JP2009263618A - Flame-retardant composition, adhesive, and filler - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant composition, an adhesive, and a filler, all having high flame retardance and low hazardousness. <P>SOLUTION: The flame-retardant composition includes (a) a silicone resin and/or a modified silicone resin and (b) a melamine derivative. Preferably, the composition further includes (c) an inorganic filler. Melamine is exemplified as the melamine derivatives. The flame-retardant composition can be used for adhering or filling a junction box. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a flame retardant composition, an adhesive, and a filler.

Silicone resins and modified silicone resins are used for sealing agents, adhesives, and the like, but flame retardancy is required depending on the site used. A flame retardant may be added to impart flame retardancy to the silicone resin or the modified silicone resin. As flame retardants, halogen flame retardants and phosphorus flame retardants are known. In addition, a technique for making flame retardant by adding an inorganic filler (expandable graphite, iron oxide, cerium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide) to a silicone resin or a modified silicone resin is disclosed ( Patent References 1 to 5).
JP-A-5-179225 JP-A-6-57140 JP-T-2006-523725 JP-A-11-106735 JP 2004-224929 A

  However, halogen-based flame retardants may generate harmful substances such as dioxins during combustion. Phosphorus flame retardants or their by-products have problems such as adverse effects on the human body, problems of promoting the eutrophication of lakes and marshes, and various physical properties such as the strength of silicone resins and modified silicone resins under high temperature and high humidity. There is a problem of lowering. Further, the inorganic filler alone cannot sufficiently improve the flame retardancy, and when used in a large amount, the adhesion of the silicone resin or the modified silicone resin to the base material is lowered.

  This invention is made | formed in view of the above point, and it aims at providing the flame-retardant composition, adhesive agent, and filler with high flame retardance and low toxicity.

The flame retardant composition of the present invention comprises (a) a silicone resin and / or a modified silicone resin, and (b) a melamine derivative.
The flame retardant composition of the present invention has high flame retardancy by containing a melamine derivative. Moreover, since the flame retardant composition of the present invention does not contain a halogen-based flame retardant or a phosphorus-based flame retardant or can reduce the amount of these components, the flame retardant composition has low toxicity. Furthermore, the flame retardant composition of the present invention is rapidly cured by containing a melamine derivative.

The adhesive of the present invention contains the flame retardant composition described above. The adhesive of the present invention may be the same as the flame retardant composition described above, and may further contain other components.
The adhesive of the present invention has high flame retardancy by containing a melamine derivative. Moreover, since the adhesive of this invention does not mix | blend a halogen-type flame retardant or a phosphorus-type flame retardant, or can reduce those compounding quantities, its toxicity is low. Furthermore, the adhesive of the present invention is rapidly cured by containing a melamine derivative.

  The adhesive of the present invention is suitable for applications in which a junction box (for example, a junction box used for a module such as a solar cell) or the like is bonded to another member because of its high flame retardancy and quick curing.

The filler of the present invention contains the flame retardant composition described above. The filler of the present invention may be the same as the above-mentioned flame retardant composition, and may further contain other components.
The filler of the present invention has high flame retardancy by containing a melamine derivative. Moreover, since the filler of this invention does not mix | blend a halogen-type flame retardant or a phosphorus-type flame retardant, or can reduce those compounding quantities, its toxicity is low. Furthermore, the filler of the present invention is rapidly cured by containing a melamine derivative.

  The filler of the present invention is suitable for applications such as filling a junction box (for example, a junction box used for a module such as a solar cell) because of its high flame retardancy and quick curing.

  It is preferable that the flame retardant composition, the adhesive, and the filler (hereinafter simply referred to as a flame retardant composition) of the present invention further contain (c) an inorganic filler. By containing an inorganic filler, it is possible to suppress a decrease in physical properties (for example, film strength) under high temperature and high humidity such as a flame retardant composition. The amount of the inorganic filler is preferably in the range of 1 to 60 parts by weight and more preferably in the range of 5 to 60 parts by weight with respect to 100 parts by weight of the flame retardant composition and the like. When the amount is 1 part by weight (preferably 5 parts by weight) or more, the effect of suppressing deterioration in physical properties is even higher, and when the amount is 60 parts by weight or less, workability is excellent. Examples of the inorganic filler include calcium carbonate, expandable graphite, iron oxide, cerium oxide, titanium oxide, magnesium hydroxide, and aluminum hydroxide.

  When the flame retardant composition of the present invention is required to have a high degree of flame retardancy, a flame retardant such as a halogen flame retardant or a phosphorus flame retardant can be used in combination with a melamine derivative. In this case, high flame retardancy can be obtained even if the amount of halogen flame retardant or phosphorus flame retardant used is small.

  The melamine derivatives are less harmful than halogen flame retardants and phosphorus flame retardants, and are less expensive than these flame retardants. Examples of the melamine derivative include melamine, dicyandiamide, acetoguanamine and the like. The blending amount of the melamine derivative is preferably in the range of 5 to 60 parts by weight and more preferably in the range of 10 to 60 parts by weight with respect to 100 parts by weight of the flame retardant composition and the like. When it is 5 parts by weight (preferably 10 parts by weight) or more, the flame retardancy is further increased, and when it is 60 parts by weight or less, workability is excellent.

  The silicone resin may be a one-pack type or a two-pack type. As the one-pack type silicone resin, for example, a silicone resin having a reactive silicon group such as a terminal alkoxysilyl group can be used. As the two-pack type silicone resin, for example, a silicone diol which is a polyorganosiloxane compound having reactive hydroxyl groups at both ends of the polysiloxane can be used. An example of a silicone diol is one represented by Chemical Formula 1 (n is an integer). A silicone diol having a viscosity of 1 to 100 Pa · s is suitable from the viewpoint of workability.

As the crosslinking agent for the silicone diol, for example, one that reacts with the hydroxyl group of the silicone diol and cures by condensation reaction can be used. As this cross-linking agent, for example, a silane or siloxane compound having two or more hydrolyzable functional groups can be used. Specifically, in the case of a one-pack type, methyltrimethylethylketooxysilane, vinyltrimethylethylketo Preferred are oxime silane, methyl triacetoxy silane, vinyl triacetoxy silane, ethyl triacetoxy silane, methyl trimethoxy silane, ethyl trimethoxy silane, vinyl trimethoxy silane, acetamide silane, siloxane having an aminoxy group, etc. , Tetraethoxysilane, tetrapropoxysilane, partial hydrolysates thereof, cyclic aminoxysiloxane, linear aminoxysiloxane, silane compound having an alkoxysilyl group and an amino group (aminosilane), and the like are preferable.

  Examples of the modified silicone resin include those that cure when a reactive silicon group-containing oligomer forms a siloxane bond. Examples of the reactive silicon group-containing oligomer include an oxyalkylene polymer having a reactive silicon group at the terminal and an acrylic polymer having a reactive silicon group at the terminal. The reactive silicon group is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond.

  In addition to the flame retardant composition of the present invention, various additives can be blended. For example, when the flame retardant composition contains a silicone diol, as a catalyst for the crosslinking reaction between the silicone diol and the crosslinking agent, organic tin, inorganic tin, titanium catalyst, bismuth catalyst, metal complex, platinum catalyst, basic substance, An organic phosphorous oxide or the like can be blended. Specific examples of the organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin diacetate and the like. Examples of metal complexes include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, aluminum acetyl acetate complex, etc. And metal acetylacetonate complexes such as metal acetylacetate complexes and vanadium acetylacetonate complexes.

  Moreover, organic tin, inorganic tin, a titanium catalyst, a bismuth catalyst, a metal complex, a platinum catalyst, a basic substance, an organic phosphorous oxide, etc. can be mix | blended as a curing catalyst when a flame retardant composition etc. contain a modified silicone resin. Specific examples of the organic tin include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin diacetate and the like. Examples of metal complexes include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, aluminum acetyl acetate complex, etc. And metal acetylacetonate complexes such as metal acetylacetate complexes and vanadium acetylacetonate complexes.

  Further, by adding a silane coupling agent having a functional group such as a vinyl group or an amino group and an alkoxysilyl group, effects such as improved storage stability, accelerated curing, and improved adhesion to a substrate can be obtained.

  Moreover, a softness | flexibility, fluidity | liquidity, etc. can be provided to a flame-retardant composition etc. by the mixing | blending of a diluent. Specific examples of diluents include phthalate-based diluents such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dimethyl silicone oil, alkyl-modified silicone oil, polyether-modified silicone oil, amino Silicone oil such as modified silicone oil, epoxy-modified silicone oil, dioctyl adipate, diisononyl adipate, dialkyl azelate, dibutyl sebacate, epoxidized soybean oil, polypropylene glycol, acrylic polymer, vegetable oil-derived 2-ethylhexyl ester compound Etc.

  In addition, antioxidants, viscosity modifiers, pigments, preservatives, and the like can be appropriately blended.

  An embodiment of the present invention will be described.

(A) Manufacture of junction box adhesives According to the formulations shown in Tables 1 and 2, the components were mixed to prepare the junction box adhesives of Examples 1-1 to 1-13. Moreover, according to the mixing | blending shown in Table 3, each component was mixed and the adhesive agent for junction boxes of Comparative Examples 1-1 to 1-6 was manufactured.

In Tables 1, 2, and 3, the modified silicone resin is EST-280 (trade name) manufactured by Kaneka Corporation. Nonen R064-3 is a trade name of an ammonium polyphosphate flame retardant manufactured by Maruhishi Oil Chemical Co., Ltd. M-300J is a trade name of surface-treated calcium carbonate manufactured by Maruo Calcium Co., Ltd. Whiteon SB is a trade name of surface untreated calcium carbonate manufactured by Shiroishi Calcium Co., Ltd. DIDP is diisodecyl phthalate. Γ- (2aminoethyl) aminopropyltrimethoxysilane is an adhesion improver. Vinyltrimethoxysilane is a dehydrating agent. 1,1,3,3-Tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane is a tin-based catalyst. Dibutyltin diacetylacetonate is a tin-based catalyst.
(B) Evaluation of junction box adhesives The adhesives for junction boxes of Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-6 produced in (a) above were cured, and the thickness was 3 mm. A sheet-like cured film was formed. This sheet-like cured film was cured at 23 ° C. and 50% RH for 7 days, and then cut into 12.7 mm × 127 mm to prepare a test piece.

  Using this test piece, the test was performed based on UL94 (Test for Flammability of Plastic Materials for Parts and Devices in Appliances UL94, Underwriter's Laboratories Inc.), which is a combustion test of plastic materials for parts of equipment. The outline of UL94 is to check the behavior of the supported test piece after flame contact with the burner and moving away the burner. The test was conducted on UL94 V0, and t1 (afterflame time) and t2 (afterflame time after the second flame contact) were measured. The test was performed with the number of n set to 5, and t1 and t2 were the average values for the five test pieces, respectively. The measurement results are shown in Tables 1 to 3 above.

The adhesives for junction boxes of Examples 1-1 to 1-13 were good in both t1 and t2, and had excellent flame retardancy. On the other hand, the adhesive for junction boxes of Comparative Examples 1-1 to 1-5 containing no melamine was significantly inferior in flame retardancy. Moreover, the flame retardance of the adhesive for junction boxes of Comparative Example 1-6, which does not contain melamine and contains an ammonium polyphosphate flame retardant, is also the same for the junction boxes of Examples 1-1 to 1-13. Compared to the adhesive, it was below the same level.
(C) Production of Junction Box Filler According to the formulations shown in Table 4, Table 5, and Table 6, the components were mixed to produce the junction box filler of Examples 1-14 to 1-23. Moreover, according to the mixing | blending shown in Table 5 and Table 6, each component was mixed and the filler for junction boxes of Comparative Examples 1-7 to 1-10 was manufactured.

The junction box fillers having the formulations shown in Table 4, Table 5, and Table 6 are of a two-agent type, and produce an A agent and a B agent, respectively. And A agent and B agent are mixed so that it may become a weight ratio shown in Table 4, Table 5, and Table 6 at the time of use.

In Tables 4, 5, and 6, the silicone diol is a silicone diol having a dimethylsiloxane skeleton and a viscosity of 20 Pa · s. Silicone oil is dimethyl silicone oil having a viscosity of 0.1 Pa · s. Aminosilane is a silane compound having an alkoxysilyl group. Ryton A is a trade name of surface-treated calcium carbonate manufactured by Shiroishi Calcium Co., Ltd. FCP-770 is a trade name of an ammonium polyphosphate flame retardant manufactured by Suzuhiro Chemical Co., Ltd. Further, tin neodecanoate is a catalyst, tetraethoxysilane is a crosslinking agent, and aminosilane is an adhesion improver. Moreover, Tioxide TR-92 (trade name) in Tables 4 and 5 is titanium oxide manufactured by Huntsman.
(D) Evaluation of Junction Box Filler (d-1) Flame Retardancy Evaluation For Junction Boxes of Examples 1-14 to 1-21 and Comparative Examples 1-7 to 1-9 produced in (c) above The filler was cured to form a sheet-like cured film having a thickness of 2 mm. This sheet-like cured film was cured for 7 days in an atmosphere of 23 ° C. and 50% RH, and then cut to 12.7 mm × 127 mm to produce a test piece. Using this test piece, a combustion test of a plastic material for equipment parts The test was conducted based on UL94, and t1 (afterflame time) and t2 (afterflame time after the second flame contact) were measured. The test was performed with the number of n set to 5, and t1 and t2 were the average values for the five test pieces, respectively. The measurement results are shown in Tables 4 to 5 above. Tables 4 to 5 also show t1 + t2, which is the total time of t1 and t2. Moreover, the number (passing number) of what cleared the specification among five test pieces is also shown. Note that the standard is that both t1 and t2 are within 10 seconds, and the average value of t1 + t2 is within 10 seconds.

The filler for junction boxes of Examples 1-14 to 1-21 was good in both t1 and t2, and had excellent flame retardancy. On the other hand, the filler for junction boxes of Comparative Examples 1-7 to 1-9 containing no melamine was significantly inferior in flame retardancy.
(D-2) Evaluation of initial curability The fillers for junction boxes of Examples 1-22 to 1-23 and Comparative Example 1-10 produced in the above (c) were respectively in an environment of 23 ° C. and 50% RH. 100 g were weighed and stirred for 1 minute with a 3-1 motor stirrer, and then degassed for 60 seconds under vacuum to prepare a sample.

Using the above samples, gelation time, skinning time, and flow stop time were measured by the following methods.
Gelation time: A sample is once accommodated in one container under an environment of 23 ° C. and 50% RH, and then the container is tilted so that the sample flows out constantly at a rate of 60 g / min. The time from the start of outflow to the start of the formation of bumps in the sample is defined as the gel time.

Skinning time: A sample is filled to a thickness of 10 mm in a cylindrical container having an inner diameter of 35 mm under an environment of 23 ° C. and 50% RH. The time until the skin is stretched on the surface of the sample after filling is defined as the skinning time.
Flow stop time: A sample is filled to a thickness of 10 mm in a cylindrical container having an inner diameter of 35 mm under an environment of 23 ° C. and 50% RH. When the cylindrical container is stood vertically after filling, the time until the sample hardens and does not flow is defined as a flow stop time.

The measurement results are shown in Table 6 above. Examples 1-22 to 1-23 containing melamine were shorter than Comparative Example 1-10 not containing melamine in any of the gelation time, the skinning time, and the flow stop time.
(E) How to Use Junction Box Adhesive and Junction Box Filler First, the configuration of the junction box 1 to which the junction box adhesive and the junction box filler are applied is based on FIGS. 1 (a) to 1 (c). I will explain. Fig.1 (a) is a top view of the junction box 1 (however, the state which removed the cover part 7 mentioned later), FIG.1 (b) is sectional drawing in the AA cross section in Fig.1 (a). FIG. 1C is a cross-sectional view taken along the line BB in FIG.

  As shown in FIGS. 1A to 1C, the junction box 1 includes a substantially box-shaped main body portion 5 whose upper surface is an open surface, a lid portion 7 that covers the open surface of the main body portion 5, and a conductive material. It comprises a pair of terminals 9 and 11 made of a metal having a property and attached inside the main body 5. The material of the main body 5 and the lid 7 is a modified polyphenylene ether resin.

  The bottom surface 13 of the main body portion 5 includes a pedestal portion 15 that is one step higher than the surroundings on the inner side, and the terminals 9 and 11 are fixed to the pedestal portion 15 at a predetermined interval. Further, a notch portion 17 penetrating vertically is formed in a portion of the bottom surface 13 close to one side surface 14 of the main body portion 5. When viewed from above (in FIG. 1 (a)), the tips of the terminals 9 and 11 are in a position overlapping the notch 17.

  In the main body 5, a pair of holes 21 and 23 are formed in the side surface 19 opposite to the side surface 14, from which lead wires 25 and 27 are drawn into the main body 5, respectively. The conducting wire 25 is connected to the end of the terminal 9 on the side surface 19 side. Moreover, the conducting wire 27 is connected to the end of the terminal 11 on the side surface 19 side.

  Next, a method of bonding the junction box 1 to the solar cell module 3 will be described with reference to FIG. First, the junction box adhesive 29 produced in (a) was applied linearly to the outer surface of the bottom surface 13. Next, the outer surface of the bottom surface 13 to which the junction box adhesive 29 was applied was brought into contact with the solar cell module 3 to bond the junction box 1 to the solar cell module 3. The material of the surface of the module 3 is a highly weather-resistant PET film, but may be a polyvinyl fluoride (PVF) film. At this time, as shown in FIG. 1B, the terminal 31 on the module 3 side of the solar cell entered the inside of the main body part 5 through the notch part 17 and connected to the terminals 9 and 11. For bonding the junction box 1, the junction box adhesives 29 of Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-6 manufactured in the above (a) were used.

  The junction box adhesive 29 of Examples 1-1 to 1-13 firmly bonds the main body 5 and the solar cell module 3, and after the main body 5 is bonded, the main body 5 is separated from the solar cell module 3. There was no such thing as peeling off.

  Moreover, the adhesive 29 for junction boxes of Examples 1-1 to 1-13 is quicker to cure than the adhesive 29 for junction boxes of Comparative Examples 1-1 to 1-6, and the curing time after bonding. It was short.

  Next, a method for filling the inside of the junction box 1 with the junction box filler 33 manufactured in the above (c) will be described. After bonding the junction box 1 to the solar cell module 3 as described above, the junction box filler 33 is poured into the main body 5, and the terminals 9, 11, The conducting wires 25 and 27 and the terminal 31 were completely covered with the junction box filler 33. In addition, the filling in the junction box 1 used the junction box filler 33 of Examples 1-14 to 1-23 and Comparative Examples 1-7 to 1-10 manufactured in the above (c), respectively.

  The junction box filler 33 of Examples 1-14 to 1-23 is solidified inside the main body 5, and after solidification, the connection between the terminals 9, 11, the conductive wires 25, 27, and the terminal 31 is performed. There was no such thing as falling off.

  Further, the junction box filler 33 of Examples 1-14 to 1-23 is faster to solidify than the junction box filler 33 of Comparative Examples 1-7 to 1-10, and the curing time after filling is high. It was short.

(F) Production of flame retardant composition (Part 1)
First, the following components were stirred and mixed at 100 ° C. under reduced pressure.
EST-280: 30 parts by weight M-300J: 30 parts by weight Melamine: 30 parts by weight Nonene R064-3 (trade name, manufactured by Maruhishi Yuka Kogyo Co., Ltd.), a phosphoric acid flame retardant: 22.5 parts by weight Diisodecyl phthalate as an agent: 10 parts by weight After cooling, 0.34 parts by weight of dibutyltin diacetylacetonate as a catalyst was added and stirred under reduced pressure to obtain a flame retardant composition of Example 2. In addition, Table 7 shows the formulation for producing this flame retardant composition.

(G) Production of Flame Retardant Composition of Comparative Example First, the following components were stirred and mixed at 100 ° C. under reduced pressure.

EST-280: 30 parts by weight M-300J: 60 parts by weight Nonene R064-3: 30 parts by weight Diisodecyl phthalate: 10 parts by weight After cooling, 0.34 parts by weight of dibutyltin diacetylacetonate as a catalyst was added and stirred under reduced pressure. Thus, a flame retardant composition of Comparative Example 2 was obtained. In addition, the compounding at the time of manufacturing this flame-retardant composition is shown in Table 7 above.
(H) Evaluation of flame retardant composition The flame retardant composition produced in the above (f) and (g) was cured to form a sheet-like cured film having a thickness of 2 mm. This sheet-like cured film was cured at 23 ° C. and 50% RH for 7 days, and then cut into 12.7 mm × 127 mm to prepare a test piece.

  Using this test piece, a test was performed based on UL94 which is a combustion test of plastic materials for parts of equipment, and t1 (afterflame time) and t2 (afterflame time after the second flame contact) were measured. The measurement results are shown in Table 7 above.

  The flame retardant composition of Example 2 was good in both t1 and t2, and had excellent flame retardancy. The flame retardant composition of Comparative Example 2 does not contain melamine. Instead, the amount of calcium carbonate is increased as compared with the flame retardant composition of the example, and the amount of phosphorus flame retardant is increased, and t1 is good. There was a long t2. From these results, it was confirmed that by using melamine, the flame retardancy can be improved even if the amount of the phosphorus-based flame retardant used is reduced.

(I) Production of flame retardant composition (part 2)
First, the following components were mixed to produce a flame retardant composition of Example 3-1.
Silicone diol having a viscosity of 20 Pa · s: 50 parts by weight Ryton A: 40 parts by weight Melamine: 40 parts by weight Silicone oil having a viscosity of 0.1 Pa · s: 20 parts by weight Methyltrimethoxysilane as a crosslinking agent: 30 parts by weight Curing 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane as catalyst: 0.15 parts by weight (j) Production of flame retardant composition (Part 3)
In addition to the compounding material used in (i) above, FCP-770 (trade name, manufactured by Suzuhiro Chemical Co., Ltd.), which is an ammonium polyphosphate flame retardant, and tetraethoxylane were used. The flame retardant compositions of −2 to 3-4 and Comparative Example 3 were produced.

(K) Evaluation of flame-retardant composition The flame-retardant composition produced in the above (i) and (j) was cured to form a sheet-like cured film having a thickness of 2 mm. This sheet-like cured film was cured at 23 ° C. and 50% RH for 7 days, and then cut into 12.7 mm × 127 mm to prepare a test piece.

  Using this test piece, a test was performed based on UL94, which is a combustion test of plastic materials for parts of equipment. The test was performed based on the UL94 vertical combustion test method, and t1 (afterflame time) and t2 (afterflame time after the second flame contact) were measured.

The results are shown in Table 8 above.
The flame retardant performance of the flame retardant compositions of Examples 3-1 to 3-4 using melamine as the flame retardant is the flame retardant performance of the flame retardant composition of Comparative Example 3 using an ammonium polyphosphate flame retardant. It was equivalent. That is, it was confirmed that the flame retardant composition containing melamine has excellent flame retardant performance. In addition, the flame retardant composition containing melamine is useful as an adhesive, a filler, a sealing material, and the like because there is no risk of adverse effects on the human body or eutrophication of lakes.

(L) Production of flame retardant composition (Part 4)
The following components were mixed to produce the flame retardant composition of Example 4-1.
Silicone diol having a dimethylsiloxane skeleton and a viscosity of 20 Pa · s: 50 parts by weight Melamine: 30 parts by weight Ryton A: 5 parts by weight Dimethyl silicone oil having a viscosity of 0.1 Pa · s: 10 parts by weight Tetra as a crosslinking agent Ethoxysilane: 2.5 parts by weight 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane as a curing catalyst: 0.15 parts by weight When producing this flame retardant composition Table 9 shows the formulation.

(M) Production of flame retardant composition (Part 5)
In addition to the compounding material used in (l) above, FCP-770 (trade name, manufactured by Suzuhiro Chemical Co., Ltd.), which is an ammonium polyphosphate flame retardant, was used. And the flame-retardant composition of Comparative Examples 4-1 to 4-3 was produced.

(N) Evaluation of flame retardant composition (evaluation of flame retardancy)
Using the flame retardant composition produced in the above (l) and (m), curing was performed in an atmosphere of 23 ° C. and 50% RH for 7 days to prepare a sample composed of a 2 mm thick film. This sample was tested based on UL94, which is a combustion test of plastic materials for parts of equipment. As a result of the test, those corresponding to V0 to V1 were evaluated as ◯, and those that were completely burned were evaluated as ×. The results are shown in Table 9 above.
(Evaluation of heat resistance)
Using the flame retardant composition produced in the above (l) and (m), a sample prepared in the same manner as in the above section (Evaluation of flame retardancy) was left under predetermined conditions, and then the appearance change was observed. The case where there was no remarkable change was evaluated as ◯, the case where there was significant discoloration and softening was evaluated as Δ, and the case where carbonized was evaluated as ×. The results are shown in Table 9 above.
(Evaluation of volume resistivity)
Using the flame retardant composition produced in the above (l) and (m), curing was performed in an atmosphere of 23 ° C. and 50% RH for 7 days to prepare a sample made of a 1 mm thick film. After leaving this sample under predetermined conditions, the volume resistivity was measured using an ultrahigh resistance meter R8340A (trade name, manufactured by Advantest Corporation). The results are shown in Table 10.

(Evaluation results)
The flame retardant compositions of Examples 4-1 to 4-2 were sufficient in both flame retardancy and heat resistance, and no significant performance degradation was observed when left at high temperatures. On the other hand, the flame retardant compositions of Comparative Examples 4-1 to 4-3 were not sufficient in flame retardancy or heat resistance. Further, in the flame retardant composition of Comparative Example 4-1 using a conventionally known flame retardant, the volume resistivity when left at high temperature was remarkably reduced. When the volume resistivity is less than 10 ¹⁰ , the insulation is not sufficient, and therefore the flame retardant composition of Comparative Example 4-1 is difficult to use for electronic devices.

Needless to say, the present invention is not limited to the above-described embodiments, and can be implemented in various modes without departing from the scope of the present invention.
For example, junction box adhesives, junction box fillers or flame retardant compositions produced in each example can be used in various applications (for example, bonding or filling junction boxes used in equipment other than solar cells, or sealing). Agent).

1A is a plan view of the junction box 1 (with the lid 7 removed), and FIG. 1B is a cross-sectional view taken along the line AA in FIG. 1A. FIG.1 (c) is sectional drawing in the BB cross section in Fig.1 (a). It is explanatory drawing showing the method to adhere | attach the junction box 1 with respect to the module 3 of a solar cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Junction box, 3 ... Solar cell module, 5 ... Main part,
7: Lid, 9, 11 ... Terminal, 13 ... Bottom, 14, 19 ... Side,
15 ... pedestal, 17 ... notch, 21, 23 ... hole,
25, 27 ... conductive wire, 29 ... adhesive for junction box, 31 ... terminal,
33 ... Junction box filler

Claims (7)

(A) a silicone resin and / or a modified silicone resin;
(B) a melamine derivative;
Containing a flame retardant composition.   The flame retardant composition according to claim 1, further comprising (c) an inorganic filler.   The flame retardant composition according to claim 1 or 2, wherein the melamine derivative is melamine.   An adhesive comprising the flame retardant composition according to claim 1.   The adhesive according to claim 4, which is used for bonding a junction box.   The filler containing the flame-retardant composition in any one of Claims 1-3.   The filler according to claim 6, which is used for filling a junction box.