TW426713B - Flame-retarded thermosetting resin composition - Google Patents

Abstract

A flame-retarded thermosetting resin composition comprising (a) a thermosetting resin and (b) an aromatic phosphate represented by the formula (I), wherein R1 and R2 are, the same or different, a lower alkyl group, R3 is a hydrogen atom or a lower alkyl group, R4 is a C6-20 aromatic hydrocarbon residue and n is an integer 2 or 3. The composition, compared with resin compositions containing conventional flame retardants, has excellent punchability at low temperatures, resistance to bleeding of the flame retardant from a laminated sheet, and particularly shows significant improvement in the tracking resistance heat resistance and insulation properties.

Description

MC Industrial and Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China Du Yinzhuang 4 267 1 3 A7 B7 V. Description of the Invention (3) Background of the Invention Iridium Jaw City The present invention relates to a flammable thermosetting resin composition. This flame-retardant thermosetting resin composition contains an aromatic phosphate. Phase M Zhixi Xicheng represents polyurethanes and phenol resins which are thermosetting resins. They are widely used in Xiaoqi parts because they are available at lower cost and have characteristics such as good plasticity. Sub-parts, automotive parts, etc. However, these resins are flammable, and once fired, they can cause uncontrollable combustion. And many efforts have been made in the industry for their flame retardancy. Currently, in some areas where these resins are used, flame retardancy is legally required. In order to obtain the flame retardancy of the thermosetting resin, a flame retardant is added when preparing the tree shrub article. Examples of such flame retardants are Wupu compounds, hafnium phosphorus compounds, hafnium halides and phosphorus compounds containing organic halogens. There are thallium halogen compounds and phosphorous compounds containing thallium halogens, which show excellent flammability, but when thermally decomposed, they will generate halogen thorium b hydrogen gas. Halogen-free flame retardants include halogen-free compounds and organic phosphorus compounds. The plutonium-free compounds represented by magnesium hydroxide and aluminum hydroxide have only a small amount of flammability and must be used in large quantities. This has a detrimental effect on the inherent properties of the resin (for example, processability and mechanical properties). Triphenyl phosphate (TPM, tricresyl phosphate (TCP) and toluene diphenyl phosphate (CDP) are representative of the skeletal phosphorus compound, which has a relatively good burning effect and is commonly used. However, due to its volatility, when used Anti-resistance resin paper size applicable to China's national standard (CMS > A4 size (210X297 mm) I -------- r installed -------- order -------- ^ J (please read H-note on the back ^ before filling this page). 3

I 42671 3 A7 B7 V. Description of the invention (4) Thermal properties and mistletoe properties. The Japanese Patent Publication No. Hei 1 (1989)-2 4 2 6 3 3 and Hei 2 (1990)-67310, disclose phenol resins containing aromatic 85 acid. These machines and gas and electricity have been made in Pintong, but the difference in sexual penetration is low. Lipid-based resins and low-quality high-quality lipids are the absolute best choices. Roads are electrical examples. Electrical properties are used for heat resistance. Wide and quality products: thin edge, good quality, good quality, good quality, good quality, thin laminated layer of hot special sheet, ο do 1

ο XX 11 and thermal resistance seconds ο 4 to 5 1 Welding example at the time of the show / 1 \ The quality of the fat tree is increased by adding ο 砠 the electrical edge 0 is the same at the same time, but the increase is positive. 祢The \ IIF- nature of the 100 ribs is such that the low flame resistance will not cause the low loss. It will not have the normal properties of the solid and fat-based tree. It is fat and tree-like. In view of the fact that the fat burning solid heat benefit from the agent burning 0 6 fla dendritic solid heat burning resistance 0-Juzhi Mingfa of the supply and withdrawal A3 This is due to the damage caused by the burning of the sister Sexually solid. The tree points to the lack of sexual skills are described before, and the first thing is the first, and the objects are divided into groups-(Please read the precautions on the back before filling this page) Printed by the Shellfish Consumer Cooperative of the Central Ladder Bureau of the Ministry of Economic Affairs .. The material ca n’t be reduced, the sex group has low cellular sex, or its sexual resistance hinders its fever, and its sexuality _ Fat burning acid tree hinders phosphorus from harming the race 拫 1 fragrance is not offered or used-Mingzuofafa The burning temperature is in the shape of resistance, the difference between the competition is hot and the details are good. There is a low-level research on the progress of the research. It has been η person t when the Ming-style school-based textual description is released. Add 0 It is used as a display of acid sour family aromatics and its resistance to 0 C. The effect of anti-fruit is modified by the good solid heat of the good tree. It is also used in the display. It can be used as a fuel to maintain resistance. The hindered position is 0. The acidity of the aromatic family is 0. The performance of the paper is described above. The paper size is applicable to China National Standard (CNS) A4 (210 X 29T mm) 4 426713 A7 B7 V. Description of the invention (5 ). That is, the aromatic phosphate of the chemical formula (U) has substituents on the 2nd and 6th positions of the stupidity. It is recognized that this position hinders the improvement of long-term hydrolysis resistance. 0 kinds of thermal combustion for the purpose of demonstrating the fact that the esters of phosphoric acid esters are shown in the table VI / I / | \ chemical formula \ IF- b and resinous solid heat \ J / a / 1-yes

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COR Chinese formula alkyl radicals with the same or lower phase are 2 R and low or protonic hydrogens are integers of 3 or 2 are Π and radicals of residual hydrocarbons. 2 I 6 C is 4 R radicals. It is a mixed phase of resinous solid heat-resistance and flame retardance of Chinese compound. \ T / b ester acid phosphorus aromatic and its resin allyl XIF · a This tallow amine cyanide polytribumin Β »tree oxygen ring tree tree tallow tree 0 acid methyl amine tree tree poly and fatty tree gland species (b dichotomous or seeded as two can be fat-mixed into the upper M- ------- i equipment-(Please read the notes on the back before filling out this page) Order the printed materials of the Central Bureau of Standards of the Ministry of Economic Affairs and the cooperation of Du Yin. Among them, and transitive ί 2, ί J s R lipids, the above description of 0 resin esters of acrylic acid peptides to reduce the alkyl II ί alkylation to show that it contains isopropyl propionate Ethyl * * For example, the alkyl stilt brace or bond is different, and the radical C is as shown in Table 5. Table 4 R 焼 〇 low-level examples of residual hydrocarbons aryl ο phenyl substituted by ethyl or methyl methyl benzyl benzyl naphthyl or benzyl benzyl isopropyl naphthyl and naphthyl naphthalene Phosphoric acid methylnaphthyl phosphate · It is better to include 1 / I / V formula of 0_0 group aromatics. The paper size is based on the country's national rate (CMS) A4 specification (210X29? Mm) 5 Printed by the Central Workers' Bureau of the Ministry of Economic Affairs, Monthly Industrial Cooperatives ^ A7 B7 V. Description of the Invention (6) 2.6- Dimethylbenzyl Ester), Europium Phosphate (2,4,6-Trimethylbenzene), and Ethyl Bis (2 · 6 -Xylyl) benzyl, bis (2,4,6-trimethylbenzene) phosphate, stupid ester, bis (2.6-xylyl) phosphate methyl ester. Bis (2,4,6-xylene) phosphate toluene Esters, bis (2,6-xylyl) oxalate, bis (2,4,6-trimethylbenzyl) phosphate xylyl ester, bis (2,6-xylyl) naphthyl phosphate and phosphoric acid Bis (2,4,6-tricresyl) naphthyl esters, of which rhenium phosphate (2,6-xylylenestilbene), phosphonium phosphate (2,4,6-trisyl esters), and bis (2,4,6-tricresyl) phosphate are particularly preferred. 6-xylyl ester) methyl benzamidine 0 as the aromatic phosphate of component (b), By the known methods per se of manufacturing. For example, an aromatic monohydroxy compound is reacted with a phosphoric acid chloride phase, or an aromatic monohydroxy compound is reacted with a tri-amorphous phosphorus phase, and then the resultant is oxidized to produce it. According to this production method, the compound represented by the chemical formula (1) (where n = l), such as diphenyl phosphate (2,6-xylose), may be a by-product. If the amount of this by-product is too small to affect the properties of the resin, it does not need to be separated. The resulting aromatic acid can be used directly as component (b). If the aromatic phosphoric acid ft contains this by-product of about 10 or more, it will adversely affect the hydrolysis resistance and heat resistance of the resin composition. The aromatic phosphate (b) is a crystalline solid or a liquid «, and the aromatic" acid _ "of the crystalline solid and the liquid hydrazone can be used in the composition of the present invention. In addition, the component (b) itself is a suitable flame retardant, and in fact, maintains the heat distortion flux and properties of the component (a). The «fatty product» of the present invention may contain various additives if necessary, for example, other Flame retardant clams, fillers, slip agents and bleaching agents. V ------ Order ------ ^-; _ (Please read the precautions on the back before filling out this page)-: This paper size is free to use Chinese National Standard (CNS) A4 Specification (210X297 (Mm) 6 426713 A7 B7 V. Description of the invention (7) In addition, as the flame retardant of the component (b), it can be used with the thermosetting resin M and the thermosetting resin (a). Among the flame retardant thermosetting resins of the present invention The mixing ratio of each component can be appropriately determined according to the type of resin used and the different flame retardants required. Generally, it is 0.1 to 100 parts by weight (preferably 5 to 50 parts by weight > The component (b) and 100 parts by weight of the component U) are used. The resin composition of the present invention is prepared according to a known method, that is, the thermosetting resin (a) is blended with the aromatic phosphate (b) by a mixer. Then, or roll the heat and add the shape of the sister to make it mixed with heat and add the M applicator and the kneading agent to form the paint. The solvent can be used to form the clear hair of the tree and the benzene agent and solvent. Ammonium methyl formaldehyde base with two ingredients, ketone base propyl make ketone, ethyl middle formamidine, wood leaven base Based on the benzene injection or injection, add the case of selenium cloth, fabricate the cloth and make the cloth 0 glass, glass cloth, glass paper as an example of the material on the substrate M 18 2 or 0 2 or 0 1% material base The nature of the flame resistance and the addition of thin pressure is 0. The heating performance is not low. '(Please read the precautions on the back before filling this page) The foreign tree of Du Yinzhen's obstruction, which is the resistance of shellfish consumer cooperation by the Central Bureau of Standards, the Ministry of Economic Affairs, is better than it is. The large object is shown into a significant group, (b Zhizhi is a tree-holding property that maintains the heat-generating nature of heat energy and is used as a fire engine to reduce resistance and reduce resistance. The use cases are examples. It ’s not clear that the standard agent is flammable; the basic basis of the hair system is basically limited to phosphorus. This is detailed by the exception of the normal application. It is stated that this is issued.簠 refers to Xingming means that there is no other than 1, except that the paper size of Cheng Zhonghui is applicable to the national standard rate (CNS) of the country. 4 4 grid (2 丨 OX297) 夔 2 2 67 1 A7 B7 V. Description of the invention (8) 2,6 -xylenol (366s, 3.0 moles) and anhydrous chlorine as a catalyst (please read the precautions on the back before filling this page) Aluminium (6. U) A four-necked flask is locked. This flask is equipped with a stirrer, a dropping funnel, a thermometer and a condenser connected to a water washer. Heat and mix. When the temperature of the reaction solution rises to 100X :, phosgene (153 g, 1.0 ear) is added in about 2 hours, and the osmium acid gas generated at the same time is sent to the water washer. After the addition of phosphorus sugar gas, the reaction temperature gradually rose to 230 in 4 hours. Then, the reaction mixture was heated at the same temperature for 2 hours, and then heated at a reduced pressure of 300 t rr for 8 hours. The reaction is complete. The reaction mixture was washed with acid and hot water. Then, the aromatic phosphate ester was hardened. The precipitated crystals are separated by filtration, washed with M formase, and reduced to dryness. Gadolinium phosphate (2,6-xylene fig) was obtained as white crystalline powder 3088 (75% yield). The crystal purity was determined to be 99.8% or more by gas decantation. Melting point is 137 to 138t. Called Compound 1. Synthesis Example 2 The same reaction was performed as described in Synthesis Example 1, but 2,4,6-trimethylphenol (409 g, 3.0 mol) was used instead of 2,6-xylenol (3.0 mol). Acquired 3,538 (78% yield) of 酸 (2,4,6-trimethylxyl ester) printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The crystal purity of the tritium gas was determined to be 99.8 or more. Melting point is 108 to 109X :. It is called compound 20. Synthesis Example 3 2,6-xylenol (2 44s, 2.0 mol) and anhydrous atmospheric magnesium (1.5s) as a catalyst, a suspected four-necked flask with stirring Device, dripping funnel, thermometer and condenser connected to a water washer, and heating and mixing. When the flux of the reaction solution rose to 1201C, phosphorus sugar gas (153g, 1.0 mol) was added in about 2 hours, and the generated acid gas «I was sent to the water washer. 8 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 42671 3 A7 B7 V. Description of the invention (9) After adding phosphorus phosphonium, the reaction temperature gradually rises to 180TS within 2 hours, and the reaction is completed. (Please sa-read the notes on the back before filling in this page) After cooling, the reaction mixture is mixed with p-cresol (108g, 1.0 mole) and anhydrous magnesium chloride (1.5g) and heated with K. The temperature of the reaction mixture gradually rose to 180 t in 2 hours: M deaerated hydrogen. Then, the reaction mixture was heated at the same temperature for 2 hours, and then matured at a reduced pressure of 2000 t r r for 2 hours, and then the reaction was completed. Then, the reaction mixture was washed with M acid and hot water. After distillation, bis (2,6-xylyl) phosphate p-toluate 3768 was obtained as a white solid (95% yield). The purity of the solid was 98.5 〆 or more as determined by gas chromatography. Melting point 70 to 71C. This is hereinafter referred to as Compound 3. Production Example 4 The same reaction was performed as described in Synthesis Example 3, but cresol (122 g, 1.0 mol) was used instead of cresol (1.0 mol). 390 g of bis (2,6-xylyl) phosphate xylene was obtained as a yellow liquid (95 yield). The purity of the liquid was 98.0 or more as determined by gas decantation. Called compound 4. g Example 1 4 to 11 4 to 1A of the combination of chemical and steaming and full steaming and full of shellfish consumer cooperation cooperation between the Ministry of Economic Affairs and the Central Government Bureau Du Yinzhong and tester 0 Autoclaved pressure to advance R然 Then the solution of small water resistance and acid value is shown in the results. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 males; t). Du Yinji 4267 1 3 A7 ____ B7 V. Description of the invention (10) Table 1 Examples of comparative examples 1 2 3 4 1 2 3 Compound compound compound compound compound compound compound 1 2 3 4 5 (TPP) 6 (TCP) 7 (TXP) Initial Acid Value 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.05 0.01 0.08 0.02 0.06 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 (Fill in this page again.) The paper size of the book is free to use China National Standards (CNS) 々 ((210 X 297 mm) i 〇42671 3 A7 Central Bureau of Standards, Ministry of Economic Affairs β; industrial and consumer cooperation Du Yinye B7 V. Description of the invention (11) Bu h 酧 pour 1 g The same measurement as described in 1 except that the following compounds 5 to 7 are used instead of the compounds of Synthesis Examples 1 to 4: Compound 5: Triphenyl phosphate (manufactured by Daihachi Chemical Co., Ltd., Japan; trade name TPΠ Compound 6: tricresium phosphate (Daihachi) Manufactured by Chemical Co., Ltd .; Trade name TCP) Compound 7: Tris (xylyl phosphate UDaihach 丨 Chemical Co., Ltd .; trade name TXP) The results are not shown in Table 1. Table 1 shows that the aromatic phosphate of the present invention is resistant to hydrolysis. Better in terms of properties 0 Rich oil 5 Li 8 In ingredients (a): 100 parts of commercially available phenol resin paint (solid hip content 60 涔), add ingredient (b): 15 parts of the above synthetic compounds 1 to 4 One, mixed with M. Then, pour it into cotton gauze paper to make it dry, to obtain a sheet impregnated with fat, resin containing 145 g. These sheets were laminated 9 g, U0TC and 90 g / c «1 2 and scrape for 50 minutes to obtain a swollen palate sheet with a thickness of 2 β a. Other synthetic compounds are also subjected to the above procedure to obtain 4 layers of flakes. The obtained calendar flakes were tested according to the following method: UL (Cinder * writers Labo 「ator * ies) -94 Sister flammability. Divided into 4 categories, VO, Vl. V-2 and HB; JiS (Japanese Industrial Standards) C-6 4 8 1 test welding «resistance, the head is shown at 26 0 C to start bulging or 剌 洱Time (seconds); perforation at 18.6kg / c * 2MASTM ·· Please read the notes on the back and fill in this f) The paper standard selects the rate of poor countries (CNS) Α4 wash grid (210X297 mm) 11 A7 4267 1 3 _B7 _ V. Description of the invention (12) quasi-D- 617 test; insulation performance MJIS C-6481 test; and heel resistance M electrolyte dripping test. Shown in the display 0 < end --------- W-install-'(Please read the precautions on the back before filling this page) Printed by the I-Consumer Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs 12 This paper uses the national standard (0 milk) 8 4 specifications (2 丨 0 > < 297 mm) 4 267 1 3

A B7 V. Description of the invention (13) Slaff 3F Howl® 1¾ Water glffs ¾ Eggplant 猓 漭 § Window Zheng Yu 谇 "sslffi 0 & 0 > 漥 一 泥 0 > 豸 3 fbn > ^ M ibn > ^ 5 ibn > Sign 6 0 == 0 > 漥 7 vo 10-2-1013 > 600 600 0 15 100 V-0 10-2-1013 > 600 73 0 15 100 (Please read the precautions on the back before filling this page)) ≫ 600 57 诹 Jing 0 10 12 — 1 15 100 order V-0 1012-1013 > 600 62 诹 cocoon 0 15 100 V-0 1091 105 500 15 & Union 15 100 Industrial and consumer cooperation

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V10 109Λ01Ο 500 55 X 15 15 100 100 rrb »The paper size of the pet is used in accordance with the national standard of China (CNS > A4 wash case (210X297 mm) 13 426713 A7 B7 V. Description of the invention (14) s at 1 2 0 C After 48 hours of storage, M was able to detect oil leakage with the naked eye. Hh 觭 Example 4 莘 fi In the same manner as described in Example 5, a thin sheet was obtained, but compounds 5 to 7 were used instead of the compounds of Synthesis Examples 1 to 4 as ingredients. (B). The obtained flakes were tested as shown in Table 5. The results are shown in Table 2. From Table 2, it is apparent that the flame-retardant thermosetting resin composition containing aromatic phosphate ester according to the present invention is better than that containing ordinary flame retardants. Thermosetting resin composition, not only in flame retardancy and low-temperature perforation, but also in the leakage resistance of the flame retardant ®® sheet, especially the resistance to the formation of conductive tracks and insulation due to the good hydrolysis resistance Performance: tt crack example 9 p. 1 2 In ingredient (a): 100 parts of commercially available epoxy resin lacquer (solid content 50%) and 3 parts of dicyandiamide, add ingredient (b): 15 parts of Synthesis Examples 1 to One of compounds 1 to 4 in 4 was mixed with β in K and then, in the same manner as in Example 5, 4 sheets of laminate were obtained. The obtained layer ® sheet was tested as described in Example 5. The results of the printed work bags of the Ministry of Economic Affairs of the quasi-government bureau are not shown in Table 3. 14 (Please read the precautions on the back before filling in this page) This paper uses China National Standard (CNS) Α4 size (210 × 297 mm) 6 2 4 3

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V 100 3 15 V-0 1013,0: > 600 121 诹 笱 0 15 100 3 (Please read the precautions on the back before filling this page) -Pack. V-0 10S-10) > 600 007 诹笱 0 15 100 3 Order V-0 10-3-1 > i 0 15 100 3

V-0 10Ξ-10 500 35 X 15 100 3 Printed by the Consumer Sample Cooperative of the Central Sample Rate Bureau of the Ministry of Economic Affairs

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IS 100 3 100 3 tb »The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 15 4 267 1 3 A7 A7 B7 V. Description of the invention (l6) 5 in 1201: After 43 hours of storage, The ML was observable by the naked eye. 9 7 cases of 0 hh used for combination but the film is thin and is obtained in the same way as described in the above 5 cases are implemented as in the example of the film into a thin film M for 7 generations of 5 to 5 of the compound 4 to test description In 5 cases, it is practically as a tree-like solid heat-burning flame. The acid-phosphorus aromatic compound contains bright hair. The present 3 is shown in the table. The results are shown in Table 31. The results are inconsistent, and the leakage of the superior anti-osmosis resistance is thin. The fat pressure tree employs a self-curing agent, and the hot burning agent is also resistant to combustion. Generally, the surface 1 is more porous, and the temperature of the material is lower than that of the fat. Only the material can form the sexual group. 0 Resistance, flammable resistance formed in the shape of ester trace acid orbital phosphorous group 専 専 aromatic resistance is Mingbeifa special edition, which is lower than the others. Jia Teliang comparison. Revealed as a large leak, the permeability of the surface is more resistant than the ratio of the physical properties of thin edge sister shaved off the fat calendar and tree self-propellant thermosetting fire resistance sister sex agent 隹Ignition is relatively deficient, and the track-like track 1 hole contains permeation and temperature resistance (please read the precautions on the back before filling this page): r.

• Central Ministry of IT, Ministry of Economic Affairs, Industrial and Commercial Cooperation, Industrial and Consumer Cooperation, Printing and Printing of Paper Paper, Standards and Standards (_: 1 «), 8 Regulations / Grid (210 乂 297 mm) 16 1267 1 3 δί. i ί Η3 Attachment II Printed by the Shell and Welfare Commission of the Central Standards Bureau of the Ministry of Economic Affairs. Patent No. 85103947 petition petition # 丨 Shenzhen Lifanyuan Amendment (November 10, 89) A flame-retardant thermosetting resin The composition includes: (a) a thermosetting tree cell and (b) an aromatic phosphoric acid represented by the following formula (I):

(I) In the formula, R1 and R2 are the same (^ -4 alkyl group, R3 is an argon atom or a Ct-4 alkyl group, IΪ 4 is a C 6-2 0 aromatic hydrocarbon residue, and η is 2 or 3 The integer (where) component (a) is derived from acrylic acid cells, polyamines, formic acid resins, phenol resins, ring gas resins, trimer resins, neem unsaturated polyester trees, and diallyl phthalate. _ Any one of the group of tree wax; 0.1 to 100 parts by weight of ingredients (b) and 100 parts by weight of ingredients (a) mixed "2. For example, the sister product of item 1 of Shenyang Patent Fanyuan, where 5 to 50 parts by weight of the component (b) is mixed with 100 parts by weight of the component (a). 3. The composition of item 1 of the patent application country, in which the aromatic phosphate (1) is citric acid silkworm (2, 6-xylene) Esters), phosphate (2, 4, 6-trimethyl cresyl) or bis (2,6-xylene) toluene vinegar. 4. If applying for the composition of item 1 of Lifanfan, which contains component (a) It is a phenol resin. 5. If the composition of item 1 of the patent application box is applied for, the component (a) is an epoxy resin. 6. If the composition of item 1 of the application is applied, it is used for preparing flame retardant Base material of this paper As quasi-engage in home (CNS) A4 size (210X297 public bad) 38140