JPS5962641A - Thermoplastic resin foam - Google Patents

Abstract

PURPOSE:A thermoplastic resin foam causing no drip during burning, having improved shape retention of combustion part, and flame retardance, comprising a composition obtained by blending a thermoplastic resin with a brominated epoxy resin of bisphenol A in such a way that a specific bromine content is attained. CONSTITUTION:A thermoplastic resin (e.g., polyolefin resin, etc.) is blended with a brominated epoxy resin of bisphenol A in such a way that the brominated epoxy resin of bisphenol A gives >=2.0wt%, preferably >=4.0wt% bromine content based on a foam, the blend is mixed with a blowing agent (e.g., azodicarbonamide, etc.), and, if necessary, flame-retardant auxiliary, inorganic filler, chemical crosslinking agent, etc., molded into a sheet, crosslinked, and heated, to give the desired thermoplastic resin foam. USE:A heat insulating ceiling material, floor covering, wall material, etc.

Description

[Detailed description of the invention] The present invention relates to a thermoplastic resin foam having poor flammability.

Do you care in general? Plastic resin foams are inexpensive, lightweight, and have excellent heat insulation, water resistance, and sound absorption and insulation properties, so they are widely used as thermal materials, insulation materials, cushioning materials, etc. talented.

Particularly in recent years, thermoplastic resin foams have come to be used in the field of construction materials, etc., taking advantage of these excellent properties, but thermoplastic resin foams inherently have the disadvantage of being easily flammable.

Applications are severely restricted. Therefore, various flame-retardant thermoplastic resin foams have been proposed. Among them, it is known that halogenated aromatic compounds such as hexabromobenzene and decazlomodiphenyl ether combined with glue 11 (combustion aid) such as antimony trioxide exhibit excellent flame retardancy.

It has been put into practical use.

However, such a combustible, biothermal, plastic, bioresin foam has the following drawbacks.

In other words, the plastic resin foam softens and melts during combustion, and the burning part drips, i.e., melts and drips, so that the body itself r, I: combustion is completely suppressed. On the other hand, there was a drawback that other lumber 1 was burnt due to this dripping combustion part.

The object of the present invention is to overcome the two drawbacks and to provide a thermoplastic resin foam that produces less dripping during combustion and has excellent shape retention and flame retardancy in the combustion part. .

The present invention has the following configuration to achieve the above object.

That is, it is a foam that is entirely composed of a composition in which a bisphenol A-based brominated epoxy resin is mixed with a thermoplastic 1 raw resin, and the bromine content in the bisphenol A-based brominated epoxy resin is The thermoplastic resin foam sound 71Q, which is placed on a 20 weight plate against the body, is a characteristic.

In the present invention, the thermoplastic 1' and resin enveloping means
It is a foamed body made of a plastic resin, preferably a foamed body made of a thermoplastic l'1.g Jffl resin, which has a closed cell structure with a uniform tit and a finely divided cell structure.

The thermal iiJ plastic resin in the invention refers to polyolefin, polyneedle such as polyacecool, ItBS(i
17. Polyamide resins and other well-known thermally plastic resins, among them polyethylene.

Polyolefin resins such as Borizo'nopylene-(j) are most preferred.

Polyolefin-based 41) fats specifically include homopolymers such as ethylene, propylene, a-olenoin such as butene-1,4-methylpentene-1, copolymers of these, kirani, and these. Monomer.

For example, copolymers obtained from monomer mixtures of one or more of vinyl compounds such as vinyl acetate and acrylic esters, conjugated gene compounds such as butadiene and isoprene, and the above-mentioned polymers are substantially Thermal IIJ Plastic 11-Resin Silk Compound ke which is the main component.

In the present invention, bisphenol A-based bromine dehydrogenation/resin and u:, evoquine equivalent is 200 to 1000°, molecular weight is 4
00-4000, all of them.

It is 111 soluble in bath agents such as acetone and methyl ethyl ketone. Q; 11. As a specific commercially available product. I, 1', Yuhigaku 1-0 work "d unmade pasumi ebogi/"+j; r+n
-540,40U.

500.700 or Tau Rimical? 1° sea bream, l)
li', R-511,542, etc., Kirani Soel Chemical 6
1: Manufactured by, 1045-B-80, DX-248-B-80
etc.

The heat ii J plastic f11 of the present invention:,) rll in the iγ・1 resin foam, the above-mentioned bisphenol A-based bromine f hieboxyl resin is added to the foam at a bromine content of 2.0 rf amount%
As mentioned above, it is necessary to include 40 or more vehicle volume factors.

If the bromine content of the hisphenol A-based brominated epoxy resin is less than 2% by weight of the foam, the shape retention due to carbonization will be insufficient when the foam is burned, and drip will occur, so it will not be heavy. T, r, y+ if you are more than a double counter! At the time of firing, the carbonization of the raw resin is promoted and the shape jj1. ', Close! -, i・l The number of cows increases, so the trip phenomenon no longer occurs. Ma / (-, Hisphenol A-based brominated epoxy resin is emitted?
If you try to maintain the shape of combustion 11.5, 1/I will become even more stable, and become self-extinguishing.

Bisphenol Δ-based brominated epoxy 1) Lipid white ↓
11+J゛ has a high percentage of iris, but not 1%, but 2 people with a high percentage of iris, preferably 40% or more by weight. j - Hf L.

1.・Bisphenol Δ-based phosphorized epoxy resin rat2., which is useful for heat 1 plastic 1'L resin. The higher the amount of bromine added, the higher the bromine content, which is preferable because it increases the flame retardancy. , other problems may occur in the manufacturing process of the body, the quality of the foam, etc.
It is desirable that the amount of the brominated epoxy resin added is less than 70 lbs.

One original i1 store of Honzushiki +411 (τ(・;11. Part 1
Mountain ((for two purposes, fi=, 7℃-' oxidized anti-sulfur, etc.);

Phosphorus compound/soutan song expansion p! If + combustion, 7N et al. Carbonic power Luciuno,.

Activity of glue, talc, aluminum chloride, barium sulfate, titanium oxide, etc.;
material filling and heat stabilizer, 1 weather control agent, 1 town plastic agent, t'j
Jirll:j; yj may be combined depending on necessity) []shi. The amount of inorganic filler added is -1.

Hysuphenol A series ebogishi is ranked January and (+ ()).

There were no problems with extrusion 1-1-, sheet formability, cross-linking 1<1-U, older brother 111- etc.
I'1gri ratio total wholesale], 1゛ possible range, J
-1 In terms of wood; 1,1jlj 1 amount of the joint agent and hisphenol A-based epoxy resin is 70% 1ii,
% or less. In addition, other substances (stabilizers, etc.) can be added as necessary.

Next, a method for manufacturing the thermoplastic 141 resin body of the present invention will be explained.

Thermoplastic resin contains bromine in the foam when it becomes a bisphenol Δ-based brominated ebogi/1 fat full foam surface]
1 part by weight of azodicarbonamide, for example, in an amount such that the ratio is 2% by weight or more; Foaming/
The total amount included in 10 parts by weight of IIJ is 110 ili
'L'', add so that it becomes 7'tli.

To mix the resin to which these additives have been added, a conventional mixer such as a hot roll, kneader, Panbury mixer, etc. can be used. In addition, the mixture of (and) may be pelletized using an extruder to form chips.

In this way, all the ingredients of the composition are well kneaded.

The entire extruded sheet is formed using a melt extruder.

This sheet is crosslinked using deuteron beam irradiation, a crosslinking agent, or the like.

Usually, cross-linking is carried out by the method using Tsuki peroxide or 'r [Jin1gyu radiation g! A method of irradiation is used.

Examples of organic peroxides include dicumyl peroxide, dicumyl peroxide, 1,5-bis(tert-butylperoxyisopropyl)benzene,
,4-tertiarybutyl peroxyvalerintll
n-Butyl ester, 1,1-ditertibutylperoxy-5,,S, 5-l-limethylchlorohexane, α,α'-bis(tert-butylperoxy)-
■]-Diisopropylbenzene.

2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-6 and the like are used in an amount of 1 to 15 parts by weight per 100 parts by weight of 9 resin acid. Suitable crosslinking conditions are a temperature of 140 to 200'a and a time of 1 to 50 minutes.

In the case of FW dissociative radiation crosslinking, as a high energy beam,
Although there are Cl rays, β rays, γ rays, X rays, accelerated proton beams, electron beams, and 1-ion beams, high-ray and Lugy electron beam irradiators are generally used. For example, 1 to 5 on a molded notebook.
Crosslinking is achieved by irradiation with a dose of 0 Mra, cl.

When the crosslinked sheet la thus obtained is heated in a hot air atmosphere or on a salt bath, one blowing agent is rapidly decomposed and the desired foam is formed.

As described above, the present invention includes a specific amount or more of bisphenol A-based brominated epoxy resin in a thermal 111J plastic resin foam, thereby promoting carbonization during combustion and reducing secondary throat ambiguity. The sound effect is what I was able to do, ie.

(11 Form protection) - 〒 completely prevents dripping in the burning part and prevents the spread of fire.

(2) Because carbonization is paralleled, the product of the present invention exhibits a high degree of flammability among the usual uses of thermoplastic resin foams. Suitable for necessary insulation purposes; Il = R, flooring, wall insulation, etc.

The measurement method and evaluation criteria in the present invention are as follows.

(1) Bromine content: Take a certain amount of the entire foam and weigh it accurately. The sample is decomposed using the flask combustion method, and the absorbed liquid is subjected to potential titration with a silver nitrate solution using a silver electrode. The amount of bromine was determined from this titration curve and the maximum amount of bromine contained in the two foams was calculated.

(2) Drip 1"2 and shape retention A combustion test of a sample held horizontally revealed that the extent to which the burnt part decreases by 7 quotients (t' 1.1 Tubularity) and the extent to which it softens (shape retention) are as follows. It is shown on the basis of i.

A: No dripping and great shape retention.

It does drip B, but it's relatively small, and the form is 4-end.'' 1JU:, L, medium speed.

There is a lot of C Ni drip, and there is no form 1 stupor 1 life.

(3) Carbon production amount After extinguishing the fire, the entire charring state of the burnt part was observed.

Judgment was made in the following 6 stages.

Thick: The amount of carbon produced in the combustion part is large and the shape is maintained.

The part of the inside that is about to drip is round and hard and partially carbonized.

There are almost no small carbonized parts.

(4) Flammability A combustion test was conducted in accordance with ASTM D1692-59TK, and one song was performed at six levels of flame retardancy.

◎: Self-extinguishing fishing - Although it burns in the flame of a Bunsen burner,
A state that disappears immediately when the flame is favored.

○: A state where the flame disappears within 6 seconds after releasing the flame.

△: The flame of the Bunsen burner does not disappear within 6 seconds even when released.

Next, the embodiments of the present invention will be fully explained based on Examples.

Example 1 Low density polyethylene (Mitsui Petrochemical, Mirason≠16
) 9 o rlj ff (l) 10 parts by weight of gsB-400 (manufactured by Sumitomo Chemical, bromine content 46-50 stacked plate) as a bisphenol A-based brominated epoxy resin and 10 parts by weight of azodicarbonamide as a blowing agent. After thoroughly mixing with a Henschel mixer, the mixture was pelletized using a 301111nφ twin-screw extrusion (using a top metal).

This berent? The raw material was melt-extruded at 5°C using a 60-dish φ extruder to obtain a sheet 14 having a thickness of 1.6 mm.

Crosslinking was carried out using this sheet laminate beam irradiation device under 5 Mrad illumination.

A polyethylene foam was obtained by heating and foaming this crosslinked sheet i220 in an O salt solution.

The density of this foam was 0.050 g/cm''.

The characteristic sound of this foam was investigated and the results are shown in Table 1, Example 1. Although it burned in the flame of a Bunsen burner, it extinguished immediately when the flame was removed after ignition, showing self-extinguishing properties. Also, no drip phenomenon was observed during combustion.

After extinguishing the fire, the combustion part produces a large amount of carbon and retains its shape well.

Examples 2-5. Comparative Examples 1 to 4 Polyethylene, bisphenol A-based brominated epoxy tree + 1 i't, flame retardant (decabromodiphenyl ether, hexabromobenzene), mlAl combustion aid (antimony trioxide), inorganic filler (aluminum oxide) All Table 1 A polyethylene foam was obtained by molding, crosslinking and foaming in the same manner as in Example 1 except that the resin composition was used in the proportions shown in .

The characteristic sound of this foam was investigated and the results are shown in Table 1. In Examples 3 to 5, the 1 bromine content was 4.0 overlapping plates or more,
It didn't drip at all. It produced a large amount of carbon, had good shape retention, and was self-extinguishing.

In Example 2, the bromine content due to the addition of bisphenol A-based brominated epoxy resin was 2.2% by weight, and the shape retention was slightly inferior compared to Examples 3 to 5, and the flammability was not self-extinguishing. 9 The objectives of the present invention have been achieved.

On the other hand, in Comparative Example 1, the amount of bisphenol A-based brominated epoxy resin added was small and did not meet the requirements of the present invention, so dripping could not be prevented.

In Comparative Examples 2 to 4, a commonly used brominated flame retardant and an inorganic filler were used in place of the bisphenol A-based brominated epoxy resin, but bromine-containing]
The difference between this rod and the present invention is clear in that it does not exhibit shape retention even though it has a weight ratio of 14 to 15 even though it is a board for placing people.

As described in detail below, it is clear that according to the present invention, the drip phenomenon during combustion is completely suppressed and the foam exhibits a high degree of flame retardancy.

Claims (1)

[Claims] (1) Is the composition based entirely on a mixture of thermal 1υ plastic resin and bisphenol A-based brominated epoxy resin? and the bromine content J ratio in the bisphenol A-based brominated epoxy/resin is 2.0 weight Mis with respect to the foam.
Thermoplastic resin foam having a content of not less than 2%.