JPH093335A - Flame-retardant resin composition and low-melting-point glass composition used therefor - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant resin compsn. by compounding a chlorine- contg. resin with a low-melting-point glass powder contg. a specified amt. of sulfur. CONSTITUTION: This flame-retardant resin compsn. comprises a chlorine-contg. resin and a low-melting-point glass powder contg. sulfur in an amt. of 0.1-38mol% in terms of SO3 . The glass powder is pref. a low-melting-point phosphate glass powder having a compsn. comprising 15-43mol% P2 O5 , 0.1-38mol% SO3 , 0-25mol% Li2 O, 0-25mol% Na2 O, 0-25mol% K2 O, 0-10mol% CaO, 0-10mol% SrO, 0-10mol% BaO, 0.1-20mol% B2 O3 , and 1-55mol% (in terms of element) oxide of at least one element selected from among transition metals including Mg, Al, Sn, Pb, and Sb.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a water-resistant low-melting glass composition and a flame-retardant resin composition using the same as a flame-retardant.

[0002]

2. Description of the Related Art Resin-based materials are widely used as materials for obtaining molded articles of various shapes because of their excellent moldability. However, in general, most resin materials are flammable and inferior in flame retardancy, so that the range of use is greatly limited.

[0003]

Various flame retardants have been developed in order to improve the flame retardancy of resins, and the following substances are generally used.

Metal hydroxides that utilize the endothermic effect during dehydration of aluminum hydroxide, magnesium hydroxide and the like. Compounds containing flame-retardant elements such as bromine and chlorine, represented by decabromodiphenyl oxide and chlorinated paraffin. Metal oxides such as molybdenum oxide and antimony trioxide, which are particularly effective in suppressing smoke generation during combustion.

Low-melting glass is effective as a flame retardant because it forms a vitreous film on the surface of a sample when heated and has a function of blocking oxygen. For example, US Pat. No. 4,544,695 discloses that a low melting glass containing a sulfur component in an amount of 40 mol% or more in terms of SO ₃ is mixed into a polymer.
However, this glass has a problem of low water resistance.

[0006]

In order to solve the above-mentioned problems, the present invention is a flame-retardant material comprising a low-melting glass powder containing a sulfur component in an amount of 0.1 to 38 mol% in terms of SO ₃ and a resin component containing chlorine. A resin composition is provided.

In the present invention, the low melting point glass contains a sulfur component in an amount of 0.1 to 38 mol% in terms of SO ₃ . The SO ₃ component is effective for improving the flame retardancy of the resin, and from this viewpoint, it is contained at 1.0 mol% or more. But,
Excessive addition lowers the water resistance of the low-melting-point glass, and is therefore set to 38 mol% or less. In order to secure more sufficient water resistance, it is preferably 20 mol% or less.

Examples of the low melting point glass include chalcogenide glass such as borate glass, phosphate glass, lead glass and telluride glass. Phosphate-based low melting point glass is particularly preferable because it has a high effect of carbonizing the resin.

The low melting point as used herein means a low melting point such that the glass flows when the resin composition containing the glass powder of the glass composition is burned, and specifically, it is 500 ° C. It has a glass transition temperature of about 400 ° C. or less, more preferably about 400 ° C. or less.

Specifically, the composition of the low-melting-point phosphate glass of the present invention is essentially composed of P ₂ O ₅ 15-.
43 mol%, SO ₃ 0.1~38 mol%, Li ₂ O 0~25 mol%, Na ₂
O 0-25 mol%, K ₂ O
0-25 mol%, CaO 0
-10 mol%, SrO 0-10 mol%, BaO 0-10 mol%, B ₂ O
₃ 0.1 to 20 mol%, transition metal, Mg,
It is preferable that the oxide of 1 to 55 mol% (converted to an element) of one or more elements selected from Al, Sn, Pb and Sb.

The term "essential" as used herein means that the above components are contained in an amount of 96 mol% or more based on the total amount of the glass composition, and other minor components are added within the range not impairing the effects of the present invention. it can.

When the content of P ₂ O ₅ is less than the above range, the melting point becomes high and it becomes difficult to form a glassy film on the resin surface during combustion, so that the flame retarding effect is lowered, and when it is high, Water resistance tends to decrease.

B ₂ O ₃ is an essential component for preventing a rapid decrease in viscosity of glass with temperature rise and forming a uniform film on the resin surface. May decrease, and the glass transition point may increase. More preferably, 1 mol% or more is added.

Li ₂ O, Na ₂ O and K ₂ O are each used as a melting point adjusting agent in an amount of 25 mol% or less, CaO, SrO and Ba.
O may be added as a viscosity modifier in an amount of 10 mol% or less.

Transition metals, Mg, Al, Sn, Pb and S
The content of the oxide of one or more elements selected from b is 1
If it is less than mol%, the effect of making the resin flame-retardant is not sufficient,
If it exceeds 55 mol%, it becomes difficult to form glass. In order to obtain a sufficient flame retardant effect, it is preferably 10 mol% or more. Here, “elemental conversion” means the number of moles converted into a metal element. For example ZnO, Fe
1 to 55 mol% in terms of O and CuO, and Al ₂ O
₃ , 0.5 to 27.5 mol% in terms of Sb ₂ O ₃ .

The transition metal element referred to here is, for example,
Yttrium, zirconium, chromium, molybdenum, manganese, iron, nickel, copper, zinc, aluminum, tin,
Lead, antimony, etc. are available. Among these, scandium called the first transition metal element, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc is preferable from the viewpoint of effective flame retardancy, especially zinc,
Iron and copper are preferable.

On the other hand, MgO is useful as a viscosity modifier, and Al ₂ O ₃ is useful for improving water resistance.
Even when an oxide of one or more elements selected from the first transition metals is added for the purpose of imparting flame retardancy, MgO, Al ₂ O
₃ can be added separately.

From the above, more preferable ones of the above composition ranges are specifically shown below.

In essence, P ₂ O ₅ 15-
43 mol%, SO ₃ 0.1~38 mol%, Li ₂ O 0~25 mol%, Na ₂
O 0-25 mol%, K ₂ O
0-25 mol%, MgO 0
~ 55 mol%, CaO 0-10 mol%, SrO 0-10 mol%, BaO
0 to 10 mol%, B ₂ O ₃
0.1-20 mol%, Al ₂ O ₃ 0
15 to 15 mol%, an oxide of one or more elements selected from the first transition metals 1 to 55 mol% (converted to elements).

The resin component in the present invention is composed of one or more kinds of resins, and a thermoplastic resin containing chlorine and a thermosetting resin are adopted. Examples thereof include vinyl chloride resin, chlorinated vinyl chloride resin, chlorinated polyethylene resin, polyepichlorohydrin resin, vinylidene chloride resin, and the like, and vinyl chloride resin is particularly preferable.

The vinyl chloride resin 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.

The vinyl chloride resin may be blended with another resin. Examples of other resins include vinyl acetate resins, ethylene-vinyl acetate resins, MBS resins (methyl methacrylate-butadiene-styrene copolymer), ABS resins (acrylonitrile-butadiene-styrene copolymer), acrylic resins, and the like. is there.

Various additives such as stabilizers and lubricants may be added to the resin component. As an additive that can be mixed,
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, flame retardants, fillers and the like are appropriately used.

The vinyl chloride resin may be a hard vinyl chloride resin or a soft vinyl chloride resin. The soft vinyl chloride resin is a vinyl chloride homopolymer resin mixed with a plasticizer such as dioctyl phthalate (DOP) or triphenyl phosphate (TPP) in an amount of 1 to 200% by weight based on the total amount of the resin portion. Is exemplified.

The flame-retardant resin composition of the present invention comprises the above chlorine-containing resin and the above low melting point glass powder. Glass powder is 1 to 80% by weight of the total amount of the composition, especially 5 to 60%.
It is preferable that the content be in a weight percentage. If the amount of glass powder is too large, the moldability tends to decrease, and if it is too small, sufficient flame retardancy tends not to be obtained.

The flame-retardant resin composition of the present invention further contains a specific metal oxide, hydroxide, silicate, carbonate, or organometallic complex as a smoke suppressant or flame retardant improver. May be added. Specifically, oxides include alumina, magnesia, molybdenum oxide, antimony oxide, zirconium oxide, iron oxide, etc., hydroxides such as aluminum hydroxide and magnesium hydroxide, and silicates such as silica. Calcium acid, aluminum silicate, and the like, carbonates such as calcium carbonate, magnesium carbonate, and clay, and organometallic complexes such as feserone and bis (acetylacetonate) copper can be cited.

When the smoke suppressor and the flame retardant improver are included, the amount thereof is preferably 1 to 20% by weight based on the total amount of the flame retardant resin composition.

The composition of the present invention can be molded by various methods. As molding methods, press molding, extrusion molding,
There are calender molding, injection molding, pultrusion molding, paste molding and the like. Further, the low melting point glass can be used also as a paint for imparting fire resistance by dispersing it in a suitable resin emulsion or a resin solution in which a resin is dissolved in a solvent.

Examples of the molded article include roof-related members such as roofs, eaves and gutters, siding materials, deck materials, exterior outer wall members such as fences, window-related members such as window frames, doors and gates, and wall materials. , Floor materials, ceiling materials, rims, frames, skirting boards, stairs, handrails, and other interior-related materials, other building materials and equipment, furniture materials, disaster troughs, signboards, wire coverings, and the like.

[0030]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. The evaluation methods for water resistance, smoke suppression, flame retardancy, etc. used in the examples are shown below.

Water resistance: 30 × by melting glass powder by heating
A 30 × 2 mm flat glass sample was obtained, immersed in warm water at 90 ° C. for 20 hours, and evaluated by the weight reduction rate per unit area. ◯: less than 5 mg / cm ² , Δ: 5 mg / cm ² or more, less than 10 mg / cm ² , x: 10 mg / cm ² or more.

Smoke suppression property: An NBS smoke emission tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used. ⊚: Maximum smoke generation is less than 30, ○: Maximum smoke generation is 30 or more and less than 50, Δ:
Maximum smoke amount is 50 or more and less than 100, x: Maximum smoke amount is 1
00 or more.

Further, the residue after this test was observed with a microscope to evaluate the surface coverage with glass. ◯: The entire surface is covered with glass, Δ: Part of the resin carbide is exposed.

Flame retardance: An oxygen index tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used. ◯: Oxygen index is 60 or more, Δ: Oxygen index is 50 or more and less than 60, X: Oxygen index is less than 50.

[Examples 1 to 10] As a raw material of each component of glass, H ₃ PO ₄ is used as a phosphorus source and Li ₂ C is used as a lithium source.
O _3, Na ₂ CO ₃ is sodium source, the source of potassium K ₂ CO _3, the aluminum source Al (OH) _3, the silicon source is SiO _2, the source of boron B ₂ O _3, zinc source, As the iron source, the lead source, the magnesium source, the copper source, and the sulfur source, oxides and / or sulfates of the respective metals are used, which are mixed at various ratios, and the resulting slurry is heated at 125 ° C.
After drying for 2 hours, it is transferred to a platinum crucible and heated at 1100 ° C. for 30 minutes. The obtained melt was poured into a stainless steel roller and cooled to obtain glass flakes, which was crushed by a ball mill for 90 minutes and then sieved with 100 mesh to obtain powdery glass.

The composition (mol%) of this glass was analyzed by ICP emission spectroscopy and atomic absorption spectroscopy after dissolving the sample in acid to evaluate the water resistance.

Further, 80% by weight of a vinyl chloride resin (PVC: average degree of polymerization: 800) composed of a vinyl chloride homopolymer,
20% by weight of each of the above glasses is mixed and kneaded with a roll at 180 ° C for 7 minutes, and then pressed at 180 ° C, 100 ° C.
Molding was performed under the condition of kg / cm ² to obtain a test piece of the flame-retardant resin composition, and the smoke suppression property and flame retardancy were evaluated.
The results are shown in Table 1.

Example 7 is an example of a glass containing no B ₂ O ₃ , and it may have sufficient water resistance, smoke suppression property, and flame retardancy depending on the application which does not require so much smoke suppression property. It can be said, however, that the surface coverage is slightly lower. From this point, in order to secure a more sufficient smoke suppression property, B
The addition of ₂ O ₃ is effective.

Example 8 is an example using lead-based glass.
Compared with the phosphoric acid type, it has slightly lower smoke suppression and flame retardancy.
After all, although it can be used depending on the application, it is preferable to use phosphoric acid-based glass when sufficient smoke emission suppressing property is required.

Example 9 is an example containing no SO ₃ and was inferior in smoke emission suppressing property, which is not preferable. In addition, Example 10 is an example in which SO ₃ is excessively included, which is inferior in water resistance and is also not preferable.

[Examples 11 to 22] The same vinyl chloride resin (PVC) as in Examples 1 to 10 and the glass A or B shown in Table 1.
Powder, and DOP, TPP, molybdenum oxide, and antimony oxide were mixed at the weight ratio shown in Table 2, and the mixture was heated at 180 ° C.
After kneading with a roll for 7 minutes, press at 180 ° C for 10
Molding was performed under the condition of 0 kg / cm ² to obtain a test piece of the flame-retardant resin composition, and the smoke suppression property and flame retardancy were evaluated. Table 2 shows the results.

Examples 11, 12, 17 and 18 are examples in which molybdenum oxide or antimony oxide was added as a smoke suppressant, and the effect can be confirmed.

Examples 13 to 16 and Examples 19 to 22 are examples in which the vinyl chloride resin is soft. Compared with the example using hard vinyl chloride, the smoke suppression property is slightly inferior, but it is within the usable range.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

EFFECTS OF THE INVENTION By blending the low melting point glass having the flame retardant effect and excellent water resistance of the present invention, the flame retardancy of the resin can be improved and the amount of smoke generated during combustion can be greatly reduced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 27/06 C08L 27/06 (72) Inventor Hiroshi Usui 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Yasuko Osaki 1150 Hazawa-machi, Kanagawa-ku, Kanagawa Prefecture In the laboratory

Claims (7)

[Claims] 1. A flame-retardant resin composition comprising a low melting point glass powder containing a sulfur component in an amount of 0.1 to 38 mol% in terms of SO ₃ and a resin component containing chlorine. 2. The flame-retardant resin composition according to claim 1, wherein the low melting glass is a phosphate low melting glass. 3. The composition of the phosphate-based low melting point glass is essentially such that P ₂ O _{5 is} 15 to 43 mol%, SO _{3 is} 0.1 to 38 mol%, Li ₂ O is 0 to 25 mol%, and Na is 25 mol%. ₂ O 0 to 25 mol%, K ₂ O 0 to 25 mol%, CaO 0 to 10 mol%, SrO 0 to 10 mol%, BaO 0 to 10 mol%, B ₂ O ₃ 0.1 to 20 mol%, Oxide of one or more elements selected from transition metals, Mg, Al, Sn, Pb and Sb 1
The flame-retardant resin composition according to claim 2, comprising 55 mol% (converted to elements). 4. The composition of the phosphate-based low melting point glass is essentially such that P ₂ O _{5 is} 15 to 43 mol%, SO _{3 is} 0.1 to 38 mol%, Li ₂ O is 0 to 25 mol%, and Na is Na. ₂ O 0 to 25 mol%, K ₂ O 0 to 25 mol%, MgO 0 to 55 mol%, CaO 0 to 10 mol%, SrO 0 to 10 mol%, BaO 0 to 10 mol%, B ₂ O ₃ 0 1-20 mol%, Al ₂ O ₃ 0-15 mol%, oxide of one or more elements selected from the first transition metals 1
The flame retardant resin composition according to claim 2, wherein the flame retardant resin composition comprises: 5. The flame-retardant resin composition according to any one of claims 1 to 4, wherein the resin component is a vinyl chloride resin. 6. Essentially, P ₂ O ₅ 15~43 mol%, SO ₃ 0.1~38 mol%, Li ₂ O 0~25 mol%, Na ₂ O 0~25 mol%, K ₂ O 0-25 mol%, CaO 0-10 mol%, SrO 0-10 mol%, BaO 0-10 mol%, B ₂ O ₃ 0.1-20 mol%, transition metals, Mg, Al, Sn, Pb and Oxide of one or more elements selected from Sb 1
A low melting point glass composition comprising 55 mol% (converted to elements). 7. Essentially, P ₂ O ₅ 15~43 mol%, SO ₃ 0.1~38 mol%, Li ₂ O 0~25 mol%, Na ₂ O 0~25 mol%, K ₂ O 0-25 mol%, MgO 0-55 mol%, CaO 0-10 mol%, SrO 0-10 mol%, BaO 0-10 mol%, B ₂ O ₃ 0.1-20 mol%, Al ₂ O ₃ Oxide of 0 to 15 mol%, one or more elements selected from the first transition metals 1
A low-melting glass composition consisting of ˜55 mol% (converted to elements).