JPWO2008117726A1 - Smoke suppressant for burning organic resin containing halogen - Google Patents

Abstract

A smoke-inhibiting agent at the time of heating and baking an organic resin containing halogen, including a low melting point phosphate glass that does not contain boron and has excellent water resistance, and a resin-containing composition having excellent moldability containing the same. . A smoke suppressant at the time of combustion of an organic resin containing a halogen, which includes a phosphate glass having the following composition expressed in mol% on an oxide basis and having a glass transition point of 400 ° C. or lower. P2O5: 20-40%, ZnO: 56-65%, SO3: 0.5-12%, Li2O + Na2O + K2O: 3-20%, provided that Li2O: 0-5%, Na2O: 3-15%, K2O: 0 10%.

Description

  The present invention relates to a smoke suppressant having a function of suppressing smoke generation during heating and burning of an organic resin containing halogen, and an organic resin composition containing the smoke suppressant.

  In general, many organic resin materials are flammable and inferior in flame retardancy, so the range of use is greatly limited. Organic resins containing halogen such as vinyl chloride resin are widely used as resins with excellent flame retardancy, but in this case as well, since they have fuming properties when burned, they give higher flame retardancy and smoke suppressants Is needed.

  Conventionally, various materials have been proposed as materials for improving the flame retardancy of organic resins and suppressing smoke generation. For example, metal hydroxides utilizing the endothermic effect during dehydration, such as aluminum hydroxide and magnesium hydroxide; 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 that are particularly effective for suppressing smoke generation during combustion are also used.

In addition, low melting point glass is effective as a flame retardant because it has a function of forming a glassy film on the surface of the sample during heating and blocking oxygen. For example, Patent Document 1 discloses that a low melting glass containing 40 mol% or more of a sulfur component in terms of SO ₃ is mixed in a polymer. However, this glass has a problem of low water resistance.

Patent Document 2 and Patent Document 3 describe that a phosphate glass containing a sulfate having good water resistance has a high smoke suppression effect when a vinyl chloride resin is burned. Furthermore, in Patent Document 4, the average particle size is 0.5 μm or more, less than 5.0 μm, and the specific surface area is 1.5 m ² / cm ³ or more, which is higher than 200 ° C. and lower than 400 ° C. It is described that glass powder having a glass transition point imparts excellent flame retardancy to a resin composition.
U.S. Pat. No. 4,544,695 JP 09-003335 A JP-A-10-101364 JP 2006-62945 A

  Since all of the conventional low-melting-point glasses of Patent Documents 1 to 3 contain boron as an essential component, they cannot meet the demand for glass that does not contain boron in recent environmental measures. Further, Patent Document 4 discloses glass that does not contain boron, but the effect of a resin that contains chlorine is not clearly disclosed in Examples.

  The present invention does not contain boron, has excellent water resistance, includes a low melting point phosphate glass having a specific composition, and suppresses the generation of smoke when the organic resin containing halogen is heated and burned. It aims at providing the organic resin containing composition excellent in the moldability containing an agent and this smoke control agent.

As a result of intensive studies to achieve the above object, the present inventor, as a glass composition not containing boron, contains ZnO and P ₂ O ₅ at a specific ratio, and in addition, Li ₂ that is SO ₃ and an alkali metal. It has been found that phosphate glass containing O, Na ₂ O, and K ₂ O in specific proportions exhibits an excellent smoke suppression function when a molded body with an organic resin containing a halogen is heated and burned.

The present invention has been achieved on the basis of such novel findings, and has the gist characterized by the following.
1. A smoke suppressant at the time of combustion of an organic resin containing a halogen, which comprises a phosphate glass having the following composition expressed in mol% on an oxide basis and having a glass transition point of 400 ° C. or lower.
_{P 2 O 5: 20~40%,} ZnO: 56~65%, SO 3: 0.5~12%, Li 2 O + Na 2 O + K 2 O: 3~20%, however, Li ₂ O: 0~5% , Na ₂ O: 3-15%, K ₂ O: 0-10%.
2. 2. The smoke suppressant according to 1 above, wherein the phosphate glass has the following composition in terms of mol% based on oxide.
_{P 2 O 5: 25~35%,} ZnO: 57~60%, SO 3: 1~8%, Li 2 O + Na 2 O + K 2 O: 5~10% ( _{however, Li 2 O: 0~5%,} Na _{2 O: 4~9%, K 2} O: 1~6%).
3. 3. The smoke suppressant according to 1 or 2 above, wherein the phosphate glass is a powder having an average particle size (D50) of 0.5 to 20 μm.
4). The smoke suppressant according to any one of 1 to 3 above, wherein 1 to 200 parts by mass is added to 100 parts by mass of an organic resin containing a halogen.
5). 5. The smoke suppressant according to any one of 1 to 4 above, wherein the organic resin containing halogen is an organic resin containing chlorine.
6). The organic resin composition containing the halogen containing 1-200 mass parts of the smoke suppression agent in any one of said 1-5 with respect to 100 mass parts of organic resins containing a halogen.
7). 7. A molded product obtained by molding the organic resin composition containing halogen as described in 6 above. The organic resin composition containing the halogen which contains 1-200 mass parts of phosphate glasses of said 1 with respect to 100 mass parts of organic resins containing a halogen.

  According to the present invention, the smoke suppression function when a halogen-containing organic resin is heated and burned, including a low melting point phosphate glass having a specific composition that does not contain boron and has excellent water resistance, is well expressed. Provided are a smoke suppressant and an organic resin-containing composition excellent in moldability containing the smoke suppressant.

The phosphate glass contained in the smoke suppressant during combustion of the organic resin containing halogen according to the present invention is expressed in mol% based on oxide (hereinafter, “%” is mol% unless otherwise specified). And has the following composition.
_{P 2 O 5: 20~40%,} ZnO: 56~65%, SO 3: 0.5~18%, Li 2 O + Na 2 O + K 2 O: 3~20% ( _however, Li 2 O: _0~5% , Na ₂ O: 3 to 15%, K ₂ O: 0 to 10%).
Among these, preferable phosphate glasses in the present invention are P ₂ O ₅ : 25 to 35%, ZnO: 57 to 60%, SO ₃ : 1 to 12%, Li ₂ O + Na ₂ O + K ₂ O: 5 to 10%. _{(However, Li 2 O: 0~5%,} Na 2 O: 4~9%, K 2 O: 1~6%) having a.

The essential components of the phosphate glass in the present invention are represented by oxides, and are P ₂ O ₅ , ZnO, SO ₃ , and alkali metal oxides. _Among, P 2 _{O 5} is an essential component to the glass forming, the content thereof is 20 to 40%, and preferably 25 to 35% and most preferably 27 to 33%. If the P ₂ O ₅ content is less than 20%, vitrification becomes difficult and a homogeneous glass cannot be obtained. On the other hand, if it exceeds 40%, the water resistance of the glass decreases, which is not preferable.

  Moreover, ZnO is a component for suppressing the fuming at the time of combustion of organic resin, The content is 56 to 65%, Preferably it is 57 to 60%. When ZnO is less than 56%, the function of suppressing smoke generation is weakened, and when it exceeds 65%, the glass tends to be devitrified and vitrification becomes difficult.

In the phosphate glass of the present invention, SO ₃ is an important component that affects the solubility when the glass is melted and also affects the water resistance of the resulting glass. Its content is 0.5-12%, preferably 1-8%. If SO ₃ is less than 0.5%, it is difficult to keep the temperature at the time of melting the glass below 1000 ° C. On the other hand, if the content exceeds 12%, the water resistance of the obtained glass is remarkably lowered, so that it becomes difficult to store and handle, which is not preferable.

Further, an alkali metal oxide _Li 2 O, _Na 2 O, and _{K 2} O are components that help melt the glass. The content is the total content of Li ₂ O + Na ₂ O + K ₂ O, and is 3 to 20%, preferably 5 to 15%. If the total content is less than 3%, the glass is insufficiently melted and hardly vitrified. On the other hand, if the total content is more than 20%, the water resistance of the glass is remarkably lowered.

In addition, as individual components of the alkali metal oxide, Li ₂ O is 0 to 5%, Na ₂ O is 3 to 15%, preferably 4 to 9%, and K ₂ O is 0 to 10%. , Preferably 1 to 6%.

In the phosphate glass of the present invention, the phrase “not containing boron” means that it is not intentionally contained unless, for example, it is mixed as an impurity from industrial raw materials. The content of less than 0.5 mol% as B ₂ O _{3 on the} oxide basis does not contain boron (B).

In the phosphate glass of the present invention, Al ₂ O ₃ is an optional component. By containing Al ₂ O ₃ , the water resistance can be improved and the viscosity at the time of glass melting can be adjusted. However, if the content is too large, the glass transition point is increased, resulting in flame retardant. It is preferable that Al ₂ O ₃ is not substantially contained since the property is hardly exhibited. “Substantially not contained” means not intentionally contained, and specifically, the content is less than 0.5%.

  In the phosphate glass contained in the smoke suppressant of the present invention, there is no problem even if components other than the above are present within a range not impairing the effects of the present invention. For example, MgO, CaO, SrO, BaO, etc. may be added for adjusting the flow characteristics and stability of the glass. Moreover, you may contain metal oxides, such as Ti, Fe, Co, Ni, Sn, Zr, and Mo, as a component of a glass composition.

  The phosphate glass in the present invention has a glass transition point of 400 ° C. or lower, preferably 300 to 370 ° C. When the glass transition point exceeds 400 ° C., the difference between the temperature at which the resin melts and decomposes at the time of combustion becomes large, so the formation of the glassy film is delayed and the oxygen blocking is delayed. This makes it difficult to achieve the object of the present invention.

  The phosphate glass constituting the smoke suppressant of the present invention is prepared by mixing and melting glass raw materials so as to obtain a desired glass composition using a known method and apparatus, and then rapidly cooling and solidifying. It can be obtained by vitrification. Such phosphate glasses can be melted at a relatively low temperature, i.e., preferably at 800-1000C.

  The form of the smoke suppressant of the present invention containing the phosphate glass can be appropriately selected from fibers, powders, flakes, balloons and the like. In particular, the specific surface area is increased, and a high smoke suppression effect and flame retardancy can be obtained. In the case of powder, the average particle diameter (D50) is 0.5 to 20 μm, preferably 1 to 10 μm. If the average particle size is smaller than 0.5 μm, it is difficult to produce glass powder, and if it is larger than 20 μm, the particles are large.

  Examples of the pulverization method for obtaining the phosphate glass powder include wet pulverization such as a medium stirring mill, colloid mill, and wet ball mill, and dry pulverization such as jet mill, dry ball mill, and roll crusher. May be used in combination. A glass powder having a predetermined average particle diameter can be obtained by using the above pulverization method. Moreover, you may perform a classification process so that the average particle diameter of the glass powder obtained by grind | pulverizing may become said preferable range. Although it does not specifically limit as a classification process, It is preferable to use a wind-type classifier, a sieving apparatus, etc.

  As a component other than the phosphate glass constituting the smoke suppressant of the present invention, a known smoke suppressant may be included, and examples thereof include a compound containing antimony.

  Next, the organic resin containing halogen in the present invention will be described. The halogen-containing organic resin is a thermoplastic resin, thermoplastic elastomer or thermosetting resin composed of one or more kinds of resins, and the phosphate glass has a function of suppressing smoke generation when the organic resin containing halogen is burned. From the viewpoint of easy expression, an organic resin containing chlorine is preferable. Examples of organic resins containing chlorine include vinyl chloride resins, chlorinated vinyl chloride resins, chlorinated polyethylene resins, polyepichlorohydrin resins, vinylidene chloride resins, chlorinated paraffins, chlorinated polyolefin resins, etc. Is mentioned.

  You may blend other resin with the organic resin containing a halogen. Examples of other resins herein include vinyl acetate resin, ethylene-vinyl acetate resin, MBS resin (methyl methacrylate-butadiene-styrene copolymer), ABS resin (acrylonitrile-butadiene-styrene copolymer), acrylic There are resins.

  In order to further improve the flame retardancy of the organic resin composition containing halogen of the present invention, for example, metal hydroxide flame retardants such as magnesium hydroxide and aluminum hydroxide, antimony trioxide, molybdenum oxide, oxidation Addition of metal oxide flame retardants such as tin (SnO) and zinc oxide (ZnO), brominated flame retardants such as decapromodiphenyl ether and tripromophenyl aliether, and chlorinated flame retardants such as chlorinated paraffin Good. Furthermore, as a flame retardant added to a resin composition, a metal hydroxide flame retardant or a metal oxide flame retardant is preferable.

  Moreover, various additives, such as a stabilizer and a lubricant, may be blended in the organic resin composition containing a halogen of the present invention. Additives that can be blended include, for example, plasticizers such as phthalate esters, lubricants such as stearic acid derivatives, antioxidants such as hindered phenols, heat stabilizers such as organotin compounds, and ultraviolet light such as benzotriazole compounds. There are colorants such as absorbers and pigments, antistatic agents such as surfactants, antibacterial agents, and fillers.

  The content of the smoke suppressant in the halogen-containing organic resin composition of the present invention is preferably 1 to 200 parts by mass, and particularly preferably 5 to 150 parts by mass with respect to 100 parts by mass of the resin. When the content is less than 1 part by mass, it is difficult to impart sufficient smoke suppression properties to the resin. On the other hand, if the content exceeds 200 parts by mass, the amount of inorganic components increases so that it is difficult to obtain a molded product, or the mechanical properties of the obtained molded product are impaired, which is not preferable.

  Furthermore, the phosphate glass used as a smoke suppressant in the present invention is preferably surface-treated with a treatment agent containing a coupling agent. This surface treatment improves the adhesion between the phosphate glass and the resin when a resin composition is obtained from the phosphate glass and a halogen-containing resin, or when the resin composition is molded. Moreover, when handling phosphate glass, it is also possible to suppress the generation of static electricity and improve handling. Moreover, the mechanical properties of the resin composition can be improved by improving the adhesion between the resin and the phosphate glass.

  As the coupling agent, a silane coupling agent or a titanate coupling agent can be used. In particular, it is preferable to use a silane coupling agent from the viewpoint of good adhesion between the resin and the glass powder.

  The amount of the coupling agent component applied to the phosphate glass is selected according to the type of resin or phosphate glass used, but based on the mass of the phosphate glass after application. The solid content is preferably 0.2 to 2.0% by mass. When the applied amount is less than 0.2% by mass, it is difficult to sufficiently improve the handling property and the adhesion property with the resin when handling the glass. On the other hand, if the applied amount is more than 2.0% by mass, the dispersion of the phosphate glass in the halogen-containing resin tends to be lowered, which is not preferable.

The halogen-containing organic resin composition of the present invention is obtained by mixing an organic resin containing a halogen, a smoke suppressant containing a phosphate glass, and other additives added as necessary. .
In particular, when the organic resin containing halogen is a thermoplastic resin or a thermoplastic elastomer, it is the same as the conventional method for producing a resin composition such as melting at the same time as mixing (for example, melt kneading) or melt kneading after mixing. A resin composition as a molding material can be obtained by the method. The form of resin to be blended is not particularly limited, and various forms such as pellets, granules, powders, and fibers can be used. After melt-kneading the above components, it is preferable to form by extrusion molding into a pellet-shaped or granular molding material.

  The organic resin composition containing the halogen of the present invention, which is a molding material, can be molded into various molded products by various methods in the same manner as conventional resin compositions. Examples of the molding method include press molding, extrusion molding, calendar molding, injection molding, and pultrusion molding. By such a molding method, the resin composition of the present invention which is a molded product is obtained. Further, without passing through the resin composition of the present invention which is a molding material, a resin, a phosphate glass, and, if necessary, other additives are added to a molding machine such as an injection molding machine or an extrusion molding machine. The molded product of the present invention can also be obtained by melting and mixing in the molten mixture.

  Examples of the molded article include roof-related members such as roofs, fences, and gutters, siding materials, deck materials, exterior exterior wall members such as fences, opening-related members such as window frames, doors, and gates, wall materials, and floors. Materials, ceiling materials, surrounding edges, picture frames, skirting boards, stairs, handrails, and other interior-related members, other building materials and building articles, furniture materials, disaster prevention troughs, signboards, and wire covering materials.

Examples of the present invention will be described below, but the present invention should not be construed as being limited thereto.
Various characteristic values were measured as follows.

(1) Water resistance of glass:
Glass cullet (a plate of about 15mm square and about 6mm thick) is weighed as a sample, immersed in a 90 ° C hot water bath, taken out from the bath after 6 hours, dried at room temperature, weighed sample, and mass loss Was measured. The ratio of mass loss with respect to the mass before immersion was calculated as a percentage, and rank evaluation was made with less than 0.1% as O, 0.1 to 1.0% as Δ, and over 1.0% as X.

(2) Glass transition point:
What grind | pulverized the glass cullet to the predetermined particle diameter was used for the measurement, and it measured in 10 degree-C / min and nitrogen atmosphere using the differential thermal analyzer (DTA). In the DTA curve, the temperature of the shoulder of the first endothermic part was read as the glass transition point.

(3) Smoke suppression test:
In accordance with the test method of ASTM-E662, a test piece having a width of 76.2 mm, a length of 76.2 mm, and a thickness of 3 mm was subjected to measurement using an NBS smoking property tester. In the test, when the test piece was heated by applying an average radiation energy of 25 kW / m ^{2 by} the flameless combustion method, the attenuation of transmitted light due to smoke generated in the test box was measured. The smoke generation amount was determined as the maximum specific optical density (Dmax), and smoke suppression properties were evaluated.

[Preparation of phosphate glass]
The glass composition is 8.6% Na ₂ O, 4.0% K ₂ O, 25.9% P ₂ O ₅ , 4.5% SO ₃ and 57, expressed as mole percent on oxide basis. Glass raw materials were mixed and melted so as to have a glass composition of 0.0% ZnO, and then solidified to produce a glass cullet as Example 1.

Further, as represented by mol% based on oxides, 4.5% of _Li 2 O, 10.2% of _Na 2 O, 5.8% of _K 2 O, 23.7% of _P 2 _O 5, 7. The glass raw materials are mixed and melted so as to have a glass composition of 1% SO ₃ , 1.6% Al ₂ O ₃ , 9.3% B ₂ O ₃ and 37.8% ZnO, and then solidified. Thus, a glass cullet to be Comparative Example 1 was produced.
For the glass cullet of Example 1 and Comparative Example 1, the glass transition point and water resistance were measured. The measurement results are shown in Table 1 together with the melting temperature of the glass.

上記の実施例１及び比較例１のガラスカレットをボールミルにより粉砕し、平均粒径（Ｄ５０）が３μｍのガラス粉末をそれぞれ得た。

The glass cullet of Example 1 and Comparative Example 1 was pulverized with a ball mill to obtain glass powders having an average particle diameter (D50) of 3 μm.

[Preparation of vinyl chloride resin composition]
100 parts by mass of polyvinyl chloride resin (PVC: TK800, manufactured by Shin-Etsu Polymer Co., Ltd.), 50 parts by mass of the glass cullet of Example 1, 3 parts by mass of dibutyltin mercaptide (ADK STAB 1291, manufactured by Asahi Denka Co., Ltd.) and steer as a lubricant 1 part by mass of calcium phosphate (GF-200, manufactured by NOF Corporation) was charged into a double kneading roll apparatus having a roll temperature of 20 rpm at a set temperature of 180 ° C., and melt-kneaded for 8 minutes to obtain a resin composition. This resin composition was molded using a flat plate press molding machine at a mold temperature of 180 ° C., a molding pressure of 10 MPa, and a molding time of 5 minutes to obtain a molded article of the vinyl chloride resin composition of Example 2.

Except for using the glass cullet of Comparative Example 1, a molded product of the vinyl chloride resin composition to be Comparative Example 2 was obtained by the same method as that for obtaining the molded product of the vinyl chloride resin composition of Example 2 above. .
Test pieces used for the smoke suppression test were obtained from the molded articles of Example 2 and Comparative Example 2, and the test was performed. The Dmax of Example 2 was 90, and the amount of smoke generation was small. The Dmax of Comparative Example 2 was 110, and the smoke generation amount was larger than that of Example 2.

The smoke suppressant containing the phosphate glass of the present invention is useful as a flame retardant compounded in an organic resin containing a halogen. The resin composition containing the smoke suppressant of the present invention is useful as a molding material for obtaining various molded products.
The resin composition containing the smoke suppressant of the present invention as a molded product can be used for applications such as electronic and electric related members and vehicle related members, and is also used for roof related members, opening related members, and other building members. Can be used for

The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2007-085227 filed on Mar. 28, 2007 are cited here as disclosure of the specification of the present invention. Incorporated.

Claims (7)

A smoke suppressant at the time of combustion of an organic resin containing a halogen, which comprises a phosphate glass having the following composition expressed in mol% on an oxide basis and having a glass transition point of 400 ° C. or lower.
_{P 2 O 5: 20~40%,} ZnO: 56~65%, SO 3: 0.5~12%, Li 2 O + Na 2 O + K 2 O: 3~20%, however, Li ₂ O: 0~5% , Na ₂ O: 3-15%, K ₂ O: 0-10%. The smoke suppressant according to claim 1, wherein the phosphate glass has the following composition in terms of mol% based on oxide.
_{P 2 O 5: 25~35%,} ZnO: 57~60%, SO 3: 1~8%, Li 2 O + Na 2 O + K 2 O: 5~10% ( _{however, Li 2 O: 0~5%,} Na _{2 O: 4~9%, K 2} O: 1~6%).   The smoke suppressant according to claim 1 or 2, wherein the phosphate glass is a powder having an average particle size (D50) of 0.5 to 20 µm.   The smoke suppressant according to any one of claims 1 to 3, which is used by adding 1 to 200 parts by mass to 100 parts by mass of an organic resin containing halogen.   The smoke suppressant according to any one of claims 1 to 4, wherein the organic resin containing halogen is an organic resin containing chlorine.   The organic resin composition containing the halogen containing 1-200 mass parts of the smoke suppression agent of Claim 1 with respect to 100 mass parts of organic resins containing a halogen.   A molded product obtained by molding the organic resin composition containing halogen according to claim 6.