JP2007180262A - Adhesive composition for printed wiring board, flexible copper-plated laminate, adhesive film, cover lay, and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition which is capable of being used for manufacturing a printed wiring board excellent in flame retardant, heat resistant, moisture-resistant, and insulating properties; and capable of displaying high reliability. <P>SOLUTION: The adhesive composition used for manufacturing the printed wiring board contains at least one kind of epoxy resin (A), a hardening agent (B) used for epoxy resin (A), a hardening accelerator (C), synthetic rubber (D), and metallic hydrate (E) as indispensable components. A metallic hydrate is processed by a glass matrix forming liquid precursor so as to obtain the metallic hydrate (E). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is an adhesive composition for a printed wiring board having excellent adhesion, folding resistance and flame retardancy, a flexible copper-clad laminate using the same, a coverlay, an adhesive film, and the like. The present invention relates to a printed wiring board.

  In recent years, with the reduction in size, weight and functionality of electronic devices, fine pitch patterns and downsizing are rapidly progressing in printed wiring boards and package / module boards used in such devices. In addition, with the growing concern about global environmental issues and human safety, the use of lead-free soldering and the use of non-halogen flame retardants reduces hazards and ensures higher safety. The demand to do is increasing.

  Therefore, the insulating material used for the flexible wiring board is required to have high heat resistance and high-density mounting, which makes the required level of solder heat resistance and copper foil peel strength more severe. It was.

  In adhesive compositions used for printed wiring boards, metal hydrates such as aluminum hydroxide and magnesium hydroxide are often used from the viewpoint of workability, characteristics and cost when ensuring flame retardancy. However, in order to ensure the flame retardancy, a large amount of metal hydrate must be added, and accordingly, workability, strength, heat resistance, and moisture resistance are accompanied by problems. In particular, since higher reliability is required for the recent halogen-free and lead-free compatibility, there is a need to improve the characteristics of metal hydrates.

Therefore, a metal hydrate obtained by sequentially laminating a first layer made of stearic acid and a second layer made of an organic silane coupling agent on the surface of the aluminum hydroxide particles is used as a flame retardant. Thus, a technique for producing a non-halogen flame retardant adhesive composition excellent in flame retardancy, adhesiveness and migration resistance is known (for example, see Patent Document 1).
JP 2005-154512 A

  An object of the present invention is to provide an adhesive composition for a printed wiring board that is excellent in flame retardancy, heat resistance, moisture resistance, and insulation and can be used for the production of a highly reliable printed wiring board. .

  Another object of the present invention is to provide a copper-clad laminate, a cover lay, an adhesive film, and a printed wiring board produced using these using the adhesive composition for printed wiring boards. .

  As a result of intensive research aimed at achieving the above object, the inventors of the present invention have achieved flame retardancy and insulation by using a metal hydrate obtained by treating the adhesive composition with a precursor for forming a glass matrix. The present invention has been completed by finding that the above-mentioned self-sufficiency is achieved by improving properties such as heat resistance, heat resistance and moisture resistance.

  That is, the printed wiring board adhesive composition of the present invention comprises (A) at least one epoxy resin, (B) a curing agent for epoxy resin, (C) a curing accelerator, and (D) a synthetic rubber. , (E) a metal hydrate as an essential component, and (E) the metal hydrate is a metal hydrate obtained by processing with a liquid precursor for forming a glass matrix. is there.

  The flexible copper-clad laminate of the present invention comprises a polyimide film and a copper foil bonded to one or both sides of the polyimide film via the adhesive composition for printed wiring boards of the present invention. To do.

  Moreover, the coverlay of this invention consists of a polyimide film and the resin layer formed in the surface of this polyimide film with the adhesive composition for printed wiring boards of this invention, It is characterized by the above-mentioned.

  Moreover, the adhesive film of this invention forms the adhesive composition for printed wiring boards of this invention in a film form, It is characterized by the above-mentioned.

  The printed wiring board of the present invention is obtained by forming a circuit on the copper foil of the flexible copper-clad laminate of the present invention.

  Another printed wiring board of the present invention is characterized in that the cover lay of the present invention is bonded to the surface of the formed circuit.

  Furthermore, the printed wiring board of the present invention comprises the flexible printed wiring board of the present invention and a reinforcing plate bonded to the surface of the printed wiring board through an adhesive film.

  According to the adhesive composition for a printed wiring board of the present invention, the cured product is excellent in flame retardancy, heat resistance, moisture resistance, and insulation, and thus is used for producing a highly reliable printed wiring board. be able to.

  Moreover, since the flexible copper-clad laminate, the coverlay and the adhesive film of the present invention use the adhesive composition for printed wiring boards of the present invention, they are flame retardant, heat resistant, moisture resistant, and insulating. By using these as components, a printed wiring board having high reliability can be manufactured.

  Furthermore, the printed wiring board of the present invention is excellent in flame retardancy, heat resistance, moisture resistance, and insulation, and has high reliability.

  Hereinafter, the present invention will be described in detail. First, each component of the adhesive composition for printed wiring boards of this invention is demonstrated.

  First, the (A) epoxy resin used in the present invention may be any compound having two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin , Glycidyl ether type epoxy resin, alicyclic epoxy resin, heterocyclic type epoxy resin, modified glycidyl ether type epoxy resin and its bromide epoxy resin, etc., these may be used alone or in combination of two or more. Can do. In addition, flame retardant properties can be imparted without halogen by modifying siloxane and phosphorus compounds.

  As the curing agent for (B) epoxy resin used in the present invention, a curing agent for general epoxy resin can be used. For example, dicyandiamide (DICY) and its derivatives, novolac type phenol resin, amino-modified novolac type Examples include phenol resin, polyvinyl phenol resin, organic acid hydrazide, diaminomaleonitrile and derivatives thereof, melamine and derivatives thereof, amine imide, polyamine salt, molecular sieve, amine, acid anhydride, polyamide, imidazole, and the like. It can be used in combination of more than one species.

  The blending amount of (B) epoxy resin curing agent used in the present invention is preferably in the range of 2 to 50 parts by mass of (B) epoxy resin curing agent with respect to 100 parts by mass of (A) epoxy resin. . At this time, the blending amount of the curing agent for (B) epoxy resin is equivalent to the equivalent ratio of (A) epoxy resin and (B) curing agent for epoxy resin, that is, the epoxy group of the curing agent reacts with the number of epoxy groups. It is particularly preferable that the ratio of the number of functional groups (amine groups, hydroxyl groups, etc.) to be in the range of 0.5 to 1.5.

  Examples of the (C) curing accelerator used in the present invention include tertiary amines, imidazole compounds, aromatic amines, boron trifluoride amine complexes, and triphenylphosphine that are used as curing accelerators for ordinary epoxy resins. It is done. These effect promoters can be used alone or in combination of two or more.

  It is preferable that the compounding quantity of (C) hardening accelerator used for this invention is the range of 0.01-5 mass parts with respect to 100 mass parts of (A) epoxy resins.

  Next, (D) synthetic rubber used in the present invention includes acrylic rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, butadiene methyl acrylate acrylonitrile rubber, butadiene rubber, carboxyl group-containing acrylonitrile butadiene rubber, vinyl group-containing acrylonitrile butadiene rubber, silicone. Examples thereof include rubber, urethane rubber, polyvinyl butyral, and the like. These rubbers can be used alone or in combination of two or more.

  The compounding amount of the (D) synthetic rubber is preferably 10 to 900 parts by mass, more preferably 20 to 150 parts by mass with respect to 100 parts by mass of the (A) epoxy resin. When it exceeds 900 parts by mass, the heat resistance is lowered, and when it is less than 10 parts by mass, the peeling strength is lowered.

  The metal hydrate (E) used in the present invention is obtained by processing with a liquid precursor for forming a glass matrix, and is usually a metal hydrate used as a filler for imparting flame retardancy. Further, it is obtained by coating the surface with a liquid precursor for forming a glass matrix and vitrifying it. That is, what was obtained by the treatment here is one in which the surface of the metal hydrate is coated with a glass film.

  The metal hydrate used here can be used without particular limitation as long as it is usually used as a filler imparting flame retardancy, but its average particle size is 0.5 to 20 μm. It is preferable. As the types of metal hydrates, aluminum hydroxide and magnesium hydroxide are preferable because they are excellent in workability, characteristics, and cost. Moreover, these can be used individually or in combination of 2 or more types.

  Specifically, as the aluminum hydroxide used in the present invention, H-42M (manufactured by Showa Denko KK, trade name; average particle size 1.0 μm), H-32 (manufactured by Showa Denko KK, trade name: average) Examples of the magnesium hydroxide include Kisuma 5 (manufactured by Kyowa Chemical Industry Co., Ltd., trade name; average particle size: 1.0 μm).

  Next, the liquid precursor for glass matrix formation used for this invention is demonstrated. This liquid precursor for forming a glass matrix is converted to inorganic glass by heat treatment, and can be converted to inorganic glass without decomposition of metal hydrate, that is, dehydration during heat treatment. Good.

  Such a liquid precursor for forming a glass matrix can be prepared by using, for example, a sol-gel method well known as a method for forming an inorganic glass.

  For example, a solution obtained by adding silicon alkoxide, water necessary for hydrolysis, and acid or alkali as a catalyst is stirred at room temperature to about 80 ° C. to cause hydrolysis and polymerization to obtain a sol. Further, the gel can be prepared by further proceeding the reaction. The liquid precursor for glass matrix formation obtained by making it gelatinize can be made into inorganic glass by heating.

Examples of the silicon alkoxide used in the sol-gel method include orthosilicate esters or those obtained by chemically polymerizing or modifying them, preferably orthosilicate esters, and more preferably Si (OR) _4. (Wherein R represents an alkyl group having 1 to 4 carbon atoms). Specifically, tetramethyl orthosilicate and tetraethyl orthosilicate are preferably used. Moreover, as an acid as a catalyst, hydrochloric acid, a sulfuric acid, nitric acid, an acetic acid, and other acids can be used, for example.

  Further, instead of such a sol-gel method, a method of preparing a liquid precursor for forming a glass matrix without adding water may be used (hereinafter referred to as a non-aqueous preparation method). As such a non-aqueous preparation method, for example, a mixture containing silicon alkoxide and a volatile organic acid is heated at 100 to 160 ° C. for 20 to 1000 minutes to form a viscous liquid (for glass matrix formation). And a liquid precursor).

  The viscous liquid obtained by such a non-aqueous preparation method solidifies at a relatively low temperature, for example, 200 ° C. or less, thereby forming an inorganic glass without inducing decomposition of the metal hydroxide. Therefore, application to an adhesive composition for printed wiring boards is possible.

Examples of the silicon alkoxide used in such a non-aqueous preparation method include orthosilicate esters or those obtained by chemically polymerizing or modifying them, preferably orthosilicate esters, more preferably An orthosilicate ester represented by Si (OR) ₄ (wherein R represents an alkyl group having 1 to 4 carbon atoms), specifically, tetramethyl orthosilicate and tetraethyl orthosilicate are preferably used.

  The volatile organic acid used in the non-aqueous preparation method is preferably one that gives a liquid when mixed and heated with silicon alkoxide and volatilizes at 200 ° C. or lower. For example, acetic acid, acetic anhydride, formic acid, etc. And preferably acetic acid or acetic anhydride. The volatile organic acid is preferably used in the range of 20 to 150 parts by mass with respect to 100 parts by mass of the silicon alkoxide.

  In the non-aqueous preparation method, it is preferable to use a volatile non-aqueous organic solvent in addition to the silicon alkoxide and the volatile organic acid as described above.

  Volatile non-aqueous organic solvents used with such silicon alkoxides and volatile organic acids are those that do not contain water and can be uniformly mixed with silicon alkoxides and volatile organic acids. For example, those that volatilize at 200 ° C. or lower are preferred, and specific examples include hexane, cyclohexane, benzene, and the like, preferably hexane and cyclohexane.

  Such a volatile non-aqueous organic solvent is preferably used in the range of 100 to 500 parts by mass with respect to 100 parts by mass of the silicon alkoxide.

  As a specific preparation method in the case of using a volatile non-aqueous organic solvent in the non-aqueous preparation method, a mixture comprising a silicon alkoxide and a volatile organic acid is, for example, 100 to 160 ° C., preferably At 120 to 130 ° C., for example, for 10 to 180 minutes, preferably 40 to 80 minutes, after heating to a liquid, a volatile nonaqueous organic solvent is added thereto, for example, 100 to 160 ° C., preferably 120 to 120 ° C. For example, a method for preparing a transparent viscous liquid (a liquid precursor for forming a glass matrix) by heating at 130 ° C. for 10 to 1000 minutes, preferably 200 to 500 minutes can be mentioned. In this case, the addition of the volatile non-aqueous organic solvent may be divided into several times, and the addition and heating may be repeated.

  In addition to the preparation method in which a mixture of silicon alkoxide and volatile organic acid is heated and then heat-treated by adding a volatile non-aqueous organic solvent, for example, silicon alkoxide, volatile organic A liquid obtained by mixing an acid and a volatile non-aqueous organic solvent and allowing to stand for 2 hours to 10 days and then filtering as necessary is, for example, 100 to 160 ° C, preferably 120 to 130 ° C. You may use the preparation method which heats for 20 to 1000 minutes, Preferably it is 100 to 400 minutes, and is set as a transparent viscous liquid (liquid precursor for glass matrix formation).

  In the present invention, the treatment with the liquid precursor for forming the glass matrix is to mix or knead the aluminum hydroxide thus obtained and the metal hydrate, and coat the surface of the metal hydrate with the glass matrix. After that, heat treatment is performed to finally form a metal hydrate covered with inorganic glass.

  The liquid precursor for forming a glass matrix obtained by the above-described non-aqueous preparation method becomes an inorganic glass by solidifying at a relatively low temperature, for example, 200 ° C. or lower. Therefore, in the present invention, the liquid precursor for forming a glass matrix is used. As described above, it is possible to form an inorganic glass without inducing the decomposition of the metal hydrate by using one obtained by such a non-aqueous preparation method. Therefore, heat processing is performed by heating at the temperature of 200 degrees C or less, and it is preferable to heat at the temperature of 100-160 degreeC.

  By using the metal hydrate treated with the liquid precursor for matrix formation of the present invention, the printed wiring board material is excellent in flame retardancy, toughness, heat resistance, etc., compared with those using conventional resin compositions The reliability of the printed wiring board material and the wiring board can be improved.

  The blending amount of this (E) metal hydrate is preferably contained in the resin composition in the range of 1 to 30% by mass, and if it is less than 1% by mass, the flame retardancy decreases and exceeds 30% by mass. In addition, workability, strength and moisture resistance are reduced.

  Furthermore, an inorganic filler can also be blended in the present invention, and the inorganic filler is used as an auxiliary additive for imparting flame retardancy, and is used as an adhesive for a resin composition. It can be added as long as the properties are not impaired. These inorganic fillers include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide and the like, and these can be used alone or in combination of two or more.

  The blending amount of the inorganic filler is preferably 5 to 50 parts by mass and more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the (A) epoxy resin. When the amount exceeds 50 parts by mass, the fluidity of the resin decreases, so that the workability decreases.

  The adhesive composition of the present invention contains an epoxy resin, a curing agent for epoxy resin, a curing accelerator, a synthetic rubber and a metal hydrate as essential components, but as long as it does not contradict the purpose of the present invention and as necessary. In addition, pigments and other flame retardants can be added and blended.

  In addition, the resin composition of the present invention can impart flame retardancy by modifying the resin or the like with an epoxy resin having halogen such as bromo in the resin skeleton or an additive-type bromo compound. Further, by modifying the resin or the like with siloxane and phosphorus compounds, it is possible to impart flame retardancy without halogen.

（但し、式中、Ｘは水素原子あるいはハロゲンを含まない有機基であって、それらが互いに同じでも異なってもよく、ｎは３〜１０の整数を表す。）が挙げられる。ここで、シクロホスファゼンオリゴマーにおけるハロゲンを含まない有機基Ｘとしては、アルコキシ基、フェノキシ基、アミノ基、アリル基等が挙げられる。 In this case, condensed phosphoric acid ester, phosphoric acid ester amide and phosphazene compound are most suitable as the phosphorus compound. For example, the phosphazene compound is substantially free of halogen and has heat resistance, moisture resistance, difficulty. A phosphazene compound having a melting point of 80 ° C. or higher can be preferably used from the viewpoints of flame resistance and chemical resistance. As a specific example, cyclophosphazene oligomer as shown in the following formula

(Wherein, X is an organic group containing no hydrogen atom or halogen, and they may be the same or different, and n represents an integer of 3 to 10). Here, examples of the organic group X containing no halogen in the cyclophosphazene oligomer include an alkoxy group, a phenoxy group, an amino group, and an allyl group.

  The adhesive composition of the present invention described above is diluted with a suitable organic solvent such as propylene glycol monomethyl ether, applied onto the polyimide film, dried by heating, and the copper foil is coated on one side of the polyimide film with a hot roll. Alternatively, a reflexible copper-clad laminate can be produced by an ordinary method of heat-curing after bonding to both sides.

  In addition, the adhesive composition of the present invention can be used to produce a coverlay by a normal method of diluting it with a suitable organic solvent such as propylene glycol monomethyl ether, applying it onto a polyimide film, and drying by heating. it can.

  Furthermore, the adhesive composition of the present invention is produced by diluting it with a suitable organic solvent such as propylene glycol monomethyl ether, applying it on a carrier film, and heating and drying it to produce an adhesive film. Can do.

  Also, a circuit is formed by etching the copper foil of the flexible copper-clad laminate obtained above, and if necessary, drilling through-hole plating is performed, and then the coverlay having holes in predetermined positions is overlaid and heated. A flexible printed wiring board can be manufactured by the usual method of press molding.

  Furthermore, a printed wiring board with a reinforcing plate can be manufactured by a normal method of superimposing a reinforcing plate on the flexible printed wiring board via the film adhesive and heating and pressing. Here, the heating and pressing can be performed in a reduced pressure environment.

  In addition, the halogen-free multilayer printed wiring board is formed by superimposing the flexible copper-clad laminate of the present invention or the glass epoxy copper-clad laminate containing no halogen on the flexible printed wiring board of the present invention via the film adhesive of the present invention. It can be manufactured by an ordinary method of forming a predetermined circuit after heating and pressure forming, forming a through hole, performing through hole plating, and then forming a predetermined circuit.

  In the above description, application to a flexible printed wiring board has been described. However, the adhesive composition for a printed wiring board of the present invention can be applied to a rigid printed wiring board or the like in the same manner as applied to a flexible printed wiring board. It can also be applied to other printed wiring boards.

  Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto.

(Reference Example 1)
[Preparation of Metal Hydrate 1]
After adding 80 parts by mass of liquid tetraethoxysilane (manufactured by Tama Chemical Co., Ltd.) into a glass heating synthesis vessel equipped with a reflux condenser, 100 parts by mass of special grade acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) The solution was added dropwise and heated at 125 ° C. for 1 hour under forced stirring to advance the chemical reaction.
Next, after the reaction product was rapidly cooled to room temperature in a heating synthesis container, 100 parts by mass of hexane was added dropwise and heated at 125 ° C. for 1 hour, and hexane was removed by heating under reduced pressure at the final stage.

  Furthermore, in order to complete the reaction, the reaction product is again cooled to room temperature in a heating and synthesis vessel, and then 100 parts by mass of hexane is added dropwise, heated at 125 ° C. for 1 hour, and hexane is heated and reduced at the final stage. Removed by distillation. Thereafter, the liquid residue was filtered to obtain a colorless and transparent liquid precursor X for forming a glass matrix. Next, to an alumina ball mill installed in a low temperature environment of 5 ° C., 1.0 part by mass of glass matrix-forming liquid precursor X, aluminum hydroxide having an average particle size of 1.0 μm (trade name: manufactured by Showa Denko KK) H-42M) 99 parts by mass and 2 parts by mass of silicone surfactant were added and stirred for 1 hour, then washed with water and dried to obtain treated aluminum hydroxide (metal hydrate 1).

(Reference Example 2)
[Preparation of Metal Hydrate 2]
Alumina ball mill placed in a low temperature environment of 5 ° C., 1.0 parts by weight of liquid precursor X for glass matrix formation obtained in Reference Example 1 and magnesium hydroxide having an average particle size of 1.0 μm (Kyowa Chemical Industry Co., Ltd.) Manufactured, trade name: Kisuma 5) 99 parts by mass and 2 parts by mass of silicone surfactant were added and stirred for 1 hour, then washed with water and dried to obtain treated magnesium hydroxide (metal hydrate 2).

  In addition, the preparation of the liquid precursor X for forming a glass matrix in Synthesis Examples 1 and 2 is as described, and is based on a non-aqueous preparation method.

  Moreover, from the measurement result of the infrared spectrum of the liquid precursor X for forming a glass matrix and the EDX analysis after the heat treatment of the liquid precursor X for forming a glass matrix, the liquid precursor X for forming a glass matrix should form an inorganic glass. Confirmed that it was possible.

Example 1
Carboxyl group-containing acrylonitrile butadiene rubber Nipol 1072 (manufactured by Nippon Zeon Co., Ltd., trade name; nitrile content 27) 300 parts by mass, bisphenol A type epoxy resin epicoat 1001 (manufactured by Japan Epoxy Resin Co., Ltd., trade name: epoxy equivalent 470) 320 masses Parts, siloxane-modified epoxy resin Albiflex 296 (manufactured by Hanse Chemie, trade name: epoxy equivalent 850) 147 parts by mass, phenol novolac resin (manufactured by Showa Polymer Co., Ltd., hydroxyl value 106) 92 parts by mass, phenoxyphosphazene oligomer (melting point 100) ° C) 300 parts by mass, 300 parts by mass of the aluminum hydroxide obtained in Synthesis Example 1 (metal hydrate 1) and 0.5 parts by mass of 2-ether-4-methylimidazole were added as a solvent. Propylene glycol monomethyl ether (PGM) and Methyl ethyl ketone was added to adjust the solid content of 40% by weight of the adhesive composition A.

  This adhesive composition A was applied to a polyimide film Kapton (trade name, manufactured by Toray DuPont Co., Ltd.) with a thickness of 25 μm using a roll coater and dried so that the thickness after drying was 15 μm. The surface and the treated surface of the rolled copper foil (35 μm) were overlapped and pressure-bonded with a laminate roll at 120 ° C., and then treated with an oven at 100 ° C. for 3 hours, 130 ° C. for 3 hours, and 160 ° C. for 3 hours. Was cured to produce a flexible copper clad laminate.

(Example 2)
Carboxyl group-containing acrylonitrile butadiene rubber Nipol 1072 (manufactured by Nippon Zeon Co., Ltd., trade name; nitrile content 27) 400 parts by mass, bisphenol A type epoxy resin Epicoat 1001 (Japan Epoxy Resin Co., Ltd., trade name: epoxy equivalent 470) 274 mass Part, siloxane-modified epoxy resin Albiflex XP544 (manufactured by Hanschemie, trade name: epoxy equivalent 750) 126 parts by mass, phenol novolac resin (manufactured by Showa Polymer Co., Ltd .; hydroxyl value 106), 80 parts by mass, phenoxyphosphazene oligomer (melting point 100 ° C. ) 300 parts by mass, aluminum hydroxide obtained in Synthesis Example 1 (metal hydrate 1) 300 parts by mass and 2-ethyl-4-methylimidazole 2 parts by mass propylene as a solvent Renglycol monomethyl ether (PGM) and methyl ethyl ketone were added to prepare an adhesive composition B having a solid content of 34% by mass.

  This adhesive composition B was applied to a polyimide film Kapton (trade name, manufactured by Toray DuPont Co., Ltd.) having a thickness of 25 μm using a roll coater and dried so that the thickness after drying was 15 μm. The surface and the treated surface of the rolled copper foil (35 μm) were overlapped and pressure-bonded with a laminate roll at 120 ° C., and then treated with an oven at 100 ° C. for 3 hours, 130 ° C. for 3 hours, and 160 ° C. for 3 hours. Was cured to produce a flexible copper clad laminate.

(Example 3)
Carboxyl group-containing acrylonitrile butadiene rubber NIPOL 1072 (manufactured by Nippon Zeon Co., Ltd., trade name; nitrile content 27) 400 parts by mass, bisphenol A type epoxy resin Epicoat 1004 (manufactured by Japan Epoxy Resin Co., Ltd., trade name: epoxy equivalent 925) 274 mass Part, siloxane-modified epoxy resin Albiflex 348 (manufactured by Hanse Chemie, trade name: epoxy equivalent 1150) 126 parts by mass, bisphenol A type novolak resin (manufactured by Dainippon Ink & Chemicals, Inc .; hydroxyl value 118), 47 parts by mass, phenoxyphosphazene oligomer ( (Melting point 100 ° C.) 300 parts by mass, 300 parts by mass of aluminum hydroxide (metal hydrate 1) obtained in Synthesis Example 1 and 2 parts by mass of 2-ethyl-4-methylimidazole were mixed as solvents. Propylene glycol monomethyl ether (PGM) and Methyl ethyl ketone was added to adjust the C adhesive composition solids 34 wt%.

  This adhesive composition C was applied to a polyimide film Kapton (trade name, manufactured by Toray DuPont Co., Ltd.) having a thickness of 25 μm using a roll coater and dried so that the thickness after drying was 15 μm. The surface and the treated surface of the rolled copper foil (35 μm) were overlapped and pressure-bonded with a laminate roll at 120 ° C., and then treated with an oven at 100 ° C. for 3 hours, 130 ° C. for 3 hours, and 160 ° C. for 3 hours. Was cured to produce a flexible copper clad laminate.

Example 4
The adhesive composition B prepared in Example 2 was applied and dried on a 25 μm-thick polyimide film, Kapton (manufactured by Toray Dubon) with a roll coater so that the thickness after drying was 25 μm, and a coverlay was obtained. . The coverlay was placed on the flexible copper-clad laminate obtained by soft etching the copper surface of the flexible copper-clad laminate obtained in Example 1, and heated and pressed at 160 ° C., 4 MPa for 1 hour, A flexible printed wiring board with a coverlay for evaluation was manufactured.

(Example 5)
The adhesive composition C prepared in Example 3 was applied and dried on a polypropylene film having a thickness of 40 μm using a roll coater so that the thickness after drying was 50 μm, thereby obtaining the adhesive film.

  After this adhesive film was pressure-bonded to a 125 μm thick polyimide reinforcing plate with a laminate roll at 120 ° C., the polypropylene film of the carrier film was peeled off, and the copper surface of the flexible copper-clad laminate obtained in Example 1 was soft etched. The film surface was superposed on the flexible copper-clad laminate, and heat-press bonding was performed at 160 ° C. and 0.5 MPa for 15 minutes to obtain a flexible printed wiring board with a reinforcing plate for evaluation.

(Examples 6 to 10)
In Example 1-5, except having replaced the aluminum hydroxide mix | blended in each composition of used adhesive composition AC with the magnesium hydroxide (metal hydrate 2) prepared in the synthesis example 2. By the same operation, a copper-clad laminate, a flexible printed wiring board with a coverlay, and a flexible printed wiring board with a reinforcing plate were produced.

(Comparative Example 1)
A flexible copper clad laminate was prepared in the same manner as in Example 1 except that the aluminum hydroxide used in Example 1 was replaced with untreated aluminum hydroxide (trade name: H-42M, manufactured by Showa Denko KK). Manufactured.

(Comparative Example 2)
A flexible copper clad laminate was prepared in the same manner as in Example 2, except that the aluminum hydroxide used in Example 2 was replaced with untreated aluminum hydroxide (trade name: H-42M, manufactured by Showa Denko KK). Manufactured.

(Comparative Example 3)
A flexible copper clad laminate was prepared in the same manner as in Example 3 except that the aluminum hydroxide used in Example 3 was replaced with untreated aluminum hydroxide (trade name: H-42M, manufactured by Showa Denko KK). Manufactured.

(Comparative Example 4)
The flexible with coverlay for evaluation was performed in the same manner as in Example 4 except that the aluminum hydroxide used in Example 4 was replaced with untreated aluminum hydroxide (trade name: H-42M, manufactured by Showa Denko KK). A substrate was created.

(Comparative Example 5)
Reinforcing plate flexible substrate for evaluation in the same manner as in Example 5 except that the aluminum hydroxide used in Example 5 was replaced with untreated aluminum hydroxide (trade name: H-42M, manufactured by Showa Denko KK). It was created.

(Comparative Examples 6 to 10)
In Examples 6 to 10, the magnesium hydroxide blended in each of the adhesive compositions A to C used was converted into untreated magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., trade name: Kisuma 5). Except for the replacement, a copper clad laminate, a flexible printed wiring board with a coverlay, and a flexible printed wiring board with a reinforcing plate were produced by the same operations as in Examples 6 to 10, respectively.

  The characteristics are evaluated about the copper clad laminated board and printed wiring board which were obtained in Examples 1-10 and Comparative Examples 1-10, and an evaluation result is shown to Tables 1-4.

1: The obtained flexible copper-clad laminate and printed wiring board were measured according to JIS C 6471.
2: Measurement was performed after processing under reflow conditions [peak temperature 240 ° C., preheat temperature 180 ° C., preheat time 90 seconds, reflow temperature 220 ° C., reflow time 40 seconds].
3: About the obtained flexible copper clad laminated board and printed wiring board, the test piece was heated and dried at 100 ° C. for 60 minutes, and then floated in a solder bath at 288 ° C. and 300 ° C. for 10 seconds to examine the presence or absence of swelling.
○: No blistering, Δ: blistering in part, x: blistering in all 4: Measurement was performed on the obtained flexible printed wiring board according to JIS C6471 6.6.
5: About the obtained flexible copper clad laminated board, it measured according to IPC-FC-241.

6: The obtained flexible copper-clad laminate was immersed in a 10% H ₂ SO ₄ aqueous solution at 40 ° C. for 10 hours, and then the discoloration of the substrate surface was confirmed.
○: No discoloration, ×: Discoloration occurrence 7: The obtained flexible copper-clad laminate and flexible printed wiring board were measured according to JIS C 6471 6.6.
8: The obtained flexible copper-clad laminate and printed wiring board were measured according to UL94.
9: Conforms to IPC-TM-650 2.2.1 for the obtained flexible copper-clad laminate.
10: About the obtained flexible copper clad laminated board, 85 degreeC, 85% RH, and DC20V were applied with a 1 mm space | interval comb pattern, and the surface resistance of 500 hours was measured.

  As described above, according to the present invention, there is provided an adhesive composition having excellent adhesiveness, heat resistance, moisture resistance, and insulation, and providing an excellent flexible copper-clad laminate, coverlay, and film adhesive. The Moreover, the printed wiring board excellent in the environmental characteristic can be manufactured by selection of this resin composition.

Claims (11)

(A) At least one kind of epoxy resin, (B) a curing agent for epoxy resin, (C) a curing accelerator, (D) a synthetic rubber, and (E) a metal hydrate are essential components,
(E) The adhesive composition for printed wiring boards, wherein the (E) metal hydrate is a metal hydrate obtained by treatment with a liquid precursor for forming a glass matrix.   The adhesive composition for printed wiring boards according to claim 1, wherein the metal hydrate (E) is blended in an amount of 1 to 30% by mass in the adhesive composition.   The glass matrix-forming liquid precursor is an inorganic glass formed by heat treatment at 200 ° C. or lower, and obtained by heating a liquid containing silicon alkoxide and a volatile organic acid. The adhesive composition for printed wiring boards according to claim 1 or 2.   The adhesive composition for printed wiring boards according to any one of claims 1 to 3, wherein the metal hydrate (E) is aluminum hydroxide or magnesium hydroxide.   A flexible copper comprising: a polyimide film; and a copper foil bonded to one or both sides of the polyimide film via the adhesive composition for printed wiring boards according to any one of claims 1 to 4. Tension laminate.   A cover lay comprising: a polyimide film; and a resin layer formed on the surface of the polyimide film by the adhesive composition for a printed wiring board according to any one of claims 1 to 4.   An adhesive film formed by forming the adhesive composition for printed wiring boards according to any one of claims 1 to 4 into a film shape.   A flexible printed wiring board obtained by forming a circuit on the copper foil of the flexible copper-clad laminate according to claim 5.   The flexible printed wiring board according to claim 8, wherein the coverlay according to claim 6 is bonded to the surface of the formed circuit.   A printed wiring board with a reinforcing plate, comprising: the flexible printed wiring board according to claim 8 or 9; and a reinforcing board bonded to the surface of the flexible printed wiring board through an adhesive film.   The printed wiring board with a reinforcing plate according to claim 10, wherein the adhesive film is the adhesive film according to claim 7.