WO2017086231A1 - 繊維強化プラスチック成形品、及びその製造方法 - Google Patents
繊維強化プラスチック成形品、及びその製造方法 Download PDFInfo
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- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
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- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Definitions
- the present invention relates to a fiber reinforced plastic molded article and a method for producing the same, and more particularly to a fiber reinforced plastic molded article having excellent mechanical strength and a method for producing the same.
- Fiber reinforced plastic is used in various fields because of its light weight, high strength, and long life.
- carbon fiber reinforced plastic Carbon FRP: CFRP
- CFRP Carbon FRP
- CFRP is manufactured by stacking sheets pre-impregnated with epoxy resin, bagging and molding by applying temperature and pressure in an autoclave, press molding using a prepreg sheet, molding while impregnating a temperature-controlled resin and winding. FW (filament winding) molding and the like. Since autoclave molding applies a uniform pressure, it is possible to obtain complicated shaped parts. However, the curing time is long and the use of autoclaves and special auxiliary materials is an issue, and improvement is necessary. Since press molding requires a mold, it is difficult to cope with a small amount of products, and FW molding is also limited in shape.
- Urethane (meth) acrylate compounds are conventionally known to have excellent adhesion to carbon fibers, and are used as carbon fiber sizing agents (for example, Patent Document 1).
- the urethane (meth) acrylate compound has good adhesion to the reinforcing fiber, it has been proposed to use the urethane (meth) acrylate compound mixed with a resin having poor adhesion to the reinforcing fiber (for example, Patent Document 2).
- an object of the present invention is to provide a fiber-reinforced plastic molded article having good adhesion to reinforcing fibers and excellent mechanical strength.
- the present inventors have conducted intensive studies, and as a result, before curing, a urethane (meth) acrylate resin component containing a urethane (meth) acrylate compound containing a free isocyanate group and an ethylenically unsaturated group, and an organic tin component.
- a fiber reinforced plastic molding material composed of a radically polymerizable resin composition and reinforced fibers mixed in the above, a reinforced plastic molded article having good adhesion to the reinforced fibers and excellent mechanical strength can be obtained.
- the present inventors have found that the obtained fiber-reinforced plastic molded article is useful as a structural member, non-structural member, exterior member, interior member or a part thereof in various applications, and has reached the present invention.
- the fiber-reinforced plastic molded article of the present invention is a fiber-reinforced plastic molded article formed by molding a fiber-reinforced plastic molding material comprising a radical polymerizable resin composition and reinforcing fibers, and the radical polymerizable resin composition Is at least the following chemical formula: (Wherein n is 2 to 100, X is a compound residue having two or more isocyanate groups, and M is the formula [Chemical Formula 2]: At least, otherwise the formula [Chemical Formula 3]: It is.
- Q represents an ethylenically unsaturated group-containing monoalcohol compound residue.
- a radically polymerizable resin composition comprising at least a urethane (meth) acrylate resin component (a) containing a urethane (meth) acrylate compound represented by formula (a) and an organotin compound component (b), wherein the component (a) And the component (b) are mixed before curing.
- the chemical formula [Chemical Formula 1] is represented by the following chemical formula [Chemical Formula 4]: (In the formula, n is 1 to 5000, X is a compound residue having two or more isocyanate groups, Y is an alcohol compound residue having two or more hydroxyl groups, and M is a formula [Formula 5]: At least, otherwise the formula [Chemical 6]: It is.
- Q represents an ethylenically unsaturated group-containing monoalcohol compound residue. ).
- the component (a) is characterized by containing 0.1 to 12% by weight of isocyanate groups.
- tin contained in the component (b) is 15 ppm or more with respect to the total weight of the radical polymerizable resin composition.
- the reinforcing fiber is at least one selected from carbon fiber, glass fiber, basalt fiber, aramid fiber, polyarylate fiber, and cellulose fiber.
- the fiber-reinforced plastic molded article is a structural member, non-structural member, exterior member in the aerospace field, sports and daily life field, industrial field, It is used as an interior member or a part thereof.
- the method for producing a fiber-reinforced plastic molded article of the present invention has at least the following chemical formula [Chemical Formula 7]: (Wherein n is 2 to 100, X is a compound residue having two or more isocyanate groups, and M is the formula [Chemical Formula 8]: At least, otherwise the formula [Chemical 9]: It is.
- Q represents an ethylenically unsaturated group-containing monoalcohol compound residue.
- the time before the curing is from 6 hours before the start of curing to the time of curing.
- the kit for a fiber-reinforced plastic molded article of the present invention is a kit for a fiber-reinforced plastic molded article formed by molding a fiber-reinforced plastic molding material comprising a radical polymerizable resin composition and a reinforced fiber, and the radical polymerization At least the following chemical formula [Chemical Formula 10]: (Wherein n is 2 to 100, X is a compound residue having two or more isocyanate groups, and M is the formula [Chemical Formula 11]: At least, otherwise the formula [Chemical 12]: It is.
- Q represents an ethylenically unsaturated group-containing monoalcohol compound residue.
- a radically polymerizable resin composition comprising at least a urethane (meth) acrylate resin component (a) containing a urethane (meth) acrylate compound represented by formula (a) and an organotin compound component (b), wherein the component (a) And the component (b) at least.
- the kit is a fiber reinforced plastic molded product kit, but is not a molded product kit, a composition kit, that is, the urethane (meth) acrylate resin component (a) and the organotin compound component. It can also be sold as a radical polymerizable resin composition kit containing at least (b).
- kit for a fiber-reinforced plastic molded product of the present invention further comprises a curing agent and / or a reinforcing fiber.
- the fiber reinforced plastic molded product of the present invention has good adhesion to the reinforced fiber and excellent mechanical strength. Even in applications where reinforced plastics have been used, there are significant effects such as further reduction in thickness and weight.
- FIG. 1 is an IR spectrum of a urethane (meth) acrylate compound having an isocyanate group and an ethylenically unsaturated group in one embodiment of the present invention (synthetic example 1 in Examples described later). Absorption of isocyanate groups can be confirmed in the vicinity of 2250 cm @ -1.
- FIG. 2 is an IR spectrum of a urethane (meth) acrylate compound having an isocyanate group and an ethylenically unsaturated group in one embodiment of the present invention (in Synthesis Example 2 in the examples described later). Absorption of isocyanate groups can be confirmed in the vicinity of 2250 cm @ -1.
- (meth) acrylate means “acrylate” and “methacrylate”.
- (meth) acrylic acid ester indicates “acrylic acid ester” and “methacrylic acid ester”.
- urethane (meth) acrylate resin component (a) that can be used in the radical polymerizable resin composition, the radical polymerizable resin composition kit used in the present invention, and the fiber reinforced plastic molded product kit of the present invention. (Hereinafter component (a)) will be described.
- Component (a) has the following chemical formula:
- the urethane (meth) acrylate compound shown by is included at least.
- n is 2 to 100
- X is a compound residue having two or more isocyanate groups
- M is a formula [Chemical Formula 11]: At least, otherwise the formula [Chemical 12]: It is.
- Q represents an ethylenically unsaturated group-containing monoalcohol compound residue.
- the component (a) is represented by the following chemical formula:
- the urethane (meth) acrylate compound shown by is included at least.
- n is 1 to 5000
- X is a compound residue having two or more isocyanate groups
- Y is an alcohol compound residue having two or more hydroxyl groups
- M is a formula [Chemical Formula 14]: At least, otherwise the formula [Chemical 15]: It is.
- Q represents an ethylenically unsaturated group-containing monoalcohol compound residue.
- the number of moles of isocyanate groups derived from the isocyanate compound is derived from an ethylenically unsaturated group-containing monoalcohol compound and an alcohol compound having two or more hydroxyl groups. More than the total number of moles of hydroxyl groups.
- the synthesis reaction temperature is preferably 40 to 140 ° C., more preferably 70 to 110 ° C., from the viewpoint of preventing gelation during synthesis due to the ethylenically unsaturated group.
- the time required for the synthesis reaction is preferably continued until the amount of remaining isocyanate groups becomes constant, that is, until the hydroxyl groups are consumed.
- the end point of the reaction can be confirmed by quantifying the isocyanate group by titration or by tracking the absorption of the isocyanate group (near 2250 cm @ -1) in an infrared absorption spectrum (hereinafter abbreviated as IR).
- an acidic catalyst or a basic catalyst can be used, but tin compounds such as dibutyltin dilaurate and dibutyltin diacetate having high activity are preferable.
- the addition amount of the catalyst can be 5 to 200 ppm, preferably 5 to 100 ppm, more preferably 5 to 50 ppm based on the charged weight from the viewpoint of storage stability.
- polymerization inhibitor examples include polyphenol polymerization inhibitors such as hydroquinone, parabenzoquinone, methylhydroquinone and trimethylhydroquinone, heterocyclic compounds such as phenothiazine, 2,2,6,6-tetramethylpiperidine 1-oxyl and the like.
- the nitroxyl radical can be used.
- the addition amount of the polymerization inhibitor is preferably 100 to 2000 ppm with respect to the charged weight from the viewpoint of preventing gelation at the time of synthesis with an ethylenically unsaturated group or a polymerizable monomer.
- the weight% of the isocyanate group contained in the component (a) is preferably 0.1 to 12% by weight, and more preferably 0.3 to 12% by weight. If it is less than 0.1% by weight, the adhesion with the carbon fiber is inferior, and there is a possibility that sufficient compressive strength and interlaminar shear strength may not be obtained. If it exceeds 12% by weight, the bending strength and tensile strength are reduced, The balance of mechanical properties may be lost.
- the ethylenically unsaturated group equivalent of the urethane (meth) acrylate compound contained in the component (a) is not particularly limited, but when it is 1500 g / eq or more, mechanical properties (bending strength, tensile strength, compressive strength, There is a risk that the balance of the interlaminar shear strength will deteriorate and the heat resistance of the molded product will be lowered.
- Component (a) can also contain a polymerizable monomer that does not react with an isocyanate group at room temperature.
- polymerizable monomers that do not react with isocyanate groups at room temperature examples include vinyl monomers, monofunctional acrylates, and polyfunctional acrylates.
- vinyl monomers examples include vinyl monomers, monofunctional acrylates, and polyfunctional acrylates.
- a polymerizable monomer that reacts with an isocyanate group is blended, the viscosity increases due to a reaction during storage, and workability may be deteriorated or sufficient mechanical properties may not be obtained.
- vinyl monomers examples include styrene, vinyl toluene, ⁇ -methyl styrene, vinyl acetate and the like.
- Monofunctional acrylic acid esters include methyl methacrylate, benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
- polymerizable monomers can be used alone or in combination of two or more.
- Styrene, methyl methacrylate, and benzyl methacrylate are preferred in terms of dilution ability and mechanical properties.
- isocyanate compound having two or more isocyanate groups examples include 1,3-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5- Aromatic isocyanate compounds such as naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, m-tetramethylxylene diisocyanate, hydrogenated xylylene diisocyanate (1,3-bis (isocyanatomethyl) cyclohexane), Isophorone diisocyanate, norbornene diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated methylenebisphenylene diisocyanate, 1,4-cyclohexane diisocyanate And alicyclic isocyanate
- isocyanate compounds can be used alone or in combination of two or more. From the viewpoints of heat resistance, weather resistance and storage stability, alicyclic isocyanate compounds are particularly preferred.
- Alcohol compound having two or more hydroxyl groups examples include aliphatic alcohols, etherified diphenols, and polyester polyols.
- chain aliphatic alcohols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2, 3-butanediol, 1,4-butenediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 2-ethyl-2-methylpropane-1,3-diol, 2 -Butyl-2-ethylpropane-1,3-diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,4-dimethyl-1 , 5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,7-heptan
- cyclic aliphatic alcohol examples include hydrogenated bisphenol A, tricyclodecane dimethanol, spiro glycol and the like.
- 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are preferably used from the viewpoint of resin viscosity and mechanical properties of the cured product.
- Examples of the etherified diphenol include a diol obtained by addition reaction of bisphenol A and alkylene oxide, and a diol obtained by bromination of an adduct of bisphenol A and alkylene oxide.
- the alkylene oxide is ethylene oxide or propylene oxide, and the average added mole number of the alkylene oxide is preferably 2 to 16 moles with respect to 1 mole of bisphenol A from the viewpoint of the balance of mechanical properties.
- polyester polyols include those obtained by polycondensation of unsaturated and / or saturated acids with the above-mentioned aliphatic alcohols and etherified diphenols.
- unsaturated acid include maleic anhydride, maleic acid, and fumaric acid.
- Saturated acids include phthalic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, succinic acid, sebacic acid, alkyl succinic acid, alkenyl succinic acid, itaconic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, Mention may be made of ester-forming derivatives such as 5-tert-butyl-1,3-benzenedicarboxylic acid and their acid anhydrides, lower alkyl esters, acid halides and the like.
- At least one selected from terephthalic acid, isophthalic acid, and ester-forming derivatives thereof, 1,3-propanediol, 1,4-butanediol, 1,5- Polyester polyols obtained by polycondensation with one or more selected from pentanediol and 1,6-hexanediol are particularly preferred.
- trivalent or higher polyol can be used as long as the effects of the present invention are not impaired.
- examples of the trivalent or higher polyol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used alone or in combination of two or more.
- the ethylenically unsaturated group-containing monoalcohol compound is a hydroxyl group-containing (meth) acrylic acid ester such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meta ) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, diacrylated isocyanurate, etc. Can be mentioned.
- ethylenically unsaturated group-containing monoalcohol compounds can be used alone or in combination of two or more.
- 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of resin viscosity and mechanical properties of the cured product.
- organotin compound component (b) that can be used in the radical polymerizable resin composition, the radical polymerizable resin composition kit, and the fiber reinforced plastic molded product kit of the present invention will be described.
- the component (a) and the component (b) can be mixed before curing and during curing.
- the time of curing refers to a point in time when the curing of the resin composition is started on site.
- the time point at which curing is started refers to, for example, a time point at which a curing agent is added in the case of room temperature curing or high temperature curing, and a time point at which a photopolymerization initiator is added in the case of photocuring.
- the addition timing of the component (b) to the radical polymerizable resin composition containing the component (a) is most preferably just before the start of curing. However, when temperature control is performed, addition 30 minutes before is preferable. When addition immediately before the start of curing is difficult, it can be added at least 12 hours before the start of curing, and preferably 6 hours before the start of curing until the time of curing. When added 12 hours before the start of curing, the gelation time may be shortened.
- the amount of component (b) added is preferably 15 ppm or more, more preferably 30 ppm or more as tin, based on the total weight of the radical polymerizable resin composition. If it is less than 15 ppm, it will be inferior to adhesiveness with a fiber.
- component (b) include, but are not limited to, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, and stannous octoate.
- the present invention is characterized in that the urethane (meth) acrylate resin component (a) and the organotin compound component (b) are mixed at the time of curing, preferably before and during curing.
- the time of curing refers to the point in time when the resin composition starts to be cured on site.
- the mixing method is not limited. For example, it is added in advance to the above-described polymerizable monomer or the below-described curing accelerator to prepare a preparation solution, You may mix a component (a) and this liquid preparation containing a component (b) at the time of hardening.
- the radical polymerizable resin composition used in the present invention is suitable as a matrix resin for fiber reinforced plastics.
- the viscosity of the radical polymerizable resin composition used in the present invention at the time of molding a fiber reinforced plastic is 30 to 700 mPa ⁇ s (25) because it is applied to hand lay-up molding, RTM (Resin Transfer Molding) molding and VaRTM (Vacuum Assisted Resin Transfer Molding) molding. ° C).
- RTM Resin Transfer Molding
- VaRTM Vaum Assisted Resin Transfer Molding
- the viscosity of the radical polymerizable resin composition used in the present invention is 300 to 1200 mPa.s. s (25 ° C.) is preferred. Since the viscosity decreases at a high temperature, resin loss occurs when the viscosity is less than 300 mPa ⁇ s, and flow failure may occur when the viscosity exceeds 1500 mPa ⁇ s.
- a known method similar to the conventional radical polymerization resin can be applied. Specific examples include curing with an organic peroxide, curing with ultraviolet rays, and curing with an electron beam.
- accelerators for adjusting the curing rate, polymerization inhibitors, and waxes for imparting air drying properties can be added in the same manner as conventional radical curable resins.
- organic peroxide curing agents examples include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butylperoxybenzoate, and cumene.
- examples thereof include hydroperoxides such as hydroperoxide, dialkyl peroxides such as dicumyl peroxide, and the like.
- the addition amount of the curing agent can be 0.05 to 5 parts by weight with respect to 100 parts by weight of the radical polymerizable resin composition from the viewpoint of maintaining the mechanical properties of the cured product and securing an appropriate working time.
- UV initiator examples include benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzoin ethers such as benzoin alkyl ether, benzyl dimethyl ketal, 2,2-diethoxyacetophenone and 2-hydroxy-2-methyl.
- Acetophenone series such as propiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, thioxanthone series such as 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc.
- the addition amount of the ultraviolet initiator can be 0.1 to 5 parts by weight with respect to 100 parts by weight of the radical polymerizable resin composition from the viewpoint of maintaining curability and maintaining mechanical properties.
- the curing accelerator examples include metal soaps such as cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate, vanadium acetyl acetate, cobalt acetyl acetate, iron acetylacetonate and the like.
- Tertiary amines such as metal chelates, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, pyridine, phenylmorpholine And the like.
- the addition amount of the curing accelerator is 0.05 to 5 parts by weight with respect to 100 parts by weight of the radical polymerizable resin composition from the viewpoint of maintaining curability and maintaining mechanical properties.
- other radical polymerization resins can be blended and used according to the purpose.
- the resin used include unsaturated polyester resins, epoxy (meth) acrylate resins, and urethane (meth) acrylate resins.
- it is preferable to blend so that the isocyanate group in the blend resin is 0.1 to 8% by weight from the viewpoint of adhesion to fibers, particularly carbon fibers.
- reinforcing fibers used at the time of molding include, but are not limited to, carbon fibers, glass fibers, aramid fibers, xylon fibers, vinylon fibers, polyethylene fibers, boron fibers, basalt fibers, and cellulose fibers. Preferably, it is at least one selected from carbon fiber, glass fiber, basalt fiber, aramid fiber, polyarylate fiber, and cellulose fiber. Carbon fiber is particularly preferred from the balance between mechanical properties and lightness of the molded product.
- the reinforcing fiber content is 10 to 90% by weight, and preferably 20 to 70% by weight from the viewpoint of mechanical properties and moldability. There is no limitation on the surface treatment agent for reinforcing fibers.
- These reinforcing fibers may be twisted, spun, spun, or non-woven processed depending on the molding method and application. Specifically, filaments, yarns, rovings, strands, chopped strands, felts, needle punches, cloths, roving cloths, milled fibers, and the like can be used.
- the respective fibers may be stacked and used in an arbitrary order, or each blended fiber may be used.
- carbon fibers and reinforcing fibers other than carbon fibers it is possible to solve the problems of carbon fiber reinforced plastics, such as crushed pieces scattered during impact.
- the fiber reinforced plastic molding material molding method includes hand lay-up molding, sheet winding molding, press molding, filament winding molding, pultrusion molding, RTM (Resin Transfer Molding) molding, VaRTM (Vacuum Assisted Resin Transfer Molding). There are molding and injection molding (injection).
- a liquid resin is impregnated and cured in a reinforcing fiber during molding to obtain a molded product
- sheet winding molding and press molding Pre-impregnated reinforced fibers with a liquid resin to obtain a sheet-shaped preform (prepreg) whose surface is tack-free by removing the solvent or partially curing, then winding the prepreg around a mandrel and curing it in a heating furnace
- prepreg sheet-shaped preform
- a molded product can be obtained by (sheet winding molding) or by prepregs being stacked in upper and lower molds and then cured by pressing and heating (press molding).
- the fiber-reinforced plastic molded article of the present invention has excellent mechanical performance, so that it can be used for applications where conventional fiber-reinforced plastics cannot be used due to insufficient performance, and applications where conventional fiber-reinforced plastics have been used. Can be made thinner and lighter.
- the fiber-reinforced plastic molded article of the present invention can be used as a structural member, non-structural member, exterior member, interior member or part thereof in, for example, the aerospace field, sports and daily life products field, and industrial field. .
- primary structure materials such as main wings, tail wings, fuselage, and floor beams
- secondary wing materials such as auxiliary wings, rudder, elevator, and fairing
- interiors such as floor panels, lavatory and seat
- Other materials such as jet engine fan blades, helicopter rotor blades, rocket related satellite fairing, interstage, motor case, nozzle float, etc., artificial satellite related antenna, solar panel, tube truss structure
- the molded article of the present invention can be applied to antennas, struts, and the like.
- fishing rods, fishing rods, reels, etc. golf-related shafts, club heads, face plates, etc., rackets-related tennis rackets, badminton rackets, squash rackets, etc., bicycles-related frames, For wheels, handles, cranks, etc., for yachts, cruisers, racing boats, masts, etc. for marine related, for baseball bats, skis, ski stocks, kendo bamboo swords, Japanese bows, archery, radio controlled cars, table tennis
- the molded product of the present invention can be applied to a racket, a billiard stick, or the like.
- molding of the present invention is applied to wheelchairs, wheelchair mobile slopes, prosthetic legs, walking sticks and other nursing care products, personal computer housings, electrical products such as acoustic speakers, daily life items such as western umbrellas, helmets, bags, furniture, etc. Goods can be applied.
- the radical polymerizable resin composition kit and the fiber reinforced plastic molded product kit of the present invention, usable urethane (meth) acrylate compound component (a) and The organotin compound component (b) can be sold as a kit as follows, for example.
- a urethane (meth) acrylate resin (a) as a resin for example, 1) a urethane (meth) acrylate resin (a) as a resin, 2) a solution containing an organotin compound component (b) as an accelerator, 3) a curing agent, and / or a reinforcing fiber, etc. , A radical polymerizable resin composition kit, or a fiber reinforced plastic molded product kit.
- kit sales can prevent the end user from using the product after storing the above 1) and 2) for a long time in a confused state. That is, as is clear from the examples described later, if the resin (a) of 1) and the organotin compound component (b) of 2) are mixed and allowed to stand, the gelation time is shortened. This is because the working time may be affected. In order to avoid this, it is convenient not to inadvertently mix the above 1) and 2) before use, and the kit of the present invention can easily avoid such problems. This is advantageous.
- the gelation time is linearly shortened immediately after mixing the above 1) and 2).
- the initial gelation time of about 60 minutes may become 20 to 30 minutes after 12 hours.
- the initial value gelation time is about 90 minutes, there is a possibility that it will be about 40 to 60 minutes after 12 hours.
- working time can be secured if it is 30 minutes or longer, and although it depends on the composition of the resin, etc., as a guide, it is best to mix the above 1) and 2) immediately before the start of curing.
- the time for adding the curing agent of 3) above after mixing 1) and 2) may exceed 12 hours after mixing. In some cases it will be possible.
- part means parts by weight unless otherwise specified.
- the isocyanate group content in the synthesis example was measured by dissolving each resin in dry toluene, adding an excess of di-n-butylamine solution to react, and back titrating the remaining di-n-butylamine with hydrochloric acid.
- the reaction was monitored by IR, and the end point was when the isocyanate group absorption (around 2270 m-1) became constant. The reaction took 3 hours.
- the isocyanate group content of urethane (meth) acrylate was 2.08% by weight, and the ethylenically unsaturated group equivalent was 505 g / eq. Then, it diluted with 160 parts of styrene monomers, and obtained urethane (meth) acrylate resin (a1) which contains 1.17 weight% of isocyanate groups.
- the isocyanate group content of urethane (meth) acrylate was 2.00% by weight, and the ethylenically unsaturated group equivalent was 423 g / eq. Then, it diluted with 0.15 part of phenothiazine and 123 parts of styrene monomers, and obtained urethane (meth) acrylate resin (a2) containing 1.14% by weight of isocyanate groups.
- Example 0-1 The initial viscosity of the urethane (meth) acrylate resin (a1) obtained in Synthesis Example 1 was measured. The viscosity obtained was 102 mPa ⁇ s. Next, 0.04 part of dibutyltin dilaurate and 0.46 part of 6% cobalt naphthenate were added to 100 parts of (a1), and 1 part of 328E (Kayaku Akzo) was added as a curing agent, and the initial gelation time was measured. The gelation time obtained was 40 minutes.
- Example 0-2 The initial viscosity of the urethane (meth) acrylate resin (a2) obtained in Synthesis Example 2 was measured. The viscosity obtained was 121 mPa ⁇ s. Next, 0.04 part of dibutyltin dilaurate and 0.46 part of 6% cobalt naphthenate were added to 100 parts of (a2), and 1 part of 328E (Kayaku Akzo) was added as a curing agent, and the initial gelation time was measured. The gel time obtained was 45 minutes.
- Example 1-1 The urethane (meth) acrylate resin (a1) obtained in Synthesis Example 1 was stored at 25 ° C. for 30 days. After storage, the viscosity was measured and found to be 112 mPa ⁇ s. Next, 0.04 part of dibutyltin dilaurate and 0.46 part of 6% cobalt naphthenate were added to 100 parts of (a1), and 328E (Kayaku Akzo) was added as a curing agent to the resulting radical polymerizable resin composition. 1 part was added and the gelation time was measured. The resulting gel time was 36 minutes.
- Example 1-2 The urethane (meth) acrylate resin (a2) obtained in Synthesis Example 2 was stored at 25 ° C. for 30 days. When the viscosity was measured after storage, it was 138 mPa ⁇ s. Next, 0.04 part of dibutyltin dilaurate and 0.46 part of 6% cobalt naphthenate were added to 100 parts of (a2), and 328E (Kayaku Akzo) was added as a curing agent to the resulting radical polymerizable resin composition. 1 part was added and the gelation time was measured. The resulting gel time was 38 minutes.
- the gelation time at the time of curing with respect to the gelation time of the urethane (meth) acrylate resin immediately after the synthesis was expressed as a percentage as a retention rate.
- the radical polymerizable resin compositions of Example 1-1 and Example 1-2 in which urethane (meth) acrylate resin and DBTDL were mixed at the time of curing after storage were obtained in Example 0-1 and Example 0-2.
- the retentions were 90% and 84%, respectively, whereas the urethane (meth) acrylate resin and DBTDL were mixed and stored immediately after synthesis and Reference Example 1-1
- the retention was 33% and 27%, respectively, compared with the initial gelation times obtained in Example 0-1 and Example 0-2.
- the storage stability was significantly impaired. Since the gelation time affects workability, it is desirable that the gelation time does not change as much as possible.
- the resin composition obtained in the reference example has a significant limitation on the work time.
- Example 2-2 A radical polymerizable resin composition obtained by adding 0.01 part of dibutyltin dilaurate and 0.49 part of 6% cobalt naphthenate to 100 parts of the urethane (meth) acrylate resin (a1) obtained in Synthesis Example 1.
- 1 part of 328E (Kayaku Akzo) was blended as a curing agent, impregnated into carbon fiber, molded and cured by hand lay-up, and then the mechanical properties of the obtained laminate were measured.
- Example 2-4 After adding 0.2 part of dibutyltin dilaurate 10% styrene solution and 1 part of benzoyl peroxide to 100 parts of the urethane (meth) acrylate resin (a1) obtained in Synthesis Example 1, the carbon fiber was impregnated at 110 ° C. After press-curing for 5 minutes in the mold, the mechanical properties of the obtained laminate were measured.
- a partition plate (2.5 m ⁇ 5 m CFRP plate) used for transportation equipment is shown as a molding example.
- the maximum load on the partition plate is 600N, but considering the safety factor of 30%, the required load capacity is 857MPa.
- Each molded plate was produced with a thickness calculated from the bending strength of the CFRP used, and subjected to a bending test.
- Example 3 After adding 0.1 part of dibutyltin dilaurate and 1.15 parts of 6% cobalt naphthenate to 250 parts of the urethane (meth) acrylate resin (a1) obtained in Synthesis Example 1, 328E (chemical compound) 2.50 parts of Akazo) was added and mixed with stirring.
- a CFRP with a thickness of 2.84 mm was produced by hand layup molding using the mixture and carbon fiber CO6343 (plain weave manufactured by Toray Industries, Inc.). Curing was performed at room temperature curing for 3 hours and post curing at 100 ° C. for 2 hours.
- the actual molded product of Example 3 is about 11% lighter than the reference examples 3-1 and 3-2. It is about 22% lighter than Reference Example 3-3.
- the resin of the present invention is used as a CFRP matrix, it is clear that the molded product can be designed to be thin with respect to the required strength because of its high strength.
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Abstract
Description
まず、本発明に用いられるラジカル重合性樹脂組成物、ラジカル重合性樹脂組成物用キット、及び本発明の繊維強化プラスチック成形品用キットにおいて、使用可能な本ウレタン(メタ)アクリレート樹脂成分(a)(以下成分(a))について説明する。
2個以上イソシアネート基を有するイソシアネート化合物としては、例えば、1,3-キシリレンジイソシアネート、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、4,4’-ジフェニルジイソシアネート、1,5-ナフタレンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、m-テトラメチルキシレンジイソシアネート等の芳香族イソシアネート化合物、水添キシリレンジイソシアネート(1,3-ビス(イソシアナトメチル)シクロヘキサン)、イソホロンジイソシアネート、ノルボルネンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、水添メチレンビスフェニレンジイソシアネート、1,4-シクロヘキサンジイソシアネート、等の脂環族イソシアネート化合物、1,6-ヘキサメチレンジイソシアネート、トリメチレンジイソシアネート等の脂肪族イソシアネート化合物、2官能イソシアネート化合物が3量化されたイソシアヌレート環を有する3官能イソシアネート、市販されているポリオールで変性されたイソシアネートプレポリマー等を挙げることができる。
2個以上の水酸基を有するアルコール化合物としては、脂肪族アルコール、エーテル化ジフェノール、及びポリエステルポリオール等が挙げられる。
エチレン性不飽和基含有モノアルコール化合物とは水酸基含有(メタ)アクリル酸エステルのことであり、例えば、2-ヒドロキシエチル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジアクリル化イソシアヌレートなどを挙げることができる。
次に、本発明に用いられるラジカル重合性樹脂組成物、ラジカル重合性樹脂組成物用キット、及び本発明の繊維強化プラスチック成形品用キットにおいて、使用可能な有機スズ化合物成分(b)について記載する。本発明において、成分(a)と成分(b)とは硬化前~硬化時の間に混合することができる。ここで硬化時とは、現場にて樹脂組成物の硬化を開始する時点を指す。硬化を開始する時点とは、例えば、常温硬化や高温硬化の場合には硬化剤が添加される時点を指し、光硬化の場合には光重合開始剤が添加される時点を指す。
本発明に用いられるラジカル重合性樹脂組成物の硬化及びこれを用いた繊維強化プラスチックの成形について記載する。
<ウレタン(メタ)アクリレート樹脂(a1)の合成>
ガス導入管、撹拌装置、冷却管、温度計を備えた反応容器にイソホロンジイソシアネート(エボニック社製)392部、スチレンモノマー210部、ジブチル錫ジウラレート0.016部、1,3-プロパンジオール(デュポン社製)75部、2-ヒドロキシエチルメタクリレート(三菱ガス化学社製)162部、トルハイドロキノン0.06部、及び4-メチルー2,6-ジターシャリーブチルフェノール0.25部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら温度を95~105℃に保持し、反応させた。反応はIRにて追跡し、イソシアネート基の吸収(2270m-1付近)が一定になったところを終点とした。反応には3時間を要した。ウレタン(メタ)アクリレートのイソシアネート基含有量は2.08重量%、エチレン性不飽和基当量505g/eqであった。その後、スチレンモノマー160部で希釈し、イソシアネート基を1.17重量%含有するウレタン(メタ)アクリレート樹脂(a1)を得た。
<ウレタン(メタ)アクリレート樹脂(a2)の合成>
合成例1と同様の反応容器にイソホロンジイソシアネートの三量体(エボニック社製)314部、スチレンモノマー307部を仕込み、撹拌下、空気を吹き込みつつ60℃まで加熱した。その後、ジブチル錫ジウラレート0.014部、ペンタエリスリトールトリアクリレート(東亞合成社製)163部、2-ヒドロキシエチルメタクリレート(三菱ガス化学社製)93部、トルハイドロキノン0.06部、4-メチルー2,6-ジターシャルブチルフェノール0.20部を分割して仕込み、温度を95~105℃に保持し反応させた。反応はIRにて追跡し、イソシアネート基の吸収(2270m-1付近)が一定になったところを終点とした。反応には3時間を要した。ウレタン(メタ)アクリレートのイソシアネート基含有量は2.00重量%、エチレン性不飽和基当量423g/eqであった。その後、フェノチアジン0.15部とスチレンモノマー123部で希釈し、イソシアネート基を1.14重量%含有するウレタン(メタ)アクリレート樹脂(a2)を得た。
上記合成例で得られた樹脂を用い、ゲル化時間、粘度を測定した。測定はJISK6901に準拠した。
前記合成例1で得られたウレタン(メタ)アクリレート樹脂(a1)の初期粘度を測定した。得られた粘度は102mPa・sであった。次いで(a1)100部にジブチル錫ジラウレート0.04部と6%ナフテン酸コバルト0.46部とを加え、硬化剤として328E(化薬アクゾ)を1部添加し初期ゲル化時間を測定した。得られたゲル化時間は40分であった。
前記合成例2で得られたウレタン(メタ)アクリレート樹脂(a2)の初期粘度を測定した。得られた粘度は121mPa・sであった。次いで(a2)100部にジブチル錫ジラウレート0.04部と6%ナフテン酸コバルト0.46部とを加え、硬化剤として328E(化薬アクゾ)を1部添加し初期ゲル化時間を測定した。得られたゲル化時間は45分であった。
前記合成例1で得られたウレタン(メタ)アクリレート樹脂(a1)を25℃にて30日間保管した。保管後、粘度を測定したところ、112mPa・sであった。次いで、(a1)100部にジブチル錫ジラウレート0.04部と6%ナフテン酸コバルトを0.46部とを加え、得られたラジカル重合性樹脂組成物に、硬化剤として328E(化薬アクゾ)を1部添加しゲル化時間を測定した。得られたゲル化時間は36分であった。
前記合成例2で得られたウレタン(メタ)アクリレート樹脂(a2)を25℃にて30日間保管した。保管後、粘度を測定したところ、138mPa・sであった。次いで、(a2)100部にジブチル錫ジラウレート0.04部と6%ナフテン酸コバルトを0.46部とを加え、得られたラジカル重合性樹脂組成物に、硬化剤として328E(化薬アクゾ)を1部添加しゲル化時間を測定した。得られたゲル化時間は38分であった。
前記合成例1で得られたウレタン(メタ)アクリレート樹脂(a1)に、合成直後、ジブチル錫ジラウレート0.04部を混合し、25℃にて30日間保管した。保管後、粘度を測定したところ、213mPa・sであった。次いで(a1)100部に6%ナフテン酸コバルトを0.46部を加え、得られたラジカル重合性樹脂組成物に、硬化剤として328E(化薬アクゾ)を1部添加しゲル化時間を測定した。得られたゲル化時間は13分であった。
前記合成例2で得られたウレタン(メタ)アクリレート樹脂(a2)に、合成直後、ジブチル錫ジラウレート0.04部を混合し、25℃にて30日間保管した。保管後、粘度を測定したところ、192mPa・sであった。次いで(a2)100部に6%ナフテン酸コバルトを0.46部を加え、得られたラジカル重合性樹脂組成物に、硬化剤として328E(化薬アクゾ)を1部添加しゲル化時間を測定した。得られたゲル化時間は12分であった。
測定結果を表1に示した。まず、粘度に関しては、合成直後のウレタン(メタ)アクリレート樹脂の粘度に対する硬化時の粘度を増粘度として倍数で示した。
上記合成例で得られた樹脂を用い、下記の条件で積層板を作成し、機械物性を測定した。測定には、引張強さ、曲げ強さ、圧縮強さ、層間せん断強さは、それぞれJISK7161、JISK7074、JISK7018、JISK7078に準拠した。
・実施例2-1、2-2,2-3及び参照例2-1、2-2
炭素繊維:平織りクロス(東レ(株)製商品名『T-6343』)
積層構成:25cm×25cm×8枚、厚さ2mm、炭素繊維コンテント40Vf(体積)%。
硬化条件:常温硬化(23℃)×6時間、80℃×2時間、100℃×2時間
・実施例2-4及び参照例2-3
炭素繊維:平織りクロス(東レ(株)製商品名『T-6343』)
積層構成:25cm×25cm×10枚、厚さ2mm、炭素繊維コンテント47Vf(体積)%。
硬化条件:110℃×5分間、プレス圧8MPa
前記合成例1で得られたウレタン(メタ)アクリレート樹脂(a1)100部にジブチル錫ジラウレート0.02部と6%ナフテン酸コバルト0.48部とを加え、得られたラジカル重合性樹脂組成物に、硬化剤として328E(化薬アクゾ)1部を配合し、炭素繊維に含浸させ、ハンドレイアップにて成形・硬化した後、得られた積層板の機械物性を測定した。
前記合成例1で得られたウレタン(メタ)アクリレート樹脂(a1)100部にジブチル錫ジラウレート0.01部と6%ナフテン酸コバルト0.49部とを加え、得られたラジカル重合性樹脂組成物に、硬化剤として328E(化薬アクゾ)1部を配合し、炭素繊維に含浸させ、ハンドレイアップにて成形・硬化した後、得られた積層板の機械物性を測定した。
前記合成例2で得られたウレタン(メタ)アクリレート樹脂(a2)100部にジブチル錫ジラウレート0.02部と6%ナフテン酸コバルト0.48部とを加え、得られたラジカル重合性樹脂組成物に、硬化剤として328E(化薬アクゾ)1部を配合し、炭素繊維に含浸させ、ハンドレイアップにて成形・硬化した後、得られた積層板の機械物性を測定した。
前記合成例1で得られたウレタン(メタ)アクリレート樹脂(a1)100部にジブチル錫ジラウレート10%スチレン溶液を0.2部とベンゾイルパーオキサイド1部を加え、炭素繊維に含浸させた後110℃の金型にて5分間プレス硬化した後、得られた積層板の機械物性を測定した。
前記合成例1で得られたウレタン(メタ)アクリレート樹脂(a1)100部に6%ナフテン酸コバルト0.5部を加え、得られたラジカル重合性樹脂組成物に、硬化剤として328E(化薬アクゾ)1部を配合し、炭素繊維に含浸させ、ハンドレイアップにて成形・硬化した後、得られた積層板の機械物性を測定した。
前記合成例2で得られたウレタン(メタ)アクリレート樹脂(a2)100部に6%ナフテン酸コバルト0.5部を加え、得られたラジカル重合性樹脂組成物に、硬化剤として328E(化薬アクゾ)1部を配合し、炭素繊維に含浸させ、ハンドレイアップにて成形・硬化した後、得られた積層板の機械物性を測定した。
前記合成例1で得られたウレタン(メタ)アクリレート樹脂(a1)100部ベンゾイルパーオキサイド1部を加え、炭素繊維に含浸させた後110℃の金型にて5分間プレス硬化した後、得られた積層板の機械物性を測定した。
測定結果を表2に示した。
輸送機器に使用される仕切り板(2.5m×5mのCFRP板)を成形実施例として示す。仕切り板にかかる最大荷重は600Nであるが、安全率30%を配慮すると、必要な耐荷重は857MPaとなる。使用するCFRPの曲げ強さから算出した厚みで、各成形板を作製し、曲げ試験を行った。
前記合成例1で得られたウレタン(メタ)アクリレート樹脂(a1)250部にジブチル錫ジラウレート0.1部と6%ナフテン酸コバルト1.15部とを加え撹拌した後、硬化剤として328E(化薬アクゾ)を2.50部添加し撹拌混合した。その混合物とカーボン繊維CO6343(東レ社製平織)を用いて、ハンドレイアップ成形にて厚み2.84mmのCFRPを作製した。硬化は常温硬化3時間と後硬化100℃2時間で行った。
液状ビスフェール系エポキシ樹脂215部にアミン系硬化剤65部添加し撹拌混合した。その混合物とカーボン繊維CO6343(東レ社製平織)を用いて、ハンドレイアップ成形にて厚み3.17mmのCFRPを作製した。硬化は常温硬化6時間と後硬化150℃2時間で行った。
ビスフェノール系エポキシアクリレート樹脂(日本ユピカ製8250L)280部に6%ナフテン酸コバルト1.4部を加え、硬化剤として328E(化薬アクゾ)を2.80部添加し撹拌混合した。その混合物とカーボン繊維CO6343(東レ社製平織)を用いて、ハンドレイアップ成形にて厚み3.19mmのCFRPを作製した。硬化は常温硬化3時間と後硬化100℃2時間で行った。
不飽和ポリエステル樹脂(日本ユピカ社製ユピカ4007A)300部に6%ナフテン酸コバルト1.5部を加え撹拌した後、硬化剤としてパーメックN(日油製)を3.00部添加し撹拌混合した。その混合物とカーボン繊維CO6343(東レ社製平織)を用いて、ハンドレイアップ成形にて厚み3.63mmのCFRPを作製した。硬化は常温硬化3時間と後硬化100℃2時間で行った。
Claims (10)
- ラジカル重合性樹脂組成物と強化繊維とからなる繊維強化プラスチック成形材料を成形してなる繊維強化プラスチック成形品であって、前記ラジカル重合性樹脂組成物が少なくとも下記化学式[化1]:
- 前記成分(a)は、0.1~12重量%のイソシアネート基を含むことを特徴とする請求項1又は2に記載の繊維強化プラスチック成形品。
- 前記成分(b)に含まれるスズは、前記ラジカル重合性樹脂組成物の総重量に対し15ppm以上であることを特徴とする請求項1~3のいずれか1項に記載の繊維強化プラスチック成形品。
- 前記強化繊維は、炭素繊維、ガラス繊維、バサルト繊維、アラミド繊維、ポリアリレート繊維、セルロース繊維から選ばれる1種以上であることを特徴とする請求項1~4のいずれか1項に記載の繊維強化プラスチック成形品。
- 前記繊維強化プラスチック成形品が、航空・宇宙分野、スポーツおよび日常生活用品分野、産業用分野における構造部材、非構造部材、外装部材、内装部材もしくはその一部として使用される請求項1~5のいずれか1項に記載の繊維強化プラスチック成形品。
- 前記硬化前は、硬化開始の6時間前から硬化時までの間である請求項7記載の方法。
- ラジカル重合性樹脂組成物と強化繊維とからなる繊維強化プラスチック成形材料を成形してなる繊維強化プラスチック成形品用キットであって、前記ラジカル重合性樹脂組成物が少なくとも下記化学式[化10]:
- さらに、硬化剤、及び/又は強化繊維を含む請求項9記載のキット。
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EP3733747A4 (en) * | 2017-12-26 | 2021-09-01 | DIC Corporation | RESIN COMPOSITION FOR CARBON FIBER REINFORCED PLASTIC, MOLDED MATERIAL, MOLDED ARTICLES AND METHOD FOR MANUFACTURING MOLDED ARTICLES |
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KR20180082456A (ko) | 2018-07-18 |
US20180272625A1 (en) | 2018-09-27 |
EP3378887B1 (en) | 2024-05-08 |
EP3378887A4 (en) | 2019-07-03 |
EP3378887A1 (en) | 2018-09-26 |
CN108350195A (zh) | 2018-07-31 |
JPWO2017086231A1 (ja) | 2018-08-30 |
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