WO2022196585A1

WO2022196585A1 - Adhesive composition, and adhesive sheet, laminate and printed circuit board containing this

Info

Publication number: WO2022196585A1
Application number: PCT/JP2022/011089
Authority: WO
Inventors: 晃一坂本; 哲生川楠
Original assignee: 東洋紡株式会社
Priority date: 2021-03-16
Filing date: 2022-03-11
Publication date: 2022-09-22
Also published as: TW202248392A

Abstract

[Problem] To provide an adhesive composition with excellent heat resistance and adhesion strength, with low relative permittivity and dielectric loss tangent, and with excellent dielectric properties, and to provide an adhesive sheet, a laminate and a printed circuit board containing said adhesive composition. [Solution] This adhesive composition contains a polyester resin, a compound A and a compound B. Compound A: a compound that has a terminal unsaturated hydrocarbon group and that has a 5% weight reduction temperature of at least 260°C. Compound B: a compound that has an epoxy group and a terminal unsaturated hydrocarbon group.

Description

Adhesive composition, and adhesive sheet, laminate and printed wiring board containing same

The present invention relates to adhesive compositions. More particularly, it relates to an adhesive composition used for bonding a resin base material and a resin base material or a metal base material. In particular, it relates to an adhesive composition for flexible printed wiring boards (hereinafter abbreviated as FPC), and adhesive sheets, laminates and printed wiring boards containing the same.

Copolyester is widely used as a raw material for resin compositions used in coating agents, inks, adhesives, etc., and is generally composed of polycarboxylic acids and polyhydric alcohols. You can freely control the flexibility and molecular weight by selecting and combining polyhydric carboxylic acid and polyhydric alcohol.

Copolyester has excellent adhesion to metals including copper, and has been used as an adhesive for FPCs, etc. by blending curing agents such as epoxy resin. (For example, Patent Document 1).

FPC has excellent flexibility, so it can be used for multi-functionality and miniaturization of personal computers (PCs) and smartphones. . In recent years, electronic devices have become smaller, lighter, denser, and higher in output, and the demand for the performance of wiring boards (electronic circuit boards) has become more and more sophisticated. In particular, high-frequency signals are being used to increase the transmission speed in FPC. Along with this, FPCs are increasingly required to have low dielectric properties (low dielectric constant, low dielectric loss tangent) in a high frequency region. In order to achieve such low dielectric properties, measures have been taken to reduce the dielectric loss of FPC substrates and adhesives. In addition to PET), base films such as liquid crystal polymer (LCP) and syndiotactic polystyrene (SPS) having low dielectric properties have been proposed. As an adhesive, development of an adhesive using polyphenylene ether (Patent Document 2) and the like is underway.

Tokuho 6-104813 WO2020/196718

However, the copolyester described in Patent Document 1 has a high dielectric constant and a high dielectric loss tangent, and does not have the above-mentioned low dielectric characteristics, making it unsuitable for FPC in a high frequency range. Moreover, it is difficult to say that the adhesive described in Patent Document 2 has excellent heat resistance as an FPC adhesive, and its dielectric properties are also insufficient.

The present invention was made against the background of such prior art problems. That is, an object of the present invention is to provide an adhesive composition having excellent heat resistance, adhesive strength, low dielectric constant and dielectric loss tangent, and excellent dielectric properties, and an adhesive sheet, a laminate and a printed wiring board containing the same. It is to be.

As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by means shown below, and have completed the present invention.
That is, the present invention consists of the following configurations.

[1] An adhesive composition comprising a polyester resin, compound A and compound B.
Compound A: a compound having a terminal unsaturated hydrocarbon group and a 5% weight loss temperature of 260° C. or higher Compound B: a compound having an epoxy group and a terminal unsaturated hydrocarbon group [2] The adhesive composition according to [1] above, which is a compound having an aromatic ring structure or an alicyclic structure as a structural unit.
[3] The adhesive composition of [1] above, wherein the compound A is a polyphenylene ether or a phenolic resin having a terminal unsaturated hydrocarbon group.
[4] The adhesive composition of [1] to [3], wherein the compound B is a compound having an isocyanuric ring.
[5] The adhesive composition according to [1] to [4], wherein the polyester resin has a dielectric loss tangent of 0.005 or less.
[6] The adhesive composition of [1] to [5], further comprising polycarbodiimide.
[7] An adhesive sheet having an adhesive layer comprising the adhesive composition of [1] to [6].
[8] A laminate having an adhesive layer comprising the adhesive composition of [1] to [6].
[9] A printed wiring board comprising the laminate of [8] as a component.

The adhesive composition of the present invention is excellent in dielectric properties, adhesive strength, and solder heat resistance. Therefore, it is suitable for printed wiring board adhesives, adhesive sheets, laminates and printed wiring boards in the high frequency range.

One embodiment of the present invention will be described in detail below. However, the present invention is not limited to this, and can be implemented in various modifications within the scope described above.

<Adhesive composition>
The adhesive composition of the present invention is an adhesive composition comprising a polyester resin, compound A and compound B. Here, compound A and compound B are the following compounds, respectively.
Compound A: a compound having a terminal unsaturated hydrocarbon group and a 5% weight loss temperature of 260°C or higher Compound B: a compound having an epoxy group and a terminal unsaturated hydrocarbon group Terminals of compound A and compound B Since the unsaturated hydrocarbon groups react with each other to cure without generating hydroxyl groups that deteriorate the dielectric properties, both excellent solder heat resistance and dielectric properties can be achieved.

<Polyester resin>
The polyester resin in the present invention has a chemical structure obtained by polycondensation of a polyhydric carboxylic acid component and a polyhydric alcohol component. It consists of selected ingredients.

The polycarboxylic acid component constituting the polyester resin of the present invention is preferably an aromatic polycarboxylic acid or an alicyclic polycarboxylic acid, and is preferably an aromatic dicarboxylic acid or an alicyclic dicarboxylic acid. more preferred. By using only the aromatic polycarboxylic acid component or the alicyclic polycarboxylic acid component as the polycarboxylic acid component, excellent dielectric properties can be exhibited.

The aromatic dicarboxylic acid component is not particularly limited, but terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-dicarboxybiphenyl, 5-sodiumsulfoisophthalic acid, naphthalenedicarboxylic acid, or esters thereof may be used. can be done. Naphthalenedicarboxylic acid is preferable, and can exhibit excellent dielectric properties. More preferably, 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol% or more of naphthalene dicarboxylic acid as a polyvalent carboxylic acid component constituting the polyester resin is contained to improve the dielectric properties. can be done.

The alicyclic dicarboxylic acid is not particularly limited, but 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride , hydrogenated naphthalenedicarboxylic acids, and the like can be used.

The polyhydric alcohol constituting the polyester resin in the present invention is not particularly limited, but 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, 2 , 2-di-n-propyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-di-n-butyl-1,3-propanediol, Aliphatic polyhydric alcohols such as 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol and dimer diol; Cyclic polyhydric alcohols, polytetramethylene glycol, polyalkylene ether glycols such as polypropylene glycol, and the like can be used, and one or more of these can be used. Preferred are dimer diol and tricyclodecanedimethanol, which can exhibit excellent dielectric properties. More preferably, the total content of dimer diol and tricyclodecanedimethanol as polyhydric alcohol components constituting the polyester resin is 20 mol% or more, more preferably 30 mol% or more, and particularly preferably 40 mol% or more. Dielectric properties can be improved. Only one of dimer diol and tricyclodecanedimethanol may be contained, or both may be contained.

In the polyester resin of the present invention, a polyhydric carboxylic acid component having a valence of 3 or more and/or a polyhydric alcohol component having a valence of 3 or more can be copolymerized. Examples of trivalent or higher polycarboxylic acid components include aromatic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, trimesic acid, trimellitic anhydride (TMA), and pyromellitic anhydride (PMDA). , 1,2,3,4-butanetetracarboxylic acid and other aliphatic carboxylic acids, and one or more of these can be used. Examples of trihydric or higher polyhydric alcohol components include glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, α-methylglucose, mannitol, and sorbitol, and one or more of these may be used. It is possible. However, if the copolymerization amount of the polyhydric carboxylic acid component having a valence of 3 or more and/or the polyhydric alcohol component having a valence of 3 or more is large, the dielectric properties of the polyester resin may deteriorate, which is not preferable.

As a method of polymerization condensation reaction for producing the polyester resin of the present invention, for example, 1) polyhydric carboxylic acid and polyhydric alcohol are heated in the presence of a known catalyst, and depolyhydric alcohol / 2) A method of heating an alcohol ester of a polyhydric carboxylic acid and a polyhydric alcohol in the presence of a known catalyst to conduct an ester exchange reaction, followed by a depolyhydric alcohol/polycondensation reaction, 3) There is a method of performing depolymerization, and the like. In the methods 1) and 2) above, part or all of the acid component may be replaced with an acid anhydride.

When producing the polyester resin of the present invention, conventionally known polymerization catalysts, for example, titanium compounds such as tetra-n-butyl titanate, tetraisopropyl titanate, titaniumoxyacetylcetonate, antimony trioxide, tributoxyantimony, etc. Antimony compounds, germanium compounds such as germanium oxide and tetra-n-butoxygermanium, and acetates such as magnesium, iron, zinc, manganese, cobalt and aluminum can be used. These catalysts can be used singly or in combination of two or more.

The number average molecular weight of the polyester resin in the present invention is preferably 5,000 or more, more preferably 10,000 or more. Also, it is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. Within the above range, it is easy to handle when dissolved in a solvent, and excellent in dielectric properties, which is preferable.

The polyester resin in the present invention preferably has a dielectric loss tangent of 0.005 or less at 10 GHz. It is preferably 0.004 or less, more preferably 0.003 or less. Although the lower limit is not particularly defined, it is practically 0.001 or more. In order to make the dielectric loss tangent of the polyester resin within the above range, as described above, naphthalene dicarboxylic acid, dimer diol, or tricyclodecanedimethanol may be included as a constituent unit of the polyester resin.

<Compound A>
Compound A in the present invention is a compound having a terminal unsaturated hydrocarbon group and a 5% weight loss temperature of 260° C. or higher. By having a terminal unsaturated hydrocarbon group, it is possible to increase crosslink density and improve solder heat resistance by reaction with compound B described later. In addition, since hydroxyl groups that deteriorate the dielectric properties are not generated after the reaction, the adhesive can have excellent dielectric properties. Having two or more terminal unsaturated hydrocarbon groups in one molecule is preferable because the crosslink density can be further increased. Here, the terminal unsaturated hydrocarbon group refers to a group having a CH ₂ =C structure such as vinyl group, vinylidene group, allyl group, acrylic group, methacrylic group, styrene group, and the like.

The 5% weight loss temperature of compound A must be 260°C or higher. It is preferably 270° C. or higher, more preferably 280° C. or higher, and still more preferably 290° C. or higher. When the 5% weight loss temperature is equal to or higher than the above value, soldering can be performed without causing poor appearance even at a temperature exceeding the melting point of solder.

Compound A preferably has an aromatic ring structure or an alicyclic structure as a structural unit. By having an aromatic ring structure or an alicyclic structure as a structural unit, solder heat resistance can be improved, and dielectric properties are also excellent. Among them, it is preferable to have an aromatic ring structure or an alicyclic structure as the skeleton of compound A, and polyphenylene ether or phenol resin is preferable. Specific examples of polyphenylene ethers having terminal unsaturated hydrocarbon groups include SA-9000 from SABIC and OPE-2St from Mitsubishi Gas Chemical. As the phenolic resin having a terminal unsaturated hydrocarbon group, Resitop FTC-809AE manufactured by Gun Ei Chemical Industry Co., Ltd. is exemplified.

The number average molecular weight of compound A is preferably 500 or more, more preferably 1000 or more. Also, it is preferably 100,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less. Within the above range, the solubility in a solvent is good, and a uniform adhesive coating film can be formed.

The content of compound A in the adhesive composition of the present invention is preferably 1 part by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the polyester resin. Also, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less. Within the above range, both excellent adhesiveness and soldering heat resistance can be achieved.

<Compound B>
Compound B in the present invention is a compound having an epoxy group and a terminal unsaturated hydrocarbon group. By having an epoxy group, it can be reacted with a polyester resin or polycarbodiimide described later, and by having a terminal unsaturated hydrocarbon group, it can be reacted with compound A, so that the crosslink density is further increased between these compounds. Thus, excellent solder heat resistance can be realized. Here, the terminal unsaturated hydrocarbon group refers to a group having a CH ₂ =C structure such as vinyl group, vinylidene group, allyl group, acrylic group, methacrylic group, styrene group, and the like.

The compound B preferably has a ring structure. When the compound B has a ring structure, the heat resistance can be improved and the dielectric properties are also excellent. The ring structure of compound B is preferably an aromatic ring structure or an isocyanuric ring structure from the viewpoint of heat resistance. Specific examples of such compound B include diallyl monoglycidyl isocyanurate and diglycidyl monoallyl isocyanurate. By using these, the crosslink density can be increased and the solder heat resistance can be improved.

The molecular weight of compound B is preferably 500 or less. It is more preferably 400 or less. When the molecular weight is equal to or less than the above value, the solubility in solvents and the reactivity with compound A, polyester resin, and polycarbodiimide are improved, the crosslink density is increased, and solder heat resistance can be improved.

The content of compound B in the adhesive composition of the present invention is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the polyester resin. Also, it is preferably 50 parts by mass or less, more preferably 20 parts by mass or less. Within the above range, both excellent adhesiveness and soldering heat resistance can be achieved. Moreover, the content of the compound B is preferably 1 equivalent or more of the terminal unsaturated hydrocarbon group with respect to the terminal unsaturated hydrocarbon group of the compound A. When the amount is 1 equivalent or more, the crosslink density can be increased and excellent solder heat resistance can be exhibited.

<Radical generator>
The adhesive composition of the present invention also preferably contains a radical generator. In the adhesive composition of the present invention, compound A and compound B can be reacted by heating, but the radicals generated by the radical generator cause the terminal unsaturated hydrocarbon groups of compound A and compound B to efficiently react with each other. By increasing the crosslink density, solder heat resistance and dielectric properties can be improved. Although the radical generator is not particularly limited, it is preferable to use an organic peroxide. Examples of organic peroxides include, but are not limited to, di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy- Peroxides such as 2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, lauroyl peroxide; azobisisobutyronitrile, azobisisopropionitrile and the like azonitriles, and the like.

The one-minute half-life temperature of the radical generator used in the present invention is preferably 140°C or higher. By setting the temperature to 140° C. or higher, it is possible to prevent radical reaction from starting when the solvent of the adhesive composition varnish is volatilized to prepare an adhesive sheet, and excellent adhesiveness can be exhibited.

The blending amount of the radical generator used in the present invention is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of compound A. Also, it is preferably 50 parts by mass or less, more preferably 10 parts by mass or less. By setting it within the above range, it is possible to obtain an optimum cross-linking density and achieve both adhesion and soldering heat resistance.

<Polycarbodiimide>
The adhesive composition of the invention can contain polycarbodiimide. Polycarbodiimide is not particularly limited as long as it has two or more carbodiimide bonds in the molecule. By using polycarbodiimide, the hydroxyl groups of the polyester resin react with the carbodiimide bonds, and heat resistance and adhesiveness can be improved. In addition, by reacting with the hydroxyl groups of the polyester resin, the hydroxyl groups disappear, thereby contributing to the improvement of the dielectric properties.

In the adhesive composition of the present invention, the content of polycarbodiimide is preferably 1 part by mass or more, more preferably 3 parts by mass or more, relative to 100 parts by mass of the polyester resin. By making it more than the said lower limit, a crosslink density can be raised and solder heat resistance becomes favorable. Also, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less. By adjusting the content to the above upper limit or less, excellent solder heat resistance and low dielectric properties can be exhibited. That is, within the above range, an adhesive composition having excellent solder heat resistance and low dielectric properties can be obtained.

<Epoxy resin>
The adhesive composition of the invention can contain an epoxy resin. The epoxy resin used in the present invention is not particularly limited as long as it has an epoxy group in the molecule, but preferably has two or more epoxy groups in the molecule. Specifically, although not particularly limited, 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, at least one selected from the group consisting of tetraglycidyldiaminodiphenylmethane, triglycidyl para-aminophenol, tetraglycidylbisaminomethylcyclohexanone, N,N,N',N'-tetraglycidyl-m-xylenediamine, and epoxy-modified polybutadiene; can be used. Preferred are N,N,N',N'-tetraglycidyl-m-xylenediamine, biphenyl type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin and epoxy-modified polybutadiene. More preferred is N,N,N',N'-tetraglycidyl-m-xylenediamine, which can exhibit excellent adhesiveness.

In the adhesive composition of the present invention, the content of the epoxy resin is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the polyester resin. It is preferably 1 part by mass or more. By making it more than the said lower limit, sufficient hardening effect can be acquired and the outstanding adhesiveness and soldering heat resistance can be expressed. Also, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. When the content is equal to or less than the above upper limit, good pot life and low dielectric properties are obtained. That is, within the above range, it is possible to obtain an adhesive composition having excellent low dielectric properties in addition to adhesiveness, solder heat resistance and pot life.

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 polyester resin, compound A and compound B. Specifically, for example, 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. Halogenated hydrocarbons such as hydrogen, trichlorethylene, dichloroethylene, chlorobenzene, and chloroform, alcoholic solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol, acetone, methyl isobutyl ketone, ketone solvents such as 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; 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. In particular, methylcyclohexane and toluene are preferred from the standpoint of working environment 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 resin. By making it more than the said lower limit, liquid state and pot-life property become favorable. Moreover, setting the content to the above upper limit or less is advantageous in terms of manufacturing costs and transportation costs.

In addition, 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 optionally contain a flame retardant. Examples of flame retardants include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds. Among them, phosphorus-based flame retardants are preferable, and known phosphorus-based flame retardants such as phosphate esters such as trimethyl phosphate, triphenyl phosphate, tricresyl phosphate, etc., phosphates such as aluminum phosphinate, and phosphazenes can be used. . These may be used alone, or may be used in any combination of two or more. When containing a flame retardant, it is preferable to contain a flame retardant in the range of 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, based on a total of 100 parts by mass of the polyester resin, compound A and compound B. , 10 to 100 parts by weight is most preferred. By setting the content within the above range, it is possible to exhibit flame retardancy while maintaining adhesiveness, solder heat resistance, and electrical properties.

<Tackifier>
A tackifier may be added to the adhesive composition of the present invention, if necessary. Examples of tackifiers include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, styrene resins and hydrogenated petroleum resins. used in These may be used alone, or may be used in any combination of two or more. When a tackifier is contained, it is preferably contained in the range of 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, with respect to the total 100 parts by mass of the polyester resin, compound A and compound B. A range of to 100 parts by weight is most preferred. By setting the amount within the above range, the effect of the tackifier can be exhibited while maintaining adhesiveness, soldering heat resistance and electrical properties.

<Filler>
The adhesive composition of the present invention may optionally contain a filler. Examples of organic fillers include powders of heat-resistant resins such as polyimide, polyamideimide, fluororesin, and liquid crystal polyester. Examples of inorganic fillers include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), boron nitride (BN), calcium carbonate ( _CaCO3 ), calcium sulfate ( _CaSO4 ), zinc oxide (ZnO), magnesium titanate (MgO- _TiO2 ), barium sulfate ( _BaSO4 ), organic bentonite, clay , mica, aluminum hydroxide, magnesium hydroxide, etc. Among these, silica is preferable from the viewpoint of ease of dispersion and 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. is used to impart moisture absorption resistance. is good. When silica is blended, the blending amount is preferably 0.05 to 30 parts by mass per 100 parts by mass of the copolyester, compound A and compound B in total. Further heat resistance can be expressed by making it more than the said lower limit. In addition, when the content is equal to or less than the above upper limit, poor dispersion of silica and excessive increase in solution viscosity are suppressed, and workability is improved.

<Silane coupling agent>
A silane coupling agent may be added to the adhesive composition of the present invention, if necessary. Addition of a silane coupling agent is very preferable because it improves adhesion to metals and heat resistance. Although the silane coupling agent is not particularly limited, examples thereof include those having an unsaturated group, those having an epoxy group, and those having an amino group. Among these, epoxy such as γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane is used from the viewpoint of heat resistance. A silane coupling agent having a group is more preferred. When the silane coupling agent is blended, the blending amount is preferably 0.5 to 20 parts by mass per 100 parts by mass of the polyester resin, compound A and compound B in total. Soldering heat resistance and adhesiveness can be improved by making it into the said range.

<Laminate>
The laminate of the present invention is obtained by laminating an adhesive composition on a base material (two-layer laminate of base material/adhesive layer), or further laminating a base material (base material/adhesive layer/ A three-layer laminate of substrates). Here, the adhesive layer refers to a layer of the adhesive composition after the adhesive composition of the present invention has been applied to a substrate and dried. The laminate of the present invention can be obtained by applying the adhesive composition of the present invention to various substrates, drying it, and further laminating another substrate in accordance with conventional methods.

<Base material>
In the present invention, the substrate is not particularly limited as long as the adhesive composition of the present invention can be applied and dried to form an adhesive layer. Examples include metal substrates such as plates and metal foils, papers, and the like.

Examples of resin substrates include polyester resins, polyamide resins, polyimide resins, polyamideimide resins, liquid crystal polymers, polyphenylene sulfides, syndiotactic polystyrene, polyolefin resins, fluorine resins, and the like. 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 circuit boards can be used as the metal base material. Examples of materials include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, and their alloys, plated products, and metals treated with other metals such as zinc and chromium compounds. Metal foil is preferred, and copper foil is more preferred. Although the thickness of the metal foil is not particularly limited, it is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 10 μm or more. Also, it is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. If the thickness is too thin, it may be difficult to obtain sufficient electrical performance of the circuit. Metal foils are 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 using a ribbon-shaped metal foil, the length is not particularly limited. Also, the width is not particularly limited, but it is preferably about 250 to 500 cm. The surface roughness of the substrate is not particularly limited, but is preferably 3 μm or less, more preferably 2 μm or less, and still more preferably 1.5 μm or less. Moreover, it is practically preferably 0.3 μm or more, more preferably 0.5 μm or more, and still more preferably 0.7 μm or more.

Examples of papers include high-quality paper, kraft paper, roll paper, and glassine paper. Moreover, glass epoxy etc. can be illustrated as a composite material.

Based on adhesive strength and durability with the adhesive composition, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, fluororesin, A SUS steel plate, copper foil, aluminum foil, or glass epoxy is preferred.

<Adhesive sheet>
In the present invention, the adhesive sheet is obtained by laminating the laminate and the release substrate via an adhesive composition. Specific configuration modes include laminate/adhesive layer/release substrate, or release substrate/adhesive layer/laminate/adhesive layer/release substrate. By laminating the release base material, it functions as a protective layer for the base material. Moreover, by using a 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. In addition, when a release base material is applied to the adhesive layer after drying, it is possible to wind up the product without set-off to the base material, resulting in excellent workability and preservability due to the protection of the adhesive layer. excellent and easy to use. Further, if the adhesive layer itself is applied to a release base material and dried, and if necessary, another release base material is applied, the adhesive layer itself can be transferred to another base material.

<Release substrate>
The release substrate is not particularly limited, but for example, a coated layer of filler such as clay, polyethylene, polypropylene, etc. is applied to both sides of paper such as woodfree paper, kraft paper, roll paper, and glassine paper. and a silicone type, fluorine type or alkyd type release agent is applied on each coating layer. Other examples include various olefin films such as polyethylene, polypropylene, ethylene-α-olefin copolymer and propylene-α-olefin copolymer alone, and films such as polyethylene terephthalate coated with the release agent. For reasons such as the release force between the release base material and the adhesive layer, and the fact that silicone has an adverse effect on electrical properties, both sides of high-quality paper are filled with polypropylene and an alkyd-based release agent is used on top of it. Alternatively, it is preferable to use an alkyd release agent on polyethylene terephthalate.

The method of coating the substrate with the adhesive composition in the present invention is not particularly limited, but includes a comma coater, a reverse roll coater, and the like. Alternatively, if necessary, an adhesive layer can be provided directly or by a transfer method on the rolled copper foil or polyimide film, which are the constituent materials of the printed wiring board. The thickness of the adhesive layer after drying may be changed as required, but 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, by setting the thickness to 200 μm or less, it becomes easier to control the amount of residual solvent in the drying process, and blisters are less likely to occur during pressing in the manufacture of printed wiring boards. The drying conditions are not particularly limited, but the residual solvent rate after drying is preferably 1% by mass or less. When the amount is 1% by mass or less, foaming of the residual solvent is suppressed during pressing of the printed wiring board, and blisters are less likely to occur.

<Printed wiring board>
The printed wiring board in the present invention includes, as constituent elements, a laminate formed of a metal foil forming a conductive circuit and a resin base material, and examples thereof include flexible substrates, rigid substrates, package substrates, and the like. A printed wiring board is manufactured, for example, by a conventionally known method such as a subtractive method using a metal-clad laminate. If necessary, so-called flexible circuit boards (FPC), flat cables, tape automated bonding ( It is a general term for circuit boards for TAB).

The printed wiring board of the present invention can have any laminated structure that can be employed as a printed wiring board. For example, 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. Further, for example, a printed wiring board can be made up of five layers: a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer.

Furthermore, if necessary, a configuration in which two or three or more of the above printed wiring boards are laminated can be used.

The adhesive composition of the present invention can be suitably used for each adhesive layer of printed wiring boards. In particular, when the adhesive composition of the present invention is used as an adhesive, it has high adhesiveness not only to conventional polyimides, polyester films, and copper foils constituting printed wiring boards, but also to low-polarity resin substrates 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, laminates, resin-coated copper foils and bonding sheets.

In the printed wiring board of the present invention, any resin film conventionally used as a base material for printed wiring boards can be used as the base film. Examples of resins for the base film include polyester resins, polyamide resins, polyimide resins, polyamideimide resins, liquid crystal polymers, polyphenylene sulfides, syndiotactic polystyrene, polyolefin resins, fluorine resins, and the like. In particular, it has excellent adhesion even to low-polarity substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resins.

<Cover film>
As the cover film, any insulating film conventionally known as an insulating film for printed wiring boards can be used. For example, films made from various polymers such as polyimide, polyester, polyphenylene sulfide, polyethersulfone, polyetheretherketone, aramid, polycarbonate, polyarylate, polyamideimide, liquid crystal polymer, syndiotactic polystyrene, and polyolefin resin are used. It is possible. Polyimide films or liquid crystal polymer films are more preferred.

The printed wiring board of the present invention can be manufactured using any conventionally known process except for using the materials for each layer described above.

In a preferred embodiment, 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. On the other hand, a semi-finished product in which a desired circuit pattern is formed by laminating a metal foil layer on a base film layer (hereinafter referred to as a "two-layer semi-finished product on the base film side"), or a semi-finished product in which an adhesive layer is laminated on a base film layer. , a semi-finished product having a desired circuit pattern formed by laminating a metal foil layer thereon (hereinafter referred to as "base film side 3-layer semi-finished product") (hereinafter referred to as "base film side 2-layer semi-finished product"). Together with the base film side three-layer semi-finished product, it is referred to as the “base film side semi-finished product”). By laminating the semi-finished product on the cover film side and the semi-finished product on the base film side thus obtained, a printed wiring board having four or five layers can be obtained.

The semi-finished product on the substrate film side includes, for example, (A) a step of applying a solution of a resin that will be the substrate film to the metal foil and initially drying the coating film, and (B) the metal foil obtained in (A) and It is obtained by a production method including a process of heat-treating and drying the laminate with the initially dried coating film (hereinafter referred to as "heat-treatment/solvent removal process").

A conventionally known method can be used to form a circuit in the metal foil layer. An additive method may be used, or a subtractive method may be used. A subtractive method is preferred.

The semi-finished product on the base film side thus obtained may be used as it is for lamination with the semi-finished product on the cover film side. may be used.

The semi-finished product on the cover film side is manufactured, for example, by applying an adhesive to the cover film. If desired, a cross-linking reaction in the applied adhesive can be performed. In a preferred embodiment, the adhesive layer is semi-cured.

The semi-finished product on the cover film side thus obtained may be used as it is for bonding to the semi-finished product on the base film side. may be used for

The semi-finished product on the base film side and the semi-finished product on the cover film side are each stored, for example, in the form of a roll, and then laminated 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. Also, both can be bonded together while being heated by a method such as using a hot press or a hot roll device.

For the semi-finished product on the reinforcing material side, for example, in the case of a soft and windable reinforcing material such as a polyimide film, it is preferable to manufacture it by applying an adhesive to the reinforcing material. In addition, in the case of reinforcing plates such as metal plates such as SUS and aluminum, and glass fiber hardened plates with epoxy resin that cannot be rolled up, the adhesive applied in advance to the release base material can be transferred and applied. It is preferably manufactured. Also, if necessary, a cross-linking reaction in the applied adhesive can be carried out. In a preferred embodiment, the adhesive layer is semi-cured.

The semi-finished product on the reinforcing material side thus obtained may be used as it is for bonding to the back surface of the printed wiring board, or it may be used for bonding to the semi-finished product on the base film side after being stored after being bonded with a release film. You may

The semi-finished product on the base film side, the semi-finished product on the cover film side, and the semi-finished product on the reinforcing material side are all printed wiring board laminates in the present invention.

The present invention will be specifically described below with reference to examples. Incidentally, in the present examples and comparative examples, parts simply indicate parts by mass.

<Physical property evaluation method>
(Measurement of composition of polyester resin)
Using a 400 MHz ¹ H-nuclear magnetic resonance spectrometer (hereinafter sometimes abbreviated as NMR), the molar ratio determination of the polyhydric carboxylic acid component and the polyhydric alcohol component constituting the polyester resin was carried out. Deuterated chloroform was used as the solvent. When the acid value of the copolyester was increased by post-acid addition, the molar ratio of each component was calculated assuming that the total amount of acid components other than the acid components used in the post-acid addition was 100 mol %.

(Measurement of glass transition temperature)
It was measured using a differential scanning calorimeter (DSC-200, SII). 5 mg of the sample was placed in an aluminum lid-type container, sealed, and cooled to -50°C using liquid nitrogen. Then, the temperature is raised to 150 ° C. at a rate of 20 ° C./min, and in the endothermic curve obtained in the heating process, the baseline extension line before the endothermic peak (below the glass transition temperature) and the endothermic peak The glass transition temperature (unit: °C) was defined as the temperature at the intersection with the tangent line (the tangent line indicating the maximum slope from the rising portion of the peak to the apex of the peak).

(Measurement of 5% weight loss temperature)
It was measured using a differential thermal/thermogravimetric simultaneous measurement device (Shimadzu Corporation, DTG-60). A 5 mg sample placed in an aluminum pan was heated at a heating rate of 10 ° C./min in an air atmosphere, and the temperature when 5% weight was lost due to thermal decomposition was 5% weight loss temperature (unit: °C).

(Measurement of acid value)
A 0.2 g sample of the polyester resin was dissolved in 40 ml of chloroform and titrated with a 0.01N potassium hydroxide ethanol solution to obtain the equivalent weight per 10 ⁶ g of the polyester resin (equivalent weight/10 ⁶ g). Phenolphthalein was used as an indicator.

(Relative permittivity (ε _c ) and dielectric loss tangent (tan δ))
A polyester resin dissolved in a solvent was applied to a Teflon (registered trademark) sheet having a thickness of 100 μm so that the thickness after drying was 25 μm, dried at 130° C. for 3 minutes, and then the Teflon (registered trademark) sheet was peeled off. to obtain a resin sheet for testing. The test resin sheet thus obtained was cut into strips of 8 cm×3 mm to obtain test samples. The relative permittivity (ε _c ) and dielectric loss tangent (tan δ) were measured by a cavity resonator perturbation method using a network analyzer (manufactured by Anritsu Corporation) at a temperature of 23° C. and a frequency of 10 GHz.

Synthesis examples of the polyester resin used in the present invention are shown below.

Synthesis Example of Polyester Resin (c1) Into a reaction vessel equipped with a stirrer, a condenser and a thermometer, 275 parts of dimethyl naphthalenedicarboxylate, 5 parts of trimellitic anhydride, 264 parts of dimer diol, 125 parts of tricyclodecanedimethanol, ethylene glycol 76 parts of tetrabutyl orthotitanate as a catalyst were added in an amount of 0.03 mol % based on the total acid components, and the temperature was raised from 160° C. to 220° C. over 4 hours, and an esterification reaction was carried out through a dehydration step. Next, in the polycondensation reaction step, the pressure in the system was reduced to 5 mmHg over 20 minutes, and the temperature was further raised to 250°C. Then, the pressure was reduced to 0.3 mmHg or less, and after the polycondensation reaction was carried out for 60 minutes, the product was taken out. As a result of composition analysis by NMR, the resulting polyester resin (c1) had a molar ratio of naphthalene dicarboxylic acid/trimellitic anhydride/dimerdiol/tricyclodecanedimethanol/ethylene glycol=97/3/40/55/5. was a copolymerized polyester of Further, the glass transition temperature was 17° C., the acid value was 3 equivalents/10 ⁶ g, and the dielectric loss tangent at 10 GHz was 0.0035.

Synthesis Example of Polyester Resin (c2) Into a reaction vessel equipped with a stirrer, a condenser and a thermometer, 348 parts of terephthalic acid, 311 parts of isophthalic acid, 99 parts of sebacic acid, 228 parts of ethylene glycol, 313 parts of neopentyl glycol, and orthotitanium as a catalyst Tetrabutyl acid was charged in an amount of 0.03 mol % based on the total acid components, and the temperature was raised from 160° C. to 220° C. over 4 hours, and an esterification reaction was carried out through a dehydration step. Next, in the polycondensation reaction step, the pressure in the system was reduced to 5 mmHg over 20 minutes, and the temperature was further raised to 250°C. Then, the pressure was reduced to 0.3 mmHg or less, and after the polycondensation reaction was carried out for 60 minutes, the product was taken out. As a result of composition analysis by NMR, the obtained polyester resin (c2) was a copolymer polyester with a molar ratio of terephthalic acid/isophthalic acid/sebacic acid/ethylene glycol/neopentyl glycol=47/42/11/55/45. rice field. Further, the glass transition temperature was 47° C., the acid value was 3 equivalents/10 ⁶ g, and the dielectric loss tangent at 10 GHz was 0.0076.

Production examples of adhesive compositions that serve as examples of the present invention and adhesive compositions that serve as comparative examples are shown below.

As compound A, the following was used.
(a1): SA-9000 (manufactured by SABIC, polyphenylene ether having a vinyl group, number average molecular weight of 1700, 5% weight loss temperature of 439°C)
(a2): FTC809AE (manufactured by Gunei Chemical Industry Co., Ltd., phenolic resin having a vinyl group, number average molecular weight of 1400, 5% weight loss temperature of 332°C)
(a3): PEGDA (manufactured by Sigma-Aldrich, polyethylene glycol diacrylate, weight average molecular weight 700, 5% weight loss temperature 220°C)
(a4): SA-90 (manufactured by SABIC, hydroxyl-terminated polyphenylene ether (having no terminal unsaturated hydrocarbon group), number average molecular weight of 1700, 5% weight loss temperature of 430°C)

As compound B, the following was used.
(b1): DA-MGIC (manufactured by Shikoku Kasei Co., Ltd., diallyl monoglycidyl isocyanurate)
(b2): MA-DGIC (manufactured by Shikoku Chemical Industry Co., Ltd., monoallyl diglycidyl isocyanurate)
(b3): diallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

Other than the above, the following were used.
V-03: Polycarbodiimide (manufactured by Nisshinbo Chemical Co., Ltd.)
Tetrad X: epoxy resin (manufactured by Mitsubishi Gas Chemical Company, glycidylamine type epoxy)
Perbutyl P: radical generator (manufactured by NOF Corporation, bis(1-t-butylperoxy-1-methylethyl)benzene, 1 minute half-life temperature 175° C.)

<Example 1>
The polyester resin (c1) obtained in the above synthesis example was dissolved in toluene to prepare a toluene varnish having a solid concentration of 40% by mass. To this toluene varnish, (a1) as compound A, (b1) as compound B, and perbutyl P were blended so as to be 20 parts, 5 parts, and 3 parts, respectively, with respect to 100 parts of polyester resin (c1). A composition (S1) was obtained.
The resulting adhesive composition (S1) was evaluated for dielectric constant, dielectric loss tangent, peel strength, solder heat resistance, and adhesive sheet flexibility. The results are listed in Table 1.

<Examples 2 to 14, Comparative Examples 1 to 5>
Adhesive compositions (S2) to (S19) were prepared in the same manner as in Example 1 except that the types and amounts of each component of the adhesive composition were changed as shown in Table 1, and each evaluation was performed. The results are listed in Table 1.

<Evaluation of Adhesive Composition>
(Relative permittivity (ε _c ) and dielectric loss tangent (tan δ))
The adhesive composition was applied to a Teflon (registered trademark) sheet having a thickness of 100 μm so that the thickness after drying was 25 μm, and dried at 130° C. for 3 minutes. After curing by heat treatment at 180° C. for 5 hours, the Teflon (registered trademark) sheet was peeled off to obtain an adhesive resin sheet for testing. The test adhesive resin sheet thus obtained was cut into strips of 8 cm×3 mm to obtain test samples. The relative dielectric constant (ε _c ) and dielectric loss tangent (tan δ) were measured by a cavity resonator perturbation method using a network analyzer (manufactured by Anritsu Corporation) under conditions of a temperature of 23° C. and a frequency of 10 GHz.
<Evaluation Criteria for Relative Permittivity>
○: 3.0 or less ×: more than 3.0
<Evaluation Criteria for Dielectric Loss Tangent>
○: less than 0.004 △: 0.004 or more and 0.006 or less ×: more than 0.006

(Peel strength (adhesiveness))
The adhesive composition was applied to a 12.5 μm thick polyimide film (manufactured by Kaneka Corporation, Apical (registered trademark)) so as to have a thickness of 25 μm after drying, and dried at 130° C. for 3 minutes. The adhesive film (B stage product) thus obtained was laminated to a 18 μm thick rolled copper foil (manufactured by Nippon Steel Chemical & Materials Co., Ltd., Espanex series). The bonding was performed by pressing the rolled copper foil so that the glossy surface of the rolled copper foil was in contact with the adhesive layer and pressing for 280 seconds under a pressure of 2 MPa at 170°C. Then, it was cured by heat treatment at 180° C. for 3 hours to obtain a sample for peel strength evaluation. The peel strength was measured under the conditions of 25° C., film pulling, tensile speed of 50 mm/min, and 90° peeling. This test shows the bond strength at room temperature.
<Evaluation Criteria>
◎: 1.0 N / mm or more ○: 0.7 N / mm or more and less than 1.0 N / mm △: 0.5 N / mm or more and less than 0.7 N / mm ×: less than 0.5 N / mm

(solder heat resistance)
A sample for evaluation was prepared by the same method as for measuring the peel strength, and a sample piece of 2.0 cm×2.0 cm was immersed in a solder bath melted at 288° C., and the presence or absence of change in appearance such as blistering was confirmed.
<Evaluation Criteria>
◎: no swelling for 60 seconds or more ○: swelling for 30 seconds or more and less than 60 seconds △: swelling for 10 seconds or more and less than 30 seconds ×: swelling for less than 10 seconds

(Adhesive sheet flexibility)
The adhesive composition is applied to a Teflon (registered trademark) sheet having a thickness of 100 μm so that the thickness after drying becomes 25 μm, and dried at 130° C. for 3 minutes. Next, the state of the coating film was checked when the sheet was bent 180°.
<Evaluation Criteria>
○: No cracks ×: Cracks present

As is clear from Table 1, Examples 1 to 14 are excellent in dielectric properties, peel strength, solder heat resistance and adhesive sheet flexibility. On the other hand, in Comparative Example 1, since the compound B did not have an epoxy group, the curing was insufficient and the solder heat resistance was insufficient. In Comparative Example 2, since compound A did not have a terminal unsaturated hydrocarbon, the curing was insufficient and the solder heat resistance was insufficient. Also, the dielectric loss tangent was high due to the influence of the terminal hydroxyl group. Comparative Example 3 was inferior in solder heat resistance because the 5% weight loss temperature of compound A was low. In Comparative Example 4, since the polyester resin was not contained, the adhesive sheet was brittle, and the dielectric properties, peel strength, and solder heat resistance were insufficient. Comparative Example 5 did not contain the compound B and was cured with an epoxy resin, resulting in poor dielectric properties.

INDUSTRIAL APPLICABILITY The adhesive composition of the present invention is excellent in heat resistance and adhesive strength, has a low dielectric constant and a low dielectric loss tangent, and has good sheet flexibility. Therefore, it is useful as an adhesive or an adhesive sheet for printed wiring boards applied to printed boards (flexible boards, rigid boards, package boards) in a high frequency range.

Claims

An adhesive composition comprising a polyester resin, compound A and compound B.
Compound A: A compound having a terminal unsaturated hydrocarbon group and having a 5% weight loss temperature of 260°C or higher Compound B: A compound having an epoxy group and a terminal unsaturated hydrocarbon group
2. The adhesive composition according to claim 1, wherein said compound A is a compound having an aromatic ring structure or an alicyclic structure as a structural unit.
2. The adhesive composition according to claim 1, wherein said compound A is a polyphenylene ether or phenolic resin having terminal unsaturated hydrocarbon groups.
The adhesive composition according to any one of claims 1 to 3, wherein said compound B is a compound having an isocyanuric ring.
The adhesive composition according to any one of claims 1 to 4, wherein the polyester resin has a dielectric loss tangent of 0.005 or less.
The adhesive composition according to any one of claims 1 to 5, further comprising polycarbodiimide.
An adhesive sheet having an adhesive layer comprising the adhesive composition according to any one of claims 1 to 6.
A laminate having an adhesive layer comprising the adhesive composition according to any one of claims 1 to 6.
A printed wiring board comprising the laminate according to claim 8 as a component.