GB2304122A - Prepreg sheet and article moulded therefrom - Google Patents
Prepreg sheet and article moulded therefrom Download PDFInfo
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- GB2304122A GB2304122A GB9616617A GB9616617A GB2304122A GB 2304122 A GB2304122 A GB 2304122A GB 9616617 A GB9616617 A GB 9616617A GB 9616617 A GB9616617 A GB 9616617A GB 2304122 A GB2304122 A GB 2304122A
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- Prior art keywords
- meth
- acrylate
- prepreg sheet
- resin
- polyurethane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/245—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using natural fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Description
2304122 Prepreg Sheet and Molded Article Therefrom The present invention
relates to a prepreg sheet produced by impregnating a thermosetting resin into, for example, a base material for impregnation such as paper, non-woven fabrics with multicolored patterns, and a molded article therefrom.
As methods for producing a molded article with patterns from FRP (Fiber Reinforced Plastics) which is a thermosetting molding material reinforced with glass fiber such as BMC (Bulk Molding Compound), SMC (Sheet Molding Compound) and TMC (Thick Molding Compound), there have been proposed several methods so far, for example, a method to obtain a flow pattern utilizing a flow of different color molding materials at molding, a method to obtain marble grain patterns by adding colored molding materials, a method to obtain a molded article with patterns by molding integrally a prepreg sheet which is produced by impregnating titan paper, non-woven fabric, glass cloth having patterns and the like with a thermosetting resin such as an unsaturated polyester resin or DAP (Diallyl Phthalate) resin in a mold (JP Kokai Publication 317311/1988).
A prepreg sheet to give a clear top layer by the use of titan-white free molding materials has been proposed in JP Kokoku Publication 4408/1987, but the resin itself has no special characteristic.
Heretofore, in the methods of producing multicolored molded articles by molding integrally a sheet impregnated with a thermosetting resin, i.e., a prepreg sheet and SMC and the like, unsaturated polyester resins and DAP resins have been employed as the thermosetting resins. When the articles are molded by a compression molding according to the above methods, the prepreg sheet is placed on a bottom tool of a mold and a molding material was laid up thereon, and then heated under pressure. However, sometimes, a slipping of the edges of the prepreg sheet and breaking of the sheet are caused by a flow of the molding materials when a curing rate of the resin in the prepreg sheet is slower than that of the resin in the molding material. In such cases, the commercially valuable product can not be obtained due to the spoiled patterns in the molded articles. Moreover, the top layer of the molded FRP with multicolored patterns obtained from the prepreg sheet impregnated with an unsaturated polyester resin or DAP resin is insufficient in abrasion resistance and there is some inconvenience that the surface of the top layer is abraded easily with a nylone brush.
In attempt to solve the problems mentioned above, the present inventors have used a polyurethane (meth)acrylate resin as the thermosetting resin for impregnation which is used in the production of multicolored molded articles by molding the prepreg sheet and a thermosetting molding material integrally, and subsequently, they have succeeded in obtaining molded articles which have no slipping and breaking patterns, much improved abrasion resistance, improved appearance such as a glossy surface and antifungal properties when compared with those of SMC base multicolored molded articles produced from a prepreg sheet impregnated with a unsaturated polvester resin or DAP resin.
The present invention relates to: (1) A prepreg sheet which comprises a base material impregnated with a polyurethane (meth)acrylate resin composition.
According to an embodiment of the invention, the polyurethane (meth)acrylate resin composition of the prepreg sheet contains polyurethane (meth)acrylate resin (A) or (A) and a diluent having polymerizable double bond (B). Optionally, the polyurethane (meth)acrylate resin (A) is one having a number average molecular weight of 500-100,000, optionally 700-20,000, a number of average functional groups of 2 or more in a molecule, optionally 6-40 in a molecule, and a urethane group concentration of 0.1-10.0 m mol/g, optionally 0.5-5.0 m mol/g.
According to a further embodiment, the base material of the prepreg sheet according to the invention for impregnation is a titan paper or non-woven fabric.
The invention further provides a molded article obtained by laying up a prepreg sheet as described hereinbefore and a thermosetting molding material, and then molding them integrally. Optionally, the thermosetting molding material is FRP.
The polyurethane (meth)acrylate resin (A) to be used in this invention can be obtained, in accordance with the conventional manner, by first reacting an organic polyisocyanate with a polyol in the reaction conditions of excess amount of isocyanate groups and then. reacting the resultant with a hydroxyl group containing (meth)acrylate or by reacting an organic polyisocyanate with a hydroxyl group containing (meth))acrylate.
As the organic polyisocyanate described above, there may be.mentioned diisocyanates such as aliphatic diisocyanate, alicyclic diisocyanate, aromatoaliphatic diisocyanate,-aromatic diisocyanate and polyisocyanate having 3 or more of isocyanate groups.
Examples of the aliphatic diisocyanate include, among others, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1, 2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4or 2,2,4-trimethylhexamethylene diisocyanate, 2,6- diisocyanato methyl caproate.
Examples of the alicyclic diisocyanate include, among others, 1,3cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4, 4'methylene bis (cyclohexylisocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane and the like.
Examples of the aromato-aliphatic diisocyanate include, among others, 1,3or 1,4- xylilene diisocyanate, or a mixture thereof, j,w'-diisocyanato-1, 4-diethylbenzene ' 1,3or 1,4- bis (1-isocyanato-l-methylethyl) benzene, or a mixture thereof and the like.
Examples of the aromatic diisocyanate include, among others, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6- tolylene diisocyanate, 4,4'-toluidine diisocyanate, 4, 4'diphenylether diisocyanate and the like.
Examples of the polyisocyanate having 3 or more of functional groups include, among others, polyisocyanate monomers such as organic triisocyanates e.g., triphenylmethane-4, 4 ' 4"-triisocyanate, 1 3, 5triisocyanato benzene, 2,4,6-triisocyanato toluene and the like, and organic tetraisocyanates, e.g., 4,4'-diphenylmethane2,2',5,5'tetraisocyanate and the like.
In addition, there may be mentioned dimers, biurets, alophanates derived from the aforementioned polyisocyanate monomers, polyisocyanate having 2, 4, 6-oxadiazinetr ion ring obtained from the aforementioned polyisocyanate monomers and carbon dioxide, adducts of the polyisocyanate monomer and a low molecular weight polyol having molecular weight of less than 200 such as ethylene glycol, propylene glyco.1, butylene glycol hexylene glycol, neopentyl glycol, 1,6- hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, cyclohexane dimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylol propane, pentaerythritol, sorbitol and the like, and adducts of polyether polyol, polyester polyol, polyetherester polyl, polyesteramide polyol, polycarbonate polyol, polyhydroxyalkane, caster oil and polyurethane polyol having a molecular weight of 200 to 5000, and the like.
Among them, aliphatic diisocyanate, alicyclic diisocyanate and aromatoaliphatic diisocyanate are preferable and aliphatic diisocyanate and aromatoaliphatic diisocyanate are more preferable. Still more preferable examples are trimers derived from 3-isocyanatomethyl-3,5, 5trimethylcyclohexyl isocyanate(IPDI), 1,3- or 1,4-bis (1isocyanato- 1 methylethyl) benzene (TMXDI), hexamethylene diisocyanate(HDI) and adducts of the said monomers with trimethylol propane(TMP) and the like.
The polyols to be reacted with an organic polyisocyanate include polyhydric alcohols such as di-, tri. tetra- and more hydric alcohols which are conventionally used.
Examples of the dihydric alcohols include, among others, ethylene glycol, propane diol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1.6-hexane diol, neopentyl glycol, alkane(C7-22)diol, diethylene glycol, triethylene glycol, dipropylene glycol, cyclohexane dimethanol, alkane(C17-20)1,2-diol, hydrogenated bisphenol A, 1.4-dihydroxy-2-butene, 2,6-dimethyl-l-octene-3,8-diol and bisphenol A and the like.
Examples.of the trihydric alcohols include glycerin, 2methyl-2hydroxymethyl-1,3-propane diol, 2,4-dihydroxy-3hydroxymethyl pentane, 1,2, 6-hexanetriol, 1,1,1tris(hydroxymethyl) propane, 2,2-bis(hydroxymethyl)3butanol and other aliphatic(C8-24)triols and the like.
Examples of the tetrahydric alcohol include, among others, tetramethylol methane, D-sorbitol, xylytol, Dmannitol and the like.
As the (meth)acrylate having hydroxyl group, any ones known can be used and, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, caprolactone modified hydroxyethyl (meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate and the like can be advantageously employed.
In order to obtain the polyurethane (meth)acrylate resin composition (A) to be used in this invention from the raw materials mentioned above, the organic polyisocyanate is reacted with a polyol under reaction conditions of an excess amount of NCO groups, preferably at the ratio of NCO/OH being about 1.5 to 10, more preferably 2 to 5 to give urethane isocyanate having terminal NCO groups, and then, the resultant is reacted with a (meth)acrylate having a hydroxyl group at the NCO/OH ratio ranging from 0. 8 to 1.2, more preferably from 0.9 to 1.1 or the organic polyisocyanate is reacted with a (meth)acrylate having a hydroxyl group in the NCO/OH ratio ranging from 0.8 to 1.2, preferable from 0.9 to 1.1.
The above reactions can be conducted using a known catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, and the like according to the conventional reaction conditions for production of polyurethanes.
In the reaction, the conventional solvents such as ethyl acetate, butyl acetate, acetone, toluene, methyl isobutyl ketone and the like, and the known polymerization inhibitors such as hydroquinone, hydroxymethyl ether, mono t-butyl hydroquinone (MTBHQ) and the like are preferably employed..
A number average molecular weight of the polyurethane (meth)acrylate resin to be used in this invention is generally, 500 to 100,000, preferably, 700 to 20,000, more preferably, 1000 to 10,000. A number of average functional groups (the number of unsaturated bond in a molecule) of the resin is generally, not less than 2, preferably 6 to 40, more preferably 10 to 30. Concentration of urethane groups of the resin is generally 0.1 to 10.0 m mol/g, preferably, 0.5 to 5.0 m mol/g and more preferably, 0.8 to 3.0 m mol/g.
When the.number average molecular weight of the polyurethane (meth)acrylate resin is less than 500, the resin composition obtained from the polyurethane acrylate resin has a tendency to increase in tackiness though the hardness of the cured product tends to increase. When the number average molecular weight is more than 100,000, the hardness of the cured product tends to be lowered and the product is too soft. In the case that the number of average functional group is less than 2, the hardness of the cured product is insufficient as well. When the concentration of the urethane group is too low, the product is insufficient in hardness and when too high, the product becomes tacky in spite of its sufficient hardness.
The polyurethane (meth)acrylate resin (A) thus obtained is mixed with or without addition of the diluent having a polymerizable double bond (B) and is incorporated with conventional polymerization initiators and other additives such as curing accelerators, polymerization inhibitors to give the polyurethane (meth)acrylate resin composition.
As the diluent having a polymerizable double bond (B) -7 to be used in this invention, any which are commonly available can be used, and there may be mentioned, among others, the compound having a structure obtainable by the amidation or esterification of the compound having an amino group or a hydroxyl group with a (meth)acrylic acid. The examples of those compounds include a mono functional polymerizable diluent such as methoxy ethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, nonyl phenoxyethyl (meth)acrylate, 3chloro-2-hydroxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, butoxy polyethylene glycol (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurturyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentadiene acrylate, 2hydroxy-3-phenoxypropyl (meth)acrylate, 2(meth)acryloyloxyethyl-2-hydroxyethyl phthalic acid, 3acryloyloxyglycerin mono(meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2hydroxy-l-(meth)acryloxy-3-(meth)acryloxy propane, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, poly icaprolactone mono(meth)acrylate, dialkylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, mono[2-(meth)acryloyloxyethyll acid phosphate, trifluoroethyl (meth)acrylate, 2,2,3,3tetrafluoropropyl (meth)acrylate, 2, 2,3,4,4,4hexafluorobutyl (meth)acrylate, perfluoroctylethyl (meth)acrylate, dicyclopentenyloxyalkyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tricyclodecanyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, morphorin (meth)acrylate, N,N'-dimethylacryl amide and N-vinylpyrrolidone, N-vinyl pyridine, N-vinyl caprolactam, neopentylglycol acrylate benzoate, ethoxydiethyleneglycol acrylic acid polymer ester, tetrahydrofurylalcohol acrylic acid polymer ester, alkylene (C6-14)phenol alkylene(C2-4) oxide adduct acrylate, 2hydroxy-3-phenyloxypropyl acrylate and the like, bifunctional polymerizable diluent such as 2,2-dimethyl-3 hydroxypropyl-2,2-dimethyl-3-hydroxypropionate di(meth)acrylate, ethyleneglycol di(meth)acrylate, tetraethyleneglycol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, propyleneglycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, 1,6hexanediol acrylic acid polymer ester, glycerin di(meth)acrylate, neopenty1glycol, di(meth)acrylate, neopenty1glycol. acrylic acid polymer ester, neopenty1glycol hyroxypivalate acrylic acid polymer ester, neopenty1glycol hydroxypivalate di(meth)acrylate, bisphenol A ethyleneoxide adduct di(meth)acrylate, bisphenol A propyleneoxide adduct di(meth)acrylate, di (meth) acrylate, di(meth)acrylate, 2,2'-(hydroxypropolxyphenyl)propane 2,2'-(hydroxyethoxyphenyl)propane tricyclodecane dimethylol di(meth)acrylate, 2,2'- di(glycyloxyphenyl)propane acrylic acid adduct and the like and polyfunctional polymerizable diluent such as trimethylolpropane tri (meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth) acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, tris(acryloxy)isocyanate, tris(hydroxyethyl) isocyanulate tri(meth)acrylate, tris(hydroxypropyl) isocyanulate tri(meth)acrylate, triallyl trimellitate, triallyl isocyanulate and the like. Among them, pentaerythritol tri (meth) acrylate, penta erythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate are desirable.
The preferable diluents having a polymerizable double bond (B) are those which do not adversely affect the adjustment of hardness of the cured product, adhesion (tackiness) of the resin composition, reactivity, weathering resistance, chemical resistance and other physical properties. Mixing ratio of the polyurethane (meth) acrylate resin (A) and the diluent (B) is preferably in the range of 60- 100 weight % of polyurethane (meth)acrylate resin relative to 0-40 weight % of the diluent, more preferably, 80-90 weight % of polyurethane (meth)acrylate resin relative to 10 to 20 weight % of the diluent.
The polymerization initiator to be used in this invention can be selected from general organic peroxides according to desired molding temperature and molding cycles.
The initiators to be incorporated in the resin composition includes among others, 2,5-dimethyl-2,5-di(tbutylperoxy)hexane (DTBPH), 1,3-bis(tbutylperoxyisopropyl) benzene, t-butyl peroxybenzoate(TBPB), t-butyl peroxyoctoate (TBPO), t-hexy peroxybenzoate (THBP), t-hexyl peroxyoctoate (THPO), 1,1-bis(t-hexylperoxy) 3,3,5-trimethylcyclohexane, t-amyl peroxyoctoate (TAPO), t-butyl peroxyisopropyl carbonate (TBPIC). In this invention, at least one of the initiators can be selected according to the desired curing rate and is incorporated in, generally, a propotion of 0.3-4 weight parts relative to 100 parts by weight of the resin. In addition to the polymerization initiator, a curing accelerator can be employed. Examples of the curing accelerator include organometal compounds of cobalt, copper and manganese such as octoate, naphthenate and acetyl acetonate of the respective metals. These may be used solely or in combination and are incorporated in, in general, a proportion of 20 to 200 ppm in the resin mixture.
As the polymerization inhibitor, one or more of parabenzoquinone (PSQ), mono t-buty 1 hydroqui none (MTBHQ) ' di t-butylhydroxytoluene (BHT), hydroquinone (HQ), tbutylcatechol (TBC) and the like can be used.
In order to improve tackiness of the present prepreg sheet, thermoplastic resins which are solid in at ordinary temperatures such as cellulose acetate butyrate, nitrocellulose, ethyl cellulose, butyl cellulose, acetyl cellulose, vinylchloride-vinyl acetate copolymer and the like may be incorporated in the resin mixture.
The present resin composition can be given antibacterial and antifungal properties by incorporating antimicrobial agents in the resin composition in a proportion of about 0.1 to 5.0 weight parts relative to 100 weight parts of the resin. As the antimicrobial agents, any inorganic and organic antimicrobial agents generally used can be used.
Internal mold releasing agent can be incorporated in the present resin in a proportion of about 0.01 to 10.0 weight parts relative to 100 weight parts of the resin as long as they do not adversely affect the properties of the resin.
As the internal mold releasing agents, there may be mentioned a metal soap such as zinc stearate, calcium stearate, fluorine containing organic compound, phosphoric acids and the like.
In addition to those disclosed above, additives such as an oxidation inhibitor, ultraviolet absorber, hydrolyzation inhibitor, thickening agent, plasticizer, slip agent, surfactant and the like can be used, if necessary.
Viscosity of the resin composition used in this invention can be adjusted by incorporating respective ingredients into the resin. As to the viscosity of the resin, the viscosity of 60 w/v% ethyl acetate solution at 25 is preferably in the range of 30-50,000 mPa.s, more preferably, 5010,OOOmPa.s.
The prepreg sheet can be obtained by, for example, impregnating the material for impregnation which includes paper such as titan paper, nonwoven fabrics, wood, particle board and the like with the resin composition prepared by the present invention according to a conventional method. Incorporation rate of the resin composition in the prepreg sheet is 20 to 80 weight %, preferably 30 to 60 weight % relative to the prepreg sheet.
When the incorporation rate of the resin composition is lower, the cured product is poor in the surface characteristics and abrasion resistance. On the other hand, when the incorporation rate is higher, the resin composition is often projected out of the pattern parts in the sheet at the compression or injection molding, and therefore, can not give a commercially valuable product.
The prepreg sheet in this invention can be cured by the heat and pressure molding according to a glass fiber reinforced thermosetting material such as SMC, BMC and TMC, for example, under pressure of 0. 1 to 12 MPa, at 70 to 160t and can give a multicolor cured product. The prepreg sheet can be cured solely by the heat and compression molding to give a cured sheet.
The following examples will illustrate the present invention in more detail but the invention is not to be limited by them so far as they do not go beyond the gist of this invention. In the examples, "part" means "part by weight". (1) Synthesis of polyurethane (meth)acrylate resin Synthesis Example 1 In a reaction vessel, 200.1 g of IPM/TMP adduct (Takenate D-140NL, produced by Takeda Chemical Industries, Ltd.) and 125 g of ethyl acetate were charged, and the mixture was warmed to 40-50t to make a solution. To the solution, 0.12 g of MTBHQ, 0.08"g of dibutyltin dilaurate were added and a temperature o: the mixture was kept at 50t. Thereto, 265.3 g of pentaerythritol triacrylate (M-305, produced by Toagosei Chemical Industries, Ltd.) was added dropwise over about 30 minutes and the reaction was continued for about six hours until absorption of isocyanate group at 2250cm-' in infrared absorption spectrum was disappeared while keeping the reaction temperature at 55 to 65t followed by addition of 240 g of ethyl acetate. A polyurethane acrylate(a) having the characteristics shown in Table 1 was obtained. Synthesis Example 2 In a reaction vessel, 365.4 g IPDI trimer (VESTANAT T1890, produced by HUls Aktiengesellschaft) and 309.5 g of ethyl acetate were placed, and the mixture was warmed to 4050" to make a solution. Thereto were added 0. 37 g of MTBHQ and 0.25 g of dibutyltin dilaurate and a temperature of the mixture was kept at 50t. Then, 871.8 g of pentaerythritol triacrylate (M- 305, Toagosei Chemical Industries, Ltd.) was added dropwise over about 30 minutes and the reaction was continued for about six hours until absorption of isocyanate group at 2,250 cm-1 in infrared absorption spectrum was disappeared while keeping the reaction temperature at 55 to 65t. Thus, polyurethane acrylate (b) having the characteristics shown in Table 1 was obtained Synthesis Example 3 In a reaction vessel, 511.5 g of IPDI trimer (VESTANAT T-1890, produced by HUls Aktiengesellschaft) and 325.9 g of ethyl acetate were charged and the mixture was warmed to 4050t to make a solution.
Thereto were added 0.3g of MTBHQ, 530.7g of pentaerythritol triacrylate ( M-305, produced by Toagosei Chemical Industries, Ltd.), and then 0.07g of dibutyltin dilaurate. The resulting mixture was reacted at 55-65t for 2 hours. Thereto were added 130g of ethyl acetate, 31.3g of trimethylol propane and 0.07g of dibutyltin dilaurate, and the reaction was continued at 55-65t for 2 hours. In the reaction mixture, 230g of pentaerythritol triacrylate (M305) and 0.12g of dibutyltin dilaurate were added and the reaction was continued for about 6 hours until infrared absorption of isocyanate group at 2250 em-' was disappeared while keeping the reaction temperature at 55-65t. Thus,polyurethane acrylate (c) having the characteristics shown in Table 1 was obtained. Synthesis Example 4 In a reaction vessel were charged 243.6g of IPDI trimer (VESTANAT T-1890, produced by HUls Aktiengesellschaft) and 220g of ethyl acetate, and the mixture was warmed to 4050t to make a solution.
Thereto were added 0.16g of MTBHO and 0.10g of dibutyltin dilaurate, and the reaction temperature was kept at 50t. Then, 273.7g of glycerin dimethacrylate (Light Ester G-101P, produced by Kyoeisha Chemical Co. Ltd. ) was added dropwise over about 30 minutes and the reaction was continued for about 6 hours at 55-65t until absorption of isocyanate group at 2,250 cm-1 in infrared absorption spectrum was dissapeared followed by addition of 279.5g of ethyl acetate to give polyurethane methacrylate (d) having the characteristics shown in Table 1. Table 1 Characteristics and physical properties of polyurethane (meth)acrylate resins (a), (b), (c) and (d).
Resin (a) (b) (c) (d) Number averace molecular weicht 23001, 22501 5350 1450 Number of average functional group (F) 9 1 9 . Concentration of urethane group (m mol/g)l 1.1 . 4 Non volatile M 1 50 80 i T Viscosity (mPa.s/25'C) 11 1 --------------- ................
3 1.68 2.08 .....................................
50 .......................
1120 27001 100 . 4 ----------------------------- -------------- 1 Tack-dry (Tackiness)' 1 i Z;i 0 '1 0 . -------------- --------------- 2 1 Pencil hardness after curing 1 6H 7H SH 2H (Note) 'Tack-.dry at 25t 0 Tack free Zl Dry to touch but tacky X Tacky to touch 2Pencil hardness after curing To 100 parts of urethane acrylate, 3 parts of photoinitiator (1-hydroxycyclohexyl phenyl ketone) was added. A glass surface was coated with the resin composition in 100p thickness. After evaporation of the solvent and curing by a high pressure mercury lamp (80W/cm), pencil hardness of the cured product was measured.
Example 1 A polyurethane acrylate resin composition was prepared from 100 parts of the polyurethane acrylate resin obtained in Synthesis Example 2, 9.5 parts of dipentaerythritol, hexaacrylate and 9.5 parts of cellulose acetate butylate (CAB). To the resin composition were added 1 part of DTBPH and 0.01 part of MTBHQ to give the resin for impregnation. Titan paper (120g/ml) with patterns was impregnated with the resin so that impregnated resin ratio may become 45% by weight relative to the whole paper. The paper impregnated with the resin was easy to handle at cutting and charging in a mold. A top tool and a bottom tool in a mold were heated at 135t and 145t respectively, and the impregnated sheet was put at the previously determined place in the bottom tool, and then SMC(Polymal Mat YEM-1364, produced by Takeda Chemical Industries Ltd.) was laid thereon. The SMC used in this Example was one used widely as a waterproof pan. The mold press was closed and the SMC was molded in the conventional conditions. The patterns in the resulting product were free from any slipping and breaking of the sheet and excellent in gloss. Example 2 To the re.sin composition prerpared in Example 1 were added I part of TBPO and 0.01 part of MTBHQ to give the resin for impregnation. Titan paper (120g/m2) with patterns was impregnated with the resin so that impregnated resin ratio may become 45% by weight relative to the whole paper. The paper impregnated with the resin was easy to handle at cutting and charging in a mold.
A top tool and a bottom tool in a mold were heated at 90t respectively, and the impregnated sheet was put at the previously determined place in the bottom tool, and then SMC to be cured at 90t was laid thereon. The mold was closed and then SMC(Selecty Mat R-101, produced by Takeda Chemical Industries Ltd.) was molded in the conventional conditions. The patterns in the resulting product were free from any slipping and breaking of the sheet and excellent in gloss. Reference Example I To 100 parts of unsaturated polyester resin, 15 parts of diallylphthalate resin and 2 parts of 1,1-bis (thexylperoxy) 3,3,5-trimethyl cyclohexane as an initiator were added and 120g/M2 titan paper was impregnated with the resin mixture to give a prepreg sheet according to the conventional manner. A top tool and a bottom tool in the mold were heated at 135t and 145t, respectively, and the sheet impregnated with the resin was put at the previously determined place in the bottom tool in the mold, and then SMC(Polymal Mat YEM-1364, produced by Takeda Chemical Industries Ltd.) was laid thereon. A part of the pattern in the resulting product were slipped and broken. The product was of no commercial value. Test Results Evaluation was conducted according to the following criteria on the molded articles obtained in Examples I and 2 and Reference Example I and the testresults were summarized in Table 2. (1) Moldability:
Whether the impregnated sheet was kept in the initial position or not, whether any slipping and breaking of the sheet were observed or not, and whether FRP covered, whole the patterns of the sheet or not were totally evaluated.
1 0: good,L: observed some slipping X: bad (2) Gloss: Gloss of a pattern surface was compared with that of FRP surface. 0: superior to FRP surface L: equal to FRP surface X: inferior to FRP surface (3) Abrasion resistance The test was carried out with "Washerbility Tester, Stroke:30cm, Rate: 37 cpm, Abrasion area: 11x17CM2). A nylon brash was installed in an abrasion part of the Tester and the part of the pattern of the product was abraded with the brush while reciprocating 500 times under 3.1 kg load, an appearance of the patterns in the molded product was observed and valuated.
0 IL No exposure of the titan paper was observed. A part of exfoliation of the pattern and an exposure of the titan paper were observed.
: All over the surface, an exfoliation of the pattern and an exposure of the titan paper were observed. (4) Pencil hardness: measured by JIS K 5400 (5) Chemical resistance: On the surface of the pattern, 1 ml each of 3% of a solution of hydrochloric acid and 5% solution of sodium hydroxide in water were placed. One hour after, the chemicals were wiped off and the surfaces were observed.
0 No c-hange A few and small cracks and blisters were observed. x Remarkable cracks and blisters were observed.
Table 2
Example 2 Reference Example 3 Example 1
Molderbility 0 Gloss 0 Abrasion resistance 0 Pencil hardness 4H Chemical resistance 0 0 0 0 4H 0 X z, 3H 0 Effect of the invention The prepreg sheet of the present invention is molded with another molding material such as SMC and the like thereon by heat and pressure molding to give a mold article which has glossy surface, high abrasion resistance, excellent antifungal and chemical resistant characteristics.
Claims (7)
1. A prepreg sheet which comprises a base material impregnated with a polyurethane (meth) acrylate resin composition.
2. The prepreg sheet according to Claim 1, wherein the polyurethane (meth) acrylate resin composition contains polyurethane (meth)acrylate resin (A) or (A) and a diluent having polymerizable double bond (B).
3. The prepreg sheet according to Claim 2, wherein the polyurethane (meth)acrylate resin (A) is one having a number average molecular weight of 500-100,000, a number of average functional groups of 2 or more in a molecule and a urethane group concentration of 0.1 to 10.0 m mol/g.
4. The prepreg sheet according to Claim 2, wherein the polyurethane (meth)acrylate resin (A) is one having a number average molecular weight of 700-20,000, a number of average functional groups of 6-40 in a molecure, and a urethane groups concentration of 0.5-5.Om mol/g.
5. The prepreg sheet according to any of Claims 1 to 4, wherein the base material is a titan iDar)er or non-woven f abrics.
6. A molded article obtained by laying up a prepreg sheet as claimed in any of Claims 1 to S and a thermosetting molding material, and then molding them integrally.
7. The molded article according to Claim 6, wherein the thermosetting molding material is FRP.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22757895 | 1995-08-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9616617D0 GB9616617D0 (en) | 1996-09-25 |
| GB2304122A true GB2304122A (en) | 1997-03-12 |
Family
ID=16863119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9616617A Withdrawn GB2304122A (en) | 1995-08-11 | 1996-08-08 | Prepreg sheet and article moulded therefrom |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE19632244A1 (en) |
| FR (1) | FR2737726A1 (en) |
| GB (1) | GB2304122A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9181380B2 (en) | 2007-03-30 | 2015-11-10 | Richard Austin Panther | Thermosetting resin composition |
| US10899856B2 (en) | 2016-05-13 | 2021-01-26 | Mitsubishi Chemical Corporation | Molding material, sheet molding compound and fiber-reinforced composite material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6011568A (en) * | 1983-06-30 | 1985-01-21 | Showa Highpolymer Co Ltd | Pressure-sensitive adhesive composition having anaerobic curability |
| GB2182074A (en) * | 1985-10-25 | 1987-05-07 | Ciba Geigy Ag | Single tow prepreg |
| US4929494A (en) * | 1986-03-05 | 1990-05-29 | Showa Denko Kabushiki Kaisha | Fibrous substrates impregnated with a curable composition |
| WO1992001015A1 (en) * | 1990-07-12 | 1992-01-23 | Herberts Gesellschaft mit beschränkter Haftung | Process and device for fixing wound-up materials and use therefor of radically polymerizable compositions |
| JPH0497839A (en) * | 1990-08-16 | 1992-03-30 | Tonen Corp | Fiber-reinforced composite resin member |
| JPH04202536A (en) * | 1990-11-30 | 1992-07-23 | Sekisui Chem Co Ltd | Sheet-molding compound |
| JPH07242757A (en) * | 1994-03-04 | 1995-09-19 | Yoshikuni Yoshimitsu | Production of prepreg |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3271526D1 (en) * | 1981-04-28 | 1986-07-10 | Ici Plc | Copolymerisation of unsaturated urethane monomers |
| DE4012946A1 (en) * | 1990-04-24 | 1991-10-31 | Basf Ag | PREPREG FOR HIGH-PERFORMANCE COMPOSITES |
| JPH089652B2 (en) * | 1991-04-03 | 1996-01-31 | 竹本油脂株式会社 | Radical-curable liquid mixture, radical-curable composition containing the same, and molded product obtained by curing these |
| DE4129348A1 (en) * | 1991-09-04 | 1993-03-11 | Basf Ag | FIBER REINFORCED MOLDS FROM UNSATURATED POLYESTER RESIN |
-
1996
- 1996-08-08 GB GB9616617A patent/GB2304122A/en not_active Withdrawn
- 1996-08-08 FR FR9609994A patent/FR2737726A1/en active Pending
- 1996-08-09 DE DE19632244A patent/DE19632244A1/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6011568A (en) * | 1983-06-30 | 1985-01-21 | Showa Highpolymer Co Ltd | Pressure-sensitive adhesive composition having anaerobic curability |
| GB2182074A (en) * | 1985-10-25 | 1987-05-07 | Ciba Geigy Ag | Single tow prepreg |
| US4929494A (en) * | 1986-03-05 | 1990-05-29 | Showa Denko Kabushiki Kaisha | Fibrous substrates impregnated with a curable composition |
| WO1992001015A1 (en) * | 1990-07-12 | 1992-01-23 | Herberts Gesellschaft mit beschränkter Haftung | Process and device for fixing wound-up materials and use therefor of radically polymerizable compositions |
| JPH0497839A (en) * | 1990-08-16 | 1992-03-30 | Tonen Corp | Fiber-reinforced composite resin member |
| JPH04202536A (en) * | 1990-11-30 | 1992-07-23 | Sekisui Chem Co Ltd | Sheet-molding compound |
| JPH07242757A (en) * | 1994-03-04 | 1995-09-19 | Yoshikuni Yoshimitsu | Production of prepreg |
Non-Patent Citations (4)
| Title |
|---|
| WPI Abstract Accession No. 85-053901/09 & JP 60 011 568 A * |
| WPI Abstract Accession No. 92-170310/21 & JP 04 097 839 A * |
| WPI Abstract Accession No. 92-295686/36 & JP 04 202 536 A * |
| WPI Abstract Accession No. 95-355334/46 & JP 07 242 757 A * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9181380B2 (en) | 2007-03-30 | 2015-11-10 | Richard Austin Panther | Thermosetting resin composition |
| US10899856B2 (en) | 2016-05-13 | 2021-01-26 | Mitsubishi Chemical Corporation | Molding material, sheet molding compound and fiber-reinforced composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2737726A1 (en) | 1997-02-14 |
| GB9616617D0 (en) | 1996-09-25 |
| DE19632244A1 (en) | 1997-02-13 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |