JPH0753817A - Molding composition - Google Patents

Abstract

PURPOSE:To obtain the composition composed of a specified ratio of a specified organic component, a specific crosslinking agent and a specified inorganic component, excellent in shape retention, fire resistance and impact strength and useful as an architectural component, etc. CONSTITUTION:The composition is composed of (A) 5-60wt.% organic component which is an organic binder containing, as the main component, an impact- resistance-improving material composed of (i) a vinyl chloride-based resin and (ii) a polymer having <=30 deg.C glass transition temperature, e.g. a chlorinated polyethylene-based polymer, (B) 40-95wt.% inorganic component having <800 deg.C melting point to softening point, e.g. a low-melting glass such as a sulfate-based glass and (C) organic substances, e.g. one or more kinds of organic compounds selected from a thiol compound such as toluenedithiol, an unsaturated compound having an alpha,beta-unsaturated bond and a radical-forming agent respectively capable of crosslinking the vinyl chloride-based polymer under high temperatures or inorganic crosslinking agents, e.g. one or more kinds of inorganic compounds selected from calcium silicate, zinc oxide and zinc chloride.

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 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, its 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. Moreover, smoke is likely to be generated at the time of fire, and it is often necessary to suppress it. In addition, since a large amount of inorganic filler is added for the purpose of improving fireproofness, strength physical properties at room temperature,
In particular, the impact strength is significantly reduced.

[0004]

Means for Solving the Problems The present invention relates to the following invention relating to a molded article capable of preventing the flow of a resin at a high temperature to suppress the deformation and at the same time maintaining the strength physical properties at room temperature. is there.

5 to 60% by weight of organic component and 4 of inorganic component
A composition of a molded product comprising 0 to 95% by weight or a molding composition for obtaining the same, wherein an organic binder containing a vinyl chloride resin and an impact modifier as main components, a melting point to
A composition comprising an inorganic substance having a softening point of less than 800 ° C. and an organic or inorganic crosslinking agent capable of crosslinking a vinyl chloride polymer at a high temperature.

In the present invention, the organic component comprises vinyl chloride resin such as vinyl chloride polymer or chlorinated vinyl chloride polymer and an impact modifier as essential components, and if necessary, additives such as stabilizer and lubricant. The composition is the main component. As described below, when using an organic cross-linking agent,
This crosslinking agent is also an organic component.

The vinyl chloride 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-based copolymers include copolymers of vinyl chloride and monomers such as vinyl acetate, ethylene, propylene, acrylic acid ester, and methacrylic acid ester. A chlorinated vinyl chloride polymer can also be used as the vinyl chloride resin. As the vinyl chloride resin in the present invention, vinyl chloride polymer units are 50% by weight or more of the total monomer polymer units, particularly 70
Polymers and polymer mixtures with a weight percentage of greater than or equal to are preferred.

The impact modifier is an additive which is dispersed in a vinyl chloride resin matrix to improve impact strength. The impact modifier is preferably a polymer having rubber elasticity or elastomer elasticity and having a glass transition point of 30 ° C. or lower. Further, in consideration of fireproofness, a polymer containing chlorine. Is preferred. The chlorine-containing polymer may be a vinyl chloride-based copolymer having a vinyl chloride polymerization unit ratio lower than the above, and may also be a vinylidene chloride-based polymer, a chloroprene-based polymer, an epichlorohydrin-based polymer, or the like. It may be a chlorine-containing polymer. Further, various chlorinated polymers such as chlorinated polyethylene-based polymers and chlorinated polypropylene-based polymers may be used. A chlorine-containing impact modifier having a chlorine content of 10% by weight or more is more preferable. Particularly, a chlorinated polyethylene polymer having a high chlorine content is most preferable. Two or more impact modifiers may be used in combination.

Including the above specific examples, examples of the impact modifier include the following polymers having rubber elasticity and elastomer elasticity. Of the following, a polymer having a glass transition point of 30 ° C. or lower is particularly preferable. Chlorinated polyethylene polymer, MBS (methyl methacrylate-butadiene-styrene copolymer), vinyl acetate polymer, ethylene vinyl acetate copolymer, ethylene / vinyl acetate-vinyl chloride graft polymer, ABS (acrylonitrile-butadiene-polymer) Styrene copolymer), ACS (acrylonitrile-chlorinated polyethylene-styrene copolymer), vinylidene chloride-based polymer, chlorinated polypropylene-based polymer, butadiene-based polymer, fluorine-based polymer, styrene-butadiene-based rubber, isoprene Rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, nitrile-butadiene rubber, chloroprene rubber, butyl rubber, urethane rubber, silicone rubber, tetrafluoroethylene-propylene rubber, acrylic System rubber
Chlorosulfonated polyethylene rubber, epichlorohydrin rubber, propylene oxide rubber, ethylene-
Acrylic rubber.

The ratio of the impact modifier to the vinyl chloride polymer is not particularly limited, but in the case of a chlorine-free impact modifier, it is not preferable to add a large amount thereof from the viewpoint of fire resistance, while the chlorine-containing impact modifier is not preferred. In the case of, a relatively large amount can be blended. The ratio of the impact modifier containing no chlorine to 100 parts by weight of the vinyl chloride polymer is 10 to 1.
50 parts by weight is preferable, and the proportion of the chlorine-containing impact modifier is 1
0 to 200 parts by weight is preferable.

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

The inorganic component is essentially an inorganic substance having a melting point to a softening point of less than 800 ° C., and when the crosslinking agent described later is an inorganic substance, it is included. The inorganic component may be composed of two or more kinds. Further, the inorganic component may further contain an inorganic component other than these. Especially, the melting point-softening point is 800 ° C.
The above-mentioned inorganic substances, compounds that release water of crystallization or the like below 800 ° C., compounds that do not react below 800 ° C. or decompose to become new refractory inorganic substances are preferable. Examples of such inorganic substances include alumina, aluminum hydroxide, magnesia, magnesium hydroxide, and silica.

As the inorganic material 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. In particular, the melting point to softening point of this inorganic substance is
300-700 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 glass include, for example,
There are amorphous low-melting glass and crystallized glass called frit. Specifically, there are boric acid glass, hydrous phosphate glass, sulfate glass, tellurite glass, chalcogenide glass, lead glass, etc., and particularly B ₂ O.
_{3 -PbO-ZnO, B 3 O} 3 -PbO-SiO 2, Z
_{nO-B 2 O 3 -PbO,} ZnO-B 2 O 3 -SiO 2
Boric acid glass such as potassium, sodium,
A sulfate-based glass containing a sulfate of a metal such as zinc, nickel, manganese, copper or vanadium as a main component is preferable.

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.

As the organic cross-linking agent capable of cross-linking the vinyl chloride polymer at high temperature, a thiol compound, an unsaturated compound having an α, β unsaturated bond, and a radical generator are preferable. 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 10
A compound that can crosslink the vinyl chloride polymer at 0 to 400 ° C. is preferable. This organic cross-linking agent is preferably one which does not cross-link the vinyl chloride polymer when molding a molded product from the molding composition. That is, it is necessary that it remains as an organic crosslinking agent in the molded product after molding. Therefore, for example, in the case of a radical generator, it is preferable that it is a so-called high temperature decomposition type compound having high temperature stability and high radical 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 above-mentioned inorganic components. The upper limit of the amount used is in accordance with the preferred quantitative range of the following inorganic components, and the lower limit is the effective amount as a crosslinking accelerator.

The thiol compound preferable as the organic crosslinking agent is preferably 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 having an α, β unsaturated bond which is preferable as the organic cross-linking agent is preferably a compound having two or more unsaturated groups. Furthermore, it is more preferable to use it together with a radical generator. Specific unsaturated compounds having α and β unsaturated bonds 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 preferable 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 decomposable radical generator, and for example, a high temperature decomposable peroxide compound, particularly dicumyl peroxide or dicumyl (ie 2,3-dimethyl-2,
Unstable compounds that generate radicals at relatively high temperatures, such as 3-diphenylbutane) are preferred.

Examples of peroxide compounds include ketone peroxide compounds, peroxyketal compounds, hydroperoxide compounds, dialkyl peroxide compounds, peroxyester compounds, peroxycarbonate compounds and the like. 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-butylhydroperoxide, 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-butyl) Peroxy) hexyne, t-butylperoxyacetate, t-butylperoxy-3,5,5-
Trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-
Butyl peroxyisophthalate, 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.

The ratio of the inorganic component to the composition is 40
.About.95% by weight is required. The respective proportions of the inorganic components to the composition are 1 to 95% by weight of the inorganic substance having a melting point to a softening point of less than 800 ° C. and 0 to 85% by weight of the inorganic crosslinking agent, provided that the total (inorganic components other than these two If included, the total including it) is 40 with respect to the composition.
It is preferably about 95% by weight. When a smoke suppressant is further added, its amount is preferably 1 to 50% by weight based on the composition.

The ratio of total inorganic components to the composition is 5
It is more preferably 5 to 85% by weight. Furthermore, the more preferable ratio of the inorganic substance having a melting point to the softening point of less than 800 ° C. is 5 to 45% 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 a smoke suppressant is further added, its amount is preferably 1 to 20% by weight based on the composition.

The proportion of the organic or inorganic crosslinking agent must be at least 1% by weight, and particularly preferably 1 to 40% by weight. In the case of an organic crosslinking agent, the upper limit is preferably about 20% by weight. The proportion of the vinyl chloride resin is preferably a majority of the organic components or more. In particular, it is preferably 10 to 40% by weight with respect to the composition and more than the majority of the organic components.

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]

【Example】

[Example 1] Vinyl chloride homopolymer (average degree of polymerization: 80)
0) 15% by weight, chlorinated polyethylene resin 15% by weight,
Alumina (average particle size 1 μm) 20% by weight, calcium silicate 30% by weight, low melting point sulfate glass (softening point 400
A composition of 20% by weight was kneaded with a roll at 140 ° C. and then molded by pressing to obtain a test piece. 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 Co., Ltd.). The evaluation result is represented by D _max (maximum smoke amount). Impact strength evaluation is J
A Charpy impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used according to ISK7111.

Example 2 The same components as in Example 1 except that MBS resin (methyl methacrylate-butadiene-styrene copolymer) was used as the impact modifier instead of chlorinated polyethylene resin, and the same as in Example 1. The test was conducted.

Example 3 The same test as in Example 1 was carried out by adding 5% by weight of zinc borate as a smoke suppressor to the same components as in Example 1.

Comparative Example 1 The same test as in Example 1 was conducted using the same components as in Example 1 except that the chlorinated polyethylene resin was not used.

The compositions of the test pieces used in Examples 1 to 3 and Comparative Example 1 and the evaluation results of the deformability, impact strength, and smoke emission are shown in Table 1 (note that the numerical values in the composition are% by weight).

The evaluation of deformability is as follows. ◯: No deformation, Δ: Slight deformation, X: Large deformation to no shape retention.

The impact strength is evaluated as follows. ◯: Impact value is 10 kJ / m ² or more, Δ: Impact value is 5 or more and 10 k
Less than J / m ² , x: Impact value less than 5 kJ / m ² .

The evaluation of the smoke generation property is as follows. ◯: Maximum amount of smoke generation is less than 50, Δ: Maximum amount of smoke generation is 50 or more and less than 100, ×: Maximum amount of smoke generation is 100 or more.

[0039]

[Table 1]

[0040]

The molded article comprising the composition of the present invention shows little deformation even when exposed to extremely high temperature conditions such as fire,
The shape retention is good, and by adding a smoke suppressor, the amount of smoke generated during a fire can be suppressed. In addition, the impact modifier maintains the impact strength at room temperature.

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Kiyoshi Tanabe 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Central Research Laboratory, Asahi Glass Co., Ltd. (72) Hiroyuki Watanabe 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Japan Asahi Glass Co., Ltd. Company Central Research Institute

Claims (8)

[Claims] 1. Organic component 5 to 60% by weight and inorganic component 4
A composition of a molded product comprising 0 to 95% by weight or a molding composition for obtaining the same, wherein an organic binder containing a vinyl chloride resin and an impact modifier as main components, a melting point to
A composition comprising an inorganic substance having a softening point of less than 800 ° C. and an organic or inorganic crosslinking agent capable of crosslinking a vinyl chloride polymer at a high temperature. 2. The composition of claim 1, wherein the impact modifier comprises a polymer having a glass transition temperature of 30 ° C. or lower. 3. The composition according to claim 1, wherein the impact modifier comprises a polymer containing 10% by weight or more of chlorine and having a glass transition temperature of 30 ° C. or lower. 4. An inorganic substance having a melting point to a softening point of less than 800 ° C.,
The composition of claim 1 which is at least one of a low melting point glass. 5. The composition according to claim 4, wherein the low melting point glass is a sulfate glass. 6. 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. 7. An 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 a radical generator. 8. The method according to claim 1, further comprising a smoke suppressant.
Composition.