JPS58136432A - Flame-retarded laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-resistant laminate, particularly a laminate having a phenolic urethane foam as a core material having excellent heat insulation properties and dimensional stability.

Conventionally, laminates have been used for ceiling materials, wall materials, and other construction materials, with a core material such as wood or plaster and a facing material such as decorative paper or iron plate, but these materials are generally heavy and have difficulty in construction. It also has the disadvantages of being hygroscopic and having low heat insulation properties.

On the other hand, materials having core materials made of lightweight organic foams with good heat insulation properties, such as rigid polyurethane foam, have been developed, but these materials generally have the drawback of low fire retardant performance.

A laminate with a polyisocyanurate foam as a core material and aluminum foil or plate-like material as a face material is known as a laminate with high fire retardant performance that uses an organic foam as a core material. In order to pass the flame retardant class 2 test described below, a considerable amount of flame retardant must be present in the polyisocyanurate foam.

Heat insulating properties due to the addition of smoke reducing agents or inorganic substances.

It is economically disadvantageous because deterioration of the form properties such as dimensional stability is unavoidable, and the aluminum foil or plate to be attached must have a thickness of 0.1 mm or more to be effective.

The present invention uses a phenolic urethane foam manufactured using a special polyol component, eliminates any flame retardant from the conventional rigid urethane foam foam formulation, passes the flame retardant class 2 test, and is inexpensive and industrially effective. To provide a flame-resistant laminate that can be produced by a method suitable for productivity.

That is, the present invention provides a laminate in which at least one side of a urethane foam is coated with a flame-resistant surface material, in which the urethane foam is a benzyl ether type obtained by condensing (a) phenol with formaldehyde in an amount equal to or more than the equivalent molar amount. A modified phenol resin in which 0.3 equivalents or more of the phenolic hydroxyl groups of the phenolic resin were converted to alcoholic hydroxyl groups with alkylene carbonate and (b) polyisocyanate were subjected to a foaming reaction in a range of 110H equivalent to 2 NCO. This invention relates to a flame-resistant laminate that is self-adhered onto a facing material.

The benzyl ether type phenol resin in the present invention is prepared by using a single compound of alkaline earth metal oxides, hydroxides, or organic weak acid salts such as acetic acid and naphthenic acid under conditions of 1 mole or more of formaldehyde per 1 mole of phenol. i or obtained by reaction under a mixed catalyst.

The term phenol referred to herein means a benzene ring in which one or more carbon atoms of the skeleton are directly bonded to a hydroxyl group, and also includes those having other substituted bonding groups within the same structure. Typical examples include phenol, cresol, bisphenol A, and resorcinol.

Further, the formaldehyde is not particularly limited, but formalin and paraformaldehyde are preferable.

Further, the alkylene carbonate used in the present invention is represented by the general formula: Specifically, for example, ethylene carbonate,
Propylene carbonate, 4-ethyldioxolone, 4
-butyldioxolone, 4,5-dimethyldioxolone, 4-pentyldioxolone, 4,4'-dimethyldioxolone, etc. are used.

Next, the amount of conversion of phenolic hydroxyl groups in the resin to alcoholic hydroxyl groups is 0.3 equivalent or more of phenolic hydroxyl groups,
Preferably it is 0.4 to 0.8 equivalent.

If the conversion amount is 0.3 equivalent or less, the modification effect will not be exhibited. Note that if alkylene carbonate is used in excess of the equivalent amount of phenolic hydroxyl groups, unreacted alkylene carbonate or hydrolyzed glycol will be produced, which will deteriorate the heat resistance of the final cured phenol urethane product and reduce the reaction rate during curing. The object of the present invention cannot be achieved because of the delay.

In the present invention, the conversion reaction of phenolic hydroxyl groups into alcoholic hydroxyl groups is carried out by adding and mixing alkylene carbonates while keeping the benzyl ether type phenol resin, which has been concentrated in advance through condensation reaction and dehydration reaction, in a non-aqueous system. A suitable alkaline catalyst is added under a temperature condition not exceeding 140° C. to 140° C., and the reaction is allowed to occur for several minutes to several hours.

Alkaline catalysts for modification include potassium carbonate,
Catalysts such as sodium carbonate and calcium carbonate that ring-open alkylene carbonate and do not generate glycol are preferable. By using these catalysts, alkylene carbonate opens the ring while generating carbon dioxide gas, and forms a bond between the phenol hydroxyl group and the ether bond. The hydroxyl groups are modified.

The obtained modified resin is further removed under reduced pressure to remove unreacted carbonate monomers and by-product glycol monomers as necessary to obtain a product. used in

The polyisocyanates used in the present invention are not particularly limited, and any conventionally and commonly used polyisocyanates may be used as appropriate. Typical examples include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, etc., and aliphatic polyisocyanates such as hexamethylene diisocyanate, inphorone diisocyanate, dicyclohexylmethane diisocyanate, etc. . Particularly preferred are diincyanates.

The reaction ratio between the modified phenol resin and the polyincyanate is in the range of NGO equivalent 10H equivalent ≦2, preferably 1.2 to 2.
It is 1.8. The term OH here refers to the sum of phenolic and alcoholic OH.

Both reactions are usually carried out in the presence of a curing catalyst, foam stabilizer and blowing agent.

As curing catalysts, amine catalysts such as triethylenediamine, N,N-dimethylethanolamine 7,N,N,
N,N,N''-hentamethyldiethylenetriamine, organotin catalysts such as dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, etc. These curing catalysts can be used to cure modified phenolic resins.
Jusha% is used.

The blowing agent is not limited, and a general blowing agent for urethane foam can be used as it is. Specific examples include chlorofluorinated hydrocarbons such as trichloromonofluoromethane and dichlorodifluoromethane, as well as methylene chloride and pentane.

Examples of foam stabilizers include nonionic surfactants such as organopolysiloxane-polyoxyalkylene copolymers and silicone-glycol copolymers.

The foamed urethane foam used in the present invention is bonded to a flame-resistant surface material.

The flame-resistant surface material may be any flame-resistant material such as asbestos paper, glass paper, aluminum foil, various flame-resistant laminate papers, and gypsum flat board, but asbestos paper is particularly preferred. Asbestos paper has excellent self-adhesive properties with the above-mentioned urethane foam, and is lightweight and economical. The appropriate thickness of the asbestos paper is about 100 to 500.

In the present invention, the urethane foam and the flame-resistant surface material are self-adhesive. Self-adhesion is easily achieved by overlapping the urethane foam core material with the face material during formation, so there is no need to use a separate adhesive to bond the urethane foam core material and the face material, resulting in excellent industrial productivity. There is.

At least one flame-resistant facing material shall be attached to any surface that may come into contact with flames. The urethane foam used in the present invention is itself extremely flame retardant, and contains special flame retardants, flame retardants,
Although it exhibits excellent flame retardancy without using smoke reducing agent I, it is not possible to obtain a product that passes the JIS-A-1321 flame retardant grade 2 fire performance test unless a flame-resistant face material is used. . Conversely, even if asbestos paper or the like is used as a surface material to protect the surface of conventional hard urethane foam or polyisocyanurate foam, it will not pass the second class flame retardant test unless a large amount of flame retardant is used. Furthermore, the use of such flame retardants impairs the thermal insulation properties and dimensional stability of the foam, as well as deteriorating its mechanical properties.

The present invention will be explained below with reference to Examples.

Example 1 200 kg of phenol and 2041'l of 47% formalin
Pour into a 1l-6001 reaction pot, 1 lead naphthenate.
.

The resulting resin was introduced into a continuous concentrator with an L/D of 1000, and the outlet of the tube was guided into a flash chamber maintained at 125° C. while the tube jacket was heated with steam at 3.5 Kg/ad. The pressure of the flash chamber was reduced to 60 mHP, and while unreacted monomers and water were removed from the system, only the resin liquid was separately taken out of the system to obtain a benzyl ether type phenol resin liquid (hereinafter referred to as resin liquid A). say).

Resin liquid A had the characteristics shown in Table 1.

Table 1 Next, 260 kg of resin liquid A and 1 ethylene carbonate
10 pieces were placed in a reaction vessel, 3 kg of K2CO3Q was added, and the mixture was reacted at 100°C for 50 minutes. Since carbon dioxide gas is generated as the reaction progresses, it is removed from the system, and after the reaction is completed, the monomer is removed under reduced pressure to obtain a modified resin (hereinafter referred to as resin liquid (1)).

Table 2 shows the properties of resin liquid (1).

Table 2 Non-volatile content■ 72 Monomer and glycol in the resin liquid■ were measured by gas chromatography and found to be 2% ethylene carbonate.
, glycol was 0%, and the modification rate was 0.56 mol per 1 mol of phenolic hydroxyl group.

Incidentally, each item in the above examples was measured based on the following measuring method.

Viscosity・・・・・・・・・−・・・・・・・・・・・・・・・B
By H-type viscometer.

Free phenol......Liquid chromatography release/form 1-7)......by hydrochloric acid/hydroxylamine method.

Non-volatile content・・・・・・・・・・・・・・・・・・
180℃×1 hour Evaporation average molecular weight・・・・・・・・・・・・
・・・・・・Based on vapor pressure osmosis method.

o H value: Based on the acetylation method.

Moisture: Based on Karl Fischer method.

Phenolic resin with methylol group equivalent lOy and 205' phenol ('
PboO, containing 2wt%) at 115-120℃
After cooling, moisture is measured by the Karl Fischer method, and free formalin is measured by the hydrochloric acid/hydrochloride method, and determined by the following formula.

R x 18 x 100 1':i carofenono'4d9) PW:
KFjJ Moisture in lophenol 8Ok: Resin amount (p)
RRF: Previously filtered, jvL/7 pieces RF = Free faW in the resin
Moisture in the resin (Tochiji Using this resin solution ■, a board was created by free foaming in the box with recipe A and foaming in the entire mold with recipe B. The physical property values of these foams are shown in Table 3. .

Go to prescription Parts by weight Resin liquid I 100 T-120,3 L -54201,5 5-116 Prescription B Parts by weight Resin liquid ■ 100 T-120,3 L-54201,5 S -160 Here, T-12 is manufactured by M&Tchem. Free foaming inside the dilaurate box is resin liquid II
After high-speed stirring for about 10 seconds at a blending ratio of J<2009,
It was placed in a 25 aa square box and allowed to foam freely. In addition, to create the board in the mold, mix the resin liquid with a mixing ratio of force ≦209, and after stirring at high speed for about 10 seconds, mix 30CIX 30CII.
Place the upper lid preheated to approximately 55°C on the mold inner core of X 20w111, which has been preheated to approximately 55°C, secure the mold and lid tightly with clamps, and allow foaming to occur within the mold. I created it.

Next, in Examples 2 to 7, laminates using resin liquid (1) will be introduced.

Example 2 Aspal cut into 30 cm squares and preheated to about 55°C (100 y of asbestos paper manufactured by Jujo Paper Co., Ltd.)
m') heated to about 5°C (30cm in length and width,
Set to a depth of 20-). Resin liquid ■, ■-12 with formulation C, resin liquid I was mixed at a blending ratio of 20y.
, sl, a predetermined amount of MR-20 in a mixed solution of L-5420.
Immediately after adding 0 and stirring at high speed for about 10 seconds, the mixed stock solution is poured into the mold. Approximately 55℃ above the injection stock solution
Place the pre-heated aspal on top, then place the top lid pre-heated to about 55°C, and secure the mold and lid firmly with a clamp. After being left at room temperature for about 10 minutes, the mold was demolded to produce a laminate of 30 cm x 30σ x 20 fins.

The cross-sectional structure of the obtained laminate is shown in FIG. In the figure, (1
) indicates asbestos paper, and (2) indicates a layer of phenolic urethane foam. The combustion test results of this laminate are shown in Table 4.

Prescription C Resin liquid ■ 100 parts by weight T-120, 4 parts by weight L-54203 parts by weight S-160 parts by weight MR-200 NCO equivalent 10H equivalent = 1.6 Table-4 Examples 3, 4 and 5 The face material was changed In addition, the following laminate was obtained in the same manner as in Example 2.

Example 3 uses aspal (100y/m') laminated with a 30μ thick polyethylene film as the facing material.
In Example 4, aluminum foil (thickness 20μ) was bonded to aspal (100y/-) through a polyethylene film (thickness 20μ) as a face material. A laminate using a laminate (with an aluminum layer as the outermost layer) and Example 5 are laminates using aluminum with a thickness of 150 μm as a face material. The combustion test results of these laminates are shown in Table 5.

Examples 6 and 7 In Example 6, asbestos was cemented as a surface material.
Glass paper laminated with a 50μ thick polyethylene film on the back material (60 μm)
y/WI). This configuration is shown in FIG. In the figure, (2) is a urethane foam layer, (3) is
A polyethylene film layer, (4) a glass paper layer and (5) a flexible board. The manufacturing method is
This is the same as in Example 2.

That is, a flexible plate was set in a mold, a liquid mixture of prescription C was injected onto the flexible plate, and a glass paper was set above the injection stock solution.

Example 7 is a laminate using glass paper (60y/-z') laminated with a 9mm thick gypsum flat board as the surface material and a 50μ thick polyethylene film as the backing material (polyethylene film and urethane foam). (glue). The manufacturing method is the same as in Example 6. The combustion test results of these laminates are shown in Table 6.

Example 8 The relationship between the modification ratio of a benzyl ether type phenol resin modified with ethylene carbonate and the fryability of the foam was investigated. The modified phenol resin was synthesized according to Example 1. On the other hand, the foam was obtained by free foaming in a box according to the recipe. Table these ρ results.
7.

Formula modified phenolic resin 100 parts by weight T-120.3
Parts by weight L-54201, 5 parts by weight S-125 parts by weight MR-200 NCO equivalent 10H equivalent - 1, 2 Next, using a resin liquid process, the same procedure as in Example 1 was made by changing the ratio of NGO equivalent and OH equivalent. A board was made by self-foaming using a mold, and its flyability was investigated. The results are shown in Table-8.

[Brief explanation of the drawing]

FIGS. 1 and 2 are cross-sectional views of one embodiment of the flame-resistant laminate of the present invention. In the figure, (1) shows asbestos paper, (2) shows urethane foam, (3) shows polyethylene film, (4) shows glass paper, and (5) shows flexible board. Patent amount - Kurashiki Spinning Co., Ltd. Figure 1

Claims (1)

[Scope of Claims] 1. A laminate in which at least one side of a urethane foam is coated with a flame-resistant face material, wherein the urethane foam is obtained by (a) condensing phenol with formaldehyde in an equivalent molar amount or more; A modified phenolic resin in which 0.3 equivalents or more of the phenolic hydroxyl groups of a benzyl ether type phenolic resin are converted into alcoholic hydroxyl groups with an alkylene carbonate and (bl polyisocyanate) are subjected to a foaming reaction in a range of NCO equivalents of 10H equivalents to 2. 2. The flame-resistant laminate according to item 1, wherein the flame-resistant facing material is asbestos paper.