TW200838960A - Flame retardant adhesive composition, flexible copper clad laminate and coverlay film - Google Patents

Abstract

A flame retardant adhesive composition characterized by containing both an amino-containing phosphoric ester represented by the general formula (1) and a halogen-free epoxy resin: (1) (wherein X1, X2, X3, X4 and X5 may be the same or different and are each hydrogen or alkyl having one to three carbon atoms). This adhesive composition can give flexible copper-clad laminates or cover lay films which are excellent in heat resistance, flame retardance, long-term reliability and so on, and is free from halogen.

Description

200838960 IX. Description of the Invention [Technical Field] The present invention relates to a flame retardant adhesive composition, a soft copper clad laminate, and a cover film. [Prior Art] Conventionally, when an adhesive composition for use in an electronic material such as a semiconductor package material or a glass epoxy-based copper laminate or the like is imparted, a bromine-containing epoxy resin or a flame retardant is blended. Phenoxy resin and the like. However, when a related compound containing a halogen such as bromine is burned, a problem of a harmful gas such as a dioxin-based compound occurs, and in recent years, the material used for the adhesive composition has been evaluated for non-halogenation. On the other hand, soft copper clad laminates which are thinner than glass epoxy-based copper clad laminates and have flexibility are widely used, and various electronic materials are thinned and densified, and soft copper clad laminates are used. The market scale has expanded. The related soft copper-clad laminate refers to a flexible insulating film obtained by thermally curing an adhesive composition by bonding an electrically insulating film such as a polyimide film to a copper foil via an adhesive composition. Copper laminated board. The adhesive composition used for the soft copper-clad laminate was evaluated for non-halogenation in the same manner as the adhesive composition used for the above-mentioned electronic material. Further, the copper foil of the soft copper-clad laminate is processed to form a circuit pattern, and the cover film is used as a material for protecting the circuit pattern. The related cover film is formed on an electrically insulating film such as a polyimide film to form a film in which the adhesive composition is semi-hardened to form an adhesive layer. This cover thin film -6- 200838960 The adhesive composition used for the film is evaluated for non-halogenation in the same manner as the adhesive composition used for the above electronic material. A halogen-free adhesive composition used as an electronic material such as a soft copper-clad laminate or a cover film, comprising an epoxy resin, an aromatic phosphate, a hardener, and a high-purity acrylonitrile butadiene rubber. An adhesive composition (for example, refer to Patent Document 1), an organic compound containing a decane-modified polyamidoximine resin, a polyepoxy compound, a hardener, an elastomer, a phosphazene compound, or a phosphate compound. An adhesive composition of a phosphorus compound and an inorganic chelating agent (for example, refer to Patent Document 2), an adhesive composition containing an epoxy resin, an elastomer, a guanamine-based flame retardant, and an inorganic chelating agent (for example, a reference patent) Literature 3). These adhesive compositions are such that no harmful gas such as a dioxin-based compound is generated during combustion, and a soft copper-clad laminate or a cover film excellent in heat resistance or flame retardancy can be produced. [Patent Document 1] JP-A-20001 - No. 2005-A No. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, in any of the adhesive compositions of Patent Documents 1 to 3, since a non-reactive phosphorus compound is used as a flame retardant, a related adhesive composition is used. Soft copper-clad laminate, the non-reactive phosphorus compound gradually moves at the interface of the layer (adhesive layer) where the relevant adhesive composition is -7-200838960, the adhesive layer and the electrically insulating film and copper foil The adhesion is reduced. Further, by using the relevant adhesive composition, a cover film is produced, and the interface of the layer (adhesive layer) in which the related adhesive composition is semi-hardened is similarly, and the non-reactive phosphorus compound gradually moves, and the adhesive layer is formed. The adhesion to the electrically insulating film is lowered. This result is related to the problem that the related soft copper-clad laminate and the cover film have a long-term reliability reduction. In order to solve the problem as described above, the present invention has been made to provide a flame-retardant non-flammable adhesive composition which is excellent in heat resistance, flame retardancy and long-term reliability. . Further, the present invention has an object of providing a soft copper-clad laminate or a cover film which is excellent in heat resistance, flame retardancy and long-term reliability. Solution to the problem The present invention contains the general formula (丨): [Chemical 1]

(In the formula, χΐ, X2, χ3, χ4, and χ5 may be the same or different, hydrogen atom or alkyl group having 1 to 3 carbon atoms), and the amine group-containing phosphate compound, -8-200838960 and A halogen-based epoxy resin is a composition of a flame retardant adhesive characterized by a flame retardant. Further, the present invention provides an electrically insulating film, a flame-retardant adhesive layer formed on the electrically insulating film, and a soft copper-clad laminate of a copper foil formed on the flame-retardant adhesive layer. The flame-retardant adhesive layer is a soft copper-clad laminate characterized by a layer obtained by hardening the flame-retardant adhesive composition. Further, the present invention provides an electrically insulating film and a cover film of a flame-retardant adhesive layer formed on the electrically insulating film, wherein the flame-retardant adhesive layer is such that the flame-retardant adhesive composition is half The hardened layer is a characteristic cover film. According to the present invention, it is possible to provide a halogen-free flame-retardant adhesive composition which imparts excellent heat-resistant, flame-retardant and long-term reliability, and the like. Further, according to the present invention, it is possible to provide a soft copper-clad laminate or a cover film which is excellent in heat resistance, flame retardancy and long-term reliability. The best mode for carrying out the invention <flammable adhesive composition> The flame retardant adhesive composition of the present invention contains an amine group-containing phosphate compound represented by a predetermined general formula, and Halogen epoxy resin. 1. Amino group-containing phosphate compound The amine group-containing phosphate compound of the present invention is based on the following general formula (-9-200838960 [Chemical 2]

(1) Subunit or alkyl group having 1 to 3 carbon atoms). The method for producing an amine group-containing phosphate ester represented by the general formula (1) has no limitation, and can be based on, for example, j 〇urna 1 〇f P 01 ymer Science Part A » Polymer Chemistry Vol. , No. 3 p. 5 65 - 5 74 (1 997), manufactured by a conventionally known method described. In the related art, a method of reacting an aminophenol compound represented by a general formula and a dichlorophosphoric acid compound represented by a general formula in the presence of an inorganic basic compound in an aprotic organic solvent It can be easily prepared by a one-stage reaction, so it is suitable in terms of production efficiency and cost. The aminophenol compound which can be used in the present invention is as shown in the following general formula (3). [Chemical 3]

(3) Examples of the aminophenol compound include o-aminophenol, m-aminophenol, and p-aminophenol. Further, the aminophenol compound may have a substituent such as an alkyl group and an alkoxy-10-200838960 group. The dichlorophosphoric acid compound which can be used in the present invention is represented by the following general formula (4). [Chemical 4]

Ο II ci—P—ci 〇

In the above formula, X1, X2, X3, X4 and X5 may be the same or different, hydrogen atom or a hospital group having a carbon number of 1 to 3.

Examples of such a dichlorophosphoric acid compound include phenyl dichlorophosphoric acid, 2-methylphenyl dichlorophosphoric acid, 4-methylphenyl dichlorophosphoric acid, and 2,6-dimethylphenyl dichlorophosphoric acid. 2,4,6-trimethylphenyldichlorophosphoric acid, 4-ethylphenyldichlorophosphoric acid, 4-propylphenyldichlorophosphoric acid, and the like. The ratio of the aminophenol compound to the dichlorophosphoric acid compound is preferably from 1 to 0 to 3.0 equivalents, more preferably from 1.1 to 1.6 equivalents, per mole of the chlorine atom of the dichlorophosphoric acid compound. If the aminophenol compound is less than 1.0 equivalent, the desired yield of the amine group-containing phosphate compound cannot be obtained, and if it exceeds 3.0 equivalents, the amount of the unreacted aminophenol compound is too large, which is not economical. The inorganic basic compound which can be used in the present invention may, for example, be a hydroxide such as sodium hydroxide or potassium hydroxide or a carbonate. Among these, -11 - 200838960 alkali metal carbonates such as sodium carbonate and potassium carbonate are suitable because they increase the selectivity of the reaction and reduce the amount of side reaction products. The amount of the inorganic basic compound to be used is preferably 1.0 to 4.0 equivalents per 1 equivalent of the chlorine atom of the dichlorophosphoric acid compound, and particularly preferably 1 to 1 to 3.0. When the amount of the inorganic basic compound used is less than 1. 〇 equivalent, the chloride ion generated in the reaction cannot be sufficiently captured, and the reaction is acid-based, and the reaction rate is lowered. On the other hand, when the amount of the inorganic basic compound used exceeds 4.0 equivalents, the excess inorganic basic compound is excessive, which is not economically advantageous. The aprotic organic solvent which can be used in the present invention may, for example, be an aromatic system such as benzene, toluene or xylene, diethyl ether, diisopropyl ether, dibutyl ether 'tetrahydrofuran and diethylene glycol dimethicone. An ether such as ether; a nitrile such as acetonitrile. Among these, the acetonitrile-based aminophenol compound and the dichlorophosphoric acid compound are excellent in solubility, and therefore are suitable. The amount of the aprotic organic solvent to be used is such that the amount of the aminophenol compound and the dichlorophosphoric acid compound can be dissolved, and is not particularly limited. In the method for producing an amine group-containing phosphate compound, the order of addition of the above components is not particularly limited, but the side reaction is suppressed, and the yield of the amine group-containing phosphate compound is improved. In the dissolved aprotic organic solvent, after dissolving or dispersing the inorganic basic compound, it is preferred to slowly add the dichlorophosphoric acid compound. The reaction temperature is changed depending on the type of the aprotic organic solvent used, etc., but it is usually preferably from 40 to 100 °C. The reaction temperature is less than 40. (: When the desired reaction rate is not obtained, and if it exceeds 1 〇〇 ° C, the product is increased by the side reaction -12-200838960. The reaction time varies depending on the amount of the above components, etc. ^ 0.5~1 0小时 is preferred. If the reaction time is less than 0.5 hours, the reaction of the amine sulfonium compound with the dichlorophosphoric acid compound is not sufficient. On the other hand, if the reaction time between the temples exceeds 1 〇, a side reaction occurs. The desired yield cannot be obtained and is not economical. After the reaction is completed, the amine group-containing phosphate compound can be isolated from the reactant by a known method such as filtration and washing. Specifically, by filtration reaction And removing impurities such as a catalyst and a salt generated from the reactants. Then, after concentrating the filtrate under reduced pressure, a large amount of water is added to the filtrate to precipitate a solid matter. Then, sodium hydroxide, potassium hydroxide, and carbonic acid are added. An inorganic base such as sodium or potassium carbonate is sufficiently stirred to dissolve the unreacted aminophenol contained in the solid matter in water. Then, after filtering the solid matter, the solid matter is washed with water or the like, thereby Dry and available Amino-based phosphate compound. The related amino group-containing phosphate compound does not have a halogen atom in the molecule, and does not occur in the case of burning during processing and after burning, so it can be used as a flame retardant. In the amine group-containing phosphate compound represented by the above general formula (1), the amine group-containing phosphate compound represented by the following general formula (2) has excellent flame retardancy, so that it has excellent flame retardancy. Effectively used as a flame retardant. -13- 200838960 [化5]

X3 In the above general formula (2), X1, X2, X3, X4 and X5 may be the same or different, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Further, among the amine group-containing phosphate compounds represented by the above formula (2), the compound represented by the following chemical formula (I) is particularly suitable as a flame retardant because it has excellent flame retardancy. Further, since the compound represented by the following chemical formula (Π) is excellent in hydrolysis resistance in addition to the above characteristics, it is more suitable as a flame retardant for electronic materials.

[Chemical 6]

-14- 1 200838960 [化7]

(Π) 2 • Non-halogen epoxy resin The non-foam epoxy resin is an epoxy resin which does not contain a halogen atom such as bromine in the molecule. The non-halogen-based epoxy resin is not particularly limited as long as it has at least two or more epoxy groups per molecule. Further, the related non-halogen epoxy resin may have, for example, a polyoxyalkylene skeleton, an urethane backbone, a polyimine skeleton, a polyamine skeleton, or the like, and may further contain a phosphorus atom or a sulfur atom. Nitrogen atom, etc. Examples of the non-halogen-based epoxy resin include a bisphenol fluorene epoxy resin, a bisphenol F epoxy resin, a bisphenol s type epoxy resin, a hydrogenated bisphenol A epoxy resin, and a phenol resin epoxy resin. Resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, bisphenol aralkyl type epoxy resin, naphthalene type epoxy resin, naphthalene aralkyl type epoxy resin, and triphenylformamidine type ring Oxygen resin % glycidyl ether type epoxy resin; hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, triglycidyl isocyanate, and tetraglycidyl diaminodiphenylmethane A glycidylamine-based epoxy resin, a chain-like aliphatic epoxy resin such as epoxidized polybutadiene or epoxidized soybean oil. -15- 200838960 Further, among the above various epoxy resins, various phosphorus-containing epoxy resins which react with a reactive phosphorus compound to bond phosphorus atoms may be used as the non-halogen epoxy resin. Specifically, (A) at least one selected from the above various epoxy resins, and (B) selected from the formula (a) or (b): [Chem. 8]

(wherein, R1, R2, R3 and R4 are each independently, and are a k-group of carbon number 丨~6 or a substituted or unsubstituted aryl group, and η and m are respectively an integer of 〇~4' 〇 and p-system The phosphorus-containing epoxy resin obtained by reacting the compound represented by the compound represented by the integer of 〇5 and the reaction product of the present invention or naphthoquinone can be used as the non-halogen epoxy resin. As the compound represented by the above formula (a), for example, 9, quinone-dihydro 9 oxy-10 phenanthroline-10 oxide (9,10-Dihydro-9-oxa 1 〇-pho sphaphenanthrene-1) 0-oxide) (Sanko (share) system 'trade name: HCA) and so on. Further, examples of the compound represented by the above formula (M) include diphenylphosphine oxide, bis(2-methylphenyl)phosphine oxide, bis(2,5-dimethylphenyl)phosphine oxide, and bis ( 2,4,6-trimethylphenyl)phosphine oxide, etc. -16- 200838960 In addition, the above-mentioned phosphorus-containing epoxy resin is also commercially available under the trade name of FX-3 05 (made by Tohto Kasei Co., Ltd.). The non-halogen type epoxy resin may be used alone or in combination of two or more. The flame retardant adhesive composition of the present invention may further contain an amine group-containing phosphate compound in addition to the above components. Other components such as a diamine compound, a hardening accelerator, a thermoplastic resin, a synthetic rubber, an inorganic chelating agent, and an organic solvent. 3. Other components (3 - 1 ) A diamine compound other than an amine group-containing phosphate compound The flame retardant adhesive composition of the present invention may contain a diamine compound other than the amine group-containing phosphate compound from the viewpoint of adjusting the physical properties of the cured product. As the diamine compound which can be used in the present invention, for example, six extensions are mentioned. Methyldiamine, trimethylhexidine Diamine, 2-dimethyl pentamethylamine, m-xylenediamine, isophoronediamine, bis(4-aminocyclohexyl)methane, diaminodiphenylmethane and diamine The diamine compound may be used alone or in combination of two or more. The compounding amount of the related diamine compound is not particularly limited as long as it does not impair the range of flame retardancy. Generally, it is preferable that the phosphorus content in the non-volatile organic component in the flame retardant adhesive composition is in the range of 0.5 to 4.0% by mass. If the phosphorus content is less than 5% by mass, it may not be sufficient. When the amount is more than 4.0% by mass, the physical properties such as adhesion are lowered. When the related diamine compound is blended, the related diamine compound and the amine group-containing -17-200838960 phosphate are obtained. The ratio of the ratio of the compound to the epoxy resin (amino group) / (epoxy group) is preferably 〇 25 to 0.75, more preferably 0.40 to 0.60. The relevant equivalent ratio is less than 0 · 2 5 or When it exceeds 〇·75, the crosslink density of the cured product becomes low, and the mechanical strength decreases. (3-2) hardening accelerator The flame retardant adhesive composition of the present invention promotes crosslinking reaction of an amine group-containing phosphate compound and any of the above diamine compound amine groups and non-halogen epoxy resins The curing accelerator which may be used in the present invention may, for example, be an organic acid such as salicylic acid, benzoic acid, phthalic acid, isophthalic acid, benzenesulfonic acid or p-toluenesulfonic acid. Or a Lewis acid such as boron trifluoride monomethylamine or a boron trifluoride piperidine or the like. These may be used singly or in combination. Further, in addition to the above, an imidazole compound or an aliphatic tertiary amine compound may be used. A hardening accelerator for a general epoxy resin, etc. The amount of the hardening accelerator to be used is not particularly limited as long as it does not impair the characteristics of the flame retardant adhesive composition of the present invention, but is generally relative to the total. 1 part by mass of the amine group-containing phosphate compound, the above-mentioned diamine compound amine group, and the non-halogen type epoxy resin are preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass. If the amount of the relevant hardening accelerator is less than 1 part by mass, the effect obtained by blending the hardening accelerator may not be sufficiently obtained. On the other hand, when the amount of the relevant hardening accelerator is more than 5 parts by mass, the required usable time cannot be obtained (p〇t Life) ° (3 - 3) thermoplastic resin·synthetic rubber-18-200838960 The flame retardant adhesive composition may contain a resin or a synthetic rubber from the viewpoint of imparting appropriate fluidity (flow characteristics). By using the flame retardant adhesive composition of the present invention to make the relevant adhesive composition's production characteristics, when the copper laminate is used, the copper foil portion of the circuit can be formed (the circuit gap is adhered) and the poly-Asian Adhesiveness of electric or copper foil such as amine. As the thermoplastic resin which can be used in the present invention, various known thermoplastic resins can be used. Examples of the phase resin include polyester resin, acrylic resin, and benzoquinone. Amine amide resin, etc. As such a thermoplastic resin "YP" series or "ERF" series (made by Tosei Chemicals Co., Ltd., phenoxy EPIKOTE 1 256" (made by Japan Epoxy Resins, benzene. VYLOMAX) is 歹ij (Toyo Textile Co., Ltd. , Polyamide 醯 鹿 KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA KA Series (Toyo Textile Co., Ltd., a polyester resin containing a carboxyl group), a co-pharmaceutical product, an acrylic resin containing a carboxyl group, and an acryl resin name containing a carboxyl group, manufactured by SG-Nagasechemtex Co., Ltd. Further, the above-mentioned resins may be used singly or in combination. As the synthetic rubber which can be used in the present invention, various known synthetic rubbers are not particularly used, and as a related synthetic composition, thermoplasticity is suitable for the flow. For the soft-patterned type, there is no special limit for the heat-moulding oxygen resin, poly, for example, resin, "oxygen resin", "^ resin", "amine resin", etc. VYLON, AW-5 (-708-6T ( ), etc., other restrictions, rubber, can be -19- 200838960 For example, carboxyl-containing acrylonitrile-butadiene rubber (hereinafter referred to as "acrylic rubber" is "NBR ") or hydrogenated NBR. Such a carboxyl group is commercially available under the trade names of Nipoll072 (manufactured by Nippon Scientific Co., Ltd.), PNR-1 (Iron manufactured by JSR), and Zetpol (JJ). The blending amount of the thermoplastic resin/synthetic rubber and the range of the characteristics of the flame-retardant adhesive composition of the present invention may be otherly limited, but generally, the total amount of the amine-containing ester compound is 10,000 parts by mass or more. The diamine compound amine group and the non-halogen resin are preferably used in an amount of from 0 to 500 parts by mass, and if the amount of the compound of 20 to 30 0 is more than 500 parts by mass, the properties are not obtained. (3 - 4 ) Inorganic sputum agent The flame retardant adhesive composition of the present invention may contain an inorganic chelating agent as appropriate. The inorganic hydrating agent which can be used in the present invention is used as long as it is a laminate or a cover film. The aluminum oxide, the cerium hydroxide, the molybdenum oxide or the like is preferably used as a flame retardant auxiliary, and aluminum hydroxide aluminum hydroxide is particularly preferred. These inorganic chelating agents may be used alone or in combination of two. The amount of the relevant inorganic chelating agent is not limited to the range of the characteristics of the composition of the present adhesive, and the acrylonitrile is composed of a flame retardant adhesive in combination with a total of 100 parts by mass. - Dingse's NBR is a pure tube. As long as it is not damaged, it is especially preferred if there is no special phosphate. A flame retardant viscous soft copper paste is required. Among them, magnesium, dioxane and hydroxide are more difficult to burn, but one of them has -20-200838960 solid content, preferably 0~100 mass parts, preferably 5~30 mass parts. . If the relevant compounding amount exceeds 100 parts by mass, the desired adhesiveness cannot be obtained. Further, the "organic solid component" means a non-volatile organic component in the flame retardant adhesive composition of the present invention, and when the flame retardant adhesive composition contains an organic solvent, the organic solvent is not contained in the organic solid component. (3 - 5) Organic solvent The flame retardant adhesive composition of the present invention may contain an organic solvent from the viewpoint of adjusting the flow characteristics of the flame retardant adhesive composition. The organic solvent which can be used in the present invention is not particularly limited, and various known organic solvents can be used. The related organic solvent may, for example, be N,N-dimethylacetamide, methyl ethyl ketone, n,N-dimethylformamide, cyclohexanone or N-methyl-2-pyrrolidine. Ketone, toluene, methanol, ethanol, isopropanol, acetone, dioxolane and the like. These organic solvents may be used alone or in combination of two or more. The compounding amount of the relevant organic solvent is generally 1 to 50% by mass, and preferably 20 to 40% by mass, based on the total concentration of the organic solid component and the inorganic solid component in the flame retardant adhesive composition. When the total concentration of the organic solid component and the inorganic solid component in the composition of the flame retardant adhesive is from 1 to 50% by mass, when a soft copper-clad laminate and a cover film are produced, a substrate such as an electrically insulating film is used. The coating property is good, the workability is excellent, and unevenness does not occur during coating. The results are excellent in terms of environmental and economic aspects. Further, the "inorganic solid component" means a nonvolatile inorganic solid component contained in the adhesive composition of the present invention - 21 - 200838960. The flame retardant adhesive composition of the present invention can be produced by mixing the above components. As a related mixing method, a ball mill, a ball mill, a homogenizer, a super mill, or the like can be used. Further, the order of the above components is not particularly limited. The flame-retardant adhesive composition of the present invention thus produced can be used for a soft copper-clad laminate, a cover film, an adhesive layer of an adhesive sheet, or the like for use in the manufacture of a flexible printed circuit board. <Soft copper-clad laminate> The soft copper-clad laminate of the present invention can be produced by using the above-mentioned flammable adhesive composition. The soft copper-clad laminate is provided with an electrically insulating film, a flame-retardant adhesive layer formed on the electrically insulating film, and a copper foil formed on the flame-retardant adhesive layer. The flammable adhesive layer is characterized by a layer obtained by hardening the above-mentioned flame retardant adhesive composition. The electrically insulating film s which can be used in the soft copper-clad laminate of the present invention is not particularly limited as long as it is a user of a soft copper-clad laminate or a cover film. The related electrically insulating film may, for example, be a polyimide film; polyethylene terephthalate; a polyester film; a polyparabanic acid film; a polyether ether ketone film; a thioether film; an aromatic polyamine (Aramid) film; and a substrate made of glass fiber, aromatic polyamide fiber or polyester fiber, such as epoxy resin, polyester resin or benzene impregnated into a base block Diallyl dicarboxylate resin (Diallyl -22- 200838960

Phthalate Resin) ‘Become a film or a sheet. Among these, polyiminoimide is preferred from the viewpoints of heat resistance, dimensional stability, and mechanical properties. The thickness of the relevant electrically insulating film can be appropriately adjusted depending on the application, but is generally 12.5 to 50/m. The copper foil which can be used in the soft copper-clad laminate of the present invention is not particularly limited as long as it is a user of the soft copper-clad laminate, and a rolled or electrolytic copper foil product can be directly used. Further, the thickness of the copper foil can be appropriately adjusted depending on the application, but it is usually 5 to 70/zm. The soft copper clad laminate of the present invention can be produced by a conventionally known method in addition to the above materials. Specifically, first, the flame retardant adhesive composition is applied onto an electrically insulating film, and then heated to cause the flame retardant adhesive composition to be semi-hardened. Here, the coating method of the flame retardant adhesive composition is not particularly limited, and it can be applied by a known means such as a reverse roll coater or a comma coater. In addition, the heating condition for making the flame-retardant adhesive composition semi-hardened may be appropriately set in accordance with the composition of the flame-retardant adhesive composition, but for example, a flame retardant adhesive composition may be applied. The electrically insulating film can be heated at 80 to 160 ° C for 2 to 10 minutes by an inline dryer or the like. Next, on the flammable adhesive composition in a semi-hardened state, the copper foil is thermally laminated (hot pressed), and post-baking (Postcure) is used to completely harden the hard-flammable adhesive composition in a semi-hardened state. , a soft copper laminate can be obtained. Here, the pressurization and pressing conditions at the time of thermal lamination may be appropriately set in accordance with the flame retardant composition of the flame retardant -23-200838960, but for example, a line pressure of 〇·5 to 5 kg/cm is used for 1 0 0 The temperature of ~1 50 °C can be hot pressed. Further, the heating condition at the time of post-baking may be appropriately set in accordance with the composition of the flame-retardant adhesive, but for example, it may be heated at a temperature of 60 to 200 ° C for 5 to 5 hours. * In the soft copper-clad laminate thus produced, the thickness of the layer obtained by hardening the flame-retardant adhesive composition is generally 5 to 45 /zm, preferably 5 to 18 // m. <Cover film> - The cover film of the present invention can be produced by using the above-mentioned flame retardant adhesive composition. The cover film is provided with an electrically insulating film and a flame-retardant adhesive layer formed on the electrically insulating film, and the flame-retardant adhesive layer semi-hardens the flame-retardant adhesive composition described above. The layer is characterized. The electrically insulating film φ which can be used as the cover film of the present invention is the same as the electrically insulating film which can be used for the above-mentioned soft copper-clad laminate. Among them, in view of improving the adhesion, it is preferable to use an electrically insulating film which has been treated with a low temperature plasma. In particular, from the viewpoints of heat resistance, dimensional stability, mechanical properties and the like, polyethylenimine treated with low temperature plasma is preferred. The cover film of the present invention can be produced by a conventionally known method, in addition to the above materials. Specifically, the coating of the flame retardant adhesive composition is semi-hardened by heating the above-mentioned flame retardant adhesive composition on the electrically insulating film, and a cover film can be obtained. Here, the coating method of the composition of the flame retardant adhesive-24-200838960 is not particularly limited, and it can be applied by a known means such as a reverse roll coater or a comma-shaped blade coater. In addition, the heating condition for making the flame-retardant adhesive composition semi-hardened may be appropriately set in accordance with the composition of the flame-retardant adhesive composition, but for example, a flame retardant adhesive composition may be applied. The electrically insulating film can be heated by a tandem dryer or the like at 80 to 160 ° C for 2 to 10 minutes. In the cover film thus produced, the thickness of the layer obtained by semi-hardening the flame-retardant adhesive composition is generally 5 to 45 / / m, preferably 5 to 18 / / m. Further, the cover film may be formed by laminating a protective layer on the flame-retardant adhesive layer from the viewpoint of handling properties and the like. Further, in this case, when used as a cover film, the release-related protective layer may be used. The protective layer which can be used in the cover film of the present invention is not particularly limited as long as it does not impair the form of the flame-retardant adhesive layer. Examples of the protective layer include a polyethylene (PE) film, a polypropylene (PP) film, a polymethylpentene (TPX) film, a polyester film, a plastic film, a coated PE film, and a PP film. The olefin film and the TPX film are equal to one or both sides of the paper material. When the protective layer is laminated to the flame-retardant resin layer, the protective layer may be laminated and pressed against the semi-hardened flame-retardant adhesive composition. Here, the pressing condition is not particularly limited, and for example, it may be pressed by a wire of 0.5 to 5 kg/cm. [Embodiment] -25-200838960 EXAMPLES Hereinafter, the present invention will be described in more detail by using examples, but the present invention is not limited by the examples. Further, the evaluation of the properties of the soft copper-clad laminates produced in the examples and the comparative examples was carried out by the following measurement. (1) Peel strength The peel strength was measured in accordance with JIS C648 1 "Test Method for Copper-clad Laminates for Printed Circuit Boards". Specifically, after forming a circuit having a pattern width of 1 mm on the soft copper-clad laminate, the copper foil (circuit) is faced to the laminate under the condition of 251:, and is measured at a direction of 90 degrees at 50 mm/min. The minimum strength required for speed stripping is expressed as peel strength. (2) Solder heat resistance The solder heat resistance is carried out in accordance with JIS C648 1 "Test method for copper-clad laminates for printed circuit boards". Specifically, a test piece was prepared by cutting a soft copper-clad laminate into 25 mm squares, and the test piece was floated on a welding bath of 28 8 t: 30 seconds, and the test piece taken out from the welding bath was Visual inspection confirmed the presence or absence of swelling, peeling, and discoloration. In the relevant tests, those without swelling, peeling, and discoloration are indicated by ,, and those of swelling, peeling, and discoloration are indicated by X. (3) Flame retardancy The soft copper-clad laminate was etched and the copper foil was completely removed to prepare a sample for evaluation of flame retardancy. Next, the flame retardancy of the sample was measured in accordance with the UL94 VTM-0 flame retardant specification. When the relevant sample shows that the flame retardancy of the U L 9 4 V T Μ — 0 specification is satisfied, it is represented by 〇, and when it is burned, it is represented by X. -26- 200838960 [Synthesis of 2,6-dimethylphenyldichlorophosphoric acid] Add 107.7 g (〇.882 mol) of 2,6-dimethylphenol, 80.7 ml (〇·8 84 mol) of phosphorus oxychloride 1.5 g of anhydrous calcium chloride was placed in a 4-necked flask equipped with a stirring device, a dry nitrogen introduction tube, a thermometer, a titration funnel, and a condenser to make the inside of the 4-neck flask a dry nitrogen atmosphere. The mixture was heated under reflux for 15 hours, and the obtained reaction product was distilled under reduced pressure to give 1 1 9.4 g (yield: 56.7%) of 2,6-dimethylphenyldichlorophosphoric acid. [Preparation of an amine group-containing phosphate compound] (Synthesis Example 1: Preparation of bis(4-aminophenyl)phenyl phosphate (4-APP)) 197 g (1.42 mol) of p-nitrophenol, 135 g of anhydrous Pyridine and 301 g of anhydrous acetonitrile were placed in a four-necked flask equipped with a stirring apparatus, a dry nitrogen introduction tube, a thermometer, a titration funnel, and a condenser, and the inside of the four-necked flask was a dry nitrogen atmosphere. Next, 150 g (0.7 10 mol) of phenyldichlorophosphoric acid was slowly added dropwise to the contents under vigorous stirring in the flask, and the mixture was heated under reflux for 1 hour. Next, the reaction solution was cooled to room temperature, and then slowly added to 3 L of cold water to precipitate crystals. The obtained crystals were filtered, washed with water, and dried at 90 ° C for 24 hours to obtain 281 g (y.68 mol) of bis(4-aminophenyl)phenyl phosphate (yield 95%). ). Next, 250 g (0.60 mol) of bis(4-aminophenyl)phenyl phosphate, 624 g of dioxane, 50 g of Raney nickel catalyst (Ni-Al alloy) and 70 g of the solution were added. The second B is smothered with the autoclave of the mixing machine -27-200838960. Subsequently, the hydrogenation reaction was carried out at 50 ° C and a pressure of 80 kg / cm 2 for 5 hours. After the hydrogen consumption was stopped and the reaction was further carried out for 2 hours, excess hydrogen was discharged from the autoclave. After filtering the reaction mixture, it was concentrated, and 3 L of a saturated aqueous sodium carbonate solution was added. Next, the precipitated solid matter was filtered, and then washed with water. Next, the relevant solid matter was dried at 901: for 24 hours to obtain 181 g of 4-APP (the yield was 85%) represented by the above formula (I). (Synthesis Example 2: Preparation 4 - APP) Adding 1 6 5 g (1 · 6 6 m ο 1 ) of anhydrous calcium carbonate, and 700 g of dehydrated acetonitrile and l lg (〇.926 mol) The mixture of aminophenols was placed in a four-necked flask equipped with a stirring device, a dry nitrogen introduction tube, a thermometer, a titration funnel, and a condenser, and the inside of the four-necked flask was in a dry nitrogen atmosphere. After stirring, the temperature was raised to 60 ° C to 5 ° C, and a mixture of 65.18 (0.309111〇1) of phenyldichlorophosphoric acid and 60 g of dehydrated and treated acetonitrile was slowly added dropwise to the contents. After the completion of the dropwise addition, the mixture was further heated under reflux for 1 hour, and then the reaction mixture was cooled to room temperature. The resulting salt and potassium carbonate were removed by filtration and washed with 50 ml of acetonitrile. After the resulting filtrate was concentrated under reduced pressure, about 600 ml of water was added. Next, about 600 ml of a 5% potassium carbonate aqueous solution was added, and after stirring for 30 minutes, the precipitated solid matter was filtered, washed with water carefully, and the solid matter was dried. The obtained solid matter was recrystallized using methanol to obtain 66.6 g of 4-APP (yield: 65%) of the above formula (I). (Synthesis Example 3: Preparation of bis(4-aminophenyl)-2,6-dimethylphenyl phosphate (4-ADMP)) -28- 200838960 Add 38.4 g (0.386 mol) of anhydrous potassium carbonate, 30.3 g (0.27 8 mol) of p-aminophenol, and 100 ml (78 g) of dehydrated acetonitrile, and the contents were stirred, and the temperature was raised to 7 5 to 80 ° C, and then 16.6 g (0.069 mol) of 2 was slowly dropped. 6-Dimethylphenyl dichlorophosphoric acid in the contents. After completion of the dropwise addition, the mixture was further heated under reflux for 2 hours, and then the reaction mixture was cooled to room temperature. The resulting salt and potassium carbonate were removed by filtration and washed with 50 ml of acetonitrile. After the resulting filtrate was concentrated under reduced pressure, about 600 ml of water was added. The precipitated solid matter was filtered, added to a 5% aqueous sodium hydroxide solution, and stirred for 30 minutes. Thereafter, the solid matter was filtered, washed with water, and dried. The obtained solid matter was recrystallized twice with toluene to obtain 7.0 g of 4-ADMP (yield: 26%) of the above formula (II). [Examples 1 to 3] The components of the flame retardant adhesive were prepared by mixing the components in the mixing ratio shown in Table 1. The flame retardant adhesive composition thus obtained was applied to a polyimide film A (trade name: KAPTON®, manufactured by DU PONT-TORAY, thickness: 25 #m), and coated with an appiicator. After the thickness of the later flame-retardant adhesive layer is 1 〇# m, it is dried in a blowing oven at 120 ° C for 10 minutes to make the flame-retardant adhesive layer semi-hardened. Then, the laminated copper foil (manufactured by Japan Energy, trade name: BHY22BT 'thickness: 35/zm) was laminated on the flame-retardant adhesive layer formed on the semi-cured polyimide film A, and then used. Roller laminator, hot pressed at 1 2 0 C 'line pressure 2 kg / cm. Thereafter, at 80 ° C for 1 hour, 270-200838960 was used for 1 60 ° C, and baked for 4 hours to prepare a soft copper-clad laminate. [Comparative Examples 1 to 2] Adhesive compositions were prepared by mixing the components in the mixing ratios shown in Table 1. Using the adhesive composition thus obtained, a soft copper-clad laminate was produced in the same manner as in Examples 1 to 3. The evaluation of the binding characteristics of the soft copper-clad laminates obtained in the above Examples 1 to 3 and Comparative Examples 1 and 2 was carried out. The results are shown in Table 1.

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[I漱] Comparative Example 2 /^-N 00 :un —d —ο ^ d 20.0 (0.041) 1 1 /*->\ Bu Bu 14.4 Ό 〇35.0 1 20.0 280 1.90 〇〇X 〇Comparative Example 1 17.5 (0.088) 17.5 (0.092) 20.0 (0.041) 1 1 10.0 (0.101) 1 vo 〇35.0 1 20.0 280 0.60 <Ν Τ·*Η 〇X Example 3 15.0 (0.075) ο ^ d 18.0 : (0.037) !1 ( ( ( ( ( ( Ο) 1—^ 〇〇 Example 1 15.0 (0.075) 15.0 (0.079) 20.0 (0.041) 15.0 (0.084) 1 ' 1 1 v〇〇| 35.0 I 20.0 280 1.91 (Ν 〇〇 cresol novolac epoxy resin υ (epoxy group) bisphenol oxime type epoxy resin 2) (epoxy group) phosphorus-containing epoxy resin 3) (epoxy group) i 4-APP (amino group) 4-ADMP (amino group) 4, 4 - Diaminodiphenylmethane (amine) Aromatic condensed phosphate ester compound 4) Boron trifluoride monoethylamine phenoxy resin 5) Hydrogenated acrylonitrile butadiene rubber 6) Aluminum hydroxide methyl ethyl ketone _ Μ m {m N chain Μ κ- ε ζ m. 焊接 Welding heat resistance and flame retardancy Prime epoxy resin amine group-containing phosphate compound diamine compound added flame retardant hardening accelerator thermoplastic resin synthetic rubber inorganic filler organic solvent & & 4 4 4 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 ¥, (0 end: __ secret ^ er distillation » ^) 2223 (1

IKp<4al^^^Hli^®, 31SI(N inch Η 2ΙΙ*Ξ)!Ή p ZSZ^B, (%1MM 9£ : ¥.s loaded with K) oszod;3N(9 Su}s9e xxodPQv 9srsliωΙΟΜΜω(s 00HSS^ , (%¥Μ0·6 : ¥霉· ) oo(Nlxd (inch chain and #嵌, (%_»0·ε :_s<nl, soo inch: __ secret) selxj (e ^S. SS3>I ycxodw §dBf v (061 : __ maple®) Ί3838 alo^Ha ((N -31 - 200838960) As shown in Table 1, the flame retardation of Examples 1 to 3 containing an amine group-containing phosphate compound was used. The soft copper-clad laminate produced by the adhesive composition was all excellent in peel strength, solder heat resistance, and flame retardancy. In contrast, the adhesive composition of Comparative Example 1 containing no phosphate group-containing compound was used. The soft copper-clad laminate has good peeling strength and solder heat resistance, but is insufficient in flame retardancy. In addition, a soft patch made of the adhesive composition of Comparative Example 2 in which a condensed phosphate compound of an additive type flame retardant is blended is used. The copper laminate has good flame retardancy, but the peel strength and the solder heat resistance are insufficient. As described above, the flame retardant adhesive composition according to the present invention can produce heat resistance. Flame resistance and excellent long-term reliability and the like of the flexible copper-clad laminate or the cover film.

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Claims (1)

200838960 X. Patent application scope 1 · ~ ® flame retardant adhesive composition, characterized by containing the general formula [Chemical 9] An amine group-containing phosphate compound represented by + ^ δ ΐ 1 to 3 alkyl group) and a non-halogen epoxy resin. 2. The flame retardant adhesive composition of claim 1, wherein the amine group-containing phosphate compound is of the general formula (2): (wherein, X1, X2, X3, X4 and X5 may be the same or different, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms). 3. The group of the flame retardant adhesive of the first or second aspect of the patent application -33-200838960, wherein the amine group-containing phosphate compound is (I), (II), [Chem. 11] 4. The flame retardant adhesive composition according to any one of claims 1 to 3, wherein the non-halogen epoxy resin is at least one selected from the group consisting of bisphenol A type epoxy resin and bisphenol F Type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac resin (cres ο 1 η ο ν ο 1 ac ) type epoxy Resin, bisphenol type epoxy resin, bisphenol aralkyl type epoxy resin, naphthalene type epoxy resin, naphthalene aralkyl type epoxy resin, triphenylmethane type epoxy resin, hexahydrophthalic acid glycidol A group of acid esters, dimer acid glycidyl esters, tetraglycidyl diaminodiphenylmethane, epoxidized polybutadiene, epoxidized soybean oil, and phosphorus-containing epoxy resins. 5. The flame-retardant adhesive composition of claim 4, wherein the phosphorus-containing epoxy resin is (A) at least one selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin. Bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenolic resin type epoxy resin, cresol novolak type epoxy resin, bisphenol type epoxy resin, bisphenol aralkyl type epoxy resin, naphthalene Type epoxy resin, naphthalene aralkyl type epoxy resin, triphenylmethane type epoxy resin, hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, tetraglycidyl diamine based di- 34- 200838960 Groups of phenylmethane, epoxidized polybutadiene, and epoxidized soybean oil, and (B) by formula (a) or (b) [12] (a) (b) (wherein, R1, R2, R3 and R4 are each independently 'are an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group, and η and m are respectively 〇~4 The compound represented by the integer, 〇 and P is an integer of 0 to 5, respectively, and the reaction product of phenylhydrazine or naphthoquinone is reacted. #6 · A soft copper-clad laminate, comprising an electrically insulating film, a flame-retardant adhesive layer formed on the electrically insulating film, and a copper foil formed on the flame-retardant adhesive layer The soft copper-clad laminate is characterized in that the flame-retardant adhesive layer is a layer obtained by hardening a flame-retardant adhesive composition according to any one of claims 1 to 5. 7. A soft copper clad laminate according to claim 6, wherein the electrically insulating film is a polyimide film. 8 - a cover film comprising a non-flammable adhesive layer comprising an electrically insulating film and a flame-retardant adhesive layer formed on the electro-35-200838960 gas-insulating film, characterized by the flame-retardant adhesive layer A layer obtained by semi-hardening a flame retardant adhesive composition according to any one of items 1 to 5 of the patent application. 9. The cover film of claim 8 wherein the electrically insulating film is a polyimide film. -36- 200838960 无• · Ming said that there is no simple: the number is the map of the map element on behalf of the map: refers to the table design represents the book one or two 匕曰 iv VIII, if there is a chemical formula in this case, please reveal the best display invention Chemical formula of characteristics: 13 [Chemical 13] (1) -5-