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
• • 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
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • 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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate

Definitions

• the present invention relates to an amorphous polyester adhesive composition containing a liquid crystal polymer. More specifically, the adhesive composition has excellent dispersibility of the liquid crystal polymer, low relative permittivity and dielectric loss tangent, excellent heat resistance, and excellent circuit embedding property and peel strength when used as an adhesive for flexible printed wiring boards. It relates to a thing, and an adhesive sheet, a laminate and a printed wiring board using the same thing.
• Amorphous polyester is a general term for non-crystalline polyesters, which are widely used as raw materials for resin compositions used in coating agents, inks, adhesives, etc., and are generally polyvalent carboxylic acids and polyhydric alcohols. Consists of. It is widely used in various applications such as coating agents and adhesives because it has flexibility by selecting and combining polyvalent carboxylic acid and polyhydric alcohol and can freely control the high and low molecular weight.
• Amorphous polyester has excellent adhesiveness to metals including copper, and has been used as an adhesive for flexible printed wiring boards (FPC) by blending a curing agent such as epoxy resin.
• FPC flexible printed wiring boards
• FPC Since FPC has excellent flexibility, it can be used for multi-functionality and miniaturization of personal computers (PCs) and smartphones, and is therefore often used for incorporating electronic circuit boards into narrow and complicated interiors. There is. In recent years, electronic devices have become smaller, lighter, higher in density, and have higher output, and due to these trends, the demand for the performance of wiring boards (electronic circuit boards) has become more and more sophisticated. In particular, as the speed of transmission signals in FPCs increases, the frequency of signals is increasing. Along with this, there is an increasing demand for FPCs having low dielectric properties (low dielectric constant, low dielectric loss tangent) in the high frequency region.
• the base material used for FPC not only the conventional polyimide (PI) and polyethylene terephthalate (PET), but also the base film such as liquid crystal polymer (LCP) and syndiotactic polystyrene (SPS) having low dielectric properties.
• LCP liquid crystal polymer
• SPS syndiotactic polystyrene
• As an adhesive a combination of polyolefin and epoxy (Patent Document 2) and the like are being developed.
• a method has been invented in which LCP powder subjected to plasma treatment or ultraviolet treatment is dispersed in a solvent to form a sheet (Patent Document 3).
• the polyester resin described in Patent Document 1 has a high relative permittivity and dielectric loss tangent, does not have the above-mentioned low dielectric properties, and is unsuitable for FPC in a high frequency region. Further, it cannot be said that the adhesive described in Patent Document 2 is excellent in heat resistance of the adhesive used for the reinforcing plate and the layers. Further, the polymer sheet using the liquid crystal polymer powder described in Patent Document 3 has a drawback that high temperature and high pressure are required for fusion with the base material.
• an object of the present invention is that a polymer sheet having excellent dispersibility of a liquid crystal polymer, low relative permittivity and dielectric loss tangent, and excellent heat resistance can be easily formed, and when used as an adhesive for a flexible printed wiring board, it is used. It is an object of the present invention to provide an adhesive composition having excellent circuit embedding property and peel strength, an adhesive sheet using the adhesive composition, a laminate, and a flexible printed wiring board.
• the present invention has the following configuration.
• It contains an amorphous polyester resin (A) and a liquid crystal polymer (B), and the average particle size (D50) of the liquid crystal polymer (B) is less than 40 ⁇ m.
• An adhesive composition having a polymer (B) content of 10 parts by mass or more and 150 parts by mass or less.
• the adhesive composition further containing a curing agent (C).
• the above-mentioned adhesive composition in which the dielectric loss tangent (tan ⁇ ) of the amorphous polyester resin (A) at 10 GHz is 0.008 or less.
• the above-mentioned adhesive composition having a dielectric loss tangent (tan ⁇ ) of 0.005 or less at 10 GHz.
• An adhesive sheet having a layer formed by the adhesive composition.
• a laminate having a layer formed by the adhesive composition having a layer formed by the adhesive composition.
• a printed wiring board that includes the laminate as a component.
• the adhesive composition of the present invention can easily form a polymer sheet having excellent dispersibility of a liquid crystal polymer, low relative permittivity and dielectric loss tangent, and excellent heat resistance. Further, it can be laminated in a low temperature region of 130 ° C. to 160 ° C., and has excellent circuit embedding property and peel strength, so that it is suitable for an FPC material in a high frequency region.
• the amorphous polyester resin (A) used in the present invention is a polyester having no melting point, and can be obtained by a polyvalent carboxylic acid component or a polycondensate of a polyvalent carboxylic acid ester component and a polyvalent alcohol component. It has a chemical structure capable of being formed, and the polyvalent carboxylic acid component or the polyvalent carboxylic acid ester component and the polyvalent alcohol component are composed of one or more selected components, respectively.
• amorphous polyester it is possible to form a resin composition that is flexible and has excellent adhesion to metals and the like.
• the polyvalent carboxylic acid component constituting the amorphous polyester resin (A) is not limited, but the following polyvalent carboxylic acids or esters thereof, and polyvalent carboxylic acid anhydrides can be used.
• the polyvalent carboxylic acid includes aromatic polyvalent carboxylic acids such as naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and orthophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, adipic acid, sebacic acid and dimer acid.
• 1,3-Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid fumaric acid, maleic acid, 5-sodium sulfodimethylisophthalic acid, trimellitic acid, or pyromellitic acid, and derivatives such as esters thereof.
• Polyvalent carboxylic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hydrogenated naphthalenedicarboxylic acid, etc. Can be mentioned.
• aromatic polyvalent carboxylic acid or dimer acid is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 70 mol% or more, out of 100 mol% of the total polyvalent carboxylic acid component. It is 80 mol% or more, particularly preferably 90 mol% or more, and 100 mol% may be used. Further, from the viewpoint of adjusting the glass transition temperature and solvent solubility, aromatic polyvalent carboxylic acid and dimer acid can be used in combination.
• the polyvalent alcohol constituting the amorphous polyester resin (A) is not particularly limited, but is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3. -Butandiol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol , 1-Methyl-1,8-octanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-propyl- 1,3-Propanediol, 2,2-din-propyl-1,3-propanediol, 2-n-butyl-2-ethy
• dimerdiol or tricyclodecanedimethanol contains dimerdiol or tricyclodecanedimethanol.
• the content of dimerdiol or tricyclodecanedimethanol is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, out of 100 mol% of the polyhydric alcohol component.
• the inclusion of dimerdiol or tricyclodecanedimethanol improves the dielectric properties of the amorphous polyester resin adhesive composition. When it contains tricyclodecanedimethanol, it is particularly excellent in dielectric loss tangent.
• the inclusion of dimerdiol also improves solvent solubility. It is also preferable to use dimerdiol and tricyclodecanediol in combination.
• the amorphous polyester resin (A) can also be copolymerized with a trivalent or higher polyvalent carboxylic acid component and / or a trivalent or higher polyhydric alcohol component.
• a trivalent or higher valent carboxylic acid component include aromatic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimesic acid, trimellitic anhydride (TMA), and pyromellitic anhydride (PMDA). , 1, 2, 3, 4-Butantetracarboxylic acid and other aliphatic carboxylic acids, and one or more of these can be used.
• trihydric or higher polyhydric alcohol component examples include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, ⁇ -methylglucose, mannitol, and sorbitol, and one or more of these may be used. It is possible.
• copolymerizing a trivalent or higher polyvalent carboxylic acid component and / or a trivalent or higher polyhydric alcohol component 5 mol% or less is preferable out of a total of 200 mol% of the polyvalent carboxylic acid component and the polyhydric alcohol component. , More preferably 4 mol% or less.
• Lactone and lactam can also be copolymerized with the amorphous polyester resin (A).
• A amorphous polyester resin
• ⁇ -caprolactone and ⁇ -caprolactam can be used.
• a polyvalent carboxylic acid and a polyhydric alcohol are heated in the presence of a known catalyst and subjected to a dehydration esterification step to remove them.
• Method of performing polyhydric alcohol / polycondensation reaction 2) Heat the alcohol ester of polyhydric carboxylic acid and polyhydric alcohol in the presence of a known catalyst, transesterify, and then perform depolyhydric alcohol / polycondensation reaction.
• Method, 3) There is a method of performing depolymerization and the like. In the methods 1) and 2) above, a part or all of the acid component may be replaced with an acid anhydride.
• amorphous polyester resin (A) When producing the amorphous polyester resin (A), conventionally known polymerization catalysts such as titanium compounds such as tetra-n-butyl titanate, tetraisopropyl titanate and titaniumoxyacetylcetonate, antimony trioxide and tri Antimony compounds such as butoxyantimony, germanium oxides, germanium compounds such as tetra-n-butoxygermanium, and acetates such as magnesium, iron, zinc, manganese, cobalt, and aluminum can be used. These catalysts may be used alone or in combination of two or more.
• a method for increasing the acid value of the amorphous polyester resin (A) for example, (1) after completion of the polycondensation reaction, a trivalent or higher polyvalent carboxylic acid and / or a trivalent or higher anhydrous polycarboxylic acid is used. There are methods such as adding and reacting (acid addition), and (2) intentionally altering the resin by allowing heat, oxygen, water, etc. to act during the polycondensation reaction, and these can be performed arbitrarily. Can be done.
• the polyvalent carboxylic acid anhydride used for acid addition in the acid addition method is not particularly limited, and is, for example, phthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, anhydrous. Pyromellitic acid, hexahydrophthalic anhydride, 3,3,4,4-benzophenone tetracarboxylic dianhydride, 3,3,4,5-biphenyltetracarboxylic dianhydride, ethylene glycol bisamhydrotrimeritate Etc., and one kind or two or more kinds of these can be used.
• the dielectric loss tangent of the amorphous polyester resin (A) at 10 GHz is preferably 0.01 or less, more preferably 0.008 or less. More preferably, it is 0.005 or less.
• an amorphous polyester resin having a low dielectric loss tangent it is possible to form an adhesive composition that maintains the low dielectric properties of the liquid crystal polymer (B).
• the relative permittivity of the amorphous polyester resin (A) at 10 GHz is preferably 3.0 or less, more preferably 2.6 or less.
• the glass transition temperature of the amorphous polyester resin (A) is preferably ⁇ 30 ° C. or higher, more preferably ⁇ 20 ° C. or higher. By setting the glass transition temperature in the range of ⁇ 30 ° C. or higher, good dielectric properties are exhibited, and the tackiness (adhesiveness) of the resin surface tends to be suppressed, so that the handleability of the resin is improved.
• the glass transition temperature is preferably 100 ° C. or lower. The lower the glass transition temperature, the better the adhesive strength tends to be.
• the number average molecular weight of the amorphous polyester resin (A) is preferably 5000 or more, and more preferably 10,000 or more. Further, it is preferably 100,000 or less, more preferably 50,000 or less, and further preferably 30,000 or less. When it is within the above range, it is preferable because it is easy to handle when dissolved in a solvent, the adhesive strength is good, and the dielectric property is excellent.
• the acid value of the amorphous polyester resin (A) is preferably from 200 eq / 10 6 g, more preferably at most 100 eq / 10 6 g, further not more than 50 eq / 10 6 g It is preferably 40 eq / 10 6 g or less, and most preferably 30 eq / 10 6 g or less.
• the liquid crystal polymer (B) used in the present invention is a polymer exhibiting liquid crystal properties, and the composition is not particularly limited, but is further limited to aromatic polyester or aromatic polyester amide, and further imide bond, carbonate bond, carbodiimide bond or isocyanate. It may be a polymer in which a bond derived from isocyanurate such as a nurate bond has been introduced.
• the average particle size (D50) of the liquid crystal polymer (B) used in the present invention needs to be less than 40 ⁇ m. More preferably, it is less than 30 ⁇ m.
• a liquid crystal polymer having an average particle size (D50) of less than 40 ⁇ m when used as an adhesive for FPC, an amorphous polyester resin or liquid crystal polymer can be embedded between circuits, and the insulation of the circuit can be improved. Can be enhanced.
• the dispersion stability of the liquid crystal polymer in the adhesive composition is improved.
• the average particle size (D50) of the liquid crystal polymer (B) can be obtained by mechanically pulverizing a lumpy, flake-like, granular, pellet-like or film-like liquid crystal polymer.
• the powdering method is not limited, but hammer mill, pin mill, disc mill, rotary mill, jet mill, fluidized floor air jet mill, jaw crusher, gyrate crusher, cage mill, pan crusher, ball mill, pebble mill, rod mill, tube. It can be mechanically crushed with a mill, disc attribution mill, attritor, disc refiner, or the like.
• the adhesive composition of the present invention one in which the liquid crystal polymer crushed by the above method is dispersed in a solvent or the like in advance, or one in the form of a paste can be used.
• the surface of the liquid crystal polymer (B) may be subjected to surface treatment such as plasma treatment, ultraviolet treatment, or corona treatment in order to improve dispersion stability.
• the adhesive composition of the present invention contains 10 parts by mass or more and 150 parts by mass or less of the liquid crystal polymer (B) with respect to 100 parts by mass of the amorphous polyester resin (A). It is more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more.
• the upper limit is more preferably 100 parts by mass or less, further preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less.
• the adhesive composition of the present invention can further contain a curing agent (C).
• a curing agent (C) an epoxy resin, polyisocyanate, polycarbodiimide or the like can be used. By cross-linking with these curing agents, the cohesive force of the resin can be increased, and the adhesive strength and heat resistance can be improved. Polyisocyanate is preferable because it has little effect on heat resistance and dielectric properties.
• the epoxy resin used in the present invention is not particularly limited as long as it has an epoxy group in the molecule, but is preferably one having two or more epoxy groups in the molecule.
• it is a biphenyl type epoxy resin, a novolak type epoxy resin, a dicyclopentadiene type epoxy resin or an epoxy-modified polybutadiene. More preferably, it is a dicyclopentadiene type epoxy resin or a novolac type epoxy resin.
• the content of the epoxy resin is preferably 0.1 part by mass or more, more preferably 0.5 part by mass with respect to 100 parts by mass of the amorphous polyester resin (A). It is more than a part, more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. By setting it to the above lower limit value or more, a sufficient curing effect can be obtained and excellent peel strength can be exhibited. Further, it is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 35 parts by mass or less. By setting the value to the upper limit or less, the pot life property and the low dielectric property are improved. That is, within the above range, an adhesive composition having excellent low dielectric properties in addition to adhesiveness and pot life can be obtained.
• the polycarbodiimide used in the present invention is not particularly limited as long as it has a carbodiimide group in the molecule. It is preferably a polycarbodiimide having two or more carbodiimide groups in the molecule.
• polycarbodiimide By using polycarbodiimide, the carboxyl group of the amorphous polyester resin (A) reacts with the carbodiimide group, the interaction between the adhesive composition and the base material can be enhanced, and the adhesiveness can be improved.
• the content of polycarbodiimide is preferably 0.1 part by mass or more, more preferably 0.5 part by mass, based on 100 parts by mass of the amorphous polyester resin (A). It is more than a part, more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. When it is set to the above lower limit value or more, the interaction with the base material is exhibited and the adhesiveness is improved. Further, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. Is. By setting the value to the upper limit or less, excellent pot life and low dielectric properties can be exhibited. That is, within the above range, an adhesive composition having excellent low dielectric properties in addition to adhesiveness, solder heat resistance and pot life property can be obtained.
• the polyisocyanate used in the present invention is not particularly limited as long as it is an isocyanate compound that reacts with the amorphous polyester resin (A) and cures.
• polyisocyanate examples include aromatic or aliphatic diisocyanate compounds and trivalent or higher valent polyisocyanate compounds. These isocyanate compounds may be either low molecular weight compounds or high molecular weight compounds.
• aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate
• aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate
• fats such as hydride diphenylmethane diisocyanate, hydride xylylene diisocyanate, dimerate diisocyanate and isophorone diisocyanate.
• Examples thereof include cyclic diisocyanates and trimerics of these isocyanate compounds.
• a terminal isocyanate group obtained by reacting an excess amount of the isocyanate compound with a low molecular weight active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine and triethanolamine. Examples include contained compounds.
• examples thereof include terminal isocyanate group-containing compounds obtained by reacting an excess amount of the isocyanate compound with various polyester polyols, polyether polyols, polymer active hydrogen compounds of polyamides and the like. These isocyanate compounds can be used alone or in combination of two or more. Of these, a trimer of a hexamethylene diisocyanate compound is particularly preferable.
• the content of polyisocyanate is preferably 0.1 part by mass or more, more preferably 0.5 part by mass, based on 100 parts by mass of the amorphous polyester resin (A). It is more than a part, more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more.
• it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. Is.
• excellent pot life and low dielectric properties can be exhibited. That is, within the above range, an adhesive composition having excellent low dielectric properties in addition to adhesiveness, solder heat resistance and pot life property can be obtained.
• the adhesive composition of the present invention can further contain an organic solvent.
• the organic solvent used in the present invention is not particularly limited as long as it dissolves the amorphous polyester resin (A) and the curing agent (C).
• aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane.
• Halogenized hydrocarbons such as hydrogen, trichloroethylene, dichloroethylene, chlorobenzene, chloroform, alcoholic solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, acetone, methylisobutylketone, Ketone solvents such as methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone, cell solves such as methyl cellsolve and ethyl cell solve, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, etc.
• alcoholic solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, acetone,
• Ethylene glycol mono n-butyl ether ethylene glycol mono iso-butyl ether, ethylene glycol mono tert-butyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono iso-butyl ether, triethylene glycol mono n-butyl ether, tetraethylene glycol mono n-butyl ether, etc.
• a glycol ether solvent or the like can be used, and one or more of these can be used in combination.
• Methylcyclohexane and toluene are particularly preferable because of their work environment and dryness.
• the organic solvent is preferably in the range of 100 to 1000 parts by mass, more preferably in the range of 200 to 900 parts by mass, and 300 to 800 parts by mass with respect to 100 parts by mass of the amorphous polyester resin (A). Most preferably, it is in the range of parts. When it is at least the above lower limit value, the liquid and pot life properties are improved. Further, setting the value to the upper limit or less is advantageous in terms of manufacturing cost and transportation cost.
• the adhesive composition of the present invention may further contain other components as required.
• specific examples of such components include flame retardants, tackifiers, fillers, and silane coupling agents.
• a flame retardant may be added to the adhesive composition of the present invention, if necessary.
• the flame retardant include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds.
• a phosphorus-based flame retardant is preferable, and a known phosphorus-based flame retardant such as a phosphate ester such as trimethyl phosphate, triphenyl phosphate, tricresyl phosphate or the like, a phosphate such as aluminum phosphinate, or phosphazene can be used. .. These may be used alone or in any combination of two or more.
• the flame retardant when the flame retardant is contained, it is preferable to contain the flame retardant in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the total of the amorphous polyester resin (A) and the curing agent (C) components, and 5 to 150 parts.
• the range of parts by mass is more preferable, and the range of 10 to 100 parts by mass is most preferable. Within the above range, flame retardancy can be exhibited while maintaining adhesiveness, solder heat resistance and electrical characteristics.
• a tackifier may be added to the adhesive composition of the present invention, if necessary.
• the tackifier include polyterpene resin, rosin resin, aliphatic petroleum resin, alicyclic petroleum resin, copolymer petroleum resin, styrene resin and hydrogenated petroleum resin, and the purpose is to improve the adhesive strength. Used in. These may be used alone or in any combination of two or more.
• the tackifier is contained, it is preferably contained in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the total of the amorphous polyester resin (A) and the curing agent (C) components, and 5 to 150 parts by mass. Is more preferable, and the range of 10 to 100 parts by mass is most preferable. Within the above range, the effect of the tackifier can be exhibited while maintaining the adhesiveness, solder heat resistance and electrical characteristics.
• a filler may be added to the adhesive composition of the present invention.
• the organic filler include powders of heat-resistant resins such as polyimide and polyamide-imide.
• the inorganic filler include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TIO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), and barium sulfate (Si 3 N).
• silica is preferable because of the ease of dispersion and the effect of improving heat resistance.
• Hydrophobic silica and hydrophilic silica are generally known as silica, but here, hydrophobic silica treated with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, etc.
• the blending amount is preferably 0.05 to 30 parts by mass with respect to 100 parts by mass in total of the amorphous polyester resin (A) and the curing agent (C) component. Further heat resistance can be exhibited by setting it to the above lower limit value or more. Further, by setting the value to the upper limit or less, it is possible to prevent poor dispersion of silica and excessively high solution viscosity, and workability is improved.
• a silane coupling agent may be added to the adhesive composition of the present invention, if necessary. It is very preferable to add a silane coupling agent because the properties of adhesion to metal and heat resistance are improved.
• the silane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having a glycidyl group, and those having an amino group.
• glycidyls such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane from the viewpoint of heat resistance.
• a silane coupling agent having a group is more preferable.
• the blending amount may be 0.5 to 20 parts by mass with respect to 100 parts by mass of the total of the amorphous polyester resin (A) and the curing agent (C) components. preferable. Within the above range, solder heat resistance and adhesiveness can be improved.
• the laminate of the present invention is one in which an adhesive composition is laminated on a base material (a two-layer laminate of a base material / adhesive layer), or one in which a base material is further bonded (base material / adhesive layer / It is a three-layer laminate of a base material).
• the adhesive layer refers to a layer of the adhesive composition after the adhesive composition of the present invention is applied to a base material and dried.
• the laminate of the present invention can be obtained by applying and drying the adhesive composition of the present invention to various substrates according to a conventional method, and further laminating other substrates.
• the base material is not particularly limited as long as the adhesive composition of the present invention can be applied and dried to form an adhesive layer, but the base material is a resin base material such as a film-like resin, or a metal. Examples include metal substrates such as plates and metal foils, papers, and the like.
• the resin base material examples include polyester resin, polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine resin.
• a film-like resin hereinafter, also referred to as a base film layer is preferable.
• any conventionally known conductive material that can be used for the circuit board can be used.
• the material include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, as well as alloys, plated products, and metals treated with other metals such as zinc and chromium compounds.
• a metal leaf is preferable, and a copper foil is more preferable.
• the thickness of the metal foil is not particularly limited, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 10 ⁇ m or more. Further, it is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 20 ⁇ m or less.
• the metal leaf is usually provided in roll form.
• the form of the metal foil used in manufacturing the printed wiring board of the present invention is not particularly limited. When a ribbon-shaped metal foil is used, its length is not particularly limited. The width thereof is also not particularly limited, but is preferably about 250 to 500 cm.
• the surface roughness of the base material is not particularly limited, but is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, and further preferably 1.5 ⁇ m or less.
• it is practically preferably 0.3 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 0.7 ⁇ m or more. Further, it is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, and further preferably 1.5 ⁇ m or less.
• Examples of papers include high-quality paper, kraft paper, roll paper, glassine paper, and the like. Further, as the composite material, glass epoxy or the like can be exemplified.
• polyester resin polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, fluorine resin, etc.
• SUS steel plate, copper foil, aluminum foil, or glass epoxy is preferable.
• the adhesive sheet is a laminate of the laminate and a release base material via an adhesive composition.
• Specific configuration embodiments include a laminate / adhesive layer / release base material, or a release base material / adhesive layer / laminate / adhesive layer / release base material.
• the release base material By laminating the release base material, it functions as a protective layer of the base material. Further, by using the release base material, the release base material can be released from the adhesive sheet and the adhesive layer can be transferred to another base material.
• the adhesive sheet of the present invention can be obtained by applying the adhesive composition of the present invention to various laminates and drying them according to a conventional method.
• a release base material is attached to the adhesive layer after drying, it can be wound up without causing set-off to the base material, which is excellent in operability and protects the adhesive layer for storage stability. It is excellent and easy to use.
• the release base material is coated and dried, and then another release base material is attached as needed, the adhesive layer itself can be transferred to another base material.
• the release base material is not particularly limited, but for example, a coating layer of a sealant such as clay, polyethylene, or polypropylene is applied to both sides of paper such as high-quality paper, kraft paper, roll paper, and glassine paper. Examples thereof include those in which a silicone-based, fluorine-based, or alkyd-based mold release agent is coated on each of the coating layers.
• various olefin films such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, and propylene- ⁇ -olefin copolymer alone, and those obtained by applying the above-mentioned release agent on a film such as polyethylene terephthalate can also be mentioned. Release force of the release base material and the adhesive layer, silicone has an adverse effect on electrical properties, etc.
• the method for coating the adhesive composition on the substrate in the present invention is not particularly limited, and examples thereof include a comma coater and a reverse roll coater.
• the adhesive layer may be provided directly or by a transfer method on the rolled copper foil or the polyimide film which is the constituent material of the printed wiring board.
• the thickness of the adhesive layer after drying is appropriately changed as needed, but is preferably in the range of 5 to 200 ⁇ m. Sufficient adhesive strength can be obtained by setting the adhesive film thickness to 5 ⁇ m or more. Further, when the thickness is 200 ⁇ m or less, it becomes easy to control the amount of residual solvent in the drying process, and blister is less likely to occur during pressing for manufacturing a printed wiring board.
• the drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 1% by mass or less. By setting the content to 1% by mass or less, foaming of the residual solvent during pressing of the printed wiring board is suppressed, and blistering is less likely to occur.
• the "printed wiring board” in the present invention includes a laminate formed of a metal foil forming a conductor circuit and a resin base material as a constituent element.
• the printed wiring board is manufactured by a conventionally known method such as a subtractive method using a metal-clad laminate, for example.
• the printed wiring board of the present invention can have any laminated structure that can be adopted as a printed wiring board.
• it can be a printed wiring board composed of four layers, a base film layer, a metal foil layer, an adhesive layer, and a cover film layer.
• it can be a printed wiring board composed of five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer.
• two or three or more of the above printed wiring boards may be laminated.
• the adhesive composition of the present invention can be suitably used for each adhesive layer of the printed wiring board.
• the adhesive composition of the present invention when used as an adhesive, it has high adhesiveness not only to the conventional polyimide, polyester film, and copper foil constituting the printed wiring board, but also to a low-polarity resin base material such as LCP. , Solder reflow resistance can be obtained, and the adhesive layer itself has excellent low dielectric properties. Therefore, it is suitable as an adhesive composition used for coverlay films, laminated boards, copper foils with resins, and bonding sheets.
• any resin film conventionally used as the base material of the printed wiring board can be used as the base film.
• the resin of the base film include polyester resin, polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine resin.
• it has excellent adhesiveness to low-polarity substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resins.
• any conventionally known insulating film as an insulating film for a printed wiring board can be used.
• films made from various polymers such as polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, polyamideimide, liquid crystal polymer, syndiotactic polystyrene, and polyolefin resin are used. It is possible. More preferably, it is a polyimide film or a liquid crystal polymer film.
• the printed wiring board of the present invention can be manufactured by any conventionally known process other than using the materials of each layer described above.
• a semi-finished product in which an adhesive layer is laminated on a cover film layer (hereinafter, referred to as "cover film side semi-finished product") is manufactured.
• a semi-finished product (hereinafter referred to as “base film side two-layer semi-finished product”) in which a metal foil layer is laminated on a base film layer to form a desired circuit pattern, or an adhesive layer is laminated on a base film layer.
• a semi-finished product (hereinafter referred to as “base film side three-layer semi-finished product”) in which a metal foil layer is laminated on the metal foil layer to form a desired circuit pattern (hereinafter referred to as a base film-side two-layer semi-finished product).
• base film side semi-finished product By laminating the cover film side semi-finished product thus obtained and the base film side semi-finished product, a four-layer or five-layer printed wiring board can be obtained.
• the base film side semi-finished product is, for example, (A) a step of applying a resin solution to be a base film to the metal foil and initially drying the coating film, and (B) the metal foil obtained in (A). It is obtained by a production method including a step of heat-treating and drying the laminate with the initial dry coating film (hereinafter, referred to as "heat treatment / solvent removal step").
• a conventionally known method can be used for forming the circuit in the metal foil layer.
• the additive method may be used, or the subtractive method may be used.
• the subtractive method is preferable.
• the obtained base film side semi-finished product may be used as it is for bonding with the cover film side semi-finished product, or for bonding with the cover film side semi-finished product after the release film is bonded and stored. You may use it.
• the cover film side semi-finished product is manufactured by applying an adhesive to the cover film, for example. If necessary, a cross-linking reaction can be carried out on the applied adhesive. In a preferred embodiment, the adhesive layer is semi-cured.
• the obtained cover film side semi-finished product may be used as it is for bonding with the base film side semi-finished product, or may be bonded to the base film side semi-finished product after the release film is bonded and stored. May be used for.
• the base film side semi-finished product and the cover film side semi-finished product are, for example, stored in the form of rolls and then bonded together to manufacture a printed wiring board. Any method can be used as the bonding method, and for example, the bonding can be performed using a press or a roll. It is also possible to bond the two together while heating by a method such as using a heating press or a heating roll device.
• the reinforcing material side semi-finished product is preferably manufactured by applying an adhesive to the reinforcing material.
• an adhesive to the reinforcing material.
• the adhesive previously applied to the release base material is transferred and applied. It is preferable to be manufactured. Further, if necessary, a cross-linking reaction can be carried out in the applied adhesive.
• the adhesive layer is semi-cured.
• the obtained reinforcing material side semi-finished product may be used as it is for bonding with the back surface of the printed wiring board, or may be used for bonding with the base film side semi-finished product after the release film is bonded and stored. You may.
• the base film side semi-finished product, the cover film side semi-finished product, and the reinforcing material side semi-finished product are all laminates for the printed wiring board in the present invention.
• a simple part means a mass part.
• Measurement of glass transition temperature Measurement was performed using a differential scanning calorimeter (SII, DSC-200). 5 mg of amorphous polyester resin was placed in an aluminum holding lid type container, sealed, and cooled to ⁇ 50 ° C. using liquid nitrogen. Next, the temperature is raised to 150 ° C. at a heating rate of 20 ° C./min, and in the heat absorption curve obtained in the temperature rise process, an extension of the baseline before the heat absorption peak appears (below the glass transition temperature) and the heat absorption peak. The temperature of the intersection with the tangent line toward (the tangent line indicating the maximum inclination from the rising portion of the peak to the peak of the peak) was defined as the glass transition temperature (Tg, unit: ° C.).
• Relative permittivity ( ⁇ c ) and dielectric loss tangent (tan ⁇ ) of amorphous polyester resin Amorphous polyester resin dissolved in toluene was applied to a Teflon (registered trademark) sheet having a thickness of 100 ⁇ m so as to have a thickness of 25 ⁇ m after drying, and dried at 130 ° C. for 3 minutes. Then, the Teflon (registered trademark) sheet was peeled off to obtain a resin sheet for testing. After that, the obtained test resin sheet was cut into strips of 8 cm ⁇ 3 mm to obtain a test sample.
• Teflon registered trademark
• the relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) were measured by a cavity resonator perturbation method using a network analyzer (manufactured by Anritsu) under the conditions of a temperature of 23 ° C. and a frequency of 10 GHz.
• amorphous polyester resin (a1) In a reaction vessel equipped with a stirrer, condenser, and thermometer, 326 parts of dimethyl 2,6-naphthalenedicarboxylic acid, 1520 parts of dimerdiol, and tetrabutyl orthotitanate as a catalyst are used as total acid components. On the other hand, 0.03 mol% was charged, the temperature was raised from 160 ° C. to 220 ° C. over 4 hours, and the esterification reaction was carried out through a dehydration step. Next, in the polycondensation reaction step, the pressure inside the system was reduced to 5 mmHg over 20 minutes, and the temperature was further raised to 250 ° C.
• the glass transition temperature was -17 ° C. The results are shown in Table 1.
• Example of Production of Liquid Crystal Polymer As a liquid crystal polymer, pellet-shaped "XYDAR" manufactured by SOLVAY SPECIALTY POLYMERS was pulverized with a jet mill to obtain powders having an average particle size (D50) of 6 ⁇ m, 20 ⁇ m, 30 ⁇ m, and 40 ⁇ m, respectively.
• the melting point of the powder measured by DSC was 320 ° C., and the dielectric loss tangent measured by the cavity resonator perturbation method was 0.001.
• the particle size of the liquid crystal polymer is measured by laser diffraction scattering particle size measurement (manufactured by Coulter Co., Ltd.) by dispersing the liquid crystal polymer in water in which 10 ppm of a dispersant (nonionic surface active emalgen manufactured by Kao Co., Ltd.) is dissolved.
• the median diameter obtained by measuring with LS12 320 Beckman) was defined as the average particle size (D50).
• Example 1 58 parts of amorphous polyester resin (a1), 40 parts of liquid crystal polymer powder having an average particle size (D50) of 6 ⁇ m, and 2 parts of Sumijur N3300 (HDI type isocyanurate manufactured by Sumika Cobestrourethane) as a curing agent are blended. , Diluted with toluene until the solid content concentration became 45%, and dispersed with homodisper to obtain an adhesive composition. Each evaluation was performed on the obtained adhesive composition. The results are shown in Table 2.
• the adhesive composition was applied to a polyimide film having a thickness of 12.5 ⁇ m (manufactured by Kaneka Corporation, Apical (registered trademark)) so as to have a thickness of 25 ⁇ m after drying, and dried at 130 ° C. for 3 minutes.
• the adhesive film (B stage product) thus obtained was bonded to a rolled copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd., BHY series) having a thickness of 18 ⁇ m.
• the bonding was performed by pressing the rolled copper foil under pressure of 2 MPa at 160 ° C. for 30 seconds so that the glossy surface of the rolled copper foil was in contact with the adhesive layer to bond the rolled copper foil.
• Relative permittivity ( ⁇ c ) and dielectric loss tangent (tan ⁇ ) of the adhesive composition The adhesive composition was applied to a Teflon (registered trademark) sheet having a thickness of 100 ⁇ m so as to have a thickness of 25 ⁇ m after drying, and dried at 130 ° C. for 3 minutes. Then, after heat-treating at 170 ° C. for 3 hours to cure, the Teflon (registered trademark) sheet was peeled off to obtain an adhesive resin sheet for testing. After that, the obtained test adhesive resin sheet was cut into strips of 8 cm ⁇ 3 mm to obtain a test sample.
• Teflon (registered trademark) sheet having a thickness of 100 ⁇ m so as to have a thickness of 25 ⁇ m after drying, and dried at 130 ° C. for 3 minutes. Then, after heat-treating at 170 ° C. for 3 hours to cure, the Teflon (registered trademark) sheet was peeled off to obtain an adhesive resin sheet for testing
• the relative permittivity ( ⁇ c ) and the dielectric loss tangent (tan ⁇ ) were measured by a cavity resonator perturbation method using a network analyzer (manufactured by Anritsu) under the conditions of a temperature of 23 ° C. and a frequency of 10 GHz.
• Dispersion Stability The adhesive composition in a glass bottle was allowed to stand at 25 ° C. for one day, and its stability was visually confirmed and evaluated according to the following criteria. ⁇ Evaluation criteria for dispersion stability> ⁇ : No change in appearance ⁇ : Liquid crystal polymer precipitates
• the circuit-embeddable adhesive composition was applied to a polyimide film (manufactured by Kaneka Corporation, Apical (registered trademark)) having a thickness of 12.5 ⁇ m so that the thickness after drying was 25 ⁇ m, and dried at 130 ° C. for 3 minutes. ..
• the adhesive film (B stage product) thus obtained was brought into contact with a two-layer CCL (trade name: Viroflex) manufactured by Toyobo Co., Ltd., which produced a comb-shaped pattern with a line spacing of 50 ⁇ m. It was pressed under pressure for 30 seconds and adhered. After that, the space between the wires was observed with an optical microscope to confirm the presence or absence of air bubbles. When there are no bubbles, the wiring between the circuits is filled with resin or liquid crystal polymer.
• the chemically heat-resistant adhesive composition was applied to a Teflon (registered trademark) sheet having a thickness of 100 ⁇ m so as to have a thickness of 25 ⁇ m after drying, and dried at 130 ° C. for 3 minutes. Then, after heat-treating at 170 ° C. for 3 hours to cure, the Teflon (registered trademark) sheet was peeled off to obtain an adhesive resin sheet for testing. After that, 30 mg of the obtained adhesive resin sheet was placed in a platinum cell, and a temperature difference of 10 ° C./min was used in a nitrogen atmosphere using a differential thermal / thermogravimetric simultaneous measuring device (DTG-60 manufactured by Shimadzu Corporation). The temperature was raised and the 50% weight loss temperature was measured. ⁇ Evaluation criteria for chemical heat resistance> ⁇ : 50% weight loss temperature ⁇ 450 °C X: 50% weight loss temperature ⁇ 450 ° C
• the adhesive composition of the present invention can easily form a polymer sheet having excellent dispersibility of a liquid crystal polymer, low relative permittivity and dielectric loss tangent, and excellent heat resistance. Therefore, it is suitable for FPC materials in the high frequency region.

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• 2021
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