TWI487762B - Resin composition for adhesive, adhesive containing the same, adhesive sheet, and printed wiring board containing the same as an adhesive layer - Google Patents

Description

Resin composition for adhesive, adhesive containing the same, adhesive sheet, and printed wiring board containing the same as an adhesive layer

The present invention relates to a resin composition excellent in adhesion to various plastic films, adhesion to metals such as copper, aluminum, stainless steel, glass adhesion, heat resistance, moisture resistance, and sheet life, and an adhesive containing the same. , adhesive sheets and printed wiring boards containing them as an adhesive layer.

Recently, adhesives have been used in various fields, but due to the diversification of use purposes, adhesives that have been used in the past have been required, adhesion to various plastic films, adhesion to metals such as copper, aluminum, and stainless steel, It has higher performance for adhesion to glass epoxy, heat resistance, moisture resistance, and sheet life. For example, an adhesive for a circuit board including a flexible printed wiring board (hereinafter sometimes referred to as FPC) requires solder heat resistance, adhesion, workability, electrical properties, and preservability. Conventionally, an epoxy/acrylic butadiene-based adhesive, an epoxy/polyvinyl butyral-based adhesive, or the like is used for this application.

In particular, adhesives having higher heat resistance have been demanded from the correspondence with lead-free solders and the environment in which FPCs are used. Further, in terms of high density of wiring, multilayering of FPC wiring boards, and operability, it is strongly required to have solder resistance under high humidity and adhesion under high temperature and high humidity. In the past, epoxy/acrylic butadiene-based adhesives and epoxy/polyvinyl butyral adhesives have poor adhesion and processability especially under high temperature and high humidity, and adhesion of metal and plastic films. Not enough. It is also impossible to ensure a long-term sheet life that can be circulated at normal temperature.

In the above-mentioned problems, for example, JP-A-H11-116930 (Patent Document 1), JP-A-2008-205370 (Patent Document 2), and JP-A-2007-204715 (Patent Document 3) have been proposed. A resin composition for an adhesive having a specific polyester ‧ polyurethane and an epoxy resin as a main component. However, the composition shown in Patent Document 1 can improve the life of the sheet, the adhesion at high temperatures and high humidity, but does not sufficiently satisfy the adhesion strength at a higher temperature, and uses various metals such as SUS for reinforcement. The board is resistant to humidification and soldering. Further, the composition shown in Patent Document 2 can improve the adhesion at high temperatures and high humidity, and the wet-weld resistance when the plastic film is used for a reinforcing plate, but does not sufficiently satisfy the use of the metal for the reinforcing plate. It is resistant to humidification and soldering. In addition, the composition shown in Patent Document 2 is such that the adhesive sheet is stored at a normal temperature and 40° C. in an 80% humidified environment, and the wet solder resistance and the adhesion are remarkably lowered, and a stable sheet life cannot be ensured. Further, Patent Document 3 has succeeded in improving the glass transition temperature of the polyurethane resin, improving the adhesion at high temperatures, and the life of the sheet. However, the elevated glass transition temperature is inevitably accompanied by a decrease in flexibility. In the manufacturing process of the flexible printed wiring board, there is a crack in the adhesive sheet when the adhesive sheet is cut, punched, and peeled off from the release film. , peeling off, and the disadvantage of reduced processing suitability.

On the other hand, an adhesive composition of two types of polyester resins having different glass transition temperatures is disclosed in JP-A-2008-019375 (Patent Document 4) and JP-A-2009-084348 (Patent Document 5). . These methods improve the processing suitability at room temperature by blending a resin having a high glass transition temperature and a resin having a low glass transition temperature, but the flexibility is low under a storage temperature of 5 ° C or less for a general adhesive sheet. It is not satisfied for the processability at low temperatures. In addition, these films exhibit excellent adhesion to PET films and tin-plated copper and are excellent in blocking resistance, especially because they exhibit excellent properties as adhesives for flexible flat cables but only by thermoplastic resins. According to this configuration, the adhesive for a flexible printed wiring board is insufficient in heat resistance and does not sufficiently satisfy the resistance to humidifying solder.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-116930

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-205370

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-204715

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-019375

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-084348

The problem of the present invention is to improve the adhesion of these conventional adhesives and to maintain adhesion to various plastic films, metals such as copper, aluminum, stainless steel, and glass epoxy resins. The adhesive of the lead-free solder under high humidity, which is excellent in heat resistance at high temperature and high humidity, and excellent in workability in the production of a flexible printed wiring board, and further provides an adhesive sheet obtained from the above-mentioned adhesive even if After circulating under high temperature and high humidity, an adhesive sheet having a good sheet life which can maintain good adhesion characteristics is used. Further, it is provided to provide a printed wiring board comprising an adhesive layer obtained from the above-mentioned adhesive or adhesive sheet.

The present inventors have made efforts to solve the above problems and have completed the present invention. That is, the present invention is constituted by the following constitution.

The resin composition for an adhesive of the present invention contains a polyester resin or a polyurethane resin and has an acid value (unit: equivalent/10 ⁶ g) of 100 or more and 1,000 or less, and a glass transition temperature of 30 ° C or more. The thermoplastic resin (A1) having a number average molecular weight of not less than 80 ° C and a number average molecular weight of 5.0 × 10 ³ or more and 1.0 × 10 ⁵ or less is formed of a polyester resin or a polyurethane resin and has a glass transition temperature of 0 ° C or less and a number average molecular weight. It is a thermoplastic resin (A2) of 5.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, an inorganic filler (B) and an epoxy resin (D) having a dicyclopentadiene skeleton, and dried at 130 ° C for 3 minutes, followed by At least a part of the thermoplastic resin (A1) and the thermoplastic resin (A2) have a phase-separated structure in the cured coating film obtained by heat-treating at 140 ° C for 4 hours.

The resin composition for an adhesive of the present invention is measured by temperature dispersion of the above-mentioned cured coating film at a frequency of 10 Hz and a temperature increase rate of 4 ° C/min, and the loss elasticity derived from the aforementioned thermoplastic resin (A1) is observed. The modulus peak portion and the loss elastic modulus peak portion from the thermoplastic resin (A2) are preferably 40 ° C or higher. .

In the resin composition for an adhesive of the present invention, it is preferred that the thermoplastic resin (A1) is made of a polyester resin, the thermoplastic resin (A2) is made of a polyurethane resin, or the thermoplastic resin ( A1) is made of a polyurethane resin, and the thermoplastic resin (A2) is made of a polyester resin.

The resin composition for an adhesive of the present invention preferably contains the thermoplastic resin (A1) in an amount of 55 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). .

In the resin composition for an adhesive of the present invention, the total amount of the thermoplastic resin (A1), the thermoplastic resin (A2), and the inorganic filler (B) is 25 by mass in the resin composition of the adhesive. The dispersion (α) of the dispersion (α) having a total amount of 45 parts by mass of methyl ethyl ketone and 30 parts by mass of toluene in a total amount of 100 parts by mass is preferably 3 or more and 6 or less at a liquid temperature of 25 ° C.

In the resin composition for an adhesive of the present invention, the acid value (unit: equivalent/10 ⁶ g) of the thermoplastic resin (A1) is set to AV (A1), and the blending amount (unit: parts by mass) is AW ( A1), the acid value of the thermoplastic resin (A2) is AV (A2), the blending amount is AW (A2), and the epoxy value of the epoxy resin (D) (unit: equivalent/10 ⁶ g) When EV (D) and the blending amount are EW (D) (unit: parts by mass), it is preferable to satisfy the following formula (1): 0.7 ≦ {EV (D) × EW (D)) / {AV(A1)×AW(A1)+AV(A2)×AW(A2)}≦4.0.

The present invention also provides a resin composition for a multi-component mixed type adhesive, wherein the resin composition (β) contains: a polyester resin or a polyurethane resin and an acid value (unit: equivalent/10 ⁶ g) a thermoplastic resin (A1) having a glass transition temperature of 30 ° C or more and a glass transition temperature of 30 ° C or more and 80 ° C or less and a number average molecular weight of 5.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and a polyester resin or a polyurethane resin A thermoplastic resin (A2) having a glass transition temperature of 0 ° C or less, a number average molecular weight of 5.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, an inorganic filler (B) and an organic solvent (C); and a resin composition (γ) The epoxy resin (D) is contained; the acid value (unit: equivalent/10 ⁶ g) of the thermoplastic resin (A1) is set to AV (A1), and the blending amount (unit: parts by mass) is AW (A1). The acid value of the thermoplastic resin (A2) is AV (A2), the blending amount is AW (A2), and the epoxy value (unit: equivalent/10 ⁶ g) of the epoxy resin (D) is set. When EV (D) and the blending amount are EW (D) (unit: parts by mass), the following formula (1) is satisfied: 0.7 ≦ {EV (D) × EW (D)} / {AV (A1) ) × AW (A1) + AV (A2) × AW (A2)} ≦ 4.0 blend ratio blending Resin composition (β) and resin composition (γ).

The present invention also provides a resin composition for a multi-component mixed type adhesive, wherein the resin composition (δ) contains: a polyester resin or a polyurethane resin and an acid value (unit: equivalent/10 ⁶ g) a thermoplastic resin (A1) having an amount of 100 or more and 1,000 or less, a glass transition temperature of 30 ° C or more and 80 ° C or less, a number average molecular weight of 5.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, an inorganic filler (B), and an organic solvent ( C); the resin composition (ε) contains: a thermoplastic resin obtained from a polyester resin or a polyurethane resin and having a glass transition temperature of 0 ° C or less and a number average molecular weight of 5.0 × 10 ³ or more and 1.0 × 10 ⁵ or less (A2), an inorganic filler (B) and an organic solvent (C); the resin composition (ζ) contains an epoxy resin (D); and the acid value (unit: equivalent/10 ⁶ g) of the thermoplastic resin (A1) It is assumed that AV (A1), the blending amount (unit: parts by mass) is AW (A1), the acid value of the thermoplastic resin (A2) is AV (A2), and the blending amount is AW (A2). When the epoxy value (unit: equivalent/10 ⁶ g) of the epoxy resin (D) is EV (D) and the blending amount is EW (D) (unit: parts by mass), the following formula is satisfied. (1): 0.7≦{EV(D)×EW(D)}/{AV(A1)×AW(A1)+AV(A2)×AW(A2)}≦4.0 blending ratio blending resin composition (δ) and Resin composition (ε) and resin composition (ζ).

In the resin composition for an adhesive of the present invention, the epoxy resin (D) is preferably 60% by mass or more and 99.9% by mass or less based on the total amount of the epoxy resin contained in the resin composition for the adhesive.

In the resin composition for an adhesive of the present invention, the amount of the inorganic filler (B) is preferably 10 parts by mass or more based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). Below the mass.

In the resin composition for an adhesive of the present invention, the amount of the solvent (C) is preferably 60 parts by mass or more and 85 parts by mass or less when the resin composition for an adhesive is 100 parts by mass.

The resin composition for an adhesive of the present invention preferably contains an epoxy resin containing a nitrogen atom.

In the resin composition for an adhesive of the present invention, it is preferred that the epoxy resin containing a nitrogen atom has a glycidyl propylene diamine structure.

The present invention also provides an adhesive comprising the above-described resin composition for an adhesive of the present invention.

The present invention also provides the thermoplastic resin (A1), the thermoplastic resin (A2), the inorganic filler (B), the epoxy resin (D), and the like contained in the resin composition for an adhesive of the present invention. The adhesive sheet of the reaction product.

The present invention also provides a printed wiring board comprising an adhesive layer using the above-described adhesive of the present invention or the adhesive sheet of the present invention.

According to the present invention, it is possible to obtain high adhesion to various plastic films and metals, high heat and humidity resistance of lead-free solders at high humidity, adhesion under high temperature and high humidity, and processing suitability in FPC manufacturing. It is an excellent adhesive, and it can provide a resin composition which adheres to an adhesive sheet and maintains good adhesion characteristics even after being circulated under high temperature and high humidity. The resin composition containing the adhesive, the adhesive sheet containing the same, and the adhesive sheet thereof are used as the adhesive. Printed wiring board of the agent layer. Further, in a preferred embodiment of the present invention, it is also possible to provide a resin composition which is excellent in adhesion to various plastic films, adhesion to metals such as copper, aluminum, and stainless steel, and adhesion to glass epoxy resins. An adhesive, an adhesive sheet, and a printed wiring board containing the same as an adhesive layer. Further, in a preferred embodiment of the present invention, the adhesion to the metal such as aluminum or stainless steel is excellent, and the heat and humidity resistance is excellent, and the adhesive is maintained in a high-temperature and high-humidity environment for a long period of time. In terms of aspects, we will play a more excellent role.

[Formation for implementing the invention]

<dispersion (α)>

In the present invention, the degree of rocking (TI value) of the dispersion (α) is determined by the thermoplastic resin (A1), the thermoplastic resin (A2), and the inorganic filler (B) in the resin composition for an adhesive of the present invention. A combination of the appropriateness of the combination and blending. The degree of shaking (TI value) of the dispersion (α) is 3 or more and 6 or less, more preferably 3.5 or more and 5 or less. The interaction between the particles of the inorganic filler (B) contained in the dispersion (α), and/or the interaction between the thermoplastic resin (A1), the thermoplastic resin (A2) and the inorganic filler (B) is high. The degree of shaking of (α) tends to become higher. If the degree of shaking is less than 3, the interaction between the particles of the inorganic filler (B), and/or the interaction between the inorganic filler (B) and the thermoplastic resin (A1) and the thermoplastic resin (A2) is lowered and the heat resistance is lowered. In addition, the inorganic filler is likely to settle and there is a tendency that a stable pot life cannot be obtained. When the degree of shaking is more than 6, the handling property is lowered and there is a tendency that it becomes difficult to apply uniformly.

The dispersion (α) is a total of 25 parts by mass of the thermoplastic resin (A1), the thermoplastic resin (A2), and the inorganic filler (B), and the mass ratio of methyl ethyl ketone 45, based on the content ratio of the resin composition for the adhesive of the present invention. The mixing ratio of 30 parts by mass of toluene is mixed, and glass beads having a diameter of 0.5 mm or more and 2 mm or less are further added to about 1/3 of the volume of the dispersion (α), and a paint shaker is used in the chamber. After dispersing for 4 hours in a room having a temperature of 20 ° C or more and 25 ° C or less, the glass beads were removed and prepared.

The degree of shaking (TI value) of the dispersion (α) was determined by the following method. The dispersion (α) was taken to a glass-made jar of 225 mL (commonly known as: a cannabis bottle), and the measurement was carried out at a temperature of 25 ± 1 ° C using a BL type viscometer (manufactured by Toki Sangyo Co., Ltd.) at a rotation number of 6 rpm. The viscosity with 60 rpm (hereinafter sometimes referred to as BL (6), BL (60), unit: dPa ‧ for short), and when BL (6) is 100 or less, the vibration is obtained by the following formula (2) Variation (TI value). In addition, when BL(6) is more than 100, the viscosity is measured at 2 rpm and 20 rpm using a BH type viscometer (manufactured by Toki Sangyo Co., Ltd.) (hereinafter sometimes referred to as BH(2), BH(20) for short. dPa‧s), the degree of rocking (TI value) is obtained by the following formula (3). In addition, the rotor used for the viscosity measurement by the BL type viscometer and the BH type viscometer is selected according to the description of the operation manual of each viscosity meter, and any one of No. 2 to 4 is selected.

Shake degree (TI value) = BL (6) / BL (60) (2)

Shake degree (TI value) = BH (2) / BH (20) (3)

<Resin composition (β)>

The resin composition (β) used in the present invention is obtained by blending a thermoplastic resin (A1), a thermoplastic resin (A2), an inorganic filler (B), a solvent (C), and other components as needed in the foregoing ratio. The method is uniformly obtained by uniformly mixing a roll mill, a mixer, a paint shaker, etc., and the dispersion method is not particularly limited as long as a method of sufficiently dispersing is obtained. Further, the solid content concentration of the resin composition (β) is preferably 15% by mass or more and 40% by mass or less. When the solid content concentration is less than 15% by mass, the thickness of the adhesive is reduced, and the heat resistance and the adhesive strength are lowered. When the viscosity is more than 40% by mass, the viscosity of the solution becomes too high, so that it becomes difficult to be uniform. The tendency to coat is carried out.

<Resin composition (γ), resin composition (ζ)>

The resin composition (γ) and the resin composition (ζ) used in the present invention may be composed only of the epoxy resin (D), but it is preferred to further contain the solvent (C). The solvent (C) contained in the resin composition (γ) and the resin composition (ζ) is not particularly limited as long as it can dissolve the components contained in the resin composition (γ) and the resin composition (ζ). Further, the solid content concentration of the resin composition (γ) and the resin composition (ζ) is preferably 15% by mass or more and 80% by mass or less. When the solid content concentration is less than 15% by mass, the thickness of the adhesive after the solvent is volatilized becomes thin, and the heat resistance and the adhesive strength tend to be lowered. When the solid content concentration is more than 80% by mass, the viscosity of the resin composition for an adhesive becomes too high, so that it tends to be difficult to apply uniformly.

<Resin composition (δ)>

The resin composition (δ) used in the present invention is obtained by blending a thermoplastic resin (A1), an inorganic filler (B), a solvent (C), and other optional components in the above ratio in a roll mill, A mixer, a paint shaker, and the like are uniformly mixed, and the dispersion method is not particularly limited as long as a method of sufficiently dispersing is obtained. Further, the solid content concentration of the resin composition (δ) is preferably 15% by mass or more and 40% by mass or less. When the solid content concentration is less than 15% by mass, the thickness of the adhesive is reduced, and the heat resistance and the adhesive strength are lowered. When the viscosity is more than 40% by mass, the viscosity of the solution is too high, which makes it difficult to increase the viscosity of the solution. The tendency to apply uniformly.

<Resin composition (ε)>

The resin composition (ε) of the present invention is obtained by blending a thermoplastic resin (A2), an inorganic filler (B), a solvent (C), and other components as needed in the foregoing ratio, in a roll mill, A mixer, a paint shaker, and the like are uniformly mixed, and the dispersion method is not particularly limited as long as a method of sufficiently dispersing is obtained. Further, the solid content concentration of the resin composition (?) is preferably 15% by mass or more and 40% by mass or less. When the solid content concentration is less than 15% by mass, the thickness of the adhesive is reduced, and the heat resistance and the adhesive strength are lowered. When the viscosity is more than 40% by mass, the viscosity of the solution is too high, which makes it difficult to increase the viscosity of the solution. The tendency to apply uniformly.

<Resin composition for adhesive>

The resin composition for an adhesive of the present invention may be a resin composition for a liquid type adhesive containing a thermoplastic resin (A1), a thermoplastic resin (A2), an inorganic filler (B), or an epoxy resin (D). It may be a resin composition for a plurality of mixed adhesives which is mixed into a plurality of agents and mixed before use. By making a mixture of plural agents, there is an advantage that it can be preserved for a long period of time. On the other hand, in the case of a mixed type of a plurality of agents, when used as an adhesive, it is necessary to uniformly mix the plurality of agents at a proper blending ratio, and the more the number of the agents is increased, the greater the difficulty of the step. Therefore, among the plurality of mixed types, it is preferably a two-liquid mixed type or a three-liquid mixed type. A preferred example of the two-liquid mixing type is a resin composition (β) containing a thermoplastic resin (A1), a thermoplastic resin (A2), an inorganic filler (B), and a solvent (C), and a ring containing the same. The case where the resin composition (γ) of the oxygen resin (D) is used as a two-liquid. A preferred example of the three-liquid mixing type is a resin composition (δ) containing a thermoplastic resin (A1), an inorganic filler (B), and a solvent (C), a thermoplastic resin (A2), and an inorganic filler. The material (B), the resin composition (ε) of the solvent (C), and the resin composition (ζ) containing the epoxy resin (D) are considered to be three liquids.

The resin composition for an adhesive of the present invention is preferably an acid value AV (A1) (unit: equivalent/10 ⁶ g) and a blending amount AW (A1) (unit: parts by mass) of the thermoplastic resin (A1), The acid value of the thermoplastic resin (A2) AV (A2) (unit: equivalent/10 ⁶ g) and the blending amount AW (A2) (unit: parts by mass), epoxy resin (D) epoxy value EV (D) (Unit: equivalent/10 ⁶ g) and the blending amount EW (D) (unit: parts by mass) satisfying the blending ratio of the following formula (1) to blend the thermoplastic resin (A1), the thermoplastic resin (A2), and the ring Oxygen resin (D).

0.7≦{EV(D)×EW(D)}/{AV(A1)×AW(A1)+AV(A2)×AW(A2)}≦4.0 (1)

When the blending ratio is less than 0.7, the crosslinking between the thermoplastic resin (A1), the thermoplastic resin (A2) and the epoxy resin is insufficient, and the heat resistance tends to decrease, and the blending ratio becomes more than 4.0. When the amount is large, the unreacted epoxy resin remains in a large amount, and the heat resistance and the moisture resistance tend to be lowered. The blend ratio is more preferably 0.8 or more and 3.5 or less, still more preferably 0.9 or more and 3.0 or less.

<thermoplastic resin (A1), thermoplastic resin (A2)>

The present invention contains a thermoplastic resin (A1) made of a polyester resin or a polyurethane resin, a thermoplastic resin (A2) made of a polyester resin or a polyurethane resin, and an inorganic filler (B). And a resin composition for an adhesive of epoxy resin (D), which is dried at 130 ° C for 3 minutes, and then heat-treated at 140 ° C for 4 hours to obtain a thermoplastic resin (A1) and a thermoplastic resin (A2). At least a portion has a separate phase separation structure. By having a phase-separated structure, a thermoplastic resin (A2) having high adhesion to a high temperature or a high temperature and high adhesion due to a thermoplastic resin (A1) having a high glass transition temperature and having a low heat transfer temperature is exhibited. The softness of the adhesive sheet is increased, and peeling or cracking of the coating film can be suppressed in the processing step at the time of manufacturing the flexible printed wiring board.

By using a combination which is low in compatibility with the thermoplastic resin (A1) and the thermoplastic resin (A2), a phase separation structure can be formed in the cured coating film. In the case of a combination having a low compatibility, one may be a polyester resin and the other may be a polyurethane resin, or the solubility parameter of the thermoplastic resin (A1) may be a thermoplastic resin ( The difference in solubility parameter of A2) increases.

In the present invention, whether or not the cured coating film has a phase-separated structure can be confirmed by, for example, dynamic viscoelasticity measurement. Whether the loss elastic modulus peak portion or the loss tangent (tan δ) peak portion from the thermoplastic resin (A1) and the thermoplastic resin (from the aforementioned thermoplastic resin) are observed in the cured coating film formed of the resin composition for an adhesive A2) is judged by the loss elastic modulus peak or the loss tangent (tan δ) peak. The peaks shown here may be slightly convex even if they are wide. Further, the difference between the loss elastic modulus peaks of the thermoplastic resin (A1) and the thermoplastic resin (A2) is preferably 40 ° C or higher.

The thermoplastic resin (A1) used in the present invention is preferably used in an amount of from 55 parts by mass to 80 parts by mass based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). When the thermoplastic resin (A1) is less than 55 parts by mass based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2), the adhesion at high temperature, high temperature and high humidity, and the adhesion strength at high temperature are lowered. When the content is more than 80 parts by mass, the flexibility of the adhesive sheet is lowered, and the workability is lowered by the crack or peeling of the coating film in the processing step at the time of FPC production, and the defective product rate is high. The tendency. The thermoplastic resin (A1) is preferably 60 parts by mass or more and 75 parts by mass or less based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2).

The number average molecular weight of the thermoplastic resin (A1) and the thermoplastic resin (A2) used in the present invention is 5 × 10 ³ or more and 1 × 10 ⁵ or less. When the number average molecular weight of the thermoplastic resin (A1) and the thermoplastic resin (A2) is less than 5 × 10 ³ , the adhesion immediately after coating is insufficient and the workability is deteriorated, and if the number average molecular weight is more than 1 × 10 ⁵ , the coating is performed. The viscosity of the solution is too high, and sometimes a uniform coating film cannot be obtained. The lower limit of the thermoplastic resin (A1) and the thermoplastic resin (A2) is preferably 8 × 10 ³ , and more preferably 1 × 10 ⁴ . The upper limit of the thermoplastic resin (A1) and the thermoplastic resin (A2) is preferably 5 × 10 ⁴ , and more preferably 3 × 10 ⁴ .

The acid value AV (A1) (unit: equivalent/10 ⁶ g) used in the thermoplastic resin (A1) of the present invention is 100 or more and 1,000 or less. When the acid value (A1) of the thermoplastic resin (A1) is less than 100 equivalents/10 ⁶ g, the adhesion to the metal substrate after curing is insufficient, and the degree of crosslinking is low and the heat resistance is lowered. tendency. When the acid value AV (A1) of the thermoplastic resin (A1) is more than 1000 equivalents/10 ⁶ g, the storage stability of the varnish is lowered when dissolved in a solvent, and the crosslinking reaction of the adhesive sheet is easily carried out at normal temperature, and it is impossible to obtain A tendency to stabilize the life of the sheet. Further, it is also expected to have an adverse effect on the durability of an ester bond, a urethane bond or the like. The lower limit of the acid value AV (A1) of the thermoplastic resin (A1) is preferably 250 equivalents/10 ⁶ g, more preferably 300 equivalents/10 ⁶ g, still more preferably 350 equivalents/10 ⁶ g. The upper limit of the acid value AV (A1) of the thermoplastic resin (A1) is preferably 900 equivalents/10 ⁶ g, more preferably 800 equivalents/10 ⁶ g, still more preferably 700 equivalents/10 ⁶ g.

The glass transition temperature of the thermoplastic resin (A1) used in the present invention is 30 ° C or more and 80 ° C or less. When the glass transition temperature of the thermoplastic resin (A1) is less than 30 ° C, the adhesion at high temperatures tends to be insufficient. When the glass transition temperature of the thermoplastic resin (A1) is more than 80 ° C, the adhesion to the substrate is lowered, the adhesion at room temperature is lowered, and the flexibility of the adhesive sheet is lowered. In the processing step, the coating film is cracked or peeled off, resulting in a tendency to decrease in workability. The lower limit of the glass transition temperature of the thermoplastic resin (A1) is preferably 35 ° C, more preferably 40 ° C. The upper limit of the glass transition temperature of the thermoplastic resin (A1) is preferably 75 ° C, more preferably 70 ° C.

The acid value AV (A2) (unit: equivalent/10 ⁶ g) used in the thermoplastic resin (A2) of the present invention is 1000 or less. When the acid value is more than 1000 equivalents/10 ⁶ g, the storage stability of the varnish is lowered when dissolved in a solvent, and the crosslinking reaction tends to proceed at normal temperature, and there is a tendency that a stable sheet life cannot be obtained. Further, there is a tendency to adversely affect the durability of an ester bond or a urethane bond or the like. The upper limit of the acid value AV (A2) of the thermoplastic resin (A2) is preferably 900 equivalents/10 ⁶ g, more preferably 800 equivalents/10 ⁶ g, still more preferably 700 equivalents/10 ⁶ g.

The glass transition temperature of the thermoplastic resin (A2) used in the present invention is 0 ° C or lower. When the glass transition temperature is more than 0 ° C, the adhesive sheet tends to be hard and brittle, and the workability is lowered by cracking or peeling of the coating film in the processing step at the time of FPC production. In addition, the adhesive becomes hard and the adhesiveness tends to be insufficient. The lower limit of the thermoplastic resin (A2) is preferably -5 ° C, more preferably -10 ° C.

In the polyester resin of the present invention, when the total amount of all the acid components in the composition is 100 mol%, the aromatic carboxylic acid is preferably 60 mol% or more, more preferably 85 mol% or more. Further preferably, it is 99 mol% or more. The aromatic carboxylic acid may also account for 100 mol%. When the aromatic carboxylic acid is less than 60 mol%, the cohesive force of the coating film is low, and the adhesion strength to various substrates can be seen to be lowered.

Examples of the aromatic carboxylic acid include aromatic dicarboxylic acids such as citric acid, isophthalic acid, o-nonanoic acid, naphthalene dicarboxylic acid, diphenylic acid, dibenzoic acid, and 5-hydroxyisodecanoic acid. Further, sulfo-p-citric acid, 5-sulfoisodecanoic acid, 4-sulfodecanoic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfophenoxy) may be mentioned. An aromatic dicarboxylic acid having a sulfonic acid group such as isophthalic acid, an aromatic dicarboxylic acid having a sulfonate group such as a metal salt or an ammonium salt, a p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, or a p-hydroxy group An aromatic hydroxycarboxylic acid such as phenylacetic acid, 6-hydroxy-2-naphthoic acid or 4,4-bis(p-hydroxyphenyl)pentanoic acid. Among these, citric acid, isophthalic acid, and a mixture thereof are particularly preferable in terms of enhancing the cohesion of the coating film.

Further, examples of the other acid component include alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and an acid anhydride thereof. An aliphatic dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, sebacic acid, dodecanedioic acid or dimer acid.

On the other hand, the diol component is preferably an aliphatic diol, an alicyclic diol, an aromatic diol, an ether bond-containing diol, or the like, and in the case of an aliphatic diol, Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, hydroxytrimethyl Examples are neopentyl glycol acetate, dimethylol butane, 2,2,4-trimethyl-1,3-pentanediol, etc., and examples of the alicyclic diol include 1,4 - cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethylol, spiro diol, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide plus Products and propylene oxide adducts, etc. Examples of the diol having an ether bond include diethylene glycol, triethylene glycol, and dipropylene glycol, and further, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and neopentyl glycol. An ethylene oxide adduct, a neopentyl glycol propylene oxide adduct, and the like. In the case of the aromatic-containing aliphatic diol, ethylene oxide of p-xylene glycol, m-xylene glycol, o-xylene glycol, 1,4-benzenediol, and 1,4-benzenediol can be exemplified. The addition product, the bisphenol A, the ethylene oxide adduct of bisphenol A and the propylene oxide adduct are equal to the two phenolic hydroxyl groups of the bisphenol, each of which is obtained by adding ethylene oxide or propylene oxide to 1 to several moles. Alcohols, etc.

Further, a hydroxycarboxylic acid compound having a hydroxyl group and a carboxyl group in the molecular structure may also be used as a polyester raw material, and examples thereof include 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenylethyl alcohol, and p-hydroxyphenylpropyl. Acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, 4,4-bis(p-hydroxyphenyl)pentanoic acid, and the like.

In the polyester resin used in the present invention, it is also possible to copolymerize a polyfunctional carboxylic acid and/or a polyhydric alcohol having a trifunctional or higher functional group of 0.1 mol% or more and 5 mol% or less for the purpose of introducing a branching skeleton as needed. . In particular, when a hardened coating film is obtained by reacting with a curing agent, the terminal group concentration (reaction point) of the resin is increased by introducing a branching skeleton, and the crosslinking density is high, whereby a coating film having strength can be obtained. In the case of a trifunctional or higher polycarboxylic acid in this case, trimellitic acid, trimesic acid, ethylene glycol bis(anhydrophthalate), glycerin (dehydrated trimellitic acid) can be used. Ester), trimellitic anhydride, pyromellitic anhydride (PMDA), oxydiphthalic acid dianhydride (ODPA), 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride (BTDA), 3 , 3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride (DSDA), 4,4'-(six a compound such as fluoroisopropylidene) diacetic acid dianhydride (6FDA) or 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA), on the other hand, a trifunctional or higher functional group As an example of the polyol, glycerin, trimethylolethane, trimethylolpropane, neopentylol or the like can be used. When a trifunctional or higher polycarboxylic acid and/or a polyhydric alcohol is used, it is preferably 0.1 mol% or more and 5 mol% or less, preferably 0.1 mol% or more, based on the total acid component or all the diol components. It is preferable to copolymerize in the range of the molar % or less, and if it is more than 5 mol%, there is a possibility that the mechanical properties such as the elongation at break of the coating film are lowered, and there is a possibility that gelation occurs in the polymerization.

In the method of introducing the acid value into the polyester resin used in the present invention, a method of introducing a carboxylic acid into the resin by acid addition after polymerization can be mentioned. When a monocarboxylic acid, a dicarboxylic acid, or a polyfunctional carboxylic acid compound is used for acid addition, there is a possibility that a molecular weight is lowered due to transesterification, and a compound having at least one carboxylic anhydride is preferably used. As the acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), or oxydiamine can be used. Decanoic acid dianhydride (ODPA), 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA) , 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene)dicarboxylic acid dianhydride (6FDA), 2,2' a compound such as bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA). When the total acid component of the polyester resin used in the present invention is 100 mol%, if acid addition is performed at 10 mol% or more, gelation may occur and polyester may be caused. The solution polymerizes and reduces the molecular weight of the resin. The acid addition system is a method in which the polyester is polycondensed and then directly carried out in a bulk state, and a method in which the polyester is solutionized and added. The reaction in the bulk state is fast, but if it is added in a large amount, it may cause gelation, and since it reacts at a high temperature, it is necessary to take care to block oxygen to prevent oxidation. On the other hand, although the reaction in the solution state is slow, a large amount of carboxyl groups can be stably introduced.

The polyester resin used in the present invention may copolymerize a lactone monomer such as β-propiolactone, γ-butyrolactone, δ-valerolactone or ε-caprolactone. From the viewpoint of versatility of the raw materials, ε-caprolactone is preferred. In the case of the copolymerization method, it is preferred to introduce the lactone monomer in a bulk state after the polycondensation and to subject the polyester resin to ring-opening polymerization. method.

The polyurethane resin used in the present invention is preferably a polyester polyol, a polyisocyanate or a chain extender as a raw material thereof. In the method of introducing an acid value, there is a method of imparting an acid value to a polyester polyol constituting a polyurethane resin in advance, or a method of using a diol containing a carboxylic acid in a chain extender.

The polyester polyol used as a raw material for the polyurethane resin used in the present invention is preferably the same as the above-mentioned polyester resin except for the number average molecular weight. The polyester polyol used in the present invention has a number average molecular weight of 5 × 10 ² or more and 5 × 10 ⁴ or less. When the number average molecular weight of the polyester polyol is less than 5 × 10 ² , the concentration of the urethane group becomes high, and the adhesiveness at high temperature and high humidity tends to decrease. If the number average molecular weight is more than 5 × 10 ⁴ , the polyamine The polymerizability of the formate is lowered, which may cause poor polymerization. The lower limit of the number average molecular weight of the polyester polyol is preferably 8 × 10 ² , more preferably 1 × 10 ³ . The upper limit of the number average molecular weight of the polyester polyol is preferably 3.5 × 10 ⁴ , more preferably 2 × 10 ⁴ .

The polyisocyanate used in the manufacture of the polyurethane resin used in the present invention may be a diisocyanate, a dimer thereof (uretdione), a terpolymer thereof (iso-isocyanate, a triol adduct, One type of biuret or the like, or a mixture of two or more of them. Examples of the diisocyanate component include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, isophthalic diisocyanate, and hexamethylene diisocyanate. , tetramethylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 4,4'-di Isocyanate diphenyl ether, 1,5-xylene diisocyanate, 1,3-diisocyanate methylcyclohexane, 1,4-diisocyanate methylcyclohexane, 4,4'-diisocyanate cyclohexane, 4 4'-diisocyanate cyclohexylmethane, isophorone diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, etc., but from the viewpoint of yellowing property, it is preferably aliphatic ‧ alicyclic Isocyanate. Further, it is particularly preferred to be hexamethylene diisocyanate or isophorone diisocyanate for reasons of easiness and economy.

In the production of the polyurethane resin used in the present invention, a chain extender may also be used as needed. Examples of the chain extender include a low molecular weight diol, a dimethylolpropionic acid, or a dimethylolbutyric acid having a carboxylic acid and two hydroxyl groups, which are constituent components of the polyester polyol. Compounds, etc. Among them, dimethylolbutanoic acid is preferred from the viewpoint of ease of introduction of an acid value and solubility in a general-purpose solvent. Further, in the method of introducing a branch, it is also preferred to use trimethylolpropane.

In the method for producing a polyurethane resin to be used in the present invention, the polyester polyol, the polyisocyanate, and optionally the chain extender may be charged into the reaction vessel at once, or may be separately introduced. In any case, the total of the hydroxyl groups of the polyester polyol and the chain extender in the system and the isocyanate groups of the polyisocyanate are reacted at a ratio of the functional group of the isocyanate group/hydroxy group to 1 or less. Further, this reaction can be carried out by reacting it in the presence or absence of a solvent inactive to an isocyanate group. Examples of the solvent include ester solvents (ethyl acetate, butyl acetate, ethyl butyrate, etc.) and ether solvents (two Alkane, tetrahydrofuran, diethyl ether, etc.), a ketone solvent (cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an aromatic hydrocarbon solvent (benzene, toluene, xylene, etc.) and a mixed solvent thereof, but From the viewpoint of industrial versatility and drying property, methyl ethyl ketone or toluene is preferred. The reaction apparatus is not limited to a reaction tank equipped with a stirring apparatus, and a kneading apparatus such as a kneader or a two-axis extruder may be used.

In order to promote the urethane reaction, a catalyst used in a general urethane reaction, for example, a tin-based catalyst (trimethyltin laurate, dimethyltin dilaurate, dibutyltin dilaurate, hydrogen) may be used. Trimethyltin oxide, dimethyltin dihydrogenate, stannous octoate, etc.), lead-based catalyst (lead oleate, lead 2-ethylhexanoate, etc.), amine-based catalyst (triethylamine, tributylamine, An oxoquinone, a diterpene bicyclooctane, a diindolyl uncycloundecene, etc.), etc., is preferably an amine-based catalyst from the viewpoint of harmfulness.

In the adhesive composition of the present invention, it is possible to blend a thermoplastic resin other than the polyester resin and the polyurethane resin to the extent that the properties of the present invention are not impaired. Examples of the thermoplastic resin include a styrene resin, a polyamide resin, a polyamidoximine resin, a polyester quinone resin, a polycarbonate resin, and a polyoxyphenylene resin. The vinyl resin, the olefin resin, the acrylic resin, and the like may be used alone or in combination of two or more.

<Inorganic Filling Material (B)>

The inorganic filler (B) used in the present invention is not particularly limited, but is preferably one which imparts a shaken to the dispersion (α). In the case of such an inorganic filler, for example, alumina, cerium oxide, titanium oxide, cerium oxide, zirconium oxide, cerium nitride, barium titanate, cerium carbonate, lead titanate, lead zirconate titanate, zirconium titanate can be used. Lead bismuth oxide, gallium oxide, spinel, mullite, cordierite, talc, aluminum hydroxide, magnesium hydroxide, aluminum titanate, zirconium oxide containing cerium oxide, cerium lanthanum silicate, boron nitride, calcium carbonate, Calcium sulfate, zinc oxide, zinc borate, magnesium titanate, magnesium borate, barium sulfate, organic bentonite, carbon, etc., these may be used alone or in combination of two or more. The cerium oxide is preferred from the viewpoints of transparency, mechanical properties, heat resistance, and shake imparting property of the resin composition for an adhesive, and is particularly preferably a fumed cerium oxide having a three-dimensional network structure. Further, hydrophobic cerium which is preferably treated with monomethyltrichloromethane, dimethyldichlorodecane, hexamethyldiazepine, octyldecane, polyoxyxane or the like is preferably imparted with hydrophobicity. . When the aerosolized cerium oxide is used as the inorganic filler (B), the average diameter of the primary particles is preferably 30 nm or less, more preferably 25 nm or less. When the average diameter of the primary particles is more than 30 nm, the interaction between the particles or the resin is lowered and the heat resistance tends to be lowered. In addition, the average diameter of the primary particles referred to herein is an average value of the equal diameters of the 100 particles randomly extracted from the primary particle image obtained by using the scanning electron microscope.

The blending amount of the inorganic filler (B) is preferably 10 parts by mass or more and 50 parts by mass or less, more preferably 13 parts by mass or more and 45 parts by mass based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). In the following, it is more preferably 15 parts by mass or more and 35 parts by mass or less. On the other hand, when the amount of the inorganic filler (B) is less than 10 parts by mass based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2), the heat resistance does not exert an upward effect. When it is more than 50 parts by mass, cerium oxide is poorly dispersed and the viscosity of the solution becomes too high to cause defects in workability or a decrease in adhesion.

<Solvent (C)>

The solvent (C) used in the present invention may be a single component or a mixed solvent of two or more plural components. The solvent (C) is not particularly limited as long as it can dissolve the thermoplastic resin (A1), the thermoplastic resin (A2), and the epoxy resin (D). Examples of such a solvent include a guanamine solvent such as dimethylacetamide or N-methyl-2-pyrrolidone, an alcohol solvent such as methanol, ethanol or isopropyl alcohol, toluene or xylene. Examples of the ketone solvent such as an aromatic solvent, acetone, methyl ethyl ketone or cyclohexanone, and an ester solvent such as ethyl acetate include toluene, xylene, methyl ethyl ketone and ethyl acetate from the viewpoint of workability. Further preferred from the viewpoint of easiness of drying are toluene, methyl ethyl ketone, and ethyl acetate. These solvents may be used alone or in combination of two or more.

<Epoxy Resin (D)>

The resin composition for an adhesive of the present invention contains an epoxy resin (D) having a dicyclopentadiene skeleton as an essential component. The hardened coating film formed of the epoxy resin having a rigid dicyclopentadiene skeleton has an extremely low moisture absorption rate, and further, since the crosslinking density of the cured coating film can be lowered and the stress at the time of peeling is relaxed, the humidification resistance is enhanced. Improved weldability. Specific examples of the epoxy resin (D) include the DIC HP7200 series.

The blending amount of the epoxy resin (D) having a dicyclopentadiene skeleton is preferably 60% by mass or more, more preferably 75% by mass or more, based on the total amount of the epoxy resin contained in the resin composition for an adhesive. Good is 90% by mass or more. By containing 60% by mass or more of the epoxy resin (D) having a dicyclopentadiene skeleton, it is possible to exhibit more excellent wet solder resistance.

In the resin composition for an adhesive of the present invention, if an epoxy resin containing a nitrogen atom is further contained as an epoxy resin, the adhesive sheet can be B-staged (semi-hardened) by heating at a low temperature and for a short period of time. In addition, it is preferable to suppress the fluidity of the adhesive sheet, suppress the extrusion and discharge of the adhesive during pressurization, and improve the workability, and it is preferable to suppress the foaming during pressurization. . Examples of the epoxy resin containing a nitrogen atom include tetra-epoxypropyldiaminediphenylmethane, triepoxypropyl-aminophenol, and tetra-epoxypropyldiaminomethylcyclohexane. A propyl propyl group such as a ketone, N, N, N', N'-tetraepoxypropyl-m-xylylenediamine or the like. The blending amount of the nitrogen atom-containing epoxy resin is preferably 20% by mass or less based on the entire epoxy resin. When the blending amount is more than 20% by mass, the rigidity increases excessively, and the adhesiveness tends to decrease, and the crosslinking reaction proceeds excessively, and the adhesion to the adherend tends to be lowered. Further, the adhesive sheet is easily crosslinked during storage, and the sheet life tends to be lowered. The upper limit of the blending amount is more preferably 10% by mass, still more preferably 6% by mass.

As the epoxy resin used in the present invention, other epoxy resins may be used in combination. Examples thereof include a epoxidized propyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolac epoxy propyl ether, and brominated bisphenol A diglycidyl ether. , propyl propyl hexahydrophthalate, glycidyl esters such as dipropyl acrylate, trisepoxypropyl isocyanurate, or 3,4-epoxycyclohexyl An alicyclic or aliphatic epoxide such as a carboxylic acid ester, an epoxidized polybutadiene or an epoxidized soybean oil may be used alone or in combination of two or more.

A hardening catalyst can be used in the hardening reaction of the epoxy resin used in the present invention. For example, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole or 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl Imidazole compounds such as 4-methylimidazole or triethylamine, triethylenediamine, N'-methyl-N-(2-dimethylaminoethyl)per 1,8-Diibibicyclo(5,4,0)-undecene-7,1,5-dioxabicyclo(4,3,0)-nonene-5,6-dibutylamino-1 a tertiary amine such as 8-dibicyclobicyclo(5,4,0)-undecene-7 and the tertiary amines thereof are made into an amine salt of phenol, octanoic acid, tetrabasic boronic acid tetraphenyl ester or the like. A cationic catalyst such as a compound, triallyl hexafluoroantimonate or diallyl hexafluoroantimonate or triphenylphosphine. Among these, 1,8-dioxinbicyclo(5,4,0)-undecene-7, 1,5-dioxinbicyclo(4,3,0)-nonene-5,6-di Tertiary amines such as butylamino-1,8-dioxabicyclo(5,4,0)-undecene-7 and the tertiary amines of the same are phenol, octanoic acid, tetrabasic boronic acid tetraphenyl ester The compound which is used as the amine salt is preferred in terms of thermosetting property, heat resistance, adhesion to metal, and storage stability after blending. In this case, the blending amount is preferably 0.01 parts by mass or more and 1.0 part by mass or less based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2), and if it is within the range, it is further increased. The catalytic effect of the reaction between the thermoplastic resin (A1) and the thermoplastic resin (A2) and the epoxy resin, and strong adhesive properties can be obtained.

<Other additives>

In the resin composition for an adhesive of the present invention, a flame retardant such as a bromine-based, phosphorus-based, nitrogen-based or metal hydroxide compound, a flame retardant auxiliary, a heat stabilizer, an antioxidant, and a decane coupling agent may be appropriately blended as needed. Additives such as slip agents, leveling agents, pigments, dyes, etc. Further, the blending of the antioxidant is preferable as a means for improving the adhesion at a high temperature, a high temperature, a high humidity, and the adhesion strength.

Examples of the antioxidant include hindered phenol-based and phosphorus-based antioxidants. Specifically, the hindered phenol type may, for example, be a 1,3,5-glycol (3,5-di-tri-butyl-4-hydroxybenzyl)isomeric cyanate or 1,1,3. -Tris(4-hydroxy-2-methyl-5-tributylphenyl)butane, 1,1-bis(3-tert-butyl-6-methyl-4-hydroxyphenyl)butane ,3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropionic acid, neopentyl quinone [3-(3,5-di-tertiary butyl-4-hydroxybenzene) Propionate, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-phenylpropionic acid, 3,9-bis[1,1-dimethyl-2-[ (3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3, 5-trimethyl-2,4,6-paran (3',5'-di-tertiary butyl-4'-hydroxybenzyl)benzene, octadecyl-3-(3,5-di- Tert-butyl-4-hydroxyphenyl)propionate, 2,5-di-tert-butylhydroquinone, 4,4'-butylene bis(3-methyl-6-tertiary butylphenol) 1,1,3-glycol(2-methyl-4-hydroxy-5-tributylphenyl)butane, 1,3,5-para-methyl-2,4,6-para (3 , 5-di-tertiary butyl-4-hydroxybenzyl)benzene, ginseng (3,5-di-tri-butyl-4-hydroxyphenyl)isocyanate, etc., or derivatives thereof For the phosphorus system, 3,9-double-(for 壬Phenoxy)2,4,8,10-tetraoxa-3,9-diphosphospiro[5.5]undecane, 3,9-bis(octadecyloxy)-2,4,8,10- Tetraoxy-3,9-diphosphospiro[5.5]undecane, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonic acid Ester, tris(monodecylphenyl) phosphite, triphenyloxyphosphine, isodecyl phosphite, isodecyl phenyl phosphite, diphenyl-2-ethylhexyl phosphite, dimercapto Phenyl bis(nonylphenyl) ester phosphorous acid, 1,1,3-glycol (2-methyl-4-di-tridecyl phosphite-5-tri-butylphenyl) butane, ginseng (2,4-di-tertiary butylphenyl) phosphite, neopentyl alcohol bis(2,4-di-tertiary butyl phenyl phosphite), 2,2-methylene bis ( 4,6-di-tertiary butylphenyl)-2-ethylhexyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)neopentanol diphosphite The esters, or derivatives thereof, may be used singly or in combination. The amount of the antioxidant added is preferably 5% by mass or less, and when it is more than 5% by mass, the adhesion may be adversely affected.

The resin composition for an adhesive of the present invention may be blended with a decane coupling agent as needed. The properties of adhesion to metal and heat resistance are enhanced by blending a decane coupling agent. The decane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having an epoxy group, and those having an amine group. Examples of the decane coupling agent having an unsaturated group include vinyl ginseng (β-methoxyethoxy) decane, vinyl triethoxy decane, vinyl trimethoxy decane, and the like. Examples of the decane coupling agent having a glycidyl group include γ-glycidoxypropyltrimethoxydecane and β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane. --(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like. Examples of the decane coupling agent having an amine group include N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane and N-β-(aminoethyl)-γ-amine. Propylmethyldimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, and the like. Among these, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, β is further preferable from the viewpoint of heat resistance. a decane coupling agent having a glycidyl group such as (3,4-epoxycyclohexyl)ethyltriethoxydecane. The blending amount of the decane coupling agent is preferably 0.5 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). When the blending amount of the decane coupling agent is less than 0.5 parts by mass based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2), the resulting adhesive may have poor heat resistance, and if it is more than 20 parts by mass There is a possibility that the heat resistance is poor and the adhesion is poor.

<Adhesive sheet>

In the present invention, the adhesive sheet contains the thermoplastic resin (A1), the thermoplastic resin (A2), the inorganic filler (B), and the epoxy resin (D) contained in the resin composition for an adhesive of the present invention. And those who are reacted from these, at least a part of the responders are referred to as a B-stage state (semi-hardened state). In the pressurizing step in the production of FPC, the fluidity and viscosity of the adhesive sheet are related to the outflow at the time of pressurization, and the excessive flow is accompanied by a decrease in the reliability of the product or an increase in the defective rate. The adhesive sheet preferably has a B-stage state in which the above-described outflow is suppressed. The adhesive sheet of the present invention may be the thermoplastic resin (A1), the thermoplastic resin (A2), the inorganic filler (B), and the epoxy resin contained in the resin composition for an adhesive of the present invention. (D) a sheet composed of a layer of the reaction product derived from the above, or a thermoplastic resin (A1) contained in the base material or the release substrate and the resin composition containing the adhesive of the present invention, a sheet composed of the thermoplastic resin (A2), the inorganic filler (B), the epoxy resin (D), and a layer derived from the reaction product, or may be a substrate or a release substrate and The thermoplastic resin (A1), the thermoplastic resin (A2), the inorganic filler (B), the epoxy resin (D), and the reaction product derived therefrom are contained in the resin composition for an adhesive of the present invention. a sheet composed of a layer and a release substrate. The thermoplastic resin (A1), the thermoplastic resin (A2), the inorganic filler (B), the epoxy resin (D), and the reaction product derived therefrom, which are contained in the resin composition for an adhesive of the present invention The layer can be formed on one side of the substrate or on both sides. Further, the adhesive sheet may contain a trace amount or a small amount of a solvent (C). The adhesive sheet has a function of adhering the substrate to the adherend by the resin composition for the adhesive. The substrate of the adhesive sheet acts as a protective layer for the adhesive after adhesion. Further, if a release substrate is used as the substrate of the adhesive sheet, the release substrate can be released from the mold, and the adhesive layer can be transferred to the other adherend.

The adhesive sheet of the present invention can be obtained by applying the resin composition for an adhesive of the present invention to various substrates in accordance with a usual method, and removing at least a part of the solvent and drying. When at least a part of the solvent is removed and dried, when the release substrate is attached to the adhesive layer, the substrate can be wound without being transferred to the substrate and is excellent in handleability, and the adhesive layer is protected. Therefore, it is excellent in preservability and easy to use. Further, after application to the release substrate and drying, if another release substrate is attached as needed, the adhesive layer may be transferred to another substrate.

Here, the base material to which the resin composition for an adhesive of the present invention is applied is not particularly limited, and examples thereof include a film-form resin, a metal plate, a metal foil, and paper. The film-like resin may, for example, be a polyester resin, a polyamide resin, a polyimide resin, a polyamide amide resin, or an olefin resin. Examples of the material of the metal plate and the metal foil include various metals such as SUS, copper ^, aluminum, iron, and zinc, and alloys and plating products thereof. Examples of the paper include good paper, kraft paper, and paper roll. Cellophane, etc. Further, as the composite material, a glass epoxy resin or the like can be exemplified. The base material to which the resin composition for an adhesive of the present invention is applied is preferably a polyester resin, a polyamide resin, or a polyimine, from the viewpoint of adhesion to a resin composition for an adhesive and durability. Resin, polyamidoximine resin, SUS steel plate, copper foil, aluminum foil, glass epoxy resin.

In addition, the release base material to which the resin composition for an adhesive of the present invention is applied is not particularly limited, and for example, clay is formed on both sides of paper such as a good quality paper, a kraft paper, a paper roll, or a cellophane. a coating layer of a filler such as ethylene or polypropylene, and a polyfluorene-based, fluorine-based or alkyd-based release agent applied to the respective coating layers, and the release agent is applied to polyethylene or polypropylene. Various kinds of olefin films such as ethylene-α-olefin copolymer and propylene-α-olefin copolymer are coated on the polyethylene phthalate film, but due to the release force from the applied adhesive layer, the polyoxygen is charged. For the reason that the characteristics are adversely affected, it is preferred to carry out the polypropylene filling treatment on both sides of the good paper, and to use the alkyd-based release agent thereon, and to use the alkyd-based release agent on the polyethylene terephthalate.

Further, in the present invention, the method of applying the resin composition for an adhesive to a substrate is not particularly limited, and examples thereof include a comma coater and a reverse roll coater. Coater) and so on. Alternatively, an adhesive layer may be provided directly or by a transfer method on the rolled copper foil or the polyimide film of the printed wiring board constituent material as needed. The thickness of the adhesive layer after drying may be appropriately changed as needed, but is preferably in the range of 5 μm or more and 200 μm or less. When the thickness of the adhesive layer is less than 5 μm, the adhesive strength is insufficient. When the thickness of the pressure-sensitive adhesive layer is more than 200 μm, there is a problem that drying is insufficient and residual solvent is increased, and bubbles are generated during pressurization of the printed wiring board. The drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 4% or less. When the residual solvent ratio after drying becomes larger than 4%, there is a problem that foaming of residual solvent occurs during pressurization of the printed wiring board, and bubbles are generated.

<Printed wiring board>

The printed wiring board according to the present invention includes a laminate formed of a metal foil forming a conductor circuit and a resin layer as a constituent element. The printed wiring board is produced by, for example, a conventional method known as a subtractive method using a metal-clad laminate. The conductor circuit formed of the metal foil is partially or completely covered with a cover film or a screen printing ink as needed, and is generally called a flexible circuit board (FPC), a flat cable, and a tape automatic. A board for bonding (TAB), etc.

The printed wiring board of the present invention can be formed as any laminated layer which can be used as a printed wiring board. For example, a printed wiring board composed of four layers of a base film layer, a metal foil layer, an adhesive layer, and an overlying film layer can be used. Further, for example, a printed wiring board composed of five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and an overcoat layer can be used. The printed wiring board may be reinforced with a reinforcing material as occasion demands, and in this case, the reinforcing material and the adhesive layer are disposed under the base film layer.

Further, it is also possible to form two or three or more layers of the above-mentioned printed wiring board as needed.

The resin composition for an adhesive of the present invention can be suitably used for each adhesive layer of a printed wiring board. In particular, when the resin composition for an adhesive of the present invention is used as an adhesive, it has high adhesion to a substrate constituting a printed wiring board, and has high heat resistance corresponding to lead-free solder, even at high temperature and high humidity. It can also maintain high adhesion. In particular, in the high-temperature field in which solder resistance is evaluated, the physical crosslinking of the resin and the inorganic filler is well balanced by chemical crosslinking with the resin and the resin, and the solder resistance test in the humidified state can be eliminated. The squeezing caused by evaporation of water causes foaming or deformation to relieve stress, and is suitable for adhesion between the metal foil layer and the overlying film layer, and adhesion between the substrate film layer and the reinforcing layer. In particular, when a metal reinforcing material such as a SUS plate or an aluminum plate is used, when it is welded in a humidified state, since the moisture cannot be evaporated from the reinforcing material side, the adhesive layer between the base film layer and the reinforcing layer is washed. It is particularly strong, and it is suitable as a resin composition for adhesion in such a case.

In the printed wiring board of the present invention, any of the resin films which have been conventionally used as a substrate of a printed wiring board can be used as the base film. As the resin of the base film, a halogen-containing resin or a halogen-free resin can be used. From the viewpoint of environmental problems, a halogen-free resin is preferred, but a halogen-containing resin can also be used from the viewpoint of flame retardancy. The substrate film is preferably a polyimide film or a polyimide film.

As the metal foil used in the present invention, any conventionally known conductive material which can be used for a circuit board can be used. As the material, for example, a copper foil, an aluminum foil, a steel foil, a nickel foil, or the like can be used, and a metal foil which is treated with other metals such as a composite metal foil, zinc, or a chromium compound can be used. It is preferably a copper foil.

The thickness of the metal foil is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 10 μm or more. Further, it is preferably 50 μm or less, more preferably 30 μm or less, further preferably 20 μm or less. When the thickness of the metal foil is too thin, the circuit may have difficulty in obtaining sufficient electrical properties. On the other hand, when the thickness of the metal foil is too thick, the processing efficiency at the time of circuit fabrication may be lowered.

The metal foil is usually provided in the form of a roll. The form of the metal foil used in the production of the printed wiring board of the present invention is not particularly limited. When a metal foil in a roll form is used, the length is not particularly limited. Further, the width thereof is not particularly limited, but is preferably in the range of 250 mm or more and 5,000 mm or less.

As the above-mentioned film, an insulating film which is conventionally known as an insulating film for a printed wiring board can be used. It can be used, for example, from polyimine, polyester, polyphenylene sulfide, polyether oxime, polyetheretherketone, aramid, polycarbonate, polyarylate, polyimine A film made of various polymers such as polyamidoximine. More preferably, it is a polyimide film or a polyimide film, and further preferably a polyimide film.

The polyimide film has a polyimine resin as a main component in terms of its resin component. Among the resin components, it is preferably 90% by mass or more of polyimine, more preferably 95% by mass or more of polyimine, more preferably 98% by mass or more of polyimine, and particularly preferably 99% by mass. More than % is polyimine. As the polyimine resin, any conventionally known resin can be used.

As the material resin of the above film, a halogen-containing resin or a halogen-free resin may be used. From the viewpoint of environmental problems, a halogen-free resin is preferred, but a halogen-containing resin can also be used from the viewpoint of flame retardancy.

In the reinforcing material, a metal plate such as a SUS plate or an aluminum plate, a polyimide film or a glass fiber (glass epoxy resin plate) which has been cured with an epoxy resin is used. In particular, the resin composition for an adhesive of the present invention exerts a great performance on the adhesion of a SUS plate, an aluminum plate and a polyimide film, and exhibits excellent properties in terms of adhesion and heat resistance.

The printed wiring board of the present invention can be produced by using any of the conventionally known processes, in addition to the materials of the respective layers described above.

In a preferred embodiment, a semi-finished product in which an adhesive layer is laminated on an overlying film layer (hereinafter referred to as "overcoat film side semi-product") is produced. On the other hand, a semi-finished product in which a metal foil is laminated on a base film layer to form a desired circuit pattern (hereinafter referred to as "substrate film side two-layer semi-product") or a layer of an adhesive layer laminated on a base film layer is produced. A semi-finished product (hereinafter referred to as "substrate film side three-layer semi-product") in which a metal foil layer is laminated to form a desired metal pattern (hereinafter, the base film side two-layer semi-product and the base film side are three layers) Semi-products are collectively referred to as "substrate film side semi-products"). By combining the obtained overcoat film side semi-finished product and the base film side semi-product, the printed wiring board of four or five layers can be obtained. Further, a semi-product (hereinafter referred to as "reinforcing material-side semi-product") in which an adhesive layer is laminated on the reinforcing material layer is further produced, and if necessary, it can be bonded to the base film layer of the printed wiring board to be reinforced. Further, an adhesive for the reinforcing material and the base film may be applied to the release substrate, transferred to the back surface of the base film of the printed wiring board, and bonded to the reinforcing member.

The substrate film side semi-product is by, for example, containing

1) a step of applying a solution of a resin to be a base film to the metal foil, and initially drying the coating film,

2) The laminate of the metal foil obtained in 1) and the initial dry coating film is subjected to a heat treatment and a drying step (hereinafter referred to as "heat treatment ‧ desolvation step").

The formation of the circuit in the metal foil layer can be carried out by a conventionally known method. Addition methods can be used, and subtraction methods can also be used. Preferably, the subtraction method.

The obtained base film side semi-finished product may be used as it is for bonding to the overcoat film side semi-finished product, or may be used for attaching and detaching the release film to the overlying film side semi-product. Hehe.

The overcoat film side product is produced, for example, by applying an adhesive to an overcoat film. The crosslinking reaction in the applied adhesive can be carried out as needed. In a preferred embodiment, the adhesive layer is semi-hardened.

The obtained overcoat film side product can be used as it is for bonding to the substrate-side semi-product, or it can be used for bonding to the substrate film-side semi-product after the release film is attached and stored.

The base film side semi-product and the overcoat film side semi-product are each stored in the form of, for example, a roll, and bonded to each other to produce a printed wiring board. In the method of bonding, any method can be used, and it can be bonded by using, for example, pressurization or a roll. Further, the two may be bonded together by heating or pressurizing or by using a heating roll device or the like while heating.

The reinforcing material side semi-product is suitably produced by applying an adhesive to a reinforcing material in the case of a soft and recyclable reinforcing material such as a polyimide film. Further, for example, in the case of a hard plate which is hard and cannot be wound up, such as a metal plate such as SUS or aluminum or a glass fiber which is cured with an epoxy resin, an adhesive previously applied to the release substrate is used. It is suitable to carry out transfer coating. Further, a crosslinking reaction in the applied adhesive can be carried out as needed. In a preferred embodiment, the adhesive layer is semi-hardened.

The obtained reinforcing material side semi-finished product can be used as it is for bonding to the back surface of the printed wiring board, or can be used for bonding to the base film side semi-product after the release film is attached and stored.

In the present invention, the base film side semi-product, the overcoat film side semi-product, and the reinforcing agent side semi-product are all cured by heat treatment after bonding to the adherend. The conditions of the heat treatment are not particularly limited, but are preferably 130 ° C or more and 180 ° C or less and 1 hour or more and 5 hours or less.

The base film side semi-product, the overcoat film side semi-product, and the reinforcing agent side semi-product are all laminated bodies for the printed wiring board of the present invention.

[Examples]

The embodiments are described below in order to explain the present invention in more detail, but the invention is not limited to the examples. In addition, in the examples, the parts are all parts by mass. Further, when it is referred to as an epoxy resin blending ratio without special attention, it is referred to as a value of the following formula (4).

{EV(D)×EW(D)}/{AV(A1)×AW(A1)+AV(A2)×AW(A2)} (4)

(Physical evaluation method)

(1) Composition of thermoplastic resin

The thermoplastic resin was dissolved in deuterated chloroform, and the molar ratio of each component was determined by ¹ H-NMR analysis. However, when the thermoplastic resin was not dissolved in deuterated chloroform, it was dissolved in deuterated dimethyl hydrazine to carry out ¹ H-NMR analysis.

(2) Number average molecular weight Mn

The sample was dissolved or diluted in tetrahydrofuran to have a resin concentration of about 0.5%, and the filter was filtered through a polytetrafluoroethylene membrane filter having a pore diameter of 0.5 μm, and the tetrahydrofuran was used as a mobile phase to provide a differential refractometer. The molecular weight was determined by gel permeation chromatography as a detector. The flow rate was set to 1 mL/min, and the column temperature system was set to 30 °C. KF-802, 804L, and 806L manufactured by Showa Denko are used for the pipe string. Monodisperse polystyrene is used in terms of molecular weight standards. However, when the sample was not dissolved in tetrahydrofuran, N,N-dimethylformamide was used to change the tetrahydrofuran.

(3) Glass transition temperature

Using a differential scanning calorimeter, 10 mg of the measurement sample was placed in an aluminum pan, the lid was pressed and sealed, and a differential scanning calorimeter (DSC) DSC-200 manufactured by Seiko Instruments Co., Ltd. was used, and the temperature was measured at a temperature increase rate of 20 ° C /min. The intersection point of the extension line of the baseline below the glass transition temperature and the tangent of the maximum inclination in the transition portion, that is, the extrapolation glass transition initiation temperature.

(4) Acid price

0.2 g of the sample was dissolved in 20 ml of chloroform, and phenolphthalein was used as an indicator, and titrated with a 0, 1 N potassium hydroxide ethanol solution to calculate an equivalent of 10 ⁶ g of the resin (eq/10 ⁶ g).

(5) Epoxy value

According to JIS K 7236, used (mass of resin containing 1 equivalent of epoxy group) perchloric acid titration of the epoxy equivalent of the equivalents per 10 ⁶ g of resin (eq / 10 ⁶ g) was calculated.

(6) Dynamic viscoelasticity measurement

The resin composition for an adhesive was applied to a polypropylene film (PYLEN, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm, and the thickness after drying was 30 μm to 40 μm, and dried at 130 ° C for 3 minutes. Adhesive sheet. Further, heat treatment at 140 ° C for 4 hours gave a hardened coating film. The hardened coating film was peeled off from the polypropylene film to prepare a short-shaped sample having a width of 4 mm and a length of 15 mm. Using the dynamic viscoelasticity measuring device DVA-220 manufactured by IT Measurement and Control Co., Ltd., the temperature dispersion of the dynamic viscoelasticity of the short-stacked sample was measured at a temperature increase rate of 10 Hz and 4 ° C/min to determine the storage elastic modulus and loss elasticity. Modulus, loss tangent (tan δ). In addition, when it is described as "-" in the table, it means that it is not measured.

(characteristic evaluation method)

(1) Solder resistance and peel strength

(1-1) Method for preparing sample 1 for evaluation

The adhesive composition described later was applied to a polyimide film (APICAL, manufactured by Kaneka Co., Ltd.) having a thickness of 25 μm, and the thickness after drying was 30 μm, and dried at 130 ° C for 3 minutes. When the adhesive sheet thus obtained is bonded to the 18 μm rolled copper foil, the shiny side of the rolled copper foil is brought into contact with the adhesive and pressurized at 160 ° C under a pressure of 35 kgf/cm ² . Seconds and stick. Subsequently, it was heat-treated at 140 ° C for 4 hours to be cured, and Sample 1 (for initial evaluation) for solder resistance and peel strength evaluation was obtained.

Further, the adhesive sheet was allowed to stand at 40 ° C and 80% humidification for 14 days, and then pressed and rolled with the rolled copper foil under the above conditions to be cured by heat treatment, thereby obtaining Sample 1 for evaluation by time.

(1-2) Method for preparing sample 2 for evaluation

The resin composition for an adhesive to be described later was applied to a polypropylene film (PYLEN, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm, and the thickness after drying was 30 μm, and dried at 130° C. for 3 minutes to obtain an adhesive sheet. The evaluation substrate is a general circuit fabrication step by using a single-sided copper-clad laminate (25 μm polyimide film, 18 μm rolled copper foil) (opening, plating, dry film photoresist (hereinafter sometimes omitted) The substrate for evaluation was obtained by DFR) lamination, exposure, development, etching, and DFR peeling. The surface of the polyimide film of the substrate for evaluation thus obtained was applied to the surface of the adhesive resin composition coated with the adhesive sheet, and the polypropylene film was peeled off, and the 500 μm SUS304 plate was placed at 160. °C was pressed under a pressure of 30 kgf/cm ² for 1 minute and adhered to a reinforcing plate. Subsequently, it was heat-treated at 140 ° C for 4 hours to be cured, and Sample 2 (sample for initial evaluation) for solder resistance and peel strength evaluation was obtained.

In addition, after the adhesive sheet was left to stand at 40° C. and 80% humidification for 14 days, the evaluation substrate was changed to a rolled copper foil, and the same conditions were applied to carry out pressurization, heat treatment, and hardening, and the evaluation was performed with time. Sample 2.

The evaluation of each characteristic was carried out by the following method;

‧ Solder resistance (humidification)

A sample of 25 mm square was placed under humidification at 40 ° C and a relative humidity of 80% for 2 days, and then floated in a heated solder bath for 1 minute, and the upper limit temperature at which no bubbles were generated was measured at a pitch of 10 ° C. In this test, those having a high measured value showed good heat resistance, but it is also necessary to suppress the evaporation caused by evaporation of water vapor contained in each substrate and the adhesive layer, and it is required to have more stringent heat resistance than the dry state. In consideration of practicality as an FPC reinforcing plate, it is preferably 250 ° C or higher, more preferably 260 ° C or higher.

‧ peel strength

The peel strength was measured at a tensile speed of 50 mm/min at 25 ° C using RTM100 manufactured by Toyo Baldwin. Further, the sample 1 for evaluation was subjected to a 90° peel test, and the sample for evaluation 2 was subjected to a 180° peel test. This test shows the adhesion strength at room temperature. When considering the practicality as an FPC reinforcing plate, it is preferably 10 N/cm or more, and more preferably 15 N/cm or more.

(2) Adhesion strength retention in high temperature environments

Using the above-mentioned sample 2 for evaluation of solder resistance and peel strength (for initial evaluation and evaluation by time), a weight of 200 g was suspended in a high temperature environment, and the distance peeled off during 15 minutes was measured, and the peeling was measured at a pitch of 10 ° C. Below 4 mm is the upper limit temperature. In addition, the suspension method of the weight was carried out in a peeling form at 180° peeling, and the sample width was tested at 10 mm. In this test, the higher the measured value, the better the adhesion strength and the adhesion strength retention at high temperatures. The practical performance is preferably 100 ° C or higher, more preferably 150 ° C or higher, and still more preferably 200 ° C or higher.

(3) High temperature and high humidity environment test

Sample 2 (for initial evaluation) having the above-mentioned solder resistance and peel strength evaluation of 10 mm in width was placed in an 85° C. and 85% humidified environment, and the 180° peel strength after 500 hours passed and after 1000 hours passed was measured. This test is evaluated for durability in a high-temperature and high-humidity environment for the purpose of confirming the reliability in actual use, and is preferably 5 N/cm or more, and more preferably 10 N/cm or more.

(4) Drop hammer rush test

The resin composition for an adhesive to be described later was applied to a polypropylene film (PYLEN, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm, and the thickness after drying was 30 μm, and dried at 130° C. for 3 minutes to obtain an adhesive sheet. The adhesive sheet was fixed to a steel plate made of steel at 25 ° C to form a layer of a resin composition for the adhesive, and a steel metal jig having a hemispherical shape of 10 mm in diameter and a binder was formed. The surfaces of the objects are fixed so as not to be slidably attached to the planar portion of the layer of the resin composition for the adhesive. From a height of 50 mm to 500 mm, a metal weight of 76 g was dropped on the flat portion of the upper part of the steel metallizing tool at a pitch of 50 mm, and the upper limit of cracks, cracks, and cracks in the adhesive sheet was measured. height. The higher the measured value, the stronger the punching or deformation. In the processing steps of FPC manufacturing, it is not easy to cause cracks, cracks and cracks during cutting, punching and slit processing, and it is related to the improvement of the operability and the defective product rate. Reduced. It is preferably 100 mm or more, more preferably 200 mm or more.

(determination)

a: 200 mm or more,

b: 100 mm or more and less than 200 mm,

c: less than 100 mm.

(5) Low temperature bending test

The resin composition for an adhesive to be described later was applied to a polypropylene film (PYLEN, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm, and the thickness after drying was 30 μm, and dried at 130° C. for 3 minutes to obtain an adhesive sheet. After the adhesive sheet was allowed to stand in an environment of 5 ° C for 24 hours or more, the layer of the resin composition for an adhesive was bent inside for 10 times in an environment of 5 ° C to confirm the presence or absence of cracks and cracks. Those who do not have cracks or cracks are less likely to cause cracks and cracks during cutting, punching, or slit processing at the time of FPC manufacturing, and can reduce the rate of defective products.

(determination)

a: no cracks, cracks,

b: There are cracks and cracks.

<Polymerization Example of Polyester Resin A>

In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 208 parts of citric acid, 208 parts of isophthalic acid, 360 parts of 2-methyl-1,3-propanediol, and 1,4-butanediol were charged. 90 parts and 0.2 parts of tetrabutyl titanate were gradually heated to 240 ° C over 4 hours, and the esterified reaction was carried out while removing the distilled water to the outside of the system. After the end of the esterification reaction, the pressure was reduced to 10 mmHg for 30 minutes for initial polymerization and the temperature was raised to 250 ° C, and then post-polymerization was carried out for 30 minutes under 1 mmHg. Thereafter, nitrogen was returned to normal pressure, and 27 parts of pyromellitic anhydride was charged, and the polyester resin A was obtained by reacting at 180 ° C for 15 minutes. The composition and characteristic values of the polyester resin A thus obtained are shown in Table 1. Each measurement evaluation item is in accordance with the above method.

<Polymerization Example of Polyester Resin B>

In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 166 parts of citric acid, 162.7 parts of isononanoic acid, 3.8 parts of trimellitic anhydride, and 306 parts of 2-methyl-1,3-propanediol were charged. 70.8 parts of 1,6-hexanediol and 0.2 part of tetrabutyl titanate were gradually heated to 240 ° C over 4 hours, and the esterified reaction was carried out while removing the distilled water to the outside of the system. After the end of the esterification reaction, it took 30 minutes to reduce the pressure to 10 mmHg for initial polymerization and the temperature was raised to 250 ° C, and then post-polymerization was carried out for 1 hour under 1 mmHg. 100 parts of the obtained resin was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, and a distillation tube, and 140 parts of toluene was added thereto, and then 60 parts of toluene was distilled, and the reaction system was azeotroped by toluene/water. Dehydration. After cooling to 60 ° C, it was added by adding 80 parts of methyl ethyl ketone, 7 parts of 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, and 0.1 part of DMAP (dimethylaminopyridine) at 70 ° C. The reaction of the hour gave a solution of the polyester resin B. The composition and characteristic values of the polyester resin B thus obtained are shown in Table 1.

<Polymerization Example of Polyester Resin C>

In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 203 parts of citric acid, 203 parts of isophthalic acid, 9.6 parts of trimellitic anhydride, 158 parts of ethylene glycol, and 177 parts of neopentyl glycol were charged. 0.2 part of tetrabutyl titanate was gradually heated to 240 ° C over 4 hours, and the esterified reaction was carried out while removing the distilled water to the outside of the system. After the end of the esterification reaction, the pressure was reduced to 10 mmHg for 30 minutes for initial polymerization and the temperature was raised to 250 ° C, and then post-polymerization was carried out for 30 minutes under 1 mmHg. Thereafter, the mixture was returned to normal pressure with nitrogen, and 399 parts of ε-caprolactone was introduced, and the mixture was reacted at 200 ° C for 1 hour to obtain a polyester resin C. The composition and characteristic values of the polyester resin C thus obtained are shown in Table 1. Each measurement evaluation item is in accordance with the above method.

<Polymerization Example of Polyester Resin D>

In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 99.6 parts of citric acid, 99.3 parts of isononanoic acid, 161.6 parts of sebacic acid, 3.8 parts of trimellitic anhydride, and 2-methyl-1 were charged. 248.4 parts of 3-propanediol, 111.6 parts of 1,4-butanediol, and 0.2 parts of tetrabutyl titanate, and the temperature was gradually raised to 240 ° C over 4 hours, and the esterified reaction was carried out while removing the distilled water to the outside of the system. . After the end of the esterification reaction, it took 30 minutes to reduce the pressure to 10 mmHg for initial polymerization and the temperature was raised to 250 ° C, and further polymerization was carried out for 45 minutes under 1 mmHg. Thereafter, the mixture was returned to normal pressure with nitrogen, and 3.8 parts of phthalic anhydride was charged, and the mixture was reacted at 220 ° C for 30 minutes to obtain a polyester resin D. The composition and characteristic values of the polyester resin D thus obtained are shown in Table 1. Each measurement evaluation item is in accordance with the above method.

<Polymerization Example of Polyester Resin E>

In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 203 parts of citric acid, 203 parts of isononanoic acid, 9.6 parts of trimellitic anhydride, 110.7 parts of ethylene glycol, and 185.6 parts of neopentyl glycol were charged. 0.2 part of tetrabutyl titanate was gradually heated to 240 ° C over 4 hours, and the esterified reaction was carried out while removing the distilled water to the outside of the system. After the end of the esterification reaction, the temperature was lowered to 180 ° C and 400 parts of polytetramethylene glycol (PTMG-1000) having a number average molecular weight of 1000 was charged, and the pressure was reduced to 10 mmHg for 30 minutes for initial polymerization and the temperature was raised to After 60 minutes of further polymerization at 250 ° C and below 1 mm Hg. Thereafter, the mixture was returned to normal pressure with nitrogen, and 9.6 parts of benzenetricarboxylic anhydride was charged, and the mixture was reacted at 220 ° C for 30 minutes to obtain a polyester resin E. The composition and characteristic values of the polyester resin E thus obtained are shown in Table 1. Each measurement evaluation item is in accordance with the above method.

<Polymerization Example of Polyester Resin F, G, H, I, J>

In the same manner as in the polymerization example of the polyester resin D, the materials shown in Table 1 were appropriately selected and used in the temperature and time to obtain polyester resins F, G, H, I, and J. The composition and characteristic values of the resin are shown in Table 1.

<Polymerization Example of Polyurethane Resin A>

After charging and dissolving 650 parts of polyester resin and 650 parts of toluene in a reaction vessel equipped with a thermometer, a stirrer, a reflux cooling tube, and a distillation tube, 413 parts of toluene was distilled off, and the reaction was carried out by azeotropy of toluene/water. System dehydration. After cooling to 60 ° C, 29.3 parts of 2,2-dimethylolbutanoic acid (DMBA) and 237 parts of methyl ethyl ketone were added. After DMBA was dissolved, 30.6 parts of hexamethylene diisocyanate (HDI) was added, and 0.03 part of dioxodicycloundecene (DBU) was further added as a reaction catalyst, and after reacting at 80 ° C for 7 hours, 444 parts of methyl ethyl ketone was charged. To the 148 parts of toluene, the solid content concentration was adjusted to 40% by mass, and a polyurethane resin A solution was obtained. A film obtained by removing the solvent by drying the solution of the polyurethane resin A at 120 ° C for 1 hour was used in accordance with each measurement evaluation item described above. The properties of the polyurethane resin are shown in Table 2.

<Polymerization Example of Polyurethane Resin B, C, D, E, F, G, H, I>

In the same manner as in the polymerization example of the polyurethane resin a, the raw materials shown in Table 2 were used to obtain polyurethane resins B, C, D, E, F, G, H, and I. The characteristic values are shown in Table 2. Each measurement evaluation item is in accordance with the above method.

<Example 1>

70 parts of polyester resin A (only the mass of the solid component, the same applies hereinafter) was adjusted as the thermoplastic resin (A1), 75 parts of the polyurethane resin solution C (solid content: 30 parts) as the thermoplastic resin (A2), 25 R972 [hydrophobic smog-like yttrium oxide manufactured by Aerosil Co., Ltd.] is an inorganic filler (B), 198 parts of methyl ethyl ketone, 132 parts of toluene as a solvent (C), and a resin composition (β) having a solid concentration of 25%. Next, the blending of 16.0 parts of epoxy resin A [HP7200-H (dicyclopentadiene type epoxy resin) manufactured by Dainippon Ink and Chemicals Co., Ltd., epoxy value = 3540 equivalent/10 ⁶ g] was adjusted as a ring. An oxygen resin (D), 6.9 parts of methyl ethyl ketone as a solvent (C), and a resin composition (γ) having a solid concentration of 70%. The resin composition for a target adhesive is obtained by blending the obtained resin composition (β) and the resin composition (γ). The blending amount of the epoxy resin is calculated and determined so as to contain an epoxy group having 1.6 times the total amount of the acid value of the polyester resin A and the polyurethane resin C. The adhesion evaluation sample was prepared by the above method, and the results of the evaluation are shown in Table 3. Both the initial evaluation and the evaluation by time showed good results.

<Example 2>

In the same manner as in Example 1, the composition and the blending amount shown in Table 3 were used to prepare a resin composition, and the properties were evaluated. Further, in all of the examples, the resin composition (β) was prepared at a solid concentration of 25% and a resin composition (γ) at a solid concentration of 70%.

<Example 3>

Adjusting blending 162.5 parts of polyurethane resin solution A (solid component 65 parts) as thermoplastic resin (A1), 35 parts of polyester resin C as thermoplastic resin (A2), 25 parts of R972 as inorganic filler (B), 159 parts of methyl ethyl ketone and toluene were used as a solvent (C) and a resin composition (β) having a solid concentration of 25%. Next, a resin composition (γ) having 10.5 parts of epoxy resin A, 0.3 part of epoxy resin B as epoxy resin (D), 4.6 parts of methyl ethyl ketone as solvent (C), and a solid concentration of 70% was adjusted. The resin composition for a target adhesive is obtained by blending the obtained resin composition (β) and the resin composition (γ). The blending amount of the epoxy resin is calculated and determined so as to contain an epoxy group having 1.6 times the total amount of the acid value of the polyurethane resin A and the polyester resin C. The adhesion evaluation sample was prepared by the above method, and the results of the evaluation are shown in Table 3. Both the initial evaluation and the evaluation by time showed good results.

<Examples 4 to 14>

In the same manner as in Example 3, the components and the blending amounts shown in Tables 3 to 5 were used to prepare a resin composition for an adhesive, and the properties were evaluated. Further, in all the examples, the composition (β) was prepared at a solid concentration of 25% and a composition (γ) at a solid concentration of 70%.

The details of each component are described below.

. Aerosil R8200: Hydrophobic smog oxide slag made by Japan Aerosil Co., Ltd.

. REOLOSIL DM-10: Hydrophobic smog oxide slag made by TOKUYAMA

. REOLOSIL HM-20L: Hydrophobic smog oxide slag made by TOKUYAMA

‧HIGILITE H-42M: Showa Denko Electric Co., Ltd.

‧Epoxy Resin B: TETRAD-X (N,N,N',N'-tetraepoxypropyl-m-xylenediamine) manufactured by Mitsubishi Gas Chemical Co., Ltd., epoxy value = 10000 equivalents/10 ⁶ g .

‧ Epoxy resin C: YDCN703 (o-cresol novolac type epoxy resin) manufactured by Dongdu Chemical Co., Ltd., epoxy value = 4550 equivalent/10 ⁶ g.

The blending amount of the epoxy resin is calculated and determined so as to contain an epoxy group in a range of 0.8 times or more and 4.5 times or less the total amount of the acid value of the thermoplastic resin (A1) and the thermoplastic resin (A2). The results of the evaluation are shown in Tables 3 to 5. Both the initial evaluation and the evaluation by time showed good results.

<Example 15>

Adjusting blending 162.5 parts of polyurethane resin solution A (solid content: 65 parts) as thermoplastic resin (A1), 16.3 parts of R972 as inorganic filler (B), 93.6 parts of methyl ethyl ketone, and 52.7 parts of toluene as solvent (C), A resin composition (δ) having a solid concentration of 25%. Adjusting 35 parts of polyester resin C as a thermoplastic resin (A2), 8.7 parts of R972 as an inorganic filler (B), 65.6 parts of methyl ethyl ketone, 65.6 parts of toluene as a solvent (C), and a resin composition having a solid concentration of 25% ( ε). Next, 10.5 parts of epoxy resin A and 0.3 part of epoxy resin B were blended as a resin composition (C) of epoxy resin (D) and 4.6 parts of methyl ethyl ketone as a solvent (C) and a solid concentration of 70%. The resin composition for a target adhesive is obtained by blending the obtained resin composition (δ) with the resin composition (ε) and the resin composition (ζ). The blending amount of the epoxy resin is calculated and determined so as to contain an epoxy group having 1.6 times the total amount of the acid value of the polyurethane resin A and the polyester resin C. The adhesion evaluation sample was prepared by the above method, and the results of the evaluation are shown in Table 6. Both the initial evaluation and the evaluation by time showed good results.

<Examples 16 to 21>

In the same manner as in Example 15, the components and the blending amounts shown in Table 6 were used to prepare a resin composition for an adhesive, and the properties were evaluated. Further, in all of the examples, the composition (δ) and the composition (ε) were prepared at a solid concentration of 25%, and the composition (ζ) was prepared at a solid concentration of 70%.

<Comparative Examples 1 to 8>

In the same manner as in Examples 1 to 14, the resin composition for an adhesive was prepared in the amounts of the components shown in Tables 7 to 8, and the properties were evaluated.

In Comparative Example 1, the polyester resin F was not in the range of the present invention because the acid value was low and did not correspond to the thermoplastic resin (A1). Resistance to humidification, high-temperature environmental adhesion strength, and low peel strength in high-temperature and high-humidity environments. The crosslinking of the cured product becomes insufficient, and it is considered that the heat resistance is lowered.

In Comparative Example 2, the polyurethane resin D was not in the range of the present invention because the acid value was high and did not correspond to the thermoplastic resin (A1). The sheet of the adhesive sheet has a low life, and has a low peel strength, a resistance to humidification weldability, and a high-temperature environmental adhesion strength.

In Comparative Example 3, the polyurethane resin E was not in the range of the present invention because the acid value was low and did not correspond to the thermoplastic resin (A1). Resistance to humidification, high-temperature environmental adhesion strength, and low peel strength in high-temperature and high-humidity environments. The crosslinking of the cured product becomes insufficient, and it is considered that the heat resistance is lowered.

In Comparative Example 4, the polyurethane resin F was not in the range of the present invention because the glass transition temperature was low and did not correspond to the thermoplastic resin (A1). The heat resistance is low, and the adhesion strength of the high temperature environment is also low.

In Comparative Example 5, the polyester resin H was not in the range of the present invention because the glass transition temperature was high and did not correspond to the thermoplastic resin (A2). The adhesive sheet has low flexibility and cannot be used as a criterion for determining the drop hammer test and the low temperature bend test.

In Comparative Example 6, the polyurethane resin G was not in the range of the present invention because the acid value was high and did not correspond to the thermoplastic resin (A2). The sheet of the adhesive sheet has a low life and is low in resistance to humidification weldability.

In Comparative Example 7, the polyurethane resin H was not in the range of the present invention because the molecular weight was low and did not correspond to the thermoplastic resin (A1). Since the adhesive is brittle and has low heat resistance, it is considered that the peel strength, the wet-resistant weldability, the high-temperature environmental adhesion strength retention force, the peel strength in the high-temperature and high-humidity environment test, the drop hammer test, and the low-temperature bending test are low. .

In Comparative Example 8, although the polyurethane resin A corresponds to the thermoplastic resin (A1), the polyurethane resin I corresponds to the thermoplastic resin (A2), but the polyurethane resin A and the polyamine A The acid ester resin I is soluble without forming a phase separation structure, and is outside the scope of the present invention. The adhesive sheet has low flexibility, and in particular, it cannot be used as a criterion for determining a low-temperature bending test which is an index of flexibility of a coating film at a low temperature.

<Comparative Example 9>

The polyester resin 1 and the polyester resin 2 were synthesized in the same manner as in Synthesis Example 1 and Synthesis Example 5 of Patent Document 4. Using the obtained polyester resin 1 and polyester resin 2, a dispersion solution (adhesive) was obtained in the same manner as in Example 1 of Patent Document 4.

<Synthesis of Polyester Resin 1>

In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 83 parts of citric acid, 81 parts of isononanoic acid, 2 parts of trimellitic anhydride, 77 parts of ethylene glycol, and 79 parts of neopentyl glycol were charged. It took 4 hours under pressure to gradually rise to 230 ° C, and the esterified reaction was carried out while removing the distilled water to the outside of the system. Next, 0.08 parts of tetrabutyl titanate was placed as a polymerization catalyst. After stirring at atmospheric pressure for 10 minutes, it took 1 hour to reduce pressure to 10 mmHg for initial polymerization and the temperature was raised to 250 ° C, and then at 1 mm Hg. The next 30 minutes of polymerization was carried out. Thereafter, the mixture was cooled to 200 ° C in a nitrogen atmosphere, and then 2 parts of trimellitic anhydride was charged and stirred for 30 minutes to obtain a polyester resin 1. The characteristic values of the polyester resin 1 thus obtained are shown below. Each measurement evaluation item is in accordance with the aforementioned method.

‧ number average molecular weight: 14000,

‧ Acid price: 100 equivalents / 10 ⁶ g,

‧ glass transfer temperature: 60 ° C,

‧Resin composition: citric acid/isodecanoic acid/trimellitic acid//ethylene glycol/neopentyl glycol///trimellitic acid=50/49/1//50/50///1 (Mo Ear ratio).

<Synthesis of Polyester Resin 2>

In a reaction tank equipped with a stirrer, a thermometer, and a chiller for effluent, 105 parts of citric acid, 17 parts of isononanoic acid, 55 parts of sebacic acid, 90 parts of ethylene glycol, and 68 parts of neopentyl glycol were charged. The temperature was gradually raised to 230 ° C in 4 hours, and the esterified reaction was carried out while removing the distilled water to the outside of the system. Next, 0.08 parts of tetrabutyl titanate was placed as a polymerization catalyst. After stirring at atmospheric pressure for 10 minutes, the pressure was reduced to 10 mmHg for 1 hour for initial polymerization and the temperature was raised by 250 ° C and then less than 1 mm Hg. The polymerization was carried out for 30 minutes to obtain a polyester resin 2. The characteristic values of the polyester resin 2 thus obtained are shown below. Each measurement evaluation item is in accordance with the aforementioned method.

‧ number average molecular weight: 30,000,

‧ Acid price: 40 equivalents / 10 ⁶ g,

‧ Glass transfer temperature: 10 ° C

‧ Resin composition: citric acid / isophthalic acid / azelaic acid / / ethylene glycol / neopentyl glycol = 63/10/27 / / 58 / 42 (Morbi).

<Production of Dispersion Solution (Adhesive)>

Each of the obtained polyester resin 1 and polyester resin 2 was dissolved in methyl ethyl ketone/toluene = 1/4 (mass ratio) to have a solid content concentration of 30%. The dissolved polyester resin is 100 parts by weight (polyester resin 1 / polyester resin 2 = 28 / 72 [mass ratio]), 50 parts of decabromodiphenyl ether, 36 parts of antimony trioxide, 14 parts of titanium dioxide, 4 parts of cerium oxide, and 100 parts of glass beads were placed in a 250 ml mayon bottle and dispersed in a shaker for 6 hours to obtain a dispersion solution.

<Evaluation of Adhesive Properties of Dispersion Solution (Adhesive)>

The obtained dispersion solution was evaluated in accordance with the above-described characteristic evaluation method.

Comparative Example 9 is outside the scope of the present invention because it does not contain an epoxy resin. Since the adhesiveness is low and the crosslinked structure is not provided, the heat resistance is lowered, and the wet soldering resistance and the high temperature environment adhesive strength retention force are lowered. Further, the blended polyester resin has a high glass transition temperature and a low temperature bendability.

[Industry use possibility]

According to the present invention, it is possible to provide an adhesive which is excellent in adhesion to various plastic films and metals, high in moisture resistance to high-humidity lead-free solder, and excellent in adhesion under high temperature and high humidity, and is adhesive. The adhesive sheet is a resin composition for an adhesive which has a good adhesive life and can maintain a good adhesive property even after being used under high temperature and high humidity, and an adhesive composition containing the same, an adhesive sheet containing the same, and a printed wiring containing the same as an adhesive layer. board. Further, in a preferred embodiment of the present invention, it is possible to provide a resin composition which is excellent in adhesion to various plastic films, adhesion to metals such as copper, aluminum, stainless steel, and adhesion to glass epoxy resins. , an adhesive containing the same, an adhesive sheet, and a printed wiring board containing the same as an adhesive layer. Moreover, in a preferred embodiment of the present invention, the adhesion to the metal such as aluminum or stainless steel is excellent, and the heat and humidity resistance is excellent, and the high adhesion is maintained after the adhesive is placed for a long period of time. The strength is more excellent in this respect.

Claims (16)

A resin composition for an adhesive comprising: a thermoplastic resin (A1), a thermoplastic resin (A2), an inorganic filler (B), and an epoxy resin (D) having a dicyclopentadiene skeleton; wherein the thermoplastic resin (A1) is a polyester resin or a polyurethane resin and has an acid value (unit: equivalent/10 ⁶ g) of 100 or more and 1000 or less, a glass transition temperature of 30 ° C or more and 80 ° C or less, and a number average molecular weight of 5.0×10 ³ or more and 1.0×10 ⁵ or less; the thermoplastic resin (A2) is formed of a polyester resin or a polyurethane resin and has an acid value (unit: equivalent/10 ⁶ g) of 1,000 or less, glass transition temperature At least 0 ° C or less, a number average molecular weight of 5.0 × 10 ³ or more and 1.0 × 10 ⁵ or less; and a cured coating film obtained by drying at 130 ° C for 3 minutes and then heat-treating at 140 ° C for 4 hours, at least the aforementioned thermoplastic resin (A1) and At least a part of the thermoplastic resin (A2) has a phase-separated structure; and the thermoplastic resin (A1), the thermoplastic resin (A2), and the inorganic filler (B) are contained in the resin composition for the adhesive. ) a total of 25 parts by mass, 45 parts by weight of methyl ethyl ketone, toluene 3 The degree of turbulence (TI value) at a liquid temperature of 25 ° C of the dispersion (α) in a total mass of 0 parts by mass is 100 or more and 6 or less. The resin composition for an adhesive according to the first aspect of the invention, wherein the thermoplastic resin (from the aforementioned thermoplastic resin) is observed by a temperature dispersion measurement of the dynamic viscoelasticity of the hardened coating film at a frequency of 10 Hz and a temperature increase rate of 4 ° C/min. A1) loss elastic modulus peak and from the aforementioned thermoplastic resin (A2) The peak of the elastic modulus is lost, and the temperature difference between the two peaks is 40 ° C or more. The resin composition for an adhesive according to the first aspect of the invention, wherein the thermoplastic resin (A1) is made of a polyester resin, and the thermoplastic resin (A2) is made of a polyurethane resin. The resin composition for an adhesive according to the first aspect of the invention, wherein the thermoplastic resin (A1) is made of a polyurethane resin, and the thermoplastic resin (A2) is made of a polyester resin. The resin composition for an adhesive according to the first aspect of the invention, wherein the composition contains 55 parts by mass or more and 80 parts by mass based on 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). The aforementioned thermoplastic resin (A1). The resin composition for an adhesive according to the first aspect of the invention, wherein the acid value (unit: equivalent/10 ⁶ g) of the thermoplastic resin (A1) is set to AV (A1) and the amount of blending (unit: parts by mass) And AW (A1), the acid value of the thermoplastic resin (A2) is AV (A2), the blending amount is AW (A2), and the epoxy value of the epoxy resin (D) (unit: When the equivalent /10 ⁶ g) is EV (D) and the blending amount is EW (D) (unit: parts by mass), the following formula (1) is satisfied, 0.7 ≦ {EV (D) × EW (D) }/{AV(A1)×AW(A1)+AV(A2)×AW(A2)}≦4.0 (1). A resin composition for a multi-component mixed type adhesive which is obtained by blending a resin composition (β) and a resin composition (γ) in a blending ratio of the following formula (1); wherein the resin composition (β) ) comprising: a thermoplastic resin (A1), a thermoplastic resin (A2), an inorganic filler (B), and an organic solvent (C); the resin composition (γ) contains an epoxy resin (D); the thermoplastic resin (A1) is a polyester resin or a polyurethane resin and has an acid value (unit: equivalent/10 ⁶ g) of 100 or more and 1000 or less, a glass transition temperature of 30 ° C or more and 80 ° C or less, and a number average molecular weight of 5.0×10 ³ or more and 1.0×10 ⁵ or less; the thermoplastic resin (A2) is made of a polyester resin or a polyurethane resin, and has a glass transition temperature of 0° C. or lower and a number average molecular weight of 5.0×10 ³ or more and 1.0 or less. ×10 ⁵ or less; and the acid value (unit: equivalent/10 ⁶ g) of the thermoplastic resin (A1) is AV (A1), and the blending amount (unit: parts by mass) is AW (A1), and the above The acid value of the thermoplastic resin (A2) is AV (A2), the blending amount is AW (A2), and the epoxy value (unit: equivalent/10 ⁶ g) of the epoxy resin (D) is EV ( D), blending When the amount is set to EW (D) (unit: parts by mass), the blending ratio satisfies the following formula (1): 0.7 ≦ {EV (D) × EW (D)} / {AV (A1) × AW (A1) ) +AV(A2)×AW(A2)}≦4.0 (1). A resin composition for a multi-component mixed type adhesive which blends a resin composition (δ), a resin composition (ε), and a resin composition (ζ) to satisfy a blending ratio of the following formula (1) The resin composition (δ) comprises: a thermoplastic resin (A1), an inorganic filler (B), and an organic solvent (C); the thermoplastic resin (A1) is a polyester resin or a polyurethane resin The acid value (unit: equivalent/10 ⁶ g) is 100 or more and 1000 or less, the glass transition temperature is 30° C. or more and 80° C. or less, and the number average molecular weight is 5.0×10 ³ or more and 1.0×10 ⁵ or less; the resin composition (ε) contains: a thermoplastic resin (A2), an inorganic filler (B), and an organic solvent (C); the thermoplastic resin (A2) is formed of a polyester resin or a polyurethane resin and has a glass transition temperature of 0. °C or less, the number average molecular weight is 5.0×10 ³ or more and 1.0×10 ⁵ or less; the resin composition (ζ) contains the epoxy resin (D); and the acid value (unit: equivalent/10) of the thermoplastic resin (A1) ⁶ g) to AV (A1), blending amount (unit: parts by mass) is set to AW (A1), the aforementioned thermoplastic resin (A2) the acid value is set to AV (A2), mixed Set amount AW (A2), the aforementioned epoxy resin (D) The epoxy value (unit: eq / 10 ⁶ g) to EV (D), the amount of blending to EW (D) (unit: parts by mass When the blending ratio satisfies the following formula (1): 0.7 ≦ {EV(D) × EW(D)} / {AV(A1) × AW(A1) + AV(A2) × AW(A2)} ≦ 4.0 (1). The resin composition for an adhesive according to the first aspect of the invention, wherein the epoxy resin (D) is 60% by mass or more and 99.9% by mass or less of the entire epoxy resin contained in the resin composition for an adhesive. The resin composition for an adhesive according to the ninth aspect of the invention, wherein the inorganic filler (B) is blended with respect to 100 parts by mass of the total of the thermoplastic resin (A1) and the thermoplastic resin (A2). It is 10 parts by mass or more and 50 parts by mass or less. In the resin composition for an adhesive according to the seventh or eighth aspect of the invention, wherein the resin composition for the adhesive is used as 100 parts by mass, the blending amount of the solvent C) is 60 parts by mass or more and 85 parts by mass or less. The resin composition for an adhesive according to claim 11, which comprises an epoxy resin containing a nitrogen atom. The resin composition for an adhesive according to claim 12, wherein the epoxy resin containing a nitrogen atom has a glycidyl propylamine structure. An adhesive composition containing the resin composition for an adhesive according to any one of claims 1 to 13. An adhesive sheet containing the aforementioned thermoplastic resin (A1), the aforementioned thermoplastic resin (A2), and an inorganic filler (including the thermoplastic resin (A2) contained in the resin composition for an adhesive according to any one of claims 1 to 13. B), epoxy resin (D) and reaction products derived therefrom. A printed wiring board comprising an adhesive layer using an adhesive as claimed in claim 14 or an adhesive sheet as in claim 15 of the patent application.