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WO2018008580A1 - Composition durcissable et produit - Google Patents

Composition durcissable et produit Download PDF

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Publication number
WO2018008580A1
WO2018008580A1 PCT/JP2017/024302 JP2017024302W WO2018008580A1 WO 2018008580 A1 WO2018008580 A1 WO 2018008580A1 JP 2017024302 W JP2017024302 W JP 2017024302W WO 2018008580 A1 WO2018008580 A1 WO 2018008580A1
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WIPO (PCT)
Prior art keywords
group
general formula
meth
acrylate
curable composition
Prior art date
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PCT/JP2017/024302
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English (en)
Japanese (ja)
Inventor
岡村　直実
尚孝 河村
敦史 角矢
寛生 阿部
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Cemedine Co Ltd
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Cemedine Co Ltd
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Priority to JP2018526356A priority Critical patent/JPWO2018008580A1/ja
Priority to CN201780035201.7A priority patent/CN109415454A/zh
Publication of WO2018008580A1 publication Critical patent/WO2018008580A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters

Definitions

  • the present invention relates to a curable composition and a product.
  • the present invention relates to a curable composition containing a compound that suppresses polymerization inhibition by oxygen, and a product.
  • a photocurable pressure-sensitive adhesive composition containing a (meth) acrylate oligomer having a polyisoprene as a skeleton and a hydrogenated terpene phenol tackifier is known (for example, see Patent Document 1).
  • the photocurable pressure-sensitive adhesive composition according to Patent Document 1 is applied onto a PET film, covered with a PET film that has been subjected to a double-sided release treatment from above the coated surface, and irradiated with UV light. A cured product having adhesiveness is obtained.
  • the photocurable pressure-sensitive adhesive composition according to Patent Document 1 it is possible to provide a photocurable pressure-sensitive adhesive composition that is excellent in workability at the time of dissolution preparation and coating, and gives a cured product having excellent adhesive strength and transparency. .
  • Non-Patent Document 1 a method of physically shielding oxygen, (b) a method of selecting an initiator system, (c) a method of selecting a monomer, and (d) a method of using thiol / ene photocuring.
  • the method (a) is a method of photocuring in a nitrogen atmosphere, a carbon dioxide atmosphere or the like.
  • the method (b) is a method of increasing the initiator concentration, and this method utilizes the fact that by increasing the concentration of the initiator and increasing the concentration of the starting radical, the number of radicals that do not react with oxygen also increases. ing.
  • a method using a polyfunctional monomer (a polyfunctional monomer suppresses inhibition of oxygen polymerization), a monomer having a hydroxyl group is used.
  • the method using a monomer having a hydroxyl group is that a hydrogen atom bonded to the ⁇ -carbon of the hydroxyl group is easily extracted, so that even if a peroxy radical is generated, a hydrogen atom is further provided to easily generate a new carbon radical.
  • the inhibition of curing is suppressed by utilizing the fact that a monomer having a hydroxyl group or a carboxyl group in the monomer is hydrogen-bonded between molecules.
  • the method (d) is a method in which thiol coexists.
  • a thiol having a small SH bond energy is reacted with a peroxy radical to generate a thiyl radical, thereby inhibiting oxygen polymerization inhibition.
  • N-vinylamide monomer since the polarity of this compound is high, there is a problem that compatibility with other compounding substances is poor, and a cured product obtained by curing is also hard. There is a problem that the effect of suppressing polymerization inhibition is small.
  • the method using a phosphorus-based secondary oxidation degradation inhibitor has a problem that the effect lasts only for about 24 hours after the addition of this inhibitor.
  • the “(d) method using thiol / ene photocuring” has a problem that storage stability is poor due to the presence of a mercapto group. Furthermore, since a polyfunctional vinyl compound and a polyfunctional thiol are combined and photocured, the cured product of the curable composition is hard and brittle.
  • an object of the present invention is to include a monoacrylate compound that can significantly suppress polymerization inhibition due to oxygen even when used in the air to allow an appropriate curing reaction to proceed and to ensure a degree of freedom in designing the composition. It aims at providing a curable composition and a product.
  • the present invention provides (A) a monoacrylate compound represented by the following general formula (1), the following general formula (2), or the following general formula (3), and (B1) a photoinitiator. And (B2) a thermal initiator, and (B3) at least one initiator selected from the group consisting of a redox initiator.
  • R 1 represents —H or —CH 3
  • R 2 represents a substituted or unsubstituted alkyl group, A substituted or unsubstituted aryl group, a heterocyclic structure-containing group, a group having a plurality of rings, or — (C m H 2m O) n R 5 (m is an integer of 2 to 4, n is an integer of 1 to 30, R 5 represents —H or an unsubstituted or substituted alkyl group or an unsubstituted or substituted phenyl group.
  • R 3 and R 4 represent —H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic structure-containing group, — (C m H 2m O) n R 5 (m is an integer of 2 to 4, n is an integer of 1 to 30, R 5 is —H or an unsubstituted or substituted alkyl group, an unsubstituted or substituted phenyl group), or a group having a plurality of rings Show.
  • R 3 and R 4 may be bonded to each other to form a cyclic structure or a heterocyclic structure together with the carbon atom to which they are bonded.
  • R 'group and R''group show an organic group or hydrogen, respectively.
  • the monoacrylate compound represented by (A) general formula (1), general formula (2), or general formula (3) may contain the crosslinkable silicon group.
  • the present invention provides a cured product of any of the above curable compositions.
  • the present invention provides a product having a cured product of any of the above curable compositions as a constituent element.
  • the curable composition and product according to the present invention even when used in the air, the polymerization inhibition by oxygen can be significantly suppressed and an appropriate polymerization reaction can be advanced, and the degree of freedom in designing the composition can be increased.
  • the curable composition and product which can be ensured can be provided.
  • the curable composition according to the present invention is a curable composition containing a compound that suppresses polymerization inhibition by oxygen. That is, the curable composition is at least selected from the group consisting of (A) a compound that inhibits polymerization inhibition by oxygen, (B1) a photoinitiator, (B2) a thermal initiator, and (B3) a redox initiator. Containing one initiator.
  • the curable composition is exposed to the air and exposed to air, for example, coating application, application to an adherend in an adhesive application, In molding applications and the like, the influence of polymerization inhibition due to oxygen is significant, and the curing reaction does not proceed properly.
  • lauryl acrylate or the like is generally used.
  • radical polymerization polymerization inhibition due to oxygen occurs, and surface curing occurs. The property becomes insufficient.
  • the present inventor examined various compounds in order to eliminate such a point, and by adding a monoacrylate compound having a specific structure to the curable composition, the above-described problems can be solved and oxygen can be used. It has been found that polymerization inhibition can be suppressed.
  • the curable composition according to the present invention includes (A) a monoacrylate compound represented by the following general formula (1), general formula (2), or general formula (3), and (B1) photoinitiation. And (B2) a thermal initiator, and (B3) at least one initiator selected from the group consisting of a redox initiator.
  • R 1 represents —H or —CH 3
  • R 2 represents a substituted or unsubstituted alkyl group, A substituted or unsubstituted aryl group, a heterocyclic structure-containing group, a group having a plurality of rings, or a — (C m H 2m O) n R 5 group
  • R 3 and R 4 represent —H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic structure-containing group, — (C m H 2m O) n R 5 group or a group having a plurality of rings is shown.
  • R 3 and R 4 may be bonded to each other to form a cyclic structure or a heterocyclic structure together with the carbon atom to which they are bonded.
  • R 'group and R''group show an organic group or hydrogen, respectively.
  • R 2 , R 3 and / or R 4 , and R ′ and / or R ′′ may be a silyl group or a group having a silyl group.
  • the curable composition can be post-cured by moisture curing (so-called dual curing type). ).
  • n is an integer of 2 to 4
  • n is an integer of 1 to 30
  • R 5 is —H, or an unsubstituted or substituted alkyl group, unsubstituted Or it is a substituted phenyl group.
  • the substituted or unsubstituted alkyl group is not particularly limited, but for example, an alkyl group having 1 to 30 carbon atoms is preferable.
  • the said alkyl group shall contain the alkyl group (broadly-defined alkyl group) containing the group which has a double bond.
  • the substituted or unsubstituted aryl group is not particularly limited, but for example, an aryl group having 6 to 20 carbon atoms is preferable. Further, the substituted or unsubstituted alkyl group may be linear, branched or cyclic.
  • the substituent in the substituted alkyl group and the substituted aryl group is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, an alkoxy group, an ester group, a ketone group, an aldehyde group, a carboxyl group, a glycidyl group, an amino group, and an amide. Groups and the like.
  • the heterocyclic structure-containing group is not particularly limited, but for example, a heterocyclic structure-containing group having 3 to 20 carbon atoms is preferable.
  • the alkoxy group is not particularly limited, but an alkoxy group having 1 to 30 carbon atoms is preferable, and an alkoxy group having 1 to 18 carbon atoms is more preferable.
  • the ester group is preferably an ester group having 2 to 30 carbon atoms, and more preferably an ester group having 2 to 18 carbon atoms.
  • the ketone group a ketone group having 2 to 30 carbon atoms is preferable, and a ketone group having 2 to 18 carbon atoms is more preferable.
  • R 2 , R 3 , R 4 , R ′, and / or R ′′ are groups having a long chain hydrocarbon group having 8 to 20 carbon atoms, a carboximide group, or a crosslinkable silicon group. Also good. From the viewpoint of excellent flexibility of the curable composition, a long-chain hydrocarbon group having 8 to 20 carbon atoms and / or — (C m H 2m O) n R 5 group is preferable, and the carbon number is 8 to 20 More preferred are 20 long-chain hydrocarbon groups, groups having a hydroxyl group, and groups having an alkoxy group, and most preferred are long-chain hydrocarbon groups having 8 to 20 carbon atoms. From the viewpoint of curing the curable composition by a dual curing mechanism that also performs a curing reaction by moisture curing, a group having a crosslinkable silicon group is preferable.
  • R 2 , R 3 , R 4 , R ′, and / or R ′′ are as follows.
  • examples of the group having a hydroxyl group include a 2-hydroxypropyl group, a 4-hydroxybutyl group, a hydroxyhexa (ethylene ether) group, a hydroxyocta (propylene ether) group, and a 2-hydroxy-3-butyloxypropyl group. It is done.
  • examples of the group having an alkoxy group include a methoxytri (ethylene ether) group, an ethoxydi (ethylene ether) group, and a dicyclopentenyloxyethyl group.
  • Examples of the aromatic group include a phenoxyethyl group, a nonylphenoxyethyl group, and a benzyl group.
  • Examples of the long-chain hydrocarbon (meth) acrylate group having 8 to 20 carbon atoms include 2-ethylhexyl group, isooctyl group, lauryl group, and isostearyl group. From the viewpoint of availability, the carbon number is 8-18 long chain hydrocarbon groups are preferred.
  • Examples of the alicyclic group include a cyclohexyl group, a dicyclopentenyl group, and an isobornyl group.
  • Examples of the group having a heterocyclic group include a tetrahydrofurfuryl group.
  • Examples of the (meth) acrylate group having a crosslinkable silicon group include a 3- (trimethoxysilyl) propyl group, and the curable composition containing such a group undergoes a moisture curing reaction to form a dual curing mechanism. .
  • a (meth) acrylate group having a crosslinkable silicon group is particularly effective as R 3 and R 4 .
  • the monoacrylate compound is a low molecular compound having a molecular weight of 1,500 or less.
  • the molecular weight is preferably 750 or less, more preferably 500 or less, from the viewpoint of ensuring an appropriate viscosity of the curable composition and ensuring good workability.
  • the molecular weight means the number average molecular weight when, for example, the — (C m H 2m O) n R 5 group includes a plurality of n values.
  • the (A) monoacrylate compound is preferably liquid at 50 ° C. That is, from the viewpoint of ensuring ease of handling when blended with other components, it is preferable to exhibit a liquid state at 50 ° C., more preferably a liquid state at 20 ° C., and a liquid state at 0 ° C. preferable
  • the monoacrylate compound represented by (A) general formula (1), general formula (2), or general formula (3) is a compound containing a crosslinkable silicon group
  • the monoacrylate compound is crosslinkable.
  • Silicon groups may be included.
  • the crosslinkable silicon group is moisture-cured by dark reaction after curing by photoreaction, thermal reaction, or redox reaction.
  • crosslinkable silicon group for example, a group represented by the general formula (4) is preferable.
  • the crosslinkable silicon group is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond.
  • R ⁇ represents an organic group.
  • R ⁇ is preferably a hydrocarbon group having 1 to 20 carbon atoms. Among these, R ⁇ is particularly preferably a methyl group.
  • R ⁇ may have a substituent.
  • W represents a hydroxyl group or a hydrolyzable group, and when two or more W exist, the plurality of W may be the same or different.
  • a is either an integer of 1, 2 or 3.
  • a in formula (4) is preferably 2 or more, and more preferably 3. From the viewpoint of obtaining a curable composition having sufficient flexibility, a is preferably 2.
  • the hydrolyzable group represented by W is not particularly limited as long as it is other than an F atom, but an alkoxy group is preferable from the viewpoint of mild hydrolyzability and easy handling. From the viewpoint of high reactivity, a methoxy group or an ethoxy group is more preferable.
  • the specific structure of the crosslinkable silicon group is preferably a trimethoxysilyl group or a triethoxysilyl group, and more preferably a trimethoxysilyl group from the viewpoint of high reactivity. From the viewpoint of obtaining a curable composition having sufficient flexibility, a methyldimethoxysilyl group and a methyldiethoxysilyl group are preferred.
  • the following formula is a schematic diagram for explaining a mechanism for inhibiting polymerization inhibition by a compound represented by general formula (1), general formula (2), or general formula (3).
  • “•” indicates a radical.
  • “(1)” indicates a hydrogen abstraction reaction
  • “(2)” indicates a polymerization initiation reaction
  • “(3)” indicates an oxygen capture (consumption) reaction.
  • R 1 is the same as described above.
  • the following mechanism is presumed as a mechanism for suppressing polymerization inhibition by oxygen.
  • the polymerization inhibition by oxygen is caused by the fact that the polymerization ability of peroxyl radicals generated by trapping the oxygen radicals generated from the polymerization initiator and the polymerization end radicals generated from the polymerization initiator is low and the polymerization reaction is stopped. Occur.
  • the monoacrylate compound of the component (A) having a function as a chain transfer agent is present in the system, the peroxy radical having a hydrogen abstraction ability abstracts hydrogen from the monoacrylate (reaction (1)).
  • the newly generated ⁇ -carbon radical of the secondary hydroxyl group is considered to initiate polymerization (reaction (2)).
  • reaction (3) the effect of reducing the oxygen concentration in the system (reaction (3)) is also conceivable. It is presumed that polymerization inhibition by oxygen is suppressed by these mechanisms. Furthermore, even when one monomer does not participate in the polymerization, the presence of the ⁇ carbon increases the chance of the polymerization reaction, so that the polymerization reaction is likely to proceed.
  • the carbon radicals are easily generated in the order of ⁇ carbon of the primary hydroxyl group ⁇ carbon of the secondary hydroxyl group ⁇ carbon of the secondary hydroxyl group to which the polar group is bonded.
  • the general formula (2), and the general formula (3), -COOR 2 , -CNR 3 R 4 , and -COOR'R '' are polar groups, Since the ⁇ -carbon radical is easily generated, the general formula (1), the general formula (2), and the general formula (3) have a preferable structure in suppressing polymerization inhibition by oxygen.
  • the monoacrylate compound according to the present invention has a hydroxyl group.
  • a monomer having a hydroxyl group is hydrogen-bonded between molecules (that is, a hydrogen bond between hydroxyl groups or a hydrogen bond between a carbonyl group and a hydroxyl group). Therefore, the presence of the monoacrylate compound increases local double bonds due to the association, so that the polymerization reaction easily proceeds.
  • the component (A) can be synthesized as follows.
  • a compound represented by the general formula (1) is synthesized by mixing a glycidyl (meth) acrylate compound, a predetermined carboxylic acid and, if necessary, a predetermined catalyst at a predetermined ratio and stirring at a predetermined temperature. Is done.
  • a compound represented by the general formula (2) is synthesized by mixing a glycidyl (meth) acrylate compound, a predetermined amine and, if necessary, a predetermined catalyst in a predetermined ratio and stirring at a predetermined temperature.
  • a predetermined compound having glycidol and an isocyanate group and a predetermined catalyst as necessary are mixed at a predetermined ratio, and stirred at a predetermined temperature to synthesize an intermediate reactant.
  • the intermediate reactant obtained in this synthesis, a predetermined (meth) acrylate, and a predetermined catalyst as required are mixed at a predetermined ratio and stirred at a predetermined temperature, and expressed by the general formula (3).
  • the compound to be synthesized is synthesized.
  • the compound represented by the general formula (3) can be obtained by reacting glycerol mono (meth) acrylate with a predetermined compound having an isocyanate group (O ⁇ C ⁇ N—R ′, R ′ is the same as described above). It can be synthesized (reaction example (IV)). For example, by mixing a predetermined glycerin mono (meth) acrylate, a predetermined compound having an isocyanate group and a predetermined catalyst as required, at a predetermined ratio, and reacting at a predetermined temperature for a predetermined time, the general formula (3 ) Is synthesized.
  • reaction catalyst of glycidyl group and carboxyl group As a catalyst for the addition reaction between a carboxyl group and an epoxy group, tertiary amine, quaternary ammonium salt, quaternary phosphonium salt, phosphine compound such as triphenylphosphine, metal salt of carboxylic acid (for example, chromium octoate, stearic acid) Sodium), and alkali metal or alkaline earth metal hydroxides.
  • triphenylphosphine from the viewpoint that the resin is less colored, and from the viewpoint of good reaction yield, a metal salt of carboxylic acid, an alkali metal or alkaline earth metal hydroxide is preferable, and an alkali More preferred are metal or alkaline earth metal hydroxides, and even more preferred are alkali metal hydroxides.
  • the catalyst for the addition reaction is preferably 0.01 equivalents or more and 0.1 equivalents or less, and more preferably 0.02 equivalents or more and 0.08 equivalents or less with respect to 1 equivalent of the epoxy group.
  • a polymerization inhibitor may be added from the viewpoint of suppressing radical polymerization during synthesis.
  • the polymerization inhibitor include alkylphenols such as 2,6-di-t-butylhydroxytoluene.
  • An amine polymerization inhibitor can also be used.
  • the amine-based polymerization inhibitor include N, N′-diphenyl-p-phenylenediamine.
  • the polymerization initiator at least one initiator selected from the group consisting of (B1) a photoinitiator, (B2) a thermal initiator, and (B3) a redox initiator is used.
  • (B1) component: photoinitiator As the photoinitiator, a photoradical generator, a photobase generator, a photoacid generator, or the like can be used.
  • the photo radical generator is a compound that generates radicals by irradiation with active energy rays such as ultraviolet rays and electron beams.
  • active energy rays such as ultraviolet rays and electron beams.
  • Photo radical generator examples include benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one. ⁇ -aminoacetophenone series, bis (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, etc.
  • Acylphosphine oxides such as (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzophenones such as methyl benzoylbenzoate, thioxanthones such as isopropylthioxanthone, 1.2-octanedione, 1- [4- ( Oxime esters such as phenylthio)-, 2- (O-benzoyloxime)], bis (Cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanium, titanocene, benzoin ether, triazine, borate, carbazole, imidazole, etc. Derivatives obtained by increasing the molecular weight thereof can be mentioned.
  • benzyl ketal, ⁇ -hydroxyacetophenone, ⁇ -aminoacetophenone, acylphosphine oxide, oxime ester, and titanocene photopolymerization initiators are preferred because they have high sensitivity and can be added in small amounts.
  • ⁇ -aminoacetophenone-based, acylphosphine oxide-based, oxime ester-based, and titanocene-based photopolymerization initiators include long-wave ultraviolet rays (i-line (wavelength 365 nm), h-line (wavelength 405 nm), g-line (wavelength 436 nm), etc.
  • Photobase generator Various photobase generators can be used as the photobase generator. Photolatent amine compounds that generate amine compounds by the action of active energy rays are preferred.
  • the photolatent amine compound includes a photolatent primary amine that generates an amine compound having a primary amino group by the action of active energy rays, and an amine compound having a secondary amino group by the action of active energy rays. Any of the photolatent secondary amine that is generated and the photolatent tertiary amine that generates an amine compound having a tertiary amino group by the action of active energy rays can be used. In view of the high catalytic activity of the generated base, a photolatent tertiary amine is more preferable.
  • photolatent primary amines and photolatent secondary amines include orthonitrobenzylurethane compounds described in WO2015 / 088021, dimethoxybenzylurethane compounds, benzoins carbamates, o-acyloximes O-carbamoyl oximes; N-hydroxyimide carbamates; formanilide derivatives; aromatic sulfonamides; cobalt amine complexes and the like.
  • photolatent tertiary amines examples include ⁇ -aminoketone derivatives, ⁇ -ammonium ketone derivatives, benzylamine derivatives, benzylammonium salt derivatives, ⁇ -aminoalkene derivatives, ⁇ -ammonium alkene derivatives described in WO2015-088021.
  • photobase generators photolatent tertiary amines are preferred from the point that the generated bases exhibit high catalytic activity, because the base generation efficiency is high and the storage stability as a photocuring composition is good.
  • Benzyl ammonium salt derivatives, benzyl substituted amine derivatives, ⁇ -amino ketone derivatives, and ⁇ -ammonium ketone derivatives are preferred.
  • a photoinitiator When using a photoinitiator, it may be used individually by 1 type and may be used combining 2 or more types by arbitrary ratios.
  • the addition amount of the photoinitiator is not particularly limited, but if the addition amount is small, the curing does not proceed to the deep part and the curing failure may occur. Therefore, “other than (A) component and (A) component is excluded. (However, other (meth) acrylates excluding component (A) include other (meth) acrylate monomers, oligomers and macromers excluding component (A). The same shall apply hereinafter) 100.
  • 0.05 weight part or more is preferable with respect to a weight part, 0.1 weight part or more is more preferable, and 1 weight part or more is still more preferable.
  • the amount added is 100 parts by weight of “(A) component and other (meth) acrylates excluding component (A)”. On the other hand, it is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and still more preferably 10 parts by weight or less.
  • thermal initiator examples include organic peroxides such as benzoyl peroxide, t-butyl perbenzoate and cumene hydroperoxide, 2,2′-azobisisobutyronitrile, And azo compounds such as 2,2′-azobis- (2-methylbutyronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile).
  • thermal initiator thermal polymerization initiator
  • one kind may be used alone, or two or more kinds may be used in combination at any ratio.
  • the addition amount is not particularly limited, but from the viewpoint of storage stability, it is preferably 5 parts by weight or less, more preferably 100 parts by weight of (A) component and other (meth) acrylates excluding component (A). 2 parts by weight or less, more preferably 1 part by weight or less. Further, from the viewpoint of curability, it is preferably 0.01 parts by weight or more, more preferably 0.025 parts by weight or more, with respect to 100 parts by weight of other (meth) acrylates excluding the component (A) and the component (A). More preferably 0.05 parts by weight or more.
  • both (B1) photoinitiator and (B2) thermal initiator can be used together to achieve both photocuring and thermosetting.
  • the redox initiator used in the present invention is not limited, but a combination of a persulfate initiator and a reducing agent (sodium metabisulfite, sodium bisulfite, thiourea compound, etc.); an organic peroxide and a tertiary amine (For example, a combination of benzoyl peroxide and dimethylaniline, a combination of cumene hydroperoxide and anilines), a combination of an organic peroxide and a transition metal, or the like.
  • a persulfate initiator and a reducing agent sodium metabisulfite, sodium bisulfite, thiourea compound, etc.
  • an organic peroxide and a tertiary amine for example, a combination of benzoyl peroxide and dimethylaniline, a combination of cumene hydroperoxide and anilines, a combination of an organic peroxide and a transition metal, or the like.
  • Preferred redox initiators include a combination of an organic peroxide and a tertiary amine, a combination of an organic peroxide and a transition metal, and more preferably a combination of cumene hydroperoxide and anilines, cumene.
  • a combination of hydroperoxide and cobalt naphthate, a combination of cumene hydroperoxide and a trivalent or tetravalent vanadium compound, and the like can be given.
  • a redox initiator may be used independently or may use 2 or more types together.
  • the amount of addition is not particularly limited, but from the viewpoint of storage stability, it is preferably based on 100 parts by weight of the (A) component and other (meth) acrylates excluding the (A) component. It is 10 parts by weight or less, more preferably 5 parts by weight or less, and further preferably 2 parts by weight or less. Further, from the viewpoint of curability, it is preferably 0.01 parts by weight or more, more preferably 0.025 parts by weight or more, with respect to 100 parts by weight of other (meth) acrylates excluding the component (A) and the component (A). More preferably 0.05 parts by weight or more. Further, a curing accelerator such as an ⁇ -hydroxycarbonyl compound can be blended.
  • both (B1) photoinitiator and (B3) redox initiator can be used together to achieve both photocuring and redox curing.
  • the curable composition according to the present invention includes a monoacrylate having a phenoxy group, an acrylate compound, a vinyl compound having an amide group or an imide group, a photosensitizer, a light as necessary or according to a curing method.
  • Polymerization accelerators such as flame retardants, anti-sagging agents, antioxidants, anti-aging agents, ultraviolet absorbers, light stabilizers (HALS), solvents, fragrances, pigments, dyes, diluents and the like may be added.
  • additives such as flame retardants, anti-sagging agents, antioxidants, anti-aging agents, ultraviolet absorbers, light stabilizers (HALS), solvents, fragrances, pigments, dyes, diluents and the like may be added.
  • R 1 represents —H or —CH 3
  • R 6 to R 10 each independently represents a hydrogen atom or a substituent.
  • substituents include a nitro group, a cyano group, a hydroxy group, a halogen atom, an acetyl group, a carbonyl group, a substituted or unsubstituted allyl group, and a substituted or unsubstituted alkyl group (preferably having 1 to 5 carbon atoms).
  • An alkyl group a substituted or unsubstituted alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, a heterocyclic structure-containing group, and a plurality of rings. And a combination thereof. Any of R 6 to R 10 may be bonded to each other to form a cyclic structure.
  • a structure in which a plurality of benzene rings are condensed, a benzene ring and a heterocyclic ring or a non-aromatic ring A structure in which a ring to which a functional group such as a carbonyl group is bonded may be formed.
  • substituents a substituted or unsubstituted alkyl group is preferable, and a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms is more preferable.
  • the monoacrylate having a phenoxy group of the general formula (5) has a secondary hydroxyl group disposed in a portion sandwiched between two —CH 2 groups, and an electron-withdrawing group (phenoxy group and (meta)
  • phenoxy group and (meta) an electron-withdrawing group
  • Specific examples include 2-hydroxy-3-phenoxypropyl acrylate.
  • (Acrylate compounds) As acrylate compounds ((meth) acrylic compounds), monofunctional (meth) acrylates ((meth) acrylates having one other (meth) acryloyloxy group excluding component (A)) and polyfunctional (meth) And acrylate.
  • (meth) acrylate represents an acrylate and / or a methacrylate.
  • acrylate compounds examples include (meth) acrylate compounds having a molecular weight (or number average molecular weight) of 1,000 or less and (meth) acrylate polymers having a number average molecular weight of 1,000 or more.
  • the number average molecular weight of the (meth) acrylate polymer is preferably 2,000 or more and more preferably 3,000 or more in terms of polystyrene in GPC from the viewpoint of securing good elongation characteristics of the curable composition. From the viewpoint of ensuring an appropriate viscosity of the curable composition and ensuring good workability, the number average molecular weight is preferably about 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. Moreover, it is preferable to show a liquid state at 20 degreeC from a viewpoint of ensuring the ease of handling in the case of mix
  • monofunctional (meth) acrylates examples include monofunctional (meth) acrylate compounds and monofunctional (meth) acrylate polymers.
  • Examples of the monofunctional (meth) acrylate compound include the following compounds. First, as the long chain hydrocarbon (meth) acrylate having 8 to 20 carbon atoms, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate, and the like are included. From the viewpoint of availability, long-chain hydrocarbon (meth) acrylates having 8 to 18 carbon atoms are preferable.
  • Examples of the alicyclic (meth) acrylate include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.
  • Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, glycerol mono ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate; polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol-polypropylene glycol copolymers be able to.
  • Examples of the (meth) acrylate having an aromatic ring include benzyl (meth) acrylate, phenol alkylene oxide modified (meth) acrylate, alkylphenol alkylene oxide modified (meth) acrylate, p-cumylphenol alkylene oxide modified (meth) acrylate, and o -Phenylphenol alkylene oxide modified (meth) acrylate and the like.
  • Examples of the alkylene oxide include ethylene oxide and propylene oxide.
  • alkoxy group-containing (meth) acrylates examples include alkoxy polyethylene glycol mono (meth) acrylates such as ethoxydiethylene glycol (meth) acrylate; alkoxypolypropylene glycol mono (meth) acrylates such as methoxytripropylene glycol (meth) acrylate; A polypropylene glycol copolymer etc. can be mentioned.
  • Examples of the (meth) acrylate having a carboxyl group include (meth) acrylic acid, modified polycaprolactone of (meth) acrylic acid, Michael addition type multimer of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and anhydrous Examples include adducts of phthalic acid and adducts of 2-hydroxyethyl (meth) acrylate and succinic anhydride.
  • Examples of the (meth) acrylate having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethyl hexahydrophthalimide, and the (meth) acrylate having an amino group includes N, N -Dimethylaminoethyl acrylate and the like.
  • Examples of the (meth) acrylate having a crosslinkable silicon group include 3- (trimethoxysilyl) propyl (meth) acrylate, and the (meth) acrylate having an epoxy group includes glycidyl (meth) acrylate and cyclohexene oxide.
  • Examples of the (meth) acrylate having a phosphoric acid group include 2- (meth) acryloyloxyethyl acid phosphate.
  • the (meth) acrylate which has a fluoroalkyl group, the (meth) acrylate which has a tribromophenyl group, etc. are mentioned.
  • the polymer which has one (meth) acryloyloxy group can be used as a monofunctional (meth) acrylate polymer.
  • an acrylic polymer having an acrylic polymer having one (meth) acryloyloxy group as a skeleton, a urethane (meth) acrylate polymer, a polyester (meth) acrylate polymer, a polyether (meth) acrylate polymer examples thereof include an epoxy polymer and an epoxy (meth) acrylate polymer.
  • the blending ratio of the monofunctional (meth) acrylate polymer is the sum of the component (A) (or the component (A) and the monoacrylate having a phenoxy group, from the viewpoint of exhibiting the effect of suppressing oxygen inhibition by the component (A). ) 400 parts by mass or less is preferable with respect to 100 parts by mass, more preferably 250 parts by mass or less, and most preferably 150 parts by mass or less. From the viewpoint of exerting the blending effect of the monofunctional (meth) acrylate polymer, the amount is preferably 10 parts by mass or more, more preferably 25 parts by mass or more, and most preferably 50 parts by mass or more with respect to 100 parts by mass.
  • polyfunctional (meth) acrylates examples include polyfunctional (meth) acrylate compounds and polyfunctional (meth) acrylate polymers.
  • polyfunctional (meth) acrylate compound examples include 1,6-hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and dicyclopentanyl di (meth).
  • Acrylate polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, etc.
  • Bifunctional (meth) acrylate compound trimethylolpropane tri (meth) acrylate, trifunctional (meth) acrylate compound such as tris [(meth) acryloyloxyethyl] isocyanurate, dimethylolpropane tetra (meth) acrylate, pentaerythritol Tetra (meta) Acrylate, or pentaerythritol ethoxy tetra (meth) acrylate 4 or more functional groups of the (meth) acrylate compounds.
  • the molecular weight of the polyfunctional (meth) acrylate compound is less than 1,000.
  • the blending ratio of the polyfunctional (meth) acrylate compound is the component (A) (or the sum of the component (A) and the monoacrylate having a phenoxy group) from the viewpoint of exhibiting the effect of suppressing oxygen inhibition by the component (A). 10 mass parts or less are preferable with respect to 100 mass parts, 5 mass parts or less are more preferable, and 2 mass parts or less are the most preferable. From the viewpoint of ensuring a sufficient cohesive force under high temperature conditions, the amount is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and most preferably 0.1 parts by mass or more with respect to 100 parts by mass.
  • Polyfunctional (meth) acrylate polymer include polyether-based urethane (meth) acrylates (eg, “UV-3700B” and “UV-6100B” manufactured by Nippon Gosei Co., Ltd.), polyester-based urethane (meth) acrylates (eg, Japan) “UV-2000B”, “UV-3000B”, “UV-7000B” manufactured by Synthetic Co., Ltd.
  • the polyfunctional (meth) acrylate polymer has a weight average molecular weight of 1,000 to 50,000, and preferably from 3,000 to 45,000 from the viewpoint of flexibility of the cured curable composition. 000 to 20,000 is more preferable.
  • the glass transition temperature (Tg) is preferably 0 ° C. or lower from the viewpoint of maintaining and improving flexibility at low temperatures. From the viewpoint of ensuring ease of handling when blended with other components, it is preferable to exhibit a liquid state at 20 ° C.
  • the blending ratio of the polyfunctional (meth) acrylate polymer is the sum of the component (A) (or the component (A) and the monoacrylate having a phenoxy group, from the viewpoint of exhibiting the effect of suppressing oxygen inhibition by the component (A).
  • 500 parts by mass or less is preferable with respect to 100 parts by mass, 300 parts by mass or less is more preferable, and 200 parts by mass or less is most preferable. From the viewpoint of exerting sufficient cohesive force under high temperature conditions, 10 parts by mass or more is preferable, 100 parts by mass or more is more preferable, and 50 parts by mass or more is most preferable.
  • vinyl compound having an amide group examples include N-vinyl cyclic amides such as N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam; N, N-diethyl (meth) acrylamide, N- (2-hydroxyethyl) ) Acrylamides such as acrylamide and (meth) acryloylmorpholine.
  • a carbonyl compound having a triplet energy of 225 to 310 kJ / mol is preferable.
  • thioxanthone such as isopropylthioxanthone and derivatives thereof
  • dialkoxyanthracene derivative such as 9,10-dibutoxyanthracene
  • 2- Benzophenone and derivatives thereof such as methyl benzoylbenzoate
  • coumarin derivatives such as 3-acylcoumarin and 3,3′-carbonylbiscoumarin. Its derivatives and coumarin derivatives are more preferred.
  • the mixing ratio of the photosensitizer is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.025 to 2% by mass in the curable composition. These photosensitizers may be used independently and may use 2 or more types together.
  • Photopolymerization accelerator A photopolymerization accelerator can be used in combination with an initiator for the purpose of accelerating the curing reaction by the photopolymerization initiator.
  • Photopolymerization accelerators include tertiary amines such as triethylamine, triethanolamine, 2-dimethylaminoethanol; aryl phosphines such as triphenylphosphine; aryl phosphine oxides such as triphenylphosphine oxide; triphenyl phosphite Phosphines including aryl phosphates such as triphenyl phosphate and the like (aryl groups may have a substituent); thiols typified by ⁇ -thioglycol and the like.
  • Preferred phosphines are trifunctional phosphine derivatives, triarylphosphine is more preferred, and triphenylphosphine is most preferred.
  • the polymerization inhibitor is not particularly limited.
  • radical scavengers such as hindered phenols and hindered amines, phosphorus secondary oxidative degradation inhibitors, diethylhydroxylamine, sulfur, t-butylcatechol, potassium triiodide, Examples thereof include N-nitrosophenylhydroxyamine aluminum salt.
  • a polymerization inhibitor may be used independently and may use 2 or more types together.
  • the content of the polymerization inhibitor is too small, the polymerization inhibitory effect tends to be insufficient, so that the (A) component and the (meth) acrylate other than the (A) component are 100 parts by weight.
  • the amount is preferably 0.001 part by weight or more, more preferably 0.005 part by weight or more, and particularly preferably 0.01 part by weight or more.
  • 2 weight part or less is preferable, More preferably, it is 0.5 weight part or less, Most preferably, it is 0.3 weight part or less.
  • a resin filler resin fine powder
  • an inorganic filler an inorganic filler
  • a functional filler can be used.
  • the filler may be subjected to a surface treatment with a silane coupling agent, a titanium chelating agent, an aluminum coupling agent, a fatty acid, a fatty acid ester, rosin or the like.
  • a particulate filler made of an organic resin or the like can be used.
  • the resin filler organic fine particles such as polyethyl acrylate resin, polyurethane resin, polyethylene resin, polypropylene resin, urea resin, melamine resin, benzoguanamine resin, phenol resin, acrylic resin, and styrene resin can be used.
  • a resin filler contains a black resin filler. Even when a single wavelength LED lamp or the like is used, good deep curability can be obtained, and excellent light shielding properties and deep curability can be achieved.
  • inorganic filler examples include talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrated silicon, calcium silicate, titanium dioxide, and carbon black.
  • conductive fillers described in JP2013-14734, JP2017-2267, JP2011-508012, and the like for example, conductive fillers described in JP2013-14734, JP2017-2267, JP2011-508012, and the like; excellent heat insulation and lightness described in JP2016-199668, etc. Hollow particles; core-shell particles having excellent sound insulation and damping properties described in JP-A-2016-199669, etc .; layered silicates having excellent gas barriers described in JP-A-2016-199670, etc .; JP-A-2016-199671, etc.
  • the light reflecting filler described in the above; the electromagnetic shielding material described in JP-A-2016-199750 and the like can be used.
  • the curable composition of the present invention can contain a diluent.
  • a solvent having a flash point (open type) of 50 ° C. or higher is used as a diluent.
  • a diluent By containing a diluent, physical properties such as viscosity can be adjusted.
  • Various diluents can be used as the diluent.
  • Diluents include, for example, saturated hydrocarbon solvents such as normal paraffin and isoparaffin, ⁇ -olefin derivatives such as linearlen dimer (trade name of Idemitsu Kosan Co., Ltd.), aromatic hydrocarbon solvents, alcohol solvents and ester solvents.
  • the solvent include various solvents such as a solvent, a citrate ester solvent such as acetyltriethyl citrate, and a ketone solvent.
  • the flash point of the diluent is preferably 60 ° C. or higher, and more preferably 70 ° C. or higher.
  • a diluent generally having a high flash point tends to have a low dilution effect on the curable composition, it is preferable to use a diluent having a flash point of 250 ° C. or lower.
  • the flash point of a liquid mixture is said flash point.
  • the diluent is preferably a saturated hydrocarbon solvent, more preferably normal paraffin or isoparaffin. Normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms.
  • the blending ratio of the diluent is preferably in the range of 0 to 50 parts by mass with respect to 100 parts by mass of the (A) component and the other (meth) acrylates excluding the component (A). More preferably, it is blended in the range of parts by mass, and even more preferably in the range of 0.1 to 15 parts by mass.
  • the diluent can be used alone or in combination of two or more.
  • the content of the liquid medium is preferably 5% by weight or less, more preferably 3% by weight or less, and more preferably 1% by weight or less based on the entire curable composition. More preferably, a composition containing substantially no liquid medium (that is, a substantially solvent-free composition) is most preferred.
  • substantially does not contain the liquid medium means that the curable composition does not contain any liquid medium or the content thereof is 0.1% by mass or less of the curable composition.
  • a solvent having a flash point of 50 ° C. or lower is used as a volatile solvent.
  • the method for producing the curable composition is not particularly limited, and includes, for example, (A) component and at least one initiator selected from the group consisting of (B1) component, (B2) component, and (B3) component. It can be manufactured by blending a predetermined amount, blending other blending substances as required, and degassing and stirring. The order of blending each component and other compounding substances is not particularly limited and can be determined as appropriate. Furthermore, a curable composition can also be made into 1 liquid type as needed, and can also be made into 2 liquid type.
  • the photocurable composition in which a curing reaction proceeds by photocuring is a curable composition containing a monoacrylate compound represented by (A) general formula (1), general formula (2), or general formula (3). And (B1) a photoinitiator as a curing initiator as described above. Moreover, the photocurable composition may further contain a curing accelerator as necessary.
  • the photocurable composition can be used in the air because the polymerization inhibition by oxygen can be significantly suppressed and an appropriate curing reaction can proceed.
  • the photo-curable composition of the present invention functions as a pressure-sensitive adhesive or an adhesive in air, since it can be temporarily fixed by adhesion immediately after light irradiation, and then moisture curing proceeds. Function as an adhesive).
  • a pressure-sensitive adhesive composed of a photocurable composition, or an adhesive is applied to the first adherend, and the photocurable composition is made to exhibit tackiness by direct light irradiation.
  • the first adherend is bonded to the second adherend (temporarily fixed), and then the photocurable composition is moisture-cured to cure the first adherend and the second adherend.
  • a product having a first adherend and a second adherend can be manufactured by bonding the adherend.
  • a polyfunctional (meth) acrylate compound, a polyfunctional (meth) acrylate polymer, or (meth) acrylamide is usually used in order to suppress polymerization inhibition by oxygen.
  • these materials have hard cured properties, small elongation, and are not suitable for applications requiring flexibility.
  • the photocurable composition according to the present invention has a structure in which a functional group suppresses polymerization inhibition by oxygen, it can be widely used for applications requiring flexibility in addition to conventional applications.
  • adhesiveness can also be provided to the photocurable composition of this invention, a photocurable composition can also be comprised as a coating agent and a gasket which have a softness
  • the photocurable composition can also be configured as a flexible paint, coating agent, ink, gasket, packing, O-ring, sealing agent, potting agent, casting material, sealing agent, and the like.
  • the photocurable composition contains a crosslinkable silicon group
  • the photocurable composition is: It is preferable to contain a photobase generator as a curing initiator. In addition, a silicon compound having a Si—F bond can be added as a curing accelerator. Since the component (A) contained in the photocurable composition has a crosslinkable silicon group, after the photocurable composition is photocured, the photocurable composition can be postcured by moisture in the air. .
  • the silicon compound having a Si—F bond various compounds containing a silicon group having a Si—F bond (hereinafter sometimes referred to as a fluorosilyl group) can be used. Either an inorganic compound or an organic compound can be used as the silicon compound having a Si—F bond.
  • a fluorosilyl group an organic compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more preferable because of high safety.
  • the low molecular organosilicon compound which has a fluoro silyl group from the point from which a photocurable composition becomes low viscosity is preferable.
  • silicon compounds having a Si—F bond examples include fluorosilanes described in WO2015-088021, compounds having a fluorosilyl group described in WO2015-088021, and fluorosilyls described in WO2015-088021 And an organic polymer having a group.
  • thermosetting composition in which the curing reaction proceeds by heat includes (A) a curable composition containing a monoacrylate compound represented by general formula (1), general formula (2), or general formula (3); And (B2) a thermal initiator as a curing initiator as described above. Moreover, the thermosetting composition may further contain a curing accelerator as necessary.
  • the thermosetting composition can be used for various applications.
  • thermosetting composition can be used for various purposes.
  • the thermosetting composition of the present invention can be suitably used in the presence of air because it can greatly suppress inhibition of polymerization due to oxygen and can promote an appropriate curing reaction.
  • the thermosetting composition of the present invention can be used for LIM molding in which the influence of oxygen in the air cannot be excluded, and can be widely used for applications requiring flexibility in addition to conventional applications.
  • adhesiveness can also be provided to the thermosetting composition of this invention, it is suitable for insert LIM shaping
  • the initiator used in the thermosetting composition for LIM molding examples include a radical initiator having a half-life of 0.5 to 120 seconds, preferably 1 to 60 seconds, at any reaction temperature between 130 and 160 ° C. It is done. In the case of an initiator having a half-life exceeding 120 seconds, the fluctuation range of the monomer conversion rate becomes large and it is difficult to ensure stable operation. In the case of an initiator having a half-life of less than 0.5 seconds, there is a problem that the amount of the initiator used is too large and the product polymer is colored.
  • Examples of the initiator used in the present invention include 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methylbutyronitrile), and the like.
  • Preferred are azo compounds and organic peroxides such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butyl peroxyisobutyrate, benzoyl peroxide, lauroyl peroxide.
  • the half-life value of the initiator is the value of technical bulletin issued by Wako Pure Chemical Industries, Ltd. for azo compounds, and the catalog (12th edition) issued by Nippon Oil & Fats Co., Ltd.
  • the polymerization reaction temperature in the LIM molding step is preferably in the range of 100 to 180 ° C, more preferably in the range of 130 to 160 ° C, and still more preferably in the range of 140 to 155 ° C.
  • the redox curable composition in which curing proceeds by a redox reaction includes (A) a curable composition containing a monoacrylate compound represented by general formula (1), general formula (2), or general formula (3); And (B3) redox initiator as a curing initiator as described above. Moreover, the redox curable composition may further contain a hardening accelerator as needed. The redox curable composition can be used for various applications for the same reason as the photocurable composition.
  • a redox curable composition containing a monoacrylate compound having a group represented by the general formula (1) can be used as a two-component mixed adhesive in the air.
  • a persulfate initiator or organic peroxide a first liquid containing the component (A), a reducing agent, a tertiary amine, or a transition metal, and a second liquid containing the component (A)
  • a two-component mixed adhesive can be constituted. Since the reaction proceeds by mixing the first liquid and the second liquid, it functions as an adhesive that bonds one adherend and the other adherend together.
  • the component (A) is contained in at least one of the first liquid and the second liquid.
  • the combination of the compound contained in the first liquid and the compound contained in the second liquid is a combination of a persulfate initiator and a reducing agent.
  • a combination of an organic peroxide and a tertiary amine, a combination of an organic peroxide and a transition metal, or the like can be appropriately employed.
  • the first liquid contains an organic peroxide, an acidic phosphate ester (storage stability improver), an ⁇ -hydroxycarbonyl compound (a curing accelerator). Agent), hydrazine compound (aldehyde emission inhibitor), etc.
  • the second liquid is a reducing agent such as trivalent or tetravalent vanadium compound, thiourea compound, saccharin, aluminum compound (storage stability) Improver) and the like, and a stabilizer such as disubstituted hydroquinone can be added to the first liquid and / or the second liquid.
  • reducing agents such as a vanadium compound and a thiourea compound, can be dissolved and used in a volatile solvent.
  • adhesives, coating agents, and gaskets usually use polyfunctional compounds, polyfunctional polymers, acrylamide, or the like in order to suppress polymerization inhibition by oxygen.
  • these materials have hard cured properties, small elongation, and are not suitable for applications requiring flexibility.
  • the redox curable composition according to the present invention has a structure in which a functional group suppresses the inhibition of polymerization by oxygen, it can be widely used for applications requiring flexibility in addition to conventional applications.
  • the product can be configured as a flexible adhesive, a coating agent or a gasket, or a pressure-sensitive adhesive for applications requiring flexibility. Adhesives, pressure sensitive adhesives, coating agents and gaskets are particularly useful for field construction.
  • redox curable compositions can also be configured as flexible paints, coating agents, inks, gaskets, packings, O-rings, sealing agents, potting agents, casting materials, sealants, etc. Useful for construction.
  • the redox curable composition of the present invention can also be used for two-component curable LIM molding.
  • the curable composition according to the present invention can be cured by photocuring, thermal curing, redox curing, or a combination thereof. By this curing, a cured product of the curable composition can be obtained. Therefore, various products, such as an electronic circuit, an electronic component, a building material, and a motor vehicle, can be manufactured using the hardened
  • the curable composition of the present invention can suppress the polymerization inhibition due to oxygen even when used in the air, and can proceed with an appropriate curing reaction, and becomes a flexible cured product. Suitable. That is, the curable composition of the present invention is applied to an adherend and cured in situ, or the curable composition of the present invention is applied in a predetermined shape (for example, a ring shape used for packing or gasket), By curing, a ring-shaped packing or gasket can be manufactured on the spot.
  • “for on-site construction” means that the curable composition is used as it is (in the air) for adhering adherends to each other and for producing a member having a predetermined shape at the site where the product is manufactured. Point to.
  • “for on-site construction” is an application in which a curable composition is directly applied to one adherend, and in that state (or on the spot), one adherend is attached to the other adherend; And / or the use etc. which manufacture the product which has the said shape by making a curable composition into a predetermined shape and hardening.
  • the curable composition of the present invention includes a pressure-sensitive adhesive, an adhesive, an elastic adhesive, a contact adhesive, a coating material, a coating material, a sealing material such as a can lid, an electric and electronic potting agent, a film, and a gasket.
  • Marine deck caulking, casting materials various molding materials, anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cutting parts), anti-vibration / damping / Liquid and sealing materials used in soundproofing and seismic isolation materials, automobile parts, electrical parts, various machine parts, waterproofing agents, sealing materials for double-glazed glass, sealing materials for vehicles, such as architectural and industrial sealing agents, solar cells It can be used for various applications such as electrical / electronic component materials such as backside sealants, and electrical insulation materials such as insulation coating materials for electric wires and cables.
  • the on-site molded body showing rubber elasticity composed of the curable composition of the present invention can be widely used mainly for gaskets and packings.
  • gaskets and packings For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket.
  • it In the field of home appliances, it can be used for on-site packing, O-rings, and the like.
  • decorations for lighting fixtures waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater unit packings , Electrode packing, waterproof packing for smartphones, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, heat insulation heater packing, steam outlet seal, etc.
  • Examples include oil gaskets, O-rings, drain packings, feed / intake packings, anti-vibration rubbers, oil filler packings, oil meter packings, speaker gaskets and speaker edges for acoustic equipment.
  • the construction field it can be used for gaskets, waterproof materials, vibration-proof materials, sound-proof materials, and the like.
  • DIY field it can be used for shoe sole repair materials, insole repair materials, and the like.
  • anti-vibration rubber it can be used for anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, and the like.
  • the curable composition of the present invention is particularly useful as a pressure-sensitive adhesive or an adhesive, and is particularly useful for applications requiring on-site construction.
  • the curable composition of the present invention can be configured as a cured product having good flexibility, it is an elastic adhesive used for bonding materials having different linear expansion coefficients to each other or a member that repeatedly undergoes displacement by heat cycle. It is also useful for applications such as coating agents for bending members that utilize flexibility and flexibility.
  • it can also be suitably used for a liquid sealing material used in on-site molded gaskets, so-called automobile parts, electrical parts, various machine parts, etc., taking advantage of its good surface curability.
  • the curable composition concerning this invention contains the monoacrylate compound represented by General formula (1), General formula (2), or General formula (3), even if it uses in air, it depends on oxygen. Since the polymerization inhibition can be significantly suppressed and an appropriate polymerization reaction can be advanced, a cured product having excellent curability can be obtained. Moreover, the curable composition which concerns on this invention is as R ⁇ 2 >, R ⁇ 3 >, R ⁇ 4 >, R 'and / or R''of General formula (1), General formula (2), or General formula (3).
  • the epoxy group of glycidyl methacrylate is ring-opened to form an ester bond with the unsaturated carboxylic acid.
  • This ring opening occurs at both the ⁇ -position and the ⁇ -position, but the ⁇ -adduct opened at the ⁇ -position is the main component, and the ⁇ -adduct opened at the ⁇ -position is the subcomponent.
  • the production ratio of the ⁇ adduct and the ⁇ adduct is 100 / 0.01 to 100/70, preferably 100 / 0.1 to 100/50 in terms of molar ratio.
  • Synthesis Example 1 a product having a compound that is usually an ⁇ -adduct as a main component and a ⁇ -adduct as a subcomponent is obtained.
  • the product can be isolated by separating it by a known separation method.
  • a mixture containing an ⁇ adduct and a ⁇ adduct is obtained as (A) a monoacrylate compound. That is, the product obtained in Synthesis Example 1 is a product obtained by leaving the whole or part of the ⁇ adduct in the product obtained by the above synthesis method, and is a curable composition containing the ⁇ adduct as a main component.
  • main component refers to a component contained in the product in an amount of 60 mol% or more
  • “subcomponent” refers to a component in an amount of 40 mol% or less.
  • the epoxy group of glycidyl methacrylate is ring-opened to form an ester bond with the unsaturated carboxylic acid.
  • This ring opening occurs at both the ⁇ -position and the ⁇ -position, but the ⁇ -adduct opened at the ⁇ -position is the main component, and the ⁇ -adduct opened at the ⁇ -position is the subcomponent.
  • the production ratio of the ⁇ adduct and the ⁇ adduct is 100 / 0.01 to 100/70, preferably 100 / 0.1 to 100/50 in terms of molar ratio.
  • Synthesis Example 1 and Synthesis Example 2 a product having a compound represented by General Formula (1), which is usually an ⁇ -adduct, as a main component and a ⁇ -adduct as a subcomponent is obtained.
  • the product When isolating the ⁇ -adduct that is the main component, the product can be isolated by separating it by a known separation method.
  • a mixture of an ⁇ adduct and a ⁇ adduct is obtained as GMADAc
  • Synthesis Example 2 a mixture of an ⁇ adduct and a ⁇ adduct is obtained as GMA2EHAc.
  • main component refers to a component contained in the product in an amount of 60 mol% or more
  • subcomponent refers to a component in an amount of 40 mol% or less.
  • Examples 1 to 5 Comparative Examples 1 to 5
  • Each compounding substance was respectively added by the compounding ratio shown in Table 1 and Table 2, mixed and stirred, and the curable composition was prepared.
  • KBM5103 3-trimethoxysilylpropyl acrylate (product name “KBM5103”, manufactured by Shin-Etsu Chemical Co., Ltd.) * 12 (Irg379): 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone (product name “IRGACURE 379EG”, manufactured by BASF).
  • Irg 379 is a photoradical generator ( ⁇ -aminoacetophenone series) and a photolatent tertiary amine ( ⁇ -aminoketone derivative).
  • the hardness test was performed in accordance with SRIS0101 of the Japan Rubber Association Standard (SRIS).
  • SRIS0101 Japan Rubber Association Standard
  • the photocurable compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 were applied to an adherend (PET film) in the form of a sheet having a length of 5 cm ⁇ width 20 cm ⁇ thickness 200 ⁇ m using a glass rod.
  • the photocurable composition on the adherend was irradiated with light and cured [irradiation conditions: metal halide lamp (illuminance: 600 mW / cm 2 , integrated light amount: 6000 mJ / cm 2 )], and obtained.
  • the cured product of the photocurable composition was cut into 20 pieces of 5 cm in length ⁇ 1 cm in width with a cutter, and the cut 20 pieces were stacked to make the total thickness of the cured product of the photocurable composition 4 mm.
  • the hardness of the cured product was measured using a hardness meter (Asuka hardness meter type C), and the test results are shown in Table 1.
  • the unit of hardness is ASKER C
  • the measured value is x.
  • the hardness is expressed in ASKER Cx.
  • a pencil hardness test was performed according to JIS K5600-5-4.
  • a photocurable composition was applied to a 10 cm ⁇ 10 cm aluminum plate using a glass rod so as to have a thickness of 100 ⁇ m, and UV irradiation [irradiation conditions: LED lamp, wavelength 365 nm, illuminance: 1,000 mW / cm 2 , integrated light quantity: 1,000 mJ / cm 2 ]. Then, it was cured for 1 hour in an environment of 23 ° C. and 50% RH in a dark room.
  • the pencil hardness was measured in accordance with the scratch hardness (pencil method) of JIS K5600-5-4. Furthermore, the pencil hardness was measured in the same manner for each of the sample cured for 24 hours and the sample cured for 168 hours in an environment of 23 ° C. and 50% RH in a dark room.
  • the curable composition according to Example 4 has a pencil hardness of 5B after curing for 1 hour in the pencil hardness test. Indicated. That is, since the curable composition which concerns on Example 4 contains a crosslinkable silicon group, it was shown that hardness and adhesiveness improve with progress of time. As in the case of the curable composition according to Example 4, when the hardness gradually increases with time, warpage generated on the adherend can be suppressed. Moreover, also in the curable composition which concerns on Example 5, the pencil hardness after 1-hour curing in a pencil hardness test is 5B, and pencil hardness improved with progress of time.
  • Examples 6 to 7, Comparative Example 6, and Reference Example 1 As shown in Table 3, a curable composition was obtained in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 5 except that the compounding material was changed, and then the resulting curable composition was peeled and adhered. Strength was evaluated. The results are shown in Table 3.
  • UV adhesion strength test The photocurable composition according to Example 6 was applied to the first adherend (PET film) using a glass rod so as to have a thickness of 200 ⁇ m. Next, the photocurable composition on the first adherend was irradiated with ultraviolet rays (UV) [Irradiation conditions: UV-LED lamp (wavelength 365 nm, illuminance: 1000 mW / cm 2 ), integrated light quantity: 3000 mJ / cm 2 ].
  • UV-LED lamp wavelength 365 nm, illuminance: 1000 mW / cm 2
  • integrated light quantity 3000 mJ / cm 2 .
  • a second adherend (made of aluminum subjected to sulfuric acid alumite treatment) with an area of 25 mm ⁇ 80 mm is applied to the first adherent so as to sandwich the UV-curable photocurable composition. Bonding and applying pressure using a 2 kg roller. This produced a test piece. Immediately after the pressure was applied to the test piece, the peel strength was measured at a test speed of 300 mm / min in accordance with JIS K6854-2 (adhesive-peeling adhesion strength test method part 2: 180 degree peeling method). . In addition, a test piece was prepared using the photocurable composition according to Example 6 in the same manner as described above, and then cured for 24 hours at 23 ° C.
  • Example 7 Reference Example 1, and Comparative Example 6 were also evaluated in the same manner as Example 6. The test results are shown in Table 3.
  • Example 6 and Example 7 to which the component (A) having a crosslinkable silicon group was added the peel adhesion strength immediately after the ultraviolet irradiation was excellent, and after 24 hours of curing It was shown that the peel adhesion strength is further increased by moisture curing.
  • Reference Example 1 which does not contain the component (A) having a crosslinkable silicon group no difference was observed in the peel adhesion strength immediately after UV irradiation and after 24 hours of curing.
  • Comparative Example 6 it was shown that although the peel adhesion strength was improved after curing for 24 hours due to poor surface curability, the peel adhesion strength immediately after UV irradiation was affected.
  • the cured product When LA is used as one of the components of the curable composition, the cured product exhibits a sticky shape. And when (A) component containing a crosslinkable silicon group is used like Example 6 or Example 7, adherends will be bonded together using adhesive hardened
  • Example 8 As shown in Table 4, after changing the compounding material to obtain a curable composition, the surface curability and hardness were evaluated. The results are shown in Table 4.
  • thermosetting composition according to Example 8 was applied to an adherend (aluminum plate) using a glass rod so that the thickness was 200 ⁇ m.
  • the thermosetting composition in the adherend was left to stand in a dryer at 180 ° C. for 10 minutes.
  • the surface curability was tested by finger touch in an environment of 23 ° C. and 50% RH. The case where the uncured material did not adhere to the finger or the liquid material adhered but was faint was evaluated as “ ⁇ ”, and the case where the liquid material adhered to the finger surface was evaluated as “x”.
  • thermosetting composition according to Example 8 was put in a metal cap having a height of 6 mm and left in an atmosphere at 180 ° C. for 10 minutes. And the hardness of the hardened
  • the two-part curable composition according to Example 9 was mixed with 1 g of the first liquid and 1 g of the second liquid at 23 ° C. for 10 seconds, and the mixture was used as an adherend (aluminum plate) with a glass rod to a thickness of 200 ⁇ m. It applied so that it might become. After 30 minutes, the surface curability was tested by finger touch in an environment of 23 ° C. and 50% RH. The case where the uncured material did not adhere to the finger or the liquid material adhered but was faint was evaluated as “ ⁇ ”, and the case where the liquid material adhered to the finger surface was evaluated as “x”.
  • the two-component curable composition according to Example 9 was mixed with 1 g of the first solution and 1 g of the second solution at 23 ° C. for 10 seconds, placed in a metal cap having a height of 6 mm, and an environment of 23 ° C. and 50% RH for 30 minutes. Left to stand. And the hardness of the hardened
  • thermosetting composition according to Example 8 and the two-component curable composition according to Example 9 have excellent surface curability and good hardness. It was.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition durcissable apte à subir une réaction de polymérisation adéquate en supprimant considérablement l'inhibition de la polymérisation par l'oxygène même si elle est utilisée à l'air, tout en permettant d'assurer un degré de liberté de conception de la composition ; et un produit. Cette composition durcissable comprend (A) un composé monoacrylate qui est représenté par la formule générale (1), la formule générale (2) ou la formule générale (3) et au moins un amorceur choisi dans le groupe constitué par (B1) un photo-amorceur, (B2) un amorceur thermique et (B3) un amorceur redox. (Dans la formule générale (1), la formule générale (2) et la formule générale (3), R1 représente -H ou -CH3. Dans la formule générale (1), R2 représente un groupe alkyle substitué ou non substitué, un groupe aryle substitué ou non substitué, un groupe comprenant une structure à noyau hétérocyclique, un groupe possédant une pluralité de cycles ou -(CmH2mO)nR5 (où m représente un nombre entier de 2 à 4, n représente un nombre entier de 1 à 30, et R5 représente -H, un groupe alkyle substitué ou non substitué ou un groupe phényle substitué ou non substitué). Dans la formule générale (2), chacun de R3 et R4 représente -H, un groupe alkyle substitué ou non substitué, un groupe aryle substitué ou non substitué, un groupe comprenant une structure à noyau hétérocyclique, -(CmH2mO)nR5 (où m représente un nombre entier de 2 à 4, n représente un nombre entier de 1 à 30, et R5 représente -H, un groupe alkyle substitué ou non substitué ou un groupe phényle substitué ou non substitué), ou un groupe possédant une pluralité de cycles ; ou en variante, R3 et R4 peuvent se combiner l'un avec l'autre et former une structure cyclique ou une structure hétérocyclique avec les atomes de carbone auxquels R3 et R4 sont liés. Dans la formule générale (3), chacun de R' et R'' représente un groupe organique ou un atome d'hydrogène.)
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JP2023503475A (ja) * 2019-11-25 2023-01-30 ボスティク エス アー （メタ）アクリレートモノマーから作製される組成物
JP2023514352A (ja) * 2020-02-20 2023-04-05 ドンジン セミケム カンパニー リミテッド 光重合性組成物、これから形成された光学部材および表示装置
WO2023139991A1 (fr) * 2022-01-19 2023-07-27 信越化学工業株式会社 Copolymère hydrophile et composition hydrophile
JP2024059104A (ja) * 2022-10-17 2024-04-30 ピーアイ・アドバンスド・マテリアルズ・カンパニー・リミテッド ポリアミック酸ワニス

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