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WO2018143446A1 - Composition de résine de polyester, agent adhésif et corps stratifié - Google Patents

Composition de résine de polyester, agent adhésif et corps stratifié Download PDF

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Publication number
WO2018143446A1
WO2018143446A1 PCT/JP2018/003714 JP2018003714W WO2018143446A1 WO 2018143446 A1 WO2018143446 A1 WO 2018143446A1 JP 2018003714 W JP2018003714 W JP 2018003714W WO 2018143446 A1 WO2018143446 A1 WO 2018143446A1
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WO
WIPO (PCT)
Prior art keywords
polyester resin
resin composition
mass
acid
parts
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/JP2018/003714
Other languages
English (en)
Japanese (ja)
Inventor
勝則 小野
文雄 浅井
麻子 奥村
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.)
Nippon Ester Co Ltd
Unitika Ltd
Original Assignee
Nippon Ester Co Ltd
Unitika 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 Nippon Ester Co Ltd, Unitika Ltd filed Critical Nippon Ester Co Ltd
Priority to CN201880005500.0A priority Critical patent/CN110121533B/zh
Priority to JP2018537681A priority patent/JP6416450B1/ja
Publication of WO2018143446A1 publication Critical patent/WO2018143446A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives 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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a polyester resin composition that has excellent adhesion to polyester films and metals and can be suitably used as an adhesive for flexible flat cables.
  • a flexible flat cable (hereinafter sometimes referred to as FFC) in which a conductor having a flat cross section is covered with an electrically insulating synthetic resin film in a sandwich shape has been widely used for internal wiring of electronic devices. In addition, the efficiency of wiring work is improved.
  • a polyester film has been conventionally used as the electrically insulating synthetic resin film constituting the FFC, and as an adhesive for bonding the electrically insulating synthetic resin film and the conductor, insulating properties and durability are used. Furthermore, polyester-based resins are used from the viewpoint of adhesiveness with an electrically insulating synthetic resin film as a base material.
  • FFCs that are thin, light, and resistant to miswiring can be modularized in parts and expanded in the car space in the automotive field, so their use in various wiring and parts is increasing. Adopted for fixed wiring such as cockpit and roof internal wiring, and moving part wiring such as steering and back monitor.
  • FFC is expected to be deployed in the engine room, which becomes a more severe usage environment, as the demand for lighter weight and higher functionality increases.
  • Parts used in the engine room are required to have not only heat resistance but also salt water resistance that can withstand the effects of water entering the engine room and salt entering when traveling near the coast.
  • the adhesive for FFC is also required to have salt water resistance that is less likely to cause a decrease in adhesive strength even under the influence of water and salt.
  • an adhesive composed of a polyester resin composition having such excellent heat resistance and salt water resistance has not been proposed yet.
  • the adhesive composition containing the polyester resin and the curing agent disclosed in Patent Documents 1 and 2 is intended to improve the adhesive strength, is not considered for salt water resistance, and is a salt spray treatment. Later, the adhesive strength was greatly reduced, and the salt water resistance was insufficient.
  • the present invention solves the above-mentioned problems, and is particularly excellent in adhesiveness to polyester films and metals, and is preferably used as an adhesive for FFC used for internal wiring of electronic equipment. It is an object of the present invention to provide a polyester resin composition having high adhesive strength under high temperature atmosphere, excellent heat resistance, small decrease in adhesive strength after salt spray treatment, and excellent performance in salt water resistance. It is.
  • the gist of the present invention is the following (1) to (8).
  • the polyester resin (A) has a glass transition temperature of ⁇ 20 to 30 ° C. and a melting point of 110 to 150 ° C.
  • the polyester resin (A) contains 60 to 90 mol% of terephthalic acid as an acid component and 10 to 50 mol% of an aliphatic dicarboxylic acid having 4 to 15 carbon atoms, and 1,4-cyclohexanedimethanol 25 as a glycol component.
  • An adhesive comprising the polyester resin composition according to any one of (1) to (4) above.
  • a laminate comprising a layer containing the polyester resin composition according to any one of (1) to (4) above.
  • the polyester resin composition of the present invention comprises a specific amount of a silane coupling agent and an isocyanate compound in a specific polyester resin, it is particularly excellent in adhesion to polyester films and metals, After bonding, the adhesive strength in a high temperature atmosphere is high and the heat resistance is excellent. Even when the salt spray treatment is performed, the decrease in the adhesive strength is small and the adhesive strength is excellent in salt water resistance. For this reason, products such as FFC using the polyester resin composition of the present invention as an adhesive layer are excellent in heat resistance and salt water resistance, and even when used in harsh environments, problems such as peeling and poor contact are unlikely to occur. It becomes.
  • the polyester resin composition of the present invention contains a polyester resin (A), a silane coupling agent (B), and an isocyanate compound (C).
  • the polyester resin (A) in the present invention needs to have a glass transition temperature of ⁇ 20 to 30 ° C., and particularly preferably ⁇ 10 to 20 ° C. If the glass transition temperature of the polyester resin (A) is less than ⁇ 20 ° C., the elastic modulus at ordinary temperature is lowered, so that the polyester resin composition has insufficient adhesion to metal. On the other hand, when the glass transition temperature exceeds 30 ° C., the polyester resin (A) has a high elastic modulus near room temperature, the resin itself becomes too hard, and the polyester resin composition adheres to the adherend. Sex does not appear.
  • the melting point of the polyester resin (A) is required to be 110 to 150 ° C., and preferably 120 to 140 ° C. among them.
  • the melting point of the polyester resin (A) is less than 110 ° C. or does not have a melting point, the polyester resin composition has low adhesive strength under a high temperature atmosphere.
  • the melting point of the polyester resin (A) exceeds 150 ° C., the polyester resin composition has poor fluidity during lamination and low adhesive strength.
  • the composition of the polyester resin (A) is preferably as follows.
  • the glycol component preferably contains 25 to 55 mol% of 1,4-cyclohexanedimethanol, more preferably 35 to 45 mol%, when the total amount of glycol components is 100 mol%.
  • the polyester resin (A) has a lower melting point, and as described in the above paragraph, the polyester resin composition has an adhesive strength in a high-temperature atmosphere. May decrease.
  • the polyester resin (A) when the content of 1,4-cyclohexanedimethanol exceeds 55 mol%, the polyester resin (A) has a high melting point, but as explained in the above paragraph, the polyester resin composition is The fluidity of the resin may decrease and the adhesive strength may decrease.
  • glycol components other than 1,4-cyclohexanedimethanol include ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, Aliphatic glycols such as ethylene glycol, tetraethylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, polyalkylene glycols such as polyethylene glycol, triethylene glycol, and polytetramethylene glycol; Hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis ( ⁇ -hydroxyethoxy) benzene, bisphenol A, 2,5-naphthalenediol, ethyleneoxy in these glycols There and aromatic glycols such as glycol was added.
  • ethylene glycol, 1,4-butanediol, triethylene glycol, and polytetramethylene glycol are preferable.
  • the polyhydric alcohol other than glycol include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.
  • the acid component of the polyester resin (A) preferably contains 60 to 90 mol% of terephthalic acid, more preferably 70 to 80 mol%, when the total amount of the acid components is 100 mol%. If the content of terephthalic acid exceeds 90 mol%, the solubility of the polyester resin (A) may decrease. On the other hand, when the content of terephthalic acid is less than 60 mol%, the polyester resin (A) has a lower crystallinity and a lower melting point, so that the polyester resin composition may have lower adhesive strength in a high-temperature atmosphere.
  • the acid component of the polyester resin (A) preferably contains 10 to 50 mol% of an aliphatic dicarboxylic acid having 4 to 15 carbon atoms, particularly 20 to 40 mol, when the total amount of the acid components is 100 mol%. % Content is preferable.
  • the polyester resin (A) has a low glass transition temperature and a low elastic modulus at high temperatures. May have insufficient adhesive strength.
  • the polyester resin (A) has a high glass transition temperature and a high elastic modulus near room temperature. Things may have reduced adhesion.
  • aliphatic dicarboxylic acids having 4 to 15 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. And pentadecanedioic acid. Among these, these are used alone or in combination of two or more. Of these, adipic acid and sebacic acid are preferred.
  • polyester resin (A) other acid components other than terephthalic acid and aliphatic dicarboxylic acid having 4 to 15 carbon atoms include isophthalic acid, 5- (alkali metal) sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, Examples thereof include aromatic dicarboxylic acids such as 4,4′-biphenyldicarboxylic acid or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid, or ester-forming derivatives thereof.
  • aromatic dicarboxylic acids such as 4,4′-biphenyldicarboxylic acid or ester-forming derivatives thereof
  • unsaturated aliphatic dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid, or ester-forming derivatives thereof.
  • polyvalent carboxylic acids other than dicarboxylic acids include butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, and ester-forming derivatives thereof. Can be mentioned.
  • the polyester resin (A) of this invention has a hydroxyl value and an acid value which are mentioned later.
  • the hydroxyl value of the polyester resin (A) is preferably 3 to 20 mgKOH / g, and more preferably 5 to 11 mgKOH / g.
  • the polyester resin (A) has a hydroxyl value of less than 3 mgKOH / g, the reaction with the isocyanate compound (C) does not proceed sufficiently, so that the polyester resin composition may be inferior in adhesive strength and heat resistance.
  • the hydroxyl value of the polyester resin (A) exceeds 20 mgKOH / g, the curing shrinkage increases, so that the polyester resin composition may have a reduced adhesive strength.
  • the acid value of the polyester resin (A) is preferably 5 mgKOH / g or less, and more preferably 3 mgKOH / g or less.
  • the acid value of the polyester resin (A) exceeds 5 mgKOH / g, the reaction with the isocyanate compound is accelerated and the solution stability may be lowered.
  • the hydroxyl value and acid value of the polyester resin (A) can be within the above ranges.
  • the inherent viscosity of the polyester resin (A) is preferably 0.52 to 1.00.
  • the polyester resin (A) and the polyester resin composition may contain an antioxidant as long as the characteristics are not impaired.
  • an antioxidant for example, as a hindered phenol-based antioxidant, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tri (4-hydroxy-2 -Methyl-5-tert-butylphenyl) butane, 1,1-bis (3-tert-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl) -4 -Hydroxy-benzenepropanoic acid, pentaerythrityl tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl- Benzenepropanoic acid, 3,9-bis [1,1-dimethyl-2-[(3-tert-but
  • thioether antioxidants 4,4′-thiobis [2-tert-butyl-5-methylphenol] bis [3- (dodecylthio) propionate], thiobis [2- (1,1-dimethylethyl) -5- Methyl-4,1-phenylene] bis [3- (tetradecylthio) -propionate], pentaerythritol tetrakis (3-n-dodecylthiopropionate), bis (tridecyl) thiodipropionate.
  • An antioxidant may be used independently and may use 2 or more types together.
  • the polyester resin (A) in the present invention can be synthesized by a conventionally known polyester synthesis method. For example, using an acid component and a glycol component as described above as raw materials and performing an esterification or transesterification reaction at a temperature of 220 to 280 ° C. by a conventional method, a polycondensation catalyst is added, and the pressure is reduced to 5 hPa or less. It can be obtained by performing a polycondensation reaction at a temperature of 230 to 280 ° C., preferably 240 to 260 ° C.
  • the polyester resin composition of the present invention needs to contain 0.1 to 5 parts by mass of the silane coupling agent (B) with respect to 100 parts by mass of the polyester resin (A). It is preferable to contain 3.5 parts by mass.
  • the polyester resin composition particularly improves the adhesion to the metal surface, improves the adhesion to the metal, and the adhesive strength after the salt spray treatment. The decrease in the resistance is small, and the salt water resistance is excellent.
  • the content of the silane coupling agent (B) is less than 0.1 parts by mass, the polyester resin composition has an insufficient effect of improving the adhesion to metal, and the adhesive strength after the salt spray treatment is greatly reduced.
  • the polyester resin composition when the content of the silane coupling agent (B) exceeds 5 parts by mass, the polyester resin composition has an insufficient effect of improving the adhesion to metal, and the adhesive strength after the salt spray treatment is greatly reduced. Moreover, a polyester resin composition will be inferior to the adhesive force in a high temperature atmosphere. Furthermore, the stability of the solution of the polyester resin composition described later is lowered.
  • the silane coupling agent (B) is preferably a hydrolyzable silane compound represented by the general formula: Y—R—Si—X 3 .
  • Y include a vinyl group, an epoxy group, a methacryl group, an isocyanate group, a hydroxy group, an amino group, and a mercapto group.
  • R is a linear or branched alkylene group.
  • X include an alkoxy group such as a methoxy group or an ethoxy group, a chloro group, an acetoxy group, an oxime group, and an isopropenoxy group. Several X may mutually be same or different. From the viewpoint that excellent salt water resistance can be imparted to the polyester resin composition, Y is preferably an epoxy group, an isocyanate group or an amino group, and more preferably an amino group having a high effect of improving salt water resistance.
  • silane coupling agent (B) examples include vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ - (methacryloyloxypropyl) trimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -Glycidyloxypropyltrimethoxysilane, ⁇ -glycidyloxypropylmethyldiethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N - ⁇ (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane.
  • silane coupling agents (B) examples include “KBE-903” (3-aminopropyltriethoxysilane) and “KBM-403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. ), “KBE-9007” (3-isocyanatopropyltriethoxysilane).
  • the polyester resin composition of the present invention needs to contain 1 to 5 parts by mass of the isocyanate compound (C) with respect to 100 parts by mass of the polyester resin (A). Part.
  • the content of the isocyanate compound (C) is less than 1 part by mass, the function of curing the polyester resin composition is insufficient. Therefore, the polyester resin composition is inferior in adhesion to metal and adhesion after salt spray treatment. , Heat resistance decreases.
  • the content of the isocyanate compound (C) exceeds 5 parts by mass, the polyester resin composition is gelled and fluidity is lowered. As a result, workability at the time of adhesion is lowered and the adhesiveness is inferior. It will be a thing.
  • the isocyanate compound (C) preferably has 2 or more isocyanate groups in the molecule, and preferably has 3 or more isocyanate groups from the viewpoint of heat resistance.
  • Specific examples of the isocyanate compound (C) include 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, 2,2, From 4- or 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, etc.
  • an isocyanurate body having two or more isocyanate groups in the molecule or a polyisocyanate having an aromatic ring is preferable.
  • isocyanate compound (C) which is an isocyanurate having two or more isocyanate groups in the molecule
  • TPA-100 an isocyanurate of hexamethylene diisocyanate manufactured by Asahi Kasei
  • Desmodur RFE tris (phenylisocyanate) thiophosphate
  • the polyester resin composition of the present invention contains a specific amount of a silane coupling agent and a curing agent in a specific polyester resin. After bonding, the adhesive strength in a high temperature atmosphere is high and the heat resistance is excellent. Even when the salt spray treatment is performed, the decrease in the adhesive strength is small, and the adhesive strength is excellent in salt water resistance. For this reason, products such as FFC using the polyester resin composition of the present invention as an adhesive layer are excellent in heat resistance and salt water resistance, and even when used in harsh environments, problems such as peeling and poor contact are unlikely to occur. It becomes.
  • the polyester resin composition of the present invention preferably contains a flame retardant (D) and a filler (E).
  • the flame retardant (D) can impart flame retardancy to the polyester resin composition, and is preferably a halogen flame retardant, a nitrogen flame retardant, or a phosphorus flame retardant, and more preferably a halogen flame retardant. preferable.
  • halogen flame retardants include hexabromocyclododecane, bis (dibromopropyl) tetrabromo-bisphenol A, bis ((dibromopropyl) tetrabromo-bisphenol S, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, Decabromodiphenylene oxide, brominated epoxy resin, bis (pentabromophenyl) ethane, tris (tribromophenoxy) triazine, ethylenebis (tetrabromophthal) imide, ethylenebispentabromophenyl, polybromophenylindane, brominated polystyrene Bromine compounds such as TBBA polycarbonate, brominated polyphenylene oxide, polypentabromobenzyl acrylate, and [2,2-bis (chloromethyl) -1,3 Propanediyl] bisoxybis
  • Nitrogen-based flame retardants include aliphatic amine compounds, aromatic amine compounds, triazine, melamine, benzoguanamine, methylguanamine, nitrogen-containing heterocyclic compounds such as cyanuric acid, cyanide compounds, aliphatic amides, aromatic amides, urea, thio Examples include urea.
  • Examples of the phosphorus-based flame retardant include polyphosphate-based, phosphinate-based, phosphate ester-based, condensed phosphate ester-based, and phosphazene-based flame retardants.
  • What is added as a filler (E) contains various additives, such as a flame retardant adjuvant for improving the flame retardance of said flame retardant, antioxidant, a heat stabilizer, and a pigment.
  • a flame retardant adjuvant for improving the flame retardance of said flame retardant include antimony trioxide, zinc stannate, and zinc borate.
  • antioxidant hindered phenol compounds and phosphorus-based antioxidants are preferable.
  • the heat stabilizer include phosphoric acid.
  • the pigment include titanium oxide and carbon black.
  • other fillers include swellable clay minerals, silica, alumina, and glass beads.
  • the filler (E) can be used alone or in combination of two or more.
  • a filler (E) can improve the adhesive force with respect to the polyester film and metal of the polyester resin composition of this invention by acting as a filler in a polyester resin composition. Accordingly, even when the flame retardant (D) is used, it is preferable to select one having such an action or one that does not inhibit, and among them, it is preferable to use a halogen flame retardant.
  • the total amount thereof is preferably 20 to 80% by mass in the polyester resin composition, and more preferably 30 to It is preferable that it is 75 mass%.
  • the content is less than 20% by mass, the action as a filler becomes insufficient, and the polyester resin composition tends to have a reduced adhesive force to a polyester film or metal.
  • these contents exceed 80% by mass, the polyester resin composition has a tendency that the adhesive force to the polyester film or metal tends to decrease because the resin content decreases.
  • the polyester resin composition of the present invention can be used as an adhesive.
  • the polyester resin composition of the present invention is preferably used after being dissolved in an organic solvent.
  • the organic solvent is not particularly limited as long as it dissolves the polyester resin composition of the present invention.
  • Aromatic solvents such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, 1, 2 -Chlorine solvents such as dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene and dichlorobenzene, ester solvents such as ethyl acetate, isophorone and ⁇ -butyrolactone, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Solvents, diethyl ether, ethyl cellosolve, butyl cellosolve, tetrahydrofuran, 1,4-dioxane and other ether solvents, methanol, ethanol, n-propanol, isopropanol, n-butanol and other alcohol solvents, n-butane, isobutane Examples
  • the content (solid content concentration) of the polyester resin composition is preferably 10 to 40% by mass, and more preferably 20 to 30% by mass. More preferred.
  • the adhesive may have reduced solution stability, whereas the adhesive having a solid content concentration of less than 10% by mass is the thickness of the adhesive layer.
  • the laminate of the present invention includes a layer containing the polyester resin composition of the present invention (hereinafter sometimes referred to as an adhesive layer). Especially, it is preferable that it is the laminated body laminated
  • the resin constituting the film layer is preferably a polyester such as polyethylene terephthalate (PET), polybutylene terephthalate, or polyethylene naphthalate.
  • PET polyethylene terephthalate
  • PET polybutylene terephthalate
  • the metal layer is preferably a layer in which a plurality of metal wires serving as conductors are arranged.
  • the metal constituting the conductor include copper, iron, aluminum, etc., and the conductor includes tin, zinc, and the like.
  • tinplate, or a chemical conversion treatment product such as zinc phosphate or chromate may be used.
  • an adhesive containing the polyester resin composition of the present invention is applied between a film layer and a metal layer, and then heat sealing, roll bonding, thermocompression bonding and the like are conventional.
  • a method in which the solvent is removed and bonded by a known method is suitable.
  • Adhesiveness with nickel-plated copper (adhesive strength with conducting wire)
  • the obtained adhesive is applied on a PET film (thickness 30 ⁇ m) (coating thickness 100 ⁇ m), dried at 150 ° C. for 3 minutes, and further treated at 50 ° C. for 72 hours.
  • five nickel-plated copper wires were laminator (SA-1010 manufactured by Tester Sangyo Co., Ltd.) at intervals of 1 to 2 mm.
  • Adhesive strength with nickel-plated copper after salt spray treatment The laminate 2 produced in the same manner as (7) above is subjected to salt spray treatment for 72 hours according to the method prescribed in JIS Z2371, and dried for 24 hours. A laminate 3 was obtained. The laminate 3 was measured for 180 ° peel adhesive strength (peel adhesive strength 2) in the same manner as in (7).
  • Adhesiveness with polyester film A PET film (thickness of 30 ⁇ m) is applied to the surface of the laminate 1 produced in the same manner as in (7) above using a laminator (SA-1010 manufactured by Tester Sangyo Co., Ltd.) Bonding was performed under the conditions of a temperature of 180 ° C., a linear pressure of 40 N / cm, and a speed of 1.0 m / min to obtain a laminate 4 laminated in the order of PET film / adhesive layer / PET film.
  • a test piece having a width of 25 mm was prepared from the obtained laminate 4 and tested using a Autograph AG-2 manufactured by Shimadzu Corporation under a 23 ° C atmosphere at a tensile rate of 50 mm / min. The force was measured. In addition, the test piece which became material destruction in the peeling test was set as the pass.
  • polyester resin (A-1) In the esterification reactor, 60.4 parts by mass of polybutylene terephthalate, 17.5 parts by mass of terephthalic acid, 29.9 parts by mass of adipic acid, 33.6 parts by mass of 1,4-cyclohexanedimethanol, triethylene The esterification reaction was carried out at a temperature of 215 ° C. for 4 hours by charging 42.0 parts by mass of glycol and 0.12 parts by mass of Irganox 1010 (manufactured by BASF).
  • Table 1 shows the compositions and characteristic values of the obtained polyester resins (A-1) to (A-17).
  • ⁇ Silane coupling agent ⁇ B-1 3-aminopropyltrimethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • B-2 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • B-3 3-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.)
  • C-1 Polyisocyanate of hexamethylene diisocyanate (TPA-100 manufactured by Asahi Kasei Corporation)
  • C-2 4,4-diphenylmethane diisocyanate (manufactured by Kanto Chemical Co., Inc.)
  • C-3 2,4- / 2,6-toluene diisocyanate [80/20 mixture] (Coronate T-80 manufactured by Tosoh Corporation)
  • Flame retardant bis (pentabromophenyl) ethane (SAYTEX 8010, manufactured by Albemarle)
  • Flame retardant aid antimony trioxide (manufactured by Yamanaka Sangyo)
  • Pigment Titanium oxide (Fuji Titanium Industry Co., Ltd.)
  • Filler Silica (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.)
  • Example 1 20 parts by weight of polyester resin (A-1), 48 parts by weight of dichloromethane, 9.6 parts by weight of toluene, and 2.4 parts by weight of methyl ethyl ketone were charged into a 100 mL glass bottle containing glass beads having a diameter of 2 mm, and a metal cap. And then completely dissolved with a high speed ball mill (Rocking Mill RM-50) manufactured by Seiwa Giken at 23 ° C. for 1 hour. Next, 80 parts by mass of the above solution is filled with 10 parts by mass of bis (pentabromophenyl) ethane as a flame retardant, 7.2 parts by mass of antimony trioxide as a flame retardant aid, and 2 parts by mass of titanium oxide as a pigment.
  • a high speed ball mill Rocking Mill RM-50
  • silica As a material, 0.8 part by mass of silica was charged, and dispersed at 23 ° C. for 1 hour using the same ball mill. Further, 0.2 part by mass of the silane coupling agent (B-1) and 0.62 part by mass of the isocyanate compound (C-1) were added to the above solution, and the mixture was stirred and mixed at 23 ° C. for 30 minutes in the same ball mill. And the adhesive agent which is a solution of the polyester resin composition containing a polyester resin, a silane coupling agent, and an isocyanate compound was obtained.
  • Tables 2-3 show the compositions and evaluation results of the polyester resin compositions obtained in Examples 1-29 and Comparative Examples 1-14.
  • the adhesives using the polyester resin compositions obtained in Examples 1 to 29 are excellent in adhesion to metal and maintain adhesion after salt spray treatment. The rate was high and the salt water resistance was excellent.
  • the content of the silane coupling agent is less than 0.1 parts by mass with respect to 100 parts by mass of the polyester resin.
  • the adhesive strength was inferior, and the adhesive strength retention after the salt spray treatment was inferior.
  • the content of the silane coupling agent exceeds 5 parts by mass with respect to 100 parts by mass of the polyester resin. It was inferior in stability. Since the polyester resin composition of Comparative Example 5 has an isocyanate compound content of less than 1 part by mass with respect to 100 parts by mass of the polyester resin, the resulting adhesive is insufficiently cured and has an adhesive strength in a high-temperature atmosphere. However, it was inferior in heat resistance and inferior in adhesion to metal.
  • the content of the isocyanate compound exceeds 5 parts by mass with respect to 100 parts by mass of the polyester resin, and gelation occurs.
  • the adhesive strength was inferior. Since the polyester resin composition of Comparative Example 8 has a glass transition temperature of less than ⁇ 20 ° C., the obtained adhesive has a low elastic modulus at room temperature and is inferior in adhesive strength to metal. It was. In the polyester resin composition of Comparative Example 9, since the glass transition temperature of the resin exceeded 30 ° C., the elastic modulus at room temperature was high, and the adhesive strength with metal was inferior.
  • the polyester resin composition of Comparative Example 10 does not have a melting point of the resin and is amorphous, and the polyester resin composition of Comparative Example 11 is obtained because the melting point of the resin is less than 110 ° C. All the adhesives had low adhesive strength in a high temperature atmosphere and were inferior in heat resistance. Since all of the polyester resin compositions of Comparative Examples 12 to 14 had a melting point of the resin that was too high, in Comparative Example 12, the fluidity of the resin during lamination was lowered and the adhesive strength was poor. No. 14 did not dissolve in the solvent, and an adhesive could not be obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne une composition de résine de polyester se caractérisant en ce qu'elle contient 100 parties en masse d'une résine de polyester (A), de 0,1 à 5 parties en masse d'un agent de couplage au silane (B) et de 1 à 5 parties en masse d'un composé d'isocyanate (C), la résine de polyester (A) ayant une température de transition vitreuse de -20°C à 30°C et un point de fusion de 110 à 150°C.
PCT/JP2018/003714 2017-02-06 2018-02-05 Composition de résine de polyester, agent adhésif et corps stratifié Ceased WO2018143446A1 (fr)

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JP2020050727A (ja) * 2018-09-26 2020-04-02 東洋インキＳｃホールディングス株式会社 食品包装フィルム用接着剤組成物及び食品包装フィルム
JP2020084153A (ja) * 2018-11-30 2020-06-04 三菱ケミカル株式会社 粉末積層造形法用共重合ポリブチレンテレフタレート
WO2021200714A1 (fr) * 2020-03-30 2021-10-07 東洋紡株式会社 Composition adhésive
JP2021195451A (ja) * 2020-06-15 2021-12-27 信越化学工業株式会社 エポキシ樹脂組成物
JP2023024399A (ja) * 2021-08-06 2023-02-16 三菱ケミカル株式会社 ポリエステル系樹脂（ａ）およびそれを用いたポリエステル系樹脂組成物、インキ用組成物、接着剤用組成物、並びに上記ポリエステル系樹脂（ａ）の製法
JP2023024126A (ja) * 2021-08-06 2023-02-16 三菱ケミカル株式会社 ポリエステル系樹脂組成物、粘着剤組成物、粘着剤、粘着シートおよび積層体、並びにポリエステル系樹脂（ａ）およびその製法
JP2024526793A (ja) * 2021-07-16 2024-07-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン ホット充填用途におけるフィルムラミネートのための２成分ポリウレタン接着剤組成物
JP2024526795A (ja) * 2021-07-16 2024-07-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン フィルムラミネートのための、メトキシシラン官能化イソシアネート化合物を含む２成分ポリウレタン接着剤組成物
US20240301259A1 (en) * 2021-07-16 2024-09-12 Henkel Ag & Co. Kgaa Polyurethane Adhesive Composition for Film Lamination
US20240336818A1 (en) * 2021-07-16 2024-10-10 Henkel Ag & Co. Kgaa Two-Component Polyurethane Adhesive Composition for Film Lamination
JP7810782B2 (ja) 2021-07-16 2026-02-03 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン フィルムラミネートのための、メトキシシラン官能化イソシアネート化合物を含む２成分ポリウレタン接着剤組成物

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JP2020050727A (ja) * 2018-09-26 2020-04-02 東洋インキＳｃホールディングス株式会社 食品包装フィルム用接着剤組成物及び食品包装フィルム
JP2020084153A (ja) * 2018-11-30 2020-06-04 三菱ケミカル株式会社 粉末積層造形法用共重合ポリブチレンテレフタレート
JP7139917B2 (ja) 2018-11-30 2022-09-21 三菱ケミカル株式会社 粉末積層造形法用共重合ポリブチレンテレフタレート
WO2021200714A1 (fr) * 2020-03-30 2021-10-07 東洋紡株式会社 Composition adhésive
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JP7740021B2 (ja) 2020-03-30 2025-09-17 東洋紡エムシー株式会社 接着剤組成物
JP7337462B2 (ja) 2020-06-15 2023-09-04 信越化学工業株式会社 エポキシ樹脂組成物
JP2021195451A (ja) * 2020-06-15 2021-12-27 信越化学工業株式会社 エポキシ樹脂組成物
US20240301259A1 (en) * 2021-07-16 2024-09-12 Henkel Ag & Co. Kgaa Polyurethane Adhesive Composition for Film Lamination
JP2024526793A (ja) * 2021-07-16 2024-07-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン ホット充填用途におけるフィルムラミネートのための２成分ポリウレタン接着剤組成物
JP2024526795A (ja) * 2021-07-16 2024-07-19 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン フィルムラミネートのための、メトキシシラン官能化イソシアネート化合物を含む２成分ポリウレタン接着剤組成物
US20240316900A1 (en) * 2021-07-16 2024-09-26 Henkel Ag & Co. Kgaa Two-Component Polyurethane Adhesive Composition Containing Methoxysilane Functionalized Isocyanate Compound for Film Lamination
US20240336818A1 (en) * 2021-07-16 2024-10-10 Henkel Ag & Co. Kgaa Two-Component Polyurethane Adhesive Composition for Film Lamination
JP7810782B2 (ja) 2021-07-16 2026-02-03 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン フィルムラミネートのための、メトキシシラン官能化イソシアネート化合物を含む２成分ポリウレタン接着剤組成物
JP2023024126A (ja) * 2021-08-06 2023-02-16 三菱ケミカル株式会社 ポリエステル系樹脂組成物、粘着剤組成物、粘着剤、粘着シートおよび積層体、並びにポリエステル系樹脂（ａ）およびその製法
JP2023024399A (ja) * 2021-08-06 2023-02-16 三菱ケミカル株式会社 ポリエステル系樹脂（ａ）およびそれを用いたポリエステル系樹脂組成物、インキ用組成物、接着剤用組成物、並びに上記ポリエステル系樹脂（ａ）の製法

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