WO2016181742A1 - Radical-curable composition and cured product thereof - Google Patents

Radical-curable composition and cured product thereof Download PDF

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WO2016181742A1
WO2016181742A1 PCT/JP2016/061780 JP2016061780W WO2016181742A1 WO 2016181742 A1 WO2016181742 A1 WO 2016181742A1 JP 2016061780 W JP2016061780 W JP 2016061780W WO 2016181742 A1 WO2016181742 A1 WO 2016181742A1
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meth
acrylate
radical
curable composition
materials
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PCT/JP2016/061780
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French (fr)
Japanese (ja)
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小谷　準
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株式会社カネカ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F

Definitions

  • the present invention relates to a radical curable composition and a cured product thereof. More specifically, the present invention relates to a radical curable composition containing a (meth) acrylic polymer having a radical crosslinkable group and a cured product thereof.
  • Rubber materials are used in various fields such as architecture, automobiles, electricity / electronics, machinery, logistics, chemistry, medical care / care / sports, adhesives and sealants, sealing materials, adhesives, paints, coating materials, resist materials, It is used as shock absorbing material, vibration damping material, pressure dispersion material, molded part, molding material, etc.
  • rubber materials it is excellent in flexibility, vibration proofing, shock absorption, heat resistance, oil resistance, moisture resistance, mechanical strength, and does not contain silicone compounds.
  • a rubber material mainly composed of a polymer has been suitably used.
  • demand for rubber material using radical reaction such as photo radical curing or thermal radical curing is increasing as a curing method that is fast and easy to handle.
  • the inventors of the present invention have proposed a (meth) acrylic polymer having a (meth) acryloyl group at the terminal and having a main chain obtained by living radical polymerization, and those suitable as such radical curable rubber materials. It has reported about the composition using this (patent documents 1, 2).
  • the demand for improving the mechanical strength of these radically curable rubber materials is increasing year by year. However, sufficient mechanical strength cannot be obtained with the conventional technology. There is a problem that the use is limited depending on the application.
  • a monomer having a Tg of a homopolymer of room temperature or higher is added as a copolymerization or compounding agent, a polyfunctional monomer is added, a reinforcing filler as a filler Means such as adding is known.
  • a monomer having a Tg of homopolymer of room temperature or higher is copolymerized, there is a problem that handling becomes very difficult due to an increase in the viscosity of the polymer.
  • compression set which is an index showing how much it will be restored to its original shape when the compressed rubber is released. The smaller the value, the better the restoration performance. Yes.
  • Patent Document 3 describes that (meth) acryloylmorpholine is used as a diluent for ultraviolet or electron beam curable resins. However, it is only disclosed that (meth) acryloylmorpholine is excellent in solubility and dilution with respect to a prepolymer, has low volatility, low odor, low skin irritation and has excellent curing activity. ) There is no description about adding acryloylmorpholine to a (meth) acrylic polymer, and it describes what effect it will have on the tensile strength, elongation, and compression set of the cured product. It has not been.
  • Patent Document 4 discloses a curable composition containing a (meth) acrylic polymer having a long-chain alkyl group and having a crosslinkable functional group at the molecular end and a vinyl monomer having a cyclic structure. Yes. However, there is no description about (meth) acryloylmorpholine, and there is no suggestion of the effect of adding (meth) acryloylmorpholine on the mechanical strength and low-temperature properties of the cured product.
  • Patent Document 5 discloses a curable composition having a low viscosity and excellent elongation of a cured product by using a vinyl polymer having a (meth) acryloyl group at a molecular end, a vinyl monomer having a cyclic structure, and an initiator. Things have been proposed. However, when a vinyl monomer having a general cyclic structure is used, the Tg of the cured product is increased, and not only the rubber elasticity at a low temperature is impaired, but also the rubber elasticity under a room temperature environment is reduced depending on the case. There was a problem.
  • isobornyl acrylate and benzyl acrylate are disclosed in Examples, and it is disclosed only that elongation is improved at low viscosity when these are added. Further, the mechanical strength is improved only when 20 to 30 parts of isobornyl acrylate is used with respect to 100 parts of the polymer, but it is limited and is insufficient for use as a molded body. There is no description of the low-temperature properties of the cured product.
  • Patent Document 6 discloses that acryloylmorpholine is added as a dilution monomer to an acrylic polymer having a (meth) acryloyl group at the molecular end.
  • acryloylmorpholine is added as a dilution monomer to an acrylic polymer having a (meth) acryloyl group at the molecular end.
  • Patent Document 7 discloses a curable composition for liquid molding comprising an acrylic polymer having at least one (meth) acryloyl group at the molecular end and an initiator, and various additives for adjusting the physical properties. It may be used. However, conventionally known monomer species and combinations thereof cannot find a combination that improves the tensile strength while maintaining low temperature characteristics.
  • Patent Document 8 discloses an active energy ray-curable adhesive composition that is superior in adhesion by using a (meth) acrylamide compound in urethane acrylate, has no warp of the resulting laminate, and has little color after wet heat test.
  • (meth) acryloylmorpholine is preferable as the (meth) acrylamide compound
  • the obtained cured product preferably has a Tg of 60 to 180 ° C.
  • the examples and comparative examples also acryloyl
  • the Tg of the cured product using morpholine is 126 ° C. to 149 ° C.
  • Patent Documents 9 to 13 disclose various curable compositions in which a (meth) acrylic monomer is added to an acrylic polymer having a (meth) acryloyl group at the molecular end. However, all of them are only listed for various monomer types, and there is no description of what effect is exerted on low temperature characteristics and compression set by using two or more specific monomers in combination. No combination can be found that improves tensile strength and compression set while maintaining low temperature properties.
  • the present invention has a (meth) acrylic group having a radical crosslinkable group that is excellent in curability, has a higher tensile strength and does not impair rubber elasticity and low-temperature properties, and can give a cured product having excellent compression set properties. It aims at obtaining the curable composition of a polymer.
  • the (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups (meth) By adding a specific amount of acryloylmorpholine and a monofunctional acrylic monomer having a straight-chain or branched hydrocarbon group having 6 or more carbon atoms, it has a higher tensile strength and a permanent compression without impairing rubber elasticity and low-temperature properties. It has been found that a cured product having excellent strain characteristics can be obtained, and the present invention has been obtained.
  • (meth) acrylate monomers having the same structure as (meth) acryloylmorpholine such as monomers having a cyclic structure and acrylamide monomers, have no effect as described above, and use of (meth) acryloylmorpholine It was found that the effect is effective only in the case of (1), and that it is effective only when a specific amount is added. In addition, with (meth) acryloylmorpholine alone, the tensile strength is increased, but the compression set is deteriorated, and a monomer other than a monofunctional acrylic monomer having a straight chain or branched hydrocarbon group having 6 or more carbon atoms is used in combination.
  • the compression set remains poor or other physical properties are inferior, but only when a specific amount of a monofunctional acrylic monomer having a straight chain or branched hydrocarbon group having 6 or more carbon atoms is used in combination, the low temperature characteristics are reduced. It was found that the tensile strength was high while maintaining the compression set and the compression set was improved.
  • the present invention provides 0.01 to 10 parts by weight of radical polymerization initiator (II) with respect to 100 parts by weight of (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups. And 30 to 70 parts by weight of (meth) acryloylmorpholine (III) and 5 to 30 parts by weight of a monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms It relates to a radical curable composition.
  • (Meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups has a group having a radically crosslinkable carbon-carbon double bond at the end of the molecular chain A polymer is preferred.
  • the (meth) acrylic polymer (I) having at least 0.8 radical crosslinkable groups on average is preferably a (meth) acrylic polymer having a (meth) acryloyl group at the molecular end.
  • the molecular weight distribution of the (meth) acrylic polymer (I) having at least 0.8 radical crosslinkable groups on average is preferably less than 1.8.
  • the (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups polymerizes or co-polymerizes a monomer having a saturated hydrocarbon group having 1 to 24 carbon atoms and / or an aliphatic ether group. It is preferably obtained by polymerization.
  • the monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms is preferably a monofunctional acrylic monomer having a linear or branched hydrocarbon group having 8 to 24 carbon atoms.
  • the radical polymerization initiator (II) is preferably a thermal radical initiator and / or a photo radical initiator.
  • the present invention also relates to a cured product obtained from the radically curable composition described above.
  • cured material is 25 degrees C or less.
  • a cured product having higher tensile strength and excellent compression set characteristics can be obtained without impairing the rubber elasticity and low temperature characteristics of the (meth) acrylic polymer.
  • the radical curable composition of the present invention has a radical polymerization initiator (II) of 0.01 with respect to 100 parts by weight of (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups. Contains 10 to 10 parts by weight, 30 to 70 parts by weight of (meth) acryloylmorpholine (III), and 5 to 30 parts by weight of a monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms It is characterized by doing.
  • (meth) acrylic acid methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate , (Meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid Cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid nonyl, (meth) acrylic acid Isononyl, decyl (meth) acrylate, isodecyl (meth) acrylic
  • (meth) acryl represents acryl and / or methacryl (hereinafter the same).
  • the main chain of (meth) acrylic polymer having an average of at least 0.8 radical crosslinkable groups in the present invention is the availability of monomers, ease of handling, ease of polymerization, and flexibility of cured products at low temperatures. From the point of being excellent in properties such as property and elongation, it is preferable to be produced mainly by polymerizing an acrylate monomer.
  • “mainly” means that 50 mol% or more of the monomer units constituting the main chain of the (meth) acrylic polymer (I) is an acrylate ester monomer, preferably 70 mol. % Or more.
  • the (meth) acrylic polymer (I) is preferably obtained by polymerizing or copolymerizing a monomer having a saturated hydrocarbon group having 1 to 24 carbon atoms and / or an aliphatic ether group.
  • a monomer having a saturated hydrocarbon group having 1 to 24 carbon atoms and / or an aliphatic ether group is preferred from the viewpoint that the cured product has excellent heat resistance and low moisture permeability.
  • Specific examples include ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, and isostearyl acrylate.
  • an acrylic acid alkyl ether ester monomer having an aliphatic ether group having 1 to 24 carbon atoms is preferable.
  • the number of carbon atoms of the aliphatic ether group is more preferably 2-6.
  • these preferable monomers may be copolymerized with other monomers, and further block copolymerized.
  • the monomer to be copolymerized include styrene monomers such as styrene, vinyl toluene, ⁇ -methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride.
  • Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide , Methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclamate
  • Maleimide monomers such as hexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, Examples thereof include vinyl esters such as vinyl cinnamate; al
  • Molecular weight distribution of (meth) acrylic polymer (I) in the present invention that is, ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (Mw / Mn) Is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, even more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less, and most preferably 1.3 or less.
  • GPC measurement uses chloroform as a mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and weight average molecular weight can be determined in terms of polystyrene.
  • the number average molecular weight of the (meth) acrylic polymer (I) is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1,000 to 100,000 when measured by GPC. 5,000 to 100,000 is more preferable. If it is less than 500, there is a tendency that sufficient rubber elasticity cannot be obtained, for example, the flexibility of the cured product is impaired and elongation is lowered. On the other hand, when it exceeds 1,000,000, the viscosity tends to be high and handling tends to be difficult.
  • the (meth) acrylic polymer (I) used in the present invention can be obtained by various polymerization methods.
  • the polymerization method is not particularly limited, but a radical polymerization method is preferable from the viewpoint of versatility of the monomer, ease of control, and the like, and among the radical polymerizations, controlled radical polymerization is more preferable.
  • This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method”.
  • living radical polymerization is preferred because the molecular weight and molecular weight distribution of the resulting (meth) acrylic polymer can be easily controlled, and atom transfer radical polymerization is preferred because of availability of raw materials and ease of introduction of functional groups at the polymer ends. Particularly preferred.
  • Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss.
  • living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. .
  • the definition in the present invention is also the latter.
  • living radical polymerization has been actively researched by various groups. Examples include cobalt porphyrin complexes (J. Am. Chem. Soc. 1994, 116, 7943), those using radical scavengers such as nitroxide compounds (Macromolecules, 1994, 27, 7228), organic halides, etc. Atom transfer radical polymerization (ATRP) (J. Am. Chem. Soc.
  • Atom transfer radical polymerization and single electron transfer polymerization are generally polymerized using an organic halide or a sulfonyl halide compound as an initiator and a copper complex having copper as a central metal as a catalyst.
  • AGET Micromolecules. 2005, 38, 4139
  • ARGET Micromolecules. 2006, 39, 39
  • ICAR PNAS. 2006, which uses a heat or photodegradable radical generator together.
  • a reducing agent and a heat or photodegradable radical generator may be used in combination.
  • radical polymerization controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods.
  • the atom transfer radical polymerization which is one of the preferred methods for synthesizing the (meth) acrylic polymer (I), will be briefly described below.
  • an organic halide particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the ⁇ -position or a compound having a halogen at the benzyl-position), or a sulfonyl halide.
  • a compound or the like is preferably used as an initiator.
  • an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. preferable.
  • transition metal complex used as a polymerization catalyst is a metal complex which uses periodic group 7th group, 8th group, 9th group, 10th group, or 11 group element as a central metal, More preferably A transition metal complex having zero-valent copper, monovalent copper, divalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex.
  • the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like.
  • divalent copper compounds include cupric chloride, cupric bromide, cupric iodide, cupric cyanide, cupric oxide, cupric perchlorate, sulfide. Cupric and the like.
  • polyamine or the like is added as a ligand in order to increase the catalytic activity.
  • polyamine compounds include 2,2-bipyridine, 1,10-phenanthroline or derivatives thereof, alkylamines such as tributylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetraamine or hexamethyltris (2 -Aminoethyl) amine ethylenediamine, N, N'-hexamethylethylenediamine, 4,4'-di- (5-nonyl) -2,2'-bipyridine, N- (n-propyl) pyridylmethanimine, N- ( n-octyl) pyridylmethanimine, diethylenetriamine, N, N, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine, N-propyl-N, N-di (2-
  • a reducing agent may be used. Although the reducing agent is illustrated below, it is not limited to these reducing agents.
  • alkali metals such as lithium, sodium and potassium
  • alkaline earth metals such as beryllium, magnesium, calcium and barium
  • aluminum typical metals such as zinc
  • transition metals such as copper, nickel, ruthenium and iron Etc.
  • Metal compound Specific examples include salts of typical metals or transition metals and salts with typical elements, and complexes in which carbon monoxide, olefins, nitrogen-containing compounds, oxygen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds and the like are coordinated. It is done.
  • Metal hydride examples include sodium hydride; germanium hydride; tungsten hydride; diisobutylaluminum hydride, lithium aluminum hydride, sodium aluminum hydride, sodium triethoxyaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, etc.
  • aluminum hydrides such as triphenyltin hydride, tri-n-butyltin hydride, diphenyltin hydride, di-n-butyltin hydride, triethyltin hydride, and trimethyltin hydride. .
  • Tin compounds include tin carboxylates such as tin octylate and tin 2-ethylhexylate; organic compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate A tin compound etc. are mentioned.
  • Silicon hydride Specific examples include trichlorosilane, trimethylsilane, triethylsilane, diphenylsilane, phenylsilane, polymethylhydrosiloxane, and the like.
  • Boron hydride Specifically, borane, diborane, sodium borohydride, sodium trimethoxyborate, sodium borohydride, sodium cyanoborohydride, lithium borohydride, lithium borohydride, lithium triethylborohydride, hydrogen And tri-s-butyl boron hydride, lithium tri-t-butyl borohydride, calcium borohydride, potassium borohydride, zinc borohydride, tetra-n-butylammonium borohydride and the like.
  • Nitrogen compounds include hydrazine and diimide.
  • Phosphorus or phosphorus compound examples include phosphorus, phosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, trimethylphosphite, triethylphosphite, triphenylphosphite, hexamethylphosphorustriamide, hexaethylphosphorustriamide, and the like.
  • Rongalite is a formaldehyde derivative of sulfoxylate and is represented by MSO 2 ⁇ CH 2 O (M represents Na or Zn). Specific examples include sodium formaldehyde sulfoxylate and zinc formaldehyde sulfoxylate.
  • Hydrosulfite is a general term for sodium hyposulfite and formaldehyde derivatives of sodium hyposulfite.
  • An organic compound that exhibits a reducing action include alcohols, aldehydes, phenols, and organic acid compounds.
  • the alcohol include methanol, ethanol, propanol, and isopropanol.
  • the aldehyde include formaldehyde, acetaldehyde, benzaldehyde, formic acid and the like.
  • phenols include phenol, hydroquinone, dibutylhydroxytoluene, tocopherol and the like.
  • the organic acid compound include citric acid, ascorbic acid, and salts and esters thereof.
  • reducing agents may be used alone or in combination of two or more.
  • the amount of the reducing agent added is preferably from 0.01 to 100 molar equivalents relative to the transition metal compound (catalyst) in terms of polymerization rate and structure control, more preferably from 0.1 to 40 molar equivalents, and from 0.5 to 10 molar The equivalent is more preferable.
  • a basic compound When using AGET or ARGET as the living radical polymerization, a basic compound may be used. Examples of basic compounds are shown below, but are not limited to these reducing agents. They are applicable to the definition of Bronsted base, have a property of accepting protons, or apply to the definition of Lewis base, non-covalent. Any compound may be used as long as it has an electron pair and can give it and can form a coordination bond.
  • amine derivatives such as ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, aniline; ethylenediamine, propylenediamine, tetramethylethylenediamine, diethylenetriamine, pentamethyldiethylenetriamine, triethylenetetramine, hexamethyltriethylenetetramine, hexamethylene Polyamine derivatives such as tetramine; nitrogen-containing heterocyclic compounds such as pyridine, bipyridine, piperidine, pyrrole, imidazole; sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium pentoxide, sodium hexoxide, potassium methoxide , Potassium ethoxide, potassium propoxide, potassium butoxide, potassium pent Inorganic bases such as side and potassium hexoxide; organometallic compounds such as methyl lithium, ethyl lithium, propyl lithium, butyl lithium, pentyl lithium
  • the basic compound may be added directly to the reaction system or may be generated in the reaction system.
  • the addition amount of the basic compound is preferably 0.01 to 400 molar equivalents relative to the transition metal compound (catalyst) from the viewpoint of polymerization rate and structure control, more preferably 0.1 to 150 molar equivalents, and 0.5 to 40 molar equivalents. A molar equivalent is more preferred.
  • the polymerization reaction can be carried out without solvent, but can also be carried out in various solvents.
  • the type of the solvent is not particularly limited, and examples thereof include a solvent described in paragraph [0067] of JP-A-2005-232419. These may be used alone or in combination of two or more.
  • Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO 2 as a medium.
  • the polymerization temperature is not limited, but can be carried out in the range of 0 to 200 ° C., preferably in the range of room temperature to 150 ° C.
  • the radical crosslinkable group is not particularly limited, and is preferably a group having a radical crosslinkable carbon-carbon double bond such as a (meth) acryloyl group, a (meth) allyl group, an exomethylene group, and a maleimide group.
  • a (meth) acrylic polymer produced by the above-mentioned atom transfer radical polymerization method it is a (meth) acryloyl group because the radical crosslinkable group is highly reactive and the crosslinkable group can be easily introduced. Is preferred.
  • a method for introducing a radical having a crosslinkable carbon-carbon double bond will be described.
  • the introduction of a group having a radically crosslinkable carbon-carbon double bond can be performed by a known method. Examples thereof include the methods described in paragraphs [0080] to [0091] of JP-A No. 2004-203932. Among these methods, a method in which the terminal halogen group of the (meth) acrylic polymer is substituted with a compound having a group having a radically crosslinkable carbon-carbon double bond is preferable because it is easier to control.
  • a (meth) acrylic polymer having a terminal halogen group is a method of polymerizing a (meth) acrylic monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a halogen compound.
  • the compound having a group having a radically crosslinkable carbon-carbon double bond is not particularly limited, but a compound represented by the following general formula (1) can be used.
  • R in the above formula (1) represents hydrogen or an organic group having 1 to 20 carbon atoms. Specific examples include —H, —CH 3 , —CH 2 CH 3 , — (CH 2 ) n CH 3 (n represents an integer of 2 to 19), —C 6 H 5 , —CH 2 OH, — CN, etc. are mentioned, and preferably —H or —CH 3 .
  • M + in the above formula (1) is a counter cation of an oxyanion
  • examples of M + include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions.
  • examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion and dimethylpiperidinium ion, and are preferable from the viewpoint of reactivity and availability.
  • the amount of the oxyanion of the general formula (1) used is preferably 1 to 5 equivalents, more preferably 1.0 to 1.2 equivalents relative to the halogen group of the (meth) acrylic polymer. Since this reaction proceeds almost quantitatively, if the amount is too small, a sufficient amount of radical-crosslinkable carbon-carbon double bond groups with respect to the halogen group will not be introduced. Economically unfavorable.
  • the solvent for carrying out this reaction is not particularly limited but is preferably a polar solvent because it is a nucleophilic substitution reaction.
  • a polar solvent because it is a nucleophilic substitution reaction.
  • tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric Triamide, acetonitrile and the like are used.
  • the temperature at which the reaction is carried out is not limited, but is generally from 0 to 150 ° C., preferably from room temperature to 100 ° C. in order to retain the polymerizable terminal group.
  • the number of radical crosslinkable groups in each molecule of the (meth) acrylic polymer (I) may be the same or different. From the viewpoint of curability and physical properties such as flexibility, elongation and tensile strength of the cured product, the number of radical crosslinkable groups in the molecule is at least 0.8 on average, preferably 0.9 or more 4.0 or less, more preferably 1.0 or more and 2.0 or less.
  • the number of radical crosslinkable groups is adjusted so that it is within the above range as the average of the entire (meth) acrylic polymer. do it.
  • the radically crosslinkable group of the (meth) acrylic polymer (I) At least one of (preferably a group having a radically crosslinkable carbon-carbon double bond, more preferably a (meth) acryloyl group) is preferably at the end of the molecular chain, and all radically crosslinkable groups are More preferably at the end.
  • the (meth) acrylic polymer (I) having a radical crosslinkable group at the molecular end has a radical crosslinkable group at both ends of the polymer (meth). It is preferable that both the acrylic polymer and a (meth) acrylic polymer having a radical crosslinkable group at one end of the polymer are included.
  • the ratio of (meth) acrylic polymer having radical crosslinkable groups at both ends to (meth) acrylic polymer having radical crosslinkable groups at one end of the polymer has radical crosslinkable groups at both ends.
  • the amount of the (meth) acrylic polymer having a radical crosslinkable group at one end is preferably 0 to 3000 parts by weight, and preferably 40 to 300 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. More preferred. The smaller the (meth) acrylic polymer having a radical crosslinkable group at one end, the harder the cured product will be and the better the compression set, and conversely, the (meth) acrylic polymer having a radical crosslinkable group at one end will be The more the cured product is, the softer and the better it becomes.
  • radical polymerization initiator (II) when hardening by active energy rays, such as UV and an electron beam, a photoradical initiator is preferable, and when making it harden
  • the photo radical initiator is not particularly limited.
  • ⁇ -hydroxy ketone compounds for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.
  • phenyl ketone derivatives for example, acetophenone, propiophenone, benzophenone, 3-methyl
  • an initiator species capable of suppressing oxygen inhibition on the surface of the cured product as a photo radical initiator having two or more photodegradable groups in the molecule, 2-hydroxy-1- [4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade name IRGACURE127, manufactured by BASF Japan), 1- [4- (4-Benzoxylphenylsulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one (trade name ESURE1001M), methylbenzoyl formate (trade name SPEDCURE MBF, manufactured by LAMBSON), O-ethoxyimino-1-phenylpropane -1-On (trade name SPEDDCURE PDO, manufactured by LAMBSON), oligo [ -Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] prop
  • 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name DAROCUR TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl) -phenylphosphine, characterized by improved deep-curability
  • examples thereof include acyl phosphine oxide photo radical initiators such as fin oxide (trade name IRGACURE819, manufactured by BASF Japan Ltd.), bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
  • 1-hydroxy-cyclohexyl-phenyl-ketone (trade name IRGACURE 184, manufactured by BASF Japan Ltd.), 2-hydroxy-2- in terms of the balance between curability and storage stability of the curable composition.
  • Methyl-1-phenyl-propan-1-one (trade name DAROCUR1173, manufactured by BASF Japan), bis (4-dimethylaminophenyl) ketone, 2-hydroxy-1- [4- [4- (2-hydroxy-2 -Methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade name IRGACURE127, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1 (trade name IRGACURE369, manufactured by BASF Japan), 2- ( -Methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl)
  • photo radical initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.
  • Specific combinations with other compounds include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, diethanolmethylamine, dimethylethanolamine, triethanolamine, ethyl Combinations with amines such as -4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate, further combinations with iodonium salts such as diphenyliodonium chloride, combinations with pigments and amines such as methylene blue, etc. Can be mentioned.
  • photo radical initiator When the photo radical initiator is used, if necessary, hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl techol, 2,2,6,6-tetramethylpiperidine-1-oxyl, N, N— Polymerization inhibitors such as N, N-dialkylhydroxylamine such as diethylhydroxylamine and N, N-distearylhydroxylamine can also be added.
  • Thermal radical initiator Although it does not specifically limit as a thermal radical initiator, An azo initiator, a peroxide initiator, a persulfate initiator, a redox initiator, etc. are contained.
  • the azo initiator is not particularly limited, and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2′-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyronitrile) (VAZO 64), 2,2'-azobis-2 -Methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2'-azobis (2-cyclopropylpropionitrile) ), And 2,2′-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries, Ltd.) It is.
  • the peroxide initiator is not particularly limited, and benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate (Perkadox). 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butylperoxy-2-ethylhexa Noate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.
  • the persulfate initiator is not particularly limited, and examples thereof include potassium persulfate, sodium persulfate, and ammonium persulfate.
  • the redox (oxidation-reduction) initiator is not particularly limited, and is a combination of the above-mentioned persulfate initiator and a reducing agent (sodium metabisulfite, sodium bisulfite, etc.); a system based on an organic peroxide and a tertiary amine
  • a reducing agent sodium metabisulfite, sodium bisulfite, etc.
  • a system based on an organic peroxide and a tertiary amine For example, systems based on benzoyl peroxide and dimethylaniline; systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.
  • initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol.
  • thermal radical initiator those selected from the group consisting of azo initiators and peroxide initiators are preferable. More preferred are 2,2′-azobis (methylisobutylate), benzoyl peroxide, dicumyl peroxide, t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and these It is a mixture of
  • a photo radical initiator and a thermal radical initiator may be used in combination.
  • the radical polymerization initiator is used in a catalytically effective amount. From the viewpoint of curability and storage stability, the amount of the radical polymerization initiator is 0.01 to 10 parts by weight, preferably about 0.1 to 10 parts by weight per 100 parts by weight of the (meth) acrylic polymer (I). 5 parts by weight.
  • the amount of radical polymerization initiator is the total amount of the mixture when a mixture of radical polymerization initiators is used.
  • (Meth) acryloylmorpholine (III) is not particularly limited, but N-acryloylmorpholine is preferred because it is readily available, has good reactivity, and has better low-temperature properties of the cured product.
  • the amount of (meth) acryloylmorpholine (III) used in the present invention is 30 to 70 with respect to 100 parts by weight of (meth) acrylic polymer (I) because a tough cured product having high tensile strength can be obtained. Parts by weight, more preferably 40 to 60 parts by weight. When the amount is less than 30 parts by weight, the effect of improving the tensile strength is low. When the amount exceeds 70 parts by weight, the elongation is reduced or sufficient flexibility as a rubber is not obtained, or the curability is lowered to obtain a cured product. May not be obtained.
  • the monofunctional acrylic monomer is a polymerizable monomer having one acryloyl group in the molecule.
  • the straight chain or branched hydrocarbon group having 6 or more carbon atoms is a straight chain hydrocarbon group or branched hydrocarbon group containing 6 or more carbon atoms, and does not include a cyclic structure.
  • the hydrocarbon group may have various atoms such as oxygen, nitrogen, phosphorus, silicon, and halogen.
  • the monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms is not particularly limited, and various types can be used. Specifically, hexyl acrylate, isohexyl acrylate, heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate , Undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, stearyl acrylate, isostearyl acrylate, oleyl acrylate, behenyl acrylate, 2-acrylate In addition to
  • ME-4S, MPE-600 methoxypolypropylene glycol acrylate (NK Nakamura Chemical Co., Ltd. NK ester AM-30PG), 2-ethylhexyl polyethylene glycol acrylate (Toagosei Co., Ltd.) Aronix M-120), Octoxy polyethylene glycol acrylate-polypropylene glycol, Lauroxy polyethylene glycol acrylate, Stearoxy polyethylene glycol acrylate, Allyloxy polyethylene glycol acrylate- Polypropylene glycol, undecylenoxypolyethylene glycol acrylate, (meth) acrylic acid ⁇ -carboxy-polycaprolactone (Aronix M-5300 manufactured by Toagosei Co., Ltd.), ⁇ - (acryloyloxypropyl) triethoxysilane, acrylic acid 2- (perfluorohexyl) ethyl (CHEMINOX FAAC-6 manufactured by Unimatec Co., Ltd.), acrylic acid 1H,
  • a monofunctional acrylic monomer having a linear or branched hydrocarbon group having 8 to 24 carbon atoms is preferable because the monomer odor of the curable composition is slight and the working environment is good.
  • Particularly preferred monofunctional acrylic monomers are lauryl acrylate, isostearyl acrylate, 2-decyltetradecanyl acrylate, polyethylene glycol acrylate (carbonized carbon) because they are easy and have excellent mechanical strength and heat resistance.
  • the amount of the monofunctional acrylic monomer (IV) having a straight chain or branched hydrocarbon group having 6 or more carbon atoms used in the present invention is 5 to 30 weights per 100 weight parts of the (meth) acrylic polymer (I). Parts, preferably 5 to 20 parts by weight. When the amount is less than 5 parts by weight, the effect of improving the compression set characteristics is low. When the amount exceeds 30 parts by weight, the tensile strength may be reduced, or the curability may be lowered and a cured product may not be obtained.
  • acryloylmorpholine As described above, the addition of acryloylmorpholine (ACMO) as a diluent to radical curable resins including various ultraviolet curable resins is known to those skilled in the art, and the effects of the addition of acryloylmorpholine include pre-treatment. It is known for its excellent solubility and dilutability in polymers, low volatility, low odor, low skin irritation, excellent curing activity, excellent adhesion, and high coating film hardness. .
  • ACMO acryloylmorpholine
  • the inventors improve the tensile strength while maintaining the low-temperature properties of the cured product, and simultaneously improve the compression set properties. I found out.
  • An antioxidant can also be used in the radical curable composition of the present invention.
  • “Antioxidant Handbook” published by Taiseisha (published on October 25, 1975), “Polymer Additive Handbook” published by CMC Publishing (Haruna) And the like described in Toru Hen, November 7, 2010, first edition)), etc., but are not limited to these, hindered phenol antioxidants, amine antioxidants Primary antioxidants such as lactone-based antioxidants and hydroxylamine-based antioxidants, and secondary antioxidants such as sulfur-based and phosphorus-based antioxidants can be used.
  • hindered phenolic antioxidants As hindered phenolic antioxidants, phenolic antioxidants that have a hindered phenolic structure or a one-hindered phenolic structure in the molecule are excellent in low coloration after heat aging tests and are excellent in maintaining rubber elasticity. Agents are preferred.
  • 2,6-di-tert-butyl-4-methylphenol 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) ( ⁇ -methylbenzyl) phenol
  • 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) 2,2'-methylenebis (4methyl-6-tert-butylphenol)
  • 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol
  • 4,4′-thiobis (3-methyl-6-tert-butylphenol
  • 2,5-di-tert-butylhydroquinone 2,5-di-tert-amylhydroquinone
  • 1,6-hexanediol Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
  • the amine-based antioxidant is not particularly limited, and conventionally known ones such as amine-ketone compounds and aromatic amine compounds can be widely used.
  • amine-ketone compounds include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and a reaction product of diphenylamine and acetone. Etc.
  • Specific product names include Nocrack 224, Nocrack AW, Nocrack AW-N, Nocrack B, Nocrack BN (all of which are manufactured by Ouchi Shinsei Chemical Co., Ltd.), Antage RD, Antage RD-G, Antage AW (all manufactured by Kawaguchi Chemical Industry Co., Ltd.), Nonflex RD, Nonflex QS, Nonflex AW, Nonflex BA, Nonflex BA-P, Nonflex BAR (all manufactured by Seiko Chemical Co., Ltd.) ), Vulcanox HS / LG, Vulcanox HS / powder (all manufactured by Bayer), KorestabTMQ (manufactured by S & S Japan), Aminox (manufactured by Shiraishi Calcium Co., Ltd.) and the like, but are not limited thereto. It is not a thing.
  • aromatic amine compounds include naphthylamine antioxidants, diphenylamine antioxidants, and p-phenylenediamine antioxidants.
  • naphthylamine antioxidants such as phenyl- ⁇ -naphthylamine; p- (p-toluenesulfonylamido) diphenylamine, 4,4′-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, 4,4 '-Distyryldiphenylamine, 4,4'-dioctyldiphenylamine, octylated diphenylamine, reaction product of diphenylamine and diisobutylene, alkylated diphenylamine, p-isopropoxy-diphenylamine, bis (phenyl-isopropylidene) -4,4-diphenylamine 4- ( ⁇ -phenylethyl) diphenylamine, 4,4′-bis ( ⁇ -phenylethyl)
  • N N′-diphenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N, N′-di-2-naphthyl-p-phenylenediamine, N— Phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, 4- (anilinophenyl) methacrylamide, 4- (mercaptoacetamido) diphenylamine, 2-[(mercaptoacetyl) oxy] ethyl -3-[[4- (Phenylamino) phenyl] amino] butanate, N, N'-bis (1-methylheptyl) -p-phenylenediam, N, N-bis (1,4-dimethylpentyl) -P-phenylenediamine, N- (1,3-dimethylbutyl
  • Specific product names include Nocrack PA, Nocrack ODA, Nocrack ODA-N, Nocrack AD-F, Nocrack CD, Nocrack TD, Nocrack White, Nocrack DP, Nocrack 810-NA, Nocrack 6C, Nocrack G-1, NOCRACK 500 (all of which are manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), ANTAGE OD, ANTAGE LDA, ANTAGE DDA, ANTAGE 3C, ANTAGE 6C, ANTAGE STDP-N, ANTAGE BC (all of which are manufactured by Kawaguchi Chemical Industry Co., Ltd.) ), Non-flex OD-R, non-flex BA, non-flex BAR, non-flex OD-3, non-flex DCD, non-flex H, non-flex F, non-flex 3CH, non-flex LAS-P, steerer LAS, steer LA STAR, Ozonon 3C, Ozonon 6C, Ozonon 35, Ozonon 35-PR, Ozonon 3
  • lactone antioxidants examples include 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one) (IRGA Commercial products such as Knox HP-136 (manufactured by BASF Japan), IRGASTAB FS 042 and blends containing it (manufactured by BASF Japan), and GENOX EP (manufactured by Crompton) can be mentioned.
  • a sulfur type oxidizing agent it does not specifically limit and a conventionally well-known thing can be used widely.
  • Specific examples include 4,4′-thiobis (3-methyl-6-tert-butylphenol), dilauryl-thiodipropionate, bis ⁇ 2-methyl-4- [3-n-alkyl (C12 or C14) thio.
  • Nocrack 300, Nocrack 400 (all of which are manufactured by Ouchi Shinsei Chemical Co., Ltd.) ADK STAB AO-23, AO-412S, AO-503A (all of which are manufactured by ADEKA), IRGANOX PS800FL, IRGANOX PS802FL, IRGANOX 1035, IRGANOX 1520L, IRGANOX 565 (all of which are manufactured by BASF Japan Ltd.), Sumilyzer TPL-R, Sumilyzer TPS, Sumilyzer TPM, Sumilyzer WX-R, Sumilyzer TP-D (all of which are Sumitomo Chemical Co., Ltd.) ), Sinox BCS (manufactured by Cypro Kasei Co., Ltd.), Vulcanol 88 (manufactured by Bayer), SONGNOX 4120, SONGNOX DLTDP, SONGNOX DMTDP, SONGNOX DSTDP, SONGNOX DTDTP (man
  • phosphorus-based oxidizing agent there are no particular limitations on the phosphorus-based oxidizing agent, and conventionally known ones can be widely used.
  • phosphoric acid and phosphoric acid ester containing active hydrogen affect the storage stability of the composition and the heat resistance of the cured product. Therefore, an alkyl phosphite, an aryl phosphite, an alkyl aryl phosphite compound and the like that do not contain phosphoric acid and phosphate ester in the molecule are preferable.
  • Such phosphorus antioxidants include tris (nonylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, diphenyl, mono (2-ethylhexyl) phosphite, diphenyl, mono (tridecyl) Phosphite, diphenyl, mono (isodecyl) phosphite, diphenyl, mono (isooctyl) phosphite, diphenyl, mono (nonylphenyl) phosphite, triphenyl phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, tris (2-ethylhexyl) phosphite, trilauryl phosphite, trioleyl phosphite, tristearyl phosphite, tris (2,4-
  • phosphorus-based antioxidants it is preferable that all of the substituents of the phosphorus atom have a hydrocarbon group having 8 or more carbon atoms from the viewpoint of being stable with respect to hydrolyzability and having good heat resistance.
  • antioxidants may be used alone or in combination of two or more.
  • primary antioxidants such as hindered phenol antioxidants, amine antioxidants, lactone antioxidants, hydroxylamine antioxidants, and secondary antioxidants such as sulfur and phosphorus antioxidants. It is well known among those skilled in the art that an excellent heat resistance performance is exhibited by combining agents.
  • the amount of the antioxidant used is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (I). .
  • the blending amount is less than 0.1 parts by weight, the effect of improving the heat aging resistance may not be sufficient.
  • the blending amount exceeds 10 parts by weight, the radical curability may be lowered, and it is obtained from the curable composition. The resulting cured product may be markedly colored.
  • the curable composition of the present invention includes a monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms for the purpose of improving workability by reducing viscosity and improving physical properties of a cured product. Monomers having radically polymerizable groups, which are different from), can also be used as reactive diluents.
  • radical polymerizable group examples include (meth) acryl group, styrene group, acrylonitrile group, vinyl ester group, N-vinyl pyrrolidone group, conjugated diene group, vinyl ketone group, vinyl chloride group and the like.
  • those having a (meth) acryloyl group and an acrylamide group similar to the radical crosslinkable group used in the (meth) acrylic polymer (I) used in the present invention are preferable.
  • the monomer examples include (meth) acrylic monomer, styrene monomer, acrylonitrile, vinyl ester monomer, N-vinylpyrrolidone, conjugated diene monomer, vinyl ketone monomer, vinyl halide / vinylidene halide monomer, A polyfunctional monomer etc. are mentioned.
  • Examples of the (meth) acrylic monomer include (meth) acrylic monomers used in the above-mentioned (meth) acrylic polymer (I).
  • styrene monomer examples include styrene and ⁇ -methylstyrene.
  • vinyl ester monomers examples include vinyl acetate, vinyl propionate, and vinyl butyrate.
  • conjugated diene monomer examples include butadiene and isoprene.
  • vinyl ketone monomer examples include methyl vinyl ketone.
  • vinyl halide / vinylidene halide monomer examples include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.
  • bifunctional or higher polyfunctional monomer examples include 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,6-hexanedi (meth) acrylate, neopentyl glycol di Di (meta) of saturated hydrocarbon diols such as (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,2-ethanediol di (meth) acrylate, etc.
  • epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin; polyol (polytetramethylene glycol, ethylene glycol and adipine) Polyester diol of acid, ⁇ -caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated polyisobutylene) and organic isocyanate (tolylene diene) Isocyanate, isophorone diisocyanate, diphenylmethane diisocyanate Urethane resin obtained from silicate, hexamethylene diisocyanate, xylylene diisocyanate, etc.
  • polyol poly
  • the addition amount in the case of adding a reactive diluent is not particularly limited, but the (meth) acrylic polymer (I) is advantageous in that the workability of the curable composition is good and the influence on the curing shrinkage rate is small.
  • the amount is preferably 0.1 to 200 parts by weight, more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight.
  • a filler can be added to the radically curable composition of the present invention in order to impart mechanical strength and abrasion resistance, or to adjust the thixotropy of the curable composition.
  • Specific examples include various fillers and fine hollow particles described in paragraphs [0134] to [0151] of JP-A-2006-291073.
  • fine silica used as reinforcing silica such as fumed silica, wet process silica, carbon black, wood powder, pulp, cotton chips, mica, walnut shell powder, rice husk powder, graphite, clay, silica ( Crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, oxidation Ferric iron, bengara, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate, shirasu balloon, beads such as polyacrylic resin, polyacrylonitrile-vinylidene chloride resin, phenolic resin, polystyrene resin
  • fumed silica, wet process silica, carbon black, and calcium carbonate are preferable from the viewpoint of excellent reinforcement.
  • fumed silica and wet process silica used as reinforcing silica those having a particle diameter of 50 ⁇ m or less and a specific surface area of 80 m 2 / g or more are preferable from the viewpoint of reinforcing effect.
  • surface-treated silica is better in kneading and fluidity of the composition than surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane, etc. It is more preferable from the point of being excellent in economy.
  • reinforcing silica examples include, but are not particularly limited to, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Sil, manufactured by Nippon Silica Kogyo Co., Ltd., which is one of the wet process silicas. It is done.
  • the said specific surface area value says the measured value by BET method (low-temperature low-humidity physical adsorption of inert gas).
  • carbon black any carbon black such as channel black, furnace black, acetylene black and thermal black is preferably used, and furnace black is more preferable from the viewpoint of good reinforcement and economical efficiency.
  • the amount of these fillers to be added is not particularly limited, but is preferably 0.1 to 100 parts by weight, and preferably 0.5 to 80 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (I). More preferred is 1 to 50 parts by weight.
  • the blending amount is less than 0.1 part by weight, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts by weight, the workability of the curable composition may be deteriorated.
  • a filler may be used independently and may be used together 2 or more types.
  • a plasticizer can be added to the radically curable composition of the present invention.
  • mechanical properties such as the viscosity of the radical curable composition, the tensile strength and elongation of the cured product, and the transparency of the cured product can be improved.
  • phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate; dioctyl adipate , Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate, isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinolinate; diethylene glycol dibenzoate, triethylene glycol dibenzoate, penta Esters of polyalkylene glycols such as erythritol esters; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Pyromellitic acid esters; Polystyrene Polys
  • the addition amount in the case of adding the plasticizer is not particularly limited, but the (meth) acrylic polymer (from the point that the workability of the radical curable composition is good and the influence on the mechanical properties of the cured product is small. I) 1 to 100 parts by weight is preferable with respect to 100 parts by weight, and 1 to 50 parts by weight is more preferable.
  • a solvent can be mix
  • Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone
  • the solvent include alcohol solvents such as methanol, ethanol and isopropanol; hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, heptane and octane. These may be used alone or in combination of two or more.
  • the addition amount in the case of adding the solvent is not particularly limited, but 100 parts by weight of the (meth) acrylic polymer (I) from the viewpoint that the workability of the curable composition is good and the influence on the curing shrinkage is small. Is preferably 0.1 to 50 parts by weight, and more preferably 1 to 30 parts by weight.
  • a thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability.
  • the thixotropic inhibitor is not particularly limited, and examples thereof include hydrogenated castor oil derivatives, metal soaps having long-chain alkyl groups, ester compounds having long-chain alkyl groups, inorganic fillers such as silica, amide waxes, and the like. Can be mentioned. These thixotropic agents may be used alone or in combination of two or more.
  • the addition amount in the case of adding a thixotropic agent is not particularly limited, but from the viewpoint of good workability of the curable composition, with respect to 100 parts by weight of the (meth) acrylic polymer (I),
  • the amount is preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight.
  • additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product.
  • additives include, for example, compatibilizers, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, antifoams.
  • additives mentioned in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904. JP-A-2001-72854 and the like.
  • the radical curable composition of the present invention is a one-part photo-curing type that is pre-blended with all blending components and cured by irradiating UV or electron beam after construction, or one-part heat that cures by heating after construction. It can be prepared as a curable type or a two-component mixed type that generates radicals by dividing the compounded component into two components and mixing them.
  • the method for preparing the curable composition of the present invention is not particularly limited.
  • the components described above are mixed and mixed with a hand mixer or a static mixer, or at room temperature or using a planetary mixer, a disper, a roll, a kneader, or the like.
  • Ordinary methods such as kneading under heating or using a small amount of a suitable solvent to dissolve and mix the components may be employed.
  • a filler it is preferable to use a planetary mixer, a disper, a roll, a kneader or the like.
  • the cured product of the present invention is obtained by curing the curable composition of the present invention.
  • the curable composition of this invention is not specifically limited, It is preferable to harden
  • a light source used for normal active energy ray curing can be used.
  • sunlight, low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), fluorescent lamp, incandescent bulb, medium Pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, gallium lamp, tungsten lamp, xenon lamp, mercury xenon lamp, chemical lamp, electrodeless discharge lamp, zirconium lamp, organic EL, LED, UV -LED etc. are mentioned.
  • a high pressure mercury lamp, a metal halide lamp, an electrodeless discharge lamp, and a UV-LED are preferable from the viewpoint of easy handling and economy.
  • the irradiation intensity of the active energy ray and the integrated light amount are appropriately adjusted according to the type and amount of the radical crosslinkable group, the type and amount of the photo radical initiator, and the desired thickness and size of the cured product.
  • a method of irradiating active energy rays for example, a method of continuously irradiating active energy rays on a belt conveyor, a method of stopping the belt conveyor only when irradiating active energy rays, and irradiating active energy rays uniformly, or
  • the belt conveyor system is suitable for continuous curing.
  • the batch method does not require a large-scale apparatus such as a belt conveyor, and has an advantage that it is easy to uniformly irradiate the target with active energy rays.
  • the curable composition is placed on the belt conveyor, and the active energy beam is irradiated from an active energy beam irradiation device fixed on the upper side, the side or the lower side of the conveyor.
  • the curable composition can be applied and cured in accordance with the movement of the application robot, the irradiation robot, or the stage using a spot type active energy ray irradiation apparatus.
  • a radical curable composition is made of PP film, PET film, Teflon (The film may be covered with a transparent barrier film such as a registered trademark film so that the surface does not come into contact with oxygen, and irradiated with active energy ultraviolet light through the film, or may be irradiated with nitrogen, carbon dioxide, You may irradiate an active energy ray in the inert zone which substituted oxygen with active gas.
  • the oxygen concentration in the irradiation atmosphere is preferably 5000 ppm or less, more preferably 500 ppm or less.
  • the temperature varies depending on the kind of the thermal radical initiator, the (meth) acrylic polymer (I) and the compound to be added, but the temperature is within the range of 50 ° C to 250 ° C. Preferably, it is within the range of 70 ° C to 200 ° C.
  • the curing time varies depending on the thermal radical initiator used, monomer, solvent, reaction temperature, etc., but is usually in the range of 1 minute to 10 hours.
  • thermosetting to obtain a molded body it is not particularly limited, and various commonly used molding methods can be used. Examples thereof include cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, and thermoforming. In particular, from the viewpoint of being able to be automated and continuous and being excellent in productivity, the one by injection molding is preferable.
  • the cured product of the present invention preferably exhibits a rubber shape.
  • the rubbery form is soft and excellent in elongation when the obtained cured product is touched, and exhibits a property of easily returning to the original shape even when stretched or bent.
  • the glass transition temperature (Tg) of the cured product is preferably 25 ° C. or less, more preferably 10 ° C. or less, and 0 ° C. or less because it exhibits sufficient rubber elasticity even in cold regions. More preferably, the temperature is ⁇ 10 ° C. or lower because sufficient rubber elasticity is exhibited even in extremely cold regions. When the glass transition temperature exceeds 25 ° C., it becomes difficult to exhibit rubber elasticity at room temperature.
  • the glass transition temperature (Tg) is measured by a method (DMA method) based on the peak top value of the loss tangent (tan ⁇ ).
  • Loss tangent is measured by the value of loss modulus / storage modulus.
  • the loss elastic modulus and storage elastic modulus are applied to the test piece at a constant frequency (5 Hz) in a shear mode (strain 0.05%), and the stress when the force is applied is determined by a dynamic viscoelasticity measuring device. It is measured by measuring using.
  • the cured product of the present invention may be used alone or in combination with other members as necessary.
  • the radical curable composition may be poured into a certain mold and solidified and taken out, or may be cured using a desired mold and used for each mold.
  • the curable composition may be applied to a dot shape, a bead shape, a planar shape, or an arbitrary shape with a roller or a dispenser, or may be printed.
  • the obtained cured product may be bonded to other members such as films, rubber, plastics, metals, ceramics, paper, nonwoven fabrics, fitted, sandwiched, or integrated via an adhesive or adhesive.
  • the composite molded body may be obtained by contact with another member in the state of the radical curable composition by a method such as application or injection, and then cured by irradiation with active energy rays or heating.
  • the cured product of the present invention is not limited to the above method of use.
  • Applications of the radical curable composition and the cured product of the present invention are not limited, but include sports equipment, toys / playground equipment, stationery, pharmaceutical / medical / care products, footwear, bedding / bedding, furniture, clothing, various miscellaneous goods, Transportation equipment, OA equipment, home appliances, audio equipment, portable equipment, industrial machinery / equipment, precision equipment, electrical / electronic equipment, electrical / electronic components, building materials, sealing materials / coating materials / adhesives / adhesives / molding Body, Encapsulant, Molded Parts, Paint, Ink, Foam, Resist Material, On-Site Molded Gasket, Shock Absorber, Shock Absorber, Pressure Dispersant, Damping Material, Damping Material, Sound Absorbing Material, Soundproofing Material, Heat Insulation It can be used for various applications such as materials and feel improving members.
  • molding member is also possible.
  • impact cushioning materials installed on fences and floors of gymnasiums, stadiums, gymnasiums, landing mats for gymnastics and exercise, floor exercise mats, gym stretch mats, kids mats, bouldering Mat (crash pad), beat board, high jump cushion material, wet suit, golf club, bat, tennis racket grip and heartwood, grab and mitt heartwood, sports shoe overlay, insole, insole, shoe sole, Ski boots, snowboard boot liners, toe shoes, ballet shoes, golf club heads, golf balls, baseball balls and other ball sports balls, sports protectors (for example, headgear and baseball used in martial arts such as rugby and boxing) And football helmets, baseball, soccer, Elbows for fighting, leggers (singards, etc.), rackets, balls, suits for riders, gloves (soccer keeper gloves, golf, skis, riders), rifle jackets (eg shoulder pads), molded products, seals It is useful for material applications, sealant applications, impact absorption applications, impact buffer applications, pressure dispersion applications, vibration suppression applications,
  • artificial skin, artificial bone, artificial cartilage, artificial organ, artificial cornea, artificial crystalline lens, artificial vitreous body, artificial muscle, artificial blood vessel, artificial joint, human body model, swimsuit and breast pad for breast augmentation Use as an insertion material, other biocompatible materials, chemical exudation pad, hemostatic pad, gas-liquid separation filter (indwelling needle filter), patch, medical liquid absorption tool, mask, compression pad, surgical disposable product , Medical tubes, caps, bags, gaskets, hoses, medical beds, treatment tables, chairs, electrocardiogram measurement electrode materials, electrode pads for low frequency treatment devices, sensor pads, bedsore prevention mattresses, posture change cushions, wheelchairs Cushions, wheelchair seats, showers and other care products, bathing care pillows, taping, cast liners, soft contact lens materials , Prosthetic hand, prosthetic leg itself, cushioning material (liner etc.) for connection to the prosthetic leg and prosthetic human body, or prosthetic leg and prosthetic hand joint parts, denture base, other dental supplies, shock absorbing pad, hip protector,
  • transdermally absorbable preparations adhesives for sticking, medical / medical sealing materials, medical adhesives, medical rubber stoppers, impression materials, dental fillers, syringe gaskets, and rubber stoppers for vacuum vessels, artificial dialysis O-rings or flat gaskets for devices, packaging materials for pharmaceuticals and medical devices, caps, cap liners, caps for vacuum blood collection tubes, catheter sealing materials and adhesives, sealing materials for implantable medical devices and attached sensors, etc. It can be used for adhesives.
  • footwear applications it can be used for men's shoes, women's shoes, children's shoes, elderly shoes, sports shoes, safety shoes, etc.
  • Bedding and bedding products include pillows, comforters, mattresses, beds, barber / beauty beds, mattresses, bed mats, bed pads, cushions, cribs, baby bed pillows, bed slip prevention, body pressure dispersion, Examples include sleeping comfort improvement applications, impact absorption applications, and molded product applications.
  • Furniture applications include chairs, seat chairs, cushions, sofas, sofa cushions / seat cushions, waist cushions, and other cushions, carpets / mats, tatami mats / comforters, toilet seat mats for spreading body pressure and improving sitting comfort , Impact absorbing applications, feel improving applications and the like.
  • Desk, chest, clothes case, bookshelf, staircase, door, door, bran, shoji, sliding door handle and handle, handrail, door stop, etc. Can be mentioned.
  • clothing applications include pad materials such as shoulders and bras, cold protection materials, helmets, bulletproof vests, etc., impact absorption applications, heat insulation applications, molded object applications, and the like.
  • bath products such as bath pillows, massage puffs, mouse pads, armrests and wrist rests for computers, anti-slip cushions, stationery (pen grips, penetrating sealants), desk pillows, earplugs, cotton swabs, hot Pack sheet, cold pack sheet, compress, eyeglass pad, underwater spectacles pad, face protector, watch pad, headphone ear pad, earphone, heat retaining cup, beverage can, ice pillow cover, folding pillow, writing instrument, bag (eg school bag) ), Daily goods / carpenter's grips, carpets, rugs such as artificial turf materials, elbow pads, knee pads, gloves, fish fishing, etc.
  • molded products such as anti-wrinkle prevention materials, sealing materials, shock absorption applications, shock absorbing applications, anti-vibration applications, Vibration applications, the sound absorbing applications, silencing applications, can be utilized as the feeling improving part application of the contact portion of the human body.
  • Transport applications include seats for automobiles, motorcycles, bicycles, electric bicycles, tricycles, strollers, construction machinery, railway vehicles, ships, aircraft, etc., child seats, headrests, armrests, footrests, headliners, saddles, rider cushions, helmets, custom Car bed mat, camper cushion, ceiling material, door trim, floor cushion instrument panel, dashboard, door panel, inner panel, shift knob, handle, grip, pillar, console box, airbag cover, parking brake cover, quarter trim , Interior materials such as lining, center pillar garnish, sun visor, in-vehicle electronics such as recording / playback devices and various sensors, control equipment for in-vehicle road navigation system Engine, harness, dust cover, hose, engine, battery, oil pan, front cover, rocker cover, etc., engine, tire, bumper, floor, under floor, door, roof, panel, wheel house, transmission, weather strip, various Auxiliary machine covers, window packings, roof moldings, door moldings, seat backs, trunk rooms, cargo bed and other molded body applications,
  • vibration isolation applications for carrying goods such as carry bags, carts, containers, flexible containers, and pallets.
  • materials to be transported include fine arts, precision instruments, fruits, fresh fish, eggs, pottery / porcelain, regenerative cells, and other cells for direct packaging, indirect packaging or packaging. It can be used for transportation purposes. Further, it can be used as shock absorbers, insulators, bushes, various mounts, film sheets, tapes, seals, chips, and molded members for transportation, transportation, and transportation.
  • anti-vibration rubber it can be used for anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials and the like.
  • 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.
  • chassis parts it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers.
  • Engine parts can be used for hoses for cooling, fuel supply, exhaust control, etc., gaskets for engine covers and oil pans, sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts.
  • tire parts in addition to bead parts, sidewall parts, shoulder parts and tread parts, it can be used as a resin for inner liners and as a sealing material for air pressure sensors and puncture sensors. Further, it can be used as a sealing material, sealing material, gasket, coating material, mold member, adhesive, and pressure-sensitive adhesive for various electronic parts and control parts. It can also be used as a covering material for copper / aluminum wire harnesses and a sealing material for connector parts.
  • OA equipment displays, personal computers, telephones, copiers, printers, copiers, game machines, TVs, DVD recorders, Blu-ray recorders, HDD recorders, various recorders, DVD players, Blu-ray players, etc.
  • molding materials sealing materials, sealants , Anti-vibration use, vibration control use, shock absorption use, shock absorbing use, sound absorption use, sound insulation use, touch improvement part for contact with human body, adhesive, adhesive, packing, O-ring, belt .
  • Household appliances refrigerator, washing machine, washing dryer, futon dryer, vacuum cleaner, air purifier, water purifier, electric toothbrush, lighting equipment, air conditioner, air conditioner outdoor unit, dehumidifier, humidifier, fan heater, fan, ventilator ⁇ Dryers, massagers, blowers, sewing machines, dishwashers, tableware dryers, door phones, rice cookers, microwave ovens, microwave ovens, IH cooking heaters, hot plates, various chargers, and irons
  • a vibration control application As an anti-vibration application, a vibration control application, an impact absorption application, and an impact buffer application for audio equipment (speakers, turntables, optical pickup devices, optical recording / reproducing devices, magnetic pickup devices, magnetic recording / reproducing devices, insulators, spacers, etc.) Useful.
  • audio equipment speaker, turntables, optical pickup devices, optical recording / reproducing devices, magnetic pickup devices, magnetic recording / reproducing devices, insulators, spacers, etc.
  • LED materials In electrical and electronic applications, for example, LED materials, various battery peripheral materials, sensors, semiconductor peripheral materials, circuit substrate peripheral materials, display peripheral materials such as liquid crystal, lighting materials, optical communication / optical circuit peripheral materials, optical recording peripheral materials It can be used for magnetic recording materials.
  • LED materials include LED element molding materials, sealing materials, sealing films, die-bonding materials, coating materials, sealing materials, adhesives, adhesives, lens materials, LED bulbs, LED display lamps, LEDs It can be used for sealing materials such as display boards and LED displays, adhesives, adhesives, coating materials and the like.
  • Battery peripheral materials include lithium ion batteries, sodium / sulfur batteries, molten sodium batteries, organic radical batteries, nickel metal hydride batteries, nickel cadmium batteries, redox flow batteries, lithium sulfur batteries, air batteries, electrolytic capacitors, electric double layer capacitors , Sealing materials for lithium ion capacitors, fuel cells, solar cells, dye-sensitized solar cells, back surface sealing materials, molding materials for each element, adhesives, adhesives, sealing materials, sealing films, coating materials, It can be used for potting materials, fillers, separators, catalyst fixing films, protective films, electrode binders, refrigerant oil sealing materials, hose materials, and the like.
  • Sensors include force, load, impact, pressure, rotation, vibration, contact, flow rate, solar radiation, light, odor, time, temperature, humidity, wind speed, distance, position, inertia, tilt, speed, acceleration, angular velocity, hardness ⁇ Seal, Sound, Magnetism, Current, Voltage, Power, Electron, Radiation, Infrared, X-ray, UV, Liquid, Weight, Gas, Ion, Metal, Color, etc. It can be used as a vibration absorbing material, vibration suppressing material, lens material, adhesive, pressure-sensitive adhesive, coating agent, film and the like.
  • Circuit board peripheral materials include rigid or flexible wiring boards on which various elements such as ICs, LSIs, semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, and coils are mounted, and MEMS (micro electro mechanical system) sealing materials , Coating materials, conformal coating materials, potting materials, molding materials, underfill materials, die-bonding materials, die-bonding films, adhesives, pressure-sensitive adhesives, sealing materials, and sealing films for the above elements.
  • elements such as ICs, LSIs, semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, and coils are mounted, and MEMS (micro electro mechanical system) sealing materials , Coating materials, conformal coating materials, potting materials, molding materials, underfill materials, die-bonding materials, die-bonding films, adhesives, pressure-sensitive adhesives, sealing materials, and sealing films for the above elements.
  • MEMS micro electro mechanical system
  • Peripheral display materials include liquid crystal displays, plasma displays, LED displays, organic EL (electroluminescence) displays, field emission displays, electronic paper, flexible displays, 3D holograms, organic thin film transistor displays, head mounted displays, and other molds.
  • Materials various filters, protective films, antireflection films, viewing angle correction films, polarizer protective films, optical correction films, etc., sealing materials, adhesives, adhesives, sealing materials, sealing films, substrates and members It can be used as a coating material, potting material, filler, visibility improving material, lens material, light guide plate, prism sheet, polarizing plate, retardation plate, and liquid crystal dam material.
  • a lighting material it can be used as a sealing material / coating material / adhesive / sealing material / molded part of a lighting LED, a lighting organic EL, and a lighting inorganic EL.
  • Optical communication and optical circuit peripheral materials include organic photorefractive elements, optical fibers, optical switches, lenses, optical waveguides, light emitting elements, photodiodes, optical amplification elements, optoelectronic integrated circuits, optical connectors, optical couplers, optical arithmetic elements, photoelectrics Molding materials, sealing materials, adhesives, adhesives, sealing materials, sealing films, coating materials, potting materials, fillers, protective films, lens materials, light guide plates, prisms for elements such as conversion devices and laser elements It can be used as a sheet, a polarizing plate and a ferrule.
  • Optical recording materials include VD (video disc), CD, CD-ROM, CD-R, CD-RW, DVD, DVD-ROM, DVD-R, DVD-RW, BD, BD-ROM, BD-R, BD-RE, MO, MD, PD (phase change disk), hologram, disk substrate material for optical card, protective film such as pickup lens, sealing material, adhesive, adhesive, sealing material, sealing film, coating It can be used as a material, anti-vibration material, and damping material.
  • Magnetic recording materials can be used as anti-vibration materials, damping materials, sealing materials, adhesives, adhesives, sealing materials, coating materials, cover gaskets, and card materials for magnetic cards such as hard disks, magnetic tapes, and credit cards. It is.
  • antifouling films for touch panels lubricant films, IC chip molding materials, Peltier element molding materials, electrolytic capacitor sealing bodies, cable joint potting materials, IGBT (vehicle propulsion control device) potting materials, and semiconductor wafer processing Dicing tape, die bond agent, die bond film, underfill, anisotropic conductive adhesive, anisotropic conductive film, conductive adhesive, conductive paste, heat conductive adhesive, heat conductive paste, film for temporary fixing, It can be used for fixing films, sealing films and the like.
  • MEMS micro electromechanical elements
  • Anti-vibration applications such as conductor manufacturing equipment, damping steel plates, rock drills, cutting machines, chainsaws, hand mixers, mowers, etc., machines with strong motor vibration, damping applications, shock buffering applications, shock absorbing applications,
  • structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.
  • applications that require vibration, vibration control, soundproof, and seismic isolation materials include electrical and electronic equipment such as stepping motors, magnetic disks, hard disks, vending machines, speaker frames, BS antennas, and vibration control materials for VTR covers. ; Building applications such as roofs, floors, shutters, curtain rails, floors, piping ducts, deck plates, curtain walls, stairs, doors, vibration-isolating isolators, damping materials for structural materials; building applications such as viscoelastic dampers and earthquake-resistant mats ; Marine use for engine room and measurement room damping material; engine (oil pan, front cover, rocker cover), car body (dash, floor, door, roof, panel, wheel house), transmission, parking brake cover, seat Automotive applications such as damping materials for bags; TV cameras, copiers, computers, Applications for cameras and office equipment such as linters, registers, cabinet damping materials; shooters, elevators, escalators, conveyors, tractors, bulldozers, generators, compressors, containers, hoppers, sound
  • railway damping materials such as bridge damping materials; damping materials for precision vibration isolator for semiconductor applications; near audible threshold It can be used as a vibration damping material for soundproofing such as for low frequency sound and high frequency sound.
  • the cured product of the present invention can be used as a molded body for packing, O-rings, belts, tubes, hoses, valves, seats, and the like.
  • Reactive hot melt agent for wiring connectors reactive hot melt adhesive, OCA (transparent adhesive for optics), elastic adhesive, contact adhesive, anaerobic adhesive, tile adhesive, UV curable adhesive, electronic It can be used as various adhesives such as a linear curable adhesive, an adhesive for a touch panel and a touch sensor.
  • butyl-based adhesives such as modification of butyl-based adhesives, masking tapes, pipe anticorrosion tapes, architectural waterproofing tapes, electrical self-fusing tapes, re-peeling adhesives, electric wire fusion tapes, and the like.
  • a heat conductive sheet a heat radiating sheet, an electromagnetic wave absorbing sheet, a conductive sheet, a waterproof sheet, an automobile protective sheet, and a panel shock absorbing sheet.
  • Shock absorbing gel, impact absorbing material such as bed, shoes, interlayer film of laminated glass, elastic paint, paint such as aqueous emulsion, prepreg, various rollers for OA equipment and transport, cap liner, ink repellent agent, ink, Seals for various refrigerants, seals and gaskets for industrial and food cans, foam gaskets, paints, powder paints, foams, seals for can lids, films, gaskets, marine deck caulking, casting materials, It can be used as various molding materials and artificial marble.
  • resist applications such as dry film resist applications and electrodeposition resist applications.
  • the cured product of the present invention is not limited to the above-mentioned use.
  • “Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804, K-802.5; manufactured by Showa Denko KK) was used, and chloroform was used as the GPC solvent.
  • the number of functional groups introduced per molecule of the polymer was calculated based on the concentration analysis by 1 H-NMR and the number average molecular weight determined by GPC. NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.
  • This polymer was dissolved in N, N-dimethylacetamide, potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. in a nitrogen atmosphere.
  • N, N-dimethylacetamide in this mixed solution was distilled off under reduced pressure, butyl acetate was added to the residue, and insoluble matter was removed by filtration.
  • the butyl acetate in the filtrate was distilled off under reduced pressure to obtain a poly (n-butyl acrylate) polymer [P1] having acryloyl groups at both ends.
  • the number average molecular weight of the polymer [P1] was 23,000, the molecular weight distribution was 1.1, and the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis to be about 1.9. Met.
  • Synthesis Example 2 Synthesis Example of Poly (n-butyl acrylate) / (ethyl acrylate) / (2-methoxyethyl acrylate) copolymer [P2] having an acryloyl group As a monomer, n-butyl acrylate / Poly (acrylic acid) having acryloyl groups at both ends in the same manner as in Synthesis Example 1, except that 73 parts / 25 parts / 2 parts of ethyl acrylate / 2-methoxyethyl acrylate was used and the monomer / initiator ratio was 240. An acid n-butyl) / (ethyl acrylate) / (2-methoxyethyl acrylate) copolymer [P2] was obtained.
  • the number average molecular weight of the copolymer [P2] was about 35,000, and the molecular weight distribution was 1.3.
  • the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis, it was about 2.0.
  • the number average molecular weight of the copolymer [P3] was about 16000, and the molecular weight distribution was 1.1.
  • the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis, it was about 1.8.
  • (Synthesis example 4) Synthesis example of poly (n-butyl acrylate) polymer having acryloyl group [P4] Synthesis example except that ⁇ -bromobutyrate is used as an initiator and the monomer / initiator ratio is 80 In the same manner as in Example 1, a poly (n-butyl acrylate) polymer [P4] having an acryloyl group at one end was obtained.
  • the number average molecular weight of the polymer [P4] was 12,000, the molecular weight distribution was 1.1, and the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis to be about 0.9. Met.
  • the number average molecular weight of the copolymer [P5] was 7,000, the molecular weight distribution was 1.2, and the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis to be about 0.9. It was a piece.
  • Test properties In accordance with JIS K 6251, a test piece obtained by punching a sheet into a dumbbell No. 3 type was prepared and used for measurement. The tensile speed was 500 mm / min, and the tensile stress at break (expressed as tensile strength) and the elongation at break (expressed as elongation) were determined.
  • compression set A compression set test under a predetermined condition was performed using a large test piece for compression set test measurement according to JIS K 6262.
  • UV curing Fusion UV Systems Japan Co., Ltd. (currently Heraeus Co., Ltd.), model LH6, H bulb, or Itech System Co., Ltd.
  • desktop batch type UV LED curing device MUVBA UV-LED microwave wavelength 365 nm
  • Peak illuminance indicated as illuminance
  • integrated light intensity indicated as light intensity
  • UV light intensity meter manufactured by EIT 4-band UV measuring instrument: UV POWER PUCK II, UVA (320-390 nm) measured value was used .
  • Example 1 For 100 parts by weight of the polymer [P1] obtained in Synthesis Example 1, 50 parts by weight of acryloylmorpholine (manufactured by KJ Chemicals) and light acrylate 130A (manufactured by Kyoeisha Chemical Co., Ltd., average carbon number 19) 20 parts by weight of an acrylic monomer having an ether straight chain: methoxypolyethylene glycol acrylate), 1 part by weight of TMP3A (manufactured by Osaka Organic Chemical Co., Ltd., trimethylolpropane triacrylate) as a reactive diluent, and IRGANOX 1010 (as an antioxidant) 1 part by weight of BASF Japan, hindered phenol antioxidant), 2 parts by weight of DAROCUR1173 (BASF Japan, 2-hydroxy-2-methyl-1-phenylpropan-1-one) as a photo radical initiator IRGACURE819 (B A mixture of 1 part by weight of bis (2,4,6-trimethylbenzoyl)
  • the rubber-like sheet cured product was obtained by pouring into a polypropylene mold so as to have a thickness of 2 mm, and performing UV irradiation (irradiation conditions: illuminance: 400 mW / cm 2, light amount: 5000 mJ / cm 2) under air. Tensile properties and dynamic viscoelasticity of the obtained cured product were measured.
  • test piece was prepared by carrying out UV irradiation (irradiation conditions: illuminance: 400 mW / cm 2, light intensity: 8500 mJ / cm 2) under air using a compression set test measurement mold, and 150 ° C. for 70 hours. The compression set was measured. The results are shown in Table 1.
  • Examples 2 and 3 Comparative Examples 1 to 4
  • a radical curable composition was prepared according to the formulation shown in Table 1, and the tensile properties, dynamic viscoelasticity and compression set of the cured product were measured in the same manner as in Example 1. The results are shown in Table 1.
  • Comparative Example 1 the compression set was not measured because the elongation was low and the behavior as a rubber was not exhibited.
  • DEAA diethylacrylamide
  • acrylamide which is an acrylamide compound similar to acryloylmorpholine
  • a remarkable improvement in tensile strength can be seen within the scope of the present invention, but if it is less than 30 parts, the improvement effect is insufficient (Comparative Example 3), and 30% acryloylmorpholine is added.
  • Examples 4 to 14 In the same manner as in Example 1, radical curable compositions having the formulations shown in Table 2 were prepared, and the tensile properties, dynamic viscoelasticity, and compression set of the cured product were measured. The results are shown in Table 2.
  • the compression set is very bad at 52% or 39% (Comparative Examples 6 and 7). If the amount is too small (Comparative Example 8), the effect of improving the compression set (20%) is very limited, and if too much (Comparative Example 9), the tensile strength is increased. However, 0.82 MPa is hardly improved. Moreover, when there is too much acryloyl morpholine (III) (comparative example 10), even if the (IV) component is added, the improvement effect of a compression set characteristic is limited.
  • Examples 15 to 17, Comparative Examples 13 to 20 In the same manner as in Example 1, radical curable compositions having the formulations shown in Table 4 were prepared, and the tensile properties, dynamic viscoelasticity, and compression set of the cured product were measured. The results are shown in Table 4.
  • acryloylmorpholine and ISTA isostearyl acrylate having a branched hydrocarbon group having 18 carbon atoms
  • LA laauryl acrylate
  • IOAA isooctyl acrylate
  • light acrylate 130A having an ether straight chain having an average carbon number of 19 (Kyoeisha Chemical Co., Ltd., methoxypolyethylene glycol acrylate) was used.
  • the tensile strength / elongation is excellent and the compression set is 10% or less.
  • IBXA isobornyl acrylate
  • acrylyl FA-511AS manufactured by Hitachi Chemical Co., Ltd., dicyclopentenyl acrylate
  • acrylyl FA-513AS having alicyclic hydrocarbon groups having 10 carbon atoms and acryloylmorpholine
  • Example 18 Comparative Examples 21 to 26
  • a radical curable composition was prepared according to the formulation shown in Table 5, and the tensile properties, dynamic viscoelasticity, and compression set of the cured product were measured. The results are shown in Table 5.
  • Comparative Example 21 since the elongation was low and the behavior as a rubber was not exhibited, the compression set was not measured.
  • a conventionally known monomer having a reinforcing effect such as IBXA has a limited improvement in tensile strength, and has a problem that it has a unique odor of IBXA and poor working environment. That is, it has been difficult to find a specific monomer combination that can improve tensile strength and compression set while maintaining low temperature characteristics.
  • Examples 19 to 22, Comparative Example 27 In the same manner as in Example 1, radical curable compositions having the formulations shown in Table 6 were prepared, and the tensile properties, dynamic viscoelasticity, and compression set of the cured product were measured. The results are shown in Table 6.
  • Example 19 From the comparison between Example 19 and Comparative Example 27, even when the number of terminal acryloyl groups was 1.2, the glass transition temperature below room temperature was maintained by using specific amounts of the components (III) and (IV). The effect of improving the tensile strength is seen.
  • Example 7 The radical curable composition prepared in Example 7 is poured into a SUS mold so as to have a thickness of 2 mm, the surface is covered with a PET film, and then UV-LED irradiation (irradiation conditions: Table 7) is performed. Thus, a cured sheet was obtained. The tensile properties of the obtained cured product were measured. The results are shown in Table 7.
  • UV-LED Similar to a conventionally known UV lamp (Hereus H bulb: equivalent to a high-pressure mercury lamp), the tensile strength and elongation are also improved when a cured product is produced by UV-LED.
  • Example 26 Acrylic monomer having 50 parts by weight of acryloylmorpholine and light acrylate 130A (manufactured by Kyoeisha Chemical Co., Ltd., average 19 carbon atoms, straight chain) with respect to 100 parts by weight of the polymer [P2] obtained in Synthesis Example 2.
  • Example 27 and 28 Comparative Examples 28 to 30
  • radical curable compositions having the formulations shown in Table 8 were prepared, and the tensile properties and compression set of the cured products were measured. The results are shown in Table 8.
  • Example 29 100 parts by weight of the polymer [P2] obtained in Synthesis Example 2 is mixed with 50 parts by weight of carbon black (# 50, manufactured by Asahi Carbon Co., Ltd.) as a reinforcing filler, and sufficiently dispersed with three paint rolls. Then, the remaining compounding agents were added, mixed and dissolved to obtain a curable composition. Further, the cured product was obtained by heating in the same manner as in Example 26, and the tensile properties and compression set of the cured product were measured. The results are shown in Table 9.
  • Examples 30 to 33 In the same manner as in Example 29, radical curable compositions having the formulations shown in Table 9 were prepared. The powder raw material was previously dispersed in the polymer with three paint rolls. The tensile properties and compression set of the cured product were measured. The results are shown in Table 9.
  • the samples for compression set obtained in Examples 31 to 33 were heated at 180 ° C. for 4 hours for secondary vulcanization.
  • the compression set at 150 ° C. for 70 hours was measured using the sample after secondary vulcanization, they were 16% (Example 31), 13% (Example 32), and 15% (Example 33). That is, the cured product obtained in the present invention has sufficient effect of cross-linking only by primary vulcanization and exhibits compression set characteristics, so that the secondary vulcanization necessary for conventional rubber materials can be omitted. It was seen.
  • IOAA Isooctyl acrylate, manufactured by Osaka Organic Chemical Industry
  • IBXA Isobornyl acrylate, Osaka Organic Chemical Co., Ltd.
  • FANCLIL FA-511AS Dicyclopentenyl Acrylate Hitachi Chemical Co., Ltd.
  • FANCLIL FA-513AS DISIC Pentanyl acrylate Viscoat OXE-10 manufactured by Hitachi Chemical Co., Ltd .: 3-ethyl-3-oxetanylmethyl acrylate
  • IRGANOX 1010 Hindered phenolic antioxidant
  • BACL JAPAN NOCLACK CD Amine antioxidant Ouchi Shinsei Chemical Co., Ltd.
  • DAROCUR1173 2-hydroxy-2-methyl-1-phenylpropan-1-one
  • IRGACURE 819 manufactured by BASF Japan Ltd .: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 4-methylbenzophenone manufactured by BASF Japan Ltd .: Tokyo Chemical Industry IRGACURE 184 manufactured by Kogyo Co., Ltd .: 1-hydroxy-cyclohexyl-phenyl-ketone
  • Unistar M9766 Stearyl stearate, NOF Corporation carbon black # 50: Asahi Carbon Co., Ltd.
  • Aeroxide P25 Titanium oxide, Nippon Aerosil Co.

Abstract

The purpose of the present invention is to obtain a curable composition of a (meth)acrylic polymer having radical-crosslinkable groups, the curable composition having excellent curability and being capable of providing a cured product that has strong tensile strength and excellent compression set without compromising rubber elasticity and low-temperature properties. The present invention relates to a radical-curable composition which is characterized by containing, relative to 100 parts by weight of (meth)acrylic polymer (I) having an average of at least 0.8 radical-crosslinkable groups, the following: 0.01 to 10 parts by weight of radical polymerization initiator (II); 30 to 70 parts by weight of (meth)acryloylmorpholine (III); and 5 to 30 parts by weight of monofunctional acrylic monomer (IV) having C6 or higher linear or branched hydrocarbon groups.

Description

ラジカル硬化性組成物およびその硬化物Radical curable composition and cured product thereof
本発明は、ラジカル硬化性組成物およびその硬化物に関する。より詳しくは、ラジカル架橋性基を有する（メタ）アクリル系重合体を含有するラジカル硬化性組成物およびその硬化物に関する。 The present invention relates to a radical curable composition and a cured product thereof. More specifically, the present invention relates to a radical curable composition containing a (meth) acrylic polymer having a radical crosslinkable group and a cured product thereof.
ゴム材料は、建築、自動車、電気・電子、機械、物流、化学、医療・介護・スポーツ等様々な分野において、接着剤やシール材、封止材、粘着剤、塗料、コーティング材、レジスト材、衝撃吸収材、制振材、圧力分散材、成形部品、成形材料等として利用されている。
ゴム材料の中でも、柔軟性、防振性、衝撃吸収性、耐熱性、耐油性、耐透湿性、機械的強度に優れ、シリコーン系化合物を含有していないなどの観点から、（メタ）アクリル系重合体を主成分としたゴム材料が最近好適に用いられている。また、ゴム材料の硬化形式としては、硬化が速く、取扱いが容易な硬化方法として、光ラジカル硬化や熱ラジカル硬化等のラジカル反応を用いたゴム材料の需要がとりわけ高まっている。 Rubber materials are used in various fields such as architecture, automobiles, electricity / electronics, machinery, logistics, chemistry, medical care / care / sports, adhesives and sealants, sealing materials, adhesives, paints, coating materials, resist materials, It is used as shock absorbing material, vibration damping material, pressure dispersion material, molded part, molding material, etc.
Among rubber materials, it is excellent in flexibility, vibration proofing, shock absorption, heat resistance, oil resistance, moisture resistance, mechanical strength, and does not contain silicone compounds. Recently, a rubber material mainly composed of a polymer has been suitably used. In addition, as a curing method of rubber material, demand for rubber material using radical reaction such as photo radical curing or thermal radical curing is increasing as a curing method that is fast and easy to handle.
発明者らは、これらのラジカル硬化性ゴム材料に好適なものとして、これまでに末端に（メタ）アクリロイル基を有し、主鎖がリビングラジカル重合により得られる（メタ）アクリル系重合体およびそれらを用いた組成物について報告している（特許文献１、２）。
これらのラジカル硬化性ゴム材料に対する機械的強度向上の要求は年々高まるばかりであるが、これまでの技術では十分な機械的強度が得られず、また、機械的強度を向上させると他の特性を損なう場合があり、用途によっては使用が制限されるといった課題がある。 The inventors of the present invention have proposed a (meth) acrylic polymer having a (meth) acryloyl group at the terminal and having a main chain obtained by living radical polymerization, and those suitable as such radical curable rubber materials. It has reported about the composition using this (patent documents 1, 2).
The demand for improving the mechanical strength of these radically curable rubber materials is increasing year by year. However, sufficient mechanical strength cannot be obtained with the conventional technology. There is a problem that the use is limited depending on the application.
機械的強度を改善するためにこれまで公知の技術として、ホモポリマーのＴｇが室温以上であるモノマーを共重合あるいは配合剤として添加したり、多官能モノマーを配合したり、充填材として補強性フィラーを添加するといった手段が知られている。しかし、ホモポリマーのＴｇが室温以上であるモノマーを共重合した場合には、重合体の粘度が上昇することにより取り扱いが非常に困難になるという課題がある。配合剤として添加した場合には、機械的強度や伸びが向上しても、得られる硬化物のＴｇが上昇し低温特性が悪化し、場合によってはゴム弾性が損なわれるという課題がある。また、２官能性架橋モノマーや３官能性架橋性モノマー、あるいはそれ以上の官能基を有する多官能性モノマーを配合した場合、機械的強度が向上しても得られる硬化物が硬くなりゴム弾性を示さなくなったり、伸びが著しく低下するといった課題がある。充填材として補強性フィラーを添加した場合、機械的強度が十分に向上する量を添加すると配合物の粘度が著しく上昇し、取り扱いが非常に困難になるといった課題がある。 In order to improve the mechanical strength, as a conventionally known technique, a monomer having a Tg of a homopolymer of room temperature or higher is added as a copolymerization or compounding agent, a polyfunctional monomer is added, a reinforcing filler as a filler Means such as adding is known. However, when a monomer having a Tg of homopolymer of room temperature or higher is copolymerized, there is a problem that handling becomes very difficult due to an increase in the viscosity of the polymer. When added as a compounding agent, even if the mechanical strength and elongation are improved, there is a problem that the Tg of the obtained cured product is increased, the low-temperature characteristics are deteriorated, and the rubber elasticity is sometimes impaired. In addition, when a bifunctional crosslinkable monomer, trifunctional crosslinkable monomer, or a polyfunctional monomer having a functional group higher than that is blended, the cured product obtained becomes hard even if mechanical strength is improved, and rubber elasticity is improved. There is a problem that it is not shown or the elongation is significantly reduced. When a reinforcing filler is added as a filler, there is a problem that if an amount that sufficiently improves the mechanical strength is added, the viscosity of the blend is remarkably increased and handling becomes very difficult.
また、ゴム材料としての特性のひとつに圧縮永久ひずみがあり、これは圧縮したゴムを開放したときにどの程度元の形状に復元するかを表す指標であり、値が小さいほど復元性能が優れている。しかしながら、前述した機械特性を損なうことなく圧縮永久ひずみ特性を向上させることは従来困難であった。 In addition, one of the characteristics as a rubber material is compression set, which is an index showing how much it will be restored to its original shape when the compressed rubber is released. The smaller the value, the better the restoration performance. Yes. However, it has heretofore been difficult to improve compression set characteristics without impairing the mechanical characteristics described above.
特許文献３には（メタ）アクリロイルモルホリンを紫外線あるいは電子線硬化性樹脂用の希釈剤として用いることが記載されている。しかし、（メタ）アクリロイルモルホリンがプレポリマーに対する溶解性及び希釈性に優れ、かつ低揮発性、低臭気性、低皮膚刺激性でさらに硬化活性に優れることが開示されているのみであり、（メタ）アクリロイルモルホリンを（メタ）アクリル系重合体に添加することについては記載されておらず、添加することにより、硬化物の引張強さや伸び、圧縮永久ひずみに対して何らの効果を奏するかは記載されていない。 Patent Document 3 describes that (meth) acryloylmorpholine is used as a diluent for ultraviolet or electron beam curable resins. However, it is only disclosed that (meth) acryloylmorpholine is excellent in solubility and dilution with respect to a prepolymer, has low volatility, low odor, low skin irritation and has excellent curing activity. ) There is no description about adding acryloylmorpholine to a (meth) acrylic polymer, and it describes what effect it will have on the tensile strength, elongation, and compression set of the cured product. It has not been.
特許文献４には、長鎖アルキル基を有し、架橋性官能基を分子末端に有する（メタ）アクリル系重合体と環式構造を有するビニル系モノマーを含有する硬化性組成物が開示されている。しかしながら、（メタ）アクリロイルモルホリンについて何ら記載はなく、（メタ）アクリロイルモルホリンを添加することによって、硬化物の機械的強度や低温特性についてどのような効果を奏するかは示唆されていない。 Patent Document 4 discloses a curable composition containing a (meth) acrylic polymer having a long-chain alkyl group and having a crosslinkable functional group at the molecular end and a vinyl monomer having a cyclic structure. Yes. However, there is no description about (meth) acryloylmorpholine, and there is no suggestion of the effect of adding (meth) acryloylmorpholine on the mechanical strength and low-temperature properties of the cured product.
特許文献５には、分子末端に（メタ）アクリロイル基を有するビニル系重合体と環式構造を有するビニル系モノマーおよび開始剤を用いることにより、低粘度、かつ硬化物の伸びが優れる硬化性組成物が提案されている。しかしながら、一般的な環式構造を有するビニル系モノマーを用いると、硬化物のＴｇが上昇し、低温でのゴム弾性を損なうばかりでなく、場合によっては室温環境下でのゴム弾性も低下するという課題があった。また、実施例で開示されているのは、イソボロニルアクリレートおよびベンジルアクリレートのみであり、これらを添加した場合に低粘度で伸びが向上することのみが開示されている。また、重合体１００部に対しイソボロニルアクリレートを２０～３０部用いた場合にのみ機械的強度が向上しているが、限定的であり、成形体としての使用には不十分なレベルであり、硬化物の低温特性についての記載もない。 Patent Document 5 discloses a curable composition having a low viscosity and excellent elongation of a cured product by using a vinyl polymer having a (meth) acryloyl group at a molecular end, a vinyl monomer having a cyclic structure, and an initiator. Things have been proposed. However, when a vinyl monomer having a general cyclic structure is used, the Tg of the cured product is increased, and not only the rubber elasticity at a low temperature is impaired, but also the rubber elasticity under a room temperature environment is reduced depending on the case. There was a problem. In addition, only examples of isobornyl acrylate and benzyl acrylate are disclosed in Examples, and it is disclosed only that elongation is improved at low viscosity when these are added. Further, the mechanical strength is improved only when 20 to 30 parts of isobornyl acrylate is used with respect to 100 parts of the polymer, but it is limited and is insufficient for use as a molded body. There is no description of the low-temperature properties of the cured product.
特許文献６には、分子末端に（メタ）アクリロイル基を有するアクリル系重合体に対し、希釈モノマーとしてアクリロイルモルフォリンを添加することが開示されている。しかしながら、硬化物の低温特性が失われるだけでなく、ゴム弾性も失われてしまうという課題がある。 Patent Document 6 discloses that acryloylmorpholine is added as a dilution monomer to an acrylic polymer having a (meth) acryloyl group at the molecular end. However, there is a problem that not only the low temperature characteristics of the cured product are lost, but also the rubber elasticity is lost.
特許文献７には、分子末端に（メタ）アクリロイル基を１個以上有するアクリル系重合体と開始剤からなる液状モールディング用硬化性組成物について開示されており、物性を調整するために各種添加剤を用いてもよいことが記載されている。しかしながら、従来知られているモノマー種やそれらの組み合わせでは、低温特性を維持したまま引張強さを改善する組み合わせを見出すことはできていなかった。 Patent Document 7 discloses a curable composition for liquid molding comprising an acrylic polymer having at least one (meth) acryloyl group at the molecular end and an initiator, and various additives for adjusting the physical properties. It may be used. However, conventionally known monomer species and combinations thereof cannot find a combination that improves the tensile strength while maintaining low temperature characteristics.
特許文献８には、ウレタンアクリレートに（メタ）アクリルアミド系化合物を用いることで、接着力に優れ、得られる積層体の反りがなく、湿熱試験後の着色の少ない活性エネルギー線硬化型接着剤組成物が提案されている。（メタ）アクリルアミド系化合物として（メタ）アクリロイルモルホリンが好ましいことが記載されているが、得られる硬化物のＴｇは６０～１８０℃を有するものが好ましいと記載され、実施例および比較例においてもアクリロイルモルホリンを用いた硬化物のＴｇは１２６℃～１４９℃である。しかしながら、ラジカル架橋性の（メタ）アクリル系重合体に関する記載はなく、Ｔｇが室温以下であるゴム状硬化物に関して（メタ）アクリロイルモルホリンの添加がどのような効果を及ぼすかは示唆されていない。 Patent Document 8 discloses an active energy ray-curable adhesive composition that is superior in adhesion by using a (meth) acrylamide compound in urethane acrylate, has no warp of the resulting laminate, and has little color after wet heat test. Has been proposed. Although it is described that (meth) acryloylmorpholine is preferable as the (meth) acrylamide compound, it is described that the obtained cured product preferably has a Tg of 60 to 180 ° C., and in the examples and comparative examples also acryloyl The Tg of the cured product using morpholine is 126 ° C. to 149 ° C. However, there is no description regarding a radically crosslinkable (meth) acrylic polymer, and it has not been suggested what effect the addition of (meth) acryloylmorpholine has on a rubber-like cured product having a Tg of room temperature or lower.
特許文献９～１３には、分子末端に（メタ）アクリロイル基を有するアクリル系重合体に対し（メタ）アクリル系モノマーを添加する種々の硬化性組成物が開示されている。しかしながら、いずれも種々のモノマー種については列挙されているのみであり、特定のモノマーを２種以上併用することで、低温特性や圧縮永久ひずみに対していかなる効果を及ぼすかについての記載はなく、低温特性を維持したまま引張強さや圧縮永久ひずみを改善する組み合わせを見出すことはできない。 Patent Documents 9 to 13 disclose various curable compositions in which a (meth) acrylic monomer is added to an acrylic polymer having a (meth) acryloyl group at the molecular end. However, all of them are only listed for various monomer types, and there is no description of what effect is exerted on low temperature characteristics and compression set by using two or more specific monomers in combination. No combination can be found that improves tensile strength and compression set while maintaining low temperature properties.
特開２０００－７２８１６号公報JP 2000-72816 A 特開２０００－９５８２６号公報JP 2000-95826 A 特開昭６２－１９９６０８号公報JP 62-199608 A 特開２０１０－１２６６８０号公報JP 2010-126680 A 特開２００７－７７１８２号公報JP 2007-77182 A 国際公開第２００９／１４８１８２号公報International Publication No. 2009/148182 特開２００６－２６５４８８号公報JP 2006-265488 A 特開２０１３－１１２７１５号公報JP 2013-127715 A 特開２００５－２３２０６号公報Japanese Patent Laid-Open No. 2005-23206 特開２０１２－１２２０２２号公報JP 2012-122202 A 特開２０１５－１０２０７号公報Japanese Patent Laying-Open No. 2015-10207 特開２００６－２９９２５７号公報JP 2006-299257 A 特開２００６－２７８４７６号公報JP 2006-278476 A
本発明は硬化性に優れ、ゴム弾性、低温特性を損なうことなく、より引張強さが高く、さらに圧縮永久ひずみ特性に優れる硬化物を与えることのできるラジカル架橋性基を有する（メタ）アクリル系重合体の硬化性組成物を得ることを目的とする。 The present invention has a (meth) acrylic group having a radical crosslinkable group that is excellent in curability, has a higher tensile strength and does not impair rubber elasticity and low-temperature properties, and can give a cured product having excellent compression set properties. It aims at obtaining the curable composition of a polymer.
上記事情に鑑み、本発明者がラジカル硬化性組成物について鋭意検討した結果、ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）に対し、（メタ）アクリロイルモルホリン、および、炭素数６以上の直鎖または分岐炭化水素基を有する単官能アクリル系モノマーを特定量添加することにより、ゴム弾性、低温特性を損なうことなく、より引張強さが高く圧縮永久ひずみ特性に優れる硬化物が得られることを見出し、本発明を得るに至った。（メタ）アクリロイルモルホリンと同じような構造を有する他の（メタ）アクリレート系モノマー、例えば環式構造を有するモノマーや、アクリルアミド系モノマーでは、上記のような効果はなく、（メタ）アクリロイルモルホリンの使用の場合でのみ効果があり、さらに特定量の添加時にのみ効果があることを見出した。また、（メタ）アクリロイルモルホリン単独では、引張強さは高くなるものの圧縮永久ひずみは悪化し、炭素数６以上の直鎖または分岐炭化水素基を有した単官能アクリル系モノマー以外のモノマーを併用した場合には、圧縮永久ひずみが悪いままか、他の物性が劣るが、炭素数６以上の直鎖または分岐炭化水素基を有した単官能アクリル系モノマーを特定量併用した場合のみ、低温特性を維持したまま引張強さが高く圧縮永久ひずみが改善することを見出した。 In view of the above circumstances, as a result of intensive studies on the radical curable composition by the present inventors, the (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups (meth) By adding a specific amount of acryloylmorpholine and a monofunctional acrylic monomer having a straight-chain or branched hydrocarbon group having 6 or more carbon atoms, it has a higher tensile strength and a permanent compression without impairing rubber elasticity and low-temperature properties. It has been found that a cured product having excellent strain characteristics can be obtained, and the present invention has been obtained. Other (meth) acrylate monomers having the same structure as (meth) acryloylmorpholine, such as monomers having a cyclic structure and acrylamide monomers, have no effect as described above, and use of (meth) acryloylmorpholine It was found that the effect is effective only in the case of (1), and that it is effective only when a specific amount is added. In addition, with (meth) acryloylmorpholine alone, the tensile strength is increased, but the compression set is deteriorated, and a monomer other than a monofunctional acrylic monomer having a straight chain or branched hydrocarbon group having 6 or more carbon atoms is used in combination. In some cases, the compression set remains poor or other physical properties are inferior, but only when a specific amount of a monofunctional acrylic monomer having a straight chain or branched hydrocarbon group having 6 or more carbon atoms is used in combination, the low temperature characteristics are reduced. It was found that the tensile strength was high while maintaining the compression set and the compression set was improved.
すなわち、本発明は、ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）１００重量部に対し、ラジカル重合開始剤（ＩＩ）０．０１～１０重量部、（メタ）アクリロイルモルホリン（ＩＩＩ）３０～７０重量部、および、炭素数６以上の直鎖または分岐炭化水素基を有する単官能アクリル系モノマー（ＩＶ）５～３０重量部を含有することを特徴とするラジカル硬化性組成物に関する。 That is, the present invention provides 0.01 to 10 parts by weight of radical polymerization initiator (II) with respect to 100 parts by weight of (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups. And 30 to 70 parts by weight of (meth) acryloylmorpholine (III) and 5 to 30 parts by weight of a monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms It relates to a radical curable composition.
ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）が、ラジカル架橋性の炭素－炭素二重結合を有する基を分子鎖末端に有する（メタ）アクリル系重合体であることが好ましい。 (Meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups has a group having a radically crosslinkable carbon-carbon double bond at the end of the molecular chain A polymer is preferred.
ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）が、（メタ）アクリロイル基を分子末端に有する（メタ）アクリル系重合体であることが好ましい。 The (meth) acrylic polymer (I) having at least 0.8 radical crosslinkable groups on average is preferably a (meth) acrylic polymer having a (meth) acryloyl group at the molecular end.
ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）の分子量分布が１．８未満であることが好ましい。 The molecular weight distribution of the (meth) acrylic polymer (I) having at least 0.8 radical crosslinkable groups on average is preferably less than 1.8.
ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）が、炭素数１～２４の飽和炭化水素基および／または脂肪族エーテル基を有するモノマーを重合または共重合して得られることが好ましい。 The (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups polymerizes or co-polymerizes a monomer having a saturated hydrocarbon group having 1 to 24 carbon atoms and / or an aliphatic ether group. It is preferably obtained by polymerization.
炭素数６以上の直鎖または分岐炭化水素基を有する単官能アクリル系モノマー（ＩＶ）が、炭素数８～２４の直鎖または分岐炭化水素基を有する単官能アクリル系モノマーであることが好ましい。 The monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms is preferably a monofunctional acrylic monomer having a linear or branched hydrocarbon group having 8 to 24 carbon atoms.
ラジカル重合開始剤（ＩＩ）が、熱ラジカル開始剤及び／または光ラジカル開始剤であることが好ましい。 The radical polymerization initiator (II) is preferably a thermal radical initiator and / or a photo radical initiator.
さらに酸化防止剤（Ｖ）を０．１～１０重量部含有することが好ましい。 Further, it is preferable to contain 0.1 to 10 parts by weight of the antioxidant (V).
また本発明は、上記に記載のラジカル硬化性組成物より得られたことを特徴とする硬化物に関する。 The present invention also relates to a cured product obtained from the radically curable composition described above.
硬化物のガラス転移温度（Ｔｇ）が２５℃以下であることが好ましい。 It is preferable that the glass transition temperature (Tg) of hardened | cured material is 25 degrees C or less.
本発明によれば、（メタ）アクリル系重合体のゴム弾性、低温特性を損なうことなく、より引張強さが高く圧縮永久ひずみ特性に優れる硬化物を得ることができる。 According to the present invention, a cured product having higher tensile strength and excellent compression set characteristics can be obtained without impairing the rubber elasticity and low temperature characteristics of the (meth) acrylic polymer.
本発明のラジカル硬化性組成物は、ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）１００重量部に対し、ラジカル重合開始剤（ＩＩ）０．０１～１０重量部、（メタ）アクリロイルモルホリン（ＩＩＩ）３０～７０重量部、および、炭素数６以上の直鎖または分岐炭化水素基を有する単官能アクリル系モノマー（ＩＶ）５～３０重量部を含有することを特徴とする。 The radical curable composition of the present invention has a radical polymerization initiator (II) of 0.01 with respect to 100 parts by weight of (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups. Contains 10 to 10 parts by weight, 30 to 70 parts by weight of (meth) acryloylmorpholine (III), and 5 to 30 parts by weight of a monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms It is characterized by doing.
以下に、本発明のラジカル硬化型組成物に含まれる成分について説明する。 Below, the component contained in the radical curable composition of this invention is demonstrated.
＜（メタ）アクリル系重合体（Ｉ）＞
＜（メタ）アクリル系重合体（Ｉ）の主鎖＞
（メタ）アクリル系重合体（Ｉ）の主鎖を構成する（メタ）アクリル系モノマーとしては特に限定されず、各種のものを用いることができる。 <(Meth) acrylic polymer (I)>
<Main chain of (meth) acrylic polymer (I)>
It does not specifically limit as a (meth) acrylic-type monomer which comprises the principal chain of (meth) acrylic-type polymer (I), Various things can be used.
具体的には、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸－ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸－ｔｅｒｔ－ブチル、（メタ）アクリル酸－ｎ－ペンチル、（メタ）アクリル酸イソアミル、（メタ）アクリル酸－ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸－ｎ－ヘプチル、（メタ）アクリル酸－ｎ－オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸イソステアリル、（メタ）アクリル酸オレイル、（メタ）アクリル酸ベヘニル、（メタ）アクリル酸２－デシルテトラデカニル、（メタ）アクリル酸フェニル、（メタ）アクリル酸トルイル、（メタ）アクリル酸トリル、（メタ）アクリル酸４－ｔｅｒｔ－ブチルシクロヘキシル、（メタ）アクリル酸ジシクロペンテニル、（メタ）アクリル酸ジシクロペンテニルオキシエチル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸ジシクロペンタニルオキシエチル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸３，３，５－トリメチルシクロヘキシル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸３－ヒドロキシ－１－アダマンチル、（メタ）アクリル酸１－メチルアダマンチル、（メタ）アクリル酸１－エチルアダマンチル、（メタ）アクリル酸３，５－ジヒドロキシ－１－アダマンチル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－ブトキシエチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸－３－メトキシプロピル、（メタ）アクリル酸３－メトキシブチル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸メチルフェノキシエチル、（メタ）アクリル酸ｍ－フェノキシベンジル、（メタ）アクリル酸エチルカルビトール、（メタ）アクリル酸－メトキシトリエチレングリコール、（メタ）アクリル酸－エトキシジエチレングリコール、（メタ）アクリル酸２－ヒドロキシ－３－フェノキシプロピル、（メタ）アクリル酸２－エチルヘキシルジエチレングリコ－ル、（メタ）アクリル酸メトキシ－ジプロピレングリコール、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸１，４－シクロヘキサンジメタノール、（メタ）アクリル酸グリセリン、（メタ）アクリル酸ポリエチレングリコール（日油（株）製ブレンマーＰＥ－９０、ＰＥ－２００、ＰＥ－３５０、ＰＥ－３５０Ｇ、ＡＥ－９０、ＡＥ－２００、ＡＥ－４００等）、（メタ）アクリル酸ポリプロピレングリコール（日油（株）製ブレンマーＰＰ－５００、ＰＰ－８００、ＰＰ－１０００、ＡＰ－１５０、ＡＰ－４００、ＡＰ－５５０等）（メタ）アクリル酸ポリエチレングリコール－ポリプロピレングリコール（日油（株）製ブレンマー５０ＰＥＰ－３００、７０ＰＥＰ－３５０Ｂ等）、（メタ）アクリル酸ポリエチレングリコール－ポリプロピレングリコール、（メタ）アクリル酸ポリエチレングリコール－ポリテトラメチレングリコール、（メタ）アクリル酸ポリプロピレングリコール－ポリテトラメチレングリコール）、（メタ）アクリル酸ポリエチレングリコール－ポリブチレングリコール、（メタ）アクリル酸グリシジル、（メタ）アクリル酸４－ヒドロキシブチル－グリシジルエーテル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸２－アミノエチル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸ジメチルアミノエチル四級化物（共栄社化学（株）製ライトエステルＤＱ－１００、ＤＱ－７５等）、４－（メタ）アクリル酸－２－メチル－２－エチル－１，３－ジオキソラン、２－（メタ）アクリル酸－１，４－ジオキサスピロ［４，５］デシ－２－イルメチル（大阪有機化学工業（株）製、ＣＨＤＯＬ－１０）、（メタ）アクリル酸３－エチル－３－オキセタニル（大阪有機化学工業（株）製、ＯＸＥ－１０）、（メタ）アクリル酸γ－ブチロラクトン、（メタ）アクリル酸２－フェニルチオエチル、（メタ）アクリル酸２－ヒドロキシ－３－（２－プロペニルオキシ）プロピル、無水フタル酸－（メタ）アクリル酸２－ヒドロキシプロピル付加物（大阪有機化学工業（株）製ビスコート＃２１００）、２－（メタ）アクリロイルオキシエチルフタル酸（共栄社化学（株）製ライトエステルＨＰＡ－ＭＰＬ、新中村化学工業（株）製ＣＢ－１等）、１，２－シクロヘキシルジカルボン酸－モノ［１－メチル－２－［（１－オキソ－２－プロペニル）オキシ］エチル］エステル（大阪有機化学工業（株）製ビスコート＃２１５０）、（メタ）アクリルロイルオキシ－エチルヘキサヒドロフタレート（共栄社化学（株）製ライトエステルＨＯ－ＨＨ、ＨＯＡ－ＨＨ等）、（メタ）アクリルロイルオキシエチルサクシネート（共栄社化学（株）製ライトエステルＨＯ－ＭＳ、ＨＯＡ－ＭＳ、新中村化学工業（株）製ＳＡ、Ａ－ＳＡ等）、２－（メタ）アクリルロイルオキシエチル－２－ヒドロキシプロピルフタル酸（共栄社化学（株）製ライトエステルＨＯ－ＭＰＰ等）、２－（メタ）アクリロイルオキシエチル－ヒドロキシエチルフタル酸（共栄社化学（株）製ＨＯＡ－ＭＰＥ等）、２－（メタ）アクリロイルオキシエチル－リン酸エステル（共栄社化学（株）製ライトエステルＰ－１Ｍ、Ｐ－２Ｍ等）、（メタ）アクリル酸エトキシ化－ｏ－フェニルフェノール、（メタ）アクリル酸メトキシポリエチレングリコール（共栄社化学（株）製ライトエステルＭＣ、１３０ＭＡ、０４１ＭＡ、ＭＴＧ、ＭＴＧ－Ａ、１３０Ａ、新中村化学工業（株）製Ｍ－９０Ｇ、ＡＭ－９０Ｇ、Ｍ－２３０Ｇ、ＡＭ１３０Ｇ、日立化成（株）製ファンクリルＦＡ－４００Ｍ、日油（株）製ブレンマーＰＭＥ－１００、ＰＭＥ－２００、ＰＭＥ－４００、ＰＭＥ－５５０、ＰＭＥ－１０００、ＰＭＥ－４０００、ＡＭＥ－４００等）、（メタ）アクリル酸フェノキシポリエチレングリコール（共栄社化学（株）製ライトアクリレートＰ－２００Ａ、新中村化学工業（株）製ＡＭＰ－２０ＧＹ、日油（株）製ブレンマーＰＡＥ－５０、ＰＡＥ－１００、ＡＡＥ－５０、ＡＡＥ－３００、東亞合成（株）製アロニックスＭ－１０１、Ｍ－１０２等）、（メタ）アクリル酸パラクミルフェノキシエチル、（メタ）アクリル酸ノニルフェノキシポリエチレングリコール（共栄社化学（株）製ライトアクリレートＮＰ－４ＥＡ、ＮＰ－８ＥＡ、日立化成（株）製ファンクリルＦＡ－３１４Ａ、ＦＡ－３１８Ａ、日油（株）製ブレンマーＡＮＥ－１３００、東亞合成（株）製Ｍ－１１１、Ｍ１１３、Ｍ－１１７等）、（メタ）アクリル酸オクトキシポリエチレングリコール－ポリプロピレングリコール、（メタ）アクリル酸ラウロキシポリエチレングリコール、（メタ）アクリル酸ステアロキシポリエチレングリコール、（メタ）アクリル酸フェノキシ－ポリエチレングリコール－ポリプロピレングリコール、（メタ）アクリル酸ノニルフェノキシ－ポリエチレングリコール－ポリプロピレングリコール、（メタ）アクリル酸３－クロロ－２－ヒドロキシプロピル、（メタ）アクリル酸２－（２－ビニロキシエトキシ）エチル、（メタ）アクリル酸アリロキシポリエチレングリコール－ポリプロピレングリコール、（メタ）アクリル酸ウンデシレノキシ、（メタ）アクリル酸ウンデシレノキシポリエチレングリコール、（メタ）アクリル酸ω－カルボキシ－ポリカプロラクトン（東亞合成（株）製Ｍ－５３００等）、アクリル酸ダイマー（東亞合成（株）製Ｍ－５６００、ダイセルサイテック（株）製β－ＣＥＡ等）、（メタ）アクリル酸Ｎ－エチルマレイミド、（メタ）アクリル酸ペンタメチルピペリジニル、（メタ）アクリル酸テトラメチルピペリジニル、γ－［（メタ）アクリロイルオキシプロピル］トリメトキシシラン、γ－［（メタ）アクリロイルオキシプロピル］トリエトキシシラン、γ－［（メタ）アクリロイルオキシプロピル］メチルジメトキシシラン、（メタ）アクリル酸２－イソシアネートエチル、（メタ）アクリル酸２－（０－［１’－メチルプロピリデンアミノ］カルボキシアミノ）エチル、（メタ）アクリル酸２－［（３，５－ジメチルピラゾリル）カルボニルアミノ］エチル、（メタ）アクリル酸亜鉛、（メタ）アクリル酸カリウム、（メタ）アクリル酸ナトリウム、（メタ）アクリル酸マグネシウム、（メタ）アクリル酸カルシウム、（メタ）アクリル酸バリウム、（メタ）アクリル酸ストロンチウム、（メタ）アクリル酸ニッケル、（メタ）アクリル酸銅、（メタ）アクリル酸アルミニウム、（メタ）アクリル酸リチウム、（メタ）アクリル酸ネオジウム、（メタ）アクリル酸トリフルオロメチルメチル、（メタ）アクリル酸トリフルオロメチルエチル、（メタ）アクリル酸２，２，２－トリフルオロエチル、（メタ）アクリル酸２，２，３，３－テトラフルオロプロピル、（メタ）アクリル酸１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル、（メタ）アクリル酸パーフルオロエチルメチル、（メタ）アクリル酸２－パーフルオロエチルエチル、（メタ）アクリル酸パーフルオロエチルパーフルオロブチルメチル、（メタ）アクリル酸２－パーフルオロエチル－２－パーフルオロブチルエチル、（メタ）アクリル酸パーフルオロエチル、（メタ）アクリル酸パーフルオロメチル、（メタ）アクリル酸ジパーフルオロメチルメチル、（メタ）アクリル酸２，２－ジ－パーフルオロメチルエチル、（メタ）アクリル酸パーフルオロメチルパーフルオロエチルメチル、（メタ）アクリル酸２－パーフルオロメチル－２－パーフルオロエチルエチル、（メタ）アクリル酸２－パーフルオロヘキシルメチル、（メタ）アクリル酸２－パーフルオロヘキシルエチル、（メタ）アクリル酸２－パーフルオロデシルメチル、（メタ）アクリル酸２－パーフルオロデシルエチル、（メタ）アクリル酸２－パーフルオロヘキサデシルメチル、（メタ）アクリル酸２－パーフルオロヘキサデシルエチル、（メタ）アクリルアミド、ジメチル（メタ）アクリルアミド、ジエチル（メタ）アクリルアミド、（メタ）アクリロイルモルホリン、ヒドロキシエチル（メタ）アクリルアミド、イソプロピル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ダイアセトン（メタ）アクリルアミド等を挙げることができる。 Specifically, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate , (Meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid Cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid nonyl, (meth) acrylic acid Isononyl, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, (meth Dodecyl acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Isostearyl acid, oleyl (meth) acrylate, behenyl (meth) acrylate, 2-decyltetradecanyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, tolyl (meth) acrylate , 4-tert-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo (meth) acrylate Pentanyloxyethyl, (meth) a Isobornyl acrylate, tetrahydrofurfuryl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, (meth) 1-methyladamantyl acrylate, 1-ethyladamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ( 2-butoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth ) Methylphenoxyethyl acrylate, m- (meth) acrylic acid Phenoxybenzyl, ethyl carbitol (meth) acrylate, (meth) acrylic acid-methoxytriethylene glycol, (meth) acrylic acid-ethoxydiethylene glycol, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl, (meth) acrylic 2-ethylhexyl diethylene glycol acid, methoxy-dipropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol (meth) acrylate, glycerin (meth) acrylate, polyethylene glycol (meth) acrylate (NOF ( stock Bremermer PE-90, PE-200, PE-350, PE-350G, AE-90, AE-200, AE-400, etc.), polypropylene glycol (meth) acrylate (Blenmer PP-500 manufactured by NOF Corporation) , PP-800, PP-1000, AP-150, AP-400, AP-550, etc.) (meth) acrylic acid polyethylene glycol-polypropylene glycol (Blenmer 50PEP-300, 70PEP-350B, etc. manufactured by NOF Corporation), (Meth) acrylic acid polyethylene glycol-polypropylene glycol, (meth) acrylic acid polyethylene glycol-polytetramethylene glycol, (meth) acrylic acid polypropylene glycol-polytetramethylene glycol), (meth) acrylic acid polyethylene glycol-poly Tylene glycol, glycidyl (meth) acrylate, 4-hydroxybutyl-glycidyl ether (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (Meth) acrylic acid dimethylaminoethyl quaternized product (Kyoeisha Chemical Co., Ltd. light ester DQ-100, DQ-75, etc.), 4- (meth) acrylic acid-2-methyl-2-ethyl-1,3- Dioxolane, 2- (meth) acrylic acid-1,4-dioxaspiro [4,5] dec-2-ylmethyl (manufactured by Osaka Organic Chemical Industry Co., Ltd., CHDOL-10), 3-ethyl-3 (meth) acrylic acid -Oxetanyl (Osaka Organic Chemical Co., Ltd., OXE-10), (meth) acrylic acid γ-butyrolactone, (meth) a 2-phenylthioethyl silylate, 2-hydroxy-3- (2-propenyloxy) propyl (meth) acrylate, phthalic anhydride- (2-hydroxypropyl) (meth) acrylate (Osaka Organic Chemical Co., Ltd.) Biscoat # 2100), 2- (meth) acryloyloxyethylphthalic acid (Kyoeisha Chemical Co., Ltd. light ester HPA-MPL, Shin-Nakamura Chemical Co., Ltd. CB-1, etc.), 1,2-cyclohexyldicarboxylic acid -Mono [1-methyl-2-[(1-oxo-2-propenyl) oxy] ethyl] ester (Biscoat # 2150 manufactured by Osaka Organic Chemical Industry Co., Ltd.), (meth) acryloyloxy-ethylhexahydrophthalate ( Kyoeisha Chemical Co., Ltd. light ester HO-HH, HOA-HH, etc.), (meth) acryloyloxyethyl ester Sinate (Kyoeisha Chemical Co., Ltd. light ester HO-MS, HOA-MS, Shin-Nakamura Chemical Co., Ltd. SA, A-SA, etc.), 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalic acid (Kyoeisha Chemical Co., Ltd. light ester HO-MPP, etc.), 2- (meth) acryloyloxyethyl-hydroxyethylphthalic acid (Kyoeisha Chemical Co., Ltd. HOA-MPE, etc.), 2- (meth) acryloyloxyethyl- Phosphate ester (Kyoeisha Chemical Co., Ltd. light ester P-1M, P-2M, etc.), (meth) acrylic acid ethoxylated o-phenylphenol, (meth) acrylic acid methoxypolyethylene glycol (Kyoeisha Chemical Co., Ltd.) Light Ester MC, 130MA, 041MA, MTG, MTG-A, 130A, Shin-Nakamura Chemical Co., Ltd. M- 90G, AM-90G, M-230G, AM130G, FANCLIL FA-400M manufactured by Hitachi Chemical Co., Ltd., Bremer PME-100 manufactured by NOF Corporation, PME-200, PME-400, PME-550, PME-1000 , PME-4000, AME-400, etc.), phenoxypolyethylene glycol (meth) acrylate (light acrylate P-200A manufactured by Kyoeisha Chemical Co., Ltd.), AMP-20GY manufactured by Shin-Nakamura Chemical Co., Ltd., manufactured by NOF Corporation Blemmer PAE-50, PAE-100, AAE-50, AAE-300, Aronix M-101, M-102 manufactured by Toagosei Co., Ltd.), paracumylphenoxyethyl (meth) acrylate, nonyl (meth) acrylate Phenoxy polyethylene glycol (Kyoeisha Chemical Co., Ltd. light acrylate NP-4E NP-8EA, manufactured by Hitachi Chemical Co., Ltd., FANCLILL FA-314A, FA-318A, NOF BREMMER ANE-1300, Toagosei Co., Ltd. M-111, M113, M-117, etc.) (Meth) acrylic acid octoxypolyethylene glycol-polypropylene glycol, (meth) acrylic acid lauroxypolyethylene glycol, (meth) acrylic acid stearoxypolyethylene glycol, (meth) acrylic acid phenoxy-polyethylene glycol-polypropylene glycol, (meth) acrylic Nonylphenoxy-polyethylene glycol-polypropylene glycol acid, 3-chloro-2-hydroxypropyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, allyloxypolyether (meth) acrylate Lenglycol-polypropylene glycol, undecylenoxy (meth) acrylate, undecylenoxy polyethylene glycol (meth) acrylate, ω-carboxy-polycaprolactone (meth) acrylic acid (M-5300 manufactured by Toagosei Co., Ltd.), acrylic Acid dimers (M-5600 manufactured by Toagosei Co., Ltd., β-CEA manufactured by Daicel Cytec Co., Ltd.), N-ethylmaleimide (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, (meth) acrylic Acid tetramethylpiperidinyl, γ-[(meth) acryloyloxypropyl] trimethoxysilane, γ-[(meth) acryloyloxypropyl] triethoxysilane, γ-[(meth) acryloyloxypropyl] methyldimethoxysilane, (Meth) acrylic acid 2-isocyanate Ethyl, (meth) acrylic acid 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl, (meth) acrylic acid 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl, (meth) Zinc acrylate, potassium (meth) acrylate, sodium (meth) acrylate, magnesium (meth) acrylate, calcium (meth) acrylate, barium (meth) acrylate, strontium (meth) acrylate, (meth) acrylic Nickel oxide, copper (meth) acrylate, aluminum (meth) acrylate, lithium (meth) acrylate, neodymium (meth) acrylate, trifluoromethylmethyl (meth) acrylate, trifluoromethylethyl (meth) acrylate , (Meth) acrylic acid 2,2,2-trifluoroethyl, (meth ) 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, perfluoroethyl methyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate Ethyl, perfluoroethyl perfluoroethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Meth) acrylic acid diperfluoromethyl methyl, (meth) acrylic acid 2,2-di-perfluoromethyl ethyl, (meth) acrylic acid perfluoromethyl perfluoroethyl methyl, (meth) acrylic acid 2-perfluoro Methyl-2-perfluoroethylethyl, (meth) acrylic 2-perfluorohexylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylmethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2- (meth) acrylic acid 2- Perfluorohexadecylmethyl, 2-perfluorohexadecylethyl (meth) acrylate, (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, (meth) acryloylmorpholine, hydroxyethyl (meth) acrylamide, isopropyl (Meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, etc. can be mentioned.
これらは、単独で用いても良いし、複数を共重合させても構わない。ここで、（メタ）アクリルとは、アクリル及び／又はメタクリルを表す（以下同じ）。 These may be used alone or a plurality of these may be copolymerized. Here, (meth) acryl represents acryl and / or methacryl (hereinafter the same).
本発明におけるラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体の主鎖は、モノマーの入手性や取り扱いやすさ、重合の容易性、硬化物の低温での柔軟性や伸びなどの物性に優れる点から、アクリル酸エステル系モノマーを主として重合して製造されるものであることが好ましい。ここで「主として」とは、（メタ）アクリル系重合体（Ｉ）の主鎖を構成するモノマー単位のうち、５０モル％以上がアクリル酸エステル系モノマーであることを意味し、好ましくは７０モル％以上である。 The main chain of (meth) acrylic polymer having an average of at least 0.8 radical crosslinkable groups in the present invention is the availability of monomers, ease of handling, ease of polymerization, and flexibility of cured products at low temperatures. From the point of being excellent in properties such as property and elongation, it is preferable to be produced mainly by polymerizing an acrylate monomer. Here, “mainly” means that 50 mol% or more of the monomer units constituting the main chain of the (meth) acrylic polymer (I) is an acrylate ester monomer, preferably 70 mol. % Or more.
（メタ）アクリル系重合体（Ｉ）は、炭素数１～２４の飽和炭化水素基および／または脂肪族エーテル基を有するモノマーを重合または共重合して得られるものであることが好ましい。
これらのモノマーの中でも、硬化物の耐熱性に優れ、透湿性が低いという点から、炭素数１～２４の飽和炭化水素基を有するアクリル酸アルキルエステルモノマーが好ましい。具体的には、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸ｔｅｒｔ－ブチル、アクリル酸２－エチルヘキシル、アクリル酸ラウリル、アクリル酸ステアリル、アクリル酸イソステアリル等である。 The (meth) acrylic polymer (I) is preferably obtained by polymerizing or copolymerizing a monomer having a saturated hydrocarbon group having 1 to 24 carbon atoms and / or an aliphatic ether group.
Among these monomers, an alkyl acrylate monomer having a saturated hydrocarbon group having 1 to 24 carbon atoms is preferred from the viewpoint that the cured product has excellent heat resistance and low moisture permeability. Specific examples include ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, and isostearyl acrylate.
また、硬化物が耐寒性、耐油性、耐熱性のバランスに優れるという点から、炭素数１～２４の脂肪族エーテル基を有するアクリル酸アルキルエーテルエステルモノマーが好ましい。具体的には、アクリル酸２－メトキシエチル、アクリル酸２－エトキシエチル、アクリル酸－エトキシジエチレングリコール等である。脂肪族エーテル基の炭素数は、２～６であることがより好ましい。 In addition, from the viewpoint that the cured product has an excellent balance of cold resistance, oil resistance, and heat resistance, an acrylic acid alkyl ether ester monomer having an aliphatic ether group having 1 to 24 carbon atoms is preferable. Specifically, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, acrylic acid-ethoxydiethylene glycol and the like. The number of carbon atoms of the aliphatic ether group is more preferably 2-6.
本発明においては、これらの好ましいモノマーを他のモノマーと共重合、更にはブロック共重合させても構わない。共重合させるモノマーとしては、例えば、スチレン、ビニルトルエン、α－メチルスチレン、クロルスチレン、スチレンスルホン酸及びその塩等のスチレン系モノマー；パーフルオロエチレン、パーフルオロプロピレン、フッ化ビニリデン等のフッ素含有ビニルモノマー；ビニルトリメトキシシラン、ビニルトリエトキシシラン等のケイ素含有ビニル系モノマー；無水マレイン酸、マレイン酸、マレイン酸のモノアルキルエステル及びジアルキルエステル；フマル酸、フマル酸のモノアルキルエステル及びジアルキルエステル；マレイミド、メチルマレイミド、エチルマレイミド、プロピルマレイミド、ブチルマレイミド、ヘキシルマレイミド、オクチルマレイミド、ドデシルマレイミド、ステアリルマレイミド、フェニルマレイミド、シクロヘキシルマレイミド等のマレイミド系モノマー；アクリロニトリル、メタクリロニトリル等のニトリル基含有ビニル系モノマー；アクリルアミド、メタクリルアミド等のアミド基含有ビニル系モノマー；酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、安息香酸ビニル、桂皮酸ビニル等のビニルエステル類；エチレン、プロピレン等のアルケン類；ブタジエン、イソプレン等の共役ジエン類；塩化ビニル、塩化ビニリデン、塩化アリル、アリルアルコール等を挙げることができる。 In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized. Examples of the monomer to be copolymerized include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Monomers; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide , Methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclamate Maleimide monomers such as hexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, Examples thereof include vinyl esters such as vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.
本発明における（メタ）アクリル系重合体（Ｉ）の分子量分布、即ち、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）は、特に限定されないが、好ましくは１．８未満であり、より好ましくは１．７以下であり、さらに好ましくは１．６以下であり、よりさらに好ましくは１．５以下であり、特に好ましくは１．４以下であり、最も好ましくは１．３以下である。分子量分布が１．８以上であると、粘度が高くなり取り扱いが困難になるだけでなく、硬化性組成物および硬化物の機械物性や温度特性のコントロールが困難になる傾向にある。ＧＰＣ測定は、移動相としてクロロホルムを用い、測定はポリスチレンゲルカラムにて行い、数平均分子量および重量平均分子量はポリスチレン換算で求めることができる。 Molecular weight distribution of (meth) acrylic polymer (I) in the present invention, that is, ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (Mw / Mn) Is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, even more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.4 or less, and most preferably 1.3 or less. When the molecular weight distribution is 1.8 or more, not only the viscosity becomes high and handling becomes difficult, but also the mechanical properties and temperature characteristics of the curable composition and the cured product tend to be difficult to control. GPC measurement uses chloroform as a mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and weight average molecular weight can be determined in terms of polystyrene.
（メタ）アクリル系重合体（Ｉ）の数平均分子量は特に制限はないが、ＧＰＣで測定した場合に、５００～１，０００，０００の範囲が好ましく、１，０００～１００，０００がより好ましく、５，０００～１００，０００がさらに好ましい。５００未満の場合、硬化物の柔軟性が損なわれ、伸びが低下するなど十分なゴム弾性が得られなくなる傾向がある。一方、１，０００，０００を超えると、粘度が高くなり取扱いが困難になる傾向がある。 The number average molecular weight of the (meth) acrylic polymer (I) is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1,000 to 100,000 when measured by GPC. 5,000 to 100,000 is more preferable. If it is less than 500, there is a tendency that sufficient rubber elasticity cannot be obtained, for example, the flexibility of the cured product is impaired and elongation is lowered. On the other hand, when it exceeds 1,000,000, the viscosity tends to be high and handling tends to be difficult.
＜（メタ）アクリル系重合体（Ｉ）の合成法＞
本発明で使用する（メタ）アクリル系重合体（Ｉ）は、種々の重合法により得ることができる。重合法は特に限定されないが、モノマーの汎用性、制御の容易性等の点からラジカル重合法が好ましく、ラジカル重合の中でも制御ラジカル重合がより好ましい。この制御ラジカル重合法は「連鎖移動剤法」と「リビングラジカル重合法」とに分類することができる。中でも、得られる（メタ）アクリル系重合体の分子量、分子量分布の制御が容易であるリビングラジカル重合が好ましく、原料の入手性、重合体末端への官能基導入の容易さから原子移動ラジカル重合が特に好ましい。 <Method for synthesizing (meth) acrylic polymer (I)>
The (meth) acrylic polymer (I) used in the present invention can be obtained by various polymerization methods. The polymerization method is not particularly limited, but a radical polymerization method is preferable from the viewpoint of versatility of the monomer, ease of control, and the like, and among the radical polymerizations, controlled radical polymerization is more preferable. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method”. Of these, living radical polymerization is preferred because the molecular weight and molecular weight distribution of the resulting (meth) acrylic polymer can be easily controlled, and atom transfer radical polymerization is preferred because of availability of raw materials and ease of introduction of functional groups at the polymer ends. Particularly preferred.
リビングラジカル重合は、重合末端の活性が失われることなく維持されるラジカル重合である。リビング重合とは狭義においては、末端が常に活性を持ち続ける重合のことを示すが、一般には、末端が不活性化されたものと活性化されたものが平衡状態にある擬リビング重合も含まれる。本発明における定義も後者である。リビングラジカル重合は近年様々なグループで積極的に研究がなされている。その例としては、コバルトポルフィリン錯体（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９９４，１１６，７９４３）やニトロキシド化合物などのラジカル捕捉剤を用いるもの（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，１９９４，２７，７２２８）、有機ハロゲン化物等を開始剤とし遷移金属錯体を触媒とする原子移動ラジカル重合（Ａｔｏｍ　Ｔｒａｎｓｆｅｒ　Ｒａｄｉｃａｌ　Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ：ＡＴＲＰ）（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９９５，１１７，５６１４）、シングルエレクトロントランスファー重合（Ｓｉｇｌｅ　Ｅｌｅｃｔｒｏｎ　Ｔｒａｎｓｆｅｒ：ＳＥＴ）などがあげられる。原子移動ラジカル重合およびシングルエレクトロントランスファー重合は、一般に有機ハロゲン化物、またはハロゲン化スルホニル化合物等を開始剤とし、銅を中心金属とする銅錯体を触媒として重合される。（例えば、Ｐｅｒｃｅｃ，Ｖら、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．２００６，１２８，１４１５６，ＪＰＳＣｈｅｍ　２００７，４５，１６０７を参照）。さらに、これらの系に還元剤を併用するＡＧＥＴ（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ．２００５，３８，４１３９）及びＡＲＧＥＴ（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ．２００６，３９，３９）、熱あるいは光分解性ラジカル発生剤を併用するＩＣＡＲ（ＰＮＡＳ．２００６，１０３，１５３０９）も本発明で使用することができ、本発明においても還元剤や、熱あるいは光分解性ラジカル発生剤を併用してもよい。 Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition in the present invention is also the latter. In recent years, living radical polymerization has been actively researched by various groups. Examples include cobalt porphyrin complexes (J. Am. Chem. Soc. 1994, 116, 7943), those using radical scavengers such as nitroxide compounds (Macromolecules, 1994, 27, 7228), organic halides, etc. Atom transfer radical polymerization (ATRP) (J. Am. Chem. Soc. 1995, 117, 5614), single electron transfer polymerization (SET), etc. using a transition metal complex as a catalyst. can give. Atom transfer radical polymerization and single electron transfer polymerization are generally polymerized using an organic halide or a sulfonyl halide compound as an initiator and a copper complex having copper as a central metal as a catalyst. (See, for example, Percec, V et al., J. Am. Chem. Soc. 2006, 128, 14156, JP Chem Chem 2007, 45, 1607). Furthermore, AGET (Macromolecules. 2005, 38, 4139) and ARGET (Macromolecules. 2006, 39, 39) which use a reducing agent in combination with these systems, ICAR (PNAS. 2006, which uses a heat or photodegradable radical generator together. 103, 15309) can also be used in the present invention, and in the present invention, a reducing agent and a heat or photodegradable radical generator may be used in combination.
上記ラジカル重合、制御ラジカル重合、連鎖移動剤法、リビングラジカル重合法、原子移動ラジカル重合は公知の重合法ではあるが、これら各重合法については、たとえば、特開２００５－２３２４１９号公報や、特開２００６－２９１０７３号公報などの記載を参照できる。 The above radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and Reference can be made to the description in Japanese Unexamined Patent Publication No. 2006-291073.
（メタ）アクリル系重合体（Ｉ）の好ましい合成法の一つである、原子移動ラジカル重合について以下に簡単に説明する。 The atom transfer radical polymerization, which is one of the preferred methods for synthesizing the (meth) acrylic polymer (I), will be briefly described below.
原子移動ラジカル重合では、有機ハロゲン化物、特に反応性の高い炭素－ハロゲン結合を有する有機ハロゲン化物（例えば、α位にハロゲンを有するカルボニル化合物や、ベンジル位にハロゲンを有する化合物）、あるいはハロゲン化スルホニル化合物等が開始剤として用いられることが好ましい。 In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is preferably used as an initiator.
ラジカル架橋性基を１分子内に２つ以上有する（メタ）アクリル系重合体を得るためには、２つ以上の開始点を持つ有機ハロゲン化物、又はハロゲン化スルホニル化合物を開始剤として用いるのが好ましい。 In order to obtain a (meth) acrylic polymer having two or more radically crosslinkable groups in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. preferable.
原子移動ラジカル重合において用いられる（メタ）アクリル系モノマーとしては特に制約はなく、例示した（メタ）アクリル系モノマーをすべて好適に用いることができる。 There is no restriction | limiting in particular as a (meth) acrylic-type monomer used in atom transfer radical polymerization, All the (meth) acrylic-type monomers illustrated can be used suitably.
重合触媒として用いられる遷移金属錯体としては特に限定されないが、好ましくは周期律表第７族、８族、９族、１０族、又は１１族元素を中心金属とする金属錯体であり、より好ましくは０価の銅、１価の銅、２価の銅、２価のルテニウム、２価の鉄又は２価のニッケルを中心金属とする遷移金属錯体、特に好ましくは銅の錯体が挙げられる。銅の錯体を形成するために使用される１価の銅化合物を具体的に例示するならば、塩化第一銅、臭化第一銅、ヨウ化第一銅、シアン化第一銅、酸化第一銅、過塩素酸第一銅等である。２価の銅化合物を具体的に例示するならば、塩化第二銅、臭化第二銅、ヨウ化第二銅、シアン化第二銅、酸化第二銅、過塩素酸第二銅、硫化第二銅等である。 Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses periodic group 7th group, 8th group, 9th group, 10th group, or 11 group element as a central metal, More preferably A transition metal complex having zero-valent copper, monovalent copper, divalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. Specific examples of divalent copper compounds include cupric chloride, cupric bromide, cupric iodide, cupric cyanide, cupric oxide, cupric perchlorate, sulfide. Cupric and the like.
銅化合物を用いる場合、触媒活性を高めるためにポリアミン等が配位子として添加される。ポリアミン化合物を例示するならば、２，２－ビピリジン、１，１０－フェナントロリン若しくはその誘導体、トリブチルアミンなどのアルキルアミン、テトラメチルエチレンジアミン、ペンタメチルジエチレントリアミン、ヘキサメチルトリエチレンテトラアミン若しくはヘキサメチルトリス（２－アミノエチル）アミンエチレンジアミン、Ｎ，Ｎ’－ヘキサメチルエチレンジアミン、４，４’－ジ－（５－ノニル）－２，２’－ビピリジン、Ｎ－（ｎ－プロピル）ピリジルメタンイミン、Ｎ－（ｎ－オクチル）ピリジルメタンイミン、ジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’－ペンタメチルジエチレントリアミン、Ｎ－プロピル－Ｎ，Ｎ－ジ（２－ピリジルメチル）アミン、トリス（２－アミノエチル）アミン、トリス［２－（ジメチルアミノ）エチル］アミン、Ｎ，Ｎ－ビス（２－ジメチルアミノエチル）－Ｎ，Ｎ’－ジメチルエチレンジアミン、２，５，９，１２－テトラメチル－２，５，９，１２－テトラアザテトラデカン、２，６，９，１３－テトラメチル－２，６，９，１３－テトラアザテトラデカン、４，１１－ジメチル－１，４，８，１１－テトラアザビシクロヘキサデカン、Ｎ’，Ｎ’’－ジメチル－Ｎ’，Ｎ’’－ビス（（ピリジン－２－イル）メチル）エタン－１，２－ジアミン、トリス［（２－ピリジル）メチル］アミン、２，５，８，１２－テトラメチル－２，５，８，１２－テトラアザテトラデカン、トリエチレンテトラミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’’，Ｎ’’’－ヘキサメチルトリエチレンテトラミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラキス（２－ピリジルメチル）エチレンジアミン、ポリエチレンイミンなどが挙げられるが、これらに限定されるものではない。 When using a copper compound, polyamine or the like is added as a ligand in order to increase the catalytic activity. Examples of polyamine compounds include 2,2-bipyridine, 1,10-phenanthroline or derivatives thereof, alkylamines such as tributylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetraamine or hexamethyltris (2 -Aminoethyl) amine ethylenediamine, N, N'-hexamethylethylenediamine, 4,4'-di- (5-nonyl) -2,2'-bipyridine, N- (n-propyl) pyridylmethanimine, N- ( n-octyl) pyridylmethanimine, diethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-propyl-N, N-di (2-pyridylmethyl) amine, tris (2- Aminoethyl) amine, tris [ -(Dimethylamino) ethyl] amine, N, N-bis (2-dimethylaminoethyl) -N, N'-dimethylethylenediamine, 2,5,9,12-tetramethyl-2,5,9,12-tetra Azatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 4,11-dimethyl-1,4,8,11-tetraazabicyclohexadecane, N ′, N ′ '-Dimethyl-N', N ″ -bis ((pyridin-2-yl) methyl) ethane-1,2-diamine, tris [(2-pyridyl) methyl] amine, 2,5,8,12-tetra Methyl-2,5,8,12-tetraazatetradecane, triethylenetetramine, N, N, N ′, N ″, N ′ ″, N ′ ″-hexamethyltriethylenetetramine, N, N, N ', N - tetrakis (2-pyridylmethyl) ethylenediamine, although polyethylene imine, but are not limited thereto.
これらは単独で使用してもよく２種以上を組み合わせて使用してもよい。 These may be used alone or in combination of two or more.
リビングラジカル重合としてＡＧＥＴまたはＡＲＧＥＴを用いる場合には、還元剤を使用してもよい。以下に還元剤を例示するが、これらの還元剤に限定されるものではない。 When AGET or ARGET is used as the living radical polymerization, a reducing agent may be used. Although the reducing agent is illustrated below, it is not limited to these reducing agents.
金属。具体例としては、リチウム、ナトリウム、カリウム等のアルカリ金属類；ベリリウム、マグネシウム、カルシウム、バリウム等のアルカリ土類金属類；アルミニウム；亜鉛等の典型金属；銅、ニッケル、ルテニウム、鉄等の遷移金属等が挙げられる。またこれらの金属は水銀との合金（アマルガム）の状態であってもよい。 metal. Specific examples include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as beryllium, magnesium, calcium and barium; aluminum; typical metals such as zinc; transition metals such as copper, nickel, ruthenium and iron Etc. These metals may be in the state of an alloy (amalgam) with mercury.
金属化合物。具体例としては、典型金属又は遷移金属の塩や典型元素との塩、さらに一酸化炭素、オレフィン、含窒素化合物、含酸素化合物、含リン化合物、含硫黄化合物等が配位した錯体等が挙げられる。具体的には、金属とアンモニア／アミンとの化合物、三塩化チタン、チタンアルコキシド、塩化クロム、硫酸クロム、酢酸クロム、塩化鉄、塩化銅、臭化銅、塩化スズ、酢酸亜鉛、水酸化亜鉛、Ｎｉ（ＣＯ）４、Ｃｏ２ＣＯ８等のカルボニル錯体、［Ｎｉ（ｃｏｄ）２］、［ＲｕＣｌ２（ｃｏｄ）］、［ＰｔＣｌ２（ｃｏｄ）］等のオレフィン錯体（ただしｃｏｄはシクロオクタジエンを表す）、［ＲｈＣｌ（Ｐ（Ｃ６Ｈ５）３）３］、［ＲｕＣｌ２（Ｐ（Ｃ６Ｈ５）３）２］、［ＰｔＣｌ２（Ｐ（Ｃ６Ｈ５）３）２］等のホスフィン錯体等が挙げられる。 Metal compound. Specific examples include salts of typical metals or transition metals and salts with typical elements, and complexes in which carbon monoxide, olefins, nitrogen-containing compounds, oxygen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds and the like are coordinated. It is done. Specifically, compounds of metal and ammonia / amine, titanium trichloride, titanium alkoxide, chromium chloride, chromium sulfate, chromium acetate, iron chloride, copper chloride, copper bromide, tin chloride, zinc acetate, zinc hydroxide, Carbonyl complexes such as Ni (CO) 4 and Co 2 CO 8 , and olefin complexes such as [Ni (cod) 2 ], [RuCl 2 (cod)] and [PtCl 2 (cod)] (where cod is cyclooctadiene) ), [RhCl (P (C 6 H 5 ) 3 ) 3 ], [RuCl 2 (P (C 6 H 5 ) 3 ) 2 ], [PtCl 2 (P (C 6 H 5 ) 3 ) 2 ], etc. And phosphine complexes.
金属水素化物。具体例としては、水素化ナトリウム；水素化ゲルマニウム；水素化タングステン；水素化ジイソブチルアルミニウム、水素化アルミニウムリチウム、水素アルミニウムナトリウム、水素化トリエトキシアルミニウムナトリウム、水素化ビス（２－メトキシエトキシ）アルミニウムナトリウム等のアルミニウム水素化物；水素化トリフェニルスズ、水素化トリ－ｎ－ブチルスズ、水素化ジフェニルスズ、水素化ジ－ｎ－ブチルスズ、水素化トリエチルスズ、水素化トリメチルスズ等の有機スズ水素化物等が挙げられる。 Metal hydride. Specific examples include sodium hydride; germanium hydride; tungsten hydride; diisobutylaluminum hydride, lithium aluminum hydride, sodium aluminum hydride, sodium triethoxyaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, etc. And aluminum hydrides such as triphenyltin hydride, tri-n-butyltin hydride, diphenyltin hydride, di-n-butyltin hydride, triethyltin hydride, and trimethyltin hydride. .
スズ化合物。具体例としては、オクチル酸スズ、２－エチルヘキシル酸スズ等のカルボン酸スズ塩；ジブチルスズジアセテート、ジブチルスズジラウレート、ジブチルスズメルカプチド、ジブチルスズチオカルボキシレート、ジブチルスズジマレエート、ジオクチルスズチオカルボキシレート等の有機スズ化合物等が挙げられる。 Tin compounds. Specific examples include tin carboxylates such as tin octylate and tin 2-ethylhexylate; organic compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate A tin compound etc. are mentioned.
ケイ素水素化物。具体例としては、トリクロロシラン、トリメチルシラン、トリエチルシラン、ジフェニルシラン、フェニルシラン、ポリメチルヒドロシロキサン等が挙げられる。 Silicon hydride. Specific examples include trichlorosilane, trimethylsilane, triethylsilane, diphenylsilane, phenylsilane, polymethylhydrosiloxane, and the like.
ホウ素水素化物。具体的には、ボラン、ジボラン、水素化ホウ素ナトリウム、水素化トリメトキシホウ酸ナトリウム、硫化水素化ホウ素ナトリウム、シアン化水素化ホウ素ナトリウム、シアン化水素化ホウ素リチウム、水素化ホウ素リチウム、水素化トリエチルホウ素リチウム、水素化トリ－ｓ－ブチルホウ素リチウム、水素化トリ－ｔ－ブチルホウ素リチウム、水素化ホウ素カルシウム、水素化ホウ素カリウム、水素化ホウ素亜鉛、水素化ホウ素テトラ－ｎ－ブチルアンモニウム等が挙げられる。 Boron hydride. Specifically, borane, diborane, sodium borohydride, sodium trimethoxyborate, sodium borohydride, sodium cyanoborohydride, lithium borohydride, lithium borohydride, lithium triethylborohydride, hydrogen And tri-s-butyl boron hydride, lithium tri-t-butyl borohydride, calcium borohydride, potassium borohydride, zinc borohydride, tetra-n-butylammonium borohydride and the like.
窒素化合物。具体的には、ヒドラジン、ジイミド等が挙げられる。 Nitrogen compounds. Specific examples include hydrazine and diimide.
リン又はリン化合物。具体的には、リン、ホスフィン、トリメチルホスフィン、トリエチルホスフィン、トリフェニルホスフィン、トリメチルホスファイト、トリエチルホスファイト、トリフェニルホスファイト、ヘキサメチルホスフォラストリアミド、ヘキサエチルホスフォラストリアミド等が挙げられる。 Phosphorus or phosphorus compound. Specific examples include phosphorus, phosphine, trimethylphosphine, triethylphosphine, triphenylphosphine, trimethylphosphite, triethylphosphite, triphenylphosphite, hexamethylphosphorustriamide, hexaethylphosphorustriamide, and the like.
硫黄又は硫黄化合物。具体的には、硫黄、ロンガリット類、ハイドロサルファイト類、二酸化チオ尿素等が挙げられる。ロンガリットとは、スルホキシル酸塩のホルムアルデヒド誘導体であり、ＭＳＯ２・ＣＨ２Ｏ（ＭはＮａ又はＺｎを示す）で表される。具体的には、ソジウムホルムアルデヒドスルホキシレート、亜鉛ホルムアルデヒドスルホキシレート等が挙げられる。ハイドロサルファイトとは、次亜硫酸ナトリウム及び次亜硫酸ナトリウムのホルムアルデヒド誘導体の総称である。 Sulfur or sulfur compounds. Specifically, sulfur, Rongalite, hydrosulfite, thiourea dioxide and the like can be mentioned. Rongalite is a formaldehyde derivative of sulfoxylate and is represented by MSO 2 · CH 2 O (M represents Na or Zn). Specific examples include sodium formaldehyde sulfoxylate and zinc formaldehyde sulfoxylate. Hydrosulfite is a general term for sodium hyposulfite and formaldehyde derivatives of sodium hyposulfite.
水素。 hydrogen.
還元作用を示す有機化合物。具体的には、アルコール、アルデヒド、フェノール類及び有機酸化合物等が挙げられる。アルコールとしては、メタノール、エタノール、プロパノール、イソプロパノール等が挙げられる。アルデヒドとしては、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、ギ酸等が挙げられる。フェノール類としては、フェノール、ハイドロキノン、ジブチルヒドロキシトルエン、トコフェロール等が挙げられる。有機酸化合物としては、クエン酸、アスコルビン酸、及びこれらの塩、エステル等が挙げられる。 An organic compound that exhibits a reducing action. Specific examples include alcohols, aldehydes, phenols, and organic acid compounds. Examples of the alcohol include methanol, ethanol, propanol, and isopropanol. Examples of the aldehyde include formaldehyde, acetaldehyde, benzaldehyde, formic acid and the like. Examples of phenols include phenol, hydroquinone, dibutylhydroxytoluene, tocopherol and the like. Examples of the organic acid compound include citric acid, ascorbic acid, and salts and esters thereof.
これら還元剤は単独で用いてもよいし、２種以上を併用してもかまわない。 These reducing agents may be used alone or in combination of two or more.
還元剤の添加量は遷移金属化合物（触媒）に対して０．０１～１００モル当量が重合速度および構造制御の点から好ましく、０．１～４０モル当量がより好ましく、０．５～１０モル当量がさらに好ましい。　 The amount of the reducing agent added is preferably from 0.01 to 100 molar equivalents relative to the transition metal compound (catalyst) in terms of polymerization rate and structure control, more preferably from 0.1 to 40 molar equivalents, and from 0.5 to 10 molar The equivalent is more preferable. *
＜塩基性化合物＞
本リビングラジカル重合としてＡＧＥＴまたはＡＲＧＥＴを用いる場合には、塩基性化合物を使用してもよい。以下に塩基性化合物を例示するが、これらの還元剤に限定されるものではなく、ブレンステッドの塩基の定義に当てはまる、プロトンを受け入れる性質を持つ化合物、あるいはルイスの塩基の定義に当てはまる、非共有電子対を持っていてそれを授与することができ配位結合をつくる性質を有する化合物であれば良い。 <Basic compound>
When using AGET or ARGET as the living radical polymerization, a basic compound may be used. Examples of basic compounds are shown below, but are not limited to these reducing agents. They are applicable to the definition of Bronsted base, have a property of accepting protons, or apply to the definition of Lewis base, non-covalent. Any compound may be used as long as it has an electron pair and can give it and can form a coordination bond.
例示するならば、アンモニア、メチルアミン、ジメチルアミン、トリメチルアミン、トリエチルアミン、アニリン等のアミン誘導体；エチレンジアミン、プロピレンジアミン、テトラメチルエチレンジアミン、ジエチレントリアミン、ペンタメチルジエチレントリアミン、トリエチレンテトラミン、ヘキサメチルトリエチレンテトラミン、ヘキサメチレンテトラミンなどのポリアミン誘導体；ピリジン、ビピリジン、ピペリジン、ピロール、イミダゾール等の含窒素複素環化合物；ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムプロポキシド、ナトリウムブトキシド、ナトリウムペントキシド、ナトリウムヘキソキシド、カリウムメトキシド、カリウムエトキシド、カリウムプロポキシド、カリウムブトキシド、カリウムペントキシド、カリウムヘキソキシド等の無機塩基；メチルリチウム、エチルリチウム、プロピルリチウム、ブチルリチウム、ペンチルリチウム、ヘキシルリチウム等の有機金属化合物；水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、水酸化アンモニウム等の水酸化物；炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸マグネシウム、炭酸アルミニウム、炭酸アンモニウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素カルシウム、炭酸水素マグネシウム、炭酸水素アルミニウム、炭酸水素アンモニウム、リン酸ナトリウム、リン酸水素ナトリウム、酢酸ナトリウム、酢酸カリウム等の弱酸塩などが挙げられる。 Illustratively, amine derivatives such as ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, aniline; ethylenediamine, propylenediamine, tetramethylethylenediamine, diethylenetriamine, pentamethyldiethylenetriamine, triethylenetetramine, hexamethyltriethylenetetramine, hexamethylene Polyamine derivatives such as tetramine; nitrogen-containing heterocyclic compounds such as pyridine, bipyridine, piperidine, pyrrole, imidazole; sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium pentoxide, sodium hexoxide, potassium methoxide , Potassium ethoxide, potassium propoxide, potassium butoxide, potassium pent Inorganic bases such as side and potassium hexoxide; organometallic compounds such as methyl lithium, ethyl lithium, propyl lithium, butyl lithium, pentyl lithium and hexyl lithium; sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, Hydroxides such as aluminum hydroxide and ammonium hydroxide; sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, aluminum carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, magnesium bicarbonate, aluminum bicarbonate And weak acid salts such as ammonium hydrogen carbonate, sodium phosphate, sodium hydrogen phosphate, sodium acetate, and potassium acetate.
これらは、単独で用いても良いし、複数を併用しても構わない。 These may be used alone or in combination.
また、塩基性化合物は、直接反応系に添加してもよいし、反応系中で発生させてもよい。 The basic compound may be added directly to the reaction system or may be generated in the reaction system.
塩基性化合物の添加量は遷移金属化合物（触媒）に対して０．０１～４００モル当量が重合速度および構造制御の点から好ましく、０．１～１５０モル当量がより好ましく、０．５～４０モル当量がさらに好ましい。 The addition amount of the basic compound is preferably 0.01 to 400 molar equivalents relative to the transition metal compound (catalyst) from the viewpoint of polymerization rate and structure control, more preferably 0.1 to 150 molar equivalents, and 0.5 to 40 molar equivalents. A molar equivalent is more preferred.
重合反応は、無溶媒でも可能であるが、各種の溶媒中で行うこともできる。溶媒の種類としては特に限定されず、特開２００５－２３２４１９号公報段落［００６７］記載の溶剤が挙げられる。これらは、単独でもよく、２種以上を併用してもよい。また、エマルジョン系または超臨界流体ＣＯ２を媒体とする系においても重合を行うことができる。 The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. The type of the solvent is not particularly limited, and examples thereof include a solvent described in paragraph [0067] of JP-A-2005-232419. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO 2 as a medium.
重合温度は、限定はされないが、０～２００℃の範囲で行うことができ、好ましくは、室温～１５０℃の範囲である。 The polymerization temperature is not limited, but can be carried out in the range of 0 to 200 ° C., preferably in the range of room temperature to 150 ° C.
＜ラジカル架橋性基＞
次に、（メタ）アクリル系重合体（Ｉ）のラジカル架橋性基について説明する。 <Radical crosslinkable group>
Next, the radical crosslinkable group of the (meth) acrylic polymer (I) will be described.
ラジカル架橋性基は特に限定されず、（メタ）アクリロイル基や（メタ）アリル基、エキソメチレン基、マレイミド基などのラジカル架橋性の炭素－炭素二重結合を有する基であることが好ましい。例えば前述の原子移動ラジカル重合法で製造された（メタ）アクリル系重合体の場合、ラジカル架橋性基の反応性が高く、また架橋性基を導入し易いことから（メタ）アクリロイル基であることが好ましい。 The radical crosslinkable group is not particularly limited, and is preferably a group having a radical crosslinkable carbon-carbon double bond such as a (meth) acryloyl group, a (meth) allyl group, an exomethylene group, and a maleimide group. For example, in the case of a (meth) acrylic polymer produced by the above-mentioned atom transfer radical polymerization method, it is a (meth) acryloyl group because the radical crosslinkable group is highly reactive and the crosslinkable group can be easily introduced. Is preferred.
ラジカル架橋性の炭素－炭素二重結合を有する基の導入方法について説明する。ラジカル架橋性の炭素－炭素二重結合を有する基の導入は、公知の方法を利用することができる。例えば、特開２００４－２０３９３２公報段落［００８０］～［００９１］記載の方法が挙げられる。これらの方法の中でも制御がより容易である点から、（メタ）アクリル系重合体の末端ハロゲン基を、ラジカル架橋性の炭素－炭素二重結合を有する基を有する化合物で置換する方法が好ましい。末端ハロゲン基を有する（メタ）アクリル系重合体は、上述した有機ハロゲン化物、またはハロゲン化スルホニル化合物を開始剤、遷移金属錯体を触媒として（メタ）アクリル系モノマーを重合する方法、あるいは、ハロゲン化合物を連鎖移動剤として（メタ）アクリル系モノマーを重合する方法により製造することができるが、好ましくは前者である。 A method for introducing a radical having a crosslinkable carbon-carbon double bond will be described. The introduction of a group having a radically crosslinkable carbon-carbon double bond can be performed by a known method. Examples thereof include the methods described in paragraphs [0080] to [0091] of JP-A No. 2004-203932. Among these methods, a method in which the terminal halogen group of the (meth) acrylic polymer is substituted with a compound having a group having a radically crosslinkable carbon-carbon double bond is preferable because it is easier to control. A (meth) acrylic polymer having a terminal halogen group is a method of polymerizing a (meth) acrylic monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a halogen compound. Can be produced by a method of polymerizing a (meth) acrylic monomer using a chain transfer agent, but the former is preferred.
ラジカル架橋性の炭素－炭素二重結合を有する基を有する化合物としては特に限定されないが、下記一般式（１）で表される化合物が使用でき、
Ｍ＋－ＯＣ（Ｏ）Ｃ（Ｒ）＝ＣＨ２（１）
上記式（１）中のＲは、水素又は炭素数１～２０の有機基を表す。具体例としては、－Ｈ、－ＣＨ３、－ＣＨ２ＣＨ３、－（ＣＨ２）ｎＣＨ３（ｎは２～１９の整数を表す）、－Ｃ６Ｈ５、－ＣＨ２ＯＨ、－ＣＮ、等が挙げられ、好ましくは－Ｈまたは－ＣＨ３である。
上記式（１）中のＭ＋はオキシアニオンの対カチオンであり、Ｍ＋の種類としてはアルカリ金属イオン、具体的にはリチウムイオン、ナトリウムイオン、カリウムイオン、および４級アンモニウムイオンが挙げられる。４級アンモニウムイオンとしてはテトラメチルアンモニウムイオン、テトラエチルアンモニウムイオン、テトラベンジルアンモニウムイオン、トリメチルドデシルアンモニウムイオン、テトラブチルアンモニウムイオンおよびジメチルピペリジニウムイオン等が挙げられ、反応性および入手のし易さから、好ましくはナトリウムイオン、カリウムイオンである。 The compound having a group having a radically crosslinkable carbon-carbon double bond is not particularly limited, but a compound represented by the following general formula (1) can be used.
M + − OC (O) C (R) ═CH 2 (1)
R in the above formula (1) represents hydrogen or an organic group having 1 to 20 carbon atoms. Specific examples include —H, —CH 3 , —CH 2 CH 3 , — (CH 2 ) n CH 3 (n represents an integer of 2 to 19), —C 6 H 5 , —CH 2 OH, — CN, etc. are mentioned, and preferably —H or —CH 3 .
M + in the above formula (1) is a counter cation of an oxyanion, and examples of M + include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion and dimethylpiperidinium ion, and are preferable from the viewpoint of reactivity and availability. Are sodium ion and potassium ion.
一般式（１）のオキシアニオンの使用量は、（メタ）アクリル系重合体のハロゲン基に対して、好ましくは１～５当量、更に好ましくは１．０～１．２当量である。この反応はほぼ定量的に進行することから、少なすぎるとハロゲン基に対して十分な量のラジカル架橋性の炭素－炭素二重結合を有する基が導入されず、また多すぎた場合には、経済的に好ましくない。 The amount of the oxyanion of the general formula (1) used is preferably 1 to 5 equivalents, more preferably 1.0 to 1.2 equivalents relative to the halogen group of the (meth) acrylic polymer. Since this reaction proceeds almost quantitatively, if the amount is too small, a sufficient amount of radical-crosslinkable carbon-carbon double bond groups with respect to the halogen group will not be introduced. Economically unfavorable.
この反応を実施する溶媒としては特に限定はされないが、求核置換反応であるため極性溶媒が好ましく、例えば、テトラヒドロフラン、ジオキサン、ジエチルエーテル、アセトン、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、ヘキサメチルホスホリックトリアミド、アセトニトリル等が用いられる。 The solvent for carrying out this reaction is not particularly limited but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric Triamide, acetonitrile and the like are used.
反応を行う温度は限定されないが、一般に０～１５０℃で、重合性の末端基を保持するために好ましくは室温～１００℃で行う。 The temperature at which the reaction is carried out is not limited, but is generally from 0 to 150 ° C., preferably from room temperature to 100 ° C. in order to retain the polymerizable terminal group.
（メタ）アクリル系重合体（Ｉ）の各分子中のラジカル架橋性基の数は、同数であっても構わないし、異なっていても構わない。硬化性、及び硬化物の柔軟性、伸び、引張強さといった物性の観点から、分子中のラジカル架橋性基の数は、平均して少なくとも０．８個であり、好ましくは０．９個以上４．０個以下、さらに好ましくは１．０個以上２．０個以下である。 The number of radical crosslinkable groups in each molecule of the (meth) acrylic polymer (I) may be the same or different. From the viewpoint of curability and physical properties such as flexibility, elongation and tensile strength of the cured product, the number of radical crosslinkable groups in the molecule is at least 0.8 on average, preferably 0.9 or more 4.0 or less, more preferably 1.0 or more and 2.0 or less.
異なる（メタ）アクリル系重合体（Ｉ）を２種類以上混合して使用する場合は、（メタ）アクリル系重合体全体の平均として、上記範囲内にあるようにラジカル架橋性基の数を調節すればよい。 When two or more different (meth) acrylic polymers (I) are used as a mixture, the number of radical crosslinkable groups is adjusted so that it is within the above range as the average of the entire (meth) acrylic polymer. do it.
（メタ）アクリル系重合体（Ｉ）を２種類以上混合した場合のラジカル架橋性基数の平均は、特表２０１４－５３１４８９公報段落［００２８］に定義されているＡＦＢ値（「ブレンドの平均官能性」）と同様にして算出される。すなわち、ラジカル架橋性基数の平均＝（（メタ）アクリル系重合体１のラジカル架橋性基数）×（混合物中の（メタ）アクリル系重合体１のｗｔ％）＋（（メタ）アクリル系重合体２のラジカル架橋性基数）×（（メタ）アクリル系重合体２のｗｔ％）＋・・・＋（（メタ）アクリル系重合体Ｘのラジカル架橋性基数）×（（メタ）アクリル系重合体Ｘのｗｔ％）として計算される。 The average number of radically crosslinkable groups when two or more kinds of (meth) acrylic polymers (I) are mixed is the AFB value (“average functionality of blend” defined in paragraph [0028] of JP-T-2014-531489. )). That is, the average number of radical crosslinkable groups = (number of radical crosslinkable groups of (meth) acrylic polymer 1) × (wt% of (meth) acrylic polymer 1 in the mixture) + ((meth) acrylic polymer) 2 (number of radically crosslinkable groups) × (wt% of (meth) acrylic polymer 2) +... + (Number of radically crosslinkable groups of (meth) acrylic polymer X) × ((meth) acrylic polymer) X wt%).
本発明の硬化物にゴム的な性質が特に要求される場合には、ゴム弾性に大きな影響を与える架橋点間分子量が大きくとれるため、（メタ）アクリル系重合体（Ｉ）のラジカル架橋性基（好ましくはラジカル架橋性の炭素－炭素二重結合を有する基、より好ましくは（メタ）アクリロイル基）の少なくとも１個は分子鎖の末端にあることが好ましく、全てのラジカル架橋性基が分子鎖末端に存在することがより好ましい。 When the cured product of the present invention is particularly required to have rubber-like properties, the molecular weight between the crosslinking points that greatly affects rubber elasticity can be increased. Therefore, the radically crosslinkable group of the (meth) acrylic polymer (I) At least one of (preferably a group having a radically crosslinkable carbon-carbon double bond, more preferably a (meth) acryloyl group) is preferably at the end of the molecular chain, and all radically crosslinkable groups are More preferably at the end.
硬化物により柔軟な性質が要求される場合には、ラジカル架橋性基を分子末端に有する（メタ）アクリル系重合体（Ｉ）が、重合体の両末端にラジカル架橋性基を有する（メタ）アクリル系重合体と重合体の片末端にラジカル架橋性基を有する（メタ）アクリル系重合体を共に含むことが好ましい。両末端にラジカル架橋性基を有する（メタ）アクリル系重合体と重合体の片末端にラジカル架橋性基を有する（メタ）アクリル系重合体との比率は、両末端にラジカル架橋性基を有する（メタ）アクリル系重合体１００重量部に対して、片末端にラジカル架橋性基を有する（メタ）アクリル系重合体０～３０００重量部であることが好ましく、４０～３００重量部であることがより好ましい。片末端にラジカル架橋性基を有する（メタ）アクリル系重合体が少ないほど硬化物は硬く圧縮永久ひずみに優れるものとなり、逆に片末端にラジカル架橋性基を有する（メタ）アクリル系重合体が多くなるほど、硬化物は柔らかく伸びに優れるものとなる。 When the cured product requires flexible properties, the (meth) acrylic polymer (I) having a radical crosslinkable group at the molecular end has a radical crosslinkable group at both ends of the polymer (meth). It is preferable that both the acrylic polymer and a (meth) acrylic polymer having a radical crosslinkable group at one end of the polymer are included. The ratio of (meth) acrylic polymer having radical crosslinkable groups at both ends to (meth) acrylic polymer having radical crosslinkable groups at one end of the polymer has radical crosslinkable groups at both ends. The amount of the (meth) acrylic polymer having a radical crosslinkable group at one end is preferably 0 to 3000 parts by weight, and preferably 40 to 300 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. More preferred. The smaller the (meth) acrylic polymer having a radical crosslinkable group at one end, the harder the cured product will be and the better the compression set, and conversely, the (meth) acrylic polymer having a radical crosslinkable group at one end will be The more the cured product is, the softer and the better it becomes.
＜ラジカル重合開始剤（ＩＩ）＞
ラジカル重合開始剤（ＩＩ）としては特に制限はないが、ＵＶや電子線などの活性エネルギー線により硬化させる場合には光ラジカル開始剤が好ましく、熱により硬化させる場合には熱ラジカル開始剤が好ましい。 <Radical polymerization initiator (II)>
Although there is no restriction | limiting in particular as radical polymerization initiator (II), when hardening by active energy rays, such as UV and an electron beam, a photoradical initiator is preferable, and when making it harden | cure, a thermal radical initiator is preferable. .
＜光ラジカル開始剤＞
光ラジカル開始剤としては特に制限はないが、例えば、アセトフェノン、プロピオフェノン、ベンゾフェノン、キサントール、フルオレイン、ベンズアルデヒド、アンスラキノン、トリフェニルアミン、カルバゾール、３－メチルアセトフェノン、４－メチルアセトフェノン、３－ペンチルアセトフェノン、２，２－ジエトキシアセトフェノン、４－メトキシアセトフェノン、３－ブロモアセトフェノン、４－アリルアセトフェノン、ｐ－ジアセチルベンゼン、３－メトキシベンゾフェノン、４－メチルベンゾフェノン、４－クロロベンゾフェノン、４，４’－ジメトキシベンゾフェノン、４－クロロ－４’－ベンジルベンゾフェノン、３－クロロキサントーン、３，９－ジクロロキサントーン、３－クロロ－８－ノニルキサントーン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインブチルエーテル、ビス（４－ジメチルアミノフェニル）ケトン、ベンジルメトキシケタール、２－クロロチオキサントーン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名ＩＲＧＡＣＵＲＥ６５１、ＢＡＳＦジャパン社製）、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（商品名ＩＲＧＡＣＵＲＥ１８４、ＢＡＳＦジャパン社製）、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（商品名ＤＡＲＯＣＵＲ１１７３、ＢＡＳＦジャパン社製）、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン（商品名ＩＲＧＡＣＵＲＥ２９５９、ＢＡＳＦジャパン社製）、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン（商品名ＩＲＧＡＣＵＲＥ９０７、ＢＡＳＦジャパン社製）、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１（商品名ＩＲＧＡＣＵＲＥ３６９、ＢＡＳＦジャパン社製）、２－（４－メチルベンジル）－２－ジメチルアミノ－１－（４－モルフォリンー４－イル－フェニル）－ブタン－１－オン（商品名ＩＲＧＡＣＵＲＥ３７９、ＢＡＳＦジャパン社製）、ジベンゾイル等が挙げられる。 <Photo radical initiator>
The photo radical initiator is not particularly limited. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3- Pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4 ' -Dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzo , Benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name IRGACURE651) 1) -hydroxy-cyclohexyl-phenyl-ketone (trade name IRGACURE 184, manufactured by BASF Japan), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade names DAROCUR1173, BASF) Manufactured by Japan), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name IRGACURE2959, manufactured by BASF Japan), 2-methyl- 1- [4- (Me Tilthio) phenyl] -2-morpholinopropan-1-one (trade name IRGACURE907, manufactured by BASF Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name) IRGACURE369, manufactured by BASF Japan), 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-1-one (trade name IRGACURE379, manufactured by BASF Japan) , Dibenzoyl and the like.
これらのうち、α－ヒドロキシケトン化合物（例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインブチルエーテル、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン等）、フェニルケトン誘導体（例えば、アセトフェノン、プロピオフェノン、ベンゾフェノン、３－メチルアセトフェノン、４－メチルアセトフェノン、３－ペンチルアセトフェノン、２，２－ジエトキシアセトフェノン、４－メトキシアセトフェノン、３－ブロモアセトフェノン、４－アリルアセトフェノン、３－メトキシベンゾフェノン、４－メチルベンゾフェノン、４－クロロベンゾフェノン、４，４’－ジメトキシベンゾフェノン、４－クロロ－４’－ベンジルベンゾフェノン、ビス（４－ジメチルアミノフェニル）ケトン等）が好ましい。さらに、硬化物表面の酸素阻害を抑制できる開始剤種として、分子内に光分解性の基を２個以上有する光ラジカル開始剤として、２－ヒドロキシ－１－［４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル］－２－メチル－プロパン－１－オン（商品名ＩＲＧＡＣＵＲＥ１２７、ＢＡＳＦジャパン社製）、１－〔４－（４－ベンゾイキシルフェニルサルファニル）フェニル〕－２－メチル－２－（４－メチルフェニルスルホニル）プロパン－１－オン（商品名ＥＳＵＲＥ１００１Ｍ）、メチルベンゾイルフォーメート（商品名ＳＰＥＥＤＣＵＲＥ　ＭＢＦ、ＬＡＭＢＳＯＮ社製）、Ｏ－エトキシイミノ－１－フェニルプロパン－１－オン（商品名ＳＰＥＥＤＣＵＲＥ　ＰＤＯ、ＬＡＭＢＳＯＮ社製）、オリゴ［２－ヒドロキシ－２－メチル－１－［４－（１－メチルビニル）フェニル］プロパノン（商品名ＥＳＡＣＵＲＥ　ＫＩＰ１５０、ＬＡＭＢＥＲＴＩ社製）、分子内に芳香環を３つ以上有する水素引き抜き型光ラジカル開始剤として１－［４－（フェニルチオ）－，２－（Ｏ－ベンゾイルオキシム）］１，２－オクタンジオン（商品名ＩＲＧＡＣＵＲＥ　ＯＸＥ　０１、ＢＡＳＦジャパン社製）、１－〔９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル〕－１－（０－アセチルオキシム）エタノン（商品名ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２、ＢＡＳＦジャパン社製）、４－ベンゾイル－４’－メチルジフェニルサルファイド、４－フェニルベンゾフェノン、４，４’，４’’－（ヘキサメチルトリアミノ）トリフェニルメタン等が挙げられる。また、深部硬化性改善を特徴とする２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド（商品名ＤＡＲＯＣＵＲ　ＴＰＯ、ＢＡＳＦジャパン社製）、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（商品名ＩＲＧＡＣＵＲＥ８１９、ＢＡＳＦジャパン社製）、ビス（２，６－ジメチルベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイド等のアシルフォスフィンオキサイド系光ラジカル開始剤が挙げられる。 Of these, α-hydroxy ketone compounds (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenyl ketone derivatives (for example, acetophenone, propiophenone, benzophenone, 3-methyl) Acetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, bis (4-dimethylaminophenyl) ketone, etc.) are preferred. Furthermore, as an initiator species capable of suppressing oxygen inhibition on the surface of the cured product, as a photo radical initiator having two or more photodegradable groups in the molecule, 2-hydroxy-1- [4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade name IRGACURE127, manufactured by BASF Japan), 1- [4- (4-Benzoxylphenylsulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one (trade name ESURE1001M), methylbenzoyl formate (trade name SPEDCURE MBF, manufactured by LAMBSON), O-ethoxyimino-1-phenylpropane -1-On (trade name SPEDDCURE PDO, manufactured by LAMBSON), oligo [ -Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone (trade name ESACURE KIP150, manufactured by LAMBERTI) as a hydrogen abstraction type photo radical initiator having three or more aromatic rings in the molecule 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] 1,2-octanedione (trade name IRGACURE OXE 01, manufactured by BASF Japan Ltd.), 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) ethanone (trade name IRGACURE OXE 02, manufactured by BASF Japan Ltd.), 4-benzoyl-4′-methyldiphenyl sulfide, 4-phenylbenzophenone , 4,4 ′, 4 ″-(Hexamethyltriamino) trife Rumetan, and the like. In addition, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name DAROCUR TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl) -phenylphosphine, characterized by improved deep-curability Examples thereof include acyl phosphine oxide photo radical initiators such as fin oxide (trade name IRGACURE819, manufactured by BASF Japan Ltd.), bis (2,6-dimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
光ラジカル開始剤としては、硬化性組成物の硬化性と貯蔵安定性のバランスの点で、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（商品名ＩＲＧＡＣＵＲＥ１８４、ＢＡＳＦジャパン社製）、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（商品名ＤＡＲＯＣＵＲ１１７３、ＢＡＳＦジャパン社製）、ビス（４－ジメチルアミノフェニル）ケトン、２－ヒドロキシ－１－［４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル］－２－メチル－プロパン－１－オン（商品名ＩＲＧＡＣＵＲＥ１２７、ＢＡＳＦジャパン社製）、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１（商品名ＩＲＧＡＣＵＲＥ３６９、ＢＡＳＦジャパン社製）、２－（４－メチルベンジル）－２－ジメチルアミノ－１－（４－モルフォリンー４－イル－フェニル）－ブタン－１－オン（商品名ＩＲＧＡＣＵＲＥ３７９、ＢＡＳＦジャパン社製）、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド（商品名ＤＡＲＯＣＵＲ　ＴＰＯ、ＢＡＳＦジャパン社製）、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（商品名ＩＲＧＡＣＵＲＥ８１９、ＢＡＳＦジャパン社製）、ビス（２，６－ジメチルベンゾイル）－２，４，４－トリメチル－ペンチルフォスフィンオキサイドがより好ましい。 As a photo radical initiator, 1-hydroxy-cyclohexyl-phenyl-ketone (trade name IRGACURE 184, manufactured by BASF Japan Ltd.), 2-hydroxy-2- in terms of the balance between curability and storage stability of the curable composition. Methyl-1-phenyl-propan-1-one (trade name DAROCUR1173, manufactured by BASF Japan), bis (4-dimethylaminophenyl) ketone, 2-hydroxy-1- [4- [4- (2-hydroxy-2 -Methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one (trade name IRGACURE127, manufactured by BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butanone-1 (trade name IRGACURE369, manufactured by BASF Japan), 2- ( -Methylbenzyl) -2-dimethylamino-1- (4-morpholin-4-yl-phenyl) -butan-1-one (trade name IRGACURE 379, manufactured by BASF Japan Ltd.), 2,4,6-trimethylbenzoyl-diphenyl- Phosphine oxide (trade name DAROCUR TPO, manufactured by BASF Japan), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name IRGACURE819, manufactured by BASF Japan), bis (2,6-dimethylbenzoyl) ) -2,4,4-trimethyl-pentylphosphine oxide is more preferred.
これらの光ラジカル開始剤は、単独、又は２種以上混合して用いても、他の化合物と組み合わせて用いてもよい。 These photo radical initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.
他の化合物との組み合わせとしては、具体的には、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、ジエタノールメチルアミン、ジメチルエタノールアミン、トリエタノールアミン、エチル－４－ジメチルアミノベンゾエート、２－エチルヘキシル－４－ジメチルアミノベンゾエート等のアミンとの組み合わせ、さらにこれにジフェニルヨードニウムクロリド等のヨードニウム塩を組み合わせたもの、メチレンブルー等の色素及びアミンと組み合わせたもの等が挙げられる。 Specific combinations with other compounds include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, diethanolmethylamine, dimethylethanolamine, triethanolamine, ethyl Combinations with amines such as -4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate, further combinations with iodonium salts such as diphenyliodonium chloride, combinations with pigments and amines such as methylene blue, etc. Can be mentioned.
なお、前記光ラジカル開始剤を使用する場合、必要により、ハイドロキノン、ハイドロキノンモノメチルエーテル、ベンゾキノン、パラターシャリーブチルテコール、２，２，６，６－テトラメチルピペリジン－１－オキシル、Ｎ，Ｎ－ジエチルヒドロキシルアミン、Ｎ，Ｎ－ジステアリルヒドロキシルアミン等Ｎ，Ｎ－ジアルキルヒドロキシルアミン等の重合禁止剤類を添加することもできる。 When the photo radical initiator is used, if necessary, hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl techol, 2,2,6,6-tetramethylpiperidine-1-oxyl, N, N— Polymerization inhibitors such as N, N-dialkylhydroxylamine such as diethylhydroxylamine and N, N-distearylhydroxylamine can also be added.
＜熱ラジカル開始剤＞
熱ラジカル開始剤としては特に限定されないが、アゾ系開始剤、過酸化物開始剤、過硫酸塩開始剤、レドックス開始剤等が含まれる。 <Thermal radical initiator>
Although it does not specifically limit as a thermal radical initiator, An azo initiator, a peroxide initiator, a persulfate initiator, a redox initiator, etc. are contained.
アゾ系開始剤としては特に限定されず、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）（ＶＡＺＯ　３３）、２，２’－アゾビス（２－アミジノプロパン）二塩酸塩（ＶＡＺＯ　５０）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）（ＶＡＺＯ　５２）、２，２’－アゾビス（イソブチロニトリル）（ＶＡＺＯ　６４）、２，２’－アゾビス－２－メチルブチロニトリル（ＶＡＺＯ　６７）、１，１－アゾビス（１－シクロヘキサンカルボニトリル）（ＶＡＺＯ　８８）（全てＤｕＰｏｎｔ　Ｃｈｅｍｉｃａｌ社から入手可能）、２，２’－アゾビス（２－シクロプロピルプロピオニトリル）、及び２，２’－アゾビス（メチルイソブチレ－ト）（Ｖ－６０１）（和光純薬工業社より入手可能）等が挙げられる。 The azo initiator is not particularly limited, and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2′-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyronitrile) (VAZO 64), 2,2'-azobis-2 -Methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2'-azobis (2-cyclopropylpropionitrile) ), And 2,2′-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries, Ltd.) It is.
過酸化物開始剤としては特に限定されず、過酸化ベンゾイル、過酸化アセチル、過酸化ラウロイル、過酸化デカノイル、ジセチルパーオキシジカーボネート、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート（Ｐｅｒｋａｄｏｘ　１６Ｓ）（Ａｋｚｏ　Ｎｏｂｅｌから入手可能）、ジ（２－エチルヘキシル）パーオキシジカーボネート、ｔ－ブチルパーオキシピバレート（Ｌｕｐｅｒｓｏｌ　１１）（Ｅｌｆ　Ａｔｏｃｈｅｍから入手可能）、ｔ－ブチルパーオキシ－２－エチルヘキサノエート（Ｔｒｉｇｏｎｏｘ　２１－Ｃ５０）（Ａｋｚｏ　Ｎｏｂｅｌから入手可能）、及び過酸化ジクミル等が挙げられる。 The peroxide initiator is not particularly limited, and benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate (Perkadox). 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butylperoxy-2-ethylhexa Noate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.
過硫酸塩開始剤としては特に限定されず、過硫酸カリウム、過硫酸ナトリウム、及び過硫酸アンモニウム等が挙げられる。 The persulfate initiator is not particularly limited, and examples thereof include potassium persulfate, sodium persulfate, and ammonium persulfate.
レドックス（酸化還元）開始剤としては特に限定されず、上記過硫酸塩開始剤と還元剤（メタ亜硫酸水素ナトリウム、亜硫酸水素ナトリウム等）との組み合わせ；有機過酸化物と第３級アミンに基づく系、例えば過酸化ベンゾイルとジメチルアニリンに基づく系；有機ヒドロパーオキシドと遷移金属に基づく系、例えばクメンヒドロパーオキシドとコバルトナフテートに基づく系等が挙げられる。 The redox (oxidation-reduction) initiator is not particularly limited, and is a combination of the above-mentioned persulfate initiator and a reducing agent (sodium metabisulfite, sodium bisulfite, etc.); a system based on an organic peroxide and a tertiary amine For example, systems based on benzoyl peroxide and dimethylaniline; systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.
他の開始剤としては、限定されるわけではないが、テトラフェニル１，１，２，２－エタンジオールのようなピナコール等が挙げられる。 Other initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol.
熱ラジカル開始剤としては、アゾ系開始剤及び過酸化物系開始剤からなる群から選ばれるものが好ましい。更に好ましいものは、２，２’－アゾビス（メチルイソブチレ－ト）、過酸化ベンゾイル、過酸化ジクミル、ｔ－ブチルパーオキシピバレート、及びジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、並びにこれらの混合物である。 As the thermal radical initiator, those selected from the group consisting of azo initiators and peroxide initiators are preferable. More preferred are 2,2′-azobis (methylisobutylate), benzoyl peroxide, dicumyl peroxide, t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and these It is a mixture of
また、場合によっては光ラジカル開始剤と熱ラジカル開始剤を併用してもよい。 In some cases, a photo radical initiator and a thermal radical initiator may be used in combination.
ラジカル重合開始剤は触媒的に有効な量が使用される。硬化性と貯蔵安定性の点から、ラジカル重合開始剤の量は、（メタ）アクリル系重合体（Ｉ）１００重量部に対し０．０１～１０重量部であり、好ましくは約０．１～５量部である。ラジカル重合開始剤の量は、ラジカル重合開始剤の混合物が使用される場合には、混合物の合計量である。 The radical polymerization initiator is used in a catalytically effective amount. From the viewpoint of curability and storage stability, the amount of the radical polymerization initiator is 0.01 to 10 parts by weight, preferably about 0.1 to 10 parts by weight per 100 parts by weight of the (meth) acrylic polymer (I). 5 parts by weight. The amount of radical polymerization initiator is the total amount of the mixture when a mixture of radical polymerization initiators is used.
＜（メタ）アクリロイルモルホリン（ＩＩＩ）＞
（メタ）アクリロイルモルホリン（ＩＩＩ）としては、特に制限はないが、入手が容易であり、反応性が良好で、硬化物の低温特性がより優れることからＮ－アクリロイルモルホリンが好ましい。 <(Meth) acryloylmorpholine (III)>
(Meth) acryloylmorpholine (III) is not particularly limited, but N-acryloylmorpholine is preferred because it is readily available, has good reactivity, and has better low-temperature properties of the cured product.
本発明に用いられる（メタ）アクリロイルモルホリン（ＩＩＩ）の量は、引張強さが高く強靭な硬化物が得られることから、（メタ）アクリル系重合体（Ｉ）１００重量部に対し３０～７０重量部であり、４０～６０重量部がより好ましい。３０重量部より少ない場合には、引張強さの改善効果が低く、７０重量部を超えると伸びが低下したりゴムとしての十分な柔軟性が得られなかったり、硬化性が低下して硬化物が得られない場合がある。 The amount of (meth) acryloylmorpholine (III) used in the present invention is 30 to 70 with respect to 100 parts by weight of (meth) acrylic polymer (I) because a tough cured product having high tensile strength can be obtained. Parts by weight, more preferably 40 to 60 parts by weight. When the amount is less than 30 parts by weight, the effect of improving the tensile strength is low. When the amount exceeds 70 parts by weight, the elongation is reduced or sufficient flexibility as a rubber is not obtained, or the curability is lowered to obtain a cured product. May not be obtained.
＜炭素数６以上の直鎖または分岐炭化水素基を有する単官能アクリル系モノマー（ＩＶ）＞
単官能アクリル系モノマーとは、分子中に１個のアクリロイル基を有する重合性モノマーのことである。炭素数６以上の直鎖または分岐の炭化水素基とは、炭素原子を６個以上含む直鎖炭化水素基または分岐炭化水素基であって、環状構造を含まない炭化水素基のことであり、炭化水素基中に酸素、窒素、リン、ケイ素、ハロゲン等の各種原子を有していてもよい。 <Monofunctional acrylic monomer (IV) having a straight chain or branched hydrocarbon group having 6 or more carbon atoms>
The monofunctional acrylic monomer is a polymerizable monomer having one acryloyl group in the molecule. The straight chain or branched hydrocarbon group having 6 or more carbon atoms is a straight chain hydrocarbon group or branched hydrocarbon group containing 6 or more carbon atoms, and does not include a cyclic structure. The hydrocarbon group may have various atoms such as oxygen, nitrogen, phosphorus, silicon, and halogen.
炭素数６以上の直鎖または分岐の炭化水素基を有す単官能アクリル系モノマー（ＩＶ）としては特に制限されず、各種のものを用いることができる。具体的には、アクリル酸ヘキシル、アクリル酸イソへキシル、アクリル酸ヘプチル、アクリル酸ｎ－オクチル、アクリル酸２－エチルヘキシル、アクリル酸イソオクチル、アクリル酸ノニル、アクリル酸イソノニル、アクリル酸デシル、アクリル酸イソデシル、アクリル酸ウンデシル、アクリル酸ドデシル、アクリル酸トリデシル、アクリル酸テトラデシル、アクリル酸ペンタデシル、アクリル酸ヘキサデシル、アクリル酸ヘプタデシル、アクリル酸ステアリル、アクリル酸イソステアリル、アクリル酸オレイル、アクリル酸ベヘニル、アクリル酸２－デシルテトラデカニル等の飽和および不飽和脂肪族類の他に、アクリル酸エチルカルビトール（大阪有機化学工業（株）製ビスコート＃１９０）、アクリル酸２－エトキシエトキシエチル、アクリル酸－エトキシトリエチレングリコール、アクリル酸２－エチルヘキシルジエチレングリコ－ル（共栄社化学（株）製ライトアクリレートＥＨＤＧ－ＡＴ）、アクリル酸エトキシ－ジプロピレングリコール、アクリル酸ポリエチレングリコール（日油（株）製ブレンマーＡＥ－２００、ＡＥ－４００、ＡＭＥ－４００、ＡＬＥ－２００等）、アクリル酸ポリプロピレングリコール（日油（株）製ブレンマーＡＰ－１５０、ＡＰ－４００、ＡＰ－５５０、ＡＰ－８００等）、アクリル酸ポリエチレングリコール－ポリプロピレングリコール、アクリル酸ポリエチレングリコール－ポリテトラメチレングリコール、アクリル酸ポリプロピレングリコール－ポリテトラメチレングリコール、アクリル酸ポリエチレングリコール－ポリブチレングリコール、大阪有機化学工業（株）製ビスコート＃１９０Ｄ、アクリル酸メトキシポリエチレングリコール（共栄社化学（株）製ライトアクリレート１３０Ａ、新中村化学工業（株）製ＮＫエステルＡＭ－９０Ｇ、ＡＭ１３０Ｇ、ＡＭ－２３０Ｇ、第一製薬工業（株）製ＭＥ－４Ｓ、ＭＰＥ－６００）、アクリル酸メトキシポリプロピレングリコール（新中村化学工業（株）製ＮＫエステルＡＭ－３０ＰＧ）、アクリル酸２－エチルヘキシルポリエチレングリコール（東亞合成（株）製アロニックスＭ－１２０）、アクリル酸オクトキシポリエチレングリコール－ポリプロピレングリコール、アクリル酸ラウロキシポリエチレングリコール、アクリル酸ステアロキシポリエチレングリコール、アクリル酸アリロキシポリエチレングリコール－ポリプロピレングリコール、アクリル酸ウンデシレノキシポリエチレングリコール、（メタ）アクリル酸ω－カルボキシ－ポリカプロラクトン（東亞合成（株）製アロニックスＭ－５３００等）、γ－（アクリロイルオキシプロピル）トリエトキシシラン、アクリル酸２－（パーフルオロヘキシル）エチル（ユニマテック（株）製ＣＨＥＭＩＮＯＸ　ＦＡＡＣ－６）、アクリル酸１Ｈ，１Ｈ，２Ｈ，２Ｈ－ヘプタデカフルオロデシル、アクリル酸２－パーフルオロエチル－２－パーフルオロブチルエチル、アクリル酸２－パーフルオロヘキシルエチル、アクリル酸２－パーフルオロデシルメチル、アクリル酸２－パーフルオロデシルエチル、アクリル酸２－パーフルオロヘキサデシルメチル、アクリル酸２－パーフルオロヘキサデシルエチル、フッ素化エポキシアクリルモノマー（共栄社化学（株）製ＬＩＮＣ－１５１ＥＰＡ）等を挙げることができる。 The monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms is not particularly limited, and various types can be used. Specifically, hexyl acrylate, isohexyl acrylate, heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate , Undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, stearyl acrylate, isostearyl acrylate, oleyl acrylate, behenyl acrylate, 2-acrylate In addition to saturated and unsaturated aliphatics such as decyltetradecanyl, ethyl carbitol acrylate (Biscoat # 190 manufactured by Osaka Organic Chemical Industry Co., Ltd.), 2-ethoxyethoxyethyl acrylate, Crylic acid-ethoxytriethylene glycol, 2-ethylhexyl diethylene glycol acrylate (light acrylate EHDG-AT manufactured by Kyoeisha Chemical Co., Ltd.), ethoxy acrylate-dipropylene glycol, polyethylene glycol acrylate (Blenmer manufactured by NOF Corporation) AE-200, AE-400, AME-400, ALE-200, etc.), polypropylene glycol acrylate (Blenmer AP-150, AP-400, AP-550, AP-800, etc. manufactured by NOF Corporation), acrylic acid Polyethylene glycol-polypropylene glycol, polyethylene glycol acrylate-polytetramethylene glycol, polypropylene glycol acrylate-polytetramethylene glycol, polyethylene glycol acrylate-polybutylene Recall, Osaka Organic Chemical Co., Ltd. Biscoat # 190D, acrylic acid methoxypolyethylene glycol (Kyoeisha Chemical Co., Ltd. Light Acrylate 130A, Shin-Nakamura Chemical Co., Ltd. NK Esters AM-90G, AM130G, AM-230G, Daiichi Pharmaceutical Co., Ltd. ME-4S, MPE-600), methoxypolypropylene glycol acrylate (NK Nakamura Chemical Co., Ltd. NK ester AM-30PG), 2-ethylhexyl polyethylene glycol acrylate (Toagosei Co., Ltd.) Aronix M-120), Octoxy polyethylene glycol acrylate-polypropylene glycol, Lauroxy polyethylene glycol acrylate, Stearoxy polyethylene glycol acrylate, Allyloxy polyethylene glycol acrylate- Polypropylene glycol, undecylenoxypolyethylene glycol acrylate, (meth) acrylic acid ω-carboxy-polycaprolactone (Aronix M-5300 manufactured by Toagosei Co., Ltd.), γ- (acryloyloxypropyl) triethoxysilane, acrylic acid 2- (perfluorohexyl) ethyl (CHEMINOX FAAC-6 manufactured by Unimatec Co., Ltd.), acrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylmethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluorohexadecylmethyl acrylate, 2-perfluorohexadecylethyl acrylate, And fluorinated epoxy acrylic monomer (LINC-151EPA manufactured by Kyoeisha Chemical Co., Ltd.).
これらの中でも硬化性組成物のモノマー臭が軽微であり作業環境性が良好であることから炭素数８～２４の直鎖または分岐炭化水素基を有する単官能アクリル系モノマーが好ましく、さらに、入手が容易で、硬化物の機械強度、耐熱性が優れるという点から、特に好ましい単官能アクリル系モノマーは、アクリル酸ラウリル、アクリル酸イソステアリル、アクリル酸２－デシルテトラデカニル、アクリル酸ポリエチレングリコール（炭化水素基の炭素数が８～２４のもの）、アクリル酸メトキシポリエチレングリコール（炭化水素基の炭素数が８～２４のもの）である。 Among these, a monofunctional acrylic monomer having a linear or branched hydrocarbon group having 8 to 24 carbon atoms is preferable because the monomer odor of the curable composition is slight and the working environment is good. Particularly preferred monofunctional acrylic monomers are lauryl acrylate, isostearyl acrylate, 2-decyltetradecanyl acrylate, polyethylene glycol acrylate (carbonized carbon) because they are easy and have excellent mechanical strength and heat resistance. A hydrogen group having 8 to 24 carbon atoms), and methoxypolyethylene glycol acrylate (a hydrocarbon group having 8 to 24 carbon atoms).
これらは、単独で用いても良いし、２種以上を混合して用いても構わない。 These may be used alone or in combination of two or more.
本発明に用いられる炭素数６以上の直鎖または分岐炭化水素基を有する単官能アクリル系モノマー（ＩＶ）の量は、（メタ）アクリル系重合体（Ｉ）１００重量部に対し５～３０重量部であり、５～２０重量部が好ましい。５重量部より少ない場合には、圧縮永久ひずみ特性の改善効果が低く、３０重量部を超えると引張強さが低下したり、硬化性が低下して硬化物が得られない場合がある。 The amount of the monofunctional acrylic monomer (IV) having a straight chain or branched hydrocarbon group having 6 or more carbon atoms used in the present invention is 5 to 30 weights per 100 weight parts of the (meth) acrylic polymer (I). Parts, preferably 5 to 20 parts by weight. When the amount is less than 5 parts by weight, the effect of improving the compression set characteristics is low. When the amount exceeds 30 parts by weight, the tensile strength may be reduced, or the curability may be lowered and a cured product may not be obtained.
前述のように、種々の紫外線硬化性樹脂を含めたラジカル硬化性樹脂に希釈剤としてアクリロイルモルホリン（ＡＣＭＯ）を添加することは、当業者にとって公知であり、アクリロイルモルホリンの添加による効果としては、プレポリマーに対する溶解性及び希釈性に優れ、かつ低揮発性、低臭気性、低皮膚刺激性でさらに硬化活性に優れる点や、接着性に優れ、塗膜の硬度が高い点等が知られている。 As described above, the addition of acryloylmorpholine (ACMO) as a diluent to radical curable resins including various ultraviolet curable resins is known to those skilled in the art, and the effects of the addition of acryloylmorpholine include pre-treatment. It is known for its excellent solubility and dilutability in polymers, low volatility, low odor, low skin irritation, excellent curing activity, excellent adhesion, and high coating film hardness. .
しかしながら、効果の有無やその程度は添加されるポリマーまたはオリゴマーの主鎖構造や分子量、アクリロイルモルホリンの配合量によって異なることから、これまでに知られていないポリマーやオリゴマー、モノマーと（メタ）アクリロイルモルホリンを組み合わせた場合や、これまで知られていない配合量によってどのような効果を奏するかを予想することは困難であり、ラジカル架橋性基を有する（メタ）アクリル系重合体と（メタ）アクリロイルモルホリンを組み合わせた場合に、硬化物の機械的強度、圧縮永久ひずみ特性に関してどのような効果を及ぼすかは示唆されておらず、さらに（メタ）アクリロイルモルホリンと併せて他のモノマーを併用した場合にどのような効果が及ぼすかを当業者が予測することは困難である。 However, since the presence or absence and the extent of the effect vary depending on the main chain structure and molecular weight of the polymer or oligomer to be added and the amount of acryloylmorpholine added, the polymer, oligomer, monomer and (meth) acryloylmorpholine that have not been known so far It is difficult to predict what effect will be produced by the combination of these compounds or the amount of compound that has not been known so far, (meth) acrylic polymer having a radical crosslinkable group and (meth) acryloylmorpholine There is no suggestion of the effect on the mechanical strength and compression set characteristics of the cured product when combined with other monomers, and what is the effect when other monomers are used in combination with (meth) acryloylmorpholine. It is difficult for those skilled in the art to predict whether such an effect will occur.
本発明者らは、（メタ）アクリロイルモルホリンおよび特定のアクリル系モノマーを一定量組み合わせることにより、硬化物の低温特性を維持したまま、引張強さが向上し、圧縮永久ひずみ特性も同時に改良されることを見出した。 By combining a certain amount of (meth) acryloylmorpholine and a specific acrylic monomer, the inventors improve the tensile strength while maintaining the low-temperature properties of the cured product, and simultaneously improve the compression set properties. I found out.
＜酸化防止剤＞
本発明のラジカル硬化性組成物には、酸化防止剤を使用することもできる。
酸化防止剤（Ｖ）としては特に制限はなく、例えば大成社発行の「酸化防止剤ハンドブック」（昭和５１年１０月２５日初版発行）、シーエムシー出版発行の「高分子添加剤ハンドブック」（春名徹編著、２０１０年１１月７日第１版発行））等に記載された種々のものが挙げられるが、これらに限定されるわけではなく、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、ヒドロキシルアミン系酸化防止剤等の一次酸化防止剤、およびイオウ系酸化剤やリン系酸化剤等の二次酸化防止剤等が使用できる。 <Antioxidant>
An antioxidant can also be used in the radical curable composition of the present invention.
There are no particular restrictions on the antioxidant (V). For example, “Antioxidant Handbook” published by Taiseisha (published on October 25, 1975), “Polymer Additive Handbook” published by CMC Publishing (Haruna) And the like described in Toru Hen, November 7, 2010, first edition)), etc., but are not limited to these, hindered phenol antioxidants, amine antioxidants Primary antioxidants such as lactone-based antioxidants and hydroxylamine-based antioxidants, and secondary antioxidants such as sulfur-based and phosphorus-based antioxidants can be used.
ヒンダードフェノール系酸化防止剤としては、耐熱老化試験後の低着色性に優れ、ゴム弾性の維持に優れている点から分子内にヒンダードフェノール構造あるいは片ヒンダードフェノール構造を有するフェノール系酸化防止剤が好ましい。 As hindered phenolic antioxidants, phenolic antioxidants that have a hindered phenolic structure or a one-hindered phenolic structure in the molecule are excellent in low coloration after heat aging tests and are excellent in maintaining rubber elasticity. Agents are preferred.
具体的には、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－エチルフェノール、モノ（又はジ又はトリ）（α－メチルベンジル）フェノール、２，２’－メチレンビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４メチル－６－ｔｅｒｔ－ブチルフェノール）、４，４’－ブチリデンビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，５－ジ－ｔｅｒｔ－ブチルハイドロキノン、２，５－ジ－ｔｅｒｔ－アミルハイドロキノン、トリエチレングリコール－ビス－［３－（３－ｔ－ブチル－５－メチル－４ヒドロキシフェニル）プロピオネート］、１，６－ヘキサンジオール－ビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，４－ビス－（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルアニリノ）－１，３，５－トリアジン、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，２－チオ－ジエチレンビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ’－ヘキサメチレンビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ヒドロシンナマミド）、３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ベンジルフォスフォネート－ジエチルエステル、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、ビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジルホスホン酸エチル）カルシウム、トリス－（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート、２，４－２，４－ビス［（オクチルチオ）メチル］ｏ－クレゾール、Ｎ，Ｎ’－ビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニル］ヒドラジン、トリス（２，４－ジ－ｔ－ブチルフェニル）フォスファイト、２－（５－メチル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－［２－ヒドロキシ－３，５－ビス（α，α－ジメチルベンジル）フェニル］－２Ｈ－ベンゾトリアゾール、２－（３，５－ジ－ｔ－ブチル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（３－ｔ－ブチル－５－メチル－２－ヒドロキシフェニル）－５－クロロベンゾトリアゾール、２－（３，５－ジ－ｔ－ブチル－２－ヒドロキシフェニル）－５－クロロベンゾトリアゾール、２－（３，５－ジ－ｔ－アミル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔ－オクチルフェニル）－ベンゾトリアゾール、メチル－３－［３－ｔ－ブチル－５－（２Ｈ－ベンゾトリアゾール－２－イル）－４－ヒドロキシフェニル］プロピオネート－ポリエチレングリコール（分子量約３００）との縮合物、ヒドロキシフェニルベンゾトリアゾール誘導体、２－（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－２－ｎ－ブチルマロン酸ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）、２，４－ジ－ｔ－ブチルフェニル－３，５－ジ－ｔ－ブチル－４－ヒドロキシベンゾエート等が挙げられる。 Specifically, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α-methylbenzyl) phenol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [ 3- (3-tert-butyl-5-methyl-4hydroxyphenyl) propionate], 1,6-hexanediol Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t- Butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3 , 5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3 , 5-Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate) Calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N′-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzo Triazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydride Roxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl)- 5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) -benzotriazole, methyl-3 -[3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3 , 5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2, , 6-pentamethyl-4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.
商品名で言えば、ノクラック２００、ノクラックＭ－１７、ノクラックＳＰ、ノクラックＳＰ－Ｎ、ノクラックＮＳ－５、ノクラックＮＳ－６、ノクラックＮＳ－３０、ノクラック３００、ノクラックＮＳ－７、ノクラックＤＡＨ（以上いずれも大内新興化学工業（株）製）、ＭＡＲＫ　ＡＯ－３０、ＭＡＲＫ　ＡＯ－４０、ＭＡＲＫ　ＡＯ－５０、ＭＡＲＫ　ＡＯ－６０、ＭＡＲＫ　ＡＯ－６１６、ＭＡＲＫ　ＡＯ－６３５、ＭＡＲＫ　ＡＯ－６５８、ＭＡＲＫ　ＡＯ－８０、ＭＡＲＫ　ＡＯ－１５、ＭＡＲＫ　ＡＯ－１８、ＭＡＲＫ　３２８、ＭＡＲＫ　ＡＯ－３７（以上いずれもＡＤＥＫＡ社製）、ＩＲＧＡＮＯＸ　２４５、ＩＲＧＡＮＯＸ　２５９、ＩＲＧＡＮＯＸ　５６５、ＩＲＧＡＮＯＸ　１０１０、ＩＲＧＡＮＯＸ　１０２４、ＩＲＧＡＮＯＸ　１０３５、ＩＲＧＡＮＯＸ　１０７６、ＩＲＧＡＮＯＸ　１０８１、ＩＲＧＡＮＯＸ　１０９８、ＩＲＧＡＮＯＸ　１２２２、ＩＲＧＡＮＯＸ　１３３０、ＩＲＧＡＮＯＸ　１４２５ＷＬ（以上いずれもＢＡＳＦジャパン社製）、ＳｕｍｉｌｉｚｅｒＧＭ、ＳｕｍｉｌｉｚｅｒＧＡ－８０（以上いずれも住友化学（株）製）、ＳＯＮＧＮＯＸ１０１０、ＳＯＮＧＮＯＸ１０７６、ＳＯＮＧＮＯＸ１０７７、ＳＯＮＧＮＯＸ１１３５、ＳＯＮＧＮＯＸ２４５０、ＳＯＮＧＮＯＸ３１１４、ＳＯＮＧＮＯＸ１０３５、ＳＯＮＧＮＯＸ１０２４、ＳＯＮＧＮＯＸ１２９０、ＳＯＮＧＮＯＸ２５９０、ＳＯＮＧＮＯＸ１０９８、ＳＯＮＧＮＯＸ４１５０、ＳＯＮＧＮＯＸ４４２５、ＳＯＮＧＮＯＸ２２４６、ＳＯＮＧＮＯＸ２５００、ＳＯＮＧＮＯＸ１３３０、ＳＯＮＧＮＯＸ１７９０、ＳＯＮＧＮＯＸ１５２０（ＳＯＮＧＷＯＮ社製）等が例示できるがこれらに限定されるものではない。 In terms of trade names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Also manufactured by Ouchi Shinsei Chemical Co., Ltd.), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO- 80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all of which are manufactured by ADEKA), IRGANOX 245, IRGANOX 259, IRGANOX 565, IRGANOX 1010, IRGANOX 1024 IRGANOX 1035, IRGANOX 1076, IRGANOX 1081, IRGANOX 1098, IRGANOX 1222, IRGANOX 1330, IRGANOX 1425WL (all manufactured by BASF Japan), Sumizer GM, Sumilizer GA-80 (all manufactured by Sumitomo Chemical 10 G, NO X 10 manufactured by Sumitomo Chemical ON G 10) , SONGNOX1077, SONGNOX1135, SONGNOX2450, SONGNOX3114, SONGNOX1035, SONGNOX1024, SONGNOX1290, SONGNOX2590, SONGNOX1098, SONGNOX4150, SONGNOX4246, , SONGNOX1330, SONGNOX1790, SONGNOX1520 (SONGWON Co.) or the like can be but is not limited to these examples.
耐熱老化性がより向上する点から、フェノール系酸化防止剤の分子量が６００以上であるテトラキス－［メチレン－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン（ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］）、トリス－［（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）］イソシアヌレート、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、３，９－ビス｛２－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］－１，１－ジメチルエチル｝－２，４，８，１０－テトラオキサスピロ［５，５］ウンデカン（ＳｕｍｉｌｉｚｅｒＧＡ－８０）がより好ましい。 Tetrakis- [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (penta) in which the molecular weight of the phenolic antioxidant is 600 or more from the point that heat aging resistance is further improved Erythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]), tris-[(3,5-di-tert-butyl-4-hydroxybenzyl)] isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9-bis {2- [3- (3-tert-butyl -4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane ( umilizerGA-80) is more preferable.
アミン系酸化防止剤については、特に限定されず、アミン－ケトン系化合物や芳香族系アミン化合物などの従来公知のものを広く使用できる。
アミン－ケトン系化合物としては、２，２，４－トリメチル－１，２－ジヒドロキノリン重合体、６－エトキシ－１，２－ジヒドロ－２，２，４－トリメチルキノリン、ジフェニルアミンとアセトンの反応物等が挙げられる。具体的に商品名を挙げると、ノクラック２２４、ノクラックＡＷ、ノクラックＡＷ－Ｎ、ノクラックＢ、ノクラックＢ－Ｎ（以上いずれも大内新興化学工業（株）製）、アンテージＲＤ、アンテージＲＤ－Ｇ、アンテージＡＷ（以上いずれも川口化学工業（株）製）、ノンフレックスＲＤ、ノンフレックスＱＳ、ノンフレックスＡＷ、ノンフレックスＢＡ、ノンフレックスＢＡ－Ｐ、ノンフレックスＢＡＲ（以上いずれも精工化学（株）製）、ブルカノックスＨＳ／ＬＧ、ブルカノックスＨＳ／粉末（以上いずれもバイエル社製）、ＫｏｒｅｓｔａｂＴＭＱ（エスアンドエスジャパン社製）、アミノックス（白石カルシウム（株）製）等が例示できるがこれらに限定されるものではない。 The amine-based antioxidant is not particularly limited, and conventionally known ones such as amine-ketone compounds and aromatic amine compounds can be widely used.
Examples of amine-ketone compounds include 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and a reaction product of diphenylamine and acetone. Etc. Specific product names include Nocrack 224, Nocrack AW, Nocrack AW-N, Nocrack B, Nocrack BN (all of which are manufactured by Ouchi Shinsei Chemical Co., Ltd.), Antage RD, Antage RD-G, Antage AW (all manufactured by Kawaguchi Chemical Industry Co., Ltd.), Nonflex RD, Nonflex QS, Nonflex AW, Nonflex BA, Nonflex BA-P, Nonflex BAR (all manufactured by Seiko Chemical Co., Ltd.) ), Vulcanox HS / LG, Vulcanox HS / powder (all manufactured by Bayer), KorestabTMQ (manufactured by S & S Japan), Aminox (manufactured by Shiraishi Calcium Co., Ltd.) and the like, but are not limited thereto. It is not a thing.
芳香族系アミン化合物としては、ナフチルアミン系酸化防止剤、ジフェニルアミン系酸化防止剤、およびｐ－フェニレンジアミン系酸化防止剤が挙げられる。具体的に例示すれば、フェニル－α－ナフチルアミン等のナフチルアミン系酸化防止剤；ｐ－（ｐ－トルエンスルホニルアミド）ジフェニルアミン、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン、４，４’－ジスチリルジフェニルアミン、４，４’－ジオクチルジフェニルアミン、オクチル化ジフェニルアミン、ジフェニルアミンとジイソブチレンの反応物、アルキル化ジフェニルアミン、ｐ－イソプロポキシ－ジフェニルアミン、ビス（フェニル－イソプロピリデン）－４，４－ジフェニルアミン、４－（α－フェニルエチル）ジフェニルアミン、４，４’－ビス（α－フェニルエチル）ジフェニルアミン、スチレン化ジフェニルアミン、ジ－ｔｅｒｔ－ブチルジフェニルアミン、ジフェニルアミン誘導体等のジフェニルアミン系酸化防止剤；Ｎ，Ｎ’－ジフェニル－ｐ－フェニレンジアミン、Ｎ－イソプロピル－Ｎ’－フェニル－ｐ－フェニレンジアミン、Ｎ，Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミン、Ｎ－フェニル－Ｎ’－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミン、４－（アニリノフェニル）メタクリルアミド、４－（メルカプトアセトアミド）ジフェニルアミン、２－〔（メルカプトアセチル）オキシ〕エチル－３－［〔４－（フェニルアミノ）フェニル〕アミノ］ブタネート、Ｎ，Ｎ’－ビス（１－メチルへプチル）－ｐ－フェニレンジアミ、Ｎ，Ｎ－ビス（１，４－ジメチルペンチル）－ｐ－フェニレンジアミン、Ｎ－（１，３－ジメチルブチル）－Ｎ’－フェニル－ｐ－フェニレンジアミン、Ｎ－シクロへキシル－Ｎ’－フェニル－ｐ－フェニレンジアミン、２，４，６－トリス（Ｎ－１，４－ジメチルペンチル－ｐ－フェニレンジアミノ）１，３，５－トリアジン、ジアリル－ｐ－フェニレンジアミン混合物、フェニル－オクチル－ｐ－フェニレンジアミン等のｐ－フェニレンジアミン系酸化防止剤等が挙げられる。具体的に商品名を挙げると、ノクラックＰＡ、ノクラックＯＤＡ、ノクラックＯＤＡ－Ｎ、ノクラックＡＤ－Ｆ、ノクラックＣＤ、ノクラックＴＤ、ノクラックＷｈｉｔｅ、ノクラックＤＰ、ノクラック８１０－ＮＡ、ノクラック６Ｃ、ノクラックＧ－１、ノクラック５００（以上いずれも大内新興化学工業（株）製）、アンテージＯＤ、アンテージＬＤＡ、アンテージＤＤＡ、アンテージ３Ｃ、アンテージ６Ｃ、アンテージＳＴＤＰ－Ｎ、アンテージＢＣ（以上いずれも川口化学工業（株）製）、ノンフレックスＯＤ－Ｒ、ノンフレックスＢＡ、ノンフレックスＢＡＲ、ノンフレックスＯＤ－３、ノンフレックスＤＣＤ、ノンフレックスＨ、ノンフレックスＦ、ノンフレックス３ＣＨ、ノンフレックスＬＡＳ－Ｐ、ステアラーＬＡＳ、ステアラーＳＴＡＲ、オゾノン３Ｃ、オゾノン６Ｃ、オゾノン３５、オゾノン３５－ＰＲ、オゾノン３Ｗ（以上いずれも精工化学（株）製）、ブルカノックスＯＣＤ／ＳＧ、ブルカノックス４０１０ＮＡ、ブルカノックス４０３０、ブルカノックス４０２０／ＬＧ、ブルカノックス３１００、レノグランＩＰＰＤ（以上いずれもバイエル社製）、ナウガードＰＡＮＡ、アラノックス、ナウガード４４５（以上いずれもケムチュラ社製）、ＩＲＧＡＮＯＸ　５０５７、イルガゾーン９９７（ＢＡＳＦジャパン社製）、Ｗｉｎｇｓｔａｙ２９（米国貿易社製）、スミライザー９Ａ、アンチゲン３Ｃ（以上いずれも住友化学（株）製）、パーマナックスＩＰＰＤ、サントフレックス４４、サントフレックス６ＰＰＤ（フレキシス社製）等が例示できるがこれらに限定されるものではない。 Examples of aromatic amine compounds include naphthylamine antioxidants, diphenylamine antioxidants, and p-phenylenediamine antioxidants. Specific examples include naphthylamine antioxidants such as phenyl-α-naphthylamine; p- (p-toluenesulfonylamido) diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, 4,4 '-Distyryldiphenylamine, 4,4'-dioctyldiphenylamine, octylated diphenylamine, reaction product of diphenylamine and diisobutylene, alkylated diphenylamine, p-isopropoxy-diphenylamine, bis (phenyl-isopropylidene) -4,4-diphenylamine 4- (α-phenylethyl) diphenylamine, 4,4′-bis (α-phenylethyl) diphenylamine, styrenated diphenylamine, di-tert-butyldiphenylamine, diphenylamine derivatives, etc. Amine antioxidants; N, N′-diphenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N, N′-di-2-naphthyl-p-phenylenediamine, N— Phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, 4- (anilinophenyl) methacrylamide, 4- (mercaptoacetamido) diphenylamine, 2-[(mercaptoacetyl) oxy] ethyl -3-[[4- (Phenylamino) phenyl] amino] butanate, N, N'-bis (1-methylheptyl) -p-phenylenediam, N, N-bis (1,4-dimethylpentyl) -P-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N Cyclohexyl-N′-phenyl-p-phenylenediamine, 2,4,6-tris (N-1,4-dimethylpentyl-p-phenylenediamino) 1,3,5-triazine, diallyl-p-phenylenediamine Examples thereof include a mixture and a p-phenylenediamine-based antioxidant such as phenyl-octyl-p-phenylenediamine. Specific product names include Nocrack PA, Nocrack ODA, Nocrack ODA-N, Nocrack AD-F, Nocrack CD, Nocrack TD, Nocrack White, Nocrack DP, Nocrack 810-NA, Nocrack 6C, Nocrack G-1, NOCRACK 500 (all of which are manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), ANTAGE OD, ANTAGE LDA, ANTAGE DDA, ANTAGE 3C, ANTAGE 6C, ANTAGE STDP-N, ANTAGE BC (all of which are manufactured by Kawaguchi Chemical Industry Co., Ltd.) ), Non-flex OD-R, non-flex BA, non-flex BAR, non-flex OD-3, non-flex DCD, non-flex H, non-flex F, non-flex 3CH, non-flex LAS-P, steerer LAS, steer LA STAR, Ozonon 3C, Ozonon 6C, Ozonon 35, Ozonon 35-PR, Ozonon 3W (all manufactured by Seiko Chemical Co., Ltd.), Vulcanox OCD / SG, Vulcanox 4010NA, Vulcanox 4030, Vulcanox 4020 / LG , Vulcanox 3100, Renogran IPPD (all manufactured by Bayer), Nowguard PANA, Alanox, Nowguard 445 (all manufactured by Chemtura), IRGANOX 5057, Irgazone 997 (BASF Japan), Wingstay 29 (made by US Trading Company) ), Sumilizer 9A, Antigen 3C (all of which are manufactured by Sumitomo Chemical Co., Ltd.), Permanax IPPD, Santoflex 44, Santoflex 6PPD (manufactured by Flexis), etc. The present invention is not limited to these.
これらの中でも、耐熱性に優れる点から、４，４’－ビス（α，α－ジメチルベンジル）ジフェニルアミン、Ｎ，Ｎ’－ジ－２－ナフチル－ｐ－フェニレンジアミン、Ｎ－フェニル－Ｎ’－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）－ｐ－フェニレンジアミンがより好ましい。 Among these, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine, N-phenyl-N′-, because of its excellent heat resistance. (3-Methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine is more preferred.
ラクトン系酸化防止剤、ヒドロキシルアミン系酸化防止剤等の具体例としては、５，７－ジ－ｔ－ブチル－３－（３，４－ジメチルフェニル）－３Ｈ－ベンゾフラン－２－オン）（イルガノックスＨＰ－１３６、ＢＡＳＦジャパン社製）、ＩＲＧＡＳＴＡＢ　ＦＳ　０４２およびそれを含むブレンド物（ＢＡＳＦジャパン社製）、ＧＥＮＯＸ　ＥＰ（クロンプトン社製）などの市販品を挙げることができる。 Specific examples of lactone antioxidants, hydroxylamine antioxidants and the like include 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one) (IRGA Commercial products such as Knox HP-136 (manufactured by BASF Japan), IRGASTAB FS 042 and blends containing it (manufactured by BASF Japan), and GENOX EP (manufactured by Crompton) can be mentioned.
イオウ系酸化剤については、特に限定されず、従来公知のものを広く使用できる。具体例としては、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、ジラウリル－チオジプロピオネート、ビス｛２－メチル－４－［３－ｎ－アルキル（Ｃ１２またはＣ１４）チオプロピオニルオキシ］－５－ｔｅｒｔ－ブチルフェニル｝スルフィド、ペンタエリスリチル－テトラキス（３－ラウリルチオプロピオネート）、ジトリデシル－３，３’－チオジプロピオネート、ジステアリル－チオジプロピオネート、２，２－チオ－ジエチレンビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、４，６－ビス［（オクチルチオ）メチル］ｏ－クレゾール、２，４－ビス－（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルアニリノ）－１，３，５－トリアジン、ジミリスチル－３，３’－チオジプロピオネート、ジブチルメチレン－ビス－チオグルコレート等が挙げられる。商品名で言えば、ノクラック３００、ノクラック４００（以上いずれも大内新興化学工業（株）製）アデカスタブＡＯ－２３、ＡＯ－４１２Ｓ、ＡＯ－５０３Ａ、（以上いずれもＡＤＥＫＡ社製）、ＩＲＧＡＮＯＸ　ＰＳ８００ＦＬ、ＩＲＧＡＮＯＸ　ＰＳ８０２ＦＬ、ＩＲＧＡＮＯＸ　１０３５、ＩＲＧＡＮＯＸ　１５２０Ｌ、ＩＲＧＡＮＯＸ　５６５（以上いずれもＢＡＳＦジャパン社製）、スミライザーＴＰＬ－Ｒ、スミライザーＴＰＳ、スミライザーＴＰＭ、スミライザーＷＸ－Ｒ、スミライザーＴＰ－Ｄ（以上いずれも住友化学（株）製）、シーノックスＢＣＳ（シプロ化成（株）製）、ブルカノール８８（バイエル社製）、ＳＯＮＧＮＯＸ４１２０、ＳＯＮＧＮＯＸ　ＤＬＴＤＰ、ＳＯＮＧＮＯＸ　ＤＭＴＤＰ、ＳＯＮＧＮＯＸ　ＤＳＴＤＰ、ＳＯＮＧＮＯＸ　ＤＴＤＴＰ（ＳＯＮＧＷＯＮ社製）等が例示できるがこれらに限定されるものではない。 About a sulfur type oxidizing agent, it does not specifically limit and a conventionally well-known thing can be used widely. Specific examples include 4,4′-thiobis (3-methyl-6-tert-butylphenol), dilauryl-thiodipropionate, bis {2-methyl-4- [3-n-alkyl (C12 or C14) thio. Propionyloxy] -5-tert-butylphenyl} sulfide, pentaerythrityl-tetrakis (3-laurylthiopropionate), ditridecyl-3,3′-thiodipropionate, distearyl-thiodipropionate, 2, 2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,6-bis [(octylthio) methyl] o-cresol, 2,4-bis- ( n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, Myristyl-3,3'-thiodipropionate, di-butyl methylene - bis - thioglycolate, and the like. In terms of product names, Nocrack 300, Nocrack 400 (all of which are manufactured by Ouchi Shinsei Chemical Co., Ltd.) ADK STAB AO-23, AO-412S, AO-503A (all of which are manufactured by ADEKA), IRGANOX PS800FL, IRGANOX PS802FL, IRGANOX 1035, IRGANOX 1520L, IRGANOX 565 (all of which are manufactured by BASF Japan Ltd.), Sumilyzer TPL-R, Sumilyzer TPS, Sumilyzer TPM, Sumilyzer WX-R, Sumilyzer TP-D (all of which are Sumitomo Chemical Co., Ltd.) ), Sinox BCS (manufactured by Cypro Kasei Co., Ltd.), Vulcanol 88 (manufactured by Bayer), SONGNOX 4120, SONGNOX DLTDP, SONGNOX DMTDP, SONGNOX DSTDP, SONGNOX DTDTP (manufactured SONGWON Corporation) does not can be exemplified as being limited thereto.
リン系酸化剤については、特に限定されず、従来公知のものを広く使用できるが、活性水素を含むリン酸およびリン酸エステルは組成物の貯蔵安定性、硬化物の耐熱性に影響を与えることから、リン酸およびリン酸エステルを分子内に含まない、アルキルホスファイト、アリールホスファイト、アルキルアリールホスファイト化合物などが好ましい。このようなリン系酸化防止剤の具体例としては、トリス（ノニルフェニル）ホスファイト、トリス（モノ，ジノニルフェニル）ホスファイト、ジフェニル，モノ（２－エチルヘキシル）ホスファイト、ジフェニル，モノ（トリデシル）ホスファイト、ジフェニル，モノ（イソデシル）ホスファイト、ジフェニル，モノ（イソオクチル）ホスファイト、ジフェニル，モノ（ノニルフェニル）ホスファイト、トリフェニルホスファイト、トリス（トリデシル）ホスファイト、トリイソデシルホスファイト、トリス（２－エチルヘキシル）ホスファイト、トリラウリルホスファイト、トリオレイルホスファイト、トリステアリルホスファイト、トリス（２，４－ジーｔ－ブチルフェニル）ホスファイト、テトラフェニルジプロピレングリコールージホスファイト、テトラフェニルテトラ（トリデシル）ペンタエリスリトール－テトラホスファイト、１，１，３－トリス（２－メチル－４－ジートリデシルホスファイト－５－ｔ－ブチルフェニル）ブタン、４，４’－ブチリデンビス（３－メチル－６－ｔ－ブチル－ジ－トリデシルホスファイト）、２，２’－メチレンビス（４，６－ジ－ｔ－ブチルフェノール）オクチルホスファイト、４，４’－イソプロピリデン－ジフェノールアルキル（Ｃ１２～Ｃ１５）ホスファイト、環状ネオペンタンテトライルビス（２，４－ジ－ｔ－ブチルフェニルホスファイト）、環状ネオペンタンテトライルビス（２，６－ジ－ｔ－ブチル－４－メチルフェニルホスファイト）、環状ネオペンタンテトライルビス（ノニルフェニルホスファイト）、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ジステアリル，ペンタエリスリトール，ジホスファイト、ビス［２，４－ビス（１，１’－ジメチルエチル）－６－メチルフェニル］エチルエステルホスファイト等が挙げられる。商品名で言えば、アデカスタブ１１７８、アデカスタブ３２９Ｋ、アデカスタブ１３５Ａ、アデカスタブＣ、アデカスタブＴＰＰ、アデカスタブ３０１０、アデカスタブ２１１２、アデカスタブ５２２Ａ、アデカスタブ２６０、アデカスタブＨＰ－１０、アデカスタブ１５００、アデカスタブＰＥＰ－２４－Ｇ、アデカスタブＰＥＰ－３６、アデカスタブＰＥＰ－４Ｃ、アデカスタＰＥＰ－８（以上いずれもＡＤＥＫＡ社製）、ＪＰＭ－３０８、ＪＰＭ－３１３、ＪＰＭ－３３３Ｅ、ＪＰＰ－１００、ＪＰＰ－６１３Ｍ、ＪＰＰ－３１、ＪＰ－３５１、ＪＰ－３０８Ｅ、ＪＰ－３１０、ＪＰ－３１２Ｌ、ＪＰ－３３３Ｅ、ＪＰ－３１８Ｏ、ＪＰ－３１８Ｅ（以上いずれも城北化学工業（株）製）、ＧＳＹ－Ｐ１０１（堺化学工業（株）製）、ＩＲＧＡＦＯＳ１６８、ＩＲＧＡＦＯＳ１２、ＩＲＧＡＦＯＳ１２６、ＩＲＧＡＦＯＳ３８、ＩＲＧＡＦＯＳ　Ｐ－ＥＰＱ（（ＢＡＳＦジャパン社製）、ＳＯＮＧＮＯＸ１６８０、ＳＯＮＧＮＯＸ６２６０、ＳＯＮＧＮＯＸ６２８０、ＳＯＮＧＮＯＸ　ＤＨＯＰ、ＳＯＮＧＮＯＸ　ＤＰＤＰ、ＳＯＮＧＮＯＸ　ＥＨＤＰＰ、ＳＯＮＧＮＯＸ　ＰＱ、ＳＯＮＧＮＯＸ　ＴＰＰ（ＳＯＮＧＷＯＮ社製）、Ｕｌｔｒａｎｏｘ　６４１（ＧＥ　Ｓｐｅｃｉａｌｔｙ　Ｃｈｅｍｉｃａｌｓ社製）等が例示できるがこれらに限定されるものではない。 There are no particular limitations on the phosphorus-based oxidizing agent, and conventionally known ones can be widely used. However, phosphoric acid and phosphoric acid ester containing active hydrogen affect the storage stability of the composition and the heat resistance of the cured product. Therefore, an alkyl phosphite, an aryl phosphite, an alkyl aryl phosphite compound and the like that do not contain phosphoric acid and phosphate ester in the molecule are preferable. Specific examples of such phosphorus antioxidants include tris (nonylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, diphenyl, mono (2-ethylhexyl) phosphite, diphenyl, mono (tridecyl) Phosphite, diphenyl, mono (isodecyl) phosphite, diphenyl, mono (isooctyl) phosphite, diphenyl, mono (nonylphenyl) phosphite, triphenyl phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, tris (2-ethylhexyl) phosphite, trilauryl phosphite, trioleyl phosphite, tristearyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetraphenyldipropylene glycol Sphite, tetraphenyltetra (tridecyl) pentaerythritol-tetraphosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-t-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-t-butyl-di-tridecyl phosphite), 2,2'-methylenebis (4,6-di-t-butylphenol) octyl phosphite, 4,4'-isopropylidene-diphenol Alkyl (C12-C15) phosphite, cyclic neopentanetetrayl bis (2,4-di-tert-butylphenyl phosphite), cyclic neopentanetetrayl bis (2,6-di-tert-butyl-4-methyl) Phenyl phosphite), cyclic neopentanetetrayl bis (nonylphenyl phosphite), bis ( Nirufeniru) pentaerythritol diphosphite, distearyl pentaerythritol, diphosphite, bis [2,4-bis (1,1'-dimethylethyl) -6-methylphenyl] ethyl ester phosphite, and the like. In terms of product names, ADK STAB 1178, ADK STAB 329K, ADK STAB 135A, ADK STAB C, ADK STAB TPP, ADK STAB 3010, ADK STAB 2112, ADK STAB 522A, ADK STAB 260, ADK STAB HP-10, ADK STAB 1500, ADK STAB PEP-24PE, -36, ADK STAB PEP-4C, ADEKASTA PEP-8 (all of which are manufactured by ADEKA), JPM-308, JPM-313, JPM-333E, JPP-100, JPP-613M, JPP-31, JP-351, JP -308E, JP-310, JP-312L, JP-333E, JP-318O, JP-318E (all manufactured by Johoku Chemical Industry Co., Ltd.), GSY-P101 (manufactured by Sakai Chemical Industry Co., Ltd.), RGAFOS168, IRGAFOS12, IRGAFOS126, IRGAFOS38, IRGAFOS P-EPQ (manufactured by BASF Japan), SONGNOX1680, SONGNOX6260, SONGNOX6DP, SONGNOXDONGTP, SONGNOXEHDPP (Specialty Chemicals) and the like can be exemplified, but not limited thereto.
リン系酸化防止剤の中でも、加水分解性に対して安定であり耐熱性が良い点で、リン原子の置換基の全てに炭素数８以上の炭化水素基を有することが好ましい。具体的には、トリス（ノニルフェニル）ホスファイト、トリス（モノ，ジノニルフェニル）ホスファイト、トリス（トリデシル）ホスファイト、トリイソデシルホスファイト、トリス（２－エチルヘキシル）ホスファイト、トリラウリルホスファイト、トリオレイルホスファイト、トリステアリルホスファイトが好ましい。 Among phosphorus-based antioxidants, it is preferable that all of the substituents of the phosphorus atom have a hydrocarbon group having 8 or more carbon atoms from the viewpoint of being stable with respect to hydrolyzability and having good heat resistance. Specifically, tris (nonylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, tris (2-ethylhexyl) phosphite, trilauryl phosphite , Trioleyl phosphite and tristearyl phosphite are preferable.
これらの酸化防止剤は単独で使用してもよく、２種以上併用しても構わない。特にヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、ヒドロキシルアミン系酸化防止剤等の一次酸化防止剤と、イオウ系酸化剤やリン系酸化剤等の二次酸化防止剤を組み合わせることで卓越した耐熱性能が発揮されることが当業者の間ではよく知られている。 These antioxidants may be used alone or in combination of two or more. In particular, primary antioxidants such as hindered phenol antioxidants, amine antioxidants, lactone antioxidants, hydroxylamine antioxidants, and secondary antioxidants such as sulfur and phosphorus antioxidants. It is well known among those skilled in the art that an excellent heat resistance performance is exhibited by combining agents.
酸化防止剤の使用量としては特に制限はないが、（メタ）アクリル系重合体（Ｉ）１００重量部に対し、０．１～１０重量部が好ましく、０．１～５重量部がさらに好ましい。配合量が０．１重量部未満の場合には、耐熱老化性の改善効果が充分でないことがあり、１０重量部を超えるとラジカル硬化性が低下する場合があり、また硬化性組成物より得られる硬化物の着色が著しくなることがある。 The amount of the antioxidant used is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (I). . When the blending amount is less than 0.1 parts by weight, the effect of improving the heat aging resistance may not be sufficient. When the blending amount exceeds 10 parts by weight, the radical curability may be lowered, and it is obtained from the curable composition. The resulting cured product may be markedly colored.
＜硬化性組成物＞
本発明の硬化性組成物においては、目的とする物性に応じて、各種の配合剤を添加しても構わない。
＜反応性希釈剤＞
本発明の硬化性組成物には、粘度低減による作業性の向上や、硬化物物性の改良等を目的として、炭素数６以上の直鎖または分岐炭化水素基を有する単官能アクリル系モノマー（ＩＶ）とは異なる、ラジカル重合性基を有するモノマー類を反応性希釈剤として使用することもできる。 <Curable composition>
In the curable composition of the present invention, various compounding agents may be added according to the intended physical properties.
<Reactive diluent>
The curable composition of the present invention includes a monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms for the purpose of improving workability by reducing viscosity and improving physical properties of a cured product. Monomers having radically polymerizable groups, which are different from), can also be used as reactive diluents.
前記ラジカル重合性の基としては、（メタ）アクリル基、スチレン基、アクリロニトリル基、ビニルエステル基、Ｎ－ビニルピロリドン基、共役ジエン基、ビニルケトン基、塩化ビニル基等が挙げられる。なかでも、本発明に使用する（メタ）アクリル系重合体（Ｉ）で使用されるラジカル架橋性基と類似する（メタ）アクリロイル系基、アクリルアミド基を有するものが好ましい。 Examples of the radical polymerizable group include (meth) acryl group, styrene group, acrylonitrile group, vinyl ester group, N-vinyl pyrrolidone group, conjugated diene group, vinyl ketone group, vinyl chloride group and the like. Among these, those having a (meth) acryloyl group and an acrylamide group similar to the radical crosslinkable group used in the (meth) acrylic polymer (I) used in the present invention are preferable.
前記モノマーの具体例としては、（メタ）アクリル系モノマー、スチレン系モノマー、アクリロニトリル、ビニルエステル系モノマー、Ｎ－ビニルピロリドン、共役ジエン系モノマー、ビニルケトン系モノマー、ハロゲン化ビニル・ハロゲン化ビニリデン系モノマー、多官能モノマー等が挙げられる。 Specific examples of the monomer include (meth) acrylic monomer, styrene monomer, acrylonitrile, vinyl ester monomer, N-vinylpyrrolidone, conjugated diene monomer, vinyl ketone monomer, vinyl halide / vinylidene halide monomer, A polyfunctional monomer etc. are mentioned.
（メタ）アクリル系モノマーとしては、前述の（メタ）アクリル系重合体（Ｉ）に用いられる（メタ）アクリル系モノマーが挙げられる。 Examples of the (meth) acrylic monomer include (meth) acrylic monomers used in the above-mentioned (meth) acrylic polymer (I).
スチレン系モノマーとしては、スチレン、α－メチルスチレン等が挙げられる。 Examples of the styrene monomer include styrene and α-methylstyrene.
ビニルエステル系モノマーとしては、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル等が挙げられる。 Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl butyrate.
共役ジエン系モノマーとしては、ブタジエン、イソプレン等が挙げられる。ビニルケトン系モノマーとしては、メチルビニルケトン等が挙げられる。 Examples of the conjugated diene monomer include butadiene and isoprene. Examples of the vinyl ketone monomer include methyl vinyl ketone.
ハロゲン化ビニル・ハロゲン化ビニリデン系モノマーとしては、塩化ビニル、臭化ビニル、ヨウ化ビニル、塩化ビニリデン、臭化ビニリデン等が挙げられる。 Examples of the vinyl halide / vinylidene halide monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.
２官能性以上の多官能モノマーとしては、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、１，６－へキサンジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，２－エタンジオールジ（メタ）アクリレート等の飽和炭化水素ジオールのジ（メタ）アクリレート；ネオペンチルグリコールポリエトキシジ（メタ）アクリレート、ネオペンチルグリコールポリプロポキシジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ポリエチレングリコール－ポリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコール－ポリテトラメチレングリコールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ポリテトラメチレングリコールジ（メタ）アクリレート、ジメチロールトリシクロデカンジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、ビスフェノールＡジエトキシジ（メタ）アクリレート、ＥＯ変性ビスフェノールＡジ（メタ）アクリレート、ＰＯ変性ビスフェノールＡジ（メタ）アクリレート、ＰＯ－ＥＯ変性ビスフェノールＡジ（メタ）アクリレート、テトラブロモビスフェノールＡジエトキシジ（メタ）アクリレート、４，４－ジメルカプトジフェニルサルファイドジ（メタ）アクリレート、ビスフェノールＦポリエトキシジ（メタ）アクリレート、ビスフェノールＡポリエトキシジ（メタ）アクリレート、２－（２－（メタ）アクリロイルオキシ－１，１－ジメチル）－５－エチル－５－アクリロイルオキシメチル－１，３－ジオキサン、２－［５－エチル－５－［（アクリロイルオキシ）メチル］－１，３－ジオキサン－２－イル］－２，２－ジメチルエチル、１，１－（ビス（メタ）アクリロイルオキシメチル）エチルイソシアネート等の２官能の（メタ）アクリレート化合物；トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、トリメチロールプロパンポリプロポキシトリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、イソシアヌル酸トリ（メタ）アクリレート、エトキシ化イソシアヌル酸トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート等の３官能（メタ）アクリレート化合物；ジペンタエリスリトールヘキサ（メタ）アクリレート、トリス（ヒドロキシエチル）イソシアヌレートポリヘキサノリドトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート等の多官能（メタ）アクリレート化合物が挙げられる。 Examples of the bifunctional or higher polyfunctional monomer include 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,6-hexanedi (meth) acrylate, neopentyl glycol di Di (meta) of saturated hydrocarbon diols such as (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,2-ethanediol di (meth) acrylate, etc. ) Acrylate; neopentyl glycol polyethoxy di (meth) acrylate, neopentyl glycol polypropoxy di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol-polypropylene glycol di (Meth) acrylate, polypropylene glycol-polytetramethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, cyclohexanedimethanol di ( (Meth) acrylate, bisphenol A diethoxydi (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, PO-EO modified bisphenol A di (meth) acrylate, tetrabromobisphenol A diethoxydi ( (Meth) acrylate, 4,4-dimercaptodiphenyl sulfide di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate Bisphenol A polyethoxydi (meth) acrylate, 2- (2- (meth) acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1,3-dioxane, 2- [5-ethyl-5 -[(Acryloyloxy) methyl] -1,3-dioxan-2-yl] -2,2-dimethylethyl, bifunctional (meth) such as 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate Acrylate compound; trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, isocyanuric acid tri (meth) acrylate Ethoxylated isocyanate Trifunctional (meth) acrylate compounds such as anuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate and glycerin tri (meth) acrylate; dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate polyhexa Examples thereof include polyfunctional (meth) acrylate compounds such as noridotri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate.
オリゴマーとしては、ビスフェノールＡ型エポキシアクリレート樹脂、フェノールノボラック型エポキシアクリレート樹脂、クレゾールノボラック型エポキシアクリレート樹脂、ＣＯＯＨ基変性エポキシアクリレート系樹脂等のエポキシアクリレート系樹脂；ポリオール（ポリテトラメチレングリコール、エチレングリコールとアジピン酸のポリエステルジオール、ε－カプロラクトン変性ポリエステルジオール、ポリプロピレングリコール、ポリエチレングリコール、ポリカーボネートジオール、水酸基末端水添ポリイソプレン、水酸基末端ポリブタジエン、水酸基末端水添ポリブタジエン、水酸基末端ポリイソブチレン等）と有機イソシアネート（トリレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート等）から得られたウレタン樹脂を、水酸基含有（メタ）アクリレート｛ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ペンタエリスリトールトリアクリレート等｝と反応させて得られたウレタンアクリレート系樹脂；前記ポリオールにエステル結合を介して（メタ）アクリル基を導入した樹脂（大阪有機化学工業（株）製ＢＡＣ－１５、ＢＡＣ－４５、ＳＰＢＤＡ－Ｓ３０等）；ポリエステルアクリレート系樹脂、不飽和ポリエステル樹脂、ポリ（メタ）アクリルアクリレート系樹脂（重合性の反応基を有するポリ（メタ）アクリル酸エステル系樹脂）等の一般的なＵＶ硬化性樹脂や酸素硬化性樹脂、片末端に（メタ）アクリロイル基を有するメチルメタクリレート樹脂、スチレン樹脂、スチレン／アクリロニトリル樹脂、ポリブチルアクリレート、ポリイソブチルメタクリレート、メチルメタクリレート／ヒドロキシエチルメタクリレート共重合樹脂、２－エチルヘキシルメタクリレート／ヒドロキシエチルメタクリレート共重合樹脂、シリコーン樹脂等のいわゆるマクロモノマー等が挙げられる。 As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin; polyol (polytetramethylene glycol, ethylene glycol and adipine) Polyester diol of acid, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated polyisobutylene) and organic isocyanate (tolylene diene) Isocyanate, isophorone diisocyanate, diphenylmethane diisocyanate Urethane resin obtained from silicate, hexamethylene diisocyanate, xylylene diisocyanate, etc.) with hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol A urethane acrylate resin obtained by reacting with a triacrylate, etc .; a resin in which a (meth) acrylic group is introduced into the polyol via an ester bond (BAC-15, BAC-45, manufactured by Osaka Organic Chemical Industry Co., Ltd.) SPBDA-S30, etc.): General UV curable such as polyester acrylate resin, unsaturated polyester resin, poly (meth) acryl acrylate resin (poly (meth) acrylate resin having a polymerizable reactive group) Resin and oxygen Curable resin, methyl methacrylate resin having (meth) acryloyl group at one end, styrene resin, styrene / acrylonitrile resin, polybutyl acrylate, polyisobutyl methacrylate, methyl methacrylate / hydroxyethyl methacrylate copolymer resin, 2-ethylhexyl methacrylate / hydroxy Examples include so-called macromonomers such as ethyl methacrylate copolymer resin and silicone resin.
反応性希釈剤を添加する場合の添加量は特に制限はないが、硬化性組成物の作業性が良好で、硬化収縮率への影響が小さい点から、（メタ）アクリル系重合体（Ｉ）１００重量部に対して、０．１～２００重量部が好ましく、０．１～１００重量部がさらに好ましい。 The addition amount in the case of adding a reactive diluent is not particularly limited, but the (meth) acrylic polymer (I) is advantageous in that the workability of the curable composition is good and the influence on the curing shrinkage rate is small. The amount is preferably 0.1 to 200 parts by weight, more preferably 0.1 to 100 parts by weight with respect to 100 parts by weight.
＜充填剤＞
本発明のラジカル硬化性組成物には、機械的強度や耐摩耗性を付与したり、硬化性組成物のチクソ性を調整したりするために、充填剤を添加することができる。具体的には、特開２００６－２９１０７３号公報段落［０１３４］～［０１５１］記載の各種充填剤や微小中空粒子が挙げられる。
充填剤としては、ヒュームドシリカ、湿式法シリカ等の補強性シリカとして用いられる微粉シリカ、カーボンブラック、木粉、パルプ、木綿チップ、マイカ、クルミ殻粉、もみ殻粉、グラファイト、白土、シリカ（結晶性シリカ、溶融シリカ、ドロマイト、無水ケイ酸、含水ケイ酸等）、重質炭酸カルシウム、膠質炭酸カルシウム、炭酸マグネシウム、ケイソウ土、焼成クレー、クレー、タルク、酸化チタン、ベントナイト、有機ベントナイト、酸化第二鉄、べんがら、アルミニウム微粉末、フリント粉末、酸化亜鉛、活性亜鉛華、亜鉛末、炭酸亜鉛、シラスバルーン、ポリアクリル樹脂・ポリアクリロニトリル－塩化ビニリデン樹脂・フェノール樹脂・ポリスチレン樹脂等のビーズ類やその中空微粒子、ガラスバルーン・シラスバルーン、フライアッシュバルーン等の無機系中空微粒子、ガラス繊維、ガラスフィラメント、炭素繊維、ケブラー繊維、ポリエチレンファイバー等の繊維状充填材等が挙げられる。 <Filler>
A filler can be added to the radically curable composition of the present invention in order to impart mechanical strength and abrasion resistance, or to adjust the thixotropy of the curable composition. Specific examples include various fillers and fine hollow particles described in paragraphs [0134] to [0151] of JP-A-2006-291073.
As the filler, fine silica used as reinforcing silica such as fumed silica, wet process silica, carbon black, wood powder, pulp, cotton chips, mica, walnut shell powder, rice husk powder, graphite, clay, silica ( Crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, etc.), heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, oxidation Ferric iron, bengara, aluminum fine powder, flint powder, zinc oxide, activated zinc white, zinc dust, zinc carbonate, shirasu balloon, beads such as polyacrylic resin, polyacrylonitrile-vinylidene chloride resin, phenolic resin, polystyrene resin The hollow fine particles, glass balloon, shirasu balloon, Inorganic hollow fine particles such as fly ash balloons, glass fibers, glass filaments, carbon fibers, Kevlar fibers, fibrous fillers such as polyethylene fiber and the like.
これらの中でも、補強性に優れる点から、ヒュームドシリカや湿式法シリカ、カーボンブラック、炭酸カルシウムが好ましい。 Among these, fumed silica, wet process silica, carbon black, and calcium carbonate are preferable from the viewpoint of excellent reinforcement.
補強性シリカとして用いられる、ヒュームドシリカや湿式法シリカの中でも、粒子径が５０μｍ以下であり、比表面積が８０ｍ２／ｇ以上のものが補強性の効果から好ましい。また、表面処理シリカ、例えば、オルガノシラン、オルガノシラザン、ジオルガノシクロポリシロキサン等で表面処理されたものよりは、表面無処理シリカの方が、混練のしやすさ、組成物の流動性が良好であり経済性にも優れるといった点からさらに好ましい。補強性シリカのより具体的な例としては、特に限定されないが、ヒュームドシリカの１つである日本アエロジル社のアエロジルや、湿式法シリカの１つである日本シリカ工業社製のＮｉｐｓｉｌ等が挙げられる。 Among fumed silica and wet process silica used as reinforcing silica, those having a particle diameter of 50 μm or less and a specific surface area of 80 m 2 / g or more are preferable from the viewpoint of reinforcing effect. In addition, surface-treated silica is better in kneading and fluidity of the composition than surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane, etc. It is more preferable from the point of being excellent in economy. More specific examples of the reinforcing silica include, but are not particularly limited to, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Sil, manufactured by Nippon Silica Kogyo Co., Ltd., which is one of the wet process silicas. It is done.
なお、上記比表面積値は、ＢＥＴ法（不活性気体の低温低湿物理吸着）による測定値をいう。 In addition, the said specific surface area value says the measured value by BET method (low-temperature low-humidity physical adsorption of inert gas).
カーボンブラックとしては、チャンネルブラック、ファーネスブラック、アセチレンブラック、サーマルブラック等いずれのカーボンブラックでも好ましく用いられ、補強性が良好で経済性にも優れる点からファーネスブラックがさらに好ましい。 As carbon black, any carbon black such as channel black, furnace black, acetylene black and thermal black is preferably used, and furnace black is more preferable from the viewpoint of good reinforcement and economical efficiency.
これらの充填剤の添加量としては特に制限はないが、（メタ）アクリル系重合体（Ｉ）１００重量部に対して、０．１～１００重量部が好ましく、０．５～８０重量部がより好ましく、１～５０重量部が特に好ましい。配合量が０．１重量部未満の場合には、補強性の改善効果が充分でないことがあり、１００重量部を超えると該硬化性組成物の作業性が低下したりすることがある。また、充填剤は単独で使用しても良いし、２種以上併用しても良い。 The amount of these fillers to be added is not particularly limited, but is preferably 0.1 to 100 parts by weight, and preferably 0.5 to 80 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer (I). More preferred is 1 to 50 parts by weight. When the blending amount is less than 0.1 part by weight, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts by weight, the workability of the curable composition may be deteriorated. Moreover, a filler may be used independently and may be used together 2 or more types.
＜可塑剤＞
本発明のラジカル硬化性組成物には可塑剤を添加することができる。可塑剤の添加により、ラジカル硬化性組成物の粘度や硬化物の引張り強度、伸びなどの機械特性を調整できたり、また硬化物の透明性を改善できたりする。
可塑剤としては特に限定されないが、物性の調整、性状の調節等の目的により、例えば、ジブチルフタレート、ジヘプチルフタレート、ジ（２－エチルヘキシル）フタレート、ブチルベンジルフタレート等のフタル酸エステル類；ジオクチルアジペート、ジオクチルセバケート、ジブチルセバケート、コハク酸イソデシル等の非芳香族二塩基酸エステル類；オレイン酸ブチル、アセチルリシリノール酸メチル等の脂肪族エステル類；ジエチレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、ペンタエリスリトールエステル等のポリアルキレングリコールのエステル類；トリクレジルホスフェート、トリブチルホスフェート等のリン酸エステル類；トリメリット酸エステル類；ピロメリット酸エステル類；ポリスチレン、ポリ－α－メチルスチレン等のポリスチレン類；ポリブタジエン、ポリブテン、ポリイソブチレン、ブタジエン－アクリロニトリル、ポリクロロプレン；塩素化パラフィン類；アルキルジフェニル、部分水添ターフェニル等の炭化水素系油；プロセスオイル類；ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリエーテルポリオールとこれらポリエーテルポリオールの水酸基をエステル基、エーテル基等に変換した誘導体等のポリエーテル類；エポキシ化大豆油、エポキシステアリン酸ベンジル等のエポキシ可塑剤類；セバシン酸、アジピン酸、アゼライン酸、フタル酸等の２塩基酸と、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール等の２価アルコールから得られるポリエステル系可塑剤類；東亞合成（株）製ＡＲＵＦＯＮシリーズのようなアクリル系可塑剤を始めとするビニル系モノマーを種々の方法で重合して得られる（メタ）アクリル系重合体類等が挙げられる。これらは、単独で用いても良いし、２種以上を併用してもよい。 <Plasticizer>
A plasticizer can be added to the radically curable composition of the present invention. By adding a plasticizer, mechanical properties such as the viscosity of the radical curable composition, the tensile strength and elongation of the cured product, and the transparency of the cured product can be improved.
Although it does not specifically limit as a plasticizer, For the purpose of adjustment of physical properties, adjustment of properties, for example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate; dioctyl adipate , Non-aromatic dibasic acid esters such as dioctyl sebacate, dibutyl sebacate, isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinolinate; diethylene glycol dibenzoate, triethylene glycol dibenzoate, penta Esters of polyalkylene glycols such as erythritol esters; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Pyromellitic acid esters; Polystyrene Polystyrenes such as poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyethylene Polyether polyols such as glycol, polypropylene glycol, polytetramethylene glycol and the like, and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc .; epoxidized soybean oil, epoxy such as epoxy benzyl stearate Plasticizers: dibasic acids such as sebacic acid, adipic acid, azelaic acid, phthalic acid, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene Polyester plasticizers obtained from dihydric alcohols such as Nglycol; obtained by polymerizing vinyl monomers including acrylic plasticizers such as ARUFON series manufactured by Toagosei Co., Ltd. ) Acrylic polymers. These may be used alone or in combination of two or more.
可塑剤を添加する場合の添加量は特に制限はないが、ラジカル硬化性組成物の作業性が良好で、硬化物の機械特性への影響が小さいという点から、（メタ）アクリル系重合体（Ｉ）１００重量部に対して、１～１００重量部が好ましく、１～５０重量部がさらに好ましい。 The addition amount in the case of adding the plasticizer is not particularly limited, but the (meth) acrylic polymer (from the point that the workability of the radical curable composition is good and the influence on the mechanical properties of the cured product is small. I) 1 to 100 parts by weight is preferable with respect to 100 parts by weight, and 1 to 50 parts by weight is more preferable.
＜溶剤＞
本発明で用いられる硬化性組成物には、必要に応じて溶剤を配合することができる。 <Solvent>
A solvent can be mix | blended with the curable composition used by this invention as needed.
配合できる溶剤としては、例えばトルエン、キシレン等の芳香族炭化水素系溶剤；酢酸エチル、酢酸ブチル、酢酸アミル、酢酸セロソルブ等のエステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン等のケトン系溶剤、メタノール、エタノール、イソプロパノール等のアルコール系溶剤；ヘキサン、シクロヘキサン、メチルシクロヘキサン、ヘプタン、オクタン等の炭化水素系溶剤が挙げられる。これらは、単独で用いても良いし、２種以上を併用してもよい。 Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone Examples of the solvent include alcohol solvents such as methanol, ethanol and isopropanol; hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, heptane and octane. These may be used alone or in combination of two or more.
溶剤を添加する場合の添加量は特に制限はないが、硬化性組成物の作業性が良好で、硬化収縮への影響が小さいという点から、（メタ）アクリル系重合体（Ｉ）１００重量部に対して、０．１～５０重量部が好ましく、１～３０重量部がさらに好ましい。 The addition amount in the case of adding the solvent is not particularly limited, but 100 parts by weight of the (meth) acrylic polymer (I) from the viewpoint that the workability of the curable composition is good and the influence on the curing shrinkage is small. Is preferably 0.1 to 50 parts by weight, and more preferably 1 to 30 parts by weight.
＜チクソ性付与剤（垂れ防止剤）＞
本発明の硬化性組成物には、必要に応じて垂れを防止し、作業性を良くするためにチクソ性付与剤（垂れ防止剤）を添加しても良い。 <Thixotropic agent (anti-sagging agent)>
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability.
チクソ性防止剤としては特に限定されないが、たとえば、水添ヒマシ油誘導体類、長鎖アルキル基を有する金属石鹸類、長鎖アルキル基を有するエステル化合物、シリカ等の無機充填剤、アミドワックス等が挙げられる。これらチクソ性付与剤は単独で用いてもよく、２種以上を併用してもよい。 The thixotropic inhibitor is not particularly limited, and examples thereof include hydrogenated castor oil derivatives, metal soaps having long-chain alkyl groups, ester compounds having long-chain alkyl groups, inorganic fillers such as silica, amide waxes, and the like. Can be mentioned. These thixotropic agents may be used alone or in combination of two or more.
チクソ性付与剤を添加する場合の添加量は特に制限はないが、硬化性組成物の作業性が良好であるという点から、（メタ）アクリル系重合体（Ｉ）１００重量部に対して、０．１～１０重量部が好ましく、０．１～５重量部がさらに好ましい。 The addition amount in the case of adding a thixotropic agent is not particularly limited, but from the viewpoint of good workability of the curable composition, with respect to 100 parts by weight of the (meth) acrylic polymer (I), The amount is preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight.
＜その他の添加剤＞
本発明の硬化性組成物には、硬化性組成物又は硬化物の諸物性の調整を目的として、必要に応じて各種添加剤を添加してもよい。このような添加物の例としては、たとえば、相溶化剤、硬化性調整剤、ラジカル禁止剤、金属不活性化剤、オゾン劣化防止剤、リン系過酸化物分解剤、滑剤、顔料、消泡剤、発泡剤、防蟻剤、防かび剤、紫外線吸収剤、光安定剤、離型剤、表面改質剤などがあげられる。本明細書にあげた添加物の他の具体例は、たとえば、特公平４－６９６５９号公報、特公平７－１０８９２８号公報、特開昭６３－２５４１４９号公報、特開昭６４－２２９０４号公報、特開２００１－７２８５４号公報などに記載されている。 <Other additives>
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, compatibilizers, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, antifoams. Agents, foaming agents, ant-proofing agents, fungicides, UV absorbers, light stabilizers, mold release agents, surface modifiers and the like. Other specific examples of the additives mentioned in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904. JP-A-2001-72854 and the like.
＜ラジカル硬化性組成物の調製＞
本発明のラジカル硬化性組成物は、全ての配合成分を予め配合し、施工後にＵＶや電子線を照射することにより硬化する一液光硬化型や、施工後に加熱することにより硬化する一液熱硬化型、あるいは配合成分を二液に分割しておき、混合することでラジカルを発生させる二液混合型として調製することができる。 <Preparation of radical curable composition>
The radical curable composition of the present invention is a one-part photo-curing type that is pre-blended with all blending components and cured by irradiating UV or electron beam after construction, or one-part heat that cures by heating after construction. It can be prepared as a curable type or a two-component mixed type that generates radicals by dividing the compounded component into two components and mixing them.
本発明の硬化性組成物の調製法には特に限定はなく、例えば上記した成分を配合し、ハンドミキサーやスタティックミキサーで混合したり、プラネタリーミキサーやディスパー、ロール、ニーダーなどを用いて常温又は加熱下で混練したり、適した溶剤を少量使用して成分を溶解させ、混合したりするなどの通常の方法が採用されうる。特に充填剤を混合する場合には、プラネタリーミキサーやディスパー、ロール、ニーダーなどを用いることが好ましい。 The method for preparing the curable composition of the present invention is not particularly limited. For example, the components described above are mixed and mixed with a hand mixer or a static mixer, or at room temperature or using a planetary mixer, a disper, a roll, a kneader, or the like. Ordinary methods such as kneading under heating or using a small amount of a suitable solvent to dissolve and mix the components may be employed. In particular, when a filler is mixed, it is preferable to use a planetary mixer, a disper, a roll, a kneader or the like.
＜硬化方法＞
本発明の硬化物は、本発明の硬化性組成物を硬化させて得られる。本発明の硬化性組成物は、特に限定されないが、ＵＶや電子線などの活性エネルギー線又は熱により硬化させることが好ましい。 <Curing method>
The cured product of the present invention is obtained by curing the curable composition of the present invention. Although the curable composition of this invention is not specifically limited, It is preferable to harden | cure by active energy rays, such as UV and an electron beam, or a heat | fever.
＜活性エネルギー線硬化＞
活性エネルギー線照射には、通常の活性エネルギー線硬化に用いられる光源を使用可能であり、例えば、太陽光線、低圧水銀ランプ（殺菌ランプ、蛍光ケミカルランプ、ブラックライト）、蛍光灯、白熱電球、中圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、カーボンアーク灯、メタルハライドランプ、ガリウムランプ、タングステンランプ、キセノンランプ、水銀キセノンランプ、ケミカルランプ、無電極放電ランプ、ジルコニウムランプ、有機ＥＬ、ＬＥＤ、ＵＶ－ＬＥＤ等が挙げられる。これらの中でも、取り扱いのし易さや経済性の点から、高圧水銀灯、メタルハライドランプ、無電極放電ランプ、ＵＶ－ＬＥＤが好適である。 <Active energy ray curing>
For active energy ray irradiation, a light source used for normal active energy ray curing can be used. For example, sunlight, low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), fluorescent lamp, incandescent bulb, medium Pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, carbon arc lamp, metal halide lamp, gallium lamp, tungsten lamp, xenon lamp, mercury xenon lamp, chemical lamp, electrodeless discharge lamp, zirconium lamp, organic EL, LED, UV -LED etc. are mentioned. Among these, a high pressure mercury lamp, a metal halide lamp, an electrodeless discharge lamp, and a UV-LED are preferable from the viewpoint of easy handling and economy.
また、活性エネルギー線の照射強度や積算光量は、ラジカル架橋性基の種類や量、光ラジカル開始剤の種類・量、所望の硬化物の厚みや大きさなどの形状により適宜調整されて照射される。 In addition, the irradiation intensity of the active energy ray and the integrated light amount are appropriately adjusted according to the type and amount of the radical crosslinkable group, the type and amount of the photo radical initiator, and the desired thickness and size of the cured product. The
活性エネルギー線照射の方法としては、例えばベルトコンベア上で活性エネルギー線を連続的に照射する方法や活性エネルギー線を照射する時のみベルトコンベアを停止し、均一に活性エネルギー線を照射する方法、あるいは照射ごとに活性エネルギー線照射装置に硬化性組成物を投入・取り出しを行う方法（バッチ式）等が挙げられる。ベルトコンベア方式は連続的に硬化する場合に向いている。バッチ式法では、ベルトコンベア等の大がかりな装置が必要なく、また、対象物に対し活性エネルギー線を均一に照射させやすいという利点がある。ベルトコンベア式の場合、例えば、硬化性組成物をベルトコンベアに載せ、コンベアの上方または横方、あるいは下方に固定された活性エネルギー線照射装置から活性エネルギー線を照射する。 As a method of irradiating active energy rays, for example, a method of continuously irradiating active energy rays on a belt conveyor, a method of stopping the belt conveyor only when irradiating active energy rays, and irradiating active energy rays uniformly, or For example, a method (batch type) in which a curable composition is charged into or taken out from an active energy ray irradiation apparatus for each irradiation. The belt conveyor system is suitable for continuous curing. The batch method does not require a large-scale apparatus such as a belt conveyor, and has an advantage that it is easy to uniformly irradiate the target with active energy rays. In the case of the belt conveyor type, for example, the curable composition is placed on the belt conveyor, and the active energy beam is irradiated from an active energy beam irradiation device fixed on the upper side, the side or the lower side of the conveyor.
あるいは、スポット型活性エネルギー線照射装置を用いて、塗布ロボットあるいは照射ロボット、またはステージの動きに合わせて、硬化性組成物の塗布・硬化を行うこともできる。 Alternatively, the curable composition can be applied and cured in accordance with the movement of the application robot, the irradiation robot, or the stage using a spot type active energy ray irradiation apparatus.
活性エネルギー線硬化の場合は、空気中の酸素の影響により表面硬化阻害を生じやすいことが知られており、これを回避するために、例えばラジカル硬化性組成物をＰＰフィルムやＰＥＴフィルム、テフロン（登録商標）フィルムなどの透明性のあるバリヤフィルムにより覆って表面が酸素と触れないようにして、該フィルムを介して活性エネルギー紫外線を照射してもよいし、窒素ガスや炭酸ガスのような不活性ガスにより酸素を置換したイナートゾーン中で活性エネルギー線を照射してもよい。後者の方法においては、ラジカル硬化性組成物の反応率を向上させるために、照射雰囲気の酸素濃度は５０００ｐｐｍ以下が好ましく、より好ましくは５００ｐｐｍ以下である。 In the case of active energy ray curing, it is known that surface curing inhibition is likely to occur due to the influence of oxygen in the air, and in order to avoid this, for example, a radical curable composition is made of PP film, PET film, Teflon ( The film may be covered with a transparent barrier film such as a registered trademark film so that the surface does not come into contact with oxygen, and irradiated with active energy ultraviolet light through the film, or may be irradiated with nitrogen, carbon dioxide, You may irradiate an active energy ray in the inert zone which substituted oxygen with active gas. In the latter method, in order to improve the reaction rate of the radical curable composition, the oxygen concentration in the irradiation atmosphere is preferably 5000 ppm or less, more preferably 500 ppm or less.
しかしながら、本発明の硬化方法が上記の方法に限定されないことは明白である。 However, it is clear that the curing method of the present invention is not limited to the above method.
＜熱硬化＞
熱により硬化させる場合には、その温度は、使用する熱ラジカル開始剤、（メタ）アクリル系重合体（Ｉ）及び添加される化合物等の種類により異なるが、５０℃～２５０℃の範囲内が好ましく、７０℃～２００℃の範囲内がより好ましい。
硬化時間は、使用する熱ラジカル開始剤、単量体、溶媒、反応温度等により異なるが、通常１分～１０時間の範囲内である。
成形体を得るために熱硬化させる場合には、特に限定されず、一般に使用されている各種の成形方法を用いることができる。例えば、注型成形、圧縮成形、トランスファー成形、射出成形、押し出し成形、回転成形、中空成形、熱成形等が挙げられる。特に自動化、連続化が可能で、生産性に優れるという観点から射出成形によるものが好ましい。 <Heat curing>
In the case of curing by heat, the temperature varies depending on the kind of the thermal radical initiator, the (meth) acrylic polymer (I) and the compound to be added, but the temperature is within the range of 50 ° C to 250 ° C. Preferably, it is within the range of 70 ° C to 200 ° C.
The curing time varies depending on the thermal radical initiator used, monomer, solvent, reaction temperature, etc., but is usually in the range of 1 minute to 10 hours.
When thermosetting to obtain a molded body, it is not particularly limited, and various commonly used molding methods can be used. Examples thereof include cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, and thermoforming. In particular, from the viewpoint of being able to be automated and continuous and being excellent in productivity, the one by injection molding is preferable.
＜硬化物の性状＞
本発明の硬化物は、ゴム状を示すことが好ましい。ゴム状とは、得られた硬化物を触ったときに、柔らかく、伸びに優れ、伸ばしたり曲げたりしても元の形状に容易に戻る性状を示すものである。 <Properties of cured product>
The cured product of the present invention preferably exhibits a rubber shape. The rubbery form is soft and excellent in elongation when the obtained cured product is touched, and exhibits a property of easily returning to the original shape even when stretched or bent.
具体的には、硬化物のガラス転移温度（Ｔｇ）が２５℃以下であることが好ましく、１０℃以下であることがさらに好ましく、寒冷地でも十分なゴム弾性を示すことから０℃以下であることがさらに好ましく、極寒地でも十分なゴム弾性を示すことから－１０℃以下であることがさらに好ましい。ガラス転移温度が２５℃を超えると、室温でゴム弾性を示しにくくなる。 Specifically, the glass transition temperature (Tg) of the cured product is preferably 25 ° C. or less, more preferably 10 ° C. or less, and 0 ° C. or less because it exhibits sufficient rubber elasticity even in cold regions. More preferably, the temperature is −10 ° C. or lower because sufficient rubber elasticity is exhibited even in extremely cold regions. When the glass transition temperature exceeds 25 ° C., it becomes difficult to exhibit rubber elasticity at room temperature.
ここで、ガラス転移温度（Ｔｇ）は、損失正接（ｔａｎδ）のピークトップの値に基づく方法（ＤＭＡ法）により測定される。損失正接は、損失弾性率／貯蔵弾性率の値により測定される。損失弾性率と貯蔵弾性率は、試験片に剪断モードで一定の周波数（５Ｈｚ）で力を付与し（歪み０．０５％）、その力を与えた時の応力を、動的粘弾性計測装置を用いて計測することで測定される。 Here, the glass transition temperature (Tg) is measured by a method (DMA method) based on the peak top value of the loss tangent (tan δ). Loss tangent is measured by the value of loss modulus / storage modulus. The loss elastic modulus and storage elastic modulus are applied to the test piece at a constant frequency (5 Hz) in a shear mode (strain 0.05%), and the stress when the force is applied is determined by a dynamic viscoelasticity measuring device. It is measured by measuring using.
＜硬化物の使用方法について＞
本発明の硬化物は、必要に応じて、単体で用いてもよいし、他の部材と複合して用いてもよい。ラジカル硬化性組成物を何らかの型に流し込んで固めてから取り出してもよいし、所望の型を用いて硬化し、その型ごと用いてもよい。あるいは硬化性組成物をローラやディスペンサ等でドット状、ビード状、面状または任意の形状に塗布したり、印刷して用いてもよい。また、得られた硬化物をフィルムやゴム、プラスチック、金属、セラミックス、紙、不織布等他の部材と貼り合わせたり、嵌め込んだり、挟み込んだり、接着剤や粘着剤を介して一体化させてもよいし、塗布や注入といった方法で、ラジカル硬化性組成物の状態で他部材と接触させた後に、活性エネルギー線の照射あるいは加熱により硬化させ、複合成形体を得てもよい。 <How to use cured products>
The cured product of the present invention may be used alone or in combination with other members as necessary. The radical curable composition may be poured into a certain mold and solidified and taken out, or may be cured using a desired mold and used for each mold. Alternatively, the curable composition may be applied to a dot shape, a bead shape, a planar shape, or an arbitrary shape with a roller or a dispenser, or may be printed. In addition, the obtained cured product may be bonded to other members such as films, rubber, plastics, metals, ceramics, paper, nonwoven fabrics, fitted, sandwiched, or integrated via an adhesive or adhesive. Alternatively, the composite molded body may be obtained by contact with another member in the state of the radical curable composition by a method such as application or injection, and then cured by irradiation with active energy rays or heating.
しかしながら、本発明の硬化物が上記の使用方法に限定されないことは明白である。 However, it is obvious that the cured product of the present invention is not limited to the above method of use.
＜用途＞
本発明のラジカル硬化性組成物および硬化物の用途としては、限定はされないが、スポーツ用品、玩具・遊具、文房具、医薬・医療・介護用品、履物、寝具・寝装品、家具、衣料、各種雑貨、輸送用品、ＯＡ機器、家電製品、オーディオ機器、携帯機器、産業用機械・機器、精密機器、電気・電子機器、電気・電子部品、建材用品のシール材・コーティング材・接着剤・粘着剤・成形体・封止材・成形部品・塗料・インク・発泡体・レジスト材・現場成形ガスケット・衝撃吸収材・衝撃緩衝材・圧力分散材・制振材・防振材・吸音材・防音材・断熱材・感触改善部材等の様々な用途に利用可能である。 <Application>
Applications of the radical curable composition and the cured product of the present invention are not limited, but include sports equipment, toys / playground equipment, stationery, pharmaceutical / medical / care products, footwear, bedding / bedding, furniture, clothing, various miscellaneous goods, Transportation equipment, OA equipment, home appliances, audio equipment, portable equipment, industrial machinery / equipment, precision equipment, electrical / electronic equipment, electrical / electronic components, building materials, sealing materials / coating materials / adhesives / adhesives / molding Body, Encapsulant, Molded Parts, Paint, Ink, Foam, Resist Material, On-Site Molded Gasket, Shock Absorber, Shock Absorber, Pressure Dispersant, Damping Material, Damping Material, Sound Absorbing Material, Soundproofing Material, Heat Insulation It can be used for various applications such as materials and feel improving members.
また、各種用途に用いる場合に、ショックアブソーバー、インシュレーター、ブッシュ、各種マウント、ローラ、フィルム、シート、テープ、シール、チップ、成形部材としての利用も可能である。 Moreover, when using for various uses, the utilization as a shock absorber, an insulator, a bush, various mounts, a roller, a film, a sheet | seat, a tape, a seal | sticker, a chip | tip, and a shaping | molding member is also possible.
スポーツ用途としては、球技場、競技場、体育館のフェンス・床面等に設置する衝撃緩衝材、体操競技や運動用の着地マット、床運動用マット、ジムのストレッチ用マット、キッズマット、ボルダリング用マット（クラッシュパッド）、ビート板、高飛び用のクッション材、ウエットスーツ、ゴルフクラブ・バット・テニスラケットなどのグリップや心材、グラブやミットの心材、スポーツシューズの上敷き、中敷き、中底、靴底、スキーブーツ・スノーボードブーツのライナー、トゥ・シューズ、バレエシューズ、ゴルフクラブヘッド、ゴルフボールや野球用ボールその他の球技用ボール、スポーツ用プロテクター類（例えば、ラグビーやボクシング等の格闘技で使用するヘッドギア、野球やフットボールのヘルメット、野球・サッカー・格闘技等のひじあて、レガース（シンガード）等）、ラケット、ボール、ライダー用スーツ、グローブ（サッカーのキーパーグローブ、ゴルフ、スキー、ライダー用）、ライフルジャケット（例えば肩パット）等の成形体用途、シール材用途、封止剤用途、衝撃吸収用途、衝撃緩衝用途、圧力分散用途、制振用途、防振用途、吸音用途、防音用途、人体との接触部の感触改善用途などに有用である。 For sports use, impact cushioning materials installed on fences and floors of gymnasiums, stadiums, gymnasiums, landing mats for gymnastics and exercise, floor exercise mats, gym stretch mats, kids mats, bouldering Mat (crash pad), beat board, high jump cushion material, wet suit, golf club, bat, tennis racket grip and heartwood, grab and mitt heartwood, sports shoe overlay, insole, insole, shoe sole, Ski boots, snowboard boot liners, toe shoes, ballet shoes, golf club heads, golf balls, baseball balls and other ball sports balls, sports protectors (for example, headgear and baseball used in martial arts such as rugby and boxing) And football helmets, baseball, soccer, Elbows for fighting, leggers (singards, etc.), rackets, balls, suits for riders, gloves (soccer keeper gloves, golf, skis, riders), rifle jackets (eg shoulder pads), molded products, seals It is useful for material applications, sealant applications, impact absorption applications, impact buffer applications, pressure dispersion applications, vibration suppression applications, vibration isolation applications, sound absorption applications, sound insulation applications, and touch improvement applications for human body contacts.
玩具・遊具用途としては、シール、ハンドエクササイザー、ヒーリンググッズ、キーホルダー、ぬいぐるみ、動くぬいぐるみ、マネキンボデイー、ボール、マッサージボール等のクッション材や詰め物、ゲームのコントローラーやマット、携帯電話やスマートフォン等のデコレート用品やその他装飾品用の作製材料、動物模型、怪獣や人形、フィギュア等の成形体用途、シール材用途、封止剤用途、衝撃吸収用途、衝撃緩衝用途、圧力分散用途、制振用途、防振用途、吸音用途、防音用途、人体との接触部の感触改善部用途などに有用である。 For toys and play equipment, seals, hand exercisers, healing goods, key holders, stuffed animals, stuffed animals, mannequin bodies, balls, massage balls and other cushion materials and fillings, game controllers and mats, mobile phones and smartphones, etc. Fabrication materials for articles and other decorative items, animal models, monsters, dolls, figures and other molded object applications, sealing material applications, sealant applications, shock absorption applications, shock absorbing applications, pressure dispersion applications, vibration control applications, and prevention It is useful for vibration application, sound absorption application, soundproofing application, touch improvement part of the contact part with the human body, and the like.
医療・介護用途としては、人工皮膚、人工骨、人工軟骨、人工臓器、人工角膜、人工水晶体、人工硝子体、人工筋肉、人工血管、人工関節、人体模型、水着や豊胸用の胸パットや挿入用材料、その他生体適合材料としての利用や、薬液染み出しパッド、止血パッド、気液分離フィルター（留置針フィルター）、貼布剤、医療用液体吸収用具、マスク、圧迫パッド、手術用ディスポ製品、医療用チューブ・キャップ・バッグ・ガスケット・、ホース、医療用のベッド・治療台・椅子、心電図測定用電極材、低周波治療器用電極パッド、センサーパッド、床ずれ予防マットレス、体位変換クッション、車椅子用クッション、車椅子の座面、シャワー椅子等の介護用品、入浴介護用枕、テーピング、ギブス用ライナー、ソフトコンタクトレンズ用材料、義手・義足そのものや義足や義手の人体への接続用緩衝材（ライナー等）、又は義足や義手の関接部分構成材、入れ歯台、その他歯科用品、衝撃吸収パッド、ヒッププロテクター、肘・膝用プロテクター、術後の身体形状補助材、湿布材、創傷被覆材、細胞培養シート、治療実習用の成体モデル等にも利用できるものである。その他、人体に接触させ使用される物品として、例えば、魚の目もしくはたこの痛み緩衝材、サポーター、パンプスなどのずれ防止材、またはひじもしくはかかとなどの乾燥防止パッド、外反母趾や巻き爪等による痛みを緩和するためのフットケア用衝撃吸収用途などに有用である。その他に、経皮吸収製剤や貼付用の粘着剤、医薬・医療用シール材、医療用粘着剤、医療用ゴム栓、印象材、歯科充填材、シリンジガスケット、および減圧血管用ゴム栓、人工透析装置用のＯリング又は平形ガスケット、医薬品・医療器具の包装材料、キャップ、キャップライナー、真空採血管のキャップ、カテーテルのシール材や接着剤、体内埋め込み型医療機器や添付形センサー類のシール材や接着剤等に利用可能である。 As medical / nursing care applications, artificial skin, artificial bone, artificial cartilage, artificial organ, artificial cornea, artificial crystalline lens, artificial vitreous body, artificial muscle, artificial blood vessel, artificial joint, human body model, swimsuit and breast pad for breast augmentation Use as an insertion material, other biocompatible materials, chemical exudation pad, hemostatic pad, gas-liquid separation filter (indwelling needle filter), patch, medical liquid absorption tool, mask, compression pad, surgical disposable product , Medical tubes, caps, bags, gaskets, hoses, medical beds, treatment tables, chairs, electrocardiogram measurement electrode materials, electrode pads for low frequency treatment devices, sensor pads, bedsore prevention mattresses, posture change cushions, wheelchairs Cushions, wheelchair seats, showers and other care products, bathing care pillows, taping, cast liners, soft contact lens materials , Prosthetic hand, prosthetic leg itself, cushioning material (liner etc.) for connection to the prosthetic leg and prosthetic human body, or prosthetic leg and prosthetic hand joint parts, denture base, other dental supplies, shock absorbing pad, hip protector, elbow / knee It can also be used as a body protector, a postoperative body shape auxiliary material, a poultice material, a wound dressing material, a cell culture sheet, an adult model for treatment training, and the like. Other items that can be used in contact with the human body include, for example, fish eye or octopus pain cushioning materials, supporters, pumps and other slip prevention materials, or elbow or heel drying prevention pads, hallux valgus and wound nails. It is useful for shock absorption applications for foot care. In addition, transdermally absorbable preparations, adhesives for sticking, medical / medical sealing materials, medical adhesives, medical rubber stoppers, impression materials, dental fillers, syringe gaskets, and rubber stoppers for vacuum vessels, artificial dialysis O-rings or flat gaskets for devices, packaging materials for pharmaceuticals and medical devices, caps, cap liners, caps for vacuum blood collection tubes, catheter sealing materials and adhesives, sealing materials for implantable medical devices and attached sensors, etc. It can be used for adhesives.
履物用途としては、紳士靴、婦人靴、子供用靴、高齢者用靴、スポーツシューズ、安全靴等に使用が可能であり、それぞれの靴の表皮材、裏打ち、中敷（インナーソール）、靴底（アウトソール、ミッドソール、ヒール）、靴擦れ防止パッド、各種靴パッド、インナーブーツ、スリッパ、スリッパ芯、サンダル、サンダル中敷等の成形体用途、衝撃緩衝用途、衝撃吸収用途、履き心地改善用途、美容・痩身用途として有用である。 As footwear applications, it can be used for men's shoes, women's shoes, children's shoes, elderly shoes, sports shoes, safety shoes, etc. Each shoe's skin material, lining, insole (inner sole), shoes Sole (outsole, midsole, heel), shoe rub pad, various shoe pads, inner boots, slippers, slipper core, sandals, sandals, insoles, etc., shock buffering applications, shock absorption applications, comfort improvement applications Useful for beauty and slimming applications.
寝具・寝装品用途としては、枕、掛け布団、敷布団、ベッド、理容用・美容用ベッド、マットレス、ベッドマット、ベッドパッド、クッション、ベビーベッド、ベビー用首まくら等の床ずれ防止用途や体圧分散用途や寝心地改善用途、衝撃吸収用途、成形体用途等が挙げられる。 Bedding and bedding products include pillows, comforters, mattresses, beds, barber / beauty beds, mattresses, bed mats, bed pads, cushions, cribs, baby bed pillows, bed slip prevention, body pressure dispersion, Examples include sleeping comfort improvement applications, impact absorption applications, and molded product applications.
家具用途としては、椅子、座イス、座布団、ソファー、ソファークッション・シートクッション、腰当クッション等の各種クッション、カーペット・マット類、コタツ敷・掛け布団、便座マットの体圧分散用途や座り心地改善用途、衝撃吸収用途、感触改善用途等が挙げられる。机、タンス、衣装ケース、本棚、階段、ドア、扉、ふすま、障子、引き戸の取手や持手、手すり、戸当たり部等の感触改善部用途、衝撃吸収用途、防音用途、成形体用途等が挙げられる。 Furniture applications include chairs, seat chairs, cushions, sofas, sofa cushions / seat cushions, waist cushions, and other cushions, carpets / mats, tatami mats / comforters, toilet seat mats for spreading body pressure and improving sitting comfort , Impact absorbing applications, feel improving applications and the like. Desk, chest, clothes case, bookshelf, staircase, door, door, bran, shoji, sliding door handle and handle, handrail, door stop, etc. Can be mentioned.
衣料用途としては、肩・ブラジャー等のパッド材や、防寒材、ヘルメット、防弾チョッキ、等に衝撃吸収用途や断熱用途、成形体用途等が挙げられる。 Examples of clothing applications include pad materials such as shoulders and bras, cold protection materials, helmets, bulletproof vests, etc., impact absorption applications, heat insulation applications, molded object applications, and the like.
各種雑貨用途としては、バスピロー等の風呂用品、マッサージ用パフ、マウスパッド、パソコン用アームレストやリストレスト、滑り止めクッション、文具（ペングリップ、浸透印材）、デスク用小まくら、耳栓、綿棒、ホットパック用シート、コールドパック用シート、湿布、めがねパッド、水中眼鏡用パッド、顔面プロテクター、腕時計パッド、ヘッドホーンイヤーパット、イヤホン、保温カップ、飲料缶、氷枕カバー、折りたたみまくら、筆記具、鞄（例えばランドセルの肩掛け部、手提げ部等）、日用雑貨・大工用品のグリップ、カーペット用部材、人工芝用部材等の敷物用部材、肘当て、膝当て、手袋、魚つり用等の疑似餌、鞍による馬の背中の鞍ずれ防止材等の成形体用途、シール材用途、衝撃吸収用途、緩衝用途、防振用途、制振用途、吸音用途、消音用途、人体との接触部の感触改善部用途として利用が可能である。 For various miscellaneous goods, bath products such as bath pillows, massage puffs, mouse pads, armrests and wrist rests for computers, anti-slip cushions, stationery (pen grips, penetrating sealants), desk pillows, earplugs, cotton swabs, hot Pack sheet, cold pack sheet, compress, eyeglass pad, underwater spectacles pad, face protector, watch pad, headphone ear pad, earphone, heat retaining cup, beverage can, ice pillow cover, folding pillow, writing instrument, bag (eg school bag) ), Daily goods / carpenter's grips, carpets, rugs such as artificial turf materials, elbow pads, knee pads, gloves, fish fishing, etc. Use of molded products such as anti-wrinkle prevention materials, sealing materials, shock absorption applications, shock absorbing applications, anti-vibration applications, Vibration applications, the sound absorbing applications, silencing applications, can be utilized as the feeling improving part application of the contact portion of the human body.
輸送用途としては、自動車・オートバイ・自転車・電動自転車・三輪車・ベビーカー・建築機械・鉄道車両・船舶・航空機等の座席、チャイルドシート、ヘッドレスト、アームレスト、フットレスト、ヘッドライナー、サドル、ライダークッション、ヘルメット、カスタムカー用のベッドマット、キャンピングカー用クッション、天井材、ドアトリム、フロアクッションインストルメントパネル、ダッシュボード、ドアパネル、インナーパネル、シフトノブ、ハンドル、グリップ、ピラー、コンソールボックス、エアバックカバー、パーキングブレーキカバー、クォータートリム、内張り、センターピラーガーニッシュ、サンバイザー等の内装材、車載型道路ナビゲーションシステムの記録再生装置や各種センサー類、制御機器等の車載電子機器、ハーネス・ダストカバー・ホース・エンジン・バッテリー・オイルパン・フロントカバー・ロッカーカバー等のエンジン周り、タイヤ、バンパー、フロア、アンダーフロア、ドア、ルーフ、パネル、ホイルハウス、トランスミッション、ウェザーストリップ、各種補機カバー、ウインドーパッキン、ルーフモール、ドア下モール、シートバック、トランクルーム、荷台等の車体周りの成形体用途、シール材用途、制振用途、防振用途、衝撃吸収用途、吸音用途、防音用途、緩衝用途、人体との接触部の感触改善用途等が挙げられる。また、キャリーバッグ・台車・コンテナ・フレキシブルコンテナー・パレット等人荷運搬用具の防振用途、制振用途、衝撃吸収用途、振動吸収用途も挙げられる。運搬するものとしては、例えば、美術品、精密機器、果物、鮮魚、卵、陶器・磁器、再生細胞等の移植用細胞類が挙げられ、これらの直接梱包用、間接梱包用あるいは梱包したものを搬送する用途に使用できる。また、輸送用、運搬用、搬送用にショックアブソーバー、インシュレーター、ブッシュ、各種マウント、フィルムシート、テープ、シール、チップ、成形部材としての利用も可能である。防振ゴムとして、自動車用防振ゴム、鉄道車両用防振ゴム、航空機用防振ゴム、防舷材等に使用できる。 Transport applications include seats for automobiles, motorcycles, bicycles, electric bicycles, tricycles, strollers, construction machinery, railway vehicles, ships, aircraft, etc., child seats, headrests, armrests, footrests, headliners, saddles, rider cushions, helmets, custom Car bed mat, camper cushion, ceiling material, door trim, floor cushion instrument panel, dashboard, door panel, inner panel, shift knob, handle, grip, pillar, console box, airbag cover, parking brake cover, quarter trim , Interior materials such as lining, center pillar garnish, sun visor, in-vehicle electronics such as recording / playback devices and various sensors, control equipment for in-vehicle road navigation system Engine, harness, dust cover, hose, engine, battery, oil pan, front cover, rocker cover, etc., engine, tire, bumper, floor, under floor, door, roof, panel, wheel house, transmission, weather strip, various Auxiliary machine covers, window packings, roof moldings, door moldings, seat backs, trunk rooms, cargo bed and other molded body applications, sealing materials, vibration control applications, vibration isolation applications, shock absorption applications, sound absorption applications, sound insulation Applications, buffer applications, applications for improving the feeling of contact with the human body, and the like. Also included are vibration isolation applications, vibration suppression applications, shock absorption applications, and vibration absorption applications for carrying goods such as carry bags, carts, containers, flexible containers, and pallets. Examples of materials to be transported include fine arts, precision instruments, fruits, fresh fish, eggs, pottery / porcelain, regenerative cells, and other cells for direct packaging, indirect packaging or packaging. It can be used for transportation purposes. Further, it can be used as shock absorbers, insulators, bushes, various mounts, film sheets, tapes, seals, chips, and molded members for transportation, transportation, and transportation. As the anti-vibration rubber, it can be used for anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials and the like.
更に、自動車分野ではボディ部品として、気密保持のためのシール材、ガラスの振動防止材、車体部位の防振材、特にウインドシールガスケット、ドアガラス用ガスケットに使用することができる。シャーシ部品として、防振、防音用のエンジンおよびサスペンジョンゴム、特にエンジンマウントラバーに使用することができる。エンジン部品としては、冷却用、燃料供給用、排気制御用などのホース類、エンジンカバーやオイルパン用のガスケット、エンジンオイル用シール材などに使用することができる。また、排ガス清浄装置部品、ブレーキ部品にも使用できる。タイヤ部品としては、ビード部位、サイドウォール部位、ショルダー部位、トレッド部位のほか、インナーライナー用の樹脂や空気圧センサー・パンクセンサーのシール材として利用可能である。また、各種電子部品・制御部品のシール材、封止材、ガスケット、コーティング材、モールド部材、接着剤、粘着剤として利用可能である。また、銅製・アルミ製ワイヤーハーネスの被覆材やコネクタ部のシール材としても利用可能である。その他、ランプ、バッテリー、ウィンドウォッシャー液ユニットやエアコンディショナーユニット、クーラントユニット、ブレーキオイルユニット、電装部品、各種内外装品、オイルフィルター等のシール材、接着剤、粘着剤、ガスケット、Ｏリングやパッキン、ベルト等の成形部品、イグナイタＨＩＣもしくは自動車用ハイブリッドＩＣのポッティング材等としても利用可能である。 Furthermore, 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. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. Engine parts can be used for hoses for cooling, fuel supply, exhaust control, etc., gaskets for engine covers and oil pans, sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. As tire parts, in addition to bead parts, sidewall parts, shoulder parts and tread parts, it can be used as a resin for inner liners and as a sealing material for air pressure sensors and puncture sensors. Further, it can be used as a sealing material, sealing material, gasket, coating material, mold member, adhesive, and pressure-sensitive adhesive for various electronic parts and control parts. It can also be used as a covering material for copper / aluminum wire harnesses and a sealing material for connector parts. In addition, lamps, batteries, window washer fluid units, air conditioner units, coolant units, brake oil units, electrical components, various interior and exterior products, sealing materials such as oil filters, adhesives, adhesives, gaskets, O-rings and packings, It can also be used as molded parts such as belts, potting materials for igniter HICs or hybrid ICs for automobiles, and the like.
各種機器用途としては、ＯＡ機器（ディスプレイ・パソコン・電話機・コピー機・プリンタ・複写機・ゲーム機・テレビ・ＤＶＤレコーダーやブルーレイレコーダー、ＨＤＤレコーダー等の各種レコーダー類・ＤＶＤプレイヤーやブルーレイプレイヤー等の各種プレイヤー類・プロジェクタ・デジタルカメラ・ホームビデオ・アンテナ・スピーカー・電子辞書・ＩＣレコーダー・ＦＡＸ・コピー機・電話機・ステッピングモーター・磁気ディスク・ハードディスク等）の成形体用途、シール材用途、封止剤用途、防振用途、制振用途、衝撃吸収用途、衝撃緩衝用途、吸音用途、防音用途、人体との接触部の感触改善部用途や接着剤、粘着剤、パッキン、Ｏリング、ベルトとして有用である。 Various equipment applications include OA equipment (displays, personal computers, telephones, copiers, printers, copiers, game machines, TVs, DVD recorders, Blu-ray recorders, HDD recorders, various recorders, DVD players, Blu-ray players, etc. Players, projectors, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, fax machines, photocopiers, telephones, stepping motors, magnetic disks, hard disks, etc.), molding materials, sealing materials, sealants , Anti-vibration use, vibration control use, shock absorption use, shock absorbing use, sound absorption use, sound insulation use, touch improvement part for contact with human body, adhesive, adhesive, packing, O-ring, belt .
家電製品（冷蔵庫・洗濯機・洗濯乾燥機・布団乾燥機・掃除機・空気清浄機・浄水器・電動歯ブラシ・照明器具・エアコン・エアコン室外機・除湿機・加湿器・ファンヒーター・扇風機・換気扇・ドライヤー・マッサージャー・送風機・ミシン・食器洗浄機・食器乾燥機・ドアホン・炊飯器・電子レンジ・オーブンレンジ・ＩＨクッキングヒーター・ホットプレート・各種充電器・アイロン）の防振用途、制振用途、衝撃吸収用途、衝撃緩衝用途、吸音用途、防音用途、取手や持手、扉・ドア・手すり等人体との接触部の感触改善部用途やシール材、接着剤、粘着剤、パッキン、Ｏリング、ベルトとして有用である。 Household appliances (refrigerator, washing machine, washing dryer, futon dryer, vacuum cleaner, air purifier, water purifier, electric toothbrush, lighting equipment, air conditioner, air conditioner outdoor unit, dehumidifier, humidifier, fan heater, fan, ventilator・ Dryers, massagers, blowers, sewing machines, dishwashers, tableware dryers, door phones, rice cookers, microwave ovens, microwave ovens, IH cooking heaters, hot plates, various chargers, and irons) Absorption applications, shock absorbing applications, sound absorption applications, soundproof applications, handles, handles, doors, doors, handrails and other parts that touch the human body, seal materials, adhesives, adhesives, packing, O-rings, belts Useful as.
オーディオ機器（スピーカー・ターンテーブル・光ピックアップ装置や光記録再生装置・磁気ピックアップ装置や磁気記録再生装置・インシュレーター・スぺーサー等）の防振用途、制振用途、衝撃吸収用途、衝撃緩衝用途として有用である。 As an anti-vibration application, a vibration control application, an impact absorption application, and an impact buffer application for audio equipment (speakers, turntables, optical pickup devices, optical recording / reproducing devices, magnetic pickup devices, magnetic recording / reproducing devices, insulators, spacers, etc.) Useful.
ノート型パソコン、携帯型ハードディスク、携帯電話、スマートフォン、携帯型音楽情報機器、携帯ゲーム機等の携帯機器の防振用途、制振用途、衝撃緩衝用途、人体との接触部の感触改善用途として有用である。 Useful as anti-vibration applications, vibration suppression applications, shock-absorbing applications, and touch-improving touch areas of human bodies, such as notebook computers, portable hard disks, mobile phones, smartphones, portable music information devices, and portable game machines It is.
電気・電子用途では、例えば、ＬＥＤ材料、各種電池周辺材料、センサー類、半導体周辺材料、回路基板周辺材料、液晶等のディスプレイ周辺材料、照明材料、光通信・光回路周辺材料、光記録周辺材料、磁気記録材料、等に利用可能である。 In electrical and electronic applications, for example, LED materials, various battery peripheral materials, sensors, semiconductor peripheral materials, circuit substrate peripheral materials, display peripheral materials such as liquid crystal, lighting materials, optical communication / optical circuit peripheral materials, optical recording peripheral materials It can be used for magnetic recording materials.
ＬＥＤ材料としては、ＬＥＤ素子のモールド材、封止材、封止フィルム、ダイボンド材、コーティング材、シール材、接着剤、粘着剤、レンズ用材料としての使用や、ＬＥＤ電球、ＬＥＤ表示灯、ＬＥＤ表示板、ＬＥＤ表示機等のシール材、接着剤、粘着剤、コーティング材等に利用可能である。 LED materials include LED element molding materials, sealing materials, sealing films, die-bonding materials, coating materials, sealing materials, adhesives, adhesives, lens materials, LED bulbs, LED display lamps, LEDs It can be used for sealing materials such as display boards and LED displays, adhesives, adhesives, coating materials and the like.
電池周辺材料としては、リチウムイオン電池、ナトリウム・硫黄電池、ナトリウム溶融塩電池、有機ラジカル電池、ニッケル水素電池、ニッケルカドミウム電池、レドックスフロー電池、リチウム硫黄電池、空気電池、電解コンデンサ、電気二重層キャパシタ、リチウムイオンキャパシタ、燃料電池、太陽電池、色素増感型太陽電池等のシール材、裏面封止材、各素子のモールド材、接着剤、粘着剤、封止材、封止フィルム、コーティング材、ポッティング材、充填材、セパレーター、触媒固定用皮膜、保護フィルム、電極の結着剤、冷媒油用シール材、ホース材等に利用可能である。 Battery peripheral materials include lithium ion batteries, sodium / sulfur batteries, molten sodium batteries, organic radical batteries, nickel metal hydride batteries, nickel cadmium batteries, redox flow batteries, lithium sulfur batteries, air batteries, electrolytic capacitors, electric double layer capacitors , Sealing materials for lithium ion capacitors, fuel cells, solar cells, dye-sensitized solar cells, back surface sealing materials, molding materials for each element, adhesives, adhesives, sealing materials, sealing films, coating materials, It can be used for potting materials, fillers, separators, catalyst fixing films, protective films, electrode binders, refrigerant oil sealing materials, hose materials, and the like.
センサー類としては、力・荷重・衝撃・圧力・回転・振動・接触・流量・日射・光・におい・時間・温度・湿度・風速・距離・位置・慣性・傾斜・速度・加速度・角速度・硬度・歪・音・磁気・電流・電圧・電力・電子・放射線・赤外線・Ｘ線・紫外線・液量・重量・ガス量・イオン量・金属量・色彩等各種センサーの封止材、封止フィルム、振動吸収材、振動抑制材、レンズ用材料、接着剤、粘着剤、コーティング剤、フィルム等として利用可能である。 Sensors include force, load, impact, pressure, rotation, vibration, contact, flow rate, solar radiation, light, odor, time, temperature, humidity, wind speed, distance, position, inertia, tilt, speed, acceleration, angular velocity, hardness・ Seal, Sound, Magnetism, Current, Voltage, Power, Electron, Radiation, Infrared, X-ray, UV, Liquid, Weight, Gas, Ion, Metal, Color, etc. It can be used as a vibration absorbing material, vibration suppressing material, lens material, adhesive, pressure-sensitive adhesive, coating agent, film and the like.
回路基板周辺材料としては、ＩＣ、ＬＳＩ、半導体チップ、トランジスタ、ダイオード、サイリスタ、コンデンサ、抵抗体、コイル等の各種素子が搭載されたリジッドまたはフレキシブル配線基板やＭＥＭＳ（マイクロエレクトロメカニカルシステム）のシール材、コーティング材、コンフォーマルコーティング材、ポッティング材、上記各素子のモールド材、アンダーフィル材、ダイボンド材、ダイボンディングフィルム、接着剤、粘着剤、封止材、封止フィルムとして利用可能である。 Circuit board peripheral materials include rigid or flexible wiring boards on which various elements such as ICs, LSIs, semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, and coils are mounted, and MEMS (micro electro mechanical system) sealing materials , Coating materials, conformal coating materials, potting materials, molding materials, underfill materials, die-bonding materials, die-bonding films, adhesives, pressure-sensitive adhesives, sealing materials, and sealing films for the above elements.
ディスプレイ周辺材料としては、液晶ディスプレイ、プラズマディスプレイ、ＬＥＤ表示装置、有機ＥＬ（エレクトロルミネッセンス）ディスプレイ、フィールドエミッションディスプレイ、電子ペーパー、フレキシブルディスプレイ、３Ｄホログラム、有機薄膜トランジスタディスプレイ、ヘッドマウントディスプレイ等の各素子のモールド材、各種フィルター、保護フィルム、反射防止フィルム、視野角補正フィルム、偏光子保護フィルム、光学補正フィルムなどのフィルム類、シール材、接着剤、粘着剤、封止材、封止フィルム、基板や部材のコーティング材、ポッティング材、充填材、視認性改良材、レンズ用材料、導光板、プリズムシート、偏光板、位相差板、液晶ダム材として利用可能である。 Peripheral display materials include liquid crystal displays, plasma displays, LED displays, organic EL (electroluminescence) displays, field emission displays, electronic paper, flexible displays, 3D holograms, organic thin film transistor displays, head mounted displays, and other molds. Materials, various filters, protective films, antireflection films, viewing angle correction films, polarizer protective films, optical correction films, etc., sealing materials, adhesives, adhesives, sealing materials, sealing films, substrates and members It can be used as a coating material, potting material, filler, visibility improving material, lens material, light guide plate, prism sheet, polarizing plate, retardation plate, and liquid crystal dam material.
照明材料としては、照明用ＬＥＤ、照明用有機ＥＬ、照明用無機ＥＬのシール材・コーティング材・接着剤・封止材・成形部品として利用可能である。 As a lighting material, it can be used as a sealing material / coating material / adhesive / sealing material / molded part of a lighting LED, a lighting organic EL, and a lighting inorganic EL.
光通信・光回路周辺材料としては、有機フォトリフラクティブ素子、光ファイバー、光スイッチ、レンズ、光導波路、発光素子、フォトダイオード、光増幅素子、光電子集積回路、光コネクタ、光カプラ、光演算素子、光電変換装置、レーザー素子等の各素子のモールド材、シール材、接着剤、粘着剤、封止材、封止フィルム、コーティング材、ポッティング材、充填材、保護膜、レンズ用材料、導光板、プリズムシート、偏光板、フェルールとして利用可能である。 Optical communication and optical circuit peripheral materials include organic photorefractive elements, optical fibers, optical switches, lenses, optical waveguides, light emitting elements, photodiodes, optical amplification elements, optoelectronic integrated circuits, optical connectors, optical couplers, optical arithmetic elements, photoelectrics Molding materials, sealing materials, adhesives, adhesives, sealing materials, sealing films, coating materials, potting materials, fillers, protective films, lens materials, light guide plates, prisms for elements such as conversion devices and laser elements It can be used as a sheet, a polarizing plate and a ferrule.
光記録材料としては、ＶＤ（ビデオディスク）、ＣＤ、ＣＤ－ＲＯＭ、ＣＤ－Ｒ、ＣＤ－ＲＷ、ＤＶＤ、ＤＶＤ－ＲＯＭ、ＤＶＤ－Ｒ、ＤＶＤ－ＲＷ、ＢＤ、ＢＤ－ＲＯＭ、ＢＤ－Ｒ、ＢＤ－ＲＥ、ＭＯ、ＭＤ、ＰＤ（相変化ディスク）、ホログラム、光カード用のディスク基板材料、ピックアップレンズ等の保護フィルム、シール材、接着剤、粘着剤、封止材、封止フィルム、コーティング材、防振材、制振材として利用可能である。 Optical recording materials include VD (video disc), CD, CD-ROM, CD-R, CD-RW, DVD, DVD-ROM, DVD-R, DVD-RW, BD, BD-ROM, BD-R, BD-RE, MO, MD, PD (phase change disk), hologram, disk substrate material for optical card, protective film such as pickup lens, sealing material, adhesive, adhesive, sealing material, sealing film, coating It can be used as a material, anti-vibration material, and damping material.
磁気記録材料としては、ハードディスク、磁気テープ、クレジットカード等の磁気カードの防振材、制振材、シール材、接着剤、粘着剤、封止材、コーティング材、カバーガスケット、カード材料として利用可能である。 Magnetic recording materials can be used as anti-vibration materials, damping materials, sealing materials, adhesives, adhesives, sealing materials, coating materials, cover gaskets, and card materials for magnetic cards such as hard disks, magnetic tapes, and credit cards. It is.
情報電気機器として、携帯電話、メディアプレーヤー、タブレット端末、スマートフォン、携帯ゲーム機、コンピュータ、プリンタ、スキャナ、プロジェクタ、インクジェットタンク等のシール材、封止材、接着剤、粘着剤、パッキン、Ｏリング、ベルト、防振材、制振材防音材などに利用可能である。 As information electrical equipment, mobile phones, media players, tablet terminals, smartphones, portable game machines, computers, printers, scanners, projectors, inkjet tanks and other sealing materials, sealing materials, adhesives, adhesives, packing, O-rings, It can be used for belts, vibration-proof materials, vibration-damping materials and sound-proof materials.
その他に、タッチパネルの防汚膜、潤滑膜、ＩＣチップのモールド材、ペルチェ素子のモールド材、電解コンデンサの封口体、ケーブルジョイントポッティング材、ＩＧＢＴ（車両推進制御装置）のポッティング材、半導体ウェハ加工用ダイシングテープ、ダイボンド剤、ダイボンドフィルム、アンダーフィル、異方導電性接着剤、異方導電性フィルム、導電性接着剤、導電性ペースト、熱伝導性接着剤、熱伝導性ペースト、仮止め用フィルム、固定用フィルム、封止用フィルム等に利用可能である。 In addition, antifouling films for touch panels, lubricant films, IC chip molding materials, Peltier element molding materials, electrolytic capacitor sealing bodies, cable joint potting materials, IGBT (vehicle propulsion control device) potting materials, and semiconductor wafer processing Dicing tape, die bond agent, die bond film, underfill, anisotropic conductive adhesive, anisotropic conductive film, conductive adhesive, conductive paste, heat conductive adhesive, heat conductive paste, film for temporary fixing, It can be used for fixing films, sealing films and the like.
その他の産業機械、電気・電子機器やその部品として、ＭＥＭＳと呼ばれる微小電気機械素子や各種センサー類、制御機器や電池、電池周辺部材、ＬＥＤ材料、半導体周辺材料、回路基板周辺材料、液晶等のディスプレイ周辺材料、照明材料、光通信・光回路周辺材料、光記録周辺材料、磁気記録材料、電子顕微鏡やその他理工学機器、各種測定装置、自動販売機、ＴＶカメラ、レジスタ、キャビネット、ロボットの皮膚シュータ、エレベータ、エスカレータ、動く歩道、コンベア、リフト、トラクタ、ブルドーザ、発電機、コンプレッサ、コンテナ、ホッパ、選果機用コンベアー、現金自動取引装置（ＡＴＭ）、両替機、計数機、自動販売機、キャッシュディスペンサー（ＣＤ）、リチウム電池等二次電池、ＩＣトレーや搬送コンベア等の半導体製造装置、制振鋼板、削岩機、切削機、チェーンソー、ハンドミキサー、草刈り機等の激しいモーター振動のある機械等の防振用途、制振用途、衝撃緩衝用途、衝撃吸収用途、人体との接触部の感触改善用途として有用である。 Other industrial machines, electrical / electronic devices and their components, such as micro electromechanical elements called MEMS, various sensors, control devices, batteries, battery peripheral members, LED materials, semiconductor peripheral materials, circuit board peripheral materials, liquid crystal, etc. Display peripheral materials, lighting materials, optical communication / optical circuit peripheral materials, optical recording peripheral materials, magnetic recording materials, electron microscopes and other scientific and engineering equipment, various measuring devices, vending machines, TV cameras, registers, cabinets, robot skins Shuters, elevators, escalators, moving walkways, conveyors, lifts, tractors, bulldozers, generators, compressors, containers, hoppers, conveyors for fruit sorting machines, automatic teller machines (ATMs), currency exchange machines, counting machines, vending machines, Cash dispensers (CD), secondary batteries such as lithium batteries, IC trays and conveyors Anti-vibration applications such as conductor manufacturing equipment, damping steel plates, rock drills, cutting machines, chainsaws, hand mixers, mowers, etc., machines with strong motor vibration, damping applications, shock buffering applications, shock absorbing applications, human body This is useful for improving the touch of the contact portion.
家電分野では、パッキン、Ｏリング、ベルトなどに使用できる。具体的には、照明器具用の飾り類、防水パッキン類、防振ゴム類、防虫パッキン類、クリーナ用の防振・吸音と空気シール材、電気温水器用の防滴カバー、防水パッキン、ヒータ部パッキン、電極部パッキン、安全弁ダイアフラム、酒かん器用のホース類、防水パッキン、電磁弁、スチームオーブンレンジ及びジャー炊飯器用の防水パッキン、給水タンクパッキン、吸水バルブ、水受けパッキン、接続ホース、ベルト、保温ヒータ部パッキン、蒸気吹き出し口シールなど燃焼機器用のオイルパッキン、Ｏリング、ドレインパッキン、加圧チューブ、送風チューブ、送・吸気パッキン、防振ゴム、給油口パッキン、油量計パッキン、送油管、ダイアフラム弁、送気管など、音響機器用のスピーカーガスケット、スピーカーエッジ、ターンテーブルシート、ベルト、プーリー等が挙げられる。 In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, 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 parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntables for acoustic equipment such as diaphragm valves and air pipes Seat, belts, pulleys, and the like.
建材用途として防音パネル、防音ガラス、一般ガラス、天井材、内壁材、外壁材、床材、配管用材、水道部材、フェンス等の建材、空気膜構造屋根材、構造用ガスケット（ジッパーガスケット）、免震ゴム、防振ゴム、シート、防水シート、不定形ガスケット、定形ガスケット、防水材、シール材、パッキング、グロメット、包装輸送資材、住宅用制振シート、制振ダンパー材、橋梁用制振材、防音材、セッティングブロック、摺動材、合わせガラスおよび複層ガラスのガラスシール材、網入りガラスや合わせガラス端面（切断部）の防錆・防水用封止材、シャッタ、カーテンレール、カーテンウォール、免振アイソレーター、地盤改良材等の防振用途、制振用途、衝撃緩衝用途、衝撃吸収用途、可聴域しきい値近傍の低周波音及び高周波音に対応する等の防音用制振用途として有用である。 Soundproof panels, soundproof glass, general glass, ceiling materials, inner wall materials, outer wall materials, flooring materials, plumbing materials, water supply materials, building materials such as fences, air membrane structure roof materials, structural gaskets (zip gaskets), exemption Seismic rubber, anti-vibration rubber, sheet, waterproof sheet, non-standard gasket, fixed gasket, waterproof material, sealing material, packing, grommet, packaging transport material, residential vibration damping sheet, vibration damper material, bridge damping material, Soundproofing materials, setting blocks, sliding materials, laminated glass and double-glazed glass sealing materials, rustproof and waterproofing sealing materials for meshed glass and laminated glass end faces (cut parts), shutters, curtain rails, curtain walls, Vibration isolation applications such as vibration isolation isolators, ground improvement materials, vibration suppression applications, shock absorbing applications, shock absorption applications, low and high frequency sounds near the audible threshold It is useful as soundproof damping applications such as corresponding.
海洋・土木分野では、構造用材料として、ゴム伸縮継手、支承、止水板、防水シート、ラバーダム、弾性舗装、防振パット、防護体等、工事副材料としてゴム型枠、ゴムパッカー、ゴムスカート、スポンジマット、モルタルホース、モルタルストレーナ等、工事補助材料としてゴムシート類、エアホース等、安全対策商品としてゴムブイ、消波材等、環境保全商品としてオイルフェンス、シルトフェンス、防汚材、マリンホース、ドレッジングホース、オイルスキマー等に使用できる。その他、板ゴム、マット、フォーム板等にも使用できる。 In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.
また防振・制振・防音・免震材料が特に求められる用途として、ステッピングモーター、磁気ディスク、ハードディスク、自動販売機、スピーカフレーム、ＢＳアンテナ、ＶＴＲカバー用制振材等の電気・電子機器用途；ルーフ、フロア、シャッタ、カーテンレール、床、配管ダクト、デッキプレート、カーテンウォール、階段、ドア、免振アイソレーター、構造材用制振材等の建築用途；粘弾性ダンパー、耐震マット等の建築用途；エンジンルーム、計測ルーム用制振材等の船舶用途；エンジン（オイルパン、フロントカバー、ロッカーカバー）、車体（ダッシュ、フロア、ドア、ルーフ、パネル、ホイルハウス）、トランスミッション、パーキングブレーキカバー、シートバック用制振材等の自動車用途；ＴＶカメラ、複写機、電算機、プリンタ、レジスタ、キャビネット用制振材等のカメラ・事務機器用途；シュータ、エレベータ、エスカレータ、コンベア、トラクタ、ブルドーザ、発電機、コンプレッサ、コンテナ、ホッパ、防音ボックス、草刈り機のモータカバー用制振材等の産業機械関係用途；鉄道車両ルーフ、側板、ドア、アンダーフロア、各種補機カバー、橋梁用制振材等の鉄道用途；半導体用途の精密除振装置用制振材；可聴域しきい値近傍の低周波音及び高周波音に対応する等の防音用制振材として利用可能である。 In addition, applications that require vibration, vibration control, soundproof, and seismic isolation materials include electrical and electronic equipment such as stepping motors, magnetic disks, hard disks, vending machines, speaker frames, BS antennas, and vibration control materials for VTR covers. ; Building applications such as roofs, floors, shutters, curtain rails, floors, piping ducts, deck plates, curtain walls, stairs, doors, vibration-isolating isolators, damping materials for structural materials; building applications such as viscoelastic dampers and earthquake-resistant mats ; Marine use for engine room and measurement room damping material; engine (oil pan, front cover, rocker cover), car body (dash, floor, door, roof, panel, wheel house), transmission, parking brake cover, seat Automotive applications such as damping materials for bags; TV cameras, copiers, computers, Applications for cameras and office equipment such as linters, registers, cabinet damping materials; shooters, elevators, escalators, conveyors, tractors, bulldozers, generators, compressors, containers, hoppers, soundproof boxes, mowing machine motor damping materials, etc. Industrial machinery-related applications; railway vehicle roofs, side plates, doors, under floors, various auxiliary equipment covers, railway damping materials such as bridge damping materials; damping materials for precision vibration isolator for semiconductor applications; near audible threshold It can be used as a vibration damping material for soundproofing such as for low frequency sound and high frequency sound.
その他に、本発明の硬化物は、成形体として、パッキン、Ｏリング、ベルト、チューブ、ホース、弁、シート等に利用可能である。 In addition, the cured product of the present invention can be used as a molded body for packing, O-rings, belts, tubes, hoses, valves, seats, and the like.
配線コネクタ用反応性ホットメルト剤、反応性ホットメルト接着剤、ＯＣＡ（光学用透明接着剤）、弾性接着剤、コンタクト接着剤、嫌気性接着剤、タイル用接着剤、紫外線硬化性接着剤、電子線硬化性接着剤、タッチパネルやタッチセンサー用接着剤等の各種接着剤として利用可能である。 Reactive hot melt agent for wiring connectors, reactive hot melt adhesive, OCA (transparent adhesive for optics), elastic adhesive, contact adhesive, anaerobic adhesive, tile adhesive, UV curable adhesive, electronic It can be used as various adhesives such as a linear curable adhesive, an adhesive for a touch panel and a touch sensor.
ブチル系粘着剤の改質や、マスキングテープ、パイプ防食テープ、建築止水テープ、電気用自己融着テープ、再剥離用粘着剤、電線用融着テープ等の各種粘着剤として利用可能である。 It can be used as various adhesives such as modification of butyl-based adhesives, masking tapes, pipe anticorrosion tapes, architectural waterproofing tapes, electrical self-fusing tapes, re-peeling adhesives, electric wire fusion tapes, and the like.
電線・ケーブル・光ファイバー類の被覆材またはその補修材、結線部の絶縁シール材、ガス管、水道管等の管内ライニング材、無機フィラー、有機フィラーのコーティング材、エポキシ型内成形用離型材等の各種コーティング用途に利用可能である。 Covering materials for electric wires, cables, optical fibers or their repair materials, insulation sealing materials for connection parts, gas pipes, pipe lining materials such as water pipes, inorganic fillers, organic filler coating materials, release materials for molding in epoxy molds, etc. It can be used for various coating applications.
熱伝導シート、放熱シート、電磁波吸収シート、導電性シート、防水シート、自動車用保護シート、パネル用衝撃吸収シート等の各種シートとして利用可能である。 It can be used as various sheets such as a heat conductive sheet, a heat radiating sheet, an electromagnetic wave absorbing sheet, a conductive sheet, a waterproof sheet, an automobile protective sheet, and a panel shock absorbing sheet.
衝撃吸収ゲル、ベッド、靴等の衝撃吸収材、合わせガラスの中間層膜、弾性塗料、水性エマルジョン等の塗料、プリプレグ、ＯＡ機器用や搬送用の各種ローラ、キャップライナー、撥インク剤、インキ、各種冷媒用シール材、工業用缶・食品用缶のシール材・ガスケット、発泡ガスケット、塗料、粉体塗料、発泡体、缶蓋等のシール材、フィルム、ガスケット、マリンデッキコーキング、注型材料、各種成形材料、人工大理石として利用可能である。 Shock absorbing gel, impact absorbing material such as bed, shoes, interlayer film of laminated glass, elastic paint, paint such as aqueous emulsion, prepreg, various rollers for OA equipment and transport, cap liner, ink repellent agent, ink, Seals for various refrigerants, seals and gaskets for industrial and food cans, foam gaskets, paints, powder paints, foams, seals for can lids, films, gaskets, marine deck caulking, casting materials, It can be used as various molding materials and artificial marble.
ドライフィルムレジスト用途、電着レジスト用途等のレジスト用途にも利用可能である。 It can also be used for resist applications such as dry film resist applications and electrodeposition resist applications.
しかしながら、本発明の硬化物が上記の用途に限定されないことは明白である。 However, it is obvious that the cured product of the present invention is not limited to the above-mentioned use.
以下に、本発明の具体的な実施例を比較例と併せて説明するが、本発明は、下記実施例に限定されるものではない。「数平均分子量」および「分子量分布（重量平均分子量と数平均分子量の比）」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いた標準ポリスチレン換算法により算出した。ただし、ＧＰＣカラムとしてポリスチレン架橋ゲルを充填したもの（ｓｈｏｄｅｘ　ＧＰＣ　Ｋ－８０４、Ｋ－８０２．５；昭和電工（株）製）を、ＧＰＣ溶媒としてクロロホルムを用いた。 Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. “Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804, K-802.5; manufactured by Showa Denko KK) was used, and chloroform was used as the GPC solvent.
また重合体１分子当たりに導入された官能基数は、１Ｈ－ＮＭＲによる濃度分析、及びＧＰＣにより求まる数平均分子量を基に算出した。ただしＮＭＲはＢｒｕｋｅｒ社製ＡＳＸ－４００を使用し、溶媒として重クロロホルムを用いて２３℃にて測定した。 The number of functional groups introduced per molecule of the polymer was calculated based on the concentration analysis by 1 H-NMR and the number average molecular weight determined by GPC. NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.
（合成例１）アクリロイル基を有するポリ（アクリル酸ｎ－ブチル）重合体［Ｐ１］の合成例
公知の方法（例えば、特開２０１２－２１１２１６号公報記載）に従い、臭化第一銅を触媒、ペンタメチルジエチレントリアミンを配位子、ジエチル－２，５－ジブロモアジペートを開始剤、アクリル酸ｎ－ブチルをモノマーとし、（アクリル酸ｎ－ブチル）／（ジエチル－２，５－ジブロモアジペート）比を１６０にして重合し、末端臭素基ポリアクリル酸ｎ－ブチルを得た。 (Synthesis Example 1) Synthesis example of poly (n-butyl acrylate) polymer having acryloyl group [P1] According to a known method (for example, described in JP-A-2012-212216), cuprous bromide was used as a catalyst. Using pentamethyldiethylenetriamine as a ligand, diethyl-2,5-dibromoadipate as an initiator, n-butyl acrylate as a monomer, and a (n-butyl acrylate) / (diethyl-2,5-dibromoadipate) ratio of 160 To obtain a terminal bromine group poly (n-butyl acrylate).
この重合体をＮ，Ｎ－ジメチルアセトアミドに溶解させ、アクリル酸カリウムを加え、窒素雰囲気下、７０℃で加熱攪拌した。この混合液中のＮ，Ｎ－ジメチルアセトアミドを減圧留去したのち、残渣に酢酸ブチルを加えて、不溶分を濾過により除去した。濾液の酢酸ブチルを減圧留去して、両末端にアクリロイル基を有するポリ（アクリル酸ｎ－ブチル）重合体［Ｐ１］を得た。重合体［Ｐ１］の数平均分子量は２３，０００、分子量分布は１．１、重合体１分子当たりに導入された平均のアクリロイル基の数を１Ｈ－ＮＭＲ分析により求めたところ約１．９個であった。 This polymer was dissolved in N, N-dimethylacetamide, potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. in a nitrogen atmosphere. N, N-dimethylacetamide in this mixed solution was distilled off under reduced pressure, butyl acetate was added to the residue, and insoluble matter was removed by filtration. The butyl acetate in the filtrate was distilled off under reduced pressure to obtain a poly (n-butyl acrylate) polymer [P1] having acryloyl groups at both ends. The number average molecular weight of the polymer [P1] was 23,000, the molecular weight distribution was 1.1, and the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis to be about 1.9. Met.
（合成例２）アクリロイル基を有するポリ（アクリル酸ｎ－ブチル）／（アクリル酸エチル）／（アクリル酸２－メトキシエチル）共重合体［Ｐ２］の合成例
モノマーとして、アクリル酸ｎ－ブチル／アクリル酸エチル／アクリル酸２－メトキシエチルを７３部／２５部／２部用い、モノマー／開始剤比を２４０とする以外は、合成例１と同様にして両末端にアクリロイル基を有するポリ（アクリル酸ｎ－ブチル）／（アクリル酸エチル）／（アクリル酸２－メトキシエチル）共重合体［Ｐ２］を得た。 Synthesis Example 2 Synthesis Example of Poly (n-butyl acrylate) / (ethyl acrylate) / (2-methoxyethyl acrylate) copolymer [P2] having an acryloyl group As a monomer, n-butyl acrylate / Poly (acrylic acid) having acryloyl groups at both ends in the same manner as in Synthesis Example 1, except that 73 parts / 25 parts / 2 parts of ethyl acrylate / 2-methoxyethyl acrylate was used and the monomer / initiator ratio was 240. An acid n-butyl) / (ethyl acrylate) / (2-methoxyethyl acrylate) copolymer [P2] was obtained.
共重合体［Ｐ２］の数平均分子量は約３５０００、分子量分布は１．３であった。重合体１分子当たりに導入された平均のアクリロイル基の数を１Ｈ－ＮＭＲ分析により求めたところ、約２．０個であった。 The number average molecular weight of the copolymer [P2] was about 35,000, and the molecular weight distribution was 1.3. When the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis, it was about 2.0.
（合成例３）アクリロイル基を有するポリ（アクリル酸ｎ－ブチル）／（アクリル酸エチル）／アクリル酸２－メトキシエチル）共重合体［Ｐ３］の合成例
モノマーとして、アクリル酸ｎ－ブチル／アクリル酸エチル／アクリル酸２－メトキシエチルを２８部／４０部／３３部用い、モノマー／開始剤比を１２０とする以外は、合成例１と同様にして両末端にアクリロイル基を有するポリ（アクリル酸ｎ－ブチル）／（アクリル酸エチル）／アクリル酸２－メトキシエチル）共重合体［Ｐ３］を得た。 (Synthesis Example 3) Synthesis example of poly (n-butyl acrylate) / (ethyl acrylate) / (2-methoxyethyl acrylate) copolymer [P3] having acryloyl group As monomer, n-butyl acrylate / acrylic Poly (acrylic acid) having acryloyl groups at both ends in the same manner as in Synthesis Example 1, except that 28 parts / 40 parts / 33 parts of ethyl acrylate / 2-methoxyethyl acrylate was used and the monomer / initiator ratio was 120. n-butyl) / (ethyl acrylate) / 2-methoxyethyl acrylate) copolymer [P3] was obtained.
共重合体［Ｐ３］の数平均分子量は約１６０００、分子量分布は１．１であった。重合体１分子当たりに導入された平均のアクリロイル基の数を１Ｈ－ＮＭＲ分析により求めたところ、約１．８個であった。 The number average molecular weight of the copolymer [P3] was about 16000, and the molecular weight distribution was 1.1. When the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis, it was about 1.8.
（合成例４）アクリロイル基を有するポリ（アクリル酸ｎ－ブチル）重合体［Ｐ４］の合成例
開始剤としてα－ブロモ酪酸エチルを用い、モノマー／開始剤比を８０とする以外は、合成例１と同様にして片末端にアクリロイル基を有するポリ（アクリル酸ｎ－ブチル）重合体［Ｐ４］を得た。 (Synthesis example 4) Synthesis example of poly (n-butyl acrylate) polymer having acryloyl group [P4] Synthesis example except that α-bromobutyrate is used as an initiator and the monomer / initiator ratio is 80 In the same manner as in Example 1, a poly (n-butyl acrylate) polymer [P4] having an acryloyl group at one end was obtained.
重合体［Ｐ４］の数平均分子量は１２，０００、分子量分布は１．１、重合体１分子当たりに導入された平均のアクリロイル基の数を１Ｈ－ＮＭＲ分析により求めたところ約０．９個であった。 The number average molecular weight of the polymer [P4] was 12,000, the molecular weight distribution was 1.1, and the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis to be about 0.9. Met.
（合成例５）アクリロイル基を有するポリ（アクリル酸ｎ－ブチル）／（アクリル酸エチル）／アクリル酸２－メトキシエチル）共重合体［Ｐ５］の合成例
開始剤としてα－ブロモ酪酸エチルを用い、モノマー／開始剤比を４８とする以外は、合成例４と同様にして片末端にアクリロイル基を有するポリ（アクリル酸ｎ－ブチル）／（アクリル酸エチル）／アクリル酸２－メトキシエチル）共重合体［Ｐ５］を得た。 (Synthesis Example 5) Synthesis Example of Poly (n-butyl acrylate) / (ethyl acrylate) / (2-methoxyethyl acrylate) copolymer [P5] having acryloyl group Ethyl α-bromobutyrate was used as an initiator. In the same manner as in Synthesis Example 4 except that the monomer / initiator ratio is 48, poly (n-butyl acrylate) / (ethyl acrylate) / (2-methoxyethyl acrylate) having an acryloyl group at one end) A polymer [P5] was obtained.
共重合体［Ｐ５］の数平均分子量は７，０００、分子量分布は１．２、重合体１分子当たりに導入された平均のアクリロイル基の数を１Ｈ－ＮＭＲ分析により求めたところ約０．９個であった。 The number average molecular weight of the copolymer [P5] was 7,000, the molecular weight distribution was 1.2, and the average number of acryloyl groups introduced per molecule of the polymer was determined by 1H-NMR analysis to be about 0.9. It was a piece.
＜物性評価方法＞
実施例及び比較例で作製された硬化物の各物性評価は、以下の方法、条件に従って実施した。 <Physical property evaluation method>
Each physical property evaluation of the cured products prepared in Examples and Comparative Examples was performed according to the following methods and conditions.
（引張物性）
ＪＩＳ　Ｋ　６２５１に準拠し、試験片としてシートをダンベル３号型に打抜いたものを用意し、これを測定に使用した。引張速度は５００ｍｍ／分とし、切断時引張応力（引張強さと表記）、切断時伸び（伸びと表記）を求めた。 (Tensile properties)
In accordance with JIS K 6251, a test piece obtained by punching a sheet into a dumbbell No. 3 type was prepared and used for measurement. The tensile speed was 500 mm / min, and the tensile stress at break (expressed as tensile strength) and the elongation at break (expressed as elongation) were determined.
（圧縮永久ひずみ）
ＪＩＳ　Ｋ　６２６２に準じて圧縮永久ひずみ試験測定用大型試験片を使用し、所定条件下での圧縮永久ひずみ試験を行なった。 (Compression set)
A compression set test under a predetermined condition was performed using a large test piece for compression set test measurement according to JIS K 6262.
（動的粘弾性）
アイティー計測制御（株）製動的粘弾性測定装置ＤＶＡ－２００にて、周波数５Ｈｚ、歪み０．０５％、剪断モードで測定し、損失正接（ｔａｎδ）のピークを示す温度をガラス転移温度（Ｔｇ）とした。 (Dynamic viscoelasticity)
Measured with a dynamic viscoelasticity measuring device DVA-200 manufactured by IT Measurement Control Co., Ltd. in a shear mode with a frequency of 5 Hz, a strain of 0.05%, and the temperature showing the peak of loss tangent (tan δ) Tg).
（紫外線硬化）
フュージョンＵＶシステムズ・ジャパン社（現ヘレウス（株））製、型式ＬＨ６、Ｈバルブ、または、（株）アイテックシステム製、卓上バッチ式ＵＶ　ＬＥＤ硬化装置ＭＵＶＢＡ　ＵＶ－ＬＥＤ（波長３６５ｎｍ）を使用した。ピーク照度（照度と表記）および積算光量（光量と表記）：紫外線光量計はＥＩＴ社製、４バンドＵＶ測定器：ＵＶ　ＰＯＷＥＲ　ＰＵＣＫ　ＩＩを使用し、ＵＶＡ（３２０－３９０ｎｍ）の測定値を用いた。 (UV curing)
Fusion UV Systems Japan Co., Ltd. (currently Heraeus Co., Ltd.), model LH6, H bulb, or Itech System Co., Ltd., desktop batch type UV LED curing device MUVBA UV-LED (wavelength 365 nm) was used. Peak illuminance (indicated as illuminance) and integrated light intensity (indicated as light intensity): UV light intensity meter manufactured by EIT, 4-band UV measuring instrument: UV POWER PUCK II, UVA (320-390 nm) measured value was used .
（実施例１）
合成例１で得られた重合体［Ｐ１］１００重量部に対し、アクリロイルモルホリン（ＫＪケミカルズ（株）製）を５０重量部と、ライトアクリレート１３０Ａ（共栄社化学（株）製、平均炭素数１９のエーテル直鎖を有するアクリルモノマー：メトキシポリエチレングリコールアクリレート）２０重量部、反応性希釈剤としてＴＭＰ３Ａ（大阪有機化学工業（株）製、トリメチロールプロパントリアクリレート）１重量部、酸化防止剤としてＩＲＧＡＮＯＸ　１０１０（ＢＡＳＦジャパン社製、ヒンダードフェノール系酸化防止剤）１重量部、光ラジカル開始剤として、ＤＡＲＯＣＵＲ１１７３（ＢＡＳＦジャパン社製、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン）２重量部を混合したものにＩＲＧＡＣＵＲＥ８１９（ＢＡＳＦジャパン社製、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキシド）１重量部をあらかじめ混合・溶解したものを添加し、十分に混合した後、脱泡して、ラジカル硬化性組成物を得た。２ｍｍ厚みになるようにポリプロピレン製型枠に流し込み、空気下でＵＶ照射（照射条件：照度４００ｍＷ／ｃｍ２、光量５０００ｍＪ／ｃｍ２）を実施することにより、ゴム状のシート硬化物を得た。得られた硬化物の引張物性・動的粘弾性を測定した。 (Example 1)
For 100 parts by weight of the polymer [P1] obtained in Synthesis Example 1, 50 parts by weight of acryloylmorpholine (manufactured by KJ Chemicals) and light acrylate 130A (manufactured by Kyoeisha Chemical Co., Ltd., average carbon number 19) 20 parts by weight of an acrylic monomer having an ether straight chain: methoxypolyethylene glycol acrylate), 1 part by weight of TMP3A (manufactured by Osaka Organic Chemical Co., Ltd., trimethylolpropane triacrylate) as a reactive diluent, and IRGANOX 1010 (as an antioxidant) 1 part by weight of BASF Japan, hindered phenol antioxidant), 2 parts by weight of DAROCUR1173 (BASF Japan, 2-hydroxy-2-methyl-1-phenylpropan-1-one) as a photo radical initiator IRGACURE819 (B A mixture of 1 part by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), manufactured by ASF Japan Co., previously added and mixed, thoroughly mixed, defoamed, and radical curable composition I got a thing. The rubber-like sheet cured product was obtained by pouring into a polypropylene mold so as to have a thickness of 2 mm, and performing UV irradiation (irradiation conditions: illuminance: 400 mW / cm 2, light amount: 5000 mJ / cm 2) under air. Tensile properties and dynamic viscoelasticity of the obtained cured product were measured.
同様に、圧縮永久ひずみ試験測定用金型を用いて、空気下でＵＶ照射（照射条件：照度４００ｍＷ／ｃｍ２、光量８５００ｍＪ／ｃｍ２）を実施することにより試験片を作製し、１５０℃７０時間の圧縮永久ひずみを測定した。結果を表１に示す。 Similarly, a test piece was prepared by carrying out UV irradiation (irradiation conditions: illuminance: 400 mW / cm 2, light intensity: 8500 mJ / cm 2) under air using a compression set test measurement mold, and 150 ° C. for 70 hours. The compression set was measured. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（実施例２、３、比較例１～４）
表１に示す処方でラジカル硬化性組成物を作製し、実施例１と同様にして硬化物の引張物性・動的粘弾性および圧縮永久ひずみを測定した。結果を表１に示す。なお、比較例１では伸びが低く、ゴムとしての挙動を示さなかったため、圧縮永久歪を測定しなかった。 (Examples 2 and 3, Comparative Examples 1 to 4)
A radical curable composition was prepared according to the formulation shown in Table 1, and the tensile properties, dynamic viscoelasticity and compression set of the cured product were measured in the same manner as in Example 1. The results are shown in Table 1. In Comparative Example 1, the compression set was not measured because the elongation was low and the behavior as a rubber was not exhibited.
表１から明らかなように、（メタ）アクリル系重合体にアクリロイルモルホリンを特定量用い、炭素数６以上の直鎖炭化水素基を有する単官能アクリル系モノマーを特定量用いた場合にのみ、低温特性を維持したまま引張強さ・圧縮永久ひずみ特性の両方ともが優れることが明らかである。 As is clear from Table 1, a low temperature is obtained only when a specific amount of acryloylmorpholine is used for a (meth) acrylic polymer and a specific amount of a monofunctional acrylic monomer having a straight-chain hydrocarbon group having 6 or more carbon atoms is used. It is clear that both tensile strength and compression set characteristics are excellent while maintaining the characteristics.
アクリロイルモルホリンと類似のアクリルアミド化合物であるＤＥＡＡ（ジエチルアクリルアミド）では、引張強さの改善効果が小さいばかりかガラス転移温度が上昇して低温特性が悪化する（比較例２）。また、アクリロイルモルホリンの添加量に関しても、本願発明範囲内であれば顕著な引張強さの改善が見られるが、３０部未満では改善効果が不十分であり（比較例３）、アクリロイルモルホリンを３０～７０重量部の間で用いた場合でも炭素数６以上の直鎖炭化水素基を有する単官能アクリル系モノマーであるライトアクリレート１３０Ａ（メトキシポリエチレングリコールアクリレート）の添加量が不十分な場合（比較例４）は、圧縮永久ひずみが非常に悪い。 DEAA (diethylacrylamide), which is an acrylamide compound similar to acryloylmorpholine, not only has a small effect of improving the tensile strength, but also increases the glass transition temperature and deteriorates the low-temperature characteristics (Comparative Example 2). Also, with regard to the amount of acryloylmorpholine added, a remarkable improvement in tensile strength can be seen within the scope of the present invention, but if it is less than 30 parts, the improvement effect is insufficient (Comparative Example 3), and 30% acryloylmorpholine is added. When the amount of light acrylate 130A (methoxypolyethylene glycol acrylate), which is a monofunctional acrylic monomer having a straight-chain hydrocarbon group having 6 or more carbon atoms, is insufficient even when used between 70 parts by weight (Comparative Example) 4) has a very bad compression set.
（実施例４～１４）
実施例１と同様にして、表２に示す処方のラジカル硬化性組成物を作製し、硬化物の引張物性・動的粘弾性および圧縮永久ひずみを測定した。結果を表２に示す。 (Examples 4 to 14)
In the same manner as in Example 1, radical curable compositions having the formulations shown in Table 2 were prepared, and the tensile properties, dynamic viscoelasticity, and compression set of the cured product were measured. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（比較例５～１２）
実施例１と同様にして、表３に示す処方のラジカル硬化性組成物を作製し、硬化物の引張物性・動的粘弾性および圧縮永久ひずみを測定した。結果を表３に示す。　 (Comparative Examples 5 to 12)
In the same manner as in Example 1, radical curable compositions having the formulations shown in Table 3 were prepared, and the tensile properties, dynamic viscoelasticity, and compression set of the cured product were measured. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
表２および表３の結果から、以下のことが明らかである。 From the results in Tables 2 and 3, the following is clear.
（ＩＩＩ）成分であるアクリロイルモルホリンが添加されない場合（比較例５）には引張強さは非常に小さく、アクリロイルモルホリンと類似のアクリルアミド化合物であるＤＥＡＡ（ジエチルアクリルアミド）を添加した場合（比較例１２）には、引張強さの改善効果が小さい。しかし、（ＩＩＩ）成分、（ＩＶ）成分が本願発明範囲内の添加量であれば、得られる硬化物は室温以下のガラス転移温度を維持したまま引張強さ・伸び・圧縮永久ひずみに顕著な改善効果が見られる（実施例４～１４）。炭素数６以上の炭化水素基を有する単官能アクリル系モノマー（ＩＶ）が添加されない場合には圧縮永久ひずみが５２％もしくは３９％と非常に悪い（比較例６、７）。また添加されていたとしても少なすぎる場合（比較例８）には圧縮永久ひずみ（２０％）の改善効果は非常に限定的であり、また多すぎる場合（比較例９）には、引張強さが０．８２ＭＰａとほとんど改善されていない。また、アクリロイルモルホリン（ＩＩＩ）が多すぎる場合（比較例１０）は、（ＩＶ）成分が添加されていても圧縮永久ひずみ特性の改善効果は限定的である。 When the acryloylmorpholine component (III) is not added (Comparative Example 5), the tensile strength is very low, and DEAA (diethylacrylamide), which is an acrylamide compound similar to acryloylmorpholine, is added (Comparative Example 12). The effect of improving the tensile strength is small. However, if the components (III) and (IV) are added within the scope of the present invention, the resulting cured product is prominent in tensile strength, elongation, and compression set while maintaining a glass transition temperature below room temperature. An improvement effect is seen (Examples 4 to 14). When the monofunctional acrylic monomer (IV) having a hydrocarbon group having 6 or more carbon atoms is not added, the compression set is very bad at 52% or 39% (Comparative Examples 6 and 7). If the amount is too small (Comparative Example 8), the effect of improving the compression set (20%) is very limited, and if too much (Comparative Example 9), the tensile strength is increased. However, 0.82 MPa is hardly improved. Moreover, when there is too much acryloyl morpholine (III) (comparative example 10), even if the (IV) component is added, the improvement effect of a compression set characteristic is limited.
（実施例１５～１７、比較例１３～２０）
実施例１と同様にして、表４に示す処方のラジカル硬化性組成物を作製し、硬化物の引張物性・動的粘弾性および圧縮永久ひずみを測定した。結果を表４に示す。 (Examples 15 to 17, Comparative Examples 13 to 20)
In the same manner as in Example 1, radical curable compositions having the formulations shown in Table 4 were prepared, and the tensile properties, dynamic viscoelasticity, and compression set of the cured product were measured. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
実施例から明らかなように、アクリロイルモルホリンと炭素数１８の分岐炭化水素基を有するＩＳＴＡ（イソステアリルアクリレート）、炭素数１２の直鎖状炭化水素基を有するＬＡ（ラウリルアクリレート）、または、炭素数８の分岐状炭化水素基を有するＩＯＡＡ（イソオクチルアクリレート）を併用した場合は、平均炭素数１９のエーテル直鎖を有するライトアクリレート１３０Ａ（共栄社化学（株）製、メトキシポリエチレングリコールアクリレート）を用いた場合と同様に室温以下のガラス転移温度を維持したまま、引張強さ・伸びに優れ、圧縮永久ひずみも１０％以下と良好な結果を示す。 As is clear from the examples, acryloylmorpholine and ISTA (isostearyl acrylate) having a branched hydrocarbon group having 18 carbon atoms, LA (lauryl acrylate) having a linear hydrocarbon group having 12 carbon atoms, or carbon number When IOAA (isooctyl acrylate) having 8 branched hydrocarbon groups was used in combination, light acrylate 130A having an ether straight chain having an average carbon number of 19 (Kyoeisha Chemical Co., Ltd., methoxypolyethylene glycol acrylate) was used. As in the case, while maintaining the glass transition temperature below room temperature, the tensile strength / elongation is excellent and the compression set is 10% or less.
一方、アクリロイルモルホリンと炭素数１０の脂環式炭化水素基を有するＩＢＸＡ（イソボルニルアクリレート）、ファンクリルＦＡ－５１１ＡＳ（日立化成（株）製、ジシクロペンテニルアクリレート）やファンクリルＦＡ－５１３ＡＳ（日立化成（株）製、ジシクロペンタニルアクリレート）、炭素数６のオキセタン環を有するビスコートＯＸＥ－１０（大阪有機化学工業（株）製、３－エチル－３－オキセタニルメチルアクリレート）を併用した場合（比較例１３～１６）では、低温特性を維持したまま引張強さは改善されるが、いずれも圧縮永久ひずみは非常に悪い（各３１％、３０％、２８％、１５％）。また、２官能モノマーであるビスコート＃３１０ＨＰ（大阪有機化学工業（株）製、トリプロピレングリコールジアクリレート）、ビスコート＃７００ＨＶ（大阪有機化学工業（株）製、ビスフェノ－ルＡ－ＥＯ（３，８）付加物ジアクリレート）を併用した場合には、引張強さが改善され、圧縮永久ひずみも良好な結果であるが、ゴム材料として重要な物性である伸びが著しく低下する欠点がある（比較例１７、１８）。また、炭素数が６に満たないアクリル酸ヒドロキシプロピル（炭素数３）を併用した場合（比較例１９）には、圧縮永久ひずみが悪化し、さらに低分子量であることからモノマーの臭気が感じられ作業環境性が悪かった。また、メタクリル系モノマーであるメタクリル酸２－ヒドロキシエチルを併用した場合（比較例２０）には、引張強さはまったく改善されず、さらに圧縮永久ひずみも悪かった。 On the other hand, IBXA (isobornyl acrylate), acrylyl FA-511AS (manufactured by Hitachi Chemical Co., Ltd., dicyclopentenyl acrylate) and acrylyl FA-513AS (having alicyclic hydrocarbon groups having 10 carbon atoms and acryloylmorpholine) When using Hitachi Chemical Co., Ltd. (dicyclopentanyl acrylate) and Biscoat OXE-10 having 6 oxetane rings (Osaka Organic Chemical Co., Ltd., 3-ethyl-3-oxetanylmethyl acrylate) In (Comparative Examples 13 to 16), the tensile strength is improved while maintaining the low temperature characteristics, but the compression set is very poor (31%, 30%, 28%, and 15%, respectively). Biscoat # 310HP (manufactured by Osaka Organic Chemical Industry Co., Ltd., tripropylene glycol diacrylate), biscoat # 700HV (manufactured by Osaka Organic Chemical Industry Co., Ltd., bisphenol A-EO (3,8)) )) When adduct diacrylate) is used in combination, the tensile strength is improved and the compression set is also a good result, but there is a drawback that the elongation, which is an important physical property of rubber materials, is significantly reduced (Comparative Example). 17, 18). Further, when hydroxypropyl acrylate (carbon number 3) having less than 6 carbon atoms is used in combination (Comparative Example 19), the compression set is deteriorated and the odor of the monomer is felt due to the low molecular weight. Work environment was bad. Further, when 2-hydroxyethyl methacrylate, which is a methacrylic monomer, was used in combination (Comparative Example 20), the tensile strength was not improved at all and the compression set was also poor.
以上の結果から、本願発明範囲内の（ＩＶ）成分を（ＩＩＩ）成分であるアクリロイルモルホリンと併用した場合にのみ、室温以下のガラス転移温度を維持したまま引張強さ・伸び・圧縮永久ひずみを改善する顕著な効果が見られる。 From the above results, only when the component (IV) within the scope of the present invention is used in combination with the component (III) acryloylmorpholine, the tensile strength / elongation / compression set is maintained while maintaining the glass transition temperature below room temperature. There is a noticeable effect of improvement.
（実施例１８、比較例２１～２６）
実施例１と同様にして、表５に示す処方でラジカル硬化性組成物を作製し、硬化物の引張物性・動的粘弾性および圧縮永久ひずみを測定した。結果を表５に示す。なお、比較例２１では伸びが低く、ゴムとしての挙動を示さなかったため、圧縮永久歪を測定しなかった。 (Example 18, Comparative Examples 21 to 26)
In the same manner as in Example 1, a radical curable composition was prepared according to the formulation shown in Table 5, and the tensile properties, dynamic viscoelasticity, and compression set of the cured product were measured. The results are shown in Table 5. In Comparative Example 21, since the elongation was low and the behavior as a rubber was not exhibited, the compression set was not measured.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
表５の結果より、単に従来知られているモノマーの組み合わせや添加量では、低温特性を維持したまま、引張強さ・伸び・圧縮永久ひずみを改善する効果が見られない。本願（ＩＶ）成分のみ（比較例２２、２３）では引張強さを改善することはできない。また、特許文献６に記載されている比較例１における重合体およびモノマーの配合を再現した比較例２４では、（ＩＩＩ）成分を用いた場合でも（ＩＶ）成分を用いなければ伸びは非常に低く、圧縮永久ひずみは１００％とまったくゴム弾性は得られないことが明白である。また、従来知られているＩＢＸＡのような補強性効果のあるモノマーについても、引張強さの改善は限定的であり、またＩＢＸＡ独特の臭気があり作業環境性が悪いという課題がある。つまり、低温特性を維持したまま引張強さと圧縮永久ひずみを改善できる特定のモノマーの組み合わせを見出すことは、従来の知見では困難であった。 From the results shown in Table 5, the effects of improving the tensile strength, elongation, and compression set are not observed while maintaining the low temperature characteristics simply by using conventionally known combinations and addition amounts of monomers. Only the component (IV) of the present application (Comparative Examples 22 and 23) cannot improve the tensile strength. Further, in Comparative Example 24 in which the blend of the polymer and the monomer in Comparative Example 1 described in Patent Document 6 is reproduced, even when the (III) component is used, the elongation is very low unless the (IV) component is used. It is clear that the compression set is 100% and no rubber elasticity is obtained. In addition, a conventionally known monomer having a reinforcing effect such as IBXA has a limited improvement in tensile strength, and has a problem that it has a unique odor of IBXA and poor working environment. That is, it has been difficult to find a specific monomer combination that can improve tensile strength and compression set while maintaining low temperature characteristics.
（実施例１９～２２、比較例２７）
実施例１と同様にして、表６に示す処方のラジカル硬化性組成物を作製し、硬化物の引張物性・動的粘弾性および圧縮永久ひずみを測定した。結果を表６に示す。 (Examples 19 to 22, Comparative Example 27)
In the same manner as in Example 1, radical curable compositions having the formulations shown in Table 6 were prepared, and the tensile properties, dynamic viscoelasticity, and compression set of the cured product were measured. The results are shown in Table 6.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
実施例１９と比較例２７の比較から、末端のアクリロイル基数が１．２個の場合でも、（ＩＩＩ）成分と（ＩＶ）成分を特定量用いることにより、室温以下のガラス転移温度を維持したまま引張強さを改善する効果が見られる。 From the comparison between Example 19 and Comparative Example 27, even when the number of terminal acryloyl groups was 1.2, the glass transition temperature below room temperature was maintained by using specific amounts of the components (III) and (IV). The effect of improving the tensile strength is seen.
（実施例２３～２５）
実施例７で作製したラジカル硬化性組成物を、２ｍｍ厚みになるようにＳＵＳ製金型に流し込み、表面をＰＥＴフィルムで覆った後、ＵＶ－ＬＥＤ照射（照射条件：表７）を実施することにより、シート硬化物を得た。得られた硬化物の引張物性を測定した。結果を表７に示す。 (Examples 23 to 25)
The radical curable composition prepared in Example 7 is poured into a SUS mold so as to have a thickness of 2 mm, the surface is covered with a PET film, and then UV-LED irradiation (irradiation conditions: Table 7) is performed. Thus, a cured sheet was obtained. The tensile properties of the obtained cured product were measured. The results are shown in Table 7.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
従来知られているＵＶランプ（ヘレウス社Ｈバルブ：高圧水銀灯相当）と同様に、ＵＶ－ＬＥＤで硬化物を作製した場合にも、引張強さ・伸びを改善する。 Similar to a conventionally known UV lamp (Hereus H bulb: equivalent to a high-pressure mercury lamp), the tensile strength and elongation are also improved when a cured product is produced by UV-LED.
（実施例２６）
合成例２で得られた重合体［Ｐ２］１００重量部に対し、アクリロイルモルホリンを５０重量部と、ライトアクリレート１３０Ａ（共栄社化学（株）製、平均炭素数１９のエーテル直鎖を有するアクリルモノマー：メトキシポリエチレングリコールアクリレート）１０重量部、ＴＭＰ３Ａ（大阪有機化学工業（株）製、トリメチロールプロパントリアクリレート）１重量部、酸化防止剤としてノクラックＣＤ（大内新興化学工業（株）製、アミン系酸化防止剤）２重量部、熱ラジカル開始剤として、パークミルＤ（日油（株）製、ジクミルパーオキサイド）０．５重量部を十分に混合・溶解した後、脱泡して、ラジカル硬化性組成物を得た。この硬化性組成物を金型内で１８０℃１０分間加熱し、厚さ２ｍｍゴム状のシート硬化物を得た。また、別の金型を用い、１８０℃１５分間加熱し、圧縮永久ひずみ測定用の硬化物を得た。得られた硬化物の引張物性および、１５０℃７０時間の圧縮永久ひずみを測定した。結果を表８に示す。 (Example 26)
Acrylic monomer having 50 parts by weight of acryloylmorpholine and light acrylate 130A (manufactured by Kyoeisha Chemical Co., Ltd., average 19 carbon atoms, straight chain) with respect to 100 parts by weight of the polymer [P2] obtained in Synthesis Example 2. 10 parts by weight of methoxypolyethylene glycol acrylate, 1 part by weight of TMP3A (manufactured by Osaka Organic Chemical Industry Co., Ltd., trimethylolpropane triacrylate), NOCRACK CD (manufactured by Ouchi Shinsei Chemical Co., Ltd.), amine-based oxidation as an antioxidant Inhibitor) 2 parts by weight, as a thermal radical initiator, 0.5 parts by weight of Park Mill D (manufactured by NOF Corporation, Dicumyl peroxide) is sufficiently mixed and dissolved, then defoamed and radical curable. A composition was obtained. This curable composition was heated in a mold at 180 ° C. for 10 minutes to obtain a rubber-like cured sheet having a thickness of 2 mm. Moreover, it heated at 180 degreeC for 15 minutes using another metal mold | die, and obtained the hardened | cured material for a compression set measurement. The tensile properties of the resulting cured product and the compression set at 150 ° C. for 70 hours were measured. The results are shown in Table 8.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
（実施例２７、２８、比較例２８～３０）
実施例２６と同様にして、表８に示す処方のラジカル硬化性組成物を作製し、硬化物の引張物性および圧縮永久ひずみを測定した。結果を表８に示す。 (Examples 27 and 28, Comparative Examples 28 to 30)
In the same manner as in Example 26, radical curable compositions having the formulations shown in Table 8 were prepared, and the tensile properties and compression set of the cured products were measured. The results are shown in Table 8.
表８から明らかなように、熱ラジカル硬化においても光ラジカル硬化と同様に、（メタ）アクリル系重合体にアクリロイルモルホリンを特定量用い、炭素数６以上の直鎖炭化水素基を有する単官能アクリル系モノマーを特定量用いた場合に、低温特性を維持したまま引張強さ・圧縮永久ひずみ特性の両方ともが優れることが明らかである。 As is apparent from Table 8, in the case of thermal radical curing, a monofunctional acrylic having a straight-chain hydrocarbon group having 6 or more carbon atoms using a specific amount of acryloylmorpholine in the (meth) acrylic polymer as in the case of photoradical curing. When a specific amount of the monomer is used, it is clear that both tensile strength and compression set characteristics are excellent while maintaining low temperature characteristics.
（実施例２９）
合成例２で得られた重合体［Ｐ２］１００重量部に対し、補強性充填材としてカーボンブラック（旭カーボン（株）製＃５０）５０重量部を混合し、三本ペイントロールで十分に分散させた後、残りの配合剤を添加し、混合・溶解させて、硬化性組成物を得た。さらに実施例２６と同様にして加熱して硬化物を得、硬化物の引張物性および圧縮永久ひずみを測定した。結果を表９に示す。 (Example 29)
100 parts by weight of the polymer [P2] obtained in Synthesis Example 2 is mixed with 50 parts by weight of carbon black (# 50, manufactured by Asahi Carbon Co., Ltd.) as a reinforcing filler, and sufficiently dispersed with three paint rolls. Then, the remaining compounding agents were added, mixed and dissolved to obtain a curable composition. Further, the cured product was obtained by heating in the same manner as in Example 26, and the tensile properties and compression set of the cured product were measured. The results are shown in Table 9.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
（実施例３０～３３）
実施例２９と同様にして、表９に示す処方のラジカル硬化性組成物を作製した。粉体原料はあらかじめ三本ペイントロールで重合体に分散した。硬化物の引張物性および圧縮永久ひずみを測定した。結果を表９に示す。 (Examples 30 to 33)
In the same manner as in Example 29, radical curable compositions having the formulations shown in Table 9 were prepared. The powder raw material was previously dispersed in the polymer with three paint rolls. The tensile properties and compression set of the cured product were measured. The results are shown in Table 9.
さらに、実施例３１～３３で得られた圧縮永久ひずみ用サンプルを１８０℃４時間加熱して二次加硫を実施した。二次加硫後のサンプルを用いて１５０℃７０時間の圧縮永久ひずみを測定したところ１６％（実施例３１）、１３％（実施例３２）、１５％（実施例３３）であった。すなわち、本発明で得られる硬化物は、一次加硫のみで十分な架橋が進行して圧縮永久ひずみ特性を示すため、従来のゴム材料では必要であった二次加硫を省略できるという効果も見られた。 Further, the samples for compression set obtained in Examples 31 to 33 were heated at 180 ° C. for 4 hours for secondary vulcanization. When the compression set at 150 ° C. for 70 hours was measured using the sample after secondary vulcanization, they were 16% (Example 31), 13% (Example 32), and 15% (Example 33). That is, the cured product obtained in the present invention has sufficient effect of cross-linking only by primary vulcanization and exhibits compression set characteristics, so that the secondary vulcanization necessary for conventional rubber materials can be omitted. It was seen.
表に記載の化合物は、下記の通りである。
＜モノマー類＞
ＡＣＭＯ：アクリロイルモルホリン　ＫＪケミカルズ（株）製
ＤＥＡＡ：ジエチルアクリルアミド　ＫＪケミカルズ（株）製
ライトアクリレート１３０Ａ：メトキシポリエチレングリコールアクリレート　共栄社化学（株）製
アクリル酸２－エトキシエトキシエチル：東京化成工業（株）製
ＩＳＴＡ：イソステアリルアクリレート　大阪有機化学工業（株）製
ＴＭＰ３Ａ：トリメチロールプロパントリアクリレート　大阪有機化学工業（株）製
ＬＡ：ラウリルアクリレート　共栄社化学（株）製
ＩＯＡＡ：イソオクチルアクリレート　大阪有機化学工業（株）製
ＩＢＸＡ：イソボルニルアクリレート　大阪有機化学工業（株）製
ファンクリルＦＡ－５１１ＡＳ：ジシクロペンテニルアクリレート　日立化成（株）製
ファンクリルＦＡ－５１３ＡＳ：ジシクロペンタニルアクリレート　日立化成（株）製
ビスコートＯＸＥ－１０：３－エチル－３－オキセタニルメチルアクリレート　大阪有機化学工業（株）製
ビスコート＃３１０ＨＰ：トリプロピレングリコールジアクリレート　大阪有機化学工業（株）製
ビスコート＃７００ＨＶ：ビスフェノ－ルＡ－ＥＯ（３，８）付加物ジアクリレート　大阪有機化学工業（株）製
アクリル酸ヒドロキシプロピル：東京化成工業（株）製
メタクリル酸２－ヒドロキシエチル：東京化成工業（株）製
ＩＮＡＡ：イソノニルアクリレート　大阪有機化学工業（株）製
ビスコート＃１５５：シクロヘキシルアクリレート　大阪有機化学工業（株）製 The compounds described in the table are as follows.
<Monomers>
ACMO: acryloylmorpholine KEA Chemicals Co., Ltd. DEAA: diethyl acrylamide KJ Chemicals Co., Ltd. light acrylate 130A: methoxypolyethylene glycol acrylate Kyoeisha Chemical Co., Ltd. 2-ethoxyethoxyethyl acrylate: Tokyo Chemical Industry Co., Ltd. ISTA : Isostearyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. TMP3A: Trimethylolpropane triacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. LA: lauryl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. IOAA: Isooctyl acrylate, manufactured by Osaka Organic Chemical Industry IBXA: Isobornyl acrylate, Osaka Organic Chemical Co., Ltd., FANCLIL FA-511AS: Dicyclopentenyl Acrylate Hitachi Chemical Co., Ltd., FANCLIL FA-513AS: DISIC Pentanyl acrylate Viscoat OXE-10 manufactured by Hitachi Chemical Co., Ltd .: 3-ethyl-3-oxetanylmethyl acrylate Biscoat # 310HP manufactured by Osaka Organic Chemical Industry Co., Ltd. Biscoat # manufactured by Osaka Organic Chemical Industry Co., Ltd. 700 HV: Bisphenol A-EO (3,8) adduct diacrylate Hydroxypropyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd .: 2-hydroxyethyl methacrylate manufactured by Tokyo Chemical Industry Co., Ltd .: Tokyo Chemical Industry Co., Ltd. INAA manufactured: isononyl acrylate Biscoat # 155 manufactured by Osaka Organic Chemical Industry Co., Ltd .: cyclohexyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.
＜酸化防止剤＞
ＩＲＧＡＮＯＸ　１０１０：ヒンダードフェノール系酸化防止剤　ＢＡＳＦジャパン社製
ノクラックＣＤ：アミン系酸化防止剤　大内新興化学工業（株）製
＜光ラジカル開始剤＞
ＤＡＲＯＣＵＲ１１７３：２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン　ＢＡＳＦジャパン社製
ＩＲＧＡＣＵＲＥ８１９：ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキシド　ＢＡＳＦジャパン社製
４－メチルベンゾフェノン：東京化成工業（株）製
ＩＲＧＡＣＵＲＥ１８４：１－ヒドロキシ－シクロヘキシル－フェニル－ケトン　ＢＡＳＦジャパン社製
＜熱ラジカル開始剤＞
パークミルＤ：ジクミルパーオキサイド　日油（株）製
＜その他添加剤＞
ユニスターＭ９６７６：ステアリン酸ステアリル　日油（株）製
カーボンブラック＃５０：旭カーボン（株）製
アエロキサイドＰ２５：酸化チタン　日本アエロジル（株）製　 <Antioxidant>
IRGANOX 1010: Hindered phenolic antioxidant BACL JAPAN NOCLACK CD: Amine antioxidant Ouchi Shinsei Chemical Co., Ltd. <photo radical initiator>
DAROCUR1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one IRGACURE 819 manufactured by BASF Japan Ltd .: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 4-methylbenzophenone manufactured by BASF Japan Ltd .: Tokyo Chemical Industry IRGACURE 184 manufactured by Kogyo Co., Ltd .: 1-hydroxy-cyclohexyl-phenyl-ketone <Thermal radical initiator> manufactured by BASF Japan
Park mill D: Dicumyl peroxide manufactured by NOF Corporation <Other additives>
Unistar M9766: Stearyl stearate, NOF Corporation carbon black # 50: Asahi Carbon Co., Ltd. Aeroxide P25: Titanium oxide, Nippon Aerosil Co., Ltd.

Claims (10)

  1. ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）１００重量部に対し、
    ラジカル重合開始剤（ＩＩ）０．０１～１０重量部、
    （メタ）アクリロイルモルホリン（ＩＩＩ）３０～７０重量部、および、
    炭素数６以上の直鎖または分岐炭化水素基を有する単官能アクリル系モノマー（ＩＶ）５～３０重量部
    を含有することを特徴とするラジカル硬化性組成物。     For 100 parts by weight of (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups,
    0.01 to 10 parts by weight of radical polymerization initiator (II),
    30-70 parts by weight of (meth) acryloylmorpholine (III), and
    A radically curable composition comprising 5 to 30 parts by weight of a monofunctional acrylic monomer (IV) having a straight chain or branched hydrocarbon group having 6 or more carbon atoms.
  2. ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）が、ラジカル架橋性の炭素－炭素二重結合を有する基を分子鎖末端に有する（メタ）アクリル系重合体であることを特徴とする請求項１に記載のラジカル硬化性組成物。 (Meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups has a group having a radically crosslinkable carbon-carbon double bond at the end of the molecular chain 2. The radical curable composition according to claim 1, which is a polymer.
  3. ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）が、（メタ）アクリロイル基を分子鎖末端に有する（メタ）アクリル系重合体であることを特徴とする請求項１または２に記載のラジカル硬化性組成物。 The (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups is a (meth) acrylic polymer having a (meth) acryloyl group at the molecular chain terminal. The radically curable composition according to claim 1 or 2.
  4. ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）の分子量分布が１．８未満であることを特徴とする請求項１～３のいずれか１項に記載のラジカル硬化性組成物。 The molecular weight distribution of the (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups is less than 1.8, according to any one of claims 1 to 3. The radically curable composition as described.
  5. ラジカル架橋性基を平均して少なくとも０．８個有する（メタ）アクリル系重合体（Ｉ）が、炭素数１～２４の飽和炭化水素基および／または脂肪族エーテル基を有するモノマーを重合または共重合して得られることを特徴とする請求項１～４のいずれか１項に記載のラジカル硬化性組成物。 The (meth) acrylic polymer (I) having an average of at least 0.8 radical crosslinkable groups polymerizes or co-polymerizes a monomer having a saturated hydrocarbon group having 1 to 24 carbon atoms and / or an aliphatic ether group. 5. The radical curable composition according to claim 1, wherein the radical curable composition is obtained by polymerization.
  6. 炭素数６以上の直鎖または分岐炭化水素基を有する単官能アクリル系モノマー（ＩＶ）が、炭素数８～２４の直鎖または分岐炭化水素基を有する単官能アクリル系モノマーであることを特徴とする請求項１～５のいずれか１項に記載のラジカル硬化性組成物。 The monofunctional acrylic monomer (IV) having a linear or branched hydrocarbon group having 6 or more carbon atoms is a monofunctional acrylic monomer having a linear or branched hydrocarbon group having 8 to 24 carbon atoms, The radical curable composition according to any one of claims 1 to 5.
  7. ラジカル重合開始剤（ＩＩ）が、熱ラジカル開始剤および／または光ラジカル開始剤であることを特徴とする請求項１～６のいずれか１項に記載のラジカル硬化性組成物。 The radical curable composition according to any one of claims 1 to 6, wherein the radical polymerization initiator (II) is a thermal radical initiator and / or a photo radical initiator.
  8. さらに酸化防止剤（Ｖ）を０．１～１０重量部含有することを特徴とする請求項１～７のいずれか１項に記載のラジカル硬化性組成物。 The radically curable composition according to any one of claims 1 to 7, further comprising 0.1 to 10 parts by weight of an antioxidant (V).
  9. 請求項１～８のいずれか１項に記載のラジカル硬化性組成物より得られたことを特徴とする硬化物。 A cured product obtained from the radically curable composition according to any one of claims 1 to 8.
  10. ガラス転移温度（Ｔｇ）が２５℃以下であることを特徴とする請求項９に記載の硬化物。 The cured product according to claim 9, wherein the glass transition temperature (Tg) is 25 ° C. or lower.
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JP2020147616A (en) * 2019-03-11 2020-09-17 株式会社カネカ Method for producing cured product of (meth)acrylic polymer
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