TWI437063B - A flame retardant adhesive resin composition and an adhesive film using the same - Google Patents

Description

Flame retardant adhesive resin composition and adhesive film using the same

The present invention relates to a heat-resistant adhesive resin composition, and more particularly to a highly heat-resistant, flame-retardant adhesive composition and an adhesive film using the same.

As a printed circuit board, a substrate made of paper-phenol resin, glass fiber-epoxy resin, a substrate of a polyimide film, a polyethylene terephthalate film, or the like can be used. .

In addition, in recent years, printed circuit board wiring used in the field of motors, electronic equipment, and precision equipment has a small occupied area, and therefore, the demand for multilayer printed boards is gradually increasing. 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 to composite a heterogeneous 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, materials that are excellent in flame retardancy have been sought from the point of ensuring fire safety.

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 incompatibility, cost-effectiveness, and difficulty in deterioration of plastics. However, the halogen contained herein is worried that it may become a toxic substance such as dioxin at the time of combustion, and it is strongly desired to exclude halogen from the material.

Adhesives used for printing substrates have been proposed, for example, in Patent Documents 1 to 5.

Any of these patent documents are based on epoxy resin, hardener, acrylonitrile butadiene rubber or phenoxy resin, and the flame retardant method is either brominated epoxy resin. Depending on the brominated phenoxy resin.

In addition, various materials which are non-halogen type have been developed as a flame retardant material instead of halogen. The most common method among them is the use of a resin containing phosphorus or the addition of an organophosphorus compound. Examples of such a flame retardant adhesive include Patent Documents 6 to 10.

Patent Documents 6, 7, and 9 are formulated with an organophosphorus compound, and Patent Documents 8 and 10 are a method in which a known phosphorus-containing epoxy resin or a phosphorus-containing phenoxy resin is blended as a non-halogen-based flame retardant.

[Patent Document 1] JP-A-2001-164226 (Patent Document 3) JP-A-2001-354242 (Patent Document 4) JP-A-2001-354936 Japanese Unexamined Patent Application Publication No. JP-A No. Publication No. Publication No. JP-A No. No. Publication No. Publication No. Publication No. JP-A No. JP-A No. No. Publication No. Publication No. JP-A No. No. No. Publication No. JP-A JP-A-2004-331783 [Patent Document 10] JP-A-2005-290229

(disclosure of the invention)

An object of the present invention is to provide a flame retardant adhesive resin composition which is excellent in workability such as cracking and peeling in a film state before curing, peeling adhesion after hardening, solder heat resistance, fluidity, and the like. The adhesive has excellent properties and can be non-halogenated in the corresponding environment. Further, it is to provide a flame retardant film and a cover film which are flame-retardant using such an adhesive resin composition.

In order to achieve the above object, the inventors of the present invention have found that the glass transition temperature of the pre-reaction mixture and the post-reaction cured product of the adhesive resin composition is suitable for a specific range, and the final preparation is completed. 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) hardening accelerator

The essential component is characterized in that the active hydrogen equivalent of the curing agent is 20 to 30, and the organic phosphorus compound or the phosphorus-containing resin is contained in an amount of 0.5 to 5 parts by weight as phosphorus in 100 parts by weight of the flame retardant adhesive resin composition. Further, the glass transition temperature after the heat curing of the resin composition is 100 ° C or higher.

Further, the flame retardant adhesive resin composition of the present invention has an excellent flame retardant adhesive resin composition by a glass transition temperature of 0 to 50 ° C before thermal curing or substantially no halogen.

Further, in the present invention, the component (A) is a phosphorus-containing phenoxy resin having a phosphorus content of 1 to 6% by weight as represented by the following formula (1).

(wherein X represents that at least one divalent group is selected from a divalent group represented by the following formula (2) or (3) as a necessary formula (2), (3), (4) or (5) The divalent group shown, Z represents a hydrogen atom or a glycidyl group, and the average value of n is 21 or more)

(In the formulae (2) to (5), Y represents a phosphorus-containing group represented by the following formula (7) or (8), and R ₁ to R ₃ , R ₁ to R ₄ and R ₁ to R ₈ are independently The ground represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; and A represents a single bond selected from -CH ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -S-, -SO ₂ -, -O-, -CO- or a divalent group of a group represented by the formula (9)

(In the formulae (7) to (9), R ₁ to R ₈ and R ₁ to R _{10 each} independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group.)

Further, the content of the component (A) is preferably in the range of 20 to 80% by weight.

Further, the component (B) of the present invention is an epoxy resin represented by the following formula (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 0.1 to 15). In the general formula (10), the content ratio of m=0 is the chromatographic surface measured by gel permeation chromatography. An epoxy resin having a percentage of 70% or more can obtain an excellent flame retardant adhesive resin composition.

Moreover, the flame-retardant adhesive film of the present invention is characterized in that the flame-retardant adhesive resin composition is formed into a film shape. Further, the cover film of the present invention is characterized by comprising a polyimide film and a layer composed of the flame retardant adhesive resin composition provided on the polyimide film. Further, the cured product of the present invention is obtained by curing the above-mentioned flame retardant adhesive resin composition.

Hereinafter, the flame-retardant adhesive resin composition of the present invention will be described, and the present invention relating to the flame-retardant adhesive film and the cover film will be described below, but the common parts will be described simultaneously.

The flame-retardant adhesive resin composition of the present invention (sometimes simply referred to as an adhesive resin composition or a resin composition) contains the above components (A) to (D) as essential components. The component (A) is a phenoxy resin, the component (B) is an epoxy resin, the component (C) is a curing agent, and the component (D) is a curing accelerator.

The phenoxy resin of the component (A) is preferably a resin having a phenoxy skeleton in its molecular structure. The phenoxy resin exhibits a high adhesion property to a metal foil, in particular, a copper foil or a copper alloy foil, and does not easily inhibit crosslinking of the epoxy resin of the component (B) and the curing agent of the component (C), and thus cannot be lowered. The glass transition temperature (Tg) after the heat curing of the obtained resin composition improves the solder heat resistance of the cured product of the resin composition. Further, when the obtained resin composition is applied to a cover film, moderate fluidity (fluidity) as an adhesive can be exhibited when thermocompression bonding and lamination integration. From the viewpoint of imparting flame retardancy in the adhesive resin composition, (A) component Preferably, the phosphorus-containing phenoxy resin is a phosphorus content of 1 to 6% by weight, preferably 2 to 5% by weight. The standard polyethylene oxide equivalent weight average molecular weight measured by gel permeation chromatography is 10,000 to 200,000, preferably 15,000 to 150,000, more preferably 20,000 to 120,000.

It is preferable to mix a phosphorus-containing phenoxy resin having a phosphorus content of 1 to 6% by weight as shown in the above formula (1). In the formula (1), X represents at least one divalent group selected from the group represented by the above formula (2), (3), (4), or (5), but in the formula ( The divalent base represented by 2) or (3) is necessary. It is preferable that X contains one of the divalent groups represented by the formula (2) or (3) or both of them at 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 value of the n system is 21 or more, but it is preferably in the range of 30 to 5,000. Such a phosphorus-containing phenoxy resin can be produced, for example, by the method described in JP-A-2001-310939.

Further, in the above formulae (2), (3), (4) and (5), Y represents a phosphorus-containing group represented by the above formula (7) or (8). A in the formula (5) represents a divalent group selected from a single bond or -CH ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -S-, -SO ₂ -, -O-, -CO- or a divalent group of the group represented by the formula (9). In the formulae (2) to (5) and (7) to (9), R ₁ to R _{10 each} independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group. It is preferably hydrogen or methyl, and the number of methyl groups is preferably 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), m is an integer of 0 or more, and m is an average of 0.1 to 15.

Examples of the epoxy resin represented by the above formula (10) include a bisphenol A epoxy resin, a bisphenol F epoxy resin, and a biphenyl epoxy resin. These may be used alone or in combination. Use more than one species. Further, a cresol novolac type epoxy resin derived from a novolak resin containing bis(cresol)methane as a main component may be used. The epoxy resin may be substantially free of halogen.

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 =0 body 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 100 parts by weight of 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 adhesiveness does not appear due to a decrease in flexibility and an increase in internal stress, and if it is more than 80 parts by weight, the ratio of the cross-linking component is reduced, 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 adhered When the heat resistance of the resin composition is lowered, when it exceeds 70 parts by weight, the flexibility is lowered and the peeling adhesive force of the adhesive resin composition is lowered. 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.

The curing agent of the component (C) may be a curing agent of an epoxy resin known as the component (B), but it is necessary to have an active hydrogen equivalent of 20 to 30. The active hydrogen equivalent hardener is required to have Y mole active hydrogen (H) per Xg, calculated as X/Y (g/eq). 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 flexibility is lowered. Such a hardener is a novolac type phenol resin, dicyanodiamine, diaminodiphenylmethane, diaminodiphenylphosphonium, an azide, an imidazole or the like, and an active hydrogen equivalent is advantageously used. 20~30. 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 to an epoxy resin of the component (B) so that the equivalent ratio (C)/(B) is 0.5 to 1.5. In general, when a phenol resin-based curing agent is used, it can be 0.8 to 1.2, and when an amine-based curing agent is used, it can be 0.5 to 1.0.

The hardening accelerator of the component (D) 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 0.01 to 3.0% by weight for the flame retardant adhesive resin composition. Further, when an organophosphorus compound is used as the component (D), other organic phosphorus compounds or phosphorus-containing resins are combined. Phosphorus is formulated so as to be in the range of 0.5 to 5 parts by weight based on 100 parts by weight of the flame retardant-adhesive resin composition.

The flame retardant adhesive resin composition of the present invention may be contained in an amount of 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, based on 100 parts by weight of the resin composition, and may be phosphorus (or resin). It is preferably 1.5 to 3 parts by weight, and the flame resistance can be imparted without lowering the heat resistance of the solder 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 alone or in combination of two or more, but it is preferred 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 0.5 to 5 parts by weight based on 100 parts by weight of the resin composition, and may be used as an organic phosphorus compound or a phosphorus-containing resin as phosphorus to enhance flame retardancy. The component does not contain a halogen (a halogen component or a halogen 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 100 ° C or more, preferably 100 to 170 ° C, of the cured product obtained by thermally curing the resin composition. When the glass transition temperature of the cured product after thermosetting is less than 100 ° C, the migration resistance is lowered. Further, the resin composition before thermosetting in the flame retardant adhesive resin composition of the present invention (corresponding to B) The glass transition temperature of the composition of the order state is preferably in the range of 0 to 50 ° C, more preferably in the range of 10 to 50 ° C. When the glass transition temperature of the composition in the B-stage state is lower than 0 ° C, the adhesion is exhibited in the film, and when it is processed into FPC, the adjustment of the positioning is difficult, and the practicality is lacking. Further, when it 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 property 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 organic pigment such as calcium carbonate, a polymeric elastomer as a softening agent, or an additive such as a viscosity modifier or a coupling agent may be added. The addition rate can be appropriately selected depending on the characteristics sought.

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 that time may be appropriately selected depending on the conditions of use, but is generally 20 to 60% by weight. Further, it is understood that the solvent is a component which is used as a solution for the composition 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.

The flame retardant adhesive resin composition of the present invention is used in the form of a film. In this case, it can be thinned by a known method. However, an example of a suitable molding method is to form a solution by diluting a flame retardant adhesive resin composition with an organic solvent such as methyl ethyl ketone, and then borrowing the obtained adhesive resin solution. A known method is applied to a substrate of a metal foil, a polyester film, a polyimide film or the like which has been subjected to release treatment to evaporate the solvent without being viscous, and the composition constituting the adhesive resin layer does not harden. The reaction temperature and time conditions are dried to form an adhesive film layer, which is then peeled off from the substrate to form a flame retardant adhesive film.

The drying conditions vary depending on the solvent or resin composition used, but generally, the temperature and time range of 130 to 160 ° C and 3 to 10 minutes are selected. Further, in the case of a bonded sheet composed of a release film of a polyester or the like and a layer of a flame-retardant adhesive film, the ratio of the thickness of the layer of the release film to the flame-retardant adhesive film is not particularly limited, but is released. When the film thickness is 10 to 15 μm, the thickness of the flame retardant adhesive film may be suitably used in the range of 15 to 30 μm.

The method of using the flame-retardant adhesive film of the present invention is applied to, for example, a flexible printed circuit board, a glass fiber-epoxy circuit board, a paper-phenol circuit board, or various printed circuit boards obtained by processing such circuits, Adhesion of adherends such as metal and resin substrates. A printed circuit board can be obtained by adhering a metal foil to a resin substrate, and a multilayer printed circuit board or a printed circuit board can be obtained by interposing a printed circuit board or a printed circuit board. By adhering the printed circuit board to the coating layer, a coating layer and a printed circuit board can be obtained. Others may be used as a bonding film for connecting a printed circuit board or a printed circuit board. Even if any one can benefit The steps 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 surface or both surfaces of the base resin film, and an adhesive film can be further formed. Here, the base resin film is a polyimide film, a polyester resin film or the like. 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 which peels the surface of the base resin film is 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 the release film of the polyester or the like and the layer of the 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. In the case of μm, the adhesive layer of 15 to 30 μm can be suitably used.

The flame retardant adhesive resin composition of the present invention can also be applied to an adhesive layer covering a film. At this time, 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 viscosifying. 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. Drying on a polyimide film with a thickness of 2 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm, and drying dry. The drying conditions vary depending on the solvent or resin composition used, but generally, the temperature and time range of 130 to 160 ° C and 3 to 10 minutes are selected. Further, the polyimide film is required to increase 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 ~30μm. 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 μm, the adhesive layer is 15 to 20 μm, and when the film thickness is 25 μm, a cover film having an adhesive layer of 25 to 35 μm is generally provided.

[Best form for implementing the invention]

Next, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples. The method for evaluating 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.

1. B-order physical properties

1.1 glass transition temperature (Tg)

The adhesive resin composition was dissolved in methyl ethyl ketone solvent to form a 35 wt% adhesive solution, and then applied to a fluororesin sheet of longitudinal × horizontal × thick = 50 × 150 × 1 mm, and dried at 135 ° C for 5 minutes to evaporate the solvent. A film before the hardening reaction (film of the B-stage state composition) is prepared. A dynamic viscoelasticity measuring device (DMS-6100 manufactured by Seiko Instrument Co., Ltd.) was used at a frequency of 10 Hz, a temperature range of -150 to 200 ° C, and a temperature increase rate of 2 ° C / min. The temperature dispersion tan δ curve of this sample was measured, and the peak temperature of the obtained temperature-tan δ curve was taken as the glass transition temperature (Tg).

1.2 Crack resistance and peeling resistance

The above-mentioned 35% by weight of the adhesive solution was applied to a single-sided coating adhesive solution of a polyimide film (Kaneka Apical NPI) of a length × width × thickness = 200 mm × 300 mm × 25 μm, and dried at 135 ° C for 5 minutes to prepare After the cover film having a thickness of 25 μm of the adhesive layer was applied, the adhesive coating layer of the cover film was placed inside, and when the film was covered with a finger, the crack was observed by the adhesive layer. When it is judged that cracks and peeling occur, it is "not possible", and when cracks are not seen, peeling is considered "good".

2. Hardened properties

2.1 glass transition temperature (Tg)

The above 35 wt% adhesive solution was applied to a fluororesin sheet of length × width × thickness = 50 mm × 150 mm × 1 μm, and dried at 135 ° C for 5 minutes to evaporate the solvent, and then another fluorine of the same shape was superposed on the adhesive-coated surface. The resin sheet was subjected to vacuum heat pressing at 170 ° C for 1 hour, and then post-hardened at 190 ° C for 2 hours to prepare a cured film of the adhesive to be a sample. The temperature dispersion tan δ curve of the sample was measured using a dynamic viscoelasticity measuring apparatus (DMS-6100 manufactured by Seiko Instrument Co., Ltd.) at a frequency of 10 Hz, a temperature range of -150 to 200 ° C, and a temperature increase rate of 2 ° C /min. The peak temperature of the -tan δ curve is taken as the glass transition temperature (Tg).

3. Material properties and film properties of FPC

3.1 heat resistance

The above-mentioned 35% by weight of the adhesive solution was applied to a single-side coating adhesive solution of a polyimide film (Kaneka, Apical NPI) of a length × width × thickness = 200 mm × 300 mm × 25 μm, and dried at 135 ° C for 5 minutes. After the cover film having a thickness of 25 μm was prepared, the 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 1 hour. Then, the sample was prepared by post-hardening at 190 ° C for 2 hours. Then, the flame resistance test of the flame resistance test was carried out in the order of 7.7 of JPCA-BM02-1991, and the flame resistance was judged by the two levels of "VTM-0" and "non-flammability" based on the UL standard 94. "VTM-0" is flame resistant.

3.2 Peel 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 170 ° C for 1 hour, and then post-cured at 190 ° C for 2 hours. The test piece produced was measured for the production of the test piece and the peel strength in accordance with the peel strength of 7.5 of JPCA-BM02-1991.

3.3 Solder heat resistance (appearance)

After the cover film was prepared under the same conditions as above, the test piece was produced and the solder heat resistance test was carried out in accordance with the heat resistance (appearance) of the solder of JPCA-BM02-1991-7.9. 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 170 ° C for 1 hour, and then post-cured at 190 ° C for 2 hours. After the test piece was dried at 105 ° C for 1 hour, it was floated in a solder bath set at 260 ° C for 5 seconds, and its adhesive state was observed. The judgment is to confirm the presence or absence of a poor condition such as foaming, swelling, peeling, etc., and it is "good" when it is not good, and it is "not" when it is not good.

3.4 bending resistance

After the cover film was prepared under the same conditions as above, a copper foil laminate (Espanex MC12-25-00CEM, manufactured by Nippon Steel Chemical Co., Ltd.), and a bending resistance test of A method of JPCA-BM02-1991-7.6.1 were used. The test piece was produced and the bending resistance test was carried out. In the same manner, the film was heat-pressed at 170 ° C for 1 hour, and then post-cured at 190 ° C for 2 hours. The radius of curvature is 0.38 mm. The judgment determines that the copper circuit of the test piece is broken, and the number of times of bending that cannot be energized. It is judged that the number of bends to the broken line is "not" when it is 1000 times or less, and it is "ok" when it is 1000 to 3000 times. "Good" when it is more than 3000 times.

3.5 Adhesive resin composition flow

After the cover film was prepared under the same conditions as above, the test piece production and flow test were carried out in accordance with JPCA-BM02-1991-7.10. Judgment system The length of the adhesive resin composition exudation was measured.

3.6 migration resistance

After the cover film was prepared under the same conditions as above, the cover film was subjected to hot stamping at 170 ° C in a comb-type circuit pattern of foil copper of the etched copper foil laminate in a line/gap of 100 μm/200 μm. After the hour, the mixture was post-hardened at 190 ° C for 2 hours to prepare a sample. The same sample was placed in a constant temperature and humidity chamber whose temperature and humidity were adjusted to 85 ° C -85 RH %. After the brush type circuit in the sample was subjected to direct current for 50 V for 500 hours, the sample was taken out, and the comb type circuit and its periphery were observed under a microscope. 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% by weight of the adhesive solution was applied to the one side of the polyester release film of the longitudinal direction × width × thickness = 200 mm × 300 mm × 25 μm, and dried at 135 ° C for 5 minutes to prepare an adhesive sheet having a thickness of 25 μm. The sample was 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 6471, and the flame resistance was judged by the two levels of "V-0" and "no flame resistance" based on the UL standard 94. "V-0" is flame resistant.

4.2 Peel strength

After the adhesive sheet is prepared under the same conditions as above, the adhesive sheet is After the release film was peeled off, two copper foils of length × width × thickness = 200 mm × 300 mm × 25 μm were prepared and kneaded between the shiny faces of the respective copper foils at 170 ° C for 1 hour, and then at 190 ° C. After the post-hardening for 2 hours, a sample was prepared, and the peel strength was measured in accordance with JIS C 6471.

4.3 Through-hole plating continuity

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 170 ° C for 1 hour, and post-cured at 190 ° C for 2 hours to prepare a cured sheet. On the hardened sheet, a through hole having a diameter of 0.3 mm was opened by a drill, and a copper plating layer of 20 to 25 μm was formed on the inner side of the same hole by electroless copper plating to obtain a sample. The samples were subjected to hot and cold cycle exposure at -40 ° C, 15 minutes, 150 ° C, and 15 minutes, and the number of cycles leading to poor conduction was measured. The judgment system 500 is "not available" for the following cycles, the 500 to 2000 cycles are "OK", and the 2000 cycles or more are "good".

[Examples]

Synthesis Example 1

The 10-(2,5-dihydroxyphenyl)-10H-9- represented by the following formula (11) was fed into a 4-port glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. oxa-10-phosphaphenanthrene-10H-9-oxide (manufactured by Sanko Chemical Co., Ltd., HCA-HQ, hydroxyl equivalent 162 g/eg, phosphorus content 9.5% by weight) 162 parts, bisphenol A type epoxy resin (Dongdu Huacheng 175 parts of YD-8125, epoxy equivalent (171.6g/eg), 144 parts of cyclohexanone, 2-ethyl-4-methylimidazole as catalyst (made by Shikoku Chemical Industry Co., Ltd.) , 2E4MZ) 0.13 parts, reacted at a temperature of 150 ° C ~ 170 ° C for 5 hours under normal pressure, and then added 156 parts of cyclohexanone and 300 parts of N,N-dimethylformamide to obtain a phosphorus-containing phenoxy resin. A solid solution of A was 937 parts by weight of a 36% by weight solution. The resin solution was applied onto a polyester release film, and then dried at 165 ° C for 5 minutes to evaporate the solvent to obtain a phosphorus-containing phenoxy resin A having a phosphorus content of 4.6% by weight.

Used as a pipe string for Shodex. AD-800P+TSKgel Super HM-H+Super HM-H+Super H2000, GPC analysis of phosphorus-containing phenoxy resin A as a dissolving solution of N,N-dimethylformamide (20 mM lithium bromide), and the same as the resin The standard polyethylene oxide equivalent weight average molecular weight is 39,200.

Synthesis Example 2

The phosphorus-containing phenoxy resin was synthesized under the same conditions as in Synthesis Example 1 except that the reaction time was changed from 5 hours to 8 hours to obtain a phosphorus-containing phenoxy resin B having a phosphorus content of 4.6% by weight. The standard polyethylene oxide equivalent weight average molecular weight is 80,600.

The abbreviations of the components used to prepare the adhesive resin composition are shown below.

YD-128: bisphenol A type epoxy resin (made by Tohto Kasei Co., Ltd.) YDF-170: bisphenol F type epoxy resin (made by Tohto Kasei Co., Ltd.) YD-011: bisphenol A type epoxy resin (made by Dongdu Chemical Co., Ltd.) BRG-555: phenolic varnish type phenol resin (made by Showa Polymer Co., Ltd.) DICY: dicyanodiamine (made by Japan Carbide Industries Co., Ltd.) DADPS: Diaminodiphenyl hydrazine (manufactured by Wakayama Seiki Co., Ltd.) A: Phosphorus-containing phenoxy resin A resin B of Synthesis Example 1: Phosphorus-containing phenoxy resin B of Synthesis Example 2 YP-50SC: phenoxy resin (manufactured by Tohto Kasei Co., Ltd.) 1072T: Acrylonitrile butadiene rubber (Japan) SPE-100: Cyclophenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd.) 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)

The GPC analysis of the epoxy resin was carried out under the following conditions.

Device: HLC-8120GPC column manufactured by Tosoh Corporation: manufactured by Tosoh Corporation, TSK-GEL: SUPER HZ2000×1, SUPER HZ3000×1, SUPER HZ4000×1 column temperature: 40°C mobile phase: tetrahydrofuran THF, flow rate: 0.35 ml/ Sub-detector: concentration of the sample type: 0.03g / THF 10ml

The content of the m=0 body was such that the peak area of the m=0 body obtained from the obtained GPC color layer analysis was divided by the area peak area of the whole component as the content (%).

The YD-128 system polymerization degree m=0 body content was 82%.

The YDF-170 system polymerization degree m=0 body content was 78%.

Examples 1-8

The components were prepared at a ratio (% 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. Confirm that the feature that shows any of them is excellent.

Comparative Example 1~7

The components were prepared 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 migration resistance and the adhesive sheet characteristics in the film properties was 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-555, DICY, DADPS are hardeners, resin A, resin B, YP-50SC are phenoxy resins, and SPE-100 is organic phosphorus. The compound, 2E4MZ, is a hardening accelerator.

[Industry use possibility]

The adhesive resin composition of the present invention, the adhesive film, the adhesive sheet, and the cover film using the same are non-halogen and flame retardant, so that it is effective in environmental countermeasures, and is resistant to bending, migration, and penetration. The FPC characteristics of the hole plating guide communication and the like are excellent.

Claims (5)

A flame retardant adhesive resin composition comprising the following components (A) to (D): (A) phenoxy resin, (B) epoxy resin, (C) hardener, and (D) hardening The accelerator is an essential component, and the active hydrogen equivalent of the curing agent is 20 to 30, and 0.5 to 5 parts by weight of the organophosphorus compound or the phosphorus-containing resin is contained in 100 parts by weight of the flame retardant adhesive resin composition. Phosphorus, the range of 30 to 70 parts by weight of the component (A), the range of 20 to 70 parts by weight of the component (B), and the range of 0.01 to 3.0 parts by weight of the component (D), and the component (C) is as described above ( B) component, the equivalent ratio (C) / (B) is 0.5 to 1.5, and the glass transition temperature after thermal hardening of the flame retardant adhesive resin composition is 100 ° C or more, and the flame retardant adhesive resin The glass transition temperature of the B-stage state composition of the composition is 0 to 50 ° C, and the component (A) is a phosphorus-containing phenoxy group having a phosphorus content of 1% by weight to 6% by weight as represented by the following formula (1). Resin, (wherein X represents that at least one divalent group is selected from a divalent group represented by the following formula (2) or (3) as a necessary formula (2), (3), (4) or (5) The divalent group shown, Z represents a hydrogen atom or a glycidyl group, and the average value of n is 21 or more) (In the formulae (2) to (5), Y represents a phosphorus-containing group represented by the following formula (7) or (8), and R ₁ to R ₃ , R ₁ to R ₄ and R ₁ to R ₈ are independently The ground represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; and A represents a single bond selected from -CH ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -S-, -SO ₂ -, -O-, -CO- or a divalent group of a group represented by the formula (9) (In the formulae (7) to (9), R ₁ to R ₈ and R ₁ to R _{10 each} independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group), and the component (B) is represented by the following formula: (10) The epoxy resin shown, (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 0.1 to 15; and A represents a single bond or -CH ₂ -, -C ( CH ₃ ) ₂ -, -CH(CH ₃ )-, -S-, -SO ₂ -, -O-, -CO- or a divalent group of a group represented by the formula (9), R ₁ ~ R ₈ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group). A flame-retardant adhesive film comprising a flame-retardant adhesive resin composition according to claim 1 of the patent application form a film. An adhesive film characterized by having a layer of a flame retardant adhesive resin composition as in the first aspect of the patent application on one or both sides of a base resin film. A cover film characterized by having a thin polyimide film A film, and a layer composed of a flame retardant adhesive resin composition as set forth in claim 1 of the polyimine film. A cured product obtained by hardening a flame retardant adhesive resin composition according to claim 1 of the patent application.