KR20070019591A - Thermosetting adhesive and pressure-sensitive adhesive composition, thermosetting adhesive and pressure-sensitive adhesive tape or sheet, and wiring circuit board - Google Patents

Abstract

The present invention provides a thermosetting adhesive composition which can exhibit good adhesiveness before curing, exhibit excellent adhesiveness after curing, and further exhibit excellent processability in UV laser processing. The said thermosetting adhesive agent composition is a monomer component, 60-75 weight% of (meth) acrylic-acid alkylesters (a) whose alkyl group has a C2-C14 alkyl group, and a cyano group containing monomer (b) are monomers with respect to monomer component whole quantity. Acrylic polymer (X) containing 20 to 35% by weight based on the total amount of components and 0.5 to 10% by weight of the carboxyl group-containing monomer (c) based on the total amount of the monomer components: represented by the following general formula (1) Phenol-based resol type phenol resin (Y): It contains 1-20 weight part, and also contains the ultraviolet absorber (Z).

Where

R ¹ represents —CH ₂ — or —CH ₂ —O—CH ₂ —,

n is a positive integer,

m is an integer of 1-4.

Description

Thermosetting adhesive composition, thermosetting adhesive tape or sheet, and wiring circuit board {THERMOSETTING ADHESIVE AND PRESSURE-SENSITIVE ADHESIVE COMPOSITION, THERMOSETTING ADHESIVE AND PRESSURE-SENSITIVE ADHESIVE TAPE OR SHEET, AND WIRING CIRCUIT BOARD}

1 is a conceptual diagram illustrating an example of peeling phenomenon of the pressure-sensitive adhesive layer when irradiated with an ultraviolet laser.

2 is a schematic cross-sectional view showing an example of a wiring circuit board of the present invention.

3 is a schematic cross-sectional view showing an example of a wiring circuit board of the present invention.

4 is a schematic cross-sectional view showing an example of a wiring circuit board of the present invention.

5 is a schematic cross-sectional view showing an example of a wiring circuit board of the present invention.

6 is a schematic cross-sectional view showing an example of a wiring circuit board of the present invention.

7 is a schematic cross-sectional view showing an example of a wiring circuit board of the present invention.

Explanation of symbols for the main parts of the drawings

1a polyimide film

1b adhesive layer

1c copper foil

A part where peeling phenomenon called so-called "dig" occurred

Part where peeling phenomenon called so-called "peel" occurred

2a to 2f wiring circuit board

2d1 to 2d2 wiring circuit board

2f1 to 2f2 wiring circuit board

3 base insulation layer

4 conductor layer

5a to 5d adhesive layer (adhesive layer formed by thermosetting of thermosetting adhesive composition)

5e1 to 5e2 adhesive layer

5f1 to 5f3 adhesive layer

6 cover insulation layer

7 gusset

The present invention relates to a thermosetting adhesive composition, a thermosetting adhesive tape or sheet, and a wiring circuit board.

Wiring circuit boards are used for electronic devices, and flexible printed circuit boards (sometimes referred to as "FPC") are widely used as wiring circuit boards. In such FPC, (1) the process of adhesively laminating conductive metal foils, such as copper foil and aluminum foil, on the heat-resistant base materials, such as a polyimide base material and a polyamide base material, and (2) FPC by an aluminum plate and a stainless plate Adhesive is used in the process of adhering to reinforcement boards, such as a polyimide board. Nitrile rubber (NBR) / epoxy resin adhesives and acrylic rubber / phenol resin adhesives (refer patent document 1 and patent document 2) have conventionally been used as an adhesive agent used at the time of adhesion | attachment of such FPC.

In addition, with the recent miniaturization of electronic devices, a flexible printed circuit board (FPC) having a multilayer structure having through holes and via holes has been used. Drilling and printing are conventionally used for the formation of through holes and via holes for this FPC. However, in these drill processing and printing processing, there exists a limit to microprocessing. Therefore, the drilling process by irradiation of an ultraviolet laser or a carbon dioxide laser is used (patent documents 3-5).

[Patent Document 1] US Patent No. 3822175

[Patent Document 2] US Patent No. 3900662

[Patent Document 3] Japanese Patent Application Laid-Open No. 2002-111229

[Patent Document 4] Japanese Patent Application Laid-Open No. 2002-121360

[Patent Document 5] Japanese Patent Application Laid-Open No. 2002-164661

However, conventional acrylic rubber / phenolic resin adhesives are non-adhesive at room temperature (23 ° C.), and thus, in the pressure-sensitive adhesive of FPC, such as when manufacturing FPC or bonding FPC to a reinforcing plate, temporary attaching work is performed at room temperature. I cannot do it. Therefore, in a processing line etc., it is thought that a special heating fixture is required and the fall of work efficiency and a danger to an operator are accompanied. Moreover, even if it is going to give adhesiveness to an acrylic rubber / phenol resin adhesive at normal temperature, in order to provide adhesiveness, since an elasticity modulus falls, adhesive force, heat resistance, etc. will fall, and it is difficult to make the balance of adhesiveness and adhesiveness favorable.

In particular, in the drilling process by irradiation of ultraviolet laser, the adhesive layer without the ultraviolet absorbing band is insufficient in workability, and for example, in the processing surface (the end of the hole side formed by processing) by the ultraviolet laser, Peeling phenomenon occurs at the end, and the end of the pressure-sensitive adhesive layer is peeled off or becomes an end of erosion, and the end of the pressure-sensitive adhesive layer and the end of the adherend such as an insulator (such as a polyimide film) used in the FPC do not coincide with each other. It may occur. Specifically, as shown in Fig. 1B, a peeling phenomenon (so-called peeling phenomenon called “dimple”) in which the pressure-sensitive adhesive layer is eroded on the pressure-sensitive adhesive layer as shown in Fig. 1A on the processed surface by irradiation of ultraviolet laser. Peeling phenomenon, such as peeling phenomenon (so-called peeling phenomenon called "peeling") which peels from an end side, may generate | occur | produce while an adhesive layer erodes.

1 is a conceptual diagram (model diagram) showing an example of the peeling phenomenon of the pressure-sensitive adhesive layer when irradiated with an ultraviolet laser, and FIG. 1A is a conceptual diagram showing an example of a peeling phenomenon called so-called "fragment", FIG. 1B Is a conceptual diagram which shows an example of the peeling phenomenon called "tear off" in a model manner. 1A and 1B, 1a is a polyimide film, 1b is an adhesive layer, 1c is copper foil, A is a part which peeled phenomenon called what is called a "dime," and B is a peeling phenomenon called what is called "peeling." Shows the part that occurred. 1A and 1B are laminates having a laminated structure of a film (polyimide film / adhesive layer / copper foil) having a structure in which copper foil 1c is laminated on a polyimide film 1a through an adhesive layer 1b. The cross section of the punched part at the time of performing the punching process which irradiates an ultraviolet laser to the copper foil 1c side from a copper foil and forms a through-hole in a laminated body is shown conceptually (modelically). In FIGS. 1A and 1B, the irradiated ultraviolet laser passes through the pressure-sensitive adhesive layer to reach the surface of the polyimide film, and the energy of the ultraviolet laser is absorbed from the surface of the polyimide film to interface between the polyimide film and the pressure-sensitive adhesive layer. Processing starts, and as a result, the peeling phenomenon (so-called peeling phenomenon called "plum") in which the pressure-sensitive adhesive layer is eroded and removed from the end of the processed surface side, and the peeling proceeds, are eroded and removed, and the polyimide agent is formed on the end side. Peeling phenomenon (so-called peeling phenomenon called "peeling") occurs at the interface with the film. Specifically, in FIG. 1A, a peeling phenomenon called so-called "dig" occurs in the portion A, and in FIG. 1B, so-called peeling phenomenon occurs in the portion B.

Therefore, the object of the present invention is to exhibit good adhesion before curing, to exhibit excellent adhesiveness and heat resistance after curing by heating, and to exhibit excellent processability during processing by ultraviolet laser after curing. It is providing the thermosetting adhesive tape or sheet which has the thermosetting adhesive agent which exists, and the thermosetting adhesive layer by the said thermosetting adhesive agent composition.

Another object of the present invention is to be able to temporarily attach at room temperature, and to be able to adhere with excellent adhesiveness after positioning by temporary attachment, and also to be produced on the processing surface even after processing by ultraviolet laser after bonding. It is providing the thermosetting adhesive tape or sheet which can suppress or prevent peeling of an adhesive bond layer, and can be used suitably at the time of adhesive bonding in a flexible printed circuit board.

Still another object of the present invention is to join the predetermined members by attaching them at room temperature with temporary attachment, and after joining them in a predetermined positional relationship, they are bonded with excellent adhesiveness, and further excellent in workability by ultraviolet laser. It is providing a wiring circuit board.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, when the thermosetting type adhesive agent which combined the specific acryl-type polymer, the specific phenol resin, and an ultraviolet absorber is used, the predetermined member of a wiring circuit board has a predetermined positional relationship. When bonding, it can be easily bonded by positioning at room temperature by temporary attachment, and when the members are firmly bonded after joining in a predetermined positional relationship, the members can be easily bonded with excellent adhesiveness by heat treatment. In addition, it was found that when the members are bonded to each other and then processed by an ultraviolet laser, they can be processed with excellent workability. The present invention has been completed in accordance with these findings.

That is, in the present invention, 60 to 75% by weight of the (meth) acrylic acid alkyl ester (a) having 2 to 14 carbon atoms of the alkyl group as the monomer component and the total amount of the cyano group-containing monomer (b) to the monomer component Acrylic polymer (X) containing 20 to 35% by weight with respect to the carboxyl group-containing monomer (c) in a proportion of 0.5 to 10% by weight based on the total amount of monomer components: Coal represented by the following general formula (1) based on 100 parts by weight Acid type resol type phenol resin (Y): It provides the thermosetting adhesive agent composition which contains 1-20 weight part and further contains a ultraviolet absorber (Z).

Formula 1

Where

R ¹ represents —CH ₂ — or —CH ₂ —O—CH ₂ —,

n is a positive integer,

m is an integer of 1-4.

As said ultraviolet absorber (Z), the ultraviolet absorber which contains a nitrogen element in a molecule | numerator can be used suitably. As a ratio of a ultraviolet absorber (Z), it is preferable that it is 1-20 weight part with respect to 100 weight part of acrylic polymer (X).

The present invention also provides a thermosetting adhesive tape or sheet having a thermosetting adhesive layer formed by the thermosetting adhesive composition. It is preferable that the storage elastic modulus (23 degreeC) of the said thermosetting adhesive agent layer is 1 * 10 <^6> -1 * 10 <^8> Pa.

In addition, the present invention is a wiring circuit board having at least an electric insulator layer and a conductor layer formed on the electric insulator layer so as to have a predetermined circuit pattern, and having an adhesive layer formed by thermosetting of the thermosetting adhesive agent composition. A wiring circuit board is provided.

In the wiring circuit board of this invention, the adhesive bond layer formed by the thermosetting of the said thermosetting adhesive agent composition is carried out between an electrical insulator layer and a conductor layer, between a conductor layer and the coating electrical insulator layer provided on the said conductor layer, and an electrical It is preferable to have it between at least any one of an insulator layer and the reinforcement board provided in the surface opposite to the conductor layer of the said electrical insulator layer. In addition, the wiring circuit board has a multilayer structure in which a plurality of wiring circuit boards are stacked, and any one set or two or more sets of wiring circuit boards have an adhesive layer formed by thermosetting of the thermosetting adhesive agent composition. You may have in between.

The adhesive layer formed by thermal curing of the thermosetting adhesive composition, may be formed using a thermosetting adhesive tape or sheet having a configuration formed only by the thermosetting adhesive layer by the thermosetting adhesive composition, In this case, after bonding a predetermined member to both surfaces of a thermosetting adhesive tape or a sheet, it is preferable to form by heating under pressure and thermosetting.

On the other hand, it is preferable that the thickness of the adhesive bond layer formed by the thermosetting of the said thermosetting adhesive agent composition is 3-100 micrometers.

EMBODIMENT OF THE INVENTION Below, embodiment of this invention is described in detail, referring drawings as needed. In addition, the same code | symbol may be attached | subjected to the same member, site | part, and the like.

Thermosetting Adhesive Adhesive Composition

The thermosetting adhesive agent composition of the present invention is a (meth) acrylic acid alkyl ester (a) having 2 to 14 carbon atoms of an alkyl group as a monomer component, based on 60 to 75% by weight of the monomer component, and a cyano group-containing monomer (b). Is an acrylic polymer (X) containing 20 to 35% by weight relative to the total amount of monomer components, and a carboxyl group-containing monomer (c) at a ratio of 0.5 to 10% by weight based on the total amount of monomer components; The sol type phenol resin (Y) and the ultraviolet absorber (Z) are contained, and the ratio of the phenolic resol type phenol resin (Y) is 1 to 20 parts by weight (preferably 100 parts by weight of the acrylic polymer (X)). 5 to 15).

Formula 1

Where

R ¹ represents —CH ₂ — or —CH ₂ —O—CH ₂ —,

n is a positive integer,

m is an integer of 1-4.

Acrylic Polymer (X)

In the thermosetting adhesive agent composition, the acrylic polymer (X) is a (meth) acrylic acid alkyl ester (a) [“meth) acrylic acid C _2-14 alkyl ester having 2 to 14 carbon atoms of an alkyl group as a monomer component (monomer component). (a) "may be 60 to 75% by weight relative to the total amount of the monomer component, 20 to 35% by weight of the cyano group-containing monomer (b) and 20 to 35% by weight of the carboxyl group-containing monomer (c) It is an acryl-type polymer contained in the ratio of 0.5 to 10 weight% with respect to monomer component whole quantity.

[(Meth) acrylic acid C _2-14 alkyl ester (a)]

The (meth) acrylic acid C _2-14 alkyl ester (a) is not particularly limited as long as it is a (meth) acrylic acid alkyl ester (alkyl acrylate ester, methacrylic acid alkyl ester) having 2 to 14 carbon atoms in the alkyl group, for example (meth) As acrylic acid C _2-14 alkyl ester (a), for example, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) S-butyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2- (meth) acrylate Ethyl hexyl, isooctyl (meth) acrylate, nonyl (meth) acrylate, isonyl (meth) acrylate, decyl (meth) acrylate, isdecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate Thread, (meth) acrylic Tridecyl, (meth) acrylic acid tetradecyl.

As the (meth) acrylic acid C _2-14 alkyl ester (a), a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms is suitable, and n-butyl acrylate can be particularly suitably used.

In addition, (meth) acrylic-acid _C2-14 alkyl ester (a) may be comprised only by 1 type, and may be comprised by the mixture combined 2 or more types. That is, the (meth) acrylic acid C _2-14 alkyl ester (a) may use one or more (meth) acrylic acid alkyl esters selected from (meth) acrylic acid alkyl esters having 2 to 14 carbon atoms in the alkyl group.

In the present invention, (meth) acrylic acid C _2-14 alkyl ester (a) is used as a monomer main component for constituting the acrylic polymer (X). The proportion of the (meth) acrylic acid C _2-14 alkyl ester (a) is 60 to 75% by weight based on the total amount of the monomer components. In addition, as a ratio of (meth) acrylic-acid _C2-14 alkyl ester (a), it is preferable that it is 68-73 weight% with respect to monomer component whole quantity.

[Cyano Group-containing Monomer (b)]

The cyano group-containing monomer (b) is not particularly limited as long as it is a monomer having a cyano group. Examples thereof include acrylonitrile and methacrylonitrile. Acrylonitrile can be used suitably as a cyano group containing monomer (b).

In addition, the cyano group containing monomer (b) may be comprised only by 1 type, and may be comprised by the mixture combined 2 or more types.

In the present invention, the cyano group-containing monomer (b) is used to improve heat resistance and adhesion. Therefore, it is important that the ratio of a cyano group containing monomer (b) is 20 to 35 weight% with respect to monomer component whole quantity. If the proportion of the cyano group-containing monomer (b) is less than 20% by weight relative to the total amount of the monomer components, the heat resistance is inferior, while if it is more than 35% by weight, the flexibility is insufficient. On the other hand, as a ratio of a cyano group containing monomer (b), it is preferable that it is 25 to 32 weight% with respect to monomer component whole quantity.

[Carboxyl group-containing monomer (c)]

The carboxyl group-containing monomer (c) is not particularly limited as long as it is a monomer having a carboxyl group, and examples thereof include (meth) acrylic acid (acrylic acid, methacrylic acid), itaconic acid, maleic acid, fumaric acid, and crotonic acid. Moreover, acid anhydrides (for example, acid anhydride containing monomers, such as maleic anhydride and itaconic anhydride) of these carboxyl group-containing monomers can also be used as a carboxyl group-containing monomer. As the carboxyl group-containing monomer (c), acrylic acid, methacrylic acid and itaconic acid can be suitably used.

In addition, the carboxyl group-containing monomer (c) may be comprised only by 1 type, and may be comprised by the mixture combined 2 or more types.

In this invention, the carboxyl group-containing monomer (c) is used in order to improve adhesiveness. Therefore, it is important that the ratio of carboxyl group-containing monomer (c) is 0.5 to 10 weight% with respect to monomer component whole quantity. If the proportion of the carboxyl group-containing monomer (c) is less than 0.5% by weight based on the total amount of the monomer components, the effect of improving the adhesion is insufficient, while if it is more than 10% by weight, the flexibility is insufficient. In addition, as a ratio of a carboxyl group-containing monomer (c), it is preferable that it is 1-2 weight% with respect to monomer component whole quantity.

[Other monomer component]

As the monomer component constituting the acrylic polymer (X), copolymerization with respect to (meth) acrylic acid C _2-14 alkyl ester (a), cyano group-containing monomer (b) and carboxyl group-containing monomer (c) is necessary. Possible monomer components (copolymerizable monomers) can be used. As such a copolymerizable monomer, For example, methyl (meth) acrylate; (Meth) acrylic acid C _15- such as pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate ₂₀ alkyl esters; Non-aromatic ring-containing (meth) acrylic acid esters such as (meth) acrylic acid cycloalkyl esters [such as cyclohexyl (meth) acrylic acid] and isobornyl (meth) acrylate; (Meth) acrylic acid aryl ester [phenyl (meth) acrylate etc.], (meth) acrylic acid aryloxyalkyl ester [such as phenoxyethyl (meth) acrylate], (meth) acrylate arylalkyl ester [(meth) acrylic acid benzyl ester], etc. Aromatic ring-containing (meth) acrylic acid esters; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate and methylglycidyl (meth) acrylate; Vinyl ester monomers such as vinyl acetate and vinyl propionate; Styrene monomers such as styrene and α-methyl styrene; Hydroxyl group-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; (Meth) acrylate alkoxyalkyl monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; (Meth) acrylic-acid aminoalkyl monomers, such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; (N-substituted) amide monomers such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-hydroxy (meth) acrylamide; Olefin monomers such as ethylene, propylene, isoprene and butadiene; Vinyl ether monomers, such as methyl vinyl ether, etc. are mentioned.

In the acrylic polymer (X), hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) as copolymerizable monomers Acrylate, neopentylglycol di (meth) acrylate, pentaerythritol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate, divinyl benzene, butyl di (meth) acrylate, hexyl di (meth) acrylate Multifunctional monomers can be used.

The acrylic polymer (X) can be produced by a known or conventional polymerization method (for example, solution polymerization method, emulsion polymerization method, suspension polymerization method, bulk polymerization method or polymerization method by ultraviolet irradiation).

In addition, the polymerization initiator, a chain transfer agent, etc. which are used in superposition | polymerization of an acrylic polymer (X) are not specifically limited, It can select suitably from well-known or a conventional thing, and can use. More specifically, examples of the polymerization initiator include 2,2'-azobisisobutyl nitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2 '. -Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) Azo polymerization initiators such as 2,2'-azobis (2,4,4-trimethylpentane) and dimethyl-2,2'-azobis (2-methylpropionate); Benzoyl peroxide, t-butylhydroperoxide, di-t-butylperoxide, t-butylperoxybenzoate, dicumylperoxide, 1,1-bis (t-butylperoxy) -3,3,5 And peroxide-based polymerization initiators such as -trimethylcyclohexane and 1,1-bis (t-butylperoxy) cyclododecane. A polymerization initiator can be used individually or in combination of 2 or more types. The usage-amount of a polymerization initiator can be suitably selected from the range of normal usage-amount.

Examples of the chain transfer agent include 2-mercaptoethanol, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-ethylhexyl thioglycolic acid, 2,3-dimethylcapto-1-propanol, and α- Methyl styrene dimer etc. are mentioned.

In addition, in solution polymerization, various general solvents can be used. As such a solvent, Ester, such as ethyl acetate and n-butyl acetate; Aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Organic solvents, such as ketones, such as methyl ethyl ketone and a methyl isobutyl ketone, are mentioned. A solvent can be used individually or in combination of 2 or more types.

Although it does not specifically limit as a weight average molecular weight of acrylic polymer (X), For example, it can select suitably from the range of 100,000-1 million (preferably 200,000-800,000). The weight average molecular weight of the acrylic polymer (X) can be controlled by the monomer concentration, the monomer dropping speed, etc., in addition to the type and amount of the polymerization initiator and the chain transfer agent, the temperature and time during the polymerization. In addition, the weight average molecular weight of an acrylic polymer (X) can be measured by gel permeation chromatography (GPC), for example, The measurement conditions in that case are not restrict | limited, It can select from well-known measurement conditions suitably.

[Polycarbonate Resol Type Phenolic Resin (Y)]

In addition, in the said thermosetting adhesive agent composition, the phenol type resol type phenol resin (Y) is used. Phenol type resol type phenol resin (Y) is a phenol type resol type phenol resin represented by following General formula (1).

Formula 1

Where

R ¹ represents —CH ₂ — or —CH ₂ —O—CH ₂ —,

n is a positive integer,

m is an integer of 1-4.

In the formula (1), n is not particularly limited as long as it is a positive integer, but may be selected from, for example, an integer in the range of 1 to 20. In addition, m is an integer of 1-4.

As the phenolic resol type phenol resin (Y), one having a liquid phase or balsam phase at 50 ° C is preferable.

Phenol type resol type phenol resin (Y) is used in order to provide thermosetting and heat resistance. As a ratio of a phenol type resol type phenol resin (Y), it is 1-20 weight part (preferably 5-15 weight part) with respect to 100 weight part of said acrylic polymers (X). If the ratio of the phenolic resol-type phenol resin (Y) is less than 1 part by weight with respect to 100 parts by weight of the acrylic polymer (X), the thermosetting property is insufficient, while if it is more than 20 parts by weight, the adhesive force is lowered.

On the other hand, in the case of using the alkyl phenol resin represented by the following formula (2) without using the phenolic resol type phenol resin (Y) represented by the formula (1) as a phenol resin, the adhesive property is insufficient, the thermosetting type having excellent adhesion An adhesive composition is not obtained.

Where

R ² represents —CH ₂ — or —CH ₂ —O—CH ₂ —,

R ³ represents an alkyl group,

p is a positive integer,

q is an integer of 1-3.

On the other hand, the alkyl group of R ³ in the formula (2) is not particularly limited, and for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, Alkyl groups, such as a hexyl group, a heptyl group, an octyl group, etc. are mentioned. Further, p is not particularly limited as long as it is a positive integer, but can be selected from, for example, an integer in the range of 1 to 20. q is an integer of 1-3.

[Ultraviolet absorber (Z)]

The ultraviolet absorbent (Z) is not particularly limited as long as it has an absorption wavelength in the wavelength region of the ultraviolet ray (that is, one having a characteristic capable of absorbing energy by ultraviolet rays), and may be appropriately selected from known ultraviolet absorbers. have. As the ultraviolet absorber (Z), for example, one having an absorption wavelength in a wavelength range of 100 to 400 nm (preferably 300 to 400 nm) can be suitably used. UV absorber (Z) can be used individually or in combination of 2 or more types.

In addition, although an ultraviolet type ultraviolet absorber may be sufficient as an ultraviolet absorber (Z), an organic type ultraviolet absorber is suitable. In addition, although the ultraviolet absorber (Z) may be any type of ultraviolet absorber among a low molecular weight type ultraviolet absorber and a high molecular weight type ultraviolet absorber, a low molecular weight type ultraviolet absorber can be used suitably.

As a ultraviolet absorber (Z), a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, an oxalic acid anilide type ultraviolet absorber, a benzoxazine type ultraviolet absorber, a salicylic acid type ultraviolet absorber, cinnamic acid type ultraviolet ray An absorbent, a benzophenol type ultraviolet absorber, a benzoate type ultraviolet absorber, a benzoic acid type ultraviolet absorber, an organic nickel type ultraviolet absorber, etc. are mentioned.

In the present invention, as the ultraviolet absorber (Z), an ultraviolet absorber (benzotriazole-based ultraviolet absorber, triazine-based ultraviolet absorber, cyanoacrylate-based ultraviolet ray, which contains nitrogen element (nitrogen atom) in a molecule (in molecular structure)) Absorbers, oxalic acid anilite ultraviolet absorbers, benzoxazine ultraviolet absorbers and the like) are suitable. Especially, a benzotriazole type ultraviolet absorber can be used suitably.

Specifically, as a benzotriazole type ultraviolet absorber, 2- (2'-hydroxy-5'-methylphenyl) -2H- benzotriazole and 2- [2'-hydroxy-3 ', 5'-di (t-butyl) phenyl] -2H-benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -2H-benzotriazole, 2- [2'-hydroxy -3 ', 5'-di (t-butyl) phenyl] -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5- Chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -2H-benzotriazole, 2- [2'-hydroxy-3 ', 5'-di (t -Pentyl) phenyl] -2H-benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) -2H-benzotriazole, 2- [2'-hydroxy-3 '-(3 " , 4 ", 5", 6 "-tetrahydrophthalimidylmethyl) -5'-methylphenyl] -2H-benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetra Methylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzot In addition to lyazoles, 2- {2'-hydroxy-5 '-[(meth) acryloyloxymethyl] phenyl} -2H-benzotriazole, 2- {2'-hydroxy-5'-[2 " -(Meth) acryloyloxyethyl] phenyl} -2H-benzotriazole, 2- {2'-hydroxy-5 '-[2 "-(meth) acryloyloxyethyl] phenyl} -5-chloro -2H-benzotriazole, 2- {2'-hydroxy-3'-t-butyl-5 '-[2 "-(meth) acryloyloxyethyl] phenyl} -2H-benzotriazole, 2- {2'-hydroxy-3'-t-butyl-5 '-[2 "-(meth) acryloyloxyethyl] phenyl} -5-chloro-2H-benzotriazole, 2- {2-hydroxy -5 '-[3 "-(meth) acryloyloxypropyl] phenyl} -2H-benzotriazole, 2- {2'-hydroxy-5'-[3"-(meth) acryloyloxypropyl ] Phenyl} -5-chloro-2H-benzotriazole, etc. are mentioned.

Examples of the triazine ultraviolet absorber include 2,4-bis (2,4-dimethylphenyl) -1,3,5-triazine-6- (2-hydroxy-4-octyloxyphenyl) and 2,4- Bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4 -Octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4- Phenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1 , 3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2 -Hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-benzyloxyphenyl) -1 , 3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy Oxy-3-methyl-4-hexyloxyphenyl) -1,3,5- In addition to triazine, 2,4-bis (4-methylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4 -Bis (2-methylphenyl) -6- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-diphenyl-6- [ 2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (4-methylphenyl) -6- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -1,3,5-triazine, 2,4-bis (2-methylphenyl) -6- [2-hydroxy-4- (2-methacrylo Yloxyethoxy) phenyl] -1,3,5-triazine, 2,4-diphenyl-6- [2-hydroxy-4- (2-methacryloyloxyethoxy) phenyl] -1, 3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2,4-dihydroxy-3-allylphenyl) -1,3,5-triazine, etc. are mentioned. have.

As a cyanoacrylate type ultraviolet absorber, 2'-ethylhexyl 2-cyano-3, 3- diphenyl acrylate (or (alpha)-cyano- (beta), (beta)-diphenyl acrylate 2'- ethylhexyl), ethyl, 2-cyano-3,3-diphenyl acrylate (or (alpha) -cyano- (beta), (beta)-diphenyl acrylate) etc. are mentioned.

Examples of the oxalic acid anilide-based ultraviolet absorber include N- (2-ethylphenyl) -N '-(2-ethoxyphenyl) oxalic acid diamide (or 2-ethoxy-2'-ethyloxanilide) and N- ( 2-ethylphenyl) -N '-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide (or 2-ethyl-2'-ethoxy-5'-t-butyloxanilide), N -(2-ethoxyphenyl) -N '-(4-dodecylphenyl) oxalic acid diamide (or 2-ethoxy-4'-dodecyl oxanilide), etc. are mentioned.

Examples of the benzoxazine type ultraviolet absorber include 2,2'-p-phenylenebis (4H-3,1-benzoxazine-4-one) and 2,2'-m-phenylenebis (4H-3,1 Benzoxazine-4-one), 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1- Benzoxazine-4-one etc. are mentioned.

Examples of the salicylic acid ultraviolet absorber include phenyl salicylate, p-t-butylphenyl salicylate, p-octylphenyl salicylate, acid chlorides of salicylic acid and salicylic acid. As cinnamic acid type ultraviolet absorber, cinnamic acid, p-methoxy cinnamic acid, p-methoxy cinnamic acid 2-ethylhexyl, p-methoxy cinnamic acid 2-ethoxyethyl etc. are mentioned, for example.

Examples of the benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, and 2-hydroxy. 4-octylbenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzo Phenone, 2,2 ', 4,4',-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoyl Phenyl) methane, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4- (2-acryloyloxy) Methoxy benzophenone, 2-hydroxy-4- (2-methacryloyloxy) ethoxy benzophenone, etc. are mentioned. As a benzoate type ultraviolet absorber, 2 ', 4'- di-t- butylphenyl-3, 5-di-t- butyl- 4-hydroxy benzoate, a resorcinol monobenzoate, ortho benzoyl Methyl benzoate etc. are mentioned. Examples of the benzoic acid ultraviolet absorbents include benzoic acid, p-aminobenzoic acid, p-methylaminobenzoic acid and acid chlorides of these benzoic acids.

Examples of the organic nickel-based ultraviolet absorber include nickel bis (octylphenyl) sulfide, 2,2'-thiobis (4-t-octylphenolate) -n-butylamine nickel (II), and [2,2'-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II), nickel- dibutyl dithio carbamate, etc. are mentioned.

Although it does not restrict | limit especially as a ratio of a ultraviolet absorber (Z), For example, it can select suitably from the range of 1-20 weight part (preferably 3-10 weight part) with respect to 100 weight part of acrylic polymer (X). When the ratio of the ultraviolet absorber (Z) is less than 1 part by weight based on 100 parts by weight of the acrylic polymer (X), the workability by the ultraviolet laser is lowered. On the other hand, when the ratio of the ultraviolet absorber (Z) is more than 20 parts by weight, adhesive properties such as adhesive force are lowered.

In the thermosetting adhesive agent composition, in addition to the acrylic polymer (X), the phenolic resol type phenol resin (Y) and the ultraviolet absorber (Z), if necessary, an antioxidant, a filler, a colorant (such as a pigment or a dye), an ultraviolet absorber, and an oxidation Known additives such as inhibitors, crosslinkers, tackifiers, plasticizers, softeners, surfactants, antistatic agents and the like may be contained within a range that does not impair the properties of the present invention.

The thermosetting adhesive composition can be prepared by mixing an acrylic polymer (X), a phenolic resol type phenol resin (Y), an ultraviolet absorber (Z), and various additives (anti-aging agent, filler, pigment, etc.) if necessary. .

In addition, an acryl-type polymer (X) and a phenolic resol type phenol resin (Y) can be used in the state of a solution or a dispersion liquid. When using acrylic polymer (X) in a solution state, it does not restrict | limit especially as a solvent, For example, it can select suitably from the solvent illustrated as a solvent used when manufacturing acrylic polymer (X) by solution polymerization. Moreover, when using a phenolic resol type phenol resin (Y) in a solution state, although it does not restrict | limit especially as a solvent, For example, monohydric alcohols, such as methanol, ethanol, a propanol, an isopropanol, butanol; Polyhydric alcohols such as ethylene glycol; Ketones; Acetic acid esters; Ethers and the like can be used.

Thermosetting Adhesive Tapes or Sheets

The thermosetting adhesive tape or sheet of the present invention is a thermosetting adhesive tape or sheet having a thermosetting adhesive layer formed by the thermosetting adhesive composition. As said thermosetting adhesive tape or sheet, if it has a thermosetting adhesive layer by the said thermosetting adhesive composition, it may have a base material and may not have a base material. Accordingly, as the thermosetting adhesive tape or sheet, (1) a thermosetting adhesive tape or sheet (substrate-member thermosetting adhesive tape or sheet) having a configuration formed only of the thermosetting adhesive layer, and (2) at least the substrate And a thermosetting adhesive tape or sheet (substrate-attached thermosetting adhesive tape or sheet) having a structure in which a thermosetting adhesive layer is formed on one side (both surfaces or one surface). As a thermosetting adhesive tape or sheet, the thermosetting adhesive tape or sheet of the structure of said (1) (namely, the base material-member thermosetting adhesive tape or sheet of the structure formed only by the thermosetting adhesive layer) is suitable. .

On the other hand, when the thermosetting adhesive tape or sheet is a substrate-adhesive thermosetting adhesive tape or sheet, a thermosetting adhesive layer by the thermosetting adhesive composition may be formed on at least one side of the substrate, and On the other side, in addition to a known adhesive layer or an adhesive layer, a thermosetting adhesive layer other than the above-mentioned thermosetting adhesive layer may be formed.

In addition, the thermosetting adhesive tape or sheet may be formed in a rolled shape, or may be formed in a stacked form. That is, the thermosetting adhesive tape or sheet may have a form such as a sheet shape or a tape shape. On the other hand, when the thermosetting adhesive tape or sheet has a form wound in a roll shape, for example, the thermosetting adhesive tape is wound in a roll shape in a state protected by a peeling treatment layer formed on the back side of the separator or the substrate. It may have a form.

On the other hand, in the thermosetting adhesive tape or sheet, since the thermosetting adhesive adhesive layer is formed by the said thermosetting adhesive composition as mentioned above, it has the adhesiveness which can be adhere | attached to a to-be-adhered body at normal temperature, and heating Thereby, hardening reaction arises and adhesive strength increases and it has the adhesiveness which can be adhere | attached firmly.

As thickness of a thermosetting adhesive agent layer, it can select from the range of 3-100 micrometers (preferably 5-50 micrometers, More preferably, 10-30 micrometers). On the other hand, the thermosetting adhesive layer can have any form of a single layer and a laminated body.

In the present invention, as the thermosetting adhesive layer, the storage modulus at 23 ° C. is 1 × 10 ⁶ to 1 × 10 ⁸ Pa (preferably 1 × 10 ⁷ to 8 × 10 ⁷ , more preferably 1.2 × 10 ⁷ to 5 × 10 ⁷ ). If the storage elastic modulus at 23 ° C. is less than 1 × 10 ⁶ Pa, the adhesiveness is improved, but heat resistance tends to decrease, while if it exceeds 1 × 10 ⁸ Pa, the heat resistance is improved but the adhesiveness tends to be lowered. In addition, the storage elastic modulus of a thermosetting adhesive agent layer can be measured by the measurement conditions of a frequency: 1 Hz and a strain: 5% using the viscoelasticity measuring apparatus of apparatus brand name "ARES" (product made from Leo Matrix).

In thermosetting adhesive tapes or sheets, the thermosetting adhesive layer may be protected by known release liners.

When a thermosetting adhesive tape or sheet has a base material, it does not restrict | limit especially as said base material, For example, Paper-based base materials, such as paper; Fibrous base materials such as cloth, nonwoven fabric and net; Metal base materials such as metal foil and metal plate; Films and sheets made of various resins (olefin resins, polyester resins, polyvinyl chloride resins, vinyl acetate resins, amide resins, polyimide resins, polyether ether ketones, polyphenylene sulfides, etc.) Plastic base materials such as these; Rubber base materials such as rubber sheets; Suitable thin bodies, such as foams, such as a foam sheet, and these laminated bodies (especially the laminated body of a plastics base material and another base material, and a laminated body of a plastic film or sheets, etc.) can be used. It does not restrict | limit especially as thickness of a base material, For example, it is about 10-500 micrometers (preferably 12-200 micrometers, More preferably, it is 15-100 micrometers). On the other hand, the substrate may have the form of a single layer, or may have the form of a multilayer. In addition, the substrate may be subjected to various treatments such as a back treatment, an antistatic treatment, and an undercoat treatment as necessary.

On the other hand, the thermosetting adhesive tape or sheet may have other layers (for example, an intermediate layer, an undercoat layer, etc.) in the range which does not impair the effect of this invention.

The thermosetting adhesive tape or sheet can be manufactured according to the manufacturing method of a normal adhesive tape or sheet. For example, in the case where the thermosetting adhesive tape or sheet is a substrate-member thermosetting adhesive tape or sheet, the method of drying by applying the thermosetting adhesive agent composition to the release surface of the release liner so that the thickness after drying becomes a predetermined thickness. It can be produced by. On the other hand, in application | coating of a thermosetting adhesive agent composition, a conventional coating machine (for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, etc.) can be used.

When the thermosetting adhesive tape or sheet of the present invention is temporarily bonded to the adherend before being cured by heating, it can be adhered to and adhered to the adherend by use of its adhesiveness. After bonding by bonding, it is hardened | cured by heating, and can adhere firmly to a to-be-adhered body. Thus, the thermosetting adhesive tape or sheet can exhibit the performance as a thermosetting adhesive adhesive in a balanced manner, and further, it can exhibit the excellent heat resistance (especially heat resistance after wet heat) after thermosetting.

Moreover, the thermosetting adhesive tape or sheet | seat can exhibit the outstanding workability at the time of processing by the ultraviolet laser after hardening. For example, using a base-member thermosetting adhesive tape or sheet as a thermosetting adhesive tape or sheet, a copper foil and a polyimide film are bonded through the substrate-member thermosetting adhesive tape or sheet, and a copper foil In the case of performing a process of punching a copper foil by irradiating an ultraviolet laser from the side, in the adhesive layer (adhesive layer) formed by the thermosetting of the thermosetting adhesive agent composition in a base material-member thermosetting adhesive tape or sheet Since the ultraviolet absorber (Z) is contained, the adhesive layer absorbs the energy of the ultraviolet laser, thereby reducing the energy of the ultraviolet laser passing through the adhesive layer and reaching the surface of the polyimide film. As a result, the adhesive layer and Abrupt heat generation at the interface of the polyimide film is suppressed or prevented, and the adhesive layer and the polyimide agent It is possible to effectively suppress or prevent the chipping process from occurring so that the adhesive layer is eroded at the interface of the rim, so that the adhesive layer has a so-called `` dimple '' (a peeling phenomenon in which the adhesive layer is eroded as shown in FIG. 1A), It can suppress or prevent generation | occurrence | production of peeling phenomenon (peeling state), such as what is called "peeling off" (peeling phenomenon which the adhesive layer as shown in FIG. 1B erodes and peels off at the edge part side).

Therefore, the thermosetting adhesive tape or sheet can be temporarily attached at room temperature, and furthermore, since it is possible to easily fix the adhesive at this time, the joining work becomes very simple and the joining workability is excellent. Moreover, after positioning by temporary attachment and bonding by adhesion, what was bonded by adhesion can be adhere | attached by the outstanding adhesiveness by causing hardening reaction by heating. Moreover, when processing an ultraviolet laser, it can process with excellent workability. Therefore, the thermosetting adhesive tape or sheet of the present invention is temporarily attached at room temperature by adhesion. After the temporary attachment, the adhesive is hardened by heating and excellent in heat resistance. It can use suitably for the use etc. which are requested | required. Specifically, a thermosetting adhesive tape or sheet can be suitably used at the time of adhesive bonding in a flexible printed circuit board (FPC). In addition, the adhesive bonding of FPC means the adhesive bonding at the time of manufacturing an FPC, or the adhesive bonding at the time of joining FPC to a reinforcement board.

[Wired Circuit Board]

The adhesive bond layer formed by the thermosetting of the said thermosetting adhesive agent composition is used for the wiring circuit board of this invention as an adhesive bond layer for bonding arbitrary members. That is, the wiring circuit board of the present invention may be referred to as an electrical insulator layer (sometimes referred to as a "base insulation layer"), and a conductor layer ("conductor layer") formed on the base insulation layer so as to have a predetermined circuit pattern. Yes), and also has an adhesive bond layer ("adhesive adhesive layer" may be called) formed by the thermosetting of the said thermosetting adhesive agent composition. In the said wiring circuit board, since the said adhesive bond layer is used in order to adhere | attach arbitrary members in a wiring circuit board, it is provided between arbitrary 1 or 2 sets or more members for bonding in a wiring circuit board. It is becoming. Therefore, a wiring circuit board may have only one layer of the said adhesive bond layer, and may have two or more layers.

In addition to the base insulating layer and the conductor layer formed so as to have a predetermined circuit pattern on the base insulating layer, the wiring circuit board is provided with a covering electric insulator layer provided on the conductor layer as necessary (called a "cover insulating layer"). And a reinforcing plate provided on the side opposite to the conductor layer of the base insulating layer. Each of these members (base insulating layer, conductor layer, cover insulating layer, reinforcing plate, etc.) can be laminated in a form bonded to another member through an adhesive layer, for example. Therefore, examples of the site where the adhesive layer is provided include a base insulating layer and a conductor layer, a conductor layer and a cover insulating layer, and a base insulating layer and a reinforcing plate.

In addition, the wiring circuit board may have a multilayer structure having a structure in which a plurality of wiring circuit boards are stacked. Such a wiring circuit board can be laminated, for example, in a form bonded to another wiring circuit board through an adhesive layer. Therefore, when the wiring circuit board has a multilayer structure in which a plurality of wiring circuit boards are stacked, for example, any one set or two sets or more of wiring circuit boards may be used as the site where the adhesive bonding layer is provided.

Thus, in the wiring circuit board of this invention, an adhesive agent layer is at least any one of a base insulating layer and a conductor layer, between a conductor layer and a cover insulating layer, between a base insulating layer and a reinforcement board, and between each wiring circuit board. Can be installed in between. Of course, when the wiring circuit board has a multilayer structure having a structure in which a plurality of wiring circuit boards are laminated, the adhesive bonding layer is formed between the singular and the plurality of wirings between the base insulating layer and the conductor layer in the singular and plural wiring circuit boards. It can be provided between the conductor layer and cover insulation layer in a circuit board, and the base insulation layer and reinforcement board in single or several wiring circuit boards.

Specifically, as a structure of a wiring circuit board, the following structure (1) thru | or a structure (5) etc. are mentioned, for example.

Structure (1): As shown in FIG. 2, a structure comprising a base insulating layer, a conductor layer formed on the base insulating layer so as to have a predetermined circuit pattern, and a point adhesive layer formed between the base insulating layer and the conductor layer.

Configuration (2): As shown in Fig. 3, a base insulating layer, a conductor layer formed to have a predetermined circuit pattern on the base insulating layer, a cover insulating layer provided on the conductor layer, and the conductor layer and the cover Structure composed of an adhesive layer formed between insulating layers

Configuration (3): As shown in Fig. 4, a base insulating layer, a conductor layer formed to have a predetermined circuit pattern on the base insulating layer, a reinforcing plate provided on the opposite side to the conductor layer of the base insulating layer, and Configuration by an adhesive layer formed between the base insulating layer and the reinforcing plate

Configuration (4): As shown in Fig. 5, a wiring circuit board formed by a base insulating layer, a conductor layer formed to have a predetermined circuit pattern on the base insulating layer, and a cover insulating layer provided on the conductor layer are Two layers are laminated | stacked and the structure which has an adhesive bond layer between two wiring circuit boards

Configuration (5): Configuration in which at least two or more configurations selected from Configurations (1) to (4) are combined

2 to 5 are schematic cross-sectional views each showing an example of the wiring circuit board of the present invention. 2 to 5, 2a to 2d are wiring circuit boards, 2d1 is a wiring circuit board on the upper side in the wiring circuit board 2d, and 2d2 is a wiring circuit board on the lower side in the wiring circuit board 2d. , 3 is a base insulating layer, 4 is a conductor layer, 5a to 5d are adhesive bonding layers, 6 is a cover insulating layer, and 7 is a reinforcing plate. In addition, adhesive layer 5a-5d is the adhesive bond layer formed by the thermosetting of the said thermosetting adhesive agent composition, respectively. The wiring circuit board 2a shown in FIG. 2 has the structure in which the conductor layer 4 which becomes a predetermined circuit pattern on the base insulating layer 3 was formed through the adhesive bond layer 5a. In the wiring circuit board 2b shown in FIG. 3, a conductor layer 4 having a predetermined circuit pattern is formed on the base insulation layer 3, and the base insulation layer 3 and the conductor layer 4 are formed. The cover insulating layer 6 covers the conductor layer 4, and has a structure formed through the adhesive layer 5b on the conductor layer 4. As for the wiring circuit board 2c shown in FIG. 4, the conductor layer 4 which becomes a predetermined | prescribed circuit pattern on the base insulation layer 3 is formed, and also the conductor layer in the base insulation layer 3 ( The reinforcing plate 7 is formed on the opposite side with respect to 4) through the adhesive bond layer 5c. In the wiring circuit board 2d shown in FIG. 5, a conductor layer 4 having a predetermined circuit pattern is formed on the base insulating layer 3, and the base insulating layer 3 and the conductor layer 4 are formed on the wiring circuit board 2d. In the wiring circuit board 2d1 in which the cover insulating layer 6 is formed in such a manner that the cover insulating layer 6 covers the conductor layer 4, an adhesive layer 5d is formed on the cover insulating layer 6. On 5d, the wiring circuit board 2d2 having the same configuration as the wiring circuit board 2d1 contacts the adhesive layer 5d with the surface on the base insulating layer 3 side of the wiring circuit board 2d2. It has the structure laminated | stacked in the form to do.

On the other hand, as the wiring circuit board having the above configuration (5), for example, as shown in Fig. 6, a base insulating layer, a conductor layer formed to have a predetermined circuit pattern on the base insulating layer, and a cover provided on the conductor layer. An insulating layer, an adhesive layer formed between the base insulating layer, the conductor layer and the cover insulating layer, a reinforcing plate provided on a side opposite to the conductor layer of the base insulating layer, and between the base insulating layer and the reinforcing plate A wiring circuit board having a structure of an adhesive bonding layer formed on the substrate, or as illustrated in FIG. 7, a base insulating layer, a conductor layer formed to have a predetermined circuit pattern on the base insulating layer, and a cover insulation provided on the conductor layer. Two wiring circuit boards formed by an adhesive layer formed between the layer, the base insulating layer, the conductor layer, and the cover insulating layer. The wiring circuit board etc. which have a structure which has an adhesive bond layer between two wiring circuit boards are mentioned.

6 and 7 are schematic cross-sectional views each showing an example of the wiring circuit board of the present invention. 6 and 7, 2e and 2f are wiring circuit boards, 2f1 are wiring circuit boards on the upper side in the wiring circuit board 2f, and 2f2 are wiring circuit boards on the lower side in the wiring circuit board 2f, respectively. And 5e1, 5e2, 5f1, 5f2 and 5f3 are adhesive bonding layers, and 3, 4, 6 and 7 are the same as above. In the wiring circuit board 2e shown in FIG. 6, the adhesive layer 5e1 is formed on the base insulating layer 3, and the conductor layer 4 has a predetermined circuit pattern on the adhesive layer 5e1. And a cover insulating layer 6 covering the conductor layer 4, and an adhesive layer 5e2 at a predetermined portion on the side opposite to the conductor layer 4 in the base insulating layer 3. Moreover, it has the structure in which the reinforcement board 7 was formed on the said adhesive bond layer 5e2. In the wiring circuit board 2f shown in FIG. 7, the adhesive layer 5f1 is formed on the base insulating layer 3, and the conductor layer 4 has a predetermined circuit pattern on the adhesive layer 5f1. And the adhesive layer 5f3 is formed on the cover insulating layer 6 in the wiring circuit board 2f1 having the cover insulating layer 6 covering the conductor layer 4. An adhesive layer 5f2 is formed on the base insulating layer 3 on 5f3, and the conductor layer 4 and the conductor layer 4 which have a predetermined circuit pattern on the adhesive layer 5f2 are covered. The wiring circuit board 2f2 having the structure in which the cover insulating layer 6 is formed is laminated in such a manner that the surface on the side of the base insulating layer 3 in the wiring circuit board 2f2 is in contact with the adhesive layer 5f3. Has a built-in configuration.

[Adhesive layer]

2 to 5, the adhesive layers 5a to 5d, the adhesive layers 5e1 to 5e2 in FIG. 6, and the adhesive layers 5f1 to 5f3 in FIG. 7 are respectively composed of the thermosetting adhesive agent composition. It is formed by thermosetting. The adhesive layer may be formed by applying the thermosetting adhesive composition to a predetermined portion on a predetermined surface and then thermally curing the adhesive layer. However, the adhesive layer or sheet may be formed by the thermosetting adhesive adhesive tape or sheet (that is, by the thermosetting adhesive adhesive composition). It is preferable to form using the thermosetting adhesive tape or sheet which has a thermosetting adhesive layer. In thermosetting adhesive tapes or sheets, the thermosetting adhesive layer is an uncured or semi-cured adhesive layer prior to thermal curing (ie, equivalent to the adhesive layer before thermal curing), and the thermosetting adhesive layer By thermosetting, an adhesive layer is formed. Therefore, the adhesive layer may be formed by applying a thermosetting adhesive composition, followed by thermal curing at the same time as drying, or by applying a thermosetting adhesive composition and drying to form a thermosetting adhesive layer, the thermosetting type It may be formed by thermosetting the adhesive layer.

The heating temperature at the time of forming the adhesive layer by thermosetting is not particularly limited as long as it is a temperature at which the thermosetting adhesive composition or the thermosetting adhesive layer can be thermally cured, for example, 50 to 200 ° C (preferably 50 to 200). 180 degreeC, More preferably, it can select from the range of 100-160 degreeC) suitably. In addition, as heating time at the time of thermosetting, it can select suitably from the range of 30 second-5 hours (preferably 1 minute-3 hours, More preferably, 5 minutes-2 hours).

In addition, the thermosetting at the time of forming an adhesive bond layer can also be performed under pressure. As a pressure at the time of thermosetting, it can select suitably from the range of 0.1-10 Mpa (preferably 0.5-8 Mpa, More preferably, 1-6 Mpa).

The adhesive layer can be further cured after the thermosetting adhesive composition or the thermosetting adhesive layer is thermally cured under the above-mentioned thermosetting conditions (heating temperature, heating time, pressure). As curing temperature after thermosetting, it can select suitably from the range of 100-160 degreeC (preferably 120-160 degreeC), for example, and also 1 to 5 hours (preferably 2 to 4 hours) as curing time. It can select from the range suitably. Cure, on the other hand, is usually carried out at atmospheric pressure.

Thus, when the adhesive layer is formed using a thermosetting adhesive tape or sheet, predetermined members (base insulating layer, conductor layer, cover insulating layer, reinforcing plate, wiring) on both sides of the thermosetting adhesive tape or sheet. After bonding a circuit board etc.), it can form by heat-setting (especially heating under pressure) and thermosetting a thermosetting adhesive agent layer.

It does not restrict | limit especially as thickness of an adhesive bond layer, For example, it can select from the range of 3-100 micrometers (preferably 5-50 micrometers, More preferably, 10-30 micrometers). The adhesive layer may have any form of a single layer and a laminate.

[Base insulation layer]

The base insulating layer is an electrical insulator layer formed of an electrical insulating material. It does not restrict | limit especially as an electrical insulation material for forming a base insulation layer, It can select suitably from the electrical insulation material used for a well-known wiring circuit board, and can use. Specifically, examples of the electrical insulating material include polyimide resins, acrylic resins, polyethernitrile resins, polyethersulfone resins, polyester resins (polyethylene terephthalate resins, polyethylene naphthalate resins, and the like) and polychlorinated salts. Plastics such as vinyl resins, polyphenylene sulfide resins, polyether ether ketone resins, polyamide resins (so-called "aramid resins"), polyallylate resins, polycarbonate resins, liquid crystal polymers, and the like Ash, ceramic materials such as alumina, zirconia, soda glass and quartz glass; composite materials having various electrical insulation properties (non-conductive); and the like. In addition, an electrical insulation material can be used individually or in combination of 2 or more types.

In the present invention, a plastic material (especially a polyimide resin) is suitable as the electric insulating material. Therefore, it is preferable that the base insulating layer is formed of a plastic film or sheet (especially a polyimide resin film or sheet).

On the other hand, as an electric insulating material, an electric insulating material (for example, photosensitive plastic material, such as a photosensitive polyimide resin, etc.) which has photosensitivity can be used.

The base insulating layer may have any form of a single layer and a laminate. Various surface treatments (eg, corona discharge treatment, plasma treatment, roughening treatment, hydrolysis treatment, etc.) may be performed on the surface of the base insulating layer.

Although it does not restrict | limit especially as thickness of a base insulating layer, For example, it can select suitably from the range of 3-100 micrometers (preferably 5-50 micrometers, More preferably, 10-30 micrometers).

[Conductor Layer]

The conductor layer is a conductor layer formed of a conductive material. The conductor layer is formed on the base insulating layer so as to have a predetermined circuit pattern. There is no restriction | limiting in particular as a electrically conductive material for forming such a conductor layer, It can select suitably from the electrically conductive material used for a well-known wiring circuit board, and can use. Specifically, examples of the conductive material include copper, nickel, gold, and chromium, as well as metal materials such as various alloys (for example, solder) and platinum, and conductive plastic materials. In addition, a electrically conductive material can be used individually or in combination of 2 or more types. In the present invention, a metal material (especially copper) is suitable as the conductive material.

The conductor layer can have any form of monolayer and laminate. The surface of the conductor layer may be subjected to various surface treatments.

Although it does not restrict | limit especially as thickness of a conductor layer, For example, it can select suitably from the range of 1-50 micrometers (preferably 2-30 micrometers, More preferably, 3-20 micrometers).

The method for forming the conductor layer is not particularly limited, and may be appropriately selected from known formation methods (eg, known patterning methods such as subtractive method, additive method, semiadditive method, etc.). Can be. For example, when the conductor layer is formed on the surface of the base insulating layer through the adhesive layer, the conductor layer is formed on the surface of the base insulating layer by the conductive material layer (for example, metal foil, etc.) through the thermosetting adhesive layer. After forming, the thermosetting adhesive layer is thermally cured to form the conductive material layer on the base insulating layer through the adhesive layer, and then the etching treatment is performed by chemical liquid treatment so that the conductive material layer has a predetermined circuit pattern. It can form by performing. In addition, when the conductor layer is formed directly on the surface of the base insulating layer, the conductive material is formed on the base insulating layer so that the conductor layer has a predetermined circuit pattern by using an electroless plating method, an electroplating method, a vacuum deposition method, a sputtering method, or the like. It can be formed by plating, vapor deposition, or the like.

[Cover insulation layer]

The cover insulating layer is a covering electrical insulator layer (protective electrical insulator layer) formed of an electrical insulating material and covering the conductor layer. The cover insulating layer is provided as needed, and does not necessarily need to be provided. It does not restrict | limit especially as an electrical insulation material for forming a cover insulation layer, It can select suitably from the electrical insulation material used for a well-known wiring circuit board like the case of a base insulation layer. Specifically, examples of the electrical insulating material for forming the cover insulating layer include an electrical insulating material exemplified as the electrical insulating material for forming the base insulating layer, and the like. In the case of the base insulating layer, a plastic material (especially, Polyimide resin) is suitable. In addition, the electrical insulation material for forming a cover insulation layer can be used individually or in combination of 2 or more types.

The cover insulation layer may have any form of a single layer and a laminate. Various surface treatments (eg, corona discharge treatment, plasma treatment, roughening treatment, hydrolysis treatment, etc.) may be performed on the surface of the cover insulating layer.

Although it does not restrict | limit especially as thickness of a cover insulating layer, For example, it can select suitably from the range of 3-100 micrometers (preferably 5-50 micrometers, More preferably, 10-30 micrometers).

The method of forming the cover insulating layer is not particularly limited, and a known forming method (for example, a method of applying and drying a liquid or a melt containing an electrical insulating material, a film or sheet formed by the electrical insulating material corresponding to the shape of the conductor layer) The method of laminating | stacking, etc.) can be selected suitably.

[Reinforcement board]

The reinforcing plate is provided on the surface (rear side) opposite to the conductor layer of the base insulating layer. The reinforcement plate is installed as needed and does not necessarily need to be installed. It does not restrict | limit especially as a reinforcement board material for forming a reinforcement board, It can select suitably from a reinforcement board material for forming a well-known reinforcement board, and can use. The reinforcing plate may be any of those having conductivity and non-conductivity. Specifically, as the reinforcing plate material, for example, metal materials such as stainless steel, aluminum, copper, iron, gold, silver, nickel, titanium, chromium, polyimide resin, acrylic resin, polyether nitrile resin, and polyether sulfone resin , Polyester resin (polyethylene terephthalate resin, polyethylene naphthalate resin, etc.), polyvinyl chloride resin, polyphenylene sulfide resin, polyether ether ketone resin, polyamide resin (so-called Amide resin ”), plastic materials such as polyallylate resin, polycarbonate resin, epoxy resin, glass epoxy resin, liquid crystal polymer, and inorganic materials such as alumina, zirconia, soda glass, quartz glass, and carbon. Can be. In addition, a reinforcement board material can be used individually or in combination of 2 or more types.

As a reinforcing plate material, metal materials, such as stainless steel and aluminum, and plastic materials, such as a polyimide resin, are suitable, and stainless steel and aluminum can be used especially suitably. Therefore, the reinforcing plate is preferably formed of a metal foil or metal plate (stainless foil or stainless plate, aluminum foil or aluminum plate, or the like), or a plastic film or sheet (such as a polyimide resin film or sheet).

The reinforcement plate may have any form of monolayers and laminates. The surface of the reinforcement plate may be subjected to various surface treatments.

Although it does not restrict | limit especially as thickness of a reinforcement board, For example, it can select suitably in the range of 50-2000 micrometers (preferably 100-1000 micrometers).

[Wired Circuit Board of Multi-Layer Structure]

The wiring circuit board of the multilayer structure has a structure in which a plurality of wiring circuit boards are stacked. In the wiring circuit board of the multilayer structure, each wiring circuit board has at least a base insulating layer and a conductor layer, and, if necessary, has a cover insulating layer, a reinforcing plate (especially a cover insulating layer), and any one set or The adhesive bond layer is provided between two or more sets of wiring circuit boards.

In such a multi-layered wiring circuit board, each member (base insulating layer, conductor layer, cover insulating layer, reinforcing plate, etc.) constituting the wiring circuit board is bonded to each wiring circuit board through the adhesive layer. It may be laminated, or may be laminated in a state of being bonded through an adhesive layer other than the adhesive layer, or may be further laminated in a firmly adhered state by another method. In addition, the wiring circuit board of the multi-layered structure may be laminated in a state where at least one set of wiring circuit boards are bonded to each other through an adhesive layer, and other wiring circuit boards may be laminated in a state of being bonded through an adhesive layer other than the adhesive layer. It may also be laminated in a tightly adhered state by another method.

On the other hand, the number of wiring circuit boards (multilayer layers) in the wiring circuit board having a multilayer structure is not particularly limited as long as it is two or more.

In the wiring circuit board of the present invention, if an adhesive layer is provided between at least one set of arbitrary members in order to adhere arbitrary members, an adhesive bond layer made of another adhesive may be provided in order to adhere the other members. Such adhesives include known adhesives (e.g., polyimide-based thermosetting adhesives, epoxy-based thermosetting adhesives, epoxy-nitrile butyl rubber-based thermosetting adhesives, epoxy-acrylic rubber-based thermosetting adhesives, acrylic-based thermosetting adhesives, beauty-based thermosetting adhesives). Thermosetting adhesives such as adhesives, urethane-based thermosetting adhesives, synthetic rubber adhesives, pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, and the like, can be appropriately selected and used, and thermosetting adhesives can be suitably used in view of heat resistance.

Since the wiring circuit board of this invention has an adhesive bond layer which is an adhesive bond layer formed by the thermosetting of the said thermosetting adhesive agent composition as an adhesive bond layer for bonding arbitrary members as mentioned above, when a member bonds together, Position by temporary adhesion at room temperature (eg, at 10 to 30 ° C.) using a thermosetting adhesive layer (an adhesive layer in which the thermosetting adhesive composition is in an uncured or semi-cured state), which is an adhesive layer before curing. The members can be produced by bonding the members firmly by bonding the members to each other in a predetermined positional relationship, heat treatment thereafter, and curing the thermosetting adhesive layer. Therefore, the wiring circuit boards of the present invention can be temporarily attached to each other at room temperature, and furthermore, since the attachment can be easily corrected at this time, the joining operation becomes very simple and can be produced with excellent joining workability. Moreover, after positioning by temporary attachment and joining members by adhesion, by hardening reaction by heating, what was joined by adhesion can be adhere | attached firmly, and members adhere | attach with excellent adhesiveness, A wiring circuit board can be manufactured. Therefore, the wiring circuit board is manufactured with excellent workability and productivity.

On the other hand, the wiring circuit board of the present invention is not particularly limited as long as it is a wiring circuit board, but a flexible printed circuit board (FPC) is suitable. The wiring circuit board of this invention can be used suitably as a wiring circuit board used in various electronic devices.

Example

EMBODIMENT OF THE INVENTION Although this invention is demonstrated further more concretely based on an Example below, this invention is not limited by these Examples.

(Example 1)

Acrylic polymer [copolymer of butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) = 69: 30: 1 (weight ratio)]: Phenol-based resol type in ethyl acetate solution in which 100 parts by weight was dissolved As a phenol resin, a brand name "Sumilite resin PR-51283" (made by Sumitomo Bakelite Co., Ltd .; has a liquid phase at 50 degreeC): The methanol solution which melt | dissolved 10 weight part was mixed and stirred, and also a brand name "TINUVIN384-2 as a ultraviolet absorber. (Product of Chiba Specialty Chemical Co., Ltd .; benzotriazole type ultraviolet absorber): 3 parts by weight was added, mixed and stirred to prepare a thermosetting adhesive agent composition solution. That is, the said thermosetting adhesive agent composition solution contains 100 weight part of acrylic polymers, 10 weight part of phenolic resol type phenol resins, and 3 weight part of ultraviolet absorbers is further contained.

The thermosetting adhesive agent composition solution was applied to a release surface of the release liner with a roll coater so that the thickness after drying was 25 μm, dried at 100 ° C. for 3 minutes, and the adhesive agent layer in the semi-cured state (thermosetting adhesive agent layer) Was formed to obtain a thermosetting adhesive sheet.

(Example 2)

Acrylic polymer [copolymer of butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) = 69: 30: 1 (weight ratio)]: Phenol-based resol type in ethyl acetate solution in which 100 parts by weight was dissolved As a phenol resin, a brand name "Tamanol AS" (made by Arakawa Chemical Co., Ltd .; has a liquid phase at 50 degreeC): The methanol solution which melt | dissolved 10 weight part was mixed and stirred, and also brand name "TINUVIN 400" (Chiba Specialty Chemical) as an ultraviolet absorber. Benzotriazole ultraviolet absorber): 3 parts by weight was added, mixed and stirred to prepare a thermosetting adhesive agent composition solution. That is, the said thermosetting adhesive agent composition solution contains 100 weight part of acrylic polymers, 10 weight part of phenolic resol type phenol resins, and 3 weight part of ultraviolet absorbers is further contained.

The thermosetting adhesive agent composition solution was applied to a release surface of the release liner with a roll coater so that the thickness after drying was 25 μm, dried at 100 ° C. for 3 minutes, and the adhesive agent layer in the semi-cured state (thermosetting adhesive agent layer) Was formed to obtain a thermosetting adhesive sheet.

(Comparative Example 1)

Acrylic polymer [copolymer of butyl acrylate (BA) / acrylonitrile (AN) / acrylic acid (AA) = 69: 30: 1 (weight ratio)]: Liquid phase at 50 ° C. in ethyl acetate solution in which 100 parts by weight was dissolved As a phenolic-type resol type phenol resin which has a brand name "Sumilite resin PR-51283" (made by Sumitomo Bakelite): The methanol solution which melt | dissolved 10 weight part was mixed, stirred, and the thermosetting type adhesive composition composition solution was prepared. That is, in the said thermosetting adhesive agent composition solution, 100 weight part of acrylic polymers are contained, 10 weight part of phenolic resol type phenol resins, and 3 weight part of ultraviolet absorbers are contained.

The thermosetting adhesive agent composition solution was applied to a release surface of the release liner with a roll coater so that the thickness after drying was 25 μm, dried at 100 ° C. for 3 minutes, and the adhesive agent layer in the semi-cured state (thermosetting adhesive agent layer) Was formed to obtain a thermosetting adhesive sheet.

(evaluation)

For each thermosetting adhesive sheet obtained in Examples and Comparative Examples, the storage elastic modulus of the thermosetting adhesive layer, the adhesive strength at room temperature before curing, the adhesive strength after curing, the heat resistance, and the workability by UV laser are the following storage elastic modulus, respectively. It measured or evaluated by the measuring method of the, the measuring method of adhesive force, the measuring method of adhesive force, the evaluation method of heat resistance, and the evaluation method of workability.

(Measurement method of storage elastic modulus)

In each thermosetting adhesive sheet produced by the Example and the comparative example, with respect to the thermosetting adhesive layer before hardening, room temperature (storage modulus (E ') (Pa) in 23 degreeC as an index of the temporary adhesiveness at normal temperature). Was measured under the conditions of frequency: 1 Hz and strain: 5% using the device brand name "ARES" (manufactured by LEOMETICS Co., Ltd.). It is shown in the column.

(Measuring method of adhesive force)

The adhesive force at normal temperature (23 degreeC) before hardening as an index of the temporary adhesiveness at normal temperature with respect to the thermosetting adhesive agent layer before hardening in each thermosetting adhesive sheet produced by the Example and the comparative example ( N / 20 mm) was measured according to JIS Z 0237. Specifically, the polyimide film was attached to the thermosetting adhesive sheet by attaching a polyester-based adhesive tape (trade name "No. 31B" manufactured by Nitto Denko Co., Ltd.) to the back and cutting the sample cut to 20 mm in width with a roller of 2 kg once. It is crimped | bonded by (brand name "Kaphton 500V" DuPont company make), and 180 degree peeling adhesive force (peel rate: 100 mm / min, 23 degreeC, a sample is tensioned; N / 20 mm), and apparatus name "TCM-1KNB" ( It measured using Minebase Co., Ltd.). In addition, the measurement or evaluation result was shown in the column of "adhesion force (N / 20mm)" of Table 1.

(Measuring method of adhesive force)

23 degreeC after hardening with respect to the thermosetting adhesive agent layer (adhesive layer formed by thermosetting of the thermosetting adhesive agent composition) after hardening in each thermosetting adhesive sheet produced by the Example and the comparative example. The adhesive force in (N / cm) was measured. Specifically, a flexible printed circuit board (FPC; area: 5 cm × 8 cm, thickness: 0.2 mm) and a thermosetting adhesive sheet were laminated at 130 ° C., and then cut into 1 cm widths, and the aluminum plate (area: 5 cm × 5 cm). , Thickness: 0.5 mm), and further laminated at 130 ° C., followed by heat pressing at 160 ° C. and 1 MPa for 90 seconds, and further curing at 150 ° C. for 3 hours to prepare a test body. The apparatus brand name "TCM-1KNB" (Minebase Co., Ltd.) was used by the method of pulling 90 degree peeling adhesive force (peel rate: 50 mm / min, 23 degreeC; N / cm) with respect to this test body from the FPC side. Measured by. In addition, the measurement or evaluation result was shown to the column of "adhesion force (N / cm)" of Table 1.

(Evaluation method of heat resistance)

The test body was produced similarly to the measuring method of the said adhesive force. The test body was left to stand for 24 hours under conditions of humidification (temperature: 60 ° C and humidity: 90% RH), and then, in a heating furnace by infrared rays (IR heating furnace), under conditions of peak temperature: 270 ° C and time: 15 seconds. When heated by the temperature profile of the thermosetting adhesive sheet, the floating peeling and foaming state of the thermosetting adhesive layer (adhesive layer) was visually confirmed, and no lifting peeling or foaming was confirmed in the thermosetting adhesive layer. It was made into "(circle)", and it evaluated that heat resistance was made into "x" that the thing which lifted peeling and foaming were confirmed to the thermosetting adhesive agent layer was "x." In addition, the measurement or evaluation result was shown in the column of "heat resistance" of Table 1.

(Evaluation method of workability)

Copper foil (thickness: 9 micrometers) was bonded to both surfaces of the polyimide film (thickness: 12.5 micrometers) using each thermosetting adhesive sheet produced by the Example and the comparative example, and copper foil / adhesive layer / The 5-layer laminated product which has the laminated constitution of the film / adhesive layer / copper foil made from polyimide was produced. Specifically, copper foil is provided on a surface of a polyimide film (trade name "Kapton" (product of E-I Dupont; thickness: 12.5 µm) through a thermosetting adhesive sheet (that is, a thermosetting adhesive layer). (Thickness: 9 mu m), and after laminating a copper foil (thickness: 9 mu m) on the other side of the polyimide film through a thermosetting adhesive sheet (i.e., a thermosetting adhesive layer), : 150 ° C., pressure: 40 kgf / cm ² (3.9 MPa) and time: hot press (heat press) under conditions of 60 minutes, further cured at 150 ° C. for 3 hours, and each thermosetting type on both sides of the polyimide film Copper foil (thickness: 9 micrometers) / adhesive layer (thickness: 25 micrometers) / film made from polyimide (thickness: 12.5 micrometers) / adhesive layer (thickness: 25 micrometers) / copper bonded each copper foil through an adhesive agent layer The 5-layer laminated product which has a laminated constitution of foil (thickness: 9 micrometers) was produced.

The 5-layer laminated article was irradiated with an ultraviolet laser (UV-YAG laser) using an ultraviolet irradiation device from one side of the copper foil surface side, and a hole was formed in the two-layered portion of the copper foil / adhesive layer on the side irradiated with the ultraviolet laser. The punching process is performed, and the processed surface is visually checked, and the peeling phenomenon such as so-called "cut" or so-called "peel" is not found at the end of the adhesive layer on the processed surface. The workability by an ultraviolet laser was evaluated as what made "x" what peeling phenomenon, such as "digging" and what is called "peeling", was confirmed at the edge part of an adhesive bond layer. Processing conditions were a laser: YAG laser with a wavelength of 355 nm, a beam diameter of 25 μm, a power of 2.56 W and a rep rate of 70 kHz. In addition, the measurement or evaluation result was shown in the column of the "laser processability" of Table 1.

In addition, in the peeling phenomenon which arises in an adhesive bond layer by the process of an ultraviolet laser, what is called "dig" means the peeling phenomenon by which an adhesive layer erodes, as shown in FIG. 1A, and what is called "peeling" is shown in FIG. As described above, it means a peeling phenomenon in which the pressure-sensitive adhesive layer is eroded and peeled off at the end side.

Since the thermosetting adhesive agent composition of this invention has the said structure, it can exhibit favorable adhesiveness before hardening, can exhibit the outstanding adhesiveness and heat resistance after hardening by heating, Furthermore, by the ultraviolet laser after hardening At the time of processing, excellent workability can be exhibited. Therefore, the thermosetting adhesive tape or sheet having the thermosetting adhesive layer by the thermosetting adhesive composition can be temporarily attached at room temperature, and can be adhered with excellent adhesiveness after positioning by temporary adhesion. In addition, after bonding, even if the process is performed by an ultraviolet laser, the peeling of the adhesive layer generated on the working surface can be suppressed or prevented, and it can be suitably used at the time of adhesive bonding on a flexible printed circuit board.

Moreover, since the wiring circuit board of this invention has the said structure, predetermined members are bonded together by positioning by provisional attachment at normal temperature, and after joining in predetermined position relationship, they are bonded by the outstanding adhesiveness, Moreover, the workability by an ultraviolet laser is excellent. Therefore, the wiring circuit board is manufactured with excellent workability and productivity, and can be processed by an ultraviolet laser with excellent workability.

Claims (11)

60 to 75 weight% of the (meth) acrylic acid alkyl ester (a) having 2 to 14 carbon atoms of the alkyl group as the monomer component, and 20 to 35 weight of the cyano group-containing monomer (b) based on the total amount of the monomer component. % Acryl-based polymer (X) containing a carboxyl group-containing monomer (c) in a proportion of 0.5 to 10% by weight based on the total amount of monomer components: Phenol-based resol type phenol resin represented by the following general formula (1) Y): The thermosetting adhesive agent composition which contains 1-20 weight part and contains a ultraviolet absorber (Z) further. Formula 1

Where R ¹ represents —CH ₂ — or —CH ₂ —O—CH ₂ —, n is a positive integer, m is an integer of 1-4. The method of claim 1, The thermosetting adhesive agent composition whose ultraviolet absorber (Z) is a ultraviolet absorber which contains a nitrogen element in a molecule | numerator. The method of claim 1, The thermosetting adhesive agent composition whose ratio of a ultraviolet absorber (Z) is 1-20 weight part with respect to an acrylic polymer (X): 100 weight part. The thermosetting adhesive tape or sheet which has a thermosetting adhesive layer formed from the thermosetting adhesive composition of Claim 1. The method of claim 4, wherein The thermosetting adhesive tape or sheet whose storage elastic modulus (23 degreeC) of a thermosetting adhesive layer is 1 * 10 <^6> -1 * 10 <^8> Pa. A wiring circuit board having at least an electric conductor layer and a conductor layer formed on the electric insulator layer so as to have a predetermined circuit pattern, and having an adhesive layer formed by thermosetting of the thermosetting adhesive agent composition according to claim 1. The wiring circuit board characterized by the above-mentioned. The method of claim 6, An adhesive layer formed by thermal curing of the thermosetting adhesive agent composition is formed between an electric insulator layer and a conductor layer, between a conductor layer and a covering electric insulator layer provided on the conductor layer, and an electric insulator layer and the electric insulator layer. A wiring circuit board provided between at least one of the reinforcing plates provided on the surface opposite to the conductor layer. The method of claim 6, The wiring circuit board has a multilayered structure in which a plurality of wiring circuit boards are stacked, and any one set or two sets or more of wiring circuit boards are formed in an adhesive layer formed by thermosetting of the thermosetting adhesive agent composition. Wiring circuit board which has in between. The method of claim 6, The wiring circuit in which the adhesive bond layer formed by the thermosetting of the said thermosetting adhesive agent composition is formed using the thermosetting adhesive tape or sheet which has a structure formed only by the thermosetting adhesive agent layer by the said thermosetting adhesive agent composition. Board. The method of claim 9, The adhesive circuit layer formed by the thermosetting of the said thermosetting adhesive agent composition is formed by bonding a predetermined | prescribed member to both surfaces of a thermosetting adhesive tape or a sheet, and heating under pressure and thermosetting. The method of claim 6, The wiring circuit board whose thickness of the adhesive bond layer formed by the thermosetting of the said thermosetting adhesive agent composition is 3-100 micrometers.

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