KR20160061916A - Polyurethane resin composition and adhesive composition, laminate, and printed wiring board using same - Google Patents

Abstract

(R1, R2는 각각 독립적으로 수소 원자, 또는 탄화수소기이며, R3, R4는 각각 독립적으로 수소 원자, 탄화수소기, 또는 히드록시기 치환 탄화수소기이고, l 및 m은 0∼4의 정수이다.)

(R5는 수소 원자, 또는 탄화수소기이며, R6, R7은 각각 독립적으로 수소 원자, 탄화수소기, 또는 히드록시기 치환 탄화수소기이다.)A polyurethane resin composition having high adhesion to various plastic films and metals, high moisture resistance and heat resistance capable of coping with brazing after humidification, excellent flame retardancy without using halogen or antimony, and adhesive compositions, laminate, .
A polyurethane resin composition comprising a polyurethane resin (A) and an epoxy resin (B) satisfying the following conditions (1) to (3):
(1) A polyester polyol containing a phosphorus compound residue represented by the general formula (1) or (2) as a constituent component.
(2) The acid value (unit: equivalent / 10 ⁶ g) is 50 or more and 1000 or less.
(3) The urethane group concentration (unit: equivalent / 10 ⁶ g) is 100 or more and 600 or less.

(Wherein R1 and R2 are each independently a hydrogen atom or a hydrocarbon group, R3 and R4 are each independently a hydrogen atom, a hydrocarbon group or a hydroxy group substituted hydrocarbon group, and l and m are an integer of 0 to 4.)

(R5 is a hydrogen atom or a hydrocarbon group, and R6 and R7 are each independently a hydrogen atom, a hydrocarbon group, or a hydroxyl group substituted hydrocarbon group)

Description

TECHNICAL FIELD [0001] The present invention relates to a polyurethane resin composition, an adhesive composition using the same, a laminate, and a printed wiring board. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a polyurethane resin composition having excellent adhesiveness to various plastic films and metals, heat resistance, heat and humidity resistance, and flame retardancy, and an adhesive composition using the same. And more particularly to a polyurethane resin composition and an adhesive composition suitable as an adhesive for a flexible printed wiring board.

BACKGROUND ART Adhesives are used in various fields. Depending on the purpose of use, adhesives, heat resistance, moisture resistance, flame retardancy, insulation reliability, sheet life, and other high performance are required. An adhesive for a circuit board including a flexible printed wiring board (hereinafter, sometimes referred to as FPC) used in electronic equipment is one of them. The adhesive mainly includes an epoxy / nitrile rubber adhesive, an epoxy / acrylbutadiene adhesive, an epoxy / Butyral adhesives, acrylic adhesives, polyester urethane adhesives, and the like.

Examples of the adhesive used for the FPC include an adhesive for a copper clad laminate, an adhesive for a cover, and an adhesive for a steel sheet. In addition, as electronic devices have become more lightweight, thinner, and smaller in size in recent years, and their densities have increased, the FPCs have become more highly integrated and multilayered, and the interlayer adhesives for bonding two or more FPCs and the interlayer adhesives And is also used as an insulating material.

These resin compositions for adhesives are essentially flammable, but since the adhesive for FPC is required to have high flame retardancy, conventionally, flame retardancy has been imparted by halides or antimony compounds. However, it is difficult to use halogen or antimony in the background of environmental problems. In recent years, phosphorus flame retardants have been used in combination. However, the phosphorus flame retardant can not satisfy the flame retardancy unless it is blended in a large amount, and deteriorates adhesiveness, heat resistance, workability, mechanical properties, insulation reliability, and the like. Further, the flame retardant has a problem of bleeding out.

To these problems, a flame retardation technique by copolymerization of a phosphorus compound has been proposed. As a concrete example thereof, for example, Patent Document 1 proposes a resin composition comprising a flame retardant composed of a linear polymeric compound or a flame retardant composed of the linear polymer blended with polystyrene, polycarbonate, polyethylene terephthalate and the like. However, the resin composition of Patent Document 1 is excellent in flame retardancy, but is thermoplastic, so that the solderability is poor and the adhesiveness is poor. In addition, even in the resin composition of Patent Document 2, there is a problem that the flame retardancy is excellent but the adhesive strength and solder resistance are poor. The resin composition of Patent Document 3 has proposed a resin composition excellent in adhesive strength, solder resistance and flame retardancy.

Japanese Patent Laid-Open No. 53-128195 Japanese Patent Application Laid-Open No. 63-150352 Japanese Patent Application Laid-Open No. 2001-002931

However, in the resin composition of Patent Document 3, there is a problem that the phosphorus compound that promotes the hydrolysis property of the resin is used in a large amount, and the solder resistance after moisture absorption is lowered. The object of the present invention is to improve each of the problems inherent in these conventional adhesives and to provide a high adhesive property to various plastic films and metals, a high humidity resistance and heat resistance capable of coping with soldering after humidification, A polyurethane resin composition having flame retardancy, an adhesive composition using the same, an adhesive layer, a laminate, and a printed wiring board.

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and have completed the present invention. That is, the present invention includes the following configuration.

A polyurethane resin composition containing a polyurethane resin (A) and an epoxy resin (B) satisfying the following (1) to (3).

(1) A polyester polyol containing a phosphorus compound residue represented by the general formula (1) or (2) as a constituent component.

(2) The acid value (unit: equivalent / 10 ⁶ g) is 50 or more and 1000 or less.

(3) The urethane group concentration (unit: equivalent / 10 ⁶ g) is 100 or more and 600 or less.

(Wherein R1 and R2 are each independently a hydrogen atom or a hydrocarbon group, R3 and R4 are each independently a hydrogen atom, a hydrocarbon group or a hydroxy group substituted hydrocarbon group, and l and m are an integer of 0 to 4.)

(R5 is a hydrogen atom or a hydrocarbon group, and R6 and R7 are each independently a hydrogen atom, a hydrocarbon group or a hydroxy group substituted hydrocarbon group)

The acid value of the polyurethane resin (A) AV (equivalents / 10 ⁶ g), the amount of AW (parts by weight), the epoxy is the BV of the epoxy resin (B) (eq / 10 ⁶ g), the amount BW (parts by weight ), It is preferable that 0.7? (BV x BW) / (AV x AW)? 3.0 is satisfied.

In addition, it is preferable to include an ion scavenger (C).

In addition, it is preferable to include a silane coupling agent (D) and / or silica (E).

The epoxy resin (B) is preferably an epoxy resin having a dicyclopentadiene skeleton.

An adhesive composition comprising the polyurethane resin composition according to any one of the above.

An adhesive layer comprising the adhesive composition; and a laminate of a film or a metal.

And the laminate.

The polyurethane resin composition of the present invention is excellent in adhesiveness to various plastic films and metals, flame retardancy, soldering heat resistance, and insulation reliability under high temperature and high humidity.

Hereinafter, the present invention will be described in detail.

<Polyurethane resin composition>

The polyurethane resin composition of the present invention is a thermosetting resin composition containing a polyurethane resin (A) and an epoxy resin (B).

The blending amount of the polyurethane resin (A) and the epoxy resin (B) is not particularly limited, but the acid value of the polyurethane resin (A) may be AV (unit: equivalent / 10 ⁶ g), the compounding amount may be AW (unit: (1), (2), and (3), when the epoxy value of the epoxy resin (B) is BV (unit: equivalent / 10 ⁶ g) and the compounding amount is BW

0.7? (BV x BW) / (AV x AW)? 3.0 (One)

Is satisfied. More preferably 0.8 or more and 2.5 or less, and still more preferably 0.9 or more and 2.0 or less. If the ratio is less than 0.7, the crosslinking between the polyurethane resin (A) and the epoxy resin (B) becomes insufficient and the heat resistance tends to decrease. When the ratio is larger than 3.0, unreacted epoxy resin remains in a large amount and heat resistance, The property tends to deteriorate.

If necessary, an optional component such as a solvent may be further contained, and it is particularly preferable to contain a solvent. The solvent is not particularly limited as long as it can dissolve the polyurethane resin (A) and the epoxy resin (B), and may be a single component or a mixed solvent composed of two or more kinds of plural components. Examples of such a solvent include amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, alcohol solvents such as methanol, ethanol and isopropanol, aromatic solvents such as toluene and xylene, acetone, methyl ethyl ketone, Ketone solvents such as hexanone, ester solvents such as ethyl acetate, and the like. From the viewpoint of workability, toluene, xylene, methyl ethyl ketone and ethyl acetate are preferred, and toluene, methyl ethyl ketone and ethyl acetate are more preferred from the viewpoint of easiness of drying. These solvents may be used singly or in combination of two or more kinds. When a solvent is contained, the solid content concentration of the polyurethane resin composition is preferably 10% by mass or more and 50% by mass or less. If the solid concentration is less than 10 mass%, the viscosity of the solution is lowered, and there is a high possibility of occurrence of thickness unevenness at the time of coating. When the solid concentration is more than 50 mass%, the viscosity of the solution becomes excessively high.

The polyurethane resin (A) and the epoxy resin (B) will be described in detail below.

&Lt; Polyurethane resin (A) >

The acid value (unit: equivalent / 10 ⁶ g) of the polyurethane resin (A) used in the present invention is 50 or more and 100 or less. If the acid value is less than 50 equivalents / 10 ⁶ g, the adhesion to the metal-based substrate after curing becomes insufficient, and the degree of crosslinking tends to be low to deteriorate the heat resistance. When the acid value exceeds 1000 equivalent / 10 ⁶ g, the elastic modulus of the coating film after curing increases, the solder resistance after humidification decreases, and the crosslinking reaction of the adhesive layer tends to proceed at room temperature, and a stable sheet life is not obtained have. It is also expected that the durability such as ester bond or urethane bond is adversely affected. Preferably, the lower limit of the acid value is 70 equivalent / 10 ⁶ g, more preferably the lower limit of the acid value is 90 equivalent / 10 ⁶ g, and still more preferably the lower limit of the acid value is 120 equivalent / 10 ⁶ g. A preferred upper limit is 400 equivalents / 10 ⁶ g, a more preferred upper limit is 370 equivalent / 10 ⁶ g, a more preferred upper limit is 3400 equivalent / 10 ⁶ g, and a particularly preferred upper limit is 310 equivalent / 10 ⁶ g.

The urethane group concentration (unit: equivalent / 10 ⁶ g) of the polyurethane resin (A) used in the present invention is 100 or more and 600 or less. If the urethane group concentration is less than 100 equivalents / 10 ⁶ g, the adhesiveness to the metal base material or the plastic substrate after curing tends to become insufficient. If the urethane group concentration exceeds 600 equivalent / 10 ⁶ g, the hygroscopicity increases and the solder resistance after humidification tends to decrease. Preferably, the lower limit of the urethane group concentration is 150 equivalent / 10 ⁶ g, more preferably the lower limit of the urethane group concentration is 200 equivalent / 10 ⁶ g, and more preferably the lower limit of the urethane group concentration is 250 equivalent / 10 ⁶ g . A preferred upper limit is 550 equivalents / 10 ⁶ g, a more preferred upper limit is 500 equivalents / 10 ⁶ g, and a more preferred upper limit is 450 equivalents / 10 ⁶ g.

The number average molecular weight of the polyurethane resin (A) used in the present invention is preferably from 5 × 10 ³ to 1 × 10 ⁵ . A number average molecular weight of 5 × 10 is less than ^3, and the case is in the adhesion between the post-application poor poor workability, the number average molecular weight more than 1 × 10 ^5, increases the solution viscosity at the time of applying too, achieved a uniform coating film . More preferably, the number average molecular weight is at least 8 × 10 ³ , and more preferably at least 1 × 10 ⁴ . The number average molecular weight is more preferably 7 x 10 ⁴ or less, and more preferably 5 x 10 ⁴ or less.

The glass transition temperature of the polyurethane resin (A) used in the present invention is preferably from -20 占 폚 to 100 占 폚. If the glass transition temperature is lower than -20 占 폚, the cohesive strength is lowered, and the adhesiveness and solder resistance at high temperatures may become insufficient. When the glass transition temperature is higher than 100 ° C, the modulus of elasticity at room temperature is increased, so that the adhesiveness to the substrate is lowered, the adhesiveness at room temperature is lowered and the flexibility of the adhesive layer is lowered. The workability tends to deteriorate due to cracking or peeling. Preferably, the lower limit of the glass transition temperature is -10 占 폚, and more preferably the lower limit of the glass transition temperature is 0 占 폚. The preferred upper limit is 80 占 폚, and the more preferred upper limit is 60 占 폚.

The polyurethane resin (A) used in the present invention is required to contain a phosphorus atom in a molecular chain by introducing a phosphorus atom-containing monomer by copolymerization or denaturation in order to impart flame retardancy without using halogen or antimony. The amount of the phosphorus atom contained is preferably 0.5% by mass or more and 6.5% by mass or less, more preferably 1.0% by mass or more and 6.0% by mass or less, and still more preferably 1.5% by mass or more in the weight of the polyurethane resin (A) 5.5 mass% or less, and most preferably 2.0 mass% or more and 5.0 mass% or less. When the phosphorus atom content is less than 0.5 mass%, the flame retardancy is insufficient. When the phosphorus atom content exceeds 6.5 mass%, the water resistance is inferior and the insulation reliability under a high temperature and high humidity environment tends to be poor.

As a method for introducing the phosphorus atom into the polyurethane resin (A), a general method is used, and in particular, a method in which a polyester polyol copolymerized with a phosphorus compound represented by the general formula 1 or 2 is used as one component of a urethane resin .

In the general formula (1), R 1 and R 2 are preferably a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, but is preferably an aliphatic hydrocarbon or an aromatic hydrocarbon having 1 to 10 carbon atoms which may have a substituent. The more preferable number of carbon atoms is 1 to 6. Specific examples include, but are not limited to, methyl, ethyl, propyl, and phenyl. R1 and R2 may be the same or different. R3 and R4 are preferably a hydrogen atom, a hydrocarbon group or a hydroxy group-substituted hydrocarbon group. The hydrocarbon group is not particularly limited, but is preferably an aliphatic hydrocarbon or an aromatic hydrocarbon having 1 to 10 carbon atoms which may have a substituent. The more preferred number of carbon atoms is 1 to 7. Specific examples include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and a benzyl group. The hydroxyl group-substituted hydrocarbon group is not particularly limited, but is preferably a hydroxyl group-substituted aliphatic hydrocarbon having 1 to 10 carbon atoms or a hydroxyl group-substituted aromatic hydrocarbon. The more preferable number of carbon atoms is 1 to 6. Specific examples thereof include, but are not limited to, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group and a 2-hydroxyethyloxyethyl group. R3 and R4 may be the same or different.

In the general formula (2), R5 is preferably a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, but is preferably an aliphatic hydrocarbon or an aromatic hydrocarbon having 1 to 10 carbon atoms which may have a substituent. The more preferable number of carbon atoms is 1 to 6. Specific examples include, but are not limited to, methyl, ethyl, propyl, and phenyl. R6 and R7 are preferably a hydrogen atom, a hydrocarbon group or a hydroxy group-substituted hydrocarbon group. The hydrocarbon group is not particularly limited, but is preferably an aliphatic hydrocarbon or an aromatic hydrocarbon having 1 to 10 carbon atoms which may have a substituent. The more preferred number of carbon atoms is 1 to 7. Specific examples include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and a benzyl group. The hydroxyl group-substituted hydrocarbon group is not particularly limited, but is preferably a hydroxyl group-substituted aliphatic hydrocarbon having 1 to 10 carbon atoms or a hydroxyl group-substituted aromatic hydrocarbon. The more preferable number of carbon atoms is 1 to 6. Specific examples include, but are not limited to, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-hydroxyethyloxyethyl and the like. R6 and R7 may be the same or different.

The polyester polyol containing a phosphorus compound residue used as a raw material for the polyurethane resin (A) used in the present invention is a polyester polyol having a phosphorus compound residue when the total amount of the acid components excluding the phosphorus compound represented by the formula 1 or 2 is 100 mol% , The aromatic carboxylic acid is preferably at least 60 mol%, more preferably at least 85 mol%, even more preferably at least 90 mol%, particularly preferably at least 95 mol%, and most preferably at least 99 mol% to be. The aromatic carboxylic acid may occupy 100 mol%. When the aromatic carboxylic acid is less than 60 mol%, the cohesive force of the coating film is weak, so that the bonding strength to various substrates is reduced, but the insulation reliability and the adhesive strength are lowered in a high temperature and high humidity environment.

Examples of the aromatic carboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, diphenic acid and 5-hydroxyisophthalic acid. For example. Further, aromatic dicarboxylic acids having a sulfonic acid group such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and 5- (4-sulfophenoxy) A carboxylic acid, a metal salt thereof, and an ammonium salt thereof. In addition, aromatic oxy compounds such as p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenyl acetic acid, 6-hydroxy-2-naphthoic acid and 4,4-bis (p- Carboxylic acid and the like. Of these, terephthalic acid, isophthalic acid, and mixtures thereof are particularly preferable in terms of increasing cohesion of the coating film.

Examples of other acid components include alicyclic dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and acid anhydrides thereof And aliphatic dicarboxylic acids such as acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimeric acid.

On the other hand, the glycol component used in the polyester polyol containing a phosphorus compound residue is not particularly limited, but an aliphatic glycol, an alicyclic glycol, an aromatic group-containing glycol, or an ether bond-containing glycol is preferably used. Examples of aliphatic glycols include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, , Neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl- Neopentyl glycol ester, dimethylolheptane, 2,2,4-trimethyl-1,3-pentanediol, and the like. Examples of alicyclic glycols include, but are not limited to, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethylol, spiroglycol, hydrogenated bisphenol A, hydrogenated bisphenol A Ethylene oxide adducts and propylene oxide adducts. Examples of ether bond-containing glycols include, but are not limited to, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ethylene oxide adduct, neopentyl glycol propylene oxide adduct Water and the like. Examples of the aromatic-containing glycols include, but are not limited to, ethylene oxide adducts of para-xylene glycol, m-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, 1,4-phenylene glycol, bisphenol A, Glycols obtained by adding 1 mole to several mole of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, such as ethylene oxide adducts and propylene oxide adducts, and the like. These glycol components may be used alone or in combination of two or more.

In the molecular structure, an oxycarboxylic acid compound having a hydroxyl group and a carboxyl group can also be used as a polyester raw material. But are not limited to, 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenethyl alcohol, p-hydroxyphenylpropionic acid, p- 4,4-bis (p-hydroxyphenyl) valeric acid, and the like.

The polyester polyol containing a phosphorus compound residue used as a raw material of the polyurethane resin (A) used in the present invention may contain 0.1 mol% or more and 5 mol% or less of trifunctional or higher polycarboxylic acid It is also possible to copolymerize the polymeric acids and / or polyols. In particular, when a cured coating film is obtained by reacting with a curing agent, introduction of a branching skeleton increases the terminal group concentration (reaction point) of the resin, and it becomes possible to control the crosslinking density. Examples of the trifunctional or higher-functionality polycarboxylic acid in this case include, but are not limited to, trimellitic acid, trimethic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate) 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA), 3,3', 4,4'-tetramethyluronic anhydride, Diphenyltetracarboxylic acid dianhydride (BPDA), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), 4,4' - (hexafluoroisopropylidene) diphthalic acid dianhydride (6FDA), and 2,2'-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA). On the other hand, examples of trifunctional or higher polyols include, but are not limited to, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. When a polycarboxylic acid and / or a polyol having a trifunctional or higher functionality is used, it is preferable that the content of the polycarboxylic acid and / or the polyol is from 0.1 mol% to 5 mol%, preferably from 0.1 mol% to 3 mol% If it exceeds 5 mol%, the physical properties such as elongation at break of the coating film may be lowered, and gelation may occur during polymerization.

As a method of introducing an acid value into a polyester polyol containing a phosphorus compound residue used as a raw material of the polyurethane resin (A) used in the present invention, a method of introducing a carboxylic acid into the resin by acid addition after polymerization . When a monocarboxylic acid, a dicarboxylic acid or a polyfunctional carboxylic acid compound is used in the acid addition, there is a possibility that the molecular weight is lowered by transesterification, and it is preferable to use a compound having at least one carboxylic acid anhydride . The acid anhydrides include, but are not limited to, succinic anhydride, maleic anhydride, phthalic anhydride, 2,5-norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA) (ODPA), 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA), 3,3', 4,4'-diphenyltetracarboxylic dianhydride (BPDA), (DSDA), 4,4'- (hexafluoroisopropylidene) diphthalic acid dianhydride (6FDA), 2,2'-bis [4,3'-diphenylsulfonetetracarboxylic acid dianhydride (Dicarboxyphenoxy) phenyl] propane dianhydride (BSAA) and the like can be used. When the total amount of the acid component constituting the polyester polyol containing the phosphorus compound residue used in the present invention is 100 mol%, it is preferably used in a range of less than 10 mol%. If an acid is added in an amount of 10 mol% or more, gelation may occur, and the polyester may be depolymerized to lower the molecular weight of the resin. The acid addition may be carried out directly after the polycondensation of the polyester in the bulk state or by adding the polyester in a solution state. The reaction in the bulk state is fast, but if added in a large amount, gelation may occur and reaction at a high temperature may occur, so care must be taken such as blocking oxygen gas to prevent oxidation. On the other hand, the addition in the solution state can stably introduce a large amount of carboxyl groups although the reaction is slow.

The polyester polyol containing a phosphorus compound residue used as a raw material for the polyurethane resin (A) used in the present invention is preferably a polyester polyol having a lactone such as? -Propiolactone,? -Butyrolactone,? -Valerolactone,? -Caprolactone, Monomers can be copolymerized. Caprolactone is preferable from the viewpoint of versatility of raw materials, and as a copolymerization method, a method of introducing a lactone monomer into a bulk state after polycondensation to perform ring-opening polymerization to a polyester resin is preferable.

The number average molecular weight of the polyester polyol containing a phosphorus compound residue used as a raw material of the polyurethane resin (A) used in the present invention is preferably 3 x 10 ³ or more and 3 x 10 ⁴ or less. If the number average molecular weight is less than 3 x 10 ³ , the number average molecular weight of the polyurethane resin (A) becomes small, and the adhesiveness immediately after the application is insufficient, resulting in poor workability. On the other hand, if the number average molecular weight exceeds 3 x 10 ⁴ , it is difficult to control the molecular weight during polymerization of the polyurethane, which is not practical. More preferably, the number-average molecular weight is 4 x 10 ³ or more, and more preferably 5 x 10 ³ or more. The number average molecular weight is more preferably 2.5 x 10 ⁴ or less, and more preferably 2 x 10 ⁴ or less.

Examples of the polyol component raw material of the polyurethane resin (A) used in the present invention include polyester polyol, polyether polyol, polycarbonate polyol and the like as a polyol component not containing phosphorus in addition to the polyester polyol containing the phosphorus compound residue, It may be used in combination with a polyester polyol containing the phosphorus compound residue.

In the polyurethane resin (A) used in the present invention, a polyisocyanate and a chain extender are preferably used in addition to the polyester polyol containing the phosphorus compound residue as a raw material thereof. As the method for introducing the acid value, there may be mentioned a method in which an acid value is previously given to a polyester polyol containing a phosphorus compound residue constituting the polyurethane resin, or a method in which a diol containing a carboxylic acid is used as a chain extending agent Method. Since the adjustment of the acid value or the molecular weight is easy, it is preferable to use the latter or in combination.

The polyisocyanate used in the production of the polyurethane resin (A) for use in the present invention is preferably a polyisocyanate compound having at least one of a diisocyanate, a dimer thereof (uretdione), a trimer thereof (isocyanurate, triol adduct, Species, or a mixture of two or more thereof. As specific examples of the diisocyanate component, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate (hereinafter also referred to as MDI) ), m-phenylene diisocyanate, hexamethylene diisocyanate (hereinafter, also referred to as HDI), tetramethylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate , 2,6-naphthalene diisocyanate, 4,4'-diisocyanate diphenyl ether, 1,5-xylylene diisocyanate, 1,3-diisocyanate methylcyclohexane, 1,4-diisocyanate methylcyclohexane, , 4'-diisocyanate cyclohexane, 4,4'-diisocyanatocyclohexylmethane, isophorone diisocyanate (hereinafter also referred to as IPDI), dimer acid diisocyanate, norbornene diisocyanate And the like. Diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are preferable because they are readily available and economical.

In producing the polyurethane resin (A) used in the present invention, it is preferable to use a chain extender. The chain extender is not particularly limited, but it is preferable to use an aliphatic glycol, an alicyclic glycol, an aromatic containing glycol, an ether bond-containing glycol, a carboxylic acid-containing glycol, or a trifunctional or higher polyol. Examples of aliphatic glycols include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, , Neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl- Neopentyl glycol ester, dimethylolheptane, 2,2,4-trimethyl-1,3-pentanediol, and the like. Examples of alicyclic glycols include, but are not limited to, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethylol, spiroglycol, hydrogenated bisphenol A, hydrogenated bisphenol A Ethylene oxide adducts and propylene oxide adducts. Examples of ether bond-containing glycols include, but are not limited to, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ethylene oxide adduct, neopentyl glycol propylene oxide adduct Water and the like. Examples of the aromatic-containing glycols include, but are not limited to, ethylene oxide adducts of para-xylene glycol, m-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, 1,4-phenylene glycol, bisphenol A, Glycols obtained by adding 1 mole to several mole of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, such as ethylene oxide adducts and propylene oxide adducts, and the like. Examples of the carboxylic acid-containing glycol include, but are not limited to, a compound having one carboxylic acid and two hydroxyl groups such as dimethylol propionic acid (hereinafter also referred to as DMPA) and dimethylolbutanoic acid (hereinafter also referred to as DMBA) . Examples of trifunctional or higher polyols include, but are not limited to, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. Among them, dimethylolpropionic acid and dimethylolbutanoic acid are preferable because acid value introduction and adjustment are easy. Also, as a method of introducing branching, use of trimethylolpropane is also preferable. These chain extenders may be used alone or in combination of two or more.

As a production method of the polyurethane resin (A) used in the present invention, a polyester polyol containing the phosphorus compound residue and the polyisocyanate and, if necessary, a chain extender may be collectively injected into a reaction vessel, . In any case, the ratio of the isocyanate group / hydroxyl group functional group to the total of the sum of the hydroxyl groups of the polyester polyol and the chain extender in the system and the isocyanate group of the polyisocyanate is preferably 1 or less. This reaction can also be carried out by reacting in the presence or in the absence of a solvent which is inert to the isocyanate group. Examples of the solvent include ester solvents such as ethyl acetate, butyl acetate, and butyric acid ethyl ether, ether solvents such as dioxane, tetrahydrofuran and diethyl ether, ketone solvents such as cyclohexanone, methyl ethyl ketone, Butyl ketone and the like), aromatic hydrocarbon solvents (benzene, toluene, xylene and the like), and mixed solvents thereof. Of these, ethyl acetate, methyl ethyl ketone and toluene are preferable from the viewpoint of industrial versatility and drying property. The reaction apparatus is not limited to a reaction tube equipped with an agitator, and a mixing and kneading apparatus such as a kneader and a twin screw extruder can also be used.

In order to promote the urethane reaction, a catalyst used in a usual urethane reaction such as a tin catalyst (such as trimethyltin laurate, dimethyltin dilaurate, dibutyltin laurate, trimethyltin hydroxide, dimethyltin dihydroxide, Zirconium-based catalysts, bismuth-based catalysts, amine-based catalysts (such as triethylamine, tributylamine, morpholine and the like) , Diazabicyclooctane, diazabicyclo undecene, etc.) and the like can be used, but an amine catalyst is preferable from the viewpoint of harmfulness.

The resin composition of the present invention may contain a thermoplastic resin other than the polyurethane resin (A) within a range that does not impair the properties of the present invention. Examples of the thermoplastic resin include, but are not limited to, polyester resins, styrene resins, polyamide resins, polyamideimide resins, polyester imide resins, polycarbonate resins, polyphenylene oxide resins, A resin, an olefin resin, and an acrylic resin. These thermoplastic resins may be used singly or in combination of two or more.

&Lt; Epoxy resin (B) >

In the polyurethane resin composition of the present invention, an epoxy resin (B) is included as an essential component in addition to the polyurethane resin (A) to form a crosslinking with the polyurethane resin (A). The thermosetting resin composition is formed by the crosslinking reaction and exhibits high heat resistance and high adhesion with the polyimide film or the copper foil.

The epoxy resin (B) used in the present invention is not particularly limited, and examples thereof include bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, bisphenol F diglycidyl Glycidyl ether types such as ether, dicyclopentadiene, novolac glycidyl ether, and phenol novolak; Terephthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, trimellitic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, Glycidyl ester type such as hexanediol glycidyl ester, hexahydrophthalic acid glycidyl ester and dimeric acid glycidyl ester; Glycidyl amines such as triglycidyl isocyanurate, tetraglycidyl aminodiphenyl methane, metaxylenediamine, and hydrogenated metaoxylenediamine; Or alicyclic or aliphatic epoxides such as 3,4-epoxycyclohexylmethyl carboxylate, epoxidized polybutadiene, and epoxidized soybean oil. These epoxy resins may be used singly or in combination of two or more kinds.

The epoxy resin (B) used in the present invention preferably further contains an epoxy resin having a dicyclopentadiene skeleton. The rigid dicyclopentadiene skeleton allows the cured coating film to have a very low moisture absorptivity and to lower the crosslinking density of the cured coating film and alleviate the stress at the time of peeling so that the solder resistance after humidification and the high temperature and high humidity environment It is possible to improve the insulation reliability under the above conditions. The blending amount of the epoxy resin having a dicyclopentadiene skeleton is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more, of the entire epoxy resin (B) contained in the polyurethane resin composition. Or more. Specific examples of the epoxy resin having a dicyclopentadiene skeleton include, but are not limited to, HP7200 series manufactured by DIC Corporation.

The polyurethane resin composition of the present invention may further contain an epoxy resin containing a nitrogen atom as the epoxy resin (B). By containing an epoxy resin containing a nitrogen atom, the adhesive layer can be made semi-cured (hereinafter also referred to as a B stage) by heating at a relatively low temperature for a short time and the fluidity of the adhesive layer can be suppressed, The layer is prevented from coming out and flowing down, and the workability tends to be improved. Further, the effect of suppressing foaming at the time of pressing can be expected, which is preferable. Examples of the epoxy resin containing a nitrogen atom include, but are not limited to, tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, tetraglycidylbisaminomethylcyclohexanone, N, N, N ' , N'-tetraglycidyl-m-xylenediamine, and the like. The blending amount of the epoxy resin containing nitrogen atoms is preferably 20% by mass or less based on the total amount of the epoxy resin (B) contained in the polyurethane resin composition. If the blending amount is more than 20 mass%, the rigidity becomes excessively high, and the adhesiveness tends to decrease. As a result, the crosslinking reaction proceeds excessively and the adhesion to the adherend tends to be lowered. Further, the crosslinking reaction tends to proceed during the preservation of the adhesive layer, and the sheet life tends to decrease. More preferably, the upper limit of the blending amount is 10% by mass, more preferably 6% by mass or less.

In the present invention, a curing catalyst can be used for the curing reaction of the polyurethane resin (A) and the epoxy resin (B). The curing catalyst is not particularly limited, and examples thereof include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, Methylamino-2-ethyl-4-methylimidazole, or an imidazole compound such as triethylamine, triethylenediamine, N'-methyl-N- (2- dimethylaminoethyl) Diazabicyclo (5,4,0) -undecene-7,1,5-diazabicyclo (4,3,0) -5-nonene, or 6-dibutylamino-1,8-diazabicyclo Tertiary amines such as cyclo (5,4,0) -7-undecene, and compounds in which these tertiary amines are made into amine salts with phenol, octylic acid, or quaternized tetraphenylborate salts; Cationic catalysts such as triallylsulfonium hexafluoroantimonate, or diallyl iodonium hexafluoroantimonate; Triphenylphosphine, and the like. These curing catalysts may be used alone or in combination of two or more. Of these, 1,8-diazabicyclo (5,4,0) -undecene-7,1,5-diazabicyclo (4,3,0) -nonene-5, or 6-dibutylamino- Tertiary amines such as 8-diazabicyclo (5,4,0) -undecene-7, and compounds in which these tertiary amines are made into amine salts with phenol, octylic acid, etc., or quaternized tetraphenylborate salts, From the viewpoint of curability and heat resistance, adhesion to metal, and storage stability after compounding. The blending amount at that time is preferably 0.01 part by mass to 1.0 part by mass with respect to 100 parts by mass of the polyurethane resin (A). Within this range, the catalytic effect on the reaction between the polyurethane resin (A) and the epoxy resin (B) is further increased, and strong adhesion performance can be obtained.

&Lt; Ion trapping agent (C) >

The incorporation of the ion trapping agent (C) into the polyurethane resin composition of the present invention is preferable because insulation reliability under high temperature and high humidity environment is improved. The ion trapping agent (C) may be an inorganic compound such as zirconium, antimony, titanium, tin, bismuth, aluminum, magnesium, rare earth, , A bipyridyl compound, a quinoline compound, a hydroxyanthraquinone compound, a polyphenol compound, a carboxyl group-containing aromatic compound, or a carboxyl group-containing aliphatic compound. An aluminum-based, magnesium-based or hydrotalcite-based compound is preferable because it does not contain a heavy metal having an excellent trapping ability of copper ions, chlorine ions, and phosphate ions and also adversely affecting the environment. These ion-capturing agents (C) may be used singly or in combination of two or more species.

Examples of rare earth metals include lanthanum oxide, gadolinium oxide, samarium oxide, thulium oxide, europium oxide, neodymium oxide, erbium oxide, terbium oxide, praseodymium oxide, dysprosium oxide, yttrium oxide, ytterbium oxide and holmium oxide.

As the mixture containing the aluminum system, the magnesium system, the hydrotalcite system compound and the hydrotalcite system compound, conventionally known ones can be used. Specific examples include IXE (registered trademark) -700, 700F, 770, 770D, IXEPLAS (registered trademark) A1, A2 manufactured by Toagosei Co., Ltd., Kyowa ward manufactured by Kyowa Hakko Kakogyo Co., 300, 500, 1000, 2000, DHT-4A (registered trademark), 6, and the like.

The amount of the ion scavenger (C) to be incorporated in the present invention is not particularly limited, but is preferably 0.5 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the polyurethane resin (A). If the addition amount is less than 0.5 part by mass, sufficient ion trapping effect can not be exhibited and insulation reliability under a high temperature and high humidity environment may deteriorate. When the addition amount exceeds 10 parts by mass, There is a possibility to generate. More preferably 1 part by mass or more and 8 parts by mass or less, and still more preferably 1.5 parts by mass or more and 6 parts by mass or less.

When the ion trapping agent (C) contained in the present invention is mixed, it is preferable to mix and disperse sufficiently by using a mill, a mixer, a paint shaker or the like as necessary. The mixing and dispersing methods are not particularly limited as far as they can sufficiently mix and disperse.

&Lt; Silane coupling agent (D) >

The polyurethane resin composition of the present invention may optionally contain a silane coupling agent (D). By adding the silane coupling agent (D), the adhesiveness to metal and the heat resistance property are improved. The silane coupling agent (D) is not particularly limited, and examples thereof include those having an unsaturated group, those having a glycidyl group, those having an amino group, and the like. The silane coupling agent having an unsaturated group is not particularly limited, and examples thereof include vinyltris (? -Methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane. Examples of the silane coupling agent having a glycidyl group include, but are not limited to,? -Glycidoxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or? - , 4-epoxycyclohexyl) ethyl triethoxysilane, and the like. The silane coupling agent having an amino group is not particularly limited, and examples thereof include N -? - (aminoethyl) -? - aminopropyltrimethoxysilane, N -? - (aminoethyl) -? - aminopropylmethyldimethoxysilane , Or N-phenyl-gamma -aminopropyltrimethoxysilane. These silane coupling agents (D) may be used singly or in combination of two or more. Among them, from the viewpoint of heat resistance,? -Glycidoxypropyltrimethoxysilane or? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane or? - (3,4-epoxycyclohexyl) ethyltriethoxysilane And a silane coupling agent having a glycidyl group.

The amount of the silane coupling agent (D) to be incorporated in the present invention is not particularly limited, but is preferably 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polyurethane resin (A). If the addition amount is less than 1 part by mass, the adhesion and the heat resistance may not be improved. On the other hand, if the addition amount is more than 10 parts by mass, the amount of methanol or ethanol to be generated increases due to hydrolysis, have. More preferably 1.5 parts by mass or more and 8 parts by mass or less, and still more preferably 2 parts by mass or more and 6 parts by mass or less.

&Lt; Silica (E) >

The incorporation of silica (E) into the polyurethane resin composition of the present invention is preferable from the viewpoints of stabilization of bonding strength, improvement of mechanical properties, improvement of moisture absorption resistance, and improvement of heat resistance. Silica (E) is not particularly limited, but from the viewpoint of imparting transparency, mechanical properties, heat resistance, and thixotropy property of the polyurethane resin composition, an enteric silica having a three-dimensional mesh structure is preferable. In addition, hydrophobic silica is preferable for imparting hydrophobicity to monomethyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, octylsilane, silicone oil or the like. These silicas (E) may be used singly or in combination of two or more. When the soft silica is used, the average diameter of the primary particles is preferably 30 nm or less, and more preferably 25 nm or less. When the average diameter of the primary particles exceeds 30 nm, there is a tendency that interactions between the particles and the resin are lowered and the heat resistance is lowered. The average diameter of the primary particles referred to herein is an average value of the circle-equivalent diameters of 100 particles randomly extracted from the primary particle image obtained using a scanning electron microscope.

The amount of the silica (E) to be added in the present invention is not particularly limited, but is preferably 5 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the polyurethane resin (A). If the addition amount is less than 5 parts by mass, the mechanical properties may be improved, the moisture absorption resistance may be improved, and the heat resistance may not be improved. On the other hand, if it exceeds 30 parts by mass, More preferably 8 parts by mass or more and 25 parts by mass or less, and still more preferably 10 parts by mass or more and 20 parts by mass or less.

<Other additives>

The polyurethane resin composition of the present invention may contain additives such as flame retardants, flame retardants, heat stabilizers, antioxidants, inorganic fillers, lubricants, leveling agents, pigments, and dyes Can be appropriately blended.

<Flame Retardant, Flame Retardant>

The polyurethane resin composition of the present invention can further enhance the flame retardant effect by using a flame retardant in combination. Various flame retardants can be used, but phosphorus flame retardants, nitrogen flame retardants, or metal hydroxide compound flame retardants are preferred from the viewpoint of both performance and environmental impact. Examples of these flame retardants include organic phosphorus flame retardants such as phosphoric acid esters, phosphoric acid amides and organic phosphine oxides; nitrogen flame retardants such as red phosphorus, ammonium polyphosphate, phosphazene, phosphinic acid derivatives, triazine and melamine cyanurate; Metal salt flame retardants such as aluminum hydroxide and magnesium hydroxide, and inorganic flame retardants in addition to inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide. In view of flame retardant performance, hydrolysis resistance and heat resistance, organic phosphinic acid metal salts, phosphazenes, Phosphinic acid derivatives are more preferable, and they may be used singly or in combination of two or more. Specific examples of these organic phosphinic acid metal salts include, but are not limited to, EXOLIT (registered trademark) OP series manufactured by Clariant, and specific examples of the phosphazene include cyclic phenoxyphosphazene SP-100), cyclic cyanophenoxyphosphazene (manufactured by Fushimi Fine Chemical Co., Ltd., trade name: FP-300), cyclic hydroxyphenoxyphosphazene (manufactured by Otsuka Chemical Co., (Trade name: SPH-100 manufactured by Kagaku Co., Ltd.), and the like. As the phosphinic acid derivative, a phenanthrene-type phosphinic acid derivative is preferable, and for example, 9,10-dihydro- 10-benzyl-10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA (registered trademark) ), Trade name: BCA).

<Antioxidant>

The combination of the antioxidant is effective in improving the adhesiveness at the high temperature, high temperature and high humidity, and the adhesive strength retention ability. Examples of the antioxidant include a hindered phenol-based antioxidant and a phosphorus-based antioxidant. Specific examples of the hindered phenol-based compound include 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3- (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, 3,5-bis (1,1-dimethylethyl Hydroxy-benzene propionic acid, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (1,1- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2 , 4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di- ) Benzene, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,5-di-t-butylhydroquinone, 4,4'-butylidenebis Butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris- 4,6-tris (3,5-di-t- (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, and derivatives thereof. Examples of the phosphorus- Bis- (p-nonylphenoxy) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (octadecyloxy) -2,4,8 Dipenta-spiro [5.5] undecane, diethyl [[3,5-bis (1,1-dimethylethyl) -4- hydroxyphenyl] methyl] phosphonate, tri (Monononylphenyl) phosphite, triphenylphosphine, isodecylphosphite, isodecylphenylphosphite, diphenyl-2-ethylhexylphosphite, dinonylphenylbis (nonylphenyl) esterphosphorous acid, 1,1 Tris (2,4-di-t-butylphenyl) phosphite, pentaerythritolbis (2,4- Di-t-butylphenylphosphite), 2,2-methylenebis (4,6-di-t-butylphenyl) Methylphenyl) pentaerythritol diphosphite, or derivatives thereof, which may be used singly or in combination. The addition amount is preferably 5% by weight or less, and if it is more than 5% by weight, adherence may be adversely affected.

<Inorganic filler>

An inorganic filler other than the silica described above can be compounded for the purpose of assisting the flame retardancy of the polyurethane resin composition of the present invention, stabilizing the bonding strength, improving the mechanical properties, improving the moisture absorption resistance, and improving the heat resistance. The inorganic filler is not particularly limited, but it is preferable that the resin composition is capable of imparting thixotropic property or thermally conductive property. Examples of such inorganic fillers include alumina, titania, tantalum oxide, zirconia, silicon nitride, barium titanate, barium carbonate, lead titanate, lead titanate zirconate, titanic zirconate lead titanate, gallium oxide, spinel, mullite, cordierite, talc, Aluminum hydroxide, magnesium hydroxide, aluminum titanate, yttrium-containing zirconia, barium silicate, boron nitride, calcium carbonate, calcium sulfate, zinc oxide, zinc borate, magnesium titanate, magnesium borate, barium sulfate, organic bentonite, These may be used alone or in combination of two or more.

The blending amount of the inorganic filler is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less based on 100 parts by mass of the polyurethane resin (A). If it exceeds 20 parts by mass, the adhesiveness and processability may be deteriorated.

&Lt; Adhesive composition >

The adhesive composition of the present invention is a composition containing the polyurethane resin composition. Further, if necessary, at least one selected from the group consisting of ion trapping agent (C), silane coupling agent (D) and silica (E) is blended. As other additives, additives such as a flame retardant, a flame retardant, a heat stabilizer, an antioxidant, an inorganic filler, a lubricant, a leveling agent, a pigment and a dye, It is properly blended.

<Adhesive Layer>

In the present invention, the adhesive layer means a layer of an adhesive composition after applying the adhesive composition of the present invention to the substrate (1) and drying it. The adhesive layer preferably has a semi-cured state (hereinafter also referred to as a B-stage state) by reacting at least a part of the polyurethane resin (A), the epoxy resin (B) and the reaction products derived therefrom contained in the adhesive composition Do. Since it is in the semi-cured state, the fluidity and viscosity of the adhesive layer are improved in the pressing step at the time of FPC production. This makes it possible to suppress the flow down during pressing. If there is much flow, the reliability of the product is lowered and the defect rate is increased. The method of coating the adhesive composition on the substrate 1 is not particularly limited, and examples thereof include a comma coater, a reverse roll coater and a die coater. Further, if necessary, it may be coated directly on a rolled copper foil or a polyimide film as a constituent material of a printed wiring board or by a transfer method. The thickness of the adhesive layer after drying can be appropriately set as required, but is preferably in the range of 5 to 200 mu m. If the thickness of the adhesive layer is less than 5 占 퐉, the adhesive strength may be insufficient. On the other hand, when the thickness exceeds 200 탆, the drying is insufficient and the amount of the residual solvent is increased, so that bubbles are generated at the time of pressing in the production of a printed wiring board. The drying conditions are not particularly limited, but the residual solvent ratio after drying is preferably 4% or less. If it is larger than 4%, there is a problem that bubbles are generated due to foaming of the residual solvent at the time of pressing the printed wiring board. The adhesive layer may be peeled off from the base material 1 and used alone or may be adhered to the base material 1. When it is adhered to the base material 1, it is referred to as a laminate.

<Laminate>

In the present invention, the laminate may be a two-layer laminate of the substrate 1 and the adhesive layer, or may be a three-layer laminate obtained by further bonding the base material 2. When the laminate is a three-layer laminate, it is possible to wind the laminate without causing the back of the laminate to be formed on the base material, thereby providing excellent workability and protecting the adhesive layer.

The substrate (1) and the substrate (2) which can be used in the present invention are not particularly limited, and examples thereof include a film type resin, a metal plate, a metal foil and paper. Examples of the film-form resin include a polyester resin, a polyamide resin, a polyimide resin, a polyamide-imide resin, and an olefin-based resin. Here, a film type resin having an insulating property is particularly preferable for a cover lay application. 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 plated products thereof. Examples of the papers are paper-like paper, kraft paper, roll paper, and gloss paper. As the composite material, glass epoxy and the like can be exemplified. In addition, it is also possible to provide a coating layer of a plug such as clay, polyethylene, polypropylene, or the like on both sides of paper such as paper, paper, kraft paper, roll paper or gloss paper, And olefin film alone such as polyethylene, polypropylene, polymethylpentene, ethylene- alpha -olefin copolymer and propylene- alpha -olefin copolymer, and a film of polyethylene terephthalate or the like, It can also be applied. A polyamide resin, a polyimide resin, a polyamide-imide resin, an SUS steel plate, a copper foil, an aluminum plate and a glass epoxy are preferable from the viewpoint of adhesion with the adhesive composition and durability. In the case of using the adhesive layer and the substrate 1 or 2 as a premix for peeling (releasing) the adhesive layer, the releasability with the adhesive layer, Polypropylene finishing with an alkyd type release agent thereon, an alkyd type release agent on polyethylene terephthalate, and polymethylpentene type are preferable.

The base material (1) and the base material (2) may be the same kind or different. Further, a plurality of substrates selected therefrom may be laminated. As a particularly preferable embodiment, the substrate (1) is a polyimide resin and the substrate (2) is copper. Thickness of the substrate 1 and the substrate 2 is not particularly limited, but is preferably 1 m to 200 m. When the substrate 1 or the substrate 2 is a metal foil, the preferable thickness is 1 占 퐉 or more, more preferably 3 占 퐉 or more, and further preferably 5 占 퐉 or more. It is preferably at most 50 μm, more preferably at most 30 μm, even more preferably at most 20 μm. When the thickness is too thin, it is difficult to obtain sufficient electrical performance of the circuit. On the other hand, when the thickness is excessively large, the processing efficiency at the time of circuit production may be lowered. The metal foil is usually provided in the form of a roll. The form of the metal foil used in producing the printed wiring board of the present invention is not particularly limited. In the case of using a roll-shaped metal foil, its length is not particularly limited. The width is not particularly limited, but is preferably about 250 mm to 5000 mm.

When a laminate of two layers of the base material 1 and the adhesive layer is bonded to the base material 2 to form a three-layer laminate, it is preferable that the base material 2 is bonded and then cured by heat treatment. The conditions of the heat treatment are not particularly limited, but it is preferably 1 to 5 hours at 120 to 180 캜.

<Printed wiring board>

The printed wiring board according to the present invention includes the laminate as a component. The printed wiring board is not particularly limited, but is manufactured by a conventionally known method such as a subtractive method or an additive method by using a laminate, and is called a flexible circuit board (FPC), a flat cable, a tape automated bonding (TAB), and the like. The FPC in the present invention includes those reinforced by a reinforcing material and those reinforced by a reinforcing material. When reinforcing with a reinforcing material, a reinforcing material and an adhesive layer are provided under the base material 1 or the base material 2. The reinforcing material is not particularly limited, but a metal plate such as an SUS plate or an aluminum plate, a polyimide film, a plate obtained by curing glass fiber with an epoxy resin (glass epoxy plate), or the like is used.

The laminate of the substrate 1 and the adhesive can be used for a coverlay film. For example, the laminate may be stored in the form of a roll and then bonded to produce a printed wiring board. As the bonding method, any method can be used. For example, bonding can be performed using a press or a roll. It is also possible to bond them while heating by a method such as a heating press or a heating roll apparatus.

The polyurethane resin composition of the present invention can be suitably used for each adhesive layer of the printed wiring board. Particularly, when the polyurethane resin composition of the present invention is used as an adhesive composition, it has a high adhesive property to a substrate constituting a printed wiring board, has a high heat resistance capable of coping with lead-free soldering, Flame retardancy, and can exhibit high insulation reliability under a high temperature and high humidity environment.

The printed wiring board of the present invention can be manufactured by any conventionally known process except that the materials for the respective layers described above are used.

Example

The following examples are provided to further illustrate the present invention, but the present invention is by no means limited to the examples. In addition, only the parts in the examples indicate the mass parts. In the case where the mixing ratio of the epoxy resin is described without specificity, the acid value AV (unit: equivalent / 10 ⁶ g) of the polyurethane resin (A), the mixing amount AW (unit: BV (unit: equivalent / 10 ⁶ g) and blending amount BW (unit: parts by mass)

(BV x BW) / (AV x AW)

Quot ;, respectively.

(Property evaluation method)

(1) Composition of polyester polyol

The polyester polyol was dissolved in deuterated chloroform, and the molar ratio of each component was determined by ¹ H-NMR analysis. In the case where the polyester polyol was not dissolved in deuterated chloroform, it was dissolved in heavy dimethylsulfoxide and subjected to ¹ H-NMR analysis.

(2) Number average molecular weight (Mn)

A sample (polyester polyol or polyurethane resin) was dissolved or diluted in tetrahydrofuran so that the resin concentration became about 0.5%, and filtered with a membrane filter made of poly (tetrafluoroethylene) having a pore diameter of 0.5 탆, . The molecular weight of the measurement sample was measured by gel permeation chromatography using tetrahydrofuran as a mobile phase and a differential refractometer as a detector. The flow rate was 1 mL / min and the column temperature was 30 [deg.] C. Columns KF-802, 804L and 806L manufactured by Showa Denko KK were used. Monodisperse polystyrene was used for the molecular weight standard. However, when the measurement sample was not dissolved in tetrahydrofuran, N, N-dimethylformamide was used instead of tetrahydrofuran.

(3) Glass transition temperature

10 mg of a measurement sample (polyester polyol or polyurethane resin) was placed in an aluminum pan using a differential scanning calorimeter and the lid was covered and sealed. Using a DSC-200 differential scanning calorimeter (DSC) manufactured by Seiko Instruments Inc. Was measured at a heating rate of 20 占 폚 / min. An extrapolated glass transition initiation temperature, which is an intersection of an extension line of the baseline below the glass transition temperature and a tangent line indicating the maximum inclination in the transition portion, was obtained.

(4) acid value

0.2 g of a sample (polyester polyol or polyurethane resin) was dissolved in 20 ml of chloroform and titrated with 0.1 N potassium hydroxide ethanol solution using phenolphthalein as an indicator. Resin 10 ⁶ g was calculated per equivalent (eq / 10 ⁶ g).

(5) Epoxy

(Eq / 10 ⁶ g) per ¹⁰⁶ g of resin was calculated from the epoxy equivalent (mass of resin containing one equivalent of epoxy group) obtained by perchloric acid titration according to JIS K 7236.

(6) Atomic content (wet decomposition molybdenum blue colorimetry method)

The sample was weighed into an Erlenmeyer flask according to the concentration of phosphorus in the sample (polyester polyol or polyurethane resin), and 3 mL of sulfuric acid, 0.5 mL of perchloric acid, and 3.5 mL of nitric acid were added. After the solution became transparent, it was further heated to generate white sulphate, and was allowed to cool to room temperature. The decomposed solution was transferred to a 50 mL volumetric flask, and 5 mL of a 2% ammonium molybdate solution and 2 mL of a 0.2% hydrazine sulfate solution were added, and the mixture was mixed with pure water and mixed well. The flask was immersed in a boiling water bath for 10 minutes, followed by heating and coloring, then water-cooled to room temperature, and degassed by ultrasonic waves. The solution was poured into 10 mm of the absorption cell and the absorbance was measured with a spectrophotometer (wavelength 830 nm) as a blank test liquid. The phosphorus content was calculated from the calibration curve prepared earlier, and the phosphorus concentration in the sample was calculated.

(Characteristic evaluation method)

(1) Sample preparation method for evaluation of steady state soldering heat resistance, resistance to soldering heat resistance after peeling, and peeling strength

A polyurethane resin composition to be described later was applied to a polyimide film having a thickness of 12.5 占 퐉 (Apical (registered trademark) NPI, manufactured by Kaneka Corporation) so that the thickness after drying was 20 占 퐉 and dried at 130 占 폚 for 3 minutes , Thereby obtaining a layered product A. The laminate A thus obtained was pressed with an 18 占 퐉 electrolytic copper foil and the electrolytic copper foil in contact with the adhesive at 160 占 폚 under a pressure of 35 kgf / cm2 for 30 seconds and adhered. Subsequently, the resultant was heat-treated at 170 DEG C for 1 hour to be cured to obtain a sample for evaluating steady-state soldering heat resistance, brazing heat resistance after soldering, and peel strength (initial evaluation sample).

Similarly, the laminate A was allowed to stand at 40 占 폚 under 80% humidification for 14 days, and then subjected to heat treatment and pressing with an electrolytic copper foil under the above conditions to obtain a sample for time-course evaluation.

(2) Sample preparation method for evaluation of insulation reliability

A polyurethane resin composition to be described later was applied to a polyimide film having a thickness of 12.5 占 퐉 (Apical (registered trademark) NPI, manufactured by Kaneka Corporation) so that the thickness after drying was 20 占 퐉 and dried at 130 占 폚 for 3 minutes , Thereby obtaining a layered product A. A comb-shaped circuit surface of a single-sided copper clad laminate on which a comb-shaped circuit of a pair of interdigital electrodes with a pitch of 200 占 퐉 (line width / space width = 100 占 퐉 / 100 占 퐉) was formed and an adhesive layer surface of the laminate A ) Were opposed to each other and pressed at 160 占 폚 under a pressure of 35 kgf / cm2 for 30 seconds to be bonded. And then heat-treated at 170 DEG C for 1 hour to be cured to obtain a sample for insulation reliability evaluation.

(3) Sample preparation method for flame retardancy evaluation

A polyurethane resin composition to be described later was applied to a polyimide film having a thickness of 12.5 占 퐉 (Apical (registered trademark) NPI, manufactured by Kaneka Corporation) so that the thickness after drying was 20 占 퐉 and dried at 130 占 폚 for 3 minutes . Then, the resultant was heat-treated at 170 DEG C for 1 hour to be cured to obtain a flame retardancy evaluation sample.

Evaluation of each characteristic was carried out in the following manner.

Steady-State Soldering Heat Resistance: A sample for initial evaluation and a sample for time-course evaluation, each of which had a square of 25 mm on one side, were allowed to stand for 2 days under a 25 ° C and 65% relative humidity environment and then heated in a soldering bath for 1 minute, The upper limit temperature at which no peeling or discoloration occurred was measured at a pitch of 10 占 폚.

(Judgment) ◎: Heat resistance temperature 280 ℃ or higher

   ○: heat resistance temperature 260 ℃ or more and less than 280 ℃

   ?: Heat resistance temperature 240 占 폚 or more and less than 260 占 폚

   ×: Heat resistance temperature less than 240 ° C

Soldering heat resistance after humidification: An initial evaluation sample and a time-lapse evaluation sample having a square of 25 mm on one side were allowed to stand for 3 days at 40 DEG C and 85% relative humidity at a relative humidity of 85%, thereby sufficiently moisturizing the sample. Thereafter, the substrate was allowed to stand for 1 minute in a heated soldering bath, and the upper limit temperature at which no expansion occurred was measured at a pitch of 10 占 폚. In this test, it is necessary to suppress impact caused by evaporation of water vapor contained in each of the substrate and the adhesive layer, and more rigorous soldering heat resistance is required than in a normal state.

(Judgment) ◎: Heat resistance temperature 270 ℃ or higher

   ○: heat resistance temperature 250 ° C or more and less than 270 ° C

   Δ: Heat resistance temperature 230 ° C. or more and less than 250 ° C.

   ×: Heat resistance temperature less than 230 ° C

Peel Strength: An initial evaluation sample having a width of 10 mm and a time-lapse evaluation sample were measured with an Autograph AG-Xplus manufactured by Shimadzu under the conditions of a temperature of 25 캜 and a tensile rate of 50 mm / And the peel strength was measured. This test shows the bonding strength at room temperature.

(Judgment) ?: 15 N / cm or more

   ?: 10 N / cm or more and less than 15 N / cm

   ?: 8 N / cm or more and less than 10 N / cm

   X: less than 8 N / cm

Insulation reliability: A DC voltage of 100 V was applied to each end of the interdigital electrodes of the sample under the environment of a temperature of 85 캜 and a relative humidity of 85% using an insulation deterioration characteristic evaluation system SIR13 manufactured by Kusumoto Chemical Co., .

(Judgment) &amp; cir &amp;&amp; cir &amp;: Insulation resistance value exceeding 1 x 10 &lt; ⁸ &gt;

∘: When the insulation resistance value is less than 1 × 10 ⁸ Ω for less than 1000 hours or more than 750 hours, or when the occurrence of dendrite is confirmed.

△: When the insulation resistance value is less than 1 × 10 ⁸ Ω in 500 hours or more and less than 750 hours, or when occurrence of dendrite is confirmed.

×: When the insulation resistance value is less than 1 × 10 ⁸ Ω in less than 500 hours, or when occurrence of dendrite is confirmed.

Flame retardancy: The flame retardancy was measured according to UL-94VTM-0 flammability standard.

(Judgment) ○: Must meet UL94VTM-0 specification.

X: Do not satisfy the UL94VTM-0 standard.

Polymerization Example of Polyester Polyol (A) Containing Phosphorus Compound Residue

171 parts of terephthalic acid, 228 parts of isophthalic acid, 9 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Chemical Co., Ltd.) HCA), 130 parts of itaconic acid, 6.6 parts of trimellitic anhydride, 158 parts of 2-methyl-1,3-propanediol, 483 parts of 1,6-hexanediol and 0.65 parts of tributylamine, The temperature was gradually raised to 240 캜 over 5 hours, and the esterification reaction and the Michael addition reaction were carried out while removing the water out of the system. After the completion of the esterification reaction, the temperature was lowered to 170 DEG C, 1.17 parts of tetrabutyl titanate was poured, the initial polymerization was carried out under reduced pressure to 10 mmHg over 30 minutes, the temperature was raised to 250 DEG C and 40 minutes later polymerization . Thereafter, the mixture was returned to normal pressure with nitrogen, 6.6 parts of trimellitic anhydride was added, and the mixture was reacted at 220 DEG C for 30 minutes to obtain a polyester polyol (A) containing phosphorus compound residue. The composition and characteristic values of the polyester polyol (A) thus obtained are shown in Table 1. Each measurement evaluation item was in accordance with the method described above. In addition, the phosphorus compound obtained by the Michael addition reaction of HCA and itaconic acid has the structure of Formula 3.

Polymerization Examples of Polyester Polyols B to F Containing Phosphorus Compound Residues

Polyester polyols B to F were obtained in the same manner as in the polymerization example of polyester polyol (A) containing phosphorus compound residue and with appropriate temperature and time. The composition and characteristic values of the resin are shown in Table 1. Each measurement evaluation item was in accordance with the method described above.

Polymerization Example of Polyurethane Resin (a)

100 parts of a polyester polyol (A) containing phosphorus compound residue and 100 parts of toluene were injected into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a distillation tube to dissolve, 67 parts of toluene was distilled off, To dehydrate the reaction system. After cooling to 60 占 폚, 1.8 parts of 2,2-dimethylolbutanoic acid (DMBA) and 33 parts of methyl ethyl ketone were added. After dissolving the DMBA, 4.2 parts of 4,4'-diphenylmethane diisocyanate (MDI) and 0.004 parts of diazabicyclo-decene (DBU) as a reaction catalyst were further added and reacted at 80 ° C for 8 hours. Then, methyl 92 parts of ethyl ketone was added to adjust the solid concentration to 40% by weight to obtain a solution of the polyurethane resin (a). The properties of the polyurethane resin (a) thus obtained are shown in Table 1. Each measurement evaluation item was in accordance with the method described above. The glass transition temperature was measured in accordance with each measurement evaluation item described above using a film from which the solvent had been removed by drying at 120 DEG C for 1 hour. The urethane group concentration (unit: equivalent / 10 ⁶ g) was calculated from the amount of injection.

Polymerization examples of polyurethane resins b to i

Polyurethane resins b to i were obtained by using the raw materials shown in Table 2 in the same manner as the polymerization examples of the polyurethane resin (a). The characteristic values are shown in Table 2. Each measurement evaluation item was in accordance with the method described above.

&Lt; Example 1 >

, 3.8 parts of an epoxy resin (B-1) as an epoxy resin (B), 0.3 parts of an epoxy resin (B-3) as the polyurethane resin (A) , And methyl ethyl ketone / toluene was added at a ratio of 1: 1 so that the solid content concentration became 37%. And sufficiently stirred to obtain a desired polyurethane resin composition. The blending amount of the epoxy resin was determined so as to include an epoxy group of 1.2 times the total amount of the acid value of the polyurethane resin (a). Table 3 shows the results of the evaluation. Both the initial evaluation and the time-lapse evaluation show good results.

&Lt; Examples 2, 8, 9 and 15, Comparative Examples 2, 4 and 8 >

In the same manner as in Example 1, resin compositions were prepared with the components and blending amounts shown in Tables 3 and 4, and their properties were evaluated. In all of the examples and comparative examples, the solid content concentration was appropriately selected within the range of 20% to 50% in order to adjust the resin composition to a suitable coatable viscosity.

&Lt; Example 3 >

100 parts of the polyurethane resin (a) as the polyurethane resin (A) and 0.6 parts of the ion trapping agent (C-1) as the ion trapping agent (C) were added to obtain methyl ethyl ketone / toluene of 1 : 1, and sufficiently stirred and dispersed. Next, 3.8 parts of an epoxy resin (B-1) and 0.4 part of an epoxy resin (B-3) were added as an epoxy resin (B) and methyl ethyl ketone / toluene was mixed at a mass ratio of 1: 1 In addition, it was prepared. And sufficiently stirred to obtain a desired polyurethane resin composition. The blending amount of the epoxy resin was determined so as to include an epoxy group of 1.2 times the total amount of the acid value of the polyurethane resin (a). Table 3 shows the results of the evaluation. Both the initial evaluation and the time-lapse evaluation show good results.

<Examples 4 to 6, 10 to 12, 16 and 17, and Comparative Examples 1, 3 and 5 to 7>

In the same manner as in Example 3, polyurethane resin compositions were prepared by the components and blending amounts shown in Tables 3 and 4, and their properties were evaluated. In all of the examples and comparative examples, the solid concentration was appropriately selected within the range of 20% to 50% in order to adjust the polyurethane resin composition to a suitable coatable viscosity.

&Lt; Example 7 >

2.0 parts of an ion trapping agent (C-1) as an ion trapping agent (C) and 15.0 parts of silica (E-1) as a silica (E) were added to 100 parts of a polyurethane resin (a) , And methyl ethyl ketone / toluene were added at a mass ratio of 1: 1 so as to have a solid content concentration of 25%, and the mixture was thoroughly stirred and dispersed. Subsequently, 6.5 parts of an epoxy resin (B-1) as an epoxy resin (B-1) and 1.0 part of a silane coupling agent (D-1) as a silane coupling agent (D) were added thereto to obtain a methyl ethyl ketone / Toluene was added at a mass ratio of 1: 1 and adjusted. And sufficiently stirred to obtain a desired polyurethane resin composition. The blending amount of the epoxy resin was determined so as to include an epoxy group of 1.7 times the total amount of the acid value of the polyurethane resin (a). Table 3 shows the evaluation results of the adhesion evaluation samples prepared by the above-mentioned methods. Both the initial evaluation and the time-lapse evaluation show good results.

&Lt; Examples 13 and 14 >

In the same manner as in Example 7, a polyurethane resin composition was prepared by the components and blending amounts shown in Table 3, and the characteristics were evaluated. In all of the examples and comparative examples, the solid concentration was appropriately selected within the range of 20% to 50% in order to adjust the polyurethane resin composition to a suitable coatable viscosity.

Details of each component are described below.

Epoxy resin (B-1): YDCN-700-10 (o-cresol novolak type epoxy resin) manufactured by Shinnitetsu Sumitomo Chemical Co., Ltd., epoxy = 4850 equivalent / 10 ⁶ g

Epoxy resin (B-2): HP7200-H (dicyclopentanediene type epoxy resin) manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent = 3540 equivalent / 10 ⁶ g

Epoxy resin (B-3): TETRAD (registered trademark) -X (N, N, N ', N'-tetraglycidyl-m-xylenediamine) manufactured by Mitsubishi Gas Chemical Co., 10 ⁶ g

Ion trapping agent (C-1): IXE (registered trademark) -700F (inorganic ion exchanger manufactured by Toagosei Co., Ltd.)

Ion trapping agent (C-2): IXE (registered trademark) -770D (inorganic ion exchanger manufactured by Toagosei Co., Ltd.)

Silane coupling agent (D-1): KBM-403 (3-glycidoxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.)

Silica (E-1): R972 (Hydrophobic soft silica produced by Nippon Aerosil Co., Ltd.)

H-43M: manufactured by Showa Denko Co.,

In Comparative Example 1, the polyurethane resin (f) has a low urethane group concentration and does not correspond to the polyurethane resin (A), and therefore falls outside the scope of the present invention. It is considered that the polarity is low and the adhesion to the base material and the strength of the coating film are lowered and the peel strength is lowered.

In the comparative examples 2 and 3, the polyurethane resin (g) has a low acid value and does not correspond to the polyurethane resin (A), and therefore is out of the scope of the present invention. It is considered that crosslinking of the cured product becomes insufficient since the acid value is low and the soldering heat resistance after steady state and humidification is lowered.

In Comparative Examples 4 to 6, since the polyurethane resin (h) does not contain a polyester polyol containing a phosphorus compound residue as a constituent component, it does not correspond to the polyurethane resin (A), and therefore, to be. The flame retardant effect of the resin becomes insufficient, and the flame retardancy decreases.

In Comparative Example 7, the polyurethane resin (i) has a high acid value and does not correspond to the polyurethane resin (A), and therefore, is outside the scope of the present invention. Since the acid value is high, the cross-linking density of the coating film increases, and the solder resistance after humidification decreases. In addition, it is considered that the reactivity is high and the sheet life is lowered, and the property over time deteriorates.

In the comparative example 8, the polyurethane resin (e) has a high urethane group concentration and does not correspond to the polyurethane resin (A), and therefore is out of the scope of the present invention. Since the polarity is high and the hygroscopicity is high, the insulation reliability under 85 ° C and 85% relative humidity is lowered.

INDUSTRIAL APPLICABILITY The polyurethane resin composition of the present invention can provide an adhesive composition excellent in high humidity resistance and heat resistance which can cope with lead-free soldering under various adhesiveness, flame resistance and high humidity to various plastic films and metals, and insulation reliability under high temperature and high humidity. Further, since the adhesive layer and the laminate maintain favorable adhesive properties even after they are used after being flowed under high temperature and high humidity, and the sheet life is good, a printed wiring board containing them can be provided. In addition, in the preferred embodiment of the present invention, although a small amount of ion scavenger is added to the polyurethane resin composition, the insulation reliability under high-temperature and high-humidity environment can be effectively improved even though it contains a large amount of phosphorus compound. Therefore, the adhesive composition, the adhesive layer and the laminate produced using the polyurethane resin composition of the present invention can be suitably used and applied particularly in the field of printed wiring boards such as FPC.

Claims (8)

A polyurethane resin composition comprising a polyurethane resin (A) and an epoxy resin (B) satisfying the following conditions (1) to (3):
(1) A polyester polyol containing a phosphorus compound residue represented by the general formula (1) or (2) as a constituent component.
(2) The acid value (unit: equivalent / 10 ⁶ g) is 50 or more and 1000 or less.
(3) The urethane group concentration (unit: equivalent / 10 ⁶ g) is 100 or more and 600 or less.

(Wherein R1 and R2 are each independently a hydrogen atom or a hydrocarbon group, R3 and R4 are each independently a hydrogen atom, a hydrocarbon group or a hydroxy group substituted hydrocarbon group, and l and m are an integer of 0 to 4.)

(R5 is a hydrogen atom or a hydrocarbon group, and R6 and R7 are each independently a hydrogen atom, a hydrocarbon group, or a hydroxyl group substituted hydrocarbon group) The method, the polyurethane resin (A) an acid value of the AV (equivalents / 10 ⁶ g), the amount AW (parts by weight) of the 1, wherein the epoxy is the BV (eq / 10 ⁶ g) of the epoxy resin (B), Satisfies 0.7? (BV x BW) / (AV x AW)? 3.0 when the compounding amount is BW (mass part). The polyurethane resin composition according to claim 1 or 2, further comprising an ion trapping agent (C). The polyurethane resin composition according to any one of claims 1 to 3, further comprising a silane coupling agent (D) and / or silica (E). The polyurethane resin composition according to any one of claims 1 to 4, wherein the epoxy resin (B) is an epoxy resin having a dicyclopentadiene skeleton. An adhesive composition comprising the polyurethane resin composition according to any one of claims 1 to 5. An adhesive layer comprising the adhesive composition according to claim 6, and a laminate of a film or a metal. A printed wiring board comprising the laminate according to claim 7.