WO2008105563A1 - Flame-retardant adhesive resin composition and flexible printed board material using the same - Google Patents

Abstract

Provided is a flame-retardant adhesive resin composition to be used for a flexible wiring board. The composition contains, as essential components, (a) a specified epoxy resin, (b) a specified phosphorus-containing phenoxy resin, (c) a curing agent, and (d) a curing accelerator. The flame-retardant adhesive resin composition has excellent adhesive characteristics, such as high peel adhesive force, high solder heat resistance, low flowability and the like by substantially not containing halogen element.

Description

 Description Flame retardant adhesive resin composition and flexible printed circuit board material using the same Technical Field

 The present invention relates to a heat-resistant adhesive resin composition, and more specifically, a high heat-resistant and flame-retardant adhesive composition substantially free of halogen elements, an adhesive film using the same, a force parlay film, and flexible copper In particular, the present invention relates to a flame-retardant adhesive resin composition suitable for a flexible printed circuit board (hereinafter also referred to as FPC). Background art

 As a printed wiring board, a base material such as paper-phenol resin, glass fiber-epoxy resin, a polyimide film, a polyethylene terephthalate film, or the like and a metal bonded to each other have been used.

 In this specification, a printed wiring board refers to a laminate before circuit processing, a circuit processed from this metal foil is referred to as a printed wiring board, and both are referred to as printed boards.

 In recent years, printed circuit boards used in the fields of electrical equipment, electronic equipment, and precision equipment have been occupying a small area, and the demand for multilayer printed circuit boards has been increasing. Various adhesives or adhesive films are used in the process of making multilayer printed wiring boards by laminating printed wiring boards and compositing different kinds of circuit materials.

 Such adhesives are widely used as adhesives for multilayer printed circuit boards and adhesives for force parlay films, but materials with excellent adhesive strength, chemical resistance, solder heat resistance, folding resistance, etc. Has come to be required. In addition, materials with excellent flame retardancy have been demanded from the viewpoint of ensuring fire safety.

In conventional adhesive films, resins or additives containing halogen such as bromine have been used to impart flame retardancy. Halogens have been widely used because they not only impart flame retardancy, but also have high cost performance and are difficult to degrade plastics. However, there is a concern that the halogens contained here may cause harmful substances such as dioxin during combustion, and the elimination of halogens from materials is strongly desired. Adhesives used for printed circuit boards have been proposed in Patent Documents 1 to 5, for example.

 Patent Document 1: Japanese Patent Application Laid-Open No. 10-1 0 20 25

 Patent Document 2: Japanese Patent Laid-Open No. 200 1-1 64 2 26

 Patent Document 3: Japanese Patent Application Laid-Open No. 200 1-3 23 242

 Patent Document 4: Japanese Laid-Open Patent Publication No. 200 1-3549 3 6

 Patent Document 5: Japanese Patent Laid-Open No. 2003-3 1 8 1 9 93

 All of the above patent documents are mainly composed of epoxy resin, curing agent, acrylonitrile butadiene rubber or phenoxy resin, and all flame retardant means are fluorinated epoxy resin, brominated phenoxy. By blending rosin.

 -On the other hand, various non-halogen materials have been developed as flame retardant materials to replace halogens. Among them, the most common method is the use of a resin containing phosphorus or the addition of an organic phosphorus compound. Examples of such a flame retardant adhesive include Patent Documents 6 to 10 and the like.

 Patent Document 6: Japanese Patent Application Laid-Open No. 200 1-3 3 9 1 3 1

 Patent Document 7: Japanese Patent Application Laid-Open No. 200 2-6 0 720

 Patent Document 8: Japanese Laid-Open Patent Publication No. 2000-3 1 764 70

 Patent Document 9: Japanese Unexamined Patent Application Publication No. 2004-3 3 1 7 8 3

 Patent Document 10: JP-A-2005-290229

Patent Documents 6, 7, and 9 blend organic phosphorus compounds, and Patent Documents 8 and 10 blend known phosphorus-containing epoxy resins and phosphorus-containing phenoxy resins as non-halogen flame retardant means, respectively. I am going to do that. Disclosure of the invention An object of the present invention is to provide a flame retardant adhesive resin composition which is excellent in adhesive properties such as peel adhesive strength, solder heat resistance, flowability, etc., and which is non-halogenated to cope with the environment. Furthermore, it is to provide a flame retardant adhesive film, a coverlay film and a flexible copper clad laminate using such an adhesive resin composition.

 As a result of intensive studies to achieve the above object, the present inventors have used the specific resin in the adhesive resin composition and found specific components, thereby completing the present invention.

 That is, the present invention provides the following components (ii) to (2):

 (I) The weight average molecular weight in terms of standard polyethylene oxide, which is represented by the following general formula (1), has a phosphorus content of 1% to 6% by weight and was measured using gel permeation chromatography. Phosphorus-containing phenolic resin, which is 60, 0 0 0-2 00, 0 0 0,

 (Mouth) Epoxy resin represented by the following general formula (1 0),

 (No,) hardener, and

 (II) curing accelerator,

一般式 （ 1 ) において、 Xは下記一般式 （2) 又は （3) で表される 2価の基を必須と する一般式 （2)、 （3)、 （4) 又は （5) から選ばれる少なく とも 1種の 2価の基を 示し、 Zは水素原子又は一般式 （6) を示し、 nは平均値で 2 1以上である。 Is a flame retardant adhesive resin composition characterized by containing an essential component and substantially free of halogen elements.

In the general formula (1), X is selected from the following general formula (2), (3), (4) or (5), which requires a divalent group represented by the following general formula (2) or (3) Represents at least one divalent group, Z represents a hydrogen atom or the general formula (6), and n is an average value of 21 or more.

Here, in the formulas (2) to (5), Y represents a phosphorus-containing group represented by the general formula (7) or (8), and scales R i to R ₄ , R! To Κ ₄ , R i Rs independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. A is a single bond or one CH ₂ —, one C (CH ₃ ) 2 —, —CH (CH ₃ ) one, one S—, — S 0 ₂ —, one O—, one CO— or general formula (9) A divalent group selected from

Where in formula (7) ~ (9)! ^ ~ Scale 1 ^ ~ _{1 10} , RR s independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

ここで、 式中、 Wは一般式 （5) で表される 2価の基を示し、 mは 0以上の整数であ り、 mの平均は 0. 1〜 1 5である。 ( Ten)

Here, in the formula, W represents a divalent group represented by the general formula (5), m is an integer of 0 or more, and the average of m is 0.1 to 15.

 Further, in the present invention, in the (mouth) component, the content of the polymerization degree m = 0 isomer in the general formula (10) is 70% in terms of the area percentage of the chromatogram measured using gel permeation chromatography. This is a flame retardant adhesive resin composition characterized by the above.

Furthermore, the present invention provides that the component (i) is a divalent group represented by the general formulas (2) and (5) in the general formula (1), and Ri Rg in the general formula (2) is hydrogen May be characterized in that Y represents the general formula (7) and Ri Rs in the general formula (5) represents a hydrogen atom, but A represents --C (CH ₃ ) _2- (I) In the general formula (1), X is a divalent group represented by the general formulas (3) and (5), and Ri Rs in the general formula (3) represents a hydrogen atom. Y represents the general formula (7), and Ri Rs in the general formula (5) represents a hydrogen atom, but A may represent one C (CH ₃ ) ₂ —, or ( Ii) In the general formula (1), X is a divalent group represented by the general formulas (2) and (5), and Ri Rs in the general formula (2) represents a hydrogen atom, but Y is Shows the general formula (7) In the general formula (5), Ri Rs represents a hydrogen atom, but A may be characterized by the general formula (9), or (i) the component is the general formula (1), and X is It is a divalent group represented by general formulas (3) and (5). In general formula (3), R to Shaku ₃ represents a hydrogen atom, but Y represents general formula (7). R i Rs in the formula (5) represents a hydrogen atom, but A may be characterized by the general formula (9).

 Furthermore, the flame retardant adhesive resin composition of the present invention may contain 20 to 80 parts by weight of component (i) with respect to 100 parts by weight of the composition.

The flame-retardant adhesive film of the present invention is characterized in that the flame-retardant adhesive resin composition of the present invention is formed into a film. The force parlay film of the present invention is characterized by having a polyimide film and a layer made of the flame-retardant adhesive resin composition of the present invention provided on the polyimide film.

 The flexible copper-clad laminate of the present invention is characterized by having a polyimide film, a layer made of the flame-retardant adhesive resin composition of the present invention provided on the film, and a copper foil. Is.

 Hereinafter, the present invention related to a flame retardant adhesive resin composition will be described, and then the power to explain the present invention related to a flame retardant adhesive film, a force parlay film and a flexible copper-clad laminate will be described. explain. First, each component of the flame retardant adhesive resin composition of the present invention will be described.

 The flame-retardant adhesive resin composition of the present invention (sometimes abbreviated as an adhesive resin composition or a resin composition) contains the above components (i) to (2) as essential components. (Ii) The component is a phosphorus-containing phenoxy resin, (Mouth) The component is an epoxy resin, (C) The component is a curing agent, (2) The component is a curing accelerator, and substantially contains a halogen element. Not included. Here, “substantially free of halogen elements” means that no halogen and halogen compounds of 90 Owtppm or more are contained as halogen elements.

(I) component Li emissions containing phenoxy resin is represented by the general formula (1), a re-emission content of 1 wt% to 6 wt. _^0/0, and using gel permeation chromatography to emissions chromatography The measured standard polyethylene oxide-converted weight average molecular weight is 60, 00 0 to 20 0, 0 0 0, preferably 70, 00 0-1 3 0, 0 0 0, more preferably 8 0, 0 0 0 Use one that is ~ 1 2 5, 0 0 0. By using a material having a weight average molecular weight within the above range, for example, folding resistance when applied as an adhesive layer of a force parlay film described later can be improved. In the general formula (1), X is the above general formula (2), (3),

It represents at least one divalent group selected from (4) or (5), but the divalent group represented by the general formula (2) or (3) is essential. Advantageously, one or both of the divalent groups represented by the general formula (2) or (3) is 20 mol ⁰ / in X. Or more, preferably 50 mol% or more It is good to include. Z represents a hydrogen atom or a glycidyl group represented by the above formula (6). n is an average value of 2 1 or more, but is preferably in the range of 30 to 500. Such a phosphorus-containing phenoxy resin can be produced, for example, by the method disclosed in Japanese Patent Application Laid-Open No. 2000-310.

In the general formulas (2), (3), (4) and (5), Y represents a phosphorus-containing group represented by the general formula (7) or (8). A in formula (5) is a single bond or one CH ₂ —, one C (CH ₃ ) ₂ —, one CH (CH ₃ ) one, one S—, one S 0 ₂ —, ten thousand, one CO— Or a divalent group selected from the above general formula (9). Ri Ri in Formula (2)-(5) and (7)-(9). Independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Preferably, they are a hydrogen atom or a methyl group, and the number of methyl groups is 4 or less.

In addition, the component (i) is a divalent group represented by the above general formulas (2) and (5) in the above general formula (1), and R Rg in the general formula (2) is a hydrogen atom Y represents the general formula (7), and R to ₈ in the general formula (5) represent a hydrogen atom, but A may represent —C (CH ₃ ) ₂ —.

In addition, the component (i) is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and Ri Rs in the general formula (3) represents a hydrogen atom. As shown, Y represents the general formula (7), and R to ₈ in the general formula (5) represent a hydrogen atom, but A may represent —C (CH ₃ ) ₂ —.

In addition, the component (i) is a divalent group represented by the general formulas (2) and (5) in the general formula (1), and R i Rs in the general formula (2) represents a hydrogen atom. shown but, Y represents the general formula (7), R ₁ to R ₈ in the general formula (5) is a hydrogen atom, may be one a represents the general formula (9).

In addition, the component (i) is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and Ri Rg in the general formula (3) represents a hydrogen atom. Y represents the general formula (7), Ri to R ₈ in the general formula (5) represent a hydrogen atom, but A represents the general formula (9) Five

8 may be indicated.

 (Mouth) The component epoxy resin is an epoxy resin represented by the above general formula (10). In the formula (1 0), W represents a divalent group represented by the general formula (5), m is an integer of 0 or more, and the average of m is 0 · 1 to 15. Examples of the epoxy resin represented by the general formula (10) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, and the like. May be used alone or in combination of two or more. It is preferable that the epoxy resin does not substantially contain a haguchigen element.

 In consideration of improvement in cracking resistance of a dried product or a film obtained by drying the resin composition (hereinafter also referred to as a B-stage state composition), the degree of polymerization m = 0 in the above general formula (1 0) Is preferably 70% or more, more preferably 80% or more in terms of the area percentage of the chromatogram measured using the area percentage of gel permeation chromatography. And it is preferable that it is liquid at normal temperature.

 In 100 parts by weight of the flame retardant adhesive resin composition of the present invention, the component (ii) is 20 to 80 parts by weight, preferably 30 to 70 parts by weight, more preferably 40 to 6 parts by weight. It is preferable to add 0 part by weight. If the amount is less than 20 parts by weight, the adhesiveness does not develop due to a decrease in flexibility and the stress at the buttock.If the amount exceeds 80 parts by weight, the soldering heat resistance decreases due to a decrease in the ratio of the cross-linking component, and the adhesive. As the performance is impaired. The (mouth) component is preferably blended in the range of 20 to 70 parts by weight. (Mouth) If the component is less than this range, the crosslink density will decrease and the heat resistance of the adhesive will decrease. On the other hand, if it is too high, the flexibility of the adhesive will decrease and the adhesive will The problem arises that the peel adhesion is reduced.

(C) Component curing agents that are known as (mouth) component epoxy resin curing agents can be used, such as nopolac-type phenolic resin, dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, azines, Imidazoles, acid anhydrides, etc. can be used. In addition, when imidazole is used as component (c), it is also calculated as component (2) because it is also component (2). (C) The amount of ingredient used is (mouth) ingredient It is preferable to blend such that the equivalent ratio ((C) / (Mouth)) of the epoxy resin is 0.5 to 1.5. In general, when using a phenol resin curing agent, 0.8 to 1.

2. When an amine curing agent is used, it is preferably 0.5 to 1.0.

 (2) As the component curing accelerator, organophosphorus compounds such as triphenylphosphine, imidazoles such as 2-phenylimidazole and 2-ethyl-4-methylimidazole, tertiary amines, and Lewis acids can be used. The blending ratio is appropriately selected according to the required curing time. Generally, however, the blending ratio for the flame-retardant adhesive resin composition is from 0.01 to

3. Good be used in an amount of 0 wt ^_0/0.

 The glass transition temperature (Tg) of a cured product obtained by thermosetting the flame retardant adhesive resin composition of the present invention is preferably 100 ° C. or higher, more preferably 100 to 1700. It should be in the range of ° C. When the glass transition temperature of the cured product after heat curing is less than 100 ° C, the migration resistance is lowered. The glass transition temperature after curing of the resin composition can be adjusted mainly by the type and amount of the (mouth) component epoxy resin and (c) component curing agent. Here, the measurement of the glass transition temperature of the cured product is based on the conditions of the property evaluation method described later: <cured product properties> [glass transition temperature (Tg)]

 The flame-retardant adhesive resin composition of the present invention includes, as components other than the above essential components, aluminum hydroxide and magnesium hydroxide as inorganic flame retardants, silica as a scavenger or extender, An extender such as calcium carbonate and a polymer elastomer can be blended as a flexibility-imparting agent, or additives such as a viscosity modifier and a coupling agent can be blended. The addition rate is appropriately selected according to the required characteristics.

The flame-retardant adhesive resin composition of the present invention is used as an adhesive resin solution dissolved or dispersed in an organic solvent such as methyl ethyl ketone, dimethylformamide, 2-ethoxyethanol or the like. . In this case, the solid content concentration is appropriately selected depending on use conditions, but is generally 20 to 60% by weight. It should be noted that the solvent is not a component constituting the flame retardant adhesive resin composition of the present invention, but a component used to make the flame retardant adhesive resin composition into a solution. Therefore, the amount of each component in the flame retardant adhesive resin composition Solvents are excluded from the calculation.

 The flame retardant adhesive resin composition of the present invention can be used after being formed into a film. In this case, it is possible to form a film using a conventionally known method, but as an example of a suitable molding method, a flame retardant adhesive resin composition is diluted with an organic solvent such as methyl ethyl ketone. Then, the obtained adhesive resin solution is applied to a base material such as a metal foil, a polyester film, or a polyimide film whose surface has been peeled off by a conventionally known method, and the solvent is evaporated. Tack-free, and the composition constituting the adhesive resin layer is dried at a temperature and time conditions that do not cause a curing reaction to form an adhesive film layer, which is peeled off from the base material, and the flame retardant adhesive film And The drying conditions vary depending on the solvent and resin composition used, but generally, a temperature of 130 to 160 ° C. and a temperature and time range of 3 to 10 minutes are selected. When used as a bonder sheet comprising a release film such as polyester and an adhesive film layer, the ratio of the thickness of the release film and the adhesive film layer is not particularly limited, but the release film thickness 1 2 An adhesive layer having 15 to 30 m provided at 5 / m can be suitably used.

 Examples of the method of using the flame retardant adhesive film of the present invention include, for example, a flexible printed wiring board, a glass fiber-epoxy wiring board, a paper-phenol wiring board, and various printed wiring boards obtained by processing these circuits. Suitable for bonding objects such as metals and resin substrates. A printed wiring board can be obtained by bonding a metal foil and a resin substrate, and a multilayer printed wiring board or printed wiring board can be obtained by bonding printed wiring boards or printed wiring boards together. By attaching the wiring board and force parlay, a printed wiring board with a coverlay can be obtained. In addition, it can be used as an adhesive film for connecting printed wiring boards or printed wiring boards. In any case, it is advantageously used in the process of manufacturing or processing printed circuit boards.

The flame retardant adhesive resin composition of the present invention can also be applied to the adhesive layer of a force parlay film. In that case, the cover lay film is formed from the polyimide film and the above adhesive resin composition. As a method of forming the force parlay film of the present invention, It is possible to form a film using a conventional method. As an example of a suitable molding method, the adhesive resin composition is diluted with an organic solvent such as methyl ethyl ketone to form a solution, and then the obtained adhesive resin solution is applied onto a polyimide film. There is a method of evaporating the solvent to make it tack-free, and drying the adhesive resin composition constituting the adhesive layer at a temperature and time conditions that do not cause a curing reaction to form a force parlay film. The polyimide film is coated with a thickness of 2 to 200 m, preferably 5 to: 100 μm πι, more preferably 10 to 50 μm, and then dried. The drying conditions vary depending on the solvent and resin composition used, but generally, a temperature of 130 to 160 ° C, 3 to: L 0 minutes, and a time range are selected. Polyimide film is necessary to increase heat resistance and flame retardancy. The thickness of this polyimide film may be an appropriate thickness as required, but preferably 3 to 50 0 iim, more preferably 5 to 30 / zm. The thickness ratio between the polyimide film and the adhesive layer is not limited, but the film thickness is 1 2.5 5 111 to the adhesive layer 1 5 to 20 m, the film thickness is 25 im to the adhesive layer 2 5 to 3 5 μ m, each of which a force-parlay film is provided.

The flame-retardant adhesive resin composition of the present invention can also be applied to an adhesive layer of a flexible copper-clad laminate (hereinafter also referred to as a three-layer copper-clad laminate). In that case, the flexible copper clad laminate is formed from a polyimide film, the adhesive resin composition, and a copper foil. As a method for forming the flexible copper clad laminate of the present invention, a conventional method is used. Can be stacked. As an example of a suitable laminating method, the adhesive resin composition is diluted with an organic solvent such as methyl ethyl ketone to form a solution, applied to one or both sides of a polyimide film, and the organic solvent content is dried. It can be manufactured by heat-curing after bonding copper foil to one or both sides of polyimide film with a hot roll. The drying conditions vary depending on the solvent and resin composition used, but in general, a temperature of 130 to 160 ° C, a temperature of 3 to 10 minutes and a time range are selected. In general, the temperature is selected from the range of temperature and time from 160 to 190, and from 10 to 120 minutes. The thickness of the polyimide film layer, the adhesive layer and the copper foil is not particularly limited, but the polyimide film thickness is 5 to 25 μπιι, and the adhesive layer 1 Generally, the thickness is 0 to 30 μm and the copper foil thickness is 10 to 35 m. BEST MODE FOR CARRYING OUT THE INVENTION

 Next, the present invention will be specifically described with reference to synthesis examples, examples and comparative examples. Properties of cured products and properties of FPC materials, such as force parlay film, bonding sheet, and three-layer copper-clad laminate, are as follows.

<Hardened material properties>

 [Glass transition temperature (T g)]

 The adhesive resin composition is dissolved in a methyl ethyl ketone solvent to form a 35% by weight adhesive solution, which is then applied onto a fluororesin sheet of length X width X thickness = 50 X 15 50 X 1 mm. 1) After drying at 35 ° C for 5 minutes to evaporate the solvent, another fluororesin sheet with the same shape is layered on the adhesive application surface, and vacuum heating press is performed at 1700 ° C for 1 hour. A cured adhesive film as a sample was prepared. The temperature dispersion tan δ curve of this sample was measured using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments Inc., DM S _ 6 1 0 0), with a frequency of 10 ζ ζ and a temperature range of 1 5 0 to 2 0 The measurement was carried out under the conditions of 0 ° C. and a heating rate of 2 ° C./min. The peak temperature of the obtained temperature-ta η δ curve was defined as the glass transition temperature (T g).

[ _Linear expansion coefficient ( _{α ι} , a ₂ )]

Use the same sample and equipment as above, create a TMA curve under the conditions of a temperature range of 1550-200 ° C and a heating rate of 2 ° C / min. The linear expansion coefficient α in the glass state was calculated from the slope of the curve, and the linear expansion coefficient α ₂ in the rubber state was calculated from the slope of the curve in the temperature range from the T g.

 [Tensile properties (strength, elongation)]

A sample obtained by punching the above cured adhesive film into the shape of a JISK 6 2 5 1 No. 1 dumbbell piece was used as a sample. This sample was set in a tensile tester (manufactured by Shimadzu Corporation, AG S-500) and a tensile test was performed at room temperature and at a crosshead speed of 1 mmZ according to the procedure of JISK 7 16 1. The strength and elongation at break of the sample were measured. <FPC material properties and force parlay film properties>

 [Crack resistance]

 Apply the above-mentioned 35 wt% adhesive solution to one side of a polyimide film (Akanel NPI, Kanechi Co., Ltd.) of length X width X thickness = 200 mm x 300 mm x 25 μm After drying for 5 minutes at 1 35 ° C, prepare a force parlay film with an adhesive layer thickness of 25 m. When the material was bent, it was visually observed whether or not cracking occurred in the adhesive, and the case where almost no cracking was observed was judged as “good” and the case where no cracking was found was judged as “excellent”. [Flame resistance] After preparing a force parlay film under the same conditions as above, JP CA—BM0 2-1 9 9 1 was cut to the dimensions described in 7.7 and the two force parlay films were bonded together on the adhesive surface. Thereafter, the sample was prepared by heating and pressing at 170 ° C. for 1 hour, and then post-curing at 190 ° C. for 2 hours. Subsequently, according to the procedure of JPCA-BM0 2— 1 9 9 1 7.7, fire resistance test and fire resistance measurement, UL standard 94 criteria “VTM-0”, “flame resistance” The flame resistance was judged based on two levels of “None”. “VTM-0” means flame resistance.

 [Stripping strength]

 After preparing the coverlay film under the same conditions as described above, the test piece was prepared and the peel strength was measured in accordance with the peel strength of 75 of JPCA—BM02-19-191. The test piece adhesive was thermally cured in the same manner at 170 ° 0 for 1 hour, followed by heating and post-curing at 190 ° C for 2 hours.

 [Solder heat resistance (dry)]

After preparing a force parlay film under the same conditions as described above, a test piece was prepared and a solder heat resistance test was performed in accordance with the solder heat resistance (appearance) of JP CA—BM0 2 — 1 9 9 1—7.9. The adhesive thermosetting conditions at the time of test piece preparation were the same as described above: after 1 hour of heating press at 170 ° C., followed by post curing at 190 ° C. for 2 hours. After drying this test piece at 105 for 1 hour, the test piece was floated in a solder bath set to each evaluation temperature for 5 seconds. Observations were made to check for defects such as foaming, blistering, and peeling. “300 ° C” in the table means that no defects are observed when evaluated in a 300 ° C solder bath.

 [Solder heat resistance (moisture resistance)]

 After preparing the coverlay film under the same conditions as above, leave it for 24 hours at 40 ° C and 90% relative humidity, and then float it in the solder bath set at each evaluation temperature for 5 seconds. We confirmed the presence of defects such as observation, foaming, blistering, and peeling. “2600 ° C” in the table means that no defects are found when evaluated in a solder bath at 2600 ° C.

 [Folding resistance]

 After preparing a force parlay film under the same conditions as above, use a copper-clad laminate (manufactured by Nippon Steel Chemical Co., Ltd., MB 1 2—2 5—1 2 RE Q) and use JP CA—BM0 2— 1 9 9 1— 7. Preparation of test piece and folding resistance test were conducted according to the A method folding resistance test of 7.6.1. The curing conditions were similarly set at 170 ° C. for 1 hour after heat-pressing the power parlay film, followed by post curing at 190 ° C. for 2 hours. The radius of curvature was 0.38 mm. Judgment is based on measuring the number of bends until the sample copper circuit is disconnected and the current cannot be supplied. If the number of bends before disconnection is 1 00 0 0 or more and less than 3 0 0 0 0, “OK”, 3 0 0 A case of zero or more was judged as “good”.

 [Adhesive flow]

 After preparing the coverlay film under the same conditions as described above, test piece preparation and adhesive flow test were performed according to JPCA—BM0 2 — 1 9 9 1 — 7.10. The determination was made by measuring the length of the adhesive that had oozed out.

 [Migration resistance]

After preparing a force parlay film under the same conditions as above, a comb-like circuit pattern was obtained by etching the copper foil of a single-sided copper-clad laminate so that the circuit line / space was 100 μm / 200 μm. The sample was prepared by post-curing the cover lay film for 1 hour at 1700 and after heating for 2 hours at 190. Place the sample in a constant temperature and humidity chamber adjusted to 85 ° C—85% RH%, energize 50 V DC for 50 hours in the comb circuit in the sample, and then remove the sample. The comb circuit and its surroundings are observed with a microscope. If dendrites are observed, The case where it was not recognized was judged as “good”.

<Bondanda sheet characteristics>

 [Flame resistance]

The 35 wt% adhesive solution, the vertical X horizontal X thickness = 20 0 mmX 3 0 0 mmX 2 5 m adhesive solution on one surface of a polyester release film was applied and dried 5 minutes at 1 ₃ 5 ° C After preparing a bonda sheet with an adhesive layer thickness of 25 μm, pre-cured at 170 ° C for 1 hour and then post-cured at 190 ° C for 2 hours. Prepared. Subsequently, a fire resistance test was conducted according to the procedure of JISC 6 4 71, and the fire resistance was judged based on the two standards of “V-0 J” and “No flame resistance”, which are the criteria of UL standard 94. “V_ 0” means flame resistance.

 [Stripping strength]

 After preparing the bonding sheet under the same conditions as above, the bonder sheet was peeled off from the release film, and then two copper foils of length x width x thickness = 200 mm x 300 mm x 25 μm The sample was sandwiched between the surfaces and heated at 70 ° C for 1 hour and then post-cured at 190 ° C for 2 hours to produce a sample. The peel strength was measured according to JISC 64 7 1 Measured according to

 [Through-hole conductivity]

 After preparing the bondinda sheet under the same conditions as above, the bondinda sheet was peeled off from the release film. 1 Precured at 70 ° C for 1 hour and postcured at 190 ° C for 2 hours. Was prepared. A through hole with a diameter of 0 to 3 mm was drilled in this cured sheet, and a copper plating layer of 20 to 25 / zm was formed inside the hole by an electroless plating method to prepare a sample. Expose the sample to a heat cycle of 40 ° C · 15 minutes, 1 50 ° C · 15 minutes, measure the number of cycles until poor continuity occurs. 0 0

Zero or more cycles were judged as “good”.

<Characteristics of 3-layer copper-clad laminate>

 [Flame resistance]

The above 35 wt% adhesive solution, length x width x thickness = 200 mm x 300 mm x 25 m Apply adhesive solution to one side of polyimide film, dry at 1 35 ° C for 5 minutes to form an insulating resin layer with an adhesive layer thickness of 25 μm, then length X width X thickness = 2 00 mmX 300 mmX 1 8 / zm copper foil is laminated on the roughened surface, heat-pressed at 170 ° C for 1 hour, post-cured at 190 ° C for 2 hours, and then triple-layered A laminate was prepared. Subsequently, a flame resistance test was conducted according to the procedure of JISC 64 71, and the flame resistance was judged based on two standards of “V-0” and “No flame resistance” which are the criteria of UL standard 94. “V-0” means flame resistance.

 [Stripping strength]

 The peel strength of the copper foil layer and the insulating resin layer in the three-layer copper-clad laminate prepared under the same conditions as described above was measured according to JI S C 64 71.

 [Folding resistance]

 The folding resistance of a three-layer copper-clad laminate prepared under the same conditions as described above was measured according to JIS C 64 71. The radius of curvature was 0.8 mm. Judgment was made by measuring the number of flexing cycles until the sample copper circuit was disconnected and could not be energized. Example

Synthesis example 1

It is a phosphorus-containing phenol represented by the following formula (1 1): 1 0— (2,5-Dihydroxyphenol-Nole)-1 0 H— 9—Oxa 1 0—Phosphaphenanthrene 1 0 H— 9-Oxide (manufactured by Sanko Chemical Co., Ltd., HCA-HQ, hydroxyl equivalent 16 2 g / eq, phosphorus content 9.5 wt%) 16 2 parts, bisphenol A type epoxy resin (Toto Kasei Co., Ltd.) YD—8 1 2 5, made by company, epoxy equivalent 1 7 1. 6 g / eq) 1 75 parts, cyclohexanone 144 parts, 2-ethyl 4-methylimidazole as catalyst (Shikoku Chemical Industries) 0.13 part of 2 E 4MZ (made by Co., Ltd.) was charged into a four-necked glass separable flask equipped with a stirrer, thermometer, cooling pipe, and nitrogen gas introduction device at atmospheric pressure, 1 5 After reacting at a temperature of 0 ° C to 1700 ° C for 8 hours, 1556 parts of cyclohexanone and 300 parts of N, N-dimethylformamide were added, Phosphorus-containing phenoloxy resin A solid content concentration 3 6 layers 7 parts of a 93% by weight solution were obtained. After applying this resin solution on a polyester release film, the solvent was evaporated by drying at 165 ° C. for 5 minutes to obtain a phosphorus-containing phenol resin A having a phosphorus content of 4.6%.

Shodex AD-8 00 P + T SK ge 1 Super HM—H + Suer HM-H + Super H2 0 0 0 as column, N, N-dimethylformamide (2 OmM lithium bromide as eluent) As a result of GPC analysis of phosphorus-containing phenoxy resin A using the above-mentioned product, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 77,300.

Synthesis example 2

 A phosphorus-containing phenoxy resin was synthesized in the same manner as in Synthesis Example 1 except that the reaction time in Synthesis Example 1 was changed from 8 hours to 10 hours. B was obtained. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 109,700.

Synthesis example 3

 The phosphorus-containing phenoxy resin was synthesized in the same manner as in Synthesis Example 1, except that the reaction time in Synthesis Example 1 was changed from 8 hours to 20 hours. C was obtained. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 19.8,400.

Synthesis example 4

Instead of the phosphorus-containing phenol represented by the above formula (11) in Synthesis Example 1, 2 2 2 g of the phosphorus-containing naphthol represented by the formula (1 2) (hydroxyl equivalent 221.6 g / eq, phosphorus content 8.2%) was used, and the reaction time in Synthesis Example 1 was 8 hours. The phosphorus-containing phenoxy resin D was synthesized in the same manner as in Synthesis Example 1 except that the phosphorus-containing phenoxy resin D having a phosphorus content of 4.0% was obtained except that the time was changed to 10 hours. As a result of GPC analysis under the same conditions, the weight average molecular weight in terms of standard polyethylene oxide of the resin was 122,470.

Synthesis example 5

 Bisphenol A type epoxy resin in synthesis example 1 (manufactured by Tohto Kasei Co., Ltd., YD_ 8 1 2 5, epoxy equivalent 1 7 1. S g / eq) is replaced by the following formula (1 3) Bisphenol fluorene type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., ER F—300, epoxy equivalent 2 3 1 gZ e ci) was used, and the reaction time in Synthesis Example 1 The phosphorus-containing phenoxy resin E was synthesized by synthesizing the phosphorus-containing phenoxy resin in the same manner as in Synthesis Example 1 except that the value was changed from 8 hours to 10 hours. . As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 1 17,000.

合成例 6

Synthesis example 6

 Except that the reaction time in Synthesis Example 1 was changed from 8 hours to 5 hours, a phosphorus-containing phenoxy resin was synthesized in the same manner as in Synthesis Example 1, and the phosphorus content was 4.6%. A phenoxy resin F was obtained. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 39,200.

Synthesis example 7

 The phosphorus-containing phenoxy resin was synthesized in the same manner as in Synthesis Example 4, except that the reaction time in Synthesis Example 4 was changed from 10 hours to 5 hours. Got G. As a result of GPC analysis under the same conditions, the standard polyethylene oxide equivalent weight average molecular weight of the resin was 41,500.

 The abbreviations of each component used for preparing the adhesive resin composition are shown below.

YD-128: Bisphenol A type epoxy resin (manufactured by Toto Kasei)

YDF-170: Bisphenol F-type epoxy resin (manufactured by Toto Kasei Co., Ltd.)

BRG-555: Novolac-type phenolic resin (Showa Polymer Co., Ltd.)

DICY: Dicyan Diamide (13 Carbide Industries Co., Ltd.)

DDM: Diaminodiphenylmethane

 DDS: Giaminodiphenyl norehon

Resin A: Phosphorus-containing fuco-oxy resin A of Synthesis Example 1 (weight average molecular weight 7 7, 300) Resin B: Phosphorus-containing fuconoxy resin B of Synthesis Example 2 (weight-average molecular weight 1 0 9, 700) Resin c : Phosphorus-containing fuconoxy resin c of Synthesis Example 3 c (weight average molecular weight 1 9 8, 400) Resin D: Phosphorus-containing fuconoxy resin D of Synthesis Example 4 D (weight average molecular weight 1 2 2, 4 70) Resin E: Phosphorus-containing fuconoxy resin E in Synthesis Example 5 (weight average molecular weight 1 1 7, 900) Resin F: Lin-containing fuco-oxy resin F in Synthesis Example 6 (weight average molecular weight 3 9, 20 0) Resin G: Synthesis Lin-containing fuconinoxy resin G from Example 7 (weight average molecular weight 4 1, 500)

YP-50SC: Phenoxy resin (manufactured by Tohto Kasei Co., Ltd.) (weight average molecular weight 5 0, 500) PNR1H: Carboxyl group-containing NBR (manufactured by JSR Corporation)

 SPE-100: Cyclophenoxyphosphazene (Otsuka Chemical Co., Ltd.)

 2E4MZ: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.)

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

Equipment: Tosoh Corporation H LC-8 1 20 GP C

Column: manufactured by Tosoichi Co., Ltd., TSK—GE L: SUP ER HZ 2 00 00 X 1, SUP

E R HZ 3000 X 1, SUP ER HZ 4000 X 1

Column temperature; 40 ° C

Mobile phase: Tetrahydrofuran (THF)

Direct flow: 0.3 5 ml / mi n

Detector: Built-in type

Sample concentration; 0.0 3 g / THF 1 0 ml

 The content of the m = 0 component was defined as the content (%) obtained by dividing the area of the peak of the m = 0 component obtained from the obtained GCC kumatograph by the peak area of all components.

As a result of GPC analysis of YD- 1 28, the content of the polymerization degree m = 0 isomer was 82%.

¥ 0 ー 1 70 0? As a result of C analysis, the content of polymerization degree m = 0 isomer was 78%. Example 1 to Example 1 6

 Each component was blended in the proportions (% by weight) described in Tables 1 to 3 to prepare an adhesive resin composition. This adhesive resin composition was evaluated for cured product characteristics, FPC material characteristics (force perlay film characteristics, bonding sheet characteristics, three-layer copper-clad laminate characteristics). The results are shown in Tables 1-3.

Comparison example: ~ Five

 Each component was blended in the proportions shown in Table 4 to prepare an adhesive resin composition. The adhesive resin composition was evaluated for cured product properties, FPC material properties (cover-lay film properties, bonding sheet properties, three-layer copper-clad laminate properties). The results are shown in Table 4.

From the above results, in Examples 1 to 16 using the adhesive resin composition of the present invention, the cover The flame resistance in the Rayfilm characteristics is VTM-0, the bond resistance in the bondinda sheet characteristics and the three-layer copper-clad laminate characteristics are V-0, both of which were confirmed to be flame retardant. In addition, the solder heat resistance (drying) is 300 ° C or higher, the solder heat resistance (humidity resistance) is 2550 ° C or higher, and the folding resistance is 2820 times or higher in the properties of force parlay film. The folding resistance in the properties of copper-clad laminates is 150 times or more, and all show good physical properties. In addition, the adhesive flow in force parlay film characteristics is 0.18 mm or less, showing good physical properties, no problem with migration resistance, and through-hole mesh conductivity in bonding sheet characteristics. Are better. Among Examples 1 to 16, in particular, an FPC material using resin B having a molecular weight of 109,700, resin D having a molecular weight of 122,470, or resin E having a molecular weight of 117,900 The characteristics are excellent in both solder heat resistance and folding resistance.

 On the other hand, Comparative Examples 1 and 2 show flame retardancy in the FPC material characteristics, but the solder heat resistance and folding resistance in the cover lay film characteristics are low, and the flowability of the adhesive is 0.8 mm or more. Lack of sex. In Comparative Examples 3 to 5, no flame resistance is observed in the FPC material characteristics.

The above results are summarized and Table 1 shows Examples 1 to 6, Table 2 shows Examples 7 to 12, Table 3 shows Examples 13 to 16 and Table 4 shows Comparative Examples 1 to 5.

table 1

2

2

3

Three

 Example

 1 3 1 4 1 5 1 6 Jeho. XD resin YD-128 30. 2 46. 4 46. 4 46. 4

 YDF-170 0 0 0 0 Curing agent BRG-555 19. 5 0 0 0

 DICY 0 3. 1 3. 1 3. 1 曰

 0 0 0 0

DDS 0 0 0 0 Phenoxy resin Resin A 0 0 0 0 Resin B 0 0 0 0 Resin c 50. 0 50. 0 0 0 Resin D 0 0 50. 0 0 Resin E 0 0 0 50. 0 Resin F 0 0 0 0 Resin G 0 0 0 0

YP-50SC 0 0 0 0

NBR PNR1H 0 0 0 0 Curing accelerator 2E4MZ 0. 3 0. 5 0. 5 0. 5 Cured properties Tg [° C] 166 170 161 160 α 1 [ppm] 68 64 52 53

 95 90 60 55 Strength [MPa] 71. 6 70. 7 67. 0 68. 5 Stretch [%] 2. 3 2. 6 2. 5 2. 6 Kaha, one lay film Crack resistance Good Good Excellent Characteristics Flame resistance VTM-0 VTM-0 VTM-0 VTM-0 Peel strength

 1. 0 1. 2 1. 2 1. 2 [kN / m]

 Solder heat resistance (dry

 320 310 310 310 dry)

 Solder heat resistance

 280 280 270 280 wet)

 Folding resistance 3900 4400 5400 5600 Adhesive flow 0. 06 0. 08 0. 10 0. 10 My resistance; r Lacing property Good Good Good Ho, ent, inter, sheet, flame resistance V- 0 vo vo vo Characteristic tear strength

 1. 0 1. 0 1. 0 1. 0

[kN / m]

 Through-hole continuity Good Good Good Good

Three-layer copper-clad laminate Flame resistance V-0 v-o V-0 V-0 Peel strength

 1. 0 1. 0 1. 0 1. 0 Characteristics [kN / m]

Folding resistance 250 280 360 370 Table 4

 Comparative example

 1 2 3 4 5 Jeho. Xylene resin 30. 2 30. 2 30. 2 33. 5 45. 0

 YDF-170 0 0 0 0 0 Curing agent BRG-555 19.5 19. 5 19. 5 17. 4 29. 3

 DICY 0 0 0 0 0

DDM 0 0 0 0 0

00

 DDS 0 0 0 0 0 Phenoxy resin Resin A 0 0 0 0 0 Resin B 0 0 0 0 0 Resin c 0 0 0 0 0 Resin!) 0 0 0 0 0 Resin E 0 0 0 0 0 Resin F 50. 0 0 0 0 0 Resin G 0 50. 0 0 0 0

YP-50SC 0 0 50. 0 0 0

NBR PNR1H 0 0 0 48. 8 25. 0 Curing accelerator 2E4MZ 0. 3 0. 3 0. 3 0. 3 0. 3 Cured material properties Tg [° C] 115 120 121 71 105

 1 [ppm] 58 63 51 79 85 a 2 [ppm] 72 80 66 121 143 Strength [MPa] 67. 6 65. 1 51. 2 16. 5 29. 7 Stretch [%] 2.3 3 2. 2 2 9 63 42 Kaha, Rayleigh film Crack resistance Good Good Good fc Good characteristics Flame resistance VTM-0 VTM-0 None None None Peel strength

 0. 8 0. 8 1. 1 1. 0 0. 5 [kN / m]

 Solder heat resistance (dry

 280 280 280 250 240 dry)

 Solder heat resistance

 220 230 250 200 200 humidity)

 Folding resistance 1800 1900 2100 1600 700 Adhesive flow 1. 0 0. 8 0. 8 0. 05 0. 10 Mic, erasion '14 Good Good Good V-0 V-0 None None None Characteristics Peel strength

 0. 9 0. 8 1. 1 1. 0 0. 5 [kN / m]

 Through hole continuity Good Good Good No No

3 layers Co-laminated laminate Flame resistance v-o V-0 None None None Peel strength

 1. 0 1. 1 1. 0 1. 0 0. 6 Characteristics [kN / m]

Folding resistance 130 140 160 130 50 Industrial applicability

 The adhesive resin composition of the present invention and the cover lay film, bonding sheet and three-layer copper-clad laminate using the same are non-halogen and flame retardant, and are effective in addressing environmental problems. Excellent FPC characteristics such as foldability, migration resistance, and through-hole plating conduction reliability.

Claims

The scope of the claims 1. The following (ii) ~ (2) ingredients,  (Ii) Standard polyethylene oxide equivalent weight expressed by the following general formula (1) and having a phosphorus content of 1% to 6% by weight and measured by gel permeation chromatography. Phosphorus-containing phenolic resin having an average molecular weight of 60,00 0 -200,000  (Mouth) Epoxy resin represented by the following general formula (1 0),  (C) a curing agent, and  (II) curing accelerator, Is a flame retardant adhesive resin composition characterized by containing an essential component and substantially free of halogen elements.

(In the formula, X is at least selected from the following general formula (2), (3), (4) or (5) which requires a divalent group represented by the following general formula (2) or (3): 1 represents a divalent group, Z represents a hydrogen atom or general formula (6), and n is an average value of 21 or more.)

(In the formulas (2) to (5), Y represents the phosphorus-containing tomb represented by the following general formula (7) or (8), Ri Rs R ₁ to R ₄ ,

Ri Rs independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. A is a single bond or one CH ₂ —, one C (CH ₃ ) ₂ —,-CH (CH ₃ ) ―, one S—, _ S 0 ₂ —, — O—, one CO— or general formula (9) It represents a divalent group selected from )

 (In formula (7) ~ (9),! ^ ~! ^, R! ~ R! 0 and Ri Rs independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

 (Ten) (In the formula, W represents a divalent group represented by the general formula (5), m is an integer of 0 or more, and the average of m is 0.1 to 15) 2. In the (mouth) component, the content of the polymerization degree m = 0 in the general formula (10) is 70% or more in the area percentage of the kutamatogram measured using gel permeation chromatography. The flame retardant adhesive composition according to claim 1, wherein the flame retardant adhesive composition is provided. 3. (i) The component is a divalent group represented by the general formulas (2) and (5) in the general formula (1), and Ri Rg in the general formula (2) represents a hydrogen atom. Wherein Y represents the general formula (7), and Ri Rs in the general formula (5) represents a hydrogen atom, but A represents -C (CH ₃ ). Flammable adhesive resin composition. 4 · (i) In the general formula (1), X is a divalent group represented by the general formulas (3) and (5), and R t Rs in the general formula (3) represents a hydrogen atom. 3, wherein Y represents the general formula (7), R Rs in the general formula (5) represents a hydrogen atom, and A represents one C (CH ₃ ) ₂ −. Flame retardant adhesive resin composition. 5. (i) In the general formula (1), X is a divalent group represented by the general formulas (2) and (5), and Ri Rg in the general formula (2) represents a hydrogen atom. Wherein Y represents general formula (7), Ri R ₈ in general formula (5) represents a hydrogen atom, and A represents general formula (9). Flammable adhesive resin composition.  6. (i) The component is a divalent group represented by the general formulas (3) and (5) in the general formula (1), and Ri Rs in the general formula (3) represents a hydrogen atom. Wherein Y represents the general formula (7), Ri Rs in the general formula '(5) represents a hydrogen atom, and A represents the general formula (9). Flame retardant adhesive resin composition. 7. The flame retardant adhesive according to claim 1, wherein 20 to 80 parts by weight of the component (i) is blended with 100 parts by weight of the flame retardant adhesive composition. Resin composition. 8. A flame retardant adhesive film comprising the flame retardant adhesive resin composition according to any one of claims 1 to 6 formed into a film shape.  9. A force-parinolem comprising a polyimide film and a layer made of the flame-retardant adhesive resin composition according to any one of claims 1 to 6 provided on the polyimide film. .  Ten. A flexible copper comprising: a polyimide film; a layer comprising the flame-retardant adhesive resin composition according to any one of claims 1 to 6 provided on the polyimide film; and a copper foil. Tension laminate.