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WO2020184054A1 - Composition contenant un sel d'acide (méth)acrylique métallique et liquide contenant un sel d'acide (méth)acrylique métallique - Google Patents

Composition contenant un sel d'acide (méth)acrylique métallique et liquide contenant un sel d'acide (méth)acrylique métallique Download PDF

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Publication number
WO2020184054A1
WO2020184054A1 PCT/JP2020/005575 JP2020005575W WO2020184054A1 WO 2020184054 A1 WO2020184054 A1 WO 2020184054A1 JP 2020005575 W JP2020005575 W JP 2020005575W WO 2020184054 A1 WO2020184054 A1 WO 2020184054A1
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Prior art keywords
meth
acrylic acid
anion
metal salt
mass
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PCT/JP2020/005575
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English (en)
Japanese (ja)
Inventor
稔 浦田
智章 田中
中村　和彦
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to JP2021505609A priority Critical patent/JP7104850B2/ja
Publication of WO2020184054A1 publication Critical patent/WO2020184054A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/60—Unsaturated compounds containing ether groups, groups, groups, or groups the non-carboxylic part of the ether being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a (meth) acrylic acid metal salt-containing composition and a (meth) acrylic acid metal salt-containing liquid.
  • (Meth) (meth) acrylic acid metal salts such as zinc acrylate, anion derived from a carboxylic acid group (-COO -) by utilizing the ionic bonds between metal cations
  • the (meth) acrylic acid metal salt A metal can be introduced into a compound such as a polymer or a cured product obtained by using. Therefore, the (meth) acrylic acid metal salt is selected from the ionic bond between the metal ion and the carboxylic acid ion and the metal species thereof, for example, such as high hardness, high elasticity, high polarity, high ion exchange property, and high gas barrier property.
  • Various performances derived from at least one species can be exhibited.
  • the (meth) acrylic acid metal salt can exhibit such various performances, it is used, for example, as a cross-linking agent for rubber used for tires and golf balls, a copolymer component of a polymer for ship bottom paint, and a gas barrier layer of a gas barrier film. It is used as a cross-linking agent and the like (for example, Patent Document 1).
  • (meth) acrylic acid metal salts especially zinc (meth) acrylic acid
  • An object of the present invention is to provide a (meth) acrylic acid metal salt-containing composition which is excellent in solubility and dispersibility in a low-polarity medium and is less likely to cause bleed-out of a metal salt.
  • Another object of the present invention is to provide a (meth) acrylic acid metal salt-containing liquid containing a component of such a (meth) acrylic acid metal salt-containing composition and a low-polarity solvent.
  • the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention is The (meth) acrylic acid anion (A1) represented by the general formula (1), the 2-((meth) allyloxymethyl) acrylic acid anion (A2) represented by the general formula (2), and zinc. Including cation (C) The ratio of the anion (A1) to the anion (A2) is 14:86 to 99: 1 in molar ratio. The content ratio of the highly polar solvent is less than 10% by mass. (In the general formula (1), R 1 represents H or CH 3. ) (In the general formula (2), R 2 represents H or CH 3. )
  • the content ratio of the zinc cation (C) to 100 mol% of the total amount of the anion (A1) and the anion (A2) is 10 mol% or more.
  • the highly polar solvent is a solvent having a Hansen solubility parameter of ⁇ H of 20 or more.
  • the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention is used as a resin modifier.
  • the above (meth) acrylic acid metal salt-containing composition is blended with the resin.
  • the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention is The (meth) acrylic acid anion (A1) represented by the general formula (1), the 2-((meth) allyloxymethyl) acrylic acid anion (A2) represented by the general formula (2), and zinc. Containing cation (C) and low polar solvent, The ratio of the anion (A1) to the anion (A2) is 14:86 to 99: 1 in molar ratio. The content of the highly polar solvent is less than 10% by mass, The content ratio of the low polar solvent is 40% by mass or more. (In the general formula (1), R 1 represents H or CH 3. ) (In the general formula (2), R 2 represents H or CH 3. )
  • the content ratio of the zinc cation (C) to 100 mol% of the total amount of the anion (A1) and the anion (A2) is 10 mol% or more.
  • the highly polar solvent is a solvent having a Hansen solubility parameter of ⁇ H of 20 or more.
  • the low-polarity solvent is a solvent having a Hansen solubility parameter ⁇ H of less than 20.
  • a (meth) acrylic acid metal salt-containing composition which is excellent in solubility and dispersibility in a low-polarity medium and is less likely to cause bleed-out of a metal salt. Further, according to the present invention, it is possible to provide a (meth) acrylic acid metal salt-containing liquid containing a component of such a (meth) acrylic acid metal salt-containing composition and a low-polarity solvent.
  • the (meth) acrylic acid metal salt when used for various reactions and preparations using a low-polarity medium, the (meth) acrylic acid metal salt can be blended in a high concentration. This not only allows the (meth) metal acrylate to dissolve from the previously undissolved state, but also for those in which the (meth) metal acrylate was previously dissolved (for example, at low concentrations). It means that it will dissolve at a higher concentration. Further, a metal salt (for example, an anion (A1) and a polyvalent metal cation) that can be contained in the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention and the (meth) acrylic acid metal salt-containing liquid of the present invention.
  • a metal salt for example, an anion (A1) and a polyvalent metal cation
  • weight which is generally used as a unit of weight in the past, and conversely, the expression “weight” in the present specification. If there is, it may be read as “mass” which is commonly used as an SI unit indicating weight.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention has an anion (A1) of (meth) acrylic acid represented by the general formula (1) and 2- represented by the general formula (2). It contains an anion (A2) of ((meth) allyloxymethyl) acrylic acid and a polyvalent metal cation (C).
  • R 1 represents H or CH 3 .
  • R 2 represents H or CH 3 .
  • the bond of "oxygen atom-carbon atom-oxygen atom" which is bonded by both the description of the dotted line and the description of the solid line and shown to be a monovalent anion. Is equivalent to the bonds of two "carbon atoms-oxygen atoms" contained in this bond, and it is preferable that the entire bond of "oxygen atom-carbon atom-oxygen atom” is a monovalent anion.
  • the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention is soluble and dispersed in a low-polarity medium by using an anion (A1), an anion (A2) and a polyvalent metal cation (C) in combination. It can exhibit the effect of being excellent in property (preferably solubility). Further, a metal salt (for example, a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C), and an anion (A2) and many of them can be contained in the (meth) acrylic acid metal salt-containing composition.
  • a metal salt for example, a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C), and an anion (A2) and many of them can be contained in the (meth) acrylic acid metal salt-containing composition.
  • the salt with the valent metal cation (C) (A2-C-A2) and the salt with the anion (A1), the anion (A2) and the polyvalent metal cation (C) (A1-C-A2)) are also polymerizable. Therefore, in the product obtained by performing a polymerization reaction, a curing reaction, or the like using the (meth) acrylic acid metal salt-containing composition, the effect that bleed-out of the metal salt is unlikely to occur can be exhibited.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention may exhibit the effect of being excellent in solubility and dispersibility in a low-polarity medium, but in particular, exhibiting the effect of being excellent in solubility. Can be done.
  • examples of the low-polarity medium include a low-polarity solvent, a raw material rubber, and a low-polarity resin, which will be described later.
  • the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention contains a polyvalent metal cation (C).
  • the polyvalent metal cation (C) may be only one kind or two or more kinds.
  • any suitable polyvalent metal cation can be adopted as long as the effect of the present invention is not impaired, and examples thereof include monatomic ions and complex ions.
  • Examples of the metal that can be such a polyvalent metal cation include a polyvalent alkaline earth metal, a polyvalent typical metal of groups 12 to 16 of the periodic table, and a polyvalent transition metal of groups 3 to 11 of the periodic table. Be done.
  • magnesium preferably magnesium, calcium, strontium, barium, scandium, ittrium, lanthanoid, titanium, zirconium, vanadium, niobium, tantalum, etc.
  • examples include chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, gold, aluminum, gallium, indium, silicon, germanium, tin, lead, antimony and bismuth.
  • Transition metal elements such as chromium, manganese, iron, and cobalt are often colored, so if you do not want to color them as much as possible, preferably magnesium, calcium, strontium, barium, aluminum, gallium, indium, germanium, tin, and lead.
  • Typical metals such as antimony and bismuth, group 3 transition metals such as yttrium and lantern, and group 4 transition metals such as titanium and zirconium.
  • the metal that can be a polyvalent metal cation magnesium, calcium, strontium, barium, aluminum, gallium, indium, germanium, tin, lead, antimony, bismuth and the like are more preferable in that the effects of the present invention can be more exhibited.
  • Typical metals of the above are mentioned, more preferably magnesium, calcium and aluminum, and particularly preferably zinc.
  • the ratio of the anion (A1) to the anion (A2) is 14:86 to 99: 1 in molar ratio.
  • the content ratio of the anion (A1) is 99 mol with respect to 100 mol% of the total amount of the anion (A1) and the anion (A2). % Or less, preferably 97 mol% or less, more preferably 94 mol% or less, still more preferably 90 mol% or less, and particularly preferably 87 mol% or less.
  • the content ratio of the anion (A1) is 14 mol% or more, preferably 27 mol% or more, based on 100 mol% of the total amount of the anion (A1) and the anion (A2). It is more preferably 39 mol% or more, and further preferably 50 mol% or more.
  • the ratio of the anion (A1) to the anion (A2) and the content ratio of the anion (A1) to 100 mol% of the total amount of the anion (A1) and the anion (A2) should be within the above range in terms of molar ratio or molar ratio.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention has excellent solubility and dispersibility (preferably solubility) in a low-polarity medium, and exhibits an effect that bleed-out is unlikely to occur. obtain.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention contains a highly polar solvent in an amount of less than 10% by mass, preferably less than 8% by mass, and more preferably less than 5% by mass. More preferably, it is less than 3% by mass, particularly preferably less than 1% by mass, and most preferably substantially 0% by mass.
  • the content ratio of the highly polar solvent in the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention is within the above range, that is, the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention.
  • the product does not contain a highly polar solvent, or even if it contains a very small amount, it exhibits an exceptionally excellent effect of being excellent in solubility and dispersibility (preferably solubility) in a low polar medium. Means that it can be done.
  • the highly polar solvent may be only one kind or two or more kinds.
  • the highly polar solvent is preferably a solvent having a general-purpose Hansen solubility parameter ⁇ H of 20 or more.
  • the Hansen solubility parameter is widely used as an index of solubility indicating how much a substance is soluble in a certain substance, and is ⁇ D (solubility parameter related to intermolecular dispersion force) and ⁇ P (intermolecular solubility parameter). It is composed of three solubility parameters (solubility parameter related to dipole interaction) and ⁇ H (solubility parameter related to intermolecular hydrogen bond).
  • ⁇ D solubility parameter related to intermolecular dispersion force
  • ⁇ P intermolecular solubility parameter
  • ⁇ H solubility parameter related to intermolecular hydrogen bond
  • solvents having a Hansen solubility parameter ⁇ H of 20 or more at least one selected from water and methanol is preferable in that the effects of the present invention can be more exhibited.
  • a low-polarity solvent which is a term paired with a high-polarity solvent, is preferably a solvent having a general-purpose Hansen solubility parameter of less than 20 in the present invention, and the ⁇ H is more preferably less than 17. It is more preferably less than 14, and particularly preferably less than 10.
  • the low-polarity solvent in which the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention exhibits excellent solubility may be only one kind or two or more kinds.
  • the content ratio of the polyvalent metal cation (C) is preferably 100 mol% of the total amount of the anion (A1) and the anion (A2). It is 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 45 mol% or more, and most preferably 50 mol% or more. ..
  • the content ratio of the polyvalent metal cation (C) to the total amount of 100 mol% of the anion (A1) and the anion (A2) is within the above range
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention Is excellent in solubility and dispersibility (preferably solubility) in a low-polarity medium, and can more exhibit the effect that bleed-out is unlikely to occur.
  • the upper limit of the content ratio of the polyvalent metal cation (C) with respect to the total amount of 100 mol% of the anion (A1) and the anion (A2) is the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention. If the contained polyvalent metal cation (C) is contained only for the purpose of neutralizing (salt forming) the anion (A1) and the anion (A2), the maximum is theoretically 50 mol%. .. However, the polyvalent metal cation (C) contained in the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention is not limited to the polyvalent metal cation contained for the purpose of neutralization (salt formation).
  • the preferable upper limit of the content ratio of the polyvalent metal cation (C) with respect to the total amount of 100 mol% of the anion (A1) and the anion (A2) is that the polyvalent metal cation (C) is an anion (A1) and an anion (A2).
  • the polyvalent metal cation (C) is an anion (A1) and an anion (A2).
  • the content ratio of the total amount of the anion (A1), the anion (A2), and the polyvalent metal cation (C) in 100% by mass of the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention is preferably. It is 0.01% by mass to 100% by mass, more preferably 0.1% by mass to 100% by mass, further preferably 1% by mass to 100% by mass, still more preferably 10% by mass to 100% by mass. It is more preferably 50% by mass to 100% by mass, particularly preferably 70% by mass to 100% by mass, and most preferably 90% by mass to 100% by mass.
  • the content ratio of the total amount of the anion (A1), the anion (A2), and the polyvalent metal cation (C) in 100% by mass of the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention is within the above range. If it is inside, the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention has excellent solubility and dispersibility (preferably solubility) in a low-polarity medium, and has an effect that bleed-out is unlikely to occur. Can be more expressed.
  • the (meth) acrylic acid metal salt-containing composition contains an anion (A1), an anion (A2) and a polyvalent metal cation (C), the (meth) acrylic acid metal salt-containing composition.
  • a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C) a salt (A2-C-A2) of an anion (A2) and a polyvalent metal cation (C), and an anion.
  • a salt (A1-C-A2) of (A1), an anion (A2) and a polyvalent metal cation (C) can be formed.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention may take various embodiments.
  • the salt (A1-C-A1) of the anion (A1) and the polyvalent metal cation (C) is referred to as component A
  • the salt of the anion (A2) and the polyvalent metal cation (C) ( If A2-C-A2) is referred to as the B component
  • the ratio of the A component to the B component is a mass ratio
  • the A component: B component is preferably 10:90 to 99: 1, and the medium has a low polarity.
  • the A component / (A component + B component) is preferably 95% or less, more preferably 90% or less, and further, in terms of mass ratio. It is preferably 85% or less, and particularly preferably 80% or less. Further, from the viewpoint of the ionic bond and the amount of metal introduced, the A component / (A component + B component) is preferably 10% or more, more preferably 20% or more, and further preferably 30% in terms of mass ratio. The above is particularly preferable, and it is 40% or more.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention is soluble in a low-polarity medium. It has excellent dispersibility (preferably solubility) and can more exhibit the effect that bleed-out is unlikely to occur.
  • the content ratio of the total amount of the A component and the B component is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and further preferably 90% by mass. It is from mass% to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably 98% by mass to 100% by mass.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention is not limited to the above embodiment.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention contains an anion (A1), an anion (A2), a polyvalent metal cation (C), and a high polarity which may be contained in an amount of less than 10% by mass.
  • A1 anion
  • A2 anion
  • C polyvalent metal cation
  • high polarity which may be contained in an amount of less than 10% by mass.
  • other components may be contained. Such other components may be only one kind or two or more kinds.
  • any appropriate component can be adopted as long as the effect of the present invention is not impaired.
  • examples of such other components include radical initiators, dryers, curing accelerators, stabilizers, leveling materials, reactive diluents, polymerizable monomers other than components A and B, organic fine particles, inorganic fine particles, and binders. Resins, fillers, coloring materials (pigments, dyes), dispersants, adhesion improvers, mold release agents, plasticizers, ultraviolet absorbers, infrared absorbers, surfactants, matting agents, defoaming agents, antistatic agents , Slip agents, surface modifiers, coupling agents, acid generators, surfactants and the like.
  • conventionally known ones can be used, and in detail, known documents such as JP-A-2004-231571, JP-A-2012-107208, and JP-A-2013-231164 can be used. The ones described in are mentioned.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention does not contain a highly polar solvent, or even if it contains a small amount. Therefore, the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention may be provided in a form which does not contain a highly polar solvent or contains a very small amount of a highly polar solvent. Such a form is preferably a "powder" form. That is, one embodiment of the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention is in the form of "powder".
  • the above-mentioned “powder” used in the description of the present invention is a form defined as a solid that can be handled as an aggregate of granules such as so-called granules or an aggregate of powder having a shape smaller than the granules.
  • the (meth) acrylic acid metal salt-containing composition has the (meth) acrylic acid anion (A1) represented by the general formula (1) and the general formula (2).
  • the represented 2-((meth) allyloxymethyl) acrylic acid anion (A2) and a polyvalent metal cation (C) are contained, and the ratio of the anion (A1) to the anion (A2) is molar.
  • the ratio is 14:86 to 99: 1, and the content ratio of the highly polar solvent is less than 10% by mass.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention is excellent in solubility and dispersibility (preferably solubility) in a low-polarity medium, and is a metal salt. Bleedout is unlikely to occur. Therefore, when the (meth) acrylic acid metal salt is used for various reactions and preparations using a low-polarity medium, the (meth) acrylic acid metal salt can be blended in a high concentration. Further, a metal salt (for example, a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C), and an anion (A2) and many of them can be contained in the (meth) acrylic acid metal salt-containing composition.
  • a metal salt for example, a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C), and an anion (A2) and many of them can be contained in the (meth) acrylic acid metal salt-containing composition.
  • the salt with the valent metal cation (C) (A2-C-A2) and the salt with the anion (A1), the anion (A2) and the polyvalent metal cation (C) (A1-C-A2)) are also polymerizable. Therefore, bleed-out of the metal salt is unlikely to occur in the product obtained by performing a polymerization reaction, a curing reaction, or the like using the (meth) acrylic acid metal salt-containing composition.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention can be produced by any suitable method as long as the effects of the present invention are not impaired.
  • a method typically, each component or a solution of each component is mixed by a usual compounding method, and if necessary, the solvent is removed by vacuum drying or the like, and the embodiment of the present invention is carried out.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention generally has an effect of being excellent in solubility and dispersibility in a low-polarity medium, considering the usage mode.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention is substantially free of low polar solvents (ie, for example, the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention. It is preferable to assume a form in which the composition is provided and then dissolved in a low-polarity solvent for use).
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention may not be the (meth) acrylic acid metal salt-containing solution according to the embodiment of the present invention, depending on the purpose.
  • a (meth) acrylic acid metal salt-containing composition according to an embodiment of the present invention which comprises an arbitrary appropriate amount of a low-polarity solvent (typically, which is not a "uniform and transparent solution” described later). It can also be provided as a formulation containing.
  • the (meth) acrylic acid metal salt-containing solution according to the embodiment of the present invention is a uniform and transparent solution or a dispersion having good dispersibility, and is an anion of (meth) acrylic acid represented by the general formula (1). It contains A1), an anion (A2) of 2-((meth) allyloxymethyl) acrylic acid represented by the general formula (2), a polyvalent metal cation (C), and a low polar solvent.
  • the "uniform and transparent solution” means, for example, a solution that is visually confirmed to be uniform and transparent at 25 ° C., 50 ° C., or 70 ° C. in a solubility test described later.
  • the “dispersion liquid having good dispersibility” means a dispersion liquid which shows a good dispersion state visually.
  • the (meth) acrylic acid metal salt-containing liquid according to the embodiment of the present invention includes an anion (A1) of (meth) acrylic acid represented by the general formula (1) and 2- (2) represented by the general formula (2).
  • the anion (A2) of (meth) allyloxymethyl) acrylic acid, the polyvalent metal cation (C), and the low-polarity solvent may be individually mixed and prepared, or at least any of these may be prepared. You may prepare by using the thing which mixed two kinds in advance.
  • a typical method for preparing the latter is a method using a (meth) acrylic acid metal salt-containing composition according to an embodiment of the present invention.
  • the (meth) acrylic acid metal salt-containing solution according to the embodiment of the present invention is soluble and dispersible in a low polar solvent by using an anion (A1), an anion (A2) and a polyvalent metal cation (C) in combination. Since it is excellent in (preferably soluble), it can be provided as a uniform and transparent solution or a dispersion having good dispersibility (preferably a uniform and transparent solution). Further, a metal salt (for example, a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C)) and an anion that can be contained in the (meth) acrylic acid metal salt-containing liquid according to the embodiment of the present invention.
  • a metal salt for example, a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C)
  • Salt (A2-C-A2) of (A2) and polyvalent metal cation (C), salt of anion (A1) and anion (A2) and polyvalent metal cation (C) (A1-C-A2)) Is also polymerizable, so that bleed-out of the metal salt is unlikely to occur in the product obtained by performing a polymerization reaction, a curing reaction, or the like using the (meth) acrylic acid metal salt-containing liquid.
  • the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention contains a polyvalent metal cation (C).
  • the polyvalent metal cation (C) may be of only one type or of two or more types.
  • the description in the section ⁇ (meth) acrylic acid metal salt-containing composition >> can be used as it is.
  • the ratio of the anion (A1) to the anion (A2) is 14:86 to 99: 1 in terms of molar ratio.
  • the content ratio of the anion (A1) is 99 mol with respect to 100 mol% of the total amount of the anion (A1) and the anion (A2). % Or less, preferably 97 mol% or less, more preferably 94 mol% or less, still more preferably 90 mol% or less, and particularly preferably 87 mol% or less.
  • the content ratio of the anion (A1) is 14 mol% or more, preferably 27 mol% or more, based on 100 mol% of the total amount of the anion (A1) and the anion (A2). It is more preferably 39 mol% or more, and further preferably 50 mol% or more.
  • the ratio of the anion (A1) to the anion (A2) and the content ratio of the anion (A1) to 100 mol% of the total amount of the anion (A1) and the anion (A2) should be within the above range in terms of molar ratio or molar ratio.
  • the (meth) acrylic acid metal salt-containing solution according to the embodiment of the present invention can be provided as a uniform and transparent solution or a dispersion having good dispersibility (preferably a uniform and transparent solution). ) Bleed-out of the metal salt is unlikely to occur in the product obtained by carrying out a polymerization reaction or a curing reaction using the acrylic acid metal salt-containing solution.
  • low-polarity solvent contained in the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention the description of "low-polarity solvent" in the section ⁇ (meth) acrylic acid metal salt-containing composition >> is incorporated as it is. Can be.
  • the (meth) acrylic acid metal salt-containing liquid of the present invention has a highly polar solvent content of less than 10% by mass, preferably less than 8% by mass, more preferably less than 5% by mass, and even more preferably. It is less than 3% by mass, particularly preferably less than 1% by mass, and most preferably substantially 0% by mass.
  • the content ratio of the highly polar solvent in the (meth) acrylic acid metal salt-containing solution in the embodiment of the present invention is within the above range, that is, the (meth) acrylic acid metal salt-containing solution in the embodiment of the present invention.
  • the content ratio of the polyvalent metal cation (C) is preferably 10 mol with respect to 100 mol% of the total amount of the anion (A1) and the anion (A2). % Or more, more preferably 20 mol% or more, further preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 45 mol% or more, and most preferably 50 mol% or more.
  • the (meth) acrylic acid metal salt-containing solution in the embodiment of the present invention is Can be provided as a uniform and transparent solution or a dispersion having good dispersibility (preferably a uniform and transparent solution), and the (meth) acrylic acid metal salt-containing solution is used to carry out a polymerization reaction, a curing reaction, or the like. Bleed-out of metal salts is unlikely to occur in the resulting product.
  • the upper limit of the content ratio of the polyvalent metal cation (C) with respect to the total amount of 100 mol% of the anion (A1) and the anion (A2) is contained in the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention. If the polyvalent metal cation (C) is contained only for the purpose of neutralizing (salt forming) the anion (A1) and the anion (A2), the maximum is theoretically 50 mol%. However, the polyvalent metal cation (C) contained in the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention is not limited to the polyvalent metal cation contained for the purpose of neutralization (salt formation).
  • the preferable upper limit of the content ratio of the polyvalent metal cation (C) with respect to the total amount of 100 mol% of the anion (A1) and the anion (A2) is that the polyvalent metal cation (C) is an anion (A1) and an anion (A2).
  • the polyvalent metal cation (C) is an anion (A1) and an anion (A2).
  • the content ratio of the low polar solvent is 40% by mass or more, preferably 50% by mass or more, and more preferably 60% by mass or more. More preferably, it is 65% by mass or more, particularly preferably 70% by mass or more, and most preferably 75% by mass or more.
  • the content ratio of the low polar solvent in the (meth) acrylic acid metal salt-containing solution in the embodiment of the present invention is within the above range, the (meth) acrylic acid metal salt-containing solution in the embodiment of the present invention is uniform.
  • It can be provided as a transparent solution or a dispersion having good dispersibility (preferably a uniform and transparent solution), and can be obtained by carrying out a polymerization reaction, a curing reaction or the like using the (meth) acrylic acid metal salt-containing solution. Bleed-out of metal salts is unlikely to occur in the product.
  • the (meth) acrylic acid metal salt-containing liquid contains an anion (A1), an anion (A2), a polyvalent metal cation (C), and a low polar solvent, the (meth) acrylic acid metal salt.
  • a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C) and a salt (A2-C-A2) of an anion (A2) and a polyvalent metal cation (C).
  • a salt (A1-C-A2) of an anion (A1), an anion (A2) and a polyvalent metal cation (C) can be formed.
  • the (meth) acrylic acid metal salt-containing liquid according to the embodiment of the present invention may take various embodiments.
  • the salt (A1-C-A1) of the anion (A1) and the polyvalent metal cation (C) is referred to as component A
  • the salt of the anion (A2) and the polyvalent metal cation (C) ( If A2-C-A2) is referred to as component B, the ratio of component A to component B is a mass ratio, and component A: component B is preferably 10:90 to 99: 1, and a low-polarity solvent is used.
  • the A component / (A component + B component) is preferably 95% or less, more preferably 90% or less, and further, in terms of mass ratio. It is preferably 85% or less, and particularly preferably 80% or less. Further, from the viewpoint of the ionic bond and the amount of metal introduced, the A component / (A component + B component) is preferably 10% or more, more preferably 20% or more, and further preferably 30% in terms of mass ratio. The above is particularly preferable, and it is 40% or more.
  • the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention is a uniform and transparent solution or a dispersible solution.
  • a metal salt can be provided as a good dispersion (preferably a uniform and transparent solution), and in a product obtained by carrying out a polymerization reaction, a curing reaction, or the like using the (meth) acrylic acid metal salt-containing solution. Bleedout is unlikely to occur.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention is not limited to the above embodiment.
  • the content ratio of the component A is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, and particularly preferably 13% by mass.
  • the above is the most preferably 15% by mass or more.
  • the (meth) acrylic acid metal salt-containing liquid according to the embodiment of the present invention contains (or substantially does not contain) a highly polar solvent in a proportion of less than 10% by mass. Since the content ratio of the component is high as in the above range, the component A can be blended in a high concentration when used for various reactions and preparations using a low-polarity solvent.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention is not limited to the above embodiment.
  • the (meth) acrylic acid metal salt-containing liquid according to the embodiment of the present invention contains an anion (A1), an anion (A2), a polyvalent metal cation (C), a low-polarity solvent, and even if it is contained in an amount of less than 10% by mass.
  • A1 anion
  • A2 anion
  • C polyvalent metal cation
  • low-polarity solvent a low-polarity solvent
  • other components may be contained.
  • Such other components may be only one kind or two or more kinds.
  • the description of “other components” in the section ⁇ (meth) acrylic acid metal salt-containing composition >> can be used as it is.
  • the (meth) acrylic acid metal salt-containing liquid according to the embodiment of the present invention is represented by the (meth) acrylic acid anion (A1) represented by the general formula (1) and the general formula (2) as described above.
  • 2-((Meta) allyloxymethyl) acrylic acid anion (A2), polyvalent metal cation (C), and a low-polarity solvent are contained, and the ratio of the anion (A1) to the anion (A2).
  • the molar ratio is 14:86 to 99: 1, the content ratio of the highly polar solvent is less than 10% by mass, and the content ratio of the low polar solvent is 40% by mass or more.
  • the (meth) acrylic acid metal salt-containing solution according to the embodiment of the present invention has excellent solubility and dispersibility (preferably solubility) in a low-polarity solvent, and bleeds the metal salt. Out is unlikely to occur. Therefore, when the (meth) acrylic acid metal salt is used for various reactions and preparations using a low-polarity solvent, the (meth) acrylic acid metal salt can be blended in a high concentration. Further, a metal salt (for example, a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C), and an anion (A2) and a polyvalent salt that can be contained in the (meth) acrylic acid metal salt-containing solution.
  • a metal salt for example, a salt (A1-C-A1) of an anion (A1) and a polyvalent metal cation (C), and an anion (A2) and a polyvalent salt that can be contained in the (meth) acrylic acid metal salt-containing solution.
  • the salt with the metal cation (C) (A2-C-A2) and the salt with the anion (A1), the anion (A2) and the polyvalent metal cation (C) (A1-C-A2)) are also polymerizable.
  • the product obtained by performing a polymerization reaction, a curing reaction, or the like using the (meth) acrylic acid metal salt-containing liquid bleed-out of the metal salt is unlikely to occur.
  • the meta) acrylic acid metal salt-containing liquid according to the embodiment of the present invention can be produced by any suitable method as long as the effects of the present invention are not impaired.
  • a method typically, each component is mixed by a usual compounding method.
  • the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention has excellent solubility and dispersibility in a low-polarity medium, and bleed-out of the metal salt is unlikely to occur, so that it can be used as a resin modifier. .. Further, the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention can be used as a resin modifier because bleed-out of the metal salt is unlikely to occur.
  • the resin to be modified is preferable. Is one in which a crosslinkable active site is generated in the structure by a radical, and is crosslinked in a crosslinking treatment step.
  • a resin include rubber and thermoplastic resins (thermoplastic plastics and thermoplastic elastomers), and those which can be classified into rubber and thermoplastic resins.
  • the rubber may be unvulcanized rubber or vulcanized rubber.
  • the resin to be modified may be only one type or a mixture (blend product) of two or more types.
  • the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention and the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention are modifications of a radically polymerizable unsaturated double bond group-containing monomer. Can also be applied to.
  • the radically polymerizable unsaturated double bond group-containing monomer may not be treated as a "resin", but in the present specification, it is treated as one of the resins to be modified.
  • Examples of the rubber include those described in JIS K 6397: 2005. Specifically, M group (rubber having a polymethylene type saturated main chain), O group (rubber having carbon and oxygen in the main chain), Q group (rubber having silicon and oxygen in the main chain), R group. (Rubber with unsaturated carbon bond in the main chain), T group (Rubber with carbon, oxygen and sulfur in the main chain), U group (Rubber with carbon, oxygen and nitrogen in the main chain), Z group (Rubber with carbon, oxygen and nitrogen in the main chain) Rubber with phosphorus and nitrogen in the main chain)
  • Those belonging to the M group include, for example, a rubber-like copolymer of ethyl acrylate or other acrylic acid esters and a small amount of monomer capable of smelting.
  • CM chlorinated polyethylene
  • CSM chlorosulfonated polyethylene
  • EBM rubber-like copolymer of ethylene and octene
  • EPDM ethylene and propylene Rubber-like copolymer with diene
  • EPM rubber-like copolymer with ethylene and propylene
  • EOM ethylene and propylene Rubber-like copolymer
  • EPM rubber-like copolymer with ethylene and propylene
  • EOM ethylene and propylene Rubber-like copolymer
  • EPM rubber-like copolymer
  • EOM ethylene and propylene Rubber-like copolymer
  • EPM rubber-like copolymer
  • EOM ethylene and vinyl acetate
  • FEPM ethylene tetrafluoride and propylene Rubber-like copolymer
  • FFKM rubber-like copolymer in which all side chains are fluoro and perfluoroalkyl or perfluoroalkoxy groups, fluor
  • Those belonging to the O group include, for example, polychloromethyloxylane (epichlorohydrin rubber; CO), and a rubbery copolymer (ECO) of ethylene oxide and epichlorohydrin.
  • CO polychloromethyloxylane
  • ECO rubbery copolymer
  • GECO rubbery copolymer of ethylene oxide, epichlorohydrin and allylglycidyl ether
  • GPO propylene oxide and allylglycidyl ether State copolymer
  • Examples of those belonging to the Q group include silicone rubber (FMQ) having a methyl substituent and a fluoro substituent on the polymer chain, and a methyl substituent and a vinyl substituent on the polymer chain.
  • FMQ silicone rubber
  • Silicone rubber (FVMQ) having a fluorosubstituted group silicone rubber (polydimethylsiloxane: MQ) having a methyl substituent on the polymer chain, silicone rubber (PMQ) having a methyl substituent and a phenyl substituent on the polymer chain, Examples thereof include silicone rubber (PVMQ) having a methyl substituent, a vinyl substituent and a phenyl substituent on the polymer chain, and silicone rubber (VMQ) having a methyl substituent and a vinyl substituent on the polymer chain.
  • Examples of those belonging to the R group include acrylate-butadiene rubber (ABR), butadiene rubber (BR), chloroprene rubber (CR), epoxidized natural rubber (ENR), and hydrogen.
  • ABR acrylate-butadiene rubber
  • BR butadiene rubber
  • CR chloroprene rubber
  • EMR epoxidized natural rubber
  • Rubberized copolymer of acrylonitrile and butadiene HNBR
  • isoprene rubber synthetic natural rubber: IR
  • rubbery copolymer of ⁇ -methylstyrene and butadiene MSBR
  • Rubber-like copolymer NBIR
  • rubber-like copolymer of acrylonitrile and butadiene nitrile rubber: NBR
  • rubber-like copolymer of acrylonitrile and isoprene NIR
  • natural rubber NR
  • norbornene rubber NOR
  • rubber-like copolymer of vinylpyridine and butadiene PBR
  • rubber-like copolymer of vinylpyridine, styrene and butadiene PSBR
  • rubber-like copolymer of styrene and butadiene SBR
  • T group as belonging to (carbon in the main chain, rubber having oxygen and sulfur), for example, -CH 2 -CH 2 -O-CH 2 -O-CH 2 -CH 2 between polysulfide bonds of polymer chains Rubber (OT) with either -groups or R groups (R is an aliphatic hydrocarbon) and usually without -CH 2- CH 2 -groups, between polysulfide bonds of polymer chains-CH 2- CH 2 -O-CH 2 -O- CH 2 -CH 2 - group and normal -CH 2 -CH 2 - such as rubber (EOT) with the like (other aliphatic groups, as the case may be) group.
  • Rubber OT
  • R is an aliphatic hydrocarbon
  • Those belonging to the U group include, for example, rubber-like copolymers (AFMU) of ethylene tetrafluoride, nitrosomethane trifluoride, and nitrosoperfluorobutyric acid. ), Polyester urethane (AU), polyether urethane (EU) and the like.
  • AFMU rubber-like copolymers
  • AU Polyester urethane
  • EU polyether urethane
  • the rubber preferably belongs to the M group, the R group, and the Q group, and more preferably belongs to the M group and the R group.
  • olefin rubbers such as ACM, EPM, EPDM, EVM, FEPM, EOM, and EBM are preferable, and EPM and EPDM are more preferable.
  • butadiene rubbers such as BR, IR, NR, NBR, SBR, and HNBR or isoprene rubbers are preferable, and HNBR and NBR are more preferable.
  • thermoplastic examples include the thermoplastics described in JIS K 6899-1: 2015. Specifically, for example, the following can be mentioned.
  • PE Polyethylene
  • PE-C Chlorinated Polyethylene
  • HDPE High Density Polyethylene
  • LDPE Low Density Polyethylene
  • LLDPE Linear Low Density Polyethylene
  • MDPE Ultra High Polymer Polyethylene
  • LDPE Ultra High Polymer Polyethylene
  • VLDPE ultra-low density polyethylene
  • PEC polyester carbonate
  • PEEK polyether ether ketone
  • PEEST polyether ester
  • PEK polyether ketone
  • PEN polyethylene naphthalate
  • PEOX polyethylene oxide
  • PES Polyether sulfone
  • PET Polyethylene terephthalate
  • PUR Polyether urethane
  • PFA Perfluoro (alkyl vinyl ether) -Tetrafluoroethylene plastic
  • PFA Polyhydroxy alkanoate
  • PHA Poly (3-hydroxybutyrate)
  • PB Polyisobutylene
  • PK Polyketone
  • PFA Polylactic acid
  • PFA Polylactic acid
  • PFA Polylactic acid
  • Polystyrene PS
  • Effervescent Polystyrene EPS
  • Impact Resistant Polystyrene HIPS
  • Spunated Polystyrene SPS
  • Syndiotactic Polystyrene STPS
  • Polysulfone PSU
  • Polytetrafluoroethylene PSU
  • Polyvinyl acetate PVAC
  • polyvinyl alcohol PVAL
  • polyvinyl butyral PVB
  • polyvinyl chloride PVC
  • chlorinated polyvinyl chloride CPVC
  • UPVC non-plastic polyvinyl chloride
  • PVDC Polyvinyl chloride
  • PVDF polyvinyl chloride
  • PVF polyvinyl chloride
  • PVFM polyvinylformal
  • PVK N-vinylcarbazole
  • PVK N-vinylpyrrolidone
  • thermoplastic elastomer examples include those described in JIS K 6418: 2007.
  • an amide-based thermoplastic elastomer (TPA: a hard block is made of an amide bond, a soft block is made of an ether and / or ester bond, and a block co-weight consisting of alternately hard segments and soft segments. Consists of coalescence);
  • Ester-based thermoplastic elastomer (TPC: The hard block of the main chain is made of ester bonds, the soft block is made of ether and / or ester bonds, and alternately consists of hard segments and soft segments.
  • TPO Olefin-based thermoplastic elastomer
  • TPS styrene-based Thermoplastic elastomer
  • Soft block is composed of polydiene or hydride polydiene); urethane-based thermoplastic elastomer (TPU: hard block is made of urethane bond, soft block is made of ether, ester, carbonate bond, or a mixture thereof. And, it is composed of a block copolymer consisting of hard segments and soft segments alternately); Thermoplastic rubber crosslinked product (TPV: a blend of a thermoplastic resin and ordinary rubber, and this rubber is a blend. Or crosslinked by dynamic sulfurization in the kneading process); other thermoplastic elastomers (TPZ: TPA, TPC, TPO, TPS, TPU and those having a composition or structure not included in the TPV classification) can be mentioned. ..
  • thermoplastic resins those having a low softening point are preferable, and for example, polyolefin-based thermoplastic resins such as PE, E / P, EVAC, and EEAK are preferable.
  • the softening point of the thermoplastic resin is preferably higher than room temperature, preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 50 ° C. or higher.
  • the softening point of the thermoplastic resin is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, and even more preferably 110 ° C. or lower, from the viewpoint of ease of crosslink suppression.
  • resin to be modified in addition to specific examples of rubber and thermoplastic resin, for example, fluororubber; polyethylene and a comonomer such as (meth) acrylic acid ester or tetracyclododecene other than those described above were copolymerized.
  • comonomer such as (meth) acrylic acid ester or tetracyclododecene other than those described above were copolymerized.
  • Other polyolefin resins such as polyethylene copolymers, polybutene-1, polymethylpentene; other polyester resins such as hydroxybenzoate polyester; polymethacrylic styrene; and the like can also be mentioned.
  • the amount of the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention and the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention with respect to the resin to be modified is determined by the embodiment of the present invention.
  • the content ratio of the solid content to 100 parts by mass of the resin is preferable in that the effect of the (meth) acrylic acid metal salt-containing composition or the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention can be more exhibited. It is 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, preferably 70 parts by mass or less, and more preferably 60 parts by mass or less. More preferably, it is 50 parts by mass or less.
  • a modified resin having properties derived from the vinyl compound By binding the vinyl compound to the raw material resin under radical generation conditions, a modified resin having properties derived from the vinyl compound can be obtained.
  • the method for modifying the raw material resin can be roughly divided into three methods, (1) melt-kneading reaction method, (2) impregnation reaction method, and (3) solution reaction method, depending on the type of environment at the time of modification. .. (1)
  • the raw material resin, the vinyl compound, and other raw materials are mixed if necessary under the conditions that the raw material resin is in a molten state and / or a softened state, and radicals are generated in the mixture.
  • the impregnation reaction method is a method in which an aqueous suspension of a raw material resin impregnated with a vinyl compound is prepared, and radicals are generated in the system while stirring the suspension to modify the suspension.
  • the solution reaction method is a method in which a raw material resin and a vinyl compound are dissolved in some solvent to generate radicals for modification. When the raw material resin is a liquid, the raw material resin may be used as a solvent.
  • the method for modifying the resin in the embodiment of the present invention is a vinyl compound containing the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention and / or the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention.
  • the liquid is mixed with the resin.
  • the method for modifying the resin in the embodiment of the present invention is preferably contained in the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention or the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention. It comprises a step of radically reacting a metal salt of (meth) acrylic acid and / or 2-((meth) allyloxymethyl) acrylic acid with a resin.
  • a thermoplastic modified resin or a non-thermoplastic modified resin can be obtained depending on the composition and the process of radical reaction.
  • One of the methods for modifying the resin in the embodiment of the present invention is the (meth) acrylic acid metal salt-containing composition in the embodiment of the present invention and / or the (meth) acrylic acid metal salt-containing liquid in the embodiment of the present invention.
  • a kneading step of kneading the composition obtained by blending the resin with a resin, a cross-linking treatment step of generating a radical in the composition after the kneading step to carry out a cross-linking treatment, and a composition before the cross-linking treatment and / or after the cross-linking treatment. Includes a molding step of molding a crosslinked body of
  • the molding step may be performed at the same time as the kneading step or after the kneading step and before the crosslinking treatment step.
  • the composition before the crosslinking treatment is molded.
  • the molding step may be performed at the same time as the molding step and the cross-linking treatment step after the kneading step, or after the cross-linking treatment step.
  • the molding step and the cross-linking treatment step are performed at the same time, the composition before the cross-linking treatment and / or the cross-linked body after the cross-linking treatment is molded. Will be done.
  • the resin modification method in the embodiment of the present invention may include any suitable other steps as long as these steps are included, as long as the effects of the present invention are not impaired.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention and / or the (meth) acrylic acid metal salt-containing liquid according to the embodiment of the present invention is blended into the resin, and the present invention is carried out.
  • the (meth) acrylic acid metal salt-containing composition according to the embodiment of the present invention and / or the composition containing the (meth) acrylic acid metal salt-containing liquid and the resin according to the embodiment of the present invention (hereinafter, may be referred to as a raw material composition). ), And the components in the raw material composition are mixed and dispersed while suppressing the cross-linking reaction.
  • the content of the resin in the raw material composition is preferably 10 parts by weight to 99 parts by mass, more preferably 20 parts by weight to 90 parts by mass, and further preferably 30 parts by mass with respect to 100 parts by mass of the raw material composition. It is a part by weight to 80 parts by mass.
  • the raw material composition may be (1) as required. ) Radical generator (often referred to as a cross-linking agent in the rubber field), (2) Cross-linking agents other than radical generators, cross-linking accelerators, cross-linking accelerator aids, (3) Other vinyl compounds (in the rubber field (Often referred to as co-crosslinking agent), (4) Filler (filler), (5) Softener / plasticizer / solvent, (6) Anti-aging agent / antioxidant, light stabilizer, UV absorber , (7) Other additives, etc. may be contained. In addition, each of these may be 1 type or 2 or more types.
  • the raw material composition preferably contains a radical generator.
  • the radical generator (often referred to as a cross-linking agent in the rubber field) can be any suitable radical generator as long as it generates radicals in its own structure by autolysis in the cross-linking process. Can be adopted.
  • the radicals generated from the radical generator abstract hydrogen from the resin to generate radicals on the resin, which are subsequently reacted with the (meth) acrylic acid metal salt. It is preferable to form a crosslinked structure by, for example, and / or by coupling radicals generated in the resin with each other.
  • radical generator examples include a thermal radical generator that generates radicals by heating, a photoradical generator that generates radicals by irradiation with active energy rays, and the like.
  • the radical generator may be only one kind or two or more kinds.
  • the thermal radical generator one that generates radicals at a temperature higher than the kneading temperature is preferable.
  • the one-minute half-life temperature of the thermal radical generator is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 120 ° C. or higher.
  • the 1-minute half-life temperature of the thermal radical generator is preferably 270 ° C. or lower, more preferably 260 ° C. or lower, and further preferably 250 ° C. or lower.
  • thermal radical generator examples include organic peroxides; sulfur; sulfur halides such as sulfur dichloride; azo compounds; and the like.
  • organic peroxide examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methylacetate acetate peroxide, acetylacetate peroxide, 1,1-bis (t-hexylperoxy) -3,3.
  • azo compound examples include 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, and 1,1'-azobis (cyclohexane-1).
  • examples thereof include imidazole compounds, oxime ester compounds, titanosen compounds, benzoic acid ester compounds, and acrydin compounds.
  • alkylphenone-based compound examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.
  • benzophenone compound examples include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 2-carboxybenzophenone and the like.
  • benzoin compounds include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
  • thioxanthone compound examples include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and the like.
  • halomethylated triazine compound examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl).
  • -S-Triazine 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine
  • halomethylated oxadiazole-based compound examples include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5-[ ⁇ - (2'-).
  • Benzofuryl) vinyl] -1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like can be mentioned.
  • biimidazole compound examples include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2). , 4-Dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5 , 5'-Tetraphenyl-1,2'-imidazole and the like.
  • oxime ester compound examples include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and the like can be mentioned.
  • titanosen-based compound examples include titanosen such as bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium. Systems compounds; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; 9-phenylaclydin; and the like.
  • the radical generator is preferably an organic peroxide or sulfur, more preferably an organic peroxide, and even more preferably a dicumyl peroxide, 1,1-di (t-) among the organic peroxides.
  • the content ratio of the radical generator in the raw material composition is preferably 0 parts by mass to 70 parts by mass with respect to 100 parts by mass of the resin.
  • the content ratio of the organic peroxide is 0 to 15 parts by mass, more preferably 0.1 parts by mass to 100 parts by mass with respect to 100 parts by mass of the resin. It is 12 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass.
  • Cross-linking agents other than radical generators, cross-linking accelerators, cross-linking promoter aids
  • cross-linking agents other than radical generators include p-quinone dioxime, p, p'-dibenzoylquinone dioxime, and tetrachloro.
  • Kinoids such as -p-benzoquinone and poly-p-dinitrobenzene; alkylphenol / formaldehyde resin, melamine-formaldehyde condensate, triazine-formaldehyde condensate, octylphenol / formaldehyde resin, alkylphenol / sulfide resin, hexamethoxymethyl / melamine resin, etc.
  • Resins Hexamethylenediamine carbamate, hexamethylenediamine, triethylene / tetramine, tetraethylene / pentamine, 4,4'-methylenebis (cyclohexylamine) carbamate, N, N'-dicinnamylidene-1,6- Amines such as hexanediamine and ammonium benzoate; metal oxides such as zinc oxide, magnesium oxide, lead oxide and calcium oxide; 2,4,6-trimercapto-s-triazine, 2-di-n-butyl Examples thereof include triazinethiols such as amino-4,6-dimercapto-s-triazine; polyols such as bisphenol A, bisphenol AF, hydroquinone and pentaerythritol; and the like.
  • the cross-linking agent other than the radical generator may be one kind or two or more kinds.
  • cross-linking accelerator commonly used ones can be used, and specifically, for example, N-cyclohexyl-2-benzothiadylsulfenamide and Nt-butyl-2-benzothiazolesulfenamide.
  • cross-linking accelerator commonly used ones can be used, and specific examples thereof include zinc oxide, stearic acid, and zinc stearate.
  • the cross-linking promoting aid may be one kind or two or more kinds.
  • the total content of the cross-linking agent other than the radical generator, the cross-linking accelerator, and the cross-linking accelerator in the raw material composition is preferably 0 parts by mass to 15 parts by mass with respect to 100 parts by mass of the resin. , More preferably 1 part by mass to 10 parts by mass.
  • vinyl compounds examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and crotonic acid, and metal salts such as zinc and magnesium; divinylbenzene and the like.
  • Polyfunctional aromatic vinyl compounds such as divinylnaphthalene; isocyanurates such as triallyl isocyanurate and trimetalyl isocyanurate; cyanurates such as triallyl cyanurate; maleimides such as N, N'-m-phenylenedi maleimide;
  • Polyallyl esters such as diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl fumarate, diallyl sebacate, and triallyl phosphate; diethylene glycol bisallyl carbonate; triallyl ether obtained by allylating ethylene glycol diallyl ether and trimethylolpropane, Examples thereof include polyallyl ethers such as allyl ether obtained by partially allylating pen
  • the content ratio of the other vinyl compound in the raw material composition is preferably 0 parts by mass to 5 parts by mass, more preferably 0 parts by mass to 3 parts by mass, and further preferably 0 parts by mass with respect to 100 parts by mass of the resin. Is 0 parts by mass to 1 part by mass.
  • filler commonly used fillers can be used. Specifically, reinforcing fillers such as carbon black and silica; calcium carbonate, calcium silicate, magnesium oxide, aluminum oxide, barium sulfate, etc. Non-reinforcing fillers such as talc and mica; and the like. In addition to these, for example, gypsum fiber, glass balun, silica balun, hydrotalcite, fly ash balun, silas balun, carbon balun, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, glass fiber, cut fiber. , Rock fiber, microfiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, recycled rubber, rubber powder, ebonyite powder, cellac, wood powder, cellulose nanofiber and the like.
  • the filler may be one type or two or more types.
  • the content ratio of the filler in the raw material composition is preferably 0 parts by mass to 500 parts by mass, more preferably 5 parts by mass to 300 parts by mass, and further, with respect to 100 parts by mass of the resin. It is preferably 30 parts by mass to 200 parts by mass.
  • Processing aids such as softeners / plasticizers / solvents
  • softeners / plasticizers / solvents / processing aids may be used. .. Each of these may be one kind or two or more kinds.
  • softener / plasticizer commonly used ones can be used. Specifically, process oils, lubricating oils, paraffins, liquid paraffins, petroleum-based softeners such as vaseline, castor oil, flaxseed oil, and rapeseed. Fat oil-based softeners such as oil and palm oil, waxes such as tall oil, sub, beeswax, carnauba wax, and lanolin, linoleic acid, palmitic acid, stearic acid, lauric acid, phthalate ester compounds, polyester compounds, ( Meta) Acrylic oligomers and the like can be mentioned.
  • process oils, lubricating oils, paraffins, liquid paraffins, petroleum-based softeners such as vaseline, castor oil, flaxseed oil, and rapeseed.
  • Fat oil-based softeners such as oil and palm oil, waxes such as tall oil, sub, beeswax, carnauba wax, and lanolin, linoleic acid,
  • solvent a commonly used solvent can be used, and specific examples thereof include toluene, xylene, ethylbenzene, cyclohexane, trimethylcyclohexane, and methyl isobutyl ketone.
  • the total content ratio of the processing aids such as the softener, the plasticizer, and the solvent in the raw material composition is preferably 0 parts by mass to 100 parts by mass, and more preferably 5 parts by mass with respect to 100 parts by mass of the resin. It is 10 parts by mass to 50 parts by mass, and more preferably 10 parts by mass to 30 parts by mass.
  • Anti-aging agent / antioxidant In order to further prevent deterioration of the molded body, an anti-aging agent / antioxidant, a light stabilizer, and an ultraviolet absorber may be used. .. Each of these may be one kind or two or more kinds.
  • anti-aging agent / antioxidant examples include a hindered phenol-based anti-aging agent, a hindered phenol-based antioxidant, a phosphite-based anti-aging agent, and a phosphite-based antioxidant.
  • Examples of the light stabilizer include hindered amine-based light stabilizers.
  • the ultraviolet absorber examples include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylic acid ester-based ultraviolet absorber, and the like.
  • the total content ratio of the anti-aging agent / antioxidant, the light stabilizer, and the processing aid of the ultraviolet absorber in the raw material composition is preferably 0 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin. Yes, more preferably 0 parts by mass to 5 parts by mass, and even more preferably 0 parts by mass to 0.53 parts by mass.
  • additives commonly used ones can be used, for example, a dewaxing agent, a lubricant, an anti-scorch agent, a coloring agent, a mold release agent, a dispersant, and a foaming agent.
  • Foaming aids flame retardants, tackifiers, adhesion enhancers, waxes, coupling agents, conductive agents, acid receivers, resins other than the above-mentioned resins and the like.
  • kneading conditions all the components in the raw material composition may be blended and kneaded at one time, or may be blended and kneaded in two or more steps. Further, a step of kneading the resin may be performed depending on the type of the resin and the like.
  • a mixing roll, a mixer, a kneader, an extruder, or the like may be used as the kneading machine depending on the form of the raw material, the use of the obtained molded product, and the like.
  • the kneading step it is preferable to knead at a temperature at which a large amount of radicals are not generated, that is, a temperature at which a cross-linking reaction does not occur in a resin that can be crosslinked with radicals.
  • a temperature at which a cross-linking reaction does not occur in a resin that can be crosslinked with radicals.
  • the kneading temperature may be set according to the type of resin (melting point or Mooney viscosity), and is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 160 ° C. or lower.
  • the kneading temperature is usually preferably 30 ° C.
  • the kneading temperature can be controlled, for example, by controlling the rotation speed of the roll of the kneading device, the rotation speed of the blades for kneading, the cooling water, and the like.
  • the method for modifying the resin in the embodiment of the present invention preferably includes a cross-linking treatment step in which radicals are generated in the composition after the kneading step to carry out a cross-linking treatment.
  • the composition to be subjected to the cross-linking treatment may be a composition before the molding step or a composition after the molding step as long as it is a composition after the kneading step.
  • any appropriate method can be adopted as the method for generating radicals. Examples of such a method include heating, irradiation with active energy rays, and the like. Further, the radicals may be generated only by irradiation with active energy rays without using the above-mentioned radical generator.
  • a radical generator When a radical generator is used in the kneading step, it may be appropriately selected depending on the radical generator to be used, and the above methods may be used in combination.
  • the active energy ray a commonly used one can be used, and examples thereof include electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible rays and infrared rays, and particle beams such as electron beams, neutron beams and proton beams.
  • electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible rays and infrared rays
  • particle beams such as electron beams, neutron beams and proton beams.
  • the method for generating radicals in the cross-linking treatment step is preferably a method by heating.
  • the heating temperature may be any suitable temperature as long as it can generate radicals.
  • the temperature of such heating is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 140 ° C. or higher.
  • the upper limit of the heating temperature is preferably 300 ° C. or lower, more preferably 260 ° C. or lower.
  • the cross-linking treatment by heating may be carried out in one step, or may be carried out in two or more steps by changing the heating temperature.
  • the heating time is, for example, preferably 10 seconds to 100 hours, and more preferably 1 minute to 24 hours. Further, the 90% vulcanization time may be obtained in accordance with JIS K 6300-2: 2001, and the heating time may be set based on this.
  • the cross-linking treatment step may be performed at the same time as the molding step.
  • the molding and the cross-linking treatment are performed at the same time by heating while molding with a molding machine.
  • the method for modifying the resin in the embodiment of the present invention preferably includes a molding step of molding the composition before the cross-linking treatment and / or the cross-linked product after the cross-linking treatment to obtain a molded product.
  • the molding step may be performed at the same time as the kneading step or after the kneading step and before the crosslinking treatment step.
  • the composition before the crosslinking treatment is molded.
  • the molding step may be performed at the same time as the molding step and the cross-linking treatment step after the kneading step, or after the cross-linking treatment step.
  • the molding step and the cross-linking treatment step are performed at the same time, the composition before the cross-linking treatment and / or the cross-linked body after the cross-linking treatment is molded. Will be done.
  • molding means adjusting the shape, and in the molding step, the kneaded composition obtained in the kneading step is, for example, sheet-shaped, film-shaped, pellet-shaped, layered, rod-shaped, spherical, or particle-shaped. It means to process into a powder shape, a member shape for various purposes, and the like.
  • any suitable molding method can be adopted as the molding method of the composition and / or the crosslinked body in the molding step.
  • a molding method include a method of processing into a desired shape by extrusion, injection, pressure, rolling, mold release processing, cutting, cutting, and polishing.
  • an extrusion molding machine for example, an injection molding machine, a commonly used molding machine such as a pressure molding machine, a mold, or the like may be used.
  • a salt (A component) consisting of an anion of (meth) acrylic acid and a polyvalent metal cation and a salt (B component) consisting of an anion of 2-((meth) allyloxymethyl) acrylic acid and a polyvalent metal cation.
  • the water content of the reagent used in the test was as follows.
  • Zinc acrylate Contains 100 ppm (0.01% by mass) of water
  • Zinc methacrylate Contains 100 ppm (0.01% by mass) of water
  • Toluene Contains 50 ppm (0.005% by mass) of water
  • dumbbell test pieces were laminated, and the hardness of the dumbbell was measured using a type A rubber meter.
  • vulcanized sheet is punched and dumbbell-shaped No. 3 type A dumbbell test piece was prepared, and the tensile strength, 100% tensile stress, and elongation at cutting were measured using a tensile tester.
  • the concentration was adjusted with toluene to obtain 66.0 parts of a toluene solution containing 20% of zinc 2- (allyloxymethyl) acrylate. Moreover, when the obtained toluene solution was measured with a Karl Fischer titer, the water content was 0.2%.
  • Synthesis Example 2 Synthesis of a salt of 2- (allyloxymethyl) acrylate ion and zinc ion The same operation as in Synthesis Example 1 was carried out, and toluene containing 50% by mass of 2- (allyloxymethyl) zinc acrylate was performed. A solution was obtained. When the obtained toluene solution was measured with a Karl Fischer titer, the water content was 0.2%.
  • Example 1 In a container containing a stirrer, 3.01 parts of zinc methacrylate, 10.01 parts of a toluene solution containing 20% of zinc 2- (allyloxymethyl) acrylate obtained in Synthesis Example 1, and toluene: 5.04 parts were added. When the obtained formulation was stirred at 25 ° C. for 1 hour, it was visually confirmed that the zinc compounds (zinc methacrylate and zinc 2- (allyloxymethyl) acrylate) were dissolved to form a uniform and transparent solution. did.
  • the obtained homogeneous transparent solution (1) contains methacrylic acid ion, 2- (allyloxymethyl) acrylic acid ion, zinc ion (these ions can form salts), and toluene (low polar solvent), and contains methacrylic acid.
  • the molar ratio of acid ion to 2- (allyloxymethyl) acrylic acid ion is 69:31, and the content ratio of water (highly polar solvent) is methacrylic acid ion, 2- (allyloxymethyl) acrylic acid ion and zinc.
  • This powder (1) is a salt of methacrylic acid ion, 2- (allyloxymethyl) acrylic acid ion and zinc ion (salt of methacrylic acid ion and zinc ion, 2- (allyloxymethyl) acrylic acid ion and zinc.
  • It contains a salt with an ion, a methacrylic acid ion and 2- (allyloxymethyl) at least one selected from a salt of an acrylic acid ion and a zinc ion), and as described above, a methacrylic acid ion and 2- (allyloxymethyl).
  • the molar ratio of acrylate ions was 69:31. Further, the content ratio of water (highly polar solvent) is naturally smaller than the above-mentioned content ratio, and is less than 0.41% by mass.
  • the resulting formulation (C1) contains methacrylate ions, zinc ions (these ions can form salts), toluene (low polar solvent) and no 2- (allyloxymethyl) acrylic acid ions.
  • this compound (C1) was vacuum-dried to obtain a zinc compound powder (C1). It was confirmed that this powder (C1) did not dissolve in toluene.
  • This powder (C1) contains a salt of methacrylic acid ion and zinc ion, does not contain 2- (allyloxymethyl) acrylate ion, and the content ratio of water (highly polar solvent) is higher than the above content ratio. Of course, it is less than 0.005% by mass.
  • Example 2 In a container containing a stirrer, 4.01 parts of zinc methacrylate, 10.01 parts of a toluene solution containing 20% of zinc 2- (allyloxymethyl) acrylate obtained in Synthesis Example 1, and toluene: 8.02 copies were added. When the obtained formulation was stirred at 70 ° C. for 1 hour, it was visually confirmed that the zinc compounds (zinc methacrylate and zinc 2- (allyloxymethyl) acrylate) were dissolved to form a uniform and transparent solution. did.
  • the obtained homogeneous transparent solution (2) contains methacrylic acid ion, 2- (allyloxymethyl) acrylic acid ion, zinc ion (these ions can form salts), and toluene (low polar solvent), and contains methacrylic acid.
  • the molar ratio of acid ion to 2- (allyloxymethyl) acrylic acid ion is 75:25, and the content ratio of water (highly polar solvent) is methacrylic acid ion, 2- (allyloxymethyl) acrylic acid ion and zinc.
  • Example 3 In a container containing a stirrer, 6.00 parts of zinc methacrylate, 10.01 parts of a toluene solution containing 20% of zinc 2- (allyloxymethyl) acrylate obtained in Synthesis Example 1, and toluene: 15.10 parts were added. When the obtained formulation was stirred at 70 ° C. for 1 hour, it was visually confirmed that the zinc compounds (zinc methacrylate and zinc 2- (allyloxymethyl) acrylate) were dissolved to form a uniform and transparent solution. did.
  • the obtained homogeneous transparent solution (3) contains methacrylic acid ion, 2- (allyloxymethyl) acrylic acid ion, zinc ion (these ions can form a salt), and toluene (low polar solvent), and contains methacrylic acid.
  • the molar ratio of acid ion to 2- (allyloxymethyl) acrylic acid ion is 82:18, and the content ratio of water (highly polar solvent) is methacrylic acid ion, 2- (allyloxymethyl) acrylic acid ion and zinc.
  • Example 4 To a container containing a stirrer, 1.50 parts of zinc acrylate and 12.50 parts of a toluene solution containing 20% of zinc 2- (allyloxymethyl) acrylate obtained in Synthesis Example 1 were added. When the obtained formulation was stirred at 50 ° C. for 1 hour, it was visually confirmed that the zinc compounds (zinc acrylate and zinc 2- (allyloxymethyl) acrylate) were dissolved to form a uniform and transparent solution. did.
  • the obtained homogeneous transparent solution (4) contains acrylate ions, 2- (allyloxymethyl) acrylate ions, zinc ions (these ions can form salts) and toluene (low polar solvent), and is acrylic.
  • the molar ratio of acid ion to 2- (allyloxymethyl) acrylic acid ion is 50:50, and the content ratio of water (highly polar solvent) is acrylic acid ion, 2- (allyloxymethyl) acrylic acid ion and zinc.
  • the content ratio of acrylate ions was 7.3% by mass.
  • the uniform transparent solution (4) was vacuum-dried to obtain a zinc compound powder (4).
  • This powder (4) was redissolved in toluene.
  • This powder (4) contains a salt of acrylate ion and 2- (allyloxymethyl) acrylate ion, and as described above, the molar ratio of acrylate ion to 2- (allyloxymethyl) acrylate ion is high. It was 50:50. Further, the content ratio of water (highly polar solvent) is naturally smaller than the above-mentioned content ratio, and is less than 0.62% by mass.
  • Example 5 To a container containing a stirrer, 0.75 parts of zinc acrylate and 12.50 parts of a toluene solution containing 20% of zinc 2- (allyloxymethyl) acrylate obtained in Synthesis Example 1 were added. When the obtained formulation was stirred at 50 ° C. for 1 hour, it was visually confirmed that the zinc compounds (zinc acrylate and zinc 2- (allyloxymethyl) acrylate) were dissolved to form a uniform and transparent solution. did.
  • the obtained homogeneous transparent solution (5) contains acrylic acid ion, 2- (allyloxymethyl) acrylic acid ion, zinc ion (these ions can form a salt), and toluene (low polar solvent), and is acrylic.
  • the molar ratio of acid ion to 2- (allyloxymethyl) acrylic acid ion is 25:75, and the content ratio of water (highly polar solvent) is acrylic acid ion, 2- (allyloxymethyl) acrylic acid ion and zinc.
  • the content ratio of the acrylate ion was 3.9% by mass.
  • the uniform transparent solution (5) was vacuum-dried to obtain a zinc compound powder (5).
  • This powder (5) was redissolved in toluene.
  • This powder (5) contains a salt of acrylate ion and 2- (allyloxymethyl) acrylate ion, and as described above, the molar ratio of acrylate ion to 2- (allyloxymethyl) acrylate ion is high. It was 25:75. Further, the content ratio of water (highly polar solvent) is naturally smaller than the above-mentioned content ratio, and is less than 0.77% by mass.
  • Zinc acrylate 4.00 parts and toluene: 40.00 parts were added to the container containing the stir bar.
  • the resulting formulation (C2) contains acrylate ions, zinc ions (these ions can form salts) and toluene (low polar solvent) and is free of 2- (allyloxymethyl) acrylate ions.
  • this compound (C2) was vacuum-dried, and the powder (C2) of the zinc compound was obtained. It was confirmed that this powder (C2) did not dissolve in toluene.
  • This powder (C2) contains a salt of acrylate ion and zinc ion, does not contain 2- (allyloxymethyl) acrylate ion, and the content ratio of water (highly polar solvent) is higher than the above content ratio. Of course, it is less than 0.005% by mass.
  • EPDM (classified as M group (raw rubber having a polymethylene type saturated main chain) in JIS K 6397: 2005) is used as the resin, and the crosslinkable resin composition is prepared, kneaded, molded, and crosslinked as follows. The treatment was carried out to obtain a molded product.
  • Preparation and kneading of crosslinkable resin composition Prepare each raw material with the compounding ratio shown in Table 1 so that the total mass of the raw materials is 600 parts, and use an open roll machine (manufactured by Takamuro Iron Works, roll size: diameter 8 inches x width 18 inches).
  • Kneading was performed at a roll rotation speed of 18 rpm and a front-rear roll rotation ratio of 1: 1.25.
  • Die vulcanization test method A (test temperature: 160) in accordance with JIS K 6300-2: 2001 "Unvulcanized rubber-Physical characteristics-Part 2: How to obtain vulcanization characteristics by vibration type vulcanization tester" 90% vulcanization time of the crosslinkable resin composition was determined from ° C., amplitude angle: ⁇ 1 °, frequency: 1.67 Hz), and this was defined as the vulcanization time. Press molding was performed at 160 ° C.
  • the (meth) acrylic acid metal salt-containing composition of the present invention and the (meth) acrylic acid metal salt-containing liquid of the present invention are copolymerized with, for example, a cross-linking agent for rubber used for tires, golf balls, etc., and a polymer for ship bottom coating materials. It can be used as a component, a cross-linking agent used for a gas barrier layer of a gas barrier film, and the like.

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Abstract

La présente invention concerne une composition contenant un sel d'acide (méth)acrylique métallique qui présente une solubilité/dispersibilité exceptionnelle (de préférence une solubilité) dans des milieux à faible polarité et qui résiste à l'exsudation du sel métallique. La présente invention concerne également un liquide contenant un sel d'acide (méth)acrylique métallique qui comprend des composants constituant une telle composition contenant un sel d'acide (méth)acrylique métallique et un solvant à faible polarité.　Selon un mode de réalisation de la présente invention, la composition contenant un sel d'acide (méth)acrylique métallique comprend un anion (A1) de l'acide (méth)acrylique représenté par la formule générale (1), un anion (A2) de l'acide 2-((méth)allyloxyméthyl)acrylique représenté par la formule générale (2), et un cation de zinc (C). Le rapport de l'anion (A1) et de l'anion (A2) est de 14 : 86-99 : 1 en rapport molaire, et la proportion de contenu du solvant à polarité élevée est inférieure à 10 % en masse.
PCT/JP2020/005575 2019-03-11 2020-02-13 Composition contenant un sel d'acide (méth)acrylique métallique et liquide contenant un sel d'acide (méth)acrylique métallique Ceased WO2020184054A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012107208A (ja) * 2010-10-06 2012-06-07 Nippon Shokubai Co Ltd ジエン系カルボン酸陰イオンとその塩、およびその重合または硬化性組成物
JP2017043665A (ja) * 2015-08-25 2017-03-02 株式会社日本触媒 硬化性組成物及びその硬化物
JP2018035310A (ja) * 2016-09-02 2018-03-08 株式会社日本触媒 硬化性組成物およびこれを用いたバリア性フィルム
JP2020002201A (ja) * 2018-06-26 2020-01-09 株式会社日本触媒 成型体の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012107208A (ja) * 2010-10-06 2012-06-07 Nippon Shokubai Co Ltd ジエン系カルボン酸陰イオンとその塩、およびその重合または硬化性組成物
JP2017043665A (ja) * 2015-08-25 2017-03-02 株式会社日本触媒 硬化性組成物及びその硬化物
JP2018035310A (ja) * 2016-09-02 2018-03-08 株式会社日本触媒 硬化性組成物およびこれを用いたバリア性フィルム
JP2020002201A (ja) * 2018-06-26 2020-01-09 株式会社日本触媒 成型体の製造方法

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