JP2002161205A - Flame-retardant heat-resistant resin composition, adhesive film using the same and polyimide film with adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant heat-resistant resin composition having an excellent thermal stress reducing effect useful for an adhesive for various printed-circuit boards and an adhesive film, to obtain an adhesive film and a polyimide film with an adhesive using the same. SOLUTION: This flame-retardant heat-resistant resin composition comprises (A) a modified polyamide-imide resin having a microphase separation structure, (B) a thermosetting resin and (C) an organophosphorus compound.

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 a polyimide film with an adhesive.

[0002]

2. Description of the Related Art In recent years, as electronic devices have rapidly become smaller and lighter, the mounting density of electronic components has also increased.
The characteristics required for various electronic components and materials used for the same have been diversified. In particular, a printed wiring board has a small and high-density wiring occupied area, and has a multilayer wiring board (build-up wiring board) and a flexible wiring board (F
Demands such as PC) are also increasing. These wiring boards use various adhesives or adhesive films in the manufacturing process, and the resins used for the adhesives mainly include epoxy resins and acrylic resins.
However, all of these resins were insufficient to satisfy properties such as heat resistance and electrical insulation.

On the other hand, polyimide resins and polyamide-imide resin-based adhesives are known as having excellent heat resistance and electrical insulation properties. There is a problem that a thermal stress is generated between the wiring boards and the wiring board is warped.

[0004] Further, as flame retardants for various printed wiring board materials, halogen compounds such as bromine compounds and antimony compounds having excellent flame retardant effects have been most commonly used. However, the use of halogen-based compounds has recently been limited mainly in European countries because recent research has produced gases containing dioxins and the like that are toxic to the human body when burned. Specific examples of such a flame retardant that does not generate toxic gas include inorganic fillers such as aluminum hydroxide and magnesium hydroxide, and phosphorus-based compounds.

However, these compounds need to be added in a large amount to the target resin in order to obtain sufficient flame retardancy, and the properties inherent in the resin may be greatly reduced. Specifically, since aluminum hydroxide is generally soluble sodium mixed in during production, for example, among various adhesives for wiring boards, an adhesive for FPC is an adherend when subjected to a long-term high-temperature and high-humidity treatment. It is known that a hydrolysis reaction occurs on the surface of a polyimide film to weaken the surface of the polyimide film, thereby lowering the peel strength. Further, magnesium hydroxide is generally known to reduce acid resistance. Further, among the phosphorus-based compounds, well-known phosphate esters function as plasticizers and reduce heat resistance and the like, so that it is necessary to limit the types and amounts 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 thermal stress reducing effect useful for various printed wiring board adhesives and adhesive films. is there. Furthermore, various printed wirings having excellent halogen-free flame retardancy due to a phosphorus compound as a flame retardant aid and excellent adhesiveness due to a stress relaxation effect caused by a microphase separation structure of a modified polyamideimide resin. An object of the present invention is to provide a flame-retardant heat-resistant resin composition useful for an adhesive for boards and an adhesive film.

[0007] Another object of the present invention is to provide a halogen-free, various heat-resistant and flame-retardant resin having excellent adhesiveness due to a stress relaxation effect caused by a microphase-separated structure of a modified polyamideimide resin. An object of the present invention is to provide an adhesive film suitable for a printed wiring board.

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

[0009]

The present invention provides (A) a modified polyamide-imide resin having a microphase-separated structure;
The present invention relates to a flame-retardant heat-resistant resin composition containing a thermosetting resin and (C) an organic phosphorus compound.

[0010] The present invention also relates to 100 parts by weight of a modified polyamideimide resin having a microphase-separated structure of component (A), 10 to 100 parts by weight of a thermosetting resin of component (B) and 10 to 100 parts by weight of component (C). The present invention relates to the flame-retardant heat-resistant resin composition containing 2 to 20 parts by weight of the above organic phosphorus compound.

The present invention also relates to a modified polyamideimide resin having a microphase-separated structure of the component (A), which comprises a mixture of a diamine having at least three aromatic rings, a polyoxypropylenediamine and a siloxanediamine, and trimellitic anhydride. General formula (1 formula) obtained by reacting

Embedded image [Wherein R ¹ is

Embedded image (However, X is

Embedded image Is shown. ). General formula (2 formulas)

Embedded image [Wherein R ² is

Embedded image (Where n is an integer of 1 to 70). ] And general formula (3 formulas)

Embedded image [Where R ³ is

Embedded image (However, R ⁴ and R ⁵ each independently represent a divalent organic group, R ^{6 to} R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, and m represents 1-5
Which is an integer of 0). And a mixture containing a diimidedicarboxylic acid represented by the general formula (4):

Embedded image [Wherein R ¹⁰ is

Embedded image Is shown. And a modified polyamideimide resin obtained by reacting the aromatic diisocyanate represented by the formula (1).

The present invention also relates to the flame-retardant heat-resistant resin composition wherein the polyoxypropylene diamine has an amine equivalent of 100 to 2,000 g / mol. Further, the present invention provides an siloxane diamine having an amine equivalent of 400 to 2,
It relates to the flame-retardant heat-resistant resin composition of 500 g / mol. The present invention also relates to the flame-retardant heat-resistant resin composition, wherein the thermosetting resin (B) is an epoxy resin and a curing accelerator or a 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.

Further, the present invention provides an organic phosphorous compound (C) having the general formula (5)

Embedded image (W is a 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 an integer of 10 to 50. ) Or a general formula (6)

Embedded image (Wherein, n2 is an integer of 10 to 50). The invention relates to the above-mentioned flame-retardant heat-resistant resin composition, which is a phosphate compound.

[0014] The present invention also relates to an adhesive film having an adhesive layer comprising the flame-retardant heat-resistant resin composition.
The present invention also relates to a polyimide film with an adhesive in which the adhesive layer is laminated on a polyimide film.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The flame-retardant heat-resistant resin composition of the present invention comprises: (A) a modified polyamideimide resin having a microphase-separated structure;
It comprises (B) a thermosetting resin and (C) an organic phosphorus compound.

The modified polyamideimide resin used in the present invention is not particularly limited as long as it has a microphase-separated structure (sea-island structure), and preferably has a microphase-separated structure after drying or curing. As such a modified polyamide-imide resin, a modified polyamide-imide resin composed of a polyoxypropylene unit and a siloxane unit as a soft segment and an aromatic unit as a hard segment is preferable. By having this micro phase separation structure, a stress relaxation action is specifically exhibited, and excellent adhesiveness can be obtained while maintaining high heat resistance.

The modified polyamideimide resin having a microphase-separated structure of the component (A) is obtained by reacting a mixture of a diamine having at least three aromatic rings, polyoxypropylenediamine and siloxanediamine with trimellitic anhydride. The obtained general formulas (1) and (2)
It is preferable to use a modified polyamideimide resin obtained by reacting a mixture of the diimide dicarboxylic acids represented by the general formula (3) and the aromatic diisocyanate represented by the general formula (4).

In the above formula (2), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group,
-Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl Group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and structural isomers thereof. In the above general formula (2 formulas),
Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like, and include a halogen atom, an amino group, a nitro group, a cyano group, a mercapto group, an allyl group, and a carbon atom having 1 carbon atom. Or 20 alkyl groups.

Examples of the diamine having three or more aromatic rings include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP) and 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, and from the viewpoint of the balance between the properties of the modified polyamideimide resin and the cost, 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferable. . These are used alone or in combination of two or more.

As the polyoxypropylenediamine used in the present invention, known ones can be used, and for example, those represented by the following general formula (7) are preferable.

Embedded image (Where n is an integer of 1 to 70)

Commercially available products include Jeffamine D-230 (amine equivalent 115 g / mol) and Jeffamine D-400 (amine equivalent 200 g / mo).
1), Jeffamine D-2000 (amine equivalent 1,0
00g / mol), Jeffamine D-4000 (amine equivalent: 2,000 g / mol) (all trade names manufactured by San Techno Chemical Co., Ltd.) and the like. These are used alone or in combination of two or more.

Here, in order to form a micro-phase-separated structure for reducing the thermal stress which causes the warpage of the modified polyamideimide resin of the component (A) and further improving the adhesiveness,
When the amine equivalent of polyoxypropylenediamine is 100
2,000 g / mol, preferably 200 g / mol.
2,000 g / mol, more preferably
It is particularly preferred to be 2,000 to 2,000 g / mol. Examples of these include Jeffamine D-2000
(Amine equivalent: 1,000 g / mol), Jeffamine D-4000 (amine equivalent: 2,000 g / mol) (all trade names manufactured by Sun Techno Chemical Co., Ltd.) and the like. These are used alone or in combination of two or more. In the present invention, the amine equivalent is a gram number of a resin containing 1 mol of an amino group.

The siloxane diamine used in the present invention may be a public one, but is preferably, for example, one represented by the following general formula (8).

Embedded image (Wherein R ⁴ and R ⁵ each independently represent a divalent organic group;
^{6 to} R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms, and m represents an integer of 1 to 50. )

In the above formula (8), examples of the divalent organic group include an alkylene group such as a methylene group, an ethylene group and a propylene group, and an arylene group such as a phenylene group, a tolylene group and a xylylene group. Can be Examples of such a siloxane diamine include those represented by the following formula.

[0025]

Embedded image [In the formula, m represents an integer of 1 to 50. ]

Commercially available products include amino-modified silicone oil X which is a siloxane-based terminal amine.
-22-161AS (amine equivalent 450 g / mol),
X-22-161A (amine equivalent 840 g / mol),
X-22-161B (amine equivalent 1540 g / mol)
(Trade name of Shin-Etsu Chemical Co., Ltd.)
853 (amine equivalent 650 g / mol), BY16-8
53B (amine equivalent: 2200 g / mol) (both products 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 modified polyamideimide resin of the component (A) and to form a microphase separation structure for improving the adhesiveness, the amine equivalent of siloxanediamine is set to 400 to 2 , 500 g / mol, more preferably 800 to 2,500 g / mol, and particularly preferably 800 to 1,600 g / mol. Examples of these include, for example, X-22-161A (amine equivalent 840 g / mo).
l), X-22-161B (amine equivalent weight 1540 g / m
ol) (all trade names manufactured by Shin-Etsu Chemical Co., Ltd.). These are used alone or in combination of two or more.

As the aromatic diisocyanate represented by the general formula (4), for example, 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 2,4
4-tolylene diisocyanate (hereinafter abbreviated as TDI), 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene dimer, etc., for imparting flexibility and preventing crystallinity. From a viewpoint, 4,4'-diphenylmethane diisocyanate is preferred. These are used alone or in combination of two or more. In addition, from the viewpoint of heat resistance, an aliphatic diisocyanate such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or isophorone diisocyanate is used in combination at about 5 to 10 mol% based on the aromatic diisocyanate. Can be.

From the viewpoint of heat resistance, aromatic dicarboxylic acids such as terephthalic acid, phthalic acid and naphthalenedicarboxylic acid, adipic acid, sebacic acid, decane diacid, dodecane diacid, dimer An aliphatic dicarboxylic acid such as an acid can be used in an amount of about 5 to 10 mol% based on the above diimide dicarboxylic acid.

The modified polyamideimide resin having a microphase-separated structure of the component (A) used in the present invention includes, for example, diamine (1 ') having three or more aromatic rings, polyoxypropylenediamine (2') and siloxanediamine The mixture of (3 ′) and trimellitic anhydride (hereinafter referred to as TMA)
In the presence of an aprotic polar solvent,
The reaction is carried out at 0 ° C. for 0.2 to 1.5 hours, and the aromatic hydrocarbon which can be azeotroped with water is further converted to an aprotic polar solvent of 0.1 to 0.1 hours.
The reaction was carried out at 120 to 180 ° C. for 2 to 5 hours, and the aromatic diimide dicarboxylic acid (1) represented by the general formula (1) and the aromatic diimide dicarboxylic acid (1) represented by the general formula (2) were added. A mixture containing the polyoxypropylene diimide dicarboxylic acid (2) represented by the formula (3) and the siloxane diimide dicarboxylic acid (3) represented by the formula (3) is produced, and a mixture thereof is represented by the formula (4). Aromatic diisocyanate (4)
Is reacted at about 150 to 250 ° C. for about 0.5 to 3 hours.

After preparing a mixture containing the diimide dicarboxylic acids represented by the general formulas (1), (2) and (3),
By heating to about 0 to 250 ° C., an aromatic hydrocarbon capable of azeotroping with water is removed from the solution, and the reaction can be performed by reacting the aromatic hydrocarbon with the aromatic diisocyanate (4). Further, the modified polyamideimide resin is preferably a varnish containing an aprotic polar solvent.

The mixing ratio of the mixture of the diamine (1 ') having three or more aromatic rings, polyoxypropylene diamine (2') and siloxane diamine (3 ') is (1') / (2 ') /(3')=10.0-79.
0 / 1.0 to 70.0 / 10.0 to 20.0 (the unit of each numerical value is mol%, and (1 ′), (2 ′) and (3 ′)
Is assumed to be 100 mol%). Resins obtained using a mixture having a ratio outside this range tend to cause warpage or decrease in flame retardancy, disappearance of a microphase separation structure or decrease in molecular weight. The range of this ratio is 45.0-65.0 / 20.0-35.0 / 1.
More preferably, it is 0.0-15.0 (mol%).

Further, the above mixture is reacted with trimellitic anhydride (TMA) to convert the diimide dicarboxylic acid represented by the general formula (1), the general formula (2) and the general formula (3). The amounts of the raw materials used to obtain the mixture containing the total number of moles of the diamine (1 '), polyoxypropylene diamine (2') and siloxane diamine (3 ') having three or more aromatic rings and the number of moles of TMA Of ((1 ′) + (2 ′) + (3 ′)) / TMA is 1/2.
05 to 1 / 2.20, preferably 1 / 2.2.
0 to 1 / 2.05, more preferably 1/2.
More preferably, it is 15 to 1 / 2.10. When this molar ratio is less than 1 / 2.20, TMA remains and the molecular weight of the finally obtained resin tends to decrease.
If it exceeds 05, the diamine remains and the molecular weight of the finally obtained resin tends to decrease.

Next, a mixture ((1) + (2) + (3)) containing the diimidedicarboxylic acid represented by the general formula (1), the general formula (2) and the general formula (3) Is reacted with the aromatic diisocyanate (4) represented by the general formula (4) to obtain a modified polyamideimide resin in a molar ratio of ((1) + (2) + (3)) / ( 4)
= 1 / 1.50 to 1 / 1.05, more preferably 1 / 1.3 to 1 / 1.1. If the 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 having three or more aromatic rings, polyoxypropylene diamine, siloxane diamine, or an organic solvent which does not react with TMA. For example, dimethylacetamide, dimethylformamide, Examples thereof include dimethyl sulfoxide, N-methyl-2-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 reaction does not sufficiently proceed due to trimellitic acid generated by hydration of TMA, and the molecular weight of the resin tends to decrease. The amount of the aprotic polar solvent used in the present invention ranges from 10 to 80% by weight based on the total amount of the diamine having three or more aromatic rings, polyoxypropylene diamine, siloxane diamine and TMA. Preferably 5
It is preferably in the range of 0 to 80% by weight. If the amount is less than 10% by weight, the solubility of TMA tends to decrease, and sufficient reaction tends to be impossible. If the amount exceeds 80% by weight, it tends to be disadvantageous as an industrial production method.

Examples of the aromatic hydrocarbon which can be azeotroped with water include toluene, xylene and the like.

The weight-average molecular weight of the modified polyamideimide resin having a microphase-separated structure of the component (A) is 30,0.
It is preferably from 00 to 300,000, and 40,0
More preferably, the number is from 200 to 200,000.
It is particularly preferred that it is between 000 and 100,000. When the weight-average molecular weight is less than 30,000, the strength and flexibility in the film state tend to decrease, the tackiness tends to increase, and the microphase separation structure tends to disappear.
If it exceeds 0, the flexibility and adhesiveness in a film state 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 modified polyamideimide resin skeleton having a microphase-separated structure of the component (A) by heat or the like. For example, epoxy resin, phenol resin, bismaleimide triazine resin and the like are preferable. Among them, an epoxy resin is preferable from the viewpoint of adhesiveness and handleability, and an epoxy resin containing a phosphorus atom in a molecule is particularly preferable from the viewpoint of flame retardancy. These are used alone or in combination of two or more.

As the epoxy resin, for example, a 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) (all trade names of Toto Kasei Co., Ltd.). These are used alone or in combination of two or more. The epoxy resin preferably has an epoxy equivalent of 200 to 500,
More preferably, it is 00.

The amount of the thermosetting resin (B) is preferably 10 to 100 parts by weight based on 100 parts by weight of the modified polyamideimide resin having a microphase-separated structure of the component (A). It is more preferably from 30 to 80 parts by weight, particularly preferably from 20 to 50 parts by weight. If the amount is less than 10 parts by weight, the flame retardancy tends to be insufficient and the function as a curing agent tends to decrease. If the amount exceeds 100 parts by weight, the crosslinked structure of the cured resin becomes dense and the resin becomes brittle. Tend to.

As the thermosetting resin (B) used in the present invention, it is preferable to use a curing accelerator in addition to the above resins. As the curing accelerator,
There is no particular limitation as long as it reacts with the phosphorus-containing epoxy resin of the component (B) or promotes the curing reaction between the component (A) and the component (B). For example, amines and imidazoles are used. it can. These are used alone or in combination of two or more. Examples of the amines include dicyandiamide, diaminodiphenylmethane,
Guanyl urea and the like can be mentioned. These are used alone or in combination of two or more. Examples of the above imidazoles include alkyl-substituted imidazoles such as 2-ethyl-4-methylimidazole, and benzoimidazoles. These are used alone or in combination of two or more.

In the case of amines, the amount of the curing accelerator is preferably such that the equivalent of the active hydrogen of the amine and the epoxy equivalent of the phosphorus-containing epoxy resin are substantially equal to each other. In the case of imidazole, the phosphorus-containing epoxy resin 10
The amount is preferably 0.1 to 2.0 parts by weight with respect to 0 parts by weight. If the amount is too small, the uncured phosphorus-containing epoxy resin tends to remain, and the glass transition temperature of the crosslinked resin tends to decrease. Properties tend to decrease.

As the organic phosphorus compound as the component (C) used in the present invention, for example, a biphenyl type phosphate compound represented by the general formula (5) or a compound represented by the general formula (6) Aromatic condensed phosphoric acid ester compound shown, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, cresyl di 2,6-xylenyl phosphate, 2-methacryloyloxy Ethyl acid phosphate, diphenyl-2-methacryloyloxyethyl phosphate, CR-733S, CR-741, CR-
Aromatic condensed phosphate ester-based compounds such as 747, PX-200 (all trade names manufactured by Daihachi Chemical Industry Co., Ltd.), SP
-703, SP-601 (trade name of Shikoku Chemical Industry Co., Ltd.), 35, 50, 65, 9 of "Leophos" series
5, 110 (the above are trade names of Ajinomoto Co., Inc.). These are used alone or in combination of two or more.

The general formula (5) and the general formula (6)
In the formula, the benzene ring in the compound has 1 to 5 carbon atoms.
May have a substituent such as an alkyl group. When there are two or more substituents, 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 organic phosphorus compound (C) is preferably 2 to 20 parts by weight based on 100 parts by weight of the modified polyamideimide resin having a microphase-separated structure of the component (A). It is more preferably from 2 to 10 parts by weight, particularly preferably from 2 to 5 parts by weight.
If the amount 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 solder heat resistance tend to decrease.

In the present invention, these compositions are preferably mixed in an organic solvent to obtain a flame-retardant heat-resistant resin composition having a solid content of about 20 to 40% by weight. The organic solvent is not particularly limited as long as solubility can be obtained.For example, dimethylacetamide, dimethylformamide,
Dimethyl sulfoxide, N-methyl-2-pyrrolidone,
γ-butyrolactone, sulfolane, cyclohexanone,
Examples include methyl ethyl ketone, methyl isobutyl ketone, toluene, acetone and the like.

The flame-retardant heat-resistant resin composition of the present invention may optionally contain, in addition to the above components, a coupling agent, a pigment, a leveling agent, an antifoaming agent, an ion trapping agent, and the like. May be.

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 directly applying it, or it may be formed into an adhesive film to form a flame-retardant film. The adhesive layer may be formed by laminating layers of the heat-resistant resin composition. When an adhesive film is used, the support substrate may be removed after lamination, or may be removed before lamination.

The adhesive film having an adhesive layer according to the present invention is obtained, for example, by applying a flame-retardant heat-resistant resin composition dissolved in a predetermined organic solvent onto a supporting substrate and then drying the solvent by heating or blowing with hot air. It can be manufactured by making it. Examples of the support substrate include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonate, Teflon (registered trademark) film, release paper, copper foil, and metal foil such as aluminum foil. The thickness of the supporting substrate is 10 to 150 μ
m is preferred. The supporting substrate 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 can obtain solubility. Examples thereof include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, butyl acetate, cellosolve acetate, and the like.
Acetates such as propylene glycol monomethyl acetate and carbitol acetate; cellosolves such as cellosolve and butyl cellosol; carbitols such as carbitol and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide and dimethylacetamide , N-methyl-2-pyrrolidone and the like. These are used alone or in combination of two or more.

The thickness of the flame-retardant heat-resistant resin composition laminated on the supporting substrate is preferably from 5 to 50 μm, more preferably from 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 viewpoints of storability, productivity and workability, it is preferable that a protective film is further laminated on the surface opposite to the flame-retardant heat-resistant resin composition, wound up in a roll shape, and stored. Examples of the protective film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonate, Teflon film, and release paper, as in the case of the support substrate. The thickness of the protective film is more preferably from 10 to 100 μm. The protective film may be subjected to a mat treatment, a corona treatment, and a release treatment.

The adhesive film having an adhesive layer of the present invention can be made into a polyimide film with an adhesive by laminating it on a polyimide film, for example, as a coverlay film for flexible wiring boards and a base film. be able to. Further, a flexible wiring board substrate or the like can be formed by laminating metal foils.

[0054]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

(Synthesis Examples 1 to 4) As a diamine having three or more aromatic rings in a 1-liter separable flask equipped with a faucet connected to a reflux condenser and having a 25-ml water content receiver, a thermometer and a stirrer. BAPP (2,2-bis [4
-(4-aminophenoxy) phenyl] propane) and Jeffamine D- as polyoxypropylenediamine
2000 (trade name, manufactured by Sun Techno Chemical Co., amine equivalent: 1000); reactive silicone oil X-22-161B as siloxane diamine (trade name, manufactured by Shin-Etsu Chemical Co., amine equivalent: 1540); TMA (trimellitic anhydride); NMP as aprotic polar solvent
(N-methyl-2-pyrrolidone) and γ-BL (γ-butyrolactone) were charged at the compounding ratio shown in Table 1, and stirred at 80 ° C. for 30 minutes. Then, 100 ml of toluene was charged as an aromatic hydrocarbon capable of azeotropic distillation with water, and then the temperature was increased and the mixture was refluxed at about 160 ° C. for 2 hours.

After confirming that about 3.6 ml or more of water has accumulated in the moisture quantification receiver and that no outflow of water has been observed, while removing the effluent accumulated in the moisture quantification receiver, about The temperature was increased to 190 ° C. to remove the toluene. Thereafter, the solution was returned to room temperature, and MDI (4,4'-diphenylmethane diisocyanate) and TDI (2,4-tolylene diisocyanate) were added as aromatic diisocyanates in the amounts shown in Table 1 and reacted at 190 ° C. for 2 hours. I let it. After completion of the reaction, the N
MP / γ-BL solutions A-1 to A-4 were obtained.

[0057]

[Table 1]

(Examples 1-3 and Comparative Examples 1-2) The modified polyamideimide resin solution (A-
1 to A-4) were mixed with the materials shown in Table 2, and the mixture was stirred for about 1 hour until the resin became uniform, and then left at room temperature for 24 hours for defoaming to obtain a resin composition. Further, the obtained resin composition was coated with a 50 μm-thick Teflon film (trade name: Naflon Tape TOMBO900 manufactured by Nitto Denko Corporation).
1) is applied so that the film thickness after drying becomes 20 μm;
Prepare what was dried at 30 ° C for 4 minutes, and
After curing at 60 ° C. for 120 minutes, a cured film with a Teflon film was obtained, and the cured film from which the Teflon film was peeled was broken in liquid nitrogen. When this fractured surface was observed using a scanning electron microscope (SEM), it was confirmed that those using the modified polyamideimide resin solutions A-1 to A-3 had a microphase separation structure. It was confirmed that the sample using No. 4 did not have a microphase separation structure.

[0059]

[Table 2]

Further, the obtained resin composition was coated to a thickness of 25 μm
Is coated on a polyimide film (trade name: Kapton 100H, manufactured by Du Pont-Toray Co., Ltd.) so that the film thickness after drying becomes 20 μm, and dried at 130 ° C. for 4 minutes to produce a rolled copper of 35 μm. The roughened side of the foil (trade name: BHY-22B-T, manufactured by Nikko Gould Wheel Co., Ltd.) is laminated, hot roll laminated at a temperature of 140 ° C. and a pressure of 0.5 MPa, and temporarily bonded, and dried at 160 ° C.
The sample was cured for 120 minutes to prepare a sample. (Sample A)

Further, the obtained resin composition was coated to a thickness of 25 μm
Is coated on a polyimide film (trade name: Kapton 100H, manufactured by Du Pont-Toray Co., Ltd.) so that the film thickness after drying becomes 20 μm, and dried at 130 ° C. for 4 minutes to produce a rolled copper of 35 μm. The glossy side of the foil (trade name: BHY-22B-T, manufactured by Nikko Gould Wheel Co., Ltd.) is laminated, hot roll laminated at a temperature of 140 ° C. and a pressure of 0.5 MPa, and temporarily bonded, and 160 ° C. with a dryer.
The sample was cured for 120 minutes to prepare a sample. (Sample B)

Further, the obtained resin composition was formed to a thickness of 25 μm
Was applied to a polyimide film (trade name: Kapton 100H, manufactured by Du Pont-Toray Co., Ltd.) so as to have a thickness of 20 μm after drying, and dried at 130 ° C. for 4 minutes to produce a film. The sample was cured for 120 minutes to prepare a sample. (Sample C)

Further, the obtained resin composition was coated to a thickness of 50 μm.
Film thickness after drying on a Teflon film (trade name: Naflon Tape TOMBO9001 manufactured by Nitto Denko Corporation)
It was coated to a thickness of μm, dried at 130 ° C. for 4 minutes, and cured by a dryer at 160 ° C. for 120 minutes to obtain a cured film with a Teflon film. The Teflon film was peeled off to obtain a sample. (Sample D)

Further, the obtained resin composition was coated with a thickness of 25 μm.
Was coated on a polyimide film (trade name: Kapton 100H, manufactured by Du Pont-Toray Co., Ltd.) so as to have a thickness of 25 μm after drying, and dried at 130 ° C. for 4 minutes to prepare a sample. (Sample E)

Using these samples, the adhesive property (Sample A,
B), solder heat resistance (Sample A), flame retardancy (Sample C), glass transition temperature (Sample D), storage modulus (Sample D), and warpage after drying (Sample E). The results are shown in Table 3. The measuring methods and conditions for these characteristics are shown below.

(Adhesion) Using Sample A (sample composition: polyimide film / resin composition / rolled copper foil roughened surface) and Sample B (sample composition: polyimide film / resin composition / rolled copper foil glossy surface) A peeling test in a 90 ° direction was performed using a rolled copper foil under the following conditions to measure the roughened surface of the rolled copper foil, the glossy surface of the rolled copper foil, and the peel strength (kN / m) from the polyimide film. Measurement temperature: 25 ° C, peeling speed: 50 mm / min

(Solder Heat Resistance) The sample A (sample composition: polyimide film / resin composition / rolled copper foil roughened surface) was immersed in a solder bath at 300 ° C. for 3 minutes to remove blisters, peelings, etc. The appearance was examined for abnormalities. ：: No abnormal appearance such as blister or peeling ×: Abnormal appearance such as blister or peeling

(Flame Retardancy) The flame retardancy grade of Sample C (sample composition: polyimide film / resin composition) was measured in accordance with UL94 flame retardancy standard.

(Glass Transition Temperature and Storage Elastic Modulus) Sample D
Dynamic viscoelasticity measurement (trade name: manufactured by Rheometric Corporation) was performed using the following (sample composition: cured film only) under the following conditions. As the glass transition temperature (Tg), the maximum value of the tan δ peak was used. Measurement mode: tension, distance between chucks: 22.5m
m, measuring temperature: -50 to 300 ° C, heating rate: 5 ° C / min, measuring frequency: 10 Hz, sample size: 5 mm width x 20 mm length

(Warpage after Drying) Sample E (sample composition: polyimide film / resin composition) was placed on a horizontal surface.
The warp height of the sample was measured. ：: no warpage (height 0 mm) △: slightly warped (height <10 mm) ×: warped (curl at height> 10 mm)

[0071]

[Table 3]

[0072]

The flame-retardant heat-resistant resin composition of the present invention contains a modified polyamideimide resin containing a polyoxypropylene unit and a siloxane unit having a thermal stress-reducing effect, and therefore has an excellent thermal stress-reducing effect. This is 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 exhibits a flame-retardant effect derived from an aromatic unit and a siloxane unit of the modified polyamideimide resin, and is halogen-free by a phosphorus-based compound as a flame-retardant auxiliary. It has excellent flame retardancy and flame retardancy, and has excellent adhesiveness due to the stress relaxation effect caused by the micro-phase separation structure of the modified polyamideimide resin. Various adhesives for printed wiring boards and adhesive films Useful for

The adhesive film of the present invention has an excellent effect of reducing thermal stress, is useful for adhesives and adhesive films for various printed wiring boards, is halogen-free, has excellent flame retardancy, and is modified. It has excellent adhesiveness due to the stress relaxation effect caused by the microphase separation structure of the polyamide-imide 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, is useful for various printed wiring board adhesives and adhesive films, and is halogen-free and excellent in difficulty. It is flammable and has excellent adhesion due to stress relaxation due to the microphase-separated structure of the modified polyamideimide resin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 85/02 C08L 85/02 C09J 7/02 C09J 7/02 Z 163/00 163/00 179/08 179 / 08 B 201/00 201/00 F-term (reference) 4F100 AH08A AH08H AH08K AK01A AK50A AK50K AK51B AK53A AL05A BA02 CA08A GB41 JA05 JA20A JB13A JJ07 JJ07A JK06 JK07 JL11A JL16 Y011CM01 EU032J01 CM01 4J004 AA11 AA13 AA17 CA02 CA03 CA04 CA06 CA08 CB02 CC02 CC03 EA01 FA05 4J040 EB022 EC002 EC182 EH022 EH031 HD24 KA16 LA06 LA08 LA09 PA23 QA01 4J043 PA05 PC015 PC016 QB58 RA06 SA11 SA42 SA43 SB01 SB02 SB03 UA01 TB02 UA1 UB012 UB022 UB062 UB132 UB142 UB152 UB302 UB352 UB402 VA051 VA081 WA05 WA09 WA22 XA03 XA16 XA19 ZB01 ZB50 ZB58

Claims (10)

[Claims] 1. A flame-retardant heat-resistant resin composition comprising (A) a modified polyamideimide resin having a microphase-separated structure, (B) a thermosetting resin, and (C) an organic phosphorus compound. 2. Component (A) (B) relative to 100 parts by weight of a modified polyamideimide resin having a microphase-separated structure.
The flame-retardant heat-resistant resin composition according to claim 1, comprising 10 to 100 parts by weight of the thermosetting resin as the component and 2 to 20 parts by weight of the organic phosphorus compound as the component (C). 3. A modified polyamideimide resin having a microphase-separated structure of component (A), which is obtained by reacting a mixture of a diamine having at least three aromatic rings, polyoxypropylenediamine and siloxanediamine with trimellitic anhydride. The following general formula (1 formula) to be obtained: Wherein R ¹ is (However, X is Is shown. ). General formula (2 formulas) Wherein R ² is (Where n is an integer of 1 to 70). ] And a general formula (3 formulas) [Wherein R ³ is (However, R ⁴ and R ⁵ each independently represent a divalent organic group; R ^{6 to} R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms; 1-5
Which is an integer of 0). And a mixture containing a diimidedicarboxylic acid represented by the general formula (4): [Wherein R ¹⁰ is Is shown. The flame-retardant heat-resistant resin composition according to claim 1 or 2, which is a modified polyamide-imide resin obtained by reacting an aromatic diisocyanate represented by the formula (1). 4. The flame-retardant heat-resistant resin composition according to claim 3, wherein the polyoxypropylene diamine has an amine equivalent of 100 to 2,000 g / mol. 5. The siloxane diamine having an amine equivalent of 40.
The flame-retardant heat-resistant resin composition according to claim 3, wherein the amount is from 0 to 2,500 g / mol. 6. The thermosetting resin as the component (B) is an epoxy resin and its curing accelerator or curing agent.
6. The flame-retardant heat-resistant resin composition according to 3, 4 or 5. 7. The flame-retardant heat-resistant resin composition according to claim 6, wherein the epoxy resin is a phosphorus-containing epoxy resin. 8. The organic phosphorus compound as the component (C) is represented by the general formula (5): (W is a 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 an integer of 10 to 50. Or a general formula (6): (Wherein, n2 is an integer of 10 to 50).
The flame-retardant heat-resistant resin composition according to 5, 6 or 7. 9. An adhesive film having an adhesive layer comprising the flame-retardant heat-resistant resin composition according to claim 1, 2, 3, 4, 5, 6, 7, or 8. 10. A polyimide film with an adhesive, wherein the adhesive layer according to claim 9 is laminated on the polyimide film.