TW200930762A - Flame-retardant composition, adhesive and filler - Google Patents

Abstract

Disclosed is a flame-retardant composition containing (a) a silicone resin and/or a modified silicone resin, and (b) a melamine derivative.

Description

The agent and the filler.

Technology for incombustible ruthenium iron, ruthenium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide 200930762 IX. Description of the invention: Technical field of the invention The present invention relates to a flame retardant composition [Prior Art] Silicone Resin Or modified gelatin resin, used in sealants, adhesives, etc. '^ According to the site of use, it is required to be flame retardant. In order to impart flame retardancy to (4) resin or modified silicone resin, it is difficult to add flame retardancy. A flame retardant is known as a flammable flame retardant or a phosphorus flame retardant. It is also disclosed that an inorganic filler (expanded graphite or oxidized) is added to a diabase resin or a modified silicone resin (refer to Patent Document 1). ～5. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problems to be Solved by the Invention] However, the "halogen-based flame retardant" has a cockroach which generates harmful substances such as dioxin during combustion. It is a problem that the flame retardant or its by-products have adverse effects on the human body, causing problems such as preferential treatment of lakes and marshes, and the characteristics such as the strength of the silicone resin or the modified silicone resin under high temperature and high humidity are reduced. -10025-PF 5 200930762. In addition, the inorganic filler "only does not sufficiently improve the flame retardancy, and the use of a large amount will reduce the stability of the stone resin or the modified (four) resin to the substrate. In view of In order to provide a flame retardant composition, a binder, and a filler which are difficult to burn, and have low toxicity, the above-mentioned points are completed. [Means for Solving the Problem] ❹ 0 Flame retardancy of the present invention The composition 'is characterized by comprising: (4) a stone base resin and/or a modified silicone resin; and (b) a trihydroamine derivative. The flame retardant composition of the present invention is difficult to contain a trimeric gas amine derivative Further, the flame retardant composition of the present invention has no harmfulness of the flame retardant or the dish-based flame retardant, or minimizes the blending/lower harmfulness of the present invention. The flame retardant composition is hardened by containing a melamine derivative. The adhesive of the invention comprising the above-mentioned flame retardant composition can be the same as the above flame retardant composition. Further, the scoop contains other components. The adhesive of the present invention is highly effective. Further, the adhesive of the present invention, the blending amount of # of the present invention is low in harmfulness. Faster. Melamine derivative, hardened as this (four) (four), suitable

The use of other components. A junction box for a module such as a solar cell, etc. 2013-10025-PF 6 200930762 The filler of the invention is a flame retardant composition comprising the above. The charge of the present invention may be the same as the above-mentioned flame retardant composition, and may further contain other components. The following 3 fillers of the present invention 'by containing a melamine derivative, and the hardener of the present invention, because of the inability to adjust the difficulty of the dance or the phosphorus flammable agent, or to minimize the amount of blending, Therefore, the harmfulness is low. The filler of the present invention hardens faster by containing a trimeric amine derivative. ❹ ❿ The filler of the present invention has a high flame retardancy and a fast hardening property, and is suitable for use as a junction terminal box (for example, a junction box for a module such as a solar battery). The flame retardant composition, the adhesive, and the filler of the present invention (hereinafter, in the case where = is a flame retardant composition, etc.) further contain (C) an inorganic filler. By containing an inorganic filler, it is possible to suppress a decrease in physical properties (e.g., film strength) of a flame retardant composition under high temperature and high humidity. The blending amount of the inorganic filler is 10 for a flame retardant composition or the like. The weight portion is preferably in the range of 60 parts by weight, and more preferably in the range of 5 to 60 parts by weight. With by! The weight 呷 (preferably 5 parts by weight or more) is more effective in suppressing the decrease in physical properties, and is excellent in workability by 6 parts by mass or less. The inorganic filler may, for example, be carbonic acid, expanded graphite, iron oxide, oxidized, titanium oxide, green hydrate or aluminum hydroxide. When a flame retardant composition or the like of the present invention is required to have high flame retardancy, a flame retardant such as a halogen-based flame retardant or a phosphorus-based flame retardant may be used in combination with a melamine derivative. At this time, even if (4) is a flame retardant or a scale-based flame retardant

2013-10025-PF 7 200930762 Low dosage can also achieve high flame retardancy. Difficult: ^ 丨 聚 聚 何 何 生物 生物 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' Amine, dicyandiamide, butylamine and the like. A flame retardant composition 10 of a melamine derivative. For the weight part, it is better to use 5~ circumference: the range of the weight part is better. With 5 weights:: . weight! The part is better than the above, and the flame retardancy is higher, and the workability is excellent by _. The above-mentioned Shixi gum resin may be of a single liquid type or a two-liquid type. A single-liquid type/knee tree date may be used as a reactive Shishiji stone resin having a terminal oxy-stone machine. For the two-liquid type of dream rubber resin, for example, a gum base rubber can be used. The <column of phthalocyanine diol, there is a dropout of 4 1 (η is an integer) The viscosity of the alcohol is 1100 Pa. S is more suitable for workability. GH3 1 CH, 1 3 Si —· 〇— 1 Si *1* 〇1 ” 1 ^ Si - OH ch3 gh3 (L3 10 ligating agent of phthalocyanine, which can be used, for example, to react with the hydroxyl group of phthalic diol to carry out condensation reaction For the bridging agent, for example, a decane or a decane-based compound having two or more hydrolyzable functional groups, specifically, in the case of a one-liquid type, methyltridecylethyl ketooxydecane , vinyl tridecyl ethyl ketone decyl decane, methyl triethoxy decane, vinyl triethoxy decane, ethyl triethoxy decane, methyl trimethoxy decane, δ

2013-10025-PF 200930762 Ethyl triethoxy (tetra), ethylene trimethoxy residue, acetaminosyl sulphur, alkoxy oxane having an amineoxy group, etc., in the case of a two-liquid type, four Ethoxylated calcined, tetrapropoxy dream or the 0 卩 hydrolyzate of the cage of the octagonal and sputum; has a cyclic amine sylvestre, a linear amine sulphate, and a oxy The group is preferably an amine-based compound (amino decane) or the like. ❹ The above-mentioned modified transester resin may be cured by, for example, forming a monoxide-fired bond by a copolymer containing a reactive Schiff base. The oligomer containing the reactive Schiff base may, for example, be an oxidized rare-chain polymer having a reactive Schindler at the terminal, or an acrylic polymer having a reactive Schiff base at the end. Reactivity Shishiji has a radical or hydrolyzable group bonded to the Shixi atom, which can be bridged by a bridge of amphetamine. The flame retardant composition of the present invention or the like can be additionally blended with various additives. For example, when a dichroic diol such as a flame retardant composition is used, an organic tin, an inorganic tin, a titanium catalyst, a rhodium catalyst, a metal complex, a platinum catalyst, a basic substance, an organic phosphorus oxide, or the like can be blended. Specific examples of the organotin include dibutyltin laurate, tin dioctyl maleate, tin dibutyl phthalate, stannous octoate, and dibutyltin diacetate. Examples of the metal complex include titanic acid compounds such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate; and acid-lowering metal salts such as lead octoate, lead acid acid, and naphthoic acid; A metal acetamethyleneacetate complex such as an acetic acid or the like; a metal acetoacetate complex such as an acetamidineacetone palladium complex or the like. Moreover, the hardening catalyst including a denatured silicone resin or the like can be adjusted to contain an organic tin, an inorganic tin, a titanium catalyst, a ruthenium catalyst, a metal thief, a basic substance, and an organic phosphorus oxidation. Things and so on. Specific examples of the organotin may be 2013-10025-PF- 9 200930762, such as dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and the like. The metal complex may be a titanic acid vinegar compound such as tetrabutyl vinegar titanate, tetraisopropyl vinegar titanate or triethanolamine titanate, or a carboxylic acid such as octanoic acid citrate, lead bromate, nickel naphthalate or naphthoic acid. A metal acetoacetate complex such as a metal salt or an aluminum acetate complex or a metal acetoacetate complex such as an acetamidineacetone palladium complex or the like. In addition, by adding a ruthenium coupling agent having a functional group decane oxime group such as a vinyl group or an amine group, it is possible to obtain an effect of improving storage stability and promoting adhesion of a hard substrate. Further, it is possible to impart flexibility, fluidity, and the like to the flame retardant composition or the like by blending the diluent. Specific examples of the diluent include phthalic acid di, phthalic acid diethyl phthalate, dibutyl phthalate, and o-benzoic acid di 8:: ethylhexyl ester and the like. Acid ester diluent; dimethyl hydrazine oil, 俨 ' ' oil. Poly (4), oil, amine modified, time oil, epoxy modified eucalyptus oil, dioctyl adipate, diisononyl adipate, bismuth - octyl-burn-burning, bismuth-acid Vinegar, epoxidized soybean oil, polypropylene glycol, acrylic acid 2-ethylhexyl ester compound derived from vegetable oil, and the like. Others may also be suitable for blending an oxidation preventive agent, a viscosity-preserving preservative, and the like.别颜科, [Embodiment] An embodiment of the present invention will be described. Example 1 (a) Production of adhesive for junction box According to the formulations shown in Tables 1 and 2, the components were mixed and manufactured.

2013-10025-PF 200930762 Example 1 -1 to 1 -13 The junction box uses an adhesive. Further, each component was mixed according to the formulation shown in Table 3, and an adhesive for a junction box of Comparative Examples 1-1 to 1-6 was produced. [Table 1] Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 Formulation modified silicone resin 100 100 100 100 100 100 100 NONNEN R064-3 0 0 0 0 0 0 0 Melamine 100 100 100 125 125 150 150 M-300J 50 150 200 150 200 150 200 WHITON SB 0 0 0 0 0 0 0 DIDP (diluent) 0 0 0 0 0 0 0 7" -(2-Aminoethyl)amine Phytate trimethoxy decane 0.25 0.25 0.25 0. 25 0.25 0.25 0.25 vinyl tridecyloxy decane 0.25 0.25 0.25 0.25 0.25 0.25 0. 25 1,1,3, 3-tetrabutyl-1,3-di Laurel oxycarbonyldistannoxane 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Diacetyl oxime dibutyltin 0 0 0 0 0 0 0 Total 250. 80 350. 80 400. 80 375.80 425.80 400. 80 450.80 Evaluation tl (seconds) 4 13 <0.5 1.5 <0.5 <0.5 <0.5 t2 (seconds) >85 30 1 1 7 <0.5 <0.5 The unit of the blending amount is the weight portion

[Table 2] Example 1-8 1-9 1-10 1"11 1-12 1-13 Formulation modified silicone resin 100 100 100 100 100 100 NONNEN R064-3 0 0 75 75 50 60 Tripolyfluoroamine 125 150 100 100 100 120 M-300J 0 0 100 100 100 120 WHITON SB 0 0 0 0 0 0 DIDP (diluent) 0 0 0 33 33 40 T - (2-aminoethyl)amine-handling trimethoxy Decane 0.25 0.25 3.3 3.3 3.3 4 Vinyltrimethoxydecane 0.25 0.25 3.3 3.3 3.3 4 1,1, 3, 3-tetrabutyl-1, 3-dilaurooxycarbonyldistannoxane 0.3 0.3 0 0 0 0 Ethylene acetonide dibutyltin 0 0 1.12 1.12 1.12 1.36 Total 225.80 250.80 382. 72 415.72 390. 72 449. 36 Evaluation tl (seconds) 1.4 <0.5 <0.5 1 1 <0.5 t2 (seconds) 34 <0.5 <0.5 2 2 , 1 The unit of the blending amount is the weight portion 11

2013-10025-PF 200930762 [Table 3] Comparative Example 1-1 1-2 1-3 1-4 1-5 1-6 Modified 矽胜树脂 100 100 100 100 100 100 NONNEN R064-3 0 0 0 27 40 100 Melamine 0 0 0 0 0 0 M-300J 150 200 0 100 100 100 WHITON SB 0 0 0 100 100 100 with DIDP (diluent) 0 0 0 33 100 33 Square r-(2-aminoethyl)amine base Trimethyl gas decane 0.25 0.25 0.25 3.3 3.3 3.3 6 alkenyl trimethoxy decane 0.25 0.25 0.25 3.3 3.3 3.3 1,1,3, 3-tetrabutyl-1,3-dilauroyloxycarbonyl dioxane 0.3 0.3 0.3 0 0 0 Diacetyl, dibutyltin 0 0 0 1.1 1.13 1.31 Total 250.80 300.80 100.80 367. 70 447.73 440. 91 Review tl (seconds) >95 >50 >50 117 >50 <0.5 Estimated t2 (seconds) t Wood% % 120 The unit of blending amount is the weight part*: It is all burned in the first time. In addition, it is in Table 1, Table 2 and Table 3. Modified silicone resin system (unit) UNEKA system EST-280 (trade name). Ν0ΝΝΕΝ R064-3 is a product of ammonium polyphosphate-based flame retardant manufactured by Maruichi Oil Chemical Industry Co., Ltd.

name. Further, M-300J is a trade name of surface-treated calcium carbonate manufactured by Maruzuki Calcium Co., Ltd. In addition, WHITON SB is the trade name of the surface untreated carbonated fish made by Shiraishi (share). Further, DIDP is isodecyl phthalate. Further, 7-(2-aminoethyl)amine-based stilbene is a tris-oxyxene-based adhesion promoter. Further, it is a trimethoxy decane dehydrating agent. Further, hydrazine, H tetrabutyl 4 3 -2 octoberoxy thioxanthene oxide is a tin-based catalyst. χ, the second type of tin-based catalyst. 1 to 1 - 13 and Comparative Example Evaluation using an adhesive The example produced in the above (a) was used.

2013-10025-PF 12 200930762 The junction box of 1-1 to 1-6 is hardened with an adhesive to form a sheet-like hardened film having a thickness of 3 mm. The flaky hardened film was cured in an atmosphere of 23t: and a relative humidity of 5% by weight for 7 days, and then cut into 127 mm x 27 min to prepare a test piece. Using this test piece, according to the burning test of plastic materials for machine parts, UL94 (Test for Flammability 〇f piastic Materials f0r

Parts in Devices and Applications UL94,

Under set iter’s Laboratoried inc.) to conduct the test. The outline of UL94 is to support the test piece with a torch to confirm the mover away from the rear ®. The test was conducted with UL94 vo, and tl (residual flame time) and . (the second residual flame time after the flame was measured) were measured. The test was carried out by taking the number of η of 5 as '11, 12', and the values of the five test pieces were averaged. The measurement results are shown in Table 3 above. In the junction boxes of Examples 1-1 to 1-13, the adhesives were good, and the steels were excellent in flame retardancy. In this regard, the junction box adhesive for the comparative example i _丨~丨_5 containing no melamine was significantly inferior in flame retardancy. Further, the flammability of the junction box for the junction box of Comparative Example 1_6 containing melamine instead of the ammonium polyphosphate-based flame retardant is the same as the binder for the junction box of Example 1 - 1 to 1 _ 1 3 Compared to the equivalent below. (C) Manufacture of filler for junction box The components of the junction box of Example 1 - 14 to 1 - 2 3 were prepared by mixing the ingredients as shown in Tables 4, 5 and 6. Further, each component was mixed according to the formulation shown in Tables 5 and 6, and a filler for a junction box of Comparative Example 1 - 74-1 was produced.

2013-10025-PF 200930762 [Table 4] Example 1-14 1-15 1-16 1-17 1-18 Silicone diol 50 50 50 70 50 LIGHTON A 40 40 40 40 10 A Tioxide TR-92 0 0 0 0 0 agent melamine 40 30 60 40 25 FCP-770 0 0 0 0 0 formula eucalyptus oil 20 20 20 0 10 methyl trimethoxy oxalate 30 0 0 30 0 tetraethyl zephyr 0 6 6 0 10 B amino decane 0 0.5 0.5 0 0 Agent 1,1,3, 3-tetrabutyl-1,3-dilauroyloxycarbonyldistannoxane 0.15 0 0 0.15 0.15 Neodymium neodymium 0 0.25 0.25 0 0 Total 180.15 146.75 176.75 180.15 105.15 Tl (sec) 0.5 2 0.5 0.5 0.5 t2 (seconds) 0.5 7 0.5 0.5 0.5 Estimated t1 + t2 (seconds) 1 9 1 1 1 Pass (5 pieces) 5 4 5 5 .5 The unit of the weight is the weight unit

[Table 5] Examples Comparative Example 1-19 1-20 1-21 1-7 1-8 1-9 Silicone diol 50 50 50 50 50 50 LIGHTON A 5 0 0 40 0 50 A Tioxide TR-92 0 0 0 0 40 0 Agent Melamine 30 40 50 0 0 0 FCP-770 0 0 0 0 0 40 Formulated oyster sauce 10 20 20 20 20 20 Mercapto trimethoxy oxalate 0 0 0 0 0 30 Tetraethyl decane 10 6 6 6 6 0 B Amine-based dreams · 0 0.5 0.5 0.5 0.5 0 Agent 1,1,3, 3-tetrabutyl-1,3-dilauroyloxycarbonyldistannoxane 0.15 0 0 0 0 0.15 Neodecanoate 0 0.25 0.25 0,25 0.25 0 Total 105.15 116.75 126.75 116.75 116.75 190.15 tl (seconds) 0.5 0.5 0.5 32 140 12 Review t2 (seconds) 0.5 1.5 2 16 Wood 5 Estimate t1 + t2 (seconds) 1 2 2.5 48 > 140 17 Qualified number (5 pieces) 5 5 5 0 0 2 The unit of the blending amount is the weight part*: The first flame test piece becomes shorter, but the fire is not caught 14

2013-10025-PF 200930762 - Table 6] Example Comparative Example 1-22 1-23 1-10 Gelatin Glycol 50 50 50 A Agent LIGHTON A 0 10 0 Melamine 35 25 0 with FCP-770 0 0 35 Fangyu Oil 10 10 10 B agent tetraethyl decane 2 2 2 amine dream 2 2 2 tin neodecanoate 0.6 0.6 0.6 evaluation gelation time (minutes) 7.5 6.5 9 skin time (minutes) 8 7.5 9 flow stop time (minutes ) 12 19 22.5 The unit of blending amount is the weight part

填充 The filler for the junction box of the formulation shown in Table 4, Table 5, and Table 6 is a two-part type 'A agent and B agent, respectively. Then, the A agent and the B agent were mixed at a weight ratio shown in Table 4, Table 5, and Table 6 at the time of use. Further, in Table 4, Table 5, and Table 6, the phthalocyanine diol is a phthalocyanol having a dimercapto oxetane skeleton viscosity of 20 Pa·s. Further, the oily viscosity is 0. IPa.s dimethyl eucalyptus oil. Further, the amino decane is a decane compound having an alkoxy fluorenyl group. In addition, LIGHTON A is a product name of calcium carbonate (sand) made of white stone calcium (stock). Further, FCP_77 is a trade name of an ammonium polyphosphate-based flame retardant manufactured by Yuyu Chemical Co., Ltd. Further, a neotin silicate-based catalyst, a tetraethyl decane-based bridging agent, and an amine-based decane-based adhesion improving agent. Further, Tioxide TR_92 (trade name) in Tables 4 and 5 is the yttrium oxide produced by the elbow (four) anal company. (d) Evaluation of fillers for junction boxes (d-Ι) Assessment of flame retardancy

2013-10025-PF 15 200930762 The junction box of the embodiment 1-u~b 21 and the comparative example manufactured by the fan (c) is hardened with a filler to form a sheet having a thickness of 2 mm, and the sheet-like hardened film is After 7 days of 23 ° C and a relative degree of dilution of 50%, the test piece was cut into 12. 7 mm x 27 mm. Xizheng film, according to the machine 11 parts with plastic materials (four) burning test = with the test, 骇 tl (residual flame time) and called the second after the flame after the flame residual time). ★ 验 ❹ ❹ 5 test strips, (1) is the value of the average value of the test. The results of the measurement are shown in Tables 4 to 5 above, and also in Table 2, which also shows tin2 in the total time of 1:2. In addition, among the five test pieces, the number of specifications is the same. The so-called specifications are t1, t2妁奂in, and the other is less than 1 second, and u is less than 10 seconds. < 卞巧值任 Example 1-14~1-21 wiring winter use a ^ /s Λ Green application filler, tl, t2 are good, with excellent flame retardancy. On the other hand, the filler for the junction box of Comparative Example 1 - 7 to 1 - 9 containing = 3 - the cyanamide was remarkably inferior in flame retardancy. (d-2) Evaluation of initial hardenability The filler for the junction box of the above-mentioned _Hb23 and the comparative example 〇1〇 was respectively 2 3 ,; j; the target 斟u relative humidity 50% of the environment Next, the measurement of 100 g' was carried out with a 3-1 motor mixer to prepare a sample. The "clock" was used in the U defoaming 60. The above sample was used, and the filming time and the flow stop time were as follows. When measuring the time of gelation and clotting, the knife should be: 23. (:, the relative degree of stability 5 is first stored in a container, and then the crying field is under the soil, the sample is tilted, so that the sample is 60g / min.

2013-10025-PF 16 200930762 The rate at which grain production began to occur in the sample was measured to flow out. The time between the outflow of the field is used as the gelation time. Sheeting time: 2 31:, the cylindrical container is filled with the sample. The time of the skin is as thick as 50% in the environment of the skin, and the inner diameter is 35mm to 1 Omm. From filling to the surface of the sample. _ / melon 彳 T stop time: in the environment of 50% relative humidity, in the inner 裎 35min, the cylindrical granules fill the sample to 1 〇 coffee thick. When the time until the cylindrical container was standing vertically, the sample was hardened and the flow did not flow as the flow stop. The measurement results are shown in Table 6. Examples containing melamine 22 to 1-23' are in the gelation time, the skinning time, and the flow stop time, which are shorter than the comparative K0 containing no melamine. (e) Method of using the adhesive for the junction box and the filler for the junction box First, the structure of the junction box 1 using the adhesive for the junction box and the filler for the junction box will be described based on Figs. 1A to 1c. Fig. 1B is a cross-sectional view of the cross section of Fig. 1B, and Fig. 1C is a cross-sectional view of the cross section of Fig. 1Ai 1C1C. As shown in FIG. 1A to FIG. 1C, the junction box 1 includes a substantially box-shaped main body portion 5 whose upper surface is an open surface, and a cover portion 7 that covers an open surface of the main body portion 5, and is made of a conductive metal. One of the terminals 9 and 11 (P13) is inside the body portion 5. The material of the main body portion 5 and the lid portion 7 is a modified polyphenylene ether resin. The bottom surface 13' of the main body portion 5 is on the inner side thereof, and has a higher-section than the surrounding 2013-1Q025-PF 17

200930762 base. In the base portion 15, the fixed terminals 9, u are fixed at a predetermined interval. Further, the portion of the abutting surface 13 that is close to the one side surface 14 of the main body portion 5 is formed with a notch 17 that penetrates the upper and lower sides. From the top (in Fig. 1A), the front ends of the terminals 9, 11 are at positions overlapping the notches 17. The main body portion 5' is formed on the side surface 169 on the side opposite to the side surface 14 with the pair of holes 21, 23' thereby introducing the wires 25, 27 into the body portion, respectively. The wire 25 is connected to the end portion of the terminal 9 on the side of the side turn 9 side. Further, the wire 27 is connected to the end portion of the terminal 11 on the side of the side surface 11. Next, a method of attaching the junction box to the solar cell module 3 will be described based on Fig. 2 . First, the (a) = manufactured junction box adhesive 29 is applied linearly on the outer surface of the bottom surface 13 . Next, the outer surface of the bottom surface 13 to which the bonding agent 29 for the junction box is applied is brought into contact with the solar battery module 3, and the junction box 1 is attached to the solar battery module 3. Further, the surface material of the module 3 is a high 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 side of the solar cell module 3 enters the inside of the main body portion 5 through the notch portion 17, and is connected to the terminals 9, and . Further, in the junction box 1, the junction box adhesives 29 for the junction boxes manufactured in the above (3) and the comparative examples 1-1 to 1-6 were used. In the junction box of the thirteenth embodiment, the main body portion 5 and the solar battery module 3 are firmly adhered by the adhesive agent 29. After that, the main body portion 5 does not have the solar battery module 3 peeled off. Further, in the junction box of the embodiment 1-13, the adhesive 29 is used, and the junction box 29 of the comparative example 1-1 to 1-6 is hardened faster, and the subsequent curing time can be shorter. · 2013-10025-^F 18 200930762 Next, a method of filling the inside of the junction box 1 with the filler 33 manufactured by the above (c) is explained. Connect the junction box, as described above, and then after the solar cell module 3, fill the junction box with the filler 33 into the interior of the body portion 5, inside the body portion 5, and connect the terminals 9, 丨1; The portions 25, 27 and the terminal 31 are completely covered with a filler 33 for the junction box. Further, for the filling in the junction box 1, the fillers 33 for junction boxes of Examples 1-14 to 1-23 and Comparative Examples 1-7 to 1-1 manufactured by the above (c) were used. The junction box of the embodiment 1-14 to 1-23 is firmly solidified inside the body portion 5 by the filler 33, and after solidification, the terminals 9, 11; the connection between the lead portions 25, 27 and the Λ% 31 are There will be no falling off. Further, the filler 33 for the junction box of Examples 1-14 to 1-23 was faster than the filler 33 for the junction box of Comparative Examples 1-7 to 1-10, and the curing time after filling was short. Example 2 (f) Production of flame retardant composition (1) First, the following components were stirred and mixed at 10 (rc, under reduced pressure. © EST-280: 30 parts by weight M-300J: 30 parts by weight of melamine: NORNEN R064-3 (manufactured by Maruta Oil Chemical Industry Co., Ltd.) of 30 parts by weight of a phosphate-based flame retardant: 22. 5 parts by weight of diisodecyl phthalate: 10 parts by weight after cooling Adding the catalyst to the dibutyltin dibutyltin 0 34 weight portion, and stirring under reduced pressure to obtain the flame retardant composition of Example 2. Further, the product will be produced.

2013-10025-PF 19 200930762 The formulation of the flame retardant composition is shown in the table [Table 7] Ingredient Example 2 Comparative Example 2 Formulation EST-280 30 30 M-300J 30 60 Melamine 30 0 NONNEN R064-3 22. 5 30 diisodecyl phthalate 10 10 diacetone acetone dibutyl tin 0. 34 0. 34 count 122. 84 130. 34 evaluation tl (seconds) -----*~--- <1 &lt ;1 t2 (sec) <1 120 Unit weight unit of the blending amount g (g) Production of the flame retardant composition of the comparative example First, the following components were stirred and mixed at 10 ° under rc. EST- 280 : 30 Weight M-300J : 60 Weights NONNEN R064-3 : 30 Weights

Diisodecyl phthalate: 10 parts by weight After cooling, a catalyst of dibutyl hydrazine dibutyltin was added. After 34 parts by weight, the mixture was stirred under reduced pressure to obtain a flame retardant composition of Comparative Example 2. Further, the formulation when the flame retardant composition was produced 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 hardened film having a thickness of 2 legs. The flaky hardened film was cured in an atmosphere of 23 MPa and a relative humidity of 5 〇 for 7 days, and then cut into i2. 7 mm x l 27 mm 13-10025 ke 20 200930762 Using the test piece 'According to the burning test of plastic materials for machine parts UL94 tests "measured tl (residual flame time) and t2 (after-flame residual flame time after the second flame). The measurement results are shown in Table 7 above. The flame retardant compositions of Example 2 were excellent in both t丨 and 12, and had excellent flame retardancy. The flame retardant composition of Comparative Example 2 is free of melamine, and the amount of calcium carbonate is increased in comparison with the flame retardant composition of the example, and the growth of the flame retardant is further improved. Longer. From this result, it is confirmed that by using melamine, even if the amount of the phosphorus-based flame retardant is reduced, the flame retardancy can be improved. Example 3 (i) Production of flame retardant composition (Part 2) First, the following components were mixed to produce the flame retardant composition of Example 3-1. Viscosity 20Pa · s bismuth diol: 50 parts by weight LIGHTON A : 40 parts by weight melamine: 40 parts by weight NONNEN R064-3 : 30 parts by weight 0. 1 Pa . s 矽 oil: 20 parts by weight as a bridging agent Tris-methoxy decane: 30 parts by weight as a hardener, 1,1,3,3~tetrabutyl-1,3-dilauroyloxydistannoxane: 0.15 parts by weight (j) flame retardant Manufacture of the composition (3). In addition to the formulation materials used in the above (i), FCP-770 (manufactured by Ryuyu Chemical Co., Ltd., a product of ammonium polyphosphate-based flame retardant 2013-10025-PF 21 200930762) is used. , tetraethoxy maifu', the flame retardant compositions of Examples 3-2 to 3-4 and Comparative Example 3 were produced in the formulation of Table 8. [Table 8] Ingredient composition & Example Comparative Example 3-1 3-2 3-3 3-4 3 sec diol 50 70 50 50 50 LIGHTON Α Ί 40 40 10 5 50 Tri-melamine 40 40 25 30 0 FCP-770 0 0 0 0 40 with dream oil 20 0 10 10 20 m-methyltrimethoxy oxalate 30 30 0 0 30 tetraethoxy decane 0 0 10 10 0 1,1,3, 3-tetrabutyl -1,3-dilaureyl carbonyl stannous oxide 0.15 0.15 0.15 0.15 0.15 _ 180.15 180.15 105.15 150.15 190.15 tl (seconds) <1 <1 <1 <1 <1 estimate t2 (seconds) <1 <1 <1 <1 <1 Harmonic unit weight unit

(m) Evaluation of flame retardant composition The flame retardant composition produced in the above (i) and (j) was cured to form a sheet-like hardened film having a thickness of 2 mm. The flaky hardened film was cured in an atmosphere of 23 ° t and a relative fishing degree of 50% for 7 days, and then cut into 12 7 nm x 27 mm to prepare a test piece. Using this test piece, the test was carried out according to UL94 of the burning test of the plastic material for machine parts. The test was carried out based on the UL94 vertical burning test method, and ΐ1 (residual flame time) and t2 (after-flame residual flame time after the second flame) were measured. The measurement results are shown in Table 8 above. 2013-10025-PF 22 200930762 The flame retardant properties of the flame retardant compositions of Examples 3-1 to 3-4 using melamine as a flame retardant, and the difficulty of Comparative Example 3 using a polyphosphoric acid-based flame retardant The flame retardant properties of the flammable composition are equivalent. Namely, it was confirmed that the flame retardant composition containing melamine has excellent flame retardancy. Further, the flame retardant composition containing a trimeric amine is used as an adhesive, a filled sword, a sealing material, etc., since it does not adversely affect the human body or oxidizes the lake. Example 4 〇 (1) Production of flame retardant composition (Part 4) The following components were mixed to produce the flame retardant composition of Example 4-1. Viscosity diol with dimethyl oxymethane skeleton 20Pa. s. 50 weight melamine: 30 weight LIGHTON A : 5 weight viscosity O.lPa· s bismuth eucalyptus oil: weight as a bridge The tetraethoxy decane of the agent: 2·5 by weight © 硬化 as a hardener, 3,3-tetrabutyl-1,3-dilauroyloxydantastan: 0. 15 parts by weight, The formulation when the flame retardant composition was produced is shown in Table 9. 2013-10025-PF 23 200930762

[Table 9] Real? & Example ------ Composition Comparison Example 4-1 4-2 4-1 4'2 AQ Mongo Glycol 50 50 4 ύ Filling melamine powder bundle 30 ---- 25 vU 0 50 ----- 35 50 π Ammonium polyphosphate 0 0 35 〇υ η Formulation LIGHTON A 5 10 0 r I. 〇U OC Square bridging agent (tetraethoxymethane) 2.5 2.5 2.5 —'· *——^ 2 ^ 矽油 10 10 10 10 in 1, 丄, 3, 3-tetradecyl-1,3-dilaure: oxycarbonyldistane aerane 0.15 0.15 0.15 0.15 0.15 flame retardant __ 180°Cx24 Hour __〇_ 〇X 评耐埶〇XX ο Estimate 140°Cx24 Hours 〇〇Δ 〇υ 100100°Cx24小时〇〇〇Γ\ 140°Cxl4 天〇----~-_ 〇〇X 〇〇 The unit weight of the blending amount (k) The manufacture of the flame retardant composition (5) In addition to the formula used in the above (1), FCP-770 (ammonium sulphate) is used. Chemically, trade name), the flame retardant composition of Example 4-2 and Comparative Examples 4-1 to 4-3 was produced in the formulation of Table 9. (η) Evaluation of flame retardant composition

Using the flame retardant composition produced in the above (1) and (m), it was cured in an atmosphere of 23 <>c and 50% relative humidity for 7 days, and then a sample composed of a film having a thickness of 2 mm was prepared. The sample was tested according to UL94 of the burning test of the plastic material for machine parts. The experimental result 'equivalent to v〇~η is evaluated as 〇, and the total burner is evaluated as X. The results are shown in Table 9 above. (Evaluation of heat resistance) Using the flame retardant composition produced in the above (1) and (m), the sample prepared in the same manner as the above (evaluation of flame retardancy) was placed under predetermined conditions.

2〇13-]〇〇25.pF -24 200930762 After observing the appearance change. No significant change A I was estimated to be 〇, and significant color change and softening were evaluated as △’ carbonization. The results are shown in the above 9 〇 (evaluation of volume resistivity), and the flame retardant composition produced by the above (1) and (4) is cured by (iv) ° C, relative position of 5 G% in an atmosphere for 7 days. Thickness _ The sample consisting of the film. The sample was placed in a predetermined strip. The residual resistance meter R8340A (manufactured by ADVANTEST Co., Ltd., trade name) was used to measure the volume resistivity. The results are shown in Table 1. Placement conditions Example 4-1 uU A 1 Volume resistivity (ΤΩ · cm) 23°C, 50%x7 days 2. 2x1 〇15 Deduction weight 1 about 4 i 1.4x1015 9. Oxl Ο8 23t, 50%x7 days + 85 ° C, 85% x 7 days 8. 2x1014 The flame retardant composition of Example 4 + 4-2 was sufficiently flame-retardant and heat-resistant - no significant decrease in performance even when placed at a high temperature. The flame retardant composition of Comparative Example 4-1 +3 was insufficient in flame retardancy or heat resistance. Further, the volume resistivity of the flame retardant composition of Comparative Example (1) using the previously known flame retardant was significantly lowered when placed at a high temperature. The body electromechanical group rate is lower than 1 〇. Since the insulating property is not sufficient, the flame retardant composition of Comparative Example (1) is difficult to use in an electronic device. Further, the present invention is not limited to the above embodiments, and various embodiments can be made without departing from the scope of the invention. For example, in the junction box manufactured in each embodiment, the junction box is used, and the junction box is used.

2013-10025-PF 25 200930762 Fillers or flame retardant compositions, such as those used for solar cells other than solar cells, etc.). ^Used for a wide variety of purposes (the subsequent junction or filling of the junction box of the device, or [simple description of the drawing] Figure 1A is the junction box ι (re-integrated <&cabinet; U re-center, remove the cover Fig. 1B is a cross-sectional view taken along line 1B-1B of Fig. 1. Fig. 1C is a cross-sectional view taken along line kic-1C of Fig. 1. B ® 2 shows the junction box 1 followed by a solar cell module Description of the method of group 3. [Description of main components] 1~ junction box; 3~ solar battery module; 5~ body part; 7~ cover part; ❹ 9, 1 terminal; 13~ bottom; 14, 1 9 ~ side; 15 ~ base part; 17 ~ notch; 21, 23 ~ hole; 25, 27 ~ wire; 29 ~ junction box with adhesive;

2013-10025-PF 26 200930762 31 ~ terminal; 33 ~ junction box with filler.

❿ 2013-1002I-PF 27

Claims (1)

200930762 X. Patent application: 1. A flame retardant composition comprising: (A) a silicone resin and/or a modified silicone wax; and (B) a melamine derivative. 2. The flame retardant composition of claim 2, further comprising: (c) an inorganic filler. 3. The flame retardant composition of claim 2, wherein the melamine derivative is melamine.接着 4· An adhesive comprising the flame retardant composition according to any one of claims 1 to 3. 5. The adhesive as described in claim 4, the use of which is followed by a junction box. A type of filler comprising the flame retardant composition according to any one of claims 1 to 3. 7. The filler according to claim 6 of the patent application, the use of which is the filling of the junction box. 2013-10025-PF 28