TW200911945A - Flame-retardant adhesive resin composition, and adhesive film utilizing the same - Google Patents

Abstract

Disclosed is a flame-retardant adhesive resin composition which shows no cracking, peeling or the like before being cured into a film and therefore has excellent workability, which shows excellent adhesion properties including peel adhesion, solder heat resistance and flow properties after being cured, and which is imparted with non-halogenation. Also disclosed are a bonding sheet and a coverlay film each produced by using the flame-retardant adhesive resin composition. The flame-retardant adhesive resin composition comprises: (A) a phenoxy resin; (B) an epoxy resin; (C) a curing agent; and (D) a curing-accelerating agent as essential components. The curing agent has an active hydrogen equivalent weight of 20 to 30. The flame-retardant adhesive resin composition further comprises an organic phosphorus compound or a phosphorus-containing phenoxy resin in an amount of 0.5 to 5 parts by weight in terms of phosphorous content relative to 100 parts by weight of the resin composition. After being thermally cured, the resin composition has a glass transition temperature of 100 DEG C or higher.

Description

200911945 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a heat-resistant adhesive resin composition, and more particularly to a highly heat-resistant, flame-retardant adhesive composition and adhesion thereof Film. [Previous Art] A printed circuit board is conventionally used as a substrate composed of paper-phenol resin, glass fiber-epoxy resin, or a substrate such as a polyimide film or a polyethylene terephthalate film. Metal fitter. In recent years, the printed circuit board wiring used in the fields of motors, electronic equipment, and precision machines has a small area occupied by wiring, and therefore, the demand for multilayer printed boards has gradually increased. A variety of adhesive or adhesive films can be used in the step of laminating a printed circuit board to form a multilayer printed circuit board or for compositing a different type of circuit material. Such an adhesive can be widely used as an adhesive for a multilayer printed circuit board or an adhesive for a cover film, but a material excellent in adhesion strength, chemical resistance, solder heat resistance, and bending resistance is required. In addition, from the point of ensuring fire safety, 'the material with excellent flame retardancy has been sought. A known adhesive film is a resin or an additive containing a halogen such as bromine to impart flame retardancy. Halogen is widely used because of its low flame retardancy and high cost-effectiveness. However, the halogen contained in the product is likely to cause toxic substances such as dioxin in the combustion. It is strongly desired to exclude the halogen-based material from the material. The adhesive used in the printed circuit board is, for example, Patent Documents 1 to 5. Been proposed. Any of these patent documents are based on epoxy resin, hardener, acrylonitrile butadiene rubber or phenoxy resin as the main component of the 'flammability method'. Resin, brominated phenoxy resin. In addition, various materials which are non-halogen type have been developed as flame retardant materials instead of halogen. The most common method is the use of a phosphorus resin or the addition of an organophosphorus compound. Such a flame retardant adhesive can be, for example, Patent Documents 6 to 10 and the like. Patent Documents 6, 7, and 9 are formulated with an organophosphorus compound, and Patent Documents 8 and 1 are a method of blending a known phosphorus-containing epoxy resin or a phosphorus-containing phenoxy resin as a non-halogen-based flame retardant. [Patent Document 1] JP-A-2001-164226 [Patent Document 3] JP-A-200-323242 [Patent Document 4] JP-A-200 1 -3 Japanese Patent Publication No. 5 493 (Patent Document 5) Japanese Patent Publication No. 2 0 0 3 - 1 8 1 9 9 3 [Patent Document 6] JP-A-20001 - 3 3 9 1 3 No. 1 [Patent Document 7] Japanese Laid-Open Patent Publication No. JP-A No. 2005-176277 (Patent Document No. JP-A-2005- No. SUMMARY OF THE INVENTION -6-200911945 (Disclosure of the Invention) (Problem to be Solved by the Invention) An object of the present invention is to provide a flame-retardant adhesive resin composition which is free from cracking and peeling in a film state before hardening. Excellent workability, excellent adhesion properties such as peel adhesion, solder heat resistance, fluidity, etc., and non-halogenation in a corresponding environment. Further, it is to provide a flame retardant adhesive film and a cover film which are made of such an adhesive resin composition. (Means for Solving the Problem) In order to achieve the above object, the present inventors have found that the glass transition temperature of the pre-reaction mixture and the post-reaction hardened material of the adhesive resin composition is a specific range as a result of intensive investigation. The composition is suitably formulated to complete the present invention. That is, the present invention is a flame retardant adhesive resin composition comprising the following components (A) to (D): (A) phenoxy resin, (B) epoxy resin, (C) hardener, And (D) a hardening accelerator as an essential component, characterized in that the active hydrogen equivalent of the curing agent is 20 to 30', and the organic phosphorus compound or the like is contained in the flame retardant adhesive resin composition 1 () () by weight 0.5 to 5 parts by weight of the phosphorus resin is phosphorus, and the glass transition temperature after thermal curing of the resin composition is 100 ° C or more. 200911945 Further, the flame retardant adhesive resin composition of the present invention is obtained by thermally hardening, that is, the glass transition temperature is 〇~50 °C, or substantially halogen-free, and an excellent flame-retardant adhesive resin can be obtained. Composition. Further, in the present invention, the component (A) is a pep-containing phenoxy resin having a pity content of 1 to 6% by weight as shown by the following formula (1). [化1] z-o-

X-〇-CH2-C—CH2-丨V. OH xo -z (1) (wherein X represents at least one divalent group selected from the group consisting of the following formula (2) or (3) The valence group is a necessary divalent group represented by the formula (2), (3), (Ο or (5), Z represents a hydrogen atom or a glycidyl group, and the average 値 of η is 2 1 or more) 】

(In the formulae (2) to (5), γ represents a phosphorus-containing group represented by the following formula (7) or (8), and 113, Ri~R4, and Ri~R8 independently represent hydrogen-8-200911945 An alkyl group having a carbon number of 1 to 4 or a phenyl group; and A is selected from a single bond or -(:112--C(CH3)2-, -CH(CH3)-, -S-, -S02-, -0-, -CO- or a divalent base based on the group shown by (9)

In the formula (7) to (9), RrRs and Ri-Rw each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or a phenyl group. Further, the content of the component (A) is preferably 20%. 80% by weight range. Further, the component (B) of the present invention is an epoxy resin represented by the following formula (10). [化4] Η H2C^7C'H2C—°-0 (10)

Oo o-ch2-c-ch2-o- OH H2 H -W—0—C—C “/CH 2 0 (wherein W represents a divalent group represented by the formula (5), and m is 0. The integer of h, the average of m is 0.1 to 15). In the general formula (10), the content of the steroid is determined by gel permeation chromatography. The chromatographic surface measured by the gel permeation chromatography layer is -70%. In the epoxy resin, an excellent flame retardant adhesive resin composition is obtained. The flame retardant adhesive film of the present invention is characterized in that the flame retardant adhesive resin composition is formed into a film. Further, the cover film of the present invention is characterized in that it has a polyimide film and a layer composed of the above-mentioned flame retardant adhesive resin composition provided on the polyimide film. The cured product is obtained by hardening the above-mentioned flame retardant adhesive resin composition. The following describes the flame retardant adhesive resin composition of the present invention, and the invention of the flame retardant adhesive film and the cover film will be described next. However, the common part is explained at the same time. The flame retardant adhesive resin of the present invention The product (sometimes referred to simply as the adhesive resin composition or the resin composition) contains the above components (A) to (D) as essential components. The component (A) is a phenoxy resin, and the component (b) is an epoxy tree S.曰, (C) component is a curing agent' (D) component is a hardening accelerator. The phenoxy resin of the component (A) is a resin which has a phenoxy skeleton in its molecular structure, and it is applicable. It is a highly adhesive component with a metal case, especially a copper foil or a copper alloy foil, and is not easily hindered from crosslinking with the epoxy resin of the component (B) and the hardener of the component (C), so that the obtained resin composition cannot be lowered. The glass transition temperature (T g ) after thermal hardening of the article, and the solder heat resistance of the cured product composition can be improved. Further, when the obtained resin composition is applied to the cover film, it is laminated by thermocompression bonding. When it is integrated, it is possible to exhibit moderate fluidity (fluidity) as an adhesive. From the viewpoint of imparting flame retardancy in the adhesive resin composition, (a) component-10-200911945 is preferably a phosphorus content of 1 to 6 % by weight, preferably 2 to 5% by weight of phosphorus Oxygen resin. The standard polyethylene oxide equivalent weight average molecular weight measured by gel permeation chromatography is from 1,000,000 to 200,000, preferably from 15 to 150000, more preferably from 20,000 to 120,000. In the above formula (1), a phosphorus-containing phenoxy resin having a phosphorus content of 1 to 6% by weight is blended. In the formula (1), X is at least one selected from the group consisting of the above formula (2). (3) The base of the divalent group of the group represented by (4) or (5) is required to be a divalent group represented by the formula (2) or (3). Advantageously, it is preferably in the X. One of the divalent groups represented by the formula (2) or (3) or both is 20 mol% or more, preferably 50 mol% or more. Z is a hydrogen atom or a glycidyl group represented by the following formula (6). The average 値 of the η system is more than 21, but it is preferably in the range of 30 to 5,000. Such a phosphorus-containing phenoxy resin can be produced by a method as disclosed in, for example, JP-A No. 200 1 - 3 1 0939. 【化5】

Further, in the above formulae (2), (3), (4) and (5), fluorene represents a phosphorus-containing group which is not represented by the above formula (7) or (8). In the formula (5), 2 represents a divalent base 'which is selected from a single bond or _<^2-, -<:(0:113)2-, -CH(CH3)-, -S- , -S〇2-, -0·, _c〇- or a divalent group of the group represented by the formula (9). In the formulae (2) to (5) and (7) to (9), Ri to Rio independently represent a hydrogen atom, a phenyl group having 1 to 4 carbon atoms, or a phenyl group. Compared with -11 - 200911945, hydrogen or methyl, the number of methyl groups should be 4 or less. As the epoxy resin of the component (B), an epoxy resin having an epoxy group of 2 or more can be used, but an epoxy resin represented by the above formula (10) is preferable. In the formula (10), W represents a divalent group represented by the above formula (5), and 1« is an integer of 0 or more, and the average of m is 〇.1 to 15. The epoxy resin represented by the above formula (10) may, for example, be a bisphenol A epoxy resin, a bisphenol F epoxy resin or a biphenyl epoxy resin, and these may be used alone or in combination. Two or more types are used. Further, a cresol novolac type epoxy resin derived from a novolac resin containing bis(methyl hydrazine) methane as a main component may be used. The epoxy resin may be substantially free of halogen elements. The glass transition temperature of the dried product or film (hereinafter referred to as the B-stage state composition) obtained by drying the resin composition is a specific range, and the degree of polymerization of the epoxy resin in the above formula (10) is 0. The content ratio of the body of 0 is 70% or more, more preferably 80% or more, as measured by the area percentage measured by gel permeation chromatography. Then, it should be liquid at room temperature. In the flame retardant adhesive resin composition of the present invention, the component (A) is preferably 20 to 80 parts by weight, preferably 30 to 70 parts by weight, more preferably 40 to 60 parts by weight. When the amount is less than 20 parts by weight, the softness is lowered and the internal stress is increased, and the adhesive force is not exhibited. When the amount is more than 80 parts by weight, the ratio of the cross-linking component is decreased, the solder heat resistance is lowered, and the performance as an adhesive is impaired. . Further, the component (B) is preferably blended in the range of 20 to 70 parts by weight. If the component (B) is less than 20 parts by weight, the crosslinking density is lowered, and the heat resistance of the resin composition of the adhesive -12-200911945 is lowered. If it exceeds 70 parts by weight, the flexibility is lowered and the adhesive resin composition is formed. The problem of peeling adhesion is reduced. Here, when the weight of the flame retardant adhesive resin composition is calculated to include the solvent to be removed by drying, the system is removed. (C) The hardener of the component may be a hardener of an epoxy resin known as a (ruthenium) component, but it must have an active hydrogen equivalent of 20 to 30. The active hydrogen equivalent hardener is calculated to have X/Y (g/eq) per Xg of active hydrogen (Η). When the active hydrogen equivalent is less than 20, the crosslinking point is localized and the heat resistance is lowered. When it exceeds 30, the ratio of the component (C) to the component (B) increases, and the bendability decreases. Such a curing agent is a novolak type phenol resin, dicyanodiamine 'diaminodiphenylmethane, diaminodiphenyl hydrazine, an azide, an imidazole, etc., and an active hydrogen equivalent is advantageously used. 2 0 to 30. These may be used alone or in combination of two or more. Further, when imidazole is used as the component (C), this is also the component (D), so that the component (D) can also be calculated. The amount of the component (C) to be used is preferably adjusted so that the equivalent ratio (C) / (B) is 0.5 to 1.5, based on the epoxy resin of the component (B). In general, when a resin-based curing agent is used, it may be 〇·8 to 1.2, and when an amine-based curing agent is used, it may be 〇 5 to 1 · 0. (D) The hardening accelerator of the component may be an organophosphorus compound such as triphenylphosphine or an imidazole such as 2-phenylimidazole or 2-ethyl-4-methylimidazole, a tertiary amine or a Lewis acid. . The blending ratio is appropriately selected depending on the hardening time to be determined, but it is generally used in the range of 0.0 1 to 3.0% by weight for the flame retardant adhesive resin composition. Further, when an organophosphorus compound is used as the component (D), other organophosphorus compounds or phosphorus-containing resins are combined, and -13-200911945 is used in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the flame retardant adhesive resin composition. Phosphorus is formulated in a range of parts. The flame retardant adhesive resin composition of the present invention is contained in an amount of 1 part by weight of the resin composition, and may be contained in an amount of 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, based on the phosphorus compound (may also be a resin). More preferably, it is 1.5 to 3 parts by weight, and the flame retardancy can be imparted without lowering the solder heat resistance after curing of the adhesive resin composition, and the migration resistance can be improved. As such a phosphorus compound, an organophosphorus compound such as a phosphazene, a phosphate decylamine, an aromatic condensed phosphate, or a metal salt of an organic phosphoric acid, or a phosphorus-containing epoxy resin such as (A) can be used. a phosphorus-containing resin such as a phosphorus-containing phenoxy resin. Advantageously, it is a phosphorus-containing phenoxy resin. These may be used singly or in combination of two or more kinds, but it is suitable to use a phosphorus-containing phenoxy resin alone. The flame retardant adhesive resin composition of the present invention may be used in an amount of 5% to 5 parts by weight based on 1 part by weight of the resin composition, and may be contained in an organic phosphorus compound or a phosphorus-containing resin as phosphorus. The flame retardant component does not contain a halogen (a halogen component or a dentate which is a halogen compound). Advantageously, it is substantially free of halogens. Here, the halogen is not contained in the form of a halogen, and the halogen is not contained in an amount of 900 wtppm or more.

The flame retardant adhesive resin composition of the present invention has a glass transition temperature of 1 〇〇 ° C or more, preferably in the range of 100 ° to 170 ° C, of the cured product obtained by thermally curing the resin composition. If the glass transition temperature of the cured product after the heat curing is less than 100 ° C, the migration resistance is lowered. Moreover, the glass transition temperature of the resin composition before thermosetting (the composition corresponding to the state of B-14-200911945) in the flame retardant adhesive resin composition of the present invention is preferably in the range of 0 to 5 〇t. More preferably in the range of 1 0~5 0 °c. When the glass transition temperature of the composition in the B-stage state is lower than 〇 °C, the adhesion is exhibited in the film, and when it is processed into FP C, the adjustment of the positioning is difficult, and the practicality is lacking. Further, when the temperature exceeds 50 °C, the flexibility of the film is lost, and cracks, peeling, and the like are liable to occur. Further, the glass transition temperature before and after the thermosetting of the resin composition can be mainly adjusted depending on the type and amount of the curing agent of the epoxy resin of the component (B) and the component (C). Here, the measurement of the glass transition temperature of the B-stage state composition or the glass transition temperature after hardening is determined according to the conditions of the characteristic evaluation method described later. The flame retardant adhesive resin composition of the present invention can be formulated as an inorganic flame retardant aluminum hydroxide and magnesium hydroxide, and as a reinforcing agent or a bulking agent for the components other than the above-mentioned essential components. An extender such as a calcium carbonate or the like, a polymer elastomer as a softness imparting agent, or an additive such as a viscosity modifier or a coupling agent. The addition rate can be appropriately selected depending on the characteristics desired. Further, the flame retardant adhesive resin composition of the present invention can be used by being formed into an adhesive resin solution which is dissolved or dispersed in an organic solvent such as methyl ethyl ketone, dimethylformamide or 2-ethoxyethanol. The solid content concentration at this time can be appropriately selected depending on the conditions of use, but is generally 20 to 60% by weight. Further, it can be understood that the solvent is a component which is used as a solution for the composition of the flame retardant adhesive resin composition which does not constitute the component of the flame retardant adhesive resin composition of the present invention. Therefore, when the formulation of each component in the flame retardant adhesive resin composition is calculated, the solvent is excluded from the calculation. -15- 200911945 The flame retardant adhesive resin composition of the present invention is used. In this case, a known method can be used, and in the case of the thin film method, the composition is diluted with an organic solvent such as methyl ethyl ketone to form a solution, and the obtained known method is applied to the surface-treated gold polyimide film. On the substrate, the composition which evaporates the solvent into the adhesive resin layer does not harden and react to form an adhesive film layer, and then from the flammable adhesive film. The drying condition is based on the solvent or tree used, but is generally selected from 130 to 160 ° C for 3 to 10 minutes. When the release film of polyester or the like is bonded to a flame-retardant adhesive sheet, the release film is used. The ratio of the flame retardant adhesive is not particularly limited, but the thickness of the release film is 10%. The use of the flame retardant adhesive film having a thickness of 15 to 30 μm is used for the flexible printed circuit board and the glass. The fiber-epoxy circuit board or the adherend of each metal or resin substrate obtained by processing these circuits. The grease substrate is adhered to obtain a printed circuit board, and between the printed circuit boards, a plurality of printed circuit boards can be obtained. The printed circuit board is bonded to the coating layer and the printed circuit board is printed. Alternatively, an adhesive film for connection to a printed circuit board can be used. That is, it is formed into a film shape, but a suitable formed flame retardant adhesive resin adhesive resin solution is not adhered to a foil or a polyester film, and the substrate is peeled off under temperature and time conditions. Changes in fat composition, temperature, time range. When the thickness of the layer of the film of the agent film is 〜15 μm, it is suitable for the range. The method is applied to, for example, a circuit board, a paper-phenol type printed circuit board, and by printing a circuit board or a printed circuit board with a metal foil and a tree, and coating can be obtained as a printed circuit board. -16- 200911945 The procedure used in the manufacture or processing of printed substrates. Further, a layer of the flame retardant adhesive resin composition of the present invention is provided on one or both sides of the base resin film to form an adhesive film. Here, the base resin film is a polyimide film or a polyester resin film. Further, the surface may be peeled off from the surface of the substrate of the flame retardant adhesive resin composition of the base resin film. The adhesive film having a layer of a flame retardant adhesive resin composition on one side is provided with a cover film. The adhesive film for peeling off the surface of the base resin film is bonded to the adhesive sheet. The adhesive sheet is obtained by providing an adhesive resin layer on a resin film having a surface such as a peeled polyester film. When the adhesive sheet composed of a release film of a polyester or the like and a layer of an adhesive film is used, the ratio of the thickness of the release film to the thickness of the adhesive film layer is not particularly limited, but the thickness of the release film is 12_5 μm. In the case where the adhesive layer is suitably used, 5 to 30 μm, the flame retardant adhesive resin composition of the present invention can also be applied to the adhesive layer covering the film. In this case, the cover film can be formed from the polyimide film and the above-mentioned adhesive resin composition, but the method of forming the cover film of the present invention can be formed into a film by a conventional method. An example of a suitable molding method is to dilute the above-mentioned adhesive resin composition with an organic solvent such as methyl ethyl ketone to form a solution, and then apply the obtained solution to a polyimide film to evaporate the solvent without sticking. Further, the adhesive resin composition constituting the adhesive layer is dried without a temperature and time condition of the hardening reaction to form a cover film. The film was applied to a polyimide film at a thickness of 2 to 2 Å μm, preferably 5 to ΙΟΟμηι, more preferably 10 to 50 μm, and dried to dry -17-200911945. The drying conditions vary depending on the solvent or resin composition used, but generally, the temperature and time range of 130 to 16 0 ° C and 3 to 10 minutes are selected. Further, the polyimide film is necessary for increasing heat resistance and flame retardancy, and the thickness of the polyimide film may be any thickness as needed, but it is preferably 3 to 50 μm, more preferably 5 ~30μιη. The ratio of the thickness of the polyimide film to the thickness of the adhesive layer is not limited, but when the film thickness is 12.5 μηι, the adhesive layer is 11 2 3 4 5 to 20 μm, and when the film thickness is 2 Wm, the adhesive layer 25 is generally provided. 35 μιη cover film. [Embodiment] [Best Mode for Carrying Out the Invention] Next, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples. The evaluation method of the properties of the cured film of the flame retardant adhesive resin composition (adhesive resin composition) and the properties of the FPC material for the cover film and the adhesive sheet are as follows. -18- 1 . Β 质 质 2 1 1 1 glass transition temperature (Tg) 3 The adhesive resin composition is dissolved in methyl ethyl ketone solvent to form 35 weight 4% by weight of the adhesive solution, applied to the longitudinal X horizontal X thickness = On a 50xl50xlmm fluorine 5 resin sheet, the solvent was evaporated by drying at 135 ° C for 5 minutes to prepare a film before the hardening reaction (film of the B-stage state composition). Using a dynamic viscoelasticity measuring apparatus (DMS-61 00 manufactured by Seiko Instrument Co., Ltd.), the temperature dispersion tan 5 curve of the sample was measured at a frequency of 10 Hz and a temperature range of -150 to 20 (TC, a temperature increase rate of 2t:/min 200911945). The peak temperature of the obtained temperature-tan 5 curve is taken as the glass transition temperature (Tg). 1.2 Crack resistance and peeling resistance The above-mentioned 35% by weight of the adhesive solution is concentrated in the longitudinal X transverse X thickness = 200 mm x 3 00 ιηιη χ 25 μιη The one-side coating adhesive solution of the imine film (Kaneka Apical NPI) was dried at 135 ° C for 5 minutes to prepare a cover film having a thickness of 25 μm of the adhesive layer, and the coated surface of the adhesive film covering the film was formed. In the case of the inner side, when the film is covered with a finger, the crack or the peeling is observed visually on the adhesive layer. It is judged that the occurrence of cracking or peeling is "not possible", and no crack or peeling is observed. The time is as good. 2. The properties of the cured product 2.1 The glass transition temperature (Tg) The above 35 wt% adhesive solution is dried on a fluororesin sheet of longitudinal X transverse X thickness = 50 mm x 15 0 ηηηη1 μηι, and dried at 135 ° C. After the solvent was evaporated, the other fluororesin sheet of the same shape was superimposed on the adhesive-coated surface, and vacuum-heat-pressed at 170 ° C for 1 hour, and then post-hardened at 190 ° C for 2 hours to prepare a sample for adhesion. The cured film of the cured product was measured using a dynamic viscoelasticity measuring apparatus (DMS-6100, manufactured by Seiko Instrument Co., Ltd.). The temperature dispersion of the sample was measured at a frequency of 10 Hz, a temperature range of -150 to 200 ° C, and a temperature rising rate of 2 t /min. Curve, the temperature of the obtained temperature-tan 5 curve is taken as the glass transition temperature (Tg). -19- 200911945 3. Material properties and film properties of FPC 3.1 Thermal resistance The above 35 wt% adhesive solution, A single-sided coating adhesive solution of a polyimine film (Kaneka, Apical N PI) of a vertical father with a thickness of 2〇〇mmx 3〇〇Π1ΐηχ25μΠ1, dried with n 5 for 5 minutes to prepare an adhesive After a cover film having a layer thickness of 25 μm, two cover films cut into the dimensions described in 7.7 of jPCA-BM02-1991 were bonded to the adhesive surface, and then heat-pressed at 170 ° C for an hour. Then lick it with 1 9 The sample was prepared by post-curing for 2 hours, and then the flame resistance test was performed in accordance with the order of 7.7 of jPCa_bm〇2-1 9 9 1 , and "VT Μ - 0", which is the criterion of u L specification 94, The 2 level of "non-flammability" determines the flame resistance. "V Τ Μ - 0" is flame resistant. 3.2 Peeling strength After the cover film was prepared under the same conditions as above, a test piece was produced by a copper foil laminate (Espanex MC-12-25-00CEM, manufactured by Nippon Steel Chemical Co., Ltd.) and hot stamping. The thermosetting conditions of the adhesive resin composition at the time of preparation of the test piece were the same as described above, and the film was heat-pressed at 1 7 ° C for 1 hour, and then post-cured at 1 90 ° C for 2 hours. The test piece produced was measured for the test piece production and peel strength in accordance with the 7.5 peel strength of JPCA-BM02-1 991. 3.3 Solder heat resistance (appearance) -20- 200911945 The heat resistance (appearance) and solder heat resistance test of the thin BM02-1 991 -7.9 solder were prepared under the same conditions as above. The thermosetting conditions at the time of preparation of the test piece were the same as described above, and after 1700 t: the following, the post-hardening was carried out at 190 ° C for 2 hours. After the bag was dried for 1 hour, the adhesive state was observed in a solder bath set at 260 °C. The judgment is to confirm the presence or absence of foaming or swelling, and it is "not good" when it is not good. 3.4 Bending resistance The film and the bending resistance test of the A film bending test piece made by Nippon Steel Chemical Co., Ltd., Espanex, JPCA-BM02-1991-7.6.1 were prepared under the same conditions as above. Hardened at 170 ° C for 1 hour roll hardening for 1 hour. The radius of curvature is 〇.38mm. The copper circuit is broken, and the number of bends that cannot be energized is. The number of times is less than 1 000. "Non" is "OK". It is "good" when it is 3,000 times or more. 3.5 Flow of the adhesive resin composition is carried out under the same conditions as above to cover the thin moon ΒΜ〇 2-1991·7·1〇 and the test is carried out. After the film is produced and filmed, the test piece is produced according to JPCA-. The adhesive resin composition is heated and stamped for 1 small 3. The test piece is floated at 1 0 5 °c for 5 seconds, and swells, etc. Poor.", see the poor situation: after the use of copper foil MC 1 2-2 5 -00CEM) fold test, and the implementation conditions are the same, at I, after 190 ° c after the 'determination determination The test piece is judged to be at the bend of the broken line 1000~3000 times, after the wife, according to the JPCA-flow Experience. Judging Department -21 - 200911945 The length of the adhesive resin composition exudation was measured. 3 · 6 migration resistance After the cover film is prepared under the same conditions as above, the comb-type circuit pattern of the foil copper of the etched copper foil laminate is made by the circuit, the line/gap becomes 100 μm / 20 () μηη. The cover film was subjected to hot stamping at 1 70 ° C for 1 hour, and then post-cured at 19 ° C for 2 hours to prepare a sample. Put the same sample into a constant temperature and humidity chamber with the temperature and humidity adjusted to 85 °C -85RH%. 'The comb circuit in the sample is connected to DC for 5 Ο V, 500 hours, then take out the sample and observe the comb with a microscope. The circuit and its surroundings. The judgment system can be seen as "not" when the tree-like projection occurs, and "good" when it is not visible. 4. Bonding sheet characteristics 4 · 1 flame resistance The above-mentioned 35 wt% adhesive solution is applied to the one side of the polyester release film of the longitudinal X width X thickness = 2000 mm X 300 mm > 25 pm. The film was dried at 1 3 5 ° C for 5 minutes to prepare an adhesive sheet having a thickness of 25 μm, and then pre-cured at 170 ° C for 1 hour, and then post-hardened at 190 ° C for 2 hours to prepare a sample. Then, the flame resistance test was carried out in the order of JIS C 647 1 and the flame resistance was judged by the level of "V-0" and "non-flammability" based on the UL standard 94. "V · 0" is flame resistant. 4·2 Peeling strength After the adhesive sheet was prepared under the same conditions as above, the adhesive sheet was peeled off from -22-200911945 and then peeled off. Two pieces of copper foil with a thickness of 200 mm x 300 inmx 25 μm were prepared. The shiny surface of the copper foil was subjected to hot stamping at i7 (rc for 1 hour, and then post-hardened at 1 90 ° C for 2 hours to prepare a sample]. The peel strength was measured in accordance with JIS C 6471. 4.3 Through-hole plating conductivity After the adhesive sheet was prepared under the same conditions as above, the adhesive sheet was peeled off from the release film, pre-cured at 1 70 ° C for 1 hour, and post-cured at 1 90 ° C for 2 hours to prepare a cured sheet. A through hole of a diameter of 33 mm was opened by a drilling machine, and a copper plating layer of 20 to 25 μm was formed on the inner side of the same hole by an electroless copper ore method as a sample. The sample was subjected to -40 ° C, 15 minutes, 150 ° C, 15 minutes of hot and cold cycle exposure, measured to the number of cycles leading to poor conduction. The determination is 500 cycles below "not available", 500 ~ 2000 cycles are "OK", 2000 cycles or more is "good". [Examples] Synthesis Example 1 with stirring A 10-cell separable flask equipped with a thermometer, a cooling tube, and a nitrogen gas introduction device was fed with 10-(2,5-dihydroxyphenyl)-10H-9-oxa as shown in the following formula (11). 10 -Phenanthrene-10H-9-oxide (manufactured by Sanko Chemical Co., Ltd., HCA-HQ, hydroxyl equivalent I62g/eg, phosphorus content: 9.5% by weight) 162 parts, bisphenol A type epoxy resin (manufactured by Dongdu Chemical Co., Ltd., YD-8125, epoxy equivalent 171.6g/eg) 175 parts, 44 parts of cyclohexanone oxime, 2-ethyl-4-methyl milate as a catalyst (made by Shikoku Chemical Industry Co., Ltd. -23-200911945, 2E4MZ 〇·13 parts, reacted at a temperature of 150 ° C to 17 ° C for 5 hours under normal pressure, and then added 156 parts of cyclohexanone and 300 parts of N,N-dimethylformamide to obtain phosphorus. The solution of the phenoxy resin A having a solid concentration of 36% by weight is 93 parts. After the resin solution is applied onto the polyester release film, it is dried at 1 65 ° C for 5 minutes to evaporate the solvent to obtain a phosphorus content. The rate of 4.6% by weight of the phenoxy resin A containing the dish.

(11) Using Shodex · AD- 8 0 0P + TSKgel Super HM-H + Super HM-H + Super H2000 as a column, N,N-dimethylformamide (20 mM lithium bromide) as a solution GPC analysis of phosphorus-containing phenoxy resin A was carried out, and as a result, the weight average molecular weight in terms of standard polyethylene oxide equivalent to the resin was 3,920. Synthesis Example 2 A phosphorus-containing phenoxy resin B having a phosphorus content of 4.6% by weight was obtained by synthesizing a phosphorus-containing phenoxy resin under the same conditions as in Synthesis Example 1 except that the reaction time was changed from 5 hours to 8 hours. Standard polyethylene oxide for dance; weight average molecular weight of 80,600. The outlines of the components used to prepare the adhesive resin composition are as follows. -24- 200911945 YD-1 28 : Bisphenol A type epoxy resin (manufactured by Tohto Kasei Co., Ltd.) YDF-170 : Double 酣F type epoxy resin (manufactured by Tohto Kasei Co., Ltd.) YD-01 1 : Double brewed A type epoxy Resin (manufactured by Tohto Kasei Co., Ltd.) BRG-5 5 5 : lyophilized varnish type phenol resin (manufactured by Showa Polymer Co., Ltd.) DICY: dicyanodiamine (manufactured by Japan car bide Industrial Co., Ltd.) DADPS: diaminodiphenyl飒 (made by Wakayama Seika Chemical Co., Ltd.) Resin A: Phosphorus-containing phenoxy resin of Synthesis Example 1 Resin B: Phosphorus-containing phenoxy resin B of Synthesis Example 2 YP-50SC: phenoxy resin (manufactured by Tohto Kasei Co., Ltd.) 1072T: Acrylonitrile butadiene rubber (manufactured by Zeon Co., Ltd.) SPE-100: Cyclophenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd.) 2E4MZ: 2-ethyl-4-methylweiwa (manufactured by Shikoku Chemical Industry Co., Ltd.) The GP C analysis of the epoxy resin was carried out under the following conditions.

Device: HLC-8120GPC pipe made by Tosoh company: Tosoh company, TSK-GEL: SUPER HZ2000xl, SUPER HZ3000xl, SUPER HZ4000xl Column temperature: 40 °C Mobile phase: tetrahydrofuran THF, flow rate: 0.35 ml / min Detector: group Inclusion sample concentration··〇.〇3g/THF l〇ml m = 0 The content of the body is such that the peak area of the m = 0 body obtained from the obtained GPC color layer analysis is the peak area of the whole component. The area % is taken as the content (%). -25- 200911945 YD-128 is a degree of polymerization m = the content of carcass is 82%. The degree of polymerization of YDF-170 is m = the content of carcass is 78%. Examples 1 to 8 The components were blended in the ratios (% by weight) shown in Tables 1 and 2 to prepare an adhesive. For the adhesive, the properties of the cured product and the properties of the material for FPC (coating characteristics, adhesive sheet characteristics) were evaluated. The results are shown in Tables 1 and 2. It is recognized that the characteristics that show any of them are excellent. Comparative Examples 1 to 7 The components were blended at the ratios shown in Tables 3 and 4 to prepare an adhesive. For this adhesive, the properties of the cured product and the properties of the material for FPC were evaluated. The results are shown in Tables 3 and 4. In Comparative Examples 1 to 5, the glass transition temperature of the B-stage was high, and the crack resistance was not possible. In Comparative Example 5, the through-hole electroplating conductivity in the film-resistance characteristics and the adhesion sheet characteristics were not possible. In Comparative Examples 6 and 7, the glass transition temperature after curing was low, and the solder heat resistance and migration resistance in the film properties and the through-hole plating conductivity in the adhesive sheet characteristics were not possible. In the table, YD-128, YDF-170, YD-011 are epoxy resins, BRG-5 5 5, DICY, DADPS are hardeners, resin A, resin B 'YP-50SC is phenoxy resin, SPE-100 is The organophosphorus compound, 2E4MZ, is a hardening accelerator. -26- 200911945 [Table i] Example 1 2 3 4 YD-128 46.4 37.1 46.4 0 YDF-170 0 0 0 46.2 YD-011 0 0 0 0 BRG-555 0 0 0 0 DICY 3.1 2.5 3.1 3.5 DADPS 0 0 0 0 Active hydrogen equivalent 21 21 21 21 Resin A 50.0 60.0 0 50.0 Resin B 0 0 50.0 0 YP-50SC 0 0 0 0 1072T 0 0 0 0 SPE-100 0 0 0 0 2E4MZ 0.5 0.4 0.5 0.3 B-order characteristic Tg( °C) 45 43 48 40 Crack resistance good good good peeling good good hardening properties Tg(0C) 147 143 158 136 Cover film properties Flame resistance VTM-0 VTM-0 VTM-0 VTM-0 Peeling strength (KN/m) 1.1 1.0 1.0 1.2 Solder heat resistance (appearance) Flow of good and good adhesive (_) 0.1 or less 0.1 or less 0.1 or less 0.1 or less Immigration resistance good adhesion sheet characteristics Flame resistance V- 0 V-0 V-0 V-0 Peel strength (KN/m) 1.1 1.0 1.0 1.0 Through-hole plating guide communication good good Liang -27- 200911945 [Table 2] Example 5 6 7 8 YD-128 0 0 38.2 0 YDF-170 37.0 46.2 0 38.0 YD-011 0 0 0 0 BRG-555 0 0 0 0 DICY 2.7 3.5 2.6 2.8 DADPS 0 0 0 0 Active hydrogen equivalent 21 21 21 21 Resin A 60.0 0 0 0 Tree Grease B 0 50.0 0 0 YP-50SC 0 0 41.0 41.0 1072T 0 0 0 0 SPE-100 0 0 17.9 17.9 2E4MZ 0.3 0.3 0.3 0.3 B-order characteristic TgfC) 40 45 44 41 Good crack resistance, good peeling resistance Good and good hardening properties TgfC) 133 145 105 101 Cover film properties Flame resistance VTM-0 VTM-0 VTM-0 VTM-0 Peel strength (KN/m) 1.1 1.2 1.2 1.1 Solder heat resistance (appearance) Liang Liangliang Flow of good adhesion agent (_) 0.1 or less 0.1 or less 0.2 0.2 Resistance to migration Good good adhesion sheet Characteristics Flame resistance V-0 V-0 V-0 V-0 Peel strength (KN/m) 1.0 1.0 1.1 1.1 Hole plating communication communication good good Liang-28 - 200911945 [Table 3] Comparative Example 1 2 3 4 YD-128 30.2 0 0 42.0 YDF-170 0 30.7 0 0 YD-011 0 0 48.3 0 BRG-555 19.5 19.0 0 0 DICY 0 0 1.3 0 DADPS 0 0 0 7.7 Active hydrogen equivalent 101 101 21 64 Resin A 0 0 50.0 50.0 Resin B 50.0 50.0 0 0 YP-50SC 0 0 0 0 1072T 0 0 0 0 SPE-100 0 0 0 0 2E4MZ 0.3 0.3 0.3 0.3 B-order characteristic Tg(°C) 62 56 69 54 Crack resistance is not indispensable Chemical properties Tgfc) 140 132 140 128 Cover film properties Flame resistance VTM-0 VTM-0 VTM-0 VTM-0 Peel strength (KN/m) 1.0 1.0 1.2 1.0 Solder heat resistance (appearance) Flow of good good adhesive (mm) 0.1 or less 0.1 or less 0.1 or less 0.1 or less migration resistance good good adhesion sheet characteristics flame resistance V-0 V-0 V-0 V-0 peel strength (KN/m) 1.1 1.0 1.0 0.8 through hole plating conduction Reliable good good -29- 200911945 [Table 4] Comparative Example 5 6 7 YD-128 0 38.2 38.2 YDF-170 0 0 0 YD-011 33.0 0 0 BRG-555 7.8 0 5.5 DICY 0 2.6 2.6 DADPS 0 0 0 Active hydrogen equivalent 101 21 21 Resin A 0 20.0 0 Resin B 0 0 0 YP-50SC 41.0 0 0 1072T 0 21.0 41.0 SPE-100 17.9 17.9 17.9 2E4MZ 0.3 0.3 0.3 B-order characteristic Tr(°C) 72 25 18 Turtle resistance Cracking unsatisfactory peeling resistance Unsatisfactory hardening property Tg(0C) 110 75 32 Cover film characteristics Flame resistance VTM-0 VTM-0 VTM-0 Peel strength (KN/m) 1.0 1.0 1.0 Solder heat resistance (appearance ) The flow of good non-adhesive agent (_) 0.1 or less 0.3 0.1 or less Flak-like characteristics Flame resistance V-0 V-0 V-0 Peel strength (KN/m) 1.0 0.8 1.0 Through-hole electric shovel communication communication is not good -30- 200911945 [Industrial use possibility] Adhesion of the present invention The resin composition, the adhesive film, the adhesive sheet, and the cover film are non-halogen and flame retardant, so they are effective in environmental countermeasures, and are resistant to bending, migration, and through-hole plating. Excellent FPC characteristics such as reliability. -31 -

Claims (1)

200911945 X. Patent Application No. 1 - A flame retardant adhesive resin composition containing the following components (A) to (D): (A) phenoxy resin, (B) epoxy resin, (C) The hardener and the (D) hardening accelerator are essential components, and the active hydrogen equivalent of the hardener is 20 to 30 'in the flame retardant adhesive resin composition}, and the organic solvent compound is contained in the weight fraction. Or phosphorus-containing resin 〇. 5 to 5 parts by weight as phosphorus, and the glass transition temperature after thermal hardening of the flame-retardant adhesive resin composition is 1 〇〇 ° C or more. 2. The flame retardant adhesive resin composition of claim 1 wherein the glass transition temperature of the flame retardant adhesive resin composition before thermal hardening is 0 to 50 °C. 3. A flame retardant adhesive resin composition as claimed in claim 1 which is substantially free of halogen. 4. The flame-retardant adhesive resin composition of the first aspect of the invention, wherein the component (A) is a phosphorus-containing compound having a phosphorus content of 1% by weight to 6% by weight as represented by the following formula (1) Phenoxy resin, Z 1 XO-CH2 — C—OH ch 2—0—X-0 (1) -32- 200911945 (wherein X represents at least one divalent group selected from the following formula The divalent group represented by (2) or (3) is a divalent group represented by the formula (2), (3), (4) or (5), and Z represents a hydrogen atom or a glycidyl group. , η average 値 is 21 or more) [Chemical 2] Y Y R1_ R4 (4) R2 R3 (In the formulas (2) to (5), Υ represents a disc substrate which is not represented by the following formula (7) or (8), R1 to Κ·3, R1 to R4, Κ·1 ~Κ·8 series independently Table 7Π: chlorine atom, alkyl group having 1 to 4 carbon atoms or phenyl group; Α represents a single bond or -CH2-, -c(ch3)2-, -ch(ch3)-, -S-, -S〇2-, -0-, -CO- or a divalent group of a group represented by the formula (9)) 33- 200911945 (in the formulas (7) to (9), 'ri~R8, R1 to RlG each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group.) 5 . The flame retardant adhesive resin composition, wherein the component (B) is an epoxy resin which is not represented by the following formula (1) Η Η 2〇^〇-Η2〇-〇- ο Η -W -〇-CH2-C-CH2O' OH -wocc-cHz (10) (wherein W represents a divalent group represented by the formula (5), m is an integer of 0 or more, and m is an average of 〇·1 to I5; and A represents a single bond selected from the group consisting of Or _CH2-, -C(CH3)2_, -CH(CH3)-, -S-, -S〇2-, -〇-, -CO- or the valence of the group represented by the formula (9) Base). 6. The flame retardant adhesive resin composition of claim 5, wherein in the general formula (10), m = the content of the steroid is determined by gel permeation chromatography. 7 〇% or more. 7. The composition of the flame-retardant adhesive resin of the first aspect of the patent application is -34-200911945, wherein the content of the component (A) is 20 to 80% by weight. 8. A flame-retardant adhesive film which is obtained by forming a flame-retardant adhesive resin composition according to any one of claims 1 to 7 into a film form. An adhesive film comprising a layer of a flame-retardant adhesive resin composition according to any one of claims 1 to 7 on one or both sides of a base resin film. 10. A cover film comprising: a polyimide film, and a flame retardant adhesive resin as set forth in any one of claims 1 to 7 of the polyimide film. A layer composed of a composition. And a hardened material obtained by curing the flame retardant adhesive resin composition according to any one of claims 1 to 7. -35- 200911945 VII. Designated representative map: (1) The designated representative figure of this case is ··(2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the inventive feature: none