JPH06508177A - filled polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] filled polymer The present invention provides improved rheological properties, particularly when used in combination with fiber reinforcing agents. The present invention relates to curable compositions containing high volume concentrations of finely divided particulate fillers having properties.

High concentrations of particulate and/or fibrous reinforcement are present in the polymer matrix. Interest in highly-filled materials has grown rapidly over the past 10-15 years. came. In one embodiment of these materials, the matrix of the material is a curable composition. obtained from. This filled curable composition is cured into the desired shape in a mold. Vine. Separately, the curable composition may be used during continuous processing, e.g. pultrusion. where the curable composition impregnates a continuous fiber structure such as a roving. This impregnated material is then formed into a profile of the desired shape and then cured. It will be done.

Manufacturers require materials for these processes to minimize operational problems. (especially in continuous processing), easy to use, and The goal is to provide high productivity as a result. The material itself has optimal properties at minimal expense. It is a place that gives sex.

Additionally, the resulting product has the desired physical properties such as mechanical strength and stiffness, soot emission It must have excellent combustion properties such as abrasion, and a good surface finish, free of burrs. stomach.

It has excellent fire protection and soot properties, good surface finish and high level of mechanical properties. Compositions with attractive rheological properties that facilitate the production of products with It is currently being developed.

In accordance with the present invention, the highly filled fluid curable composition comprises (A) a solid polymer; (B) 0.5 to 7 microns, preferably 3 ．． Weight average particle size from 0 to 5.0 microns and measured by BET nitrogen absorption method 35-85% by weight, preferably 50-85% by weight, with a surface area lower than 5m''7g 85% by weight of finely divided inorganic filler and (C) sulfate, sulfonate , bosphates and phosphonates with terminal acidic groups. acid ester or, provided that when the composition is cured, the polymer component At least 15%, preferably 40% methacrylate based on total polymer weight or containing repeating units of acrylate monomers.

"The polymerizable organic liquid J for forming a solid polymer is (a) Repeat units may be joined through carbon-carbon bonds or interrupted by heteroatoms. to form a solid polymer that is not bonded by such bonds. a polymerizable organic liquid in which polymerization occurs without forming products to be removed or (b) as described in (a). is soluble in the liquid monomer and component (a) and is soluble in the polymerization of component (a). one or more polymers that are either compatible or incompatible with the polymer produced means a mixture of mer.

of the polymer matrix of the cured product obtained from the curable composition. 15% by weight should constitute repeating units by methyl methacrylate. Liquid component (a) is selected from various ethylenically unsaturated monomers, with the condition that It can be done. Acrylic and methacrylic alcohols containing 1-18 carbon atoms Esters with L are preferred.

The final matrix resin is a cross-linked polymer or is not processed by heat or pressure. It is advantageous for the polymer to be highly branched. This means that the liquid polyethylenically unsaturated monomers or oligos in proportions that are copolymerizable with component (a); This is achieved by including the polymer in the polymerizable liquid (A). If produced hardened At least 50% by weight of the material is recycled from acrylate or methacrylate monomers. Optionally, a reactive diluent such as methyl methacrylate if it constitutes a return unit. final derived from oligourethane acrylates or methacrylates containing Matrix polymers are particularly advantageous. Unsaturated polyester monomers or oligomers The crosslinked polymer derived from the -component also contains at least 15% acrylate. or a final product containing repeating units of methacrylate monomer. It is suitable if the polymerization is carried out in the presence of

Preferred polymerizable liquids are (i) at least one ethylene having an average double bond functionality greater than 1.0; urethane compounds containing unsaturated urethane compounds or precursors of such urethane compositions. a thyrenic unsaturated urethane composition, (ii) present as a preformed species; or a precursor for urethane compositions in at least one ethylenically unsaturated monomer. A vehicle for an unsaturated urethane composition that is formed by reacting substances. for, and also copolymerizable with such unsaturated urethane compositions. One type of ethylenically unsaturated monomer. Preferably an unsaturated urethane composition is at least one hydroxy-containing vinyl monomer, an average of at least 2.0 at least one organic polyisocyanate having isocyanate functionality or an isocyanate-functional derivative, and optionally contains multiple isocyanate-reactive groups. the product obtained by the reaction of a reaction mixture containing at least one saturated compound containing It is.

In a preferred embodiment, the unsaturated urethane composition comprises (1) at least one hydroxide. loxyalkyl aqueous or methacrylate compounds, (2) an isocyanate functionality of at least 2.0, preferably greater than 2.0; At least one polyisocyanate having a high isocyanate functionality a reaction product of a derivative and (3) optionally at least one saturated polyol. IJ'7 urethane polyacrylate and/or polymethacrylate It is a composition.

The viscosity of component A is less than 1000 poise, preferably 2 It is desirable that it be lower than 0.00 poise.

Component (B) has a weight average particle size of 0.5 to 7 microns, preferably 3 to 5 microns. Kron's granular inorganic filler. Suitable filler material (well, alumina, especially alumina Forms of trihydrate, forms of silica, e.g. Phosphorus and its calcined products, magnesium hydroxide, dolomite, gypsum and and other metal silicates, aluminates, aluminosilicates, phosphates, sulfates, carbonates and and oxides.

The filler will be selected based on the properties desired in the final composite.

For example, products with a high level of flame retardancy may require suitable fillers, e.g. trihydrate, magnesium hydroxide, dimagnesium phosphate trihydrate, trima Gnesium phosphate octahydrate, magnesium hydroxide, hydrated carbonate and sulfuric acid It will contain magnesium as well as other fillers that exhibit endothermic decomposition.

In general, the particles of a given filler should not be considered spherical. Specification With this in mind, the particle sizes quoted in the book are determined by observation through a microscope and or average particle dimensions given from photographic records.

Filler particle size distribution, surface area and other surface chemical/morphological aspects are It has a profound effect on the processability of the described compositions. This ensures good fire protection and High levels of particulate filler, typically 50-80% by weight, to achieve smoke and soot properties. This is particularly evident when used in compositions.

The particle size distribution of the filler does not exceed 25% by weight, but most preferably 1 Take care to ensure that the particles do not exceed 0% by weight and have an average diameter greater than θ microns. Must be deeply selected. Particles with an average diameter larger than 10 microns are more The presence of high concentrations can be used in resin transfer molding (RTM), cold press molding (C When using PM) and pultrusion, it causes poor processability.

The surface area of the filler (BET method) is also carefully determined to ensure that a composition of appropriate viscosity is achieved. must be closely controlled. The surface area is 5m! Should be lower than g-1 However, preferred fillers are lower than 3 m2 g-1, especially as low as 2 m"g-1". has a lower surface area. With particle sizes as described above, such low To achieve surface area, the particle shape is approximately spherical, and the particle size distribution It is desirable that the distribution is such that optimum particle packing can occur.

Component (C) is a carboxylic acid ester or amide having a terminal acidic group. child Compounds of the general type are disclosed in published European Patent Application No. 164817 has been done.

Preferred compounds that can be used as component (C) have the general formula % formula % , where A and D are terminal groups, one of which is sulfate, with terminal acidic groups selected from sulfonates, phosphates, and phosphonates. is or has one, and the other is a terminal group that does not make the compound hydrophilic.

B is a divalent hydrocarbon group. m is 1-100.

In the compound of formula I, when D has an acidic group, A preferably has the formula A'-COOH is a carboxylic acid residue (A'-Co-) that can be esterified . Here AI is a H1 hydrocarbon or a substituted hydrocarbon.

A1 conveniently optionally contains up to 50, more preferably up to 35 carbon atoms. substituted alkyl, alkenyl, cycloalkyl or polycycloalkyl group However, it can be any convenient monovalent group. In this case, D is preferably A valent, more preferably di- or trivalent, bridge comprises a group in which the group is an acidic group. is the ester @A' Co (0-B-Co), -1 for example of D2 defined below. It binds to such groups. When D has a value greater than 2, two or more acidic groups can be combined into a single Can be attached to an ester or two or more ester chains to a single acidic group . When the acidic group has a valence of more than one, the two bridges can form two or more esters through the groups. Can be combined.

In compounds of formula I, when A has an acidic group, D is preferably an alcohol. a thiol or a primary or secondary amine, Dl-XH, where Dl is an aliphatic or cycloaliphatic group as described above for AI, and X is 10- 1-8- or -NR-, R is H1 alkyl, alkenyl, cycloalkyl or phenyl, where the alkyl and alkenyl groups contain up to 20 cycloalkyl groups contain from 4 to 8 carbon atoms. in this case, A is a polyvalent bonding group like D above that bonds an acidic group to a polyester chain. However, it is preferably the acidic group itself, where the acidic group has a valence of 1 or more. If so, it can be attached to more than one polyester chain.

The hydrocarbon group represented by B is preferably an optionally substituted alkyl or alkyl group. Nyl, cycloalkyl or polycycloalkyl group, preferably up to 50 more preferably from 3 to 24 carbon atoms, -0- and and at least 3 carbon atoms separating the -C- groups. AI, DI and The optional substituents of B are such that they do not impart hydrophilic character to the ester/amide chain. In addition, halo, especially chloro, hydroxy, amino, alkoxy and other nonionic species including.

m is from 2 to 7, such that the compound of formula I is an oligo- or polyester. 5, more preferably 3 to 30.

When m is l, the group represented by A or D apart from the acidic group has at least 6 containing 12 carbon atoms, and a small amount of surfactant (both containing 12 carbon atoms) is desirable. It is also generally preferred that B is a pentamethylene group.

One preferred compound that can be used as component (C) has the chemical formula, [A'-C A compound that is O-(0-B'-Co), -〇'], -LM II ,here, A'-Co is an esterifiable carboxylic acid residue with the chemical formula A'-COOH. can be, B1 is alkylene, alkenylene, cycloalkylene, polycycloalkylene or and their halo derivatives, and D2 is a bridging group of the chemical formula -X-G-Y-. , where -X- is -〇-1-8- or -NR-, and Y is 10-1- NR- or a direct bond, where each R is independently as defined above. or when X and Y are both -NR-, R is May form a single alkylene or alkenylene group linking two nitrogens , G is alkylene, alkenylene, cycloalkylene or arylene, L is a phosphonate or sulfonate, M is a cation, k is 1 or 2, m is as defined above.

Particularly preferred compounds used as component (C) have the chemical formula: [DI-X- (Co-B'-0), ], -L M I[l, where D ' is an aliphatic or alicyclic group, and B', L, M, X, m and k are all the above As defined in .

The residue of the esterifiable carboxylic acid represented by A'CO in the chemical formula II is , preferably up to 50 carbon atoms, more preferably 1 to 35 carbon atoms optionally substituted alkyl, alkenyl, cycloalkyl or polycyclo Alkyl group, but any convenience for the ester chain, -(0-B'-Co) It may also be a convenient terminal hydrophobic group. Optional substituents are preferably hydroxy, a selected from amino, halogen and alkoxy, where A1 makes the compound hydrophilic. Don't make it a characteristic.

The aliphatic or alicyclic group represented by D' in formula III is preferably 3 Optionally substituted alkyl, alkenyl, cycloalkyl containing up to 5 carbon atoms or polycycloalkyl group, and optional substituents are preferably halogen, selected from triamino and alkoxy.

Alkylene, alkenylene, cycloalkylene and polycylene represented by B1 The chloroalkylene group preferably has 4 to 20 carbon atoms, more preferably 4 to 20 carbon atoms. at least three containing 20 carbon atoms and separating -0- and -〇〇-, and more preferably at least 4 carbon atoms, preferably unsubstituted. Ru. It is particularly preferred that B1 is a pentamethylene group. Al represented by G Kylene and alkenylene groups preferably contain up to 10 carbon atoms, more preferably Preferably it contains 4 to 6 carbon atoms. The cycloalkylene group represented by G is preferably contains 4 to 8 carbon atoms, particularly preferably 1,4-cyclohexylene It is. The arylene group represented by G is preferably monocyclic, particularly preferably For details 1. 4=phenylene.

Alkyl and alkenyl groups represented by R contain up to 25 carbon atoms. and preferably contains up to 5 carbon atoms.

If the two radicals R form a single radical, this preferably has up to 10 carbon atoms. including.

In the compound of formula II, when Y is 10-, the acidic group and L represent the oxygen atom. through the ester/amide chain, the phosphonate and the 10- , sulfonate and 10- form sulfate. Similarly chemical formula In the compound of 1[, when Y is -NR-, the phosphonate and -NR- forms a phosphoramide, and sulfonate and -NR- form a sulfonamide. to be accomplished. In the compound of formula Il, the group is connected to the ester chain through the oxygen atom. and phosphonate-1 and sulfonate are phosphate and sulfonate, respectively. Forms sulfate.

The cation represented by M is preferably Hl, metal ion, ammonium ion. or substituted ammonium ions; examples of suitable cations are Na'', K ",Ca",NH,",NH(CH2CH20H)s",NH(CB 3)! ” and N (CH,),”.

A specific example of a bridging group represented by B2 is:

-N! IC2114+, -0C2H4+, -0C2H40+, -0C2Fi 4 Nagi-1-N! ! (cH2,)n dish- (where n is 2 to 5), pyridin-1,4-ylene and phen-1 , 4-ylene-diamino.

Examples of groups represented by A1 and A2 are methyl, ethyl, CEI3 (CIiz )4-, CH3(CIllz)1o+, Cl13(CEI2):L4+, CH13 (CE [z) 1g +.

! l0(CEI2)5+, Cf3(CB2)7CE-CB(Cf2)7-” EI3) Cf2) 28-1C! ! 3(CH2)5CEI(OB)(CH2)10 -, CEI3(CH2)4CH-CHCH2CII-CB(CH2)7+.

Cf13(CEIz)5CI! (QB)CH2Cl-CFl(CB2)7-u and CH30CH2-CEI3(CEI2)9-, CEI3(CEI2)11 +, CH3 (C:E12) 15-, CEI3 (CEI2) 17 +.

Four 3 (CHz)z9-1C! 13 (“2) 7C Hee C! [(CB12) Two, CH30CH2- and CH3(CH2)4Cday-CHCH2CEI-CB(C H2) 7 -.

Examples of groups represented by B and B1 are -CH-(CH2)lo--CEI-( CP1218- -CB-(CH2)7- -CB-CHlCFi-CTICC H2'r7-(CH12)5, (CIllz)7, (CEI2)B, (CH2)5C11!3 CH3CH3CB5 Preferably it is -(CH2)6-.

Component (C) is present in a concentration of 0.5 to 5.0% based on the weight of filler component (B). It is preferably used in an amount of 1.5 to 2.5% by weight.

The compositions of the present invention can be used with continuous fiber reinforcement, especially glass fibers. finds specific uses. Fibers are manufactured by curing the composition. It is preferable that the fiber be continuous throughout the major dimensions of the product, but "continuous fiber" means at least also means a fiber with a length of 20 mm. This improves shock and stiffness properties and Make products with high specific strength. The composition also contains textile fibers of length of at least 20 mm. manufactured from continuous fiber filaments in the form of rovings or random fibers or from continuous fiber filaments in the form of rovings. It may also be used to collapse fibrous structures such as mats. This composition Products include resin transfer molding (RTM), cold pressure molding (CP), and pultrusion molding. It is particularly suitable for crushing fiber reinforcements using processing techniques such as in the final product The concentration of fiber reinforcement will depend on the properties required. higher level fiber If fibers are present, the mechanical strength will be higher. Fibers with high overall resin content in the product Fire protection and soot properties would also be improved if the levels were reduced by incorporation. . The fiber content may range from 10 to 70% by volume of the final product. RTM and For the CP processing method, the fiber content is preferably 15 to 40% by volume. Pulling out For molding, the fiber content is preferably 25 to 50% by volume.

The composition of the present invention with particulate fillers is suitable for use in chopped fiber mats or woven fibers. The composition is crushed into a mat-like fibrous structure and then hardened to produce a reinforced product. ideally suited for building For RTM and CP processing methods, matte is usually , the curable composition is placed in the mold before being filled and cured in the mold. appropriate Prior art compositions having a low viscosity are characterized in that the filler is at least There was a significant tendency to be partially filtered.

Compositions given in combination with low viscosity resins, especially fillers near the surface and dispersion The low viscosity of the agent means that the mold fills quickly and the filler passes through the glass reinforcement. and allows for uniform distribution of the resin.

For RTM processing, the viscosity is less than 25 poise, preferably less than 15 poise ( The composition (as measured by a Type B viscometer) is preferred to enable quick mold filling. Yes. The CP fabric treatment has a viscosity lower than 100 poise, preferably lower than 60 poise. A low composition is desirable.

The excellent processability of the compositions of the invention is such that, for example, fibers can be drawn through a bath of material. A continuous pultrusion process in which the material is crushed into continuous fibers and the composite is then cured. ideally suited for use in

For pultrusion, the viscosity is less than 100 poise, preferably less than 60 poise. Compositions are preferred. Low viscosity and good noological properties make the fiber roving attractive Even when the cutting speed is high, it is possible to easily crush the fibers. liquid-containing The ease gives uniformity of filler and resin distribution, which makes the roving This is particularly likely to occur when producing profile extrusions through profile extrusion dies. caused by the deposition of filtered fluid material on the crushed rovings such as Provides continuous operation machining that is rarely interrupted due to damage.

The pultrusion process gives the product very high strength and stiffness.

This is because the parallel array of fibers can fill a very high volume through a close packing of parallel fibers. This is to enable fibers to be mixed into products.

The resulting resin content wets the fibers and dispersed filler and also It can be reduced to the minimum necessary to fill the gaps between fibers. If the matrix resin is good for the fibers, Through these high fiber levels, very high levels of mechanical mechanical properties can be achieved.

Although the bond between the inorganic material and the matrix resin may be sufficient for most purposes, The particle-filled composition of the present invention allows the inorganic material to bond more firmly to the base resin after curing. Coupling additives may be included to ensure that the This feature Coupling agents that accomplish this are well known in the art.

Fibers are typically sized to withstand the fiber manufacturing process without undue damage to the fiber surface. Supplied by textile manufacturers, including: For fiberglass, the size is usually The silane cutter is designed to achieve the optimum properties for the application in which the glass fiber will be used. Contains pulling agent. Fiberglass manufacturers typically choose the most suitable coupling for their application. Fibers with anti-gluing agents could be recommended. provided by continuous fibers Strength governs the strength of the cured composite. Structures made from the compositions of the invention Shaped products, whether or not reinforced with fibers, are both flame retardant and smoke-breathing. It exhibits remarkable good combustion properties.

The invention is further illustrated by reference to the following examples.

Example 1 Add 170 g of dispersing additive prepared as described below to 135 centipoise The mixture was stirred in a Modar 826HT with a viscosity of 5 kg. Modar826) IT is 40% by weight methyl methacrylate, 55% by weight oligourethane chain extension frame. A low shrinkage resin suitable for pultrusion containing a crosslinking agent and 5% by weight of a low shrinkage agent. (Modar 826HT is ICI Chemical Sand Polyme available from RS Ltd). Stir at 45°C to 50°C until the solution is complete. It was held in This solution was cooled to room temperature and L 5 kg of precipitated alumina trihydrate ( Grad supplied by Sumitomo Chemical Company e C305B, which has a weight average particle size of 4.8 μm and has a BE 1. Measured by T nitrogen absorption method. am”/g and 5 to 10% by weight of particles grows an average diameter greater than 10 μm and is roughly spherical. ) manually to 1 Stirred for 5 minutes.

This mixture was rotated in a drum. The viscosity of the dispersion was 40 poise (6r (measured with a Type B viscometer at 23C using spindle NO3 at pm).

The dispersion additive used in this example was prepared as follows.

500 g of ε-caprolactam, 67 g of dodecanol and 0.1 g of tetra Butyl titanate mixture at 160°C to 180°C under nitrogen flow for 19 hours. Stirred. The reaction was then removed and solidified to a waxy solid.

105 g of this solid was stirred at 60-65°C and 5 g of phosphorus (V) oxide (Pho Sphorus pentoxide) was added gradually over 30 minutes. temperature The temperature was increased to 90° C. and the reactants were stirred at this temperature for an additional 16 hours.

It was then taken out and solidified into a waxy solid.

Add the following initiators to the heat-activated initiator at room temperature in the dispersion using a stirrer with a handle. It was added to the above dispersion by dissolving it.

2.0 parts of Triganox C (t-butylperbenzoe) per 100 parts of resin ). 0.2 parts of Parkadox' 16 (Bis-4 -t-butylcyclohexylperoxydicarbonate).

The activated dispersion is drawn into continuous glass fibers by the following method. Used to crush roving.

Pu1trex 50 with 75mm x 4mm chrome steel flat die attached Using a zero drawing device, with the die heated to 120-140°C, 48 glass rovings of 0 tex were placed in a bath containing a dispersion and a heated die. It was pulled out at a speed of 0.5 m/min. Continuous filament with a density of 450g/m The mat was passed through a bath of dispersion and a die having a total glass content of 39% by volume. A cured composite material was obtained that came out of the die. This product has an excellent surface finish. did. Processing continued for one hour without any problems. The pull-out force is controlled by a load cell. The weight remained virtually stable at 220 kg.

The resulting product is very rigid and has a good combination of flame retardant and soot properties. Ta.

Comparative example A Repeat the procedure of Example 1, but using Sumitomo Chemical Co. Precipitated alumina trihydrate obtained as Grade C308 from Mpany was used as a filler. It was used for.

It had a weight average particle size of 8 μm and a surface area of 0.9 m”/g. . Approximately 35-40% by weight of the total filler had an average diameter greater than 108 m. .

The viscosity of the obtained dispersion was 35 poise, which was slightly lower than that of Example 1. When this dispersion was used in the drawing process of Example 1, more than 500 kg could be pulled out. When the load was increased, the profiled material got stuck in the die.

Comparative example B The procedure of Example 1 was repeated using BA FRF obtained from BA Chemicals Ltd. Repeated with alumina hydrate designated 85. This is 5.5μm It has a weight average particle size of 6 m”/g (measured using BET nitrogen absorption method) It had a surface area of The weight content of particles with an average diameter greater than 10 μm is It was 1 to 5% by weight. These particles have a flat shape and are produced by fine grinding. .

The resulting dispersion has very low wettability and has a B hard viscosity using spindle NO3. It was very expensive to be able to measure it with a meter (>250 poise).

When a drawing experiment was attempted according to the procedure of Example 1, the profiled material was packed in the die immediately after starting. wait.

Example 2 The procedure of Example 1 was adapted from Sumitomo Chemical Company. Repeat with the obtained precipitated alumina trihydrate of Grade CL303. this is It had a weight average particle size of 3 μm and a surface area of 2 m”/H. The weight content of particles with a larger average diameter was between 1 and 5% by weight.

A viscosity of the dispersion of 31 poise was obtained. When the drawing process of Example 1 is used, the material becomes It was operated smoothly with a pulling load of 280 kg. The obtained profiled material is an example It had the same appearance and characteristics as No. 1.

Example 3 The procedure of Example 1 was repeated using lo kg of the same filler, but with 200 g of dispersion. Additives and Modar 865 (ICI Chemicals and Pol 5 kg of resin of the brand (available from YMERS Ltd.) was used.

Modar 865 contains approximately 50% by weight methyl methacrylate and 50% by weight Contains oligourethane chain extension crosslinking agent. This resin has a viscosity of 130 centipoise have Had a dispersion viscosity of 45 poise (Brookfield spindle 3) .

2.0 phr Irganox C and 2.0 phr °Perkadox Activation was performed using a 16° mixture.

For the pull-out experiment (40 rovings were used instead of 48 in Example 1) The drawing speed was initially set at 0.5 m/min. very to the load cell Low pullout loads were recorded. If the speed is increased by 50%, the load cell will be pulled out. Weight was recorded between 100 and 200 kg.

The drawn profile had a total glass content of 35% by volume and was similar to Example I. It had appearance and characteristics.

Example 4 11.35 kg C305B filler, 250 g dispersing additive and Modar 865/1 ([CI Chemicals and Polymers Lt. The procedure of Example 3 was repeated using 5 kg of resin of I returned it.

Modar 865/1 contains approximately 45% by weight methyl methacrylate, 45% by weight Contains oligourethane chain extension crosslinker and 10% by weight methacrylic acid.

This dispersion had a viscosity of 45 poise (Brookfield spindle 3).

The dispersion was evaluated in the drawing process of Example 1 and behaved as in Example 3. Ta. This pultruded product had similar appearance and properties to Example 3.

Example 5 10 kg C305B filler, 200 g dispersing additive of Example 1 and Moda The procedure of Example 1 was carried out to obtain a composition containing 5 kg of resin of the brand 835S. A dispersion was prepared using the following procedure. Modar 835S is manufactured by ICI Chemica ls and Polymers Ltd, approximately 40% by weight of methyl methacrylate, 20% by weight of oligomeric chain extension crosslinker and 20% % polyester resin mixture. Modar 835S is 60 centipos It has a viscosity of azure.

The dispersion has a viscosity of 15 poise, which is sufficient for resin transfer molding RTM. was rated low.

In the evaluation, 1.5 phr of benzoyl peroxide and 0.3 phr of di- Methylaniline was mixed into the dispersion using a mixing head. activated The dispersion was prepared using three glass fiber mats with a density of 450 g/m'' and a thickness of 3 mm. Placed in a closed plate mold with a cavity of The amount was adjusted to 18% by volume. Cure for 30 minutes and store the cured product below 5°C. After cooling to a certain temperature, it was taken out from the mold. This product does not incorporate air. Ta. The glass fibers were crushed uniformly, and no filtration of the filler by the fiber mat was observed. won.

Example 6 Samples with compositions shown in Table 1 (C305B filled according to the procedure of Example 1) Modar 865 as a dispersing additive and resin at 2.0% by weight of the filler. Manufactured using. ) into a mold containing 18% by volume glass fiber mat. was injected and cured to obtain a shaped article. The initiator was previously added to the dispersion (1 ．． 5 phr benzoyl peroxide and 0.3 phr dimethylaniline) . This dispersion was cured without applying external heat. Curing occurs within 30 minutes It's so bad.

After conditioning for 24 hours at room temperature, fire test using the following approved standard test: The samples were evaluated at

[305657 (30Kw) Eipiradiateur NFP 92-501BS 6401: Par t3 (Flaming) These tests increase the content of alumina trihydrate resistance to ignition (ISO5657, r) is substantially improved.

Epiradiateur NFP 92-501 classification is Ml or M2 This is desirable for public transportation and architectural applications.

A reduction in soot was observed using higher loadings of alumina trihydrate (B S6401: Part 3).

Table 1 Filler resin dispersion [So 5657 (30Kw) Epiradiat eur BS 6401: Amount Amount Viscosity Time until ignition NFP 92-50 1 D-max (parts) (parts) (seconds) 150 100 20P 300 M3 223200 100 45P 40 0 M2 169250 100 75P 600 M2/Ml, mlA-1 cmwN@PCT/GB 93100669Continuation of front page (51) Int, C1,5 identification symbol Internal reference number C08K 7/18K CL 7242-4JCO8L 33100 LHT 7921-4J75/1 6 N F X 8620-4 J (81) Designated country EP (AT, BE, CH, D.E.

DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, S E), AU, BB, BG, BR, CA, CZ, FI, HU, JP, KP , KR, LK, MG, MN, MW, No, NZ, PL, RO, RU, S D.

S I

Claims (1)

[Claims] 1. (A) a polymerizable organic liquid for forming a solid polymer, (B) 0.5-7 Weight average particle size in microns and 5 m2/ as measured by BET nitrogen absorption method 35-85% by weight of a finely divided inorganic filler having a surface area lower than g (C) selected from sulfates, sulfonates, phosphates and phosphonates; a carboxylic acid ester or amide with a terminal acidic group, and optionally, (D) continuous fiber reinforcement; , except that when the composition is cured, the polymer components add up to a total polymer weight of Concentration of at least 15% methacrylate or acrylate monomer to standard A highly filled fluid curable composition comprising a silica unit. 2. The curable composition according to claim 1, wherein the polymerizable liquid (A) is (i) at least one ethylene having an average double bond functionality greater than 1.0; urethane compounds containing unsaturated urethane compounds or precursors of such urethane compositions. a thyrenic unsaturated urethane composition; and (ii) present as a preformed species. or in at least one ethylenically unsaturated monomer. of unsaturated urethane compositions that are either formed by reacting precursors for For the vehicle, there is also a small amount that is copolymerizable with such unsaturated urethane compositions. A composition comprising at least one ethylenically unsaturated monomer. 3. 3. The curable composition of claim 2, wherein the unsaturated polyurethane composition comprises: (1) At least one hydroxyalkyl acrylate and/or methacrylate rylate compounds, (2) an isocyanate functionality of at least 2.0, preferably greater than 2.0; at least one polyisocyanate or isocyanate functionally derived and (3) optionally at least one saturated polyol. polyurethane polyacrylate and/or polymethacrylate composition. A composition that looks like this. 4. Claims 1 to 3, wherein the viscosity of the polymerizable liquid (A) is lower than 1000 centipoise. The curable composition according to any one of Item 3. 5.5 finely divided inorganic fillers with a weight average particle size of 0.5 to 7 microns The curable composition according to any one of claims 1 to 4, comprising an amount of 0 to 80% by weight. thing. 6. The finely divided inorganic filler preferably has a weight average particle size of 3.0 to 5.0 microns. The curable composition according to any one of claims 1 to 5, which has a 7. Any one of claims 1 to 6, wherein the finely divided inorganic filler exhibits endothermic decomposition. The curable composition described. 8. The curable composition according to any one of claims 1 to 7, comprising the component (C ) is the general formula, A-(O-B-CO)m-D(I) where A and D are terminal groups, one of which is sulfate, with terminal acidic groups selected from sulfonates, phosphates, and phosphonates. is or has an end group that does not make the compound hydrophilic; A curable composition in which B is a divalent hydrocarbon group and m is 1 to 100. 9. The curable composition according to any one of claims 1 to 7, comprising the component (C ) is the general formula, [A1-CO-(O-B1-CO)m-D2]k-LM(II), where , A1-CO is the residue of an esterifiable carboxylic acid with the chemical formula A1-COOH. the law of nature, B1 is alkylene, alkenylene, cycloalkylene, polycycloalkylene or and their halo derivatives, D2 is a bridging group with the chemical formula -X-G-Y- , where -X- is -O-, -S- or -NR-, and Y is -O-, - NR- or a direct bond, where each R is independently as defined above. or when X and Y are both -NR-, the two R two nitrogens that combine to form a single alkylene or alkenylene group Also, G is alkylene, alkenylene, cycloalkylene or arylene. , L is a phosphonate or sulfonate, M is a cation, k is 1 or 2, m is 1 to 100, Composition. 10. The curable composition according to any one of claims 1 to 7, comprising the component ( C) is a general formula, [D1-X-(CO-B1-O)m]k-LM(III), where D1 is an aliphatic or alicyclic group, B1 is alkylene, alkenylene, cycloalkylene, polycycloalkylene or and their halo derivatives, L is a phosphonate or a sulfonate. ri, M is a cation, k is 1 or 2, m is 1 to 100, Composition. 11. Claims 1 to 10 comprising continuous fiber reinforcement formed from glass fibers. The curable composition according to any one of the above. 12. Curing the curable composition according to any one of claims 1 to 11. A shaped product formed by