JPH06240084A - Molding composition - Google Patents

Abstract

PURPOSE:To obtain a composition giving a molding which lowly deforms even when exposed to very high temperature conditions in, e.g. a fire and has good shape retention and excellent fireproofness. CONSTITUTION:This molding composition is prepared by mixing a composition comprising 5-60wt.% organic component based on a vinyl chloride resin and an inorganic component containing a metal sulfate with an organic or inorganic crosslinking agent which can crosslink the vinyl chloride resin at high temperatures.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition of a molding which exhibits an excellent deformation suppressing effect at high temperature and a smoke suppressing effect at the time of combustion, and a molding composition for obtaining the molding.

[0002]

2. Description of the Related Art Since resin materials have excellent moldability, they are widely used as materials for obtaining molded products of various shapes. However, in general, most resin-based materials are flammable and disappear at high temperatures such as in a fire and the shape of the molded article cannot be retained. In addition, even if the resin-based material itself is flame-retardant,
Since the thermoplastic resin has fluidity at a temperature equal to or higher than the melting point or equal to or higher than the softening point, the molded product is likely to be significantly deformed at a high temperature. As described above, since the resin-based material is inferior in fire resistance, the range of use is limited in the construction field.

[0003]

Conventionally, in a molded article of a composition obtained by blending a thermoplastic resin material with an inorganic filler,
It was difficult to prevent the flow of the resin at high temperature and suppress the deformation of the molded product. That is, the thermoplastic resin has fluidity at a temperature equal to or higher than the softening point, so that the inorganic filler dispersed in the resin also flows with it. As a result, the molded product is significantly deformed and its shape is lost. In addition, smoke is likely to be generated during a fire, and it is often necessary to suppress it.

[0004]

DISCLOSURE OF THE INVENTION The present invention is the following invention relating to a molded article capable of preventing the flow of a resin at high temperature to suppress deformation and at the same time suppress smoke generation during combustion.

5 to 60% by weight of organic component and 4 of inorganic component
A molding composition comprising 0 to 95% by weight or a molding composition for obtaining the same, comprising: an organic component containing a vinyl chloride resin as a main component; an inorganic component containing a metal sulfate; A composition comprising an organic or inorganic cross-linking agent capable of cross-linking a vinyl polymer.

In the present invention, the organic component is mainly composed of a vinyl chloride polymer or a chlorinated vinyl chloride resin, and a vinyl chloride resin containing an additive such as a blend polymer, a stabilizer and a lubricant. This organic component acts as a binder for the inorganic component. The vinyl chloride-based polymer is composed of a vinyl chloride homopolymer or copolymer, and in the case of a copolymer, it is preferably a copolymer containing vinyl chloride as a main monomer.

Examples of vinyl chloride copolymers include:
Examples thereof include copolymers of vinyl chloride and monomers such as vinyl acetate, ethylene, propylene, acrylic acid ester, and methacrylic acid ester. Examples of the blend polymer blended with the vinyl chloride polymer include vinyl acetate resin, ethylene-vinyl acetate resin, MBS resin (methyl methacrylate-butadiene-styrene copolymer), chlorinated polyethylene resin, chlorosulfone resin. There are polyethylene-based resins and vinyl chloride-based polymers having a monomer composition different from that of the main vinyl chloride-based polymer.

The vinyl chloride resin used in the present invention is preferably a polymer or polymer mixture in which vinyl chloride polymer units account for 50% by weight or more, and particularly 70% by weight or more of the total monomer polymerized units.

Examples of the additives that can be added to the vinyl chloride polymer include various additives that can be usually added to the vinyl chloride resin. For example, plasticizers such as phthalate esters, lubricants such as stearic acid derivatives, antioxidants such as hindered phenols, heat stabilizers such as organotin compounds, UV absorbers such as benzotriazole compounds,
Examples include colorants such as pigments, antistatic agents such as surfactants, flame retardants, and fillers (excluding the inorganic fillers described below).

The inorganic component essentially requires a metal sulfate, and when the organic cross-linking agent described below is not used, an inorganic cross-linking agent capable of cross-linking the vinyl chloride polymer at higher temperature is required.
Each component may be composed of two or more kinds. Further, the inorganic component may contain an inorganic component other than these.

The metal sulfate is a compound composed of one or more kinds of metal and sulfate, and may contain other salt or water of crystallization. Specifically, zinc, aluminum, antimony, ytterbium, yttrium, indium, uranium, erbium, cadmium, gadolinium, potassium, gallium, calcium, gold, silver, chromium, cobalt, samarium, zirconium, mercury, scandium, tin, strontium. , Cesium, cerium, thallium, titanium,
Iron, terbium, copper, thorium, sodium, lead, nickel, neodymium, platinum, vanadium, palladium, barium, bismuth, praseodymium, beryllium, magnesium, manganese, europium, lanthanum, lithium,
1 selected from lutetium, rubidium, rhodium, etc.
It is a sulfate containing one or more metals. A preferable metal sulfate is a sulfate containing sodium, magnesium, potassium and calcium, and it is more preferable to use two or more kinds in combination.

As the inorganic cross-linking agent capable of cross-linking the vinyl chloride polymer at high temperature, calcium silicate, zinc oxide,
There are zinc chloride and the like, and calcium silicate is particularly preferable. This calcium silicate is preferably a fibrous or plate-like powder (such as zonotolite, wollastonite, tobermorite). This inorganic cross-linking agent is a compound capable of cross-linking a vinyl chloride polymer at a high temperature of less than 800 ° C.
A compound which can crosslink the vinyl chloride polymer at 00 to 700 ° C. is preferable.

The organic cross-linking agent capable of cross-linking the vinyl chloride polymer at a high temperature is at least one selected from a thiol compound, an unsaturated compound having an α, β unsaturated bond, and a radical generator. Is preferred. This organic cross-linking agent is a compound capable of cross-linking a vinyl chloride polymer at a high temperature of less than 800 ° C, particularly 100 to 400 ° C.
It is preferable that the compound is a compound capable of crosslinking a vinyl chloride polymer. In the case of a radical generator, it is preferable to use a so-called high temperature decomposition type radical-generating compound having high temperature stability.

This organic crosslinking agent is preferably used in combination with a crosslinking accelerator. For example, when a thiol compound is used, it is preferable to use a crosslinking accelerator such as magnesium oxide together. This magnesium oxide itself is an inorganic compound and can be used as one of the inorganic components described below. The upper limit of the amount used is according to the preferred quantitative range of the inorganic components described below, and the lower limit is the effective amount as a crosslinking accelerator.

A preferred thiol compound as the organic crosslinking agent is a compound having two or more mercapto groups.
Furthermore, a compound having a 1,3,5-triazine ring (s
-Triazine compounds) are more preferable. Specific thiol compounds include, for example, aromatic thiols such as 3,4-toluenedithiol, aliphatic thiols such as butanedioldi (thioglycolate), 2-dibutylamino-4,6-dimercapto-s-triazine, 2-phenylamino-4,6-dimercapto-s-triazine,
S such as 2,4,6-trimercapto-s-triazine
-Triazine thiols, etc. 2-Dibutylamino-4,6-dimercapto-s-triazine is particularly preferable.

The unsaturated compound preferable as the organic crosslinking agent is preferably a compound having two or more functional groups. It is more preferable to use it together with a radical generator. Specific unsaturated compounds include triallyl isocyanurate (TAI
C), 2,4,6-triallyloxy-1,3,5-triazine (TAC), 1,3,5-triacryloylhexahydro-s-triazine (TAF), trimetaallyl isocyanurate, p- Quinone dioxime, p, p '
-Dibenzoylquinone dioxime, triallyl 1,2,4-benzenetricarboxylate, diallyl terephthalate, diallyl isophthalate, 1,4,5,6,7,7
-Hexacyclobicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid-di-2-propenyl ester and the like. In particular, it is more preferred to use triallyl isocyanurate in combination with dicumyl peroxide as a radical generator.

A preferred radical generator as the organic cross-linking agent is a so-called high temperature decomposition type radical generator, and for example, a high temperature decomposition type peroxide compound, particularly dicumyl peroxide or dicumyl (that is, 2,3-dimethyl-).
Unstable compounds that generate radicals at relatively high temperatures, such as 2,3-diphenylbutane) are preferred.

Examples of peroxide compounds include ketone peroxide compounds, peroxyketal compounds, hydroperoxide compounds, dialkyl peroxide compounds, peroxyester compounds, and peroxycarbonate compounds. Specific peroxide compounds include, for example, the following compounds.

Methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1
-Bis (t-butylperoxy) cyclohexane, 2,
2-bis (t-butylperoxy) octane, 2,2-
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
Diisopropylbenzene hydroperoxide, p-
Menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,
3,3-Tetramethylbutyl hydroperoxide.

Di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide,
α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-
Butylperoxy) hexane, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexyne, t-butylperoxyacetate, t-butylperoxy-3,
5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate,
Di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, t-butylperoxyallyl Carbonate.

The composition of the present invention preferably further contains a smoke suppressant. This smoke suppressant is preferably an inorganic compound, that is, one of the inorganic components. However, other smoke suppressants such as organometallic complexes can be used. In the present invention, this organometallic complex is one of the inorganic components. This is because the smoke suppression effect is mainly due to this metal component. As the smoke generation inhibitor, borate, organometallic complex, and specific metal oxide are preferable. A particularly preferred smoke suppressant is a borate such as zinc borate.

Specific examples of smoke suppressants include the following compounds. That is, examples of the borate include zinc borate, magnesium borate, manganese borate, barium borate, aluminum borate, and borax. Examples of the organometallic complex include ferrocene, bis (acetylacetonate) copper, bis (dimethylglyoximo) copper, bis (8-hydroxyquinolino) copper, and bis (salicylaldehyde) copper. Specific metal oxides include oxides of metals selected from antimony, molybdenum, zirconium, nickel, titanium, iron, and cobalt. Preferred smoke suppressants other than borates are ferrocene and oxides of metals selected from molybdenum, zirconium, and iron.

Furthermore, as the inorganic component in the present invention, an inorganic compound other than the above can be used. As the optionally usable inorganic component, a refractory inorganic substance having a melting point to a softening point of 800 ° C. or higher is preferable. Inorganic substances having a melting point to a softening point of less than 800 ° C can also be used.

The refractory inorganic material is an inorganic material having no melting point or softening point below 800 ° C., but it is a compound that releases water of crystallization or the like below 800 ° C. or reacts or decomposes below 800 ° C. May be a compound or the like. Specific examples include alumina, aluminum hydroxide, magnesia, magnesium hydroxide, magnesium carbonate, basic magnesium carbonate, basic magnesium sulfate, silica, aluminum silicate, calcium carbonate and clay. A particularly preferred refractory inorganic material is at least one of alumina, aluminum hydroxide, magnesia, magnesium hydroxide, basic magnesium carbonate, and basic magnesium sulfate. These are also effective in suppressing smoke.

As the inorganic substance having a melting point to a softening point of less than 800 ° C., so-called low melting point glass is preferable. The melting point to softening point of this inorganic material is preferably higher than the molding temperature of the composition of the present invention. That is, it is preferable to have a melting point to a softening point higher than 200 ° C. which is the upper limit of the molding temperature of a usual vinyl chloride resin. The melting point to softening point of this inorganic substance is 30.
0-700 degreeC is preferable. Two or more kinds of these inorganic substances can be used in combination, and in that case, the melting point to the softening point may be different. It is also preferable to use this inorganic substance having a relatively low melting point-softening point and this inorganic substance having a relatively high melting point-softening point in combination.

Examples of so-called low melting point glass include, for example,
There are amorphous low-melting glass and crystallized glass called frit. Specifically, there are boric acid-based glass, hydrous phosphate-based glass, telluride glass, chalcogenide glass, lead-based glass, and the like, and particularly B ₂ O ₃ -PbO-Z.
_{nO, B 2 O 3 -PbO-} SiO 2, ZnO-B 2 O 3
Examples include boric acid-based glass such as —PbO and ZnO—B ₂ O ₃ —SiO ₂ . Further, sulfate glass can also be used. Sulfate glass is an amorphous compound, unlike the above-mentioned sulfate.

The ratio of the inorganic component to the composition is 40
.About.95% by weight is required. The ratio of each of the inorganic components to the composition is 1 to 90% by weight of metal sulfate,
It is preferable that the inorganic cross-linking agent is 0 to 85% by weight, but the total (when the inorganic components other than these two types are included, the total including them) is 40 to 95% by weight with respect to the composition. When a smoke suppressant is further added, its amount is preferably 1 to 50% by weight based on the composition.

The ratio of all inorganic components to the composition is 5
It is more preferably 0 to 85% by weight. Furthermore, the more preferable ratio of the metal sulfate is 5 to 60% by weight, and the more preferable ratio of the inorganic crosslinking agent is 0 to 40% by weight. Further, the amount of the inorganic cross-linking agent used is preferably about 1/2 to 1 times the weight of the vinyl chloride resin. When an organic crosslinking agent is used, the proportion thereof is preferably 1 to 30% by weight, particularly 3 to 20% by weight, based on the composition. The total proportion of both crosslinkers is at least 1% by weight, in particular 5% by weight. When a smoke suppressant is further added, its amount is preferably 1 to 20% by weight based on the composition.

The composition of the present invention is a composition for molding or a composition of molded articles. The molding composition of the present invention is a composition that can be molded by various molding means. Examples of the molding means include a press molding means, an extrusion molding means, a calender molding means, and an injection molding means. Examples of the molded product include window frames, wall materials, doors, floor materials, other building members, building accessories, furniture materials, and the like.

The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples.

[0031]

EXAMPLES Example 1 A composition comprising 40% by weight of a vinyl chloride resin composed of a vinyl chloride homopolymer (average degree of polymerization of 800), 40% by weight of sodium sulfate, and 20% by weight of calcium silicate was prepared at 140 ° C. After kneading with a roll of No. 1 and pressing, a test piece was obtained. The temperature was raised from room temperature to 800 ° C. in an electric furnace for 20 minutes, and the degree of deformation was observed. The smoke emission was evaluated using an NBS smoke emission tester (manufactured by Toyo Seiki Seisakusho).

[Examples 2 to 3] Instead of sodium sulfate,
The same test as in Example 1 was conducted using the same components as in Example 1 except that potassium sulfate and zinc sulfate were used, and using the composition in the indicated proportions.

[Example 4] The same components as in Example 1 were used except that sodium sulfate, potassium sulfate, zinc sulfate and a mixture of the above three types were used instead of sodium sulfate, and the composition in the indicated proportions was used. The same test as in Example 1 was performed.

[Example 5] 2 instead of calcium silicate
-Dibutylamino-4,6-dimercapto-s-triazine (hereinafter referred to as DBDMT) and magnesium oxide (hereinafter referred to as MgO) were used, except that the same components as in Example 4 were used and the composition in the indicated proportions was used. The same test as in Example 1 was conducted.

Example 6 Instead of calcium silicate, dicumyl peroxide (hereinafter referred to as DCP) and TAI.
The same components as in Example 4 were used except that C was used, and the same test as in Example 1 was performed using the composition in the indicated proportions.

Example 7 The same test as in Example 1 was carried out by adding molybdenum trioxide to the components of Example 4 and using the composition in the indicated proportions.

Comparative Example 1 The same test as in Example 1 was conducted using the composition in the indicated proportions without using the metal sulfate.

Comparative Example 2 The same test as in Example 1 was conducted using the composition in the indicated proportions without using calcium silicate.

Table 1 shows the composition of the test pieces used in Examples 1 to 7 and Comparative Examples 1 to 2 and the evaluation results of the deformability and smoke generation (the numerical values in the composition are% by weight).

The evaluation of the deformability is as follows. ◯: No deformation, Δ: Slight deformation, X: Large deformation to no shape retention. The evaluation of smoke emission is as follows. ◯: Maximum smoke amount is less than 50, Δ: Maximum smoke amount is 50 or more and less than 100,
X: The maximum smoke amount is 100 or more.

[0041]

[Table 1]

[0042]

The molded article comprising the composition of the present invention shows little deformation even when exposed to extremely high temperature conditions such as fire,
Good shape retention and excellent fire resistance. In addition, the amount of smoke generated during a fire can be suppressed by incorporating a smoke suppressor.

Continuation of the front page (72) Hiroyuki Watanabe Inventor Hiroyuki Watanabe 1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory

Claims (6)

[Claims] 1. Organic component 5 to 60% by weight and inorganic component 4
A molding composition comprising 0 to 95% by weight or a molding composition for obtaining the same, comprising: an organic component containing a vinyl chloride resin as a main component; an inorganic component containing a metal sulfate; A composition comprising an organic or inorganic cross-linking agent capable of cross-linking a vinyl polymer. 2. The composition according to claim 1, wherein the inorganic cross-linking agent is at least one selected from calcium silicate, zinc oxide, and zinc chloride. 3. The composition according to claim 1, wherein the inorganic cross-linking agent is fibrous or tabular calcium silicate. 4. The organic cross-linking agent is a thiol compound, α, β
The composition according to claim 1, which is an unsaturated compound having an unsaturated bond and at least one organic compound selected from radical generators. 5. The composition according to claim 1, wherein the ratio of the crosslinking agent to the composition is 5 to 50% by weight when the crosslinking agent is an inorganic crosslinking agent, and 1 to 30% by weight when the crosslinking agent is an organic crosslinking agent. . 6. The method according to claim 1, further comprising a smoke suppressant.
Composition.