JP2003238807A - Flame-retardant and heat-resistant resin composition, adherent film using the same and polyimide film with adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive for various printed-wiring boards which is halogen-free, has excellent flame retardance and excellent adhesion due to the stress relaxation action, a flame-retardant and heat-resistant resin composition useful for adherent films, an adherent film, and a polyimide film with an adhesive. <P>SOLUTION: The flame-retardant and heat-resistant resin composition comprises (A) a modified polyamideimide resin having a microphase separated structure composed of a siloxane unit and an alicyclic unit as the soft segments and an aromatic unit as the hard segment, (B) a thermosetting resin, and (C) an organic phosphorus compound. The adherent film has an adhesive layer formed from this flame-retardant and heat-resistant resin composition, and the polyimide film with an adhesive has this adhesive layer formed on a polyimide film. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant heat-resistant resin composition, an adhesive film using the same, and an adhesive-attached polyimide film.

[0002]

2. Description of the Related Art In recent years, with the rapid progress of miniaturization and weight reduction of various electronic devices, the mounting density of electronic parts has increased,
The characteristics required for various electronic parts and materials used for it are also diversifying. Among these, especially printed wiring boards have small wiring densities and high densities, so that they are multilayer wiring boards (build-up wiring boards) and flexible wiring boards (F
The demand for PCs, etc. is also increasing. These wiring boards use various adhesives or adhesive films in the manufacturing process, and as the resin used for the adhesives,
Epoxy resin, acrylic resin, etc. are mainly mentioned. However, all of these resins are insufficient to satisfy the characteristics such as heat resistance and electric insulation.

On the other hand, polyimide resin and polyamide-imide resin adhesives are known as those having excellent heat resistance and electrical insulation. However, due to the heat history in the wiring board manufacturing process, the adherend and the adhesive are There has been a problem that a thermal stress is generated between them and the wiring board is warped.

Further, as the flame retardant for various printed wiring board materials, halogen compounds such as bromine compounds and antimony compounds having an excellent flame retarding effect have been most commonly used. However, since halogen-based compounds generate gas containing toxic substances such as dioxins which are toxic to the human body when burned by recent research, their use is being restricted mainly in European countries. As a flame retardant that does not generate such a toxic gas, specifically, an inorganic filler such as aluminum hydroxide or magnesium hydroxide, or a phosphorus compound is known.

However, it is necessary to add a large amount of these compounds to the target resin in order to obtain sufficient flame retardancy, and the characteristics of the original resin may be significantly reduced. Specifically, since aluminum hydroxide is generally soluble sodium mixed in during manufacturing, for example, among various kinds of wiring board adhesives, FPC adhesives are adherends when subjected to long-term high temperature and high humidity treatment. It is known that a hydrolysis reaction occurs on the surface of the polyimide film, the surface of the polyimide film becomes brittle, and the peel strength decreases. Further, magnesium hydroxide is generally known to reduce acid resistance. Further, among well-known phosphoric acid compounds, phosphoric acid esters function as plasticizers and reduce heat resistance and the like, so it is necessary to limit the type and the amount used.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant heat-resistant resin composition having an excellent effect of reducing thermal stress, which is useful for various printed wiring board adhesives and adhesive films. . Furthermore, various prints with halogen-free excellent flame retardancy due to the phosphorus compound, which is a flame retardant aid, and excellent adhesiveness due to the stress relaxation effect due to the micro phase separation structure of the modified polyamidimide resin. An object of the present invention is to provide a flame-retardant heat-resistant resin composition useful as an adhesive for wiring boards and an adhesive film.

Another object of the present invention is that it is halogen-free, has excellent heat resistance and flame retardancy, and has excellent adhesiveness due to the stress relaxation action due to the microphase-separated structure of the polyamide-imide resin, An object of the present invention is to provide an adhesive film suitable for various printed wiring boards.

Another object of the present invention is to provide a polyimide film with an adhesive, which has excellent heat resistance and is suitable for various printed wiring boards having excellent adhesiveness.

[0009]

The present invention provides (A) general formula (A formula)

[Chemical 17] (Wherein R and R ′ each independently represent a divalent organic group), and R and R ′ in all the repeating units are

[Chemical 18] (Where X is

[Chemical 19] ), And

[Chemical 20] (In the formula, R ³ and R ⁴ each independently represent a divalent organic group, and R ^{5 to} R ⁸ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, n is 1 to 5
Is an integer of 0),

[Chemical 21] Flame-retardant heat resistance containing a polyamide-imide resin having at least three divalent organic groups and having a microphase-separated structure, (B) thermosetting resin, and (C) organic phosphorus compound It relates to a resin composition.

In the present invention, the component (A) is R

[Chemical formula 22] (Where X is

[Chemical formula 23] And)

[Chemical formula 24] (In the formula, R ³ and R ⁴ each independently represent a divalent organic group, and R ^{5 to} R ⁸ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, n is 1 to 5
Is an integer of 0), and as R '

[Chemical 25] And the flame-retardant heat-resistant resin composition.

Further, in the present invention, the component (A) is obtained by reacting trimellitic anhydride with a mixture of a diamine (a) having three or more aromatic rings and a siloxanediamine (b) and represented by the general formula (1). formula)

[Chemical formula 26] [Wherein R ¹ is

[Chemical 27] (Where X is

[Chemical 28] Is shown). ] The aromatic diimide dicarboxylic acid (1) and general formula (2 formula)

[Chemical 29] [Wherein R ² is

[Chemical 30] (However, R ³ and R ⁴ each independently represent a divalent organic group, R ^{5 to} R ⁸ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, and n is 1-5
It is an integer of 0. ) Is shown. ] The flame-retardant heat-resistant resin composition, which is a polyamideimide resin having a microphase-separated structure obtained by reacting a mixture containing siloxane diimide carboxylic acid (2) with norbornene diisocyanate. The present invention also includes (A) 100 parts by weight of polyamide-imide resin and (B) thermosetting resin 10.
To 100 parts by weight and (C) 2 to 20 parts by weight of the organophosphorus compound, the flame-retardant heat-resistant resin composition.

The present invention also relates to the flame-retardant heat-resistant resin composition, wherein the siloxane diamine (b) has an amine equivalent of 400 to 2,500 g / mol. The present invention also relates to the flame-retardant heat-resistant resin composition (B), in which the thermosetting resin comprises an epoxy resin and a curing accelerator or curing agent thereof. The present invention also relates to the flame-retardant heat-resistant resin composition, wherein the epoxy resin is a phosphorus-containing epoxy resin.

In the present invention, the (C) organophosphorus compound is represented by the general formula (3):

[Chemical 31] (Wherein, W talk (single bond), an alkylene group having 1 to 5 carbon _{atoms, -S -, - SO 2 -} , - O-, or -N = represents a bonding group which is a N-, n1 is 10 to It is an integer of 50.)
Or a general formula (4 formula)

[Chemical 32] (In formula, n2 is an integer of 10-50.) It is related with the said flame-retardant heat-resistant resin composition which is a phosphate compound.

The present invention also relates to an adhesive film having an adhesive layer formed from the flame-retardant heat-resistant resin composition. The present invention also relates to an adhesive-attached polyimide film in which the adhesive layer is laminated on one side or both sides of a polyimide film.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The flame-retardant heat-resistant resin composition of the present invention comprises (A) a polyamideimide resin having a repeating unit represented by the general formula (A formula) and having a micro phase separation structure, (B) a thermosetting resin and ( C) Contains an organic phosphorus compound.
The polyamide-imide resin as the component (A) has the general formula (A formula)
As R and R ′ in all repeating units represented by

[Chemical 33] (In the formula, X has the same meaning as above.),

[Chemical 34] (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and n
Has the same meaning as above. )When,

[Chemical 35] And at least three kinds of divalent organic groups.

Since the polyamide-imide resin of the component (A) used in the present invention has the repeating unit represented by the formula (A), it has a siloxane unit as a soft segment, an alicyclic unit and an aromatic group as a hard segment. It is composed of units and has a micro phase separation structure (sea island structure). The microphase-separated structure in the present specification means a structure in which dispersed particles are present in the resin, the dispersed particles are islands, and a portion without particles forms a sea. It is presumed that the sea in this microphase-separated structure is composed of siloxane units and the islands are composed of units other than siloxane units. The flame-retardant heat-resistant resin composition of the present invention is usually used as a solution dissolved in a solvent when forming the adhesive layer, but the polyamide-imide resin is a flame-retardant heat-resistant resin composition. It is preferable that the above microphase-separated structure is obtained after the solution is applied and dried, or after the flame-retardant heat-resistant resin composition is cured after drying. When the polyamide-imide resin in the adhesive layer has this microphase-separated structure, a stress relaxation action is specifically developed, and excellent adhesiveness can be obtained while maintaining high heat resistance.

The polyamide-imide resin as the component (A) is, for example, R in the formula (A).

[Chemical 36] (In the formula, X has the same meaning as described above.)

[Chemical 37] (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and n
Has the same meaning as above. ) And as R '

[Chemical 38] Some have. Such a polyamide-imide resin is obtained by, for example, reacting a mixture of (A) a diamine (a) having three or more aromatic rings and a siloxane diamine (b) with trimellitic anhydride (the formula (1) ) Aromatic diimide dicarboxylic acid (1) and the general formula (2)
It can be obtained by reacting a mixture containing the siloxane diimide dicarboxylic acid (2) with norbornene diisocyanate.

In the above general formulas (A formula) and (2 formula), R ³
Examples of the divalent organic group represented by R ⁴ include an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, and a propylene group, a phenylene group, a tolylene group, and a 6 to 18 carbon atoms such as a xylylene group. Examples thereof include an arylene group.

In the above general formulas (A formula) and (2 formula), R ⁵
Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁸ to R ⁸ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
Hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and structural isomers thereof can be mentioned. In the above general formulas (A formula) and (2 formula), R ^{5 to} R ⁸
Examples of the aryl group having 6 to 18 carbon atoms represented by
Examples thereof include a phenyl group, a naphthyl group, an anthryl group and a phenanthryl group, and examples thereof include a halogen atom, an amino group, a nitro group, a cyano group, a mercapto group, an aryl group having 6 to 18 carbon atoms and an alkyl group having 1 to 20 carbon atoms. It may be replaced.

The diamine (a) having three or more aromatic rings is represented by the following general formula (5). H ₂ N—R ¹ —NH ₂ (5 formula) (In the formula, R ¹ has the same meaning as in the general formula (1 formula).) As the diamine (a) having 3 or more aromatic rings, , For example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter, BAPP
Abbreviated. ), Bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4
-(4-aminophenoxy) phenyl] methane, 4,4
-Bis (4-aminophenoxy) biphenyl, bis [4
-(4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone,
1,3-bis (4-aminophenoxy) benzene, 1,
4-bis (4-aminophenoxy) benzene and the like can be mentioned, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferable from the viewpoint of the balance of the properties of the polyamideimide resin and the cost. These are used alone or in combination of two or more.

Siloxanediamine (b) used in the present invention
Is represented by the following general formula (6).

[Chemical Formula 39] ^(R 3 -R ⁸ and n in the formulas have the same meaning as in the general formula (2 type).)

Examples of such a siloxane diamine (b) include those represented by the following formula.

[Chemical 40] (In the formula, n represents an integer of 1 to 50.)

Amino-modified silicone oil X, which is a siloxane-based amine having both ends, is commercially available.
-22-161AS (amine equivalent 450, Shin-Etsu Chemical Co., Ltd. trade name), X-22-161A (amine equivalent 840, Shin-Etsu Chemical Co., Ltd. trade name), X-22-
161B (amine equivalent 1540, product name manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-853 (amine equivalent 650, product name manufactured by Toray Dow Corning Silicone Co., Ltd.), BY
16-853B (amine equivalent 2200, trade name manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.
These are used alone or in combination of two or more.

Here, in order to impart a flame retardancy to the (A) polyamide-imide resin and to form a microphase-separated structure for improving the adhesiveness, the amine equivalent of the siloxane diamine (b) is 400 to 2 , 500 g / mol, preferably 800 to 2,300 g / mol, more preferably 800 to 2,000 g / mol, and particularly preferably 800 to 1,800 g / mol. preferable. Examples of these are, for example, X-22-161A (amine equivalent 840), X-2.
2-161B (amine equivalent 1540), the above, Shin-Etsu Chemical Co., Ltd. brand name etc. are mentioned. The siloxane diamine (b) is used alone or in combination of two or more kinds.

In addition to the norbornene diisocyanate used for the synthesis of the (A) component polyamideimide resin, 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) and 2,4-tolylene diisocyanate are used from the viewpoint of heat resistance. Isocyanate (hereinafter abbreviated as TDI), 2,6-
Aromatic diisocyanates such as tolylene diisocyanate, naphthalene-1,5-diisocyanate, and 2,4-tolylene dimer may be used alone or in combination of two or more, and the amount thereof may be 5 to 2 with respect to norbornene diisocyanate.
It can be used at about 0 mol%. From the viewpoint of imparting flexibility, hexamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
Aliphatic diisocyanate such as isophorone diisocyanate is added to norbornene diisocyanate in an amount of 5 to 2
It can be used together at about 0 mol%.

From the viewpoint of heat resistance, in addition to the aromatic diimidedicarboxylic acid and siloxanediimidedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, phthalic acid and naphthalenedicarboxylic acid, adipic acid, sebacic acid and decane dicarboxylic acid. Aliphatic dicarboxylic acids such as acid, dodecanedioic acid and dimer acid are also used in an amount of 5 to 5 relative to the mixture of the aromatic diimide dicarboxylic acid and siloxane diimide dicarboxylic acid.
It can be used together at about 10 mol%.

The polyamideimide resin having a micro phase separation structure of the component (A) used in the present invention is, for example, a mixture of a diamine (a) and a siloxane diamine (b) having three or more aromatic rings and trimellitic anhydride. (Hereinafter, TM
Abbreviated as A) in the presence of an aprotic polar solvent,
The reaction is carried out at .about.90.degree. C. for 0.2 to 1.5 hours, and an aromatic hydrocarbon which is azeotropic with water is added to the aprotic polar solvent of 0.
1 to 0.5 weight ratio, the reaction is carried out at 120 to 180 ° C., and is represented by the aromatic diimidedicarboxylic acid (1) represented by the general formula (1) and the general formula (2). A mixture containing siloxane diimide dicarboxylic acid (2) is synthesized, and norbornene diisocyanate is further added to the aromatic diimide dicarboxylic acid (1) represented by the general formula (1) and the general formula (2). A mixture containing the represented siloxane diimide dicarboxylic acid (2) and 150-25
It can be produced by reacting at about 0 ° C. for about 0.5 to 3 hours.

After preparing a mixture containing the aromatic diimidedicarboxylic acid (1) represented by the general formula (1) and the siloxane diimidedicarboxylic acid (2) represented by the general formula (2), Alternatively, it can also be produced by heating the solution to about 150 to 250 ° C. to remove an aromatic hydrocarbon that can be azeotropic with water from the solution, and then performing a reaction with norbornene diisocyanate. Further, the polyamide-imide resin is preferably a varnish containing an aprotic polar solvent.

The mixing ratio of the mixture of the diamine (a) having 3 or more aromatic rings and the siloxane diamine (b) is (a) / (b) = (50.0-90.0) /
(10.0 to 50.0) (the unit of each numerical value is mol% and the total amount of (a) and (b) is 100 mol%) is preferable. A resin obtained by using a mixture in a ratio outside this range tends to cause warpage, decrease in flame retardancy, disappearance of microphase-separated structure, or decrease in molecular weight. The range of this ratio is (60.0-90.0) /
(10.0 to 40.0) (mol%) is more preferable, and (70.0 to 90.0) / (10.0 to 30.
0) (mol%) is more preferable.

Further, the above mixture is reacted with trimellitic anhydride (TMA) to produce the aromatic diimidedicarboxylic acid (1) of the general formula (1) and the siloxane diimidedicarboxylic acid (2) of the general formula (2). The amount of the raw material used to obtain a mixture containing) is a molar ratio of the total number of moles of the diamine (a) having 3 or more aromatic rings and the siloxanediamine (b) to the number of moles of TMA ((a) + ( b)) / T
MA = 1 / 2.20 to 1 / 2.05 is preferable, and 1 / 2.15 to 1 / 2.10 is more preferable. If this molar ratio is less than 1 / 2.20, TMA will remain, and the molecular weight of the resin finally obtained tends to decrease. If it exceeds 1 / 2.05, diamines will remain and be finally obtained. The molecular weight of the resin tends to decrease.

Then, the aromatic diimidedicarboxylic acid (1) represented by the general formula (1) and the general formula (2)
The mixture ((1) + (2)) containing the siloxane diimide dicarboxylic acid (2) and norbornene diisocyanate are reacted to obtain a polyamide-imide resin, the molar ratio is ((1) + (2)). ) / Norbornene diisocyanate = 1 / 1.50 to 1 / 1.05 is more preferable, and 1 / 1.3 to 1 / 1.1 is more preferable. If this molar ratio is less than 1 / 1.50, the molecular weight of the obtained resin tends to decrease, and if it exceeds 1 / 1.05, the molecular weight of the obtained resin tends to decrease.

The aprotic polar solvent is preferably a diamine (a) having three or more aromatic rings, a siloxanediamine (b), or an organic solvent that does not react with TMA. For example, dimethylacetamide and dimethylformamide. , Dimethyl sulfoxide, N-methyl-2-
Examples include pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone and the like. Since the imidization reaction requires a high temperature, N-methyl-2-pyrrolidone having a high boiling point is more preferable. These are used alone or in combination of two or more.

The amount of water contained in these aprotic polar solvents is preferably 0.1 to 0.2% by weight. When the water content exceeds 0.2% by weight, the trimellitic acid produced by hydration of TMA does not allow the reaction to proceed sufficiently and the molecular weight of the polymer tends to decrease. Also,
The amount of the aprotic polar solvent used in the present invention is 2.1 to 2. with respect to the total amount of the diamine (a) having 3 or more aromatic rings, the siloxane diamine (b) and TMA.
The amount is preferably in the range of 5 times, more preferably in the range of 2.2 to 2.4 times. This usage is 2.
If the amount is less than 1 time, the solubility of TMA tends to be low, and a sufficient reaction tends to be impossible. If the amount exceeds 2.6 times, the industrial production method tends to be disadvantageous.

Examples of the aromatic hydrocarbons include toluene and xylene.

The weight average molecular weight of the (A) polyamide-imide resin having a microphase-separated structure is 30,000 to 30.
It is preferably 50,000 and 40,000 to 20
More preferably 50,000, and more preferably 50,000 to
It is particularly preferably 10,000. If the weight average molecular weight is less than 30,000, the strength and flexibility in the film state may decrease, the tackiness may increase, and the micro-layer separation structure may disappear, and if it exceeds 300,000, the film state may deteriorate. Flexibility and adhesiveness tend to decrease. The weight average molecular weight in the present invention is measured by a gel permeation chromatography method and converted by a calibration curve prepared using standard polystyrene.

The thermosetting resin of the component (B) used in the present invention is not limited as long as it reacts with the amide group in the polyamide-imide resin skeleton having the microphase-separated structure of the component (A) by heat or the like. , Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin and its modified products, bixylenyl diglycidyl ether, YDC1312 (Toto) Kasei Co., Ltd.
(Trade name), Epotote YD-8125 (trade name, manufactured by Toto Kasei Co., Ltd.), TMH574 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), Epicoat 1031S (produced by Yuka Shell Epoxy Co., Ltd., trade name) ) Etc., aromatic epoxy resins such as neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, aliphatic epoxy resins such as tetrahydrophthalic acid diglycidyl ester, and heterocyclic epoxy compounds such as triglycidyl isocyanate. . Of these, aromatic epoxy resins are preferred from the viewpoint of adhesiveness and heat resistance,
Furthermore, from the viewpoint of flame retardancy, an aromatic epoxy resin containing a phosphorus atom in the molecule is particularly preferable. These are used alone or in combination of two or more.

Examples of the epoxy resin include phosphorus-containing epoxy resin ZX-1548-1 (phosphorus content:
2.0% by weight), ZX-1548-2 (phosphorus content:
2.5% by weight), ZX-1548-3 (phosphorus content:
3.0% by weight), ZX-1548-4 (phosphorus content:
4.0% by weight) (above, trade name manufactured by Tohto Kasei Co., Ltd.) and the like. These are used alone or in combination of two or more. The phosphorus content of the phosphorus-containing epoxy resin is preferably 1 to 30% by weight and 1 to 20% by weight.
More preferably, it is wt%. The epoxy resin preferably has an epoxy equivalent of 200 to 500, more preferably 250 to 400, and a molecular weight or a weight average molecular weight measured by gel permeation chromatography is preferably 100 to 2000. , 150 to 1500 is more preferable. .

The blending amount of the thermosetting resin as the component (B) is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the polyamide-imide resin having the microphase-separated structure as the component (A). It is more preferably -80 parts by weight, and particularly preferably 30-50 parts by weight. If the blending amount is less than 10 parts by weight, the flame retardance tends to be insufficient and the function as a curing agent tends to deteriorate, and if it exceeds 100 parts by weight, the crosslinked structure of the resin after curing becomes dense and weakened. Tend to do.

The thermosetting resin as the component (B) used in the present invention more preferably comprises an epoxy resin and a curing accelerator or curing agent therefor. Examples of the curing accelerator include (B)
There is no particular limitation as long as it is a component that reacts with an epoxy resin such as a phosphorus-containing epoxy resin or that accelerates the curing reaction between the component (A) and the component (B). For example, amines and imidazoles are Can be used. These are used alone or in combination of two or more. Examples of the amines include dicyandiamide, diaminodiphenylmethane, guanylurea and the like. These are used alone or in combination of two or more. Examples of the imidazoles include alkyl group-substituted imidazoles such as 2-ethyl-4-methylimidazole and benzimidazoles. These are used alone or in combination of two or more.

In the case of amines, the compounding amount of the above-mentioned curing accelerator is preferably such that the active hydrogen equivalent of the amine and the epoxy equivalent of the phosphorus-containing epoxy resin are substantially equal to each other. In the case of imidazole, phosphorus-containing epoxy resin 10
It is preferably 0.1 to 2.0 parts by weight with respect to 0 parts by weight. If the blending amount is small, the uncured phosphorus-containing epoxy resin remains, the glass transition temperature of the crosslinked resin becomes low, and if it is too large, the unreacted curing accelerator remains.
Pot life, insulation, etc. tend to decrease.

As the curing agent for the epoxy resin, amine,
Polyamide, acid anhydride, and compounds such as bisphenol A, bisphenol F, and bisphenol S having two or more phenolic hydroxyl groups in one molecule can be used.
Particularly, it is preferable to use phenol novolac resin, bisphenol novolac resin, cresol novolac resin, or the like. The amount of the above curing agent is 100% epoxy resin.
It is preferable to mix 5 to 20 parts by weight with respect to parts by weight.

The organic phosphorus compound as the component (C) used in the present invention is, for example, a phosphoric acid ester compound represented by the general formula (3) or the general formula (4). Phosphate ester compounds, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, cresyl di2,6-xylenyl phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl -2-
Methacryloyloxyethyl phosphate and the like can be mentioned. Commercially available products of these organophosphorus compounds are CR
-733S, CR-741, CR-747, PX-20
0 (above, trade name by Daihachi Chemical Industry Co., Ltd.), SP-703, SP-601 (trade name by Shikoku Chemicals Co., Ltd.), 35, 50, 65 of "Reophos" series , 95, 110 (these are product names manufactured by Ajinomoto Co., Inc.) and the like. These alone or 2
Used in combination with more than one type.

The general formula (3) and the general formula (4)
In the formula), the benzene ring in the compound has 1 to 5 carbon atoms.
It may have a substituent such as an alkyl group. When the number of the substituents is two or more, the two or more substituents may be the same or different. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, sec
-Butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like.

The amount of the organophosphorus compound as the component (C) is preferably 2 to 20 parts by weight per 100 parts by weight of the polyamide-imide resin having the microphase-separated structure as the component (A). It is more preferably from 10 to 10 parts by weight, and particularly preferably from 2 to 5 parts by weight. If the content is less than 2 parts by weight, the flame retardancy tends to be insufficient, and if it exceeds 20 parts by weight, the adhesiveness and the solder heat resistance tend to decrease.

In the present invention, the components (A), (B) and (C) are mixed in an organic solvent to give a solid content of 20-40.
It is preferable to use the flame-retardant heat-resistant resin composition in an amount of about% by weight. The organic solvent is not particularly limited as long as it has solubility, and examples thereof include dimethylacetamide, dimethylformamide, dimethylsulfoxide, and N.
-Methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, toluene, acetone and the like can be mentioned.

The flame-retardant heat-resistant resin composition of the present invention may further contain a coupling agent, if necessary, in addition to the above-mentioned components.
You may mix | blend a pigment, a leveling agent, a defoaming agent, an ion trap agent, etc. suitably.

In order to form an adhesive layer using the flame-retardant heat-resistant resin composition of the present invention, for example, the adhesive layer may be formed by coating as it is, or an adhesive film may be used to form a heat-resistant composition. The adhesive layer may be formed by laminating layers of the resin composition. When the adhesive film is used, the supporting base material may be removed after being laminated, or may be removed before being laminated.

The adhesive film of the present invention is prepared, for example, by applying a flame-retardant heat-resistant resin composition dissolved in a predetermined organic solvent on a supporting substrate and then drying the solvent by heating or blowing hot air to form an adhesive layer. Can be formed by forming. The heating conditions for drying the solvent are such that the flame-retardant heat-resistant resin composition does not cure, or even if it cures, it only cures to the B-stage state. Usually, the heating temperature is preferably 120 to 140 ° C. Examples of the supporting substrate include polyolefin such as polyethylene and polyvinyl chloride, polyester such as polyethylene terephthalate, polycarbonate, Teflon (registered trademark) film, release paper, metal foil such as copper foil and aluminum foil. The thickness of the supporting substrate is 10 to 150 μm
Is preferred. The supporting base material may be subjected to a mat treatment, a corona treatment, and a release treatment.

The organic solvent is not particularly limited as long as it has solubility, and examples thereof include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, butyl acetate, cellosolve acetate,
Acetic acid esters such as propylene glycol monomethyl acetate and carbitol acetate, cellosolves such as cellosolve and butyl cellosolve, carbitols such as carbitol and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide and dimethylacetamide. , N-methyl-2-pyrrolidone, γ-butyrolactone and the like. These are used alone or in combination of two or more.

The thickness of the adhesive layer formed of the flame-retardant heat-resistant resin composition laminated on the above-mentioned supporting substrate is 5 to 50 μm.
It is preferably m, and more preferably 10 to 40 μm. Examples of the form of the adhesive film include a sheet shape and a roll shape cut into a certain length. From the standpoints of storability, productivity and workability, it is preferable to further laminate a protective film on the adhesive layer made of the flame-retardant heat-resistant resin composition, and wind it into a roll for storage. Examples of the protective film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonates, Teflon (registered trademark) films, and release papers, like the support substrate. The thickness of the protective film is more preferably 10 to 100 μm.
The protective film may be subjected to matte treatment, corona treatment, and release treatment.

The adhesive film of the present invention can be made into a polyimide film with an adhesive by laminating it on a polyimide film or the like, for example, a cover lay film for a flexible wiring board and a base film. Further, by laminating metal foil, it can be used as a substrate for a flexible wiring board or the like. Further, an adhesive layer formed of the flame-retardant heat-resistant resin composition of the present invention may be laminated on one side or both sides of the polyimide film to obtain a polyimide film with an adhesive.

[0052]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

(Synthesis Examples 1 to 4)
Equipped with a 25 ml moisture meter receiver with thermos, thermometer and stirrer
Add 3 aromatic rings to the 1 liter separable flask.
As the diamine having the above, BAPP (2,2-bis [4
-(4-aminophenoxy) phenyl] propane),
Reactive silicone oil X-2 as roxane diamine
2-161-B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.
Equivalent weight 1540, R in the general formula (2 formula) ^ThreeAnd R^Four: P
Ropylene group, R⁵~ R⁸: Methyl group), TMA (anhydrous
(Limellitic acid), NMP as aprotic polar solvent
(N-methyl-2-pyrrolidone, water content: 0.1 times
%) And γ-BL (γ-butyrolactone, water content
Amount: 0.1% by weight) at the compounding ratio shown in Table 1
And stirred at 80 ° C. for 30 minutes. And azeotropic with water
Inject 100 ml of toluene as a functional aromatic hydrocarbon
After that, the temperature was raised and the mixture was refluxed at about 160 ° C. for 2 hours.

It was confirmed that about 3.6 ml or more of water was accumulated in the moisture quantitative receiver and that no outflow of water was observed. While removing the effluent water accumulated in the moisture quantitative receiver, The temperature was raised to 190 ° C. to remove toluene. Then, the solution was returned to room temperature, norbornene diisocyanate was added in the amount shown in Table 1, and reacted at 190 ° C. for 2 hours. After completion of the reaction, polyamideimide resin NM
P / γ-BL solutions A-1 to A-4 were obtained.

[0055]

[Table 1] * 1: 2,2-bis [4- (4-aminophenoxy) phenyl] propane * 2: Reactive silicone oil (trade name of Shin-Etsu Chemical Co., Ltd., amine equivalent 1540) * 3: trimellitic anhydride * 4: N-methyl-2-pyrrolidone * 5: γ-butyrolactone

Examples 1 to 3 and Comparative Examples 1 to 2 Polyamideimide resin solutions (A-1 to 1) obtained in Synthesis Examples 1 to 4
A-4) was blended with the materials shown in Table 2 and stirred for about 1 hour until the resin became uniform, and then at room temperature for 24 hours for defoaming.
The mixture was allowed to stand for a time to obtain a flame-retardant heat-resistant resin composition solution. In addition, the thickness of the obtained flame-retardant heat-resistant resin composition solution is 50 μm.
m Teflon (registered trademark) film (trade name: Niflon tape TOMBO9001 manufactured by Nichias Co., Ltd.) so that the film thickness after drying would be 20 μm,
Prepare a product that has been dried for 1 minute, and use a dryer at 160 ° C x 1
After curing for 20 minutes, a cured film with a Teflon (registered trademark) film was obtained, and the cured film with the Teflon (registered trademark) film peeled off was broken in liquid nitrogen. Observation of this fracture surface using a scanning electron microscope (SEM) confirmed that those using the polyamideimide resin solutions A-1 to A-3 have a microphase-separated structure,
It was confirmed that those using A-4 did not have a microphase-separated structure.

[0057]

[Table 2] * 6: Product name of Tohto Kasei Co., Ltd. * 7: Product name of Daihachi Chemical Industry Co., Ltd. (general formula (3 formulas)) * 8: Product name of Dainippon Ink and Chemicals Co., Ltd.

The obtained flame-retardant heat-resistant resin composition solution was applied to a polyimide film having a thickness of 25 μm (trade name: Kapton 100H manufactured by Toray DuPont Co., Ltd.) so that the film thickness after drying would be 20 μm. And dried at 130 ° C. for 4 minutes to prepare a rolled copper foil having a thickness of 35 μm (trade name: BHY-2 manufactured by Nikko Gould Wheel Co., Ltd.).
2B-T) was pasted together on the roughened surface side, hot roll lamination was performed at a temperature of 140 ° C. and a pressure of 490 kPa (5 kgf / cm ² ) for temporary adhesion, followed by curing with a drier at 160 ° C. for 120 minutes to prepare a sample. (Sample A)

The obtained flame-retardant heat-resistant resin composition solution was applied to a 25 μm-thick polyimide film (trade name: Kapton 100H manufactured by Toray DuPont Co., Ltd.) so that the film thickness after drying was 20 μm. And dried at 130 ° C. for 4 minutes to prepare a rolled copper foil having a thickness of 35 μm (trade name: BHY-2 manufactured by Nikko Gould Wheel Co., Ltd.).
2B-T) was pasted together on the glossy side, hot roll lamination was performed at a temperature of 140 ° C. and a pressure of 490 kPa (5 kgf / cm ² ) for temporary adhesion, followed by curing with a dryer at 160 ° C. for 120 minutes to prepare a sample. (Sample B)

The obtained flame-retardant heat-resistant resin composition solution was applied to a 25 μm thick polyimide film (trade name: Kapton 100H manufactured by Toray DuPont Co., Ltd.) so that the film thickness after drying would be 20 μm. Then, a product dried at 130 ° C. for 4 minutes was prepared and cured at 160 ° C. for 120 minutes by a dryer to obtain a sample. (Sample C)

A 50 μm thick Teflon (registered trademark) film (trade name: Niflon Tape TOMBO9 manufactured by Nichias Co., Ltd.) was used as the flame-retardant heat-resistant resin composition solution.
001) so that the film thickness after drying is 20 μm and dried at 130 ° C. for 4 minutes to prepare a film, which is then cured by a dryer at 160 ° C. for 120 minutes and cured with a Teflon (registered trademark) film. A film was obtained, and the Teflon (registered trademark) film was peeled off to obtain a sample. (Sample D)

The obtained flame-retardant heat-resistant resin composition solution was applied to a 25 μm-thick polyimide film (trade name: Kapton 100H manufactured by Toray DuPont Co., Ltd.) so that the film thickness after drying would be 25 μm. Then, the sample was dried at 130 ° C. for 4 minutes to prepare a sample. (Sample E)

Adhesiveness (Sample A,
B), solder heat resistance (Sample A), flame retardancy (Sample C), glass transition temperature (Sample D), and storage elastic modulus (Sample D),
The warpage after drying (Sample E) was measured, and the results are shown in Table 3. The measuring method and conditions of these characteristics are shown below.

(Adhesiveness) Sample A (Sample structure: polyimide film / flame-retardant heat-resistant resin composition / rolled copper foil roughened surface), Sample B (sample structure: Polyimide film / flame-retardant heat-resistant resin composition) / Rolled copper foil glossy surface) is used to perform a peeling test in the direction of 90 ° by rolling copper foil pulling under the following conditions:
The peeled strength (kN / m) from the roughened surface of the rolled copper foil, the glossy surface of the rolled copper foil and the polyimide film was measured. Measurement temperature: 25 ° C, peeling speed: 50 mm / min

(Solder heat resistance) Sample A (sample structure: polyimide film / flame-retardant heat-resistant resin composition / rolled copper foil roughened surface) was immersed in a solder bath at 300 ° C. for 3 minutes, The presence or absence of abnormal appearance such as blister and peeling was examined. ○: No abnormalities in appearance such as blister and peeling ×: Abnormalities in appearance such as blistering and peeling

(Flame Retardancy) Sample C (Sample composition: polyimide film / flame retardant heat resistant resin composition) was used for UL94
The flame-retardant grade was measured according to the flame-retardant standard.

(Glass Transition Temperature and Storage Elastic Modulus) Sample D
Dynamic viscoelasticity measurement (trade name, manufactured by Rheometric Co., Ltd.) was performed using (Sample structure: cured film only) under the following conditions. The maximum value of the tan δ peak was used as the glass transition temperature (Tg). Measurement mode: Tension, Chuck distance: 22.5m
m, measurement temperature: -50 to 300 ° C., temperature rising rate: 5 ° C./min, measurement frequency: 10 Hz, sample size: 5 mm width × 20 mm length

(War after Drying) Sample E (sample constitution: polyimide film / flame-retardant heat-resistant resin composition) was placed on a horizontal surface, and the height of warpage of the sample was measured. ◯: No warp (height 0 mm) Δ: Some warp (height <10 mm) X: Warp (height> 10 mm curled)

[0069]

[Table 3]

[0070]

EFFECTS OF THE INVENTION The flame-retardant heat-resistant resin composition of the present invention, which contains a polyamideimide resin containing an alicyclic unit and a siloxane unit having a thermal stress reducing effect, exhibits an excellent thermal stress reducing effect. A flame-retardant heat-resistant resin composition useful for various printed wiring board adhesives and adhesive films. Furthermore, the flame-retardant heat-resistant resin composition of the present invention,
It shows a flame retardant effect derived from an aromatic unit and a siloxane unit of a polyamide-imide resin, and has excellent halogen-free flame retardancy due to an organic phosphorus compound which is a flame retardant auxiliary, and has a microscopic structure of a polyamide-imide resin. It has excellent adhesiveness due to the stress relaxation effect due to the phase-separated structure, and is useful as an adhesive and an adhesive film for various printed wiring boards.

The adhesive film of the present invention has an excellent effect of reducing thermal stress, is useful as an adhesive and an adhesive film for various printed wiring boards, is halogen-free and has excellent flame retardancy, and is polyamideimide. It has excellent adhesiveness due to the stress relaxation effect due to the microphase separation structure of the resin.

The polyimide film with an adhesive of the present invention is excellent in heat resistance and has an excellent effect of reducing thermal stress, and is useful as an adhesive and an adhesive film for various printed wiring boards, and is halogen-free and has excellent flame retardancy. And has excellent adhesiveness due to the stress relaxation action due to the microphase-separated structure of the polyamide-imide resin.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/00 C08L 63/00 A 4J040 C09J 7/02 C09J 7/02 Z 163/00 163/00 179 / 08 179/08 B 183/10 183/10 F-term (reference) 4F006 AA39 AB34 AB38 AB55 BA01 BA04 CA08 4J002 AA022 CD002 CD012 CD042 CD052 CD062 CD112 CD142 CM041 CQ013 EJ037 EN077 ER027 001F07A01J02 017G01 FD136 FD136 FD136 FD136 FD136FD01 FD136 FD136FD01 FD136 FD136FD01 AA13 CA04 CA06 CA08 CC02 FA05 4J034 BA06 CA24 CB03 CB07 CC12 CC28 CC33 CC44 CC52 CC54 CC61 CC68 CC69 CD04 CD05 CD09 CD12 CD15 DM01 HA01 HA07 HC17 HC22 HC45 HC53 HC61 HC71 QA07 QB17 RA08 RA08 4J036 AA01 AB01 AD08 AD08 AB05 AB08 AB08 AB08 AB08 AB07 AB08 CC02 DA01 DA02 DB06 DC03 DC10 DC25 DC31 DC41 FA12 FB07 FB14 JA06 JA08 4J040 EC002 EC142 EH031 EK111 JA09 KA16 LA09 MA02 MA10 MB03 MB 09

Claims (10)

[Claims] 1. (A) General formula (A formula) (Wherein R and R ′ each independently represent a divalent organic group), and R and R ′ in all the repeating units are as follows: (In the formula, X is Is shown), and (In the formula, R ³ and R ⁴ each independently represent a divalent organic group, and R ^{5 to} R ⁸ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, n is 1 to 5
Is an integer of 0), and Flame-retardant heat resistance containing a polyamide-imide resin having at least three divalent organic groups and having a microphase-separated structure, (B) thermosetting resin, and (C) organic phosphorus compound Resin composition. 2. The component (A) is represented by R as follows: (In the formula, X is Is shown), and (In the formula, R ³ and R ⁴ each independently represent a divalent organic group, and R ^{5 to} R ⁸ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, n is 1 to 5
Is an integer of 0) and R ′ is The flame-retardant heat-resistant resin composition according to claim 1. 3. The component (A) is obtained by reacting trimellitic anhydride with a mixture of a diamine (a) having three or more aromatic rings and a siloxanediamine (b), and the following general formula (1): Chemical 10] [Wherein R ¹ is (In the formula, X is Is shown). ] And an aromatic diimide dicarboxylic acid (1) represented by the following general formula (2) [Wherein R ² is (However, R ³ and R ⁴ each independently represent a divalent organic group, R ^{5 to} R ⁸ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, and n is 1-5
Is an integer of 0). ] The polyamide imide resin having a microphase-separated structure obtained by reacting a mixture containing siloxane diimide dicarboxylic acid (2) with norbornene diisocyanate represented by
The flame-retardant heat-resistant resin composition as described. 4. (A) 100 parts by weight of polyamide-imide resin, (B) 10 to 100 parts by weight of thermosetting resin, and (C).
The flame-retardant heat-resistant resin composition according to claim 3, which comprises 2 to 20 parts by weight of an organic phosphorus compound. 5. The flame-retardant heat-resistant resin composition according to claim 3, wherein the siloxane diamine (b) has an amine equivalent of 400 to 2,500 g / mol. 6. The thermosetting resin as the component (B) comprises an epoxy resin and a curing accelerator or a curing agent therefor.
The flame-retardant heat-resistant resin composition according to any one of 5 above. 7. The flame-retardant heat-resistant resin composition according to claim 6, wherein the epoxy resin is a phosphorus-containing epoxy resin. 8. The organophosphorus compound as the component (C) has the general formula (3): (Wherein, W talk (single bond), an alkylene group having 1 to 5 carbon _{atoms, -S -, - SO 2 -} , - O-, or -N = represents a bonding group which is a N-, n1 is 10 to It is an integer of 50.)
Or a phosphoric acid ester compound represented by the general formula (4): (In formula, n2 is an integer of 10-50.) The flame-retardant heat-resistant resin composition in any one of Claims 1-7 which is a phosphate compound. 9. An adhesive film having an adhesive layer formed from the flame-retardant heat-resistant resin composition according to claim 1. 10. A polyimide film with an adhesive in which the adhesive layer according to claim 9 is laminated on one side or both sides of a polyimide film.