WO2003082978A1 - Composition de resine durcissant a froid, procede de durcissement de la composition de resine et produit durci de la composition de resine - Google Patents

Composition de resine durcissant a froid, procede de durcissement de la composition de resine et produit durci de la composition de resine Download PDF

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Publication number
WO2003082978A1
WO2003082978A1 PCT/JP2003/002064 JP0302064W WO03082978A1 WO 2003082978 A1 WO2003082978 A1 WO 2003082978A1 JP 0302064 W JP0302064 W JP 0302064W WO 03082978 A1 WO03082978 A1 WO 03082978A1
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Prior art keywords
meth
resin composition
acrylate
oligo
curing
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PCT/JP2003/002064
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English (en)
Inventor
Eiichiro Takiyama
Susumu Yoshimura
Shinichi Otsuka
Kenji Shimamura
Shinya Saihata
Hiroshi Uchida
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Djk Laboratories Inc.
Showa Denko K. K.
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Priority to AU2003208611A priority Critical patent/AU2003208611A1/en
Publication of WO2003082978A1 publication Critical patent/WO2003082978A1/fr

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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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C08L67/07—Unsaturated polyesters 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
    • 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

Definitions

  • the present invention relates to an ordinary temperature curable resin composition useful in various fields, a curing method of the resin composition and a cured product of the resin composition.
  • the present invention relates to a resin composition which can be used for uses such as fiber reinforced plastic (hereinafter simply referred to as "FRP"), coating materials, casting molds and linings and does not require heating or the like for curing but is curable at an ordinary temperature.
  • FRP fiber reinforced plastic
  • the present invention also relates to a curing method of the resin composition and a cured product of the resin composition.
  • radical curable resin compositions represented by an unsaturated polyester resin composition and a vinyl ester resin composition are being used for FRP products such as marine vessels, bathtubs and septic tanks.
  • the vinyl ester resin composition having excellent chemical resistance is useful for corrosion- resistant equipment and is widely used not only for FRP but also for coating materials, casting molds, linings and the like.
  • the polyester resin composition namely, a resin composition where an unsaturated polyester containing an ⁇ , ⁇ -unsaturated polybasic acid (or an acid anhydride thereof) as one component and obtained by the esterification from a desired polyhydric alcohol using an optional polybasic acid (or an acid anhydride thereof) in combination is dissolved in a diluent such as styrene
  • the unsaturated polyester as the main component usually has a molecular weight (Mn) of approximately from 1,500 to 3,000 and this is a very highly viscous liquid, or nearly a solid, at an ordinary temperature. Therefore, it is difficult to mold the unsaturated polyester alone by a molding method.
  • Mn molecular weight
  • the unsaturated polyester is diluted with from 30 to 60 mass% of styrene to reduce the viscosity and is thereby adjusted to a viscosity suitable for various molding methods.
  • Styrene is a general industrial product and advantageously, is available at a low cost with ease.
  • the resin composition containing styrene has a polymerizable functional group and shows excellent curability and therefore, can be cured at an ordinary temperature and the cured product after curing this resin composition has good physical properties. Thus, the resin composition containing styrene has very excellent points.
  • oligo(meth)acrylate In place of a polyester resin composition containing styrene, the present inventors have made extensive investigations to use an oligoacrylate and/or an oligomethacrylate (hereinafter these are simply referred to as "oligo(meth)acrylate” ) having a relatively low viscosity for its molecular weight. However low the viscosity is, some diluent is necessary for ensuring satisfactory workability and although the amount of styrene used can be reduced, this is not yet satisfied. The present inventors then investigated the use of allyl monomers represented by diallyl phthalate, as a diluent taking the place of styrene.
  • Allyl monomers generally have a low viscosity and a high boiling point and are faintly odorous and considered to have less affect on the human body due to volatilization and therefore, this is a promising diluent.
  • allyl monomers are low in the polymerizability and particularly, in comparison with styrene, the curability at an ordinary temperature is poor. Therefore, when this monomer is cured at an ordinary temperature, curing proceeds to gelling but does not reach complete curing.
  • Examples of conventional techniques for improving the curability of a radical curable resin composition containing an allyl monomer include one shown in Japanese Unexamined Patent Publication No. 3-195715 (JP-A-3- 195715).
  • This patent publication describes an ordinary temperature curing method of an allyl-based polyester resin composition comprising an unsaturated polyester and an allyl monomer and using an organic hydroperoxide as a curing agent and a vanadium compound as an accelerator or using an organic ketone peroxide as a curing agent and a vanadium compound as an accelerator and also states that an allyl-based resin composition further containing a vinyl monomer is curable at an ordinary temperature.
  • a special accelerator containing a vanadium compound is essential and it is revealed that curing is not attained by a commonly employed curing method using a combination of methyl ethyl ketone peroxide as a curing agent and cobalt naphthenate as an accelerator.
  • a vinyl monomer is essential and in all of examples, styrene, methyl methacrylate or vinyl acetate having a high volatility is used as the vinyl monomer in an amount of 7 to 10 parts by mass per 100 parts by mass of the unsaturated polyester resin composition or vinyl ester resin composition.
  • this technique does not provide an alternate of styrene.
  • JP-A-1- 254722 representative examples of conventional techniques for improving curability of a radical curable resin composition
  • This patent publication describes a technique where at the time of curing an unsaturated polyester resin composition or a vinyl ester resin composition by adding a curing agent, even if the amount added of cobalt naphthenate as a general accelerator is reduced to a level of usually not causing a curing reaction, when an aliphatic acetamide compound is added as a curing accelerator, a curing reaction takes place at an ordinary temperature and a cured product is obtained.
  • the present inventors have also found that when an unsaturated polyester is added to the resin composition and the resin composition is cured, a cured product having higher strength can be obtained, and have accomplished the present invention. More specifically, the present invention (I) provides an ordinary temperature curable resin composition comprising,
  • an oligo(meth) aerylate having one or more (meth)acryloyl groups within one molecule (2) an allyl monomer of a saturated and/or unsaturated polybasic acid, and
  • the present invention (II) provides a curing method of the resin composition of the present invention (I).
  • the present invention (III) provides a cured product of the resin composition of the present invention (I).
  • the present invention comprises, for example, the following embodiments.
  • composition according to above item 1 or 2 wherein the oligo(meth)acrylate is a polyester- (meth) aerylate.
  • a composition according to above item 1 or 2 wherein the oligo(meth)acrylate is at least one member selected from vinyl ester resin compositions which are a reaction product of a (meth) acrylic acid and an epoxy resin composition or a reaction product of a polyvalent phenol compound and an unsaturated epoxy compound.
  • composition according to above item 1 or 2 wherein the oligo(meth)acrylate is a urethane-
  • composition according to above item 1 or 2 wherein the oligo(meth)acrylate is an oligo(meth)acrylate obtained by reacting (A) a composition containing a (meth) acrylic acid, an alkylene monoepoxide and a polybasic acid anhydride in the presence of (B) an organic and/or inorganic antimony compound at a temperature of 140 to 210°C.
  • oligo(meth)acrylate is an oligo(meth)acrylate obtained by reacting (A) a composition resulting from adding a polybasic acid anhydride to an unsaturated monoalcohol-containing composition obtained by the reaction between a (meth) acrylic acid and an alkylene monoepoxide, in the presence of (B) an organic and/or inorganic antimony compound at a temperature of 140 to 210°C.
  • a composition according to any one of above items 1 to 10, wherein the ratio of (1) the oligo(meth) aerylate having one or more (meth) aeryloyl groups within one molecule to (2) the allyl monomer of a saturated and/or unsaturated polybasic acid is (1):(2) 1:9 to 9:1 in terms of weight ratio.
  • the amount of (4) the unsaturated polyester is from 5 to 500 parts by mass per 100 parts by mass as a total of (1) the oligo(meth)acrylate having one or more (meth)acryloyl groups within one molecule and (2) the allyl monomer of a saturated and/or unsaturated polybasic acid.
  • a method for curing an ordinary temperature curable resin composition comprising adding a curing agent to an ordinary temperature curable resin composition as claimed in any one of above items 1 to 13 and curing the composition at an ordinary temperature.
  • the curing agent is a composite curing agent comprising an organic peroxide and a curing accelerator.
  • the composite curing agent is at least one member selected from methyl ethyl ketone peroxide-cobalt naphthenate, benzoyl peroxide-N,N-dimethylaniline, and benzoy1 peroxide- ,N-dimethylparatoluidine.
  • the "ordinary temperature” in the ordinary temperature curing as used herein refers to a temperature region classified by the common use form.
  • the curing by charging a curing agent at a resin composition temperature of 50 °C or less is classified into “ordinary temperature curing”
  • the curing under heating at 50 to 100 °C after the charging of a curing agent is classified into “medium temperature curing”
  • the curing under heating at 100°C or more after the charging of a curing agent is classified into "high temperature curing” .
  • the "curing" at an ordinary temperature curing means that the composition loses flowability due to crosslinking or polymerization reaction and is solidified from the molten state, and excludes the case where a thermoplastic resin composition or the like is, after fusing under heat, cooled and solidified.
  • the polymerization speed is known to greatly vary depending on the temperature of resin composition or the kind or amount of curing agent, accelerator, acceleration aid or polymerization inhibitor.
  • the curing time can be controlled by the kind or amount of curing agent, accelerator, acceleration aid or polymerization inhibitor.
  • the cured product may vary in the physical properties depending on the kind or amount of curing agent, accelerator, acceleration aid or polymerization inhibitor.
  • the viscosity varies depending on the temperature of resin composition. In order to obtain a viscosity suitable for molding and control the physical properties of the cured product, the resin composition is sometimes cured under heating at a temperature approximately from 20 to 30 °C.
  • the temperature of resin composition is adjusted to approximately from 15 to 25 °C and a curing agent is charged into the composition.
  • This resin composition is laminated by impregnation on a mat cloth or the like place in a mold. After a while, curing starts and heat is generated. After the completion of heat generation, the resin composition is in a solidified state.
  • This composition is postcured by heating it at 60 to 80 °C in a heating furnace and thereby, the complete curing is attained.
  • gelling starts within 24 hours to provide a state capable of after-curing. More preferably, the gelling starts within 1 hour.
  • the gelling time is not particularly limited.
  • the "ordinary temperature curable resin composition" as used in the present invention refers to a resin composition such that a resin composition having flowability can be changed into a solid having no flowability by charging a curing agent or the like at the resin composition temperature of 50°C or less. This does not limit to maintain the ordinary temperature through all steps in the curing of the resin composition of the present invention but the temperature may elevate accompanying heat generation due to heat of polymerization or an operation may be performed for postcuring.
  • one of these materials may be used and/or two or more thereof may be used in combination.
  • an oligo(meth)acrylate other than those described above may be used.
  • the polyester- (meth)acrylate is an oligomer having a (meth)acryloyl group at the molecular terminal and preferably having a mass average molecular weight of 150 to 3,000, which is generally synthesized by the reaction of a polyester oligomer and a (meth) acrylic acid.
  • polyester- (meth)acrylate examples include a method of esterifying an acrylic acid and/or a methacrylic acid (hereinafter, these are collectively called simply as “ (meth) acrylic acid”) with a polyhydric alcohol and a polybasic acid under heating at a temperature of 80 to 100 °C together with a solvent capable of azeotropically removing water, such as benzene or toluene, in the presence of a sulfuric acid catalyst, neutralizing the sulfuric acid with an alkali after the completion of reaction, repeating water washing to remove salts produced, and then distilling off the solvent to obtain the objective polyester- (meth) aerylate, and a method of using a transesterification reaction between a methyl ester of polybasic acid and an unsaturated alcohol.
  • This production method is described in detail below.
  • This production method is characterized in that raw materials of an oligo(meth)acrylate are reacted at a temperature of 140 to 210°C in the presence of an organic and/or inorganic antimony compound. Specific examples thereof include the following production methods (1) and (2).
  • Production Method (2) A method of reacting (A) a composition resulting from adding a polybasic acid anhydride to an unsaturated monoalcohol-containing composition obtained by the reaction between a (meth) acrylic acid and an alkylene monoepoxide, in the presence of (B) an organic and/or inorganic antimony compound at a temperature of 140 to 210°C.
  • the production method (1) more specifically includes a production method comprising the following first to third steps: First Step: a step of obtaining a starting material composition containing a (meth) acrylic acid, an alkylene monoepoxide and polybasic acid anhydride, Second Step: a step of reacting the starting material composition obtained in the first step, under heating in the presence of a catalyst in a closed system to obtain a reaction mixture ( 1 ) , and Third Step: a step of reacting the reaction mixture (1) obtained in the second step, at a temperature of 140 to 210 °C in the presence of an organic and/or inorganic antimony compound to obtain an oligo(meth)acrylate-containing resin composition.
  • First Step a step of obtaining a starting material composition containing a (meth) acrylic acid, an alkylene monoepoxide and polybasic acid anhydride
  • Second Step a step of reacting the starting material composition obtained in the first step, under heating in the presence of a catalyst in a closed system to obtain a reaction
  • the production method (2) more specifically includes a production method comprising the following first to fourth steps: First Step: a step of obtaining a starting material composition containing a (meth) acrylic acid and an alkylene monoepoxide, Second Step: a step of reacting the starting material composition obtained in the first step, under heating in the presence of a catalyst in a closed system to obtain a reaction mixture ( 2 ) , Third Step : a step of adding a polybasic acid anhydride to the reaction mixture (2) obtained in the second step to obtain a reaction mixture (3), and Fourth Step: a step of reacting the reaction mixture (3) obtained in the third step, at a temperature of 140 to 210°C in the presence of an organic and/or inorganic antimony compound to obtain an oligo(meth)acrylate-containing resin composition.
  • First Step a step of obtaining a starting material composition containing a (meth) acrylic acid and an alkylene monoepoxide
  • Second Step a step of reacting the starting material composition obtained in the first step,
  • the polyester- (meth) aerylate as one of (1) the oligo(meth)acrylate having one or more (meth)acryloyl groups within one molecule in the ordinary temperature curable resin composition of the present invention (I) is of course not limited to that produced by the above- described production methods and a polyester- (meth) aerylate produced by any production method may be used.
  • the above-described production method of an oligo(meth)acrylate comprising performing a reaction at a temperature of 140 to 210°C in the presence of an organic and/or inorganic antimony compound, is simple and easy as compared with conventional production methods of an oligo(meth)acrylate and therefore, is preferred as the production method of an oligo(meth)acrylate for use in the ordinary temperature curable resin composition of the present invention (I).
  • an antimony compound as a catalyst in the synthesis of an oligo(meth) aerylate, it may be considered to separate and remove the antimony compound by distillation, extraction and/or other methods, however, the antimony catalyst used in the synthesis of an oligo(meth)acrylate may have been changed from the compound before use and for completely removing the compound, at least one or more of distillation, extraction and other separation methods must be performed, which may be expensive.
  • the resin composition is preferably used while containing the antimony.
  • the present invention is not limited to contain antimony but the antimony may be separated and removed.
  • respective raw materials except for (a) the (meth)acrylic acid for use in the production of a polyester- (meth)acrylate include the followings.
  • Specific examples of (b) the alkylene monoepoxides include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide and glycidyl (meth) aerylate.
  • Specific examples of (c) the alkylene monoepoxide adduct of (meth) acrylic acid include compounds obtained by adding an acrylic acid and/or a methacrylic acid to the above-described alkylene monoepoxides.
  • polybasic acid and/or polybasic acid anhydride and/or polybasic acid ester include phthalic acid anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, dimethyl orthophthalate, dimethyl isophthalate, dimethyl terephthalate, endomethylene tetrahydrophthalic acid anhydride, endomethylene tetrahydrophthalic acid, dimethyl endomethylenetetrahydrophthalate, methyltetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid, dimethyl methyltetrahydrophthalate, adipic acid, dimethyl adipate, sebacic acid, trimellitic acid anhydride, trimellitic acid and tetramethyl trimellitate.
  • the polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1 , 3-propanediol, neopentyl glycol, 1 , 4-cyclohexane dimethanol, xylylene glycol, 1,3- butanediol, 1,4-butanediol, 2-methylpropanediol and pentaerythritol.
  • the vinyl ester resin composition as one of the oligo(meth)acrylate for use in the present invention (I) is described below.
  • the vinyl ester resin composition is a resin composition having a (meth) aeryloyl group at the molecular terminal and having a molecular weight of 500 to 3,000, which is generally synthesized by the addition reaction of an epoxy resin composition and a (meth) acrylic acid, and/or a composition obtained by dissolving the above-described resin composition in a reactive monomer, however, the "vinyl ester composition" as referred to in the present invention is defined not to contain a reactive monomer.
  • Examples of the epoxy resin composition used in the synthesis of the vinyl ester resin composition include the following types:
  • an epoxy resin composition modified using a phenol, a saturated or unsaturated polybasic acid, a phosphoric acid, a urethane, a silicone, an allyl ether or a ketene dimer may be used so as to modify the physical properties of the epoxy resin composition.
  • the modification method of the epoxy resin composition is described in detail in Vinyl Ester Jushi (Vinyl Ester
  • polyhydric alcohol- (meth) aerylate as one of the oligo(meth)acrylate for use in the present invention (I) and the present invention (II) is described below.
  • polyhydric alcohol as used herein is not only a general “polyhydric alcohol” but also includes a so-called
  • (meth) aerylate includes the following production methods
  • Production Method ( 4 ) A method of transesterifying a (meth) acrylic acid ester and a polyhydric alcohol or polyalkylene glycol to obtain a polyhydric alcohol- (methJacrylate.
  • the compounds used in these production methods ( 3 ) to (5) are not limited but specific examples of the general polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
  • 1,4-butanediol 2-methylpropanediol, glycerin, pentaerythritol, trimethylolpropane and trimethylolmethane .
  • polyalkylene glycol examples include polyethylene glycol and polypropylene glycol.
  • alkylene monoepoxide examples include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide and styrene oxide.
  • urethane- (meth) aerylate as one of the oligo(meth) aerylates for use in the present invention (I), is described below.
  • urethane- (meth)acrylate as used herein means a urethane compound having an unsaturated group and capable of radical curing. Specifically, this is, for example, a compound having one or more (meth) aeryloyl group and two or more urethane bonds within one molecule and this compound is obtained by reacting a polyvalent isocyanate compound with, as one component, an unsaturated alcohol covalently having a (meth)acryloyl group and a hydroxyl group within one molecule, which is obtained by reacting an alkylene monoepoxide with a (meth)acrylic acid. Those obtained by adding to this compound a polyhydric alcohol or a polyester or polyether having a terminal hydroxyl group and reacting these are also included.
  • Examples of the polyvalent isocyanate compound which can be used in the urethane- (meth) acrylates include 2,6- tolylene diisocyanate, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer .
  • the molecular weight of (1) the oligo(meth)acrylate having one or more (meth) aeryloyl groups within one molecule for use in the ordinary temperature curable resin composition of the present invention (I) is not particularly limited.
  • the molecular weight is preferably from 150 to 3,000 in terms of the weight average molecular weight (hereinafter sometimes referred to as
  • the molecular weight of (1) the oligo(meth)acrylate having one or more (meth) aeryloyl groups within one molecule for use in the ordinary temperature curable resin composition of the present invention (I) can be measured by a known method. Specific examples of the measuring method include gel permeation chromatography.
  • the allyl monomer which can be used in the present invention is not particularly limited and any compound may be used if it has at least one allyl group within one molecule.
  • allyl esters are preferred.
  • Specific examples of the allyl esters include diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, diallyl endomethylene tetrahydrophthalate, diallyl 1,4-cyclohexanedicarboxylate monomer, triallyl trimellitate, diallyl maleate and diallyl fumarate.
  • allyl monomer examples include triallyl isocyanurate and triallyl cyanurate.
  • an allyl monomer is selected by taking account of easy availability, easy producibility, curability and physical properties of the cured product, preferred are diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl fumarate and triallyl trimellitate.
  • diallyl orthophthalate diallyl isophthalate
  • diallyl terephthalate diallyl maleate
  • diallyl fumarate diallyl fumarate
  • triallyl trimellitate diallyl trimellitate
  • the acetoacetamide compound is not particularly limited and may be sufficient if it is a compound having any one of the structures represented by the following formulae (1) to (3) which are a so-called acetoacetamide structures.
  • R 1 , R 2 and R 3 each independently represents hydrogen or an alkyl group having from 1 to 10 carbon atoms, which may have a branch or a substituent.
  • R 4 represents hydrogen or an alkyl group having from 1 to 10 carbon atoms, which may have a branch or a substituent
  • R 5 and R 6 each independently represents hydrogen, an alkyl group having from 1 to 10 carbon atoms, which may have a branch or a substituent, or a phenyl group which may have a substituent, provided that at least one of R 5 and R 6 is a phenyl group which may have a substituent.
  • aliphatic acetoacetamide compound represented by formula ( 1 ) include acetoacetamide, (N-methyl) acetoacetamide, (N,N- dimethy1 ) acetoacetamide, (N,N-diethy1 ) acetoacetamide, (N,N-diisopropy1 ) acetoacetamide, N,N- dibutylacetoacetamide, [N-methyl-N-
  • aromatic acetoacetamide compound represented by formula (2) examples include N- methylacetoacetanilide and (N-acetoacetoxyethyl)aceto- acetanilide.
  • acetoacetyl heterocyclic compound represented by formula (3) examples include ( 1-acetoacetyl)pyrrole, ( l-acetoacetyl)imidazole, (1- acetoacetyl Jindole, ( 1-acetoacetyl )indazole, (7- acetoacetyl)purine, (9-acetoacetyl)carbazole, (10- acetoacetyl )phenothiazine , ( 10-acetoacetyl )phenoxazine, ( 1-acetoacetyl )pyrrolidine, ( 1-acetoacetyl )pyrroline, (1- acetoacetyl ) imidazolidine, ( 1-acetoacetyl ) imidazoline, ( 1-acetoacetyl )pyrazolidine, ( 1-acetoacetyl )pyrazoline, ( 1-acetoacetyl Jpiperidine, ( l-acetoacetyl Jpiperidine
  • the unsaturated polyester which can be used in the present invention (I) is not particularly limited if it is an unsaturated polyester having a molecular weight of approximately from 1,000 to 3,000, obtained by esterifying a polybasic acid (or an anhydride thereof) and a polyhydric alcohol. Commonly available unsaturated polyesters can be used.
  • polybasic acid or an anhydride thereof which can be used as a raw material of the unsaturated polyester
  • polybasic acid or an anhydride thereof which can be used as a raw material of the unsaturated polyester
  • examples of the polybasic acid (or an anhydride thereof) which can be used as a raw material of the unsaturated polyester include, maleic anhydride, maleic acid, fumaric acid, itaconic acid, phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, tetrahydroorthophthalic acid, methyltetrahydrophthalic anhydride, methyltetrahydro-orthophthalic acid, endomethylene tetrahydrophthalic anhydride, endomethylene tetrahydroorthophthalic acid, adipic acid, sebacic acid, HET acid, tetrabromophthalic anhydride, dimethyl 2,6- na
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1 , 4-cyclohexane- dimethanol, xylylene glycol, 1 ,3-butanediol, 1,4- butanediol, 2-methylpropanediol, pentaerythritol, bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin monoallyl ether and pentaerythritol diallyl ether.
  • polycondensation is performed in an inert gas stream at a temperature between 180 °C and 220 °C according to an ordinary method.
  • the resulting unsaturated polyester having a molecular weight on the order of 1,000 to 3,000 can be used as it is in the present invention.
  • the polyester may be subjected to some purification operation, if desired, before use.
  • the content and proportion of respective components (1) to (4) in the ordinary temperature curable resin composition of the present invention (I) are not particularly limited. These can be selected according to the viscosity required in view of workability at the time of molding the resin composition, the curing properties such as curing time and curing temperature, and various physical properties which the cured product after curing are required to have.
  • the ratio of (1) the oligo(meth)acrylate having one or more (meth) aeryloyl groups within one molecule to (2) the allyl monomer of a saturated and/or unsaturated polybasic acid in the present invention (I) is not particularly limited.
  • the ratio of (1) the oligo(meth)acrylate having one or more (meth) aeryloyl groups within one molecule to (2) the allyl monomer of a saturated and/or unsaturated polybasic acid in the resin composition of the present invention (I) can be measured, for example, generally known gas chromatography or gel permeation chromatography .
  • the amount of ( 3 ) the acetoacetamide compound used in the present invention (I) is described below.
  • the amount of (3) the acetoacetamide compound is not particularly limited. The preferred amount varies depending on the ratio of (1) the oligo(meth)acrylate having one or more (meth)acryloyl groups within one molecule to (2) the allyl monomer of a saturated and/or unsaturated polybasic acid, the proportion of their total amounts occupying in the entire resin composition, and the physical properties such as structure and molecular weight of (1) and (2), however, this amount is generally from 0.01 to 5 parts by mass per 100 parts by mass as a total of (1) the oligo(meth) aerylate having one or more (meth)acryloyl groups within one molecule and (2) the allyl monomer of a saturated and/or unsaturated polybasic acid contained in the ordinary temperature curable resin composition.
  • the resin composition may be colored or stink or the ordinary temperature curability of the resin composition itself may deteriorate and this is not advantageous.
  • the amount is more preferably from 0.05 to 2 parts by mass, still more preferably from 0.1 to 1 part by mass.
  • the amount of (4) the unsaturated polyester used in the present invention (I) is also not particularly limited.
  • the ordinary temperature curable resin composition of the present invention (I) is resultant from further adding (4) an unsaturated polyester to the ordinary temperature curable resin composition and by this addition, the cured product can be increased in the strength. Accordingly, (4) may be used in any proportion as long as the ordinary temperature curability is maintained.
  • the preferred amount also varies depending on the state and property of the resin composition as a whole, however, this is generally from 5 to 500 parts by mass per 100 parts by mass as a total of (1) the oligo(meth)acrylate having one or more (meth) aeryloyl groups within one molecule and (2) the allyl monomer of a saturated and/or unsaturated polybasic acid contained in the ordinary temperature curable resin composition.
  • the amount is more preferably from 5 to 200 parts by mass, still more preferably from 5 to 100 parts by mass.
  • the ordinary temperature curable resin composition of the present invention (I) can be used in combination with various conventionally known materials.
  • the material which can be used in combination include an inorganic and/or organic reinforcing agent, a filler, a mold releasing agent, a defoaming agent, a coloring agent, a polymerization inhibitor, a wax, and an oil and fat .
  • the inorganic and/or organic reinforcing agent include glass fiber, carbon fiber, aramid fiber, vinylon fiber and metal fiber.
  • the filler include calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, aluminum hydroxide, clay, talc, kaolin, kieselguhr, mica powder, glass fiber powder, powdered asbestos, silica gel and rock wool.
  • Specific examples of the mold releasing agent include waxes and stearic acid metal salts represented by zinc stearate.
  • the polymerization inhibitor is not only added at the synthesis of the oligo(meth)acrylate, the synthesis of the unsaturated polyester or the synthesis of the allyl monomer but also may be added so as to prevent the resin composition of the present invention (I) and the present invention (II) from alteration before use or to adjust the time until gelling at the molding.
  • polymerization inhibitor examples include para- benzoquinone, methoxyphenol, naphthoquinone, phenanthraquinone, toluquinone, 2,5-diacetoxy-p- benzoquinone, 2 , 5-dicaproxy-p-benzoquinone, 2 , 5-acyloxy- p-benzoquinone, hydroquinone, p-tert-butylcatechol, 2,5- di-tert-butylhydroquinone, mono-tert-butylhydroquinone, 2 , 5-di-tert-amylhydroquinone, di-tert-butyl-para-cresol hydroquinone monomethyl ether, ⁇ -naphthol, copper naphthenate, acetoamidine acetate, acetoamidine sulfate, phenylhydrazine hydrochloride, hydrazine hydrochloride, trimethylbenzylammonium chlor
  • the present invention (II) is described below.
  • the present invention (II) is a method for curing the resin composition of the present invention (I).
  • the curing method of the resin composition, as the present invention (II), is not particularly limited. Curing may be attained by a conventionally known curing method for resin compositions.
  • the resin composition can be cured if a radical can be generated by some means such as light or heat and, needless to say, use of a curing agent (radical generator).
  • a curing agent radical generator
  • curing at an ordinary temperature using a curing agent is particularly effective because this method is suitable for the properties of the resin composition of the present invention (I ) .
  • the curing agent which can be used in the present invention (II) at the time of curing the resin composition of the present invention (I) is not particularly limited and any may be used as long as it has an ability of generating a radical necessary for curing conventionally known radical curable resin compositions.
  • a peroxide is preferred.
  • peroxide examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylacetoacetate peroxide, acetylacetone peroxide, bis ( 1-hydroxycyclohexyl)peroxide, 1, l-bis( tert- butylperoxy) -3 , 3 , 5-trimethylcyclohexane, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, bis (4- tert-butylcyclohexyl)peroxy dicarbonate, tert-butylperoxy benzoate, tert-butylperoxy pivalate, tert-butylperoxy-2- ethyl hexanoate and lauroyl peroxide.
  • curing agents may be used individually or in combination.
  • the curing agent for use in the curing method of resin composition which is the present invention (II) may be only the above-described peroxide but a curing accelerator may be used in combination.
  • the combination of the peroxide and the curing accelerate is sometimes referred to as a "composite curing agent" .
  • Examples of the curing accelerator which can be used include at least one compound selected from the group consisting of a cobalt salt, a copper salt, a manganese salt and a calcium salt of organic acid compound, at least one compound selected from the group consisting of a sulfonic acid compound and a salt thereof, and at least one compound selected from tertiary amines.
  • the combination of the peroxide and the curing accelerator greatly affects the curability.
  • Preferred examples of the combination in the composite curing agent suitable for the present invention include the following. However, the present invention is not limited to these combinations.
  • an acceleration aid for accelerating the curing may also be used.
  • the acceleration aid means a tertiary component added in addition to the peroxide and the curing accelerator. Accordingly, use of a curing accelerator as the acceleration aid is also included.
  • acceleration aid examples include acetylacetone, dimedone, dibenzoylmethane, acetylcyclopentane, acetoacetic acid ester and acetylbutyrolactone .
  • the amount of the curing agent used is not particularly limited and the preferred range varies depending on the state and property of the resin composition as a whole or the state and property of the curing agent itself, but this range is generally from 0.01 to 10 parts by mass per 100 parts by mass as a total of (1) the oligo(meth) aerylate having one or more (meth) aeryloyl group within one molecule and (2) the allyl monomer of a saturated and/or unsaturated polybasic acid contained in the ordinary temperature curable resin composition.
  • the amount used is preferably from 0.05 to 8 parts by mass, more preferably from 0.1 to 5 parts by mass.
  • the amount used of the composite curing agent where a peroxide is used as the curing agent, and this is combined with a curing accelerator, is also not particularly limited.
  • the preferred amount varies depending on the state and property of the resin composition as a whole or the state and property of the composite curing agent itself, but this is generally from 0.001 to 10 parts by mass per 100 parts by mass as a total of (1) the oligo(meth) aerylate having one or more (meth) aeryloyl groups within one molecule and (2) the allyl monomer of a saturated and/or unsaturated polybasic acid contained in the ordinary temperature curable resin composition.
  • the composite curing agent is less than 0.001 part by mass, curing may be seriously retarded and this is not preferred, whereas if the composite curing agent is used in excess of 10 parts by mass, the curing product may be disadvantageously deteriorated in physical properties.
  • the amount used is preferably from 0.01 to 8 parts by mass, more preferably from 0.05 to 5 parts by mass.
  • the molding method is not particularly limited but preferred are hand lay-up molding and spray-up molding.
  • the hand lay-up molding is a molding method of applying the resin composition to a mold using a roller and the spray-up molding is a method of atomizing the resin composition using a compressed air and spraying it on a mold. These are described in detail in Polyester Jushi Handbook (Handbook of Polyester Resin) . 1st ed., 1st imp., pp. 507-539 (June 30, 1988)).
  • the present invention (III) is described below.
  • the present invention (III) is a cured product of the resin composition of the present invention (I).
  • the cured product of the present invention (III) may have any state and property as long as it is obtained by curing the resin composition of the present invention (I).
  • the curing method is also not particularly limited, however, the curing product is preferably obtained by curing the resin composition of the present invention (I) at an ordinary temperature by making use of its ordinary temperature curability, using a curing agent (including a composite curing agent) used in the curing method of the present invention (II).
  • An excess active energy such as heat or ultraviolet ray needs not be applied at the curing and the curing can be performed under mild conditions.
  • a cured product particularly excellent in the physical properties such as color tone can be obtained.
  • the physical properties of the cured product can be advantageously controlled with ease by changing the state and property or the blending ratio of each component used in the resin composition of the present invention (I) as a starting material.
  • the present invention is further illustrated below by referring to Examples, however, the present invention is not limited thereto.
  • the tensile strength and tensile modulus of the cured product obtained by a casting method were measured according to JIS K 7113:1995.
  • the tensile strength and tensile modulus of FRP obtained by a lamination method were measured according to JIS K 7054:1995.
  • the bending strength and bending modulus of the cured product obtained by a casting method were measured according to JIS K 7203:1995.
  • the bending strength and bending modulus of the cured product obtained by a lamination method were measured according to JIS K
  • a composite curing agent (hereinafter simply referred to as a "curing agent") comprising PERMEC N (produced by NOF, 35-45 mass* methyl ethyl ketone peroxide dimethyl phthalate solution) and cobalt naph
  • the numerical values are values showing the proportion of each component in the whole composition in terms of weight ratio.
  • a commercially available dipentaerythritol hexaacrylate (produced by Nippon Kayaku Co., Ltd.) was used for the oligo(meth)acrylate.
  • Example 8 Polyester-Methacrylate (A) was used for the oligo(meth) acrylate and Unsaturated Polyester (G) was used for the unsaturated polyester.
  • Example 9 Polyester-Methacrylate (A) and Polyester-Acrylate (H) were used in combination for the oligo(meth) acrylate and Unsaturated Polyester (G) was used for the unsaturated polyester.
  • the resin compositions and compounds except for the curing agent, shown in Table 1, were thoroughly mixed and after adjusting the resin temperature to 25 °C, the curing agent and p-tert-butylcatechol for adjusting the polymerization time were added and mixed with stirring. As a result, gelling occurred in 31 minutes and thereafter, heat was continuously generated to cause curing. The maximum exothermic temperature reached 100 °C.
  • the composition was cast-molded and the cured product was completely cooled and then postcured at 120 °C for 2 hours.
  • the physical properties of the cured product are shown in Table 2. Comparative Example 1
  • Unsaturated Polyester (G) was used for the unsaturated polyester.
  • Polyester-Acrylate (H) was used for the oligo(meth) acrylate and Unsaturated Polyester (G) was used for the unsaturated polyester.
  • the resin composition of the present invention comprising (1) an oligo(meth) acrylate having one or more (meth) aeryloyl groups within one molecule, (2) an allyl monomer of a saturated and/or unsaturated polybasic acid and (3) an acetoacetamide compound has ordinary temperature curability equal to that of conventional general-purpose radical curable resin compositions.
  • styrene need not be used for adjusting the viscosity which is an important factor for providing satisfactory moldability.
  • a "non-styrene type resin composition" most keenly demanded as the general-purpose resin composition can be provided.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une composition de résine qui comprend un oligo(méth)acrylate contenant un ou plusieurs groupes (méth)acryloyl dans une molécule, un monomère allyle d'acide polybasique saturé et/ou insaturé ainsi qu'un composé d'acétoacétamide. Le problème de durcissement insuffisant à température ordinaire peut être résolu dans une composition de résine durcissable radicalaire qui comprend un oligo(méth)acrylate dilué avec un monomère allyle.
PCT/JP2003/002064 2002-03-28 2003-02-25 Composition de resine durcissant a froid, procede de durcissement de la composition de resine et produit durci de la composition de resine WO2003082978A1 (fr)

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JP2002091723 2002-03-28
JP2002-263914 2002-09-10
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57133107A (en) * 1981-02-10 1982-08-17 Osaka Soda Co Ltd Thermosetting liquid resin composition
US4534888A (en) * 1982-10-25 1985-08-13 The General Tire & Rubber Company In-mold coating
EP0315101A2 (fr) * 1987-11-03 1989-05-10 The Dow Chemical Company Méthode pour réparer des articles composites endommagés
JPH01254722A (ja) * 1988-04-01 1989-10-11 Showa Highpolymer Co Ltd ラジカル硬化型樹脂の硬化促進方法
EP0338870A1 (fr) * 1988-02-24 1989-10-25 SOCIETE FRANCAISE HOECHST Société anonyme dite: Dispersion aqueuse de polymères du type styrène-acrylique et son application pour l'obtention de compositions adhésives résistant à l'eau convenant notamment dans le domaine du carrelage
JPH02191633A (ja) * 1989-01-20 1990-07-27 Showa Highpolymer Co Ltd 硬化促進作用を有する組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57133107A (en) * 1981-02-10 1982-08-17 Osaka Soda Co Ltd Thermosetting liquid resin composition
US4534888A (en) * 1982-10-25 1985-08-13 The General Tire & Rubber Company In-mold coating
EP0315101A2 (fr) * 1987-11-03 1989-05-10 The Dow Chemical Company Méthode pour réparer des articles composites endommagés
EP0338870A1 (fr) * 1988-02-24 1989-10-25 SOCIETE FRANCAISE HOECHST Société anonyme dite: Dispersion aqueuse de polymères du type styrène-acrylique et son application pour l'obtention de compositions adhésives résistant à l'eau convenant notamment dans le domaine du carrelage
JPH01254722A (ja) * 1988-04-01 1989-10-11 Showa Highpolymer Co Ltd ラジカル硬化型樹脂の硬化促進方法
JPH02191633A (ja) * 1989-01-20 1990-07-27 Showa Highpolymer Co Ltd 硬化促進作用を有する組成物

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 006, no. 231 (C - 135) 17 November 1982 (1982-11-17) *
PATENT ABSTRACTS OF JAPAN vol. 014, no. 007 (C - 673) 10 January 1990 (1990-01-10) *
PATENT ABSTRACTS OF JAPAN vol. 014, no. 466 (C - 0768) 11 October 1990 (1990-10-11) *

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