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CN115315499A - Adhesive composition, adhesive sheet, laminate, and printed wiring board - Google Patents

Adhesive composition, adhesive sheet, laminate, and printed wiring board Download PDF

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Publication number
CN115315499A
CN115315499A CN202180022016.0A CN202180022016A CN115315499A CN 115315499 A CN115315499 A CN 115315499A CN 202180022016 A CN202180022016 A CN 202180022016A CN 115315499 A CN115315499 A CN 115315499A
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CN
China
Prior art keywords
polyester
adhesive composition
adhesive
component
mass
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.)
Pending
Application number
CN202180022016.0A
Other languages
Chinese (zh)
Inventor
坂本晃一
三浦航
川楠哲生
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.)
Dongyang Textile Mc Co ltd
Original Assignee
Toyobo 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
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Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Publication of CN115315499A publication Critical patent/CN115315499A/en
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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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • 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
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides an adhesive composition which is excellent in solvent solubility, heat resistance and adhesive strength, low in relative dielectric constant and dielectric loss tangent and excellent in dielectric property, and an adhesive sheet, a laminate and a printed wiring board comprising the same. The present invention is an adhesive composition comprising a polyester and a curing agent, wherein the polyester has a polycarboxylic acid component and a polyhydric alcohol component as structural units, and contains 50mol% or more of a naphthalenedicarboxylic acid component and at least one of a dimer diol component and a tricyclodecanedimethanol component as the polyhydric alcohol component, with the polycarboxylic acid component being 100mol%.

Description

Adhesive composition, adhesive sheet, laminate, and printed wiring board
Technical Field
The present invention relates to an adhesive composition. More specifically, the present invention relates to an adhesive composition used for bonding a resin base material to a resin base material or a resin base material to a metal base material. In particular, the present invention relates to an adhesive composition for a flexible printed wiring board (hereinafter, abbreviated as FPC), and an adhesive sheet, a laminate and a printed wiring board each having a layer formed of the adhesive composition.
Background
Polyesters are widely used as raw materials for resin compositions used in coating agents, inks, adhesives, and the like, and are generally composed of polycarboxylic acids and polyhydric alcohols. Since flexibility and molecular weight due to selection and combination of a polycarboxylic acid and a polyhydric alcohol can be freely controlled, the resin composition is widely used for various applications including coating agent applications and adhesive applications.
Among them, polyester has excellent adhesion to metals including copper, and is used as an adhesive for FPC or the like in combination with a curing agent such as an epoxy resin. (for example, patent document 1).
Since FPCs have excellent flexibility, they are widely used for assembling electronic circuit boards in narrow and complicated interiors, because they can cope with the multifunctionalization and miniaturization of Personal Computers (PCs), smartphones, and the like. In recent years, electronic devices have been reduced in size, weight, density, and power, and with the spread of these devices, performance requirements for wiring boards (electronic circuit boards) have been increasing. Particularly, as the signal transmission speed in FPC increases, the frequency of the signal increases. Accordingly, the demand for low dielectric characteristics (low dielectric constant, low dielectric loss tangent) in the high frequency region of FPC has been increasing. In addition, as a substrate used for FPC, not only conventional Polyimide (PI) and polyethylene terephthalate (PET), but also a substrate film such as Liquid Crystal Polymer (LCP) and Syndiotactic Polystyrene (SPS) having low dielectric characteristics has been proposed. In order to realize low dielectric characteristics, a guideline for reducing dielectric loss of a substrate or an adhesive of an FPC has been proposed. As the adhesive, a combination of polyolefin and epoxy resin has been developed (patent document 2).
Documents of the prior art
Patent literature
Patent document 1: japanese examined patent publication (Kokoku) No. 6-104813
Patent document 2: international publication WO2016/047289
Disclosure of Invention
Problems to be solved by the invention
However, the polyester resin described in patent document 1 has a high relative dielectric constant and a high dielectric loss tangent, does not have the above low dielectric characteristics, and is not suitable for FPC in a high frequency region. The adhesive described in patent document 2 cannot be said to have excellent heat resistance as an adhesive used between a reinforcing plate and an interlayer.
The present invention has been made in view of the above-mentioned problems of the prior art. That is, an object of the present invention is to provide an adhesive composition having excellent solvent solubility, heat resistance and adhesive strength, low relative permittivity and dielectric loss tangent, and excellent dielectric characteristics, and an adhesive sheet, a laminate and a printed wiring board comprising the same.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by the means shown below, and have completed the present invention.
That is, the present invention has the following configuration.
An adhesive composition comprising a polyester and a curing agent, wherein the polyester has a polycarboxylic acid component and a polyhydric alcohol component as structural units, and wherein the polyester contains 50mol% or more of a naphthalenedicarboxylic acid component and at least one of a dimer diol component and a tricyclodecanedimethanol component as the polyhydric alcohol component, based on 100mol% of the polycarboxylic acid component.
An adhesive composition, wherein the glass transition temperature of the polyester is-30 ℃ or higher.
The adhesive composition has a relative dielectric constant (ε c) of 3.0 or less and a dielectric loss tangent (tan δ) of 0.008 or less at 10 GHz.
An adhesive sheet having a layer formed from the adhesive composition.
A laminate having a layer formed from the adhesive composition.
A printed wiring board comprising the laminate as a constituent element.
ADVANTAGEOUS EFFECTS OF INVENTION
The adhesive composition of the present invention is excellent in solvent solubility, heat resistance, adhesive strength, and dielectric characteristics. Therefore, the adhesive is suitable for FPC, adhesive sheet, laminate and printed wiring board in high frequency region.
Detailed Description
Hereinafter, one embodiment of the present invention will be described in detail. However, the present invention is not limited to this, and can be implemented by adding various modifications within the range described above.
< polyester >
The polyester of the present invention has a chemical structure obtainable by a polycondensate of a polycarboxylic acid component and a polyol component, and 1 or 2 or more components selected from the polycarboxylic acid component and the polyol component.
The polyester of the present invention contains 50mol% or more of naphthalenedicarboxylic acid component based on 100mol% of the total polycarboxylic acid components. Preferably 70mol% or more, more preferably 80mo1% or more, particularly preferably 90mol% or more, and may be 100mol%. By using a large amount of the naphthalenedicarboxylic acid component, the dielectric characteristics of the polyester are improved.
The naphthalenedicarboxylic acid component includes 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and the like, and any of these may be used, and 2 or more may be used. Among them, 2,6-naphthalenedicarboxylic acid is preferable because it is excellent in reactivity and acquisition property at the time of polymerization.
The polyester of the present invention may contain a polycarboxylic acid component other than the naphthalenedicarboxylic acid component. The polycarboxylic acid component other than the naphthalenedicarboxylic acid component is not particularly limited, but the polycarboxylic acid component is preferably an aromatic polycarboxylic acid component or an alicyclic polycarboxylic acid component, and more preferably an aromatic dicarboxylic acid component or an alicyclic dicarboxylic acid component. By using an aromatic polycarboxylic acid component or an alicyclic polycarboxylic acid component as a copolymerization component, excellent dielectric characteristics can be exhibited.
The aromatic dicarboxylic acid component is not particularly limited, and terephthalic acid, isophthalic acid, phthalic acid, 4,4' -dicarboxybiphenyl, sodium 5-sulfoisophthalic acid, esters thereof, and the like can be used.
The alicyclic dicarboxylic acid is not particularly limited, and 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hydrogenated naphthalenedicarboxylic acid, and the like can be used.
The polyester of the present invention needs to contain at least one of dimer diol and tricyclodecane dimethanol as a polyol component. The total amount of dimer diol and tricyclodecanedimethanol is preferably 20mol% or more based on 100mol% of the polyol component. More preferably 30mol% or more, and still more preferably 40mol% or more. The adhesive composition containing the polyester has improved low dielectric characteristics by containing a dimer diol or tricyclodecane dimethanol. When tricyclodecanedimethanol is contained, the dielectric loss tangent is particularly excellent. When dimer diol is contained, the solubility of the solvent is also improved. It is also preferable to use a dimer diol and tricyclodecane diol in combination.
The dimer diol is obtained by reducing carboxyl groups of a dimer acid having 20 to 48 carbon atoms obtained by dimerizing a C10 to 24 unsaturated fatty acid and a saturated dimer acid obtained by hydrogenating the dimer acid. Further, as a raw material of the dimer diol, vegetable oil may be used. Further, the dimer diol may include a trimer which is a trimer of unsaturated fatty acids having 10 to 24 carbon atoms, and a saturated trimer obtained by hydrogenating the trimer.
The polyester of the present invention may contain a dimer diol and a polyol component other than tricyclodecanedimethanol. The polyhydric alcohol other than dimer diol and tricyclodecane dimethanol is not particularly limited, and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-n-propyl-1,3-propanediol, 3925-di-n-propyl-3283 zxft 5483-propylene glycol, n-butyl-74962-n-butyl-ethyl-8696-ethyl-24 zxft-pentanediol, 2-n-butyl-ethyl-32969696969696, 1,4-cyclohexanedimethanol, and the like alicyclic polyols, polytetramethylene glycol, polypropylene glycol, and the like polyalkylene ether glycols, and these may be used in 1 or 2 or more species.
The polyester of the present invention may be copolymerized with a trivalent or higher polycarboxylic acid component and/or a trivalent or higher polyhydric alcohol component. Examples of the trivalent or higher polycarboxylic acid component include aromatic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimesic acid, trimellitic anhydride (TMA) and pyromellitic anhydride (PMDA), and aliphatic carboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, and 1 or 2 or more of these can be used. Examples of the trihydric or higher polyhydric alcohol component include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, α -methylglucose, mannitol and sorbitol, and 1 or 2 or more kinds thereof can be used. However, if the amount of the trivalent or higher polycarboxylic acid component and/or the trivalent or higher polyhydric alcohol component copolymerized is large, the dielectric characteristics of the polyester may be deteriorated, which is not preferable. When copolymerizing a trivalent or higher polycarboxylic acid component and/or a trivalent or higher polyol component, the amount of the polycarboxylic acid component and the polyol component is preferably 5mol% or less, and more preferably 4mol% or less, of the total 200 mol%.
The glass transition temperature of the polyester of the present invention is preferably-30 ℃ or higher, more preferably-20 ℃ or higher. When the glass transition temperature is in the range of-30 ℃ or higher, good dielectric properties are exhibited, and the tackiness (adhesiveness) of the resin surface tends to be suppressed, thereby improving the handling properties of the resin. Further, the glass transition temperature is preferably 100 ℃ or lower. By setting the glass transition temperature to 100 ℃ or lower, lamination can be performed even at a low temperature of about 80 ℃. Further, the lower the glass transition temperature, the better the adhesive strength tends to be.
Examples of the polycondensation reaction for producing the polyester of the present invention include: 1) A method of heating a polycarboxylic acid and a polyhydric alcohol in the presence of a known catalyst to conduct a dehydro-polycondensing reaction through a dehydro-esterification step; 2) A method of heating an alcohol ester of a polycarboxylic acid and a polyhydric alcohol in the presence of a known catalyst to perform a polyol-removing/polycondensation reaction through an ester exchange reaction; 3) A method of performing depolymerization, and the like. In the method of 1) 2), a part or all of the acid component may be replaced with an acid anhydride.
In the production of the polyester of the present invention, conventionally known polymerization catalysts can be used, for example, titanium compounds such as tetra-n-butyl titanate, tetra-isopropyl titanate and titanium oxide acetylacetonate, antimony compounds such as antimony trioxide and antimony tributoxide, germanium compounds such as germanium oxide and germanium tetra-n-butoxide, and other acetates of magnesium, iron, zinc, manganese, cobalt, aluminum and the like can be used. These catalysts may be used in combination of 1 or 2 or more.
The number average molecular weight of the polyester of the present invention is preferably 5000 or more, more preferably 10000 or more. Further, it is preferably 100000 or less, more preferably 50000 or less, and further preferably 30000 or less. Within the above range, the operation when dissolved in a solvent is easy, the adhesive strength is good, and the dielectric characteristics are excellent, so that the use is preferable.
The acid value of the polyester of the present invention is not particularly limited, and can be appropriately designed according to the curing agent used in combination. In the case of isocyanate curing, it is preferably 200eq/10 6 g or less, more preferably 100eq/10 6 g or less, more preferably 50eq/10 6 g or less, particularly preferably 40eq/10 6 g or less, most preferably 30eq/10 6 g is below. When the epoxy resin is cured, it is preferably 20eq/10 6 g or more, more preferably 50eq/10 6 g is represented byAbove, most preferably 100eq/10 6 g is above. When the resin acid value is within the above range, the low dielectric characteristics and pot life are excellent, and the effects of improving the adhesion to a substrate and the crosslinking property can be expected.
Examples of the method for increasing the acid value of the polyester of the present invention include: (1) A method in which a trivalent or higher polycarboxylic acid and/or a trivalent or higher polycarboxylic acid anhydride is added after the completion of the polycondensation reaction to cause the reaction (acid addition); (2) In the polycondensation reaction, a method such as intentionally modifying a resin by the action of heat, oxygen, water or the like may be used, and these methods may be arbitrarily carried out. The polycarboxylic acid anhydride used for acid addition in the above-mentioned acid addition method is not particularly limited, and examples thereof include trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3,3,4,4-benzophenonetetracarboxylic dianhydride, 3,3,4,4-biphenyltetracarboxylic dianhydride, and ethylene glycol bistrimellitic anhydride, and 1 or 2 or more of these can be used. Trimellitic anhydride is preferred.
< curing agent >
The adhesive composition of the present invention comprises a polyester and a curing agent. As the curing agent, epoxy resin, polyisocyanate, polycarbodiimide, or the like can be used. Crosslinking by these curing agents can improve the cohesive force of the resin and improve the heat resistance. Among them, polyisocyanates are preferable because of less influence on heat resistance and dielectric characteristics.
< epoxy resin >
The epoxy resin used in the present invention is not particularly limited as long as it has an epoxy group in a molecule, and an epoxy resin having 2 or more epoxy groups in a molecule is preferable. Specifically, although not particularly limited, at least one selected from the group consisting of biphenyl-type epoxy resin, naphthalene-type epoxy resin, bisphenol a-type epoxy resin, bisphenol F-type epoxy resin, novolac-type epoxy resin, alicyclic epoxy resin, dicyclopentadiene-type epoxy resin, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl bisaminomethylcyclohexanone, N' -tetraglycidyl-m-xylylenediamine, and epoxy-modified polybutadiene may be used. Biphenyl type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, or epoxy-modified polybutadiene is preferable. More preferably a dicyclopentadiene type epoxy resin or a novolak type epoxy resin.
In the adhesive composition of the present invention, the content of the epoxy resin is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more, relative to 100 parts by mass of the polyester. When the content is not less than the lower limit, a sufficient curing effect can be obtained, and excellent adhesiveness and solder heat resistance 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. When the content is less than the above upper limit, the pot life and the low dielectric characteristics are improved. That is, when the amount is within the above range, an adhesive composition having excellent low dielectric characteristics can be obtained in addition to adhesiveness, solder heat resistance and pot life.
< polycarbodiimide >
The polycarbodiimide used in the present invention is not particularly limited as long as it has a carbodiimide group in the molecule. Polycarbodiimides having 2 or more carbodiimide groups in the molecule are preferred. By using polycarbodiimide, the carboxyl group of the polyester reacts with a carbodiimide group, and the interaction between the adhesive composition and the base material is improved, whereby the adhesiveness can be improved.
In the adhesive composition of the present invention, the content of the polycarbodiimide is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more, based on 100 parts by mass of the polyester. When the amount is not less than the lower limit, the adhesion property is improved by the interaction with the base material. 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, further preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. When the content is less than the above upper limit, excellent pot life and low dielectric characteristics can be exhibited. That is, when the content is within the above range, an adhesive composition having excellent low dielectric characteristics can be obtained in addition to adhesiveness, solder heat resistance and pot life.
< polyisocyanates >
The polyisocyanate used in the present invention is not particularly limited as long as it is an isocyanate compound which reacts with the polyester and is cured.
Examples of the polyisocyanate include aromatic or aliphatic diisocyanate compounds and ternary or higher-order polyisocyanate compounds. These isocyanate compounds may be any of low molecular weight compounds and high molecular weight compounds. Examples thereof include aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate and isophorone diisocyanate, and trimers of these isocyanate compounds. Further, there may be mentioned compounds having a terminal isocyanate group obtained by reacting an excessive amount of the above isocyanate compound with a low molecular weight active hydrogen compound such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or the like. Further, there may be mentioned compounds containing a terminal isocyanate group obtained by reacting an excessive amount of the above isocyanate compound with various polyester polyols, polyether polyols, polyamide-based polymer active hydrogen compounds, and the like. These isocyanate compounds may be used alone or in combination of 2 or more. Among them, a trimer of the hexamethylene diisocyanate compound is particularly preferable.
In the adhesive composition of the present invention, the content of the polyisocyanate is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more, based on 100 parts by mass of the polyester. When the amount is not less than the lower limit, the adhesion property is improved by the interaction with the base material. 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, further preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. When the content is less than the above upper limit, excellent pot life and low dielectric characteristics can be exhibited. That is, when the content is within the above range, an adhesive composition having particularly excellent low dielectric characteristics can be obtained in addition to adhesiveness, solder heat resistance and pot life.
< organic solvent >
The adhesive composition of the present invention may further contain an organic solvent. The organic solvent used in the present invention is not particularly limited as long as it can dissolve the polyester and the curing agent. Specifically, for example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane and ethylcyclohexane, halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene and chloroform, alcohol solvents such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol and phenol, ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone and acetophenone, cellosolves such as methyl cellosolve and ethyl cellosolve, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate and butyl formate, glycol ether solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl ether, triethylene glycol mono-n-butyl ether and tetraethylene glycol mono-n-butyl ether can be used, and these solvents can be used in combination of 1 kind or 2 kinds or more. Particularly, methylcyclohexane and toluene are preferable in view of environmental properties and drying properties.
The organic solvent is preferably in the range of 100 to 1000 parts by mass with respect to 100 parts by mass of the polyester. When the content is not less than the lower limit, the liquid properties and pot life become good. In addition, 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 necessary. Specific examples of such components include flame retardants, tackifiers, fillers, and silane coupling agents.
< flame retardant >
The adhesive composition of the present invention may contain a flame retardant, if necessary. Examples of the flame retardant include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide. Among these, phosphorus flame retardants are preferable, and known phosphorus flame retardants such as phosphate esters (e.g., trimethyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.), phosphate salts (e.g., aluminum phosphinate, etc.), phosphazenes, and the like can be used. These may be used alone, or 2 or more of these may be used in any combination. When the flame retardant is contained, the flame retardant is contained in an amount of preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, and most preferably 10 to 100 parts by mass, based on 100 parts by mass of the total of the polyester and the curing agent component. Within the above range, flame retardancy can be exhibited while maintaining adhesiveness, solder heat resistance and electrical characteristics.
< adhesion promoter >
A tackifier may be blended as necessary in the adhesive composition of the present invention. Examples of the tackifier include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, styrene resins, and hydrogenated petroleum resins, and they are used for the purpose of improving the adhesive strength. These may be used alone, or 2 or more of them may be used in any combination. When the tackifier is contained, the tackifier is contained in an amount of preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, and most preferably 10 to 100 parts by mass, based on 100 parts by mass of the total of the polyester and the curing agent component. Within the above range, the effect of the thickener can be exhibited while maintaining the adhesiveness, solder heat resistance and electrical characteristics.
< Filler >
The adhesive composition of the present invention may contain a filler as needed. Examples of the organic filler include powders of polyimide, polyamideimide, and the like, which are heat-resistant resins. Further, as the inorganic filler, for example, silica (SiO) can be mentioned 2 ) Alumina (Al) 2 O 3 ) Titanium dioxide (TiO) 2 ) Tantalum oxide (Ta) 2 O 5 )、Zirconium oxide (ZrO) 2 ) Silicon nitride (Si) 3 N 4 ) Boron Nitride (BN), calcium carbonate (CaCO) 3 ) Calcium sulfate (CaSO) 4 ) Zinc oxide (ZnO), magnesium titanate (MgO. TiO) 2 ) Barium sulfate (BaSO) 4 ) And organobentonite, clay, mica, aluminum hydroxide, magnesium hydroxide, and the like, among which silica is preferable because of the effects of improving the ease of dispersion and heat resistance.
As the silica, usual hydrophobic silica and hydrophilic silica are known, and hydrophobic silica treated with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, or the like is preferable in order to impart moisture absorption resistance. When silica is blended, the blending amount is preferably 0.05 to 30 parts by mass with respect to 100 parts by mass of the total of the polyester and the curing agent component. When the content is not less than the lower limit, further heat resistance can be exhibited. When the amount is not more than the above upper limit, dispersion failure of silica and an excessively high solution viscosity can be suppressed, and the workability can be improved.
< silane coupling agent >
The adhesive composition of the present invention may contain a silane coupling agent as needed. The silane coupling agent is preferably added because the properties of adhesion to metal and heat resistance are improved. The silane coupling agent is not particularly limited, and examples thereof include a silane coupling agent having an unsaturated group, a silane coupling agent having an epoxy group, and a silane coupling agent having an amino group. Among these, silane coupling agents having an epoxy group such as γ -glycidoxypropyltrimethoxysilane, β - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and β - (3,4-epoxycyclohexyl) ethyltriethoxysilane are more preferable from the viewpoint of heat resistance. When the silane coupling agent is blended, the blending amount is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the total of the polyester and the curing agent. Within the above range, the solder heat resistance and adhesiveness can be improved.
< layered product >
The laminate of the present invention is obtained by laminating the adhesive composition on a base material (2-layer laminate of base material/adhesive layer), or is obtained by further laminating a base material (3-layer laminate of base material/adhesive layer/base material). Here, the adhesive layer refers to a layer of the adhesive composition of the present invention applied to a substrate and dried. The adhesive composition of the present invention is applied to various substrates by a conventional method and dried, and further, other substrates are laminated, whereby the laminate of the present invention can be obtained.
< substrate >
The base material in the present invention is not particularly limited as long as the adhesive composition of the present invention can be applied and dried to form an adhesive layer, and examples thereof include resin base materials such as film-like resins, metal base materials such as metal plates and metal foils, and papers.
Examples of the resin base material include polyester resins, polyamide resins, polyimide resins, polyamideimide resins, liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resins, and fluorine resins. A film-like resin (hereinafter, also referred to as a base film layer) is preferable.
As the metal base material, any conventionally known conductive material that can be used for a circuit board can be used. Examples of the raw material include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, alloys of these metals, plated products, and metals treated with other metals such as zinc and chromium compounds. Preferably a metal foil, more preferably a copper foil. The thickness of the metal foil is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 10 μm or more. Further, it is preferably 50 μm or less, more preferably 30 μm or less, and further preferably 20 μm or less. If the thickness is too thin, it may be difficult to obtain sufficient electrical performance of the circuit, while if the thickness is too thick, the processing efficiency and the like at the time of manufacturing the circuit may be reduced. The metal foil is usually provided in a roll form. The form of the metal foil used for manufacturing the printed wiring board of the present invention is not particularly limited. When a metal foil in a band form is used, the length thereof is not particularly limited. The width is not particularly limited, and is preferably about 250 to 500 cm. The surface roughness of the base material is not particularly limited, but is preferably 3 μm or less, more preferably 2 μm or less, and further preferably 1.5 μm or less. In practice, the particle diameter is preferably 0.3 μm or more, more preferably 0.5 μm or more, and still more preferably 0.7 μm or more.
As the paper, forest paper, kraft paper, roll paper, glassine paper, and the like can be exemplified. Further, as the composite raw material, glass epoxy resin or the like can be exemplified.
The base material is preferably a polyester resin, a polyamide resin, a polyimide resin, a polyamideimide resin, a liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, a polyolefin resin, a fluorine resin, a SUS steel plate, a copper foil, an aluminum foil, or a glass epoxy resin, based on the adhesion force to the adhesive composition and the durability.
< adhesive sheet >
In the present invention, the adhesive sheet is a sheet obtained by laminating the laminate and a release substrate with an adhesive composition interposed therebetween. Specific configuration modes include a laminate/adhesive layer/release base material, or release base material/adhesive layer/laminate/adhesive layer/release base material. The release base material is laminated to function 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 further 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 the same according to a conventional method. Further, when the release base material is adhered to the adhesive layer after drying, the release base material can be wound up without blocking with the base material, and the release base material is excellent in handling property, and also excellent in storage property because the adhesive layer is protected, and is easy to use. Further, after the release base material is applied and dried, if necessary, another release base material is adhered, and the adhesive layer itself can be transferred to another base material.
< mold release substrate >
The release substrate is not particularly limited, and examples thereof include release substrates in which a pore-filling agent coating layer of clay, polyethylene, polypropylene or the like is provided on both surfaces of paper such as dow paper, kraft paper, roll paper, glassine paper or the like, and a silicone-based, fluorine-based or alkyd-based release agent is further applied to each coating layer. Further, there may be mentioned various olefin films alone such as polyethylene, polypropylene, ethylene- α -olefin copolymer, propylene- α -olefin copolymer, and a release base material obtained by coating the release agent on a film such as polyethylene terephthalate. For the reason that the release force between the release substrate and the adhesive layer, silicone, or the like adversely affects the electrical characteristics, a release substrate using an alkyd-based release agent after pore-filling with polypropylene on both sides of the release substrate or a release substrate using an alkyd-based release agent on polyethylene terephthalate is preferable.
The method for applying the adhesive composition to the substrate in the present invention is not particularly limited, and a comma coater, a reverse roll coater, and the like can be mentioned. Alternatively, if necessary, an adhesive layer may be provided on a rolled copper foil or a polyimide film as a constituent material of a printed wiring board, directly or by a transfer method. The thickness of the adhesive layer after drying may be appropriately changed as necessary, and is preferably in the range of 5 to 200 μm. Sufficient adhesive strength can be obtained by setting the thickness of the adhesive film to 5 μm or more. Further, when the thickness is 200 μm or less, the amount of the residual solvent in the drying step can be easily controlled, and foaming is less likely to occur in the pressing for manufacturing a printed wiring board. The drying conditions are not particularly limited, and the residual solvent ratio after drying is preferably 1% by mass or less. When the amount is 1% by mass or less, foaming of the residual solvent during pressing of the printed wiring board can be suppressed, and foaming is less likely to occur.
< printed Wiring Board >
The printed wiring board of the present invention includes a laminate of a metal foil forming a conductor circuit and a resin substrate as a constituent element. The printed wiring board can be manufactured by a conventionally known method such as a Subtractive method (reactive) using a metal-clad laminate. A so-called flexible printed circuit board (FPC), a flat cable, a circuit board for Tape Automated Bonding (TAB), and the like, which partially or entirely covers a conductor circuit formed of a metal foil with a cover film, screen printing ink, or the like, are collectively referred to as a printed wiring board as necessary.
The printed wiring board of the present invention may have any laminate structure that can be used as a printed wiring board. For example, the printed wiring board may be a printed wiring board including 4 layers of a base film layer, a metal foil layer, an adhesive layer, and a cover film layer. For example, the printed wiring board may be a printed wiring board including 5 layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer.
Further, the printed wiring board may be configured by stacking 2 or 3 or more printed wiring boards as needed.
The adhesive composition of the present invention can be suitably used for each adhesive layer of a printed wiring board. In particular, when the adhesive composition of the present invention is used as an adhesive, the adhesive composition has high adhesiveness not only to conventional polyimide, polyester film, and copper foil constituting a printed wiring board but also to a low-polarity resin base material such as LCP, reflow resistance can be obtained, and the adhesive layer itself has excellent low dielectric characteristics. Therefore, the resin composition is suitable for use as a coating film, a laminate, a resin-coated copper foil, and an adhesive sheet.
In the printed wiring board of the present invention, as the base film, any resin film conventionally used as a base material of a printed wiring board can be used. Examples of the resin of the base film include polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluorine resin. In particular, the adhesive composition has excellent adhesion to low-polarity substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resins.
< cover film >
As the cover film, any conventionally known insulating film can be used as the insulating film for the printed wiring board. For example, films made of various polymers such as polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, polyamide imide, liquid crystal polymer, syndiotactic polystyrene, and polyolefin resin can be used. More preferably 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, except for using the materials of the above layers.
In a preferred embodiment, a semi-finished product in which an adhesive layer is laminated on a cover film layer (hereinafter referred to as a "cover film side semi-finished product") is manufactured. On the other hand, the following semi-finished products were manufactured: a semi-finished product in which a metal foil layer is laminated on a base film layer to form a desired circuit pattern (hereinafter, referred to as "base film side 2-layer semi-finished product") or a semi-finished product in which an adhesive layer is laminated on a base film layer and a metal foil layer is further laminated thereon to form a desired circuit pattern (hereinafter, referred to as "base film side 3-layer semi-finished product") (hereinafter, the base film side 2-layer semi-finished product and the base film side 3-layer semi-finished product are collectively referred to as "base film side semi-finished product"). By bonding the thus obtained cover film side semi-finished product to the base film side semi-finished product, a 4-layer or 5-layer printed wiring board can be obtained.
The substrate film side semi-finished product can be obtained, for example, by a manufacturing method including the following steps: (A) A step of coating a resin solution to be a base film on the metal foil and initially drying the coating film; (B) A step of heat-treating and drying the laminate of the metal foil obtained in (a) and the initially dried coating film (hereinafter referred to as "heat-treating and desolvating step").
The formation of the circuit in the metal foil layer may be performed by a conventionally known method. Either Additive or subtractive methods may be used. The subtractive method is preferred.
The obtained base material film-side semi-finished product may be used as it is for bonding to a cover film-side semi-finished product, or may be used for bonding to a cover film-side semi-finished product after being bonded to a release film and stored.
The cover film side semi-finished product can be produced by, for example, applying an adhesive to the cover film. If necessary, a crosslinking reaction may be carried out in 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 to the base film side semi-finished product, or may be used for bonding to the base film side semi-finished product after being bonded to the release film and stored.
The base film side semi-finished product and the cover film side semi-finished product are stored in a roll form, for example, and then bonded to each other to manufacture a printed wiring board. As a method of bonding, any method can be used, and for example, bonding can be performed using a press, a roller, or the like. Alternatively, the two may be bonded together by heating with a heating press or a heating roller device.
The reinforcing material side semi-finished product is preferably produced by applying an adhesive to a reinforcing material in the case of a soft windable reinforcing material such as a polyimide film. In the case of a hard and non-windable reinforcing plate such as a metal plate of SUS, aluminum, or the like, a plate obtained by curing glass fibers with an epoxy resin, or the like, for example, the reinforcing plate is preferably produced by transfer coating of an adhesive previously applied to a release substrate. If necessary, the crosslinking reaction may be performed in the applied adhesive. In a preferred embodiment, the adhesive layer is semi-cured.
The obtained reinforcing material side semi-finished product may be used as it is for bonding to the back surface of a printed wiring board, or may be used for bonding to a base material film side semi-finished product after being bonded to a release film and stored.
The substrate film side semi-finished product, the cover film side semi-finished product, and the reinforcing material side semi-finished product are all laminates for printed wiring boards of the present invention.
Examples
The present invention will be specifically described below with reference to examples. In the present example and comparative example, "part" for short means part by mass.
(method of evaluating physical Properties)
Determination of the composition of the polyester
Using 400MHz 1 An H-nuclear magnetic resonance spectrometer (hereinafter, may be abbreviated as NMR) quantitatively determines the molar ratio of the polycarboxylic acid component and the polyol component constituting the polyester. Deuterated chloroform was used as solvent. When the acid value of the polyester is increased by acid post-addition, the acid component other than the acid component used for the acid post-addition isThe total amount was 100mol%, and the molar ratio of each component was calculated.
Determination of glass transition temperature
The measurement was carried out using a differential scanning calorimeter (SII Co., ltd., DSC-200). 5mg of the sample (polyester) was sealed in an aluminum cap type container and cooled to-50 ℃ using liquid nitrogen. Then, the temperature was raised to 150 ℃ at a temperature raising rate of 20 ℃/min, and in the endothermic curve obtained during the temperature raising, the temperature at the intersection of the extension of the base line before the onset of the endothermic peak (glass transition temperature or less) and the tangent of the endothermic peak (the tangent having the largest slope from the rising portion of the peak to the peak apex) was taken as the glass transition temperature (Tg, unit:. Degree. C.).
Determination of number average molecular weight
The polyester sample was dissolved and/or diluted in tetrahydrofuran so that the resin concentration became about 0.5 wt%, and the solution was filtered through a polytetrafluoroethylene membrane filter having a pore diameter of 0.5 μm to prepare a sample for measurement. The molecular weight was measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a mobile phase and a differential refractometer as a detector. The flow rate was 1 mL/min and the column temperature was 30 ℃. The columns were KF-802, 804L and 806L manufactured by Showa Denko K.K. The molecular weight standard used was monodisperse polystyrene.
Measurement of acid value
0.2g of the polyester sample was dissolved in 40ml of chloroform, and the solution was titrated with 0.01N potassium hydroxide ethanol solution to obtain 10-fold volume of the solution 6 g equivalent weight of polyester (eq/10) 6 g) In that respect Phenolphthalein was used as an indicator.
Hereinafter, examples of synthesis of the polyester used in the present invention will be shown.
Synthesis example of polyester (a 1)
In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 326 parts of 2,6-naphthalenedicarboxylic acid dimethyl ester, 1520 parts of dimer diol (Croda, pripol 2033) and 0.03mol% of tetrabutyl titanate as a catalyst to the whole acid components were charged, and the temperature was raised from 160 ℃ to 220 ℃ over 4 hours, and the esterification reaction was carried out while passing through a dehydration step. Then, the pressure in the system was reduced to 5mmHg over 20 minutes, and the temperature was further raised to 250 ℃ to perform a polycondensation reaction. Then, the pressure was reduced to 0.3mmHg or less, and after a polycondensation reaction was carried out for 60 minutes, the reaction mixture was taken out. As a result of composition analysis by NMR of the obtained polyester (a 1), the molar ratio was 2,6-naphthalenedicarboxylic acid/dimer diol =100/100[ molar ratio ]. Furthermore, the glass transition temperature was-17 ℃. The evaluation results are set forth in table 1.
Examples of Synthesis of polyesters (a 2) to (a 15)
Polyesters (a 2) to (a 15) were synthesized by changing the types and blending ratios of the raw materials according to the production example of the polyester (a 1). Further, 8 parts by mass of trimellitic anhydride was added to the polyester (a 9) after completion of the polymerization reaction, and the mixture was reacted at 230 ℃ for 30 minutes to carry out acid post-addition. The results are set forth in Table 1. In addition, PTMG1000 is polytetramethylene ether glycol (average molecular weight 1000).
Figure BDA0003849770230000171
(evaluation of adhesive composition)
Relative dielectric constant (. Epsilon.) and dielectric loss tangent (tan. Delta.)
The adhesive composition was applied to a Teflon (registered trademark) sheet having a thickness of 100 μm so that the thickness after drying became 25 μm, and dried at 130 ℃ for 3 minutes. Subsequently, the sheet was cured by heat treatment at 170 ℃ for 3 hours, and the Teflon (registered trademark) sheet was peeled off to obtain an adhesive resin sheet for testing. Then, the obtained adhesive resin sheet for test was cut into a strip sample of 8cm × 3mm to obtain a sample for test. Relative dielectric constant (. Epsilon.) c ) And the dielectric loss tangent (tan. Delta.) were measured by the resonance cavity perturbation method at a temperature of 23 ℃ and a frequency of 10GHz using Network Analyzers (manufactured by Anritsu Corp.).
< evaluation criteria for relative dielectric constant >
Very good: 2.3 or less
O: more than 2.3 and less than 3.0
X: over 3.0
< evaluation criteria for dielectric loss tangent >
Very good: 0.005 or less
O: more than 0.005 and less than 0.008
X: over 0.008
Solubility in solvent
The solvent solubility was evaluated using a toluene varnish of polyester before the addition of the curing agent. The polyester was dissolved in toluene so that the solid content concentration became 60 mass%, 50 mass% or 30 mass% while stirring at 80 ℃ for 6 hours, and the solubility at this time was evaluated according to the following criteria.
< evaluation criteria for solvent solubility >
Very good: the solid content was 60% by mass, and the solution was completely dissolved without any dissolution residue
O: the solid content was 50% by mass, and the solution was completely dissolved without any dissolution residue
Δ: the solid content was 30% by mass, and the solution was completely dissolved without any dissolution residue
X: a solid content of 30% by mass, a resin-dissolved residue
Peel Strength (adhesiveness)
The adhesive composition was applied to a polyimide film (manufactured by Kaneka, application (registered trademark)) having a thickness of 12.5 μm so that the thickness after drying became 25 μm, and dried at 130 ℃ for 3 minutes. The adhesive film (B-stage) thus obtained was bonded to a rolled copper foil (BHY series, manufactured by JX Metal Co., ltd.) having a thickness of 18 μm. The bonding was performed by pressing the glossy surface of the rolled copper foil and the adhesive layer at 160 ℃ under a pressure of 2MPa for 30 seconds. Subsequently, the film was cured by heat treatment at 170 ℃ for 3 hours to obtain a sample for peel strength evaluation. As for the peel strength, the film was pulled at 25 ℃ and subjected to a 90 ℃ peel test at a stretching speed of 50mm/min to measure the peel strength. This test shows the adhesive strength at normal temperature.
< evaluation criteria >
Very good: 1.0N/mm or more
O: 0.8N/mm or more and less than 1.0N/mm
Δ:0.5N/mm or more and less than 0.8N/mm
X: less than 0.5N/mm
Heat resistance
The adhesive composition was applied to a Teflon (registered trademark) sheet having a thickness of 100 μm so that the thickness after drying became 25 μm, and dried at 130 ℃ for 3 minutes. Subsequently, the sheet was cured by heat treatment at 170 ℃ for 3 hours, and the Teflon (registered trademark) sheet was peeled off to obtain a test adhesive resin sheet.
The measurement was carried out using a differential thermal/thermogravimetric simultaneous measurement apparatus (DTG-60, shimadzu Corp.). 50mg of an adhesive resin sheet was placed in a platinum tank, and the temperature was raised to 1000 ℃ at a temperature rise rate of 5 ℃/min under a nitrogen atmosphere at a flow rate of 20 ml/min. Decomposition was carried out at a high temperature, and the temperature at which the weight became 95% of the initial weight was taken as the 5% weight loss temperature, which was used as an index of heat resistance.
< evaluation criteria for Heat resistance >
O: 5% weight loss at a temperature of 300 ℃ or higher
X: the 5% weight loss temperature is below 300 deg.C
The following are descriptions of an adhesive composition as an example of the present invention and a production example of an adhesive composition as a comparative example.
As the curing agent, the following compounds were used.
(b1) The method comprises the following steps Polyisocyanate (SUMIDUR N3300 (スミジユール N3300, manufactured by Sumika Covestro Urethane Co., ltd.))
(b2) The method comprises the following steps Epoxy resin (EPICLON HP-7200H (available from DIC Co., ltd.))
(example 1)
The polyester (a 1) obtained in the above synthesis example was dissolved in toluene to prepare a toluene varnish having a solid content of 30 mass%. The adhesive composition (A1) was obtained by adding 2 parts of the curing agent (b 1) to 100 parts of the polyester (A1).
The obtained adhesive composition (A1) was evaluated for solvent solubility, relative dielectric constant, dielectric loss tangent, heat resistance, and peel strength. The results are shown in Table 2.
(examples 2 to 12 and comparative examples 1 to 5)
Adhesive compositions (A2) to (a 17) were prepared and evaluated in the same manner as in example 1, except that the type of polyester, the type of curing agent, and the amount of the curing agent were changed as shown in table 2. The results are set forth in Table 2.
[ Table 2]
Figure BDA0003849770230000211
Industrial applicability of the invention
The adhesive composition of the present invention has excellent solvent solubility and low relative permittivity and dielectric loss tangent, and is useful as an adhesive for FPC in a high frequency region.

Claims (6)

1. An adhesive composition comprising a polyester and a curing agent, wherein the polyester has a polycarboxylic acid component and a polyol component as constituent units, and contains 50mol% or more of a naphthalenedicarboxylic acid component and at least one of a dimer diol component and a tricyclodecane dimethanol component as the polyol component, assuming that the polycarboxylic acid component is 100mol%.
2. The adhesive composition according to claim 1, wherein the glass transition temperature of the polyester is-30 ℃ or higher.
3. The adhesive composition according to claim 1 or 2, wherein the relative dielectric constant ε c is 3.0 or less and the dielectric loss tangent tan δ is 0.008 or less at 10 GHz.
4. An adhesive sheet having a layer formed from the adhesive composition according to any one of claims 1 to 3.
5. A laminate having a layer formed from the adhesive composition according to any one of claims 1 to 3.
6. A printed wiring board comprising the laminate according to claim 5 as a constituent element.
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