WO2016163434A1 - Primer composition and method for producing same - Google Patents

Primer composition and method for producing same Download PDF

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Publication number
WO2016163434A1
WO2016163434A1 PCT/JP2016/061334 JP2016061334W WO2016163434A1 WO 2016163434 A1 WO2016163434 A1 WO 2016163434A1 JP 2016061334 W JP2016061334 W JP 2016061334W WO 2016163434 A1 WO2016163434 A1 WO 2016163434A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylic
group
primer composition
monomer
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PCT/JP2016/061334
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French (fr)
Japanese (ja)
Inventor
寿江 秋山
隆裕 岡松
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横浜ゴム株式会社
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Priority to JP2016552542A priority Critical patent/JP6677164B2/en
Publication of WO2016163434A1 publication Critical patent/WO2016163434A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a primer composition and a method for producing the same.
  • a waterproof material is sometimes provided on a ground such as mortar.
  • a primer layer is provided between the base and the waterproof material so that the base and the waterproof material are not peeled off, thereby improving the adhesion between the base and the waterproof material.
  • a primer composition comprising an acrylic emulsion has been proposed (for example, Patent Document 1).
  • acrylic particles contained in an acrylic emulsion are produced by polymerizing a polymerizable monomer having a (meth) acryloyl group in the presence of a persulfate as a polymerization initiator.
  • a primer composition made of an acrylic emulsion is water as a dispersion medium, it is necessary to dry the water from the primer layer after the primer composition is applied to the base. If a waterproof material is provided on the primer layer in a state where the drying is insufficient and water remains in the primer layer, there is a problem that the adhesion between the base and the waterproof material is difficult to be exhibited.
  • a primer composition comprising an acrylic emulsion was prepared based on Patent Document 1, and this primer composition was applied to the base and dried for a short time (30 minutes at 25 ° C.), and moisture was applied to the primer layer.
  • an evaluation was made such that a waterproofing material was provided and the base and the waterproofing material were brought into close contact with each other, and it was found that the adhesiveness between the baseing and the waterproofing material might be low.
  • an object of this invention is to provide the primer composition which is excellent in the adhesiveness of a base
  • the present inventors have found that a composition comprising a (meth) acrylic emulsion containing predetermined (meth) acrylic particles and a silane coupling agent having a glycidyl group.
  • the inventors have found that a desired effect can be obtained, and have reached the present invention.
  • the present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.
  • (Meth) acrylic particles are polymer particles obtained by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator,
  • the polymerizable monomer (B) is a (meth) acrylic acid alkyl ester monomer (b1), a (meth) acrylic acid monomer (b2) having a carboxy group, and a hydroxy group-containing polymerizable monomer (b3) having a hydroxy group.
  • the radical initiator is at least one selected from the group consisting of a dihalogen radical initiator (dihalogen compound), an azo compound and an organic peroxide;
  • the molar ratio (A / b1) of the silane coupling agent (A) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.020 or less,
  • the primer composition whose content of (meth) acryl particles is 15% by mass or more based on the total amount of the composition.
  • the (meth) acrylic acid alkyl ester monomer (b1) contains methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2EHA), 2.
  • the primer composition according to 1 above wherein the molar ratio of methyl methacrylate to 2-ethylhexyl acrylate (MMA / 2EHA) is 1.470-2.310. 3.
  • the primer according to 1 or 2 above, wherein the molar ratio (b2 / b1) of the (meth) acrylic acid monomer (b2) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.038 to 0.075.
  • Composition. 4 The molar ratio (b3 / b1) of the hydroxy group-containing polymerizable monomer (b3) having a hydroxy group to the (meth) acrylic acid alkyl ester monomer (b1) is 0.050 to 0.100,
  • a primer composition used for adhering a base and a waterproof material A (meth) acrylic emulsion containing (meth) acrylic particles and a silane coupling agent (A) having a glycidyl group,
  • the polymer constituting the (meth) acrylic particles is a (meth) acrylic polymer having an alkyl group, a hydroxy group, and a carboxy group, and the main skeleton being a poly (meth) acryl skeleton,
  • the molar ratio of the silane coupling agent (A) to the repeating unit having an alkyl group is 0.020 or less
  • the primer composition whose content of (meth) acryl particles is 15% by mass or more based on the total amount of the composition. 10.
  • a (meth) acrylic polymer is produced by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator, and a silane coupling having a (meth) acrylic polymer, water and a glycidyl group.
  • a method for producing a primer composition wherein the primer composition according to any one of 1 to 4 and 7 to 9 is produced by mixing the agent (A). 11. Furthermore, the manufacturing method of the primer composition of said 10 containing tertiary amine (C).
  • the (meth) acrylic emulsion contained in the primer composition described in 9 corresponds to the (meth) acrylic emulsion contained in the primer composition described in 1 above.
  • the repeating unit having an alkyl group in the (meth) acrylic polymer corresponds to a repeating unit formed from the (meth) acrylic acid alkyl ester monomer (b1) described later.
  • the primer composition of the present invention is excellent in adhesion between the base and the waterproof material even when the drying time is short. According to the production method of the present invention, it is possible to produce a primer composition having excellent adhesion between the base and the waterproofing material even when the drying time is short.
  • (meth) acrylate represents acrylate or methacrylate
  • (meth) acryloyl represents acryloyl or methacryloyl
  • (meth) acryl represents acryl or methacryl.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • each component used can be used alone or in combination of two or more kinds of substances corresponding to the component.
  • the content of the above components refers to the total content of two or more types of substances.
  • the organic group is not particularly limited.
  • the hydrocarbon group which may have a hetero atom is mentioned, for example.
  • the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
  • the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • a heteroatom may be combined with a hydrogen atom, a carbon atom or another heteroatom to form a functional group.
  • the monomer ratio of the monomers used when producing the (meth) acrylic particles is reflected in the ratio of repeating units of the polymer constituting the (meth) acrylic particles.
  • the primer composition of the present invention (the composition of the present invention) It is a primer composition used for adhering a base and a waterproof material, A (meth) acrylic emulsion containing (meth) acrylic particles and a silane coupling agent (A) having a glycidyl group, (Meth) acrylic particles are polymer particles obtained by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator,
  • the polymerizable monomer (B) is a (meth) acrylic acid alkyl ester monomer (b1), a (meth) acrylic acid monomer (b2) having a carboxy group, and a hydroxy group-containing polymerizable monomer (b3) having a hydroxy group.
  • the radical initiator is at least one selected from the group consisting of dihalogen radical initiators, azo compounds and organic peroxides;
  • the molar ratio (A / b1) of the silane coupling agent (A) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.020 or less, It is a primer composition whose content of (meth) acrylic particles is 15% by mass or more based on the total amount of the composition.
  • the composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but it is presumed that it is as follows. As described above, it is difficult to dry a general aqueous primer composition in a short time, and it is necessary to sufficiently dry the primer composition in order to develop high adhesion.
  • a waterproof material is provided on the primer composition in a state where it is not sufficiently dried, the water in the composition is vaporized, or when the waterproof material is urethane, the isocyanate group is decomposed by water and carbon dioxide is generated.
  • a cavity may be formed between the waterproof material and the base. When such a cavity is generated, the present inventors infer that the waterproofing material cannot form a bond with the primer layer and thus the adhesiveness is lowered.
  • the glycidyl contained in the silane coupling agent (A) contained in the composition even after the composition of the present invention is dried and moisture remains in the dried primer composition. Since the group can react or interact with one or both of the base and the waterproof material, it is considered that the adhesion between the base and the waterproof material is excellent.
  • the (meth) acrylic emulsion contained in the composition of the present invention includes (meth) acrylic particles as a dispersoid and a dispersion medium, and the (meth) acrylic particles are dispersed in the dispersion medium.
  • an emulsion includes a suspension (a system in which a dispersoid as a solid phase is dispersed in a dispersion medium as a liquid phase) and a system in which a dispersoid as a liquid phase is dispersed in a dispersion medium as a liquid phase.
  • the dispersion medium is not particularly limited as long as it is an aqueous solvent.
  • the aqueous solvent include water; a mixed solvent obtained by mixing an organic solvent soluble in water with water.
  • the organic solvent include alcohols; ketones such as methyl ethyl ketone (MEK).
  • (Meth) acrylic particles as a dispersoid are polymer particles obtained by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator.
  • the shape of the (meth) acrylic particles is not particularly limited as long as it is granular.
  • the average particle diameter of the (meth) acrylic particles can be, for example, 0.01 to 0.6 ⁇ m.
  • the average particle diameter of (meth) acrylic particles can be measured using a particle size distribution analyzer (Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.).
  • the (meth) acrylic particles can have a carboxy group on the surface.
  • the polymerizable monomer (B) having a (meth) acryloyl group used when producing (meth) acrylic particles is a (meth) acrylic acid alkyl ester monomer (b1) and a (meth) acrylic having a carboxy group. It is preferable to contain an acid monomer (b2) and a hydroxy group-containing polymerizable monomer (b3) having a hydroxy group.
  • the (meth) acrylic acid alkyl ester monomer (b1) is an alkyl ester of (meth) acrylic acid.
  • the alkyl group (aliphatic hydrocarbon group) bonded to the ester bond is not particularly limited. It may be linear, branched or cyclic, or a combination thereof.
  • (meth) acrylic acid alkyl ester monomer (b1) examples include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, Examples include 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, butylcyclohexyl (meth) acrylate, pentyl (meth) acrylate, octyl (meth) acrylate, and nonyl (meth) acrylate.
  • methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable, and methyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable.
  • the (meth) acrylic acid alkyl ester monomer (b1) can be used alone or in combination of two or more.
  • the combination of the (meth) acrylic acid alkyl ester monomer (b1) is preferably a combination of methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2EHA).
  • the molar ratio of methyl methacrylate to 2-ethylhexyl acrylate (MMA / 2EHA) is preferably from 1.470 to 2.310, more preferably from 1.650 to 2.030.
  • the (meth) acrylic acid alkyl ester monomer (b1) does not have a carboxy group or a hydroxy group.
  • the (meth) acrylic acid monomer (b2) is a compound having a (meth) acryloyl group and a carboxy group.
  • the (CO) of the (meth) acryloyl group may form a carboxy group.
  • the (meth) acryloyl group and the carboxy group can be bonded via an organic group.
  • the (meth) acryloyl group may be, for example, a (meth) acryloyloxy group.
  • Examples of the (meth) acrylic acid monomer (b2) include (meth) acrylic acid; carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and the like.
  • the (meth) acrylic acid monomer (b2) can be used alone or in combination of two or more.
  • the molar ratio (b2 / b1) of the (meth) acrylic acid monomer (b2) to the (meth) acrylic acid alkyl ester monomer (b1) is preferably 0.038 to 0.075, preferably 0.047 to 0. 0.066 is more preferred.
  • the hydroxy group-containing polymerizable monomer (b3) having a hydroxy group is a compound having a hydroxy group and a (meth) acryloyl group as a polymerizable functional group.
  • Hydroxy group-containing polymerizable monomer (b3) One molecule can have one or more hydroxy groups. The number of hydroxy groups is preferably one.
  • the (meth) acryloyl group that one molecule of the hydroxy group-containing polymerizable monomer (b3) has may be, for example, a (meth) acryloyloxy group.
  • One preferred embodiment is that the hydroxy group and the (meth) acryloyl group are bonded via an organic group (for example, a hydrocarbon group which may have a hetero atom).
  • an organic group for example, a hydrocarbon group which may have a hetero atom.
  • the organic group is not particularly limited.
  • hydroxy group-containing polymerizable monomer (b3) examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyhexyl (meth).
  • hydroxy group-containing polymerizable monomer (b3) can be used alone or in combination of two or more.
  • the molar ratio (b3 / b1) of the hydroxy group-containing polymerizable monomer (b3) having a hydroxy group to the (meth) acrylic acid alkyl ester monomer (b1) is preferably 0.050 to 0.100, and preferably 069 to 0.100 is more preferable.
  • a compound having an ethylenically unsaturated bond can be further used in addition to the monomers (b1) to (b3).
  • the compound having an ethylenically unsaturated bond include olefins; vinyl aromatic hydrocarbon compounds such as styrene; carboxylic acid compounds such as crotonic acid, itaconic acid, maleic acid, and fumaric acid.
  • the radical initiator used when producing the (meth) acrylic particles is at least one selected from the group consisting of a dihalogen radical initiator, an azo compound, and an organic peroxide.
  • the radical initiator can radicalize the (meth) acryloyl group of the polymerizable monomer (B).
  • the dihalogen radical initiator is not particularly limited as long as it is a substance having a halogen-halogen bond (including a compound having a halogen-halogen bond and a halogen molecule).
  • Halogen is not particularly limited.
  • Organic peroxide examples include benzoyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide.
  • an azo compound is preferable from the viewpoint that the radical initiator is superior due to the effects of the present invention.
  • the azo compound is not particularly limited as long as it is a compound having an azo bond.
  • the organic group bonded to the azo bond is not particularly limited.
  • azo compound examples include azobisisobutyronitrile, azodicarbonamide, 2,2'-azobis- (2-amidinopropane) dihydrochloride, dimethyl 2,2'-azobis (isobutyrate), azobis-cyan
  • valeric acid 1,1′-azobis- (2,4-dimethylvaleronitrile), azobismethylbutyronitrile, 2,2′-azobis- (4-methoxy-2,4-dimethylpareronitrile). It is done.
  • the radical initiators can be used alone or in combination of two or more.
  • the radical initiator is substantially free of persulfate.
  • the persulfate is not particularly limited. Examples thereof include ammonium persulfate, potassium persulfate, and sodium persulfate.
  • the radical initiator substantially free of persulfate means that the amount of persulfate used is 0 to 0.1% by mass with respect to the radical initiator.
  • the radical initiator does not substantially contain a redox initiator.
  • the redox initiator is not particularly limited. For example, a combination of an oxidizing agent such as persulfate and a reducing agent such as sodium bisulfite can be mentioned.
  • the radical initiator substantially not containing a redox initiator means that the amount of the redox initiator used is 0 to 0.1% by mass with respect to the radical initiator.
  • the amount (molar ratio) of the radical initiator used with respect to the total amount of the polymerizable monomer (B) is preferably 0.0013 to 0.0100, and more preferably 0.0026 to 0.0090.
  • the polymer ((meth) acrylic polymer) constituting the (meth) acrylic particles can be obtained by polymerizing the polymerizable monomer (B) in the presence of a radical initiator.
  • the polymerization can be carried out at a temperature of about 60 to 80 ° C. under an inert gas stream such as nitrogen.
  • the said (meth) acrylic-type polymer is manufactured in an aqueous solvent or an organic solvent.
  • the radical initiator, polymerizable monomer (B), aqueous solvent, and organic solvent are the same as described above.
  • the (meth) acrylic polymer is in the form of particles and can be a (meth) acrylic emulsion containing (meth) acrylic particles.
  • Method for producing (meth) acrylic emulsion As a method for producing a (meth) acrylic emulsion containing (meth) acrylic particles contained in the composition of the present invention, for example, polymerization having a (meth) acryloyl group in an aqueous solvent in the presence of a radical initiator A method of polymerizing the polymerizable monomer (B); producing a (meth) acrylic polymer as described above (for example, when the polymerization is carried out in an organic solvent), and after the polymerization, adding an aqueous solvent to the reaction system and stirring The method of doing is mentioned.
  • the radical initiator, polymerizable monomer (B), aqueous solvent, and organic solvent are the same as described above.
  • the composition of the present invention may further contain a tertiary amine (C).
  • tertiary amine (C) can be used as a base.
  • the tertiary amine (C) ionizes the carboxy group of the (meth) acrylic particles contained in the composition, thereby improving the dispersion of the (meth) acrylic particles. be able to.
  • the tertiary amine (C) is preferably a tertiary amine having an aliphatic hydrocarbon group, and more preferably all the hydrocarbon groups bonded to the nitrogen atom are aliphatic hydrocarbon groups.
  • Examples of the tertiary amine (C) include triethylamine, N, N-dimethyllaurylamine, and N, N-dimethylpalmitylamine.
  • the tertiary amine (C) can be used alone or in combination of two or more.
  • the molar ratio (C / b2) of the tertiary amine (C) to the (meth) acrylic acid monomer (b2) is preferably 0.560 to 1.140, more preferably 0.760 to 0.940. preferable.
  • Method for producing (meth) acrylic emulsion when tertiary amine (C) is used As a method for producing a (meth) acrylic emulsion when using a tertiary amine (C), for example, adding a tertiary amine (C) to the (meth) acrylic emulsion produced as described above, These can be mixed to produce a (meth) acrylic emulsion containing a tertiary amine (C).
  • a polymerizable monomer (B) having a (meth) acryloyl group is mixed with an agitator in the presence of a radical initiator and a tertiary amine (C) in an aqueous solvent.
  • a method of radical polymerization under conditions of 60 to 90 ° C. can be mentioned.
  • a (meth) acrylic polymer is produced by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator.
  • Water for example, distilled water
  • tertiary amine (C) are added to the reaction system later, and these are mixed to produce a (meth) acrylic emulsion containing the tertiary amine (C). The method of doing is mentioned.
  • the polymerizable monomer (B) having a (meth) acryloyl group is polymerized in the presence of a radical initiator
  • the above organic solvent is used (specifically, for example, when only the above organic solvent is used)
  • polymerization is performed.
  • the organic solvent may be distilled off after adding water (for example, distilled water) and the tertiary amine (C) to the post-reaction system.
  • (Meth) acrylic emulsions can be used alone or in combination of two or more.
  • the polymer constituting the (meth) acrylic particles contained in the (meth) acrylic emulsion has an alkyl group, a hydroxy group, and a carboxy group, and the main skeleton is a poly (meth) acryl skeleton (
  • One preferred embodiment is that the molar ratio of the silane coupling agent (A) to the repeating unit that is a (meth) acrylic polymer and has an alkyl group is 0.020 or less.
  • the alkyl group that the (meth) acrylic polymer has is not particularly limited.
  • the alkyl group can be introduced into the (meth) acrylic polymer by the (meth) acrylic acid alkyl ester monomer (b1).
  • the (meth) acrylic polymer is a repeating unit formed by methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2EHA) as a repeating unit formed by the (meth) acrylic acid alkyl ester monomer (b1). It is preferable to contain.
  • the carboxy group of the (meth) acrylic polymer can be bonded to the main skeleton directly or via an organic group.
  • the organic group is the same as described above.
  • the carboxy group can be introduced into the (meth) acrylic polymer by the (meth) acrylic acid monomer (b2).
  • the (meth) acrylic polymer has a repeating unit formed by the (meth) acrylic acid monomer (b2).
  • the carboxy group may be ionized with a tertiary amine (C).
  • the hydroxy group of the (meth) acrylic polymer can be bonded to the main skeleton directly or via an organic group.
  • the organic group is the same as described above.
  • the hydroxy group can be introduced into the (meth) acrylic polymer by the hydroxy group-containing polymerizable monomer (b3).
  • the (meth) acrylic polymer has a repeating unit formed by the hydroxy group-containing polymerizable monomer (b3).
  • the main skeleton of the (meth) acrylic polymer has a repeating unit formed of a polymerizable monomer (B) having a (meth) acryloyl group.
  • the (meth) acryloyl group may be a (meth) acryloyloxy group.
  • the weight average molecular weight (Mw) of the (meth) acrylic polymer can be, for example, 10,000 to 500,000.
  • the weight average molecular weight (Mw) of the (meth) acrylic polymer is a weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
  • the silane coupling agent (A) contained in the composition of the present invention has a glycidyl group and a hydrolyzable silyl group.
  • the hydrolyzable silyl group include an alkoxysilyl group.
  • the number of alkoxy groups bonded to one silicon atom is preferably 2 or 3.
  • the hydrocarbon group that can be bonded to the silicon atom is not particularly limited.
  • an alkyl group is mentioned.
  • the organic group that binds the glycidyl group and the hydrolyzable silyl group is not particularly limited.
  • the hydrocarbon group which may have a hetero atom like an oxygen atom, a nitrogen atom, and a sulfur atom is mentioned.
  • the silane coupling agent (A) is preferably glycidoxyalkyltrialkoxysilane.
  • Examples of the glycidoxyalkyltrialkoxysilane include 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane.
  • a silane coupling agent (A) can be used individually or in combination of 2 types or more, respectively.
  • the molar ratio (A / b1) of the silane coupling agent (A) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.020 or less.
  • the molar ratio (A / b1) is more preferably 0.006 to 0.02, and more preferably 0.008 to 0.017, from the viewpoint of being excellent in the effects of the present invention and excellent in storage stability.
  • the composition of the present invention further comprises a leveling agent, an antioxidant, a corrosion inhibitor, a light stabilizer, an ultraviolet absorber, a silane coupling agent other than the silane coupling agent (A), and a filler.
  • a leveling agent an antioxidant, a corrosion inhibitor, a light stabilizer, an ultraviolet absorber, a silane coupling agent other than the silane coupling agent (A), and a filler.
  • Such additives can be contained. It is mentioned as one of the aspects with preferable that the composition of this invention contains only a (meth) acrylic-type emulsion and a silane coupling agent (A). In this case, the carboxy group of the (meth) acryl particles may be ionized with the tertiary amine (C).
  • composition of the present invention is not particularly limited with respect to its production method.
  • the method of mixing the said (meth) acrylic-type emulsion, a silane coupling agent (A), and arbitrary components is mentioned.
  • the composition of the present invention contains (meth) acrylic particles as a solid content.
  • the content of (meth) acrylic particles (solid content) is 15% by mass or more, preferably 15 to 60% by mass, and more preferably 15 to 40% by mass with respect to the total amount of the composition.
  • composition of the present invention includes, as one preferred embodiment, substantially free of the above-mentioned persulfate or redox initiator, or components derived therefrom (hereinafter simply referred to as persulfate, etc.). It is done.
  • the fact that the composition of the present invention is substantially free of persulfate or the like means that the content of persulfate or the like is 0 to 0.1% by mass with respect to the entire composition of the present invention. .
  • the composition of this invention is used in order to adhere
  • the waterproof material is not particularly limited.
  • a urethane waterproof material, a silicone waterproof material, and a polysulfide waterproof material can be used. Among these, a urethane waterproof material is preferable.
  • the form of the waterproof material is not particularly limited. For example, liquid form and sheet form are mentioned.
  • the foundation is not particularly limited. Examples thereof include inorganic hard materials, and specific examples include mortar, glass, silicone hard coat, ceramic, concrete, porcelain, and metal.
  • the composition of the present invention is first applied to the substrate and dried at 20 to 28 ° C. as a method for bringing the substrate and the waterproof material into close contact with each other using the composition of the present invention.
  • the primer layer formed from the composition of the present invention is excellent in the adhesion between the base and the waterproofing material even if water remains in the primer layer. Can be shortened.
  • the drying time of the primer can be 25 to 40 minutes.
  • a waterproof material is provided on the base after drying.
  • the waterproofing material is liquid
  • the waterproofing material is poured onto the dried substrate, and when the waterproofing material is in a sheet form, the sheet is laid on the dried substrate, By curing for 3 to 5 days under conditions of 25 ° C. and 45% RH, the substrate and the waterproof material can be brought into close contact with each other.
  • the molar ratio of the silane coupling agent (A) to the repeating unit having an alkyl group in the (meth) acrylic polymer was 0.020 or less.
  • Each (meth) acrylic emulsion prepared as described above was used as it was in the production of the following composition.
  • Radical initiator 1 (comparative) (APS): ammonium persulfate (molecular weight: 228) Radical initiator 2 (AIBN): 2,2′-azobisisobutyronitrile (molecular weight: 164) Reducing agent 1 (SBS): sodium bisulfite (molecular weight: 104)
  • composition ⁇ Production of composition> The (meth) acrylic emulsion prepared as described above and each silane coupling agent A (compounding) shown in the column “Silane coupling agent A / blending amount used when using the composition” in Table 1 below.
  • the unit of the amount was mol) and was mixed with a stirrer to produce a composition.
  • content (mass%) of the (meth) acryl particle with respect to the whole composition may become the value (unit: mass%) shown in the "solid content” column of Table 1. Distilled water was appropriately added to the product.
  • the solid content means (meth) acrylic particles.
  • silane coupling agent A used in preparing the composition shown in Table 1 below are as follows.
  • Silane coupling agent A1 (comparative): 3-methacryloxypropyltriethoxysilane, KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Silane coupling agent A2 (comparative): 3-mercaptopropyltrimethoxysilane, KBM-803, Made by Shin-Etsu Chemical Co., Ltd.
  • Silane coupling agent A3 (comparative): 3-aminopropyltriethoxysilane, KBM-903, made by Shin-Etsu Chemical Co., Ltd.
  • Silane coupling agent A4 3-glycidoxypropyltriethoxysilane, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the evaluation criteria of the normal peel test are as follows. The case where the waterproof material layer could not be peeled from the mortar was evaluated as being excellent in adhesion between the base and the waterproof material, and this was indicated as “A”. When the waterproof material layer could be peeled off from the mortar, it was evaluated that the adhesion between the base and the waterproof material was low, and this was indicated as “B”.
  • Comparative Example 6 that does not use a predetermined radical initiator or Comparative Examples 1 to 5 that does not contain a predetermined silane coupling agent
  • the waterproof material layer is the base. It was peeled off by hand peeling, and the adhesion between the base and the waterproof material was low.
  • Comparative Example 7 in which the silane coupling agent (A) / (meth) acrylic acid alkyl ester monomer (b1) exceeds the predetermined range, when the primer composition is dried for a short time, the waterproof material layer is formed in the same manner as in the above Comparative Example. It peeled off from the substrate by hand peeling, and the adhesion between the substrate and the waterproof material was low.
  • Example 1 was excellent in adhesion between the substrate and the waterproof material even when the drying time was short.

Abstract

The purpose of the present invention is to provide a primer composition which enables the achievement of excellent adhesion between a base and a waterproof material even if the drying time thereof is short. The present invention is a primer composition which is used for the purpose of achieving good adhesion between a base and a waterproof material, and which contains a silane coupling agent (A) having a glycidyl group and a (meth)acrylic emulsion containing (meth)acrylic particles. The (meth)acrylic particles are polymer particles that are obtained by polymerizing a polymerizable monomer (B) having a specific (meth)acryloyl group in the presence of a specific radical initiator. The molar ratio of the silane coupling agent (A) to an alkyl (meth)acrylate ester monomer (b1), namely (A)/(b1) is 0.020 or less. The content of the (meth)acrylic particles relative to the whole composition is 15% by mass or more.

Description

プライマー組成物及びその製造方法Primer composition and method for producing the same
　本発明はプライマー組成物及びその製造方法に関する。 The present invention relates to a primer composition and a method for producing the same.
　従来、建築物を雨等から保護するため、モルタル等のような下地の上に防水材を設けることがある。そして下地と防水材とが剥がれないように、下地と防水材との間にプライマー層を設けて、下地と防水材との密着性を高くすることがある。このようなプライマー層に使用できる組成物として、例えば、アクリル系エマルジョンからなるプライマー組成物が提案されている（例えば特許文献１）。特許文献１において、アクリル系エマルジョンに含有されるアクリル粒子は（メタ）アクリロイル基を有する重合性モノマーを重合開始剤である過硫酸塩の存在下で重合させることによって製造される。 Conventionally, in order to protect a building from rain, a waterproof material is sometimes provided on a ground such as mortar. In some cases, a primer layer is provided between the base and the waterproof material so that the base and the waterproof material are not peeled off, thereby improving the adhesion between the base and the waterproof material. As a composition that can be used for such a primer layer, for example, a primer composition comprising an acrylic emulsion has been proposed (for example, Patent Document 1). In Patent Document 1, acrylic particles contained in an acrylic emulsion are produced by polymerizing a polymerizable monomer having a (meth) acryloyl group in the presence of a persulfate as a polymerization initiator.
特開２０１４－１７２９９２号公報JP 2014-172992 A
　アクリル系エマルジョンからなるプライマー組成物は分散媒が水であるため、プライマー組成物を下地に塗布した後、プライマー層から水を乾燥させる必要がある。上記乾燥が不十分で水がプライマー層に残留した状態でプライマー層の上に防水材を設けると、下地と防水材との密着力が発現しにくいという問題がある。 Since a primer composition made of an acrylic emulsion is water as a dispersion medium, it is necessary to dry the water from the primer layer after the primer composition is applied to the base. If a waterproof material is provided on the primer layer in a state where the drying is insufficient and water remains in the primer layer, there is a problem that the adhesion between the base and the waterproof material is difficult to be exhibited.
　このようななか、特許文献１をもとにアクリル系エマルジョンからなるプライマー組成物を調製し、このプライマー組成物を下地に塗布し短時間（２５℃条件下で３０分間）乾燥させ、プライマー層に水分が残留した状態で、これに防水材を設けて下地と防水材とを密着させる評価を行ったところ、下地と防水材との密着力が低い場合があることが明らかとなった。
　そこで、本発明は、乾燥時間が短くとも下地と防水材との密着性に優れるプライマー組成物を提供することを目的とする。 Under such circumstances, a primer composition comprising an acrylic emulsion was prepared based on Patent Document 1, and this primer composition was applied to the base and dried for a short time (30 minutes at 25 ° C.), and moisture was applied to the primer layer. In the state where the waterproofing material remains, an evaluation was made such that a waterproofing material was provided and the base and the waterproofing material were brought into close contact with each other, and it was found that the adhesiveness between the baseing and the waterproofing material might be low.
Then, an object of this invention is to provide the primer composition which is excellent in the adhesiveness of a base | substrate and a waterproofing material, even if drying time is short.
　本発明者らは、上記課題を解決すべく鋭意研究した結果、所定の（メタ）アクリル粒子を含有する（メタ）アクリル系エマルジョンとグリシジル基を有するシランカップリング剤とを含む組成物によれば、所望の効果が得られることを見出し、本発明に至った。
　本発明は上記知見等に基づくものであり、具体的には以下の構成により上記課題を解決するものである。 As a result of intensive studies to solve the above problems, the present inventors have found that a composition comprising a (meth) acrylic emulsion containing predetermined (meth) acrylic particles and a silane coupling agent having a glycidyl group. The inventors have found that a desired effect can be obtained, and have reached the present invention.
The present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.
　１．　下地と防水材とを密着させるために使用されるプライマー組成物であって、
　（メタ）アクリル粒子を含有する（メタ）アクリル系エマルジョンとグリシジル基を有するシランカップリング剤（Ａ）とを含み、
　（メタ）アクリル粒子が、ラジカル開始剤の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を重合させて得られるポリマー粒子であり、
　重合性モノマー（Ｂ）が、（メタ）アクリル酸アルキルエステルモノマー（ｂ１）と、カルボキシ基を有する（メタ）アクリル酸系モノマー（ｂ２）と、ヒドロキシ基を有するヒドロキシ基含有重合性モノマー（ｂ３）とを含み、
　ラジカル開始剤が、ジハロゲン系ラジカル開始剤（ジハロゲン化合物）、アゾ化合物及び有機過酸化物からなる群から選ばれる少なくとも１種であり、
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対するシランカップリング剤（Ａ）のモル比（Ａ／ｂ１）が、０．０２０以下であり、
　（メタ）アクリル粒子の含有量が、組成物全量に対して、１５質量％以上である、プライマー組成物。
　２．　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）が、メタクリル酸メチル（ＭＭＡ）とアクリル酸－２－エチルヘキシル（２ＥＨＡ）とを含み、
　アクリル酸－２－エチルヘキシルに対するメタクリル酸メチルのモル比（ＭＭＡ／２ＥＨＡ）が１．４７０～２．３１０である、上記１に記載のプライマー組成物。
　３．　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対する（メタ）アクリル酸系モノマー（ｂ２）のモル比（ｂ２／ｂ１）が、０．０３８～０．０７５である、上記１又は２に記載のプライマー組成物。
　４．　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対するヒドロキシ基を有するヒドロキシ基含有重合性モノマー（ｂ３）のモル比（ｂ３／ｂ１）が、０．０５０～０．１００である、上記１～３のいずれかに記載のプライマー組成物。
　５．　（メタ）アクリル粒子が有するカルボキシ基が、第３級アミン（Ｃ）でイオン化されている、上記１～４のいずれかに記載のプライマー組成物。
　６．　（メタ）アクリル酸系モノマー（ｂ２）に対する第３級アミン（Ｃ）のモル比（Ｃ／ｂ２）が、０．５６０～１．１４０である、上記５に記載のプライマー組成物。
　７．　防水材が、ウレタン防水材である、上記１～６のいずれかに記載のプライマー組成物。
　８．　下地が、無機系硬質素材である、上記１～７のいずれかに記載のプライマー組成物。
　９．　下地と防水材とを密着させるために使用されるプライマー組成物であって、
　（メタ）アクリル粒子を含有する（メタ）アクリル系エマルジョンとグリシジル基を有するシランカップリング剤（Ａ）とを含み、
　（メタ）アクリル粒子を構成するポリマーは、アルキル基とヒドロキシ基とカルボキシ基とを有し、主骨格がポリ（メタ）アクリル骨格である（メタ）アクリル系ポリマーであり、
　アルキル基を有する繰り返し単位に対するシランカップリング剤（Ａ）のモル比が、０．０２０以下であり、
　（メタ）アクリル粒子の含有量が、組成物全量に対して、１５質量％以上である、プライマー組成物。
　１０．　ラジカル開始剤の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を重合させて（メタ）アクリル系ポリマーを製造し、（メタ）アクリル系ポリマーと水とグリシジル基を有するシランカップリング剤（Ａ）とを混合することによって、上記１～４及び７～９のいずれかに記載のプライマー組成物を製造する、プライマー組成物の製造方法。
　１１．　更に第３級アミン（Ｃ）を含有する、上記１０に記載のプライマー組成物の製造方法。 1. It is a primer composition used for adhering a base and a waterproof material,
A (meth) acrylic emulsion containing (meth) acrylic particles and a silane coupling agent (A) having a glycidyl group,
(Meth) acrylic particles are polymer particles obtained by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator,
The polymerizable monomer (B) is a (meth) acrylic acid alkyl ester monomer (b1), a (meth) acrylic acid monomer (b2) having a carboxy group, and a hydroxy group-containing polymerizable monomer (b3) having a hydroxy group. Including
The radical initiator is at least one selected from the group consisting of a dihalogen radical initiator (dihalogen compound), an azo compound and an organic peroxide;
The molar ratio (A / b1) of the silane coupling agent (A) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.020 or less,
The primer composition whose content of (meth) acryl particles is 15% by mass or more based on the total amount of the composition.
2. The (meth) acrylic acid alkyl ester monomer (b1) contains methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2EHA),
2. The primer composition according to 1 above, wherein the molar ratio of methyl methacrylate to 2-ethylhexyl acrylate (MMA / 2EHA) is 1.470-2.310.
3. The primer according to 1 or 2 above, wherein the molar ratio (b2 / b1) of the (meth) acrylic acid monomer (b2) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.038 to 0.075. Composition.
4). The molar ratio (b3 / b1) of the hydroxy group-containing polymerizable monomer (b3) having a hydroxy group to the (meth) acrylic acid alkyl ester monomer (b1) is 0.050 to 0.100, The primer composition according to any one of the above.
5. 5. The primer composition according to any one of 1 to 4 above, wherein the carboxy group of the (meth) acrylic particles is ionized with a tertiary amine (C).
6). 6. The primer composition according to 5 above, wherein the molar ratio (C / b2) of the tertiary amine (C) to the (meth) acrylic acid monomer (b2) is 0.560 to 1.140.
7). 7. The primer composition according to any one of 1 to 6 above, wherein the waterproof material is a urethane waterproof material.
8). 8. The primer composition according to any one of 1 to 7 above, wherein the base is an inorganic hard material.
9. It is a primer composition used for adhering a base and a waterproof material,
A (meth) acrylic emulsion containing (meth) acrylic particles and a silane coupling agent (A) having a glycidyl group,
The polymer constituting the (meth) acrylic particles is a (meth) acrylic polymer having an alkyl group, a hydroxy group, and a carboxy group, and the main skeleton being a poly (meth) acryl skeleton,
The molar ratio of the silane coupling agent (A) to the repeating unit having an alkyl group is 0.020 or less,
The primer composition whose content of (meth) acryl particles is 15% by mass or more based on the total amount of the composition.
10. A (meth) acrylic polymer is produced by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator, and a silane coupling having a (meth) acrylic polymer, water and a glycidyl group. A method for producing a primer composition, wherein the primer composition according to any one of 1 to 4 and 7 to 9 is produced by mixing the agent (A).
11. Furthermore, the manufacturing method of the primer composition of said 10 containing tertiary amine (C).
　上記９に記載のプライマー組成物に含有される（メタ）アクリル系エマルジョンは、上記１に記載のプライマー組成物に含有される（メタ）アクリル系エマルジョンと対応する。それ以外の成分についても同様である。
　上記９に記載のプライマー組成物において、（メタ）アクリル系ポリマーが有する、アルキル基を有する繰り返し単位は、後述する（メタ）アクリル酸アルキルエステルモノマー（ｂ１）から形成される繰り返し単位に対応する。 The (meth) acrylic emulsion contained in the primer composition described in 9 corresponds to the (meth) acrylic emulsion contained in the primer composition described in 1 above. The same applies to other components.
In the primer composition described in 9 above, the repeating unit having an alkyl group in the (meth) acrylic polymer corresponds to a repeating unit formed from the (meth) acrylic acid alkyl ester monomer (b1) described later.
　本発明のプライマー組成物は、乾燥時間が短くとも下地と防水材との密着性に優れる。
　本発明の製造方法によれば、乾燥時間が短くとも下地と防水材との密着性に優れるプライマー組成物を製造することができる。 The primer composition of the present invention is excellent in adhesion between the base and the waterproof material even when the drying time is short.
According to the production method of the present invention, it is possible to produce a primer composition having excellent adhesion between the base and the waterproofing material even when the drying time is short.
　本発明について以下詳細に説明する。
　なお、本明細書において、（メタ）アクリレートとは、アクリレートまたはメタクリレートを表し、（メタ）アクリロイルとは、アクリロイルまたはメタクリロイルを表し、（メタ）アクリルとは、アクリルまたはメタクリルを表す。
　また、本明細書において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　また、本明細書において、使用される各成分は特に断りがない限り、その成分に該当する物質をそれぞれ単独でまたは２種以上を組み合わせて使用することができる。成分が２種以上の物質を含む場合、上記成分の含有量とは、２種以上の物質の合計の含有量を指す。
　本明細書において有機基は特に制限されない。有機基としては例えば、ヘテロ原子を有してもよい炭化水素基が挙げられる。炭化水素基としては、例えば、脂肪族炭化水素基、芳香族炭化水素基、これらの組合せが挙げられる。ヘテロ原子としては例えば、酸素原子、窒素原子、硫黄原子が挙げられる。ヘテロ原子は、水素原子、炭素原子又は別のヘテロ原子と組み合わせて官能基を形成してもよい。
　本明細書において、（メタ）アクリル粒子を製造する際に使用されるモノマーのモノマー比は、（メタ）アクリル粒子を構成するポリマーが有する繰り返し単位の比に反映されるものとする。 The present invention will be described in detail below.
In this specification, (meth) acrylate represents acrylate or methacrylate, (meth) acryloyl represents acryloyl or methacryloyl, and (meth) acryl represents acryl or methacryl.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Further, in the present specification, unless otherwise specified, each component used can be used alone or in combination of two or more kinds of substances corresponding to the component. When a component contains 2 or more types of substances, the content of the above components refers to the total content of two or more types of substances.
In the present specification, the organic group is not particularly limited. As an organic group, the hydrocarbon group which may have a hetero atom is mentioned, for example. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. A heteroatom may be combined with a hydrogen atom, a carbon atom or another heteroatom to form a functional group.
In this specification, the monomer ratio of the monomers used when producing the (meth) acrylic particles is reflected in the ratio of repeating units of the polymer constituting the (meth) acrylic particles.
［プライマー組成物］
　本発明のプライマー組成物（本発明の組成物）は、
　下地と防水材とを密着させるために使用されるプライマー組成物であって、
　（メタ）アクリル粒子を含有する（メタ）アクリル系エマルジョンとグリシジル基を有するシランカップリング剤（Ａ）とを含み、
　（メタ）アクリル粒子が、ラジカル開始剤の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を重合させて得られるポリマー粒子であり、
　重合性モノマー（Ｂ）が、（メタ）アクリル酸アルキルエステルモノマー（ｂ１）と、カルボキシ基を有する（メタ）アクリル酸系モノマー（ｂ２）と、ヒドロキシ基を有するヒドロキシ基含有重合性モノマー（ｂ３）とを含み、
　ラジカル開始剤が、ジハロゲン系ラジカル開始剤、アゾ化合物及び有機過酸化物からなる群から選ばれる少なくとも１種であり、
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対するシランカップリング剤（Ａ）のモル比（Ａ／ｂ１）が、０．０２０以下であり、
　（メタ）アクリル粒子の含有量が、組成物全量に対して、１５質量％以上である、プライマー組成物である。 [Primer composition]
The primer composition of the present invention (the composition of the present invention)
It is a primer composition used for adhering a base and a waterproof material,
A (meth) acrylic emulsion containing (meth) acrylic particles and a silane coupling agent (A) having a glycidyl group,
(Meth) acrylic particles are polymer particles obtained by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator,
The polymerizable monomer (B) is a (meth) acrylic acid alkyl ester monomer (b1), a (meth) acrylic acid monomer (b2) having a carboxy group, and a hydroxy group-containing polymerizable monomer (b3) having a hydroxy group. Including
The radical initiator is at least one selected from the group consisting of dihalogen radical initiators, azo compounds and organic peroxides;
The molar ratio (A / b1) of the silane coupling agent (A) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.020 or less,
It is a primer composition whose content of (meth) acrylic particles is 15% by mass or more based on the total amount of the composition.
　本発明の組成物はこのような構成をとるため、所望の効果が得られるものと考えられる。その理由は明らかではないが、およそ以下のとおりと推測される。
　一般的な水系プライマー組成物は上述のとおり短時間で乾燥させることは困難であり、高い密着性を発現させるためには、プライマー組成物を十分乾燥させる必要がある。
　プライマー組成物を十分に乾燥させない状態でその上に防水材を設けると、上記組成物中の水が気化する、又は、防水材がウレタン系である場合水によってイソシアネート基が分解し二酸化炭素が発生する等の理由から、防水材と下地との間に空洞が生じる場合がある。このような空洞が生じると、防水材はプライマー層と結合を形成することができないため密着性が低くなると本発明者らは推察する。 Since the composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but it is presumed that it is as follows.
As described above, it is difficult to dry a general aqueous primer composition in a short time, and it is necessary to sufficiently dry the primer composition in order to develop high adhesion.
When a waterproof material is provided on the primer composition in a state where it is not sufficiently dried, the water in the composition is vaporized, or when the waterproof material is urethane, the isocyanate group is decomposed by water and carbon dioxide is generated. For example, a cavity may be formed between the waterproof material and the base. When such a cavity is generated, the present inventors infer that the waterproofing material cannot form a bond with the primer layer and thus the adhesiveness is lowered.
　本発明によれば、本発明の組成物を乾燥後し乾燥後のプライマー組成物に水分が残留している状態であっても、組成物に含有されるシランカップリング剤（Ａ）が有するグリシジル基が下地及び防水材のうちの一方又は両方と反応又は相互作用ができるため、下地と防水材との密着性に優れると考えられる。 According to the present invention, the glycidyl contained in the silane coupling agent (A) contained in the composition even after the composition of the present invention is dried and moisture remains in the dried primer composition. Since the group can react or interact with one or both of the base and the waterproof material, it is considered that the adhesion between the base and the waterproof material is excellent.
　以下、本発明の組成物に含有される各成分について詳述する。
＜＜（メタ）アクリル系エマルジョン＞＞
　本発明の組成物に含有される（メタ）アクリル系エマルジョンは、分散質としての（メタ）アクリル粒子と分散媒とを含み、（メタ）アクリル粒子は分散媒中に分散している。なお本発明においてエマルジョンはサスペンション（液相である分散媒に固相である分散質が分散した系）及び液相である分散媒に液相である分散質が分散した系を含む概念とする。
　分散媒は水系溶媒であれば特に制限されない。水系溶媒としては、例えば、水；水に可溶な有機溶媒を水に混合した混合溶媒が挙げられる。上記有機溶媒としては、例えば、アルコール；メチルエチルケトン（ＭＥＫ）のようなケトンが挙げられる。 Hereinafter, each component contained in the composition of this invention is explained in full detail.
<< (Meth) acrylic emulsion >>
The (meth) acrylic emulsion contained in the composition of the present invention includes (meth) acrylic particles as a dispersoid and a dispersion medium, and the (meth) acrylic particles are dispersed in the dispersion medium. In the present invention, an emulsion includes a suspension (a system in which a dispersoid as a solid phase is dispersed in a dispersion medium as a liquid phase) and a system in which a dispersoid as a liquid phase is dispersed in a dispersion medium as a liquid phase.
The dispersion medium is not particularly limited as long as it is an aqueous solvent. Examples of the aqueous solvent include water; a mixed solvent obtained by mixing an organic solvent soluble in water with water. Examples of the organic solvent include alcohols; ketones such as methyl ethyl ketone (MEK).
＜（メタ）アクリル粒子＞
　分散質としての（メタ）アクリル粒子は、ラジカル開始剤の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を重合させて得られるポリマーの粒子である。
　（メタ）アクリル粒子の形状は粒状であれば特に制限されない。
　（メタ）アクリル粒子の平均粒子径は、例えば、０．０１～０．６μｍとすることができる。（メタ）アクリル粒子の平均粒子径は、粒度径分布測定機（Ｎａｎｏｔｒａｃ　ＵＰＡ－ＥＸ１５０、日機装社製）を用いて測定することができる。
　（メタ）アクリル粒子はその表面にカルボキシ基を有することができる。 <(Meth) acrylic particles>
(Meth) acrylic particles as a dispersoid are polymer particles obtained by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator.
The shape of the (meth) acrylic particles is not particularly limited as long as it is granular.
The average particle diameter of the (meth) acrylic particles can be, for example, 0.01 to 0.6 μm. The average particle diameter of (meth) acrylic particles can be measured using a particle size distribution analyzer (Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.).
The (meth) acrylic particles can have a carboxy group on the surface.
＜重合性モノマー（Ｂ）＞
　（メタ）アクリル粒子を製造する際に使用される、（メタ）アクリロイル基を有する重合性モノマー（Ｂ）は、（メタ）アクリル酸アルキルエステルモノマー（ｂ１）と、カルボキシ基を有する（メタ）アクリル酸系モノマー（ｂ２）と、ヒドロキシ基を有するヒドロキシ基含有重合性モノマー（ｂ３）とを含むことが好ましい。 <Polymerizable monomer (B)>
The polymerizable monomer (B) having a (meth) acryloyl group used when producing (meth) acrylic particles is a (meth) acrylic acid alkyl ester monomer (b1) and a (meth) acrylic having a carboxy group. It is preferable to contain an acid monomer (b2) and a hydroxy group-containing polymerizable monomer (b3) having a hydroxy group.
＜（メタ）アクリル酸アルキルエステルモノマー（ｂ１）＞
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）は、（メタ）アクリル酸のアルキルエステルである。 <(Meth) acrylic acid alkyl ester monomer (b1)>
The (meth) acrylic acid alkyl ester monomer (b1) is an alkyl ester of (meth) acrylic acid.
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）において、エステル結合に結合するアルキル基（脂肪族炭化水素基）は特に制限されない。直鎖状、分岐状若しくは環状のいずれか、又はこれらの組合せであってもよい。 In the (meth) acrylic acid alkyl ester monomer (b1), the alkyl group (aliphatic hydrocarbon group) bonded to the ester bond is not particularly limited. It may be linear, branched or cyclic, or a combination thereof.
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）としては具体的には例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、へキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ブチルシクロヘキシル（メタ）アクリレート、ペンチル（メタ）アクリレート、オクチル（メタ）アクリレート、ノニル（メタ）アクリレートが挙げられる。
　なかでも、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレートが好ましく、メチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレートがより好ましい。 Specific examples of the (meth) acrylic acid alkyl ester monomer (b1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, Examples include 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, butylcyclohexyl (meth) acrylate, pentyl (meth) acrylate, octyl (meth) acrylate, and nonyl (meth) acrylate.
Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable, and methyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable.
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）はそれぞれ単独でまたは２種以上を組み合わせて使用することができる。
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）の組合せとしては、メタクリル酸メチル（ＭＭＡ）とアクリル酸－２－エチルヘキシル（２ＥＨＡ）との組合せが好ましい。
　アクリル酸－２－エチルヘキシルに対するメタクリル酸メチルのモル比（ＭＭＡ／２ＥＨＡ）が、１．４７０～２．３１０であることが好ましく、１．６５０～２．０３０がより好ましい。
　なお、（メタ）アクリル酸アルキルエステルモノマー（ｂ１）はカルボキシ基又はヒドロキシ基を有さないことが好ましい態様として挙げられる。 The (meth) acrylic acid alkyl ester monomer (b1) can be used alone or in combination of two or more.
The combination of the (meth) acrylic acid alkyl ester monomer (b1) is preferably a combination of methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2EHA).
The molar ratio of methyl methacrylate to 2-ethylhexyl acrylate (MMA / 2EHA) is preferably from 1.470 to 2.310, more preferably from 1.650 to 2.030.
In addition, it is mentioned as a preferable aspect that the (meth) acrylic acid alkyl ester monomer (b1) does not have a carboxy group or a hydroxy group.
＜（メタ）アクリル酸系モノマー（ｂ２）＞
　（メタ）アクリル酸系モノマー（ｂ２）は、（メタ）アクリロイル基とカルボキシ基とを有する化合物である。
　（メタ）アクリロイル基の－ＣＯ－がカルボキシ基を形成してもよい。
　また、（メタ）アクリロイル基とカルボキシ基とは有機基を介して結合することができる。（メタ）アクリロイル基は例えば（メタ）アクリロイルオキシ基であってもよい。
　（メタ）アクリル酸系モノマー（ｂ２）としては、例えば、（メタ）アクリル酸；カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレートのようながカルボキシアルキル（メタ）アクリレート挙げられる。
　（メタ）アクリル酸系モノマー（ｂ２）は、それぞれ単独でまたは２種以上を組み合わせて使用することができる。 <(Meth) acrylic acid monomer (b2)>
The (meth) acrylic acid monomer (b2) is a compound having a (meth) acryloyl group and a carboxy group.
The (CO) of the (meth) acryloyl group may form a carboxy group.
Further, the (meth) acryloyl group and the carboxy group can be bonded via an organic group. The (meth) acryloyl group may be, for example, a (meth) acryloyloxy group.
Examples of the (meth) acrylic acid monomer (b2) include (meth) acrylic acid; carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and the like.
The (meth) acrylic acid monomer (b2) can be used alone or in combination of two or more.
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対する（メタ）アクリル酸系モノマー（ｂ２）のモル比（ｂ２／ｂ１）は、０．０３８～０．０７５であることが好ましく、０．０４７～０．０６６がより好ましい。 The molar ratio (b2 / b1) of the (meth) acrylic acid monomer (b2) to the (meth) acrylic acid alkyl ester monomer (b1) is preferably 0.038 to 0.075, preferably 0.047 to 0. 0.066 is more preferred.
＜ヒドロキシ基含有重合性モノマー（ｂ３）＞
　ヒドロキシ基を有するヒドロキシ基含有重合性モノマー（ｂ３）は、ヒドロキシ基と重合性官能基としての（メタ）アクリロイル基とを有する化合物である。
　ヒドロキシ基含有重合性モノマー（ｂ３）１分子が有するヒドロキシ基は、１個又は複数とすることができる。上記ヒドロキシ基は１個であることが好ましい。
　ヒドロキシ基含有重合性モノマー（ｂ３）１分子が有する（メタ）アクリロイル基は、例えば、（メタ）アクリロイルオキシ基であってもよい。
　ヒドロキシ基と（メタ）アクリロイル基とは有機基（例えば、ヘテロ原子を有してもよい炭化水素基）を介して結合することが好ましい態様の１つとして挙げられる。有機基（ヘテロ原子、炭化水素基）は特に制限されない。 <Hydroxy group-containing polymerizable monomer (b3)>
The hydroxy group-containing polymerizable monomer (b3) having a hydroxy group is a compound having a hydroxy group and a (meth) acryloyl group as a polymerizable functional group.
Hydroxy group-containing polymerizable monomer (b3) One molecule can have one or more hydroxy groups. The number of hydroxy groups is preferably one.
The (meth) acryloyl group that one molecule of the hydroxy group-containing polymerizable monomer (b3) has may be, for example, a (meth) acryloyloxy group.
One preferred embodiment is that the hydroxy group and the (meth) acryloyl group are bonded via an organic group (for example, a hydrocarbon group which may have a hetero atom). The organic group (hetero atom, hydrocarbon group) is not particularly limited.
　ヒドロキシ基含有重合性モノマー（ｂ３）は具体的には例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシヘキシル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、１２－ヒドロキシラウリル（メタ）アクリレート、（４－ヒドロキシメチルシクロへキシル）メチルアクリレート、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ヒドロキシ（メタ）アクリルアミド、ビニルアルコール、アリルアルコール、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、ジエチレングリコールモノビニルエーテル等が挙げられる。
　なかでも、２－ヒドロキシエチル（メタ）アクリレートが好ましい。
　ヒドロキシ基含有重合性モノマー（ｂ３）はそれぞれ単独でまたは２種以上を組み合わせて使用することができる。 Specific examples of the hydroxy group-containing polymerizable monomer (b3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyhexyl (meth). Acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glyco Mono vinyl ether, and the like.
Of these, 2-hydroxyethyl (meth) acrylate is preferable.
The hydroxy group-containing polymerizable monomer (b3) can be used alone or in combination of two or more.
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対するヒドロキシ基を有するヒドロキシ基含有重合性モノマー（ｂ３）のモル比（ｂ３／ｂ１）は、０．０５０～０．１００であることが好ましく、０．０６９～０．１００がより好ましい。 The molar ratio (b3 / b1) of the hydroxy group-containing polymerizable monomer (b3) having a hydroxy group to the (meth) acrylic acid alkyl ester monomer (b1) is preferably 0.050 to 0.100, and preferably 069 to 0.100 is more preferable.
　（メタ）アクリル粒子を製造する際に使用されるモノマーとして、上記（ｂ１）～（ｂ３）のモノマー以外にエチレン性不飽和結合を有する化合物を更に使用することができる。上記エチレン性不飽和結合を有する化合物としては、例えば、オレフィン；スチレンのようなビニル性芳香族炭化水素化合物；クロトン酸、イタコン酸、マレイン酸、フマル酸のようなカルボン酸化合物などが挙げられる。 As the monomer used when producing the (meth) acrylic particles, a compound having an ethylenically unsaturated bond can be further used in addition to the monomers (b1) to (b3). Examples of the compound having an ethylenically unsaturated bond include olefins; vinyl aromatic hydrocarbon compounds such as styrene; carboxylic acid compounds such as crotonic acid, itaconic acid, maleic acid, and fumaric acid.
＜ラジカル開始剤＞
　（メタ）アクリル粒子を製造する際に使用されるラジカル開始剤は、ジハロゲン系ラジカル開始剤、アゾ化合物及び有機過酸化物からなる群から選ばれる少なくとも１種である。
　ラジカル開始剤は、重合性モノマー（Ｂ）が有する（メタ）アクリロイル基をラジカル化することができる。 <Radical initiator>
The radical initiator used when producing the (meth) acrylic particles is at least one selected from the group consisting of a dihalogen radical initiator, an azo compound, and an organic peroxide.
The radical initiator can radicalize the (meth) acryloyl group of the polymerizable monomer (B).
（ジハロゲン系ラジカル開始剤）
　ジハロゲン系ラジカル開始剤は、ハロゲン－ハロゲン結合を有する物質（ハロゲン－ハロゲン結合を有する化合物及びハロゲン分子を含む。）であれば特に制限されない。ハロゲンは特に制限されない。 (Dihalogen radical initiator)
The dihalogen radical initiator is not particularly limited as long as it is a substance having a halogen-halogen bond (including a compound having a halogen-halogen bond and a halogen molecule). Halogen is not particularly limited.
（有機過酸化物）
　有機過酸化物としては、例えば、ベンゾイルパーオキサイド、ｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイドが挙げられる。 (Organic peroxide)
Examples of the organic peroxide include benzoyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide.
（アゾ化合物）
　ラジカル開始剤は、なかでも、本発明の効果により優れるという観点から、アゾ化合物が好ましい。
　アゾ化合物は、アゾ結合を有する化合物であれば特に制限されない。アゾ結合に結合する有機基は特に制限されない。
　アゾ化合物としては、例えば、アゾビスイソブチロニトリル、アゾジカーボンアミド、２，２′－アゾビス－（２－アミジノプロパン）ジハイドロクロライド、ジメチル２，２′－アゾビス（イソブチレート）、アゾビス－シアン吉草酸、１，１′－アゾビス－（２，４－ジメチルバレロニトリル）、アゾビスメチルブチロニトリル、２，２′－アゾビス－（４－メトキシ－２，４－ジメチルパレロニトリル）が挙げられる。
　ラジカル開始剤はそれぞれ単独でまたは２種以上を組み合わせて使用することができる。 (Azo compound)
Among these, an azo compound is preferable from the viewpoint that the radical initiator is superior due to the effects of the present invention.
The azo compound is not particularly limited as long as it is a compound having an azo bond. The organic group bonded to the azo bond is not particularly limited.
Examples of the azo compound include azobisisobutyronitrile, azodicarbonamide, 2,2'-azobis- (2-amidinopropane) dihydrochloride, dimethyl 2,2'-azobis (isobutyrate), azobis-cyan Examples include valeric acid, 1,1′-azobis- (2,4-dimethylvaleronitrile), azobismethylbutyronitrile, 2,2′-azobis- (4-methoxy-2,4-dimethylpareronitrile). It is done.
The radical initiators can be used alone or in combination of two or more.
　本発明において、ラジカル開始剤は過硫酸塩を実質的に含まないことが好ましい態様の１つとして挙げられる。
　過硫酸塩は特に制限されない。例えば、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウムが挙げられる。
　ラジカル開始剤が過硫酸塩を実質的に含まないとは、過硫酸塩の使用量が、上記ラジカル開始剤に対して、０～０．１質量％であることをいう。 In the present invention, one preferred embodiment is that the radical initiator is substantially free of persulfate.
The persulfate is not particularly limited. Examples thereof include ammonium persulfate, potassium persulfate, and sodium persulfate.
The radical initiator substantially free of persulfate means that the amount of persulfate used is 0 to 0.1% by mass with respect to the radical initiator.
　本発明において、ラジカル開始剤はレドックス開始剤を実質的に含まないことが好ましい態様の１つとして挙げられる。
　レドックス開始剤は特に制限されない。例えば、過硫酸塩のような酸化剤と亜硫酸水素ナトリウムのような還元剤との組合せが挙げられる。
　ラジカル開始剤がレドックス開始剤を実質的に含まないとは、レドックス開始剤の使用量が、上記ラジカル開始剤に対して、０～０．１質量％であることをいう。 In the present invention, one preferred embodiment is that the radical initiator does not substantially contain a redox initiator.
The redox initiator is not particularly limited. For example, a combination of an oxidizing agent such as persulfate and a reducing agent such as sodium bisulfite can be mentioned.
The radical initiator substantially not containing a redox initiator means that the amount of the redox initiator used is 0 to 0.1% by mass with respect to the radical initiator.
　上記重合性モノマー（Ｂ）全量に対するラジカル開始剤の使用量（モル比）は、０．００１３～０．０１００が好ましく、０．００２６～０．００９０がより好ましい。 The amount (molar ratio) of the radical initiator used with respect to the total amount of the polymerizable monomer (B) is preferably 0.0013 to 0.0100, and more preferably 0.0026 to 0.0090.
（（メタ）アクリル粒子を構成するポリマーの製造）
　（メタ）アクリル粒子を構成するポリマー（（メタ）アクリル系ポリマー）は、ラジカル開始剤の存在下で上記重合性モノマー（Ｂ）を重合させることによって得ることができる。
　上記重合は、例えば、窒素などの不活性ガス気流下で、６０～８０℃程度の温度で行うことができる。
　また、上記（メタ）アクリル系ポリマーは、水系溶媒又は有機溶媒中で製造されることが好ましい態様の１つとして挙げられる。ラジカル開始剤、重合性モノマー（Ｂ）、水系溶媒、有機溶媒は上記と同様である。
　上記重合を水系溶媒中で行った場合、上記（メタ）アクリル系ポリマーは粒子状となり、（メタ）アクリル粒子を含有する（メタ）アクリル系エマルジョンとなることができる。 (Manufacture of polymer constituting (meth) acrylic particles)
The polymer ((meth) acrylic polymer) constituting the (meth) acrylic particles can be obtained by polymerizing the polymerizable monomer (B) in the presence of a radical initiator.
The polymerization can be carried out at a temperature of about 60 to 80 ° C. under an inert gas stream such as nitrogen.
Moreover, it is mentioned as one of the preferable aspects that the said (meth) acrylic-type polymer is manufactured in an aqueous solvent or an organic solvent. The radical initiator, polymerizable monomer (B), aqueous solvent, and organic solvent are the same as described above.
When the polymerization is carried out in an aqueous solvent, the (meth) acrylic polymer is in the form of particles and can be a (meth) acrylic emulsion containing (meth) acrylic particles.
（（メタ）アクリル系エマルジョンの製造方法）
　本発明の組成物に含有される、（メタ）アクリル粒子を含む（メタ）アクリル系エマルジョンの製造方法としては、例えば、水系溶媒中、ラジカル開始剤の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を重合させる方法；上記のとおり（メタ）アクリル系ポリマーを製造し（例えば上記重合を有機溶媒中で行った場合）、上記重合後、反応系内に水系溶媒を加えて撹拌する方法が挙げられる。
　ラジカル開始剤、重合性モノマー（Ｂ）、水系溶媒、有機溶媒は上記と同様である。 (Method for producing (meth) acrylic emulsion)
As a method for producing a (meth) acrylic emulsion containing (meth) acrylic particles contained in the composition of the present invention, for example, polymerization having a (meth) acryloyl group in an aqueous solvent in the presence of a radical initiator A method of polymerizing the polymerizable monomer (B); producing a (meth) acrylic polymer as described above (for example, when the polymerization is carried out in an organic solvent), and after the polymerization, adding an aqueous solvent to the reaction system and stirring The method of doing is mentioned.
The radical initiator, polymerizable monomer (B), aqueous solvent, and organic solvent are the same as described above.
（第３級アミン（Ｃ））
　本発明の組成物は更に第３級アミン（Ｃ）を含有することができる。
　本発明において、第３級アミン（Ｃ）を塩基として使用することができる。第３級アミンを使用することによって、第３級アミン（Ｃ）が、組成物に含有される（メタ）アクリル粒子が有するカルボキシ基をイオン化して、（メタ）アクリル粒子の分散を良好にすることができる。 (Tertiary amine (C))
The composition of the present invention may further contain a tertiary amine (C).
In the present invention, tertiary amine (C) can be used as a base. By using the tertiary amine, the tertiary amine (C) ionizes the carboxy group of the (meth) acrylic particles contained in the composition, thereby improving the dispersion of the (meth) acrylic particles. be able to.
　第３級アミン（Ｃ）は、脂肪族炭化水素基を有する第３級アミンが好ましく、窒素原子に結合する炭化水素基がすべて脂肪族炭化水素基であることがより好ましい。
　第３級アミン（Ｃ）としては、例えば、トリエチルアミン、Ｎ，Ｎ－ジメチルラウリルアミン、Ｎ，Ｎ－ジメチルパルミチルアミンが挙げられる。
　第３級アミン（Ｃ）はそれぞれ単独でまたは２種以上を組み合わせて使用することができる。 The tertiary amine (C) is preferably a tertiary amine having an aliphatic hydrocarbon group, and more preferably all the hydrocarbon groups bonded to the nitrogen atom are aliphatic hydrocarbon groups.
Examples of the tertiary amine (C) include triethylamine, N, N-dimethyllaurylamine, and N, N-dimethylpalmitylamine.
The tertiary amine (C) can be used alone or in combination of two or more.
　（メタ）アクリル酸系モノマー（ｂ２）に対する第３級アミン（Ｃ）のモル比（Ｃ／ｂ２）は、０．５６０～１．１４０であることが好ましく、０．７６０～０．９４０がより好ましい。 The molar ratio (C / b2) of the tertiary amine (C) to the (meth) acrylic acid monomer (b2) is preferably 0.560 to 1.140, more preferably 0.760 to 0.940. preferable.
（第３級アミン（Ｃ）を使用する場合の（メタ）アクリル系エマルジョンの製造方法）
　第３級アミン（Ｃ）を使用する場合の（メタ）アクリル系エマルジョンの製造方法としては、例えば、上記のとおり製造した（メタ）アクリル系エマルジョンに第３級アミン（Ｃ）を添加して、これらを混合して、第３級アミン（Ｃ）を含有する（メタ）アクリル系エマルジョンを製造することができる。 (Method for producing (meth) acrylic emulsion when tertiary amine (C) is used)
As a method for producing a (meth) acrylic emulsion when using a tertiary amine (C), for example, adding a tertiary amine (C) to the (meth) acrylic emulsion produced as described above, These can be mixed to produce a (meth) acrylic emulsion containing a tertiary amine (C).
　上記とは別の方法としては、例えば、水系溶媒中でラジカル開始剤及び第３級アミン（Ｃ）の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を撹拌機で混合しながら６０～９０℃の条件下で、ラジカル重合させる方法が挙げられる。 As another method different from the above, for example, a polymerizable monomer (B) having a (meth) acryloyl group is mixed with an agitator in the presence of a radical initiator and a tertiary amine (C) in an aqueous solvent. A method of radical polymerization under conditions of 60 to 90 ° C. can be mentioned.
　また、上記とは別の方法としては、例えば、まず、ラジカル開始剤の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を重合させて（メタ）アクリル系ポリマーを製造し、製造後の反応系内に水（例えば、蒸留水）及び第３級アミン（Ｃ）を添加して、これらを混合して、第３級アミン（Ｃ）を含有する（メタ）アクリル系エマルジョンを製造する方法が挙げられる。
　ラジカル開始剤の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を重合させる際、上記有機溶媒を使用した場合（具体的には例えば、上記有機溶媒のみを使用した場合）、重合後反応系内に水（例えば、蒸留水）及び第３級アミン（Ｃ）を添加した後に上記有機溶媒を留去してもよい。 Moreover, as another method different from the above, for example, first, a (meth) acrylic polymer is produced by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator. Water (for example, distilled water) and tertiary amine (C) are added to the reaction system later, and these are mixed to produce a (meth) acrylic emulsion containing the tertiary amine (C). The method of doing is mentioned.
When the polymerizable monomer (B) having a (meth) acryloyl group is polymerized in the presence of a radical initiator, when the above organic solvent is used (specifically, for example, when only the above organic solvent is used), polymerization is performed. The organic solvent may be distilled off after adding water (for example, distilled water) and the tertiary amine (C) to the post-reaction system.
　（メタ）アクリル系エマルジョンはそれぞれ単独でまたは２種以上を組み合わせて使用することができる。 (Meth) acrylic emulsions can be used alone or in combination of two or more.
（（メタ）アクリル粒子を構成するポリマー）
　本発明において、（メタ）アクリル系エマルジョンに含有される（メタ）アクリル粒子を構成するポリマーは、アルキル基とヒドロキシ基とカルボキシ基とを有し、主骨格がポリ（メタ）アクリル骨格である（メタ）アクリル系ポリマーであり、アルキル基を有する繰り返し単位に対するシランカップリング剤（Ａ）のモル比が０．０２０以下であることが好ましい態様の１つとして挙げられる。 (Polymer constituting (meth) acrylic particles)
In the present invention, the polymer constituting the (meth) acrylic particles contained in the (meth) acrylic emulsion has an alkyl group, a hydroxy group, and a carboxy group, and the main skeleton is a poly (meth) acryl skeleton ( One preferred embodiment is that the molar ratio of the silane coupling agent (A) to the repeating unit that is a (meth) acrylic polymer and has an alkyl group is 0.020 or less.
（アルキル基）
　上記（メタ）アクリル系ポリマーが有するアルキル基は特に制限されない。例えば、上記（メタ）アクリル酸アルキルエステルモノマー（ｂ１）のアルキルエステルが有するアルキル基と同様のものが挙げられる。
　アルキル基は、上記（メタ）アクリル酸アルキルエステルモノマー（ｂ１）によって（メタ）アクリル系ポリマーに導入することができる。 (Alkyl group)
The alkyl group that the (meth) acrylic polymer has is not particularly limited. For example, the thing similar to the alkyl group which the alkylester of the said (meth) acrylic-acid alkylester monomer (b1) has is mentioned.
The alkyl group can be introduced into the (meth) acrylic polymer by the (meth) acrylic acid alkyl ester monomer (b1).
　（メタ）アクリル系ポリマーは、（メタ）アクリル酸アルキルエステルモノマー（ｂ１）によって形成される繰り返し単位として、メタクリル酸メチル（ＭＭＡ）とアクリル酸－２－エチルヘキシル（２ＥＨＡ）とによって形成される繰り返し単位を含むことが好ましい。 The (meth) acrylic polymer is a repeating unit formed by methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2EHA) as a repeating unit formed by the (meth) acrylic acid alkyl ester monomer (b1). It is preferable to contain.
（カルボキシ基）
　上記（メタ）アクリル系ポリマーが有するカルボキシ基は、主骨格と直接又は有機基を介して結合することができる。有機基は上記と同様である。
　カルボキシ基は、（メタ）アクリル酸系モノマー（ｂ２）によって（メタ）アクリル系ポリマーに導入することができる。
　（メタ）アクリル系ポリマーは、（メタ）アクリル酸系モノマー（ｂ２）によって形成される繰り返し単位を有する。
　カルボキシ基は第３級アミン（Ｃ）によってイオン化されていてもよい。 (Carboxy group)
The carboxy group of the (meth) acrylic polymer can be bonded to the main skeleton directly or via an organic group. The organic group is the same as described above.
The carboxy group can be introduced into the (meth) acrylic polymer by the (meth) acrylic acid monomer (b2).
The (meth) acrylic polymer has a repeating unit formed by the (meth) acrylic acid monomer (b2).
The carboxy group may be ionized with a tertiary amine (C).
（ヒドロキシ基）
　上記（メタ）アクリル系ポリマーが有するヒドロキシ基は、主骨格と直接又は有機基を介して結合することができる。有機基は上記と同様である。
　ヒドロキシ基は、上記ヒドロキシ基含有重合性モノマー（ｂ３）によって（メタ）アクリル系ポリマーに導入することができる。
　（メタ）アクリル系ポリマーは、ヒドロキシ基含有重合性モノマー（ｂ３）によって形成される繰り返し単位を有する。 (Hydroxy group)
The hydroxy group of the (meth) acrylic polymer can be bonded to the main skeleton directly or via an organic group. The organic group is the same as described above.
The hydroxy group can be introduced into the (meth) acrylic polymer by the hydroxy group-containing polymerizable monomer (b3).
The (meth) acrylic polymer has a repeating unit formed by the hydroxy group-containing polymerizable monomer (b3).
（主骨格）
　上記（メタ）アクリル系ポリマーの主骨格は、（メタ）アクリロイル基を有する重合性モノマー（Ｂ）で形成される繰り返し単位を有する。（メタ）アクリロイル基は（メタ）アクリロイルオキシ基であってもよい。 (Main skeleton)
The main skeleton of the (meth) acrylic polymer has a repeating unit formed of a polymerizable monomer (B) having a (meth) acryloyl group. The (meth) acryloyl group may be a (meth) acryloyloxy group.
　（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）は、例えば、１０，０００～５００，０００とすることができる。
　（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）は、テトラヒドロフランを溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によりポリスチレン換算で表わされる重量平均分子量である。 The weight average molecular weight (Mw) of the (meth) acrylic polymer can be, for example, 10,000 to 500,000.
The weight average molecular weight (Mw) of the (meth) acrylic polymer is a weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
＜＜シランカップリング剤（Ａ）＞＞
　本発明の組成物に含有されるシランカップリング剤（Ａ）はグリシジル基と加水分解性シリル基とを有する。
　加水分解性シリル基としては、例えば、アルコキシシリル基が挙げられる。１個のケイ素原子に結合するアルコキシ基の数は、２個又は３個であることが好ましい。
　上記アルコキシ基の数が２個以下である場合、ケイ素原子に結合できる炭化水素基は特に制限されない。例えば、アルキル基が挙げられる。
　グリシジル基と加水分解性シリル基とを結合する有機基は特に制限されない。例えば、酸素原子、窒素原子、硫黄原子のようなヘテロ原子を有してもよい炭化水素基が挙げられる。 << Silane coupling agent (A) >>
The silane coupling agent (A) contained in the composition of the present invention has a glycidyl group and a hydrolyzable silyl group.
Examples of the hydrolyzable silyl group include an alkoxysilyl group. The number of alkoxy groups bonded to one silicon atom is preferably 2 or 3.
When the number of the alkoxy groups is 2 or less, the hydrocarbon group that can be bonded to the silicon atom is not particularly limited. For example, an alkyl group is mentioned.
The organic group that binds the glycidyl group and the hydrolyzable silyl group is not particularly limited. For example, the hydrocarbon group which may have a hetero atom like an oxygen atom, a nitrogen atom, and a sulfur atom is mentioned.
　シランカップリング剤（Ａ）はグリシドキシアルキルトリアルコキシシランが好ましい。グリシドキシアルキルトリアルコキシシランとしては、例えば、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシランが挙げられる。
　シランカップリング剤（Ａ）はそれぞれ単独でまたは２種以上を組み合わせて使用することができる。 The silane coupling agent (A) is preferably glycidoxyalkyltrialkoxysilane. Examples of the glycidoxyalkyltrialkoxysilane include 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropyltrimethoxysilane.
A silane coupling agent (A) can be used individually or in combination of 2 types or more, respectively.
　（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対するシランカップリング剤（Ａ）のモル比（Ａ／ｂ１）は、０．０２０以下である。上記モル比（Ａ／ｂ１）は、本発明の効果により優れ、貯蔵安定性に優れるという観点から、０．００６～０．０２がより好ましく、０．００８～０．０１７がより好ましい。 The molar ratio (A / b1) of the silane coupling agent (A) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.020 or less. The molar ratio (A / b1) is more preferably 0.006 to 0.02, and more preferably 0.008 to 0.017, from the viewpoint of being excellent in the effects of the present invention and excellent in storage stability.
（そのほかの成分）
　本発明の組成物は、上記成分以外に、更に、レベリング剤、酸化防止剤、腐食防止剤、光安定剤、紫外線吸収剤、シランカップリング剤（Ａ）以外のシランカップリング剤、充填剤のような添加剤を含有することができる。
　本発明の組成物は、（メタ）アクリル系エマルジョン及びシランカップリング剤（Ａ）のみを含有することが好ましい態様の１つとして挙げられる。この場合、（メタ）アクリル粒子が有するカルボキシ基が、第３級アミン（Ｃ）でイオン化されていてもよい。 (Other ingredients)
In addition to the above components, the composition of the present invention further comprises a leveling agent, an antioxidant, a corrosion inhibitor, a light stabilizer, an ultraviolet absorber, a silane coupling agent other than the silane coupling agent (A), and a filler. Such additives can be contained.
It is mentioned as one of the aspects with preferable that the composition of this invention contains only a (meth) acrylic-type emulsion and a silane coupling agent (A). In this case, the carboxy group of the (meth) acryl particles may be ionized with the tertiary amine (C).
　本発明の組成物はその製造方法について特に制限されない。例えば、上記（メタ）アクリル系エマルジョン、シランカップリング剤（Ａ）及び任意成分を混合する方法が挙げられる。 The composition of the present invention is not particularly limited with respect to its production method. For example, the method of mixing the said (meth) acrylic-type emulsion, a silane coupling agent (A), and arbitrary components is mentioned.
　本発明の組成物は、固形分として、（メタ）アクリル粒子を含有する。
　（メタ）アクリル粒子（固形分）の含有量は、組成物全量に対して、１５質量％以上であり、１５～６０質量％が好ましく、１５～４０質量％がより好ましい。 The composition of the present invention contains (meth) acrylic particles as a solid content.
The content of (meth) acrylic particles (solid content) is 15% by mass or more, preferably 15 to 60% by mass, and more preferably 15 to 40% by mass with respect to the total amount of the composition.
　本発明の組成物は、上記過硫酸塩若しくはレドックス開始剤、又はこれらに起因する成分（以下これらを単に過硫酸塩等と称する。）を実質的に含有しないことが好ましい態様の１つとして挙げられる。
　本発明の組成物が過硫酸塩等を実質的に含まないとは、過硫酸塩等の含有量が、本発明の組成物全体に対して、０～０．１質量％であることをいう。 The composition of the present invention includes, as one preferred embodiment, substantially free of the above-mentioned persulfate or redox initiator, or components derived therefrom (hereinafter simply referred to as persulfate, etc.). It is done.
The fact that the composition of the present invention is substantially free of persulfate or the like means that the content of persulfate or the like is 0 to 0.1% by mass with respect to the entire composition of the present invention. .
　本発明の組成物は、下地と防水材とを密着させるために使用される。
　上記防水材は特に制限されない。例えば、ウレタン防水材、シリコーン系防水材、ポリサルファイド系防水材が挙げられる。なかでも、ウレタン防水材が好ましい。
　防水材の形態は特に制限されない。例えば、液状、シート状が挙げられる。
　上記下地は特に制限されない。例えば、無機系硬質素材が挙げられ、具体的には例えば、モルタル、ガラス、シリコーンハードコート、セラミック、コンクリート、磁器、金属が挙げられる。 The composition of this invention is used in order to adhere | attach a base | substrate and a waterproofing material.
The waterproof material is not particularly limited. For example, a urethane waterproof material, a silicone waterproof material, and a polysulfide waterproof material can be used. Among these, a urethane waterproof material is preferable.
The form of the waterproof material is not particularly limited. For example, liquid form and sheet form are mentioned.
The foundation is not particularly limited. Examples thereof include inorganic hard materials, and specific examples include mortar, glass, silicone hard coat, ceramic, concrete, porcelain, and metal.
　本発明の組成物を用いて下地と防水材とを密着させる方法としては、例えば、まず、本発明の組成物を下地に塗布し、２０～２８℃の条件下で乾燥させる。
　本発明の組成物から形成されるプライマー層は、その中に水が残留していても、下地と防水材との密着性に優れるので、本発明の組成物を使用する場合、その乾燥時間を短くすることができる。
　プライマーの乾燥時間は２５～４０分とすることができる。
　次に、乾燥後の下地の上に、防水材を設ける。防水材が液状である場合は防水材を上記乾燥後の下地の上に流し込み、防水材がシート状である場合はシートを上記乾燥後の下地の上に敷いて、その後、
２５℃、４５％ＲＨの条件下で３～５日間養生させることによって、下地と防水材とを密着させることができる。 For example, the composition of the present invention is first applied to the substrate and dried at 20 to 28 ° C. as a method for bringing the substrate and the waterproof material into close contact with each other using the composition of the present invention.
The primer layer formed from the composition of the present invention is excellent in the adhesion between the base and the waterproofing material even if water remains in the primer layer. Can be shortened.
The drying time of the primer can be 25 to 40 minutes.
Next, a waterproof material is provided on the base after drying. When the waterproofing material is liquid, the waterproofing material is poured onto the dried substrate, and when the waterproofing material is in a sheet form, the sheet is laid on the dried substrate,
By curing for 3 to 5 days under conditions of 25 ° C. and 45% RH, the substrate and the waterproof material can be brought into close contact with each other.
　以下に実施例を示して本発明を具体的に説明する。ただし本発明は実施例に限定されない。
＜（メタ）アクリル系エマルジョンの調製＞
　下記表１中の「（メタ）アクリル系エマルジョンを調製する際に使用された成分・配合量」欄に示す各成分（配合量の単位はｍｏｌ。ただし第３級アミン（Ｃ）１を除く。）を有機溶媒（ＭＥＫ）中、撹拌機で混合しながら８０℃の条件下でラジカル重合させ、反応開始から５時間後に重合を停止し、得られた反応液に水と下記表１に示す第３級アミン（Ｃ）１（トリエチルアミン）とを加え撹拌して乳化した後、上記有機溶媒（ＭＥＫ）を留去し、（メタ）アクリル系エマルジョンを調製した。
　上記のとおり調製された（メタ）アクリル系エマルジョンはいずれも、分散媒としての水中に、分散質としての（メタ）アクリル粒子（（メタ）アクリル系ポリマー）が分散していた。
　（メタ）アクリル粒子を構成するポリマーは、アルキル基とヒドロキシ基とカルボキシ基とを有し、主骨格がポリ（メタ）アクリル骨格である（メタ）アクリル系ポリマーであった。（メタ）アクリル系ポリマーにおいてアルキル基を有する繰り返し単位に対するシランカップリング剤（Ａ）のモル比が０．０２０以下であった。
　上記のとおり調製された各（メタ）アクリル系エマルジョンをそのまま以下の組成物の製造に使用した。 The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples.
<Preparation of (meth) acrylic emulsion>
Each component (unit of blending amount is mol, except for the tertiary amine (C) 1) shown in the column “Components and blending amounts used when preparing (meth) acrylic emulsion” in Table 1 below. ) In an organic solvent (MEK) while mixing with a stirrer under the condition of 80 ° C., and after 5 hours from the start of the reaction, the polymerization was stopped, and water and the reaction solution shown in Table 1 below were added. Tertiary amine (C) 1 (triethylamine) was added and stirred to emulsify, and then the organic solvent (MEK) was distilled off to prepare a (meth) acrylic emulsion.
In any of the (meth) acrylic emulsions prepared as described above, (meth) acrylic particles ((meth) acrylic polymer) as a dispersoid were dispersed in water as a dispersion medium.
The polymer constituting the (meth) acrylic particles was a (meth) acrylic polymer having an alkyl group, a hydroxy group, and a carboxy group, and the main skeleton being a poly (meth) acryl skeleton. The molar ratio of the silane coupling agent (A) to the repeating unit having an alkyl group in the (meth) acrylic polymer was 0.020 or less.
Each (meth) acrylic emulsion prepared as described above was used as it was in the production of the following composition.
　下記表１の「（メタ）アクリル系エマルジョンを調製する際に使用された成分・配合量」欄に示す各成分の詳細は以下のとおりである。
　・（メタ）アクリル酸アルキルエステルモノマー（ｂ１）－１（ＭＭＡ）：メチルメタクリレート（分子量：１００）
　・（メタ）アクリル酸アルキルエステルモノマー（ｂ１）－２（２ＥＨＡ）：２－エチルヘキシルアクリレート（分子量：１８４） The details of each component shown in the column of “Components and Blending Amounts Used in Preparing (Meth) acrylic Emulsion” in Table 1 are as follows.
(Meth) acrylic acid alkyl ester monomer (b1) -1 (MMA): methyl methacrylate (molecular weight: 100)
(Meth) acrylic acid alkyl ester monomer (b1) -2 (2EHA): 2-ethylhexyl acrylate (molecular weight: 184)
　・（メタ）アクリル酸系モノマー（ｂ２）－１（ＭＡＡ）：メタクリル酸（分子量：８７） ・ (Meth) acrylic acid monomer (b2) -1 (MAA): methacrylic acid (molecular weight: 87)
　・ヒドロキシ基含有重合性モノマー（ｂ３）－１（ＨＥＭＡ）：２－ヒドロキシエチルメタクリレート（分子量：１３０） ・ Hydroxy group-containing polymerizable monomer (b3) -1 (HEMA): 2-hydroxyethyl methacrylate (molecular weight: 130)
　・ラジカル開始剤１（比較）（ＡＰＳ）：過硫酸アンモニウム（分子量：２２８）
　・ラジカル開始剤２（ＡＩＢＮ）：２，２’－アゾビスイソブチロニトリル（分子量：１６４）
　・還元剤１（ＳＢＳ）：亜硫酸水素ナトリウム（分子量：１０４） Radical initiator 1 (comparative) (APS): ammonium persulfate (molecular weight: 228)
Radical initiator 2 (AIBN): 2,2′-azobisisobutyronitrile (molecular weight: 164)
Reducing agent 1 (SBS): sodium bisulfite (molecular weight: 104)
　・第３級アミン（Ｃ）１（ＴＥＡ）：トリエチルアミン ・ Tertiary amine (C) 1 (TEA): Triethylamine
＜組成物の製造＞
　上記のとおり調製された（メタ）アクリル系エマルジョンと、下記表１中の「組成物を使用する際に使用されたシランカップリング剤Ａ・配合量」欄に示す各シランカップリング剤Ａ（配合量の単位はｍｏｌ）とを撹拌機で混合し、組成物を製造した。
　なお、組成物を製造する際、組成物全体に対する（メタ）アクリル粒子の含有量（質量％）が、表１の「固形分」欄に示す値（単位：質量％）となるように、組成物に適宜蒸留水を添加した。上記固形分は、（メタ）アクリル粒子を意味する。 <Production of composition>
The (meth) acrylic emulsion prepared as described above and each silane coupling agent A (compounding) shown in the column “Silane coupling agent A / blending amount used when using the composition” in Table 1 below. The unit of the amount was mol) and was mixed with a stirrer to produce a composition.
In addition, when manufacturing a composition, it is a composition so that content (mass%) of the (meth) acryl particle with respect to the whole composition may become the value (unit: mass%) shown in the "solid content" column of Table 1. Distilled water was appropriately added to the product. The solid content means (meth) acrylic particles.
　下記表１の組成物を調製する際に使用されたシランカップリング剤Ａの詳細は以下のとおりである。
　・シランカップリング剤Ａ１（比較）：３－メタクリロキシプロピルトリエトキシシラン、ＫＢＭ－５０３、信越化学工業社製
　・シランカップリング剤Ａ２（比較）：３－メルカプトプロピルトリメトキシシラン、ＫＢＭ－８０３、信越化学工業社製
　・シランカップリング剤Ａ３（比較）：３－アミノプロピルトリエトキシシラン、ＫＢＭ－９０３、信越化学工業社製 The details of the silane coupling agent A used in preparing the composition shown in Table 1 below are as follows.
Silane coupling agent A1 (comparative): 3-methacryloxypropyltriethoxysilane, KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd. Silane coupling agent A2 (comparative): 3-mercaptopropyltrimethoxysilane, KBM-803, Made by Shin-Etsu Chemical Co., Ltd. ・ Silane coupling agent A3 (comparative): 3-aminopropyltriethoxysilane, KBM-903, made by Shin-Etsu Chemical Co., Ltd.
　・シランカップリング剤Ａ４：３－グリシドキシプロピルトリエトキシシラン、ＫＢＭ－４０３、信越化学工業社製 Silane coupling agent A4: 3-glycidoxypropyltriethoxysilane, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.
＜評価＞
　上記のとおり製造された組成物を用いて以下の常態剥離試験を行った。結果を表１に示す。
・常態剥離試験
（試験体の作製）
　まず、上記のとおり製造された各組成物を、被着体であるモルタル（１０ｃｍ×２０ｃｍ、パルテック社製）の上に刷毛で塗布し、２５℃の条件下で短時間乾燥（３０分間の乾燥）させた。
　次に、上記乾燥後のモルタルの上に、防水材（商品名ハマタイト　アーバンルーフ　Ｕ－８０００、横浜ゴム株式会社製、ウレタン防水材）を流し込んだ。流し込んだ後の防水材層の厚みは５ｍｍであった。
　防水材を流し込んだ後のモルタルを、２５℃、４５％ＲＨの条件下で３日間養生させて、試験体を作製した。 <Evaluation>
The following normal peel test was conducted using the composition produced as described above. The results are shown in Table 1.
・ Normal peel test (preparation of specimen)
First, each composition produced as described above was applied onto a mortar (10 cm × 20 cm, manufactured by Partec Co.), which is an adherend, with a brush and dried for a short time at 25 ° C. (drying for 30 minutes) )
Next, a waterproof material (trade name Hamatite Urban Roof U-8000, manufactured by Yokohama Rubber Co., Ltd., urethane waterproof material) was poured onto the dried mortar. The thickness of the waterproof material layer after pouring was 5 mm.
The mortar after pouring the waterproof material was cured for 3 days under conditions of 25 ° C. and 45% RH to prepare a test specimen.
（常態剥離試験）
　上記のとおり作製した各試験体から防水材層を２３℃の条件下で１８０℃の角度で手剥離した。 (Normal peel test)
The waterproof material layer was manually peeled off at an angle of 180 ° C. under the condition of 23 ° C. from each test body prepared as described above.
（評価基準）
　常態剥離試験の評価基準は以下のとおりである。
　モルタルから防水材層を引きはがすことができなかった場合を、下地と防水材との密着性に優れると評価し、これを「Ａ」と表示した。
　モルタルから防水材層を引きはがすことができた場合を、下地と防水材との密着性が低いと評価し、これを「Ｂ」と表示した。 (Evaluation criteria)
The evaluation criteria of the normal peel test are as follows.
The case where the waterproof material layer could not be peeled from the mortar was evaluated as being excellent in adhesion between the base and the waterproof material, and this was indicated as “A”.
When the waterproof material layer could be peeled off from the mortar, it was evaluated that the adhesion between the base and the waterproof material was low, and this was indicated as “B”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、所定のラジカル開始剤を使用しない比較例６又は所定のシランカップリング剤を含有しない比較例１～５は、プライマー組成物を短時間乾燥させる場合、防水材層が下地から手剥離で剥がれてしまい、下地と防水材との密着性が低かった。
　シランカップリング剤（Ａ）／（メタ）アクリル酸アルキルエステルモノマー（ｂ１）が所定の範囲を超える比較例７も、プライマー組成物を短時間乾燥させる場合、上記比較例と同様に防水材層が下地から手剥離で剥がれてしまい、下地と防水材との密着性が低かった。 As shown in Table 1, in Comparative Example 6 that does not use a predetermined radical initiator or Comparative Examples 1 to 5 that does not contain a predetermined silane coupling agent, when the primer composition is dried for a short time, the waterproof material layer is the base. It was peeled off by hand peeling, and the adhesion between the base and the waterproof material was low.
In Comparative Example 7 in which the silane coupling agent (A) / (meth) acrylic acid alkyl ester monomer (b1) exceeds the predetermined range, when the primer composition is dried for a short time, the waterproof material layer is formed in the same manner as in the above Comparative Example. It peeled off from the substrate by hand peeling, and the adhesion between the substrate and the waterproof material was low.
　これに対して、実施例１は、乾燥時間が短くとも下地と防水材との密着性に優れた。 On the other hand, Example 1 was excellent in adhesion between the substrate and the waterproof material even when the drying time was short.
　また、表１には示されていないが、比較例７の組成物を２５℃、４５％ＲＨの条件下に２週間置いたところ、比較例７の組成物は水と固形分とが分離してしまい、貯蔵安定性が悪かった。
　これに対して、実施例１の組成物は上記と同様に貯蔵した後も組成物に変化はなく、貯蔵安定性に優れた。
　このように本発明の組成物は貯蔵安定性にも優れることが明らかとなった。 Although not shown in Table 1, when the composition of Comparative Example 7 was placed at 25 ° C. and 45% RH for 2 weeks, the composition of Comparative Example 7 was separated from water and solids. The storage stability was poor.
On the other hand, the composition of Example 1 did not change after storage in the same manner as described above, and was excellent in storage stability.
Thus, it was revealed that the composition of the present invention is excellent in storage stability.

Claims (11)

  1. 　下地と防水材とを密着させるために使用されるプライマー組成物であって、
    　（メタ）アクリル粒子を含有する（メタ）アクリル系エマルジョンとグリシジル基を有するシランカップリング剤（Ａ）とを含み、
    　前記（メタ）アクリル粒子が、ラジカル開始剤の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を重合させて得られるポリマー粒子であり、
    　前記重合性モノマー（Ｂ）が、（メタ）アクリル酸アルキルエステルモノマー（ｂ１）と、カルボキシ基を有する（メタ）アクリル酸系モノマー（ｂ２）と、ヒドロキシ基を有するヒドロキシ基含有重合性モノマー（ｂ３）とを含み、
    　前記ラジカル開始剤が、ジハロゲン系ラジカル開始剤、アゾ化合物及び有機過酸化物からなる群から選ばれる少なくとも１種であり、
    　前記（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対する前記シランカップリング剤（Ａ）のモル比（Ａ／ｂ１）が、０．０２０以下であり、
    　前記（メタ）アクリル粒子の含有量が、組成物全量に対して、１５質量％以上である、プライマー組成物。     It is a primer composition used for adhering a base and a waterproof material,
    A (meth) acrylic emulsion containing (meth) acrylic particles and a silane coupling agent (A) having a glycidyl group,
    The (meth) acrylic particles are polymer particles obtained by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator,
    The polymerizable monomer (B) is a (meth) acrylic acid alkyl ester monomer (b1), a (meth) acrylic acid monomer (b2) having a carboxy group, and a hydroxy group-containing polymerizable monomer (b3) having a hydroxy group. ) And
    The radical initiator is at least one selected from the group consisting of a dihalogen radical initiator, an azo compound, and an organic peroxide;
    The molar ratio (A / b1) of the silane coupling agent (A) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.020 or less,
    The primer composition whose content of the said (meth) acryl particle is 15 mass% or more with respect to the composition whole quantity.
  2. 　前記（メタ）アクリル酸アルキルエステルモノマー（ｂ１）が、メタクリル酸メチル（ＭＭＡ）とアクリル酸－２－エチルヘキシル（２ＥＨＡ）とを含み、
    　前記アクリル酸－２－エチルヘキシルに対する前記メタクリル酸メチルのモル比（ＭＭＡ／２ＥＨＡ）が１．４７０～２．３１０である、請求項１に記載のプライマー組成物。     The (meth) acrylic acid alkyl ester monomer (b1) contains methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2EHA),
    The primer composition according to claim 1, wherein a molar ratio (MMA / 2EHA) of the methyl methacrylate to 2-ethylhexyl acrylate is 1.470-2.310.
  3. 　前記（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対する前記（メタ）アクリル酸系モノマー（ｂ２）のモル比（ｂ２／ｂ１）が、０．０３８～０．０７５である、請求項１又は２に記載のプライマー組成物。 3. The molar ratio (b2 / b1) of the (meth) acrylic acid monomer (b2) to the (meth) acrylic acid alkyl ester monomer (b1) is 0.038 to 0.075. The primer composition described.
  4. 　前記（メタ）アクリル酸アルキルエステルモノマー（ｂ１）に対する前記ヒドロキシ基を有するヒドロキシ基含有重合性モノマー（ｂ３）のモル比（ｂ３／ｂ１）が、０．０５０～０．１００である、請求項１～３のいずれか１項に記載のプライマー組成物。 The molar ratio (b3 / b1) of the hydroxy group-containing polymerizable monomer (b3) having a hydroxy group to the (meth) acrylic acid alkyl ester monomer (b1) is 0.050 to 0.100. 4. The primer composition according to any one of items 1 to 3.
  5. 　前記（メタ）アクリル粒子が有するカルボキシ基が、第３級アミン（Ｃ）でイオン化されている、請求項１～４のいずれか１項に記載のプライマー組成物。 The primer composition according to any one of claims 1 to 4, wherein the carboxy group of the (meth) acrylic particles is ionized with a tertiary amine (C).
  6. 　前記（メタ）アクリル酸系モノマー（ｂ２）に対する前記第３級アミン（Ｃ）のモル比（Ｃ／ｂ２）が、０．５６０～１．１４０である、請求項５に記載のプライマー組成物。 The primer composition according to claim 5, wherein a molar ratio (C / b2) of the tertiary amine (C) to the (meth) acrylic acid monomer (b2) is 0.560 to 1.140.
  7. 　前記防水材が、ウレタン防水材である、請求項１～６のいずれか１項に記載のプライマー組成物。 The primer composition according to any one of claims 1 to 6, wherein the waterproof material is a urethane waterproof material.
  8. 　前記下地が、無機系硬質素材である、請求項１～７のいずれか１項に記載のプライマー組成物。 The primer composition according to any one of claims 1 to 7, wherein the base is an inorganic hard material.
  9. 　下地と防水材とを密着させるために使用されるプライマー組成物であって、
    　（メタ）アクリル粒子を含有する（メタ）アクリル系エマルジョンとグリシジル基を有するシランカップリング剤（Ａ）とを含み、
    　前記（メタ）アクリル粒子を構成するポリマーは、アルキル基とヒドロキシ基とカルボキシ基とを有し、主骨格がポリ（メタ）アクリル骨格である（メタ）アクリル系ポリマーであり、
    　前記アルキル基を有する繰り返し単位に対する前記シランカップリング剤（Ａ）のモル比が、０．０２０以下であり、
    　前記（メタ）アクリル粒子の含有量が、組成物全量に対して、１５質量％以上である、プライマー組成物。     It is a primer composition used for adhering a base and a waterproof material,
    A (meth) acrylic emulsion containing (meth) acrylic particles and a silane coupling agent (A) having a glycidyl group,
    The polymer constituting the (meth) acrylic particles is a (meth) acrylic polymer having an alkyl group, a hydroxy group, and a carboxy group, and the main skeleton being a poly (meth) acryl skeleton,
    The molar ratio of the silane coupling agent (A) to the repeating unit having an alkyl group is 0.020 or less,
    The primer composition whose content of the said (meth) acryl particle is 15 mass% or more with respect to the composition whole quantity.
  10. 　ラジカル開始剤の存在下で（メタ）アクリロイル基を有する重合性モノマー（Ｂ）を重合させて（メタ）アクリル系ポリマーを製造し、前記（メタ）アクリル系ポリマーと水とグリシジル基を有するシランカップリング剤（Ａ）とを混合することによって、請求項１に記載のプライマー組成物を製造する、プライマー組成物の製造方法。 A (meth) acrylic polymer is produced by polymerizing a polymerizable monomer (B) having a (meth) acryloyl group in the presence of a radical initiator, and the silane cup having the (meth) acrylic polymer, water and a glycidyl group. The manufacturing method of a primer composition which manufactures the primer composition of Claim 1 by mixing a ring agent (A).
  11. 　更に第３級アミン（Ｃ）を含有する、請求項１０に記載のプライマー組成物の製造方法。 The method for producing a primer composition according to claim 10, further comprising a tertiary amine (C).
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JP2017075213A (en) * 2015-10-13 2017-04-20 横浜ゴム株式会社 Aqueous primer composition for sealant
JP2017075211A (en) * 2015-10-13 2017-04-20 横浜ゴム株式会社 Aqueous primer composition for sealant
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JPWO2016163434A1 (en) 2018-02-01
TW201702327A (en) 2017-01-16

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