JP2019012793A - Conductive layer built-in flexible printed circuit board - Google Patents

Abstract

To provide a conductive layer built-in flexible printed circuit board excellent in electric insulation reliability, and in which exfoliation from a conductive layer does not occur during reflow mounting.SOLUTION: In a conductive layer built-in flexible printed circuit board constituted in the order of (A) a conductive layer having an electromagnetic wave shield function, (B) an insulator film, and (C) a film with a wiring pattern, the (B) insulator film contains at least (a) binder polymer, and (b) a black coloring agent having a reflection region in an infrared region, (A) the conductive layer having the electromagnetic wave shield function is formed on at least one surface of the (B) insulator film, and the surface has a portion not coated with the conductive layer having the electromagnetic wave shield function.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductive layer integrated flexible printed circuit board, and more particularly to a conductive layer integrated flexible printed circuit board that has excellent electrical insulation reliability and does not peel off from the conductive layer during reflow mounting. is there.

  In recent years, electronic devices such as mobile phones, video cameras, and notebook computers are rapidly becoming smaller and lighter. Therefore, flexible and flexible flexible printed circuit boards are indispensable. On the other hand, electronic circuits are becoming narrower in pitch and higher in frequency, and countermeasures against electromagnetic noise generated along with this have become increasingly important. Therefore, efforts have been made in the past to construct an electromagnetic wave shielding material that shields or absorbs electromagnetic wave noise generated from an electronic circuit on a flexible printed board. As a flexible printed board having an electromagnetic wave shielding function, a shield layer having a conductive adhesive layer, a metal thin film layer, or the like is bonded to the insulating layer of the flexible printed board, and the metal thin film layer is electrically connected to the ground line of the flexible printed board. What has been connected to each other is known (for example, see Patent Document 1).

  On the other hand, regarding the insulating film of the surface protective material for flexible printed circuit boards, the insulating film is colored black, and the insulating film is concealed, thereby concealing the circuit pattern and including the confidential information contained in the circuit pattern. Attempts have been made to protect information (see, for example, Patent Documents 2 and 3).

JP 2009-290103 A JP 2008-257045 A JP 2002-294131 A

  In Patent Document 1, attention is paid to an electromagnetic wave shielding material, and it is an object to maintain an electromagnetic wave shielding effect for a long time even when bending and sliding are repeatedly performed. However, the electromagnetic wave shielding material is an element constituting the electromagnetic wave shielding material integrated flexible printed circuit board, but even if only the characteristics of the electromagnetic wave shielding material are improved, desired characteristics cannot be satisfied. For example, unless the adhesion between the electromagnetic wave shielding material and the insulating film of the flexible printed circuit board is improved, good characteristics as an electromagnetic wave shielding material integrated flexible printed circuit board are not exhibited.

  Therefore, the present inventors have paid attention to the insulating film of the flexible printed circuit board and have intensively studied the characteristics of the electromagnetic wave shielding material integrated flexible printed circuit board.

  The inventions described in Patent Documents 2 and 3 are merely black inventions, and are not intended to improve the adhesion between the insulation film and the electromagnetic shielding material. Therefore, according to Patent Document 2 and Patent Document 3, when an electromagnetic shielding material is pasted on a black insulating film, reflow mounting for mounting components on a flexible printed circuit board after pasting the electromagnetic shielding material In the process, there arises a problem that the electromagnetic wave shielding material is peeled off from the insulating film (hereinafter, the problem is expressed as reflow heat resistance).

  As a result of diligent research to solve the above-mentioned problems, the inventors have (A) a conductive layer having an electromagnetic wave shielding function, (B) an insulating film, and (C) a conductive layer integrated type configured in the order of a film with a wiring pattern. A flexible printed circuit board, wherein the (B) insulating film contains at least (a) a binder polymer, and (b) a black colorant having a reflective region in the infrared region, and the (A) electromagnetic wave shielding function. The conductive layer is formed on at least one surface of the insulating film (B), and the surface has a portion not covered with the conductive layer having the electromagnetic shielding function (A). The conductive layer-integrated flexible printed circuit board has excellent electrical insulation reliability, and further has obtained knowledge that peeling from the conductive layer does not occur during reflow mounting. The present invention has been achieved based on such findings. The present invention can solve the above problems by the following conductive printed circuit board integrated flexible printed circuit board.

  That is, one embodiment of the present invention can be configured as follows.

  <1> (A) A conductive layer having an electromagnetic wave shielding function, (B) an insulating film, (C) a conductive layer integrated flexible printed circuit board in the order of a film with a wiring pattern, wherein (B) the insulating film Contains at least (a) a binder polymer, and (b) a black colorant having a reflective region in the infrared region, and (A) the conductive layer having an electromagnetic wave shielding function is at least the (B) insulating film. A conductive layer-integrated flexible printed board formed on one surface, wherein the surface has a portion not covered with the conductive layer having the electromagnetic wave shielding function (A).

  <2> The conductive layer-integrated flexible printed board according to <1>, wherein the area of the portion is 10% to 60% of the total area of the surface.

  <3> The conductive layer-integrated flexible printed board according to <1> or <2>, wherein the (b) black colorant having a reflective region in the infrared region has a reflectance of 5% or more. .

  <4> The conductive layer (A) having an electromagnetic wave shielding function is formed on the surface of the (B) insulating film so as to be in direct contact with each other. <1> to <1> 3> The flexible printed board integrated with a conductive layer according to any one of 3).

  <5> Any of <1> to <3>, wherein the (B) insulating film is formed on the surface of the film with the wiring pattern (C) so that both are in direct contact with each other A flexible printed circuit board with a conductive layer integrated therein.

  <6> Any one of <1> to <3>, wherein an intervening layer is formed between (A) the conductive layer having an electromagnetic wave shielding function and (B) the insulating film. The conductive layer integrated flexible printed board as described.

  <7> The conductive layer according to any one of <1> to <3>, wherein an intervening layer is formed between the (B) insulating film and the (C) film with a wiring pattern. Layer-integrated flexible printed circuit board.

  The conductive layer-integrated flexible printed board of the present invention is excellent in electrical insulation reliability and does not peel off from the conductive layer during reflow mounting.

It is a block diagram which shows a conductive layer integrated flexible printed circuit board. It is a figure which shows the electromagnetic wave shielding property evaluation by KEC method. It is a figure which shows the site | part of the conductive layer integrated flexible printed circuit board in evaluation of the reflow heat resistance of an Example.

  An embodiment of the present invention will be described in detail below. In addition, all the academic literatures and patent literatures described in this specification are incorporated by reference in this specification. Unless otherwise specified in this specification, “A to B” indicating a numerical range means “A or more and B or less”.

  The present invention is described in detail below.

  The conductive layer-integrated flexible printed board of the present invention is a conductive layer-integrated flexible printed board configured in the order of (A) a conductive layer having an electromagnetic wave shielding function, (B) an insulating film, and (C) a film with a wiring pattern. The (B) insulating film contains at least (a) a binder polymer, and (b) a black colorant having a reflective region in the infrared region, and the (A) conductive layer having an electromagnetic wave shielding function is The (B) insulating film is formed on at least one surface, and the surface has a portion not covered with the conductive layer having the electromagnetic wave shielding function (A). I just need it.

  The present inventors have found that the conductive layer integrated flexible printed board of the present invention is excellent in various properties. This is presumed to be due to the following reasons.

  Regarding the conductive layer integrated flexible printed circuit board in which the conductive layer is bonded onto the black insulating film obtained from the resin composition, the problem that the conductive layer is peeled off during the reflow mounting process is This is a newly discovered problem when conducting extensive research on a flexible printed circuit board integrated with a conductive layer using a film. Here, the black insulating film is used for the following reason. As shown in FIG. 1, the conductive layer integrated flexible printed circuit board generally has a boundary between the conductive layer and the insulating film, which makes it difficult to understand the boundary. Since the conductive layer is generally black, the insulating film is also black. Since the heating method of the reflow mounting process is a method of heating with an infrared heater, the surface temperature of the insulating film is reduced by the infrared absorption of the black colorant contained in the insulating film on which the conductive layer is not formed. As shown in FIG. 1, a large amount of outgas of the insulating film is generated at the boundary between the conductive layer and the insulating film in the vicinity of the portion (10) where peeling occurs in FIG. It is assumed that it will peel off from the surface of the insulating film. Therefore, the present inventors speculate that outgassing during the reflow mounting process can be suppressed by using a black colorant having a reflective region in the infrared region, which is the component (b) in the present invention, as the black colorant. doing. Furthermore, since the component (b) in the present invention is more insulative than carbon black or the like generally used as a black colorant, the obtained conductive layer integrated flexible printed board is excellent in electrical insulation reliability. The present inventors infer that.

  Hereinafter, (A) a conductive layer having an electromagnetic wave shielding function, (B) an insulating film, (C) a film with a wiring pattern, other components, and a conductive layer integrated flexible printed board will be described.

<Conductive layer integrated flexible printed circuit board>
FIG. 1 shows a configuration diagram of a conductive layer integrated flexible printed board of the present invention, but the present invention is not limited to this. First, the (B) insulating film (4) is formed on the (C) film with wiring pattern (1) composed of the wiring pattern (2) and the base film (3) to obtain a flexible printed circuit board (5). Subsequently, (A) a conductive layer (6) having an electromagnetic wave shielding function is formed on (B) the insulating film (4), and the conductive layer integrated flexible printed board of the present invention can be obtained. Here, (A) the area of the conductive layer (6) having the electromagnetic wave shielding function is smaller than the area of (B) the insulating film (4). That is, since a part of (B) insulating film (4) is not covered with (A) conductive layer (6) having an electromagnetic wave shielding function, (A) the conductive layer having an electromagnetic wave shielding function is B) It is formed on at least one surface of the insulating film, and the surface has a portion which is not covered with the conductive layer having the (A) electromagnetic wave shielding function.

  In a conventional conductive layer integrated flexible printed board, (A) a conductive layer having an electromagnetic wave shielding function is formed on at least one surface of (B) an insulating film, and the surface is (A) an electromagnetic wave shield. When the conductive layer having the function has an uncoated portion, outgas is generated from the (B) insulating film during the reflow mounting process, and (A) the conductive layer having the electromagnetic wave shielding function is separated from the (B) insulating film. There was a problem. Note that the peeling tends to occur frequently in the vicinity of a region where the (B) insulating film is exposed without being covered with the conductive layer (A) having an electromagnetic wave shielding function. On the other hand, in the present invention, at least (a) a binder polymer and (b) a black colorant having a reflective region in the infrared region is used. As a result, (A) the conductive layer having the electromagnetic wave shielding function can be suppressed from (B) peeling from the insulating film.

  The part may be provided at one place on the insulating film or may be provided at a plurality of places.

  The area of the portion is preferably 10% to 60% and more preferably 30% to 50% of the total area of the surface. If it is the said structure, since a shield function can be provided to a conductive layer integrated flexible printed circuit board, it is preferable. Note that the area of a portion where a plurality of the above portions are provided over the insulating film is a total area of the plurality of portions.

  The conductive layer having the electromagnetic wave shielding function may be formed on the surface of the insulating film, and an intervening layer may be formed between the conductive layer having the electromagnetic wave shielding function and the insulating film. . When the conductive layer having the electromagnetic wave shielding function is formed on the surface of the insulating film, it is preferable from the viewpoint of adhesion between the conductive layer and the insulating film. Further, when an intervening layer is formed between the conductive layer having the electromagnetic wave shielding function and the insulating film, outgassing of the insulating film is unlikely to occur at the boundary between the conductive layer and the insulating film in the reflow mounting process. The conductive layer is preferable because it is difficult to peel off from the surface of the insulating film.

  The insulating film may be formed on the surface of the film with a wiring pattern, and an intervening layer may be formed between the insulating film and the film with a wiring pattern. When the said insulating film is formed on the surface of the said film with a wiring pattern, since it is easy to manufacture, it is preferable. Moreover, when the intervening layer is formed between the said insulating film and the said film with a wiring pattern, since the adhesiveness of an insulating film and a film with a wiring pattern can be strengthened, it is preferable.

  The intervening layer is intended to be an adhesive layer.

<(A) Conductive layer having electromagnetic wave shielding function>
The conductive layer (A) having an electromagnetic wave shielding function in the present invention is a layer that exhibits an electromagnetic wave shielding effect of 10 dB or more and exhibits conductivity. Generally, the higher the conductivity of the conductive layer, the higher the electromagnetic shielding effect. Accordingly, the conductive layer (A) having an electromagnetic wave shielding function in the present invention contains at least one element selected from the group consisting of metals having high conductivity, for example, (f) silver, copper, aluminum and nickel. More preferably.

  Although it does not specifically limit as a method to evaluate the electromagnetic wave shielding effect of the conductive layer which has (A) electromagnetic wave shielding function in this invention, For example, KEC method is mentioned. FIG. 2 shows an electromagnetic shielding effectiveness evaluation diagram by the KEC method. The KEC method is divided into a receiving antenna (8) and a transmitting antenna (9) jig, and a measurement sample (7) is inserted between the receiving antenna (8) and the transmitting antenna (9). This is a method for evaluating how much the signal is attenuated by the receiving antenna. Here, the electromagnetic wave shielding effect can be obtained by (Equation 1).

SE (shield effect) = 20 log 10 Eo / Ex [dB] (Formula 1)
Electric field strength of space when there is no shield material: Eo
Electric field strength in the space when there is a shielding material: Ex.

  The conductive layer having the electromagnetic wave shielding function (A) in the present invention is not particularly limited, and examples thereof include (A-1) film type, (A-2) paste type, and (A-3) metal thin film type. In particular, the film type (A-1) is preferable because it can impart shielding properties without impairing the flexibility of the conductive layer integrated flexible printed board.

(A-1) Film Type The conductive layer having a film type electromagnetic wave shielding function in the present invention is not particularly limited. For example, a film in which conductive particles are dispersed in a resin, conductive adhesive / metal thin film / insulating layer Examples of such a multilayer film are as follows. Specifically, examples of the film in which the conductive particles are dispersed in the resin include trade names TSS100-18 and TSS100-22 manufactured by Toyochem Co., Ltd. Moreover, as a multilayer film formed into a multilayer like the conductive adhesive / metal thin film / insulating layer, trade names SF-PC5000, SF-PC5100, SF-PC5500, SF-PC5600, SF-PC5900 of Tatsuta Electric Cable Co., Ltd. And SF-PC6000.

The method for forming the film-type conductive layer having an electromagnetic wave shielding function in the present invention on the insulating film is not particularly limited, and examples thereof include a pressurization / heat forming method using a hot press. There are no particular restrictions on the conditions of the pressurization and thermoforming method using a hot press. For example, the hot press temperature is 100 to 180 ° C., the hot press pressure is 0.5 to 5.0 kgf / cm ² , and the hot press is used. A conductive layer having an electromagnetic wave shielding function can be formed on the insulating film by heating and pressing under conditions of time of 10 to 90 minutes. It is preferable to control the pressurization / thermoforming conditions within the above range because the adhesion between the conductive layer and the insulating film can be expressed.

(A-2) Paste Type The conductive layer having a paste type electromagnetic wave shielding function in the present invention is not particularly limited, and examples thereof include a paste in which silver particles are dispersed in a resin, a paste in which nickel particles are dispersed in a resin, and the like. Can be mentioned. Specifically, examples of the paste in which the silver particles are dispersed in the resin include trade name RA FS039 manufactured by Toyochem Co., Ltd. and trade name XA-9015 manufactured by Fujikura Kasei Co., Ltd. Examples of the paste in which the nickel particles are dispersed in the resin include trade name FN-101 manufactured by Fujikura Kasei Co., Ltd., trade name K-3435G manufactured by Pernox Co., Ltd., and the like.

  The method for forming the conductive layer having the paste type electromagnetic wave shielding function in the present invention on the insulating film is not particularly limited, but conventionally known printing methods such as flexographic printing, gravure printing, screen printing, rotary screen printing, etc. Can be used for printing. After forming a coating film on an insulating film using the above printing method, heating is performed using a hot-air circulating oven at a heating temperature of 25 ° C. to 150 ° C. and a heating time of 10 minutes to 180 minutes. Thus, a conductive layer having an electromagnetic wave shielding function can be formed on the insulating film. Controlling the printing / heating conditions within the above range is preferable because conductivity can be exhibited and adhesion between the conductive layer and the insulating film can be exhibited.

(A-3) Metal thin film type The conductive layer having a metal thin film type electromagnetic wave shielding function in the present invention is a conductive layer obtained by directly forming a metal thin film on an insulating film. The method for forming a metal thin film type conductive layer having an electromagnetic wave shielding function on the insulating film according to the present invention is not particularly limited. For example, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method is used. (PVD), chemical vapor deposition (CVD), or liquid phase growth methods such as electroless plating. In particular, in consideration of mass productivity, vacuum deposition is desirable, and it is preferable because an inexpensive and stable metal thin film can be obtained. The vacuum deposition method in the present invention is a method of forming a metal thin film on the target substrate surface by heating the metal under vacuum conditions to vaporize or sublimate it. Although it does not specifically limit as a metal to vapor-deposit, For example, silver, copper, aluminum, gold | metal | money etc. are mentioned.

<(B) Insulating film>
The (B) insulating film in the present invention is a film having a thickness of 5 to 100 μm, and is obtained by curing the resin composition.

  Although the thickness of the (B) insulating film in this invention can be measured by arbitrary methods, it can be measured by the method based on JISK54003.5, for example.

  By controlling the thickness of the insulating film within the above range, (B) the electrical insulation reliability of the insulating film is excellent, which is preferable. If the thickness of the insulating film is 5 μm or less, the electrical insulation reliability of (B) the insulating film may be reduced, and if the thickness of the insulating film is 100 μm or more, (B) the flexibility of the insulating film is May decrease.

  The (B) insulating film in the present invention preferably contains at least (a) a binder polymer and (b) a black colorant having a reflective region in the infrared region. The (B) insulator is black by containing the component (b), and the conductive layer is integrated to prevent the conductive layer from peeling off during the reflow mounting process and to which electrical insulation reliability is imparted. It is preferable because a flexible printed circuit board can be obtained.

[(A) Binder polymer]
The (a) binder polymer in the present invention is a polymer that is soluble in an organic solvent and has a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol.

  The organic solvent is not particularly limited, and examples thereof include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, Examples thereof include acetamide solvents such as N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, hexamethylphosphoramide, and γ-butyrolactone. Furthermore, if necessary, these organic polar solvents and aromatic hydrocarbons such as xylene or toluene can be used in combination.

  Furthermore, examples of the organic solvent include methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyethyl) ether), methyl triglyme (1,2-bis (2-methoxyethoxy). ) Ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ether), Symmetric glycol diethers such as butyl diglyme (bis (2-butoxyethyl) ether); methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate Diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Acetates such as dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate; or dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n -Propyl ether, propylene glycol n-butyl ether, dipropylene group Coal n-butyl ether, tripylene glycol n-propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, etc. And ethers.

  The solubility of the organic solvent, which is an index for determining whether or not the binder polymer is soluble in the organic solvent, can be measured by measuring the weight part of the binder polymer dissolved in 100 parts by weight of the organic solvent. it can. If the weight part of the binder polymer dissolved with respect to 100 parts by weight of the organic solvent is 5 parts by weight or more, it can be determined that the binder polymer is soluble in the organic solvent. The method for measuring the solubility of the organic solvent is not particularly limited. For example, 5 parts by weight of a binder polymer is added to 100 parts by weight of the organic solvent, stirred at 40 ° C. for 1 hour, and then cooled to room temperature (25 ° C.). And leaving it for 24 hours or longer. And it is judged that a binder polymer is soluble with respect to an organic solvent by confirming that there is no generation | occurrence | production of an insoluble matter or a precipitate and it is a uniform solution.

  The weight average molecular weight of the component (a) in the present invention can be measured, for example, under the following measurement conditions.

(Weight average molecular weight measurement)
Equipment used: Tosoh HLC-8220GPC equivalent column: Tosoh TSK gel Super AWM-H (6.0 mm ID x 15 cm) x 2 guard columns: Tosoh TSK guard column Super AW-H
Eluent: 30 mM LiBr + 20 mM H3PO4 in DMF
Flow rate: 0.6 mL / min
Column temperature: 40 ° C
Detection conditions: RI: Polarity (+), response (0.5 sec)
Sample concentration: about 5 mg / mL
Standard product: PEG (polyethylene glycol).

  In the present invention, the weight average molecular weight of component (a) is controlled within the range of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol. (B) Flexibility of insulating film obtained and chemical resistance It is preferable because of its excellent properties. When the weight average molecular weight is less than 1,000, the flexibility and chemical resistance of the (B) insulating film may be lowered. When the weight average molecular weight is larger than 1,000,000, the resin composition Viscosity may increase.

  Although it does not specifically limit as (a) component in this invention, For example, polyurethane-type resin, poly (meth) acrylic-type resin, polyvinyl-type resin, polystyrene-type resin, polyethylene-type resin, polypropylene-type resin, polyimide-type resin, polyamide Resin, polyacetal resin, polycarbonate resin, polyester resin, polyphenylene ether resin, polyphenylene sulfide resin, polyether sulfone resin, polyether ether ketone resin, and the like. The above can be used in combination. As the component (a) in the present invention, when a polyurethane resin or a poly (meth) acrylic resin, which is a resin containing a urethane bond in the molecule, is used, (B) the flexibility and fold resistance of the insulating film This is preferable because (B) the warp of the insulating film is reduced.

  The polyurethane resin, which is a resin containing a urethane bond in the molecule in the present invention, is soluble in an organic solvent and contains a repeating unit containing at least one urethane bond in the molecule. Is a polymer of 1,000 to 1,000,000 in terms of polyethylene glycol.

  The polyurethane resin, which is a resin containing a urethane bond in the molecule in the present invention, can be obtained by any reaction. For example, the following general formula (1)

(Wherein R ₁ represents a divalent organic group)
A diol compound represented by the following general formula (2)

(Wherein X ₁ represents a divalent organic group)
Is reacted with a diisocyanate compound represented by the following general formula (3):

(Wherein R ₁ and X ₁ each independently represent a divalent organic group, and n represents an integer of 1 or more)
It is obtained as a structure containing a repeating unit containing a urethane bond represented by

  The diol compound in the present invention is not particularly limited as long as it is a structure represented by the general formula (1). For example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1, Alkylene diols such as 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, tetra Methylene glycol Polyoxyalkylene diols such as random copolymers with neopentyl glycol, polyester diols obtained by reacting polyhydric alcohols with polybasic acids, polycarbonate diols having a carbonate skeleton, γ-butyllactone, ε-caprolactone, δ -Polycaprolactone diol obtained by ring-opening addition reaction of lactone such as valerolactone, bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, ethylene of hydrogenated bisphenol A Examples thereof include an oxide adduct, a propylene oxide adduct of hydrogenated bisphenol A, and the like can be used alone or in combination of two or more.

  In particular, when a long-chain diol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyalkylene diol, polyester diol, polycarbonate diol, polycaprolactone diol is used as the diol compound in the present invention, (B) the insulating film It is preferable because the elastic modulus is lowered, flexibility and folding resistance are improved, and warping of the insulating film is reduced.

  The diisocyanate compound in the present invention is not particularly limited as long as it is a structure represented by the general formula (2). For example, diphenylmethane-2,4′-diisocyanate, 3,2′-dimethyldiphenylmethane-2,4 ′. -Diisocyanate, 3,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 4,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 4,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 5, 2'-dimethyldiphenylmethane-2,4'-diisocyanate, 5,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 6,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 6,3'-dimethyldiphenylmethane -2,4'-diisocyanate 3,3′-diethyldiphenylmethane-2,4′-diisocyanate, 3,3′-diethyldiphenylmethane-2,4′-diisocyanate, 4,2′-diethyldiphenylmethane-2,4′-diisocyanate, 4,3 '-Diethyldiphenylmethane-2,4'-diisocyanate, 5,2'-diethyldiphenylmethane-2,4'-diisocyanate, 5,3'-diethyldiphenylmethane-2,4'-diisocyanate, 6,2'-diethyldiphenylmethane- 2,4′-diisocyanate, 6,3′-diethyldiphenylmethane-2,4′-diisocyanate, 3,2′-dimethoxydiphenylmethane-2,4′-diisocyanate, 3,3′-dimethoxydiphenylmethane-2,4′- Diisocyanate, 4,2'-dimeth Sidiphenylmethane-2,4′-diisocyanate, 4,3′-dimethoxydiphenylmethane-2,4′-diisocyanate, 5,2′-dimethoxydiphenylmethane-2,4′-diisocyanate, 5,3′-dimethoxydiphenylmethane-2, 4'-diisocyanate, 6,2'-dimethoxydiphenylmethane-2,4'-diisocyanate, 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3 ' -Diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene- 2,4-diisocyanate, tolylene-2,6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2-bis (4-phenoxyphenyl) ) Propane] aromatic diisocyanate compound such as diisocyanate; alicyclic diisocyanate compound such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate; aliphatic such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate These can be used alone or in combination of two or more.

  In the method of synthesizing a polyurethane-based resin, which is a resin containing a urethane bond in the molecule in the present invention, the blending amount of the diol compound and the diisocyanate compound is determined by the ratio of the number of hydroxyl groups to the number of isocyanate groups (isocyanate group / hydroxyl group). , 0.5 or more and 2.0 or less, and the reaction is performed without a solvent or in an organic solvent.

  In the case where two or more kinds of diol compounds are used in the method for synthesizing a polyurethane-based resin, which is a resin containing a urethane bond in the molecule in the present invention, the reaction with the diisocyanate compound is performed by mixing two or more kinds of diol compounds together It may be performed later or each diol compound and diisocyanate compound may be reacted separately. As another method, after reacting the diol compound with the diisocyanate compound, the isocyanate group at the terminal of the obtained resin is further reacted with another diol compound, and the product after the reaction is further reacted with the diisocyanate compound. May be. The same applies when two or more types of diisocyanate compounds are used. Using the method described above, a desired resin containing a urethane bond in the molecule can be produced.

  The reaction temperature between the diol compound and the diisocyanate compound is preferably 40 to 160 ° C, and more preferably 60 to 150 ° C. The reaction temperature between the diol compound and the diisocyanate compound is preferably 40 to 160 ° C. because gelation hardly occurs. If it is less than 40 ° C., the reaction time becomes too long. If it exceeds 160 ° C., a three-dimensional reaction occurs during the reaction and gelation tends to occur. The reaction time between the diol compound and the diisocyanate compound can be appropriately selected depending on the scale of the batch or the reaction conditions employed. If necessary, the reaction may be performed in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium, cobalt, or a metalloid compound.

  The reaction between the diol compound and the diisocyanate compound can be performed in the absence of a solvent, but in order to control the reaction, it is desirable to perform the reaction in an organic solvent system. Although the organic solvent used here is not specifically limited, For example, what was illustrated above can be used.

  The amount of the organic solvent used for the reaction between the diol compound and the diisocyanate compound is desirably an amount such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% by weight or more and 90% by weight or less. More preferably, the solute weight concentration in the reaction solution is 10 wt% or more and 80 wt% or less. A solution concentration of 5% by weight or more and 90% by weight or less is preferable because a uniform polymerization reaction is likely to occur. When the solution concentration is less than 5% by weight, the polymerization reaction is unlikely to occur and the reaction rate is lowered, and a desired structural substance may not be obtained. On the other hand, when the solution concentration is larger than 90% by weight, the viscosity of the reaction solution becomes high and the reaction may become non-uniform.

  The polyurethane resin having a urethane bond in the molecule in the present invention preferably further contains at least one organic group selected from the group consisting of a (meth) acryloyl group, a carboxyl group, and an imide group. The (meth) acryloyl group is an acryloyl group and / or a methacryloyl group. When the (meth) acryloyl group is contained, the photosensitivity of the resin composition is improved. Is possible. In addition, when the polyurethane resin having a urethane bond in the molecule in the present invention contains a carboxyl group, the solubility of the resin composition in a developing solution of a dilute alkaline aqueous solution used when forming a fine pattern is improved. Thus, a fine pattern can be formed by developing in a short time. Moreover, when it contains an imide group, the heat resistance of the (B) insulating film and the electrical insulation reliability under high temperature and high humidity conditions are improved.

  A resin containing a (meth) acryloyl group and containing a urethane bond in the molecule can be obtained by any reaction. For example, in addition to the diol compound and the diisocyanate compound, the following general formula (4)

(In the formula, R ₂ represents an m + 1 valent organic group, R ₃ represents hydrogen or an alkyl group, and m represents an integer of 1 to 3)
A compound containing a hydroxyl group and at least one (meth) acryloyl group, and / or the following general formula (5)

(Wherein X ₂ represents an l + 1 valent organic group, X ₃ represents hydrogen or an alkyl group, and l represents an integer of 1 to 3)
It is obtained by reacting a compound containing an isocyanate group and at least one (meth) acryloyl group.

  The compound containing a hydroxyl group and at least one (meth) acryloyl group in the present invention is not particularly limited as long as it is a structure represented by the general formula (4). For example, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, o-phenylphenol Glycidyl ether (meth) acrylate, polyethylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, 1,4-cyclohexane dimethano Mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth) acrylate, N-methylolacrylamide, 3,5-dimethyl-4-hydroxybenzylacrylamide, and the like. These can be used alone or in combination of two or more.

  In the present invention, the compound containing an isocyanate group and at least one (meth) acryloyl group is not particularly limited as long as it is a structure represented by the general formula (5). For example, 2- (meth) acryloyloxy Examples include ethyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, and these can be used alone or in combination of two or more.

  Moreover, the polyurethane-type resin which contains a carboxyl group and contains a urethane bond in a molecule | numerator can be obtained by arbitrary reaction. For example, in addition to the diol compound and the diisocyanate compound, the following general formula (6)

(Wherein R ₄ represents a trivalent organic group)
It can be obtained by reacting a compound containing two hydroxyl groups and one carboxyl group.

  The compound containing two hydroxyl groups and one carboxyl group in the present invention is not particularly limited as long as it is a structure represented by the general formula (6). For example, 2,2-bis (hydroxymethyl) propionic acid 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxymepropyl) propionic acid, 2,3-dihydroxy-2-methylpropionic acid, 2,2-bis (hydroxymethyl) ) Butanoic acid, 2,2-bis (2-hydroxyethyl) butanoic acid, 2,2-bis (3-hydroxypropyl) butanoic acid, 2,3-dihydroxybutanoic acid, 2,4-dihydroxy-3,3- Dimethylbutanoic acid, 2,3-dihydroxyhexadecanoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydro Shi benzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid and the like, may be used singly or in combinations of two or more.

  In particular, when an aliphatic compound containing two hydroxyl groups and one carboxyl group is used as the compound containing two hydroxyl groups and one carboxyl group, the photosensitive resin composition has excellent photosensitivity. Therefore, it is preferable.

  The polyurethane resin containing the imide group and containing a urethane bond in the molecule can be obtained by any reaction. For example, in addition to the diol compound and the diisocyanate compound, the following general formula (7)

(Wherein Y represents a tetravalent organic group)
It is obtained by reacting a tetracarboxylic dianhydride represented by

  The tetracarboxylic dianhydride in the present invention is not particularly limited as long as it is a structure represented by the above general formula (7). For example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Pyromellitic dianhydride, 3,3 ′, 4,4′-oxydiphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2, 2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl)- 3-me -3-tetracarboxylic acid dianhydride, such as cyclohexene-1,2-dicarboxylic anhydride and the like, may be used singly or in combinations of two or more.

  The poly (meth) acrylic resin in the present invention is a polymer that is soluble in an organic solvent, and contains a repeating unit obtained by copolymerizing (meth) acrylic acid and / or (meth) acrylic acid ester derivatives. The polymer has a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol. Here, (meth) acryl is methacryl and / or acrylic.

  The poly (meth) acrylic resin in the present invention can be obtained by an arbitrary reaction. For example, a (meth) acrylic acid and / or a (meth) acrylic ester derivative is used as a radical polymerization initiator in a solvent. It is obtained by reacting in the presence.

  Although it does not specifically limit as (meth) acrylic acid ester derivative in this invention, For example, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid propyl, (meth) acrylic acid butyl, Isobutyl acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic acid Examples include decyl, dodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, and the like. These can be used alone or in combination of two or more. (B) From the viewpoint of the flexibility and chemical resistance of the insulating film, among the above (meth) acrylate derivatives, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate are particularly used. It is preferable.

  Examples of the radical polymerization initiator include azo compounds such as azobisisobutyronitrile, azobis (2-methylbutyronitrile), 2,2′-azobis-2,4-dimethylvaleronitrile; t-butyl Organic peroxides such as hydroperoxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide; persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate; Hydrogen etc. are mentioned, These can be used individually or in combination of 2 or more types.

  The amount of the radical polymerization initiator used is preferably 0.001 to 5 parts by weight and more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer used. When the usage-amount of the said radical polymerization initiator is 0.001-5 weight part, since the polymer which has a desired molecular weight is obtained, it is preferable. When the amount of the radical polymerization initiator used is less than 0.001 part by weight, the reaction is difficult to proceed, and when it is more than 5 parts by weight, the molecular weight may be lowered.

  The amount of solvent used in the reaction for synthesizing the poly (meth) acrylic resin is preferably an amount such that the solute weight concentration in the reaction solution, that is, the solution concentration is 5% by weight or more and 90% by weight or less. 20% by weight or more and 70% by weight or less is more preferable. A solution concentration of 5% by weight or more and 90% by weight or less is preferable because a uniform polymerization reaction is likely to occur. When the solution concentration is less than 5%, the polymerization reaction is difficult to occur and the reaction rate is decreased, and a desired structural substance may not be obtained. When the solution concentration is more than 90% by weight, the reaction solution has a high viscosity. And the reaction may become non-uniform.

  The reaction temperature for the synthesis of the poly (meth) acrylic resin is preferably 20 to 120 ° C, and more preferably 50 to 100 ° C. The reaction temperature for synthesizing the poly (meth) acrylic resin is preferably 20 to 120 ° C. because the reaction time is appropriate and side reactions are unlikely to occur. When the temperature is lower than 20 ° C., the reaction time becomes too long, and when it exceeds 120 ° C., gelation due to rapid progress of reaction or three-dimensional crosslinking accompanying side reaction may be caused. The reaction time for the synthesis of the poly (meth) acrylic resin can be appropriately selected depending on the scale of the batch or the reaction conditions employed.

  When the component (a) in the present invention is a polyimide resin, (B) the heat resistance of the insulating film is improved, which is preferable. The polyimide resin is a polymer having a repeating unit containing at least one imide group in the molecule and having a weight average molecular weight of 1,000 or more and 1,000,000 or less in terms of polyethylene glycol.

  The polyimide resin in the present invention can be obtained by any reaction. For example, the following general formula (7)

(Wherein Y represents a tetravalent organic group)
It can be obtained by reacting a tetracarboxylic dianhydride represented by the formula with a diamino compound.

  The tetracarboxylic dianhydride in the present invention is as described above.

  Although it does not specifically limit as a diamino compound in this invention, For example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide , (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4 -Aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4 ' -Diaminobenzophenone, 3,3'-di Minobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether Bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfoxide, bis [4- ( 3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfide, bis [4- (aminophenoxy) phenyl] sulfide, (4-aminophenoxyphenyl) (3-aminophenoxyphenyl) phenyl] sulfide, 3,3′-diaminobenzanilide, 3,4′-diamino Benzanilide, 4,4′-diaminobenzanilide, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, [4- (4-aminophenoxyphenyl) ] [4- (3-aminophenoxyphenyl)] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2- [4- (4-aminophenoxy) Phenyl)] [4- (3-aminophenoxyphenyl)] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2- [4- (4-aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1 , 1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2- [4- (4- Aminophenoxyphenyl)] [4- (3-aminophenoxyphenyl)]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4- Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4 , 4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) ) Phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, polytetramethylene oxide-di-p-aminobenzoate , Poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4-aminobenzoate), m-phenylene-bis ( 4-aminobenzoate), bisphenol A-bis (4-aminobenzoate), 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3′-diamino-4, 4′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, [bis (4-amino-2-carboxy) Phenyl] methane, [bis (4-amino-3-carboxy) phenyl] methane, [bis (3-amino-4-carboxy) Boxy) phenyl] methane, [bis (3-amino-5-carboxy) phenyl] methane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino-3- Carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 2,2-bis [4-amino-3-carboxyphenyl] hexafluoropropane, 3,3′-diamino- 4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4,4′-diamino-2,2′-dicarboxydiphenyl ether, 3,3′-diamino-4, 4′-dicarboxydiphenyl sulfone, 4,4′-diamino-3,3′-dicarboxydiphenyl sulfone, 4 Diaminophenols such as 4′-diamino-2,2′-dicarboxydiphenylsulfone, 2,3-diaminophenol, 2,4-diaminophenol, 2,5-diaminophenol, 3,5-diaminophenol; 3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino- Hydroxybiphenyl compounds such as 2,2 ′, 5,5′-tetrahydroxybiphenyl; 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, Dihydroxydiphenyl metas such as 4,4′-diamino-2,2′-dihydroxydiphenylmethane Bis [hydroxyphenyl] propanes such as 2,2-bis [3-amino-4-hydroxyphenyl] propane and 2,2-bis [4-amino-3-hydroxyphenyl] propane; Bis [hihydroxyphenyl] hexafluoropropanes such as bis [3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2-bis [3-amino-4-hydroxyphenyl] hexafluoropropane; 3,3 ′ Hydroxydiphenyl ethers such as -diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether; 3,3 ' -Diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-di Dihydroxydiphenyl sulfones such as mino-3,3′-dihydroxydiphenylsulfone and 4,4′-diamino-2,2′-dihydroxydiphenylsulfone; 3,3′-diamino-4,4′-dihydroxydiphenyl sulfide, 4 , 4′-diamino-3,3′-dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfides such as 4,4′-diamino-2,2′-dihydroxydiphenyl sulfide; 3,3′-diamino-4,4′-dihydroxy Dihydroxy diphenyl sulfoxides such as diphenyl sulfoxide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfoxide, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfoxide; 2,2-bis [4- ( 4-amino-3-hydroxy Bis [(hydroxyphenyl) phenyl] alkane compounds such as phenoxy) phenyl] propane; Bis (hydroxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl; 2 Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as 2,4-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone; 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4 , 4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 4,4'-bis (4-amino-3-hydroxyphenoxy) biphenyl Bis (hydroxyphenoxy) biphenyl compounds such as Can be used in combination of two or more.

  The reaction between the tetracarboxylic anhydride and the diamino compound can be performed by any method. For example, the tetracarboxylic acid anhydride and the diamino compound can be reacted by the method shown below.

  Method 1: A diamino compound is added to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent and reacted to prepare a polyamic acid solution. The total amount of the diamino compound added is 0.50 to 1.50 moles per mole of tetracarboxylic dianhydride. After the reaction between the tetracarboxylic dianhydride and the diamino compound is completed, the resulting polyamic acid solution is heated to 100 ° C. or more and 300 ° C. or less, more preferably 150 ° C. or more and 250 ° C. or less to perform imidization. Do.

  Method 2: A polyamic acid solution is prepared in the same manner as in Method 1 above. A catalyst for imidization (preferably pyridine, picoline, isoquinoline, trimethylamine, triethylamine, tributylamine, etc. are used) and a dehydrating agent (such as acetic anhydride) are added to the polyamic acid solution, and 60 ° C. or higher. The imidization is carried out by heating to 180 ° C. or lower.

  Method 3: A polyamic acid solution is prepared in the same manner as in Method 1 above. The polyamic acid solution is placed in a vacuum oven heated to 100 ° C. or higher and 250 ° C. or lower, and imidized by drawing a vacuum while heating and drying.

[(B) Black colorant having a reflective region in the infrared region]
In the present invention, (b) the black colorant having a reflective region in the infrared region may be any material that has an effect of coloring other materials such as black dyes and black pigments to black. The black colorant is preferably a substance having a reflectance of 5% or more in a wavelength region of 800 nm to 2000 nm that is an infrared region. Although it does not specifically limit as a measuring method of the reflectance of the black colorant which has a reflection area | region in (b) infrared region in this invention, For example, it can measure with the following method. (B) The reflectance of the black colorant having a reflective region in the infrared region can be measured with a Japanese spectrophotometer U-4100 by introducing a measurement specimen into the cell.

  The black pigment having a reflective region in the infrared region is not particularly limited. For example, iron-manganese composite oxide, iron-cobalt-chromium composite oxide, iron-chromium-manganese composite oxide, which are metal composite oxides. Products, copper / chromium composite oxide, and copper / chromium / manganese composite oxide. Specific examples of the metal composite oxide include trade names manufactured by Kawamura Chemical Co., Ltd., AB820 black, AG235 black, trade names manufactured by Asahi Chemical Industry Co., Ltd., Black 6350, Black 6301, Black 6302, Black 6303, and the like. Examples of the black pigment having a reflective region in the infrared region include organic pigments such as aniline compounds, anthraquinone compounds, and perylene compounds. Specifically, for example, trade names manufactured by BASF, Palogen Black S0084, Lumogen Black FK4280, Lumogen Black FK4281, etc. are mentioned. These can be used alone or in combination of two or more.

  As the black pigment having a reflective region in the infrared region, the metal composite oxide is more preferably a metal composite oxide containing iron, chromium, manganese, or bismuth from the viewpoint of insulation. Moreover, as a black pigment having a reflective region in the infrared region, the organic pigment is more preferably a perylene compound from the viewpoint of insulation.

  The content of the component (b) in the present invention is preferably 0.1 to 30 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the component (a). Thereby, the blackness and concealment property of the obtained (B) insulating film are excellent. When the content of the component (b) is less than 0.1 parts by weight with respect to 100 parts by weight of the component (a), the blackness of the insulating film and the concealability may be inferior, and the component (b) When there is more content than 30 weight part with respect to 100 weight part of (a) component, there exists a possibility that the transmittance | permeability of the photosensitive resin composition may fall and photosensitivity may fall.

[(C) Flame retardant that does not substantially dissolve in organic solvent]
In the present invention, (c) a flame retardant that does not substantially dissolve in an organic solvent exists as a solid without dissolving in the organic solvent, and has an effect of suppressing the combustion of organic matter, and is a solid compound at room temperature (25 ° C.) It is. Here, the said organic solvent means the organic solvent which is one of the other components which comprises the resin composition in this invention.

  “Substantially insoluble in the organic solvent” herein means that it does not dissolve in the organic solvent at all, or does not dissolve in the range that does not impair the effects of the present invention. The range not impairing the expression of the effect of the present invention means that the weight of the component (c) dissolved in 100 parts by weight of the organic solvent at room temperature (25 ° C.) is less than 0.1 parts by weight. Therefore, the flame retardant which does not substantially dissolve in the organic solvent (c) in the present invention refers to a flame retardant having a dissolution amount of less than 0.1 parts by weight with respect to 100 parts by weight of the organic solvent at room temperature (25 ° C.). The organic solvent is not particularly limited, and for example, the organic solvents exemplified above can be used.

  Although the method of measuring the weight part of the component (c) dissolved in 100 parts by weight of the organic solvent at room temperature (25 ° C.) is not particularly limited, for example, 1 component (c) is added to 100 parts by weight of the organic solvent. After adding parts by weight and stirring at 40 ° C. for 1 hour, the mixture was cooled to room temperature (25 ° C.), allowed to stand for 24 hours or longer, and then filtered under reduced pressure using a PTFE membrane filter having a pore size of 0.45 μm. There is a method in which the filter is washed three times with the organic solvent used, the filter is dried at 60 ° C. under reduced pressure for 8 hours, and then the weight change of the filter is measured.

  In the case where the component (c) in the present invention is at least one selected from the group consisting of a phosphorus compound, a melamine compound and a metal hydroxide, the flame retardancy of the (B) insulating film is improved, and the outgas is increased. Generation is reduced, the electrical insulation reliability is excellent, and the warp of the cured film is reduced.

  The phosphorus compound in the present invention is not particularly limited as long as it does not substantially dissolve in an organic solvent and contains a phosphorus element. For example, aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, trisdiphenylphosphinic acid Aluminum, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanyl bismethylethylphosphinate, titanyl bisdiphenylphosphinate, melamine polyphosphate, etc. It can be used alone or in combination of two or more.

  The melamine-based compound in the present invention is not particularly limited as long as it does not substantially dissolve in an organic solvent and contains a melamine structure. And melamine oligomer condensate, and the like, and these can be used alone or in combination of two or more.

  The metal hydroxide in the present invention is not particularly limited as long as it is a metal compound that does not substantially dissolve in an organic solvent and contains crystal water. For example, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, Examples include zinc zinc hydroxide, zinc borate 3.5 hydrate, calcium aluminate hydrate, and the like. These can be used alone or in combination of two or more.

  The content of the component (c) in the present invention may be 5 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight as a total of the components (a) and (b). Thereby, an insulating film is excellent in a flame retardance and electrical insulation reliability. When the amount of the component (c) is less than 5 parts by weight, the flame retardancy of the insulating film may be inferior. When the coating property is deteriorated, the appearance of the coating film may be deteriorated due to foaming or insufficient leveling during coating.

[(D) Thermosetting resin]
The (d) thermosetting resin in the present invention is a compound having a structure containing at least one thermosetting organic group in the molecule.

  The component (d) in the present invention is not particularly limited as long as it has the above structure. For example, epoxy resin, oxetane resin, phenol resin, isocyanate resin, block isocyanate resin, bismaleimide resin, bisallyl nadiimide resin, polyester Resin (for example, unsaturated polyester resin), diallyl phthalate resin, silicon resin, vinyl ester resin, melamine resin, polybismaleimide triazine resin (BT resin), cyanate resin (for example, cyanate ester resin), urea resin, guanamine resin, Sulfoamide resins, aniline resins, polyurea resins, thiourethane resins, polyazomethine resins, episulfide resins, ene-thiol resins, benzoxazine resins, copolymer resins of these resins, and modified trees obtained by modifying these resins , Or mixtures of these resins with each other or other resins and the like.

  As the component (d) in the present invention, among the above-mentioned thermosetting resins, in particular, the use of a polyfunctional epoxy resin can impart heat resistance to the insulating film, and can provide adhesion to conductors such as metal foil and circuit boards. Since it can provide, it is preferable.

  The polyfunctional epoxy resin is a compound containing at least two epoxy groups in the molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin. , Biphenyl type epoxy resin, phenoxy type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, dicyclopentadiene type epoxy resin, amine type epoxy resin, flexible Examples include epoxy resins, urethane-modified epoxy resins, rubber-modified epoxy resins, chelate-modified epoxy resins, and heterocyclic-containing epoxy resins.

  Specifically, as the bisphenol A type epoxy resin, trade names jER828, jER1001, jER1002 manufactured by Japan Epoxy Resin Co., Ltd., trade names Adeka Resin EP-4100E, Adeka Resin EP-4300E manufactured by ADEKA Co., Ltd., Nippon Kayaku Co., Ltd. Brand names RE-310S and RE-410S manufactured by the company, brand names Epicron 840S, Epicron 850S, Epicron 1050 and Epicron 7050 manufactured by DIC Corporation, brand names Epototo YD-115 and Epototo YD-127 manufactured by Toto Kasei Co., Ltd. Epototo YD-128 is exemplified. As the bisphenol F type epoxy resin, trade names jER806 and jER807 manufactured by Japan Epoxy Resin Co., Ltd., trade names Adeka Resin EP-4901E, Adeka Resin EP-4930, Adeka Resin EP-4950, manufactured by Nippon Kayaku Co., Ltd. Trade names RE-303S, RE-304S, RE-403S, RE-404S, trade names Epicron 830, Epicron 835 manufactured by DIC Corporation, trade names Epototo YDF-170, Epototo YDF-175S manufactured by Toto Kasei Co., Ltd. Epototo YDF-2001 is mentioned. As said bisphenol S type epoxy resin, the brand name Epiklon EXA-1514 by DIC Corporation is mentioned. As the hydrogenated bisphenol A type epoxy resin, trade names jERYX8000, jERYX8034, jERYL7170, trade name Adeka Resin EP-4080E, trade name ADEKA Resin EP-4080E, DIC Corporation, trade name, manufactured by Japan Epoxy Resin Co., Ltd. Examples include Etototo YD-3000 and Etototo YD-4000D manufactured by Toto Kasei Co., Ltd. Examples of the biphenyl type epoxy resin include trade names jERYX4000, jERYL6121H, jERYL6640, jERYL6677 manufactured by Japan Epoxy Resin Co., Ltd., and trade names NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd. Examples of the phenoxy type epoxy resin include trade names jER1256, jER4250, and jER4275 manufactured by Japan Epoxy Resin Co., Ltd. As said naphthalene type epoxy resin, the brand name NC-7000L made from DIC Corporation brand name Epicron HP-4032, Epicron HP-4700, Epicron HP-4200, Nippon Kayaku Co., Ltd. is mentioned. As the phenol novolac type epoxy resin, trade names jER152 and jER154 manufactured by Japan Epoxy Resin Co., Ltd., trade names EPPN-201-L manufactured by Nippon Kayaku Co., Ltd., trade names Epicron N-740 manufactured by DIC Corporation, and Epicron N-770, trade name Epototo YDPN-638 manufactured by Toto Kasei Co., Ltd. may be mentioned. Examples of the cresol novolac epoxy resin include trade names EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, and trade names Epicron N-660 and Epicron N-670 manufactured by Nippon Kayaku Co., Ltd. , Epicron N-680 and Epicron N-695. As said trisphenol methane type epoxy resin, Nippon Kayaku Co., Ltd. brand name EPPN-501H, EPPN-501HY, and EPPN-502H are mentioned. Examples of the dicyclopentadiene type epoxy resin include trade name XD-1000 manufactured by Nippon Kayaku Co., Ltd., and trade name Epicron HP-7200 manufactured by DIC Corporation. Examples of the amine type epoxy resin include trade names jER604 and jER630 manufactured by Japan Epoxy Resin Co., Ltd., trade names Epototo YH-434 and Epototo YH-434L manufactured by Toto Kasei Co., Ltd., trade names TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd. , TERRAD-C. Examples of the flexible epoxy resin include trade names jER871, jER872, jERYL7175, jERYL7217 manufactured by Japan Epoxy Resin Co., Ltd., and trade name Epicron EXA-4850 manufactured by DIC Corporation. Examples of the urethane-modified epoxy resin include Adeka Resin EPU-6, Adeka Resin EPU-73, and Adeka Resin EPU-78-11 manufactured by ADEKA Corporation. Examples of the rubber-modified epoxy resin include Adeka Resin EPR-4023, Adeka Resin EPR-4026, and Adeka Resin EPR-1309 manufactured by ADEKA Corporation. Examples of the chelate-modified epoxy resin include trade names Adeka Resin EP-49-10 and Adeka Resin EP-49-20 manufactured by ADEKA Corporation. Examples of the heterocyclic ring-containing epoxy resin include trade name TEPIC (triglycidyl isocyanurate) manufactured by Nissan Chemical Co., Ltd.

  Moreover, you may use a hardening | curing agent or a hardening accelerator for the resin composition in this invention in order to accelerate | stimulate hardening of the said thermosetting resin. Although it does not specifically limit as a hardening | curing agent used for the resin composition in this invention, For example, phenol resins, such as a phenol novolak resin, a cresol novolak resin, and a naphthalene type phenol resin; Amino resin, urea resin, melamine, dicyandiamide, etc. are mentioned. These can be used alone or in combination of two or more.

  Further, the curing accelerator used in the resin composition in the present invention is not particularly limited. For example, phosphine compounds such as triphenylphosphine; tertiary amines, trimethanolamine, triethanolamine, tetraethanolamine and the like. Amine compounds; borate compounds such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate; imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Imidazoles such as 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole and 2-phenyl-4-methylimidazole ; 2-methylimida Phosphorus, 2-ethylimidazoline, 2-isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline and the like; 2,4-diamino-6 -[2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2, And azine-based imidazoles such as 4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine; Can be used in combination.

[(E) Photopolymerization initiator]
The (e) photopolymerization initiator in the present invention is a compound that is activated by energy such as UV and initiates / promotes the reaction of the radical polymerizable group-containing resin. Therefore, when the resin composition in the present invention contains a radical polymerizable resin having a radical polymerizable group and (e) a photopolymerization initiator, the resin composition becomes a photosensitive resin composition. Here, examples of the radical polymerizable group include an acryloyl group, a methacryloyl group, and a vinyl group. As the radical polymerizable resin in the present invention, the (a) binder polymer may have a radical polymerizable group or a radical polymerizable compound as another component may be contained. In the reinforcing plate-integrated flexible printed board of the present invention, it is preferable that (B) the insulating film is obtained from a photosensitive resin composition containing (e) a photopolymerization initiator. The component (e) in the present invention is not particularly limited, and examples thereof include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, 2, 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, acetophenone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Ether, benzoin isobutyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, methylanthraquinone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1-hydroxycyclohexyl phenyl ketone , Zia Tyl benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, 2- (2′-furylethylidene) -4,6-bis (trichloromethyl) -S-triazine, 2- [2 ′-(5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,6-di (p-azidobenzal) -4 -Methylcyclohexanone, 4,4'-diazidochalcone, di (tetraalkylammonium) -4,4'-diazidostilbene-2,2'-disulfonate, 2,2-dimethoxy-1,2-diphenylethane-1 -One, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-o 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpho Linopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2 , 6-Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propane-1 -Ketone, bis (n-5,2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyro) 1-yl) -phenyl) titanium, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], iododium, (4-methylphenyl) [4 -(2-Methylpropyl) phenyl] -hexafluorophosphate (1-), ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxyome) and the like. The (e) photopolymerization initiator is preferably selected as appropriate, and it is desirable to use a mixture of one or more.

  The (e) photopolymerization initiator in the present invention is preferably blended in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight as a total of the components (a) and (b). Since the photosensitivity of the photosensitive resin composition in this invention improves by making the mixture ratio of said (e) photoinitiator into said range, it is preferable. (E) When the mixture ratio of a photoinitiator is less than the said range, reaction of the radically polymerizable group at the time of light irradiation hardly occurs, and there exists a possibility that hardening may become inadequate. Moreover, when there are more (e) components than the said range, adjustment of light irradiation amount becomes difficult and there exists a possibility of becoming an overexposed state. Therefore, in order to advance the photocuring reaction efficiently, it is preferable to adjust the blending ratio of (e) the photopolymerization initiator within the above range.

[Other ingredients]
In the resin composition of the present invention, if necessary, an organic solvent, a radical polymerizable compound, a filler, an adhesion aid, an antifoaming agent, a leveling agent, a polymerization inhibitor, and (c) an organic solvent substantially. Various additives such as a flame retardant other than the flame retardant that does not dissolve can be added.

  The organic solvent is not particularly limited as long as it is an organic polar solvent. For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide and other acetamide solvents, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone and other pyrrolidone solvents, hexamethylphosphoramide, γ-butyrolactone, etc. Is mentioned. Further, if necessary, the organic polar solvent and an aromatic hydrocarbon such as xylene or toluene can be used in combination.

  Furthermore, examples of the organic solvent in the present invention include methyl monoglyme (1,2-dimethoxyethane), methyl diglyme (bis (2-methoxyethyl) ether), methyl triglyme (1,2-bis (2- Methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldiglyme (bis (2-ethoxyethyl) ether) ), Symmetric glycol diethers such as butyl diglyme (bis (2-butoxyethyl) ether), methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl A Acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate), diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Acetates such as dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, or dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, di Lopylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, etc. And ether solvents.

  The radical polymerizable compound is a compound containing in its molecule a radical polymerizable group that undergoes a polymerization reaction by a radical polymerization initiator. Among the above compounds, the radical polymerizable compound is more preferably a resin having at least one unsaturated double bond as a radical polymerizable group in the molecule. Furthermore, the unsaturated double bond is preferably a (meth) acryloyl group or a vinyl group.

  The radical polymerizable compound is preferably used when the component (a) does not contain a (meth) acryloyl group. Moreover, even if (a) component contains the (meth) acryloyl group, you may use it.

  Examples of the radical polymerizable compound include bisphenol F EO modified (n = 2 to 50) diacrylate, bisphenol A EO modified (n = 2 to 50) diacrylate, and bisphenol S EO modified (n = 2 to 50) diacrylate. Bisphenol F EO modified (n = 2-50) dimethacrylate, bisphenol A EO modified (n = 2-50) dimethacrylate, bisphenol S EO modified (n = 2-50) dimethacrylate, 1,6-hexanediol dimethacrylate Acrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethyl Roll propane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol Hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hy Roxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyloxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis [4- (Methacryloxy Etoxy Si) phenyl] propane, 2,2-bis [4- (methacryloxy-diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy-polyethoxy) phenyl] propane, polyethylene glycol diacrylate, tripropylene glycol diacrylate , Polypropylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy-1-acryloxy-3- Methacryloxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene Recall acrylate, nonylphenoxypolyethylene glycol acrylate, nonylphenoxypolypropylene glycol acrylate, 1-acryloyloxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4 -Butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 2,4-diethyl-1,5-pentanediol di Methacrylate, 1,4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate Tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane, 2,4 -Diethyl-1,5-pentanediol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated Pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate , Glycidyl allyl ether, 1,3,5-triacryloylhexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, triallylamine, triallyl citrate, triallyl phosphate, alloverbital, diallylamine, Diallyldimethylsilane, diallyl disulfide, diallyl ether, diallyl cyanurate, diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4'-isopropylidene diphenol dimethacrylate, 4 , 4′-isopropylidenediphenol diacrylate and the like, and these can be used alone or in combination of two or more. In particular, when the radical polymerizable compound contains 2 to 50 mol of EO (ethylene oxide) repeating units contained in one molecule of diacrylate or dimethacrylate, the alkali of the photosensitive resin composition is used. This is preferable because solubility in an aqueous developer typified by an aqueous solution is improved and development time is shortened.

  Examples of the filler include fine inorganic fillers such as silica, mica, talc, barium sulfate, wollastonite, and calcium carbonate.

  Examples of the antifoaming agent include acrylic compounds, vinyl compounds, butadiene compounds, and the like.

  Examples of the leveling agent include acrylic compounds and vinyl compounds.

  Examples of the adhesion assistant (also referred to as adhesion-imparting agent) include silane coupling agents, triazole compounds, tetrazole compounds, and triazine compounds.

  Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether.

  As the flame retardant other than the flame retardant that does not substantially dissolve in the organic solvent (c), for example, a phosphoric ester compound, a halogen-containing compound, a metal hydroxide, an organic phosphorus compound, a silicone, or the like is used. Can do. As a method of using a flame retardant other than the flame retardant that does not substantially dissolve in the organic solvent (c), it can be used as an additive-type flame retardant or a reactive flame retardant. Moreover, you may use the said flame retardant suitably combining 1 type (s) or 2 or more types.

  Among these flame retardants, non-halogen compounds are more preferable from the viewpoint of environmental pollution, and phosphorus flame retardants are particularly preferable.

[Method for mixing resin composition and method for producing insulating film]
In the present invention, the (B) insulating film uniformly comprises the components (a), (b), and (c), (d), (e), and other components as necessary. Mix to obtain a resin composition. Thereafter, the resin composition is formed on the upper surface of the film with the wiring pattern (C), and then fine openings are formed by exposure / development as necessary, followed by heat treatment. A flexible printed circuit board can be obtained. The method of uniformly mixing the components used for the insulating film (B) is not particularly limited, and may be mixed using a general kneading apparatus such as a three roll or bead mill apparatus. Moreover, when the viscosity of the solution of each said component is low, you may mix using a general stirring apparatus. Among the above-mentioned mixing apparatuses, it is preferable to mix and pulverize and disperse using three rolls because the component (c) has a uniform size. The particle diameter of each component in the resin composition after mixing can be measured by a method using a gauge defined in JIS K 5600-2-5. Moreover, if a particle size distribution measuring apparatus is used, the average particle diameter of each component in a resin composition after mixing, a particle diameter, and a particle size distribution can be measured.

  Next, an insulating film can be obtained by an arbitrary method using the obtained resin composition. As a method for obtaining the insulating film, for example, (1) the resin composition as it is (C) a method in which the resin composition is applied to a film with a wiring pattern and cured, and (2) the resin composition is formed on a support. And the method of affixing the film of a non-hardened state on the film with a (C) wiring pattern, and hardening and forming is mentioned. (1) As a method of forming the resin composition (C) by applying it to a film with a wiring pattern and curing it, first, the resin composition is applied onto the film with a wiring pattern (C) and dried to remove the solvent. Remove. (C) Application to the film with the wiring pattern can be performed by screen printing, roller coating, curtain coating, spray coating, spin coating using a spinner, or the like. The coating film (preferably having a thickness of 5 to 100 μm) is dried at 120 ° C. or lower, preferably 40 to 100 ° C.

  Next, after drying as necessary, a negative photomask is placed on the dried coating film, and exposure is performed by irradiating active rays such as ultraviolet rays, visible rays, and electron beams. Next, the fine opening can be obtained by developing the unexposed portion with a developer using various methods such as shower, paddle, immersion, or ultrasonic wave. Since the time until the pattern is exposed varies depending on the spraying pressure and flow rate of the developing device and the temperature of the etching solution, it is desirable to find the optimum device conditions as appropriate.

  As the developer, an alkaline aqueous solution is preferably used. The developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone. Examples of the alkaline compound that provides the alkaline aqueous solution include hydroxides, carbonates, bicarbonates, and amine compounds of alkali metals, alkaline earth metals, or ammonium ions. Specific examples of the alkaline compound include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, triisopropylamine, etc. Of course, other compounds can be used as long as the aqueous solution exhibits basicity. Further, the temperature of the developer depends on the composition of the resin composition or the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. It is preferable to do.

  The fine opening formed by the development step is rinsed to remove unnecessary residue. Examples of the rinsing liquid include water and acidic aqueous solutions.

  Next, heat treatment is performed. By performing the heat treatment, an insulating film (B) having excellent heat resistance and chemical resistance can be obtained. (B) Although the thickness of an insulating film is determined in consideration of (C) film thickness with a wiring pattern, etc., it is preferable that it is about 5-100 micrometers. The final heat treatment temperature at this time is preferably 100 ° C. or higher and 250 ° C. or lower for the purpose of preventing oxidation of the conductor circuit and the like and (C) not lowering the adhesion with the film with a wiring pattern. Is 120 ° C. or higher and 200 ° C. or lower, particularly preferably 130 ° C. or higher and 180 ° C. or lower. When the heat treatment temperature is higher than 250 ° C., the oxidative deterioration of the conductor circuit or the like proceeds, and (C) the adhesion with the film with a wiring pattern may be lowered.

  (2) As a method of forming a resin composition on a support and attaching an uncured film to a film with a wiring pattern (C) and curing it, first, the resin composition is formed on the support. Is uniformly applied, followed by heating and / or hot air blowing. Thereby, a part of solvent is removed and the film of the resin composition of an unhardened state can be obtained.

  The temperature at which the solvent is removed by performing the heating and / or hot air spraying may be such that the thermosetting resin of the component (d) contained in the resin composition does not undergo a crosslinking reaction by heating. Here, the support to be used is not particularly limited, but various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used. Of the supports, a PET film is often used because it has a certain degree of heat resistance and is relatively inexpensive. In addition, about the joint surface of a support body and a resin composition, you may use what is surface-treated in order to improve adhesiveness and peelability. Moreover, you may laminate | stack a protective film on a resin composition. By laminating a protective film on the resin composition, it is possible to prevent dust and dust in the air from adhering and to prevent quality deterioration due to drying of the resin composition. The protective film is preferably laminated and laminated on the surface of the resin composition at a temperature of 10 ° C to 50 ° C. A temperature of 10 ° C. to 50 ° C. during the laminating process is preferable because wrinkles and curls of the protective film after the laminating process are unlikely to occur. In addition, when the temperature at the time of laminating process becomes higher than 50 degreeC, there exists a possibility that the thermal expansion of a protective film may be caused and the wrinkle and curl of the protective film after a laminating process may arise. In addition, since a protective film peels at the time of use, it is desirable for the joint surface of a protective film and a resin composition to have appropriate adhesiveness at the time of storage, and to be excellent in peelability.

  Although it does not specifically limit as a material of a protective film, For example, a polyethylene film (PE film), a polyethylene vinyl alcohol film (EVA film), "the copolymer film of polyethylene and ethylene vinyl alcohol" (following ( (PE + EVA) copolymer film), “PE film and (PE + EVA) copolymer film laminate”, or “(PE + EVA) copolymer and polyethylene film by simultaneous extrusion” (one side is PE film side) And the other side of the film is a (PE + EVA) copolymer film side).

  Subsequently, a protective film is peeled from the film which has a protective film, a resin composition, and a support body. And a film with a wiring pattern is covered with the film of a resin composition so that a resin composition and a film with a wiring pattern oppose, and it bonds together by thermocompression bonding. The bonding by thermocompression bonding may be performed by hot pressing, laminating (thermal laminating), hot roll laminating or the like, and is not particularly limited. When the bonding is performed by a thermal laminating process or a hot roll laminating process (hereinafter referred to as a laminating process), the processing temperature may be equal to or higher than a lower limit temperature at which the laminating process is possible (hereinafter, a pressure bonding possible temperature). Specifically, the pressure-bondable temperature is preferably in the range of 50 to 150 ° C, more preferably in the range of 60 to 120 ° C, and particularly preferably in the range of 80 ° C to 120 ° C. If the temperature at which crimping is possible is in the range of 50 to 150 ° C., a resin composition having a desired hardness can be obtained, and the pattern circuit is easily embedded, which is preferable. If the temperature at which crimping can be performed exceeds 150 ° C., a crosslinking reaction due to heating of the resin composition may occur during the laminating process, and curing of the resin composition may proceed. On the other hand, when the pressure bonding temperature is less than 50 ° C., the fluidity of the resin composition is low, and it becomes difficult to embed the pattern circuit.

  Here, the film-formed resin composition is kept in an uncured state. Therefore, when thermocompression treatment such as thermal laminating treatment is performed, it has appropriate fluidity and can be suitably embedded in a conductor circuit of a film with a wiring pattern.

  By the above-described thermocompression treatment, a bonded sample in which the resin composition is laminated on the film with the wiring pattern and the support is further laminated is obtained.

  Next, if necessary, a negative photomask is placed on the support of the bonded sample, and exposure is performed by irradiating active light such as ultraviolet light, visible light, or electron beam. Next, the support is peeled off, and a fine opening can be obtained by developing the unexposed portion with a developer using various methods such as shower, paddle, immersion, or ultrasonic wave. Since the time until the pattern is exposed varies depending on the spraying pressure and flow rate of the developing device and the temperature of the etching solution, it is desirable to find the optimum device conditions as appropriate.

  As the developer, an alkaline aqueous solution is preferably used. The developer may contain a water-soluble organic solvent such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone. Examples of the alkaline compound that provides the alkaline aqueous solution include hydroxides, carbonates, bicarbonates, and amine compounds of alkali metals, alkaline earth metals, or ammonium ions. Specific examples of the alkaline compound include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, triisopropylamine, etc. Of course, other compounds may be used as long as the aqueous solution exhibits basicity. Further, the temperature of the developer depends on the composition of the resin composition or the composition of the alkali developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 10 ° C. or higher and 60 ° C. or lower. It is preferable to do.

  The fine opening formed by the development step is rinsed to remove unnecessary residue. Examples of the rinsing liquid include water and acidic aqueous solutions.

  Next, heat treatment is performed. By performing the heat treatment, an insulating film (B) having excellent heat resistance and chemical resistance can be obtained. (B) Although the thickness of an insulating film is determined in consideration of (C) film thickness with a wiring pattern, etc., it is preferable that it is about 5-100 micrometers. The final heat treatment temperature at this time is preferably 100 ° C. or more and 250 ° C. or less, and more preferably 120 for the purpose of preventing oxidation of the conductor circuit and the like and (C) not lowering the adhesion with the film with the wiring pattern. It is 130 degreeC or more and 180 degrees C or less especially preferably. When the heat treatment temperature is higher than 250 ° C., the oxidative deterioration of the conductor circuit or the like proceeds, and (C) the adhesion with the film with a wiring pattern may be lowered.

<(C) Film with wiring pattern>
The film with a wiring pattern in the present invention is a film having a wiring pattern on one side or both sides of a base film having a thickness of 5 to 100 μm. The method for producing a film with a wiring pattern in the present invention is not particularly limited. For example, a flexible metal-clad laminate is produced by forming a conductor layer on a base film, and the conductor layer is produced by pattern etching. Can do.

  The base film in the present invention is not particularly limited as long as it is flexible and has an insulating property. For example, polypropylene, crosslinked polyethylene, polyester, polybenzimidazole, polyimide, polyimideamide, polyetherimide, polyphenylene sulfide , Liquid crystal polymer, polyether ether ketone and the like. In the case where heat resistance is not required for the base film, an inexpensive polyester film is preferable, and in the case where heat resistance is required, a polyimide film is preferable.

  The conductor layer in the present invention is not particularly limited, and examples thereof include copper or a copper alloy, stainless steel or an alloy thereof, nickel or a nickel alloy (including 42 alloy), aluminum or an aluminum alloy. In general flexible metal-clad laminates, copper foil such as rolled copper foil and electrolytic copper foil is frequently used, but it can also be preferably used in the present invention. In addition, the antirust layer, the heat-resistant layer, or the contact bonding layer may be apply | coated to the surface of these metal foil.

  The method for forming the conductor layer on the base film in the present invention, that is, the method for producing the flexible metal-clad laminate is not particularly limited, and examples thereof include a casting method, a laminating method, and a metalizing method. The casting method is a method in which a liquid base film solution is applied on a conductor layer, dried and thermally cured. The laminating method is a method of forming a base film and a conductor layer by thermocompression bonding. In the laminating method, a so-called three-layer metal-clad laminate in the case of producing an adhesive between the base film and the conductor layer, and a so-called case of not using an adhesive between the base film and the conductor layer. There are two-layer metal-clad laminates. Examples of the adhesive include an epoxy resin and an acrylic resin. The metallizing method is a method in which a metal thin film is formed on a base film by a vacuum deposition method or a sputtering method, and a conductor layer is formed by wet plating. In the metallizing method, a conductor layer may be formed by wet plating without forming a metal thin film. In any of the above methods, the conductor layer can be formed on one side or both sides of the base film.

  The method for pattern etching of the conductor layer in the present invention is not particularly limited, and examples thereof include a photoresist method. The photoresist method is a method in which a photoresist layer is formed on a metal-clad laminate, and a wiring pattern is formed by exposure, development, etching of a conductor layer, and peeling of a dry film. As the photoresist layer, a negative type or a positive type can be used, and a liquid form, a film form, or the like can be used. The method of forming the photoresist layer is not particularly limited. For example, a method of forming a negative dry film type resist on a metal-clad laminate by thermal lamination, or a positive type liquid type resist is applied. The method of forming and drying on a metal-clad laminate is mentioned. In the case of a method using a negative photoresist, parts other than the exposed part are removed by development. On the other hand, in the case of a method using a positive type photoresist, the exposed portion is removed by development. A dry film type resist can be easily thickened. Examples of the negative dry film type photoresist include trade name SPG-152 manufactured by Asahi Kasei Corporation, trade name RY-3215 manufactured by Hitachi Chemical Co., Ltd., and the like. In the method of developing and removing the photoresist layer, a known agent for developing and removing the photoresist layer can be appropriately selected and used. For example, a sodium carbonate aqueous solution (0.2 to 1.5%, etc.) is sprayed. The photoresist layer can be developed and removed. In the etching of the conductor layer, known conductor layer etching can be appropriately selected and used. For example, potassium ferricyanide aqueous solution, iron chloride aqueous solution, copper chloride aqueous solution, ammonium persulfate aqueous solution, sodium persulfate aqueous solution, hydrogen peroxide solution , Hydrofluoric acid aqueous solutions, and combinations thereof can be used.

  The conductive layer integrated flexible printed circuit board (FPC) in the present invention is excellent in adhesion between the conductive layer having an electromagnetic wave shielding function and the insulating film, and further has flexibility, flame retardancy, and electrical insulation reliability capable of withstanding repeated bending. Since it is excellent and warpage is small, it is particularly suitable as a flexible printed circuit board for liquid crystal displays, sensors, and camera modules of small portable terminals. Further, it is also used for hinge bending, slide bending, cable, connector, FPC for optical pickup of hard disk, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
<(A) Binder polymer 1>
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen introducing tube was charged with 100.0 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) as a polymerization solvent, and nitrogen was added. The temperature was raised to 80 ° C. with stirring under an air stream. To this, 12.0 g (0.14 mol) of methacrylic acid, 28.0 g (0.16 mol) of benzyl methacrylate, and 60.0 g of butyl methacrylate (0. 0 mol) previously mixed at room temperature (25 ° C). 42 mol), 0.5 g of azobisisobutyronitrile as a radical polymerization initiator was added dropwise from a dropping funnel over 3 hours while keeping the temperature at 80 ° C. After completion of the dropping, the reaction solution was heated to 90 ° C. while stirring, and the reaction solution was further stirred for 2 hours while maintaining the temperature of the reaction solution at 90 ° C. for reaction. By performing the above reaction, a poly (meth) acrylic resin solution (a-1) was obtained. The resulting resin solution had a solid content concentration of 50%, a weight average molecular weight of 48,000, and a solid content acid value of 78 mgKOH / g. The solid content concentration, weight average molecular weight, and acid value were measured by the following methods.

<Concentration of solid content>
The measurement was performed according to JIS K 5601-1-2. The drying conditions were 170 ° C. × 1 hour.

<Weight average molecular weight>
Measurement was performed under the following conditions.
Equipment used: Tosoh HLC-8220GPC equivalent column: Tosoh TSK gel Super AWM-H (6.0 mm ID x 15 cm) x 2 guard columns: Tosoh TSK guard column Super AW-H
Eluent: 30 mM LiBr + 20 mM H3PO4 in DMF
Flow rate: 0.6 mL / min
Column temperature: 40 ° C
Detection conditions: RI: Polarity (+), response (0.5 sec)
Sample concentration: about 5 mg / mL
Standard product: PEG (polyethylene glycol).

<Acid value>
Measurement was performed according to JIS K 5601-2-1.

(Synthesis Example 2)
<(A) Binder polymer 2>
Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a cooling pipe and a nitrogen introduction pipe, 30.00 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) was charged as a solvent for polymerization. In addition, 10.31 g (0.050 mol) of norbornene diisocyanate was added and dissolved by heating to 80 ° C. with stirring under a nitrogen stream. To this solution, 50.00 g (0.025 mol) of polycarbonate diol (manufactured by Asahi Kasei Corporation, product name PCDL T5652, weight average molecular weight 2000) and 6.51 g (0.050 mol) of 2-hydroxyethyl methacrylate were added to methyltriglyme. A solution dissolved in 30.00 g was dropped from the dropping funnel over 1 hour. After completion of the dropwise addition, this solution was reacted by heating and stirring at 80 ° C. for 5 hours. By performing the above reaction, a urethane resin solution (a-2) having a urethane bond in the molecule was obtained. The resulting resin solution had a solid content concentration of 53% and a weight average molecular weight of 5,200. The solid content concentration and the weight average molecular weight were measured in the same manner as in Synthesis Example 1.

(Synthesis Example 3)
<(A) Binder polymer 3>
130.60 g of methyltriglyme (= 1,2-bis (2-methoxyethoxy) ethane) was added as a polymerization solvent to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen introducing tube. To this, 31.02 g (0.100 mol) of 3,3 ′, 4,4′-oxydiphthalic dianhydride, 34.45 g (0.080 mol) of bis [4- (3-aminophenoxy) phenyl] sulfone ), 24.76 g (0.020 mol) of poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate), and stirred for 30 minutes under a nitrogen stream to obtain a polyamic acid solution. It was. Then, this solution was heated to 190 ° C. and reacted for 2 hours. By performing the above reaction, a polyimide resin solution (a-3) was obtained. The resulting resin solution had a solid content concentration of 49% and a weight average molecular weight of 36,000. The solid content concentration and the weight average molecular weight were measured in the same manner as in Synthesis Example 1.

(Examples 1-9 and Comparative Examples 1-3)
<Preparation of resin composition>
(A) a binder polymer obtained in the synthesis example, (b) a black colorant having a reflective region in the infrared region, (c) a flame retardant that does not substantially dissolve in an organic solvent, (d) a thermosetting resin, (e ) A photopolymerization initiator and other components were added to prepare a resin composition. Tables 1 and 2 show the blending amount of each constituent raw material in the resin solid content and the kind of raw material. Note that 1,2-bis (2-methoxyethoxy) ethane, which is an organic solvent in the table, is the total amount of solvent including the solvent contained in the synthesized resin solution. The resin composition was first mixed by a stirring device equipped with a general stirring blade, and then passed twice through a three-roll mill to obtain a uniform solution. When the particle size was measured with a grindometer, all were 10 μm or less. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device.

However, <1> to <11> in Tables 1 and 2 are as follows.
<1> Product name of black colorant (metal composite oxide) manufactured by Asahi Kasei Kogyo Co., Ltd., reflectivity in wavelength region 800 nm to 2000 nm is 5% or more <2> Black colorant manufactured by Asahi Kasei Kogyo Co., Ltd. (metal composite oxide) Product name, reflectance in wavelength region 800 nm to 2000 nm is 5% or more <3> manufactured by BASF Japan Ltd. Product name of black colorant (organic pigment), reflectance in wavelength region 800 nm to 2000 nm is 5% or more <4> Product name manufactured by Mitsubishi Chemical Corporation, which has an absorption region in the wavelength range of 800 nm to 2000 nm <5> Product name of phosphinic acid salt manufactured by Clariant Japan Co., Ltd., 100 parts by weight of 1,2-bis (2-methoxyethoxy) ethane <6> Product name of melamine cyanurate manufactured by BASF Japan Ltd. Solubility in 100 parts by weight of 2-bis (2-methoxyethoxy) ethane Less than 0.01 parts by weight <7> Product name of boehmite type aluminum hydroxide manufactured by Navaltech Co., 1,2-bis (2-methoxyethoxy) Solubility in 100 parts by weight of ethane Less than 0.01 part by weight <8> Product name of polyfunctional epoxy resin (triglycidyl isocyanurate) manufactured by Nissan Chemical Co., Ltd. <9> Product name of butadiene type antifoaming agent manufactured by Kyoeisha Chemical Co., Ltd. <10> Product name of oxime ester photopolymerization initiator manufactured by BASF Japan Ltd. <11> Product name of EO-modified bisphenol A dimethacrylate manufactured by Hitachi Chemical Co., Ltd.

<Evaluation of insulating film>
(I) Electrical insulation reliability Line width / space on flexible copper-laminated laminate (electrolytic copper foil thickness 12 μm, polyimide film is made of Kaneka Corporation's Apical 25 NPI, polyimide adhesive bonded with copper foil) A comb-shaped pattern having a width = 100 μm / 100 μm was prepared, immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, washed with pure water, and subjected to a copper foil surface treatment. Thereafter, the resin composition was cast and applied on the comb pattern so that the final dry thickness was 20 μm, and dried at 80 ° C. for 20 minutes. Thereafter, it was cured by heating in an oven at 150 ° C. for 30 minutes to obtain an insulating film, thereby obtaining a test piece. When the resin composition is a photosensitive resin composition, the resin composition is cast and applied on the comb pattern so that the final dry thickness is 20 μm, dried at 80 ° C. for 20 minutes, and then 300 mJ. / Cm ² of ultraviolet light with an accumulated exposure dose and exposure, followed by spraying for 90 seconds at a discharge pressure of 1.0 kgf / mm ² using a 1.0% by weight aqueous solution of sodium carbonate heated to 30 ° C. Developed. After development, the sample was sufficiently washed with pure water, and then heat-cured in an oven at 150 ° C. for 30 minutes to obtain an insulating film, thereby obtaining a test piece. A 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed. In Table 3, the observed results are indicated by the following “◯” or “×”.
A: A resistance value of 10 8 or more after 1000 hours from the start of the test, and no occurrence of migration or dendrite.
X: The occurrence of migration, dendrite, etc. after 1000 hours from the start of the test.

(Ii) Concealing property The above resin composition is flowed on a 25 μm polyimide film (manufactured by Kaneka Co., Ltd .: trade name: 25 NPI) using a Baker-type applicator in an area of 100 mm × 100 mm so that the final dry thickness is 20 μm. This was spread and applied, and dried at 80 ° C. for 20 minutes. Thereafter, it was cured by heating in an oven at 150 ° C. for 30 minutes to obtain an insulating film, thereby obtaining a test piece. When the resin composition is a photosensitive resin composition, the resin composition is cast and applied on the comb pattern so that the final dry thickness is 20 μm, dried at 80 ° C. for 20 minutes, and then 300 mJ. / Cm ² of ultraviolet light with an accumulated exposure dose and exposure, followed by spraying for 90 seconds at a discharge pressure of 1.0 kgf / mm ² using a 1.0% by weight aqueous solution of sodium carbonate heated to 30 ° C. Developed. After development, the sample was sufficiently washed with pure water, and then heat-cured in an oven at 150 ° C. for 30 minutes to obtain an insulating film, thereby obtaining a test piece. The test piece was placed on a graph paper having a 1 mm square grid, and the concealability was evaluated by visually checking the grid from above the test piece. In Table 3, the evaluation results are indicated by the following “◯” or “×”.
○: A cell with invisible cells ×: A cell with visible cells.

<Production of conductive layer integrated flexible printed circuit board evaluation test piece>
Using the Baker-type applicator, the resin composition prepared above was flowed on a 75 μm-thick polyimide film (manufactured by Kaneka Corporation: trade name: 75NPI) over an area of 100 mm × 100 mm so that the final dry thickness was 25 μm. This was spread and applied, and dried at 80 ° C. for 20 minutes. Subsequently, it was heat-cured for 30 minutes in an oven at 150 ° C. to produce an insulating film.

In addition, when the resin composition is a photosensitive resin composition, the final dry thickness is applied to a 75 μm-thick polyimide film (manufactured by Kaneka Corporation: trade name 75 NPI) using a Baker type applicator. After casting and coating to an area of 100 mm × 100 mm so as to be 25 μm, drying at 80 ° C. for 20 minutes, exposure was performed by irradiating with an ultraviolet ray with an accumulated exposure amount of 300 mJ / cm ² , and then 1.0 wt% Spray development was performed for 90 seconds at a discharge pressure of 1.0 kgf / mm ² using a solution obtained by heating an aqueous sodium carbonate solution to 30 ° C. After development, the film was thoroughly washed with pure water, and then heat-cured in an oven at 150 ° C. for 30 minutes to produce an insulating film. Next, on the obtained insulating film, as a conductive layer having an electromagnetic wave shielding function, a product name SF-PC5500 of Tatsuta Electric Wire Co., Ltd., which is a film-type conductive layer, is cut into an area of 50 mm × 50 mm, 150 ° C., 2. Bonding was performed by hot pressing at 5 MPa for 60 minutes to prepare a conductive layer integrated flexible printed board evaluation test piece in which a part of the insulating film was not covered with a conductive layer having an electromagnetic wave shielding function. At this time, the area of the insulating film not covered with the conductive layer having the electromagnetic wave shielding function was 25% with respect to the area of the insulating film.

<Evaluation of conductive layer integrated flexible print>
The obtained conductive layer integrated flexible print was evaluated for the following items.

(Iii) Adhesiveness between conductive layer and insulating layer Using the test piece obtained in <Preparation of conductive layer-integrated flexible print evaluation test piece>, it was evaluated by a cross-cut tape method according to JIS K5400. In Table 3, the evaluation results are indicated by the following “◯”, “Δ”, or “×”. The cut was made from the conductive layer side (on the surface of the conductive layer not bonded to the insulating film), and the adhesion between the conductive layer and the insulating film was evaluated.
○: No peeling by cross-cut tape method.
Δ: 95% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Iv) Reflow heat resistance Using the test piece obtained in the above <Preparation of conductive layer-integrated flexible print evaluation test piece>, the reflow condition of 260 ° C .: peak top 260 ° C. × 20 sec (reflow furnace: Ambe Co., Ltd.) Observe the appearance of the test piece after reflow treatment with FC-220 manufactured by SMT. Thereafter, a tape peel test is performed. Details of the tape peel test are as follows. As the test tape, cellotape (registered trademark) having a width of 12 to 19 mm defined in JIS Z 1522 is used. After affixing the tape on the test piece after the reflow treatment, the tape is peeled off. Thereafter, the peeled tape and the test piece are observed, and the presence or absence of peeling of the insulating film or the conductive layer having an electromagnetic wave shielding function is confirmed. In Table 4, the evaluation results are indicated by the following “◯”, “Δ”, or “×”. Further, the observation location, site A, site B and site C in Table 4 are the site of the conductive layer integrated flexible printed circuit board shown in FIG. 3, site A (11), site B (12), site C (13 ) Respectively.
○: No change in appearance before and after the test, and no peeling of the insulating film or conductive layer having an electromagnetic wave shielding function after tape peeling. Δ: No change in the appearance before and after the test, and after the tape peeling, the insulating film or The conductive layer having the electromagnetic wave shielding function is peeled off. ×: The test piece is swollen at any laminated interface after the test.

  The present invention is a conductive layer-integrated flexible printed circuit board constructed in the order of (A) a conductive layer having an electromagnetic wave shielding function, (B) an insulating film, and (C) a film with a wiring pattern. The film contains at least (a) a binder polymer, and (b) a black colorant having a reflective region in the infrared region, and the conductive layer having the (A) electromagnetic wave shielding function is formed of the (B) insulating film. The conductive layer-integrated flexible printed board is formed on at least one surface, and the surface has a portion not covered with the conductive layer having the electromagnetic wave shielding function (A). The area of the portion is preferably 10% or more and 60% or less of the total area of the surface. Moreover, it is preferable that the reflectance of the black colorant having the reflection region in the infrared region (b) is 5% or more. Furthermore, it is preferable that the conductive layer having the electromagnetic wave shielding function is formed on the surface of the insulating film so that they are in direct contact with each other, and the insulating film is formed on the surface of the film with the wiring pattern. More preferably, it is formed so as to be in direct contact. In addition, an intervening layer is preferably formed between the conductive layer having the electromagnetic wave shielding function and the insulating film, and the intervening layer is more preferably located between the insulating film and the film with the wiring pattern. preferable.

  The present invention also provides a conductive layer integrated flexible printed circuit board comprising (A) a conductive layer having an electromagnetic wave shielding function, (B) an insulating film, and (C) a film with a wiring pattern in this order. A conductive layer-integrated flexible printed board, wherein the insulating film contains at least (a) a binder polymer and (b) a black colorant having a reflective region in the infrared region. The (B) insulating film preferably contains a flame retardant that does not substantially dissolve in the organic solvent (c), and the (B) insulating film contains (d) a thermosetting resin. More preferably, it is obtained from the resin composition. Furthermore, the (B) insulating film is more preferably obtained from a photosensitive resin composition containing (e) a photopolymerization initiator. More preferably, the conductive layer (A) having an electromagnetic wave shielding function contains (f) at least one element selected from the group consisting of silver, copper, aluminum and nickel.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention. Furthermore, a new technical feature can be formed by combining the technical means disclosed in each embodiment.

  The conductive layer integrated flexible printed circuit board according to the present invention can be used for circuit boards of various electronic devices.

DESCRIPTION OF SYMBOLS 1 Film with wiring pattern 2 Wiring pattern 3 Base film 4 Insulating film 5 Flexible printed circuit board 6 Conductive layer which has an electromagnetic wave shielding function 7 Measurement sample 8 Reception antenna 9 Transmission antenna 10 Place where peeling occurs 11 Site A
12 Site B
13 Site C

Claims (7)

(A) a conductive layer having an electromagnetic wave shielding function, (B) an insulating film, (C) a conductive layer integrated flexible printed circuit board configured in the order of a film with a wiring pattern,
The (B) insulating film contains at least (a) a binder polymer, and (b) a black colorant having a reflective region in the infrared region,
The (A) conductive layer having an electromagnetic wave shielding function is formed on at least one surface of the (B) insulating film,
The said surface has a part which is not coat | covered with the conductive layer which has the said (A) electromagnetic wave shielding function, The conductive layer integrated flexible printed board characterized by the above-mentioned.   2. The conductive layer integrated flexible printed board according to claim 1, wherein the area of the portion is 10% or more and 60% or less of the total area of the surface.   The conductive layer-integrated flexible printed board according to claim 1 or 2, wherein the (b) black colorant having a reflective region in the infrared region has a reflectance of 5% or more.   The conductive layer having the (A) electromagnetic wave shielding function is formed on the surface of the (B) insulating film so that both are in direct contact with each other. The conductive layer-integrated flexible printed board according to Item 1.   The said (B) insulating film is formed on the surface of the said (C) film with a wiring pattern so that both may contact | connect directly, The any one of Claims 1-3 characterized by the above-mentioned. Conductive layer integrated flexible printed circuit board.   The conductive layer according to any one of claims 1 to 3, wherein an intervening layer is formed between the conductive layer (A) having an electromagnetic wave shielding function and the (B) insulating film. Layer-integrated flexible printed circuit board.   The conductive layer integrated type according to any one of claims 1 to 3, wherein an intervening layer is formed between the (B) insulating film and the (C) film with a wiring pattern. Flexible printed circuit board.

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