WO2013069441A1 - Composition de résine pour des récipients sous pression et récipient sous pression - Google Patents

Composition de résine pour des récipients sous pression et récipient sous pression Download PDF

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Publication number
WO2013069441A1
WO2013069441A1 PCT/JP2012/077228 JP2012077228W WO2013069441A1 WO 2013069441 A1 WO2013069441 A1 WO 2013069441A1 JP 2012077228 W JP2012077228 W JP 2012077228W WO 2013069441 A1 WO2013069441 A1 WO 2013069441A1
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Prior art keywords
resin
pressure vessel
resin composition
meth
mass
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PCT/JP2012/077228
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English (en)
Japanese (ja)
Inventor
一博 黒木
小林　健一
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昭和電工株式会社
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Priority to MYPI2014701118A priority Critical patent/MY185532A/en
Priority to JP2013542910A priority patent/JP6005054B2/ja
Priority to KR1020147014349A priority patent/KR101632127B1/ko
Publication of WO2013069441A1 publication Critical patent/WO2013069441A1/fr

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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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J12/00—Pressure vessels in general
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/02—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge involving reinforcing arrangements
    • F17C1/04—Protecting sheathings
    • F17C1/06—Protecting sheathings built-up from wound-on bands or filamentary material, e.g. wires
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/16—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge constructed of plastics materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C2203/00—Vessel construction, in particular walls or details thereof
    • F17C2203/06—Materials for walls or layers thereof; Properties or structures of walls or their materials
    • F17C2203/0634—Materials for walls or layers thereof
    • F17C2203/0658—Synthetics
    • F17C2203/0675—Synthetics with details of composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

Definitions

  • the present invention relates to a resin composition for a pressure vessel and a pressure vessel. Specifically, the present invention relates to a pressure vessel for storing air, oxygen, hydrogen, liquefied propane gas, liquefied natural gas, etc. used in aerospace equipment, fuel cells, natural gas vehicles, fire fighting, medical care, leisure, etc. The present invention relates to a resin composition used for production and a pressure vessel produced using the resin composition.
  • a pressure vessel made of a fiber reinforced resin is one in which a fiber reinforced resin layer is formed on the surface of a hollow container (inner tank) formed from a liner material. It is manufactured by a filament winding molding method, a tape winding molding method, or a braiding molding method in which it is cured by winding it on the surface of a hollow container (see, for example, Patent Documents 1 to 3).
  • This pressure vessel must have impact resistance so that it can withstand external pressure, internal pressure, and other external shocks, and it is sufficient to make it easy to check the remaining amount of liquid and gas inside. It is also necessary to have high transparency. In particular, since the transparency of the pressure vessel is reduced by peeling the fiber reinforced resin layer from the hollow vessel, the adhesion between the hollow vessel and the fiber reinforced resin layer must be good.
  • Examples of the resin used in the resin composition for producing the pressure vessel made of fiber reinforced resin include epoxy resin, unsaturated polyester resin, vinyl ester resin, etc., but epoxy resin excellent in physical properties such as heat resistance is used. Often used. However, since the epoxy resin has a high viscosity, the impregnation property to the fiber material is poor. Epoxy resins are generally cured by room temperature curing with amines such as modified polyamines or heat curing with acid anhydrides, but with amines, the pot life is limited, and acid anhydrides require a long time for curing. Requires a long molding time. Therefore, there exists a fault that the cost required for shaping
  • unsaturated polyester resins and vinyl ester resins are low in viscosity and have good impregnation into fiber materials, and can be radically polymerized using a peroxide catalyst system or a photopolymerization initiator. There is an advantage that the curing time is short compared to the case of using a resin.
  • unsaturated polyester resins and vinyl ester resins generally have a drawback that they give a cured product having low adhesion to a resin hollow container and insufficient impact resistance.
  • a representative method is a method of applying a frame treatment to the surface of a resin hollow container (for example, Patent Documents). 4).
  • this frame treatment gives a certain degree of adhesion improvement effect, but it is difficult to sufficiently enhance the adhesion between the resin hollow container and the fiber reinforced resin layer only by this treatment.
  • various studies have been made as a method for improving the impact resistance of the cured resin.
  • a resin composition containing an epoxy vinyl ester resin, a urethane (meth) acrylic resin, and a co-reactive monomer such as styrene (for example, Patent Documents 5 to 7).
  • this resin composition can give a cured product excellent in impact resistance, the adhesion of the cured product to a resin hollow container is not sufficient.
  • the conventional resin composition can provide a cured product having excellent impact resistance among the properties required for the pressure vessel, but has excellent adhesion to the resin hollow container.
  • a cured product cannot be given.
  • the present invention has been made to solve such a problem, and has a characteristic required for a pressure vessel (that is, excellent in impact resistance and adhesion to a hollow resin container). It aims at providing the resin composition for pressure vessels which gives.
  • an object of this invention is to provide the pressure vessel excellent in impact resistance and transparency.
  • the present inventors have found that adhesion to a resin-made hollow container can be improved by using a specific radical polymerizable unsaturated monomer.
  • the headline, the present invention has been reached. That is, the present invention includes the following [1] to [14].
  • the component (B) is an isocyanate compound having two or more isocyanate groups in one molecule, a (meth) acryl compound having one or more hydroxyl groups in one molecule, polyethylene glycol, polyether polyol.
  • the organic peroxide is at least one selected from the group consisting of cumene hydroperoxide, methyl ethyl ketone peroxide and t-butyl peroxybenzoate, and the organic metal salt is cobalt naphthenate, octylic acid
  • the present invention it is possible to provide a resin composition for a pressure vessel which gives a cured product having characteristics required for the pressure vessel (that is, excellent in impact resistance and adhesion to a resin hollow container). it can. Moreover, according to this invention, the pressure vessel excellent in impact resistance and transparency can be provided.
  • the resin composition for pressure vessels of the present embodiment includes the following components (A) to (E) as essential components.
  • the component (A) is a vinyl ester compound.
  • This vinyl ester compound also called epoxy acrylate, is generally polymerizable by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid.
  • a compound having an unsaturated bond is a vinyl ester compound.
  • This vinyl ester compound also called epoxy acrylate
  • the polymerizable monomer used for this vinyl ester resin can be the following (C) component and / or (D) component.
  • the content of the polymerizable monomer in the vinyl ester resin is not particularly limited, but is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 60% by mass.
  • the content of the polymerizable monomer is less than 20% by mass, workability may be deteriorated due to an increase in the viscosity of the vinyl ester resin.
  • the content of the polymerizable monomer exceeds 80% by mass, a cured product having desired characteristics (impact resistance and adhesion) may not be obtained.
  • the vinyl ester compound is not particularly limited, and may be produced by a known method.
  • vinyl esters include a compound obtained by reacting an epoxy resin with an unsaturated monobasic acid, or a saturated polyester or unsaturated polyester having a terminal carboxyl group obtained from a saturated dicarboxylic acid and / or an unsaturated dicarboxylic acid and a polyhydric alcohol.
  • examples include compounds obtained by reacting saturated polyester with an epoxy compound having an ⁇ , ⁇ -unsaturated carboxylic acid ester group.
  • epoxy resins include bisphenol A diglycidyl ether and high molecular weight homologues thereof, novolac-type polyglycidyl ether and high molecular weight homologues thereof, and aliphatic glycidyl ethers such as 1,6-hexanediol diglycidyl ether. Can be mentioned. Among these, from the viewpoint of toughness, bisphenol A type epoxy resins, novolac type polyglycidyl ethers, and brominated products thereof are preferable.
  • unsaturated monobasic acids include acrylic acid and methacrylic acid.
  • saturated dicarboxylic acid and / or unsaturated dicarboxylic acid include adipic acid, sebacic acid, dimer acid and the like.
  • polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2- Examples include methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and the like.
  • the epoxy compound having an ⁇ , ⁇ -unsaturated carboxylic acid ester group include glycidyl methacrylate.
  • the weight average molecular weight of the vinyl ester compound is not particularly limited, but is preferably 1,000 to 6,000, more preferably 1,500 to 5,000. If the weight average molecular weight of the vinyl ester compound is out of the above range, a cured product having desired characteristics (impact resistance and adhesion) may not be obtained.
  • “weight average molecular weight” is measured at normal temperature using gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK) under the following conditions and calculated in terms of polystyrene. (The “weight average molecular weight” of each of the following components means that calculated by the same method and conditions). Column: Showa Denko LF-804, 2 Column temperature: 40 ° C Sample: 0.4 mass% tetrahydrofuran solution of polymer Flow rate: 1 mL / min Eluent: Tetrahydrofuran
  • the (B) component is a urethane (meth) acrylic compound.
  • the urethane (meth) acrylic compound means both a urethane acrylic compound and a urethane methacrylic compound.
  • the urethane (meth) acrylic compound is not particularly limited as long as the weight average molecular weight is in the range of 2,000 to 8,000. If the weight average molecular weight of the urethane (meth) acrylic compound is within the above range, it becomes excellent in compatibility with the vinylester compound. Therefore, the vinylester compound and the urethane (meth) acrylic compound are stored during storage of the resin composition. And a cured product having desired characteristics (impact resistance and adhesion) can be obtained.
  • the weight average molecular weight of the urethane (meth) acrylic compound is preferably 2,500 to 7,500, and most preferably 3,000 to 7,000, from the viewpoint of stably obtaining desired properties.
  • a urethane (meth) acrylic resin in the said technical field.
  • the polymerizable monomer used for this urethane (meth) acrylic resin can be the following (C) component and / or (D) component.
  • the content of the polymerizable monomer in the urethane (meth) acrylic resin is not particularly limited, but is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 60% by mass.
  • the content of the polymerizable monomer is less than 20% by mass, workability may be reduced due to an increase in the viscosity of the urethane (meth) acrylic resin.
  • the content of the polymerizable monomer exceeds 80% by mass, the adhesiveness of the cured product may not be sufficiently obtained.
  • the urethane (meth) acrylic compound may be produced by a known method. Among them, from the viewpoint of various properties of the obtained cured product, an isocyanate compound having two or more isocyanate groups in one molecule, a (meth) acrylic compound having one or more hydroxyl groups in one molecule, and polyethylene glycol A urethane (meth) acrylic compound obtained by reacting with one or more polyols selected from the group consisting of polyether polyols and adipate polyester polyols is preferred.
  • isocyanate compounds having two or more isocyanate groups in one molecule include diphenylmethane diisocyanate, 2,4-tolylene diisocyanate and its isomers, hexamethylene disisocyanate, isophorone diisocyanate, xylylene diisocyanate, and triphenyl. Examples include methane triisocyanate. These isocyanate compounds can be used alone or in combination of two or more. Among these isocyanate compounds, diphenylmethane diisocyanate is preferable because it has excellent reactivity and is less harmful to the human body.
  • the amount of the isocyanate compound used is preferably 5 parts by mass to 90 parts by mass, more preferably 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total raw material of the urethane (meth) acrylic compound. If the amount of the isocyanate compound used is less than 5 parts by mass, desired characteristics (particularly, adhesion of the cured product) may not be obtained. On the other hand, when the usage-amount of this isocyanate compound exceeds 90 mass parts, the softness
  • Examples of (meth) acrylic compounds having one or more hydroxyl groups in one molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol Examples thereof include mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, and pentaerythritol tri (meth) acrylate. These (meth) acrylic compounds can be used alone or in combination of two or more. Among these (meth) acrylic compounds, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable from the viewpoint of cost and safety.
  • the amount of the (meth) acrylic compound used is preferably 5 to 90 parts by mass, more preferably 10 to 50 parts by mass with respect to a total of 100 parts by mass of the urethane (meth) acrylic raw material.
  • the amount of the (meth) acrylic compound used is less than 5 parts by mass, a cured product having desired characteristics (particularly impact resistance) may not be obtained.
  • the usage-amount of this (meth) acrylic compound exceeds 90 mass parts, the softness
  • Polyethylene glycol is not particularly limited, but preferably has a weight average molecular weight of 200 to 2,000, more preferably 400 to 1,500. If the weight average molecular weight is less than 200, the viscosity of the resin composition may be too low. On the other hand, when the weight average molecular weight exceeds 2,000, the compatibility of the urethane (meth) acrylic compound with the vinyl ester compound is lowered, and a cured product having desired characteristics (particularly adhesion) may not be obtained. is there.
  • the amount used is preferably 0.1 parts by weight to 90 parts by weight, more preferably 5 parts by weight to 50 parts by weight with respect to 100 parts by weight as a total of the raw materials of the urethane (meth) acrylic compound. Part. If the amount of polyethylene glycol used is less than 0.1 parts by mass, the compatibility of the urethane (meth) acrylic compound with the vinyl ester compound may be lowered. On the other hand, when the usage-amount of polyethyleneglycol exceeds 90 mass parts, the water resistance of hardened
  • the polyether polyol is not particularly limited, but preferably has a weight average molecular weight of 500 to 1,500, more preferably 800 to 1,200. When the weight average molecular weight is less than 500, the viscosity of the resin composition may be too low. On the other hand, when the weight average molecular weight exceeds 1,500, the compatibility of the urethane (meth) acrylic compound with the vinyl ester compound is lowered, and a cured product having desired characteristics (particularly adhesion) may not be obtained. is there.
  • the amount used is preferably 5 parts by mass to 90 parts by mass, more preferably 20 parts by mass to 60 parts by mass with respect to 100 parts by mass in total of the raw materials of the urethane (meth) acrylic compound. It is.
  • the blending amount of the polyether polyol is less than 5 parts by mass, the flexibility of the cured product may be lowered.
  • the blending amount of the polyether polyol exceeds 90 parts by mass, the compatibility of the urethane (meth) acrylic compound with the vinyl ester compound is lowered, and a cured product having desired characteristics (particularly adhesion) is obtained. There may not be.
  • the adipate-based polyester polyol is not particularly limited, but preferably has a weight average molecular weight of 600 to 3,000, more preferably 800 to 2,500. If the weight average molecular weight is less than 600, the viscosity of the resin composition may be too low. On the other hand, when the weight average molecular weight exceeds 3,000, the compatibility of the urethane (meth) acrylic compound with the vinyl ester compound is lowered, and a cured product having desired characteristics (particularly adhesion) may not be obtained. is there.
  • the amount used is preferably 0.1 parts by mass to 90 parts by mass, more preferably 5 parts by mass to 100 parts by mass in total of the raw materials of the urethane (meth) acrylic compound. 50 parts by mass.
  • the amount of the adipate-based polyester polyol used is less than 0.1 parts by mass, the compatibility of the urethane (meth) acrylic compound with the vinyl ester compound decreases, and a cured product having desired characteristics (particularly adhesion) is obtained. It may not be obtained.
  • the amount of adipate-based polyester polyol used exceeds 90 parts by mass, the water resistance of the cured product may decrease.
  • the method for producing the urethane (meth) acrylic compound is not particularly limited, and can be produced by a known method using the above components.
  • an isocyanate compound having two or more isocyanate groups in one molecule and polyethylene glycol are mixed and reacted to form a terminal isocyanate-containing prepolymer, and then such prepolymer is converted to one in one molecule.
  • a urethane (meth) acrylic compound can be obtained by mixing and reacting the above (meth) acrylic compound having a hydroxyl group. In the above reaction, it is also possible to add a catalyst such as dibutyltin dilaurate, tertiary amines and phosphones.
  • the blending amount is preferably 0.0001 parts by mass to 1 part by mass, more preferably 0.001 parts by mass to 0 parts by mass with respect to 100 parts by mass of the total raw material of the urethane (meth) acrylic compound. .5 parts by mass. If the blending amount of the catalyst is less than 0.0001 parts by mass, the reaction may not proceed sufficiently. On the other hand, when the compounding amount of the catalyst exceeds 1 part by mass, it may be difficult to control the reaction.
  • the reaction temperature and reaction time may be appropriately set.
  • the reaction temperature is preferably 40 ° C. to 120 ° C., and the reaction time is preferably 1 hour to 24 hours.
  • the reaction temperature is less than 40 ° C. or the reaction time is less than 1 hour, the reaction does not proceed sufficiently, and a urethane (meth) acryl compound having desired characteristics may not be obtained.
  • the reaction temperature exceeds 120 ° C. or the reaction time exceeds 24 hours, it may not be preferable in terms of cost and reaction control.
  • the blending ratio of the component (A) and the component (B) in the resin composition is 95: 5 to 30:70, preferably 90:10 to 30:70, more preferably 80:20 to 30 in terms of mass ratio. : 70.
  • cured material will fall.
  • the proportion of the component (B) is too large, the impact resistance of the cured product is lowered.
  • Component (C) is one or more radically polymerizable unsaturated monomers selected from the following general formulas (1) to (3).
  • CH 2 CR-COO (CH 2 ) x OH (1)
  • CH 2 CR-COO (C 3 H 6 O) z H (3)
  • R is a hydrogen atom or a methyl group:
  • x, y and z are natural numbers of 1 to 20, preferably 1 to 10. When x, y, and z exceed 20, workability may be reduced when the pressure vessel is manufactured.
  • Examples of radically polymerizable unsaturated monomers having the above general formula include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) ) Acrylate, polypropylene glycol mono (meth) acrylate, and the like.
  • the mixing ratio of the component (C) is not particularly limited, but is 0.01 to 20% by mass, preferably 0.1 to 10% by mass with respect to the total of the components (A) to (D).
  • the blending ratio of the component (C) is out of the range, the cured product may not have sufficient adhesion and water resistance.
  • the component is a radically polymerizable unsaturated monomer having no hydroxyl group.
  • radically polymerizable unsaturated monomers having no hydroxyl group include styrene, ⁇ -, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene, chlorostyrene, vinyltoluene, Styrene monomers such as divinylbenzene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; ethyl (meth) acrylate, methyl (meth) acrylate, (meth) acrylate-n-propyl, ( (Meth) acrylic acid-i-propyl, (meth) acrylic acid hexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid dodecyl,
  • (Meth) acrylic acid amides vinyl compounds such as (meth) acrylic acid anilide; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid; monomaleimide compounds such as N-phenylmaleimide; N- (meth) acryloylphthalimide and the like It is done.
  • ethylene glycol di (meth) acrylate diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate
  • a (meth) acrylic acid ester compound having two or more (meth) acryloyl groups.
  • These radically polymerizable unsaturated monomers can be used alone or in combination of two or more.
  • a styrene monomer is preferable from the viewpoints of workability, cost, and curability.
  • the blending ratio of the component (D) is not particularly limited, but is 20% by mass to 80% by mass, preferably 25% by mass to 60% by mass, and more preferably 30% by mass with respect to the total of the components (A) to (D). 50% by mass.
  • the content is less than 20% by mass, workability may be reduced due to an increase in the viscosity of the resin composition.
  • the content exceeds 80% by mass, a cured product having desired characteristics may not be obtained.
  • the component (E) is an organic peroxide and / or an organic metal salt. It does not specifically limit as an organic peroxide, A well-known thing can be used. Examples of the organic peroxide include ketone peroxide, perbenzoate, hydroperoxide, diacyl peroxide, peroxyketal, hydroperoxide, diallyl peroxide, peroxyester, and peroxydicarbonate. An azo compound or the like can also be used.
  • More specific examples include methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl perbenzoate, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate.
  • the blending amount is preferably 0.1 to 7 parts by mass, more preferably 0.5 to 5 parts per 100 parts by mass in total of the components (A) to (D). Part by mass.
  • the compounding amount of the organic peroxide is less than 0.1 parts by mass, a cured product having desired characteristics may not be obtained.
  • the amount of the organic peroxide exceeds 7 parts by mass, it is economically disadvantageous and sufficient working time may not be obtained.
  • the organic metal salt is not particularly limited, and known ones can be used.
  • Examples of the organic metal salt include copper naphthenate, cobalt octylate, cobalt naphthenate, cobalt hydroxide, zinc hexate, manganese octylate and the like.
  • cobalt naphthenate, cobalt octylate, and zinc octylate are preferable. These can be used alone or in combination.
  • the blending amount is preferably 0.02 to 10 parts by mass, more preferably 0.1 to 3.3 parts per 100 parts by mass in total of the components (A) to (D). 0 parts by mass.
  • the compounding amount of the organic metal salt is less than 0.02 parts by mass, a desired curing time and a cured state may not be obtained, resulting in poor drying properties.
  • the compounding amount of the organic metal salt exceeds 10 parts by mass, desired pot life and storage stability may not be obtained.
  • the resin composition of the present embodiment contains the above-mentioned components (A) to (D) as essential components, but contains various additives known in the art as long as the effects of the present invention are not impaired. May be.
  • the additive include a photopolymerization initiator, a polymerization inhibitor, a co-promoter, an ultraviolet absorber, a filler, a surface treatment agent and a wetting agent.
  • the photopolymerization initiator is not particularly limited as long as it has photosensitivity in the visible light region and / or the ultraviolet light region, and those known in the technical field can be used.
  • a photopolymerization initiator is generally also called an ultraviolet polymerization initiator or a visible light polymerization initiator.
  • the ultraviolet polymerization initiator include acetophenone-based, benzyl ketal-based, and (bis) acylphosphine oxide-based ultraviolet polymerization initiators. These ultraviolet polymerization initiators can be used alone or in combination of two or more.
  • ultraviolet light such as (bis) acylphosphine oxide having short wavelength ultraviolet light has a relatively long wavelength, preferably visible light region of 380 nm or more, because of its low light transmittance to fiber reinforced resin. It is preferred to use an initiator.
  • UV polymerization initiators examples include 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals) and bis (2,6-dimethoxybenzoyl) -Irgacure-1700 (manufactured by Ciba Specialty Chemicals Co., Ltd.) mixed with -2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) at a mass ratio of 75% / 25% 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgakiure 184, manufactured by Ciba Specialty Chemicals) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (Ciba Special) 7 made by Tea Chemicals Co., Ltd.
  • Darocur 1173 manufactured by Ciba Specialty Chemicals
  • Trade name Irgacure-1800 (manufactured by Ciba Specialty Chemicals Co., Ltd.) mixed at a mass ratio of 25% / 25%, trade name Irgacure-1850 (Ciba Specialty Chemicals (mixed by Ciba Specialty Chemicals Co., Ltd.), 50% / 50% by mass ratio) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure-819, manufactured by Ciba Specialty Chemicals); 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Trade name Lucirin® TPO, manufactured by BASF Corporation); 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,4,6 -Trimethylbenzoyl-diphenylphosphine oxa Examples include trade name Darocur 4265 in which id
  • visible light polymerization initiators examples include visible light polymerization initiators.
  • Independent initiator systems such as camphorquinone, benzyl, trimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, biscyclopentadienyltitanium-di (pentafluorophenyl); organic peroxide catalyst / dye system, diphenyliodonium salt / dye Biimidazole / keto compound, hexaarylbiimidazole compound / hydrogen donating compound, mercaptobenzothiazole / thiopyrylium salt, metal arene / cyanine dye, hexaarylbiimidazole / radical generator described in JP-B-45-37777, etc. Examples of complex initiator systems It is. These can be used alone
  • L ⁇ 1 >, L ⁇ 2 > and L ⁇ 3 > represent an aryl group or a substituted aryl group each independently.
  • the aryl group include a phenyl group and a naphthyl group.
  • Specific examples of hexaarylbiimidazole include bis (2,4,5-triphenyl) imidazole, bis (2-o-chlorophenyl-4,5-diphenyl) imidazole, and bis (2-o, p-dichlorophenyl-4). , 5-diphenyl) imidazole, bis (2-o-bromophenyl-4,5-diphenyl) imidazole, and the like. Among these, bis (2-o-bromophenyl-4,5-diphenyl) imidazole is preferable. Further, hexaarylbiimidazoles described in JP-B 41-3545 may be used.
  • the polymerization inhibitor is not particularly limited, and those known in the technical field can be used.
  • Examples of the polymerization inhibitor include hydroquinone, trimethylhydroquinone, tertiary butyl catechol and the like. These can be used alone or in combination of two or more.
  • the auxiliary promoter is not particularly limited, and those known in the technical field can be used.
  • co-promoters include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N-methyl-N- ⁇ -hydroxyethylaniline, N-butyl-N— ⁇ -hydroxyethylaniline, N-methyl-N- ⁇ -hydroxyethyl-p-toluidine, N-butyl-N- ⁇ -hydroxyethyl-p-toluidine, N-methyl-N- ⁇ -hydroxypropylaniline, N- Methyl-N- ⁇ -hydroxypropyl-p-toluidine, N, N-di ( ⁇ -hydroxyethyl) aniline, N, N-di ( ⁇ -hydroxypropyl) aniline, N, N-di ( ⁇ -hydroxyethyl) Aromatic tertiary amines such as p-toluidine, N,
  • the blending amount is preferably 0.02 to 10 parts by weight, more preferably 0.05 to 5 parts per 100 parts by weight in total of the components (A) to (D). Part by mass. If the blending amount of the auxiliary accelerator is outside this range, the workability and the properties of the cured product may be deteriorated.
  • the ultraviolet absorber is not particularly limited, and those known in the technical field can be used.
  • Examples of ultraviolet absorbers include benzophenone-based, salicylic acid ester-based, benzotriazole-based, benzoate-based, cyanoacrylate-based, and hindered amine-based ultraviolet absorbers. These can be used alone or in combination of two or more.
  • the filler is not particularly limited, and inorganic and organic fillers known in the technical field can be used.
  • examples of the filler include fillers such as silica, alumina, aluminum hydroxide, calcium carbonate, aluminum, and titanium, and short fibers such as glass, carbon, and ceramic stainless steel.
  • the surface treatment agent and the wetting agent are not particularly limited, and those known in the technical field can be used.
  • Examples of the surface treatment agent and the wetting agent include a silane coupling agent and the like, and by blending these surface treatment agent and the wetting agent, it is possible to improve the adhesion to the fiber material.
  • the resin composition of the present embodiment can contain an additive such as paraffin wax for the purpose of improving the drying property.
  • an additive such as paraffin wax for the purpose of improving the drying property.
  • paraffin wax A natural wax, a synthetic wax, etc. are mentioned. Specific examples include paraffin wax having a melting point of about 40 to 80 ° C., BYK-S-750, BYK-S-740, BYK-LP-S6665 (manufactured by BYK Chemie Co., Ltd.), etc. You may use it in combination.
  • a drying property imparting agent as described in JP-A-2002-97233 may be used in combination.
  • the blending amount is not particularly limited, but is generally 0.1 to 5.0 parts by mass with respect to 100 parts by mass in total of the components (A) to (D).
  • the resin composition of the present embodiment may also contain other known additives such as a diluent solvent, an antioxidant, a dye, a pigment, a thixotropic agent, a flame retardant, a low shrinkage agent, and a curing accelerator.
  • the resin composition of the present embodiment can be easily produced by mixing the above components.
  • the mixing method is not particularly limited, and a known method can be used.
  • the resin composition of the present embodiment thus obtained can be used as a primer for producing a pressure vessel because it provides a cured product having excellent adhesion to a resin hollow container.
  • this resin composition can form the fiber reinforced resin layer excellent in adhesiveness and impact resistance with a resin-made hollow container by impregnating and hardening a fiber material. Therefore, this resin composition is suitable for use in the production of pressure vessels.
  • the pressure vessel of the present embodiment includes a resin hollow container and a fiber reinforced resin layer formed on the hollow container.
  • the fiber reinforced resin layer is formed by impregnating the fiber composition with the resin composition of Embodiment 1 and curing it.
  • the fiber material is not particularly limited, and various known inorganic and / or organic fibers can be used. Examples of such fiber materials include glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, high density polyethylene fiber, nylon fiber, vinylon fiber and the like. Among these, glass fiber is preferable from the viewpoint of heat resistance and the like. Moreover, these fiber materials can be used individually or in combination of 2 or more types. Further, the shape of the fiber material is not particularly limited, and those such as roving, tape, and mat can be used.
  • the amount of the fiber material used is preferably 5 to 400 parts by mass, more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the resin composition. If the amount of the fiber material used is less than 5 parts by mass, the desired strength may not be obtained. On the other hand, when the amount of the fiber material used exceeds 400 parts by mass, the adhesiveness and impact resistance may decrease.
  • the fiber material impregnated with the resin composition can be formed on the surface of the hollow container using a winding method.
  • the winding method is not particularly limited, and can be performed by a known method.
  • the winding can be performed by hoop winding or helical winding.
  • the resin hollow container is not particularly limited as long as it is transparent, and various known shapes can be used. Among these, it is preferable that the resin-made hollow containers have a shape having dome portions on both sides of the cylindrical body portion.
  • the hollow resin container may be made of a thermoplastic resin liner material such as polyethylene, high-density polyethylene, polypropylene, polyurethane, polyamide resin, polybutylene terephthalate resin, or a composite material of these resins. preferable.
  • a hollow container can be manufactured by a known method. For example, a hollow container formed from a thermoplastic resin liner material can be manufactured using blow molding, rotational molding, thermal fusion molding, injection molding, or the like.
  • the surface of the resin hollow container is subjected to a known surface treatment such as application of an adhesive (primer), UV treatment, corona discharge treatment, flame treatment, chemical treatment, etc., as necessary, before winding. Also good. These treatments may be used alone or in combination. By these treatments, the adhesion between the fiber reinforced resin layer and the hollow container can be further enhanced. It does not specifically limit as an adhesive agent, A well-known thing can be used.
  • Known adhesives include the use of epoxy adhesives, urethane adhesives, acrylic adhesives, and the like, and special adhesives such as polyolefin resins to which maleic anhydride has been added may be used.
  • Epoxy adhesives include Karenz PE-1 (thiol manufactured by Showa Denko KK), and urethane adhesives include UM-50P (moisture-curable one-part urethane adhesive manufactured by Mitsui Chemicals, Inc.). Adhesive), Scotch Weld DP-8005 and DP-8010 (two-component mixed acrylic adhesives manufactured by Sumitomo 3M Limited) as acrylic adhesives, and Cornova MPO (Nippon Cima Co., Ltd., anhydrous) as special adhesives Amorphous polypropylene resin-based special resin modified with maleic acid), Arrow Base SE-1200 (manufactured by Unitika Ltd.), and the like. These can be used alone or in combination of two or more.
  • the pressure vessel of the present embodiment thus obtained has a fiber reinforced resin layer excellent in adhesion to a resin-made hollow vessel, so that transparency is maintained and an internal liquid or gas is maintained. It becomes easy to check the remaining amount of the like over a long period of time. Moreover, since this pressure vessel has a fiber reinforced resin layer excellent in impact resistance, it can sufficiently withstand pressures such as external pressure and internal pressure and external impacts.
  • the pressure vessel of the present embodiment includes a resin hollow container, a primer layer formed on the hollow container, and a fiber reinforced resin layer formed on the primer layer.
  • the primer layer is formed using the resin composition of the first embodiment. It does not specifically limit as a method of apply
  • the coating amount of the resin composition is not particularly limited, but is preferably 0.01 to 1 kg / m 2 , more preferably 0.05 to 0.8 kg / m 2 .
  • the coating amount is less than 0.01 kg / m 2 , there may be a case where sufficient adhesion between the resin hollow container and the fiber reinforced resin layer cannot be ensured.
  • the coating amount exceeds 1 kg / m 2 , the performance as a pressure vessel may not be sufficiently obtained.
  • the resin hollow container is not particularly limited as long as it is transparent, and various known shapes can be used.
  • This resin hollow container can be the same as the pressure container of the second embodiment. It does not specifically limit as a fiber reinforced resin layer, A well-known thing can be used in the said technical field.
  • the fiber reinforced resin layer used for the pressure vessel of Embodiment 2 as a fiber reinforced resin layer.
  • the pressure vessel according to the present embodiment thus obtained has improved the adhesion between the resin hollow container and the fiber reinforced resin layer by the primer layer, so that the transparency is maintained and the internal liquid or gas is maintained. It becomes easy to check the remaining amount of the like over a long period of time. Moreover, since this pressure vessel has a fiber reinforced resin layer excellent in impact resistance, it can sufficiently withstand pressures such as external pressure and internal pressure and external impacts.
  • the mixture was cooled to 90 ° C., and methacrylic acid: 602 g, tetradecyldimethylbenzylammonium chloride: 9 g, hydroquinone: 0.9 g, and styrene: 1000 g were added to the reaction product, and air was blown at 90 ° C. for 20 hours.
  • the reaction was further terminated, and the reaction was terminated when the acid value reached 10 mgKOH / g to obtain a vinyl ester compound.
  • the weight average molecular weight of the obtained vinyl ester compound was 3,420.
  • the weight average molecular weight was measured by gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK) at room temperature under the following conditions, calculated in terms of polystyrene, and the following synthesis examples And the measurement of the weight average molecular weight in the comparative synthesis example was also performed using the same apparatus.
  • Eluent Tetrahydrofuran
  • 2318 g of styrene monomer was added to this vinyl ester compound, the viscosity at 25 ° C. was 0.3 Pa ⁇ s, and the solid content was 55 mass% bisphenol A vinyl ester resin (VE-1) was used.
  • urethane (meth) acrylic compound [(B) Preparation of urethane (meth) acrylic compound]
  • synthesis examples of urethane (meth) acrylic compounds will be shown.
  • the prepared urethane (meth) acrylic compound was mixed with various radical polymerizable unsaturated monomers (component (C) and / or (D)) to obtain urethane (meth) acrylic resin.
  • Table 1 shows the type and structure of the component (C) used at this time.
  • adipate polyester polyol weight average molecular weight 1000
  • dibutyltin dilaurate 0.15 g
  • 260 g of 2-hydroxyethyl methacrylate was added dropwise to the reaction product over a period of 2 hours, and after completion of the addition, the reaction product was stirred for 5 hours to obtain a urethane methacrylic compound.
  • the weight average molecular weight of the obtained urethane methacrylic compound was 5,821.
  • styrene monomer 662 g and polypropylene glycol monomethacrylate: 265 g were added to the urethane methacrylic compound to obtain a urethane methacrylic resin (U-3).
  • adipate polyester polyol weight average molecular weight 2000
  • dibutyltin dilaurate 0.15 g
  • 260 g of 2-hydroxyethyl methacrylate was added dropwise to the reaction product over a period of 2 hours, and after completion of the addition, the reaction product was stirred for 5 hours to obtain a urethane methacrylic compound.
  • the weight average molecular weight of the obtained urethane methacrylic compound was 6,890.
  • 673 g of styrene monomer and 269 g of polyethylene glycol monoacrylate were added to the urethane methacrylic compound to obtain a urethane methacrylic resin (U-4).
  • cured products were prepared and subjected to impact resistance tests.
  • the cured product was prepared by pouring each resin composition between glass plates arranged to have a thickness of 3 mm, allowing it to stand at room temperature for 1 day, and then curing at 120 ° C. for 2 hours. At the time of evaluation, this cured product was cut and used as a sample.
  • the impact resistance test was conducted in accordance with JIS K6911 (General Thermosetting Plastics Test Method) to determine the Izod impact value. The results are shown in Table 3.
  • the resin compositions of Examples 1 to 8 and Comparative Examples 1 and 5 to 6 gave cured products having high Izod impact values.
  • the cured products obtained from the resin compositions of Comparative Examples 2 to 4 had low Izod impact values, and the resin compositions of Comparative Examples 7 and 8 could not be prepared even with samples that could be tested.
  • a bowl-shaped high-density polyethylene hollow container having dome portions on both sides of a cylindrical body portion (length of the body portion: 593 mm, outer diameter of the body portion: 380 mm, total length including the dome portion: 830 mm, wall thickness: 4 mm) was passed through a flame having a calorific value of 5857 KJ and a temperature of 1300 ° C. using propane gas as a fuel over 10 seconds, and the entire surface of the hollow container was subjected to flame treatment.
  • the primer layer formed using the resin composition of Examples 1 to 8 has a strong adhesion even when an environmental load is applied due to heat cycle.
  • the primer layers formed using the resin compositions of Comparative Examples 1 to 6 did not have sufficient adhesion.
  • the helical winding was wound to a layer thickness of 0.98 mm, and then the hoop winding was wound to a thickness of 0.6 mm.
  • the usage-amount of T glass roving in T glass roving impregnated with each resin composition was 226 mass parts with respect to 100 mass parts of resin compositions. After the winding, it was cured in a heating furnace at 80 ° C.
  • a pressure vessel which gives a cured product having characteristics required for a pressure vessel (that is, excellent impact resistance and adhesion to a hollow resin container).
  • a resin composition can be provided.
  • the pressure vessel excellent in impact resistance and transparency can be provided.

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Pressure Vessels And Lids Thereof (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention concerne une composition de résine pour des récipients sous pression, qui est caractérisée par le fait qu'elle contient (A) un composé ester vinylique, (B) un composé (méth)acrylate d'uréthane ayant une masse moléculaire moyenne en poids de 2 000-8 000, (C) un ou plusieurs monomères insaturés polymérisables par voie radicalaire qui sont choisis parmi des monomères représentés par les formules générales (1)-(3), (D) un monomère insaturé polymérisable par voie radicalaire n'ayant pas de groupe hydroxyle et (E) un peroxyde organique et/ou un sel de métal organique, et qui est également caractérisée en ce que le rapport massique du composant (A) au composant (B) est de 95:5 à 30:70. Cette composition de résine pour des récipients sous pression est apte à fournir un produit durci qui a des caractéristiques requises pour un récipient sous pression (à savoir une excellente résistance au choc et une excellente adhésion à un contenant creux qui est formé d'une résine). CH2=CR-COO(CH2)xOH (1) CH2=CR-COO(C2H4O)yH (2) CH2=CR-COO(C3H6O)zH (3) (Dans les formules, R représente un atome d'hydrogène ou un groupe méthyle, et chacun parmi x, y et z représente un nombre naturel de 1-20.)
PCT/JP2012/077228 2011-11-07 2012-10-22 Composition de résine pour des récipients sous pression et récipient sous pression WO2013069441A1 (fr)

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KR1020147014349A KR101632127B1 (ko) 2011-11-07 2012-10-22 압력 용기용 수지 조성물 및 압력 용기

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WO2017086231A1 (fr) * 2015-11-16 2017-05-26 日本ユピカ株式会社 Article moulé en matière plastique renforcée par des fibres et procédé de production associé
WO2019225055A1 (fr) * 2018-05-22 2019-11-28 昭和電工株式会社 Composition de résine, tampon à polir, et procédé de production d'un tampon à polir
WO2020040052A1 (fr) * 2018-08-24 2020-02-27 昭和電工株式会社 Composition de résine durcissable et produit durci obtenu à partir de celle-ci

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WO2017086231A1 (fr) * 2015-11-16 2017-05-26 日本ユピカ株式会社 Article moulé en matière plastique renforcée par des fibres et procédé de production associé
JPWO2017086231A1 (ja) * 2015-11-16 2018-08-30 日本ユピカ株式会社 繊維強化プラスチック成形品、及びその製造方法
WO2019225055A1 (fr) * 2018-05-22 2019-11-28 昭和電工株式会社 Composition de résine, tampon à polir, et procédé de production d'un tampon à polir
CN111819211A (zh) * 2018-05-22 2020-10-23 昭和电工株式会社 树脂组合物、研磨垫、和研磨垫的制造方法
JPWO2019225055A1 (ja) * 2018-05-22 2021-07-01 昭和電工株式会社 樹脂組成物、研磨パッド、及び研磨パッドの製造方法
JP7110337B2 (ja) 2018-05-22 2022-08-01 昭和電工株式会社 樹脂組成物、研磨パッド、及び研磨パッドの製造方法
CN111819211B (zh) * 2018-05-22 2023-01-24 昭和电工株式会社 树脂组合物、研磨垫、和研磨垫的制造方法
WO2020040052A1 (fr) * 2018-08-24 2020-02-27 昭和電工株式会社 Composition de résine durcissable et produit durci obtenu à partir de celle-ci
JPWO2020040052A1 (ja) * 2018-08-24 2021-08-10 昭和電工株式会社 硬化性樹脂組成物及びその硬化物

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MY185532A (en) 2021-05-19

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