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WO2016042683A1 - Composition de peinture primaire et élément stratifié - Google Patents

Composition de peinture primaire et élément stratifié Download PDF

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Publication number
WO2016042683A1
WO2016042683A1 PCT/JP2015/001244 JP2015001244W WO2016042683A1 WO 2016042683 A1 WO2016042683 A1 WO 2016042683A1 JP 2015001244 W JP2015001244 W JP 2015001244W WO 2016042683 A1 WO2016042683 A1 WO 2016042683A1
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WO
WIPO (PCT)
Prior art keywords
polyolefin resin
acid residue
polyester resin
carboxylic acid
modified polyolefin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/001244
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English (en)
Japanese (ja)
Inventor
輝 榊原
前田　浩司
伸哉 駒引
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Goo Chemical Industries Co Ltd
Original Assignee
Goo Chemical Industries Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Goo Chemical Industries Co Ltd filed Critical Goo Chemical Industries Co Ltd
Priority to JP2016548528A priority Critical patent/JP6346669B2/ja
Priority to KR1020177007504A priority patent/KR101976550B1/ko
Priority to CN201580049519.1A priority patent/CN106715612B/zh
Publication of WO2016042683A1 publication Critical patent/WO2016042683A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

  • the present invention relates to a primer composition and a laminated member, and more particularly to a primer composition for forming a primer layer, and a laminated member provided with a primer layer formed from the primer composition.
  • Coatings may be applied to various substrates, for example, films made of polyolefin resin such as polypropylene and polyethylene, an ink may be provided for printing, and a metal deposition layer may be provided for imparting gas barrier properties.
  • a metal deposition layer may be provided for imparting gas barrier properties.
  • the substrate is subjected to corona discharge, plasma treatment, flame treatment, ultraviolet irradiation treatment, Surface treatment such as solvent treatment may be performed.
  • Examples of such a primer include a primer composed mainly of an organic solvent such as toluene, but when the primer contains an organic solvent, problems such as deterioration of working environment occur.
  • International Publication WO 2010/038643 includes a compound having a hydroxyl group, an unsaturated carboxylic acid ester, styrene, an unsaturated carboxylic acid, an unsaturated hydrocarbon, a vinyl ester and a vinyl halide.
  • Main agent (A) consisting of a copolymer having the above unsaturated compound as a monomer
  • curing agent (B) consisting of a compound having an isocyanate group, and two or more carboxylic acid groups in one molecule or anhydrous
  • a primer containing a compound (C) having one or more carboxylic acid groups is disclosed.
  • the present invention has been made in view of the above problems, and by applying to a substrate, it is possible to impart adhesiveness to the substrate, and a hydrophilic primer composition having good handleability, and this It is an object of the present invention to provide a laminated member comprising a primer layer formed from a primer composition.
  • a primer composition according to the present invention comprises a polyester resin comprising at least one of a trivalent or higher polyvalent carboxylic acid residue and a polyvalent carboxylic acid residue comprising a metal sulfonate group; Containing a modified polyolefin resin,
  • the mass ratio of the polyester resin to the modified polyolefin resin is in the range of 8/2 to 2/8.
  • the acid value of the polyester resin is preferably in the range of 2 to 100 mg KOH / g.
  • the percentage ratio of the polyvalent carboxylic acid residue having the metal sulfonate group to the total polyvalent carboxylic acid residue in the polyester resin is in the range of 1 to 60 mol%.
  • the modified polyolefin resin preferably contains an acid-modified polyolefin resin.
  • the acid-modified polyolefin resin preferably contains at least one of a maleic acid-modified polyolefin resin and a maleic anhydride-modified polyolefin resin.
  • the modified polyolefin resin is preferably not chlorinated.
  • the laminated member according to the present invention is A substrate, And a primer layer on the substrate and made from the primer composition.
  • the laminated member may further include an outer layer made of metal or resin on the primer layer.
  • adhesion can be imparted to a substrate, and a hydrophilic primer composition having good handleability can be obtained.
  • a laminated member provided with a primer layer formed of a hydrophilic primer composition capable of imparting adhesiveness to a substrate and having good handleability.
  • the primer composition according to the present embodiment contains a polyester resin and a modified polyolefin resin.
  • the primer composition is used, for example, to obtain a laminated member 1 as shown in FIG.
  • the laminated member 1 includes a base 2, a primer layer 3 formed on the base 2 and made of a primer composition, and an outer layer 4 made of metal or resin on the primer layer 3.
  • the polyester resin comprises a polyvalent carboxylic acid residue and a glycol residue.
  • the polyester resin comprises at least one of a trivalent or higher polyvalent carboxylic acid residue and a polyvalent carboxylic acid residue having a metal sulfonate group. That is, the polyvalent carboxylic acid residue in the polyester resin contains at least one of a trivalent or more polyvalent carboxylic acid residue and a polyvalent carboxylic acid residue having a metal sulfonate group. When the polyvalent carboxylic acid residue contains a trivalent or higher polyvalent carboxylic acid residue, an unreacted carboxyl group tends to remain in the trivalent or higher polyvalent carboxylic acid residue.
  • the polyester resin when the polyvalent carboxylic acid residue contains a trivalent or higher polyvalent carboxylic acid residue, the polyester resin is provided with a carboxyl group derived from the polyvalent carboxylic acid residue.
  • the polyester resin contains a metal sulfonate group derived from a polyvalent carboxylic acid residue containing a metal sulfonate group.
  • the polyester resin has at least one of a carboxyl group which is a polar group and a metal sulfonate group, so that the polyester resin is provided with water solubility, and adhesion to a metal, a resin having a polar site, etc. Sex is also given.
  • the acid value of the polyester resin is preferably in the range of 2 to 100 mg KOH / g.
  • high water solubility is imparted to the polyester resin, and high adhesiveness to the base material 2, metal, resin, etc. is also imparted to the polyester resin.
  • the acid value of the polyester resin is more preferably in the range of 5 to 100 mg KOH / g, further preferably in the range of 20 to 80 mg KOH / g, and further preferably in the range of 30 to 70 mg KOH / g. It is particularly preferable if it is within the range of ⁇ 68 mg KOH / g.
  • the acid value of the polyester resin is the molar ratio of the polyvalent carboxylic acid residue to the glycol residue in the polyester resin, and the trivalent or higher polyvalent carboxylic acid residue with respect to all polyvalent carboxylic acid residues in the polyester resin. Is adjusted by changing the ratio of That is, the molar ratio of the polyvalent carboxylic acid residue to the glycol residue in the polyester resin and the amount of the trivalent or higher polyvalent carboxylic acid residue in the polyester resin are preferably 2 to 5 of the acid value of the polyester resin.
  • 100 mg KOH / g more preferably 5 to 100 mg KOH / g, still more preferably 20 to 80 mg KOH / g, still more preferably 30 to 70 mg KOH / g, particularly preferably 35 to 68 mg KOH / g Adjusted.
  • the percentage of polyvalent carboxylic acid residue having a metal sulfonate group to the total polyvalent carboxylic acid residue in the polyester resin is 1 to 60 mol% Is preferably in the range of 1 to 30 mol%, more preferably in the range of 1 to 20 mol%, and particularly preferably in the range of 2 to 18 mol%. .
  • the weight average molecular weight of the polyester resin is preferably in the range of 3000 to 100000, more preferably in the range of 4000 to 80000, and particularly preferably in the range of 5000 to 60000.
  • the weight average molecular weight of the polyester resin is easily adjusted by appropriately setting the synthesis conditions of the polyester resin.
  • the weight average molecular weight of polyester resin is a value (polystyrene conversion) measured by gel permeation chromatography.
  • the modified polyolefin resin is a polyolefin resin modified to have a polar group. That is, the modified polyolefin resin has a polyolefin skeleton which is a nonpolar site, and a polar site introduced by modification. Since the modified polyolefin resin comprises a nonpolar polyolefin backbone, the modified polyolefin resin has adhesion to nonpolar materials. Furthermore, since the modified polyolefin resin is provided with a polar site, the modified polyolefin resin has water solubility.
  • the value of mass ratio of polyester resin to modified polyolefin resin is in the range of 8/2 to 2/8.
  • mass ratio of the polyester resin By setting the mass ratio of the polyester resin within the above range, a site having an appropriate polarity is imparted to the primer composition, and the primer layer 3 formed from the primer composition is excellent for metal, resin having polarity, etc. Adhesiveness is given.
  • mass ratio of the modified polyolefin resin when the mass ratio of the modified polyolefin resin is within the above range, an appropriate nonpolar portion is imparted to the primer composition, and the primer layer 3 formed from the primer composition is excellent for nonpolar materials and the like. Adhesion is given.
  • the primer layer 3 formed from the primer composition has excellent adhesion to metals, resins, and the like.
  • the value of the mass ratio of the polyester resin to the modified polyolefin resin is in the range of 7/3 to 3/7.
  • the primer layer 3 formed from the primer composition has particularly excellent adhesion to metals, resins and the like.
  • polyester resin and the modified polyolefin resin will be described in more detail.
  • the polyester resin will be described.
  • trivalent or higher polyvalent carboxylic acid residues examples include hemimellitic acid residues, trimellitic acid residues, trimedic acid residues, merophonic acid residues, pyromellitic acid residues, benzenepentacarboxylic acid residues, and mellitic acid.
  • At least one member selected from the group consisting of residues, cyclopropane-1,2,3-tricarboxylic acid residues, cyclopentane-1,2,3,4-tetracarboxylic acid residues, and ethanetetracarboxylic acid residues Can be contained.
  • polyvalent carboxylic acid residues provided with a metal sulfonate group examples include dicarboxylic acid residues provided with a metal sulfonate group. More specifically, polyvalent carboxylic acid residues having a metal sulfonate group are, for example, 5-sulfoisophthalic acid residue, 2-sulfoisophthalic acid residue, 4-sulfoisophthalic acid residue, 2-sulfoterephthalic acid residue And at least one group selected from the group consisting of 4-sulfonaphthalene-2,6-dicarboxylic acid residues.
  • the polyvalent carboxylic acid residue in the polyester resin is, in addition to the polyvalent carboxylic acid residue having a trivalent or higher polyvalent carboxylic acid residue and a metal sulfonate group, an aromatic dicarboxylic acid residue, an aliphatic dicarboxylic acid residue And the like may further contain a dicarboxylic acid residue such as
  • the aromatic dicarboxylic acid residue is, for example, terephthalic acid residue, isophthalic acid residue, phthalic acid residue, diphenic acid residue, naphthalic acid residue, 1,2-naphthalenedicarboxylic acid residue, 1,4-naphthalenedicarboxylic acid And at least one selected from the group consisting of an acid residue, a 1,5-naphthalenedicarboxylic acid residue, and a 2,6-naphthalenedicarboxylic acid residue.
  • Aliphatic dicarboxylic acid residues such as linear, branched and alicyclic oxalic acid residues, malonic acid residues, succinic acid residues, maleic acid residues, itaconic acid residues, glutaric acid residues, adipic acid Residue, Pimelic acid residue, 2,2-dimethyl glutaric acid residue, suberic acid residue, azelaic acid residue, sebacic acid residue, dodecanedioic acid residue, 1,3-cyclopentanedicarboxylic acid residue And at least one selected from the group consisting of 1,4-cyclohexanedicarboxylic acid residues, diglycolic acid residues, and dipropionic acid residues.
  • Acid residues, dodecanedioic acid residues, and 1,4-cyclohexanedicarboxylic acid residues are preferable from the viewpoint of easiness of reaction, adhesiveness of the resulting resin, weatherability, durability and the like.
  • the aromatic dicarboxylic acid residue and the 1,4-cyclohexanedicarboxylic acid residue are the main components of the polyvalent carboxylic acid residue.
  • glycol residue is, for example, ethylene glycol residue, diethylene glycol residue, triethylene glycol residue, tetraethylene glycol residue, pentaethylene glycol residue, hexaethylene glycol residue, heptaethylene glycol residue, octaethylene glycol residue
  • Polyethylene glycol residues such as propylene glycol residues, dipropylene glycol residues, tripropylene glycol residues, polypropylene glycol residues such as tetrapropylene glycol residues; 1,3-propanediol residues, 1,3-butane Diol residue, 1,4-butanediol residue, 1,5-pentanediol residue, 1,6-hexanediol residue, 2,2-dimethyl-1,3-propanediol residue, 2-ethyl- 2-Butyl-1,3-propane All residue, 2-ethyl-2-isobutyl-1,3-propanediol residue, 2,2,
  • glycol residues are ethylene glycol residues; diethylene glycol residues; butanediol residues such as 1,4-butanediol residues; hexanediol residues such as 1,6-hexanediol residues; It is preferable to contain at least one group selected from the group consisting of cyclohexane dimethanol residue; neopentyl glycol residue; and bisphenol A residue. In this case, synthesis of the polyester resin is easy, and the polyester resin has high durability.
  • the polyester resin is obtained, for example, by polymerizing a reactive raw material containing a compound having an ester-forming functional group.
  • the ester forming functional group means a functional group capable of reacting with a carboxyl group or a hydroxyl group to form an ester bond.
  • the ester forming functional group includes a carboxyl group, a hydroxyl group, an ester forming derivative group of the carboxyl group and an ester forming derivative group of the hydroxyl group.
  • the ester forming derivative group of the carboxyl group is a group which is obtained by reacting a compound with a carboxyl group and which can form an ester bond by reacting with a hydroxyl group.
  • ester group-forming derivative group of the carboxyl group examples include, for example, a group obtained by anodizing a carboxyl group, a group obtained by esterifying a carboxyl group, an acid chloride of a carboxyl group, and a halogen And the group obtained by The ester forming derivative group of the hydroxyl group is a group which is obtained by reacting any compound with the hydroxyl group, and which can react with the carboxyl group to form an ester bond.
  • the ester-forming derivative group of a hydroxyl group the group obtained by acetating a hydroxyl group is mentioned.
  • the ester-forming functional group is a carboxyl group or a hydroxyl group in that the reactivity during production of the polyester resin is good.
  • the reactive raw material includes a polyvalent carboxylic acid component corresponding to a polyvalent carboxylic acid residue in the polyester resin and a glycol component corresponding to a glycol residue in the polyester resin.
  • the polyvalent carboxylic acid component includes at least one compound selected from the group consisting of polyvalent carboxylic acids and ester-forming derivatives of polyvalent carboxylic acids.
  • the ester-forming derivative of polyvalent carboxylic acid is a compound in which a carboxyl group in polyvalent carboxylic acid is substituted with an ester-forming derivative group of carboxyl group.
  • the glycol component comprises at least one compound selected from the group consisting of glycols and ester-forming derivatives of glycols.
  • the ester-forming derivative of glycol is a compound in which a hydroxyl group in glycol is substituted with an ester-forming derivative of hydroxyl group.
  • the molar ratio between the polyvalent carboxylic acid component and the glycol component contained in the reactive raw material is preferably in the range of 1: 1 to 2.5.
  • the polyester resin is synthesized from reactive raw materials by a known polyester production method.
  • a polyester resin is synthesized by direct esterification reaction in which polyvalent carboxylic acid and glycol are reacted in one step reaction.
  • the first transesterification reaction between the ester-forming derivative of the polybasic carboxylic acid and the glycol may be synthesized through a stage reaction and a second stage reaction in which the reaction product of the first stage reaction is polycondensed.
  • the reaction product of the first stage reaction is polycondensed.
  • all of the reactive raw materials may be contained in the reaction system from the beginning, and a part of the reactive raw materials may be added to the reaction system during the ester polycondensation reaction.
  • the reaction system is 150 to 260 ° C.
  • the second stage reaction proceeds in a temperature range of 160 to 280 ° C. under a reduced pressure of, for example, 6.7 hPa (5 mmHg) or less.
  • the modified polyolefin resin will be described.
  • the modified polyolefin resin is a polyolefin resin modified to have a group having polarity as described above.
  • the modified polyolefin resin can contain a resin obtained by modifying a polyolefin resin with at least one type of polarizing agent selected from acid, chlorine and radically polymerizable monomers.
  • the modified polyolefin resin may be further modified with an ethylene ⁇ -olefin copolymer.
  • the modified polyolefin resin preferably contains at least one of an acid-modified polyolefin resin and a polyolefin resin modified with (meth) acrylamide which is a radical polymerizable monomer.
  • the polariser does not contain chlorine. That is, it is preferable that the modified polyolefin resin is not chlorinated.
  • the polyolefin resin is, for example, a polymer of a monomer containing an alkene having 2 to 8 carbon atoms.
  • the C 2-8 alkene contains, for example, at least one compound selected from the group consisting of ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene, and 1-octene be able to.
  • the acid-modified polyolefin resin is, for example, modified with unsaturated carboxylic acids.
  • Unsaturated carboxylic acids include at least one of unsaturated carboxylic acids and their derivatives.
  • the derivatives of unsaturated carboxylic acids include unsaturated carboxylic anhydrides, esters of unsaturated carboxylic acids and the like.
  • Unsaturated carboxylic acids are, for example, from acrylic acid, methacrylic acid, maleic acid, maleic acid anhydride, itaconic acid, itaconic acid anhydride, fumaric acid, crotonic acid, half esters of unsaturated dicarboxylic acids, and half amides of unsaturated dicarboxylic acids.
  • the unsaturated carboxylic acids preferably contain at least one of maleic acid and maleic anhydride. That is, the acid-modified polyolefin resin preferably contains at least one of a maleic acid-modified polyolefin resin and a maleic anhydride-modified polyolefin resin.
  • the acid-modified polyolefin resin can be obtained, for example, by copolymerizing unsaturated carboxylic acids and alkenes.
  • the unsaturated carboxylic acids and the alkene may be randomly copolymerized, block copolymerized or graft copolymerized.
  • the (meth) acrylamide contains at least one of acrylamide and methacrylamide. That is, the (meth) acrylamide modified polyolefin resin is modified with at least one of acrylamide and methacrylamide.
  • the (meth) acrylamide modified polyolefin resin is obtained, for example, by copolymerizing (meth) acrylamide and an alkene.
  • the (meth) acrylamide and the alkene may be randomly copolymerized, block copolymerized, or graft copolymerized.
  • modified polyolefin resin trade name: Auroran, manufactured by Nippon Paper Industries Co., Ltd., trade name: APTOLOK, manufactured by Mitsubishi Chemical Corp., trade name: GENPOLY, manufactured by LOTTE CHEMICAL CORPORATION, trade name: Hard Ren, manufactured by Toyobo Co., Ltd. Chem-Tex Co., Ltd. trade name Sumifit, Nippon Paper Industries Co., Ltd. trade name Super-Clon Japan Polypropylene Co., Ltd. trade name Wintech, Mitsui Chemical Co., Ltd. trade name Toughmer XM, Sumitomo Chemical Co., Ltd. product Name Tough Selenium, product name LMPO manufactured by Idemitsu Retail Sales Co., Ltd., etc. may be mentioned.
  • the primer composition can contain a solvent.
  • the solvent is preferably water, and may be a mixed solvent containing water and a hydrophilic organic solvent.
  • hydrophilic organic solvents include alcohols such as methanol, ethanol and 2-propanol, glycol ethers such as propylene glycol monomethyl ether, ethyl cellosolve and butyl cellosolve, and ketones such as cyclohexanone.
  • the solvent contains a hydrophilic organic solvent
  • the percentage of the hydrophilic organic solvent to the total solvent is preferably in the range of 0.1 to 50% by mass.
  • the polyester resin and the modified polyolefin resin are preferably dissolved in the solvent in the primer composition.
  • the primer composition can be considered aqueous.
  • the primer composition may contain a leveling agent.
  • a leveling agent such as alcohol or glycol ether
  • this hydrophilic organic solvent can function as a leveling agent.
  • the primer composition may contain a crosslinking agent.
  • the crosslinking agent can contain, for example, at least one selected from the group consisting of an oxazoline crosslinking agent, a carbodiimide crosslinking agent, an isocyanate crosslinking agent, and an epoxy crosslinking agent.
  • the primer composition may further contain appropriate additives such as an antifoaming agent, a coalescent agent, a pigment, and a dye.
  • the lamination member 1 in the present embodiment will be described with reference to FIG.
  • the laminated member 1 includes a substrate 2, a primer layer 3 on the substrate 2, and an outer layer 4 on the primer layer 3. That is, the base material 2, the primer layer 3 and the outer layer 4 are laminated in this order.
  • the shape of the substrate 2 is, for example, a plate, a sheet or a film.
  • the material of the substrate 2 is not particularly limited, but in the present embodiment, the adhesiveness between the substrate 2 and the primer layer 3 is high even if the substrate 2 is made of a nonpolar material.
  • the substrate 2 is made of resin such as thermoplastic resin or metal such as steel plate, for example.
  • the substrate 2 is particularly preferably a film made of a thermoplastic resin.
  • thermoplastic resins include polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate and polybutylene naphthalate; polyhydroxy acids such as polyglycolic acid and polylactic acid Carboxylic acids; aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate); polyamide resins such as nylon 6, nylon 66 and nylon 46; polypropylene, polyethylene, ethylene-vinyl acetate copolymer, etc.
  • the substrate 2 is preferably made of a polyolefin resin, and particularly preferably made of a polypropylene resin.
  • the primer layer 3 can be formed on the substrate 2 by applying the primer composition to the substrate 2 and then drying it.
  • the polyolefin resin is dried and then melt-extruded to obtain an unstretched polyolefin resin sheet.
  • the uniaxially stretched polyolefin resin film is obtained by stretching this polyolefin resin sheet in one direction with a heating roll or the like.
  • a biaxially oriented polyolefin resin film is obtained by stretching the uniaxially oriented polyolefin resin film in a direction perpendicular to the above direction while heating and subsequently performing the heat treatment to complete the orientation.
  • the primer composition is applied to the unstretched polyolefin resin sheet, uniaxially stretched polyolefin resin film, or biaxially stretched polyolefin resin film at any stage in the process of producing the biaxially stretched polyolefin resin film as described above, and then dried.
  • the primer layer 3 can be formed.
  • the primer layer 3 can be formed by the off-line method. That is, after the biaxially oriented polyolefin resin film is completed, the primer layer 3 can be formed by applying the primer composition to the biaxially oriented polyolefin resin film and then drying it.
  • the primer layer 3 can also be formed by an in-line method. That is, the primer layer 3 can also be formed in the middle of the process of producing a biaxially oriented polyolefin resin film from a polyolefin resin. In this case, for example, after the primer composition is applied to an unstretched polyolefin resin sheet and dried, the primer layer 3 is formed, and then the unstretched polyolefin resin sheet is sequentially stretched in two directions, and heat treatment is further performed. By applying, a biaxially oriented polyolefin resin film can be produced.
  • the primer layer 3 is formed by applying and drying a primer composition on a uniaxially stretched polyolefin resin film
  • the uniaxially stretched polyolefin resin film is stretched and further subjected to a heat treatment to form a biaxially stretched polyolefin.
  • a resin film can also be produced.
  • the primer composition is aqueous, that is, when the solvent in the primer composition is water or a mixed solvent containing water and 50% by mass or less of a hydrophilic organic solvent, the primer composition In the process of forming the primer layer 3 from a substance, the organic solvent does not volatilize, or the volatilization amount of the organic solvent is suppressed. For this reason, even if the solvent is volatilized from the primer composition in the process of producing a biaxially oriented polyolefin resin film from a polyolefin resin, ignition of the solvent by heat during stretching or heat treatment is suppressed. Therefore, in any of the off-line method and the in-line method, the primer layer 3 can be formed from the primer composition while suppressing the risk of ignition.
  • the primer composition is an aqueous composition
  • the organic solvent is less likely to be released to the environment, which is environmentally friendly.
  • An appropriate resin or metal outer layer 4 is formed on the primer layer 3.
  • a layer comprising a photosensitive layer, a diazo photosensitive layer, a matte layer, a magnetic layer, an inkjet ink receiving layer, a hard coat layer, an ultraviolet curable resin, a thermosetting resin, a printing ink, a UV ink, etc., dry lamination or extrusion
  • a layer of an adhesive by lamination, a vacuum evaporation, an electron beam evaporation, a sputtering, an ion plating, a thin film layer formed by CVD or plasma polymerization, and an organic barrier layer made of metal, inorganic substance or oxide thereof can be mentioned.
  • the primer layer 3 can obtain good adhesive strength with the outer layer 4 made of various resins or metals.
  • the primer composition is formed into a film on the resin or metal substrate 2 to form a film, and the adhesive strength between the substrate 2 and the primer layer 3 is high when the primer layer 3 is formed. .
  • the adhesive strength between the primer layer 3 and the outer layer 4 is also high when the resin or metal outer layer 4 is formed on the primer layer 3.
  • the tackiness of the primer layer 3 at normal temperature is low. For this reason, for example, when a metallic or resinous member is simply pressed against the primer layer 3, this member is difficult to stick to the primer layer 3.
  • the primer layer 3 is stuck to some member during the time from the formation of the primer layer 3 to the formation of the outer layer 4 on the primer layer 3 or a foreign matter adheres on the primer layer 3 Hateful.
  • the primer layer 3 may be stuck to any member, or on the primer layer 3 It is hard for foreign substances to adhere to
  • a reaction vessel having a volume of 1000 ml equipped with a stirrer, a nitrogen gas inlet, a thermometer, a rectification column, and a cooling condenser was prepared.
  • the raw material shown to each of A column, B column, and C column of following Table 1 was put into this reaction container, and the mixture was obtained.
  • the mixture was heated to 200 ° C. with stirring and mixing in a nitrogen atmosphere under normal pressure, and then gradually heated to 250 ° C. over 4 hours to complete the transesterification reaction.
  • polyester resin solution 100 parts by mass of this polyester resin, 40 parts by mass of butyl cellosolve, and 260 parts by mass of water are mixed, and kept at a temperature of 80 to 90 ° C. for 2 hours while stirring them to obtain a polyester resin concentration of 25 mass% A polyester resin solution was obtained.
  • trimellitic anhydride shown in column D is added to this mixture, and the pressure is gradually reduced to 0.67 hPa (0.5 mmHg) at a temperature of 250 ° C., and then polycondensation is performed by holding for 2 hours in this state. The reaction proceeded. Thus, a polyester resin was obtained.
  • polyester resin solution having a polyester resin concentration of 25% by mass was obtained.
  • polyester resin solution having a polyester resin concentration of 25% by mass was obtained.
  • trimellitic anhydride shown in each of the F column and the G column is added to this mixture, and the pressure is gradually reduced to 0.67 hPa (0.5 mmHg) at a temperature of 250 ° C., and maintained for 2 hours in this state The polycondensation reaction was allowed to proceed. Thus, a polyester resin was obtained.
  • polyester resin solution having a polyester resin concentration of 25% by mass was obtained.
  • a polyester resin solution, a modified polyolefin resin solution and, if necessary, an additive were mixed at a solid content ratio shown in Tables 2 to 4 to obtain a mixed solution.
  • the primer composition was obtained by adding 20% by mass of butyl cellosolve as a leveling agent to this mixed solution.
  • Paint Layer Adhesion Test An acrylic resin-based aqueous white paint was applied by a bar coater on the primer layer on the substrate, and then heated at 120 ° C. for 5 minutes. Thus, a paint layer of about 2 ⁇ m in thickness was formed on the primer layer. A cellophane adhesive tape was adhered to this paint layer and peeled off, and the appearance of the remaining paint layer was observed. As a result, "A” indicates that peeling of the paint layer is not observed, “B” indicates that peeling is observed at a part of the paint layer, and “C” indicates that peeling is observed at most of the paint layer. ,evaluated.
  • the modified polyolefin resin solution in the table is an aqueous dispersion of a maleic anhydride modified polyolefin resin, the details of which are as follows.
  • APTOLOK BW-5550 manufactured by Mitsubishi Chemical Corporation, trade name APTOLOK BW-5550.
  • Auroran AE-301 manufactured by Nippon Paper Industries Co., Ltd., trade name Auroran AE-301.
  • Genpoly HGW9566 manufactured by LOTTE CHEMICAL CORPORATION, trade name Genpoly HGW9566. Aqueous dispersion of maleic anhydride modified polypropylene resin. Weight average molecular weight 40000 or more.
  • Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd., trade name Epocross WS-700, an oxazoline crosslinking agent.
  • Carbodilight SV-02 manufactured by Nisshinbo Chemical Co., Ltd., trade name Carbodilight SV-02, a carbodiimide type crosslinking agent.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de peinture primaire hydrophile qui peut conférer une adhésivité à un substrat lorsqu'elle est appliquée à ce dernier et qui présente de bonnes propriétés de manipulation. Cette composition de peinture primaire contient une résine de polyester comportant un résidu carboxylique multivalent et d'un résidu glycol, et une résine de polyoléfine modifiée. Le résidu carboxylique multivalent contient un résidu carboxylique trivalent ou multivalent supérieur et/ou un résidu carboxylique multivalent comportant un groupe sulfonate métallique. La valeur du rapport en masse de la résine de polyester à la résine de polyoléfine modifiée se situe dans la plage de 8/2 à 2/8.
PCT/JP2015/001244 2014-09-16 2015-03-06 Composition de peinture primaire et élément stratifié Ceased WO2016042683A1 (fr)

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JP2016548528A JP6346669B2 (ja) 2014-09-16 2015-03-06 プライマー組成物及び積層部材
KR1020177007504A KR101976550B1 (ko) 2014-09-16 2015-03-06 프라이머 조성물 및 적층 부재
CN201580049519.1A CN106715612B (zh) 2014-09-16 2015-03-06 底漆组合物和层合材料

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019123228A (ja) * 2018-01-17 2019-07-25 メック株式会社 一体成形物とその製造方法、およびプライマー組成物
WO2021181449A1 (fr) * 2020-03-09 2021-09-16 互応化学工業株式会社 Composition de protection

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020251153A1 (fr) * 2019-06-14 2020-12-17 주식회사 케이씨씨 Composition de sous-couche de peinture
US11319458B2 (en) * 2020-03-09 2022-05-03 Goo Chemical Co., Ltd. Method for fabricating semiconductor device chips and protective composition

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08103988A (ja) * 1994-10-06 1996-04-23 Teijin Ltd 易接着性白色ポリエステルフィルム
JPH0987582A (ja) * 1995-09-20 1997-03-31 Nippon Zeon Co Ltd プライマー組成物およびプライマー層を有する成形体
JP2005089647A (ja) * 2003-09-18 2005-04-07 Nippon Bee Chemical Co Ltd 水性プライマー塗料およびこれを用いた塗膜形成方法
WO2007094510A1 (fr) * 2006-02-16 2007-08-23 Kansai Paint Co., Ltd. Composition aqueuse de sous-couche et procede de revetement d'un article moule en plastique en utilisant une telle composition
WO2007119760A1 (fr) * 2006-04-11 2007-10-25 Kansai Paint Co., Ltd. Composition aqueuse d'apprêt
JP2008111076A (ja) * 2006-10-31 2008-05-15 Toyobo Co Ltd 共重合ポリエステルおよび被覆ポリエステルフィルム
JP2011219545A (ja) * 2010-04-06 2011-11-04 Goo Chemical Co Ltd ポリエステル樹脂組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60155225A (ja) * 1984-01-24 1985-08-15 Kuraray Co Ltd 新規なポリエステル、それからなる接着剤、及びそれから構成される積層物と積層中空容器
JP4272393B2 (ja) * 2002-08-07 2009-06-03 互応化学工業株式会社 水性難燃性ポリエステル樹脂の製造方法
JP5297085B2 (ja) * 2008-05-16 2013-09-25 互応化学工業株式会社 層状珪酸塩とハイブリッド化した水性ポリエステル樹脂、皮膜形成用樹脂組成物、ポリエステルフィルム及び繊維
KR101679436B1 (ko) 2008-10-01 2016-11-24 디아이씨 가부시끼가이샤 프라이머 및 상기 프라이머로 이루어지는 수지 도막을 가지는 적층체

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08103988A (ja) * 1994-10-06 1996-04-23 Teijin Ltd 易接着性白色ポリエステルフィルム
JPH0987582A (ja) * 1995-09-20 1997-03-31 Nippon Zeon Co Ltd プライマー組成物およびプライマー層を有する成形体
JP2005089647A (ja) * 2003-09-18 2005-04-07 Nippon Bee Chemical Co Ltd 水性プライマー塗料およびこれを用いた塗膜形成方法
WO2007094510A1 (fr) * 2006-02-16 2007-08-23 Kansai Paint Co., Ltd. Composition aqueuse de sous-couche et procede de revetement d'un article moule en plastique en utilisant une telle composition
WO2007119760A1 (fr) * 2006-04-11 2007-10-25 Kansai Paint Co., Ltd. Composition aqueuse d'apprêt
JP2008111076A (ja) * 2006-10-31 2008-05-15 Toyobo Co Ltd 共重合ポリエステルおよび被覆ポリエステルフィルム
JP2011219545A (ja) * 2010-04-06 2011-11-04 Goo Chemical Co Ltd ポリエステル樹脂組成物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019123228A (ja) * 2018-01-17 2019-07-25 メック株式会社 一体成形物とその製造方法、およびプライマー組成物
WO2021181449A1 (fr) * 2020-03-09 2021-09-16 互応化学工業株式会社 Composition de protection
JPWO2021181449A1 (fr) * 2020-03-09 2021-09-16
JP7096625B2 (ja) 2020-03-09 2022-07-06 互応化学工業株式会社 保護用組成物
US12054640B2 (en) 2020-03-09 2024-08-06 Goo Chemical Co., Ltd. Protective composition

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KR20170042777A (ko) 2017-04-19
KR101976550B1 (ko) 2019-05-09
JPWO2016042683A1 (ja) 2017-06-08
JP6346669B2 (ja) 2018-06-20
CN106715612B (zh) 2019-10-11

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