weight resole phenolic resins. A foam can be obtained by, for example, adding a curing agent to the phenol resin component containing the above components, mixing the mixture, and stirring vigorously at room temperature.

As described above, the laminate of the present invention is obtained by integrally foaming a rigid urethane foam and a resol-based phenol foam obtained from the above-mentioned resol-type phenolic resin mixture. The adhesive is formed on the surface of various surface materials such as boards and the surface of a skeleton such as concrete, and can be used as a heat insulating material, a floor base material and the like.

In this laminate, as a method of laminating and molding a rigid urethane foam and a phenol foam, a molding method such as a method by in-situ spray foaming and a lamination method used for obtaining a laminate board can be adopted.

In this case, when forming by a method by in-situ spray foaming, for example, a mixture of a raw material of a hard urethane foam is sprayed on the surface of a surface material, a concrete frame, etc. using a spray or the like, and foamed to form a hard urethane foam. When a mixture of phenol foam raw materials is sprayed on the rigid urethane foam layer using a spray or the like and foamed to form a phenol foam layer, the rigid urethane foam and phenol foam are integrally foamed to obtain a laminate. Here, as described above, a low-molecular-weight resole-type phenol resin having a number average molecular weight of less than 200 and a high-molecular-weight resole-type phenol resin having a number average molecular weight of 200 or more as a phenol foam raw material in a weight ratio of 5/95 to 80/20.
Of the resole-type phenolic resin mixture, foaming agent, and curing agent blended at a ratio of 2. The foaming and curing takes place in a short period of time, so that the on-site foaming spray can be performed efficiently and adhered to the cured urethane foam. The phenol foam layer can be integrally laminated with good efficiency. Further, such spraying may be performed so that one layer of phenol foam is laminated on one layer of rigid urethane foam 1 as shown in FIG. 1 or two layers of rigid urethane foam as shown in FIG. Two layers of phenolic foams 2 and 2 may be sequentially laminated on 1, 1 or rigid urethane foams 1 and phenolic foams 2 may be alternately laminated as shown in FIGS. Good, in this case, a low molecular weight resol type phenol resin having a number average molecular weight of less than 200 and a high molecular weight resol type phenol resin having a number average molecular weight of 200 or more as a phenol foam raw material in a ratio of 5/95 to 80/20 by weight. Since a mixture of a mixed resole-based phenolic resin mixture, a foaming agent, and a curing agent is used, as shown in FIG. It is directly sprayed foam, phenolic foam 2 for these facings, concrete skeleton like 3
Can be formed with good adhesiveness.

In addition, in the laminate of FIGS. 1 to 4, the phenol foam 2 side is disposed on the side that requires fire resistance for the fire resistance of the phenol foam, but both sides of the laminate of FIG. Since it is formed of phenol foams 2, 2, it has high fire resistance.

When molding using a laminating method, for example, foaming and laminating a raw material of urethane foam on the surface of various face materials, concrete skeletons, etc., and further foaming and laminating a raw material of phenol foam on this rigid urethane foam layer are performed. After that, a method of pressing the laminate with the face material in a cure tunnel can be used.

Effect of the Invention As described above, the laminate of the present invention has excellent heat insulation and high fire resistance, and also has good adhesion to various face materials, concrete skeletons, etc. It can be widely used as a heat insulating material for hot and cold water pipes, bathtub tanks and the like, a floor base material for railway cars and the like.

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1 and 2 and Comparative Examples 1 and 2] According to the formulation of the first evaluation, the components A and B of the raw material of the rigid urethane foam were first mixed, and the mixture was uniformly stirred and mixed with 500 mm × 500 mm × 7 mm. Was sprayed onto a gypsum board with a spray to foam, thereby forming a rigid urethane foam. Then, according to the formulation shown in Table 1, a homogeneous mixture of the components A and B of the phenol foam raw material was obtained, and this mixture was spray-foamed on the rigid urethane foam to integrate the rigid urethane foam with the phenol foam. Molded.

In the above method, a hard urethane foam raw material and a phenol foam raw material are sprayed once each on a gypsum board, and a composite heat insulating material (Example 1) in which the average thickness of each foam is 10 mm, and both foam raw materials are each 2 Spraying each time gave a composite heat insulating material (Example 2) in which the average thickness of each foam was 20 mm.

For comparison, in the same manner as described above, only the hard urethane foam raw material shown in Table 1 was sprayed twice by spraying to form a foam having an average thickness of 20 mm (Comparative Row 1). Only the phenol foam raw material shown in the table was sprayed twice with a spray to obtain a heat insulating material (Comparative Example 2) in which the foam was formed to an average thickness of 20 mm.

 Physical properties of these heat insulating materials were measured, and physical properties were evaluated.

In the physical properties, the foam density was measured according to JIS A-9514, and the flammability was measured using phenol foam as the fire source side. The adhesiveness was evaluated by performing a vertical peel test using a gypsum test piece of 50 cm × 50 cm. When the adhesiveness was extremely good, the evaluation was ◎.

 The results are shown in Table 1.

* 1 BM-34: Adeka Polyol (OH value 820) * 2 BM-54: Adeka PolyOw (OH value 450) * 3 TCEP: Tris (β-chloroethyl) phosphate (Daichi Chemical) * 4 Freon F-11: trichloromonofluoromethane (manufactured by Asahi Glass Co., Ltd.) * 5 DABCO-33LV: triethylenediamine / dipropylene glycol (weight ratio 1/2) (manufactured by Sankyo Air Products) * 6 DBTDL: dibutyltin dilaurate (Nitto Kasei) * 7 SH-193: Polydimethylsiloxane (Toray Silicone) * 8 MR-100: Crude diphenylmethane-4,4'-diisocyanate (Nippon Polyurethane) * 9 R-1: Number average molecular weight 175, Low molecular weight resole phenolic resin with a viscosity of 3050 cp / 25 ° C (phenol formaldehyde resin) * 10 R-2: High molecular weight resole phenolic resin with a number average molecular weight of 260 and a viscosity of 5000 cp / 25 ° C (Phenol * 11 F-113: Trichlorotrifluoroethane (manufactured by Asahi Glass Co., Ltd.) * 12 F-140: Castor oil-based surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) * 13 PS-65: 65% phenolsulfonic acid Aqueous solution (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) From the results in Table 1, it can be seen that the heat insulating material made of rigid urethane foam alone (Comparative Example 1) has low heat conductivity and excellent heat insulating properties, but is inferior in flammability and phenol foam. The single heat insulating material (Comparative Example 2) has good flammability, but has high thermal conductivity and poor heat insulation. Compared to these, the composite heat insulating material (Examples 1 and 2) in which the rigid urethane foam and the phenol foam are integrally combined has good heat insulating properties and good combustibility, and also has high adhesiveness to the face material. It was confirmed that.

[Brief description of the drawings]

1 to 4 are cross-sectional views each showing an embodiment of the present invention. 1 ... Rigid urethane foam 2 ... Phenol foam

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-52-18246 (JP, A) JP-A-55-92451 (JP, A) JP-A-60-138148 (JP, A) 148622 (JP, U)

Claims (1)

(57) [Claims] 1. A foam laminate comprising a rigid urethane resin foam and a phenol resin foam integrally foamed, wherein said phenol resin foam is a low molecular weight resol type having a number average molecular weight of less than 200 as a resol type phenol resin. A resol based on a resole type phenol resin mixture obtained by mixing a phenol resin and a high molecular weight resol type phenol resin having a number average molecular weight of 200 or more at a weight ratio of 5/95 to 80/20, and a resol type obtained from a foam raw material having a main component. A foam laminate, which is a phenolic resin foam.