JP2003238806A - 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, simultaneously, excellent adhesion due to the stress relaxation action, a flame-retardant and heat-resistant resin composition useful for adherent films, an adherent film using the same, and a polyimide film with an adhesive. <P>SOLUTION: The flame-retardant and heat-resistant resin composition comprises (A) a 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. . Further, various halogen-free excellent flame retardancy due to the organic phosphorus compound which is a flame retardant aid, and excellent adhesiveness due to the stress relaxation action due to the microphase separation structure of the modified polyamidimide resin. An object of the present invention is to provide a flame-retardant heat-resistant resin composition which is useful as an adhesive for printed wiring boards and an adhesive film.

Another object of the present invention is to provide various prints which are halogen-free, have excellent heat resistance and flame retardancy, and have excellent adhesiveness due to the stress relaxation effect resulting from the microphase separation structure of the polyamideimide resin. An object is to provide an adhesive film suitable for a wiring board.

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 formula 23] (Wherein R and R'independently represent a divalent organic group), and R and R'in all repeating units are represented by the following general formula (A1).

[Chemical formula 24] (Where X is

[Chemical 25] Indicates. ) And a group represented by the following formula (A2)

[Chemical formula 26] And a group represented by (A3)

[Chemical 27] (In the formula, 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 n is an integer of 1 to 50. ), And (A4) the following general formula —R ¹⁰ — (wherein R ¹⁰ is

[Chemical 28] Indicates. ) A polyamideimide resin having at least 4 kinds of divalent organic groups, which has a microphase-separated structure, (B) a thermosetting resin, and (C) an organophosphorus compound. It relates to a flame-retardant heat-resistant resin composition.

Further, in the present invention, the component (A) is represented by R as (A1)

[Chemical 29] (Where X is

[Chemical 30] Indicates. ) And a group represented by the following formula (A2)

[Chemical 31] And a group represented by (A3)

[Chemical 32] (In the formula, 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 n is an integer of 1 to 50. ) And a group represented by
4) the following general formula -R ¹⁰ - (wherein, R ¹⁰ is,

[Chemical 33] Indicates. ) The flame-retardant heat-resistant resin composition having a group represented by

In the present invention, the component (A) is obtained by reacting a mixture of aromatic diamine having 3 or more aromatic rings, alicyclic diamine and siloxane diamine with trimellitic anhydride. (1 set)

[Chemical 34] [Wherein R ¹ is

[Chemical 35] (However, X is

[Chemical 36] Is shown). ] The aromatic diimide dicarboxylic acid (1) represented by the general formula (2)

[Chemical 37] [Wherein R ² is

[Chemical 38] An alicyclic diimidedicarboxylic acid (2) and a general formula (3 formula)

[Chemical Formula 39] [Wherein R ³ is

[Chemical 40] (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 n is an integer of 1 to 50. ) Is shown. ] The mixture containing the siloxane diimide dicarboxylic acid (3) represented by the following general formula (4)

[Chemical 41] [Wherein R ¹⁰ is

[Chemical 42] Indicates. ] It is related with the said flame-retardant heat-resistant resin composition which is a polyamide imide resin obtained by making it react with the aromatic diisocyanate (4) shown by these.

The present invention further comprises (A) 100 parts by weight of a polyamide-imide resin, (B) 10 to 100 parts by weight of a thermosetting resin, and (C) 2 to 20 parts by weight of an organophosphorus compound. It relates to a flame-retardant heat-resistant resin composition.

The present invention also relates to the flame-retardant heat-resistant resin composition, wherein the alicyclic diamine has an amine equivalent of 60 to 100 g / mol. Further, the present invention relates to the flame-retardant heat-resistant resin composition, wherein the amine equivalent of siloxane diamine is 400 to 2,500 g / mol. Further, the present invention relates to the flame-retardant heat-resistant resin composition, wherein the (B) thermosetting resin is 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 organophosphorus compound (C) has the general formula (5)

[Chemical 43] (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 (6 formula)

[Chemical 44] (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.

[0016]

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
1) The following general formula

[Chemical formula 45] (Wherein X has the same meaning as above), and (A2) the following formula

[Chemical formula 46] And a group represented by (A3)

[Chemical 47] (In the formula, R ^{4 to} R ⁹ and n have the same meanings as described above.)
And a group (A4) represented by the following general formula —R ¹⁰ — (wherein R ¹⁰ has the same meaning as described above) and has at least four 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.

Examples of the polyamide-imide resin as the component (A) include, for example, in the formula (A), R is (A1)

[Chemical 48] (Wherein X has the same meaning as above), and (A2) the following formula

[Chemical 49] And a group represented by (A3)

[Chemical 50] (Wherein R ^{4 to} R ⁹ and n have the same meanings as described above), and R ′ is (A4) represented by the following general formula —R ¹⁰ — (wherein R ¹⁰ is , Have the same meanings as above.). Such a polyamide-imide resin is obtained by, for example, reacting a mixture of an aromatic diamine having 3 or more aromatic rings, an alicyclic diamine and a siloxane diamine with trimellitic anhydride and the above-mentioned general formula (1 formula). A mixture of the aromatic diimide dicarboxylic acid (1), the alicyclic diimide dicarboxylic acid (2) of the general formula (2) and the siloxane diimide dicarboxylic acid (3) of the general formula (3), and It can be obtained by reacting with an aromatic diisocyanate of formula (4).

Examples of the aromatic diamine having three or more aromatic rings used in the present invention include 2,2-bis [4-
(4-aminophenoxy) phenyl] propane (hereinafter,
Abbreviated as BAPP. ), 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 2 from the viewpoint of the balance of the properties of the polyamide-imide resin and the cost. , 2-Bis [4- (4-aminophenoxy) phenyl] propane is particularly preferred.
These are used alone or in combination of two or more.

The alicyclic diamine used in the present invention includes
2,5-bis (aminomethyl) bicyclo [2.2.1]
Heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane or 1-amino-3-aminomethyl-3,3,5-trimethylcyclohexyne are preferred. From the viewpoint of the property balance and cost of the polyamide-imide resin, 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane or 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane Is preferred.

The siloxane diamine used in the present invention is represented by the following general formula (7).

[Chemical 51] (In the formula, R ^{4 to} R ⁹ and n have the same meanings as in the general formula (3)).

The above general formulas (A formula), (3 formula) and (7)
In the formula), the divalent organic group represented by R ⁴ and R ⁵ is, for example, an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a propylene group, a phenylene group, a tolylene group,
Examples thereof include an arylene group having 6 to 18 carbon atoms such as a xylylene group.

The above general formulas (A formula), (3 formula) and (7)
In the formula), examples of the alkyl group having 1 to 20 carbon atoms represented by R ^{6 to} R ⁹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s
ec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group,
Examples thereof include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and structural isomers thereof. The above general formula (A formula), (3 formula) and (7)
In the formula), examples of the aryl group having 6 to 18 carbon atoms represented by R ^{6 to} R ⁹ include a phenyl group, a naphthyl group, an anthryl group and a phenanthryl group, and a halogen atom, an amino group, a nitro group, a cyano group. Group, mercapto group, carbon number 6
It may be substituted with an aryl group having 18 to 18 or an alkyl group having 1 to 20 carbons.

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

[Chemical 52] (In the formula, n represents an integer of 1 to 50.)

Amino-modified silicone oil X which is a siloxane-based amine having both terminals 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 polyamide-imide resin as the component (A) and to form a microphase-separated structure that improves the adhesiveness, the amine equivalent of siloxane diamine is set to 400 to 2, The amount is preferably 500 g / mol, more preferably 800 to 2,000 g / mol, and particularly preferably 800 to 1,600 g / mol. Examples of these are, for example, X
-22-161A (amine equivalent 840), X-22-1
61B (amine equivalent 1540), and the like, the trade names of Shin-Etsu Chemical Co., Ltd., etc. are mentioned. These are used alone or in combination of two or more.

Examples of the aromatic diisocyanate (4) represented by the general formula (4) include, for example, 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) and 4,4'-bis (3-methyl). Phenyl) methane diisocyanate, 2,4-tolylene diisocyanate (hereinafter abbreviated as TDI), 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and the like, from the viewpoint of imparting flexibility and preventing crystallinity. From 4,
4'-Diphenylmethane diisocyanate is preferred.
These are used alone or in combination of two or more. Further, from the viewpoint of heat resistance, an aliphatic diisocyanate such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate should be used together in an amount of about 5 to 10 mol% with respect to the aromatic diisocyanate. You can

From the viewpoint of heat resistance, in addition to the aromatic diimide dicarboxylic acid (1), the alicyclic diimide dicarboxylic acid (2) and the siloxane diimide dicarboxylic acid (3), terephthalic acid, phthalic acid and naphthalenedicarboxylic acid are also included. Aromatic dicarboxylic acids such as acids, adipic acid, sebacic acid,
Aliphatic dicarboxylic acids such as decanedioic acid, dodecanedioic acid and dimer acid are also used in an amount of about 5 to 10 mol% with respect to the total number of moles of the aromatic diimide dicarboxylic acid, alicyclic diimide dicarboxylic acid and siloxane diimide dicarboxylic acid can do.

The polyamide-imide resin having the microphase-separated structure of the component (A) used in the present invention is, for example, an aromatic diamine (1 ') or an alicyclic diamine (2') having three or more aromatic rings as described above. ) And siloxane diamine (3 ')
Mixture of and trimellitic anhydride (hereinafter abbreviated as TMA)
And are reacted in the presence of an aprotic polar solvent at 50 to 90 ° C. for 0.2 to 1.5 hours, and an azeotropic aromatic hydrocarbon with water is added to the aprotic polar solvent of 0.1 to 0.1%. 0.5
An aromatic diimide dicarboxylic acid (1) represented by the general formula (1) and an alicyclic diimide represented by the general formula (2) are charged at a weight ratio and reacted at 120 to 180 ° C. A mixture containing a dicarboxylic acid (2) and a siloxane diimidedicarboxylic acid (3) represented by the general formula (3) is produced, and an aromatic diisocyanate (4) represented by the general formula (4) is prepared therein. And a mixture of the above-mentioned three kinds of diimidedicarboxylic acids and 0.5 at 150 to 250 ° C.
It can be produced by reacting for about 3 hours.

Further, after preparing a mixture containing three kinds of diimidodicarboxylic acids represented by the general formula (1), the general formula (2) and the general formula (3), the solution is mixed with 150 It can also be produced by removing aromatic hydrocarbon which can be azeotropic with water from the solution by heating to about 250 ° C. and reacting this with aromatic diisocyanate (4). Further, the polyamide-imide resin is preferably a varnish containing an aprotic polar solvent.

The mixture ratio of the aromatic diamine (1 ') having 3 or more aromatic rings, the alicyclic diamine (2') and the siloxane diamine (3 ') is (1').
/(2')/(3')=(20.0 to 70.0) / (2
0.0-60.0) / (10.0-20.0) (the unit of each numerical value is mol% and is (1 '), (2') and (3 ')
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 (25.0 to 65.0) / (20.0 to 55.
0) / (10.0 to 15.0) (mol%) is more preferable.

Further, the above mixture is reacted with trimellitic anhydride (TMA) to give an aromatic diimidedicarboxylic acid (1) of the general formula (1) and an alicyclic diimidedicarboxylic acid of the general formula (2). (2) and the general formula (3
The amount of the raw material used to obtain the mixture containing the siloxane diimidedicarboxylic acid (3) of the formula) is the aromatic diamine (1 ′) having 3 or more aromatic rings, the alicyclic diamine (2 ′) and the siloxane. The molar ratio of the total number of diamines (3 ') to the number of TMA ((1') + (2 ') +
(3 ')) / TMA = 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 tends to remain, and the molecular weight of the resin finally obtained tends to decrease. If it exceeds 1 / 2.05, diamine remains and the resin finally obtained. The molecular weight of is likely to decrease.

Then, the aromatic diimide dicarboxylic acid (1) of the general formula (1), the alicyclic diimide dicarboxylic acid (2) of the general formula (2) and the siloxane diimide dicarboxylic acid of the general formula (3). To obtain a polyamide-imide resin by reacting a mixture ((1) + (2) + (3)) containing an acid (3) with an aromatic diisocyanate (4) represented by the general formula (4) The molar ratio is ((1) +
(2) + (3)) / (4) = 1 / 1.50 / 1 / 1.0
5 is more preferable, and 1 / 1.3 to 1 / 1.1
Is more preferable. This molar ratio is 1 / 1.50
If it is less than 1, the molecular weight of the obtained resin tends to decrease,
If it exceeds 1 / 1.05, the molecular weight of the obtained resin tends to decrease.

The aprotic polar solvent is preferably an aromatic diamine having 3 or more aromatic rings, an alicyclic diamine, a siloxane diamine, or an organic solvent which does not react with TMA, and examples thereof include dimethylacetamide and dimethyl. Formamide, dimethyl sulfoxide, N
-Methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone and the like can be exemplified. Since the imidization reaction requires high temperature, N-methyl-2, which has a high boiling point,
-Pyrrolidone is more preferred. 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 based on the total amount of the aromatic diamine having 3 or more aromatic rings, the alicyclic diamine, the siloxane diamine, and the TMA.
It is preferably in the range of 2.1 to 2.5 times.
It is more preferable that the amount is in the range of 2 to 2.4 times. If the amount used is less than 2.2 times, the solubility of TMA will decrease,
There is a tendency that a sufficient reaction cannot be performed, and if it exceeds 2.6 times, it tends to be disadvantageous as an industrial production method.

Examples of the aromatic hydrocarbon include toluene and xylene.

The weight average molecular weight of the polyamide-imide resin having the microphase-separated structure of the component (A) is 30,000.
˜300,000, preferably 40,000
It is more preferably ˜200,000, and 50.0
It is particularly preferable that it is from 00 to 100,000. 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 skeleton of the polyamideimide resin having the microphase-separated structure of the component (A) by heat, , 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,
More preferably, it is wt%. The epoxy resin preferably has an epoxy equivalent of 200 to 500, more preferably 250 to 400, a molecular weight or a weight average molecular weight of 100 to 2000, and 150 to 1500. More preferable.

The blending amount of the thermosetting resin as the component (B) is preferably 10 to 100 parts by weight based on 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.

As the thermosetting resin of the component (B) used in the present invention, it is preferable to use a curing accelerator or a curing agent in addition to the above resins. The curing accelerator is not particularly limited as long as it reacts with an epoxy resin such as the phosphorus-containing epoxy resin as the component (B) or accelerates the curing reaction between the component (A) and the component (B). Instead, for example, amines and imidazoles can be used as curing accelerators for epoxy resins. 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 amine and the epoxy equivalent of epoxy resin such as phosphorus-containing epoxy resin are substantially equal. In the case of imidazole, with respect to 100 parts by weight of an epoxy resin such as a phosphorus-containing epoxy resin,
It is preferably 0.1 to 2.0 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, resulting in pot life, insulation properties, etc. Tends to decline. As the curing agent for epoxy resin, for example, amine, polyamide, acid anhydride and bisphenol A, bisphenol F, bisphenol S, which are compounds having two or more phenolic hydroxyl groups in one molecule, can be used, but especially phenol novolac Resin, bisphenol novolac resin, cresol novolac resin and the like are preferable, and the amount thereof is preferably 5 to 20 parts by weight based on 100 parts by weight of the epoxy resin.

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 (5) or the general formula (6). 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, CR-73
3S, CR-741, CR-747, PX-200 (above, trade name manufactured by Daihachi Chemical Industry Co., Ltd.), phosphate compounds, SP-703, SP-601 (trade name manufactured by Shikoku Chemicals Co., Ltd.) ), 3 of the "Leophos" series
5, 50, 65, 95, 110 (these are product names manufactured by Ajinomoto Co., Inc.) and the like. 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.
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 with respect to 100 parts by weight of the polyamideimide 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 a solution of the flame-retardant heat-resistant resin composition of about wt%. The organic solvent is not particularly limited as long as it has solubility, and for example, dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, cyclohexanone, methyl ethyl ketone, methyl. Examples include isobutyl ketone, toluene, acetone and the like.

In addition to the above components, the non-halogen flame-retardant heat-resistant resin composition of the present invention may optionally contain a coupling agent, a pigment, a leveling agent, an antifoaming agent, an ion trap agent, etc. You may mix.

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 to the adherend or the adhesive layer. Alternatively, the adhesive layer may be formed by laminating an adhesive layer made of a flame-retardant heat-resistant resin composition in the form of an adhesive film formed on a supporting substrate. When using an adhesive film, the supporting base material may be removed after laminating,
It may be removed before stacking.

The adhesive film having the adhesive layer 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. It is possible to manufacture it. The heating conditions for drying the organic 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 1
The temperature is preferably 20 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 preferably 10 to 150 μm. The supporting base material may be subjected to a mat treatment, a corona treatment, and a release treatment.

The above 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 made of the flame-retardant heat-resistant resin composition laminated on the supporting substrate is preferably 5 to 50 μm, 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 viewpoints 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 1
It is more preferably 0 to 100 μm. The protective film may be subjected to matte treatment, corona treatment, and release treatment.

The adhesive layer of 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. You can Further, by laminating metal foil, it can be used as a substrate for a flexible wiring board or the like.
It is also possible to laminate an adhesive layer on both sides of a film such as a polyimide film to produce an adhesive-coated film having an adhesive layer on both sides.

[0053]

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) As a diamine having 3 or more aromatic rings in a 1 liter separable flask equipped with a 25 ml water quantitative receiver with a cock connected to a reflux condenser, a thermometer, and a stirrer. BAPP (2,2-bis [4
-(4-aminophenoxy) phenyl] propane), NBDA as alicyclic diamine (trade name of Mitsui Chemicals, Inc., 2,6-bis (aminomethyl) bicyclo [2.2.
1] Heptane, amine equivalent 77), reactive silicone oil as siloxane diamine X-22-161-B
(Shin-Etsu Chemical Co., Ltd. product name, amine equivalent 154
0, (formula 3), R ⁴ and R ⁵ : propylene group, R ⁶ to
R ⁹ : methyl group), TMA (trimellitic anhydride), NMP (N-methyl-2-pyrrolidone, water content: 0.1% by weight) as an aprotic polar solvent, and γ-BL (γ.
-Butyrolactone, water content: 0.1% by weight) were added at the compounding ratios shown in Table 1, and stirred at 80 ° C for 30 minutes. Then, after adding 100 ml of toluene as an aromatic hydrocarbon azeotropic with water, the temperature is raised to about 160 ° C.
Reflux for 2 hours.

It was confirmed that about 3.6 ml or more of water had accumulated in the moisture quantitative receiver and that no outflow of water was observed. While removing the effluent accumulated in the moisture quantitative receiver, The temperature was raised to 190 ° C. to remove toluene. Then, the solution was returned to room temperature, and MDI (4,4′-diphenylmethane diisocyanate) and TDI (2,4-tolylene diisocyanate) as aromatic diisocyanates were added in the amounts shown in Table 1 and reacted at 190 ° C. for 2 hours. Let After completion of the reaction, NMP of polyamide-imide resin
/ Γ-BL solutions A-1 to A-5 were obtained.

[0056]

[Table 1] * 1: 2,2-bis [4- (4-aminophenoxy) phenyl] propane * 2: NBDA (Mitsui Chemicals, Inc., trade name, amine equivalent 77) * 3: Reactive silicone oil (Shin-Etsu Chemical Co., Ltd. Brand name, amine equivalent 1540) * 4: trimellitic anhydride * 5: N-methyl-2-pyrrolidone * 6: γ-butyrolactone * 7: 4,4'-diphenylmethane diisocyanate * 8: 2,4- Tolylene diisocyanate

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.

[0058]

[Table 2] * 9: Product name manufactured by Tohto Kasei Co., Ltd. * 10: Product name manufactured by Daihachi Chemical Industry Co., Ltd. (general formula (5 formulas)
* 11: Trade name of Dainippon Ink and Chemicals, Inc.

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 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 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 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 on 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. 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)

Further, the obtained flame-retardant heat-resistant resin composition solution was applied to a Teflon (registered trademark) film having a thickness of 50 μm (trade name: Niflon Tape TOMBO9 manufactured by Nichias Co., Ltd.).
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 was 25 μm. Then, the sample was dried at 130 ° C. for 4 minutes to prepare a sample. (Sample E)

Adhesiveness (Sample A, 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 composition: polyimide film / flame-retardant heat-resistant resin composition / rolled copper foil roughened surface), Sample B (sample composition: 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, and the peeling strength (kN / m)
Was measured. Measurement temperature: 25 ° C, peeling speed: 50 mm / min

(Solder Heat Resistance) Using sample A (sample structure: polyimide film / flame retardant heat resistant resin composition / rolled copper foil roughened surface), the sample 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 constitution: polyimide film / flame retardant heat resistant resin composition) was used to measure a flame retardant grade in accordance with UL94 flame retardancy standard.

(Glass Transition Temperature and Storage Elastic Modulus) Dynamic viscoelasticity measurement (trade name of Rheometric Co., Ltd.) was performed under the following conditions using Sample D (sample constitution: cured film only). 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)

[0070]

[Table 3]

[0071]

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 adhesive-attached polyimide film 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. It 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) C08J 7/04 CFG C08J 7/04 CFGF C08K 5/521 C08K 5/521 C08L 63/00 C08L 63/00 A F-term (reference) 4F006 AA39 AB34 AB38 AB55 BA01 BA04 CA08 4F100 AH10B AH10C AK01B AK01C AK49A AK50B AK50C AK53B AK53C AL05B AL05C BA03 BA06 BA10B BA10C CA02B CA02C CB00B CB00C GB41 JB13B JB13C JJ03B JJ03C JJ07B JJ07C JL11 4J002 AA022 CD002 CD012 CD042 CD052 CD062 CD112 CD142 CM041 CQ013 EJ037 EN077 ER027 ET017 EU117 EW046 FD133 FD136 FD147 FD157 GJ01 GQ01 4J034 BA06 CA24 CB03 CB07 CC12 CC26 CC28 CC33 CC44 CC45 CC52 CC53 CC54 CC61 CC68 CC69 CD04 CD05 CD09 CD12 CD15 DM01 HA01 HA07 HC12 HC13 HC61 HC64 HC67 HC71 QA07 QB17 RA08 RA14 4J036 AA01 AB01 AB10 AB17 AC01 AC05 AD08 AD21 AF06 AF08 AG06 CC02 DA01 DA02 DB06 DC03 DC10 DC25 DC31 DC41 FA12 FB07 FB14 JA06 JA08

Claims (11)

[Claims] 1. (A) General formula (A formula) (In the formula, R and R'independently represent a divalent organic group.), And R and R'in all the repeating units are represented by the following general formula: 2] (In the formula, X is Indicates. ) And a group represented by the following formula (A2): And a group represented by (A3) (In the formula, 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 n is an integer of 1 to 50. ), And (A4) the following general formula —R ¹⁰ — (wherein R ¹⁰ is Indicates. ), Which has at least four kinds of divalent organic groups and has a microphase-separated structure, a polyamideimide resin, (B) a thermosetting resin, and (C) an organophosphorus compound. Flame-retardant heat-resistant resin composition. 2. A component (A), wherein R is (A1), represented by the following general formula: (In the formula, X is Indicates. ) And a group represented by the following formula (A2): And a group represented by (A3) (In the formula, 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 n is an integer of 1 to 50. ) And a group represented by
4) The following general formula —R ¹⁰ — (wherein R ¹⁰ is Indicates. ) The flame-retardant heat-resistant resin composition according to claim 1, which has a group represented by 3. The component (A) is obtained by reacting trimellitic anhydride with a mixture of aromatic diamine having 3 or more aromatic rings, alicyclic diamine and siloxane diamine, and the following general formula (1): [Chemical 12] [Wherein R ¹ is (However, X is Is shown). ] The aromatic diimide dicarboxylic acid (1) represented by the general formula (2), [Wherein R ² is The alicyclic diimidedicarboxylic acid (2) represented by and the general formula (3): [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, and n is an integer of 1 to 50). ] A mixture containing a siloxane diimide dicarboxylic acid (3) represented by the following general formula (4): [Wherein R ¹⁰ is Indicates. ] The flame-retardant heat-resistant resin composition according to claim 1 or 2, which is a polyamide-imide resin having a microphase-separated structure obtained by reacting with the aromatic diisocyanate (4). 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 alicyclic diamine has an amine equivalent of 60 to 1.
The flame-retardant heat-resistant resin composition according to claim 3 or 4, which is 00 g / mol. 6. The amine equivalent of siloxane diamine is 40.
The flame-retardant heat-resistant resin composition according to any one of claims 3 to 5, which is 0 to 2,500 g / mol. 7. The thermosetting resin as the component (B) comprises an epoxy resin and a curing accelerator or curing agent for the epoxy resin.
A flame-retardant heat-resistant resin composition as described in any one of 1. 8. The flame-retardant heat-resistant resin composition according to claim 7, wherein the epoxy resin is a phosphorus-containing epoxy resin. 9. The organophosphorus compound as the component (C) has the general formula (5): (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 (6): (In formula, n2 is an integer of 10-50.) The flame-retardant heat-resistant resin composition in any one of Claims 1-8 which is a phosphate compound. 10. An adhesive film having an adhesive layer formed from the flame-retardant heat-resistant resin composition according to claim 1. 11. A polyimide film with an adhesive in which the adhesive layer according to claim 10 is laminated on one side or both sides of a polyimide film.