JP2007224147A - Flame-retarding composite composition and flame-retarding composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retarding composite composition having flame retardancy of such an extent as to meet the UL specification in spite of not containing a silicone and flame retardants and provide a flame-retarding composite material. <P>SOLUTION: The flame-retarding composite composition is formed by incorporating 30-90 pts.vol. of a metallic filler or a ceramic filler into 100 pts.vol. of a host material that is a gel-like resin formed by incorporating 30-200 pts.vol. of a plasticizer into 100 pts.vol. of a urethane resin or an acrylic resin. The flame-retarding composite material is the one in which the above flame-retarding composite composition and a thermoplastic resin film are laminated. Because the flame-retarding composite composition has high specific gravity and the fluidity of the gel-like resin increases when heating such as leading to cause inflammation is applied, the part that has received the heating drips gravitationally as burning drippings and the inflammation does not proceed regarding the remnant left after the burning drippings have dripped. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flame retardant composite composition and a flame retardant composite material.

  Various members made of a resin material having a relatively low hardness are disposed in the electronic device. For example, a heat conducting material obtained by blending a heat conductive filler with a rubber-based or thermoplastic elastomer-based low-hardness resin material is disposed at a location where heat from a heat source is transmitted to another member. Further, a conductive material or an electromagnetic wave absorbing material obtained by blending a metal filler or a magnetic filler with a rubber-based or thermoplastic elastomer-based low-hardness resin material is disposed at a location where transmission of electromagnetic waves is desired to be blocked. Furthermore, the rubber-based or thermoplastic elastomer-based low-hardness resin material may be disposed as a buffer material, a vibration damping material, or the like.

  Various members made of these resin-based materials are generally required to have flame retardancy. For example, UL standards (well-known standards defined by UL (Underwriters Laboratories Inc.), a US private organization) There are many cases where it is necessary to be a conforming product.

Therefore, as a measure for imparting flame retardancy to a resin material, conventionally, a method using non-flammable silicone as a base material (for example, see Patent Document 1), or adding a flame retardant to the base material The method (for example, refer patent document 2) etc. which were performed were employ | adopted. By adopting such a method, it was possible to produce a resin-based material having flame resistance to the extent that it complies with UL standards.
JP-A-8-174765 JP-A-8-113662

However, the method of using nonflammable silicone as a base material and the method of adding a flame retardant to the base material have the following problems.
First, when silicone is used as the base material, the low molecular weight component contained in the silicone volatilizes and becomes an insulator such as silicon dioxide in the electrical contact, which may cause problems such as increased contact resistance and contact failure. It was.

  In addition, when using a flame retardant, the hardness of the material obtained is often relatively high, and there is a drawback that it is difficult to obtain a low-hardness material. In addition, when a flame retardant is used, dioxins may be generated during incineration or it may become a pollution-causing substance such as an environmental hormone. Substances; harmful effects on the environment, such as being subject to regulations in the European Union (EU), are now subject to regulation.

  The present invention has been made in order to solve the above-mentioned problems, and the object thereof is to provide a flame retardance sufficient to meet the UL standard even though it does not contain silicone or a flame retardant. It is providing the flame-retardant composite material and the flame-retardant composite material comprised using the flame-retardant composite composition.

The characteristic configuration employed in the present invention will be described below.
The flame retardant composite composition of the present invention is based on 100 parts by volume of the base material, with a gel-like resin formed by blending 30 to 200 parts by volume of a plasticizer with 100 parts by volume of urethane resin or acrylic resin. And 30 to 90 parts by volume of a metal filler or a ceramic filler.

  In the flame retardant composite composition of the present invention, the metal filler or ceramic filler is blended in an amount of 30 to 90 parts by volume with respect to 100 parts by volume of the base material made of a gel resin. Therefore, the specific gravity of the flame retardant composite composition is large, and when subjected to heating that causes combustion, the fluidity of the gel-like resin increases with heating, so that the heated portion combusts. Drop (drip) by its own weight as a drop. As a result, the combustion does not proceed with respect to the remaining portion after the combustion droppings are dropped, and the remaining portion does not burn out.

  Therefore, if it is a flame retardant composite composition comprised in this way, it will become a flame retardant material which conforms to UL94 V-2 standard, although it does not contain a silicone or a flame retardant, for example, UL standard The flame-retardant composite composition of the present invention can be used when manufacturing various members in an electronic device that are required to be compatible.

  If the mixing ratio of the metal filler or the ceramic filler is less than 30 parts by volume, the flowability of the gel-like resin increases with heating, but the specific gravity of the flame retardant composite composition does not increase sufficiently. Becomes difficult to dripping, and it becomes difficult to ensure sufficient flame retardancy. Further, when the blending ratio of the metal filler or ceramic filler exceeds 90 parts by volume, the specific gravity of the flame retardant composite composition is increased, but the amount of the gel-like resin that is the base material is relatively reduced. Even if the fluidity of the base material is increased, the fluidity of the flame retardant composite composition as a whole does not increase so much, and the combustion part is also difficult to drip, making it difficult to ensure sufficient flame resistance. That is, in the flame retardant composite composition of the present invention, it becomes difficult to ensure sufficient flame retardancy even if the metal filler or ceramic filler is excessively large or small.

  Further, in the flame retardant composite composition of the present invention, the plasticizer is a fluid component for gelling the urethane resin or acrylic resin, depending on whether the urethane resin or acrylic resin is based. Any suitable plasticizer may be selected. If a specific example is given, if it is a case where it is based on a urethane resin, for example, a gel-like resin mixes 30-200 volume parts of olefin oil which is a plasticizer to 100 volume parts of urethane resin. It should be. Moreover, if it is a case where it is based on an acrylic resin, for example, gel-like resin is good to mix | blend 30-200 volume parts of trimethic acid ester which is a plasticizer with respect to 100 volume parts of acrylic resins. .

  When the blending ratio of the plasticizer is less than 30 parts by volume, the hardness of the gel resin tends to be excessively high, and the combustion part tends to be difficult to drip, so that sufficient flame retardancy is ensured. Becomes difficult. In addition, if the blending ratio of the plasticizer exceeds 200 parts by volume, the plasticizer tends to bleed out from the surface of the gel-like resin. There is a risk of disappearing.

  Moreover, what is necessary is just to select a suitable metal filler or ceramic filler according to the use of a flame-retardant composite composition. For example, if this flame retardant composite composition is used as a heat conductive composition, a ceramic filler having high heat conductivity may be used as the filler. Specifically, alumina, magnesia, silicon carbide, Boron nitride, aluminum hydroxide, magnesium hydroxide, talc, expanded graphite, aluminum nitride, silicon nitride, and graphite powder may be used. For example, if this flame-retardant composite composition is used as a conductive composition, copper, silver, aluminum, or the like may be used as the filler. Moreover, if it uses as an electromagnetic wave absorption composition, it is good to use powders, such as Sendust, permalloy, and ferrite.

  In addition, these metal fillers or ceramic fillers may be fillers having any particle shape as long as desired performance (thermal conductivity, conductivity, electromagnetic wave absorption characteristics, etc.) can be imparted. A filler having a particle shape such as a spherical shape, a crushed shape, a scale shape, or a needle shape may be used. Further, the particle diameter and particle size distribution are arbitrary as long as the desired performance can be imparted.

Next, the flame-retardant composite material of the present invention is characterized in that the flame-retardant composite composition of the present invention and a thermoplastic resin film are laminated.
With such a flame retardant composite material, even if the mechanical strength of the portion formed by the flame retardant composite composition is relatively low, the thermoplastic resin film supplements the mechanical strength. The portion formed by the composite composition can be made thin or thin, and even in that case, the mechanical strength of the entire flame retardant composite material can be sufficiently ensured. In addition, since the plasticizer in the flame retardant composite composition does not permeate the thermoplastic resin film and bleed out, the plasticizer bleed out more reliably on the surface on which the thermoplastic resin film is laminated. Can be prevented.

  In addition, the thermoplastic resin film itself is often easily combusted, but in the case of a laminate with the flame retardant composite composition of the present invention, it is heated when heated to cause combustion. Along with this, the fluidity of the gel-like resin in the flame-retardant composite composition is increased, and the fluidity of the thermoplastic resin film is also increased. Therefore, the heated portion is dripped by its own weight as a combustion drop. As a result, the combustion does not proceed with respect to the remaining portion after the combustion droppings are dropped, and the remaining portion does not burn out.

  Therefore, in the case of the flame retardant composite material configured as described above, the flame retardant composite material that conforms to the UL94 V-2 standard despite being provided with a thermoplastic resin film that is normally easily combustible. Thus, for example, the flame-retardant composite material of the present invention can be used when manufacturing various members in an electronic device that are required to be UL standard compliant products.

  In the flame retardant composite material of the present invention, the thermoplastic resin film preferably has a thickness of 1 to 100 μm. A film having a thickness of less than 1 μm is not practical because it is usually too expensive to produce the film. In addition, when the thickness exceeds 100 μm, the rigidity of the film is likely to be high, and the film portion is easily combusted, so that it is difficult to ensure sufficient flame retardancy.

  Further, in the flame-retardant composite material of the present invention, the thermoplastic resin film may be a film made of any thermoplastic resin, but the adhesiveness and heat resistance with the flame-retardant composite composition Considering favorable points, etc., a polyester film is preferable.

Next, embodiments of the present invention will be described with more specific examples.
(1) Manufacturing method Samples 1 to 12 shown in Table 1 below were manufactured by the procedure described below.

  First, a urethane resin, a plasticizer, and a filler are blended in a volume ratio as shown in Table 1 below (however, only the sample 1 is not blended with a plasticizer), and each raw material composition is kneaded to perform vacuum defoaming. went. Thereafter, using a coater, molding was performed at a temperature of 150 ° C. and a molding time of 7 minutes to obtain a sheet-like molded product having a thickness of 2.0 mm. For samples 2, 3, 4, 5, and 11, each thermoplastic resin film shown in Table 1 was laminated.

  In the present embodiment, the urethane resins in Table 1 are polyols (manufactured by Idemitsu Oil Co., Ltd., product name: Epaul), modified polyols (manufactured by Ito Oil Co., Ltd., trade name: URIC Y-202), and isocyanates. A mixture of (IPDI; isophorone diisocyanate) is used as a precursor, and these precursors are polymerized. As the plasticizer in Table 1, olefin oil (kinematic viscosity 63 cSt (at 40 ° C.)) was used. As the filler, a mixture of alumina powder and magnesia powder (average particle size 10 μm) was used. As the thermoplastic resin film, a polyester film (PET; polyethylene terephthalate, thickness 1 μm, 100 μm) was used. However, each of these materials is exemplified as an embodiment of the present invention, and does not indicate that the above-described specific materials are essential for carrying out the present invention.

Also, an acrylic resin is used instead of the urethane resin, and a trimet acid ester is used as a plasticizer. Other than these (mixing ratio, production procedure, etc.), the sheet-like molded product is the same as in the case of the urethane resin. And the laminated body with a thermoplastic resin film was obtained.
(2) Performance test About the said samples 1-12, the combustion test was implemented based on UL94 V-2 specification.

  Specifically, first, five strip-shaped test pieces were prepared for each of the samples 1 to 12, and the upper end of the test piece was held and supported vertically. And the burner flame was applied to the lower end of this test piece for 10 seconds, the burner flame was separated from the test piece after that, and the flammable combustion duration after completion | finish of flame contact was measured. Next, when the flame at the lower end of the test piece disappeared, the burner flame was immediately applied for another 10 seconds, the burner flame was separated from the test piece, and the flaming combustion duration after completion of the flame contact was measured again.

  As a result of the above test, the first and second flammable combustion durations are each within 30 seconds, and the total of the second flammable combustion duration and the flameless combustion time is within 60 seconds. The total flammable combustion duration of the test pieces is within 250 seconds, the test piece does not burn out, and “○” for a sample that satisfies all of the above conditions. The sample was judged as “x”. Table 2 shows the determination results.

  From the test results shown in Table 2 above, it was found that Samples 2, 3, 4, 5, 6, 7, 10, and 11 were UL94 V-2 standard compliant products. In particular, for Samples 2, 3, 4, 5, and 11, even though the thermoplastic resin film is laminated, the burning portion drip before the thermoplastic resin film burns up, so the remainder of the test piece burns up. It never happened.

  In addition, since the plasticizer is not mix | blended with the sample 1, the fluidity | liquidity of a combustion part does not become high enough, and it seems that the combustion part did not drip easily because of this. Sample 12 is an experimental result showing the same tendency. Although the amount of plasticizer is larger than that of sample 1, the fluidity of the combustion part is not sufficiently high because the plasticizer is not blended as much as the other samples. It seems that the combustion part did not drip easily because of this.

  Further, since the amount of filler in Sample 8 is small, even if the fluidity of the combustion portion increases with heating of the combustion portion, the weight of the other sample does not act as much as the other samples, and it can be dripped by its own weight. Probably not. On the contrary, since the sample 10 has a large amount of filler, the amount of the gel resin, which is the base material, is relatively small, and the fluidity of the combustion part is not sufficiently high due to this, and the combustion part is easy. Seems not to drip.

Each sample in which the burning part did not drip burned as it was, and the test piece was eventually burned out.
In addition, when the above combustion test was performed on a sheet-like molded article using an acrylic resin instead of the urethane resin, and a laminate of a thermoplastic resin film, as with the urethane resin, drip accompanied with combustion. Even in the case of a laminate with a thermoplastic resin film, the burning portion drip before the thermoplastic resin film burns up, so that the remaining part of the test piece does not burn up.

  As is clear from the above description, the composite compositions such as Samples 6, 7, and 10 are flame retardant composite compositions that exhibit flame retardance to the extent that conforms to the UL94 V-2 standard. Using the flame retardant composite composition, a molded product that conforms to the UL94 V-2 standard can be produced.

  In addition, the composite compositions used in Samples 2, 3, 4, 5, and 11 exhibit flame retardancy to the extent that conforms to the UL94 V-2 standard when laminated with a thermoplastic resin film to form a composite material. The resulting flame retardant composite material.

  Furthermore, the composite compositions used in Samples 2, 3, 4, 5, and 11 are UL94 V-2 compliant products even when laminated with thermoplastic resin films. , 11 is also considered to be a flame retardant composite composition exhibiting flame retardance to the extent that conforms to the UL94 V-2 standard, and using this flame retardant composite composition, UL94 V -2 It is considered that a molded product that conforms to the standard can be manufactured.

As mentioned above, although embodiment of this invention was described, this invention is not limited to said specific one Embodiment, In addition, it can implement with a various form.
For example, in the above embodiment, the example in which the heat conductive material is configured by blending the alumina resin and the magnesia powder, which are heat conductive fillers, with the gel resin as the base material has been shown. The composite composition may contain a filler other than the heat conductive filler. Specifically, for example, a conductive material can be configured by blending a conductive filler, or an electromagnetic wave shielding material can be configured by blending a conductive filler or a magnetic filler.

  As the ceramic filler, for example, powders such as alumina, magnesia, silicon carbide, boron nitride, aluminum hydroxide, magnesium hydroxide, talc, expanded graphite, aluminum nitride, silicon nitride, and graphite can be used. Moreover, as a metal filler, it is good to use copper, silver, aluminum, etc., for example. Moreover, if used as an electromagnetic wave absorbing composition, powders such as sendust, permalloy, and ferrite can be used. What is necessary is just to select a suitable ceramic filler and metal filler according to the use of a flame-retardant composite composition.

Claims (6)

A gel-like resin formed by blending 30 to 200 parts by volume of a plasticizer with 100 parts by volume of a urethane resin or an acrylic resin is used as a base material. A flame retardant composite composition comprising: The flame retardant composite composition according to claim 1, wherein the gel-like resin is obtained by blending 30 to 200 parts by volume of an olefinic oil as the plasticizer with respect to 100 parts by volume of a urethane resin. The flame-retardant composite composition according to claim 1, wherein the gel-like resin is obtained by blending 30 to 200 parts by volume of a trimetic acid ester, which is the plasticizer, with 100 parts by volume of an acrylic resin. A flame retardant composite material comprising a laminate of the flame retardant composite composition according to any one of claims 1 to 3 and a thermoplastic resin film. The flame-retardant composite material according to claim 4, wherein the thermoplastic resin film has a thickness of 1 to 100 μm. The flame-retardant composite material according to claim 4, wherein the thermoplastic resin film is a polyester film.