JPS6189280A - Flame-retardant sealing material composition - Google Patents

Abstract

PURPOSE:The titled industrially useful composition having improved filler dispersibility, thixotropic properties, and weather resistance, comprising a high polymer substrate, a flame-retardance imparting filler, a specific fatty acid and polyether as essential components. CONSTITUTION:(A) A high polymer substance is blended with (B) a flame- retardance imparting filler (e.g., alumina, aluminum hydroxide, or antimony trioxide), (C) (i) 6-22C fatty acid alkanol amide or an adduct of it with an alkylene oxide, and (ii) a polyether compound, an adduct of a compound (e.g., polyethyleneimine) containing >=3 active hydrogens with an alkylene oxide, containing 0-80wt%, preferably 3-40wt% oxyethylene group based on total molecular weight, having 1,000-1,000,000 molecular weight, as essential components, to give the aimed composition. A weight ratio of the component i/B is preferably 3/7-7/3.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a flame-retardant sealant composition, and more particularly to a flame-retardant sealant composition using a flame-retardant filler as a filler.

[Conventional technology]

Sealing materials are used in mechanical, electrical, chemical, and other various industries for the purpose of making joints and contact areas watertight and airtight. The base material for this sealant is rubber,
Including plastics, leather, hemp, asbestos, asphalt,
Although there are metals, the present invention is mainly directed to elastic, irregularly shaped or molded sealing materials mainly made of rubber or plastic.

In recent years, flame retardant properties have been required for building materials and interior items, and sealing materials are no exception.

Many studies have been conducted over the past ten years regarding general flame retardancy, including methods of adding halogen- and phosphorus-containing compounds, as well as alumina, aluminum hydroxide, trioxide, etc., as shown in Japanese Patent Publication No. 45-263. A method of filling with an inorganic filler typified by antimony has been proposed.

However, making flame retardant sealants poses a very difficult problem that is different from other fields. In other words, in addition to the ease of dispersion of the flame retardant added to the sealant into the polymer base material, the sealant also requires good thixotropy to prevent sagging when applied as a sealant, and excellent weather resistance. is required. However, when inorganic fillers such as alumina, aluminum hydroxide, and antimony trioxide are used as the flame retardant, it is difficult to obtain a sealing material that satisfies all of the above properties.

In other words, in order to satisfy the above properties, for example, even if higher fatty acids and higher fatty acid salts, which have been conventionally used as surface modifiers for inorganic fillers, are used in combination, easy dispersibility, thixotropy, and weather resistance are sufficient. Furthermore, when an alkanolamide of fatty acid or its alkylene oxide adduct as shown in Japanese Patent Publication No. 56-45424 is used in combination, easy dispersibility can be obtained, but thixotropy and There were problems such as insufficient weather resistance, sagging during construction, and cracking when exposed to the sun and exposed to high temperatures.

[Problem that the invention seeks to solve]

This invention solves the problem that it is difficult to satisfy the dispersibility of the filler, as well as thixotropy and weather resistance with a sealant containing a flame-retardant filler as described above. The purpose of the present invention is to obtain a sealant composition that provides a suitable sealant composition.

[Means for solving problems]

As a result of intensive studies to achieve the above object, the inventors have decided to mix a specific polyether compound with the alkanolamide of fatty acid or its alkylene oxide adduct as an additive to be used in combination with the flame retardant filler. The present invention was completed based on the knowledge that the above-mentioned problems could be successfully solved when used in this manner.

That is, the present invention relates to a v1 flammable sealing material composition which contains a polymeric base material, a flammability-imparting filler, and an additive consisting of the following components A and B as essential components.

A) Pulkaroo, a fatty acid with 6 to 22 carbon atoms? mido or its alkylene oxide adduct.

B) An alkylene oxide adduct of a compound having 3 or more active hydrogen atoms, with oxyethylene groups ranging from 0 to 0 in the total molecular weight.
A polyether compound containing 80% by weight and having a molecular weight of 1,000 to 1,000,000.

[Structure and operation of the invention]

Component A in the additive of this invention includes caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, oleic acid, linoleic acid,
These mixtures include coconut oil fatty acids, palm oil fatty acids,
monoethanolamides of straight or branched, saturated or unsaturated fatty acids having 6 to 22 carbon atoms, such as beef tallow fatty acids, hydrogenated beef tallow fatty acids, fish oil fatty acids, soybean oil fatty acids, rapeseed oil fatty acids, safflower oil fatty acids; These are alkanolamides such as jetanolamide, monoisopropanolamide, diisopropanolamide, and aminoethylethanolamide, and their alkylene oxide adducts such as ethylene oxide, propylene oxide, butylene oxide, and styrene oxide.

In the case of an alkylene oxide adduct, the number of moles added and the type of alkylene oxide are selected depending on the type of flame-retardant inorganic filler and the type of polymer base material. The number of moles added is generally preferably 200 moles or less per mole of alkanolamide, and if it exceeds 200 moles, the wetting and dispersibility of the flame-retardant inorganic filler to the polymer base material will deteriorate.

Two or more alkylene oxides may be added,
Further, they may be added randomly or in blocks, and the order of addition does not matter. A particularly preferred adduct is a propylene oxide single adduct or a co-adduct of propylene oxide and ethylene oxide, and the ratio of propylene oxide to ethylene oxide in the latter co-adduct is selected such that the ratio of propylene oxide to ethylene oxide is such that the HLB is soluble in the polymeric substrate. be done.

Component B in the additive of this invention is a polyether compound which is an alkylene oxide adduct of a compound having three or more active hydrogens, and the compounds having three or more active hydrogens include hydroxy compounds, nitrogen compounds, etc. ,
There are carboxy compounds, etc.

Examples of hydroxy compounds include glycerin, butanetriol, hexanetriol, trimethylolpropane, triethanolamine, diglycerin, pentaerythritol, sorbitol, sorbitan, glucose, sucrose, partially saponified vinyl acetate (co)polymer, polyglycerin , cellulose, starch, etc., as well as derivatives such as partially esterified products and etherified products of polyhydric alcohols, as long as they have 3 or more active hydrogen atoms remaining. Further, any formaldehyde condensate of phenol may be used as long as it has three or more hydroxy groups.

Examples of nitrogen compounds include ammonia, ethylenediamine, N-F decylethylenediamine, propylenediamine, N-octadecylpropylenediamine, tetramethylenediamine, hexamethylenediamine, phenylenediamine, benzidine, cyclohexyldiamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentaamine. In addition to mine, polyethyleneimine, etc.
Various derivatives such as fatty acid partial amides of amines having four or more active hydrogens may be used as long as three or more active hydrogens remain.

Examples of carboxy compounds include hemimellitic acid,
In addition to trimellitic acid, butanetetracarboxylic acid, pyromellitic acid, acrylic acid (co)polymer, methacrylic acid (co)polymer, maleic acid (co)polymer, etc., maleic anhydride (co)polymer part Any amidated product or partially esterified product with three or more remaining active hydrogen atoms may be used.

Among the above, nitrogen compounds are particularly preferred, and among these, polyethyleneimine is also preferred.

The reason for this is that the polyether compound, which is more exclusive thereto, has a strong affinity for inorganic fillers. The reason why a compound having three or more active hydrogens as described above is used as a starting material for obtaining component B is that the molecular structure of the polyether compound obtained from this becomes bulky, so an appropriate barrier between the filler particles is used. This is because a preferable thixotropic property can be obtained.

Component B is produced by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or styrene oxide to a compound having three or more of these active hydrogens, generally under pressure using a catalyst such as an alkali or acid. Of these, the content of ethylene oxide groups is 0 to 80% of the molecular weight of the final polyether compound.
% by weight, preferably 3-40% by weight, and its molecular weight is 1,000-1,000,000, preferably 7,000-1,000,000.
It is 600,000. If the ethylene oxide content and molecular weight are outside the above ranges, it is difficult to obtain good results in terms of thixotropy and weather resistance.

In addition, when the above-mentioned B component is a co-adduct of ethylene oxide and other alkylene oxide, it may be a random adduct or a block adduct, and the order of addition is not limited.
A block adduct in which ethylene oxide is added to the end is preferred.

In this invention, it is important to mix and use the above-mentioned components A and B. In other words, when only component A is used, the filler has good wettability or dispersibility in the polymer base material, but thixotropic properties cannot be obtained, and when only component B is used, the wettability or dispersibility is poor, and both are poor. Satisfactory wettability or dispersibility as well as thixotropy can be obtained only when used in combination.

In addition, the flame-retardant sealant composition of the present invention has excellent weather resistance and does not cause cracks after application, but this is because the filler is wetted with the polymer base material by component A. In addition, because component B imparts thixotropy, that is, component B makes the filler particles in a chain-like agglomerated state, there is almost no separation of the filler particles in the polymer base material, and therefore the process is carried out in a homogeneous state. This is thought to be due to the fact that the strain can be reduced.

The mixing ratio of the above-mentioned A component and B component in order to exhibit such an effect is such that the weight ratio of A component/B component is 1/
The ratio should be 9 to 9/l, preferably 3/7 to 7/3. If the amount of either one is too little or too much, the above effects cannot be sufficiently obtained.

In the composition of the present invention, the amount of the additive consisting of the above-mentioned A component and B component is as follows: flame retardant filler 1
The amount is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

If it is less than 0.1 part by weight, the wettability and thixotropy of the filler will be insufficient, and if it is more than 20 parts by weight, the strength as a sealing material will be weakened, which is not preferable.

As the polymeric base material constituting this invention, a polymeric substance capable of providing an elastic amorphous or molded sealing material is preferably used. For example, polysulfide, silicone,
Polyurethane, chlorosulfonated polyethylene, acrylic rubber, butyl rubber, butadiene rubber, epoxy rubber, etc. Also, polyvinyl chloride, chloroprene rubber, butyl rubber, silicone rubber, chlorosulfonated polyethylene, SBR, NR, etc. for elastic molded sealing materials.
Examples include EPR and polyurethane.

゛ As the flame retardant filler, alumina, aluminum hydroxide, and antimony dioxide are preferable, and those having an average particle size of usually 0.1 to 10 #m, preferably about 1 μm are used. The amount of this filler used is 1
5 to 150 parts by weight per 00 parts by weight, preferably 20 to 150 parts by weight
The amount is preferably 100 parts by weight.

The flame-retardant sealant composition of the present invention includes the above-described polymer base material, the flame-retardant filler, and the components A and B.
The additives consisting of these ingredients are essential ingredients, but optional ingredients such as talc and other inorganic fillers, plasticizers, colorants, curing rate regulators, curing catalysts, etc. can be added as necessary to suit their performance as a sealant. It can be contained as appropriate within the range of usage amount.

In preparing the above-mentioned composition of the present invention, methods for mixing the polymeric base material, filler, and additives consisting of component A and component B include (1) a method of mixing the two components simultaneously; (2) a method of mixing the filler in advance; Any method may be used, such as (3) mixing the additive and the polymer base material in advance, and then mixing the filler with the polymer base material. I can do it. Use a tumbler when mixing.

It is preferable to mix thoroughly using a kneader or homo mixer.

〔Effect of the invention〕

As described above, in this invention, alkanolamide of fatty acid or its alkylene oxide adduct as component A and a specific polyether compound as component B are used together as additives to be used in combination with the flame retardant filler. Accordingly, it is possible to provide a flame-retardant sealing material composition in which the filler has good dispersibility and is also excellent in thixotropy and weather resistance.

〔Example〕

Examples of the present invention will be described below along with comparative examples.

In addition, in the following, parts shall mean parts by weight. Further, the additives used in the following Examples and Comparative Examples are as shown in Tables 1 to 3 below.

Table 1 Notes: 1) EO is an ethylene oxide adduct, PO is a propylene oxide (fi, and the parentheses indicate its addition monomer. Co-adducts indicate block adducts in that order. Table 3 Characteristic evaluations of the following Examples and Comparative Examples were conducted using the following method.

Dispersibility> The dispersibility of the filler was determined using a grind gauge, and the dispersibility of the filler was evaluated according to the 5-point method of 5.4 and 3.2.1 in descending order of favorable.

Thixotropy> The sealant composition was applied to a semi-cylindrical shape with a radius of 51mm and a length of 100mm on a steel plate, and the sample was held vertically at 24mm.
5.4. Measure the length of dripping after a certain amount of time and rank it in descending order of dripping.
Evaluation was made using the 5-point method in 3.2.1.

Weather resistance> The sealant composition was applied to a steel plate to a thickness of 21111 mm, and left in the summer room of the weather meter for 30 days, and in each room for 30 days in a horizontal position, and then checked for cracks. We conducted a three-point evaluation with 3 being not at all, 2 being a little bit, and 1 being a lot.

Example 1 100 parts of vinyl chloride resin, 50 parts of aluminum hydroxide powder with an average particle size of 1 μm as a filler, 80 parts of dioctyl phthalate as a plasticizer, and 2 parts of the additive according to the present invention shown in Table 3 above. These were mixed for 30 minutes using a Ni-Goo to produce 10 types of elastic type Id retardant sealant compositions.

Comparative Example 1 As additives, in addition to component A shown in Table 1 above and component B shown in Table 2 above, stearic acid (additive N12
7) Fourteen types of elastic flame-retardant sealant compositions were produced in the same manner as in Example 1, except that the same amounts of sodium stearate (additive Na28) were used.

The characteristics of each composition of Example 1 and Comparative Example 1 were evaluated, and the results were as shown in Table 4 below.

Table 4 Example 2 100 parts of butadiene rubber, 60 parts of alumina powder with an average particle size of 0.8 μm as a filler, and the third
The additives according to the present invention shown in the table were added to the above alumina powder 10.
They were used at a ratio of 0 parts to 5 parts, and mixed for 30 minutes in a Ni-Goo to produce four types of elastic flame-retardant sealant compositions.

Comparative Example 2 In addition to the additives shown in Table 1 above, component A shown in Table 2, and component B shown in Table 2 shown in Table 2, the same amount of stearic acid as Additive 27 was used as in Example 2. Five kinds of elastic flame-retardant sealant compositions were produced in the same manner as in Example 2.

The characteristics of each of the compositions of Example 2 and Comparative Example 2 were evaluated, and the results were as shown in Table 5 below.

Table 5 Example 3 100 parts of acrylic rubber, average particle size 1 as filler
．． 70 parts of 2 μm antimony trioxide powder and the additives according to the invention shown in Table 3 above were used in a ratio of 5 parts per 100 parts of antimony dioxide powder, and these were mixed in a Nigu for 30 minutes to form an elastic mold. Three types of flame-retardant sealant compositions were manufactured.

Comparative Example 3 The same amount as in Example 3 was used, except that the additives A component alone shown in Table 1, B component alone shown in Table 2, and sodium stearate (Na28) were used in the same amounts as in Example 3. Five types of elastic flame-retardant sealant compositions were produced in the same manner as in Example 3.

The characteristics of each of the compositions of Example 3 and Comparative Example 3 were evaluated, and the results were as shown in Table 6 below.

As is clear from the results in Tables 6 and above and Tables 4 to 6, the Hm sealant composition containing the additive according to the present invention has better R'l properties than the comparative example. It is clear that it has thixotropic properties and is also excellent in weather resistance. Note that all of the above sealing material compositions of the present invention exhibited flame retardancy as expected.

Claims (8)

[Claims] (1) Polymer base material, flame retardant filler and the following A
A flame-retardant sealant composition containing as an essential component an additive consisting of Component B and Component B. A) Alkanolamide of a fatty acid having 6 to 22 carbon atoms or an alkylene oxide adduct thereof. B) An alkylene oxide adduct of a compound having 3 or more active hydrogen atoms, with oxyethylene groups ranging from 0 to 0 in the total molecular weight.
A polyether compound containing 80% by weight and having a molecular weight of 1,000 to 1,000,000. (2) The flame-retardant sealant composition according to claim (1), wherein the polymeric base material is a polymeric substance capable of imparting an elastic, amorphous or molded sealant. (3) The flame-retardant sealant composition according to claim (1) or (2), wherein the flame-retardant filler is alumina and/or aluminum hydroxide. (4) The flame-retardant sealing material composition according to claim (1) or (2), wherein the flame-retardant filler is antimony trioxide. (5) Claims (1) to (4) in which the compound having three or more active hydrogens in component B is a nitrogen compound.
The flame-retardant sealant composition according to any one of Items 1-2. (6) The flame-retardant sealant composition according to claim (5), wherein the nitrogen compound is polyethyleneimine. (7) The ratio of A component to B component is 1/9 to 9/9 by weight.
1. The flame-retardant sealant composition according to any one of claims (1) to (6). (8) The flame retardant filler is 5 to 150 parts by weight per 100 parts by weight of the polymer base material, and the additive consisting of component A and B is 0.1 to 2 parts by weight per 100 parts by weight of the flame retardant filler.
The flame retardant sealant composition according to any one of claims (1) to (7), which contains 0 parts by weight.