WO2000050486A1 - Resine ignifuge en polyester non sature - Google Patents

Resine ignifuge en polyester non sature Download PDF

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Publication number
WO2000050486A1
WO2000050486A1 PCT/JP2000/000953 JP0000953W WO0050486A1 WO 2000050486 A1 WO2000050486 A1 WO 2000050486A1 JP 0000953 W JP0000953 W JP 0000953W WO 0050486 A1 WO0050486 A1 WO 0050486A1
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WO
WIPO (PCT)
Prior art keywords
unsaturated polyester
flame
retardant
weight
parts
Prior art date
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PCT/JP2000/000953
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English (en)
Japanese (ja)
Inventor
Hiroshi Takeuchi
Tomoko Inoue
Hiroya Okumura
Hiroyuki Shiraki
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Takeda Chemical Industries, Ltd.
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Priority claimed from JP33391699A external-priority patent/JP2001152000A/ja
Priority claimed from JP11333917A external-priority patent/JP2000309697A/ja
Application filed by Takeda Chemical Industries, Ltd. filed Critical Takeda Chemical Industries, Ltd.
Publication of WO2000050486A1 publication Critical patent/WO2000050486A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'

Definitions

  • the present invention provides an unsaturated polyester which is halogen-free, has high flame retardancy, and is excellent in heat resistance, moisture resistance, mechanical properties, chemical resistance, etc., and is also excellent in productivity.
  • the present invention relates to a resin containing the resin, a resin composition containing the resin, and a cured product thereof. Background art
  • Thermosetting resins having unsaturated bonds have been widely used in various industrial fields in recent years due to their excellent heat resistance, mechanical properties, electrical properties, and the like.
  • the flame retardation of these resins has been achieved by using halogen-based flame retardants or by introducing a halogen element into resin molecules.
  • halogen-based flame retardants or by introducing a halogen element into resin molecules.
  • it has become difficult to use cured products of resins using halogens for example, because they become sources of dioxin during combustion.
  • flame-retardant resins using elements such as phosphorus and antimony are being studied.
  • a reactive diluent such as styrene or methyl methacrylate
  • flame retardants are not usually incorporated into the molecules of the resin, and when used in large quantities, the mechanical properties of the cured product are reduced.
  • many phosphorus-based flame retardants have a phosphate ester structure, but the phosphate ester structure is inherently high in hygroscopicity and low in heat resistance. The heat resistance and moisture resistance may be reduced.
  • Japanese Unexamined Patent Publication (Kokai) No. 53-111297 states that some of the unsaturated groups in unsaturated polyesters Although a phosphorus-containing unsaturated polyester obtained by adding an organic phosphorus compound used in the present invention is described, the resin disclosed therein has a low phosphorus content of 1.6% by weight or less, so that it is not sufficient. Since flame retardancy cannot be achieved and the viscosity is high, it is difficult to impregnate glass cloth and glass nonwoven fabric. Disclosure of the invention
  • An object of the present invention is to obtain a cured product having high flame retardancy despite being halogen-free, and also having good properties such as good heat resistance, moisture resistance, and mechanical properties, and also having excellent productivity.
  • An object of the present invention is to provide a polyester, a resin containing the same, a resin composition, and a cured product thereof.
  • the present inventors have conducted intensive research in order to solve the above-mentioned drawbacks of the conventional technology.
  • the compound represented by the formula (I) has a phosphate ester structure
  • the cured product has a higher moisture resistance than a conventionally known phosphate ester compound. It has been found that it does not easily decrease and exhibits high heat resistance.
  • a certain amount of compound (I) is introduced into the molecule of unsaturated polyester by a method of adding it to unsaturated bonds derived from itaconic acid, it can be subjected to severe high-temperature and humidity resistance tests such as pressure cooker test (PCT test).
  • PCT test pressure cooker test
  • the present inventors have also found that very good results can be obtained, and that flame retardancy can be achieved with a lower phosphorus content than in the case of using a conventional phosphate compound, thereby completing the present invention.
  • the present invention provides:
  • the unsaturated group of the unsaturated polyester has the formula (I)
  • R 1 and R 2 are the same or different aliphatic groups or aromatic groups, and m and n are the same or different integers of 0 to 4).
  • a flame-retardant unsaturated polyester having a phosphorus content of 2 to 10% by weight and an unsaturated bond equivalent of 200 to 1,000 g / mo 1,
  • the unsaturated polyester contains an unsaturated polyester obtained by reacting a compound having one group reactive with a carboxyl group in a molecule with an unsaturated polyester having a carboxyl group at a terminal.
  • the flame-retardant unsaturated polyester according to the above (1) comprising (a) 100 parts and an ethylenically reactive diluent (b) 100 to 100 parts, and has a viscosity at 30 ° C.
  • a flame-retardant unsaturated polyester resin having a Q content of 70 Q mPa ⁇ s or less and a phosphorus content of 1.5 wt% or more,
  • a resin composition comprising the flame-retardant unsaturated polyester (a) according to the above (1), a reactive diluent (b) and a phosphorus-based flame retardant (c), wherein the resin composition In 100 parts, (a) is 25-90 parts, (b) is 5-70 parts and (c) force S 1-25 parts Yes, a flame-retardant unsaturated polyester resin composition having a phosphorus content of the resin composition of 2.0 to 10.0%,
  • a metal foil-clad laminate obtained by curing a reinforcing fiber layer impregnated with the flame-retardant unsaturated polyester resin composition according to the above (13) or (14) integrally with a metal foil. is there.
  • examples of the aliphatic group represented by R 1 and R 2 include an alkyl group such as methyl, ethyl and propyl, and examples of the aromatic group include an aryl group such as phenyl and naphthyl.
  • No. m and n are integers of 0 to 4, preferably 0 or 1, and particularly preferably 0.
  • Compound (I) can be easily produced by the method described in Polymer Bulletin No. 41, 45-52 (1998).
  • the unsaturated polyester used in the present invention can be synthesized by the condensation of a polyolefin-unsaturated dicarboxylic acid with a glycol.
  • a polyolefin-unsaturated dicarboxylic acid with a glycol.
  • unsaturated polyester in addition to these two components, aliphatic saturated dicarboxylic acid and aromatic dicarboxylic acid Saturated dicarboxylic acids such as can be used in combination.
  • Examples of c,] 3-olefinic unsaturated dicarboxylic acids include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid and anhydrides of these dicarboxylic acids.
  • Examples of the saturated dicarboxylic acids which can be used in combination with these ⁇ ,] 3-olefin unsaturated dicarboxylic acids include, for example, adipic acid, sebacic acid, succinic acid, darconic acid, o-, m-, p-phthalic acid Acids, tetrahydrophthalic acid, hexahydrophthalic acid and anhydrides of these dicarboxylic acids.
  • glycol for example, alkanediol, cycloalkanediol, oxaalkanediol, hydrogenated bisphenol A or bisphenol A, and the like are used.
  • monohydric or trihydric alcohols can be used.
  • alkanediols include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentinoglycol , 1,5-pentanediol and 1,6 hexanediol; and examples of cycloalkanediol include cyclohexanediol.
  • oxaalkanediol examples include diethylene glycol and triethylene glycol.
  • the monohydric or trihydric alcohol used in combination with these glycols includes, for example, octylanolole, oleylanolole, and trimethylolpropane.
  • the synthesis of unsaturated polyester is generally carried out under heating, and the reaction proceeds while removing by-product water.
  • the crosslink density and glass transition temperature of the cured product can be adjusted by selecting the raw materials to be used. For example, using a compound having a long-chain molecular structure as a raw material, such as adipic acid or sebacic acid as a saturated fatty acid, or diethylene glycol or dipropylene glycol as a glycol, as a raw material, the glass transition temperature can be lowered.
  • the glass transition temperature can be increased by using a compound having a rigid structure such as bisphenol A hydride as a glycol as a raw material.
  • the compound (I) may be introduced into the above-mentioned ⁇ , / 3-olefin unsaturated dicarboxylic acid or its anhydride.
  • the desired phosphorus-containing flame-retardant unsaturated polyester by synthesizing the corresponding phosphorus-containing dicarboxylic acid or its anhydride by using it as a raw material for the synthesis of unsaturated polyester. be able to.
  • the conditions under which the compound (I) is added vary depending on the structure of the unsaturated dicarboxylic acid to be added, but are generally 150 ° C. to 200 ° C.
  • the addition of the compound (I) to the unsaturated group can be performed after the unsaturated polyester is synthesized.
  • a polymerization inhibitor for preventing thermal polymerization of unsaturated groups for the purpose of preventing gelation, it is preferable to use, for example, a polymerization inhibitor for preventing thermal polymerization of unsaturated groups.
  • the unsaturated dicarboxylic acid to which the compound (I) is added itaconic acid, maleic acid or an anhydride thereof is preferable.
  • itaconic acid is easy to add the compound (I), and is excellent in heat resistance and moisture resistance. Resin can be obtained.
  • the structure of bisphenol A in the molecule of unsaturated polyester using the ethylene oxide or propylene oxide adduct of bisphenol A as the glycol that is, the remaining residue obtained by removing two hydroxyl groups from bisphenol A, is used.
  • Introducing a structure increases the heat resistance of the cured product, and at the same time, is effective in improving the fragility of the cured product and imparting toughness, which were problems when introducing phosphorus into unsaturated polyester molecules.
  • the phosphorus content in the unsaturated polyester of the present invention is usually in the range of 2 to 10% due to the manifestation of the flame retardancy of the cured product, but the laminate is particularly required to have strict flame retardancy and heat resistance. It is preferably in the range of 3 to 7% for use in When the phosphorus content is 2% or less, it is difficult to exhibit flame retardancy in the cured product, and when it exceeds 10%, high flame retardancy can be exhibited, but the mechanical properties, heat resistance, and moisture resistance of the cured product tend to decrease. In some cases, the productivity of the flame-retardant unsaturated polyester may be reduced.
  • the flame-retardant unsaturated polyester of the present invention must have an unsaturated bond equivalent of 200 to 1,000 g Zmo1 in order to impart high heat resistance, moisture resistance, and mechanical properties to the cured product. It is necessary, and preferably 200 to 700 g / mo1. If the unsaturated bond equivalent is less than 200 g / mo1, the crosslink density becomes too high, and the cured product becomes brittle, which hinders practical use. On the other hand, if it exceeds 1,000 g, the crosslink density becomes insufficient, and as a result, it becomes difficult to obtain a cured product having sufficiently high Tg and other necessary physical properties.
  • the Tg of the cured product of the phosphorus-containing unsaturated polyester and the resin obtained by diluting the same with a reactive diluent having an ethylenic double bond is 12
  • the temperature is preferably 0 ° C or higher, more preferably 120 to 190 ° C.
  • Examples of the compound having one group that reacts with a carboxyl group in the molecule include a compound having one epoxy group or hydroxyl group in the molecule. Further, such a compound preferably further has a double bond in the molecule in addition to the above-mentioned functional group in order to improve the heat resistance of the cured product.
  • Such compounds include glycidyl (meth) acrylate, vinyl glycidyl ether, (meth) acrylate
  • the reaction between the compound having one reactive group and the phosphorus-containing flame-retardant unsaturated polyester in the molecule is performed at 80 to 180 ° after the synthesis of the phosphorus-containing flame-retardant unsaturated polyester. About 0.2 to 8 hours at a temperature of about C in the presence or absence of a known catalyst used for polyesterification or bulesterification By reacting, the desired phosphorus-containing flame-retardant unsaturated polyester having reduced terminal carboxyl groups can be obtained.
  • the ratio of the compound having one group having a reactivity with the carboxyl group to the carboxyl group present at the terminal of the flame-retardant unsaturated polyester in the molecule is 0.5 to 1 with respect to 1 equivalent of the carboxyl group. .2 equivalents are preferred, and 0.8 to 1.05 equivalents are more preferred.
  • the obtained flame-retardant unsaturated polyester (a) may be diluted with a reactive diluent (b) having at least one ethylenic double bond in the molecule for the purpose of lowering the viscosity and the like.
  • a reactive diluent b
  • the reactive diluent include unsaturated fatty acids such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate.
  • Unsaturated carboxylic esters such as 2-ethylhexyl acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylamide , (Meth) acrylonitrile and other nitrogen-based monomers, styrene, vinyltoluene, dibutylbenzene, pt-butylstyrene and other aromatic vinyl compounds, ethylene glycol di (meth) acrylate, diethylene glycol diethylene glycol (Meta) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 hexane Examples thereof include polyfunctional (meth) acrylates such as di (meth) acrylate, trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol
  • the mixing ratio of ( a ) and (b) in the flame-retardant unsaturated polyester resin containing the flame-retardant unsaturated polyester (a) and the reactive diluent (b) is (a) 100 parts.
  • (b) is 10 to 100 parts, but (b) is preferably 10 to 80 parts in order to exhibit higher flame retardancy.
  • the viscosity of the flame-retardant unsaturated polyester resin comprising the flame-retardant unsaturated polyester (a) and the reactive diluent (b) at 30 ° C. is usually not more than 700 mPa ⁇ s, preferably 500 mPa ⁇ s or less, and the phosphorus content is 1.5% or more. Therefore, the ethylenic reactive diluent in the flame-retardant unsaturated polyester resin of the present invention is used.
  • the type and amount of the excipient may be selected so as to satisfy those conditions.
  • phosphorus-based flame retardant (c) used in the present invention those having a low hydrolyzability, a high phosphorus content and a structure that does not affect the curing of the radical-based o are preferable.
  • Suitable examples include condensed phosphoric acid-based and phosphazene-based phosphorus-based flame retardants.
  • R 3 is an alkylene group which may have a substituent, a (poly) oxyalkylene group which may have a substituent or an arylene group which may have a substituent, X is an integer of 1 to 20.
  • the alkylene group represented by R 3 is, for example, 3 alkylene groups such as methylene, ethylene, and propylene; and the arylene group is, for example, phenylene, naphthylene, a group represented by the formula:
  • (Poly) oxyalkylene groups include, for example, (poly) oxyethylene
  • (Poly) oxy d alkylene groups examples include C and alkyl groups such as methyl and ethyl.
  • substituent in each group examples include C and alkyl groups such as methyl and ethyl.
  • group in which the hydroxyl group of the compound of the formula (III) is esterified include C, -3 alkoxy groups such as methoxy and ethoxy, and aryloxy groups such as phenoxy, naphthoxy, methylphenoxy and dimethylphenoxy. From the viewpoint of the heat resistance of the cured product, the esterified hydroxyl group is preferably an aryloxy group.
  • X is an integer of 1 to 20, preferably an integer of 1 to 10.
  • Preferred examples of the condensed phosphate ester-based flame retardant include ⁇ -200 (manufactured by Daihachi Chemical Industry Co., Ltd.).
  • phosphazene-based flame retardants include the formula (m)
  • R 4 , R s , R 6 and R 7 are the same or different and each may be an alkyl group which may have a substituent or an aryl group which may have a substituent, y is 1 to 1
  • R 8 and R 9 are the same or different and are an alkyl group which may have a substituent or an aryl group which may have a substituent, and z is 3 or 4.
  • examples of the alkyl group represented by R 4 to R 9 include an alkyl group of d such as methyl, ethyl, propyl, and an aryl group.
  • W is, for example, phenyl, naphthyl or the like, and examples of the substituent thereof include an alkyl group having 13 to 13 carbon atoms such as methyl, ethyl, propyl and the like.
  • y is an integer of 1 to 10, preferably 3 to 6, and z is preferably 3.
  • R 4 to R S are preferably aryl groups such as phenyl.
  • phosphazene-based flame retardant examples include CP-134H (manufactured by Chemipro Kasei Co., Ltd.) belonging to the compound represented by the formula (IV) (wherein R 8 and R s are phenyl groups).
  • CP-134H manufactured by Chemipro Kasei Co., Ltd.
  • R 8 and R s are phenyl groups.
  • the proportion of each component in the flame-retardant unsaturated polyester resin composition containing the flame-retardant unsaturated polyester (a), the reactive diluent (b) and the phosphorus-based flame retardant (c) is as follows: In 100 parts of the product, (a) is preferably 25 to 90 parts, (b) is preferably 5 to 70 parts, and (c) is preferably 1 to 25 parts.
  • the flame-retardant unsaturated polyester resin and the resin composition of the present invention may be a vinyl ester resin, an unsaturated polyester resin, etc., which have been well known as a resin having an unsaturated bond, for the purpose of improving physical properties and improving productivity. Can also be used as a mixture. These amounts are appropriately determined depending on the performance required for the cured product, but from the viewpoint of flame retardancy, preferably 5 to 200 parts, more preferably 100 parts per 100 parts of the flame-retardant resin or resin composition. Is from 10 to 150 parts.
  • the flame-retardant resin or resin composition of the present invention may contain a rubber component for imparting toughness, impact resistance, panning workability, interlayer adhesion, and the like to the cured product.
  • a rubber component for imparting toughness, impact resistance, panning workability, interlayer adhesion, and the like to the cured product examples include liquid rubbers such as carboxyl-terminated NBR, epoxy-terminated NBR, vinyl-terminated NBR and the like, and modified products thereof, and fine-grained rubber such as cross-linked acrylic fine particles (average particle diameter 0.1 l). 5050 / zm).
  • the amount of the rubber component to be used is generally 1 to 30 parts, preferably 2 to 15 parts, per 100 parts of the flame-retardant resin or the resin composition.
  • the flame-retardant resin containing the components (a) and (b) or the flame-retardant resin composition containing the components (a), (b) and (c) of the present invention may be a general unsaturated polyester resin or a vinyl ester resin.
  • the composition can be easily cured by adding a curing agent used for curing the composition and, if necessary, a curing accelerator.
  • the curing agent used in the present invention include organic peroxides such as methyl ethyl ketone peroxide, t-butyl peroxybenzoate, benzoy peroxide, dicumyl baroxide, cumenehydroxide and the like.
  • the amount of the curing agent used is preferably 0.1 to 5 parts, more preferably 0.5 to 3 parts, per 100 parts of the flame-retardant resin.
  • the curing accelerator include cobalt naphthenate, cobalt octoate, manganese naphthenate, dimethylaniline, getylaniline, acetylacetone and the like.
  • the amount of the curing accelerator used is preferably 0.01 to 3 parts with respect to 100 parts of the flame-retardant resin or the resin composition.
  • the flame-retardant resin or resin composition of the present invention may further comprise a filler, a low-shrinking agent, a curing agent, a pigment, a dye, a polymerization inhibitor, a fiber reinforcing agent, an internal mold release agent, and a thickening agent which are conventionally used. Etc., and various cured products can be obtained.
  • the filler include inorganic fillers such as aluminum hydroxide, glass powder, calcium carbonate, talc, silica, clay, glass balloon and the like. These are usually used in an amount of 400 parts or less, preferably 50 to 300 parts, per 100 parts of the flame-retardant resin or resin composition.
  • low shrinkage agent examples include saturated polyester, polymethyl methacrylate, polyvinyl acetate, cross-linked polystyrene, styrene-butadiene (block) copolymer and its hydrogenated product, vinyl acetate-styrene (block) copolymer, (meth) Acryl-styrene (block) copolymer or the like is used.
  • These low-shrinkage agents are usually used in an amount of 30 parts or less per 100 parts of the flame-retardant resin or the resin composition.
  • the internal mold release agent examples include metal lithography such as calcium stearate and zinc stearate, and silicon and fluorine-based organic compounds, and phosphoric acid-based compounds. It is usually used in an amount of 100 parts or less based on 100 parts of the resin composition.
  • pigment examples include titanium oxide, carbon black, red iron oxide, and phthalocyanine blue.
  • thickener examples include oxides and hydroxides such as magnesium and calcium.
  • glass fiber having a diameter of about 8 to 15 ⁇ and a length of 25 mm or less is used as the fiber reinforcing material.
  • Fiber reinforcement is usually resin Out of 100 parts of the whole product: About 40 parts are blended.
  • the flame-retardant resin composition of the present invention is obtained by using a part or all of the above-mentioned compounding agents to form a resin composition, and then impregnating a glass cloth, a glass nonwoven fabric, or the like, and curing to obtain a laminate.
  • a resin composition obtained by using a part or all of the above-mentioned compounding agents to form a resin composition, and then impregnating a glass cloth, a glass nonwoven fabric, or the like, and curing to obtain a laminate.
  • a glass cloth, a glass nonwoven fabric, or the like or the like
  • the type and amount of the filler and the phosphorus content in the composition vary depending on the thickness of the laminate. Contains 20-70% of medium filler, and the phosphorus content is 0.4-8.0 ° /. Is preferably in the range of
  • the resin composition of the present invention is impregnated into a reinforcing fiber layer such as a glass cloth or a glass nonwoven fabric, and if necessary, a plurality of the impregnated materials are laminated, and a metal foil such as a copper foil is laminated and heated.
  • a metal foil-clad laminate in which the reinforcing fiber layer and the metal foil are integrally cured can be obtained.
  • a phosphorus-containing oligoester having a titer of 2.6 mg KOHZg was obtained. 406.3 g of fumaric acid and 0.17 g of hydroquinone were added to the reaction mixture containing the oligoester, 21 The dehydration condensation reaction was carried out at 5 ° C for 5 and a half hours to obtain a phosphorus-containing unsaturated polyester having an acid value of 20.3 mgKOH / g (phosphorus content 2.75%, unsaturated bond equivalent 394 g / mo 1 0 ) This unsaturated polyester was diluted with 91.1 Og of styrene monomer to obtain an unsaturated polyester resin (A).
  • the reaction mixture containing the oligoester was cooled to 140 ° C, charged with 245.2 g of fumaric acid and 0.14 g of hydroquinone, and subjected to a dehydration condensation reaction at 215 ° C for 6 hours to obtain an acid value of 16 3 mg KOHZg of a phosphorus-containing unsaturated polyester was obtained (phosphorus content: 5.38 ° /., Unsaturated bond equivalent: 564 gZmo 1).
  • the unsaturated polyester was diluted with 705.1 g of a styrene monomer to obtain an unsaturated polyester resin (D).
  • This oligo 343.6 g of fumaric acid and 0.12 g of hydroquinone were further added to the reaction mixture containing the steal, followed by a half-hour dehydration condensation reaction at 210 ° C for 5 hours and a phosphorus-containing unsaturated acid having an acid value of 21.3 mg KOH / g Polyester was obtained (phosphorus content: 2.64%, unsaturated bond equivalent: 410 g / mo 1).
  • This unsaturated polyester was diluted with 81.5 g of a styrene monomer to obtain an unsaturated polyester resin (F).
  • reaction mixture containing the oligomer 174.2 g of fumaric acid and 0.10 g of hydroquinone were further added, and a dehydration condensation reaction was performed at 210 ° C. for 3.5 hours. At this point, the acid value was measured and was 55. OmgKOHZg.
  • the reaction mixture was cooled to 150 ° C, added with 158.5 g of daricidyl methacrylate (1.0 equivalent to acid) and 0.20 g of hydroquinone, and reacted at 150 ° C for 1 hour.
  • the reaction mixture is cooled to 150 ° C, glycidyl methacrylate 160.6 g (1.0 equivalent to acid) and hydroquinone 0.20 g are added, and the mixture is reacted at 150 ° C for 1 hour.
  • the acid value is 4.2 mg KOH / g and the end is capped with glycidyl methacrylate.
  • a phosphorus-containing unsaturated polyester was obtained (phosphorus content: 6.66%, unsaturated bond equivalent: 790 g / mo 1).
  • This unsaturated polyester was diluted with 808.5 g of styrene monomer to obtain an unsaturated polyester resin (H).
  • An unsaturated polyester resin was synthesized according to the description in Example 1 of JP-A-53-112997.
  • an epoxy resin (YD128, manufactured by Toto Kasei Co., Ltd.) was used in the presence of 0.3 g of hydroquinone and 0.3 g of benzyldimethylamine. 1772 g of methacrylic acid was added to 3874 g of epoxy equivalent and reacted at 120 ° C. for 6 hours to obtain vinyl ester having an acid value of 2.Omg KOHZg. 294 g of a styrene monomer was added to the beer ester to obtain a phosphorus-free bullet ester resin (J).
  • the unsaturated polyester resins (A) to (1), vinyl ester resin (J), styrene monomer, cross-linked acrylic rubber fine particles, phosphorus-based flame retardant, and curing agent were blended at the weight ratios shown in Table 1.
  • a resin composition was manufactured. Each resin composition is poured into a glass mold equipped with a silicone spacer, and is cured by heating at 100 ° C. for 1 hour and then at 150 ° C. for 30 minutes. A casting plate containing no was prepared. Using these casting plates, the strength and Tg were measured by the following methods.
  • Flexural strength Compliant with JISK 7203
  • Flexural modulus Conforms to JISK7203
  • T g peak temperature of ta ⁇ ⁇ obtained by measuring dynamic elastic modulus
  • the unsaturated polyester resins ( ⁇ ) to (1), butyl ester resin (J), styrene monomer, crosslinked acrylic rubber fine particles, phosphorus-based flame retardant, curing agent, The materials were blended to produce a resin composition.
  • the obtained resin composition was poured into a glass mold equipped with a silicone spacer, and was cured by heating at 100 ° C. for 1 hour, and then at 175 ° C. for 30 minutes to cure.
  • a casting plate containing mm filler was prepared. Using this casting plate, flame resistance, heat resistance, heat resistance after PCT, and alkali resistance were measured by the following methods.
  • Heat resistance Time required to immerse the casting plate in a 260 ° C solder tank until blistering occurs (seconds)
  • Heat resistance after PCT 1 hour at 121 ° C under 95% humidity And then measure the above heat resistance
  • the casting plate was immersed in a 10% aqueous solution of sodium hydroxide at 60 for 1 hour, and the appearance and weight change were evaluated according to the following criteria.
  • the additives used are as follows.
  • Phosphorus-based flame retardant P X—200 (manufactured by Daihachi Chemical Industry Co., Ltd.)
  • Curing agent Cumene high dropper oxide 80% product, Parkmill H-80 (Nippon Yushi Co., Ltd.)
  • the cured product obtained from the flame-retardant unsaturated polyester resin of Example 19 has good mechanical properties, high flame retardancy, heat resistance, heat resistance after PCT, It turns out that it has alkali resistance.
  • compound (I) The casting plate of Comparative Example 1 using an unsaturated polyester resin (I) with a low addition rate of the resin had poor flame retardancy (burned), and the phosphorus content was adjusted to the same level as in the example by adding a phosphorus-based flame retardant It can be seen that the cast plates of Comparative Examples 2 and 3 also have lower flame retardancy than those of the examples, and have low heat resistance, particularly low heat resistance after PCT.
  • the resin composition was prepared by mixing the unsaturated polyester resins (K) to (M), the butyl ester resin (J), the phosphorus-based flame retardant, the crosslinked acrylic rubber fine particles, and the curing agent at the weight ratios shown in Table 2. It was prepared and the mechanical properties and Tg were measured in the same manner as in Example 1.
  • the unsaturated polyester resins (K) to (M), the butyl ester resin (J), the phosphorus-based flame retardant, the crosslinked acrylic rubber fine particles, the curing agent, and the filler are blended in the weight ratios shown in Table 2.
  • a resin composition was prepared.
  • Each resin composition is poured into a glass mold equipped with a silicone spacer and cured by heating at 100 ° C for 1 hour, followed by heating at 175 ° C for 30 minutes, and contains a 1 mm thick filler.
  • a casting plate was made. Using these casting plates, flame retardancy, heat resistance, heat resistance after PCT, and alkali resistance were measured by the following methods.
  • Heat resistance time until the blisters are formed by immersing the casting plate in a 260 ° C solder bath (seconds)
  • Heat resistance after PCT The casting plate is subjected to one-hour presser test at 121 ° C under 95% humidity for 1 hour, and the above heat resistance is measured.
  • Alkali resistance Immerse the casting plate in 10% aqueous sodium hydroxide solution at 60 for 1 hour Pickled, then evaluated appearance and weight change based on the following criteria
  • the flame retardants and additives used are as follows.
  • Condensed phosphate ester-based flame retardant PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.)
  • Phosphazene-based flame retardant CP-134H (manufactured by Chemipro Kasei Co., Ltd.) Industrial Co., Ltd.)
  • Curing agent Cumene Halo Dropper Oxide 80%, Park Mill H-80 (Nippon Yushi Co., Ltd.)
  • the flame-retardant unsaturated polyester of the present invention provides a cured product having high flame retardancy, heat resistance, moisture resistance, chemical resistance, and good mechanical properties while being halogen-free, and has excellent productivity. Therefore, it is particularly suitable as a material for a laminate.

Abstract

La présente invention concerne un polyester non saturé ignifuge dont la structure comporte un polyester non saturé et un composé phosphoreux ajouté à une partie des groupes non saturés, composé représenté par la formule (I) (dans laquelle R1 et R2 sont identiques ou différents et chacun d'eux représente un groupe aliphatique ou aromatique; et m et n sont identiques ou différents et chacun représente un nombre entier compris entre 0 et 4), et ayant une teneur phosphorique comprise entre 2 et 10 % en poids et une liaison non saturée comprise entre 200 et 1000 g/mol. En outre, on peut utiliser ce polyester pour obtenir un article cuit présentant une ignifugation élevée bien qu'il soit exempt d'halogène, ainsi que d'excellentes propriétés mécaniques, d'excellentes propriétés de résistance à la chaleur, à l'humidité et aux produits chimiques. Le polyester non saturé ignifuge de cette invention présente également une excellente productivité. Il est par conséquent particulièrement employé comme matériau pour stratifiés utilisés en électricité et en électronique.
PCT/JP2000/000953 1999-02-22 2000-02-18 Resine ignifuge en polyester non sature WO2000050486A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP11/42508 1999-02-22
JP4250899 1999-02-22
JP11/333917 1999-11-25
JP33391699A JP2001152000A (ja) 1999-11-25 1999-11-25 難燃性不飽和ポリエステル樹脂組成物
JP11/333916 1999-11-25
JP11333917A JP2000309697A (ja) 1999-02-22 1999-11-25 難燃性不飽和ポリエステル、それを含む樹脂および硬化物

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WO2000050486A1 true WO2000050486A1 (fr) 2000-08-31

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112759720A (zh) * 2021-01-11 2021-05-07 广东锐涂精细化工有限公司 一种耐水煮含磷水性丙烯酸改性聚酯分散体树脂及其制备方法与应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53112997A (en) * 1977-03-14 1978-10-02 Sanko Kaihatsu Kagaku Kenkiyuu Phosphorusscontaining unsaturated polyester

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53112997A (en) * 1977-03-14 1978-10-02 Sanko Kaihatsu Kagaku Kenkiyuu Phosphorusscontaining unsaturated polyester

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112759720A (zh) * 2021-01-11 2021-05-07 广东锐涂精细化工有限公司 一种耐水煮含磷水性丙烯酸改性聚酯分散体树脂及其制备方法与应用

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