WO2012093465A1 - Procédé de production d'une résine d'acrylate d'acryle - Google Patents

Procédé de production d'une résine d'acrylate d'acryle Download PDF

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Publication number
WO2012093465A1
WO2012093465A1 PCT/JP2011/007289 JP2011007289W WO2012093465A1 WO 2012093465 A1 WO2012093465 A1 WO 2012093465A1 JP 2011007289 W JP2011007289 W JP 2011007289W WO 2012093465 A1 WO2012093465 A1 WO 2012093465A1
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Prior art keywords
meth
monomer
acrylic
side chain
acryloyl group
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PCT/JP2011/007289
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English (en)
Japanese (ja)
Inventor
史延 北山
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株式会社カネカ
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Priority to JP2012551762A priority Critical patent/JP5863673B2/ja
Publication of WO2012093465A1 publication Critical patent/WO2012093465A1/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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—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 side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Definitions

  • the present invention has low adhesiveness after volatilization of the solvent, low volume shrinkage during curing, surface hardness, scratch resistance, abrasion resistance, flexibility, heat resistance, mechanical strength, substrate
  • the present invention relates to a method for producing a curable resin having excellent adhesion, adhesive strength, initial adhesion, chemical resistance, water resistance, and weather resistance.
  • An acrylic acrylate resin having a (meth) acryloyl group in the side chain is used for various applications such as a photosensitive resist, a coating material, and an adhesive as a very useful raw material for improving the performance of the UV curable resin.
  • a photosensitive resist e.g., a photosensitive resist
  • a coating material e.g., a coating material
  • an adhesive e.g., an adhesive for preventing the surface hardness and scratch resistance of the coating film.
  • the surface hardness and scratch resistance of the coating film can be imparted.
  • a method for synthesizing such an acrylic acrylate resin a two-step synthesis method in which a polymer having a functional group is first synthesized and then a monomer having another functional group reactive with the functional group is reacted. Is.
  • Patent Document 1 discloses a method for synthesizing an acrylic acrylate resin having a molecular weight exceeding 1000, in which methacrylic acid is added to a glycidyl-type epoxy group-containing acrylic resin to introduce a methacryloyl group that is a polymerizable double bond. ing.
  • Patent Document 2 includes a layer of a photocurable resin composition containing an acrylic resin having a radically polymerizable unsaturated group in the side chain and a photopolymerization initiator, and substantially free of a crosslinkable compound other than the acrylic resin; And a photocurable sheet including a base sheet that is a thermoplastic acrylic resin sheet having a crosslinked rubber component, and has an excellent appearance, design, abrasion resistance, chemical resistance, and weather resistance.
  • a non-tacky photocurable sheet, a method for producing a molded product using the same, and a photocurable composition that provides such a photocurable sheet are disclosed.
  • Patent Document 3 a polymer is obtained by polymerization of a monomer component containing a monomer having a functional group modified by (meth) acrylic acid, and the number average molecular weight is reduced by modifying this polymer with (meth) acrylic acid.
  • a method for synthesizing a polymer having a (meth) acryloyl group in the side chain of 2000 to 100000 is disclosed, and is characterized by a volume shrinkage rate of less than 3% particularly at the time of three-dimensional crosslinking.
  • Patent Document 1 a copolymer of methyl methacrylate, ethyl acrylate, and glycidyl methacrylate was synthesized by solution polymerization in xylene, and then methacrylic acid. It is disclosed that an acrylic acrylate resin having a methacryloyl group in the side chain can be synthesized by adding.
  • the molecular weight of the obtained polymer in the examples, and since it is generally solution polymerization, it is difficult to obtain a higher molecular weight polymer relatively easily.
  • Patent Document 2 by synthesizing a homopolymer of glycidyl methacrylate or a copolymer of methyl methacrylate and glycidyl methacrylate by solution polymerization in methyl ethyl ketone in the examples, acrylic acid is added.
  • an acrylic acrylate resin having an acryloyl group in the side chain can be synthesized.
  • the number average molecular weight of the obtained polymer is about 15,000 to 25,000, and considering that it is solution polymerization, it is difficult to obtain a higher molecular weight polymer relatively easily. is there.
  • Patent Document 3 in the examples, a copolymer of styrene and epoxycyclohexylmethyl methacrylate was synthesized by solution polymerization in methyl isobutyl ketone, and then acrylic acid was added to the polymer solution, whereby acryloyl was added to the side chain. An acrylic acrylate resin having a group is synthesized.
  • the obtained polymer has a number average molecular weight of 5600 to 56000, detailed molecular weight data such as weight average molecular weight and polydispersity (Mw / Mn) is not described, and is generally a solution polymerization. It is difficult to obtain a higher molecular weight polymer relatively easily.
  • Patent Document 3 is a polymer that uses a large amount of styrene, and is difficult to use in applications that require weather resistance.
  • the conventional method synthesizes an acrylic acrylate resin by solution polymerization, and it is difficult to easily obtain a wide molecular weight region, particularly a high molecular weight acrylic acrylate resin.
  • high molecular weight of acrylic acrylate resin can be easily implemented, in various fields such as photosensitive resists, coating materials, adhesives, etc., the adhesiveness after volatilization of the solvent is low, and the volumetric shrinkage ratio upon curing is small. Excellent surface hardness, scratch resistance, abrasion resistance, flexibility, heat resistance, mechanical strength, adhesion to substrate, adhesive strength, initial adhesion, chemical resistance, water resistance, and weather resistance It becomes possible to provide a curable resin.
  • An object of the present invention is to provide a method for producing an acrylic acrylate resin having a wide molecular weight range, particularly a high molecular weight, which has been difficult to obtain with good productivity by the conventionally proposed solution polymerization method.
  • (meth) acryl means acryl and / or methacryl.
  • the present invention provides an acrylic acrylate resin having a (meth) acryloyl group in the side chain, wherein a (meth) acryloyl group is introduced into the side chain of the acrylic resin P having a weight average molecular weight (Mw) of 150,000 or more.
  • the present invention relates to a manufacturing method of Q.
  • the polydispersity of the acrylic resin P (Mw / Mn, Mn is the number average molecular weight) is preferably 3.0 or more.
  • both the monomer (A) and the monomer (C) are composed of a monomer containing an epoxy group, a monomer containing a hydroxyl group, and a monomer containing a carboxyl group.
  • the monomer (A) preferably contains a monomer containing an epoxy group
  • the monomer (C) contains a monomer containing a carboxyl group.
  • the present invention is characterized in that after the acrylic resin P having a weight average molecular weight (Mw) of 10,000 or more is produced by suspension polymerization, a (meth) acryloyl group is introduced into the side chain of the acrylic resin P.
  • the present invention relates to a method for producing an acrylic acrylate resin Q having a (meth) acryloyl group in the side chain.
  • the polydispersity (Mw / Mn) of the acrylic resin P obtained by suspension polymerization is preferably 1.8 or more.
  • a (meth) acryloyl group is introduced into the side chain of the acrylic resin P by reacting the acrylic resin P with the monomer (C).
  • both the monomer (A) and the monomer (C) are composed of a monomer containing an epoxy group, a monomer containing a hydroxyl group, and a monomer containing a carboxyl group.
  • the monomer (A) preferably contains a monomer containing an epoxy group
  • the monomer (C) contains a monomer containing a carboxyl group.
  • the acrylic resin P is produced by suspension polymerization, the polymerization is started after the polymerization is started in the presence of 350 ppm or less of the initial suspension stabilizer with respect to the monomer constituting the acrylic resin P.
  • the late suspension stabilizer is preferably added when the rate reaches 20 to 90%.
  • the initial suspension stabilizer is preferably a nonionic water-soluble polymer and / or a hardly water-soluble inorganic fine particle.
  • the initial suspension stabilizer is preferably a nonionic water-soluble polymer.
  • the nonionic water-soluble polymer is preferably a polyoxyethylene-polyoxypropylene block copolymer.
  • the acrylic acrylate resin Q having a (meth) acryloyl group in the obtained side chain can be easily adjusted to a wide molecular weight. It is particularly excellent in increasing the molecular weight, and such a high molecular weight acrylic acrylate resin Q is used after various solvents are volatilized when used in various fields such as photosensitive resists, coating materials and adhesives. Adhesiveness, volume shrinkage during curing, surface hardness, scratch resistance, abrasion resistance, flexibility, heat resistance, mechanical strength, adhesion to substrate, adhesive strength, initial adhesion, chemical resistance Excellent in water resistance, water resistance and weather resistance.
  • the acrylic acrylate resin Q having a (meth) acryloyl group in the side chain can be synthesized by, for example, the following two production steps.
  • the acrylic resin P is reacted with a monomer (C) for functional group conversion to a (meth) acryloyl group to obtain an acrylic acrylate resin Q having a (meth) acryloyl group in the side chain.
  • monomers having a hydroxyl group N-methylolacrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Acrylate, etc. 2.
  • Monomers having a carboxyl group (meth) acrylic acid, acryloyloxyethyl monosuccinate, etc.
  • Monomers having an epoxy group glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc. 4.
  • Monomers having an aziridinyl group 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate, etc.
  • Monomers having an amino group (meth) acrylamide, diacetone acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. 6.
  • Monomers having a sulfone group 2-acrylamido-2-methylpropanesulfonic acid, etc.
  • Monomer having an isocyanate group an adduct of a radically polymerizable monomer having a diisocyanate and an active hydrogen, such as an equimolar adduct of 2,4-toluene diisocyanate and 2-hydroxyethyl acrylate
  • the monomer (A) is preferably a monomer having an epoxy group or a monomer having a hydroxyl group from the viewpoint of coloring during coating or processing, weather resistance, etc. More preferred are monomers having
  • Examples of the monomer having an epoxy group include (meth) acrylic acid esters, styrene derivatives containing an epoxy group, fumaric acid esters containing an epoxy group, and vinyl compounds containing an epoxy group.
  • Examples of the monomer having a hydroxyl group include (meth) acrylic acid esters containing a hydroxyl group, styrene derivatives containing a hydroxyl group, fumaric acid esters containing a hydroxyl group, and vinyl compounds containing a hydroxyl group. .
  • epoxy cyclomethyl acrylate epoxy cyclohexyl methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, [ (4-ethenylphenyl) methyl] oxirane, 4- (glycidyloxy) styrene, 4-vinylepoxycyclohexane, diglycidyl fumarate, diepoxycyclohexylmethyl fumarate, 2-hydroxyethyl (meth) acrylate, 2- Examples include hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • the monomer (B) is not particularly limited as long as it is copolymerizable with the monomer (A), and various known monomers can be used.
  • the monomer (B) for example, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms is preferred.
  • the monomer (B) include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate; methyl acrylate, ethyl acrylate, Acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate; vinylcyans such as acrylonitrile and methacrylonitrile; vinylarenes such as styrene, ⁇ -methylstyrene, monochlorostyrene and dichlorostyrene; maleic acid and fumaric acid And their esters; vinyl halides such as vinyl chloride, vinyl bromide and chloroprene; vinyl acetate; alkenes such as ethylene, propylene, butylene, butadiene and isobutylene; Halogenated alkenes; polyfunctional monomers such as allyl methacrylate, diallyl phthalate;
  • the monomer (A) used in the acrylic resin P is contained in an amount of 1 to 100% by weight, preferably 10 to 99.9% by weight, more preferably 10 to 98% by weight, and further preferably 10 to 60% by weight.
  • the monomer (B) is contained in an amount of 99 to 0% by weight, preferably 90 to 0.1% by weight, more preferably 90 to 2% by weight, and still more preferably 40 to 90% by weight.
  • the content of the monomer (A) is less than 1% by weight, the number of (meth) acryloyl groups introduced into the polymer side chain is small, the crosslinking density when cured is too low, and sufficient physical properties after curing, for example, , Surface hardness, abrasion resistance, heat resistance, chemical resistance, water resistance, weather resistance and the like tend to be lowered.
  • the glass transition temperature of the obtained acrylic resin P is not particularly limited, and may be arbitrarily adjusted according to the use to be used. However, the glass transition temperature is -40 to 200 ° C., preferably 0 to 175 ° C. It is preferable to adjust the usage-amount of a monomer (A) and a monomer (B).
  • the polymerization method for polymerizing the monomer (A) alone or the monomer (A) and the monomer (B) is not particularly limited, and a conventionally known polymerization method can be adopted.
  • polymerization methods such as solution polymerization, dispersion polymerization, suspension polymerization, and emulsion polymerization can be used.
  • Solvents that can be used when polymerizing monomer components using the solution polymerization method include toluene, xylene, and other high boiling aromatic solvents; ester solvents such as butyl acetate, ethyl acetate, and cellosolve acetate; Examples thereof include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and alcohol solvents such as methanol, ethanol and isopropyl alcohol.
  • the solvent which can be used is not limited to these solvents. These solvents may be used alone or in combination of two or more. Note that the amount of the solvent used may be appropriately determined in consideration of the concentration of the product.
  • the suspension polymerization method is most preferable from the viewpoint that a wide range of molecular weight adjustment can be easily performed, and in particular, a high molecular weight polymer can be obtained.
  • the acrylic resin P When the acrylic resin P is synthesized by the suspension polymerization method, it may be carried out by a known suspension polymerization method and is not limited. In particular, when high purity is required, such as when acrylic acrylate resin Q is used for applications such as electronic parts, or used for molding processes such as secondary molding, acrylic resin is treated by suspension polymerization as described below.
  • a method for producing the resin P is preferred. That is, the presence of an initial suspension stabilizer of 350 ppm or less based on the monomer (A) alone or the polymerization of the monomer (A) and the monomer (B). Start below. Then, when the polymerization conversion rate of the monomer reaches 20 to 90%, preferably 20 to 75%, the late suspension stabilizer is added.
  • a polymer-type suspension stabilizer composed of a nonionic water-soluble polymer, water such as tribasic calcium phosphate and barium sulfate. Soluble inorganic particulate type suspension stabilizers can be used.
  • Suspension stabilizers composed of anionic water-soluble polymers include polyacrylic acid, sodium polyacrylate, potassium polyacrylate, polymethacrylic acid, polysodium methacrylate, polypotassium methacrylate, sodium methacrylate-alkyl methacrylate. An ester copolymer etc. are mentioned. Of these, sodium polyacrylate and polysodium methacrylate are preferable.
  • Water-soluble polymers such as block copolymers, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene lauryl amine are listed.
  • Preferred are polyvinyl alcohol, polyoxyethylene-polyoxypropylene copolymer, and more preferred are polyoxyethylene-polyoxypropylene block copolymers.
  • suspension stabilizer composed of inorganic fine particles having poor water solubility
  • examples of the suspension stabilizer composed of inorganic fine particles having poor water solubility include barium sulfate, tricalcium phosphate, and magnesium carbonate. Tricalcium phosphate is preferred.
  • the poorly water-soluble herein means that the solubility in water at 25 ° C. is 1% by weight or less.
  • the initial suspension stabilizer of the present invention refers to a suspension stabilizer present at the start of polymerization. Since the initial suspension stabilizer is present in the system from the beginning of the polymerization, it is easily taken into the resulting granular polymer, and the initial suspension stabilizer remains in the granular polymer even after various post-treatment steps. To do. As a result, the purity of the granular polymer is lowered, and problems such as deterioration of transparency and yellowing are brought about during the molding process. For example, when a small amount of water-insoluble inorganic fine particles is used as a suspension stabilizer in a large amount from the initial stage of polymerization, transparency in the molding process is inevitably inferior because it remains inside the granular polymer. Further, when a large amount of a water-soluble polymer is used as a suspension stabilizer from the initial stage of polymerization, yellowing occurs due to thermal deterioration during the molding process by remaining inside the granular polymer.
  • the amount of the initial suspension stabilizer used is 350 ppm or less, preferably 200 ppm or less, more preferably 40 ppm or less, and most preferably the initial suspension stabilizer is not used with respect to the monomer constituting the acrylic resin P. Highly preferred.
  • the amount of the initial suspension stabilizer used is the same as that used throughout the polymerization reaction. It means the relative amount to the total amount of the mer. In the prior art, it was considered essential to initiate polymerization in the presence of a relatively large amount of initial suspension stabilizer in order to ensure polymerization stability.
  • the polymerization conversion rate is a value based on the total amount of monomers used in the entire process of the polymerization reaction. It is.
  • the initial suspension stabilizer is selected from polymer types such as anionic water-soluble polymers and nonionic water-soluble polymers, and inorganic fine particle types. These can be used alone or in combination of two or more. However, when an anionic water-soluble polymer is used, if it remains in the granular polymer, it tends to cause yellowing particularly during molding, so an initial stage selected from nonionic water-soluble polymers and poorly water-soluble inorganic fine particles It is preferred to use a suspension stabilizer. Furthermore, it is more preferable to use a nonionic water-soluble polymer as an initial suspension stabilizer because poorly water-soluble inorganic fine particles also remain in the granular polymer because it tends to deteriorate transparency during molding. .
  • a polyoxyethylene-polyoxypropylene block copolymer is most preferred because yellowing during molding is less.
  • the polyoxyethylene-polyoxypropylene block copolymer itself has good thermal stability during molding and is not easily yellowed.
  • a highly hydrophobic polyoxypropylene (PPO) chain is a monomer oil. Adsorbing to a hydrophobic surface such as droplets or polymer particles, and the hydrophilic polyoxyethylene (PEO) chain is hydrated and spreads widely in the aqueous phase, thereby exhibiting an excellent dispersion effect. As a result, the amount of the suspension stabilizer used can be greatly reduced, transparency deterioration and yellowing hardly occur during the molding process, and it is advantageous in terms of cost.
  • the late suspension stabilizer added when the polymerization conversion of the monomer reaches 20 to 90%, preferably 20 to 75%, increases the polymer ratio in the monomer oil droplets as the polymerization proceeds, Since the monomer oil droplets are added at the stage where the coalescence and dispersion of the monomer oil droplets are settled and fixed, it is difficult to remain inside the granular polymer. Therefore, purity is high and it becomes possible to suppress deterioration of transparency and yellowing during molding. If the suspension stabilizer is added later when the polymerization conversion rate is less than 20%, the suspension stabilizer is incorporated into the resulting granular polymer, leaving only a granular polymer with low purity. It is not obtained and fine powder is easily generated.
  • the late suspension stabilizer is used in an amount of 0.005 to 2.0 parts by weight, preferably 0.005 to 1.0 parts by weight, more preferably 0.005 to 0 parts per 100 parts by weight of the monomer. It is selected from the range of 2 parts by weight, but is preferably as small as possible within the range where the polymerization system is stable.
  • the late suspension stabilizer is selected from polymer types such as anionic water-soluble polymers and nonionic water-soluble polymers, and inorganic fine particle types. These can be used alone or in combination of two or more.
  • a nonionic water-soluble polymer and an inorganic fine particle type are preferable, and a nonionic water-soluble polymer is more preferable.
  • a nonionic water-soluble polymer a polyoxyethylene-polyoxypropylene block copolymer is most preferable.
  • the late suspension stabilizer can be added all at once, all at once, or continuously.
  • a suspension aid can be used in combination with the suspension stabilizer.
  • the suspension aid here is a substance also known as a dispersion aid, for example, an anionic interface such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, etc.
  • Low-molecular surfactants such as activators, water-soluble inorganic salts such as boric acid, sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfate, and the like.
  • disodium hydrogen phosphate is preferable.
  • the suspension aid may be present in the polymerization system from the start of the polymerization because it does not easily cause deterioration of transparency or yellowing during the molding process.
  • inorganic fine particles when used as a suspension stabilizer, the surface of the inorganic fine particles becomes amphiphilic to the interface between the monomer and water by using a low molecular surfactant as a suspension aid. The effect can be enhanced.
  • a water-soluble polymer such as polyvinyl alcohol
  • the crosslinking reaction of the hydroxyl group of polyvinyl alcohol proceeds by using an inorganic salt such as boric acid or disodium hydrogen phosphate as a suspension aid.
  • an inorganic salt such as boric acid or disodium hydrogen phosphate
  • suspension stabilizer is a nonionic water-soluble polymer
  • the crosslinking reaction between ether bonds proceeds, and the protective ability can be improved.
  • suspension aids are preferably used in combination with a suspension stabilizer because the polymerization system can be further stabilized.
  • water-soluble inorganic salts are preferable from the viewpoint of suppressing yellowing during molding.
  • the suspension aid of the present invention refers to those having a solubility in water at 25 ° C. of 2% by weight or more. In this respect, it is clearly distinguished from the above-described suspension stabilizer composed of poorly water-soluble inorganic fine particles.
  • the polymerization initiator used in the suspension polymerization of the present invention may be a well-known one for the polymerization of vinyl monomers.
  • Peroxyesters organic peroxides such as di-8,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, benzoyl peroxide, etc., and one or more of these are used. It is done. These polymerization initiators are used in an amount of 0.02 to 2% by weight based on the monomer or monomer mixture.
  • a known chain transfer agent may be used.
  • the chain transfer agent include alkyl mercaptans, alkyl sulfides, alkyl disulfides, thioglycolic acid esters such as 2-ethylhexyl thioglycolate, mercapto acids such as ⁇ -methylstyrene dimer and ⁇ -mercaptopropionic acid, benzyl mercaptan, and thiophenol.
  • Aromatic mercaptans such as thiocresol and thionaphthol.
  • the molecular weight of the polymer is not particularly limited, and may be adjusted to a molecular weight suitable for the intended use.
  • the acrylic resin P has a high molecular weight, which reduces the adhesiveness after volatilizing the solvent. , Volume shrinkage during curing is small, surface hardness, scratch resistance, abrasion resistance, flexibility, heat resistance, mechanical strength, adhesion to substrate, adhesive strength, chemical resistance, water resistance, Since it becomes curable resin excellent in weather resistance, it is preferable.
  • the initial adhesive strength is strong and the sagging is difficult, so workability is improved.
  • the molecular weight of the acrylic resin P is 10,000 or more in terms of weight average molecular weight (Mw), preferably 80,000 or more, more preferably 100,000 or more, further preferably 150,000 or more, and most preferably 200,000 or more. is there.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • handling properties solution viscosity
  • the polydispersity is 1.8 or more, preferably 2.0 or more, more preferably 2.5 or more, and most preferably 3.0 or more.
  • the method for adding the polymerization initiator and the chain transfer agent is not particularly limited, but after the polymerization initiator and the chain transfer agent are both dissolved in the monomer, the monomer is suspended in water and the polymerization reaction is carried out as it is. Is most preferred.
  • the ratio of the aqueous medium to the monomer or monomer mixture is in the range of 1: 1 to 10: 1, preferably 1: 1 to 4: 1. If the amount of the aqueous medium is too small, the dispersion of the monomers tends to be uneven, the polymerization system becomes unstable, and if it is large, the production efficiency is disadvantageous.
  • a monomer or a monomer mixture is suspended in water and a polymerization reaction is carried out as it is, or a part of the monomer or monomer mixture is washed with water.
  • the polymerization reaction is started by suspending in water, and as the polymerization reaction proceeds, the remaining monomer or monomer mixture, or the aqueous suspension of the monomer or monomer mixture is divided into one or several stages.
  • all known methods such as a method of continuously adding to a polymerization reaction tank and carrying out a polymerization reaction can be used.
  • the polymerization temperature condition is about 60 to 120 ° C., and may be a temperature suitable for the polymerization initiator used.
  • the time required for the polymerization varies depending on the kind and amount of the polymerization initiator or the polymerization temperature, but is usually 1 to 24 hours.
  • Stirring conditions may be the same as those for producing a (meth) acrylic resin by ordinary suspension polymerization.
  • a polymerization vessel equipped with a well-known stirring blade for example, a turbine blade, a fiddler blade, a propeller blade, a blue margin blade, an H-shaped blade, or the like is used, and the vessel is provided with a baffle. It is common.
  • a granular polymer can be obtained by washing, dehydrating and drying by a known method.
  • the average particle diameter of the polymer particles of the acrylic resin P obtained by suspension polymerization is not particularly limited, but is preferably 50 to 4000 ⁇ m obtained by a normal suspension polymerization operation. From the viewpoint of handling properties in the next functional group conversion step (Production Step 2), a more preferable average particle size is 50 to 1000 ⁇ m, and further preferably 50 to 800 ⁇ m.
  • the monomer (C) described in (a) to (d) below is reacted with the acrylic resin P synthesized from the monomer (A) having a functional group convertible to a (meth) acryloyl group.
  • a (meth) acryloyl group is introduced into the side chain of the acrylic resin P, and an acrylic acrylate resin Q having a (meth) acryloyl group in the side chain is obtained.
  • the acrylic resin P is a polymer synthesized from the monomer (A) having an epoxy group, an isocyanate group or an aziridinyl group, the monomer (C) having a hydroxyl group or a monomer having a carboxyl group
  • the body (C) is subjected to an addition reaction.
  • the acrylic resin P is a polymer synthesized from a monomer (A) having a hydroxyl group or a carboxyl group, a monomer (C) having an epoxy group, a monomer having an aziridinyl group (C ), An isocyanate group-containing monomer (C), or an equimolar adduct (C) of a diisocyanate compound and a hydroxyl group-containing acrylate monomer.
  • the molar fraction of the monomer (A) and the monomer (C) is preferably 0.1 to 1.5. However, if the monomer (C) remains after the reaction, the physical properties of the final product may be lowered. Thus, it is possible to control the number of (meth) acryloyl groups by controlling the molar fraction of the monomer (A) and the monomer (C), and the physical properties of the cured product are easily and preferable. Can be adjusted.
  • the solvent used in the reaction of the acrylic resin P and the monomer (C) is not particularly limited, but is preferably a solvent in which the acrylic resin P is soluble.
  • a solvent in which the acrylic resin P is soluble for example, toluene, xylene, and other high boiling aromatic solvents; ester solvents such as butyl acetate, ethyl acetate, and cellosolve acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohols such as methanol, ethanol, and isopropyl alcohol A solvent etc. are mentioned. These solvents may be used alone or in combination of two or more.
  • the amount of the solvent used, that is, the solid content concentration may be appropriately determined in consideration of the solution viscosity, the reaction rate, the heat removal efficiency of heat generated during the reaction, the productivity, etc.
  • the solid content concentration is 10 to 90% by weight, Preferably, it is 20 to 60% by weight.
  • the reaction temperature is not particularly limited, but is preferably in the range of 20 to 200 ° C, more preferably 40 to 140 ° C.
  • a catalyst such as triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium ion is used to promote the reaction of the monomer (C) with the side chain functional group of the acrylic resin P. It is preferable to use dye, triphenylphosphine, triphenylstibine, chromium octoate, zirconium octoate or the like.
  • the amount of the catalyst used is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, based on the reaction raw material mixture.
  • a polymerization inhibitor such as hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, H-TEMPO (4-hydroxy-2,2,6,6- Tetramethylpiperidine-1-oxyl) or the like is preferably used.
  • the amount used is not particularly limited, but is preferably 0.01 to 5% by weight, more preferably 0.01 to 1% by weight, based on the reaction raw material mixture.
  • it is preferable to prevent the polymerization by reacting air or a mixed gas containing oxygen, for example, an oxygen / nitrogen mixed gas, into the reaction solution, preferably in the reaction solution. .
  • the amount of side chain (meth) acryloyl groups of acrylic acrylate resin Q is not particularly limited, and is introduced according to the intended use. What is necessary is just to adjust the (meth) acryloyl group amount. Above all, the average value of 1 to 700 g / mol calculated from the charged values has low adhesion after volatilization of the solvent, surface hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance. From the viewpoint of improving the mechanical strength and the like. A more preferable range of double bond equivalent is 1 to 600 g / mol on average.
  • the acrylic acrylate resin Q obtained by the present invention, for example, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, isopropyl alcohol, etc.
  • the acrylic resin P the acrylic acrylate resin Q can be diluted with an organic solvent and / or monomers as used in the synthesis.
  • monomers used for dilution known and commonly used monomers such as vinyl ether compounds, propenyl ether compounds, styrene derivatives, epoxy compounds, lactone compounds, oxetane compounds, (meth) acrylic acid esters and the like can be used. These may be used independently and may use multiple types together.
  • the method of curing the composition containing the acrylic acrylate resin Q having a (meth) acryloyl group in the side chain obtained by the present invention is not particularly limited, and a known method such as thermosetting or photocuring can be used. If photocuring such as ultraviolet rays is performed, a photopolymerization initiator that generates radicals by light irradiation is added as necessary.
  • the type of the photopolymerization initiator is not particularly limited, and known ones can be used. Typical examples include 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyl dimethyl ketal, benzoin isopropyl ether, benzophenone and the like.
  • an initiator that does not contain an amino group in the molecule such as an acetophenone series, a benzophenone series, or an acylphosphine oxide series, is preferable.
  • care must be taken because depending on the molding method, the temperature may be temporarily higher than the boiling point of the compound during molding.
  • an oxygen polymerization-inhibiting curing inhibitor such as n-methyldiethanolamine may be added.
  • various peroxides may be added in consideration of curing using heat during molding.
  • a peroxide having a low critical temperature such as lauroyl peroxide, t-butylperoxy-2, etc. -Ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like are preferably used.
  • the addition amount of the photopolymerization initiator is desirably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic acrylate resin Q having a (meth) acryloyl group in the side chain because the residual amount after curing affects the weather resistance. Further, 0.1 to 5 parts by weight is preferable. Especially, when using the amino type photoinitiator relevant to yellowing at the time of hardening, 1 mass part or less is desirable.
  • sensitizers modifying resins, dyes, pigments and leveling agents and repellency inhibitors, UV absorbers, light stabilizers, oxidation stabilizers, catalysts, antifoaming agents, polymerization accelerators, flame retardants, Additives such as infrared absorbers can be blended.
  • the above sensitizer accelerates the curing reaction, and examples thereof include benzophenone, benzoin isopropyl ether, and thioxanthone.
  • the energy ray source for curing the acrylic acrylate resin Q obtained by the present invention is not particularly limited, but examples include high pressure mercury lamp, electron beam, ⁇ ray, carbon arc lamp, xenon lamp, metal halide lamp, LED-UV, etc. Is mentioned.
  • the polymerization conversion rate was calculated according to the following procedure.
  • Polymerization conversion rate (%) [(Total weight of charged raw materials ⁇ solid component ratio ⁇ total weight of raw materials other than water / monomer) / weight of charged monomer] ⁇ 100 (Formula 1) The volume average particle diameter was measured using Microtrac MT3000II (manufactured by Nikkiso Co., Ltd.).
  • the molecular weight was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a high-speed GPC device HEC-8220GPC manufactured by Tosoh Corporation
  • a column using TSK guard column SuperHZ-H manufactured by Tosoh Corporation and tetrahydrofuran as a GPC solvent were used.
  • Example 1 Manufacture of acrylic resin P-1> An 8-liter glass reactor equipped with an H-type stirrer was charged with 200 parts by weight of deionized water and 0.5 parts by weight of disodium hydrogen phosphate as a suspension aid. Next, while stirring at 250 rpm, 0.95 parts by weight of lauroyl peroxide was dissolved in the reactor, and 60 parts by weight of methyl methacrylate, 40 parts by weight of glycidyl methacrylate, and 0.35 parts by weight of 2-ethylhexyl thioglycolate. The monomer mixture was added and the temperature was raised to 60 ° C. while the inside of the reactor was purged with nitrogen to initiate polymerization. No initial suspension stabilizer was added.
  • Adekapluronic F-68 manufactured by ADEKA Corporation, polyoxyethylene-polyoxypropylene block copolymer
  • ADEKA Corporation polyoxyethylene-polyoxypropylene block copolymer
  • the polymerization conversion rate was 42%.
  • the mixture was further reacted at 60 ° C. for 60 minutes, and then heated to 80 ° C. and stirred for 3 hours to complete the polymerization.
  • the obtained polymer was washed four times with deionized water three times the amount of the resin and dried to obtain beads-like suspension polymer particles (acrylic resin P-1).
  • the average particle size of the acrylic resin P-1 was 665 ⁇ m
  • Mw was 225000
  • Mw / Mn 3.9.
  • the number of stirring was adjusted to 250 rpm, and H-- was added while bubbling nitrogen / oxygen mixed gas into the methyl ethyl ketone solution under a nitrogen stream.
  • the reaction was started by adding 0.12 parts by weight of TEMPO, 20.3 parts by weight of acrylic acid, and 9.62 parts by weight of N, N-dimethylbenzylamine. After 440 minutes from the start of the reaction, 1.20 parts by weight of N, N-dimethylbenzylamine was added and the mixture was further stirred for 100 minutes to obtain an acrylic resin Q-1 having an acryloyl group in the side chain. It was also confirmed that the reaction between the glycidyl group and acrylic acid progressed almost 100% by quantifying the remaining acrylic acid by neutralization titration with potassium hydroxide.
  • Irgacure 184 manufactured by BASF, 1-hydroxy-cyclohexyl-phenyl- was used as a photopolymerization initiator. 3 parts by weight with respect to 100 parts by weight of the pure polymer, and applied with a bar coater with a film thickness of 9 ⁇ m on a commercially available transparent acrylic film. After drying at 80 ° C.
  • a UV curing device (LC-6B, Fusion UV Systems Japan Co., Ltd.) was used to cure by irradiating with ultraviolet rays having an integrated illuminance of 467 mJ / cm 2 , and the following evaluation was performed.
  • the obtained laminated sheet conforms to the accelerated weather resistance test JIS K7102, using a sunshine weatherometer (manufactured by Suga Test Instruments, model: WEL-SUN-HC (H)) with a black panel temperature of 63 ° C and water spray. The appearance after exposure for 5000 hours under the condition of 12 minutes in 60 minutes was visually evaluated.
  • ⁇ good, ⁇ : whitening or cracking ⁇ curing shrinkage (volumetric shrinkage) 3 parts by weight of Irgacure 184 with respect to 100 parts by weight of the polymer is added to the methyl ethyl ketone solution of the acrylic acrylate resin Q-1 obtained in Example 1, and applied onto a glass plate with a bar coater having a film thickness of 9 ⁇ m. After drying at 80 ° C. for 1 minute with a drier, the UV curable apparatus (LC-6B, Fusion UV Systems Japan Co., Ltd.) was used to irradiate UV light with an integrated light amount of 467 mJ / cm 2 to obtain acrylic acrylate resin Q- 1 cured product was prepared. The specific gravity at 23 ° C.
  • Adhesive strength 45 parts by weight of acrylic acrylate resin Q-1 obtained in Example 1, 10 parts by weight of acryloylmorpholine, 20 parts by weight of phenoxyethyl acrylate, isobornyl acrylate 15 parts by weight, 5 parts by weight of vinylcaprolactam and 5 parts by weight of Irgacure 184 were charged into a reaction vessel equipped with a stirrer and stirred at 50 to 60 ° C. to prepare an adhesive composition.
  • the number of stirring was adjusted to 250 rpm, 0.12 parts by weight of H-TEMPO, 20.3 parts by weight of acrylic acid, N 2 while bubbling nitrogen / oxygen mixed gas into the methyl ethyl ketone solution , N-dimethylbenzylamine 9.62 parts by weight was added to initiate the reaction. After 440 minutes from the start of the reaction, 1.20 parts by weight of N, N-dimethylbenzylamine was added and the mixture was further stirred for 100 minutes to obtain an acrylic resin Q-2 having an acryloyl group in the side chain. It was also confirmed that the reaction between the glycidyl group and acrylic acid progressed almost 100% by quantifying the remaining acrylic acid by neutralization titration with potassium hydroxide.
  • Example 2 Manufacture of acrylic resin P-3> An 8-liter glass reactor equipped with an H-type stirrer was charged with 200 parts by weight of deionized water and 0.5 parts by weight of disodium hydrogen phosphate as a suspension aid. Next, while stirring at 250 rpm, the reactor comprises 90 parts by weight of methyl methacrylate in which 0.95 parts by weight of lauroyl peroxide was dissolved, 10 parts by weight of glycidyl methacrylate, and 0.20 parts by weight of 2-ethylhexyl thioglycolate. The monomer mixture was added and the temperature was raised to 60 ° C. while the inside of the reactor was purged with nitrogen to initiate polymerization. No initial suspension stabilizer was added.
  • Adekapluronic F-68 manufactured by ADEKA Corporation, polyoxyethylene-polyoxypropylene block copolymer which is a nonionic water-soluble polymer as a late suspension stabilizer Part by weight was added.
  • the polymerization conversion rate at this point was 40%.
  • the mixture was further reacted at 60 ° C. for 65 minutes, and then heated to 80 ° C. and stirred for 3 hours to complete the polymerization.
  • the obtained polymer was washed four times with deionized water three times the amount of the resin and dried to obtain bead-like suspension polymer particles (acrylic resin P-3).
  • Example 3 Manufacture of acrylic resin P-4> An 8-liter glass reactor equipped with an H-type stirrer was charged with 200 parts by weight of deionized water and 0.5 parts by weight of disodium hydrogen phosphate as a suspension aid. Next, while stirring at 250 rpm, 0.95 parts by weight of lauroyl peroxide was dissolved in the reactor, 80 parts by weight of methyl methacrylate, 20 parts by weight of glycidyl methacrylate, and 0.25 parts by weight of 2-ethylhexyl thioglycolate. The monomer mixture was added and the temperature was raised to 60 ° C. while the inside of the reactor was purged with nitrogen to initiate polymerization. No initial suspension stabilizer was added.
  • Adekapluronic F-68 manufactured by ADEKA Corporation, polyoxyethylene-polyoxypropylene block copolymer which is a nonionic water-soluble polymer as a late suspension stabilizer Part by weight was added.
  • the polymerization conversion rate at this point was 40%.
  • the mixture was further reacted at 60 ° C. for 60 minutes, and then heated to 80 ° C. and stirred for 3 hours to complete the polymerization.
  • the obtained polymer was washed four times with deionized water three times the amount of the resin and dried to obtain bead-like suspension polymer particles (acrylic resin P-4).
  • Example 4 Synthesis of acrylic resin Q-5 having (meth) acryloyl group in side chain> To a 200 ml glass reactor equipped with a meniscus stirrer, 390 parts by weight of 1-methoxy-2-propanol and 100 parts by weight of acrylic resin P-4 were added and stirred at 300 rpm while nitrogen gas and a nitrogen / oxygen mixed gas ( The temperature was raised to 115 ° C. under an air flow (oxygen content 9%).
  • Example 5 Manufacture of acrylic resin P-5> An 8-liter glass reactor equipped with an H-type stirrer was charged with 200 parts by weight of deionized water and 0.5 parts by weight of disodium hydrogen phosphate as a suspension aid. Next, while stirring at 250 rpm, the reactor comprises 85 parts by weight of methyl methacrylate in which 0.95 parts by weight of lauroyl peroxide was dissolved, 15 parts by weight of glycidyl methacrylate, and 0.20 parts by weight of 2-ethylhexyl thioglycolate. The monomer mixture was added and the temperature was raised to 60 ° C. while the inside of the reactor was purged with nitrogen to initiate polymerization. No initial suspension stabilizer was added.
  • Adekapluronic F-68 manufactured by ADEKA Corporation, polyoxyethylene-polyoxypropylene block copolymer
  • ADEKA Corporation polyoxyethylene-polyoxypropylene block copolymer
  • the polymerization conversion rate at this point was 38%.
  • the mixture was further reacted at 60 ° C. for 65 minutes, and then heated to 80 ° C. and stirred for 3 hours to complete the polymerization.
  • the obtained polymer was washed four times with deionized water three times the amount of the resin and dried to obtain bead-like suspension polymer particles (acrylic resin P-5).
  • the average particle size of the acrylic resin P-5 was 500 ⁇ m
  • Mw was 209000
  • Mw / Mn 2.5.
  • the acrylic acrylate resin having a (meth) acryloyl group in the side chain obtained by the present invention has low tackiness after coating and drying and is non-adhesive. Therefore, a non-adhesive photocurable printing sheet that can be printed in color or design can be easily obtained.
  • a surface with good appearance, wear resistance, weather resistance and chemical resistance can be formed on the resin molded product with a design such as color or design. .
  • abrasion resistance, weather resistance, and chemical resistance are also good, a surface having good abrasion resistance, weather resistance, and chemical resistance while taking advantage of the transparency on the transparent resin. It can be formed, and can be suitably used for automobiles, railway vehicles, airplane windows, headlamp covers, windshield parts, and the like. In addition, the number of steps can be omitted compared to the case where the surface of the molded product is painted, the productivity is good, and the influence on the environment is small. Furthermore, since the transparency is good, application to the optical field is also possible. In addition, since it has excellent adhesive properties, it is suitable as various adhesives, particularly as an ultraviolet ray or electron beam curable adhesive.
  • UV curable adhesives include bonding of substances, Utilizing the difference in adhesive curing caused by irradiation, it is used for uneven image formation, printing, printed wiring and the like.
  • Other common examples include glued cut glass, glass crafts, pendant glass glue, optical lens glue, stained glass frame glue, injection needle
  • the electron beam curable adhesive include curing of magnetic recording media, curing of printing ink, lamination of food packaging film, release paper, etc. The product of the present invention is suitably used in each application. can do.

Abstract

L'invention concerne un procédé de production d'une résine durcissable avec une faible viscosité après volatilisation d'un solvant, un faible rétrécissement du volume pendant le durcissement, et une dureté de surface, une résistance à l'abrasion, une résistance à l'usure, une flexibilité, une résistance à la chaleur, une résistance mécanique, une adhésion aux substrats, une résistance adhésive, une capacité d'adhésion initiale, une résistance aux produits chimiques, une résistance à l'eau et une résistance aux intempéries qui sont excellentes. Une résine d'acrylate d'acryle portant un groupe (méth)acryloyle sur sa chaîne latérale est produite en introduisant un groupe (méth)acryloyle sur la chaîne latérale d'une résine acrylique (P) ayant un poids moléculaire moyen en poids (Mp) de 150 000 min. La résine d'acrylate d'acryle avec un groupe (méth)acryloyle sur sa chaîne latérale est produite en produisant en premier lieu, par polymérisation en suspension, la résine acrylique ayant un poids moléculaire moyen en poids (Mp) de 150 000 min, puis en introduisant un groupe (méth)acryloyle sur la chaîne latérale de la résine acrylique (P).
PCT/JP2011/007289 2011-01-06 2011-12-27 Procédé de production d'une résine d'acrylate d'acryle WO2012093465A1 (fr)

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WO2016051915A1 (fr) * 2014-09-29 2016-04-07 株式会社スリーボンド Composition de résine durcissable
WO2017038731A1 (fr) * 2015-08-28 2017-03-09 株式会社日本触媒 Particules fines de polymère organique
WO2019086793A1 (fr) 2017-10-30 2019-05-09 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant une amine specifique et un systeme de reticulation a base de peroxyde et d'un derive d'acrylate
WO2019106292A1 (fr) 2017-11-29 2019-06-06 Compagnie Generale Des Etablissements Michelin Composition de caoutchouterie dont le systeme de reticulation comprend un coupage de peroxydes et un derive d'acrylate
WO2020038763A1 (fr) 2018-08-23 2020-02-27 Compagnie Generale Des Etablissements Michelin Pneumatique muni d'une composition comprenant un elastomere riche en ethylene, un peroxyde et un derive d'acrylate specifique
WO2020216635A1 (fr) 2019-04-26 2020-10-29 Compagnie Generale Des Etablissements Michelin Bandage pour roue de véhicule transportable manuellement

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WO2016051915A1 (fr) * 2014-09-29 2016-04-07 株式会社スリーボンド Composition de résine durcissable
CN106715499A (zh) * 2014-09-29 2017-05-24 三键有限公司 固化性树脂组合物
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WO2019086793A1 (fr) 2017-10-30 2019-05-09 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc comprenant une amine specifique et un systeme de reticulation a base de peroxyde et d'un derive d'acrylate
WO2019106292A1 (fr) 2017-11-29 2019-06-06 Compagnie Generale Des Etablissements Michelin Composition de caoutchouterie dont le systeme de reticulation comprend un coupage de peroxydes et un derive d'acrylate
WO2020038763A1 (fr) 2018-08-23 2020-02-27 Compagnie Generale Des Etablissements Michelin Pneumatique muni d'une composition comprenant un elastomere riche en ethylene, un peroxyde et un derive d'acrylate specifique
FR3085166A1 (fr) 2018-08-23 2020-02-28 Compagnie Generale Des Etablissements Michelin Pneumatique muni d'une composition comprenant un elastomere riche en ethylene, un peroxyde et un derive d'acrylate specifique
WO2020216635A1 (fr) 2019-04-26 2020-10-29 Compagnie Generale Des Etablissements Michelin Bandage pour roue de véhicule transportable manuellement
FR3095447A1 (fr) 2019-04-26 2020-10-30 Compagnie Generale Des Etablissements Michelin Bandage pour roue de véhicule transportable manuellement

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