JP2757588B2 - Thermosetting resin composition and film adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermosetting resin composition and a film adhesive.

[0002]

2. Description of the Related Art A resin composition obtained by adding a polymaleimide to a polyamic acid or a polyimide has been used in various applications because its cured product is tough and has heat resistance. For example, they are used as adhesives and varnishes in the production of printed wiring boards and prepregs. The prepreg is further used for producing a printed wiring board and the like.

[0003] For example, USP 4,362,826 includes:
A thermosetting resin composition containing a polyamic acid obtained from 4,4'-diaminodiphenyl ether and pyromellitic dianhydride and a bismaleimide compound is disclosed. For example, the composition is cast and applied to a substrate such as a copper foil, and then dried by heating to form a cured film (a film supported on the substrate).

However, since the resin composition obtained by adding bismaleimide to polyamic acid as described above uses polyamic acid, it is necessary not only to react the polymaleimide during curing but also to imidize the polyamic acid. is there. For this reason, it is necessary to heat to a temperature of 300 ° C. or more at the time of curing, and it cannot be applied to a substrate weak to heat. In addition, since condensed water is generated with the imidization of the polyamic acid, the generation of voids cannot be ignored even if the amount of water is reduced by the presence of polymaleimide. In particular, when the above composition is interposed between the Kapton film (polyimide film) and a metal foil such as a copper foil to cure the metal foil such as a copper foil, the generation of such voids causes a significant decrease in the adhesive strength. Cause. USP 4,36
It is well known to those skilled in the art that the polyimide obtained by imidizing the amic acid disclosed in US Pat. No. 2,826 is insoluble and infusible in an organic solvent. further,
U.S. Pat. No. 4,362,826 does not specifically illustrate polyimides soluble in organic solvents.

As a composition containing a polyimide and a polymaleimide, for example, a low molecular weight polyimide having amino groups at both terminals obtained by reacting USP 3,842,143 with a tetracarboxylic dianhydride and an excess of a diamine can be used. A composition comprising a maleimide is disclosed.
However, when using such a low molecular weight polyimide,
The film obtained from the above composition has no flexibility,
It cannot be a self-supporting film. USP
No. 3,842,143 does not illustrate a composition which is so flexible that a self-supporting film can be obtained and a polyimide therefor.

Further, Japanese Patent Application Laid-Open No. Sho 62-30112 discloses that 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (4- (3-aminophenoxy) phenyl) sulfone and Accordingly, it is disclosed that a composition comprising polyimide and polymaleimide obtained using 2,4-diaminotoluene has good film-forming properties and this film exhibits excellent adhesion. Also,
It is disclosed that this polyimide dissolves in a mixed solvent of toluene and m-cresol. However, Japanese Patent Application Laid-Open No. Sho 62-3
The polyimide disclosed in No. 0112 does not dissolve in organic solvents having a small polarity such as tetrahydrofuran, dioxane, and methylene chloride. The composition is meltable and cures at a relatively low temperature of 250 ° C. to 275 ° C., and exhibits excellent adhesiveness. However, at a cure temperature of 230 ° C. or lower, the properties deteriorate.

As is evident from the above, compositions containing polyimide and polymaleimide which exhibit excellent properties at sufficiently low curing temperatures and polyimides for such compositions are known in the art. Absent.

[0008]

In a resin composition containing a polyimide and a polymaleimide, a novel polyimide is selected and used as a polyimide, so that excellent properties can be obtained even at a low curing temperature. It is to provide what is shown.

[0009]

Means for Solving the Problems The thermosetting resin composition of the present invention is represented by the following formula (I):

Embedded image [However, in the general formula (I), Ar is a tetravalent organic group;
X represents a monovalent group containing an unsaturated bond], and a thermosetting polyimide containing a structural unit represented by the general formula (I)
I))

Embedded image (However, in the general formula (II), R is an integer-valent group having 2 or more carbon atoms, and m is an integer of 2 or more).

[0010] The thermosetting polyimide is represented by the following chemical formula (III):

Embedded image Wherein X represents a monovalent group containing an unsaturated bond in the general formula (III), and a method comprising reacting an aromatic tetracarboxylic dianhydride with a diamine compound represented by the formula: Can be.

In the general formula (III), X represents allyloxycarbonyl, vinyl, allyl, acryloyloxyalkoxycarbonyl, methacryloyloxyalkoxycarbonyl, acryloyloxyalkyl, methacryloyloxyalkyl, ethynyl, etc. There is.

Specific examples of the diamine represented by the general formula (III) include allyl 3,5-diaminobenzoate, 2,4
-Allyl diaminobenzoate, allyl 2,5-diaminobenzoate, 3,5-diaminostyrene, 2,4-diaminostyrene, 2,5-diaminostyrene, 2- (3,5-
Diaminobenzoyloxy) ethyl methacrylate, 2
-(2,4-diaminobenzoyloxy) ethyl methacrylate, 2- (2,5-diaminobenzoyloxy)
Ethyl methacrylate, 3,5-diaminophenylacetylene, 3,5-diaminobenzyl acrylate, 3,
5-Diaminobenzyl methacrylate, 2,4-diaminophenylacetylene, 2,5-diaminophenylacetylene and the like.

In the present invention, another diamine may be used in combination with the diamine represented by the general formula (III). Other diamines include 4,4'-diaminodiphenyl ether (DDE), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone,
1,4-bis (4-aminocumyl) benzene (BA
P), 1,3-bis (4-aminocumyl) benzene,
1,3-bis (3-aminophenoxy) benzene, 2,
2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone (m-APPS), 2,2-bis [4-
(4-aminophenoxy) phenyl] hexafluoropropane, 4,4′-bis [3- (4-amino-α, α ′
-Dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [3- (4-amino-α, α′-dimethylbenzyl) phenoxy] benzophenone, 4,
4′-bis [4- (4-amino-α, α′-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-
Bis [4- (4-amino-α, α′-dimethylbenzyl) phenoxy] benzophenone, a diamine represented by the following formula (IV), and a diamine represented by the following formula (V) Siloxane diamine and the like.

Embedded image [However, in the general formula (IV), Y represents an amino group or an isocyanate group, and R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group or an alkoxy group having 1 to 4 carbon atoms.] .

Embedded image [However, in the general formula (V), R ¹ and R ⁴ are a divalent organic group, R ² and R ³ are a monovalent organic group, and n is 1 to 100.
Is an integer.

The diamine represented by the above general formula (IV) includes 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 4,4'-diamino-
3,3 ′, 5,5′-tetraethyldiphenylmethane,
4,4'-diamino-3,3 ', 5,5'-tetra-n-
Propyldiphenylmethane, 4,4'-diamino-3,
3 ′, 5,5′-tetraisopropyldiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetrabutyldiphenylmethane, 4,4′-diamino-3,
3′-dimethyl-5,5′-diethyldiphenylmethane, 4,4′-diamino-3,3′-dimethyl-5,
5′-diisopropyldiphenylmethane, 4,4′-diamino-3,3′-diethyl-5,5′-diisopropyldiphenylmethane, 4,4′-diamino-3,5-dimethyl-3 ′, 5′-diethyldiphenylmethane, 4,
4'-diamino-3,5-dimethyl-3 ', 5'-diisopropyldiphenylmethane, 4,4'-diamino-
3,5-diethyl-3 ', 5'-diisopropyldiphenylmethane, 4,4'-diamino-3,5-diethyl-
3 ', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,5-diisopropyl-3', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-
Diisopropyl-5,5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,
5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dibutyldiphenylmethane and the like.

[0015] the general formula (V) respectively as R ¹ and R ⁴ in the general formula (V) independently trimethylene the siloxane diamine represented by, tetramethylene group, a phenylene group, there are toluylene group, R ² And R ³ each independently include a methyl group, an ethyl group, a phenyl group and the like, and a plurality of R ² and a plurality of R ³ may be the same or different. In the general formula (V), when R ¹ and R ⁴ are both trimethylene groups and R ² and R ³ are both methyl groups, n is 1, about 10 on average, about 20 on average. Stuff, about 30 on average,
Those with an average of around 50 and those with an average of around 100 are LP-7100, X-22-161AS and X-22, respectively.
-161A, X-22-161B, X-22-161C
And X-22-161E (both trade names of Shin-Etsu Chemical Co., Ltd.).

The diamine represented by the above-mentioned general formula (III) and the other diamine are in a molar ratio of the former: the latter of 100:
It is preferable to use it so that it becomes 0: 5: 95. If the amount of the diamine represented by the general formula (III) is too small, the effect is not sufficient. The general formula (III)
If the diamine represented by the formula is too large, the cured product of the obtained thermosetting resin composition becomes brittle, making it difficult to use as a film. Particularly preferred.

The tetracarboxylic dianhydride includes:
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA),
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2-bisphthalic acid hexafluoroisopropylidene dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 4,4′-bis (3,4-
Dicarboxyphenoxy) diphenylsulfone dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, ethylene glycol bis trimellitate dianhydride (EBTA), decamethylene glycol bistri Melitate dianhydride (DBT
A), bisphenol A bistrimellitate dianhydride (BABT), 2,2-bis [4- (3,4-dicarboxyphenylbenzoyloxy) phenyl] hexafluoropropane dianhydride, 4,4 ′-[1 , 4-phenylenebis (1-methylethylidene)] bisphenylbistrimellitate dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclobutanetetracarboxylic dianhydride. Those containing an aromatic group are preferred from the viewpoint of heat resistance. In the present invention, the tetravalent organic group is a residue of the above-mentioned acid dianhydride.

The thermosetting polyimide can be manufactured as follows. The tetracarboxylic dianhydride and the diamine are heated to 100 ° C. or higher, preferably 180 ° C. or higher in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, and triphenyl phosphite to obtain imidization. To obtain polyimide directly (catalyst is 0 to 15% based on the total amount of reaction components).
% By weight, particularly preferably 0.01 to 15% by weight), a varnish of a polyamic acid which is a precursor of polyimide by reacting an acid dianhydride and a diamine in an organic solvent at a temperature lower than 100 ° C. And then the varnish is heated for imidation or acetic anhydride,
A ring-closing agent such as an acid anhydride such as propionic anhydride and benzoic anhydride, a carbodiimide compound such as dicyclohexylcarbodiimide, and, if necessary, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, and imidazole are added to form a chemical ring-closing (imide). (Each of the ring-closing agent and the ring-closing catalyst is preferably used in a range of 1 to 8 mol per 1 mol of the acid anhydride) and the like.

Examples of the organic solvent include N-methyl-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone and the like. And phenolic solvents such as phenol, cresol, xylenol, and p-chlorophenol.

Further, benzene, toluene,
Xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetate, methanol,
Among ethanol, isopropanol, methylene chloride, chloroform, tricrene, tetrachloroethane, etc., those which dissolve the raw material monomer and the polyimide or polyamic acid may be used, and those which do not dissolve these may be used within a range that does not impair the solubility. It can be used by mixing with other solvents.

In the production of the above-mentioned polyimide and polyamic acid as a precursor thereof, solid-state reaction,
A melting reaction at a temperature of 00 ° C. or lower can be used.

In the present invention, the tetracarboxylic dianhydride and the diamine are preferably used in approximately equimolar amounts.
The excess amount of one of them is 10 mol%, particularly preferably 5 mol%.
Up to mole% is acceptable.

In the present invention, the thermosetting polyimide can be easily dissolved in an organic solvent by selecting its components. Components having a bulky substituent such as a diamine represented by the general formula (IV) as the component that facilitates dissolving the thermosetting polyimide in an organic solvent;
1,3-bis (4-aminocumyl) benzene, 1,3-
Bis (3-aminophenoxy) benzene and bis [4-
(3-Aminophenoxy) phenyl] sulfone (mA
PPS), those having a bent main chain structure such as alkylene bis trimellitate, siloxane diamines represented by the general formula (V), and those having a fluorine atom.

Specific examples of the polymaleimide include N,
N '-(4,4'-diphenylmethane) bismaleimide, N, N'-(4,4'-diphenyloxy) bismaleimide, N, N'-p-phenylenebismaleimide,
N, N'-m-phenylenebismaleimide, N, N'-
2,4-tolylenebismaleimide, N, N'-2,6-
Tolylenebismaleimide, N, N'-ethylenebismaleimide, N, N '-[4,4'-[2,2'-bis (4,4'-phenoxyphenyl) isopropylidene]] bismaleimide, There are N, N'-hexamethylenebismaleimide, compounds represented by the following formulas (8) to (13), which are used alone or in combination of two or more.

Embedded image (Hereinafter, abbreviated as BMIM),

Embedded image

Embedded image (Hereinafter, this is abbreviated as ATUBMI),

Embedded image

Embedded image

Embedded image (Where r represents an integer)

The mixing ratio of the polyimide and the polymaleimide is appropriately determined according to the purpose, but it is preferable to use the polymaleimide in an amount of 5 to 180 parts by weight based on 100 parts by weight of the polyimide. If the amount of the polymaleimide is too small, the curing is not sufficient, and if it is too large, the resin composition becomes brittle. Particularly in the case of producing a self-supporting film, it is particularly preferable to use the polymaleimide in a proportion of 100 parts by weight or less with respect to 100 parts by weight of the polyimide in terms of maintaining sufficient flexibility.

The thermosetting resin composition according to the present invention comprises 2
It can be cured at a temperature lower than 75 ° C. (further, a temperature lower than 230 ° C.) to obtain a cured product having excellent heat resistance and the like. To cure at a lower temperature, t-butyl perbenzoate, t-butyl perbenzoate, -Butyl hydroperoxide,
Benzoyl peroxide, 2,5-dimethyl-2,5-
It is preferable to incorporate a curing accelerator such as an organic peroxide such as di (t-butylperoxy) hexine-3 and a radical polymerization initiator such as azobisisobutyronitrile. It can be woken at around ° C. The curing accelerator is preferably used in an amount of 0.1 to 10% by weight based on the total amount of the thermosetting polyimide and polymaleimide.

The thermosetting resin composition of the present invention may be a mixture of polyimide and polymaleimide and, if necessary, a curing accelerator in the form of a powder. These may be dissolved in an organic solvent (varnish). You may. Examples of the organic solvent that can be used at this time include aprotic polar solvents such as N, N-dimethylformamide and N-methylpyrrolidone, ether solvents such as dioxane, tetrahydrofuran, diglyme and monoglyme, and chlorine solvents such as methylene chloride. And low-boiling solvents such as aromatic solvents such as toluene and organic solvents having a small polarity.

The thermosetting resin composition of the present invention can be cast on a glass plate, a stainless steel plate or the like, dried, and then heat-cured to form a cured film. This film is useful as an insulating film, a base film for a laminated board, and the like.

The thermosetting resin composition of the present invention can be used as an adhesive itself. This adhesive may be used in the form of a varnish. The varnish is cast on a glass plate, a stainless steel plate, etc., dried, and then peeled off, containing no base material, having high flexibility and being uncured. Agent (self-supporting film adhesive) before use. Such adhesives can be used for various applications, but a metal-clad laminate is obtained by laminating a metal plate such as an aluminum plate, a core material such as a plastic film such as a polyimide film and a metal foil such as a copper foil or an aluminum foil. It is particularly useful as an adhesive for the production of The adhesive exhibits excellent adhesion at relatively low heat (at the curing temperature).

The varnish-like thermosetting resin composition of the present invention can be used as a prepreg by impregnating and drying a base material such as glass cloth or carbon cloth.

In the production of the above film adhesive and prepreg, the drying temperature and time vary depending on the type of solvent and polymaleimide used. The temperature must be kept lower than the temperature at which polymerization of the polymaleimide becomes remarkable, but the resin composition of the present invention can be dissolved in a low-boiling solvent or an organic solvent having a small polarity and easy to volatilize. Can be dried. At this time, even if a radical initiator is present, polymerization can be suppressed and drying can be easily performed. Preferably, the time is such that the amount of residual solvent is 5% by weight or less.

Further, the thermosetting resin composition according to the present invention can be used as a molding material in powder form.
The curing temperature varies depending on the type of the polymaleimide, but by heating and curing these, a tough heat-resistant molded article can be obtained.

[0033]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these ranges.

Synthesis Example 1 In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a calcium chloride tube, 4,4′-diamino-3,4
1.28 g (3.5 mmol) of 3 ′, 5,5′-tetraisopropyldiphenylmethane (IPDDM), 3,5
-Allyl diaminobenzoate (DAAB) 1.25 g
(6.5 mmol) and 25.7 g of N, N-dimethylformamide (DMF) were added and dissolved. Next, 5 ° C
5.76 g (10 mmol) of bisphenol A bistrimellitate dianhydride (BABT) were added little by little while cooling so as not to exceed 5 ° C., and then cooling was performed so as not to exceed 5 ° C. for 1 hour and then at room temperature. After reacting for 6 hours, a polyamic acid was synthesized. 2.55 g of acetic anhydride and 1.98 g of pyridine were added to the obtained varnish of polyamic acid and reacted at room temperature for 3 hours to synthesize a polyimide. The resulting polyimide varnish was poured into water, and the resulting precipitate was separated, crushed and dried to obtain a polyimide powder.

This polyimide powder was added to DMF in an amount of 0.1 g /
It was dissolved at a concentration of dl and the reduced viscosity measured at 30 ° C. was 0.63 dl / g.

A solubility test was conducted by adding the polyimide powder to various organic solvents to a concentration of 5% by weight and observing the dissolution state at room temperature. As a result, this polyimide powder was soluble in DMF, N-methylpyrrolidone (NMP), methylene chloride, dioxane, and tetrahydrofuran (THF).

Further, this polyimide powder was dissolved in DMF, and the obtained varnish was cast on a glass plate. 80 ℃
, And then peeled off, fixed to an iron frame and dried at 150 ° C for 1 hour to obtain a film.

The softening point of the polyimide thus obtained was measured at 235 ° C. by a penetration method under the conditions of a load of 25 kg / cm 2 and a heating rate of 10 ° C./min. The obtained film was 18
When the film was bent at an angle of 0 degree and subjected to a flexibility test, the film did not crack and showed good flexibility. When the obtained film was heated at 230 ° C. for 1 hour, it was insoluble in any solvent.

Synthesis Example 2 In a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and calcium chloride tube, 2.93 g (8 mmol) of IPDDM and 25.7 g of DMF were put and dissolved. next,
5.76 g of BABT while cooling so as not to exceed 5 ° C
(10 mmol) was added little by little, and the mixture was reacted for 30 minutes. Then, 0.38 g (2 mmol) of DAAB was added, and the mixture was added at 5 ° C.
The reaction was carried out for 1 hour while cooling so as not to exceed the temperature, and then for 6 hours at room temperature to synthesize a polyamic acid. 2.55 g of acetic anhydride and 1.98 g of pyridine were added to the obtained varnish of polyamic acid and reacted at room temperature for 3 hours to synthesize a polyimide. The resulting polyimide varnish was poured into water, and the resulting precipitate was separated, crushed and dried to obtain a polyimide powder.

Using the obtained polyimide powder, Synthesis Example 1
The measurement of the reduced viscosity, the solubility test and the measurement of the softening point were carried out according to the procedures described in the above. As a result, the reduced viscosity was 0.76 dl / g, it was soluble in DMF, NMP, THF, dioxane, methylene chloride, and toluene, and the softening point was 260 ° C.

Synthesis Example 3 Bis [4- (3-aminophenoxy) phenyl] sulfone (m-APPS) 3.02 g instead of IPDDM
(7 mmol) and the amount of DAAB was 0.58 g (3
(Mmol), and a polyimide powder was obtained according to Synthesis Example 1. Using the obtained polyimide powder, measurement of reduced viscosity, solubility test, and measurement of softening point were performed according to Synthesis Example 1. As a result, the reduced viscosity was 0.46 dl / g, it was soluble in DMF, NMP, dioxane, and methylene chloride, and the softening point was 218 ° C.

Synthesis Example 4 The amounts of IPDDM and DAAB were 2.75 g (7.
5 mmol), 0.48 g (2.5 mmol),
3.22 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA) instead of BABT
(10 mmol), and a polyimide powder was obtained according to Synthesis Example 1 except that (10 mmol) was used. Using the obtained polyimide powder, measurement of reduced viscosity, solubility test, and measurement of softening point were performed according to Synthesis Example 1. As a result, the reduced viscosity was 0.52 dl /
g, soluble in DMF, NMP, THF, dioxane, and methylene chloride, and had a softening point of 286 ° C.

Synthesis Example 5 Instead of IPDDM, 1.72 g (5 mmol) of 1,4-bis (4-aminocumyl) benzene (BAP) and X-22-161A, a siloxane diamine (the above-mentioned product, Shin-Etsu Chemical Co., Ltd.) A polyimide powder was obtained in the same manner as in Synthesis Example 1 except that 5.15 g (3 mmol) of a company (trade name) was used, the amount of DAAB was 0.38 g (2 mmol), and THF was used instead of DMF. Using the obtained polyimide powder, measurement of reduced viscosity, solubility test, and measurement of softening point were performed according to Synthesis Example 1. As a result, the reduced viscosity was 0.54 dl / g, it was soluble in DMF, NMP, dioxane, THF, and methylene chloride, and the softening point was 18
5 ° C.

Synthesis Example 6 Using 1.83 g (5 mmol) of IPDDM, DAAB
Instead of 2- (3,5-diaminobenzoyloxy)
A polyimide powder was obtained according to Synthesis Example 1 except that 1.32 g (5 mmol) of ethyl methacrylate (BEM) and 4.10 g (10 mmol) of ethylene glycol bistrimellitate dianhydride (EBTA) instead of BABT were used. Was. Using the obtained polyimide powder, measurement of reduced viscosity, solubility test, and measurement of softening point were performed according to Synthesis Example 1. As a result, the reduced viscosity was 0.74 dl / g, it was soluble in DMF, NMP, and methylene chloride, and the softening point was 255 ° C.

Synthesis Example 7 DDE 0.6 instead of IPDDM, DAAB, BABT
g (3 mmol), BEM 1.85 g (7 mmol),
A polyimide powder was obtained according to Synthesis Example 1, except that 5.22 g (10 mmol) of decamethylene glycol bistrimellitate dianhydride (DBTA) was used. Using the obtained polyimide powder, measurement of reduced viscosity, solubility test, and measurement of softening point were performed according to Synthesis Example 1. as a result,
The reduced viscosity is 0.43 dl / g, and DMF, NMP,
It was soluble in methylene chloride. The softening point was 143 ° C.

Example 1 100 g of the polyimide powder obtained in Synthesis Example 1 and 2,2-
50 g of bis [4- (4-maleimidophenoxy) phenyl] propane (BBMI) is dissolved in 400 g of N, N-dimethylformamide (DMF), and 3 g of t-butylperoxybenzoate is added to the resin composition (varnish).
I got This resin composition was cast on a glass plate,
, And then peeled off to obtain a film. This film was fixed on an iron frame and heated at 150 ° C. for 1 hour to obtain a well-dried uncured film adhesive. This film adhesive had a thickness of 25 μm and a softening point of 168 ° C. and exhibited excellent flexibility without breaking even when bent at an angle of 180 °.

When this film adhesive was cured by heating at 200 ° C. for 2 hours, the cured film obtained had a glass transition point of 230 ° C. and an elongation of 4.2%.
In the same solubility test as described above, it was insoluble in any of the solvents described in Synthesis Example 1.

The above film-like adhesive was pressed between a polyimide film having a thickness of 50 μm and a roughened copper foil having a thickness of 35 μm on one side at 30 kg / cm ² , at 200 ° C. for 2 hours, to form a flexible printed wiring board. A substrate was obtained. 9 of this board
0 degree copper foil peeling strength is 1.2 kgf / c at room temperature
m, 1.1Kgf / cm at 200 ° C atmosphere (in each case,
(Measured at a tensile speed of 50 mm / min). Even when this substrate was immersed in a 300 ° C. solder bath for 60 seconds, no blistering or peeling occurred.

Example 2 100 g of the polyimide powder obtained in Synthesis Example 2 and ATUB
30 g of MI was added to N, N-dimethylformamide (DM
F) The resin composition was dissolved in 400 g, and 3 g of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 was added to obtain a resin composition (varnish). This resin composition was cast on a glass plate, dried at 80 ° C. for 30 minutes, and peeled off to obtain a film. This film was fixed on an iron frame and heated at 150 ° C. for 1 hour to obtain a well-dried uncured film adhesive. This film adhesive had a thickness of 25 μm and a softening point of 172 ° C., and exhibited excellent flexibility without breaking even when bent at an angle of 180 °.

When this film adhesive was cured by heating at 230 ° C. for 2 hours, the resulting cured film had a glass transition point of 253 ° C. and an elongation of 13.0%. In a sex test, it was insoluble in any of the solvents described in Synthesis Example 1.

A substrate for a flexible printed wiring board was obtained in the same manner as in Example 1 using the above film-like adhesive. The 90 degree copper foil peeling strength of this substrate was 1. at room temperature atmosphere.
It was 2 kgf / cm and 1.2 kgf / cm in a 200 ° C. atmosphere (in each case, when measured at a pulling speed of 50 mm / min). Even when this substrate was immersed in a 300 ° C. solder bath for 60 seconds, no blistering or peeling occurred.

Example 3 100 g of the polyimide powder obtained in Synthesis Example 3 and BMI
30 g was dissolved in 400 g of DMF and 2,5-dimethyl-
2,5-di (t-butylperoxy) hexyne-3 was added to 3
g was added to obtain a resin composition (varnish). This resin composition was cast on a glass plate, dried at 100 ° C. for 30 minutes, and peeled off to obtain a film. This film was fixed on an iron frame and further heated at 150 ° C. for 1 hour to obtain a well-dried uncured film adhesive. This film adhesive had a thickness of 25 μm and a softening point of 165 ° C., did not crack even when bent at an angle of 180 °, and exhibited excellent flexibility.

When this film adhesive was cured by heating at 230 ° C. for 2 hours, the resulting cured film had a glass transition point of 220 ° C. and an elongation of 10.2%. In a sex test, it was insoluble in any of the solvents described in Synthesis Example 1.

A substrate for a flexible printed wiring board was obtained in the same manner as in Example 1 using the above film adhesive. The 90 degree copper foil peeling strength of this substrate is 1.3 kg at room temperature.
f / cm and 1.1 kgf / cm at 200 ° C. (when measured at a pulling speed of 50 mm / min in each case). Even when this substrate was immersed in a 300 ° C. solder bath for 60 seconds, no blistering or peeling occurred.

Example 4 100 g of the polyimide powder obtained in Synthesis Example 4 and BMI
50 g was dissolved in 400 g of DMF and 2,5-dimethyl-
2,5-di (t-butylperoxy) hexyne-3 was added to 3
g was added to obtain a resin composition (varnish). This resin composition was cast on a glass plate, dried at 100 ° C. for 30 minutes, and peeled off to obtain a film. This film was fixed on an iron frame and further heated at 150 ° C. for 1 hour to obtain a well-dried uncured film adhesive. This film adhesive had a thickness of 25 μm and a softening point of 185 ° C., did not crack even when bent at an angle of 180 °, and exhibited excellent flexibility.

When this film adhesive was cured by heating at 230 ° C. for 2 hours, the cured film obtained had a glass transition point of 292 ° C. and an elongation of 7.3%.
In a solubility test similar to the above, the compound was insoluble in any of the solvents described in Synthesis Example 1.

A substrate for a flexible printed wiring board was obtained in the same manner as in Example 1 by using the above film adhesive. The 90 degree copper foil peeling strength of this substrate is 0.9 kg at room temperature.
f / cm and 0.8 kgf / cm at 200 ° C. (when measured at a pulling speed of 50 mm / min in each case). Even when this substrate was immersed in a 300 ° C. solder bath for 60 seconds, no blistering or peeling occurred.

Example 5 100 g of the polyimide powder obtained in Synthesis Example 5 and BMI
70 g was dissolved in 400 g of DMF and 2,5-dimethyl-
2,5-di (t-butylperoxy) hexyne-3 was added to 3
g was added to obtain a resin composition (varnish). This resin composition was cast on a glass plate, dried at 100 ° C. for 30 minutes, and peeled off to obtain a film. This film was fixed on an iron frame and further heated at 150 ° C. for 1 hour to obtain a well-dried uncured film adhesive. This film adhesive had a thickness of 25 μm, a softening point of 128 ° C., did not crack even when bent at an angle of 180 °, and exhibited excellent flexibility.

When this film adhesive was cured by heating at 230 ° C. for 2 hours, the cured film obtained had a glass transition point of 202 ° C. and an elongation of 15.7%. In a sex test, it was insoluble in any of the solvents described in Synthesis Example 1.

A substrate for a flexible printed wiring board was obtained in the same manner as in Example 1 using the above film adhesive. The 90 degree copper foil peeling strength of this substrate is 1.3 kg at room temperature.
f / cm and 1.3 kgf / cm at 200 ° C. (when measured at a pulling speed of 50 mm / min in each case). Even when this substrate was immersed in a 300 ° C. solder bath for 60 seconds, no blistering or peeling occurred.

Example 6 100 g of the polyimide powder obtained in Synthesis Example 6 and BMI
20 g was dissolved in 400 g of DMF and 2,5-dimethyl-
2,5-di (t-butylperoxy) hexyne-3 was added to 3
g was added to obtain a resin composition (varnish). This resin composition was cast on a glass plate, dried at 100 ° C. for 30 minutes, and peeled off to obtain a film. This film was fixed on an iron frame and further heated at 150 ° C. for 1 hour to obtain a well-dried uncured film adhesive. This film adhesive had a thickness of 25 μm and a softening point of 185 ° C., did not crack even when bent at an angle of 180 °, and exhibited excellent flexibility.

When this film adhesive was cured by heating at 230 ° C. for 2 hours, the cured film obtained had a glass transition point of 270 ° C. and an elongation of 11.4%. In a sex test, it was insoluble in any of the solvents described in Synthesis Example 1.

A substrate for a flexible printed wiring board was obtained in the same manner as in Example 1 using the above film adhesive. The 90 degree copper foil peel strength of this substrate is 1.1 kg at room temperature.
f / cm and 1.0 kgf / cm at 200 ° C. (when measured at a pulling speed of 50 mm / min in each case). Even when this substrate was immersed in a 300 ° C. solder bath for 60 seconds, no blistering or peeling occurred.

Example 7 100 g of the polyimide powder obtained in Synthesis Example 7 and BMI
10 g was dissolved in 400 g of DMF and 2,5-dimethyl-
2,5-di (t-butylperoxy) hexyne-3 was added to 3
g was added to obtain a resin composition (varnish). This resin composition was cast on a glass plate, dried at 100 ° C. for 30 minutes, and peeled off to obtain a film. This film was fixed on an iron frame and further heated at 150 ° C. for 1 hour to obtain a well-dried uncured film adhesive. This film adhesive had a thickness of 25 μm and a softening point of 117 ° C., did not crack even when bent at an angle of 180 °, and exhibited excellent flexibility.

When this film adhesive was cured by heating at 200 ° C. for 2 hours, the resulting cured film had a glass transition point of 165 ° C. and an elongation of 8.6%.
In a solubility test similar to the above, the compound was insoluble in any of the solvents described in Synthesis Example 1.

A substrate for a flexible printed wiring board was obtained in the same manner as in Example 1 by using the above film adhesive. The 90 degree copper foil peel strength of this substrate is 1.6 kg at room temperature.
f / cm, 1.2 kgf / cm at 200 ° C. (measured at a pulling speed of 50 mm / min in each case). Even when this substrate was immersed in a 300 ° C. solder bath for 60 seconds, no blistering or peeling occurred.

Example 8 100 g of the polyimide powder obtained in Synthesis Example 1 and 2,2-
50 g of bis [4- (4-maleimidophenoxy) phenyl] propane (BBMI) was dissolved in 400 g of N, N-dimethylformamide (DMF) to obtain a resin composition (varnish). This resin composition was cast on a glass plate, and 8
After drying at 0 ° C. for 30 minutes, the film was peeled off to obtain a film. This film was fixed on an iron frame and heated at 150 ° C. for 1 hour to obtain a well-dried uncured film adhesive. This film adhesive has a thickness of 25μ.
m, the softening point was 165 ° C., and it exhibited excellent flexibility without breaking even when bent at an angle of 180 °.

When this film adhesive was cured by heating at 230 ° C. for 3 hours, the cured film obtained had a glass transition point of 225 ° C. and an elongation of 6.8%.
In the same solubility test as described above, it was insoluble in any of the solvents described in Synthesis Example 1.

The above film adhesive was pressed between a polyimide film having a thickness of 50 μm and a roughened copper foil having a thickness of 35 μm on one side at 30 kg / cm ² , at 230 ° C. for 3 hours to form a flexible printed wiring board. A substrate was obtained. 9 of this board
The 0 degree copper foil peeling strength is 1.3 kgf / c at room temperature.
m, 1.2Kgf / cm in 200 ° C atmosphere (in each case,
(Measured at a tensile speed of 50 mm / min). Even when this substrate was immersed in a 300 ° C. solder bath for 60 seconds, no blistering or peeling occurred.

[0070]

The thermosetting resin composition according to the first aspect and the film adhesive according to the second aspect have excellent properties such as adhesiveness and heat resistance when cured at a low temperature.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09J 7/00 C09J 7/00 135/00 135/00 151/08 151/08 179/08 179/08 Z (72) Inventor Naoto Ota No.48, Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Tsukuba Development Laboratory (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 79/08 C08F 283/04 C08F 290/14 C08K 5 / 3415 C08L 35/00 C09J 7/00 C09J 135/00 C09J 151/08 C09J 179/08 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) a repeating unit represented by the general formula (I): [However, in the general formula (I), Ar is a tetravalent organic group;
X is an allyloxycarbonyl group, a vinyl group, an allyl group,
Acryloyloxyalkoxycarbonyl group, methacrylic
Loyloxyalkoxycarbonyl group, acryloylo
A xyalkyl group, a methacryloyloxyalkyl group or
Which represents an ethynyl group ] and a thermosetting polyimide represented by the general formula (II): A thermosetting resin composition comprising a polymaleimide having a maleimide group represented by the formula: 2. A film adhesive comprising the thermosetting resin composition according to claim 1.