JP2002121333A - Polyolefin resin molded product and film thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin molded product such as a polyolefin flame retardant- film or -coating membrane which is safe at the time of a fire, is harmlessly treated in a disposal such as burning, has good recyclability, strength performances, and convenience in use. SOLUTION: The resin molded product comprises such a polyolefin resin that a polyolefin resin of a propylene homopolymer or a copolymer having the principal component thereof is added with a specified amount of a hindered amine derivative, as a flame retardancy-affecting agent, of a radical collector of a high molecular-weight hindered amine, in which an imino group (>N-H) is substituted with an N-alkoxy imino group (>N-O-R), and with a specified amount of allyl phosphite of a phosphorus-based antioxidant, as a process heat stabilizer to prevent the above flame retardancy-affecting agent from denaturing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyolefin resin molded product and a film comprising the same. More specifically, packaging materials, interior materials, home appliance housings, and car interior materials that require flame-retardant products are safer in the event of a fire, can be disposed of harmlessly by incineration, and can be recycled. A product with flame retardancy of polyolefin resin using non-halogen, polymer additive as a flame retardant, and high performance such as high strength and the same usability of products as before. The present invention relates to a flame retarded film and a flame retardant composite film.

[0002]

[Prior Art] Packaging materials such as polyethylene shopping bags at mass retailers, interior materials such as wallpaper and pea tiles, refrigerators,
In fields where products have traditionally required flame retardancy, such as housings for home appliances such as televisions and AVs, and interior materials for automobiles, vinyl chloride products and products using halogen compound flame retardants are frequently used. However, if incinerated and disposed of after use, harmful substances such as dioxin may be generated, and harmful substances such as hydrogen halide and soot are generated at the time of fire. Recently,
There is a strong demand for recyclability, etc., and it is required to make the above materials with a polyolefin resin that is easier to recycle than polyethylene terephthalate. As described above, flame retardants of halogen compounds have been used.

[0003] Conventional polyolefin-based flame retardant materials include:
Halogen-based flame retardant, which is generated by thermal decomposition of heavy halogen gas and covers the material surface to block oxygen, making it flame-retardant. Mainly effective with polycondensation resins. Phosphorus compounds such as ammonium phosphates and red phosphorus, which promotes carbonization by extracting hydrogen in the dehydration reaction to promote carbonization, as well as non-flammable inorganic substances and inorganic substances which are released when crystallization water is heated, generally in a majority amount Then, using hydroxides such as magnesium hydroxide that becomes flame-retardant by reducing the amount of flammable resin, these were examined,
No flame retardant effect was found to be much better than conventional ones, and no other companies have put it to practical use in the last decade.

In particular, a film product is thinner and harder to produce than an electric cord or the like, so a flame retardant that can be made flame-retardant with a small amount is indispensable, and there is no good product.

[0005]

In the field where the above products are required to have flame retardancy, halogen compounds having a high flame retardant effect, for example, vinyl chloride resins and halogen-based flame retardants have been widely used for this purpose. However, when harmful substances such as hydrogen halide and soot are generated in a fire, these harmful substances cause severe damage to the victims, and when they can no longer be used due to damage or deterioration, they should be incinerated and disposed of. Since harmful substances such as dioxin are generated, they cannot be incinerated and cannot be disposed of by microorganisms. Therefore, their use has a serious problem in disposal. In addition, when these products are manufactured or recycled, harmful substances such as hydrogen halides are generated, leading to deterioration of the manufacturing environment and deterioration of the manufacturing equipment, causing serious problems. There is a problem that it cannot be regenerated due to elution.

[0006] In addition to known halogen-based flame retardants, phosphorus-based and ammonium salt-based flame retardants have been disclosed. Magnesium hydroxide and the like have been known as resin flame retardants. However, the polyolefin film has no effect unless the halogen-based flame retardant is used as a main component, and these have been mainly used.

However, there are various problems as described above, and it is required that the flame retardancy of a film using a polyolefin resin be achieved by using a chemical containing no halogen element. Safe in the event of a fire, harmless disposal such as incineration,
There is still a strong demand for polyolefin-based flame-retardant films and coating film molding materials that are recyclable and have the same level of performance as conventional and do not hinder the usability of products.

Further, the present inventors have studied the correlation between the flame retardant agent used in the present invention and various polyolefin resins, but some polypropylene resins having the flame retardant effect and those having no flame retardant effect have appeared. The effect varies greatly depending on the manufacturer and grade, and it is economically problematic to ensure the effect with a limited specific resin, and always obtain the best flame retardant effect with a smaller amount of the flame retardant. Therefore, it was necessary to find a condition that can achieve the same effect even with a less expensive resin and can cope with the cost reduction, and to make the resin versatile.

[0009]

Means for Solving the Problems In order to make a polyolefin resin exhibit flame retardancy, it is necessary to shut off oxygen as an oxidizing agent,
The conventional method of imparting flame retardancy is to reduce the content of combustible resin so as to generate low heat even when ignited by coating with heat-resistant carbide by pyrolyzing at a low temperature without ignition. When these are arranged, it shuts off the oxidizing agent, suppresses the generation of combustible gas during combustion, and lowers the temperature of the flame. Polyolefin-based flame-retardant resins are mainly halogen-based flame retardants that have the effect of Although it was a flame retardant composition, it had major problems in manufacturing, use, and in the event of a fire. Therefore, the concept of the conventional flame retardant was discarded and reexamined from scratch.

According to the present invention, the combustion mechanism of the polyolefin resin is as follows. First, the resin is thermally decomposed by heat to release low molecular weight monomers and the like, which are ignited and further burn by causing a thermal decomposition chain. As a result of continued investigation assuming the mechanism, the resin was thermally decomposed by an external flame by adding a larger amount of Hals-based radical scavenger not as a stabilizer of polyolefin but as a flame retardant. Alkyl radicals (R.) are generated first, but by trapping these radicals, if the thermal decomposition chain is interrupted, generation of low molecular weight substances from medium molecular weight substances can be suppressed, and polyolefin resins and films thereof can be used. I thought it could be flame retardant.

The inventors of the present invention have studied variously whether the film can be made flame-retardant by increasing the concentration of a Hals radical scavenger having an imino group (> NH), but the expected flame-retardant effect can be obtained. Did not. That is, radicals (R.) and (ROO.) Generated by combustion are converted to imino groups (> NH)
It was found that Hals could not capture enough and did not exhibit the flame retardant effect.

The mechanism of action of the Hals radical scavenger is as follows:
There are descriptions in various books, and the myth is almost fixed. For example, there is a new development of polymer additives issued by the Nikkan Kogyo Shimbun in 1998, and the cycle includes an imino group (> NH)
Not only that, but also includes hydroxylimino groups (> NOH), alkoxyimino groups (> NOR), and (> NO.) Radicals, and radicals (R.) generated by combustion
Reacts very quickly with oxygen molecules (O ₂ ) (ROO
()), But the (> NO.) Radical also reacts with the radical (R.) as quickly as described above to become an alkoxyimino group (> NOR) and annihilates the radical (R.). Therefore, a Hals-based drug having a (> NO.) Radical can be expected, but is unstable due to the radical and cannot be obtained as a drug. It is the alkoxyimino group (> NOR) that easily generates the (> NO.) Radical, which emits a readily volatile alkyl to generate the (> NO.) Radical, and the polyolefin resin is decomposed instead. We thought that by trapping and stabilizing low molecular weight substances from the generated medium molecular weight substances, the generation of combustible substances could be quantitatively suppressed and the flame retardant effect could be exhibited. Incidentally, the alkyl group of (> NOR) is preferably an alkyl group which is easily volatilized and is hardly oxidized or decomposed at all, and a cyclic group is more preferable than a linear group. Note that an alkoxyimino group (> NO
R) is more advantageous for capturing a radical in a solid phase, and can also capture radicals (R.) inside a molded product such as a film.

Also, if there is little or no burnable material, it should not burn if it runs out, and if it hits with a flame, it will melt quickly,
By shrinking the resin with the melt tension from the flame part and keeping the resin away, that is, by using a thin film that can be easily melted and drilled larger holes, if you devise a specification to use, as a result, the flame retardant effect will be further improved We thought that it could be expressed and came to the invention.

Recently, an alkoxyimino group (> NOR) type polymer huls has become available, and a polypropylene (PP) film has been experimentally manufactured using a resin into which the chemical has been kneaded. A result showing good flame retardant effect was obtained. Therefore, when the study was expanded to polyolefin resins of various manufacturers, the expected results could not be obtained with most of the resins. As illustrated in the comparative example, even with the addition of 2%, the result of burning was obtained.
Only the P resin was found to have the highest flammability rating of tertiary, and only 0.5% addition was stable. Then, the correlation of the stabilizer of the polyolefin resin used was investigated, and allyl phosphite, tris (2,4-di-ter
It was found that a fiber having a resin to which t-butylphenyl) phosphite (referred to as a stabilizer T) was added as a base resin of a masterbatch had a flame-retardant effect or a flame-retardant tendency.

Therefore, a master batch (MB) in which the (NOR) type polymer hulse and the stabilizer T used in the present invention are kneaded together and an MB containing only the stabilizer T were prepared and examined. Also, by adding the same 2% of the flame-retardant agent used in the present invention and using the stabilizer T together, it was possible to obtain a tertiary fiber having the highest flame-retardant grade, leading to the present invention.

The so-called phosphorus antioxidant allylphosphite used in the present invention is prepared by melting and mixing
B, melt to make a film, melt resin 200
Above ℃, in order to exert an excellent effect on deterioration prevention, at the time of the production of MB or film made by melting the resin, at least to prevent thermal deterioration of (NOR) type polymer Hals used in the present invention, It is estimated that the flame retardant effect is exhibited. Further, it is presumed that some good synergistic effect is given because the surface of a molded product such as a film is melted during combustion. In any case, stabilizer T is essential for the present invention.

Polyethylene is less likely to impart a flame-retardant effect with the flame-retardant agent used in the present invention than polypropylene, and it is difficult to use α-polyolefin resins having side chains such as polybutene-1 and polymethylpentene-1. It seems to be effective for burning. This may be due to the effect that the lifetime of the generated radical is extended by the tertiary carbon.

The present invention relates to a resin of propylene, butene-1 or pentene-1 homopolymer or copolymer,
When the imino group (> N—H) of the high molecular weight hindered amine radical scavenger is an N-alkoxy imino group (> N—O—
A hindered amine derivative substituted by R) as a flame retardant; a phosphorus antioxidant allyl phosphite as a processing heat stabilizer for preventing deterioration of the flame retardant when the resin to be added is in a molten state; 0.2 <a <10, when the concentration of the flame retardant is a mass% and the concentration of the processing heat stabilizer is b mass%,
5 <a / b <30, and 0.02 ≦ b, so as to provide a flame-retardant property to an olefin resin. Uses a hindered amine-based stabilizer, which is a stabilizer for polyolefin resins, instead of conventional flame retardants.As a result, it is a non-environmental hormone, achieving non-halogen flame retardancy and harmful in the event of fire. It is safe because it does not generate gas and does not emit harmful substances during disposal.
A polyolefin with the characteristics that the effect agent is similar to a resin stabilizer, so that recycling is easy and the required addition amount is smaller than that of conventional flame retardants, so that the performance of molded products such as films does not decrease much. It is a resin molded product.

Further, in the case of the composite film, not all need to be the resin to which the flame retardant used in the present invention is added, and other polyolefin resins can be used. When the total content of the resin to which the agent is added is c mass%, 30 ≦ c, and the flame-retardant effect agent is at least 0.
If it is contained at a ratio of 3 parts by mass, a flame retardant effect is produced.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention relates to a phosphorus-based antioxidant which is prepared by adding a high molecular weight hindered amine stabilizer to a propylene, butene-1 or pentene-1 homopolymer or copolymer resin as a flame retardant. Agents are used in combination as processing heat stabilizers for preventing deterioration during processing, and the addition rate of the flame retardant is a mass% and the addition rate of the processing heat stabilizer is b
Assuming mass%, 0.2 <a <10 and 5 <a / b <3
The present invention relates to a molded product of a polyolefin resin such as a film which is flame-retarded by imparting flame retardancy to an olefin resin by adding 0 and 0.02 ≦ b.

The polyolefin resin to which the flame retardant of the present invention is added includes propylene having tertiary carbon and butene-1.
Or a pentene-1 homopolymer or a copolymer containing these as a main component, and / or a polyolefin resin containing a mixture containing these as a main component is particularly preferable, and a homopolymer of an α-olefin having mainly 2 to 8 carbon atoms. These copolymers, ethylene-modified products such as ethylene carboxylic acid and vinyl acetate, propylene-modified products, copolymers with styrene and rubber monomers, and mixtures thereof, containing these as main components may be used.

The olefin resin containing no flame retardant used in the present invention is almost the same, except that ethylene-vinyl acetate, ethylene-vinyl alcohol, ethylene-acrylic acid, and ethylene-acrylate containing less α-olefin. Olefin copolymers such as can be conveniently used.

When the molded article of the present invention is in a composite film, the thermoplastic resin other than the polyolefin resin to which the flame retardant of the present invention is added may have a melting point of 100 to 300 ° C. in addition to the polyolefin resin. Polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), sulfonated polyester, aliphatic polyester, copolymerized polyester or polyester ether, polyamide 6, polyamide 66, polyamide 12, MXD nylon, copolyamide, polycondensates such as polyamides such as aliphatic polyamides or polycarbonates, polystyrene, polybutadiene or radical copolymers thereof, and the like. Adult or mixture can be used conveniently also preferable additives such as these coloring agents and fillers are added depending on the application.

In the hindered amine stabilizer used as the flame retardant of the present invention, the nitrogen moiety of the imino group is an N-alkoxyimino group (> NOR) (R is an alkyl group), and the group is an alkyl-peroxy group. Oxy radical (RO ₂
•) and easily become (> NO.) Radicals to exhibit a flame retardant effect. The flame retardant used in the present invention is M
It is indispensable to use a phosphorus-based antioxidant in combination because it is liable to be deteriorated during thermal processing of B or film formation.

As the above-mentioned phosphorus antioxidant, at least one phenyl group having an alkyl substituent represented by tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168 from Ciba) is used.
Allyl phosphite is convenient, specifically, HP-10 of ADK STAB manufactured by Asahi Denka Kogyo Co., Ltd.
PEP-24 and PEP-36 are also listed.

The flame-retardant agent of the present invention is a high molecular weight type in which a number of imino groups are present as side chains, such as Timosolve 944 (trade name of Ciba Geigy),
Since it is made three-dimensional by radical collection, volatile substances can be suppressed, which is the most preferable. As an example of the hindered amine-based stabilizer of the present invention having a specific N-alkoxyimino group (> NOR), there is CGL116, a trade name of Ciba Specialty Chemicals. As a conventional stabilizer, it is preferable to add a normal amount of a hindered amine-based stabilizer such as (> NH) type, and the addition of other stabilizers in a normal amount also has no effect on the flame retardant effect. Is preferred in maintaining the physical properties of

The amount of the flame retardant agent of the present invention added to the resin (a
Mass%) may be 0.2 <a <10, and most preferably 0.5 to 5 mass%. If the amount is less than 0.2% by mass, the flame retardancy is not sufficient, and if it exceeds 10% by mass, it is not economically preferable.

Further, among all the molding components, the flame retardant is used in an amount of at least 0.3 with respect to the polyolefin resin.
If it is not contained in proportion to the mass%, the flame retardant properties cannot be exhibited, which is not preferable. If at least 30 mass% of the resin to which the flame retardant is added is not used in the molded product, the molded product becomes difficult. It is not preferable because the fuel property cannot be exhibited.

Addition ratio of phosphorus-based antioxidant allyl phosphite (b mass%) which is used in combination as a processing heat stabilizer for preventing deterioration of the flame retardant effect agent when the resin to be added is in a molten state.
Is preferably added so that 0.02 ≦ b and 5 <a / b <30, and most preferably 0.1 to 1% by mass. In addition,
The present antioxidant is particularly preferred to coexist at least when the flame retardant used in the present invention is subjected to thermal processing.
Addition by mass% is preferred. If the content is less than 0.02% by mass, the effect of preventing deterioration is not sufficient, and economically, if the ratio a / b to the flame retardant is less than 5, the addition is excessive, and if it exceeds 30, the addition becomes too small. Not preferred.

The polyolefin resin molded article such as the film of the present invention is a molded article composed of one component or a mixed polymer, or a composite molded article such as a composite film composed of plural kinds of thermoplastic resins. And a composite film of a resin to which no is added. The resin to which the flame retardant effect agent of the present invention is added does not need to be exposed on the surface of the molded product to exhibit the flame retardant effect, even if the other component is a polyolefin resin. The flame retardant effect can be exhibited as long as it is done. Further, as described above, the amount of the molded product per unit area is small, that is, a molded product having a thin film shape is more preferable.

Further, the resin molded product of the present invention may be a thin flat body such as a film or a sheet, a housing of a home appliance which is a combination of sheet-like members, a housing of an electronic device such as a personal computer or a mobile phone, or a vehicle. Extrusion moldings and injection moldings such as surface interior materials, electric wire covering materials, building air-conditioning and building materials, laminating construction materials, and toys and household goods.

For applications requiring recyclability, the resin molded product of the present invention is preferably composed mostly of a polyolefin resin. Propylene copolymer, polyethylene, ethylene copolymer,
Particularly preferred are composite resin molded products containing polybutene 1, butene 1 copolymer, or a mixture thereof as another component, and composite resin molded products containing polymethylpentene as one component and the above-mentioned polyolefin resin as another component.

In the above-mentioned composite resin molded product, a thickness of 5 μm to 5 mm is preferable for use in a film or a surface coating, and a thickness of 10 to 500 μm is particularly preferable.

[0034] Other components of the composite resin molded product of the present invention include:
In addition to films made of other resins, there are paper, nonwoven fabric, wooden boards and plywood, iron plates, cement boards, and heat insulating materials made of inorganic fibers.

The resin molded product of the present invention contains a resin to which the flame retardant of the present invention is added, and the flame retardant of the present invention is added to the polyolefin resin constituting the molded product. It is preferable that the amount is held at a rate of at least 0.3% by mass. If the amount is less than this, a problem may occur in the flame retardancy, which is not preferable.

[0036]

Next, the effects of the present invention will be specifically described with reference to examples and comparative examples. In addition, although mainly described with reference to the film which is one embodiment of the present invention, it goes without saying that resin molded products of other forms can be similarly easily produced by referring to the examples.

(Examples 1 to 6, Comparative Examples 1 to 3) The films of Examples and Comparative Examples of the present invention were prepared in the form of a master batch (MB) in which additives were previously kneaded, and this was extruded together with a diluting resin into an extruder. And disperse to make a strand,
It was made by pressing with a hot press set to the same temperature as or lower than the extruder. When pressing the thickness,
Adjusted using a spacer. This film was evaluated for flame retardancy, and the results are shown in Table 1.

The additives used are as follows. Flame retardant (N) Ciba Specialty Chemicals CGL
-116, phosphorus-based antioxidant (T agent) Same as above, Ciba Irgafos 168. Comparative Example 2 is a film to which 2% by mass of Hals stabilizer, Cimasolve 944 manufactured by Ciba Co., was added.

[0039]

[Table 1]

(Examples 7 to 18, Comparative Examples 4 to 7) The two-layer laminated films of Examples and Comparative Examples of the present invention were prepared according to the conditions shown in Table 2, and then each having a 1: 1 thickness ratio. Combinations were selected, these were stacked and pressed to form a laminar film with a predetermined thickness, and evaluated as a sample.
The results are shown in Tables 2 and 3. Those with no indication of the second layer are single-layer films.

In the case where the additives did not need to be kneaded, each of the raw material pellets was pressed at a temperature optimum for forming each film and used as a film. In each table, PP is polypropylene, EP is a copolymer of propylene with ethylene, PM is polymethylpentene, HPE is high-density polyethylene, M is
PP is medium density polyethylene, EMA is ethylene-methyl acrylate copolymer, PB1 is polybutene 1,
PET stands for polyethylene terephthalate, and those marked with * are the flame retardant of the present invention, CGL-116 (N agent), trade name of Ciba Specialty Chemicals.
%, And 0.2% by mass of a phosphorus-based antioxidant (trade name: Irgafos 168 (T agent)). The addition ratio (% by mass) to the first layer is shown in the table. Also, M
FR means the melt flow rate and the measured temperature is 230
° C according to ASTM-1238 (L), and the unit is g /
10 minutes, provided that the measurement temperature of the polymethylpentene PM is 260 ° C. (* Mark in the table) Further, the IV value of the polyester means the limiting viscosity of the ordinary method, and the PET in Table 1 is a value of 0.64. These flame retardants are based on JIS L1
091, A-1 method.

In the table, the temperature is ° C., the density is g / cm ³ , the carbonization area in the combustion test is cm ² , the residual flame and the residual dust time are seconds, and the combustion test is heated for 1 minute and heated for 1 minute. Means 3 seconds after the arrival of the flame.

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

According to the present invention, a polyolefin resin molded article using the flame retardant resin of the present invention does not generate harmful gas even in the event of fire, despite its good flame retardancy. It has no toxic substances even when it is disposed of, and can be easily manufactured by adopting an appropriate combination of easily recyclable products. is there. Further, since it does not contain environmental hormones which have been recently mentioned, it is most suitable as an environmentally friendly flame-retardant resin molded product.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA20 AA21 AC12 AC15 AE05 AE07 AH03 AH04 AH12 AH19 BC01 4J002 BB111 BB171 ES006 EW067 FD067 FD136 GC00 GG00 GL00 GQ01

Claims (4)

[Claims] 1. A polyolefin resin comprising a homopolymer of propylene, butene-1 or pentene-1 or a copolymer containing these as a main component and / or a mixture containing these as a main component, and a high molecular weight hindered amine radical A hindered amine derivative in which an imino group (> N—H) of a collector is replaced with an N-alkoxyimino group (> N—O—R) is used as a flame-retardant agent as an allyl phosphite, a phosphorus-based antioxidant. Are added as processing heat stabilizers for preventing the deterioration of the flame retardant, and the concentration of the flame retardant is a mass% and the concentration of the processing heat stabilizer is b mass%. 0.2 <a <1
A polyolefin resin molded product having a flame retardant effect, comprising a polyolefin resin satisfying 0, 5 <a / b <30, and 0.02 ≦ b. 2. A polyolefin resin comprising a homopolymer of propylene, butene-1 or pentene-1 or a copolymer containing these as a main component, and / or a mixture containing these as a main component, having a high molecular weight hindered amine radical A hindered amine derivative in which an imino group (> N—H) of a collector is replaced with an N-alkoxyimino group (> N—O—R) is used as a flame-retardant agent as an allyl phosphite, a phosphorus-based antioxidant. Are added as processing heat stabilizers for preventing the deterioration of the flame retardant, and the concentration of the flame retardant is a mass% and the concentration of the processing heat stabilizer is b mass%. 0.2 <a <1
0, 5 <a / b <30, and a composite resin molded product comprising a polyolefin resin satisfying 0.02 ≦ b and another polyolefin resin, wherein the total content of the resin to which the flame retardant is added is When c% by mass, 30 ≦ c, and the flame retardant is contained in at least 0.3% by mass with respect to all polyolefin resins used, and has a flame retardant effect. A molded article of a polyolefin resin, characterized in that: 3. A polyolefin resin comprising a propylene homopolymer or a copolymer containing these as a main component, wherein an imino group (> NH) of a high molecular weight hindered amine / radical scavenger is an N-alkoxyimino group ( > N-
The hindered amine derivative replaced by OR) is added as a flame retardant, and allyl phosphite as a phosphorus antioxidant is added as a processing heat stabilizer for preventing deterioration of the flame retardant. When the addition concentration of the flame retardant is a mass% and the addition concentration of the processing heat stabilizer is b mass%, 0.2 <a <10, 5 <a / b <30 and 0.02 A polyolefin film comprising a polyolefin resin satisfying ≤b and having a flame retardant effect. 4. A composite film wherein the polyolefin film according to claim 3 is used as a constituent material.