WO2014119234A1 - ウレタン(メタ)アクリレート化合物 - Google Patents
ウレタン(メタ)アクリレート化合物 Download PDFInfo
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- WO2014119234A1 WO2014119234A1 PCT/JP2014/000160 JP2014000160W WO2014119234A1 WO 2014119234 A1 WO2014119234 A1 WO 2014119234A1 JP 2014000160 W JP2014000160 W JP 2014000160W WO 2014119234 A1 WO2014119234 A1 WO 2014119234A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
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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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08J2375/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/04—Crosslinking with phenolic resin
Definitions
- the present invention relates to a urethane (meth) acrylate compound and a urethane (meth) acrylate resin using the compound.
- Carbon fiber reinforced plastic is lightweight and has high strength, so it is used in many fields such as aircraft and automobile parts, concrete reinforcement, and sports equipment. Particularly in recent years, the demand for weight reduction in aircraft and automobile parts has increased due to energy problems, and the use ratio of carbon fiber reinforced plastic has increased.
- These carbon fiber reinforced plastics are manufactured by laminating sheets pre-impregnated with epoxy resin, bagging and molding by applying temperature and pressure in an autoclave, press molding using a prepreg sheet, and impregnating a temperature-controlled resin.
- Examples include FW (filament winding) molding that forms while winding. 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.
- RTM Resin Transfer Molding
- VaRTM Vaum Assisted Resin Transfer Molding
- Urethane (meth) acrylate is conventionally known to be excellent in adhesion to carbon fibers, and is used as a sizing agent for carbon fibers (for example, Patent Document 1).
- the problem to be solved by the present invention is that carbon fiber reinforced plastic having good workability and excellent mechanical properties is formed by HUP (hand lay-up) molding, RTM (Resin Transfer Molding) molding, VaRTM (Vacuum Assisted Resin Transfer Molding). ) To provide a thermosetting resin that can be produced by molding.
- a urethane (meth) acrylate resin having an isocyanate group and an ethylenically unsaturated group provides a carbon fiber reinforced plastic having excellent workability and excellent mechanical properties as a carbon fiber matrix. I found out.
- the urethane (meth) acrylate compound (A) of the present invention has the general formula [Chemical Formula 1]: (Wherein, X is a compound residue having two or more isocyanate groups, and M is the formula [Chemical Formula 2]: At least, except for the above [Chemical Formula 2], the formula [Chemical Formula 3]: And Q represents an ethylenically unsaturated group-containing monoalcohol compound residue. n is 2 to 7. ).
- the urethane (meth) acrylate compound (A) of the present invention has the general formula [Chemical Formula 4]: (Wherein, 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 the formula [Chemical Formula 5]: Except for the above [Chemical Formula 5], the formula [Chemical Formula 6]: And Q represents an ethylenically unsaturated group-containing monoalcohol compound residue. n is 1 to 5000. ).
- the urethane (meth) acrylate (A) compound of the present invention reacts a compound having two or more isocyanate groups with an ethylenically unsaturated group-containing monoalcohol compound, or a compound having two or more isocyanate groups.
- the isocyanate group in the urethane (meth) acrylate (A) is 0.1 to 12% by weight.
- the alcohol compound having two or more hydroxyl groups is 1,3-propanediol, 1,4-butanediol, 1,5- It is one or more selected from pentanediol and 1,6-hexanediol.
- the alcohol compound having two or more hydroxyl groups is a polyester polyol obtained by polycondensation of dicarboxylic acid or an ester-forming derivative thereof and glycol. It is characterized by being.
- the alcohol compound having two or more hydroxyl groups is one or more selected from terephthalic acid, isophthalic acid, and ester-forming derivatives thereof.
- a polyester polyol obtained by polycondensation of 1,3-propanediol, 1,4-propanediol, 1,5-pentanediol and 1,6-hexanediol .
- the compound having two or more isocyanate groups is 1,6-hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl). It is characterized by being at least one selected from cyclohexane, isophorone diisocyanate, multimers thereof, and polymethylene polyphenyl polyisocyanate.
- the urethane (meth) acrylate resin (B) of the present invention is characterized by comprising the urethane (meth) acrylate (A) compound of the present invention and a polymerizable monomer.
- the isocyanate group in the urethane (meth) acrylate resin (B) is 0.1 to 8% by weight.
- the resin composition for carbon fiber reinforced plastic of the present invention is 0.1 to 8 wt% in which the urethane (meth) acrylate (A) compound of the present invention is blended with a thermosetting resin having an ethylenically unsaturated group. % Isocyanate group.
- thermosetting resin used for a carbon fiber reinforced plastic that is lightweight and high in strength.
- carbon fiber reinforced plastic having excellent workability and mechanical properties (bending strength, compressive strength, interlaminar shear strength) can be obtained, and therefore carbon fiber reinforced plastic can be applied to various fields. There is an advantageous effect of being able to.
- FIG. 1 is an IR spectrum of a urethane (meth) acrylate compound (A) having an isocyanate group and an ethylenically unsaturated group in one embodiment of the present invention (having a basic structure of [Chemical Formula 1]) 2250 cm ⁇ 1. Absorption of isocyanate groups can be confirmed in the vicinity.
- FIG. 2 is an IR spectrum of a urethane (meth) acrylate compound (A) having an isocyanate group and an ethylenically unsaturated group in one embodiment of the present invention (having a basic structure of [Chemical Formula 4]) 2250 cm ⁇ 1. Absorption of isocyanate groups can be confirmed in the vicinity.
- FIG. 1 is an IR spectrum of a urethane (meth) acrylate compound (A) having an isocyanate group and an ethylenically unsaturated group in one embodiment of the present invention (having a basic structure of [Chemical Formula 4]) 2
- FIG. 3 is an IR spectrum of a urethane (meth) acrylate compound (A) having an isocyanate group and an ethylenically unsaturated group in one embodiment of the present invention (in Synthesis Example 10 in the examples described later (two or more).
- the compound having the isocyanate group is polymethylene polyphenyl polyisocyanate.)
- urethane (meth) acrylate refers to urethane methacrylate and urethane acrylate
- (meth) acrylic acid ester refers to methacrylic acid ester and acrylic acid ester
- the urethane (meth) acrylate compound (A) of the present invention has the general formula [Chemical Formula 7]:
- n 2 to 7.
- the urethane (meth) acrylate compound (A) of the present invention has the general formula [Chemical Formula 10]:
- n 1 to 5000.
- a compound having two or more isocyanate groups and an ethylenically unsaturated group-containing monoalcohol compound are reacted, or a compound having two or more isocyanate groups and an ethylenically unsaturated group-containing monoalcohol compound and two or more Urethane (meth) acrylate (A) having an isocyanate group and an ethylenically unsaturated group obtained by reacting an alcohol compound having a hydroxyl group, and a urethane (meth) acrylate compound (A) having an isocyanate group and an ethylenically unsaturated group, and
- the urethane (meth) acrylate resin (B) made of a polymerizable monomer will be described.
- Urethane (meth) acrylate (A) having an isocyanate group and an ethylenically unsaturated group is a compound having two or more isocyanate groups and an ethylenically unsaturated group-containing monoalcohol compound, or a compound having two or more isocyanate groups. And an ethylenically unsaturated group-containing monoalcohol compound and an alcohol compound having two or more hydroxyl groups.
- it is made to react so that the isocyanate group mole number of an isocyanate compound may become larger than the total hydroxyl group mole number of the alcohol compound which has an ethylenically unsaturated group containing monoalcohol compound and two or more hydroxyl groups.
- the reaction is preferably continued until the amount of remaining isocyanate groups is constant, in other words until the hydroxyl groups are almost consumed.
- the resulting urethane (meth) acrylate (A) preferably has from 0.1% to 12% by weight of isocyanate groups. More preferably, it has from 0.3% to 12% by weight of isocyanate groups. If the isocyanate group is less than 0.1% by weight, the adhesion to the carbon fiber is inferior, and there is a possibility that sufficient compressive strength and interlaminar shear strength may not be obtained. There is a risk that the balance of mechanical properties will be lost.
- isocyanate compound having two or more isocyanate groups used in the present invention examples include 1,3-xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenyl diisocyanate, Aromatic isocyanate compounds such as 1,5-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 Alicyclic isocyanate compounds such as sun diisocyanate, ali
- isocyanate compounds from the viewpoint of heat resistance and light resistance, 1,6-hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, and multimers thereof, polymethylene polyisocyanate Phenyl polyisocyanate is particularly preferred.
- alcohol compounds having two or more hydroxyl groups include aliphatic alcohols, etherified diphenols, and polyester polyols.
- Examples of the aliphatic alcohol 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-hept
- Examples of the alicyclic alcohol include hydrogenated bisphenol A, tricyclodecane dimethanol, and spiroglycol.
- Examples of the aliphatic alcohol compounds 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are preferable from the viewpoint of resin viscosity and the 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 preferably ethylene oxide or propylene oxide, and the average added mole number of the alkylene oxide is 2 to 16 moles relative to 1 mole of bisphenol A.
- polyester polyols include those obtained by polycondensation of unsaturated acids and / or saturated acids with the above-mentioned aliphatic alcohols and etherified diphenols.
- unsaturated acids 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, Such as alkyl succinic acid, alkenyl succinic acid, itaconic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid and their acid anhydrides, lower alkyl esters, acid halides etc. Examples include ester-forming derivatives. Particularly preferred dicarboxylic acids include terephthalic acid and isophthalic acid.
- terephthalic acid and isophthalic acid lower alkyl esters thereof may be used.
- examples include dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, and dibutyl isophthalate. From the viewpoint of (handling), dimethyl terephthalate and dimethyl isophthalate are preferable.
- These unsaturated acids and saturated acids can be used alone or in combination of two or more.
- the alcohol compound having two or more hydroxyl groups is a polyester polyol obtained by polycondensation of dicarboxylic acid or an ester-forming derivative thereof and glycol. It is.
- the polyester polyol includes one or more selected from terephthalic acid, isophthalic acid, and ester-forming derivatives thereof, and 1,3-propanediol, 1,4-propanediol, from the viewpoint of resin viscosity and mechanical properties of the cured product. Polyester polyols obtained by one or more polycondensations selected from 1,5-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, pentaerythritol, and the like. 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 ( (Meth) 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.
- hydroxyl group-containing (meth) acrylic acid ester such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth
- 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.
- the urethane (meth) acrylate (A) of the present invention is a compound having two or more isocyanate groups and an alcohol compound having an ethylenically unsaturated group, or a compound having two or more isocyanate groups and an alcohol having two or more hydroxyl groups.
- the compound can be obtained by reacting an ethylenically unsaturated group-containing monoalcohol compound, but the reaction temperature is preferably 40 to 140 ° C., more preferably 70 to 110 ° C.
- the end point of the reaction can be confirmed by quantifying the isocyanate group by titration or by following the absorption of the isocyanate group (near 2250 cm @ -1) in an infrared absorption spectrum (hereinafter abbreviated as IR).
- catalysts and polymerization inhibitors can be used.
- an acidic catalyst and a basic catalyst can be used for the catalyst, tin compounds such as dibutyltin dilaurate and dibutyltin diacetate are preferable.
- the amount of catalyst added is preferably 100 to 2000 ppm based on the charged weight.
- the polymerization inhibitor for example, a polyhydric phenol polymerization inhibitor such as hydroquinone, parabenzoquinone, methylhydroquinone, and trimethylhydroquinone can be used.
- the addition amount of the polymerization inhibitor is preferably 100 to 2000 ppm with respect to the charged weight.
- the ethylenically unsaturated group equivalent of the urethane (meth) acrylate (A) of the present invention is not particularly limited.
- the balance of (strength) becomes worse, and the heat resistance of the molded product may be lowered. However, this is not the case when blended with other thermosetting resins described later and blended so that the isocyanate groups in the blended resin are 0.1 to 7% by weight.
- the urethane (meth) acrylate resin (B) of the present invention is characterized by comprising the urethane (meth) acrylate (A) compound of the present invention and a polymerizable monomer.
- a urethane (meth) acrylate resin (B) comprising a urethane (meth) acrylate compound (A) having an isocyanate group and an ethylenically unsaturated group and a polymerizable monomer will be described.
- the polymerizable monomer used in the present invention is preferably a compound that does not react with an isocyanate group at room temperature.
- a polymerizable monomer that reacts with an isocyanate group is blended, there is a possibility that the viscosity increases due to a reaction during storage, resulting in poor workability and insufficient mechanical properties.
- examples thereof include vinyl monomers, monofunctional acrylic acid esters, and polyfunctional acrylic acid esters.
- styrene vinyl toluene, ⁇ -methyl styrene, vinyl acetate as a vinyl monomer, and methyl methacrylate
- benzyl (meth) acrylate n-butyl (meth) acrylate, i-butyl (meth) as a monofunctional acrylate ester Acrylate
- t-butyl (meth) acrylate 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate
- the polymerization is performed so that the isocyanate group weight% in the urethane (meth) acrylate resin (B) exceeds 0 and is 8% by weight, preferably 0.1 to 8% by weight.
- 100 parts by weight of urethane (meth) acrylate (A) can be dissolved in 20 to 200 parts by weight of the polymerizable monomer.
- 100 parts by weight of urethane (meth) acrylate (A) is dissolved in 40 to 150 parts by weight of the polymerizable monomer.
- the amount of the polymerizable monomer with respect to 100 parts by weight of the urethane (meth) acrylate (A) is less than 40 parts, the viscosity becomes extremely high and the moldability may be inferior.
- the amount of the polymerizable monomer with respect to 100 parts by weight of the urethane (meth) acrylate (A) exceeds 150 parts, the performance of the resulting cured molded product may be deteriorated.
- the isocyanate group in the urethane (meth) acrylate resin (B) is less than 0.1% by weight, the adhesion to the carbon fiber is poor, and sufficient compression strength and interlayer shear strength may not be obtained. If it exceeds 50%, the bending strength and tensile strength are lowered, and the balance of mechanical properties may be lost.
- the viscosity of the urethane (meth) acrylate resin (B) is 30 to 700 mPa ⁇ s ( 25 ° C.). If it is less than 30 mPa ⁇ s, there is a possibility that the resin will be removed when impregnating the carbon fiber, and if it exceeds 700 mPa ⁇ s, there is a possibility that an unimpregnated part may remain. However, this is not the case when the resin viscosity is intentionally lowered or increased using temperature control equipment.
- urethane (meth) acrylate (A) and the urethane (meth) acrylate resin (B) of the present invention a known method similar to a conventional radical polymerization resin can be applied. Examples include curing with an organic peroxide, curing with an ultraviolet initiator, and curing with an electron beam. In addition, 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 and dialkyl peroxides such as dicumyl peroxide.
- the addition amount of the curing agent is 0.05 to 5 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate (A) and the urethane (meth) acrylate resin (B) resin.
- 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 is 0.1 to 5 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin.
- the curing accelerator examples include metal soaps such as cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, and barium naphthenate, metals such as vanadium acetyl acetate, cobalt acetyl acetate, and iron acetylacetonate.
- Chelates, tertiary amines such as N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, pyridine, phenylmorpholine Etc.
- the addition amount of the curing accelerator is 0.05 to 5 parts by weight.
- the resin composition for carbon fiber reinforced plastic of the present invention is 0.1 to 8 wt% in which the urethane (meth) acrylate (A) compound of the present invention is blended with a thermosetting resin having an ethylenically unsaturated group. % Isocyanate group.
- the urethane (meth) acrylate (A) and the urethane (meth) acrylate resin (B) of the present invention can be used by blending with other thermosetting resins having an ethylenically unsaturated group.
- the thermosetting resin is, for example, an unsaturated polyester resin, an epoxy (meth) acrylate resin, or a urethane (meth) acrylate resin, and any of the isocyanate groups in the blend resin is 0.1 to 8% by weight. It is preferable from the viewpoint of adhesion with carbon fibers.
- mixing immediately before molding is desirable from the viewpoint of storage stability.
- the resin composition for carbon fiber reinforced plastics of the present invention can also be applied to reinforced plastics with reinforcing fibers other than carbon fibers.
- reinforcing fibers other than carbon fibers include, but are not limited to, glass fibers, aramid fibers, xylon fibers, vinylon fibers, polyethylene fibers, boron fibers, basalt fibers, and cellulose.
- 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.
- Synthesis example 1 A reaction vessel equipped with a gas introduction tube, a stirrer, a cooling tube, and a thermometer was charged with 404 parts of isophorone diisocyanate (Evonik) and 0.13 part of dibutyltin dilaurate. , 76 parts of 3-propanediol (manufactured by DuPont), 169 parts of 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Gas Chemical) and 0.32 parts of monomethyl ether hydroquinone were added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant.
- isophorone diisocyanate Evonik
- 2-hydroxyethyl methacrylate manufactured by Mitsubishi Gas Chemical
- the reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 2.10% by weight and the ethylenically unsaturated group equivalent was 500 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.37% by weight of isocyanate groups (a-1).
- Synthesis example 2 In the same apparatus as in Synthesis Example 1, 394 parts of isophorone diisocyanate and 0.13 part of dibutyltin dilaurate were charged. While stirring and heating with blowing air, 86 parts and 2 parts of 1,4-butanediol (Mitsubishi Chemical Corporation) were added. -A mixed solution of 169 parts of hydroxyethyl methacrylate and 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 2.11 wt%, and the ethylenically unsaturated group equivalent was 500 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.37% by weight of isocyanate groups (a-2).
- Synthesis example 3 687 parts of dimethyl terephthalate and 539 parts of 1,3-propanediol were charged into a stainless steel reaction vessel equipped with a stirrer, a heating device, a thermometer, a fractionation device, and a nitrogen gas introduction tube, and stirred under a nitrogen atmosphere for 200 Transesterification was carried out at 5 ° C. for 5 hours to obtain a polyester polyol (P-1) having a hydroxyl group equivalent of 138 g / eq.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 2.09% by weight, and the ethylenically unsaturated group equivalent was 500 g / eq. Thereafter, it was diluted with 133 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.36% by weight of an isocyanate group (a-3).
- Synthesis example 4 In the same apparatus as in Synthesis Example 1, 206 parts of hexamethylene diisocyanate and 0.13 part of dibutyltin dilaurate were charged, and tetrabromobisphenol A (2-hydroxyethyl ether) (Meisei Chemical Co., Ltd.) was heated with stirring and blowing air. 417 parts, 96 parts of 2-hydroxyethyl methacrylate, 0.32 parts of monomethyl ether hydroquinone, and 240 parts of styrene monomer were added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant.
- the reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate was 2.31% by weight, and the ethylenically unsaturated group equivalent was 977 g / eq. Thereafter, it was diluted with 40 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.66% by weight of isocyanate groups (a-4).
- Synthesis example 5 In the same apparatus as in Synthesis Example 1, 396 parts of isophorone diisocyanate and 0.13 part of dibutyltin dilaurate were charged. While stirring and heating with blowing air, 85 parts of 1,3-propanediol and 169 parts of 2-hydroxyethyl methacrylate And a mixed solution of 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 0.21 wt%, and the ethylenically unsaturated group equivalent was 500 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 0.14% by weight of an isocyanate group (a-5).
- Synthesis Example 6 In the same apparatus as in Synthesis Example 1, 425 parts of isophorone diisocyanate and 0.13 part of dibutyltin dilaurate were charged, and while stirring and heating with blowing air, 55 parts of 1,3-propanediol and 169 parts of 2-hydroxyethyl methacrylate And a mixed solution of 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 6.85% by weight, and the ethylenically unsaturated group equivalent was 500 g / eq. Thereafter, it was diluted with 350 parts of styrene monomer to obtain a urethane (meth) acrylate resin containing 4.45% by weight of isocyanate groups (a-6).
- Synthesis example 7 In the same apparatus as in Synthesis Example 1, 445 parts of isophorone diisocyanate and 0.13 part of dibutyltin dilaurate were charged, and 35 parts of 1,3-propanediol and 169 parts of 2-hydroxyethyl methacrylate were stirred and heated while blowing air. And a mixed solution of 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 11.59% by weight, and the ethylenically unsaturated group equivalent was 500 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 7.53% by weight of an isocyanate group (a-7).
- Synthesis example 8 In the same apparatus as in Synthesis Example 1, 333 parts of 1,3-bis (isocyanatomethyl) cyclohexane (manufactured by Takeda Pharmaceutical Co., Ltd.) and 0.13 part of dibutyltin dilaurate were charged, and while stirring and heating while blowing air, , A mixture of 37 parts of 3-propanediol, 279 parts of 2-hydroxyethyl methacrylate and 0.32 parts of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 2.06 wt%, and the ethylenically unsaturated group equivalent was 300 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.34% by weight of an isocyanate group (a-8).
- Synthesis Example 9 In the same apparatus as in Synthesis Example 1, 411 parts of 2,5-bis (isocyanatomethyl) bicyclo [2.2.1] heptane (manufactured by Takeda Pharmaceutical Co., Ltd.) and 0.13 part of dibutyltin dilaurate were charged and stirred under air. A mixture of 127 parts of 1,4-butanediol, 112 parts of 2-hydroxyethyl methacrylate and 0.32 parts of monomethyl ether hydroquinone was added dropwise over 40 minutes while heating while blowing. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant.
- the reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 1.94% by weight and the ethylenically unsaturated group equivalent was 758 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.26% by weight of isocyanate groups (a-9).
- Synthesis Example 10 356 parts of polymethylene polyphenyl polyisocyanate (manufactured by Nippon Polyurethane Co., Ltd.) and 0.13 part of dibutyltin dilaurate were charged into the same apparatus as in Synthesis Example 1, and 2-hydroxyethyl methacrylate 293 was heated with stirring and blowing air. And a mixed solution of 0.32 part of monomethyl ether hydroquinone were added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 1.98 wt%, and the ethylenically unsaturated group equivalent was 288 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.29% by weight of an isocyanate group (a-10).
- Synthesis Example 11 In the same apparatus as in Synthesis Example 1, 309 parts of isophorone diisocyanate and 0.13 part of dibutyltin dilaurate were charged. While stirring and heating with blowing air, 294 parts of polyester polyol (P-1) and 2-hydroxyethyl methacrylate 47 A mixture of 217 parts of styrene monomer and 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 1.90% by weight, and the ethylenically unsaturated group equivalent was 1804 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.24% by weight of an isocyanate group (a-11).
- Synthesis Example 12 In the same apparatus as in Synthesis Example 1, 393 parts of isophorone diisocyanate and 0.13 part of dibutyltin dilaurate were charged. While stirring and heating with blowing air, 87 parts of 1,3-propanediol and 169 parts of 2-hydroxyethyl methacrylate And a mixed solution of 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was monitored by IR, and the point where the isocyanate group absorption (near 2250 cm @ -1) disappeared was regarded as the end point. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 0.00 wt%, and the ethylenically unsaturated group equivalent was 500 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing no isocyanate group (a-12).
- Synthesis Example 13 In the same apparatus as in Synthesis Example 1, 395 parts of isophorone diisocyanate and 0.13 part of dibutyltin dilaurate were charged. While stirring and heating with blowing air, 85 parts of 1,3-propanediol and 169 parts of 2-hydroxyethyl methacrylate And a mixed solution of 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 0.10 wt%, and the ethylenically unsaturated group equivalent was 500 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 0.07% by weight of an isocyanate group (a-13).
- Synthesis Example 14 In the same apparatus as in Synthesis Example 1, 503 parts of hexamethylene diisocyanate and 0.13 part of dibutyltin dilaurate were charged. While stirring and heating with blowing air, 347 parts of 2-hydroxyethyl acrylate and 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 14.77% by weight, and the ethylenically unsaturated group equivalent was 284 g / eq. Thereafter, it was diluted with 150 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 12.55% by weight of an isocyanate group (a-14).
- Synthesis Example 15 In the same apparatus as in Synthesis Example 1, 454 parts of a bisphenol A type epoxy compound (JER “# 1004”), 85 parts of methacrylic acid, 1.65 parts of 2-methylimidazole, and 0.3 part of monomethyl ether hydroquinone were charged. While blowing, the mixture was heated with stirring to maintain the temperature at 110 to 120 ° C. and reacted for 10 hours. Thereafter, it was diluted with 460 parts of a styrene monomer to obtain an epoxy acrylate resin having an ethylenically unsaturated group equivalent of 549 g / eq (a-15).
- JER “# 1004” bisphenol A type epoxy compound
- Synthesis Example 16 A stainless steel reaction vessel equipped with a stirrer, a heating device, a thermometer, a fractionator, and a nitrogen gas introduction tube was charged with 360 parts of phthalic anhydride, 282 parts of fumaric acid, 90 parts of ethylene glycol, and 399 parts of propylene glycol, and a nitrogen atmosphere Under stirring, the polycondensation reaction was carried out at 210 ° C. for 11 hours. Thereafter, the resultant was diluted with 430 parts of a styrene monomer, and an unsaturated polyester resin (a-16) having an ethylenically unsaturated group equivalent of 411 g / eq.
- a-16 unsaturated polyester resin having an ethylenically unsaturated group equivalent of 411 g / eq.
- Synthesis Example 17 In the same apparatus as in Synthesis Example 1, 397 parts of isophorone diisocyanate and 0.13 part of dibutyltin dilaurate were charged, and while stirring and heating with blowing air, 84 parts of 1,3-propanediol and 169 parts of 2-hydroxyethyl methacrylate And a mixed solution of 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 0.41% by weight, and the ethylenically unsaturated group equivalent was 500 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 0.26% by weight of isocyanate groups (a-17).
- Synthesis Example 18 In the same apparatus as in Synthesis Example 1, 377 parts of isophorone diisocyanate and 0.13 part of dibutyltin dilaurate were charged, and while stirring and heating with blowing air, 105 parts of 1,6-hexanediol (manufactured by Ube Industries) and 2 A mixed solution of 167 parts of hydroxyethyl methacrylate and 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction. The reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 2.08 wt%, and the ethylenically unsaturated group equivalent was 505 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.35% by weight of an isocyanate group (a-18).
- Synthesis Example 19 After charging 358 parts of isophorone diisocyanate trimer (VESTANT T 1890 manufactured by Evonik Co., Ltd.) and 0.13 part of dibutyltin dilaurate in the same apparatus as in Synthesis Example 1, the mixture was dissolved while heating and blowing air under stirring. A mixed solution of 106 parts of 2-hydroxyethyl methacrylate, 186 parts of pentaerythritol triacrylate (Aronix M-305 manufactured by Toagosei Co., Ltd.) and 0.32 part of monomethyl ether hydroquinone was added dropwise over 40 minutes. The temperature was kept at 85 to 95 ° C. for reaction.
- the reaction was followed by IR, and the end point was when the isocyanate group absorption (around 2250 cm @ -1) became constant. The reaction took 3 hours.
- the isocyanate group content of the urethane (meth) acrylate before dilution with the polymerizable monomer was 2.01% by weight, and the ethylenically unsaturated group equivalent was 234 g / eq. Thereafter, it was diluted with 350 parts of a styrene monomer to obtain a urethane (meth) acrylate resin containing 1.31% by weight of an isocyanate group (a-19).
- Synthesis Example 20 In the same apparatus as in Synthesis Example 1, 405 parts of a phenol novolac type epoxy compound (“N-740” manufactured by DIC), 195 parts of methacrylic acid, 1.65 parts of 2-methylimidazole, and 0.3 part of monomethyl ether hydroquinone were charged. While blowing air, the mixture was heated with stirring to maintain the temperature at 110 to 120 ° C. and reacted for 10 hours. Thereafter, the resultant was diluted with 400 parts of a styrene monomer to obtain an epoxy acrylate resin having an ethylenically unsaturated group equivalent of 264 g / eq (a-20).
- Example 1 to 13 Reference Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Tables 1 to 3. Methyl methacrylate was used for viscosity adjustment. The following evaluation results are shown in Tables 4-6.
- Reference Example 4 is urethane methacrylate (Iupica 8921 manufactured by Nippon Iupica Co., Ltd.) using polyester polyol as an alcohol compound.
- Examples 14 to 16 and Comparative Example 5 are shown in Tables 7 and 8. The following evaluation results are shown in Tables 10 and 11. Comparative Example 5 is for Example 16.
- Lamination structure 25 cm ⁇ 25 cm ⁇ 8 sheets, thickness 2 mm, carbon fiber content 40 Vf (volume)%.
- Curing conditions normal temperature curing (23 ° C.) ⁇ 6 hours, 80 ° C. ⁇ 2 hours, 100 ° C. ⁇ 2 hours
- JIS K 7018 the compressive strength
- JIS K 7078 interlaminar shear strength
- JIS K 7074 bending strength
- JIS K 7113 tensile strength
- the cast product of each resin was produced by the same curing method as that for producing the laminated plate, and the heat distortion temperature (JIS K 6911) was measured according to JIS.
- Carbon fiber reinforced plastics using the resins of Examples 1 to 16 in which the urethane (meth) acrylate compound (A) having an isocyanate group and an ethylenically unsaturated group according to the present invention shown in Tables 1, 2 and 7 is blended are as follows: The results showed excellent workability and mechanical properties. Particularly good results were obtained in terms of compressive strength and interlaminar shear strength. Moreover, Example 3, Example 8, Example 10, and Example 16 showed the favorable result also in heat resistance. On the other hand, in Comparative Examples 1 to 5, sufficient compressive strength and interlayer shear strength could not be obtained.
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Abstract
Description
本発明の炭素繊維強化プラスチック用樹脂組成物は炭素繊維以外の強化繊維との強化プラスチックにも適用できる。炭素繊維以外の強化繊維として、ガラス繊維、アラミド繊維、ザイロン繊維、ビニロン繊維、ポリエチレン繊維、ボロン繊維、バサルト繊維、セルロース等をあげることができるが、これらには限定されない。
ガス導入管、攪拌装置、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)404部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,3-プロパンジオール(デュポン社製)76部と2-ヒドロキシエチルメタクリレート(三菱ガス化学社製)169部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、2.10重量%、エチレン性不飽和基当量500g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を1.37重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-1)。
合成例1と同様の装置にイソホロンジイソシアネート394部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,4-ブタンジオール(三菱化学社製)86部と2-ヒドロキシエチルメタクリレート169部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、2.11重量%、エチレン性不飽和基当量500g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を1.37重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-2)。
撹拌装置、加熱装置、温度計、分留装置、窒素ガス導入管を備えたステンレス製反応容器にテレフタル酸ジメチル687部、1,3-プロパンジオール539部を仕込み、窒素雰囲気下、撹拌しながら200℃で5時間エステル交換反応させ、水酸基当量138g/eqのポリエステルポリオール(P-1)を得た。次いで合成例1と同様の装置にイソホロンジイソシアネート314部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、ポリエステルポリオール(P-1)166部と2-ヒドロキシエチルメタクリレート169部とスチレンモノマー217部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、2.09重量%、エチレン性不飽和基当量500g/eqであった。その後、スチレンモノマー133部で希釈し、イソシアネート基を1.36重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-3)。
合成例1と同様の装置に、ヘキサメチレンジイソシアネート206部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、テトラブロモビスフェノールA(2-ヒドロキシエチルエーテル)(明成化学社製)417部と2-ヒドロキシエチルメタクリレート96部とモノメチルエーテルハイドロキノン0.32部とスチレンモノマー240部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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、2.31重量%、エチレン性不飽和基当量977g/eqであった。その後、スチレンモノマー40部で希釈し、イソシアネート基を1.66重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-4)。
合成例1と同様の装置にイソホロンジイソシアネート396部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,3-プロパンジオール85部と2-ヒドロキシエチルメタクリレート169部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、0.21重量%、エチレン性不飽和基当量500g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を0.14重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-5)。
合成例1と同様の装置にイソホロンジイソシアネート425部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,3-プロパンジオール55部と2-ヒドロキシエチルメタクリレート169部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、6.85重量%、エチレン性不飽和基当量500g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を4.45重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-6)。
合成例1と同様の装置にイソホロンジイソシアネート445部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,3-プロパンジオール35部と2-ヒドロキシエチルメタクリレート169部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、11.59重量%、エチレン性不飽和基当量500g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を7.53重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-7)。
合成例1と同様の装置に1,3-ビス(イソシアナトメチル)シクロヘキサン(武田薬品社製)333部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,3-プロパンジオール37部と2-ヒドロキシエチルメタクリレート279部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、2.06重量%、エチレン性不飽和基当量300g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を1.34重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-8)。
合成例1と同様の装置に2,5-ビス(イソシアナトメチル)ビシクロ[2.2.1]ヘプタン(武田薬品社製)411部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,4-ブタンジオール127部と2-ヒドロキシエチルメタクリレート112部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、1.94重量%、エチレン性不飽和基当量758g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を1.26重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-9)。
合成例1と同様の装置にポリメチレンポリフェニルポリイソシアネート(日本ポリウレタン社製)356部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、2-ヒドロキシエチルメタクリレート293部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、1.98重量%、エチレン性不飽和基当量288g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を1.29重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-10)。
合成例1と同様の装置にイソホロンジイソシアネート309部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、ポリエステルポリオール(P-1)294部と2-ヒドロキシエチルメタクリレート47部とスチレンモノマー217部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、1.90重量%、エチレン性不飽和基当量1804g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を1.24重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-11)。
合成例1と同様の装置にイソホロンジイソシアネート393部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,3-プロパンジオール87部と2-ヒドロキシエチルメタクリレート169部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-1付近)が無くなったところを終点とした。反応には3時間を要した。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、0.00重量%、エチレン性不飽和基当量500g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を含有しないウレタン(メタ)アクリレート樹脂を得た(a-12)。
合成例1と同様の装置にイソホロンジイソシアネート395部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,3-プロパンジオール85部と2-ヒドロキシエチルメタクリレート169部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、0.10重量%、エチレン性不飽和基当量500g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を0.07重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-13)。
合成例1と同様の装置にヘキサメチレンジイソシアネート503部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、2-ヒドロキシエチルアクリレート347部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、14.77重量%、エチレン性不飽和基当量284g/eqであった。その後、スチレンモノマー150部で希釈し、イソシアネート基を12.55重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-14)。
合成例1と同様の装置に、ビスフェノールA型エポキシ化合物(JER「#1004」)454部、メタクリル酸85部、2-メチルイミダゾール1.65部、モノメチルエーテルハイドロキノン0.3部を仕込み、空気を吹き込みながら、攪拌下、加熱して温度を110~120℃に保持し10時間反応させた。その後、スチレンモノマー460部で希釈し、エチレン性不飽和基当量549g/eqのエポキシアクリレート樹脂を得た(a-15)。
撹拌装置、加熱装置、温度計、分留装置、窒素ガス導入管を備えたステンレス製反応容器に無水フタル酸360部、フマル酸282部、エチレングリコール90部、プロピレングリコール399部を仕込み、窒素雰囲気下、撹拌しながら210℃で11時間、重縮合反応させた。の後、スチレンモノマー430部で希釈し、エチレン性不飽和基当量411g/eqの不飽和ポリエステル樹脂(a-16)。
合成例1と同様の装置にイソホロンジイソシアネート397部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,3-プロパンジオール84部と2-ヒドロキシエチルメタクリレート169部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、0.41重量%、エチレン性不飽和基当量500g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を0.26重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-17)。
合成例1と同様の装置にイソホロンジイソシアネート377部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら、1,6-ヘキサンジオール(宇部興産社製)105部と2-ヒドロキシエチルメタクリレート167部とモノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(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350部で希釈し、イソシアネート基を1.35重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-18)。
合成例1と同様の装置にイソホロンジイソシアネートの3量体(エボニック社製VESTANT T 1890)358部とジブチル錫ジラウレート0.13部を仕込み、撹拌下、空気を吹き込みつつ加熱しながら溶解させたのち、2-ヒドロキシエチルメタクリレート106部とペンタエリスリトールトリアクリレート(東亜合成社製アロニックスM-305)186部、モノメチルエーテルハイドロキノン0.32部の混合液を40分かけて滴下した。温度を85~95℃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(2250cm-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。重合性単量体による希釈前のウレタン(メタ)アクリレートのイソシアネート基含有量は、2.01重量%、エチレン性不飽和基当量234g/eqであった。その後、スチレンモノマー350部で希釈し、イソシアネート基を1.31重量%含有するウレタン(メタ)アクリレート樹脂を得た(a-19)。
合成例1と同様の装置に、フェノールノボラック型エポキシ化合物(DIC製「N-740」)405部、メタクリル酸195部、2-メチルイミダゾール1.65部、モノメチルエーテルハイドロキノン0.3部を仕込み、空気を吹き込みながら、攪拌下、加熱して温度を110~120℃に保持し10時間反応させた。その後、スチレンモノマー400部で希釈し、エチレン性不飽和基当量264g/eqのエポキシアクリレート樹脂を得た(a-20)。
実施例14~16、比較例5を表7、8に示す。下記評価結果を表10、11に示す。比較例5は、実施例16に対するものである。
実施例1~13、参照例1~4及び比較例1~3の各樹脂150部に促進剤として6%ナフテン酸コバルト0.5部を加え攪拌した後に、硬化剤メチルエチルケトンパーオキサイド1.0部を配合し、炭素繊維の平織りクロス(東レ(株)製 商品名『T-6343』)に含浸させ、ハンドレイアップ成形にて成形した。比較例4では、ビスフェノールF型エポキシ樹脂(三菱化学製JER807)100部に脂肪族ポリアミン(三菱化学製JERキュアST11)53部を加えたものを含浸させ、積層板を成形した。
ハンドレイアップ成形の積層開始から終了までの時間を計測し、作業性の指標とした。◎:~15分 ○:15~20分 △:25~30分 ×:30分~
各積層板について、圧縮強さ(JIS K 7018)、層間せん断強さ(JIS K 7078)、曲げ強さ(JIS K 7074)、引張り強さ(JIS K 7113)を各JISに準拠し測定した。
各樹脂の注型物を積層板作製時と同様の硬化方法で作製し、熱変形温度(JIS K 6911)をJISに準拠し測定した。
20cm×2mmの断面をマイクロスコープ(200倍)で観察し、下記基準で評価した。○:0~3個、△:3~9個、×:10個以上
Claims (11)
- 2個以上のイソシアネート基を有する化合物とエチレン性不飽和基含有モノアルコール化合物を反応させるか、又は2個以上のイソシアネート基を有する化合物とエチレン性不飽和基含有モノアルコール化合物及び2個以上の水酸基を有するアルコール化合物を反応させて得られるウレタン(メタ)アクリレートにあって、イソシアネート基とエチレン性不飽和基を有することを特徴とするウレタン(メタ)アクリレート(A)化合物。
- 前記ウレタン(メタ)アクリレート(A)中のイソシアネート基は、0.1~12重量%である請求項1~3項のいずれか1項に記載のウレタン(メタ)アクリレート(A)化合物。
- 前記2個以上の水酸基を有するアルコール化合物は、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオールから選ばれる1種以上である請求項1~4項のいずれか1項に記載のウレタン(メタ)アクリレート(A)化合物。
- 前記2個以上の水酸基を有するアルコール化合物は、ジカルボン酸又はそのエステル形成性誘導体とグリコールの重縮合により得られるポリエステルポリオールである請求項1~4項のいずれか1項に記載のウレタン(メタ)アクリレート(A)化合物。
- 前記2個以上の水酸基を有するアルコール化合物は、テレフタル酸、イソフタル酸、それらのエステル形成性誘導体から選ばれる1種以上と1,3-プロパンジオール、1,4-プロパンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオールから選ばれる1種以上との重縮合により得られるポリエステルポリオールである請求項1~6項のいずれか1項に記載のウレタン(メタ)アクリレート(A)化合物。
- 前記2個以上のイソシアネート基を有する化合物は、1,6-ヘキサメチ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、及びこれらの多量体、ポリメチレンポリフェニルポリイソシアネートから選ばれる1種以上である請求項1~7項のいずれか1項に記載のウレタン(メタ)アクリレート(A)化合物。
- 請求項1~8項のいずれか1項に記載のウレタン(メタ)アクリレート(A)化合物と重合性単量体から成るウレタン(メタ)アクリレート樹脂(B)。
- 請求項9記載のウレタン(メタ)アクリレート樹脂(B)中のイソシアネート基が0.1~8重量%であるウレタン(メタ)アクリレート樹脂。
- エチレン性不飽和基を有する熱硬化性樹脂に請求項1~8項のいずれか1項に記載のウレタン(メタ)アクリレート(A)化合物が配合された0.1~8重量%のイソシアネート基を有する炭素繊維強化プラスチック用樹脂組成物。
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KR101765775B1 (ko) | 2017-08-07 |
JPWO2014119234A1 (ja) | 2017-01-26 |
US20150361035A1 (en) | 2015-12-17 |
EP2952532A4 (en) | 2016-07-06 |
TWI619737B (zh) | 2018-04-01 |
US9518007B2 (en) | 2016-12-13 |
JP6282602B2 (ja) | 2018-02-21 |
KR20150108847A (ko) | 2015-09-30 |
TW201431897A (zh) | 2014-08-16 |
EP2952532A1 (en) | 2015-12-09 |
CN104955862B (zh) | 2018-01-09 |
CN104955862A (zh) | 2015-09-30 |
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