WO2008026580A1 - Composition de résine insaturée polymérisable par voie radicalaire et article moulé à l'aide de ladite composition - Google Patents

Composition de résine insaturée polymérisable par voie radicalaire et article moulé à l'aide de ladite composition Download PDF

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Publication number
WO2008026580A1
WO2008026580A1 PCT/JP2007/066642 JP2007066642W WO2008026580A1 WO 2008026580 A1 WO2008026580 A1 WO 2008026580A1 JP 2007066642 W JP2007066642 W JP 2007066642W WO 2008026580 A1 WO2008026580 A1 WO 2008026580A1
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Prior art keywords
resin composition
polymerizable unsaturated
group
compound
radically polymerizable
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PCT/JP2007/066642
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English (en)
Japanese (ja)
Inventor
Ou Shibata
Yukiko Fujita
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Dh Material Inc.
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Publication of WO2008026580A1 publication Critical patent/WO2008026580A1/fr

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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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • 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
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated 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
    • 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
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • 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 a radically polymerizable unsaturated resin composition for molding that can provide a molded article having high toughness, and a molded article using the same.
  • Radical polymerizable unsaturated resin compositions having excellent toughness include burester oligomers, polyester (meth) acrylate oligomers, urethane (meth) acrylate oligomers, maleate esters and / or fumarate ester oligomers. And / or a polymerizable monomer is known! /, (See Patent Document 1).
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-10771
  • the physical properties of such a cured resin product are those having a small area surrounded by a stress-strain curve of a tensile test, which is not high tensile strength and high tensile elongation. It was not obtained.
  • Such as those in the tensile strength of 30MPa in Patent Document 1 Example 8, it NakaBikushi 44 0/0 approximately at that force, et al., From about 30 X 44 1320 could force, without area surrounded by stress-strain observed curve Is even smaller. This was not a high-toughness molded product.
  • the present invention has been made in view of the above circumstances, and is a radically polymerizable unsaturated resin composition from which a cured product showing a large tensile elongation and a large tensile strength can be obtained as a molded article, It is an object to provide a radically polymerizable unsaturated resin composition capable of giving a cured product having high toughness, that is, large absorbed energy, and a molded article using the same.
  • the present invention provides a terminal by reacting a polycarbonate diol (a) obtained from a carbonate ester and an aliphatic or cycloaliphatic diol and having a number average molecular weight of 900 to 3000 with a diisocyanate (b).
  • the present invention also relates to a molded product obtained by curing and molding the radical polymerizable resin composition, wherein the cured product of the radical polymerizable resin composition has a tensile stress rupture strain in a tensile test according to JIS-K-7113.
  • a molded product characterized in that the absorbed energy force calculated from the curve is not less than 0.015 a / mm 3 ).
  • the radical polymerizable resin composition of the present invention can provide a molded article having high toughness.
  • high toughness means the absorbed energy unit (j / mm 3 ) force S 0. 015j obtained by the tensile test of JIS K 7113 using the resin composition of the present invention as a cured product by the following method. It means that it is more than / mm 3 .
  • the value obtained by multiplying the value of tensile strength (Mpa) of test piece No. 1 by the tensile test of JIS-K-7113 and the value of tensile elongation (%) is 2 000 or more, preferably 3000 or more It means that.
  • a release agent was applied to two 30cm x 30cm glass plates, a synthetic rubber tube was sandwiched between the glass plates, and a spacer was used to adjust the gap to 3mm, and a curing agent and a curing accelerator were added. Pour the resin composition and cure at room temperature for 1 day. After curing, put the whole glass plate in a dryer, completely cure at 120 ° C for 2 hours, cool, remove the glass plate, and smooth the thickness 3 Obtain a casting plate of mm. From now on, it will be cut into the first specimen of the tensile test of JIS-K-7113.
  • test equipment Autograph AG-I (manufactured by Shimadzu Corporation) is used to measure the tensile strength and the tensile elongation by the tensile test method of JIS 7113. Absorbed energy is calculated using energy calculation analysis software: TRPEZIUM2.
  • the carbonate skeleton-containing urethane resin (A) having a methacryloyl group has at least one, preferably two, methacryloyl groups in the molecule, and 5 to 15 carbonate bonds in the resin skeleton. It is preferable to have one. Within this range, a sufficiently high toughness can be obtained.
  • a resin is obtained from a carbonate ester and an aliphatic or alicyclic diol, and has a number average molecular weight of 900 to 3000 and a diisocyanate, preferably an alicyclic or aliphatic diisocyanate (b).
  • the polycarbonate diol (a) is obtained from a carbonate ester and an aliphatic or alicyclic diolene force, and has a number average molecular weight force of 900 to 3000, preferably (also in the range of 1000 to 2000).
  • Examples of the polycarbonate diol (a) include 1,6-hexane carbonate diol, 1,4-cyclohexane carbonate diol, etc.
  • the number average molecular weight is less than 900, it is difficult to obtain characteristics derived from carbonate.
  • Diol (a) can be produced by a known method, for example, aliphatic chain diol or alicyclic diol and dimethyl carbonate or Carbonate diols obtained by transesterification with carbonates such as ethyl carbonate, ring-opening reaction of cyclic carbonates having an alkylene group, reaction of phosgene with aliphatic chain diols or alicyclic diols, etc.
  • aliphatic chain diol or alicyclic dial those having an arbitrary structure can be used. N-glycolanol, 1,3-propylene glycolol, 1,2-propylene glycolanol, diethylene glycolol, dipropylene glycolanol, neopentinoglycolanol, 1,3-butanediol, 1,4-butanediol, 1,6- Xanthdiol, 1,9-nonanediol, 1,10-decanediol, cyclohexanedimethylol, 1,4-cyclohexanediol and the like.
  • a commercially available product may be used as the polycarbonate diol (a).
  • polyester polyol which is a condensate with a functional carboxylic acid, can be used in combination as long as the effects of the present invention are not impaired.
  • the proportion is preferably 40% by mass or more of polycarbonate diol as diol (a) from the viewpoint of high toughness.
  • the hydroxyl value of the polycarbonate diol (a) is preferably 50 to 135 KOHmg / g.
  • diisocyanate (b) examples include 2,4-tolylene diisocyanate, its different form or a mixture of these isomers, hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate.
  • examples thereof include cyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, and tolidine diisocyanate, and these can be used alone or in combination of two or more.
  • isophorone diisocyanate which is an isocyanate composed of an aliphatic hydrocarbon which is preferred for alicyclic or aliphatic diisocyanate, is particularly preferably used from the viewpoint of discoloration of the molded article to be obtained.
  • a methacrylic acid ester containing one hydroxyl group is preferable.
  • metatalylates having one hydroxyl group such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate; and polyethylene glycol monomethacrylate.
  • Monometatalylates of alcohols having two hydroxyl groups such as polypropylene glycol monometatalylate; 3 or more hydroxyl groups such as dimetatalate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol trimetatalylate It is possible to add a small amount of alcohol metatarylates having
  • a method for producing a carbonate skeleton-containing urethane resin (A) having a methacryloyl group in the present invention will be described below.
  • compound (c) is formed and then reacted with a methallyl compound (d) containing one hydroxyl group and one methacryloyl group so that the hydroxyl group is approximately equivalent to the isocyanate group.
  • the polycarbonate diol (a) is preferably used in the range of 55% by mass to 85% by mass with respect to the total amount of the above (a) + (b) + (d). Within this range, sufficient toughness can be obtained when cured with the radically polymerizable unsaturated monomer (B).
  • the radical polymerizable unsaturated resin composition of the present invention includes the carbonate skeleton-containing urethane resin (A) and the radical polymerizable unsaturated monomer (B) having one unsaturated group. Specifically, for example, the carbonate skeleton-containing urethane resin (A) is dissolved in the radical polymerizable unsaturated monomer (B).
  • radical polymerizable unsaturated monomer (B) examples include styrene, butyltoluene, methylstyrene, paramethylstyrene, chlorostyrene, dichloroenostyrene, vinylenonaphthalene, ethinolevinoleatenole, methinolevini nore, and ketone.
  • the carbonate skeleton-containing urethane resin (A) 90 to 10 parts by mass and the radical polymerizable unsaturated monomer (B) 10 to 90 parts by mass were mutually dissolved. More preferably, the carbonate skeleton-containing urethane resin (A) 80-20 parts by mass and the radically polymerizable unsaturated monomer (B) 20-80 parts by mass are mutually dissolved! / ,.
  • a hydroxyl group-containing aryl ether compound is used in combination as a part of the component (d) for the purpose of preventing curing inhibition by air when the radical polymerizable unsaturated resin composition of the present invention is cured. You can also.
  • hydroxyl group-containing aryl ether compound examples include ethylene glycol mono-mono mono etherate, diethylene glyco mono mono mono etherate, tri-ethylene glycol mono mono mono etherate, polyethylene glyco mono mono mono etherate, Propylene glycol mono-mono-enoate ethere, Dipropylene glyco-mono-mono mono-enoate ether, Tripropylene glyco-mono-mono mono-enoate ether, Polypropylene glycol mono-mono mono ether ether, 1,2-butylene glycol monoallyl ether 1,3-butylene glycol monoarynoleatenore, hexylene glycolenomonolinoleatenore, otylene glycolenole monoallyl ether, trimethylolpropane diallyl ether, glycerin dia Rue ether, cited Ariruete Le compounds of polyvalent alcohols such as pentaerythritol triallyl ether, preferably is
  • Examples of the polymerization inhibitor to which a polymerization inhibitor is preferably added to the resin composition of the present invention include, for example, trihydroquinone, hydroquinone, 1,4-naphthoquinone, and parabenzo.
  • Examples include quinone, tonolehydride non-pour, p-tert-butynoleic power, teconole, 2,6-tert-butynole 4-methylphenol and the like.
  • the amount of the polymerization inhibitor used is preferably 10 to 1000 ppm in the resin composition.
  • the resin composition of the present invention is cured by adding a commonly used known curing agent.
  • examples of the curing agent include one or more selected from thermosetting agents.
  • the amount of the curing agent used is preferably 0.;! To 10 parts by mass, more preferably! To 5 parts by mass with respect to 100 parts by mass of the resin composition.
  • thermosetting agent examples include organic peroxides. Specific examples include dialkyl peroxides, peroxide esters, hydride peroxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peroxides, and carbonates. These are selected as appropriate depending on the kneading conditions, curing temperature, and the like.
  • an organic metal salt such as cobalt naphthenate or oleate oleate can be used in combination with the resin composition of the present invention as a curing accelerator.
  • the resin composition of the present invention includes generally known unsaturated polyester resins, vinyl urethane resins, butyl ester urethane resins, polyisocyanates, polyepoxides, acrylic resins, alkyd resins, urea.
  • Resins Melamine Resins, Polyacetate Bull, Acetic Acid Bull Copolymers, Polygen Elastomers, Saturated Polyesters, Saturated Polyethylenols; Cenorelose Derivatives such as Nitrosenorose, Cenorelose Acetate Butyrate; Amami Oil
  • Other conventional natural and synthetic polymer compounds such as oils such as tung oil, soybean oil, castor oil, and epoxidized oil can be added.
  • a glass fiber, carbon fiber, organic fiber, metal fiber or the like can be added to the resin composition of the present invention as a reinforcing material in an amount of 5 to 70% by mass to obtain a molded product.
  • These fiber reinforcements are preferably used in combination with organic fiber reinforcements from the viewpoint of the environment.
  • the resin composition of the present invention contains a filler such as calcium carbonate, talc, my strength, clay, silica powder, colloidal silica, asbestos powder, barium sulfate, aluminum hydroxide, glass powder, glass beads, and crushed sand.
  • a filler such as calcium carbonate, talc, my strength, clay, silica powder, colloidal silica, asbestos powder, barium sulfate, aluminum hydroxide, glass powder, glass beads, and crushed sand.
  • a filler such as calcium carbonate, talc, my strength, clay, silica powder, colloidal silica, asbestos powder, barium sulfate, aluminum hydroxide, glass powder, glass beads, and crushed sand.
  • other additives such as zinc stearate, titanium white, zinc white, various pigment stabilizer
  • the method for obtaining a molded product from the resin composition of the present invention is not particularly limited, and specific examples include so-called no, drain-up, spray-up molding, RTM (resin transfer one molding) molding, Various molding methods such as continuous molding and pultrusion molding can be listed. Moreover, the method of apply
  • the resin composition of the present invention may be used for a covering material such as a top coat, a gel coat, a putty, an adhesive, and a lining material, but the resin composition is particularly cured. From the high toughness of the product, it is preferably used for molding applications. Examples of molded products that can be obtained include indoor molded products, electrical and electronic components, boat members, automobile components, motorcycle components, indoor components, bathtubs, waterproof pans, kitchen counters, bathroom counters, bathroom vanities, and various types. Examples include artificial marble molded products, separate plates, corrugated plates, flat plates, lining materials, civil engineering and building materials.
  • a molded product obtained by curing and molding the resin composition of the present invention has an absorption energy calculated from a tensile stress-breaking strain curve of a tensile test according to JIS-K-7113. Is 0.0015 (j / mm 3 ) or more, and has high toughness.
  • part means “part by mass”.
  • polycarbonate diol Ube Industries UH- CARB100, 1,6-hexadiol-based polycarbonate diol, A number average molecular weight of 1000
  • IPDI isophorone diisocyanate
  • a cured product was obtained in the same manner as in Example 1 except that the urethane resin obtained in Synthesis Example 2 was used, and the physical properties of the cured product were evaluated. fi.
  • the toughness was evaluated by measuring the physical properties of the cast plate, which is the basis of various molded products.
  • the casting plate was prepared as follows. That is, a release agent was applied to two glass plates each having a size of 30 cm ⁇ 30 cm, a synthetic rubber tube was sandwiched between the glass plates, and a gap was adjusted to 3 mm using a spacer.
  • Each resin composition shown in the Examples and Comparative Examples was poured and cured at room temperature for 1 day. After curing, the whole glass plate was placed in a dryer and completely cured at 120 ° C for 2 hours. After cooling, the glass plate was removed to obtain a smooth molded product with a thickness of 3 mm. A test piece was cut from the obtained cast plate, and a tensile test was conducted by the test method of IS-K-7113 using the test piece to measure physical properties.
  • the tensile strength and the tensile elongation were measured by the test method: Autograph AG-1 (manufactured by Shimadzu Corporation) using the test piece and the tensile test method of JIS-7113.
  • the area between the tensile stress rupture strain curve obtained by plotting the tensile stress on the vertical axis and the rupture strain on the horizontal axis and the horizontal axis is expressed as “thickness of specimen (mm) X distance between marked lines ( The value (value per unit volume) divided by “50 mm) X-neck center width (mm)” was calculated as the absorbed energy (j / mm 3 ).
  • Energy calculation analysis software: TRPEZIUM2 was used to calculate the absorbed energy.
  • the cast plate obtained from the resin composition of the present invention has an excellent balance of tensile strength and tensile elongation, and exhibits a conventional so-called high toughness characteristic. It was confirmed that
  • the present invention can be used in a wide range of fields, such as the medical field, electrical and electronic field, mechanical field, civil engineering and building field, which require a high toughness molded article.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une composition de résine insaturée polymérisable par voie radicalaire, caractérisée par le fait qu'elle contient une résine d'uréthane contenant un squelette de polycarbonate (A), ayant un groupe méthacryloyle et un monomère insaturé polymérisable par voie radicalaire (B) ayant un groupe insaturé. La résine d'uréthane contenant un squelette de polycarbonate (A) ayant un groupe méthacryloyle est obtenue par l'obtention d'un composé carbonate contenant un groupe isocyanate terminal (c) par réaction d'un polycarbonate diol (a), qui est obtenu à partir d'un ester d'acide carbonique et d'un diol aliphatique ou alicyclique et possède une masse moléculaire moyenne en nombre de 900-3 000, avec un diisocyanate (b), puis par la réaction du composé (c) avec un composé méthacrylique (d) contenant un groupe hydroxy et un groupe méthacryloyle. L'invention concerne également un article moulé obtenu par l'utilisation de la composition de résine insaturée polymérisable par voie radicalaire.
PCT/JP2007/066642 2006-08-31 2007-08-28 Composition de résine insaturée polymérisable par voie radicalaire et article moulé à l'aide de ladite composition WO2008026580A1 (fr)

Applications Claiming Priority (2)

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JP2006-236600 2006-08-31
JP2006236600A JP2008056823A (ja) 2006-08-31 2006-08-31 ラジカル重合性不飽和樹脂組成物及びそれを用いた成形品

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010073003A1 (fr) * 2008-12-22 2010-07-01 Scott Bader Company Limited Composition du type enduit gélifié et articles contenant cette composition
JP2012102193A (ja) * 2010-11-08 2012-05-31 Dh Material Kk （メタ）アクリロイル基含有ポリウレタン、（メタ）アクリロイル基含有ポリウレタンの製造方法、ラジカル重合性樹脂組成物、硬化物

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JP5324726B2 (ja) * 2011-09-01 2013-10-23 日本ペイント株式会社 クリヤー塗料組成物及びそれを用いた複層塗膜の形成方法
CN113853412B (zh) * 2019-06-27 2023-12-15 湛新比利时股份有限公司 具有户外性能的可固化的组合物

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WO2010073003A1 (fr) * 2008-12-22 2010-07-01 Scott Bader Company Limited Composition du type enduit gélifié et articles contenant cette composition
JP2012102193A (ja) * 2010-11-08 2012-05-31 Dh Material Kk （メタ）アクリロイル基含有ポリウレタン、（メタ）アクリロイル基含有ポリウレタンの製造方法、ラジカル重合性樹脂組成物、硬化物

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