JPH039917A - Resin composition for foaming, foamed body and flame-retardant structure - Google Patents

Abstract

PURPOSE:To provide a resin compsn. for foaming with no decrease in pH and providing a foam, etc., with excellent flame-retardant characteristics, etc., by compounding an aq. soln. of a sugar contg. a specified amt. of fructose, a reaction catalyst, an isocyanate compd. and tris(monochloropropyl) phosphate together. CONSTITUTION:A resin compsn. for foaming is prepd. by mixing an aq. soln. and (or) a slurry of a sugar with a fructose content of 85wt.% or more, a reaction catalyst (e.g. triethanolamine), an isocyanate compd. (e.g. diphenylmethane diisocyanate) and tris(monochloropropyl) phosphate as a flame-retardant. This resin compsn. for foaming is poured into a mold on the bottom of which a flame-retardant sheet is placed and the mold is clamped. Heating and foaming is performed and a foamed body and the sheet are adhered in one body to prepare a flame-retardant structure.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a foaming resin composition, and a foam and a flame-retardant structure using this composition.

[Conventional technology]

Recently, flame-retardant requirements for building materials, especially residential exterior wall materials, have become more stringent, and a model box test No. 1372 has been added to the Ministry of Construction Notification No. 1231 semi-flammability test. This Ministry of Construction Notification No. 1372 model box test is the afterflame, temperature time area,
After satisfying the regulatory value of smoke emission coefficient, the test specimen was enlarged,
It is extremely difficult to judge the calorific value during combustion and the shape after combustion.

Conventionally, as foams, incyanurate foams (incyanurate foams) having isocyanurate rings made from industrial polyols (
Known examples include polyurethane foam (a type of polyurethane foam), phenol foam, and foam made from carbohydrates.

However, structures using the isocyanurate foam undergo significant shape change after combustion and generate a large amount of heat, making it difficult to pass the Model Box Test No. 1372. Structures using the phenol foam have little change in shape after combustion, but have a drawback of having a long afterflame time after combustion. When switching the production equipment for molding isocyanurate foams to molding phenol foams, it is necessary to change the heating equipment during and after foaming to equipment that can heat at high temperatures and for long periods of time. The method used to produce the phenol foam has extremely poor workability. Furthermore, this phenol foam has problems in terms of physical properties, such as being brittle, having poor adhesion to iron plates, and having a high water absorption rate. The flame retardance of the structure using the carbohydrate-based foam is somewhat improved compared to the structure using the isocyanurate foam, but it is still not sufficient, and the flame retardance is further improved. If this happens, problems such as a decrease in strength (bending strength) and an increase in water absorption will occur.

In addition, with foams using carbohydrates (V!! quality) and phenol (resol type) foams, when the foam is immersed in water, the immersion water becomes acidic with a pH of 3 or less, which causes rust. has become a big problem.

[Problem to be solved by the invention]

An object of the present invention is to solve the problems of the prior art, and to obtain a foam and a flame-retardant structure that do not cause a decrease in the pH of the foam and have excellent flame retardancy. )
An object of the present invention is to provide a foaming resin composition using.

[Means to solve the problem]

The present invention relates to a foaming resin composition comprising an aqueous solution and/or slurry of carbohydrates having a fructose content of 85% by weight or more, a reaction catalyst, an isocyanate compound, and tris (monochloropropyl) phosphate, and a foaming resin composition comprising the foaming resin composition. The present invention relates to a foam obtained from a resin composition for use in a fire, and a flame-retardant structure comprising a flame-retardant or non-combustible plate or sheet provided on at least one side of the foam.

The saccharide used in the present invention has a fructose content of 85% by weight or more, preferably 90% by weight or more of the total saccharide. This is because if the fructose content is less than 85% by weight, the pH of the foam cannot be prevented from decreasing. Fructose generally has the advantage that it is more soluble and less likely to crystallize than other carbohydrates, is inexpensive, and has excellent flame retardancy.

Although fructose may be used alone in the aqueous solution and/or slurry of carbohydrates of the present invention, examples of carbohydrates other than fructose include glucose, xylose, mantos, etc. Sugar, malt PI (maltose),
Milk P! (lactose), sugar alcohols such as sorbitol, mannitol, arabitol, xylit, and glycosts such as methyl glycosts, I! Derivatives may also be used. These carbohydrates can be used alone or in combination of two or more.

Carbohydrates are used in the form of an aqueous solution and/or slurry, and the water content in this case is preferably 20% by weight or more, more preferably 25 to 30% by weight. If the water content is less than 20% by weight, the viscosity will be extremely high, or it will crystallize or become paste-like when taken orally.
Handling efficiency is extremely poor, and when using a foaming machine, problems such as inability to foam or clogging in the nozzle may occur.

Commercially available carbohydrates include Rep07 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
, 5F-A, L/Pos LF-A (100% by weight fructose aqueous solution, water content = 30% by weight), Suncraft 900 manufactured by Benbo Kogyo Co., Ltd. (9% by weight fructose aqueous solution, water content 25% by weight) %), etc. In addition, isomerized tM F-42, F-55 manufactured by Oji Cornstarch Co., Ltd., Suncraft 550 manufactured by HC1 Sanmatsu Kogyo Co., Ltd., etc., with a fructose content of 8
The content can also be adjusted to 5% by weight or more. For example, HC made by Oji Cornstarch is 1!55.9
% by weight, grape va 39.2% by weight and oligo 125
．． The mixture contains 1% by weight of fructose and has a water content of 24.5% by weight, but the mixture may be used by adjusting the fructose content to 85% by weight or more. In addition, Towa Kasei Kogyo Co., Ltd. (Tsurupit) D-70, Sorbit W-70 (aqueous solution of Sorbit), Xylit (solid), Mannitol P (
Sugar alcohols such as (solid), mannilla) S (solid), xylose XL (solid), Multi-Towa (reduced maltose aqueous solution), Po-Towa (reduced starch saccharide aqueous solution), Crysta (buto) manufactured by Benbo Kogyo Co., Ltd. sugar, solid), LG-85 (glucose aqueous solution), C! manufactured by Nissin Pharmaceutical Industries, Ltd. Sugar etc. can also be used. When using these, those commercially available in solid form are prepared in the form of an aqueous solution and/or slurry, and are used after 8 rounds so that 85% by weight or more is fructose. These cars J! Among these substances, fructose, high fructose sugar, sorbitol, xylit, or a mixture thereof are preferably used.

The isocyanate compound used in the present invention is not particularly limited, and examples thereof include monoisocyanate compounds such as phenyl isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, diphenylmethane-4,4' diisocyanate, rose phenylene diisocyanate, etc. Examples include diisocyanate compounds, triisocyanate compounds such as triphenylmethane-4,4'', 4''-triisocyanate, and low-molecular or high-molecular isocyanate-terminated prepolymers derived from these isocyanates.

Examples of reaction catalysts used in the present invention include tin compounds such as dibutyltin dilaurate and dibutyltin dioctoate, triethylamine, triethylenediamine, triethanolamine, 2-dimethylamino-2-methyl-1
- Amine compounds such as propatool, 2-amino-2-methyl-1-propatur, cobalt naphthenate, calcium naphthenate, copper naphthenate, manganese naphthenate,
Examples include organic metals such as dibutyltin dilaurate.

Tris (monochloropropyl) phosphate used in the present invention is used as a flame retardant, and can prevent the pH of the foam from decreasing and improve the brittleness of the foam. Examples of commercially available products include Anflame 3PX Boxui manufactured by NOF Corporation and Dolgat TMCP manufactured by Braun. In addition, organic flame retardants such as chlorinated paraffin and hexabromobenzene, and inorganic flame retardants such as antimony dioxide and aluminum hydroxide can also be used in combination with this flame retardant. The organic and inorganic flame retardants can be used alone or in combination.

A foam stabilizer such as a silicone polymer can be used in the foaming resin composition of the present invention, if necessary. As the M1 silicone polymer, L-5 manufactured by Nippon Unicar Co., Ltd.
20, L-540, L-5340, L-5350, L-
5410, L-5430, 190 manufactured by Dow Corning
, 191.193, 5H-193 manufactured by Rate Silicon Co., Ltd.
,5F2931.5H2933,5H-190,5RX
298 etc.

In addition, in order to improve workability by adjusting the viscosity of the composition and obtain a foam with a high expansion ratio, the composition may contain low-containing agents such as monofluorotrichloromethane and trifluorotrichloroethane. It is also possible to use boiling point solvents as blowing agents.

Commercially available products include Freon 11 (boiling point 23.8°C) and Freon 113 (boiling point 23.8°C) manufactured by DuPont Mitsui Fluorochemicals.
boiling point 47.6°C).

Furthermore, in order to improve the strength and flame retardance of the foam, inorganic fibers such as glass milled fibers, and organic fibers such as nylon and vinylon may be added to the composition for foaming.

Although a foam can be obtained using the foaming resin composition of the present invention, a structure including this foam can also be obtained. When building a structure, at least one side of the foam is provided with a flame-retardant or noncombustible plate or sheet. This board or sheet includes aluminum kraft paper, metal foil such as aluminum foil, copper foil, aluminum asbestos sheet, wood wool cement board, iron plate, steel plate, stainless steel plate, aluminum plate, copper plate, etc., slate plate, and metal foil such as copper foil. Inorganic noncombustible boards such as calcium acid boards, gypsum boards, cement boards, glass fiber reinforced cement boards, glass fiber reinforced plastic (FRP) boards, etc. are preferred.

These boards or sheets may be painted for appearance and corrosion prevention purposes. The material or thickness of the coating used for coating must be carefully considered so as not to reduce flame retardancy, but there are no particular restrictions on the material as long as the coating is thin. Moreover, a commercially available colored iron plate can also be used as a noncombustible plate.

Although there is no particular restriction on the blending ratio of each component in the foamable resin composition of the present invention, preferably (a) Carbohydrate M (fructose content 8
5% by weight or more) aqueous solution and/or slurry
~200 parts by weight, more preferably 50 to 150 parts by weight,
(b) The reaction catalyst is 0.1 to 5 parts by weight, more preferably 0
．． 5 to 4 parts by weight, (C) isocyanate compound is 50 to 4 parts by weight
200 parts by weight, more preferably 50 to 150 parts by weight, (
b) Tris (monochloropropyl) phosphate is 0
．． 1 to 1001 parts by weight, more preferably 5 to 50 parts by weight, and 0.1 to 5 parts by weight of a foam stabilizer added if necessary, more preferably 0.5 to 4 parts by weight.

From the viewpoint of workability, for example, (a) and (b)
It is possible to prepare a mixture of (C), (d), and (e) in advance, and then mix the two to react and foam.

There is no particular restriction on the reaction temperature during foaming, but it is between 10 and 50°C.
°C is preferred. There is also no particular limit to the number of rotations of the stirrer during mixing, but a rotary furnace of 1,000 to 7,000 rotations is preferred.

Although there are no particular limitations on the method for molding the foam or flame-retardant structure of the present invention, it is preferable to use a mold, and the molding is carried out, for example, as follows. First, a flame retardant or non-combustible plate or sheet is placed on the underside of a mold with an open top and a bottom, and this mold is heated to a temperature of 3.
Each material of the foaming resin composition that has been heated to 0°C to 60°C is stirred and mixed, and the mixture is poured into the mold. Next, a flame retardant or noncombustible board or sheet is provided,
And the preferred temperature to obtain a uniform foam is 30°C to 6
An upper mold that has been heated to 0° C. is placed on the plate or sheet with the side of the plate or sheet facing the solution mixture, the mold is clamped, and foaming is performed to obtain a structure in which the foam and the plate or sheet are in close contact with each other. Although the plate or sheet may be provided on either one or both sides of the foam, it is preferable to provide it on both sides to form a sandwich structure in order to improve flame retardant properties. In this case, the plates or sheets provided on both sides of the foam may be the same or a combination of different types.

〔Example〕

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

Example 1 Fruit I! 75 parts by weight, 25 parts by weight of tap water and 1.5 parts by weight of triethanolamine were added and mixed well to form a solution (A
) was obtained. In addition, diphenylmethane diisocyanate (trade name, Millionate MR-100 manufactured by Nippon Polyurethane Co., Ltd.)
) to 80 parts by weight, a foam stabilizer (trade name manufactured by Dow Corning Co., Ltd.,
1.0 parts by weight of foam stabilizer 190) and 20 parts by weight of flame retardant tris (monochloropropyl) phosphate (trade name, Anflame 3PX, manufactured by NOF Corporation) were added and mixed to obtain a solution (B).

Next, 150 parts by weight of solution (B) was added to 100 parts by weight of solution (^), stirred and mixed for 5 seconds in a rotary furnace with 5°000 rotation using a stirrer equipped with a turbine blade, and the mixture was kept at 40°C. A wooden mold with an open top and bottom (220mm x 2
20 am
A thickness of 15 mm) was obtained.

The density of the obtained foam was 0.030 g/c-.

2 g of this foam was immersed in 100 cc of ionized water in a bottle, and daily changes in the pH of the foam were measured by oral changes in the pH of the immersion water (0 days, 1 month, 2 months, 3 months, and 4 months). The results are shown in Table 1, and almost no decrease in pH was observed.

Also, the wooden mold (220sX 220mmX 15mm)
A colored iron plate (thickness: 0.27 mm) was placed on the bottom surface of the mold, the mold was heated to 40°C, and a mixture of 100 parts by weight of the solution (A) and 150 parts by weight of the solution (B) was poured into the mold. Pour it in, then paste and paste aluminum kraft paper on the top for 40 minutes.
Place the aluminum kraft paper on the upper mold heated to ℃, facing the solution, clamp the mold, and remove the mold after 10 minutes to form a foam (thickness 15
color iron plate (thickness 0.27+mn) on the surface of
A structure with aluminum kraft paper adhered to the back was obtained.

Using this structure, a quasi-noncombustible test was conducted based on Ministry of Construction Notification No. 1231, and the results are shown in Table 1. (perforation test).

Comparative Example 1 41.2 parts by weight of fructose, 30 parts by weight of glucose, Oligo 23
．． 8 parts by weight, 25 parts by weight of tap water and 1.5 parts by weight of triethanolamine were added and mixed well to obtain a solution (C).

Add 150 parts by weight of the solution (B) used in Example 1 to 100 parts by weight of the obtained solution (C), stir and mix for 5 seconds at 5,000 rpm with a stirrer equipped with turbine blades. A foam (thickness: 15 nm+m) and a structure were obtained in the same manner as in Example 1. The density of this foam is 0.031 g/c
It was +a. In addition, in the same manner as in Example 1, the pH of the foam was
A quasi-incombustibility test was conducted on the structure based on the oral change in the composition and the Ministry of Construction Notification No. 1231, and the results are shown in Table 1. The structure was as good as Example 1 in terms of external shape, afterflame, smoke generation coefficient, and temperature-time area after combustion, but the foam's p
H decreased to 2.8 after 4 months.

Comparative Example 2 80 parts by weight of diphenylmethane diisocyanate (trade name, Millionate MR-100, manufactured by Nippon Polyurethane Co., Ltd.) and 1 part by weight of a foam stabilizer (trade name, foam stabilizer 190, manufactured by Dow Corning Co., Ltd.)
．． 0 parts by weight and 20 parts by weight of flame retardant tris(2-chloroethyl)phosphate were added and mixed to obtain a solution (D).

Add 150 parts by weight of this solution (D) to the solution used in Example 1 (
A) 100 parts by weight was added and stirred and mixed for 5 seconds at 5,000 rpm using a stirrer equipped with a turbine blade, and the same procedure as in Example 1 was carried out to obtain a foam (thickness: 15 mm). The density of this foam was 0.0.30 g/cd. In addition, in the same manner as in Example 1, the oral change in pH of the foam and the semi-flammability test of the structure based on Ministry of Construction Notification No. 1231 were conducted, and the results are shown in Table 1. The structure was similar to Example 1 in terms of external shape, afterflame, smoke generation coefficient, and temperature/time area after combustion.
However, the pH of the foam was 3 after 4 months.
．． It had dropped to 0.

Comparative Example 3 Heteroform 28264 (polyol, Hooker Company product name) 21.1 parts by weight, Heteroform 29696
(Polyol, product name manufactured by Hooker Company) 23.5 parts by weight, DC-193 (foam stabilizer, product name manufactured by Dow Corning Company)
1 part by weight, Polycat 41 (catalyst, trade name manufactured by Sun Abbott), 1.42 parts by weight, and Freon 11 (blowing agent,
Add 101 parts by weight of Isonate 580 (isocyanate compound, trade name manufactured by Amp John Company) to a solution containing 25 parts by weight (trade name manufactured by DuPont Mitsui Fluorochemical Co., Ltd.),
5 at 2,000 rpm with a stirrer with turbine blades
The mixture was stirred and mixed for seconds, and the same procedure as in Example 1 was carried out to obtain an isocyanurate foam (thickness: 15 mm) and a structure.

The density of this foam was 0.035 g/cd. Although the pH of the foam did not decrease after 4 months, the appearance of the structure changed significantly after burning, most of the foam was burned out, and the smoke coefficient and temperature/time area were significantly inferior. was.

Comparative Example 4 Danphenon 110B curing agent ( Hodogaya Chemical Co., Ltd. (product name) 40 parts by weight and Danphenone 1
A solution containing 15 parts by weight of 0C (isocyanate, trade name manufactured by Hodogaya Chemical Co., Ltd.) was added, and the mixture was stirred and mixed for 5 seconds at 2,000 rpm with a stirrer equipped with a turbine blade, and the same procedure as in Example 1 was carried out. Phenolic foam (thickness 15aa)
and got the structure. In addition, since the phenol foam has significantly poor curing properties, after-curing was performed at 100°C for 30 minutes. The density of this foam was 0.04 g/ail. The pH of the foam was acidic at 3.1 and after 4 months the pH decreased to 2.4.

Furthermore, since flyability (chipping) occurred on the surface of the phenol foam, the adhesion between the foam and the aluminum craft paper and the colored iron plate was poor. Furthermore, although the appearance of the structure after combustion was good, the afterflame was long (inferior).

〔Effect of the invention〕

According to the foaming resin composition of the present invention, it is possible to obtain a foam and a flame-retardant structure that do not have a drop in pH and have excellent flame-retardant properties, so there are no problems such as rust formation, and Can pass the Ministry of Construction Announcement No. 1372 Model Box Test.

Claims (1)

[Claims] 1. A foaming resin composition comprising an aqueous solution and/or slurry of carbohydrates with a fructose content of 85% by weight or more, a reaction catalyst, an isocyanate compound, and tris (monochloropropyl) phosphate. thing. 2. The foaming resin composition according to claim 1, wherein the water content of the aqueous solution and/or slurry of carbohydrates is 20% by weight or more. 3. A foam obtained from the foaming resin composition according to claim 1 or 2. 4. A flame-retardant structure obtained by providing a flame-retardant or non-flammable plate or sheet on at least one side of a foam obtained from the foamable resin composition according to claim 1 or 2.