WO1992005206A1 - Composition de resine synthetique ignifuge thermodurcissable - Google Patents

Composition de resine synthetique ignifuge thermodurcissable Download PDF

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Publication number
WO1992005206A1
WO1992005206A1 PCT/JP1991/001214 JP9101214W WO9205206A1 WO 1992005206 A1 WO1992005206 A1 WO 1992005206A1 JP 9101214 W JP9101214 W JP 9101214W WO 9205206 A1 WO9205206 A1 WO 9205206A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame
thermosetting resin
retardant
resin composition
composition according
Prior art date
Application number
PCT/JP1991/001214
Other languages
English (en)
Japanese (ja)
Inventor
Hiromi Kochi
Kiyoshi Mishima
Atsushi Sakabayashi
Original Assignee
Manac Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Manac Inc. filed Critical Manac Inc.
Publication of WO1992005206A1 publication Critical patent/WO1992005206A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement

Definitions

  • thermosetting resin composition Flame retardant thermosetting resin composition
  • the present invention relates to a flame-retardant thermosetting resin composition containing brominated polystyrene having a specific molecular weight range.
  • Thermosetting resins have excellent heat resistance, high mechanical strength, good dimensional accuracy, and high cost performance, so they can be used as molding materials for electric and electronic parts, civil engineering and construction materials, and automotive parts. It is widely used in household goods.
  • a laminate obtained by impregnating a thermosetting resin into a laminate base material, drying and heating and pressing is used as a material for a printed wiring board used in industrial and consumer electric and electronic equipment. I have high expectations.
  • thermosetting resins have the drawback of being easily flammable. Therefore, when they are used for electric and electronic parts, flame retardancy is strongly demanded from the viewpoint of disaster prevention.
  • a commonly used method for imparting flame retardancy is to use a compound containing a halogen such as chlorine or bromine or a phosphorus-containing compound such as a phosphoric acid ester alone or in combination.
  • halogen-containing compounds have excellent flame retardant effects.
  • These flame retardants include reactive flame retardants and additive flame retardants.
  • the reactive flame retardant reacts to become a component of the polymer, but the reactive flame retardant has poor storage stability of the resin varnish and pre-bleder, making it difficult to adjust the curing reaction.
  • Additive type flame retardant The higher the halogen content, the greater the flame-retardant effect, but the higher the melting point, the higher the melting point of the crystals and the lower the solubility in solvents, resulting in poor compatibility with other resins.
  • the disadvantage is that the properties of the processed product are degraded because of the pan.
  • thermosetting resin flame-retardant As described above, various methods for making a thermosetting resin flame-retardant have been proposed, but there are very few that are practically satisfactory.
  • thermosetting resins having a specific molecular weight has been obtained.
  • brominated polystyrene having a specific molecular weight was obtained.
  • thermosetting resins containing the brominated polystyrene The processed product obtained by curing the resin composition was found to be excellent in flame retardancy and other properties, and reached the present invention.
  • the present invention relates to a brominated polyolefin having a weight average molecular weight of 600 to 100,000 as a flame retardant and a bromine content of 30 to 80% by weight as a flame retardant. It is a flame-retardant thermosetting resin composition containing styrene.
  • thermosetting resin examples include a fuanol resin, a urethane resin, a melamine resin, an epoxy resin, an unsaturated polyester resin, a diaryl phthalate resin, and a polyurethane resin. Resin that is cured by heating.
  • the flame-retardant thermosetting resin composition of the present invention may contain a flame retardant such as an antimony compound and / or a phosphoric acid ester, a flame retardant auxiliary, a plasticizer, a curing agent, and a curing accelerator, if necessary.
  • Additives such as agents, surface treatment agents, surfactants, protective colloids, heat stabilizers, light stabilizers, coloring agents, fillers, lubricants, solvents, and water can be added.
  • the flame retardant of the present invention has a weight average molecular weight of 600 to 100,000 as measured by gel permeation chromatography, and a bromine content of 30 to 80% by weight. is necessary.
  • the weight-average molecular weight is less than 600, the heat resistance of brominated pristine is inferior, so that it is not practical as a flame retardant.
  • the weight-average molecular weight is more than 10.0, the solubility of the brominated polystyrene in the solvent will be reduced, and the compatibility with the luster will be poor, resulting in low mechanical and other physical properties of the resin. Let it down.
  • a preferred range of the weight average molecular weight is 700 to 8,000, a more preferred range is 800 to 6,000, and a most preferred range is 850 to 4.500.
  • the bromine content of the flame retardant is less than 30% by weight, it is necessary to increase the blending amount of the flame retardant, thereby deteriorating physical properties such as mechanical properties of the resin. Further, brominated polystyrene having a bromine content of more than 80% by weight cannot be practically synthesized.
  • the method for synthesizing the brominated polystyrene of the present invention is not particularly limited. It can be obtained by a method of brominating polystyrene and a method of polymerizing a promostylene monomer.
  • a solvent such as methylene chloride, ethylene dichloride, carbon tetrachloride, and methylene bromide can be used as a solvent for the bromination reaction.
  • a reaction catalyst a catalyst such as anhydrous aluminum chloride, anhydrous ferric chloride, or antimony trichloride is used. Succinic acid and metal powders such as aluminum, iron and antimony can be used.
  • brominating agent bromine, bromine chloride or the like can be used.
  • the amount of the flame retardant in the flame-retardant thermosetting resin composition of the present invention is determined by considering the effective flame retardancy, various physical properties such as mechanical properties of the resin, and the economical efficiency.
  • a preferred range is 3 to 40 parts by weight based on parts by weight.
  • thermosetting resin composition of the present invention With the flame-retardant thermosetting resin composition of the present invention, molded articles such as various molded articles, films, synthetic resin-impregnated paper, laminated articles, paints, adhesives and the like can be obtained. Further, a laminated board can be obtained by impregnating the flame-retardant thermosetting resin composition of the present invention into a laminated board substrate, followed by drying and heating and pressing.
  • the base material for a laminated board include paper and cloth made of various cellulosic fibers, synthetic fiber, cloth sheet made of glass fiber and mineral fiber, mat and nonwoven fabric.
  • a paper phenol or glass epoxy base material is preferable.
  • a copper-clad laminate obtained by laminating a copper foil on a brig reg impregnated and dried with the flame-retardant thermosetting resin composition of the present invention, and subjecting the copper-clad laminate to heat-press molding is subjected to an etching treatment on the copper foil portion, and a circuit It can be used as a printed wiring board for manufacturing the formed wiring board.
  • a 70% toluene solution was prepared for each of the brominated polystyrenes obtained in Examples 1 to 3, and a 50% toluene solution was prepared for the brominated polystyrene obtained in Comparative Example 1. Then, the viscosity at 25 ° C was measured with a B-type viscometer (Type BM, manufactured by Tokyo Keiki Co., Ltd.). Storage stability ''
  • the reaction product was washed with water, and the organic layer was dropped and crystallized in 3,000 g of methanol. After the crystals were overdried, 410 g of brominated polystyrene was obtained.
  • the weight average molecular weight of this brominated polystyrene was 1,190, and the bromine content was 70.5%.
  • the solubility in toluene (20 ° C.) was 78.1%.
  • the storage stability of the toluene solution was good.
  • a brominated polystyrene having a weight-average molecular weight of 2,300 (softening point: 93 ° C) was used in place of polystyrene in Example 1 in the same manner. There was obtained 418 g of polystyrene. The weight average molecular weight was 3.450, and the bromine content was 65.6%. The solubility (20.C) was 77.8%. 1 1
  • Bromine was produced in the same manner except that polystyrene having a weight average molecular weight of 8,150 (softening point: 120 ° C) was used in place of polystyrene in Example 1. 421 g of polystyrene was obtained. The weight average molecular weight was 12,600, and the bromine content was 64.0%. The solubility (20 ° C.) was 57.3%.
  • a brominated polystyrene was produced in the same manner except that polystyrene having a weight average molecular weight of 24,000 (softening point: 145 ° C) was used instead of the polystyrene in Example 1. 4 24 g were obtained. The weight average molecular weight was 64.000, and the bromine content was 68.2%. The solubility (20 ° C) was 10% or less. Table 1 summarizes the analysis results of Examples 1, 2 and 3 and Comparative Examples 1 and 2. Table 1 Weight average molecular weight Bromine content (%) Solubility (%) Viscosity (cps) Storage stability Example 1 1, 190 70.5 78.1 254 No precipitation
  • the flame retardants of Examples 1 and 2 and Comparative Example 1 were each dissolved in toluene, and the solutions adjusted to a flame retardant solid content of 70% were added to 100 parts of tung oil-modified phenol resin for a laminate, respectively. 30 parts were added, and 20 parts of cresyldiphenylphosphine were further added to prepare a resin varnish for impregnation. In addition, each of the impregnating resin varnishes was left at room temperature to observe a change in state. The varnish was impregnated with craft paper to adjust the resin content to 50% by weight. The prepreg was further dried to obtain a prepreg. A predetermined number of the prepregs were stacked, and the prepreg was breathed at 170 ° C. for 70 minutes under a pressure of 100 kg cm 2 to obtain a laminate. The appearance and flammability (UL-94) of the obtained laminate were evaluated. Table 2 shows the results.
  • Unsaturated polyester oligomer composition: 1 mol of maleic anhydride, 1 mol of tetrahydrophthalic anhydride and 2.1 mol of ethylene glycol
  • composition 100 parts of Examples 1, 2 and Comparative Example 2
  • Each of the flame retardants was dissolved in styrene, and 16 parts, 22 parts of styrene, and 2 parts of tris (2-chloroethyl) phosphine were adjusted to a flame retardant solid content of 50%. Two parts were mixed and dissolved to obtain a resin composition liquid. This resin solution was left at room temperature to observe a change in state.
  • the flame retardants of Examples 1, 2 and Comparative Example 1 were dissolved in 100 parts of a bisphenol A-type epoxy resin having an epoxy equivalent of 18.6 in molysyl glycidyl ether of Jib mouth, and the flame retardant solid content was reduced to 50%. 25 parts of the prepared solution, 3 parts of antimony trioxide, 2 parts of dicyandiamide and 0.5 part of 2-ethyl-4-methylimidazole were added to prepare a resin composition varnish. Each varnish was impregnated into epoxy silane-treated plain woven glass cloth so that the resin content was 35%, and dried to obtain a prepreg. A predetermined number of the obtained pre-bledas were stacked and hot-pressed with a press at 160 ° C. and 70 kgZcm 2 for 1 hour to obtain a laminate. The flammability (UL-94) of the obtained laminate was measured and evaluated. The results are shown in Table 4.
  • Example 8 100 parts G: 25 parts 3 parts 2 parts 0.5 part V-0.
  • the flame retardants of Examples 1, 2 and Comparative Example 1 were dissolved in 100 parts of a polypropylene triol having a hydroxyl value of 56 in moclesyl glycidyl ether of Jib mouth, and the solid content was adjusted to 50%. Each 15 parts of the solution was dissolved. This solution was stored at room temperature and the condition was observed. 0.1 parts of triethylenediamine, 1.2 parts of a silicone foam stabilizer (Toray Silicone SH190), 0.4 parts of tin octylate and 4 parts of water are added to the mixture, and the mixture is added. After stirring for 10 minutes, add 50 parts of TDI-8 (a mixture of 2,4—trirange isocyanate and 2,6—trirange isocyanate 80/20) and add vigorously. After thorough stirring, it was cured in a dryer at 80 for 1 hour. The flammability (JISD-121) of the obtained polyurethane was measured and evaluated. Table 5 shows the results.
  • Comparative Example 6 100 parts 50 parts 1:15 parts Phase separation Slow flame 2nd grade Flame retardant G: 50% solution of brominated polystyrene of Example 1 in moclesyl glycidyl ether solution at 50% jib mouth
  • the flame retardant of the present invention has extremely good solubility in a solvent and compatibility with a resin varnish, and has a low viscosity when dissolved in a solvent.
  • the resin composition has good storage stability. Further, molded articles obtained by curing the composition have good flame retardancy, and their physical properties such as heat resistance and mechanical properties are satisfactory, so that processed articles with excellent commercial value can be obtained. .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention se rapporte à une composition de résine synthétique ignifuge thermodurcissable, qui contient une résine synthétique thermodurcissable et un polystyrène bromé, comme agent ignifuge, et qui présente un poids moléculaire moyen pondéral compris entre 600 et 10 000 et une teneur en brome comprise entre 30 et 80 % en poids. Cette composition possède une excellente durée de conservation et peut fournir, une fois cuite, un produit possédant d'excellentes propriétés ignifuges, une excellente résistance thermique et d'excellentes propriétés mécaniques.
PCT/JP1991/001214 1990-09-13 1991-09-12 Composition de resine synthetique ignifuge thermodurcissable WO1992005206A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2/241145 1990-09-13
JP2241145A JP2854948B2 (ja) 1990-09-13 1990-09-13 難燃性熱硬化性樹脂組成物

Publications (1)

Publication Number Publication Date
WO1992005206A1 true WO1992005206A1 (fr) 1992-04-02

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PCT/JP1991/001214 WO1992005206A1 (fr) 1990-09-13 1991-09-12 Composition de resine synthetique ignifuge thermodurcissable

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JP (1) JP2854948B2 (fr)
WO (1) WO1992005206A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0765887A1 (fr) * 1995-09-26 1997-04-02 Manac Incorporated Procédé de préparation de polystyrène bromé
EP1032602A1 (fr) * 1996-06-14 2000-09-06 Ferro Corporation Procede de preparation de polystyrene brome dote de caracteristiques de couleur ameliorees

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5147034A (en) * 1974-10-21 1976-04-22 Dai Ichi Kogyo Seiyaku Co Ltd Nannenseino jugotaisoseibutsu
JPS63193904A (ja) * 1987-01-28 1988-08-11 グレート・レークス・ケミカル・コーポレーション 臭素を反応溶剤として用いるポリスチレン芳香族環の臭素化

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5147034A (en) * 1974-10-21 1976-04-22 Dai Ichi Kogyo Seiyaku Co Ltd Nannenseino jugotaisoseibutsu
JPS63193904A (ja) * 1987-01-28 1988-08-11 グレート・レークス・ケミカル・コーポレーション 臭素を反応溶剤として用いるポリスチレン芳香族環の臭素化

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0765887A1 (fr) * 1995-09-26 1997-04-02 Manac Incorporated Procédé de préparation de polystyrène bromé
EP1032602A1 (fr) * 1996-06-14 2000-09-06 Ferro Corporation Procede de preparation de polystyrene brome dote de caracteristiques de couleur ameliorees
EP1032602A4 (fr) * 1996-06-14 2004-08-25 Albemarle Corp Procede de preparation de polystyrene brome dote de caracteristiques de couleur ameliorees

Also Published As

Publication number Publication date
JPH04122776A (ja) 1992-04-23
JP2854948B2 (ja) 1999-02-10

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