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WO2011161817A1 - Coating material and primer using the same, ink for ink-jet - Google Patents

Coating material and primer using the same, ink for ink-jet Download PDF

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Publication number
WO2011161817A1
WO2011161817A1 PCT/JP2010/060856 JP2010060856W WO2011161817A1 WO 2011161817 A1 WO2011161817 A1 WO 2011161817A1 JP 2010060856 W JP2010060856 W JP 2010060856W WO 2011161817 A1 WO2011161817 A1 WO 2011161817A1
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WO
WIPO (PCT)
Prior art keywords
mgkoh
acid
mass
component
resin
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Application number
PCT/JP2010/060856
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French (fr)
Japanese (ja)
Inventor
道久 田坂
弘康 管野
Original Assignee
リケンテクノス株式会社
ビーエーエスエフ ソシエタス・ヨーロピア
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Application filed by リケンテクノス株式会社, ビーエーエスエフ ソシエタス・ヨーロピア filed Critical リケンテクノス株式会社
Priority to PCT/JP2010/060856 priority Critical patent/WO2011161817A1/en
Publication of WO2011161817A1 publication Critical patent/WO2011161817A1/en

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Classifications

    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to a paint, a primer using the same, and an ink jet ink, and more specifically, long-term storage stability, various substrates such as soft and hard vinyl chloride resin; styrene resin; polycarbonate resin; glass; Steel sheet; Polyolefin resin; Polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; Magnesium; Acrylonitrile-butadiene-styrene copolymer; Polyester resin; or acrylic resin layer
  • the present invention relates to a coating material and an ink-jet ink that are excellent in adhesion to the ink and excellent in color development of images.
  • the present invention also relates to a primer layer provided on an ink jet recording medium containing the coating material, and a printed matter printed using the ink jet ink.
  • an image recording method for forming an image on a recording medium such as paper based on an image data signal
  • an electrophotographic method there are an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like.
  • the electrophotographic system requires a process of forming an electrostatic latent image on a photosensitive drum by charging and exposure, and there is a problem that the system becomes complicated, resulting in high manufacturing costs.
  • the thermal transfer system is inexpensive, there are problems such as high running costs and waste materials due to the use of ink ribbons.
  • the ink jet method is an inexpensive device and ejects ink only to a required image portion to form an image directly on a recording medium. Therefore, the ink can be used efficiently and the running cost is low. Furthermore, there is little noise and it is excellent as an image recording method.
  • Patent Document 1 discloses an ink composition containing vinylcaprolactam as an ink composition having excellent flexibility and adhesion to a substrate.
  • the ink composition described in Patent Document 1 is a high-viscosity ink composition containing a polymer and an oligomer as main components of the ink, and is difficult to be ejected by inkjet.
  • Patent Document 2 discloses (a) an oligo / resin component; (B) (i) 0.1 to 50 weight percent comprising one or more heterocyclic radiation curable monomers and / or alkoxylated monomers containing pendant alkoxylated functionality and not containing backbone alkoxylation functionality An adhesion promoting radiation curable component of (Ii) a radiation curable reactive diluent comprising about 10 weight percent or less of an optional alkoxylated radiation curable monomer comprising a main chain alkoxylated functionality; An ink jettable radiation curable ink jet ink composition is disclosed.
  • Patent Document 3 a film having at least one side jet ink receiving layer of the synthetic resin base material film, the receptor layer contains a hydrophobic polyurethane resin and the hydrophilic polyurethane resin, and the An ink jet printing film in which the mass ratio of the content of the hydrophobic polyurethane resin and the hydrophilic polyurethane resin is 20 to 400 parts by mass of the hydrophilic polyurethane resin with respect to 100 parts by mass of the hydrophobic polyurethane resin. It is disclosed.
  • the object of the present invention is to provide long-term storage stability, various substrates such as soft and hard vinyl chloride resins; styrene resins; polycarbonate resins; glass; aluminum; steel plates; Polyolefin resin or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or adhesion to acrylic resin layer, color development of image, impact resistance
  • Another object of the present invention is to provide a coating material excellent in properties and flexibility, an ink jet ink, a primer layer provided on an ink jet recording medium containing the coating material, and a printed matter printed using the ink jet ink.
  • the present invention is as follows. 1.
  • the component (e) does not include a cyclic structure containing a hetero atom.
  • 2. The paint according to 1 above, wherein the component (a) is urethane (meth) acrylate. 3. 3. The paint according to 1 or 2 above, wherein the component (b) is a monomer having an N-vinyl group. 4).
  • the component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g Modified rubber (c-3); at least one selected from the group consisting of compound (c-4) having an epoxy equivalent of 150 to 700 g / mol; The paint described. 5.
  • the component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 5.
  • the paint as described in 4 above which is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product (c-1-3) thereof. 6). 6.
  • the coating adherend is soft and hard vinyl chloride resin; styrene resin; polycarbonate resin; glass; aluminum; steel plate; polyolefin resin; polyolefin resin modified with polar group-containing compound or olefin and polar group-containing compound 11.
  • the paint according to any one of 1 to 10 above which is a copolymer with: magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin.
  • An ink-jet ink comprising the paint according to any one of 1 to 11 above. 13.
  • the paint of the present invention contains the components (a), (b), (c), (d) and (e) in a specific quantitative relationship, it is excellent in long-term storage stability and various groups.
  • Materials for example, soft and hard vinyl chloride resins; styrene resins; polycarbonate resins; glass; aluminum; steel plates; polyolefin resins; polyolefin resins modified with polar group-containing compounds or olefins and polar group-containing compounds Magnesium; Magnesium; Acrylonitrile-Butadiene-Styrene Copolymer; Polyester resin; or Adhesive with acrylic resin layer, and color development, impact resistance and flexibility of image are greatly improved .
  • the paint of the present invention is useful for ink jet ink because it has the above-mentioned properties and has a low viscosity. Moreover, since the coating material of the present invention is excellent in adhesion to various substrates, it is useful for a primer layer provided on an ink jet recording medium. In addition, a printed matter printed using the ink-jet ink has excellent image coloring properties, and has excellent impact resistance and flexibility, and thus has excellent image robustness.
  • Component (a) of the paint of the present invention is a vinyl ester resin or an unsaturated polyester resin.
  • the vinyl ester resin is specifically selected from a urethane (meth) acrylate resin, an epoxy (meth) acrylate resin, and a polyester (meth) acrylate resin, and more preferably has excellent flexibility and impact resistance.
  • urethane (meth) acrylate resins that are excellent in adhesion between different materials can be used.
  • the (meth) acrylate referred to in the present invention refers to acrylate or methacrylate.
  • Such urethane (meth) acrylate resin is preferably obtained by reaction of polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups in one molecule, and two or more (meth) acrylates in one molecule. ) It has an acryloyl group.
  • the polyol used in the urethane (meth) acrylate resin preferably has a number average molecular weight of 200 to 3000, particularly preferably 400 to 2000.
  • Typical examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, and the like. These polyols are used alone or in combination of two or more.
  • the polyether polyol may include a polyol obtained by adding the alkylene oxide to bisphenol A and bisphenol F, in addition to a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • the polyester polyol is a condensation polymer of dibasic acids and polyhydric alcohols or a ring-opening polymer of a cyclic ester compound such as polycaprolactone.
  • Dibasic acids used here are, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 3-naphthalenedicarboxylic acid, 2,3-naphthal
  • Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3 -Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cycl Hexane dimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin
  • Examples of the polyisocyanate used in the urethane (meth) acrylate resin include 2,4-TDI and its isomer or a mixture of isomers, MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene.
  • MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene examples of the polyisocyanate used in the urethane (meth) acrylate resin.
  • Examples of the (meth) acrylate (hydroxyl group-containing (meth) acrylate) having one or more hydroxyl groups per molecule used in the urethane (meth) acrylate resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Mono (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, And polyvalent (meth) acrylates such as pentaerythritol tri (meth) acrylate.
  • the epoxy (meth) acrylate resin used as the vinyl ester resin preferably has two or more (meth) acryloyl groups in one molecule, and is an esterification catalyst for epoxy resin and unsaturated monobasic acid. It is obtained by reacting in the presence of.
  • Examples of the epoxy resin mentioned here include a bisphenol type or novolac type epoxy resin alone, or a resin in which a bisphenol type and a novolac type epoxy resin are mixed, and the average epoxy equivalent is preferably 150 to It is in the range of 450.
  • the bisphenol type epoxy resin a glycidyl ether type epoxy resin substantially having two or more epoxy groups in one molecule obtained by the reaction of epichlorohydrin and bisphenol A or bisphenol F is used.
  • An epoxy resin a methyl glycidyl ether-type epoxy resin obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, an epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin, or the like.
  • Typical examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.
  • Typical examples of unsaturated monobasic acids used for epoxy (meth) acrylate resins include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, and monoester maleate. (2-ethylhexyl) or sorbic acid. These unsaturated monobasic acids may be used alone or in combination of two or more.
  • the reaction between the epoxy resin and the unsaturated monobasic acid is preferably carried out using an esterification catalyst at a temperature of 60 to 140 ° C., particularly preferably 80 to 120 ° C.
  • esterification catalyst known catalysts such as tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane, triphenylphosphine or diethylamine hydrochloride Can be used as is.
  • the polyester (meth) acrylate resin used as the vinyl ester resin is a saturated or unsaturated polyester having two or more (meth) acryloyl groups in one molecule, and (meth) acrylic at the end of the saturated or unsaturated polyester. the compound is obtained by reacting.
  • the number average molecular weight of such a resin is preferably 500 to 5,000.
  • the saturated polyester used in the present invention is a condensation reaction between a saturated dibasic acid and a polyhydric alcohol
  • the unsaturated polyester is a dibasic acid containing an ⁇ , ⁇ -unsaturated dibasic acid and a polyhydric alcohol. It is obtained by the condensation reaction.
  • the resin which made the terminal of unsaturated polyester react with the (meth) acryl compound shall be contained in vinyl ester resin in this invention, and shall be distinguished from the unsaturated polyester resin demonstrated below.
  • saturated dibasic acid examples include the compounds shown in the above-mentioned polyester polyol, and examples of the ⁇ , ⁇ -unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And itaconic anhydride.
  • the compound shown to the term of the said polyester polyol can be mentioned also about polyhydric alcohol.
  • the (meth) acrylic compound of the polyester (meth) acrylate resin used as the vinyl ester resin includes unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. is there.
  • glycidyl (meth) acrylate is used.
  • the unsaturated polyester resin is obtained by polycondensing an acid component and an alcohol component by a known method, and the kind thereof is not particularly limited as long as it is known as a thermosetting resin.
  • the acid component for example, unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid are used. If necessary, use a saturated dibasic acid such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid, and acids other than dibasic acids such as benzoic acid and trimellitic acid. be able to.
  • the alcohol component include polyhydric alcohols shown in the above-mentioned polyester polyol section.
  • Component (b) used in the present invention is a compound having a cyclic structure containing a hetero atom and one ethylenically unsaturated group It is.
  • the component (b) has a function of imparting adhesiveness, flexibility, and impact resistance.
  • Examples of the component (b) include acryloyl morpholine, vinyl imidazole, and vinyl pyridine.
  • compounds represented by the following formulas (1) to (2) can be given.
  • R 2 represents a hydrogen atom or a methyl group
  • R 3 represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms
  • R 4 represents a hydrogen atom or a methyl group
  • p is preferably Shows the number from 1 to 4.
  • component (b) typically metal, engineering plastics, monomers mentioned with the viewpoint of excellent ceramic adhesive N- vinyl group, such as N- vinylpyrrolidone, N- vinylcaprolactam, N- vinylimidazole , N-vinylcarbazole and the like.
  • N-vinylcaprolactam is preferable in terms of excellent adhesion, particularly metal adhesion, viscosity-reducing properties, safety, impact resistance, and flexibility.
  • Such a monomer having an N-vinyl group serves as a reactive diluent and improves the curing rate of the composition by blending an appropriate amount.
  • Denaturant Component (c) used in the present invention is a denaturant.
  • Component (c) has a function of imparting adhesiveness and flexibility.
  • Examples of the modifier include a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g (c— 2); modified rubber (c-3); and at least one selected from the group consisting of polyolefin polymer (c-4) having an epoxy equivalent of 500 to 700 g / mol.
  • the hydroxyl value of component (c) is as follows: substrate (B) (soft and hard vinyl chloride resin; styrene resin; polycarbonate resin; glass; aluminum; steel plate; polyolefin resin; polyolefin resin modified with polar group-containing compound Or it contributes to the improvement of the selective adhesive force to the adherend consisting of copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin).
  • substrate (B) soft and hard vinyl chloride resin; styrene resin; polycarbonate resin; glass; aluminum; steel plate; polyolefin resin; polyolefin resin modified with polar group-containing compound Or it contributes to the improvement of the selective adhesive force to the adherend consisting of copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or
  • the (i) polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g includes aromatic, aliphatic, polybutadiene, castor oil, polyisoprene, and the like. As long as it is any type, the selective adhesive force to the adherend comprising the base material (B) is good.
  • the hydroxyl value is preferably 40 to 330 mgKOH / g from the viewpoint of the selective adhesive strength, and more preferably 150 to 300 mgKOH / g.
  • the polyol of component (c) can be used as a mixture of two or more if necessary.
  • the “castor oil” is an oil containing a triester compound of ricinoleic acid and glycerin. Usually, it is a natural fat or oil or a processed natural fat or oil, but it may be a synthetic fat or oil if it contains the above compounds.
  • the ricinoleic acid constituting the triester compound contained in this castor oil is preferably contained in an amount of 90 mol% or more of the fatty acids constituting the whole triester compound.
  • the castor oil may be a processed product such as a hydrogenated product (usually hydrogenated to an intercarbon unsaturated bond in the ricinoleic acid skeleton). Usually, castor oil contains 90 mol% or more (including 100 mol%) of the above-described triester compound (in the case of a hydrogenated product, a hydrogenated product of the triester compound).
  • the “castor oil-based polyol” is an ester compound of ricinoleic acid and / or hydrogenated ricinoleic acid and a polyhydric alcohol. If it has this structure, it may be a polyol obtained by using castor oil as a starting material, or a polyol obtained by using a raw material other than castor oil as a starting material. This polyhydric alcohol is not particularly limited.
  • Castor oil-based polyols include polyols derived from castor oil and polyols obtained by modifying castor oil.
  • the polyol derived from castor oil is a glycerin ester in which part of the ricinoleic acid is replaced with oleic acid, and ricinoleic acid obtained by saponifying castor oil is esterified with trimethylolpropane or other short molecular polyols.
  • fatty acid ester polyols derived from castor oil such as a mixture of these and castor oil.
  • polyols obtained by modifying castor oil include vegetable oil-modified polyols and modified polyols having an aromatic skeleton (such as bisphenol A).
  • a vegetable oil-modified polyol is obtained by replacing a part of glycerin ester ricinoleic acid with a fatty acid obtained from other plants, for example, higher fatty acids such as linoleic acid, linolenic acid, oleic acid obtained from soybean oil, rapeseed oil, olive oil, etc. It is obtained.
  • castor oil-based polyol (c-1-1) having a component (i) hydroxyl value of 40 to 330 mgKOH / g is preferable from the viewpoint of the effect of the present invention.
  • toughness (impact resistance) of the adhesive layer, the flexibility, and the substrate (B) consists in improving the adhesion to an adherend from (i) hydroxyl value 40 ⁇ 330 mg KOH / g aromatic castor of Oil-based polyol (c-1-1-1) is preferred. More preferably, it is 150 to 240 mg KOH / g.
  • the component (c-1-1-1) is a modified polyol derived from castor oil having an aromatic skeleton (for example, bisphenol A).
  • the component (c-1-1-1) is commercially available, and examples thereof include “URIC AC series” (Ito Oil Co., Ltd.).
  • an adduct obtained by adding polyalkylene glycol and bisphenol A to ricinoleic acid has preferable adhesion to an adherend composed of the base material (B), and can be represented by, for example, the following formula (3).
  • n represents an average number of 2 to 5.
  • Modified polyols derived from castor oil represented by the formula (3) are, for example, trade names URIC AC-005 (hydroxyl value 194 to 214 mg KOH / mg, viscosity 700 to 1500 mPa ⁇ s / 25 ° C.), AC-006 ( Hydroxyl value 168 to 187 mgKOH / mg, viscosity 3000 to 5000 mPa ⁇ s / 25 ° C., AC-008 (hydroxyl value 180 mgKOH / mg, viscosity 1600 mPa ⁇ s / 25 ° C.), AC-009 (hydroxyl value 225 mgKOH / mg, viscosity 1500 mPa -It can obtain from Ito Oil Co., Ltd. as s / 25 degreeC.
  • polybutadiene-based polyol used in the present invention examples include homopolymers such as 1,2-polybutadiene polyol and 1,4-polybutadiene polyol, poly (pentadiene / butadiene) polyol, poly (butadiene / styrene) polyol, poly ( Examples thereof include copolymers such as butadiene / acrylonitrile) polyols, and hydrogenated polybutadiene-based polyols obtained by adding hydrogen to these polyols.
  • Polybutadiene-based polyols are commercially available.
  • the hydroxyl value of the (c-1-2) polybutadiene-based polyol is preferably 40 to 330 mgKOH / g, more preferably 40 to 110 mgKOH / g.
  • the mass average molecular weight (GPC method) of the polybutadiene-based polyol is preferably 50 to 3000, and more preferably 800 to 1500.
  • Examples of such component (c-1-3) include Polyip (registered trademark) (hydroxyl-terminated liquid polyisoprene) manufactured by Idemitsu. “Poly ip (registered trademark)” (hydroxyl value 46.6 mg KOH / mg, Mn 2500) is a polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end.
  • An example of the hydrogenated product is Epole (registered trademark) (hydroxyl-terminated liquid polyolefin) manufactured by Idemitsu.
  • Epol® hydroxyl value 50.5 mg KOH / mg, Mn 2500
  • the epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g used in the present invention is obtained by reacting an epoxy resin with an active hydrogen compound.
  • epoxy resin used here examples include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis ( Orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4- Hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobis Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as enol, oxybisphenol, phenol novolak,
  • Gurishijiruami An epoxy compound having a hydrogen group; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6- Epoxidized products of cyclic olefin compounds such as methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, Examples include heterocyclic compounds such as triglycidyl isocyanurate. In addition, these epoxy resins may be internally crosslinked by a prepolymer of terminal isocyanate.
  • biphenol methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (bisphenol AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A
  • a bisphenol type epoxy resin such as a polyglycidyl ether compound such as 1,3-bis (4-hydroxycumylbenzene) or 1,4-bis (4-hydroxycumylbenzene) is used, a coating having excellent adhesion and the like can be obtained. preferred order to be able to form a film.
  • An epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is obtained by reacting an epoxy group of the epoxy resin with an active hydrogen compound such as a carboxylic acid compound, a polyol or an amino compound. It is what
  • carboxylic acid compound examples include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, 12-hydroxystearic acid, lactic acid, butyric acid, octylic acid, ricinoleic acid, lauric acid, benzoic acid, toluic acid, cinnamic acid, phenyl Aliphatic, aromatic or cycloaliphatic monocarboxylic acids such as acetic acid and cyclohexanecarboxylic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, Examples include hexahydro acid and hydroxypolycarboxylic acid.
  • polyol examples include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, trimethylolpropane, pentaerythritol
  • amino compounds examples include dialkylamine compounds such as dibutylamine and dioctylamine; alkanolamine compounds such as methylethanolamine, butylethanolamine, diethanolamine, diisopropanolamine, and dimethylaminopropylethanolamine; morpholine, piperidine, 4-methylpiperazine And heterocyclic amine compounds such as
  • alkanolamine compounds such as diethanolamine are preferable.
  • the epoxy resin can be chain-extended with a compound having two or more active hydrogen groups such as monoethanolamine and monoisopropanolamine.
  • a normal method of adding the active hydrogen compound to the epoxy resin can be employed.
  • a known catalyst such as a tertiary amine compound or a phosphonium salt.
  • a method in which both are heated to 60 to 200 ° C. and reacted for 3 to 10 hours can be used.
  • a preferable hydroxyl value of the epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is 100 to 140 mgKOH / g from the viewpoint of the effect of the present invention.
  • Examples of the epoxy polyol resin (c-1-4) having (i) a hydroxyl value of 40 to 330 mgKOH / g include EPICLON U-125-60BT (hydroxyl value 100 to 140 mgKOH / g) manufactured by DIC Corporation.
  • (I) a hydroxyl value 40 ⁇ 330 mg KOH / g, and as the polyol (ii) an acid value of 2 ⁇ 20mgKOH / g (c-2) is a by aromatic, aliphatic, or castor oil based Even when the hydroxyl value of (i) and the acid value of (ii) are satisfied, the selective adhesive force to the adherend comprising the substrate (B) is improved.
  • the hydroxyl value of (i) is more preferably 230 to 300 mgKOH / g.
  • the acid value of (ii) is more preferably 4 to 15 mg KOH / g.
  • a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g is a polyol derived from castor oil. As disclosed in JP-A-2005-89712, it contains a castor oil-based polyol derived from ricinoleic acid, an acidic phosphate ester compound having a total carbon number of 12 or more, and, if necessary, terpene phenols Polyol compositions can also be used. These can be obtained from Ito Refinery under the trade names URIC H-1262 and H2151U, for example.
  • the Ito Oil URIC H-1262 is a polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more (viscosity: 3,500 to 8,500 mPa ⁇ s / 25 ° C., hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), excellent adhesion to the adherend comprising the base material (B), especially for metal adhesion and hydrolysis resistance Excellent.
  • the Ito Oil URIC H-2151U is a polyol containing a castor oil-based polyol, an acidic phosphate compound having 12 or more carbon atoms and terpene phenols (viscosity: 3,500 to 8,500 mPa ⁇ s / 25). ° C, hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), excellent adhesion to the adherend comprising the base material (B), particularly metal adhesion Excellent in resistance and hydrolysis resistance.
  • the modified rubber (c-3) will be described.
  • Examples of the modified rubber (c-3) used in the present invention include (c-3-1) liquid carboxylated polyisoprene and (c-3-2) carboxylated polybutadiene.
  • (C-3-1) Carboxylated polyisoprene
  • the carboxylated polyisoprene (c-3-1) used in the present invention improves the adhesive force with the adherend comprising the substrate (B) of the present invention. Fulfills the function.
  • Examples of the component (c-3-1) include LIR-420 manufactured by Kuraray as maleated polyisoprene.
  • the carboxylated polybutadiene (c) used in the present invention has a function of improving the adhesive force with the adherend comprising the substrate (B).
  • Component (c-3-2) is a liquid liquid which is transparent at room temperature, and has a main chain microstructure of polybutadiene consisting of vinyl 1,2-bond type, trans 1,4-bond type, cis 1,4-bond type. It is a polymer.
  • the vinyl 1,2-bond is preferably 30% by mass or less, and the vinyl 1,2-bond exceeding 30% by mass is not preferable because the storage stability of the resulting paint deteriorates.
  • the cis 1,4-bond is preferably 40% by mass or more, and if the cis 1,4-bond is less than 40% by mass, the adhesiveness of the resulting coating material is lowered, which is not preferable.
  • the carboxylated polybutadiene (c-3-2) component is obtained by reacting liquid polybutadiene with a carboxyl group-introducing compound, and the ratio of 1,3-butadiene and carboxyl group-introducing compound constituting the liquid polybutadiene is 1,3. -80 to 98% by mass of butadiene and 2 to 20% by mass of the carboxyl group-introducing compound are preferable.
  • the liquid polybutadiene used in the reaction preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 7,000, and a wide molecular weight distribution.
  • the liquid polybutadiene more preferably has an iodine value measured according to DIN 53241, iodine of 30 to 500 g / 100 g of substance.
  • the liquid polybutadiene preferably has a molecular structure of 70 to 90% cis-double bonds, 10 to 30% trans-double bonds and 0 to 3% vinyl double bonds.
  • an ethylenically unsaturated dicarboxy compound such as an ethylenically unsaturated dicarboxylic acid, its anhydride or monoester
  • the compound include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, monomethyl maleate or monoethyl maleate.
  • maleic anhydride is preferred for reasons of safety, economy and reactivity. (Maleed polybutadiene is preferred.)
  • Production of a polybutadiene / maleic anhydride-addition product comprising polybutadiene and maleic anhydride can be carried out by a known method.
  • the acid value of maleated liquid polybutadiene according to DIN ISO 3682 is preferably 50 to 120 (mgKOH / g), more preferably 70 to 90 (mgKOH / g).
  • the acid value is less than 50 (mgKOH / g)
  • the adhesiveness of the obtained paint is lowered
  • it exceeds 120 (mgKOH / g) the viscosity of the obtained paint is increased and workability is lowered.
  • the maleation rate of the maleated liquid polybutadiene is related to the viscosity, but is preferably 6 to 20%, more preferably 6 to 15%, and still more preferably 7 to 10%.
  • the viscosity (20 ° C.) of maleated liquid polybutadiene measured by DIN 53214 is preferably 3 to 16 Pa ⁇ s, more preferably 5 to 13 Pa ⁇ s, and further preferably 6 to 9 Pa ⁇ s.
  • maleated liquid polybutadiene has a vinyl-double bond of 30% or less, and those having a cis-double bond in the above range have higher flexibility than liquid polybutadiene in which the cis-double bond is less than the above lower limit. And has a high maleation rate (acid value) as described above. Therefore, the paint obtained is rich in adhesiveness, and since the polarity is sufficiently imparted, the paint of the present invention can be made more flexible, the flexibility can be easily adjusted, and the decoration is excellent.
  • Liquid polybutadiene having a cis-double bond less than the above lower limit rapidly increases in viscosity as the maleation rate increases, but those having a cis-double bond in the above range have a small increase in viscosity. Since the viscosity is low as in the above range, the reactivity is increased and workability is improved. Further, the obtained paint is excellent in terms of adhesiveness.
  • Examples of commercially available maleated liquid polybutadiene include POLYVEST OC 800S (registered trademark) and 1200S manufactured by Degussa.
  • One form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol. .
  • Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol in the paint of the present invention include mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol.
  • Polyglycidyl ether compounds dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1, 3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2 Polyglycols of polynuclear polyhydric phenol compounds such as tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol Zyl
  • Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol used in the present invention include biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropyl Ridenbisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1, Polyphenols of bisphenol compounds such as 1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, terpene diphenol Glycidyl Jill ether is more preferable in terms of the metal adhesion.
  • polyglycidyl ethers of bisphenol compounds having an epoxy equivalent of 150 to 250 g / mol examples include Adeka Resin EP-4100E (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190).
  • Another form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyolefin polymer (c-4-2) having an epoxy equivalent of 500 to 700 g / mol. It is.
  • a polyolefin polymer having a hydroxyl group at one end and having an epoxy group introduced is preferred. More preferably, it is liquid.
  • a specific example of the polymer (c-4) having an epoxy equivalent of 150 to 700 g / mol is Kuraray L-207 (same as KRATON LIQUID TM L-207 POLYMER).
  • L-207 has a fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure) having an epoxy equivalent of 590 g / mol, a hydroxyl equivalent of 7000 g / mol, and a glass transition temperature of ⁇ 53 ° C. It is a coalescence and is preferable from the viewpoint of metal adhesion as a reason for use in the present invention.
  • the coating material of the present invention comprises (d) an ultraviolet reaction initiator as an essential component.
  • the oligomer component for example, vinyl ester resin or unsaturated polyester resin (a)
  • the oligomer component has a double bond such as a (meth) acryloyl group. Therefore, if a photopolymerization initiator is added, an ultraviolet fluorescent lamp or It can be easily cured in a short time by ultraviolet irradiation using a high-pressure mercury lamp or the like.
  • photopolymerization initiator examples include benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n- Butyl ether, benzoin isobutyl ether, benzyl-1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl 1-phenylpropan-1-one, benzyl sulfide, thioxanthone Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-chlorothixant and the like.
  • Component (e) of the coating material of the present invention is a monomer having a vinyl group and / or (meth) acryloyl group.
  • Component (e) A monomer having a vinyl group and / or a (meth) acryloyl group has functions of lowering viscosity, adhesion to a substrate, and pigment dispersibility.
  • trimethylolpropane tri (meth) acrylate pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tricyclodecane dimethanol (Meth) acrylate, dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), PO-modified neopentyl glycol diacrylate, modified vinyl Phenol A diacrylate and the like can be mentioned.
  • DPGDA dipropylene glycol diacrylate
  • TPGDA tripropylene glycol diacrylate
  • Others include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl
  • the viscosity at 25 ° C. of the component (e) is preferably 110 mPa ⁇ s or less, and more preferably 50 mPa ⁇ s or less in terms of lowering the viscosity.
  • Specifically preferred components (e) in the present invention are trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol divinyl ether, dipropylene glycol diacrylate, tripropylene glycol Diacrylate.
  • the viscosity was measured according to JIS K7233 using a total TVC-7 rotational viscometer at 25 ° C. The unit was mPa ⁇ S.
  • SR238NS manufactured by Sartomer Corp.
  • 1,6-hexanediol diacrylate 25 ° C.
  • SR351NS manufactured by Sartomer Co.
  • trimethylol propane triacrylate 25 ° C.
  • Optional Component (f) Colorant When the paint of the present invention is used as an ink or primer, it is preferable to contain (f) a colorant.
  • the colorant that can be used in the present invention is not particularly limited, but pigments and oil-soluble dyes that are excellent in weather resistance and excellent in color reproducibility are preferable, and are arbitrarily selected from known colorants such as soluble dyes. Can be used.
  • the colorant that can be suitably used when the paint of the present invention is used as an ink or a primer does not function as a polymerization inhibitor in a polymerization reaction that is a curing reaction from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation. It is preferred to select a compound.
  • ⁇ Pigment> Although it does not necessarily limit as a pigment which can be used for this invention, for example, the organic or inorganic pigment of the following number described in a color index can be used.
  • red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53: 1.
  • the oil-soluble dye that can be used in the present invention means a dye that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the mass of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Therefore, the oil-soluble dye means a so-called water-insoluble pigment or oil-soluble dye, and among these, an oil-soluble dye is preferable.
  • any yellow dye can be used.
  • phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components for example, azomethine dyes having open-chain active methylene compounds as coupling components;
  • methine dyes such as benzylidene dyes and monomethine oxonol dyes
  • quinone dyes such as naphthoquinone dyes and anthraquinone dyes
  • other dye species such as quinophthalone dyes, nitro / nitroso dyes, and acridines.
  • dyes and acridinone dyes for example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components;
  • methine dyes such as
  • any magenta dye can be used.
  • aryl or heteroaryl azo dyes having phenols, naphthols, anilines as coupling components for example, azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; for example arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; condensed polycyclic dyes such as dioxazine dyes, etc. it can be mentioned.
  • any cyan dye can be used.
  • indoaniline dyes indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components
  • polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes
  • carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes
  • anthraquinone dyes for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components
  • indigo / thioindigo dyes indigo / thioindigo dyes
  • Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of chromophore (chromogenic atomic group) is dissociated.
  • the counter cation may be an alkali metal or ammonium.
  • Such inorganic cations may be used, and organic cations such as pyridinium and quaternary ammonium salts may be used, and furthermore, polymer cations having such a partial structure may be used.
  • Oil-soluble dye may be used alone or in combination of several kinds.
  • a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent.
  • the disperse dye generally includes a water-soluble dye, but in the present invention, the disperse dye is preferably used as long as it is soluble in a water-immiscible organic solvent.
  • the disperse dye include C.I. I.
  • the colorant that can be used in the present invention is used as an ink or a primer, it is preferable that the colorant is appropriately dispersed in the ink after being added.
  • a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.
  • colorants may be used by appropriately selecting one kind or two or more kinds according to the purpose of use.
  • the average particle diameter of the colorant particles is preferably 0 when using a colorant such as a pigment that remains solid in the paint.
  • Selection of colorant, dispersant, dispersion medium, dispersion conditions, and filtration conditions are set to 0.005 to 0.5 ⁇ m, more preferably 0.01 to 0.45 ⁇ m, and even more preferably 0.015 to 0.4 ⁇ m. It is preferable to do.
  • This particle size control is preferable because clogging of the head nozzle can be suppressed and ink storage stability, ink transparency, and curing sensitivity can be maintained.
  • the content of the colorant in the paint of the present invention is appropriately selected depending on the color and the purpose of use, but in general, it is preferably 0.01 to 30% by mass with respect to the mass of the whole paint.
  • the paint of the present invention preferably contains (f) a colorant and (g) a dispersant.
  • the dispersant (g) is preferably an acidic dispersant.
  • An acidic dispersant is a dispersant having an acidic functional group.
  • the acidic dispersant preferably has an acid value of 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and further preferably 40 mgKOH / g or more.
  • the acidic dispersant preferably has an acid value greater than the amine value.
  • the amine value indicates the total amount of 1, 2, and tertiary amines, and is expressed in mg of KOH equivalent to hydrochloric acid required to neutralize 1 g of the sample.
  • the acid value is the number of mg of KOH required to neutralize free fatty acid, resin acid, etc. contained in 1 g of a sample.
  • the dispersant is not particularly limited as long as it is an acidic dispersant. However, it is preferable to use a polymer dispersant, and it is more preferable to use a polymer dispersant having an acid value larger than the amine value.
  • the difference between the acid value and the amine value of the dispersant is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.
  • DisperBYK-101 (acid value: 30 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-102 (acid value: 101 mgKOH / g, amine value: 0 mgKOH) / G), DisperBYK-103 (acid value: 101 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-106 (acid value: 132 mgKOH / g, amine value: 74 mgKOH / g), DisperBYK-111 (acid value: 129 mgKOH) / G, amine value: 0 mgKOH / g) (above, manufactured by BYK Chemie), EFKA4010 (acid value: 10-15 mgKOH / g, amine value: 4-8 mgKOH / g) (above, manufactured by Fuka Additive) Polymer
  • the dispersing agent (g) may be used alone or in combination.
  • other known dispersants can be used in combination.
  • DisperBYK-161 (amine value: 11 mgKOH / g, acid value: 0 mgKOH / g)
  • DisperBYK-162 (amine value: 13 mgKOH / g, acid value: 0 mgKOH / g)
  • DisperBYK-163 (amine value: 10 mgKOH / g, acid value: 0 mgKOH / g)
  • DisperBYK-164 amine value: 18 mgKOH / g, acid value: 0 mgKOH / g
  • DisperBYK-166 (amine value: 20 mgKOH / g, acid value: 0 mgKOH / g)
  • DisperBYK-167 (amine value: 13 mgKOH / g, acid value: 0 mgKOH / g)
  • DisperBYK-168 (amine value: 10 mgK
  • the content of the dispersant in the paint of the present invention is appropriately selected depending on the purpose of use, but is preferably 0.01 to 50% by mass, and preferably 0.1 to 30% by mass with respect to the mass of the colorant. More preferred is 1 to 10% by mass. It is preferable that the added amount of the dispersant is 0.01% by mass or more because the dispersibility of the pigment is excellent and the dispersion stability is good. Further, it is preferable that the amount of the dispersant added is 50% by mass or less because the stability with time of the ink is good.
  • the component (a) is blended in an amount of 10 to 40% by mass from the viewpoints of adhesion, flexibility and impact resistance.
  • a more preferable blending ratio of the component (a) is 15 to 35% by mass in terms of a viscosity that is easy to process.
  • the compounding amount of component (a) exceeds 40% by mass, the adhesiveness deteriorates, and the processability decreases due to the increase in viscosity.
  • it is less than 10 mass% the adhesiveness with respect to the to-be-adhered body which consists of a base material (B), a softness
  • the component (b) is blended in an amount of 30 to 70% by mass from the viewpoints of adhesion, flexibility and impact resistance.
  • a more preferable amount of component (b) is 40 to 65% by mass from the viewpoint of easy processing viscosity. If the blending amount of component (b) exceeds 70% by mass, adhesiveness, flexibility and impact resistance are lowered. Moreover, if it is less than 30 mass%, adhesiveness, a softness
  • the component (c) is blended in an amount of 5 to 40% by mass from the viewpoints of adhesiveness and flexibility. Further, the blending ratio of the component (c) is 10 to 30% by mass, particularly preferably 10 to 25% by mass in terms of adhesion, toughness (impact resistance) and bleed resistance.
  • the toughness (impact resistance) is lowered due to deterioration of the bleed resistance, and the adhesive strength, impact resistance and flexibility are also lowered.
  • it is less than 5% by mass adhesiveness, flexibility and impact resistance are lowered.
  • the component (d) is a total of 100 parts by mass of the components (a) to (c) from the viewpoint of practical photocuring time (irradiation intensity of 500 mJ / cm 2 for 10 seconds or less). 0.1 to 15 parts by mass with respect to the amount.
  • the amount of the component (d) is more preferably 1 to 10 parts by weight, particularly preferably 2 to 5 parts by weight in terms of practical photocuring time (irradiation intensity of 500 mJ / cm 2 for 3 seconds or less). Part.
  • the compounding amount of the component (d) exceeds 15 parts by mass, flexibility, adhesiveness and impact resistance are lowered.
  • it is less than 0.1 mass part since photocuring is inadequate, it is inferior to adhesiveness.
  • the component (e) is blended in an amount of 3 to 20 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c) from the viewpoint of low viscosity and adhesion to the substrate.
  • a more preferable amount of component (e) is 5 to 15 parts by mass in terms of low viscosity, adhesion to a substrate, and curing speed.
  • the blending amount of the component (e) is less than the lower limit specified in the present invention, the viscosity is high, so that it is not suitable for coating with an ink jet recording apparatus, and the color developability of the ink deteriorates.
  • the viscosity of the paint of the present invention at 25 ° C. is not particularly limited, but is preferably 3,000 mPa ⁇ s or less, more preferably 100 to 2,000 mPa ⁇ s. If the viscosity is within this range, the printability by the ink jet recording apparatus is extremely good, and stable storage stability that does not separate over time can be obtained, bubbles are not easily generated, and smooth surface properties can be obtained. .
  • the viscosity can be measured with a B-type viscometer.
  • the paint of the present invention comprises a base material (B), that is, a soft and hard vinyl chloride resin; a styrene resin; a polycarbonate resin; a glass; an aluminum; a steel plate; a polyolefin resin (for example, polyethylene, polypropylene, polycyclic olefin, etc.); A polyolefin resin modified with a group-containing compound or a copolymer of an olefin and a polar group-containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester-based resin (for example, polyethylene terephthalate (PET), polybutylene terephthalate, etc.); Or the adhesiveness with respect to the adherend which consists of acrylic resins (for example, PMMA etc.) is especially favorable.
  • a paint having good adhesion to these adherends is not disclosed in the prior art.
  • Method for preparing the paint of the present invention for example, components (a), (b), (c) and (e) are added to a container equipped with a stirrer and sufficiently stirred at room temperature. If the viscosity is too high, stirring may be performed while heating at 100 ° C. or lower. If it exceeds 100 ° C., the vapor generation of the component (b) becomes remarkable, which is not preferable in the working environment. Thereafter, when the liquid temperature reaches room temperature, the component (d) is added and sufficiently stirred so as not to remain undissolved. When adding other components, add them at the end and stir well. The adhesive composition obtained by stirring is quickly processed or stored in a cool and dark place.
  • the coating material of the present invention prepared as described above may be applied on the adherend comprising the substrate (B).
  • a method using an ink jet recording apparatus, a spin coating method, a (doctor) knife coating method, a micro gravure coating method, a direct gravure coating method, an offset gravure method, a reverse gravure method, a reverse roll coating method, (Meyer ) Bar coating method, die coating method, spray coating method, dip coating method and the like can be preferably applied.
  • a manual spinner ASS-301 type manufactured by Able Co., Ltd.
  • ASS-301 type manufactured by Able Co., Ltd. can be cited as an apparatus for spin coating.
  • the thickness of the coating layer (A) (cured coating film) is not particularly limited, but is about 2 ⁇ m to 50 ⁇ m, preferably about 5 ⁇ m to 30 ⁇ m, and more preferably about 8 ⁇ m to 20 ⁇ m.
  • the paint of the present invention is excellent in adhesiveness to the adherend comprising the base material (B), has low viscosity, and is excellent in color development, impact resistance and flexibility of an image. Yes.
  • the composition of the inkjet ink is not particularly limited.
  • known additives usually used in ink jet inks such as colorants, dispersants, surfactants, sensitizers, anti-fading agents, and conductive salts can be added.
  • the colorant and the dispersant are as described above.
  • the paint of the present invention is provided on an ink jet recording medium because it has excellent adhesion to an adherend comprising the base material (B) and also has excellent adhesion to a commercially available inkjet ink.
  • Suitable for ink-jet ink primer can be provided by an inkjet recording apparatus.
  • the thickness of the primer layer for inkjet ink is not particularly limited, but is, for example, 20 to 150 ⁇ m, preferably 10 to 40 ⁇ m, particularly preferably 15 ⁇ m to 35 ⁇ m.
  • the well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used.
  • the printed matter of the present invention is obtained by curing the ink-jet ink of the present invention.
  • the printed matter of the present invention is excellent in the color developability of the image, and is excellent in the fastness of the image because the impact resistance and the flexibility are greatly improved.
  • the raw materials used in the examples and comparative examples are as follows.
  • Component (b) Compound having a cyclic structure containing a heteroatom and one ethylenically unsaturated group
  • Component (c) Modifier (c-1-2) Polybutadiene polyol manufactured by Idemitsu Kosan Co., Ltd., Poly bd R-15HT Viscosity: 1.5 Pa ⁇ s / 30 ° C., hydroxyl value: 102.7 mg KOH / g (C-1-1-1) Aromatic castor oil-based polyol manufactured by Ito Oil Co., Ltd., URIC (trademark) AC-006, a polyol derived from castor oil represented by the above formula (4), viscosity: 0.7 to 1.5 Pa ⁇ s / 25 ° C., hydroxyl value: 194 to 214 mg KOH / g (C-1-3) Polyisoprene-based polyol manufactured by Idemitsu Kosan Co., Ltd.
  • Epol (trademark) hydroxyl terminated liquid polyolefin (viscosity (Pa ⁇ s / 30 ° C) 75, hydroxyl value (mgKOH / g) 50.5, number average Molecular weight 2500) (C-3-1) Maleinized polyisoprene Kuraray LIR-420 (acid value (mgKOH / g) 40) (C-3-2) Maleic acid-modified polybutadiene SARTOMER Ricon130MA8 (viscosity (Pa ⁇ s / 30 ° C) 6.5, acid value (mgKOH / g) 46, number average molecular weight 2700) (C-3-2) Maleic acid-modified polybutadiene EVONIK Co.
  • Polyvest (TM) OC 800 S (1,4-cis double bond in polybutadiene: 75%, 1,4-trans double bonds: 24%, vinyl bond: 1%, maleinized rate: 7.5 %, Number average molecular weight: 3300 (GPC), mass average molecular weight: 13,600 (GPC), viscosity (20 ° C.): 6 to 9 Pa ⁇ s (measured with DIN 53214), acid value: 70 to 90 mg KOH / g, iodine Value: 380 to 420 g / 100 g, (polymerized with Ziegler-Natta catalyst) (C-1-4) Epoxy polyol resin DIC Corporation EPICLON (trademark) U-125-60BT (Viscosity (Pa ⁇ s / 30 ° C) 70, hydroxyl value (mgKOH / g) 120) (C-4-1) Polyepoxy compound Adeka Resin EP-4100E having an epoxy equivalent of 150 to 250 g / mol (A
  • the characteristics of each polyol were measured as follows.
  • -Viscosity measurement method The viscometer is measured using a single cylindrical rotational viscometer (B type TVC--5) according to JIS K7117-1. 1.
  • a 500ml beaker (standard) is used for the measuring instrument.
  • the standard rotor is selected from two types: M1 to M4 rotors for low and medium viscosity and H1 to H7 rotors for medium and high viscosity.
  • Hydroxyl value measurement method Hydroxyl value is included in 1g of sample. This is the number of mg of potassium hydroxide required to acetylate the OH group. According to JIS K 1557-1, OH groups in the sample are acetylated using acetic anhydride, and acetic acid not used is titrated with potassium hydroxide solution.
  • A Amount of 0.5 mol / l potassium hydroxide ethanol solution used for the blank test (ml)
  • B 0.5mol / l potassium hydroxide ethanol solution used for titration (ml)
  • f Factor
  • -Acid value measuring method It represents with the mg number of potassium hydroxide required to neutralize the acidic component contained in 1g of sample oils.
  • End-point pH measurement Take 10 mL of buffer stock solution B in a 200-mL beaker, add 100 mL of titration solvent, immerse the electrode, and use the pH that changes within 0.1 pH within 30 seconds as the buffer end point.
  • Measurement of acid value 1. Weigh accurately 20 g of sample into a 200 mL beaker. 2. Add 125mL of toluene / 2-propanol / pure water mixed solvent and titrate with 0.1mol / L potassium hydroxide titrant.
  • Component (d) Component Initiator (i) Photopolymerization initiator CIBA, IRGACURE TM 819, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
  • Examples 1-20, Comparative Examples 1-8 Components ((a), (b), (c) and (e) were added to a container equipped with a stirrer at the blending ratio (parts by mass) shown in Tables 1 to 8 below, and the mixture was sufficiently stirred at room temperature. When the liquid temperature reached room temperature, component (d) was added, and the mixture was sufficiently stirred so that there was no undissolved residue, to obtain a paint.
  • the viscosity (mPa ⁇ s) of the obtained paint at 25 ° C. was measured. That is, using a handy digital viscometer TVC-7 type viscometer (Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured using an appropriate rotor (No. 0 to No. 5) according to the viscosity. The results are shown in Tables 1 to 8.
  • a coating was applied on the adherend (dimensions: 150 mm ⁇ 25 mm ⁇ thickness 1 mm) shown in Tables 1 to 8 by a spin coat method using Able's manual spinner ASS-301 type (application) This was cured by irradiating with ultraviolet rays having an energy of 500 mJ / cm 2 under air to prepare a laminate.
  • the obtained laminate was subjected to the following cross-cut tape test.
  • Adhesion test cross-cut tape test
  • the measurement was performed as follows in accordance with the cross cut tape test method described in Japanese Industrial Standard K5400.
  • Cross-cut tape test Cross-cut Test (Cross-cut Test, coating thickness 15 ⁇ 20 [mu] m (spin coating method)): the test surface (layer of paint (A) side) with a cutter knife, a crosscut of cuts 1 ⁇ 1 mm square Put in. Use the cutter guide.
  • the results are also shown in Tables 1 to 8.
  • Impact resistance test Test method Apply a paint with a thickness of 15 to 20 ⁇ m on a 25mm wide and 1mm thick steel plate by spin coating, drop a 1kgw spherical weight from 1m height after curing, and evaluate according to the following criteria went.
  • ⁇ not peeled
  • ⁇ partly peeled / cracked
  • ⁇ whole face peeled / cracked
  • JIS-K7136 laminates of Examples and Comparative Examples based on the 2000 haze of (substrate glass), haze meter was measured using a (NDH2000 Nippon Denshoku) .
  • ⁇ indicates that the measured value is less than 1.0%
  • ⁇ indicates that the measured value is 1.0% or more and less than 2.0%
  • x indicates 2.0% or more.
  • the measurement surface was a coating surface.
  • Pigment-1 (f) Solsperse 36000 with respect to 80 parts by mass of Pigment-1 (f) IRGALITE BLUE GLVO (Cyan Pigment, Ciba Specialty Chemicals (CSC), surface acid amount: 18.0, surface base amount: 34.0) (Dispersant, manufactured by LUBRIZOL, acid value: 45 mgKOH / g, amine value: 0 mgKOH / g) was blended in an amount of 20 parts by mass to obtain Pigment-1.
  • Pigment-1 was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.
  • Pigment-2 (f) Tipaque CR60-2 (white pigment (titanium oxide), manufactured by Ishihara Sangyo Co., Ltd., surface acid amount: 8, surface base amount: 25) with respect to 90 parts by mass, (g) Solsperse 36000 (dispersant, LUBRIZOL Pigment-2 was obtained by blending 10 parts by mass of an acid value of 45 mg KOH / g and an amine value of 0 mg KOH / g. Pigment-2 was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm. In the color development evaluation, the printed sample was visually confirmed, and the color development was evaluated according to the following criteria. ⁇ : No problem in color developability ⁇ : Some problem in color developability, practical problem ⁇ : Clearly in color developability, unsuitable for practical use
  • the prepared paints have the components (a), (b), (c), (d) and (e) having a specific quantitative relationship. Therefore, since it contains, it is excellent in long-term storage stability, it is excellent in adhesiveness with various to-be-adhered bodies, and the image coloring property, impact resistance, and flexibility are also improved.
  • the amount of component (a) is less than the lower limit specified in the present invention, and the amount of component (b) exceeds the upper limit specified in the present invention. The adhesiveness to the resin deteriorated, and the impact resistance and flexibility deteriorated.
  • Comparative Example 2 the amount of component (a) exceeds the upper limit specified in the present invention, and the amount of component (b) is less than the lower limit specified in the present invention.
  • the adhesion to the body deteriorated, and the impact resistance and flexibility also deteriorated.
  • the comparative example 3 did not mix
  • the adhesiveness with respect to various to-be-adhered bodies deteriorated, and impact resistance and the softness
  • Comparative Example 4 since the blending amount of the component (c) exceeded the upper limit defined in the present invention, the adhesion to various adherends deteriorated, and the impact resistance and flexibility also deteriorated.
  • Comparative Example 5 since the blending amount of component (d) was less than the lower limit specified in the present invention, the adhesion to various adherends deteriorated. In Comparative Example 6, since the blending amount of the component (d) exceeded the upper limit defined in the present invention, the adhesion to various adherends was deteriorated, and the impact resistance and flexibility were also deteriorated. In Comparative Example 7, since the component (e) was not blended, the viscosity was high, and it was not suitable for coating with an ink jet recording apparatus, and the color developability of the ink was deteriorated.
  • Comparative Example 8 since the blending amount of the component (e) exceeds the upper limit defined in the present invention, the adhesion to each substrate is poor, the adhesion of the inkjet ink is poor, and it can serve as a primer. In addition, impact resistance and flexibility deteriorated.
  • the paint composition used in the ink color development test for ink jet in Examples and a paint composition not containing a pigment was used. Also good printing was made.
  • the ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion. Temperature sensors were provided near the ink supply tank and the nozzle of the ink jet head, respectively, and temperature control was performed so that the nozzle portion was always 45 ° C. ⁇ 2 ° C.
  • the piezo-type inkjet head was driven so that multi-size dots of 8 to 30 pl could be ejected at a resolution of 720 ⁇ 720 dpi.
  • UV light was condensed to an exposure surface illuminance of 1,630 mW / cm 2 , and the exposure system, main scanning speed, and ejection frequency were adjusted so that irradiation started 0.1 seconds after ink landed on the recording medium. . Further, the integrated light amount irradiated to the image was set to 4,500 mJ / cm 2 .
  • a HAN250NL high-cure mercury lamp manufactured by GS Yuasa Corporation was used as the ultraviolet lamp.
  • dpi represents the number of dots per 2.54 cm.
  • an ester film E5000 film thickness 125 ⁇ m, manufactured by Toyobo Co., Ltd.
  • the paint of the present invention can also be used as an ink used in an ink jet recording apparatus. It is also effective as a primer.
  • the primer of the present invention having a low viscosity is useful because the primer is usually often applied by an ink jet recording apparatus.

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Abstract

The disclosed coating material contains (a) a vinyl ester resin or an unsaturated polyester resin (10-40 mass%), (b) a compound having a ring structure containing a heteroatom and having one ethylenically unsaturated group (30-70 mass%), (c) a denaturant (5-40 mass%) (wherein the sum of the mass percentages of the aforementioned components (a) to (c) is 100 mass%), and (d) a UV reaction initiator (0.1-15 parts mass per 100 parts mass of the aforementioned components (a) to (c)) combined, and (e) a monomer having a vinyl group and/or a (meth) acryloyl group (3-20 parts mass per 100 parts mass of the aforementioned components (a) to (c) combined). (Moreover, the aforementioned component (e) does not contain a ring structure containing a heteroatom.)

Description

塗料およびこれを用いたプライマー、インクジェット用インクPaint, primer using the same, and inkjet ink
　本発明は、塗料およびこれを用いたプライマー、インクジェット用インクに関し、詳しくは、長期保存安定性、各種基材、例えば、軟質および硬質塩化ビニル樹脂；スチレン系樹脂；ポリカーボネート系樹脂；ガラス；アルミニウム；鋼板；ポリオレフィン系樹脂；極性基含有化合物で変性されたポリオレフィン樹脂またはオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層との接着性に優れ、画像の発色性にも優れる塗料およびインクジェット用インクに関する。
　また本発明は、該塗料を含有する、インクジェット記録媒体上に設けられたプライマー層と、該インクジェット用インクを用いて印刷された印刷物にも関する。 The present invention relates to a paint, a primer using the same, and an ink jet ink, and more specifically, long-term storage stability, various substrates such as soft and hard vinyl chloride resin; styrene resin; polycarbonate resin; glass; Steel sheet; Polyolefin resin; Polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; Magnesium; Acrylonitrile-butadiene-styrene copolymer; Polyester resin; or acrylic resin layer The present invention relates to a coating material and an ink-jet ink that are excellent in adhesion to the ink and excellent in color development of images.
The present invention also relates to a primer layer provided on an ink jet recording medium containing the coating material, and a printed matter printed using the ink jet ink.
　画像データ信号に基づき、紙などの被記録媒体に画像を形成する画像記録方法として、電子写真方式、昇華型および溶融型熱転写方式、インクジェット方式などがある。電子写真方式は、感光体ドラム上に帯電および露光により静電潜像を形成するプロセスを必要とし、システムが複雑となり、結果的に製造コストが高価になるなどの問題がある。また熱転写方式は、装置は安価であるが、インクリボンを用いるため、ランニングコストが高く、かつ廃材が出るなどの問題がある。
　一方、インクジェット方式は、安価な装置で、且つ、必要とされる画像部のみにインクを吐出し被記録媒体上に直接画像形成を行うため、インクを効率良く使用でき、ランニングコストが安い。さらに、騒音が少なく、画像記録方式として優れている。 As an image recording method for forming an image on a recording medium such as paper based on an image data signal, there are an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like. The electrophotographic system requires a process of forming an electrostatic latent image on a photosensitive drum by charging and exposure, and there is a problem that the system becomes complicated, resulting in high manufacturing costs. In addition, although the thermal transfer system is inexpensive, there are problems such as high running costs and waste materials due to the use of ink ribbons.
On the other hand, the ink jet method is an inexpensive device and ejects ink only to a required image portion to form an image directly on a recording medium. Therefore, the ink can be used efficiently and the running cost is low. Furthermore, there is little noise and it is excellent as an image recording method.
　特許文献１には、硬化膜の柔軟性、基材密着性に富むインク組成物として、ビニルカプロラクタムを含有するインク組成物が開示されている。しかし、特許文献１に記載されているインク組成物は、ポリマー、オリゴマーをインクの主成分として含む高粘度のインク組成物であり、インクジェット吐出することは難しい。
　また、特許文献２には、（ａ）オリゴ／樹脂成分と；
（ｂ）（ｉ）ペンダントアルコキシル化官能性を含み、主鎖アルコキシル化官能性を含まない１つ以上の複素環式放射線硬化性モノマーおよび／またはアルコキシル化モノマーを含む、０．１～５０質量パーセントの接着促進放射線硬化性成分と、
（ｉｉ）主鎖アルコキシル化官能性を含む、約１０質量パーセント以下の任意選択のアルコキシル化放射線硬化性モノマーとを含む放射線硬化性反応性希釈剤と、
を含むインクジェット可能な放射線硬化性インクジェットインク組成物が開示されている。
　また、特許文献３には、合成樹脂製基材フィルムの少なくとも片面にインクジェットインキ受容層を有するフィルムであって、該受容層が疎水性ポリウレタン系樹脂及び親水性ポリウレタン系樹脂を含有し、かつ該疎水性ポリウレタン系樹脂と該親水性ポリウレタン系樹脂の含有量の質量比が、該疎水性ポリウレタン系樹脂１００質量部に対し該親水性ポリウレタン系樹脂が２０～４００質量部であるインクジェット印刷用フィルムが開示されている。
　しかしながら特許文献２および３に記載の技術、あるいはその他の従来の技術では、塗料の長期保存安定性、各種基材、例えば、軟質および硬質塩化ビニル樹脂；スチレン系樹脂；ポリカーボネート系樹脂；ガラス；アルミニウム；鋼板；ポリオレフィン系樹脂；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層との接着性が不十分であり、画像の発色性も不十分であり、さらに耐衝撃性、柔軟性にも改善の余地があった。 Patent Document 1 discloses an ink composition containing vinylcaprolactam as an ink composition having excellent flexibility and adhesion to a substrate. However, the ink composition described in Patent Document 1 is a high-viscosity ink composition containing a polymer and an oligomer as main components of the ink, and is difficult to be ejected by inkjet.
Patent Document 2 discloses (a) an oligo / resin component;
(B) (i) 0.1 to 50 weight percent comprising one or more heterocyclic radiation curable monomers and / or alkoxylated monomers containing pendant alkoxylated functionality and not containing backbone alkoxylation functionality An adhesion promoting radiation curable component of
(Ii) a radiation curable reactive diluent comprising about 10 weight percent or less of an optional alkoxylated radiation curable monomer comprising a main chain alkoxylated functionality;
An ink jettable radiation curable ink jet ink composition is disclosed.
In Patent Document 3, a film having at least one side jet ink receiving layer of the synthetic resin base material film, the receptor layer contains a hydrophobic polyurethane resin and the hydrophilic polyurethane resin, and the An ink jet printing film in which the mass ratio of the content of the hydrophobic polyurethane resin and the hydrophilic polyurethane resin is 20 to 400 parts by mass of the hydrophilic polyurethane resin with respect to 100 parts by mass of the hydrophobic polyurethane resin. It is disclosed.
However, in the techniques described in Patent Documents 2 and 3, or other conventional techniques, the long-term storage stability of paints, various substrates such as soft and hard vinyl chloride resins; styrene resins; polycarbonate resins; glass; Steel plate; polyolefin resin; polyolefin resin modified with polar group-containing compound or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin Adhesiveness with the layer was insufficient, color development of the image was insufficient, and there was room for improvement in impact resistance and flexibility.
特許第２８８０８４５号公報Japanese Patent No. 2880845 特表２００４－５１４０１４号公報JP-T-2004-514014 特開２００７－０５０６２０号公報JP 2007-050620 A
　したがって本発明の目的は、長期保存安定性、各種基材、例えば、軟質および硬質塩化ビニル樹脂；スチレン系樹脂；ポリカーボネート系樹脂；ガラス；アルミニウム；鋼板；ポリオレフィン系樹脂；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層との接着性、、画像の発色性、耐衝撃性および柔軟性に優れる塗料、インクジェット用インク、該塗料を含有する、インクジェット記録媒体上に設けられたプライマー層、並びに、該インクジェット用インクを用いて印刷された印刷物を提供することにある。 Accordingly, the object of the present invention is to provide long-term storage stability, various substrates such as soft and hard vinyl chloride resins; styrene resins; polycarbonate resins; glass; aluminum; steel plates; Polyolefin resin or copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or adhesion to acrylic resin layer, color development of image, impact resistance Another object of the present invention is to provide a coating material excellent in properties and flexibility, an ink jet ink, a primer layer provided on an ink jet recording medium containing the coating material, and a printed matter printed using the ink jet ink.
　本発明者は鋭意研究を行った結果、下記成分（ａ）、（ｂ）、（ｃ）、（ｄ）および（ｅ）を特定の量的関係でもって含有する組成物が、前記課題を解決し得ることを見出し、本発明を完成した。 As a result of intensive studies, the present inventor has solved the above-described problems by a composition containing the following components (a), (b), (c), (d) and (e) in a specific quantitative relationship. The present invention has been completed.
　すなわち本発明は、以下の通りである。
　１．（ａ）ビニルエステル樹脂または不飽和ポリエステル樹脂　１０～４０質量％
（ｂ）ヘテロ原子を含む環状構造および１個のエチレン性不飽和基を有する化合物　３０～７０質量％
（ｃ）変性剤　５～４０質量％、
（ただし、前記成分（ａ）～（ｃ）の合計は１００質量％である）
（ｄ）紫外線反応開始剤　前記成分（ａ）～（ｃ）の合計１００質量部に対し０．１～１５質量部、および
（ｅ）ビニル基および／または（メタ）アクリロイル基を持つモノマー　前記成分（ａ）～（ｃ）の合計１００質量部に対し３～２０質量部
を含有する塗料。
（ただし、前記成分（ｅ）はヘテロ原子を含む環状構造を含まない。）
　２．前記成分（ａ）が、ウレタン（メタ）アクリレートであることを特徴とする前記１に記載の塗料。
　３．前記成分（ｂ）が、Ｎ－ビニル基を有するモノマーであることを特徴とする前記１または２に記載の塗料。
　４．前記成分（ｃ）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）；変性ゴム（ｃ－３）；エポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）からなる群から選択された少なくとも１種であることを特徴とする前記１～３のいずれかに記載の塗料。
　５．前記成分（ｃ－１）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）；水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリブタジエン系ポリオール（ｃ－１－２）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリイソプレン系ポリオールまたはその水素添加物（ｃ－１－３）からなる群から選択された少なくとも１種であることを特徴とする前記４に記載の塗料。
　６．前記成分（ｃ－１）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇの芳香族系ヒマシ油系ポリオール（ｃ－１－１－１）であることを特徴とする前記５に記載の塗料。
　７．前記成分（ｃ－２）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるヒマシ油系ポリオール（ｃ－２－１）であることを特徴とする前記４に記載の塗料。
　８．前記成分（ｃ－３）が酸変性ポリブタジエンまたは酸変性ポリイソプレンであることを特徴とする前記４に記載の塗料。
　９．前記成分（ｃ－４）がエポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）であることを特徴とする前記４に記載の塗料。
　１０．前記成分（ｃ－４）がエポキシ当量が５００～７００ｇ／モルである飽和骨格を持つ重合体（ｃ－４－２）であることを特徴とする前記４に記載の塗料。
　１１．前記塗料の被着体が、軟質および硬質塩化ビニル樹脂；スチレン系樹脂；ポリカーボネート系樹脂；ガラス；アルミニウム；鋼板；ポリオレフィン系樹脂；極性基含有化合物で変性されたポリオレフィン樹脂またはオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂であることを特徴とする前記１～１０のいずれかに記載の塗料。
　１２．前記１～１１のいずれかに記載の塗料を含有することを特徴とするインクジェット用インク。
　１３．さらに着色剤を含有することを特徴とする前記１２に記載のインクジェット用インク。
　１４．前記１～１１のいずれかに記載の塗料を含有することを特徴とする、インクジェット記録媒体上に設けられたプライマー層。
　１５．インクジェット記録媒体上に、前記１２または１３に記載のインクジェット用インクを用いてインクジェット印刷してなる印刷物。 That is, the present invention is as follows.
1. (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
(B) Compound having a cyclic structure containing a heteroatom and one ethylenically unsaturated group 30 to 70% by mass
(C) modifying agent 5-40% by mass,
(However, the total of the components (a) to (c) is 100% by mass)
(D) UV reaction initiator 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c), and (e) a monomer having a vinyl group and / or (meth) acryloyl group A paint containing 3 to 20 parts by mass with respect to a total of 100 parts by mass of (a) to (c).
(However, the component (e) does not include a cyclic structure containing a hetero atom.)
2. 2. The paint according to 1 above, wherein the component (a) is urethane (meth) acrylate.
3. 3. The paint according to 1 or 2 above, wherein the component (b) is a monomer having an N-vinyl group.
4). The component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g Modified rubber (c-3); at least one selected from the group consisting of compound (c-4) having an epoxy equivalent of 150 to 700 g / mol; The paint described.
5. The component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 5. The paint as described in 4 above, which is at least one selected from the group consisting of a polyisoprene-based polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product (c-1-3) thereof.
6). 6. The coating material according to 5 above, wherein the component (c-1) is an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mg KOH / g.
7). Wherein said ingredients (c-2), characterized in that a hydroxyl value 40 ~ 330mgKOH / g, and a acid value is 2 ~ 20 mgKOH / g castor oil based polyol (c-2-1) 4 The paint described in 1.
8). 5. The paint according to 4 above, wherein the component (c-3) is acid-modified polybutadiene or acid-modified polyisoprene.
9. 5. The coating material as described in 4 above, wherein the component (c-4) is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol.
10. 5. The paint according to 4 above, wherein the component (c-4) is a polymer (c-4-2) having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol.
11. The coating adherend is soft and hard vinyl chloride resin; styrene resin; polycarbonate resin; glass; aluminum; steel plate; polyolefin resin; polyolefin resin modified with polar group-containing compound or olefin and polar group-containing compound 11. The paint according to any one of 1 to 10 above, which is a copolymer with: magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester resin; or an acrylic resin.
12 An ink-jet ink comprising the paint according to any one of 1 to 11 above.
13. 13. The inkjet ink as described in 12 above, further comprising a colorant.
14 A primer layer provided on an ink jet recording medium, comprising the paint according to any one of 1 to 11 above.
15. A printed matter obtained by performing inkjet printing on an inkjet recording medium using the inkjet ink described in 12 or 13 above.
　本発明の塗料は、前記成分（ａ）、（ｂ）、（ｃ）、（ｄ）および（ｅ）を特定の量的関係でもって含有しているので、長期保存安定性に優れ、各種基材、例えば、軟質および硬質塩化ビニル樹脂；スチレン系樹脂；ポリカーボネート系樹脂；ガラス；アルミニウム；鋼板；ポリオレフィン系樹脂；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂の層との接着性に優れ、また、画像の発色性、耐衝撃性および柔軟性も大幅に改善されている。また、本発明の塗料は、上記の各特性を有するとともに、低粘度であるのでインクジェット用インクに有用である。また、本発明の塗料は、各種基材への接着性に優れることから、インクジェット記録媒体上に設けられたプライマー層に有用である。また該インクジェット用インクを用いて印刷された印刷物は、画像の発色性に優れ、耐衝撃性および柔軟性も大幅に改善されていることから、画像の堅牢性にも優れる。 Since the paint of the present invention contains the components (a), (b), (c), (d) and (e) in a specific quantitative relationship, it is excellent in long-term storage stability and various groups. Materials, for example, soft and hard vinyl chloride resins; styrene resins; polycarbonate resins; glass; aluminum; steel plates; polyolefin resins; polyolefin resins modified with polar group-containing compounds or olefins and polar group-containing compounds Magnesium; Magnesium; Acrylonitrile-Butadiene-Styrene Copolymer; Polyester resin; or Adhesive with acrylic resin layer, and color development, impact resistance and flexibility of image are greatly improved . In addition, the paint of the present invention is useful for ink jet ink because it has the above-mentioned properties and has a low viscosity. Moreover, since the coating material of the present invention is excellent in adhesion to various substrates, it is useful for a primer layer provided on an ink jet recording medium. In addition, a printed matter printed using the ink-jet ink has excellent image coloring properties, and has excellent impact resistance and flexibility, and thus has excellent image robustness.
　以下、本発明をさらに詳細に説明する。
（ａ）ビニルエステル樹脂または不飽和ポリエステル樹脂
　本発明の塗料の成分（ａ）は、ビニルエステル樹脂または不飽和ポリエステル樹脂である。
　ビニルエステル樹脂として、具体的にはウレタン（メタ）アクリレート樹脂、エポキシ（メタ）アクリレート樹脂、ポリエステル（メタ）アクリレート樹脂から選択されるものであり、より好ましくは柔軟性、耐衝撃性が特に優れ、かつ異材質間での接着性にも優れるウレタン（メタ）アクリレート樹脂が挙げられる。なお本発明でいう（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指す。 Hereinafter, the present invention will be described in more detail.
(A) Vinyl ester resin or unsaturated polyester resin Component (a) of the paint of the present invention is a vinyl ester resin or an unsaturated polyester resin.
The vinyl ester resin is specifically selected from a urethane (meth) acrylate resin, an epoxy (meth) acrylate resin, and a polyester (meth) acrylate resin, and more preferably has excellent flexibility and impact resistance. In addition, urethane (meth) acrylate resins that are excellent in adhesion between different materials can be used. In addition, the (meth) acrylate referred to in the present invention refers to acrylate or methacrylate.
　かかるウレタン（メタ）アクリレート樹脂としては、好ましくはポリオール、ポリイソシアネートおよび１分子に１個以上の水酸基を有する（メタ）アクリレートの反応により得られるものであり、１分子中に２個以上の（メタ）アクリロイル基を有するものである。 Such urethane (meth) acrylate resin is preferably obtained by reaction of polyol, polyisocyanate and (meth) acrylate having one or more hydroxyl groups in one molecule, and two or more (meth) acrylates in one molecule. ) It has an acryloyl group.
　前記ウレタン（メタ）アクリレート樹脂に用いられるポリオールとしては、好ましくは数平均分子量が２００～３０００、特に好ましくは４００～２０００のものである。
　このポリオールは、代表的にはポリエーテルポリオール、ポリエステルポリオール、ポリカ－ボネ－トポリオール、ポリブタジエンポリオール等が挙げられ、単独または２種以上を併用して用いられる。 The polyol used in the urethane (meth) acrylate resin preferably has a number average molecular weight of 200 to 3000, particularly preferably 400 to 2000.
Typical examples of the polyol include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, and the like. These polyols are used alone or in combination of two or more.
　ここで言うポリエーテルポリオールとは、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリアルキレンオキサイドの他に、ビスフェノールＡおよびビスフェノールＦに前記アルキレンオキサイドを付加させたポリオールも含むことができる。 As used herein, the polyether polyol may include a polyol obtained by adding the alkylene oxide to bisphenol A and bisphenol F, in addition to a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
　また、ポリエステルポリオールとは、二塩基酸類と多価アルコール類の縮合重合体またはポリカプロラクトンの様に環状エステル化合物の開環重合体である。ここで使用する二塩基酸類とは、例えば、フタル酸、無水フタル酸、ハロゲン化無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロフタル酸、ヘキサヒドロ無水フタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸、コハク酸、マロン酸、グルタル酸、アジピン酸、セバシン酸、１，１２－ドデカンジカルボン酸、２，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸無水物、４，４'－ビフェニルジカルボン酸、またこれらのジアルキルエステル等を挙げることができる。また、多価アルコール類とは、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール、２－メチル－１，３－プロパンジオール、１，３－ブタンジオール、ネオペンチルグリコール、水素化ビスフェノールＡ、１，４－ブタンジオール、１，６－ヘキサンジオール、ビスフェノールＡとプロピレンオキシドまたはエチレンオキシドの付加物、１，２，３，４－テトラヒドロキシブタン、グリセリン、トリメチロールプロパン、１，３－プロパンジオール、１，２－シクロヘキサングリコール、１，３－シクロヘキサングリコール、１，４－シクロヘキサングリコール、１，４－シクロヘキサンジメタノール、パラキシレングリコール、ビシクロヘキシル－４，４'－ジオール、２，６－デカリングリコール、２，７－デカリングリコール等を挙げることができる。 The polyester polyol is a condensation polymer of dibasic acids and polyhydric alcohols or a ring-opening polymer of a cyclic ester compound such as polycaprolactone. Dibasic acids used here are, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, Hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3 -Butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cycl Hexane dimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, and 2,7-decalin glycol, and the like.
　前記ウレタン（メタ）アクリレート樹脂に用いられるポリイソシアネートとしては、２，４－ＴＤＩおよびその異性体または異性体の混合物、ＭＤＩ、ＨＤＩ、ＩＰＤＩ、ＸＤＩ、水添ＸＤＩ、ジシクロヘキシルメタンジイソシアネート、トリジンジイソシアネート、ナフタリンジイソシアネート、トリフェニルメタントリイソシアネート等を挙げることができ、それらの単独または２種以上で使用することができる。 Examples of the polyisocyanate used in the urethane (meth) acrylate resin include 2,4-TDI and its isomer or a mixture of isomers, MDI, HDI, IPDI, XDI, hydrogenated XDI, dicyclohexylmethane diisocyanate, tolidine diisocyanate, and naphthalene. A diisocyanate, a triphenylmethane triisocyanate, etc. can be mentioned, These can be used individually or in mixture of 2 or more types.
　前記ウレタン（メタ）アクリレート樹脂に用いられる１分子に１個以上の水酸基を有する（メタ）アクリレート（水酸基含有（メタ）アクリレート）としては、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、３－ヒドロキシブチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等のモノ（メタ）アクリレート類、トリス（ヒドロキシエチル）イソシアヌル酸ジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート等の多価（メタ）アクリレート類等を挙げることができる。 Examples of the (meth) acrylate (hydroxyl group-containing (meth) acrylate) having one or more hydroxyl groups per molecule used in the urethane (meth) acrylate resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Mono (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, And polyvalent (meth) acrylates such as pentaerythritol tri (meth) acrylate.
　前記ウレタン（メタ）アクリレート樹脂の製造方法の例を挙げれば、（１）先ずポリイソシアネートとポリオールを好ましくはＮＣＯ／ＯＨ＝１．３～２で反応させ、末端イソシアネート化合物を生成させ、次いでそれに水酸基含有（メタ）アクリレートをイソシアネート基に対して水酸基がほぼ等量になるように反応する方法と、（２）ポリイソシアネート化合物と水酸基含有（メタ）アクリレートをＮＣＯ／ＯＨ＝２以上で反応させ、片末端イソシアネートの化合物を生成させ、次いでポリオールを加えて反応する方法等が挙げられる。 Examples of the method for producing the urethane (meth) acrylate resin include: (1) First, a polyisocyanate and a polyol are preferably reacted at NCO / OH = 1.3 to 2 to form a terminal isocyanate compound, and then a hydroxyl group is produced. A method of reacting the containing (meth) acrylate so that the hydroxyl groups are approximately equal to the isocyanate group, and (2) reacting the polyisocyanate compound and the hydroxyl-containing (meth) acrylate at NCO / OH = 2 or more, Examples include a method in which a compound of a terminal isocyanate is produced and then a polyol is added to react.
　また、ビニルエステル樹脂として用いられるエポキシ（メタ）アクリレート樹脂とは、好ましくは１分子中に２個以上の（メタ）アクリロイル基を有するもので、エポキシ樹脂と不飽和一塩基酸とをエステル化触媒の存在下で反応して得られるものである。 The epoxy (meth) acrylate resin used as the vinyl ester resin preferably has two or more (meth) acryloyl groups in one molecule, and is an esterification catalyst for epoxy resin and unsaturated monobasic acid. It is obtained by reacting in the presence of.
　ここでいうエポキシ樹脂の例を挙げれば、ビスフェノールタイプまたはノボラックタイプのエポキシ樹脂単独、または、ビスフェノールタイプとノボラックタイプのエポキシ樹脂とを混合した樹脂などであって、その平均エポキシ当量が好ましくは１５０～４５０の範囲のものである。 Examples of the epoxy resin mentioned here include a bisphenol type or novolac type epoxy resin alone, or a resin in which a bisphenol type and a novolac type epoxy resin are mixed, and the average epoxy equivalent is preferably 150 to It is in the range of 450.
　ここで、前記ビスフェノールタイプのエポキシ樹脂として代表的なものを挙げれば、エピクロルヒドリンとビスフェノールＡ若しくはビスフェノールＦとの反応により得られる実質的に１分子中に２個以上のエポキシ基を有するグリシジルエーテル型のエポキシ樹脂、メチルエピクロルヒドリンとビスフェノールＡ若しくはビスフェノールＦとの反応により得られるメチルグリシジルエーテル型のエポキシ樹脂、あるいはビスフェノールＡのアルキレンオキサイド付加物とエピクロルヒドリン若しくはメチルエピクロルヒドリンとから得られるエポキシ樹脂などである。また、前記ノボラックタイプのエポキシ樹脂として代表的なものには、フェノールノボラックまたはクレゾールノボラックと、エピクロルヒドリンまたはメチルエピクロルヒドリンとの反応により得られるエポキシ樹脂などがある。 Here, as a typical example of the bisphenol type epoxy resin, a glycidyl ether type epoxy resin substantially having two or more epoxy groups in one molecule obtained by the reaction of epichlorohydrin and bisphenol A or bisphenol F is used. An epoxy resin, a methyl glycidyl ether-type epoxy resin obtained by reaction of methyl epichlorohydrin and bisphenol A or bisphenol F, an epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin, or the like. Typical examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.
　また、エポキシ（メタ）アクリレート樹脂に用いられる不飽和一塩基酸として代表的なものには、例えばアクリル酸、メタアクリル酸、桂皮酸、クロトン酸、マレイン酸モノメチル、マレイン酸モノプロピル、マレイン酸モノ（２－エチルヘキシル）あるいはソルビン酸などが挙げられる。なお、これらの不飽和一塩基酸は、単独でも、２種以上混合しても用いられる。前記エポキシ樹脂と不飽和一塩基酸との反応は、好ましくは６０～１４０℃、特に好ましくは８０～１２０℃の温度においてエステル化触媒を用いて行われる。 Typical examples of unsaturated monobasic acids used for epoxy (meth) acrylate resins include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, and monoester maleate. (2-ethylhexyl) or sorbic acid. These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the epoxy resin and the unsaturated monobasic acid is preferably carried out using an esterification catalyst at a temperature of 60 to 140 ° C., particularly preferably 80 to 120 ° C.
　前記のエステル化触媒としては、たとえばトリエチルアミン、Ｎ，Ｎ－ジメチルベンジルアミン、Ｎ，Ｎ－ジメチルアニリン若しくはジアザビシクロオクタンなどの如き三級アミン、トリフェニルホスフィンあるいはジエチルアミン塩酸塩などの如き公知の触媒がそのまま使用できる。 As the esterification catalyst, known catalysts such as tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane, triphenylphosphine or diethylamine hydrochloride Can be used as is.
　ビニルエステル樹脂として用いられるポリエステル（メタ）アクリレート樹脂とは、１分子中に２個以上の（メタ）アクリロイル基を有する飽和若しくは不飽和ポリエステルであり、飽和若しくは不飽和ポリエステルの末端に（メタ）アクリル化合物を反応させたものである。かかる樹脂の数平均分子量としては、好ましくは５００～５０００である。 The polyester (meth) acrylate resin used as the vinyl ester resin is a saturated or unsaturated polyester having two or more (meth) acryloyl groups in one molecule, and (meth) acrylic at the end of the saturated or unsaturated polyester. the compound is obtained by reacting. The number average molecular weight of such a resin is preferably 500 to 5,000.
　本発明で用いられる飽和ポリエステルとは、飽和二塩基酸類と多価アルコール類との縮合反応、また、不飽和ポリエステルとはα，β－不飽和二塩基酸を含む二塩基酸類と多価アルコール類との縮合反応で得られるものである。なお、不飽和ポリエステルの末端に（メタ）アクリル化合物を反応させた樹脂は、本発明においてはビニルエステル樹脂に含まれるものとし、下記で説明する不飽和ポリエステル樹脂とは区別されるものとする。 The saturated polyester used in the present invention is a condensation reaction between a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester is a dibasic acid containing an α, β-unsaturated dibasic acid and a polyhydric alcohol. It is obtained by the condensation reaction. In addition, the resin which made the terminal of unsaturated polyester react with the (meth) acryl compound shall be contained in vinyl ester resin in this invention, and shall be distinguished from the unsaturated polyester resin demonstrated below.
　ここでいう飽和二塩基酸類とは、前記のポリエステルポリオールの項に示した化合物を挙げることができ、α，β－不飽和二塩基酸としては、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸等を挙げることができる。また、多価アルコール類についても、前記のポリエステルポリオールの項に示した化合物を挙げることができる。 Examples of the saturated dibasic acid herein include the compounds shown in the above-mentioned polyester polyol, and examples of the α, β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And itaconic anhydride. Moreover, the compound shown to the term of the said polyester polyol can be mentioned also about polyhydric alcohol.
　また、ビニルエステル樹脂として用いられるポリエステル（メタ）アクリレート樹脂の（メタ）アクリル化合物としては、不飽和グリシジル化合物、アクリル酸またはメタクリル酸の如き各種の不飽和一塩基酸、およびそのグリシジルエステル類等である。好ましくは、グリシジル（メタ）アクリレートの使用が望ましい。 The (meth) acrylic compound of the polyester (meth) acrylate resin used as the vinyl ester resin includes unsaturated glycidyl compounds, various unsaturated monobasic acids such as acrylic acid or methacrylic acid, and glycidyl esters thereof. is there. Preferably, glycidyl (meth) acrylate is used.
　不飽和ポリエステル樹脂とは、酸成分およびアルコール成分を公知の方法により重縮合させて得られるものであり、熱硬化性樹脂として知られているものであればその種類は特に限定されるものではない。酸成分としては、例えば無水マレイン酸、マレイン酸、フマル酸、イタコン酸等の不飽和二塩基酸が用いられる。また必要に応じてフタル酸、無水フタル酸、イソフタル酸、テレフタル酸、コハク酸、アジピン酸、セバチン酸等の飽和二塩基酸、安息香酸、トリメリット酸等の二塩基酸以外の酸等を用いることができる。アルコール成分としては、前記のポリエステルポリオールの項に示した多価アルコール類を挙げることができる。 The unsaturated polyester resin is obtained by polycondensing an acid component and an alcohol component by a known method, and the kind thereof is not particularly limited as long as it is known as a thermosetting resin. . As the acid component, for example, unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid are used. If necessary, use a saturated dibasic acid such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid, and acids other than dibasic acids such as benzoic acid and trimellitic acid. be able to. Examples of the alcohol component include polyhydric alcohols shown in the above-mentioned polyester polyol section.
（ｂ）ヘテロ原子を含む環状構造および１個のエチレン性不飽和基を有する化合物
　本発明で用いられる成分（ｂ）は、ヘテロ原子を含む環状構造および１個のエチレン性不飽和基を有する化合物である。
　成分（ｂ）は、接着性、柔軟性、耐衝撃性を付与する機能を有する。
　成分（ｂ）としては、例えば、アクリロイルモルホリン、ビニルイミダゾール、ビニルピリジン等が挙げられる。
　さらに、下記式（１）～（２）で表される化合物を挙げることができる。 (B) Compound having a cyclic structure containing a hetero atom and one ethylenically unsaturated group Component (b) used in the present invention is a compound having a cyclic structure containing a hetero atom and one ethylenically unsaturated group It is.
The component (b) has a function of imparting adhesiveness, flexibility, and impact resistance.
Examples of the component (b) include acryloyl morpholine, vinyl imidazole, and vinyl pyridine.
Furthermore, compounds represented by the following formulas (1) to (2) can be given.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（式中、Ｒ2は水素原子またはメチル基を示し、Ｒ3は炭素数２～８、好ましくは２～５のアルキレン基を示し、Ｒ4は水素原子またはメチル基を示し、ｐは好ましくは１～４の数を示す。） (Wherein R 2 represents a hydrogen atom or a methyl group, R 3 represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms, R 4 represents a hydrogen atom or a methyl group, and p is preferably Shows the number from 1 to 4.)
　また、成分（ｂ）としては一般的に金属、エンジニアリングプラスチックス、セラミックス接着性に優れる点でＮ－ビニル基を有するモノマーが挙げられ、例えばＮ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－ビニルイミダゾール、Ｎ－ビニルカルバゾール等が挙げられる。その中でもＮ－ビニルカプロラクタムが接着性、特に金属接着性、減粘特性、安全性、耐衝撃性、柔軟性に優れる点で好ましい。
　このようなＮ－ビニル基を有するモノマーは、反応性希釈剤となると共に、適当量配合することにより、組成物の硬化速度向上をはかれる。 Further, as the component (b) typically metal, engineering plastics, monomers mentioned with the viewpoint of excellent ceramic adhesive N- vinyl group, such as N- vinylpyrrolidone, N- vinylcaprolactam, N- vinylimidazole , N-vinylcarbazole and the like. Among these, N-vinylcaprolactam is preferable in terms of excellent adhesion, particularly metal adhesion, viscosity-reducing properties, safety, impact resistance, and flexibility.
Such a monomer having an N-vinyl group serves as a reactive diluent and improves the curing rate of the composition by blending an appropriate amount.
（ｃ）変性剤
　本発明で用いられる成分（ｃ）は、変性剤である。
　成分（ｃ）は接着性、柔軟性を付与する機能を有する。
　（ｃ） 変性剤としては、例えば水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）；変性ゴム（ｃ－３）；およびエポキシ当量が５００～７００ｇ／モルであるポリオレフィン系重合体（ｃ－４）からなる群から選択された少なくとも１種が挙げられる。 (C) Denaturant Component (c) used in the present invention is a denaturant.
Component (c) has a function of imparting adhesiveness and flexibility.
(C) Examples of the modifier include a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g (c— 2); modified rubber (c-3); and at least one selected from the group consisting of polyolefin polymer (c-4) having an epoxy equivalent of 500 to 700 g / mol.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）について説明する。 (I) The polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g will be described.
　成分（ｃ）の水酸基価は、基材（Ｂ）（軟質および硬質塩化ビニル樹脂；スチレン系樹脂；ポリカーボネート系樹脂；ガラス；アルミニウム；鋼板；ポリオレフィン系樹脂；極性基含有化合物で変性されたポリオレフィン樹脂又はオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂）からなる被着体に対する選択的接着力向上へ寄与する。 The hydroxyl value of component (c) is as follows: substrate (B) (soft and hard vinyl chloride resin; styrene resin; polycarbonate resin; glass; aluminum; steel plate; polyolefin resin; polyolefin resin modified with polar group-containing compound Or it contributes to the improvement of the selective adhesive force to the adherend consisting of copolymer of olefin and polar group-containing compound; magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin).
　また、（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）としては、芳香族系、脂肪族系、ポリブタジエン系、ヒマシ油系、ポリイソプレン系等が挙げられるが水酸基価が上記範囲であればいずれのタイプであっても基材（Ｂ）からなる被着体に対する選択的接着力は良好である。
　（ｉ）水酸基価は４０～３３０ｍｇＫＯＨ／ｇであるのが上記選択的接着力の点で好ましく、１５０～３００ｍｇＫＯＨ／ｇであるのがさらに好ましい。 The (i) polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g includes aromatic, aliphatic, polybutadiene, castor oil, polyisoprene, and the like. As long as it is any type, the selective adhesive force to the adherend comprising the base material (B) is good.
(I) The hydroxyl value is preferably 40 to 330 mgKOH / g from the viewpoint of the selective adhesive strength, and more preferably 150 to 300 mgKOH / g.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）として、基材（Ｂ）からなる被着体に対する選択的接着力の点でさらに好ましくは、
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリブタジエン系ポリオール（ｃ－１－２）
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリイソプレン系ポリオールまたはその水素添加物（ｃ－１－３）
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）
が挙げられる。 (I) As a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g, it is more preferable in terms of selective adhesive strength to an adherend comprising the substrate (B),
(I) Castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g
(I) Polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g
(I) Polyisoprene polyol having a hydroxyl value of 40 to 330 mgKOH / g or a hydrogenated product thereof (c-1-3)
(I) Epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g
Is mentioned.
　本発明においては、成分（ｃ）のポリオールは必要に応じて２種類以上を混合して用いることができる。 In the present invention, the polyol of component (c) can be used as a mixture of two or more if necessary.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）について説明する。 (I) A castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g will be described.
　前記「ヒマシ油」は、リシノレイン酸とグリセリンとのトリエステル化合物を含む油脂である。通常、天然油脂または天然油脂加工物であるが、上記化合物を含めば合成油脂であってもよい。このヒマシ油に含まれるトリエステル化合物を構成するリシノレイン酸は、トリエステル化合物全体を構成する脂肪酸のうちの９０モル％以上含有されることが好ましい。また、このヒマシ油は、水素添加物（通常、リシノレイン酸骨格中の炭素間不飽和結合に対する水添）等の加工品であってもよい。通常、ヒマシ油には、上記トリエステル化合物（水添物である場合には、上記トリエステル化合物の水添物）が、油脂全体の９０モル％以上（１００モル％を含む）含有される。 The “castor oil” is an oil containing a triester compound of ricinoleic acid and glycerin. Usually, it is a natural fat or oil or a processed natural fat or oil, but it may be a synthetic fat or oil if it contains the above compounds. The ricinoleic acid constituting the triester compound contained in this castor oil is preferably contained in an amount of 90 mol% or more of the fatty acids constituting the whole triester compound. Further, the castor oil may be a processed product such as a hydrogenated product (usually hydrogenated to an intercarbon unsaturated bond in the ricinoleic acid skeleton). Usually, castor oil contains 90 mol% or more (including 100 mol%) of the above-described triester compound (in the case of a hydrogenated product, a hydrogenated product of the triester compound).
　前記「ヒマシ油系ポリオール」は、リシノレイン酸および／または水添リシノレイン酸と多価アルコールとのエステル化合物である。この構成を有すればヒマシ油を出発原料して得られたポリオールであっても、ヒマシ油以外の原料を出発原料として得られたポリオールであってもよい。この多価アルコールは特に限定されない。 The “castor oil-based polyol” is an ester compound of ricinoleic acid and / or hydrogenated ricinoleic acid and a polyhydric alcohol. If it has this structure, it may be a polyol obtained by using castor oil as a starting material, or a polyol obtained by using a raw material other than castor oil as a starting material. This polyhydric alcohol is not particularly limited.
　ヒマシ油系ポリオールとしては、ヒマシ油より誘導されるポリオール、ヒマシ油を変性して得られるポリオールが挙げられる。 Castor oil-based polyols include polyols derived from castor oil and polyols obtained by modifying castor oil.
　ヒマシ油より誘導されるポリオールとは、このグリセリンエステルのリシノレイン酸の一部をオレイン酸に置換したもの、ヒマシ油を鹸化して得られるリシノレイン酸をトリメチロールプロパンその他の短分子ポリオールとエステル化したもの、これらとヒマシ油との混合物等、ヒマシ油由来の脂肪酸エステル系ポリオールである。 The polyol derived from castor oil is a glycerin ester in which part of the ricinoleic acid is replaced with oleic acid, and ricinoleic acid obtained by saponifying castor oil is esterified with trimethylolpropane or other short molecular polyols. These are fatty acid ester polyols derived from castor oil, such as a mixture of these and castor oil.
　ヒマシ油を変性して得られるポリオールとしては、例えば植物油変性ポリオール、芳香族骨格（例えばビスフェノールＡ等）を有する変性ポリオール等が挙げられる。植物油変性ポリオールは、グリセリンエステルのリシノレイン酸の一部を、他の植物より得られる脂肪酸、例えば大豆油、なたね油、オリーブ油等より得られるリノール酸、リノレン酸、オレイン酸等の高級脂肪酸に置換して得られるものである。 Examples of polyols obtained by modifying castor oil include vegetable oil-modified polyols and modified polyols having an aromatic skeleton (such as bisphenol A). A vegetable oil-modified polyol is obtained by replacing a part of glycerin ester ricinoleic acid with a fatty acid obtained from other plants, for example, higher fatty acids such as linoleic acid, linolenic acid, oleic acid obtained from soybean oil, rapeseed oil, olive oil, etc. It is obtained.
　ヒマシ油系ポリオールの中でも、本発明の効果の点から、前記成分（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）が好ましい。
　さらに、接着層の強靭性（耐衝撃性）、柔軟性、および基材（Ｂ）からなる被着体に対する接着性を向上させる点で（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇの芳香族系ヒマシ油系ポリオール（ｃ－１－１－１）が好ましい。より好ましくは、１５０～２４０ｍｇＫＯＨ／ｇである。 Among the castor oil-based polyols, castor oil-based polyol (c-1-1) having a component (i) hydroxyl value of 40 to 330 mgKOH / g is preferable from the viewpoint of the effect of the present invention.
Further, toughness (impact resistance) of the adhesive layer, the flexibility, and the substrate (B) consists in improving the adhesion to an adherend from (i) hydroxyl value 40 ~ 330 mg KOH / g aromatic castor of Oil-based polyol (c-1-1-1) is preferred. More preferably, it is 150 to 240 mg KOH / g.
　前記成分（ｃ－１－１－１）は、芳香族骨格（例えばビスフェノールＡ等）を有する、ヒマシ油から誘導された変性ポリオールである。当該成分（ｃ－１－１－１）は、市販されており、例えば「ＵＲＩＣ  ＡＣシリーズ」（伊藤製油（株））等が挙げられる。中でも、リシノレイン酸にポリアルキレングリコールとビスフェノールＡを付加させた付加物が、基材（Ｂ）からなる被着体に対する接着性が好ましく、例えば、次の式（３）で表すことができる。 The component (c-1-1-1) is a modified polyol derived from castor oil having an aromatic skeleton (for example, bisphenol A). The component (c-1-1-1) is commercially available, and examples thereof include “URIC AC series” (Ito Oil Co., Ltd.). Among them, an adduct obtained by adding polyalkylene glycol and bisphenol A to ricinoleic acid has preferable adhesion to an adherend composed of the base material (B), and can be represented by, for example, the following formula (3).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式（３）中、ｍは平均２～５の数を表し、ｎは平均２～５の数を表す。 In formula (3), m represents an average number of 2 to 5, and n represents an average number of 2 to 5.
　前記式（３）で表されるヒマシ油から誘導された変性ポリオールは、例えば商品名ＵＲＩＣ　ＡＣ―００５（水酸基価１９４～２１４ｍｇＫＯＨ／ｍｇ、粘度７００～１５００ｍＰａ・ｓ／２５℃）、ＡＣ－００６（水酸基価１６８～１８７ｍｇＫＯＨ／ｍｇ、粘度３０００～５０００ｍＰａ・ｓ／２５℃）、ＡＣ－００８（水酸基価１８０ｍｇＫＯＨ／ｍｇ、粘度１６００ｍＰａ・ｓ／２５℃）、ＡＣ－００９（水酸基価２２５ｍｇＫＯＨ／ｍｇ、粘度１５００ｍＰａ・ｓ／２５℃）として伊藤製油（株）から入手できる。 Modified polyols derived from castor oil represented by the formula (3) are, for example, trade names URIC AC-005 (hydroxyl value 194 to 214 mg KOH / mg, viscosity 700 to 1500 mPa · s / 25 ° C.), AC-006 ( Hydroxyl value 168 to 187 mgKOH / mg, viscosity 3000 to 5000 mPa · s / 25 ° C., AC-008 (hydroxyl value 180 mgKOH / mg, viscosity 1600 mPa · s / 25 ° C.), AC-009 (hydroxyl value 225 mgKOH / mg, viscosity 1500 mPa -It can obtain from Ito Oil Co., Ltd. as s / 25 degreeC.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリブタジエン系ポリオール（ｃ－１－２）について説明する。 (I) A polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g will be described.
　本発明で使用されるポリブタジエン系ポリオールとしては、例えば、１，２－ポリブタジエンポリオール、１，４－ポリブタジエンポリオール等のホモポリマー、ポリ（ペンタジエン・ブタジエン）ポリオール、ポリ（ブタジエン・スチレン）ポリオール、ポリ（ブタジエン・アクリロニトリル）ポリオール等のコポリマー、それらポリオールに水素を付加した水素添加ポリブタジエン系ポリオールが挙げられる。
　ポリブタジエン系ポリオールは市販されており、例えば、出光興産（株）製の「Ｐｏｌｙ ｂｄ Ｒ－１５ＨＴ（水酸基価１０２．７ｍｇＫＯＨ／ｍｇ、Ｍｗ１２００）」、「Ｐｏｌｙ ｂｄ Ｒ－４５ＨＴ（水酸基価４６．６ｍｇＫＯＨ／ｍｇ、Ｍｗ２８００）」等が挙げられる。
　また、本発明の効果の点から（ｃ－１－２）ポリブタジエン系ポリオールの水酸基価は４０～３３０ｍｇＫＯＨ／ｇであるのが好ましく、４０～１１０ｍｇＫＯＨ／ｇであるのがさらに好ましい。
　（ｃ－１－２）ポリブタジエン系ポリオールの質量平均分子量（ＧＰＣ法）は、５０～３０００であるのが好ましく、８００～１５００であるのがさらに好ましい。 Examples of the polybutadiene-based polyol used in the present invention include homopolymers such as 1,2-polybutadiene polyol and 1,4-polybutadiene polyol, poly (pentadiene / butadiene) polyol, poly (butadiene / styrene) polyol, poly ( Examples thereof include copolymers such as butadiene / acrylonitrile) polyols, and hydrogenated polybutadiene-based polyols obtained by adding hydrogen to these polyols.
Polybutadiene-based polyols are commercially available. For example, “Poly bd R-15HT (hydroxyl value 102.7 mgKOH / mg, Mw1200)” and “Poly bd R-45HT (hydroxyl value 46.6 mgKOH / manufactured by Idemitsu Kosan Co., Ltd.) are available. mg, Mw2800) "and the like.
In view of the effects of the present invention, the hydroxyl value of the (c-1-2) polybutadiene-based polyol is preferably 40 to 330 mgKOH / g, more preferably 40 to 110 mgKOH / g.
(C-1-2) The mass average molecular weight (GPC method) of the polybutadiene-based polyol is preferably 50 to 3000, and more preferably 800 to 1500.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリイソプレン系ポリオールまたはその水素添加物（ｃ－１－３）について説明する。 (I) A polyisoprene-based polyol having a hydroxyl value of 40 to 330 mgKOH / g or a hydrogenated product thereof (c-1-3) will be described.
　このような成分（ｃ－１－３）としては、例えば出光社のPoly ip（登録商標）（水酸基末端液状ポリイソプレン）が挙げられる。「Poly ip（登録商標）」（水酸基価４６．６ｍｇＫＯＨ／ｍｇ、Ｍｎ２５００）は、分子末端に反応性の高い水酸基を備えたポリイソプレンタイプの液状ポリマーである。
　水素添加物としては、出光社のエポール（登録商標）（水酸基末端液状ポリオレフィン）が挙げられる。「エポール（登録商標）」（水酸基価５０．５ｍｇＫＯＨ／ｍｇ、Ｍｎ２５００）は、「Poly ip（登録商標）」に水添して得られる液状のポリオレフィンである。分子内に二重結合はほとんど残っていない。 Examples of such component (c-1-3) include Polyip (registered trademark) (hydroxyl-terminated liquid polyisoprene) manufactured by Idemitsu. “Poly ip (registered trademark)” (hydroxyl value 46.6 mg KOH / mg, Mn 2500) is a polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end.
An example of the hydrogenated product is Epole (registered trademark) (hydroxyl-terminated liquid polyolefin) manufactured by Idemitsu. “Epol®” (hydroxyl value 50.5 mg KOH / mg, Mn 2500) is a liquid polyolefin obtained by hydrogenating “Poly ip®”. Almost no double bonds remain in the molecule.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４） (I) Epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g
　本発明において使用される（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）は、エポキシ樹脂に活性水素化合物を反応させて得られるものである。 (I) The epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g used in the present invention is obtained by reacting an epoxy resin with an active hydrogen compound.
　ここで使用されるエポキシ樹脂としては、例えば、ハイドロキノン、レゾルシン、ピロカテコール、フロログルシノール等の単核多価フェノール化合物のポリグリシジルエーテル化合物；ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、チオビスフェノール、スルホビスフェノール、オキシビスフェノール、フェノールノボラック、オルソクレゾールノボラック、エチルフェノールノボラック、ブチルフェノールノボラック、オクチルフェノールノボラック、レゾルシンノボラック、ビスフェノールＡノボラック、ビスフェノールＦノボラック、テルペンジフェノール等の多核多価フェノール化合物のポリグリジルエーテル化合物；上記単核多価フェノール化合物あるいは多核多価フェノール化合物のエチレンオキシドおよび／またはプロピレンオキシド付加物のポリグリシジルエーテル化合物；上記単核多価フェノール化合物の水添物のポリグリシジルエーテル化合物；エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサンジオール、ポリグリコール、チオジグリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ビスフェノールＡ－エチレンオキシド付加物等の多価アルコール類のポリグリシジルエーテル；マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、スベリン酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸、トリマー酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸、ピロメリット酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸等の脂肪族、芳香族または脂環族多塩基酸のグリシジルエステル類およびグリシジルメタクリレートの単独重合体または共重合体；Ｎ，Ｎ－ジグリシジルアニリン、ビス（４－（Ｎ－メチル－Ｎ－グリシジルアミノ）フェニル）メタン等のグリシジルアミノ基を有するエポキシ化合物；ビニルシクロヘキセンジエポキシド、ジシクロペンタンジエンジエポキサイド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－６－メチルシクロヘキシルメチル－６－メチルシクロヘキサンカルボキシレート、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート等の環状オレフィン化合物のエポキシ化物；エポキシ化ポリブタジエン、エポキシ化スチレン－ブタジエン共重合物等のエポキシ化共役ジエン重合体、トリグリシジルイソシアヌレート等の複素環化合物が挙げられる。また、これらのエポキシ樹脂は、末端イソシアネートのプレポリマーによって内部架橋されたものでもよい。 Examples of the epoxy resin used here include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis ( Orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4- Hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobis Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as enol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, bisphenol A novolak, bisphenol F novolak, terpene diphenol; Polyglycidyl ether compound of ethylene oxide and / or propylene oxide adduct of the above mononuclear polyhydric phenol compound or polynuclear polyhydric phenol compound; polyglycidyl ether compound of hydrogenated mononuclear polyhydric phenol compound; ethylene glycol, propylene glycol , Butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin Polyglycidyl ethers of polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, Aliphatic and aromatic such as sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Or homopolymers or copolymers of glycidyl esters of alicyclic polybasic acids and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, etc. Gurishijiruami An epoxy compound having a hydrogen group; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6- Epoxidized products of cyclic olefin compounds such as methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymer, Examples include heterocyclic compounds such as triglycidyl isocyanurate. In addition, these epoxy resins may be internally crosslinked by a prepolymer of terminal isocyanate.
　これらのエポキシ樹脂の中でも、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール（ビスフェノールＡＤ）、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）等のポリグリシジルエーテル化合物等のビスフェノール型エポキシ樹脂を使用すると、接着力等の優れた塗膜を形成し得るため好ましい。 Among these epoxy resins, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol (bisphenol AD), isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, When a bisphenol type epoxy resin such as a polyglycidyl ether compound such as 1,3-bis (4-hydroxycumylbenzene) or 1,4-bis (4-hydroxycumylbenzene) is used, a coating having excellent adhesion and the like can be obtained. preferred order to be able to form a film.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）は、上記エポキシ樹脂のエポキシ基と、カルボン酸化合物、ポリオール、アミノ化合物等の活性水素化合物とを反応して得られるものである。 (I) An epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is obtained by reacting an epoxy group of the epoxy resin with an active hydrogen compound such as a carboxylic acid compound, a polyol or an amino compound. It is what
　上記カルボン酸化合物としては、酢酸、プロピオン酸、２，２－ジメチロールプロピオン酸、１２－ヒドロキシステアリン酸、乳酸、酪酸、オクチル酸、リシノール酸、ラウリン酸、安息香酸、トルイル酸、桂皮酸、フェニル酢酸、シクロヘキサンカルボン酸等の脂肪族、芳香族または脂環式モノカルボン酸、マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、アジピン酸、ダイマー酸、フタル酸、イソフタル酸、テレフタル酸、ヘキサヒドロ酸、ヒドロキシポリカルボン酸等が挙げられる。 Examples of the carboxylic acid compound include acetic acid, propionic acid, 2,2-dimethylolpropionic acid, 12-hydroxystearic acid, lactic acid, butyric acid, octylic acid, ricinoleic acid, lauric acid, benzoic acid, toluic acid, cinnamic acid, phenyl Aliphatic, aromatic or cycloaliphatic monocarboxylic acids such as acetic acid and cyclohexanecarboxylic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, Examples include hexahydro acid and hydroxypolycarboxylic acid.
　上記ポリオールとしては、例えば、エチレングリコール、ジエチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、２－メチル－１，３－プロピレングリコール、２，２－ジメチル－１，３－プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、２，２，４－トリメチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、２－エチル－１，６－ヘキサンジオール、１，２－オクタンジオール、１，８－オクタンジオール、２－メチル－１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，１２－オクタデカンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の低分子ポリオールが挙げられる。 Examples of the polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, trimethylolpropane, pentaerythritol Like low molecular weight polyols is.
上記アミノ化合物としては、ジブチルアミン、ジオクチルアミン等のジアルキルアミン化合物；メチルエタノールアミン、ブチルエタノールアミン、ジエタノールアミン、ジイソプロパノールアミン、ジメチルアミノプロピルエタノールアミン等のアルカノールアミン化合物；モルホリン、ピペリジン、４－メチルピペラジン等の複素環式アミン化合物が挙げられる。 Examples of the amino compounds include dialkylamine compounds such as dibutylamine and dioctylamine; alkanolamine compounds such as methylethanolamine, butylethanolamine, diethanolamine, diisopropanolamine, and dimethylaminopropylethanolamine; morpholine, piperidine, 4-methylpiperazine And heterocyclic amine compounds such as
　上記活性水素化合物の中でも、ジエタノールアミン等のアルカノールアミン化合物が好ましい。 Among the above active hydrogen compounds, alkanolamine compounds such as diethanolamine are preferable.
　また、モノエタノールアミン、モノイソプロパノールアミン等の活性水素基を２個以上有する化合物で、エポキシ樹脂を鎖延長することもできる。 Also, the epoxy resin can be chain-extended with a compound having two or more active hydrogen groups such as monoethanolamine and monoisopropanolamine.
　上記エポキシ樹脂に上記活性水素化合物を反応させる際には、エポキシ樹脂に活性水素化合物を付加させる通常の方法を採用することができ、例えば、三級アミン化合物、ホスホニウム塩等の周知の触媒の存在下に、両者を６０～２００℃に加熱し、３～１０時間反応させる方法を用いることができる。 When the active hydrogen compound is reacted with the epoxy resin, a normal method of adding the active hydrogen compound to the epoxy resin can be employed. For example, the presence of a known catalyst such as a tertiary amine compound or a phosphonium salt. Below, a method in which both are heated to 60 to 200 ° C. and reacted for 3 to 10 hours can be used.
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）の好ましい水酸基価は本発明の効果の点から１００～１４０ｍｇＫＯＨ／ｇである。 (I) A preferable hydroxyl value of the epoxy polyol resin (c-1-4) having a hydroxyl value of 40 to 330 mgKOH / g is 100 to 140 mgKOH / g from the viewpoint of the effect of the present invention.
　上記（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇのエポキシポリオール樹脂（ｃ－１－４）の例としてはＤＩＣ株式会社製ＥＰＩＣＬＯＮ　Ｕ－１２５－６０ＢＴ（水酸基価１００～１４０ｍｇＫＯＨ／ｇ）が挙げられる。 Examples of the epoxy polyol resin (c-1-4) having (i) a hydroxyl value of 40 to 330 mgKOH / g include EPICLON U-125-60BT (hydroxyl value 100 to 140 mgKOH / g) manufactured by DIC Corporation.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）について説明する。 (I) A polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g will be described.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）としては、芳香族系、脂肪族系、あるいはヒマシ油系であっても(i)の水酸基価、(ii)の酸価を満たすことにより基材（Ｂ）からなる被着体に対する選択的接着力が向上する。
　（ｉ）の水酸基価は、２３０～３００ｍｇＫＯＨ／ｇであるのがさらに好ましい。
　(ii)の酸価は、４～１５ｍｇＫＯＨ／ｇであるのがさらに好ましい。 (I) a hydroxyl value 40 ~ 330 mg KOH / g, and as the polyol (ii) an acid value of 2 ~ 20mgKOH / g (c-2) is a by aromatic, aliphatic, or castor oil based Even when the hydroxyl value of (i) and the acid value of (ii) are satisfied, the selective adhesive force to the adherend comprising the substrate (B) is improved.
The hydroxyl value of (i) is more preferably 230 to 300 mgKOH / g.
The acid value of (ii) is more preferably 4 to 15 mg KOH / g.
　（ｉ）かつ(ii)を満たす場合は、
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）としては、
（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるヒマシ油系ポリオール（ｃ－２－１）
が例示される。 If (i) and (ii) are satisfied,
As the polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g,
(I) a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and (ii) an acid value of 2 to 20 mgKOH / g
Is exemplified.
　（ｉ）水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ(ii)酸価が２～２０ｍｇＫＯＨ／ｇであるヒマシ油系ポリオール（ｃ－２－１）は、ヒマシ油由来のポリオールであり、例えば、特開２００５－８９７１２号公報に開示されているように、リシノレイン酸から誘導されたヒマシ油系ポリオールと、全炭素数が１２以上の酸性リン酸エステル化合物と、必要に応じてテルペンフェノール類を含有するポリオール組成物も使用することができる。これらは例えば商品名ＵＲＩＣ　Ｈ－１２６２、Ｈ２１５１Ｕとして伊藤製油（株）から入手できる。 (I) A castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mg KOH / g and (ii) an acid value of 2 to 20 mg KOH / g is a polyol derived from castor oil. As disclosed in JP-A-2005-89712, it contains a castor oil-based polyol derived from ricinoleic acid, an acidic phosphate ester compound having a total carbon number of 12 or more, and, if necessary, terpene phenols Polyol compositions can also be used. These can be obtained from Ito Refinery under the trade names URIC H-1262 and H2151U, for example.
　上記伊藤製油　ＵＲＩＣ　Ｈ－１２６２は、ヒマシ油系ポリオールと全炭素数が１２以上の酸性リン酸エステル化合物を含むポリオール（粘度：３，５００～８，５００ｍＰａ・ｓ／２５℃、水酸基価：２４０～２９０（単位ｍｇＫＯＨ／ｇ）、酸価：４～１５（単位ｍｇＫＯＨ／ｇ））であり、基材（Ｂ）からなる被着体に対する接着性に優れ、特に金属接着性・耐加水分解性に優れる。
　また、上記伊藤製油　ＵＲＩＣ　Ｈ－２１５１Ｕは、ヒマシ油系ポリオールと全炭素数が１２以上の酸性リン酸エステル化合物とテルペンフェノール類を含有するポリオール　（粘度：３，５００～８，５００ｍＰａ・ｓ／２５℃、水酸基価：２４０～２９０（単位ｍｇＫＯＨ／ｇ）、酸価：４～１５（単位ｍｇＫＯＨ／ｇ））であり、基材（Ｂ）からなる被着体に対する接着性に優れ、特に金属接着性・耐加水分解性に優れる。 The Ito Oil URIC H-1262 is a polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more (viscosity: 3,500 to 8,500 mPa · s / 25 ° C., hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), excellent adhesion to the adherend comprising the base material (B), especially for metal adhesion and hydrolysis resistance Excellent.
The Ito Oil URIC H-2151U is a polyol containing a castor oil-based polyol, an acidic phosphate compound having 12 or more carbon atoms and terpene phenols (viscosity: 3,500 to 8,500 mPa · s / 25). ° C, hydroxyl value: 240 to 290 (unit mgKOH / g), acid value: 4 to 15 (unit mgKOH / g)), excellent adhesion to the adherend comprising the base material (B), particularly metal adhesion Excellent in resistance and hydrolysis resistance.
　変性ゴム（ｃ－３）について説明する。
本発明で使用される変性ゴム（ｃ－３）としては、（ｃ－３－１）液状のカルボキシル化ポリイソプレンおよび（ｃ－３－２）カルボキシル化ポリブタジエンが挙げられる。 The modified rubber (c-3) will be described.
Examples of the modified rubber (c-3) used in the present invention include (c-3-1) liquid carboxylated polyisoprene and (c-3-2) carboxylated polybutadiene.
（ｃ－３－１）カルボキシル化ポリイソプレン
本発明で使用されるカルボキシル化ポリイソプレン（ｃ－３－１）は、本発明の基材（Ｂ）からなる被着体との接着力を向上させる機能を果たす。
　成分（ｃ－３－１）としては、例えばマレイン化ポリイソプレンとしてクラレ社製のＬＩＲ－４２０が挙げられる。 (C-3-1) Carboxylated polyisoprene The carboxylated polyisoprene (c-3-1) used in the present invention improves the adhesive force with the adherend comprising the substrate (B) of the present invention. Fulfills the function.
Examples of the component (c-3-1) include LIR-420 manufactured by Kuraray as maleated polyisoprene.
（ｃ－３－２）カルボキシル化ポリブタジエン
　本発明で使用されるカルボキシル化ポリブタジエン（ｃ）は、基材（Ｂ）からなる被着体との接着力を向上させる機能を果たす。
　成分（ｃ－３－２）は、ポリブタジエンにおける主鎖のミクロ構造がビニル１，２－結合型、トランス１，４－結合型、シス１，４－結合型からなる、室温において透明な液状の重合体である。ここで、ビニル１，２－結合は３０質量％以下であることが好ましく、ビニル１，２－結合が３０質量％を超えては、得られる塗料の貯蔵安定性が悪化するため好ましくない。また、シス１，４－結合は、４０質量％以上であることが好ましく、シス１，４－結合が４０質量％未満では、得られる塗料の接着性が低下するため好ましくない。 (C-3-2) Carboxylated Polybutadiene The carboxylated polybutadiene (c) used in the present invention has a function of improving the adhesive force with the adherend comprising the substrate (B).
Component (c-3-2) is a liquid liquid which is transparent at room temperature, and has a main chain microstructure of polybutadiene consisting of vinyl 1,2-bond type, trans 1,4-bond type, cis 1,4-bond type. It is a polymer. Here, the vinyl 1,2-bond is preferably 30% by mass or less, and the vinyl 1,2-bond exceeding 30% by mass is not preferable because the storage stability of the resulting paint deteriorates. Further, the cis 1,4-bond is preferably 40% by mass or more, and if the cis 1,4-bond is less than 40% by mass, the adhesiveness of the resulting coating material is lowered, which is not preferable.
　カルボキシル化ポリブタジエン（ｃ－３－２）成分は、液状ポリブタジエンにカルボキシル基導入化合物を反応させて得られ、液状ポリブタジエンを構成する１，３－ブタジエンとカルボキシル基導入化合物との比率は、１，３－ブタジエン８０～９８質量％とカルボキシル基導入化合物２～２０質量％であることが好ましい。 The carboxylated polybutadiene (c-3-2) component is obtained by reacting liquid polybutadiene with a carboxyl group-introducing compound, and the ratio of 1,3-butadiene and carboxyl group-introducing compound constituting the liquid polybutadiene is 1,3. -80 to 98% by mass of butadiene and 2 to 20% by mass of the carboxyl group-introducing compound are preferable.
　反応に用いる液状ポリブタジエンは、数平均として分子量５００～１０，０００であることが好ましく、より好ましくは１，０００～７，０００であり、分子量分布は広いことが望ましい。また、液状ポリブタジエンは、ＤＩＮ５３２４１に準じ測定したヨウ素価、ヨウ素３０～５００ｇ／物質１００ｇを有することがより好ましい。さらに、液状ポリブタジエンは、シス－二重結合７０～９０％、トランス－二重結合１０～３０％およびビニル二重結合０～３％の分子構造を有するものであることが好ましい。 The liquid polybutadiene used in the reaction preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 7,000, and a wide molecular weight distribution. The liquid polybutadiene more preferably has an iodine value measured according to DIN 53241, iodine of 30 to 500 g / 100 g of substance. Furthermore, the liquid polybutadiene preferably has a molecular structure of 70 to 90% cis-double bonds, 10 to 30% trans-double bonds and 0 to 3% vinyl double bonds.
　カルボキシル基導入化合物としては、エチレン系不飽和ジカルボキシ化合物、例えば、エチレン系不飽和ジカルボン酸、その無水物またはモノエステルを使用することができる。具体的化合物としては、マレイン酸、フマル酸、イタコン酸、３，６－テトラヒドロフタル酸、無水イタコン酸、１，２－ジメチルマレイン酸無水物、マレイン酸モノメチルエステルまたはマレイン酸モノエチルエステル等をで挙げることができる。これらの中でも安全性、経済性および反応性の理由から、無水マレイン酸が好ましい。（マレイン化ポリブタジエンが好ましい。） As the carboxyl group-introducing compound, an ethylenically unsaturated dicarboxy compound such as an ethylenically unsaturated dicarboxylic acid, its anhydride or monoester can be used. Specific examples of the compound include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, monomethyl maleate or monoethyl maleate. Can be mentioned. Of these, maleic anhydride is preferred for reasons of safety, economy and reactivity. (Maleed polybutadiene is preferred.)
　ポリブタジエンと無水マレイン酸からなるポリブタジエン／無水マレイン酸－付加生成物の製造は公知の方法で行うことができる。 Production of a polybutadiene / maleic anhydride-addition product comprising polybutadiene and maleic anhydride can be carried out by a known method.
　また、マレイン化液状ポリブタジエンのＤＩＮ　ＩＳＯ　３６８２に準じた酸価は、５０～１２０（ｍｇＫＯＨ／ｇ）が好ましく、更に好ましくは７０～９０（ｍｇＫＯＨ／ｇ）である。酸価が５０（ｍｇＫＯＨ／ｇ）未満では、得られる塗料の接着性が低下し、１２０（ｍｇＫＯＨ／ｇ）を超えると、得られる塗料の粘度が高くなり作業性が低下する。 The acid value of maleated liquid polybutadiene according to DIN ISO 3682 is preferably 50 to 120 (mgKOH / g), more preferably 70 to 90 (mgKOH / g). When the acid value is less than 50 (mgKOH / g), the adhesiveness of the obtained paint is lowered, and when it exceeds 120 (mgKOH / g), the viscosity of the obtained paint is increased and workability is lowered.
　さらに、マレイン化液状ポリブタジエンのマレイン化率は粘度とのかねあいがあるが、６～２０％が好ましく、より好ましくは６～１５％、さらに好ましくは７～１０％である。 Furthermore, the maleation rate of the maleated liquid polybutadiene is related to the viscosity, but is preferably 6 to 20%, more preferably 6 to 15%, and still more preferably 7 to 10%.
　また、マレイン化液状ポリブタジエンのＤＩＮ５３２１４にて測定した粘度（２０℃）は、３～１６Ｐａ・ｓが好ましく、より好ましくは５～１３Ｐａ・ｓであり、さらに好ましくは６～９Ｐａ・ｓである。 Further, the viscosity (20 ° C.) of maleated liquid polybutadiene measured by DIN 53214 is preferably 3 to 16 Pa · s, more preferably 5 to 13 Pa · s, and further preferably 6 to 9 Pa · s.
　さらに、マレイン化液状ポリブタジエンのビニル－二重結合は３０％以下であり、シス－二重結合が上記範囲にあるものはシス－二重結合が上記下限未満である液状ポリブタジエンに比べて高い柔軟性と上記のような高いマレイン化率（酸価）を持つ。そのため得られる塗料は接着性に富み、充分に極性が付与されているため本発明の塗料はより柔軟化が可能、柔軟性の調整が容易であり、かつ加飾性に優れる。
　シス－二重結合が上記下限未満である液状ポリブタジエンはマレイン化率上昇と共に急激に粘度が上昇するが、シス－二重結合が上記範囲にあるものは粘度上昇が少ない。粘度が上記範囲のように低いことから、反応性が高くなり作業性が向上する。また、得られる塗料は接着性の点で優れる。 In addition, maleated liquid polybutadiene has a vinyl-double bond of 30% or less, and those having a cis-double bond in the above range have higher flexibility than liquid polybutadiene in which the cis-double bond is less than the above lower limit. And has a high maleation rate (acid value) as described above. Therefore, the paint obtained is rich in adhesiveness, and since the polarity is sufficiently imparted, the paint of the present invention can be made more flexible, the flexibility can be easily adjusted, and the decoration is excellent.
Liquid polybutadiene having a cis-double bond less than the above lower limit rapidly increases in viscosity as the maleation rate increases, but those having a cis-double bond in the above range have a small increase in viscosity. Since the viscosity is low as in the above range, the reactivity is increased and workability is improved. Further, the obtained paint is excellent in terms of adhesiveness.
　マレイン化液状ポリブタジエンの市販品としては、例えば、デグサ社製　ＰＯＬＹＶＥＳＴ　ＯＣ　８００Ｓ（登録商標）、１２００Ｓが挙げられる。 Examples of commercially available maleated liquid polybutadiene include POLYVEST OC 800S (registered trademark) and 1200S manufactured by Degussa.
　エポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）について説明する。 The compound (c-4) having an epoxy equivalent of 150 to 700 g / mol will be described.
　本発明において使用されるエポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）の一つの形態は、エポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）である。 One form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol. .
　本発明の塗料における、エポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）としては、例えば、ハイドロキノン、レゾルシン、ピロカテコール、フロログルクシノールなどの単核多価フェノール化合物のポリグリシジルエーテル化合物；ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、チオビスフェノール、スルホビスフェノール、オキシビスフェノール、フェノールノボラック、オルソクレゾールノボラック、エチルフェノールノボラック、ブチルフェノールノボラック、オクチルフェノールノボラック、レゾルシンノボラック、テルペンフェノールなどの多核多価フェノール化合物のポリグリジルエーテル化合物；エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキサンジオール、ポリグリコール、チオジグリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、ビスフェノールＡ－エチレンオキシド付加物などの多価アルコール類のポリグリシジルエーテル；マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、スベリン酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸、トリマー酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸、ピロメリット酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸等の脂肪族、芳香族または脂環族多塩基酸のグリシジルエステル類およびグリシジルメタクリレートの単独重合体または共重合体；Ｎ，Ｎ－ジグリシジルアニリン、ビス（４－（Ｎ－メチル－Ｎ－グリシジルアミノ）フェニル）メタン、ジグリシジルオルトトルイジン等のグリシジルアミノ基を有するエポキシ化合物；ビニルシクロヘキセンジエポキシド、ジシクロペンタンジエンジエポキサイド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－６－メチルシクロヘキシルメチル－６－メチルシクロヘキサンカルボキシレート、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート等の環状オレフィン化合物のエポキシ化物；エポキシ化ポリブタジエン、エポキシ化スチレン－ブタジエン共重合物等のエポキシ化共役ジエン重合体、トリグリシジルイソシアヌレート等の複素環化合物などがあげられる。 Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol in the paint of the present invention include mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol. Polyglycidyl ether compounds: dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1, 3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2 Polyglycols of polynuclear polyhydric phenol compounds such as tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene phenol Zyl ether compounds; polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct Maleic acid, fumaric acid, itaconic acid, succinic acid, gluta Acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endo Homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as methylenetetrahydrophthalic acid and glycidyl methacrylate; N, N-diglycidylaniline, bis (4- (N-methyl) Epoxy compounds having a glycidylamino group such as —N-glycidylamino) phenyl) methane and diglycidylorthotoluidine; vinylcyclohexene diepoxide, dicyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Epoxidized products of cyclic olefin compounds such as carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; epoxidized polybutadiene, Examples thereof include epoxidized conjugated diene polymers such as epoxidized styrene-butadiene copolymer, and heterocyclic compounds such as triglycidyl isocyanurate.
　本発明で使用されるエポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）としては、例えば、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、チオビスフェノール、スルホビスフェノール、オキシビスフェノール、テルペンジフェノール等のビスフェノール化合物のポリグリジルエーテルが金属接着性の点でさらに好ましい。 Examples of the polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol used in the present invention include biphenol, methylene bisphenol (bisphenol F), methylene bis (orthocresol), ethylidene bisphenol, isopropyl Ridenbisphenol (bisphenol A), isopropylidenebis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1, Polyphenols of bisphenol compounds such as 1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, terpene diphenol Glycidyl Jill ether is more preferable in terms of the metal adhesion.
　エポキシ当量が１５０～２５０ｇ／モルであるビスフェノール化合物のポリグリジルエーテルの例としては、アデカレジンＥＰ－４１００Ｅ（旭電化工業  製；ビスフェノールＡジグリシジルエーテル、エポキシ当量１９０）が例示される。 Examples of polyglycidyl ethers of bisphenol compounds having an epoxy equivalent of 150 to 250 g / mol include Adeka Resin EP-4100E (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190).
　本発明において使用されるエポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）のもう一つの形態は、エポキシ当量が５００～７００ｇ／モルであるポリオレフィン系重合体（ｃ－４－２）である。好ましくは、片末端に水酸基を持ちかつエポキシ基を導入されたポリオレフィン系重合体である。さらに好ましくは液状である。 Another form of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol used in the present invention is a polyolefin polymer (c-4-2) having an epoxy equivalent of 500 to 700 g / mol. It is. A polyolefin polymer having a hydroxyl group at one end and having an epoxy group introduced is preferred. More preferably, it is liquid.
　エポキシ当量が１５０～７００ｇ／モルである重合体（ｃ－４）の具体的な例としてはクラレ社製Ｌ－２０７（ＫＲＡＴＯＮ　ＬＩＱＵＩＤ（商標）Ｌ－２０７ＰＯＬＹＭＥＲに同じ）である。Ｌ－２０７とは、エポキシ当量が５９０ｇ／モルであり、水酸基当量は７０００ｇ／モル、ガラス転移温度－５３℃である完全飽和骨格（エポキシ化エチレン・プロピレン－エチレン・ブチレン－ＯＨ構造）を持つ重合体であり、本発明に使用される理由として金属接着性の点で好ましい。 A specific example of the polymer (c-4) having an epoxy equivalent of 150 to 700 g / mol is Kuraray L-207 (same as KRATON LIQUID ™ L-207 POLYMER). L-207 has a fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure) having an epoxy equivalent of 590 g / mol, a hydroxyl equivalent of 7000 g / mol, and a glass transition temperature of −53 ° C. It is a coalescence and is preferable from the viewpoint of metal adhesion as a reason for use in the present invention.
（ｄ）紫外線反応開始剤
　本発明の塗料は、（ｄ）紫外線反応開始剤を必須成分とする。 (D) Ultraviolet reaction initiator The coating material of the present invention comprises (d) an ultraviolet reaction initiator as an essential component.
　本発明の塗料は、オリゴマー成分（例えばビニルエステル樹脂や不飽和ポリエステル樹脂（ａ））が、（メタ）アクリロイル基等の二重結合を有するため、光重合開始剤を添加すれば紫外線蛍光ランプあるいは高圧水銀灯等を用いた紫外線照射により容易に短時間で硬化させることが可能である。 In the paint of the present invention, the oligomer component (for example, vinyl ester resin or unsaturated polyester resin (a)) has a double bond such as a (meth) acryloyl group. Therefore, if a photopolymerization initiator is added, an ultraviolet fluorescent lamp or It can be easily cured in a short time by ultraviolet irradiation using a high-pressure mercury lamp or the like.
　光重合開始剤としては、例えば、ベンゾフェノン、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、アセトフェノン、ベンゾイン、ベンゾインエチルエーテル、ベンゾイン－ｎ－プロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン－ｎ－ブチルエーテル、ベンゾインイソブチルエーテル、ベンジル－１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、２－ヒドロキシ－２－メチル１－フェニルプロパン－１－オン、ベンジルサルファイド、チオキサントン、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、および２－クロロチキサント等が挙げられる。 Examples of the photopolymerization initiator include benzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin isopropyl ether, benzoin-n- Butyl ether, benzoin isobutyl ether, benzyl-1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl 1-phenylpropan-1-one, benzyl sulfide, thioxanthone Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-chlorothixant and the like.
（ｅ）ビニル基および／または（メタ）アクリロイル基を持つモノマー
　本発明の塗料の成分（ｅ）は、ビニル基および／または（メタ）アクリロイル基を持つモノマーである。
　成分（ｅ）ビニル基および／または（メタ）アクリロイル基を持つモノマーは、低粘度化、基材への接着性、顔料分散性の機能を有する。
　具体的例としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、ジプロピレングリコールジアクリレート（ＤＰＧＤＡ）、トリプロピレングリコールジアクリレート（ＴＰＧＤＡ）、ＰＯ変性ネオペンチルグリコールジアクリレート、変性ビスフェノールＡジアクリレート等を挙げる事ができる。 (E) Monomer having vinyl group and / or (meth) acryloyl group Component (e) of the coating material of the present invention is a monomer having a vinyl group and / or (meth) acryloyl group.
Component (e) A monomer having a vinyl group and / or a (meth) acryloyl group has functions of lowering viscosity, adhesion to a substrate, and pigment dispersibility.
Specific examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tricyclodecane dimethanol (Meth) acrylate, dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), PO-modified neopentyl glycol diacrylate, modified vinyl Phenol A diacrylate and the like can be mentioned.
　その他には、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、２－ヒドロキシブチル（メタ）アクリレート、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、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、アミル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ウンデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、エトキシエトキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリプロピレングリコール（メタ）アクリレート、ジシクロペンタジエン（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、ジアセトン（メタ）アクリルアミド、イソブトキシメチル（メタ）アクリルアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、ｔ－オクチル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、７－アミノ－３，７－ジメチルオクチル（メタ）アクリレート、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ′－ジメチルアミノプロピル（メタ）アクリルアミド、ビニルエーテル類である、トリエチレングリコールジビニルエーテル、ヒドロキシブチルビニルエーテル、ラウリルビニルエーテル、セチルビニルエーテル、２－エチルヘキシルビニルエーテルなどを挙げることができる。 Others include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) ) Acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isode (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, Phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (Meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentanyl ( Acrylate), dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N-vinyl Pyrrolidone, N-vinylcaprolactam, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (Meth) acrylate, N, N-diethyl (meth) acrylamide, N, N′-dimethylaminopropyl (meth) acrylamide, vinyl ethers such as triethylene glycol divinyl ether, Examples include droxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, and 2-ethylhexyl vinyl ether.
　中でも低粘度化の点で、成分（ｅ）の２５℃における粘度は、１１０ｍＰａ・ｓ以下が好ましく、５０ｍＰａ・ｓ以下がさらに好ましい。本発明で好ましい成分（ｅ）は、具体的にはトリメチロールプロパントリ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリエチレングリコールジビニルエーテル、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレートである。
　なお、上記粘度は、ＪＩＳ Ｋ７２３３に従い、２５℃ において計TVC-7形回転粘度計を用いて測定した。単位をｍＰａ・Ｓとした。 Among them, the viscosity at 25 ° C. of the component (e) is preferably 110 mPa · s or less, and more preferably 50 mPa · s or less in terms of lowering the viscosity. Specifically preferred components (e) in the present invention are trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol divinyl ether, dipropylene glycol diacrylate, tripropylene glycol Diacrylate.
The viscosity was measured according to JIS K7233 using a total TVC-7 rotational viscometer at 25 ° C. The unit was mPa · S.
　上記の市販品としては、
　SR238NS(サートマー社製)、 1,6ヘキサンジオールジアクリレート、25℃粘度=9ｍＰａ・ｓ、官能基数=2、速硬化性、低揮発性、4類3石、皮膚刺激性（PII）=4.1
　SR351NS(サートマー社製) 、トリメチロールプロパントリアクリレート、25℃粘度=106ｍＰａ・ｓ、官能基数=3、速硬化性、低揮発性、4類3石、皮膚刺激性（PII）=3.0
　DVE-3（BASF社製）、トリエチレングリコールジビニルエーテル、２５℃粘度＝２．６ｍＰａ・ｓ
　ジプロピレングリコールジアクリレート（ＢＡＳＦ社製）２５℃粘度＝１０ｍＰａ・ｓ
　トリプロピレングリコールジアクリレート（ＢＡＳＦ社製）２５℃粘度＝２０ｍＰａ・ｓ
が挙げられる。 As said commercial item,
SR238NS (manufactured by Sartomer Corp.), 1,6-hexanediol diacrylate, 25 ° C. Viscosity = 9 mPa · s, functionality = 2, fast curing, low volatility, 4 such 3 stone, skin irritation (PII) = 4.1
SR351NS (manufactured by Sartomer Co.), trimethylol propane triacrylate, 25 ° C. Viscosity = 106mPa · s, functionality = 3, fast curing, low volatility, 4 such 3 stone, skin irritation (PII) = 3.0
DVE-3 (manufactured by BASF), triethylene glycol divinyl ether, 25 ° C. viscosity = 2.6 mPa · s
Dipropylene glycol diacrylate (BASF) 25 ° C. viscosity = 10 mPa · s
Tripropylene glycol diacrylate (manufactured by BASF) 25 ° C. viscosity = 20 mPa · s
Is mentioned.
任意成分（ｆ）着色剤
　本発明の塗料をインクあるいはプライマーとして使用する場合には、（ｆ）着色剤を含有することが好ましい。
　本発明に用いることができる着色剤としては、特に制限はないが、耐候性に優れ、色再現性に富んだ顔料及び油溶性染料が好ましく、溶解性染料等の公知の着色剤から任意に選択して使用することができる。本発明の塗料をインクあるいはプライマーとして使用する場合に好適に使用し得る着色剤は、活性放射線による硬化反応の感度を低下させないという観点からは、硬化反応である重合反応において重合禁止剤として機能しない化合物を選択することが好ましい。 Optional Component (f) Colorant When the paint of the present invention is used as an ink or primer, it is preferable to contain (f) a colorant.
The colorant that can be used in the present invention is not particularly limited, but pigments and oil-soluble dyes that are excellent in weather resistance and excellent in color reproducibility are preferable, and are arbitrarily selected from known colorants such as soluble dyes. Can be used. The colorant that can be suitably used when the paint of the present invention is used as an ink or a primer does not function as a polymerization inhibitor in a polymerization reaction that is a curing reaction from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation. It is preferred to select a compound.
＜顔料＞
　本発明に使用できる顔料としては、特に限定されるわけではないが、例えばカラーインデックスに記載される下記の番号の有機又は無機顔料が使用できる。
　赤或いはマゼンタ顔料としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ  ３，５，１９，２２，３１，３８，４３，４８：１，４８：２，４８：３，４８：４，４８：５，４９：１，５３：１，５７：１，５７：２，５８：４，６３：１，８１，８１：１，８１：２，８１：３，８１：４，８８，１０４，１０８，１１２，１２２，１２３，１４４，１４６，１４９，１６６，１６８，１６９，１７０，１７７，１７８，１７９，１８４，１８５，２０８，２１６，２２６，２５７、Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　３，１９，２３，２９，３０，３７，５０，８８、Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　１３，１６，２０，３６、
　青又はシアン顔料としては、Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，１７－１，２２，２７，２８，２９，３６，６０、
　緑顔料としては、Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７，２６，３６，５０、
　黄顔料としては、Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１，３，１２，１３，１４，１７，３４，３５，３７，５５，７４，８１，８３，９３，９４，９５，９７，１０８，１０９，１１０，１３７，１３８，１３９，１５３，１５４，１５５，１５７，１６６，１６７，１６８，１８０，１８５，１９３、
　黒顔料としては、Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　７，２８，２６、
　白色顔料としては、ＰｉｇｍｅｎｔＷｈｉｔｅ　６，１８，２１
などが目的に応じて使用できる。 <Pigment>
Although it does not necessarily limit as a pigment which can be used for this invention, For example, the organic or inorganic pigment of the following number described in a color index can be used.
Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53: 1. 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144, 146 , 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13 , 16, 20, 36,
Pigment Blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,17-1,22,27,28,29,36,60 as blue or cyan pigments ,
As a green pigment, Pigment Green 7, 26, 36, 50,
As yellow pigments, Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138 , 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193,
As the black pigment, Pigment Black 7, 28, 26,
As a white pigment, Pigment White 6, 18, 21
Etc. can be used according to the purpose.
＜油溶性染料＞
　以下に、本発明で使用することのできる油溶性染料について説明する。
　本発明で使用することのできる油溶性染料とは、水に実質的に不溶な染料を意味する。具体的には、２５℃での水への溶解度（水１００ｇに溶解できる染料の質量）が１ｇ以下であり、好ましくは０．５ｇ以下、より好ましくは０．１ｇ以下であるものを指す。したがって、油溶性染料とは、所謂水に不溶性の顔料や油溶性色素を意味し、これらの中でも油溶性色素が好ましい。 <Oil-soluble dye>
Below, the oil-soluble dye which can be used by this invention is demonstrated.
The oil-soluble dye that can be used in the present invention means a dye that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the mass of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Therefore, the oil-soluble dye means a so-called water-insoluble pigment or oil-soluble dye, and among these, an oil-soluble dye is preferable.
　本発明に使用可能な前記油溶性染料のうち、イエロー染料としては、任意のものを使用することができる。例えばカップリング成分としてフェノール類、ナフトール類、アニリン類、ピラゾロン類、ピリドン類、開鎖型活性メチレン化合物類を有するアリールもしくはヘテリルアゾ染料；例えばカップリング成分として開鎖型活性メチレン化合物類を有するアゾメチン染料；例えばベンジリデン染料やモノメチンオキソノール染料等のようなメチン染料；例えばナフトキノン染料、アントラキノン染料等のようなキノン系染料；等が挙げられ、これ以外の染料種としてはキノフタロン染料、ニトロ・ニトロソ染料、アクリジン染料、アクリジノン染料等を挙げることができる。 Among the oil-soluble dyes that can be used in the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, azomethine dyes having open-chain active methylene compounds as coupling components; Examples include methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; and other dye species such as quinophthalone dyes, nitro / nitroso dyes, and acridines. And dyes and acridinone dyes.
　本発明に使用可能な前記油溶性染料のうち、マゼンタ染料としては、任意のものを使用することができる。例えばカップリング成分としてフェノール類、ナフトール類、アニリン類を有するアリールもしくはヘテリルアゾ染料；例えばカップリング成分としてピラゾロン類、ピラゾロトリアゾール類を有するアゾメチン染料；例えばアリーリデン染料、スチリル染料、メロシアニン染料、オキソノール染料のようなメチン染料；ジフェニルメタン染料、トリフェニルメタン染料、キサンテン染料のようなカルボニウム染料；例えばナフトキノン、アントラキノン、アントラピリドンなどのようなキノン系染料；例えばジオキサジン染料等のような縮合多環系染料；等を挙げることができる。 Of the oil-soluble dyes that can be used in the present invention, any magenta dye can be used. For example, aryl or heteroaryl azo dyes having phenols, naphthols, anilines as coupling components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; for example arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; condensed polycyclic dyes such as dioxazine dyes, etc. it can be mentioned.
　本発明に適用可能な前記油溶性染料のうち、シアン染料としては、任意のものを使用することができる。例えばインドアニリン染料、インドフェノール染料或いはカップリング成分としてピロロトリアゾール類を有するアゾメチン染料；シアニン染料、オキソノール染料、メロシアニン染料のようなポリメチン染料；ジフェニルメタン染料、トリフェニルメタン染料、キサンテン染料のようなカルボニウム染料；フタロシアニン染料；アントラキノン染料；例えばカップリング成分としてフェノール類、ナフトール類、アニリン類を有するアリールもしくはヘテリルアゾ染料；インジゴ・チオインジゴ染料；等を挙げることができる。 Of the oil-soluble dyes applicable to the present invention, any cyan dye can be used. For example, indoaniline dyes, indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes; anthraquinone dyes; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components; indigo / thioindigo dyes;
　前記の各染料は、クロモフォア（発色性の原子団）の一部が解離して初めてイエロー、マゼンタ、シアンの各色を呈するものであってもよく、その場合のカウンターカチオンはアルカリ金属や、アンモニウムのような無機のカチオンであってもよいし、ピリジニウム、４級アンモニウム塩のような有機のカチオンであってもよく、さらにはそれらを部分構造に有するポリマーカチオンであってもよい。 Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of chromophore (chromogenic atomic group) is dissociated. In this case, the counter cation may be an alkali metal or ammonium. Such inorganic cations may be used, and organic cations such as pyridinium and quaternary ammonium salts may be used, and furthermore, polymer cations having such a partial structure may be used.
　以下に限定されるものではないが、好ましい具体例としては、例えば、Ｃ．Ｉ．ソルベント・ブラック　３，７，２７，２９及び３４；Ｃ．Ｉ．ソルベント・イエロー　１４，１６，１９，２９，３０，５６，８２，９３及び１６２；Ｃ．Ｉ．ソルベント・レッド　１，３，８，１８，２４，２７，４３，４９，５１，７２，７３，１０９，１２２，１３２及び２１８；Ｃ．Ｉ．ソルベント・バイオレット　３；Ｃ．Ｉ．ソルベント・ブルー　２，１１，２５，３５，３８，６７及び７０；Ｃ．Ｉ．ソルベント・グリーン　３及び７；並びにＣ．Ｉ．ソルベント・オレンジ　２；等が挙げられる。
　これらの中で特に好ましいものは、Ｎｕｂｉａｎ　Ｂｌａｃｋ　ＰＣ－０８５０、Ｏｉｌ　Ｂｌａｃｋ　ＨＢＢ、Ｏｉｌ　Ｙｅｌｌｏｗ　１２９、Ｏｉｌ　Ｙｅｌｌｏｗ　１０５、Ｏｉｌ　Ｐｉｎｋ　３１２、Ｏｉｌ　Ｒｅｄ　５Ｂ、Ｏｉｌ　Ｓｃａｒｌｅｔ　３０８、Ｖａｌｉ　Ｆａｓｔ　Ｂｌｕｅ　２６０６、Ｏｉｌ　Ｂｌｕｅ　ＢＯＳ（オリエント化学（株）製）、Ａｉｚｅｎ　Ｓｐｉｌｏｎ　Ｂｌｕｅ　ＧＮＨ（保土ヶ谷化学（株）製）、ＮｅｏｐｅｎＹｅｌｌｏｗ　０７５、Ｎｅｏｐｅｎ　Ｍａｚｅｎｔａ　ＳＥ１３７８、Ｎｅｏｐｅｎ　Ｂｌｕｅ　８０８、Ｎｅｏｐｅｎ　Ｂｌｕｅ　ＦＦ４０１２、Ｎｅｏｐｅｎ　Ｃｙａｎ　ＦＦ４２３８（ＢＡＳＦ社製）等である。
　本発明においては、油溶性染料は１種単独で用いてもよく、また、数種類を混合して用いてもよい。 Although not limited to the following, preferred specific examples include C.I. I. Solvent Black 3, 7, 27, 29 and 34; C.I. I. Solvent Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162; C.I. I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218; I. Solvent Violet 3; C.I. I. Solvent Blue 2,11,25,35,38,67 and 70; I. Solvent Green 3 and 7; I. Solvent orange 2; and the like.
Particularly preferred among these are: Nubian Black PC-0850, Oil Black HBB, Oil Yellow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B, Oil Scallet 308, Vali Fast Blue Chemical 2606e Oil 2606e, (Manufactured by Co., Ltd.), Aizen Spiron Blue GNH (manufactured by Hodogaya Chemical Co., Ltd.), Neopen Yellow 075, Neopen Magenta SE1378, Neopen Blue 808, Neopen Blue FF4012, and Neo42 Cy FF4012.
In the present invention, the oil-soluble dye may be used alone or in combination of several kinds.
　また、着色剤として油溶性染料を使用する際、本発明の効果を阻害しない範囲で、必要に応じて、他の水溶性染料、分散染料、顔料等の着色剤を併用することもできる。
　本発明においては、水非混和性有機溶媒に溶解する範囲で分散染料を用いることもできる。分散染料は一般に水溶性の染料も包含するが、本発明においては水非混和性有機溶媒に溶解する範囲で用いることが好ましい。分散染料の好ましい具体例としては、Ｃ．Ｉ．ディスパースイエロー　５，４２，５４，６４，７９，８２，８３，９３，９９，１００，１１９，１２２，１２４，１２６，１６０，１８４：１，１８６，１９８，１９９，２０１，２０４，２２４及び２３７；Ｃ．Ｉ．ディスパーズオレンジ　１３，２９，３１：１，３３，４９，５４，５５，６６，７３，１１８，１１９及び１６３；Ｃ．Ｉ．ディスパーズレッド　５４，６０，７２，７３，８６，８８，９１，９２，９３，１１１，１２６，１２７，１３４，１３５，１４３，１４５，１５２，１５３，１５４，１５９，１６４，１６７：１，１７７，１８１，２０４，２０６，２０７，２２１，２３９，２４０，２５８，２７７，２７８，２８３，３１１，３２３，３４３，３４８，３５６及び３６２；Ｃ．Ｉ．ディスパーズバイオレット　３３；Ｃ．Ｉ．ディスパーズブルー　５６，６０，７３，８７，１１３，１２８，１４３，１４８，１５４，１５８，１６５，１６５：１，１６５：２，１７６，１８３，１８５，１９７，１９８，２０１，２１４，２２４，２２５，２５７，２６６，２６７，２８７，３５４，３５８，３６５及び３６８；並びにＣ．Ｉ．ディスパーズグリーン　６：１及び９；等が挙げられる。 Moreover, when using an oil-soluble dye as a colorant, other water-soluble dyes, disperse dyes, pigments, and other colorants can be used in combination as long as the effects of the present invention are not impaired.
In the present invention, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. The disperse dye generally includes a water-soluble dye, but in the present invention, the disperse dye is preferably used as long as it is soluble in a water-immiscible organic solvent. Preferable specific examples of the disperse dye include C.I. I. Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184: 1,186,198,199,201,204,224 and 237 C. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1,177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; I. Disperse Violet 33; C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 , 257, 266, 267, 287, 354, 358, 365 and 368; I. Disperse Green 6: 1 and 9;
　本発明に使用することができる着色剤は、本発明の塗料をインクあるいはプライマーとして使用する場合には、添加された後、適度に当該インク内で分散することが好ましい。着色剤の分散には、例えば、ボールミル、サンドミル、アトライター、ロールミル、アジテータ、ヘンシェルミキサ、コロイドミル、超音波ホモジナイザー、パールミル、湿式ジェットミル、ペイントシェーカー等の各分散装置を用いることができる。 When the colorant that can be used in the present invention is used as an ink or a primer, it is preferable that the colorant is appropriately dispersed in the ink after being added. For dispersing the colorant, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.
　これらの着色剤は使用目的に応じて、１種又は２種以上を適宜選択して用いればよい。 These colorants may be used by appropriately selecting one kind or two or more kinds according to the purpose of use.
　なお、本発明の塗料をインクあるいはプライマーとして使用する場合には、当該塗料中において固体のまま存在する顔料などの着色剤を使用する際には、着色剤粒子の平均粒径は、好ましくは０．００５～０．５μｍ、より好ましくは０．０１～０．４５μｍ、さらに好ましくは０．０１５～０．４μｍとなるよう、着色剤、分散剤、分散媒体の選定、分散条件、ろ過条件を設定することが好ましい。この粒径管理によって、ヘッドノズルの詰まりを抑制し、インクの保存安定性、インク透明性及び硬化感度を維持することができるので好ましい。
　本発明の塗料中における着色剤の含有量は色、及び使用目的により適宜選択されるが、一般的には、塗料全体の質量に対し、０．０１～３０質量％であることが好ましい。 When the paint of the present invention is used as an ink or a primer, the average particle diameter of the colorant particles is preferably 0 when using a colorant such as a pigment that remains solid in the paint. Selection of colorant, dispersant, dispersion medium, dispersion conditions, and filtration conditions are set to 0.005 to 0.5 μm, more preferably 0.01 to 0.45 μm, and even more preferably 0.015 to 0.4 μm. It is preferable to do. This particle size control is preferable because clogging of the head nozzle can be suppressed and ink storage stability, ink transparency, and curing sensitivity can be maintained.
The content of the colorant in the paint of the present invention is appropriately selected depending on the color and the purpose of use, but in general, it is preferably 0.01 to 30% by mass with respect to the mass of the whole paint.
（ｇ）分散剤
　本発明において、（ｆ）着色剤の分散を行う際に（ｇ）分散剤を添加することが好ましい。すなわち、本発明の塗料は、（ｆ）着色剤及び（ｇ）分散剤を含有することが好ましい。
　本発明において、前記（ｇ）分散剤は、酸性分散剤であることが好ましい。
　酸性分散剤とは酸性の官能基を有する分散剤である。
　酸性分散剤は、酸価が１０ｍｇＫＯＨ／ｇ以上であることが好ましく、２０ｍｇＫＯＨ／ｇ以上であることがより好ましく、４０ｍｇＫＯＨ／ｇ以上であることがさらに好ましい。また、酸性分散剤は、酸価がアミン価より大きいことが好ましい。
　ここで、アミン価とは、１、２、３級アミンの総量を示すもので、試料１ｇを中和するのに要する塩酸に当量のＫＯＨのｍｇ数で表わしたものである。また、酸価とは、試料１ｇ中に含有する遊離脂肪酸、樹脂酸などを中和するのに必要なＫＯＨのｍｇ数である。
　分散剤としては、酸性分散剤であれば、特に限定はされないが、高分子分散剤を使用することが好ましく、酸価がアミン価より大きい高分子分散剤を使用することがより好ましい。
　また、本発明において、分散剤の酸価とアミン価の差は５ｍｇＫＯＨ／ｇ以上であることが好ましく、１０ｍｇＫＯＨ／ｇ以上であることがより好ましく、２０ｍｇＫＯＨ／ｇ以上であることがさらに好ましい。 (G) Dispersant In the present invention, it is preferable to add (g) a dispersant when dispersing the colorant (f). That is, the paint of the present invention preferably contains (f) a colorant and (g) a dispersant.
In the present invention, the dispersant (g) is preferably an acidic dispersant.
An acidic dispersant is a dispersant having an acidic functional group.
The acidic dispersant preferably has an acid value of 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and further preferably 40 mgKOH / g or more. The acidic dispersant preferably has an acid value greater than the amine value.
Here, the amine value indicates the total amount of 1, 2, and tertiary amines, and is expressed in mg of KOH equivalent to hydrochloric acid required to neutralize 1 g of the sample. The acid value is the number of mg of KOH required to neutralize free fatty acid, resin acid, etc. contained in 1 g of a sample.
The dispersant is not particularly limited as long as it is an acidic dispersant. However, it is preferable to use a polymer dispersant, and it is more preferable to use a polymer dispersant having an acid value larger than the amine value.
In the present invention, the difference between the acid value and the amine value of the dispersant is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more.
　酸価がアミン価より大きい分散剤として、具体的には、ＤｉｓｐｅｒＢＹＫ－１０１（酸価：３０ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１０２（酸価：１０１ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１０３（酸価：１０１ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１０６（酸価：１３２ｍｇＫＯＨ／ｇ、アミン価：７４ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１１１（酸価：１２９ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）（以上、ＢＹＫケミー社製）、ＥＦＫＡ４０１０（酸価：１０～１５ｍｇＫＯＨ／ｇ、アミン価：４～８ｍｇＫＯＨ／ｇ）（以上、エフカアディティブ社製）等の高分子分散剤；ソルスパース３６０００（酸価：４５ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース４１０００（酸価：５０ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース３０００（酸価：３，０００ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース２１０００（酸価：７２ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース２６０００（酸価：５０ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース３６６００（酸価：２３ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース３９０００（酸価：３３ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース４１０９０（酸価：２３ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース４３０００（酸価：８ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース４４０００（酸価：１２ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース５３０９５（酸価：４７ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）、ソルスパース５４０００（酸価：４７ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）などの各種ソルスパース分散剤（以上、ゼネカ社製）が例示できる。 As a dispersant having an acid value larger than the amine value, specifically, DisperBYK-101 (acid value: 30 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-102 (acid value: 101 mgKOH / g, amine value: 0 mgKOH) / G), DisperBYK-103 (acid value: 101 mgKOH / g, amine value: 0 mgKOH / g), DisperBYK-106 (acid value: 132 mgKOH / g, amine value: 74 mgKOH / g), DisperBYK-111 (acid value: 129 mgKOH) / G, amine value: 0 mgKOH / g) (above, manufactured by BYK Chemie), EFKA4010 (acid value: 10-15 mgKOH / g, amine value: 4-8 mgKOH / g) (above, manufactured by Fuka Additive) Polymer dispersant; Solsperse 36000 (acid : 45 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 41000 (acid value: 50 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 3000 (acid value: 3,000 mgKOH / g, amine value: 0 mgKOH / g) Solsperse 21000 (acid value: 72 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 26000 (acid value: 50 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 36600 (acid value: 23 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 39000 (acid value: 33 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 41090 (acid value: 23 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 43000 (acid value: 8 mgKOH / g) , Min value: 0 mgKOH / g), Solsperse 44000 (acid value: 12 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 53095 (acid value: 47 mgKOH / g, amine value: 0 mgKOH / g), Solsperse 54000 (acid value: Examples include various Solsperse dispersants (manufactured by Zeneca) such as 47 mgKOH / g, amine value: 0 mgKOH / g).
　本発明において、（ｇ）分散剤は一種を単独で使用してもよいし、複数の種類を使用することもできる。
　また、その他の公知の分散剤を併用することもできる。具体的には、ＤｉｓｐｅｒＢＹＫ－１６１（アミン価：１１ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１６２（アミン価：１３ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１６３（アミン価：１０ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１６４（アミン価：１８ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１６６（アミン価：２０ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１６７（アミン価：１３ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１６８（アミン価：１０ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＤｉｓｐｅｒＢＹＫ－１８２（アミン価：１３ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）（以上、ＢＹＫケミー社製）、ＥＦＫＡ４０４６（アミン価：１７～２１ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＥＦＫＡ４０６０（アミン価：６～１０ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＥＦＫＡ４０８０（アミン価：３．６～４．１ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＥＦＫＡ４８００（アミン価：３７～４３ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）、ＥＦＫＡ７４６２（アミン価：８ｍｇＫＯＨ／ｇ、酸価：０ｍｇＫＯＨ／ｇ）（以上、エフカアディティブ社製）、ソルスパース１３２４０（塩基性分散剤）、ソルスパース１３９４０（塩基性分散剤）、ソルスパース２４０００（アミン価：４７ｍｇＫＯＨ／ｇ、酸価：２４ｍｇＫＯＨ／ｇ）、ソルスパース２８０００（塩基性分散剤）、ソルスパース３２０００（アミン価：１８０ｍｇＫＯＨ／ｇ、酸価：１５ｍｇＫＯＨ／ｇ）などの各種ソルスパース分散剤（以上、ゼネカ社製）、ディスパロン  ＤＡ－２３４（アミン価：２０ｍｇＫＯＨ／ｇ、酸価：１６ｍｇＫＯＨ／ｇ）、ディスパロン　ＤＡ－３２５（アミン価：２０ｍｇＫＯＨ／ｇ、酸価：１４ｍｇＫＯＨ／ｇ）（以上、楠本化成社製）が挙げられる。 In the present invention, the dispersing agent (g) may be used alone or in combination.
In addition, other known dispersants can be used in combination. Specifically, DisperBYK-161 (amine value: 11 mgKOH / g, acid value: 0 mgKOH / g), DisperBYK-162 (amine value: 13 mgKOH / g, acid value: 0 mgKOH / g), DisperBYK-163 (amine value: 10 mgKOH / g, acid value: 0 mgKOH / g), DisperBYK-164 (amine value: 18 mgKOH / g, acid value: 0 mgKOH / g), DisperBYK-166 (amine value: 20 mgKOH / g, acid value: 0 mgKOH / g), DisperBYK-167 (amine value: 13 mgKOH / g, acid value: 0 mgKOH / g), DisperBYK-168 (amine value: 10 mgKOH / g, acid value: 0 mgKOH / g), DisperBYK-182 (amine value: 13 mgKOH / g, acid) Price: 0 gKOH / g) (above, manufactured by BYK Chemie), EFKA4046 (amine value: 17 to 21 mgKOH / g, acid value: 0 mgKOH / g), EFKA4060 (amine value: 6 to 10 mgKOH / g, acid value: 0 mgKOH / g) , EFKA4080 (amine value: 3.6 to 4.1 mgKOH / g, acid value: 0 mgKOH / g), EFKA4800 (amine value: 37-43 mgKOH / g, acid value: 0 mgKOH / g), EFKA7462 (amine value: 8 mgKOH / g) g, acid value: 0 mgKOH / g) (manufactured by Fuka Additive Co., Ltd.), Solsperse 13240 (basic dispersant), Solsperse 13940 (basic dispersant), Solsperse 24000 (amine number: 47 mgKOH / g, acid value: 24 mg KOH / g), Solsperse 28000 (basic dispersion) ), Solsperse 32000 (amine value: 180 mgKOH / g, acid value: 15 mgKOH / g) and other Solsperse dispersants (manufactured by Zeneca), Disparon DA-234 (amine value: 20 mgKOH / g, acid value: 16 mgKOH / g), Disparon DA-325 (amine value: 20 mgKOH / g, acid value: 14 mgKOH / g) (supplied by Enomoto Kasei Co., Ltd.).
　本発明の塗料中における分散剤の含有量は使用目的により適宜選択されるが、着色剤の質量に対し、０．０１～５０質量％であることが好ましく、０．１～３０質量％であることがより好ましく、１～１０質量％であることがさらに好ましい。
　分散剤の添加量が０．０１質量％以上であると、顔料の分散性に優れ、分散安定性が良好であるので好ましい。また分散剤の添加量が５０質量％以下であると、インクの経時安定性が良好であるので好ましい。 The content of the dispersant in the paint of the present invention is appropriately selected depending on the purpose of use, but is preferably 0.01 to 50% by mass, and preferably 0.1 to 30% by mass with respect to the mass of the colorant. More preferred is 1 to 10% by mass.
It is preferable that the added amount of the dispersant is 0.01% by mass or more because the dispersibility of the pigment is excellent and the dispersion stability is good. Further, it is preferable that the amount of the dispersant added is 50% by mass or less because the stability with time of the ink is good.
（塗料の配合割合）
　本発明の塗料において、成分（ａ）は、接着性、柔軟性、耐衝撃性の観点から、１０～４０質量％配合される。さらに好ましい成分（ａ）の配合割合は、加工しやすい粘度の点で１５～３５質量％である。
　成分（ａ）の配合量が４０質量％を超えると接着性が悪化し、また増粘により加工性が低下する。また、１０質量％未満では基材（Ｂ）からなる被着体に対する接着性、柔軟性、耐衝撃性が低下する。 (Coating ratio of paint)
In the paint of the present invention, the component (a) is blended in an amount of 10 to 40% by mass from the viewpoints of adhesion, flexibility and impact resistance. A more preferable blending ratio of the component (a) is 15 to 35% by mass in terms of a viscosity that is easy to process.
When the compounding amount of component (a) exceeds 40% by mass, the adhesiveness deteriorates, and the processability decreases due to the increase in viscosity. Moreover, if it is less than 10 mass%, the adhesiveness with respect to the to-be-adhered body which consists of a base material (B), a softness | flexibility, and impact resistance will fall.
　本発明の塗料において、成分（ｂ）は、接着性、柔軟性、耐衝撃性の観点から、３０～７０質量％配合される。さらに好ましい成分（ｂ）の配合量は、加工しやすい粘度の点で４０～６５質量％である。
　成分（ｂ）の配合量が７０質量％を超えると接着性、柔軟性、耐衝撃性が低下する。また、３０質量％未満では接着性、柔軟性、耐衝撃性が悪化し、また増粘により加工性が低下する。 In the paint of the present invention, the component (b) is blended in an amount of 30 to 70% by mass from the viewpoints of adhesion, flexibility and impact resistance. A more preferable amount of component (b) is 40 to 65% by mass from the viewpoint of easy processing viscosity.
If the blending amount of component (b) exceeds 70% by mass, adhesiveness, flexibility and impact resistance are lowered. Moreover, if it is less than 30 mass%, adhesiveness, a softness | flexibility, and impact resistance will deteriorate, and workability will fall by thickening.
　本発明の塗料において、成分（ｃ）は、接着性、柔軟性の観点から、５～４０質量％配合される。さらに好ましい成分（ｃ）の配合割合は、接着性、強靭性（耐衝撃性）、耐ブリード性の点で１０～３０質量％であり、とくに好ましくは１０～２５質量％である。
　成分（ｃ）の配合量が４０質量％を超えると耐ブリード性の悪化により強靭性（耐衝撃性）が低下し、接着力、耐衝撃性、柔軟性も低下する。また、５質量％未満では接着性、柔軟性、耐衝撃性が低下する。 In the paint of the present invention, the component (c) is blended in an amount of 5 to 40% by mass from the viewpoints of adhesiveness and flexibility. Further, the blending ratio of the component (c) is 10 to 30% by mass, particularly preferably 10 to 25% by mass in terms of adhesion, toughness (impact resistance) and bleed resistance.
When the compounding amount of the component (c) exceeds 40% by mass, the toughness (impact resistance) is lowered due to deterioration of the bleed resistance, and the adhesive strength, impact resistance and flexibility are also lowered. On the other hand, if it is less than 5% by mass, adhesiveness, flexibility and impact resistance are lowered.
　本発明の塗料において、成分（ｄ）は、実用的な光硬化時間（照射強さ５００ｍJ ／ｃｍ2で１０秒以下照射）の観点から、前記成分（ａ）～（ｃ）の合計１００質量部に対し０．１～１５質量部配合される。さらに好ましい成分（ｄ）の配合量は、さらに実用的な光硬化時間（照射強さ５００ｍJ ／ｃｍ2で３秒以下照射）の点で１～１０質量部であり、とくに好ましくは２～５質量部である。
　成分（ｄ）の配合量が１５質量部を超えると柔軟性、接着性、耐衝撃性が低下する。また、０．１質量部未満では光硬化が不十分であることから接着性に劣る。 In the paint of the present invention, the component (d) is a total of 100 parts by mass of the components (a) to (c) from the viewpoint of practical photocuring time (irradiation intensity of 500 mJ / cm 2 for 10 seconds or less). 0.1 to 15 parts by mass with respect to the amount. The amount of the component (d) is more preferably 1 to 10 parts by weight, particularly preferably 2 to 5 parts by weight in terms of practical photocuring time (irradiation intensity of 500 mJ / cm 2 for 3 seconds or less). Part.
When the compounding amount of the component (d) exceeds 15 parts by mass, flexibility, adhesiveness and impact resistance are lowered. Moreover, if it is less than 0.1 mass part, since photocuring is inadequate, it is inferior to adhesiveness.
　本発明の塗料において、成分（ｅ）は、低粘度、基材への接着性の観点から、前記成分（ａ）～（ｃ）の合計１００質量部に対し３～２０質量部配合される。さらに好ましい成分（ｅ）の配合量は、低粘度、基材への接着性、硬化速度の点で５～１５質量部である。
　成分（ｅ）の配合量が本発明で規定する上限を超えると、各基材との接着性に劣り、プライマーとしてのインクジェット用インクの密着性が悪く、耐衝撃性、柔軟性が悪化する。また、成分（ｅ）の配合量が本発明で規定する下限未満であると、粘度が高いためインクジェット記録装置による塗装に適さず、インクの発色性が悪化する。 In the coating composition of the present invention, the component (e) is blended in an amount of 3 to 20 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c) from the viewpoint of low viscosity and adhesion to the substrate. A more preferable amount of component (e) is 5 to 15 parts by mass in terms of low viscosity, adhesion to a substrate, and curing speed.
When the blending amount of the component (e) exceeds the upper limit specified in the present invention, the adhesion to each substrate is poor, the adhesion of the ink jet ink as a primer is poor, and the impact resistance and flexibility are deteriorated. Further, if the blending amount of the component (e) is less than the lower limit specified in the present invention, the viscosity is high, so that it is not suitable for coating with an ink jet recording apparatus, and the color developability of the ink deteriorates.
　また、本発明の塗料の２５℃における粘度は特に限定されないが、３，０００ｍＰａ・ｓ以下、より好ましくは１００～２，０００ｍＰａ・ｓであるのがよい。粘度がこの範囲であれば、インクジェット記録装置による印字性が極めて良好であり、かつ経時変化で分離しない安定な貯蔵安定性が得られ、気泡が発生しにくく、平滑な表面性を得ることができる。なお、粘度は、Ｂ型粘度計により測定できる。 The viscosity of the paint of the present invention at 25 ° C. is not particularly limited, but is preferably 3,000 mPa · s or less, more preferably 100 to 2,000 mPa · s. If the viscosity is within this range, the printability by the ink jet recording apparatus is extremely good, and stable storage stability that does not separate over time can be obtained, bubbles are not easily generated, and smooth surface properties can be obtained. . The viscosity can be measured with a B-type viscometer.
　本発明の塗料は、基材（Ｂ）、すなわち軟質および硬質塩化ビニル樹脂；スチレン系樹脂；ポリカーボネート系樹脂；ガラス；アルミニウム；鋼板；ポリオレフィン系樹脂（例えばポリエチレン、ポリプロピレン、ポリ環状オレフィン等）；極性基含有化合物で変性されたポリオレフィン樹脂またはオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂（例えばポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート等）；またはアクリル系樹脂（例えばＰＭＭＡ等）からなる被着体に対する接着性がとくに良好である。これらの被着体に対し良好な接着性を有する塗料は、従来技術には開示されていない。 The paint of the present invention comprises a base material (B), that is, a soft and hard vinyl chloride resin; a styrene resin; a polycarbonate resin; a glass; an aluminum; a steel plate; a polyolefin resin (for example, polyethylene, polypropylene, polycyclic olefin, etc.); A polyolefin resin modified with a group-containing compound or a copolymer of an olefin and a polar group-containing compound; magnesium; an acrylonitrile-butadiene-styrene copolymer; a polyester-based resin (for example, polyethylene terephthalate (PET), polybutylene terephthalate, etc.); Or the adhesiveness with respect to the adherend which consists of acrylic resins (for example, PMMA etc.) is especially favorable. A paint having good adhesion to these adherends is not disclosed in the prior art.
（本発明の塗料の調製方法）
　本発明の塗料の調製方法としては、例えば、攪拌機を備えた容器に、成分（ａ）、（ｂ）、（ｃ）および（ｅ）を添加し、常温で十分に攪拌する。粘度が高すぎる場合は１００℃以下で加温しながら攪拌しても差し支えない。１００℃を超えると成分（ｂ）の蒸気発生が顕著になり作業環境上好ましくない。その後、液温が常温になった時点で、成分（ｄ）を添加して、溶け残りがないように十分攪拌する。
　その他の成分を添加する場合は、最後に添加し、十分に攪拌する。
　攪拌して得られた接着剤組成物は、速やかに加工するか、冷暗所に保存する。 (Method for preparing the paint of the present invention)
As a method for preparing the coating material of the present invention, for example, components (a), (b), (c) and (e) are added to a container equipped with a stirrer and sufficiently stirred at room temperature. If the viscosity is too high, stirring may be performed while heating at 100 ° C. or lower. If it exceeds 100 ° C., the vapor generation of the component (b) becomes remarkable, which is not preferable in the working environment. Thereafter, when the liquid temperature reaches room temperature, the component (d) is added and sufficiently stirred so as not to remain undissolved.
When adding other components, add them at the end and stir well.
The adhesive composition obtained by stirring is quickly processed or stored in a cool and dark place.
（本発明の塗料を用いた塗装方法）
　本発明の塗料を用いた塗装方法としては、前記のようにして調製した本発明の塗料を、前記基材（Ｂ）からなる被着体上に塗布すればよい。塗工方法としては、、インクジェット記録装置を用いる方法、スピンコート法、（ドクター）ナイフコート法、マイクログラビヤコート法、ダイレクトグラビヤコート法、オフセットグラビヤ法、リバースグラビヤ法、リバースロールコート法、（マイヤー）バーコート法、ダイコート法、スプレーコート法、ディップコート法等の方法が好ましく適用できる。例えばスピンコート法の装置としてマニュアルスピナー（(株)エイブル製ASS-301型））が挙げられる。 (Coating method using the paint of the present invention)
As a coating method using the coating material of the present invention, the coating material of the present invention prepared as described above may be applied on the adherend comprising the substrate (B). As the coating method, a method using an ink jet recording apparatus, a spin coating method, a (doctor) knife coating method, a micro gravure coating method, a direct gravure coating method, an offset gravure method, a reverse gravure method, a reverse roll coating method, (Meyer ) Bar coating method, die coating method, spray coating method, dip coating method and the like can be preferably applied. For example, a manual spinner (ASS-301 type manufactured by Able Co., Ltd.) can be cited as an apparatus for spin coating.
　塗料の層（Ａ）（硬化塗膜）の厚みは、特に限定されないが２μｍ～５０μｍ、好ましくは５μｍ～３０μｍ、更に好ましくは８μｍ～２０μｍ程度である。 The thickness of the coating layer (A) (cured coating film) is not particularly limited, but is about 2 μm to 50 μm, preferably about 5 μm to 30 μm, and more preferably about 8 μm to 20 μm.
　本発明の塗料は、前記基材（Ｂ）からなる被着体に対する接着性に優れ、低粘度であり、画像の発色性、耐衝撃性および柔軟性に優れることから、インクジェット用インクに適している。
　インクジェット用インクの組成は、とくに制限されない。例えば、着色剤、分散剤、界面活性剤、増感剤、褪色防止剤、導電性塩類等のインクジェット用インクに通常用いられる公知の添加剤を添加することができる。例えば着色剤、分散剤については、前記で例示したとおりである。 The paint of the present invention is excellent in adhesiveness to the adherend comprising the base material (B), has low viscosity, and is excellent in color development, impact resistance and flexibility of an image. Yes.
The composition of the inkjet ink is not particularly limited. For example, known additives usually used in ink jet inks such as colorants, dispersants, surfactants, sensitizers, anti-fading agents, and conductive salts can be added. For example, the colorant and the dispersant are as described above.
　また本発明の塗料は、前記基材（Ｂ）からなる被着体に対する接着性に優れ、また、市販のインクジェット用インクに対する接着性にも優れていることから、インクジェット記録媒体上に設けられたインクジェット用インク用プライマーに適している。インクジェット用インク用プライマー層は、インクジェット記録装置により設けることができる。インクジェット用インク用プライマー層の厚さは、特に制限はないが、例えば20～150μｍであり、好ましくは10～40μｍであり、特に好ましくは15μｍ～35μｍである。 The paint of the present invention is provided on an ink jet recording medium because it has excellent adhesion to an adherend comprising the base material (B) and also has excellent adhesion to a commercially available inkjet ink. Suitable for ink-jet ink primer. The primer layer for inkjet ink can be provided by an inkjet recording apparatus. The thickness of the primer layer for inkjet ink is not particularly limited, but is, for example, 20 to 150 μm, preferably 10 to 40 μm, particularly preferably 15 μm to 35 μm.
　インクジェット記録装置としては、特に制限はなく、目的とする解像度を達成し得る公知のインクジェット記録装置を任意に選択して使用することができる。本発明のインクジェット用インクを硬化させて得られたものが本発明の印刷物である。本発明の印刷物は、画像の発色性に優れ、耐衝撃性および柔軟性も大幅に改善されていることから、画像の堅牢性に優れる。 There is no restriction | limiting in particular as an inkjet recording device, The well-known inkjet recording device which can achieve the target resolution can be selected arbitrarily and can be used. The printed matter of the present invention is obtained by curing the ink-jet ink of the present invention. The printed matter of the present invention is excellent in the color developability of the image, and is excellent in the fastness of the image because the impact resistance and the flexibility are greatly improved.
　以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されない。 Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the following examples.
　実施例および比較例で使用した原料は以下の通りである。
成分（ａ－１）ビニルエステル樹脂
（ｉ）ウレタンアクリレート
　サートマー社製　CN963B80 ウレタンアクリレート（HDDAブレンド）、タイプ=ポリエステル、60℃粘度=1,100、官能基数=2
（ｉｉ）ポリエステルアクリレート
　サートマー社製　CN292 ポリエステルアクリレート、タイプ=脂肪族ポリエステル、25℃粘度=630、官能基数=4
（ｉｉｉ）エポキシアクリレート
　サートマー社製　CNUVE151 エポキシアクリレート、タイプ=ポリエステル、25℃粘度=150,000、官能基数=2
（ｉｖ）脂肪族ウレタンアクリレート
　サートマー社製　CN966J75 脂肪族ウレタンアクリレート（IBOAブレンド）、タイプ=ポリエステル、60℃粘度=4,240、25℃粘度=105,000、官能基数=2
成分（ａ－２）不飽和ポリエステル樹脂
　昭和高分子社製、ＲＩＧＯＬＡＣ　２１Ｅ－Ａ－２（商標）
成分（ａ－３）ビニルエステル樹脂
　昭和高分子社製、ＲＩＰＯＸＹ　ＶＲ－７７（商標）
　粘度：１，０００（ｄＰａ・ｓ／２５℃）
　分子量：５１０ The raw materials used in the examples and comparative examples are as follows.
Component (a-1) Vinyl ester resin (i) Urethane acrylate Sartomer CN963B80 Urethane acrylate (HDDA blend), Type = Polyester, 60 ° C. viscosity = 1,100, Number of functional groups = 2
(Ii) Polyester acrylate CN292 polyester acrylate manufactured by Sartomer, type = aliphatic polyester, viscosity at 25 ° C. = 630, number of functional groups = 4
(Iii) Epoxy acrylate Sartomer CNUVE151 epoxy acrylate, type = polyester, viscosity at 25 ° C. = 150,000, number of functional groups = 2
(Iv) Aliphatic urethane acrylate manufactured by Sartomer CN966J75 Aliphatic urethane acrylate (IBOA blend), type = polyester, 60 ° C. viscosity = 4,240, 25 ° C. viscosity = 105,000, number of functional groups = 2
Component (a-2) Unsaturated polyester resin RIGOLAC 21E-A-2 (trademark) manufactured by Showa Polymer Co., Ltd.
Component (a-3) Vinyl ester resin, manufactured by Showa Polymer Co., Ltd., RIPOXY VR-77 (trademark)
Viscosity: 1,000 (dPa · s / 25 ° C)
Molecular weight: 510
成分（ｂ）　ヘテロ原子を含む環状構造および１個のエチレン性不飽和基を有する化合物
（ｉ）日本触媒社製、Ｎ－ビニルピロリドン
分子量：１１１.１４
沸点 219℃
蒸気圧(24℃) 0.10mm Hg
引火点 98℃
粘度(25℃)  2 cps
融点 13℃
（ｉｉ）ＢＡＳＦ社製、Ｎ－ビニルカプロラクタム
沸点 117℃(10mm Hg)
蒸気圧 <0.1 mm Hg (20℃)
引火点 110℃
融点 35℃
粘度 3.5 cps (40℃) Component (b) Compound having a cyclic structure containing a heteroatom and one ethylenically unsaturated group (i) Nippon Shokubai Co., Ltd., N-vinylpyrrolidone Molecular weight: 111.14
Boiling point 219 ° C
Vapor pressure (24 ℃) 0.10mm Hg
Flash point 98 ° C
Viscosity (25 ° C) 2 cps
Melting point 13 ° C
(Ii) NSF-caprolactam boiling point 117 ° C (10mm Hg) manufactured by BASF
Vapor pressure <0.1 mm Hg (20 ℃)
Flash point 110 ° C
Melting point 35 ℃
Viscosity 3.5 cps (40 ° C)
成分（ｃ）　変性剤
（ｃ－１－２）ポリブタジエン系ポリオール
出光興産社製、Ｐｏｌｙ　ｂｄ　Ｒ-１５ＨＴ
粘度：１．５Ｐａ・ｓ／３０℃、水酸基価：１０２．７ｍｇＫＯＨ／ｇ
（ｃ－１－１－１）芳香族系ヒマシ油系ポリオール
伊藤製油社製、ＵＲＩＣ（商標）ＡＣ－００６、前記式（４）で表されるヒマシ油由来のポリオール、粘度：０．７～１．５Ｐａ・ｓ／２５℃、水酸基価：１９４～２１４ｍｇＫＯＨ／ｇ
（ｃ－１－３）ポリイソプレン系ポリオール
出光興産社製、Poly ip（登録商標）分子末端に反応性の高い水酸基を備えたポリイソプレンタイプの液状ポリマー（水酸基価４６．６ｍｇＫＯＨ／ｍｇ、数平均分子量Ｍｎ＝２５００）
（ｃ－２－１）ヒマシ油系ポリオール
伊藤製油　ＵＲＩＣ　Ｈ－１２６２
ヒマシ油系ポリオールと全炭素数が１２以上の酸性リン酸エステル化合物を含むポリオール　粘度：３，５００～８，５００Ｐａ・ｓ／２５℃、酸価：４～１５（単位ｍｇＫＯＨ／ｇ）、水酸基価：２４０～２９０（単位ｍｇＫＯＨ／ｇ）
（ｃ－２－１）ヒマシ油系ポリオール
伊藤製油　ＵＲＩＣ　Ｈ－２１５１Ｕ
ヒマシ油系ポリオールと全炭素数が１２以上の酸性リン酸エステル化合物とテルペンフェノール類を含有するポリオール　粘度：３，５００～８，５００Ｐａ・ｓ／２５℃、酸価：４～１５（単位ｍｇＫＯＨ／ｇ）、水酸基価：２４０～２９０（単位ｍｇＫＯＨ／ｇ）
（ｃ－１－３）ポリイソプレン系ポリオールの水素添加物
出光興産社製　エポール（商標）水酸基末端液状ポリオレフィン
（粘度（Pa・s/30℃）75、水酸基価(mgKOH/g) 50.5、数平均分子量2500）
（ｃ－３－１）マレイン化ポリイソプレン
株式会社 クラレ　LIR-420  （酸価(mgKOH/g) 40）
（ｃ－３－２）マレイン酸変性ポリブタジエン
SARTOMER社製　Ricon130MA8  （粘度（Pa・s/30℃）6.5、酸価(mgKOH/g) 46、数平均分子量2700）
（ｃ－３－２）マレイン酸変性ポリブタジエン
EVONIK社製　POLYVEST（商標） OC 800 S  （ポリブタジエンにおける１，４－シス二重結合：７５％、１，４－トランス二重結合：２４％、ビニル結合：１％、マレイン化率：７．５％、数平均分子量：３３００（ＧＰＣ）、質量平均分子量：１３，６００（ＧＰＣ）、粘度（２０℃）：６～９Ｐａ・ｓ（ＤＩＮ５３２１４にて測定）、酸価：７０～９０ｍｇＫＯＨ／ｇ、ヨウ素価：３８０～４２０ｇ／１００ｇ、（チグラー－ナッタ触媒で重合））
（ｃ－１－４）エポキシポリオール樹脂
DIC株式会社　EPICLON（商標）U-125-60BT
（粘度（Pa・s/30℃）70、水酸基価(mgKOH/g) 120）
（ｃ－４－１）エポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物
アデカレジンＥＰ－４１００Ｅ（旭電化工業  製；ビスフェノールＡジグリシジルエーテル、エポキシ当量１９０）
（ｃ－４－２）エポキシ当量が５００～７００ｇ／モルである飽和骨格を持つ重合体
クラレ社製Ｌ－２０７（ＫＲＡＴＯＮ　ＬＩＱＵＩＤ（商標）Ｌ－２０７ＰＯＬＹＭＥＲに同じ）　（エポキシ当量が５９０ｇ／モルで、水酸基当量は７０００ｇ／モル、ガラス転移温度－５３℃、完全飽和骨格（エポキシ化エチレン・プロピレン－エチレン・ブチレン－ＯＨ構造）を持つ重合体） Component (c) Modifier (c-1-2) Polybutadiene polyol manufactured by Idemitsu Kosan Co., Ltd., Poly bd R-15HT
Viscosity: 1.5 Pa · s / 30 ° C., hydroxyl value: 102.7 mg KOH / g
(C-1-1-1) Aromatic castor oil-based polyol manufactured by Ito Oil Co., Ltd., URIC (trademark) AC-006, a polyol derived from castor oil represented by the above formula (4), viscosity: 0.7 to 1.5 Pa · s / 25 ° C., hydroxyl value: 194 to 214 mg KOH / g
(C-1-3) Polyisoprene-based polyol manufactured by Idemitsu Kosan Co., Ltd. Polyisoprene type liquid polymer having a highly reactive hydroxyl group at the molecular end (hydroxyl value 46.6 mgKOH / mg, number average) Molecular weight Mn = 2500)
(C-2-1) Castor oil-based polyol Ito Oil URIC H-1262
Polyol containing a castor oil-based polyol and an acidic phosphate ester compound having a total carbon number of 12 or more Viscosity: 3,500 to 8,500 Pa · s / 25 ° C., acid value: 4 to 15 (unit mgKOH / g), hydroxyl value : 240-290 (unit mgKOH / g)
(C-2-1) Castor oil-based polyol Ito Oil URIC H-2151U
A polyol containing a castor oil-based polyol, an acidic phosphate ester compound having 12 or more carbon atoms and terpene phenols Viscosity: 3,500 to 8,500 Pa · s / 25 ° C., acid value: 4 to 15 (unit: mgKOH / g), hydroxyl value: 240 to 290 (unit: mgKOH / g)
(C-1-3) Hydrogenated polyisoprene polyol manufactured by Idemitsu Kosan Co., Ltd. Epol (trademark) hydroxyl terminated liquid polyolefin (viscosity (Pa · s / 30 ° C) 75, hydroxyl value (mgKOH / g) 50.5, number average Molecular weight 2500)
(C-3-1) Maleinized polyisoprene Kuraray LIR-420 (acid value (mgKOH / g) 40)
(C-3-2) Maleic acid-modified polybutadiene
SARTOMER Ricon130MA8 (viscosity (Pa · s / 30 ° C) 6.5, acid value (mgKOH / g) 46, number average molecular weight 2700)
(C-3-2) Maleic acid-modified polybutadiene
EVONIK Co. Polyvest (TM) OC 800 S (1,4-cis double bond in polybutadiene: 75%, 1,4-trans double bonds: 24%, vinyl bond: 1%, maleinized rate: 7.5 %, Number average molecular weight: 3300 (GPC), mass average molecular weight: 13,600 (GPC), viscosity (20 ° C.): 6 to 9 Pa · s (measured with DIN 53214), acid value: 70 to 90 mg KOH / g, iodine Value: 380 to 420 g / 100 g, (polymerized with Ziegler-Natta catalyst)
(C-1-4) Epoxy polyol resin
DIC Corporation EPICLON (trademark) U-125-60BT
(Viscosity (Pa · s / 30 ° C) 70, hydroxyl value (mgKOH / g) 120)
(C-4-1) Polyepoxy compound Adeka Resin EP-4100E having an epoxy equivalent of 150 to 250 g / mol (Asahi Denka Kogyo; bisphenol A diglycidyl ether, epoxy equivalent 190)
(C-4-2) Polymer having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol L-207 manufactured by Kuraray (same as KRATON LIQUID ™ L-207 POLYMER) (Epoxy equivalent is 590 g / mol, Hydroxyl equivalent weight is 7000 g / mol, glass transition temperature -53 ° C, polymer with fully saturated skeleton (epoxidized ethylene / propylene / ethylene / butylene-OH structure)
　各ポリオールの特性は、次のようにして測定した。
・粘度測定方法
　粘度計は、JIS K7117-1に従って、単一円筒型回転粘度計（B形TVC--5 ）を用いて測定。
　1.測定器に500mlビーカ（標準）を使用。
　2.標準ロータは、低・中粘度用としてのM1～M4ロータ、中・高粘度用としてのH1～H7ロータの2種から選択
・水酸基価測定方法
　水酸基価とは、試料1g中に含まれるOH基をアセチル化するために要する水酸化カリウムのmg数である。JIS K 1557-1に準じて、無水酢酸を用いて試料中のOH基をアセチル化し、使われなかった酢酸を水酸化カリウム溶液で滴定する。 The characteristics of each polyol were measured as follows.
-Viscosity measurement method The viscometer is measured using a single cylindrical rotational viscometer (B type TVC--5) according to JIS K7117-1.
1. A 500ml beaker (standard) is used for the measuring instrument.
2. The standard rotor is selected from two types: M1 to M4 rotors for low and medium viscosity and H1 to H7 rotors for medium and high viscosity. Hydroxyl value measurement method Hydroxyl value is included in 1g of sample. This is the number of mg of potassium hydroxide required to acetylate the OH group. According to JIS K 1557-1, OH groups in the sample are acetylated using acetic anhydride, and acetic acid not used is titrated with potassium hydroxide solution.
Figure JPOXMLDOC01-appb-M000003
Figure JPOXMLDOC01-appb-M000003
A：空試験に用いた0.5mol/l水酸化カリウムエタノール溶液の量(ml)
B：滴定に用いた0.5mol/l水酸化カリウムエタノール溶液の量(ml)
f：ファクター A: Amount of 0.5 mol / l potassium hydroxide ethanol solution used for the blank test (ml)
B: 0.5mol / l potassium hydroxide ethanol solution used for titration (ml)
f: Factor
・酸価測定方法
　試料油１ｇに含まれる酸性成分を中和するのに要する水酸化カリウムのｍｇ数で表す。JIS K 1557-5に準じて、
(1)終点pHの測定
　200mLビーカに緩衝貯蔵液Bを10mL採取し、滴定溶剤を100mL加えて電極を浸け、30秒間で0.1pH以内の変化となったpHを緩衝の終点とする。
(2）酸価の測定
　1.試料20gを200mLビーカに正確に秤量する。
　2.トルエン・2-プロパノール・純水混合溶剤125mLを加え、0.1mol/L水酸化カリウム滴定液で滴定する。
（1）の結果 11.72 pHを終点として設定し、次式で酸価を求める。また、同手順でブランクを求める。
酸価（mgKOH/g）＝（D－B）×K×F×M/S
　D：滴定値（mL）
　B：ブランク（0.085mL）
　K：KOHの分子量（56.1）
　F：滴定液のファクタ（1.000）
　M：滴定液のモル濃度（0.1mol/L）
　S：試料採取量（g） -Acid value measuring method It represents with the mg number of potassium hydroxide required to neutralize the acidic component contained in 1g of sample oils. According to JIS K 1557-5,
(1) End-point pH measurement Take 10 mL of buffer stock solution B in a 200-mL beaker, add 100 mL of titration solvent, immerse the electrode, and use the pH that changes within 0.1 pH within 30 seconds as the buffer end point.
(2) Measurement of acid value 1. Weigh accurately 20 g of sample into a 200 mL beaker.
2. Add 125mL of toluene / 2-propanol / pure water mixed solvent and titrate with 0.1mol / L potassium hydroxide titrant.
Result of (1) 11.72 Set pH as the end point and calculate the acid value by the following formula. Moreover, a blank is calculated | required in the same procedure.
Acid value (mgKOH / g) = (D−B) × K × F × M / S
D: Titration value (mL)
B: Blank (0.085mL)
K: Molecular weight of KOH (56.1)
F: Factor of titrant (1.000)
M: Molar concentration of titrant (0.1 mol / L)
S: Sampling amount (g)
成分（ｅ）成分　ビニル基および／または（メタ）アクリロイル基を持つモノマー
　（ｅ－１）SR238NS(サートマー社製)、 1,6ヘキサンジオールジアクリレート、25℃粘度=9ｍＰａ・ｓ、官能基数=2、速硬化性、低揮発性、4類3石、皮膚刺激性（PII）=4.1
　（ｅ－２）SR351NS(サートマー社製) 、トリメチロールプロパントリアクリレート、25℃粘度=106ｍＰａ・ｓ、官能基数=3、速硬化性、低揮発性、4類3石、皮膚刺激性（PII）=3.0
　（ｅ－３）DVE-3（BASF社製）、トリエチレングリコールジビニルエーテル、２５℃粘度＝２．６ｍＰａ・ｓ
　（ｅ－４）ジプロピレングリコールジアクリレート（ＢＡＳＦ社製）２５℃粘度＝１０ｍＰａ・ｓ
　（ｅ－５）トリプロピレングリコールジアクリレート（ＢＡＳＦ社製）２５℃粘度＝２０ｍＰａ・ｓ Component (e) component vinyl and / or (meth) monomers having an acryloyl group (e-1) SR238NS (manufactured by Sartomer Corp.), 1,6-hexanediol diacrylate, 25 ° C. Viscosity = 9 mPa · s, functionality = 2 , Fast curing, low volatility, 4 types 3 stones, skin irritation (PII) = 4.1
(E-2) SR351NS (manufactured by Sartomer), trimethylolpropane triacrylate, 25 ° C. viscosity = 106 mPa · s, functional group number = 3, fast-curing property, low volatility, Class 4 3 stone, skin irritation (PII) = 3.0
(E-3) DVE-3 (manufactured by BASF), triethylene glycol divinyl ether, 25 ° C. viscosity = 2.6 mPa · s
(E-4) Dipropylene glycol diacrylate (BASF) 25 ° C. viscosity = 10 mPa · s
(E-5) Tripropylene glycol diacrylate (BASF) 25 ° C. viscosity = 20 mPa · s
成分（ｄ）成分　開始剤
（ｉ）光重合開始剤
ＣＩＢＡ社製、ＩＲＧＡＣＵＲＥ（商標）８１９、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド Component (d) Component Initiator (i) Photopolymerization initiator CIBA, IRGACURE ™ 819, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
実施例１～２０、比較例１～８
　下記表１～８に示す配合割合（質量部）において、攪拌機を備えた容器中に成分（（ａ）、（ｂ）、（ｃ）および（ｅ）を添加し、常温で十分に攪拌し、液温が常温になった時点で、成分（ｄ）を添加して、溶け残りがないように十分攪拌し、塗料を得た。得られた塗料の２５℃における粘度（mPa・s）を測定した。 すなわち、ハンディタイプのデジタル粘度計TVC-7形粘度計（東機産業社）を用いて、粘度に合わせた適当なロータ（０号～５号）を用いて、２５℃粘度を測定した。結果を表１～８に併せて示す。 Examples 1-20, Comparative Examples 1-8
Components ((a), (b), (c) and (e) were added to a container equipped with a stirrer at the blending ratio (parts by mass) shown in Tables 1 to 8 below, and the mixture was sufficiently stirred at room temperature. When the liquid temperature reached room temperature, component (d) was added, and the mixture was sufficiently stirred so that there was no undissolved residue, to obtain a paint.The viscosity (mPa · s) of the obtained paint at 25 ° C. was measured. That is, using a handy digital viscometer TVC-7 type viscometer (Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was measured using an appropriate rotor (No. 0 to No. 5) according to the viscosity. The results are shown in Tables 1 to 8.
　次に、表１～８に示す被着体（寸法：１５０ｍｍ×２５ｍｍ×厚さ１ｍｍ）上に、(株)エイブル製マニュアルスピナーASS-301型を用いたスピンコート法により塗料を塗布し（塗布厚１５～２０μｍ）、これを空気下で５００ｍＪ／ｃｍ2のエネルギーの紫外線を照射して硬化させ、積層体を調製した。 Next, a coating was applied on the adherend (dimensions: 150 mm × 25 mm × thickness 1 mm) shown in Tables 1 to 8 by a spin coat method using Able's manual spinner ASS-301 type (application) This was cured by irradiating with ultraviolet rays having an energy of 500 mJ / cm 2 under air to prepare a laminate.
　使用した各被着体は、次の通りである。
・硬質塩化ビニル樹脂ＰＶＣ（リケンテクノス社製、商品名Riken  PVC　Compound　RE-3844）
・軟質塩化ビニル樹脂ＰＶＣ（リケンテクノス社製、商品名Leonyl　BZL6060N）
・ポリスチレンＰＳ（東洋スチレン社製、商品名トーヨースチロールGP　G100C  ）
・ポリカーボネートＰＣ（帝人化成社製、商品名パンライトL-1225L）
・アクリロニトリル－ブタジエン－スチレン共重合体ＡＢＳ（UMG社製、商品名UMG  ABS　EX114）
・ガラス（顕微鏡プレパラート用スライドグラス）
・アルミニウム（Ｈ５０５２、Ａｌ－Ｍｇ系）
・マグネシウム（大阪富士工業社製、ＡＺ３１Ｂ、Ｍｇ含有量９１％以上）
・鋼板（ＳＰＣＣ：冷間圧延鋼板）
・ＰＥＴ：ユニチカ　ユニチカポリエステル樹脂MA-2103
・ＰＭＭＡ：三菱レイヨン　アクリペット　VH Each adherend used is as follows.
・ Hard vinyl chloride resin PVC (Riken Technos, trade name Riken PVC Compound RE-3844)
-Soft vinyl chloride resin PVC (manufactured by Riken Technos, trade name Leonyl BZL6060N)
・ Polystyrene PS (Toyo Styrol GP G100C, manufactured by Toyo Styrene Co., Ltd.)
・ Polycarbonate PC (trade name Panlite L-1225L, manufactured by Teijin Chemicals Ltd.)
・ Acrylonitrile-butadiene-styrene copolymer ABS (manufactured by UMG, trade name UMG ABS EX114)
・ Glass (slide glass for microscope preparation)
・ Aluminum (H5052, Al-Mg)
Magnesium (Osaka Fuji Kogyo Co., Ltd., AZ31B, Mg content 91% or more)
・ Steel (SPCC: Cold rolled steel)
・ PET: Unitika Unitika polyester resin MA-2103
・ PMMA: Mitsubishi Rayon Acrypet VH
　得られた積層体について、以下の碁盤目テープ試験を行なった。
（密着性試験：碁盤目テープ試験）
　日本工業規格Ｋ５４００に記載されている碁盤目テープ試験法に準拠して以下のように測定を行った。
　碁盤目テープ試験（Cross-cut  Test、塗布厚１５～２０μｍ（スピンコート法））：試験面（塗料の層（Ａ）側）にカッターナイフを用いて、1×1mm四方の碁盤目の切り傷を入れる。カッターガイドを使用する。碁盤目の数は、縦10個×横10個＝100個入れる。碁盤目を入れた所にセロハンテープを強く圧着させ、テープの端を45°の角度で急速に引き剥がし、碁盤目の状態（剥離しないで残った碁盤目の個数）を見る。
　結果を併せて表１～８に示す。 The obtained laminate was subjected to the following cross-cut tape test.
(Adhesion test: cross-cut tape test)
The measurement was performed as follows in accordance with the cross cut tape test method described in Japanese Industrial Standard K5400.
Cross-cut tape test (Cross-cut Test, coating thickness 15 ~ 20 [mu] m (spin coating method)): the test surface (layer of paint (A) side) with a cutter knife, a crosscut of cuts 1 × 1 mm square Put in. Use the cutter guide. The number of grids is 10 vertical x 10 horizontal = 100. Strongly press the cellophane tape into the grid, and peel off the end of the tape rapidly at an angle of 45 ° to see the grid pattern (number of grids remaining without peeling).
The results are also shown in Tables 1 to 8.
耐衝撃試験
　試験方法：25mm巾、1mm厚の鋼板にスピンコート法で１５～２０μｍの厚みで塗料を塗布し、硬化後1m高さから1kgwの球状である重りを落下し以下の基準で評価を行った。
○：剥離しない
△：一部剥離・割れ
×：全面剥離・割れ Impact resistance test Test method: Apply a paint with a thickness of 15 to 20μm on a 25mm wide and 1mm thick steel plate by spin coating, drop a 1kgw spherical weight from 1m height after curing, and evaluate according to the following criteria went.
○: not peeled △: partly peeled / cracked ×: whole face peeled / cracked
柔軟性
　試験方法：25mm巾、1mm厚の鋼板にスピンコート法で１５～２０μｍの厚みで塗料を塗布し、硬化後90度折り曲げ試験を行い以下の基準で評価を行った。
○：剥離しない
△：一部剥離・割れ
×：全面剥離・割れ Flexibility Test method: A paint was applied to a steel sheet of 25 mm width and 1 mm thickness by a spin coating method to a thickness of 15 to 20 μm, and after curing, a 90-degree bending test was performed and evaluation was performed according to the following criteria.
○: not peeled △: partly peeled / cracked ×: whole face peeled / cracked
透明性試験
　透明性を評価するため、JIS-K7136： 2000に基づいて実施例および比較例の積層体（基材ガラス）のヘーズを、ヘーズメーター（ＮＤＨ２０００：日本電色社） を用いて測定した。評価は、測定値が１．０％未満であったものを「◎」、１．０％以上２．０％未満であったものを「○」、２．０％以上「×」とした。なお、測定面は、塗膜面とした。 To evaluate the transparency test transparency, JIS-K7136: laminates of Examples and Comparative Examples based on the 2000 haze of (substrate glass), haze meter was measured using a (NDH2000 Nippon Denshoku) . In the evaluation, “◎” indicates that the measured value is less than 1.0%, “◯” indicates that the measured value is 1.0% or more and less than 2.0%, and “x” indicates 2.0% or more. The measurement surface was a coating surface.
発色性
　以下の顔料を分散剤と混合した後、上記塗料組成物８５質量部に対し、１５質量部加え分散させ、高速水冷式撹拌機により撹拌し、ポリカーボネート基材上にスピンコート法で約３０μｍの厚さに塗布した後、ＵＶ照射して発色性を評価した。
　顔料－１　（ｆ）ＩＲＧＡＬＩＴＥ  ＢＬＵＥ  ＧＬＶＯ（シアン顔料、チバスペシャリティーケミカルズ（ＣＳＣ）社製、表面酸量：１８．０、表面塩基量：３４．０）の８０質量部に対し、（ｇ）Ｓｏｌｓｐｅｒｓｅ３６０００（分散剤、ＬＵＢＲＩＺＯＬ社製、酸価：４５ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）を２０質量部配合して、顔料－１を得た。なお、顔料－１の調製は分散機モーターミルＭ５０（アイガー社製）に入れて、直径０．６５ｍｍのジルコニアビーズを用い、周速９ｍ／ｓで４時間分散を行った。
　顔料－２　（ｆ）Ｔｉｐａｑｕｅ  ＣＲ６０－２（ホワイト顔料（酸化チタン）、石原産業社製、表面酸量：８、表面塩基量：２５）９０質量部に対し、（ｇ）Ｓｏｌｓｐｅｒｓｅ３６０００（分散剤、ＬＵＢＲＩＺＯＬ社製、酸価：４５ｍｇＫＯＨ／ｇ、アミン価：０ｍｇＫＯＨ／ｇ）を１０質量部配合して、顔料－２を得た。なお、顔料－２の調製は分散機モーターミルＭ５０（アイガー社製）に入れて、直径０．６５ｍｍのジルコニアビーズを用い、周速９ｍ／ｓで４時間分散を行った。
　発色性評価は、印字サンプルを目視で確認して、発色性を以下の基準に従って評価した。
○：発色性に問題なし
△：若干発色性に問題があり、実用上問題あり
×：明らかに発色性に問題があり、実用には向かない Colorability After mixing the following pigment with a dispersant, 15 parts by mass are added to and dispersed in 85 parts by mass of the coating composition, and the mixture is stirred with a high-speed water-cooled stirrer, and about 30 μm by spin coating on a polycarbonate substrate. After coating to a thickness of, UV irradiation was performed to evaluate color development.
(G) Solsperse 36000 with respect to 80 parts by mass of Pigment-1 (f) IRGALITE BLUE GLVO (Cyan Pigment, Ciba Specialty Chemicals (CSC), surface acid amount: 18.0, surface base amount: 34.0) (Dispersant, manufactured by LUBRIZOL, acid value: 45 mgKOH / g, amine value: 0 mgKOH / g) was blended in an amount of 20 parts by mass to obtain Pigment-1. Pigment-1 was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.
Pigment-2 (f) Tipaque CR60-2 (white pigment (titanium oxide), manufactured by Ishihara Sangyo Co., Ltd., surface acid amount: 8, surface base amount: 25) with respect to 90 parts by mass, (g) Solsperse 36000 (dispersant, LUBRIZOL Pigment-2 was obtained by blending 10 parts by mass of an acid value of 45 mg KOH / g and an amine value of 0 mg KOH / g. Pigment-2 was prepared in a disperser motor mill M50 (manufactured by Eiger) and dispersed for 4 hours at a peripheral speed of 9 m / s using zirconia beads having a diameter of 0.65 mm.
In the color development evaluation, the printed sample was visually confirmed, and the color development was evaluated according to the following criteria.
○: No problem in color developability △: Some problem in color developability, practical problem ×: Clearly in color developability, unsuitable for practical use
プライマー層としての評価
　前記実施例および比較例と同様に塗料を調製し、表に示す被着体上に塗料を厚さ約２０μｍとして塗布し、硬化させ、積層体を調製した。この積層体上にインクジェット用インク（ＵＶインクシアン（SPC-0371C、ミマキエンジニアリング社製、5%未満ピグメントブルー15、80～90%アクリル酸エステル、5～15％他）またはＵＶインクライトシアン（SPC-0371LC-2、ミマキエンジニアリング社製、1%未満ピグメントブルー15、80～90%アクリル酸エステル、10～20％他））をスピンコート法で約３０μｍ厚でコートし、乾燥後、前記の碁盤目テープ試験を行った。結果を表１～８に示す。 Evaluation as a primer layer A paint was prepared in the same manner as in the above Examples and Comparative Examples, and the paint was applied on the adherend shown in the table to a thickness of about 20 μm and cured to prepare a laminate. Ink jet ink (UV ink cyan (SPC-0371C, manufactured by MIMAKI ENGINEERING CO., LTD., Less than 5% Pigment Blue 15, 80 to 90% acrylic ester, 5 to 15%, etc.) or UV ink light cyan (SPC- 0371LC-2, Mimaki engineering Co., Ltd., 1% less than Pigment Blue 15,80 to 90% of acrylic acid ester, 10-20% other)) were coated with about 30μm thickness by a spin coating method, dried, the cross-cut of A tape test was performed. The results are shown in Tables 1-8.
長期保存安定性の評価
　長期保存安定性評価は、塗料をアズワン社製 グッドボーイ褐色瓶（400nm以下の紫外線透過率は0.3％以下、容量250mL）に入れて２３℃の暗所に保存し、168時間後の粘度を測定して、以下の基準に従って評価した。
○：粘度上昇が5%未満で問題なし
△：粘度上昇が10%未満だが、実用上問題あり
×：粘度上昇が10%以上、実用には向かない
結果を表１～８に示す。 Long-term storage stability evaluation long-term storage stability evaluation saves coating material AS ONE Corp. Good boy brown bottle (400 nm following ultraviolet transmittance of 0.3% or less, volume 250 mL) to dark put 23 ° C. to 168 The viscosity after time was measured and evaluated according to the following criteria.
○: Viscosity increase is less than 5% and there is no problem Δ: Viscosity increase is less than 10%, but there is a problem in practical use ×: Viscosity increase is 10% or more, and results not suitable for practical use are shown in Tables 1-8.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　表より明らかなように、本発明の実施例１～２０では、調製された塗料が、前記成分（ａ）、（ｂ）、（ｃ）、（ｄ）および（ｅ）を特定の量的関係でもって含有しているので、長期保存安定性に優れ、各種被着体との接着性に優れ、また、画像の発色性、耐衝撃性および柔軟性も改善されている。
　一方、比較例１は、成分（ａ）の配合量が本発明で規定する下限未満であり、かつ成分（ｂ）の配合量が本発明で規定する上限を超えているので、各種被着体に対する接着性が悪化し、また、耐衝撃性、柔軟性も悪化した。
　比較例２は、成分（ａ）の配合量が本発明で規定する上限を超え、かつ成分（ｂ）の配合量が本発明で規定する下限未満であるので、粘度が高くなり、各種被着体に対する接着性が悪化し、また、耐衝撃性、柔軟性も悪化した。
　比較例３は、成分（ｃ）を配合していないので、各種被着体に対する接着性が悪化し、また、耐衝撃性、柔軟性も悪化した。
　比較例４は、成分（ｃ）の配合量が本発明で規定する上限を超えているので、各種被着体に対する接着性が悪化し、また、耐衝撃性、柔軟性も悪化した。
　比較例５は、成分（ｄ）の配合量が本発明で規定する下限未満であるので、各種被着体に対する接着性が悪化した。
　比較例６は、成分（ｄ）の配合量が本発明で規定する上限を超えているので、各種被着体に対する接着性が悪化し、また、耐衝撃性、柔軟性も悪化した。
　比較例７は、成分（ｅ）を配合していないので、粘度が高く、インクジェット記録装置による塗装に適さず、インクの発色性が悪化した。
　比較例８は、成分（ｅ）の配合量が本発明で規定する上限を超えているので、各基材との接着性に劣り、インクジェット用インクの密着性が悪く、プライマーとしての役割が果たせず、また、耐衝撃性、柔軟性が悪化した。 As is apparent from the table, in Examples 1 to 20 of the present invention, the prepared paints have the components (a), (b), (c), (d) and (e) having a specific quantitative relationship. Therefore, since it contains, it is excellent in long-term storage stability, it is excellent in adhesiveness with various to-be-adhered bodies, and the image coloring property, impact resistance, and flexibility are also improved.
On the other hand, in Comparative Example 1, the amount of component (a) is less than the lower limit specified in the present invention, and the amount of component (b) exceeds the upper limit specified in the present invention. The adhesiveness to the resin deteriorated, and the impact resistance and flexibility deteriorated.
In Comparative Example 2, the amount of component (a) exceeds the upper limit specified in the present invention, and the amount of component (b) is less than the lower limit specified in the present invention. The adhesion to the body deteriorated, and the impact resistance and flexibility also deteriorated.
Since the comparative example 3 did not mix | blend a component (c), the adhesiveness with respect to various to-be-adhered bodies deteriorated, and impact resistance and the softness | flexibility also deteriorated.
In Comparative Example 4, since the blending amount of the component (c) exceeded the upper limit defined in the present invention, the adhesion to various adherends deteriorated, and the impact resistance and flexibility also deteriorated.
In Comparative Example 5, since the blending amount of component (d) was less than the lower limit specified in the present invention, the adhesion to various adherends deteriorated.
In Comparative Example 6, since the blending amount of the component (d) exceeded the upper limit defined in the present invention, the adhesion to various adherends was deteriorated, and the impact resistance and flexibility were also deteriorated.
In Comparative Example 7, since the component (e) was not blended, the viscosity was high, and it was not suitable for coating with an ink jet recording apparatus, and the color developability of the ink was deteriorated.
In Comparative Example 8, since the blending amount of the component (e) exceeds the upper limit defined in the present invention, the adhesion to each substrate is poor, the adhesion of the inkjet ink is poor, and it can serve as a primer. In addition, impact resistance and flexibility deteriorated.
　なお、実施例のインクジェット用インク発色性試験に用いた塗料および顔料を含まない塗料組成物について、ピエゾ型インクジェットノズルを有するインクジェット記録実験装置を用いて、被記録媒体への記録を行った結果いずれも良好な印刷がなされた。
　インク供給系は、元タンク、供給配管、インクジェットヘッド直前のインク供給タンク、フィルター、ピエゾ型のインクジェットヘッドから成り、インク供給タンクからインクジェットヘッド部分までを断熱及び加温を行った。温度センサーは、インク供給タンク及びインクジェットヘッドのノズル付近にそれぞれ設け、ノズル部分が常に４５℃±２℃となるよう、温度制御を行った。ピエゾ型のインクジェットヘッドは、８～３０ｐｌのマルチサイズドットを７２０×７２０ｄｐｉの解像度で射出できるよう駆動した。着弾後はＵＶ光を露光面照度１，６３０ｍＷ／ｃｍ2、に集光し、被記録媒体上にインク着弾した０．１秒後に照射が始まるよう露光系、主走査速度及び射出周波数を調整した。また、画像に照射される積算光量を４，５００ｍＪ／ｃｍ2となるようにした。紫外線ランプには、ＨＡＮ２５０ＮＬ　ハイキュア水銀ランプ（ジーエス・ユアサ　コーポレーション社製）を使用した。なお、本発明でいうｄｐｉとは、２．５４ｃｍ当たりのドット数を表す。被記録媒体として、エステルフィルムＥ５０００（膜厚１２５μｍ、東洋紡社製）を用いた。
　本発明の塗料は、インクジェット記録装置で使用されるインクとしても使用できる。プライマーとしても有効である。プライマーも通常インクジェット記録装置で塗布されることが多いので低粘度である本発明の塗料は有用である。 In addition, as a result of recording on a recording medium using an ink jet recording experimental apparatus having a piezo type ink jet nozzle, the paint composition used in the ink color development test for ink jet in Examples and a paint composition not containing a pigment was used. Also good printing was made.
The ink supply system was composed of an original tank, supply piping, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head, and heat insulation and heating were performed from the ink supply tank to the inkjet head portion. Temperature sensors were provided near the ink supply tank and the nozzle of the ink jet head, respectively, and temperature control was performed so that the nozzle portion was always 45 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that multi-size dots of 8 to 30 pl could be ejected at a resolution of 720 × 720 dpi. After landing, UV light was condensed to an exposure surface illuminance of 1,630 mW / cm 2 , and the exposure system, main scanning speed, and ejection frequency were adjusted so that irradiation started 0.1 seconds after ink landed on the recording medium. . Further, the integrated light amount irradiated to the image was set to 4,500 mJ / cm 2 . A HAN250NL high-cure mercury lamp (manufactured by GS Yuasa Corporation) was used as the ultraviolet lamp. In the present invention, dpi represents the number of dots per 2.54 cm. As a recording medium, an ester film E5000 (film thickness 125 μm, manufactured by Toyobo Co., Ltd.) was used.
The paint of the present invention can also be used as an ink used in an ink jet recording apparatus. It is also effective as a primer. The primer of the present invention having a low viscosity is useful because the primer is usually often applied by an ink jet recording apparatus.

Claims (15)

  1. （ａ）ビニルエステル樹脂または不飽和ポリエステル樹脂　１０～４０質量％
    （ｂ）ヘテロ原子を含む環状構造および１個のエチレン性不飽和基を有する化合物　３０～７０質量％
    （ｃ）変性剤　５～４０質量％、
    （ただし、前記成分（ａ）～（ｃ）の合計は１００質量％である）
    （ｄ）紫外線反応開始剤　前記成分（ａ）～（ｃ）の合計１００質量部に対し０．１～１５質量部、および
    （ｅ）ビニル基および／または（メタ）アクリロイル基を持つモノマー　前記成分（ａ）～（ｃ）の合計１００質量部に対し３～２０質量部
    を含有する塗料。
    （ただし、前記成分（ｅ）はヘテロ原子を含む環状構造を含まない。）     (A) Vinyl ester resin or unsaturated polyester resin 10 to 40% by mass
    (B) Compound having a cyclic structure containing a heteroatom and one ethylenically unsaturated group 30 to 70% by mass
    (C) modifying agent 5-40% by mass,
    (However, the total of the components (a) to (c) is 100% by mass)
    (D) UV reaction initiator 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of the components (a) to (c), and (e) a monomer having a vinyl group and / or (meth) acryloyl group A paint containing 3 to 20 parts by mass with respect to a total of 100 parts by mass of (a) to (c).
    (However, the component (e) does not include a cyclic structure containing a hetero atom.)
  2. 　前記成分（ａ）が、ウレタン（メタ）アクリレートであることを特徴とする請求項１に記載の塗料。 The paint according to claim 1, wherein the component (a) is urethane (meth) acrylate.
  3. 　前記成分（ｂ）が、Ｎ－ビニル基を有するモノマーであることを特徴とする請求項１または２に記載の塗料。 3. The paint according to claim 1, wherein the component (b) is a monomer having an N-vinyl group.
  4. 　前記成分（ｃ）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリオール（ｃ－１）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるポリオール（ｃ－２）；変性ゴム（ｃ－３）；エポキシ当量が１５０～７００ｇ／モルである化合物（ｃ－４）からなる群から選択された少なくとも１種であることを特徴とする請求項１～３のいずれかに記載の塗料。 The component (c) is a polyol (c-1) having a hydroxyl value of 40 to 330 mgKOH / g; and a polyol (c-2) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g The modified rubber (c-3) is at least one selected from the group consisting of the compound (c-4) having an epoxy equivalent of 150 to 700 g / mol. paint according to.
  5. 　前記成分（ｃ－１）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇのヒマシ油系ポリオール（ｃ－１－１）；水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリブタジエン系ポリオール（ｃ－１－２）；および水酸基価４０～３３０ｍｇＫＯＨ／ｇのポリイソプレン系ポリオールまたはその水素添加物（ｃ－１－３）からなる群から選択された少なくとも１種であることを特徴とする請求項４に記載の塗料。 The component (c-1) is a castor oil-based polyol (c-1-1) having a hydroxyl value of 40 to 330 mgKOH / g; a polybutadiene-based polyol (c-1-2) having a hydroxyl value of 40 to 330 mgKOH / g; 5. The paint according to claim 4, wherein the paint is at least one selected from the group consisting of a polyisoprene polyol having a value of 40 to 330 mg KOH / g or a hydrogenated product (c-1-3) thereof.
  6. 　前記成分（ｃ－１）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇの芳香族系ヒマシ油系ポリオール（ｃ－１－１－１）であることを特徴とする請求項５に記載の塗料。 The paint according to claim 5, wherein the component (c-1) is an aromatic castor oil-based polyol (c-1-1-1) having a hydroxyl value of 40 to 330 mgKOH / g.
  7. 　前記成分（ｃ－２）が、水酸基価４０～３３０ｍｇＫＯＨ／ｇであり、かつ酸価が２～２０ｍｇＫＯＨ／ｇであるヒマシ油系ポリオール（ｃ－２－１）であることを特徴とする請求項４に記載の塗料。 The component (c-2) is a castor oil-based polyol (c-2-1) having a hydroxyl value of 40 to 330 mgKOH / g and an acid value of 2 to 20 mgKOH / g. paint according to 4.
  8. 　前記成分（ｃ－３）が酸変性ポリブタジエンまたは酸変性ポリイソプレンであることを特徴とする請求項４に記載の塗料。 The paint according to claim 4, wherein the component (c-3) is acid-modified polybutadiene or acid-modified polyisoprene.
  9. 　前記成分（ｃ－４）がエポキシ当量が１５０～２５０ｇ／モルであるポリエポキシ化合物（ｃ－４－１）であることを特徴とする請求項４に記載の塗料。 The paint according to claim 4, wherein the component (c-4) is a polyepoxy compound (c-4-1) having an epoxy equivalent of 150 to 250 g / mol.
  10. 　前記成分（ｃ－４）がエポキシ当量が５００～７００ｇ／モルである飽和骨格を持つ重合体（ｃ－４－２）であることを特徴とする請求項４に記載の塗料。 The paint according to claim 4, wherein the component (c-4) is a polymer (c-4-2) having a saturated skeleton having an epoxy equivalent of 500 to 700 g / mol.
  11. 　前記塗料の被着体が、軟質および硬質塩化ビニル樹脂；スチレン系樹脂；ポリカーボネート系樹脂；ガラス；アルミニウム；鋼板；ポリオレフィン系樹脂；極性基含有化合物で変性されたポリオレフィン樹脂またはオレフィンと極性基含有化合物との共重合体；マグネシウム；アクリロニトリル－ブタジエン－スチレン共重合体；ポリエステル系樹脂；またはアクリル系樹脂であることを特徴とする請求項１～１０のいずれかに記載の塗料。 The coating adherend is soft and hard vinyl chloride resin; styrene resin; polycarbonate resin; glass; aluminum; steel plate; polyolefin resin; polyolefin resin modified with polar group-containing compound or olefin and polar group-containing compound The coating material according to any one of claims 1 to 10, wherein the coating material is magnesium; acrylonitrile-butadiene-styrene copolymer; polyester resin; or acrylic resin.
  12. 　請求項１～１１のいずれかに記載の塗料を含有することを特徴とするインクジェット用インク。 An ink-jet ink comprising the paint according to any one of claims 1 to 11.
  13. 　さらに着色剤を含有することを特徴とする請求項１２に記載のインクジェット用インク。 The ink-jet ink according to claim 12, further comprising a colorant.
  14. 　請求項１～１１のいずれかに記載の塗料を含有することを特徴とする、インクジェット記録媒体上に設けられたプライマー層。 A primer layer provided on an inkjet recording medium, comprising the paint according to any one of claims 1 to 11.
  15. 　インクジェット記録媒体上に、請求項１２または１３に記載のインクジェット用インクを用いてインクジェット印刷してなる印刷物。 A printed matter obtained by performing inkjet printing on an inkjet recording medium using the inkjet ink according to claim 12 or 13.
PCT/JP2010/060856 2010-06-25 2010-06-25 Coating material and primer using the same, ink for ink-jet WO2011161817A1 (en)

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JP2017022125A (en) * 2016-08-23 2017-01-26 大日本印刷株式会社 Copper nanoparticle dispersion and method of manufacturing conductive substrate
JPWO2020174869A1 (en) * 2019-02-27 2020-09-03

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WO2014077171A1 (en) * 2012-11-16 2014-05-22 富士フイルム株式会社 White photosensitive resin composition, white cured film, white pattern, and method for producing white pattern
JP2015034961A (en) * 2012-11-16 2015-02-19 富士フイルム株式会社 White photosensitive resin composition, white cured film, white pattern, and production method of the same
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WO2015090076A1 (en) * 2013-12-20 2015-06-25 湖北久瑞核技术股份有限公司 Self-luminous coating/printing ink cured on tyre by radiation and preparation method thereof
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WO2016088703A1 (en) * 2014-12-01 2016-06-09 コニカミノルタ株式会社 Primer, ink set and image forming method
JP2017022125A (en) * 2016-08-23 2017-01-26 大日本印刷株式会社 Copper nanoparticle dispersion and method of manufacturing conductive substrate
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WO2020174869A1 (en) * 2019-02-27 2020-09-03 株式会社ノリタケカンパニーリミテド Inkjet ink
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