TW201402638A - Thermosetting resin compositions, resin films, copper clad boards and flexible printed circuit boards - Google Patents

Abstract

The topic of the present invention lies in providing a thermosetting resin composition, whose warpage behavior, dimensional stability, and bendability are excellent, and which can be used to manufacture a flexible printed circuit board without using a substrate such as a polyimide film. The solution of the present invention is a thermosetting resin composition, which contains (A) a cycloaliphatic epoxy resin, (B) an aromatic diamine compound, (C) at least one of a solvent-soluble polyimide with Tg above 250 DEG C and a solvent-soluble polyamideimide with Tg above 250 DEG C. Moreover, when the total amount of the (A) cycloaliphatic epoxy resin and the (B) aromatic diamine compound is 100 mass parts, the total amount of the (C) solvent-soluble polyimide and the solvent-soluble polyamideimide is above 30 mass parts and below 100 mass parts.

Description

Thermosetting resin composition, resin film, copper clad plate and flexible printed circuit board Technical field

The present invention relates to a thermosetting resin composition for producing a flexible printed circuit board excellent in warpage, dimensional stability, and flexibility, and also relates to a resin film or a copper clad plate obtained by using the composition.

Background technique

Heretofore, the insulator used for the flexible printed circuit board has a case where a substrate such as a polyimide film is used, and a case where a substrate is not used. When a substrate such as polyimide or the like is used, although the warpage property, the dimensional stability, the flexibility, and the like are excellent, the polyimide film itself is expensive, and since it is necessary between the substrate and the copper foil. To use an adhesive, it is more expensive.

On the other hand, when a base material such as polyimide or the like is not used, an epoxy resin or a urethane resin-based adhesive is generally used as the bonding sheet. It has also been used for copper clad laminates, cover lays, and the like. Such an epoxy resin-based adhesive or a urethane-based adhesive is described in Patent Document 1 (Japanese Patent Laid-Open Publication No. 2007-224242) and Patent Document 2 (Japanese Patent Laid-Open No. 2011-105950).

Patent literature

[Patent Document 1] Japanese Patent Laid-Open No. 2007-224242

[Patent Document 2] Japanese Patent Special Open 2011-105950

Summary of invention

However, since the epoxy resin-based adhesives have high elastic modulus at normal temperature, warpage is large when a flexible printed circuit board is formed, and dimensional stability is poor because Tg is low. Further, since the urethane resin-based adhesive is excellent in warpage property at a low temperature at a normal temperature, since the Tg is low, dimensional stability, letterability, and the like are poor.

Therefore, an object of the present invention is to provide a thermosetting resin composition which is excellent in warpage property, dimensional stability, and flexibility, and can produce a flexible printed circuit board without using a substrate such as a polyimide film.

Further, another object of the present invention is to provide a resin film, a copper clad plate, and a flexible printed circuit board using such a thermosetting resin.

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that the above object can be attained by a specific composition, and completed the present invention.

The thermosetting resin composition relating to the present invention is characterized by comprising: (A) an alicyclic epoxy resin; (B) an aromatic diamine compound; and (C) at least one of a solvent-soluble polyimine of Tg at 250 ° C or higher and a solvent-soluble polyamidoximine having a Tg of 250 ° C or higher; (A) When the total amount of the alicyclic epoxy resin and the (B) aromatic diamine compound is 100 parts by mass, (C) the total amount of the solvent-soluble polyimine and the solvent-soluble polyamidoximine is 30 mass More than 100 parts by weight.

The cured product of the composition of the present invention is excellent in warpage, dimensional stability, and flexibility. Further, even if a substrate such as a polyimide film is not used, a flexible printed circuit board can be manufactured, and since it is extremely suitable for an insulating resin film or a copper-clad plate, industrial advantages are extremely high.

Form for implementing the invention ((A) alicyclic epoxy resin)

In the present invention, the reason why (A) an alicyclic epoxy resin is used is that the elastic modulus at a normal temperature is lowered by introducing a soft chain into the skeleton.

The alicyclic epoxy resin refers to a resin having an alicyclic skeleton, which is an epoxy resin which forms a skeleton by an aliphatic cyclic compound chain.

Although the epoxy equivalent of the alicyclic epoxy resin is not particularly limited, it is usually used in an amount of 1,000 or less, and preferably 100 to 500.

The alicyclic epoxy resin is preferably any one which can be used as long as it is an alicyclic epoxy resin having two or more glycidyl groups. Specifically, for example, 1,6-hexanediol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3', 4 '-Epoxycyclohexene carboxylate, etc., and can be used individually or in combination of 2 or more types.

Representative examples include: "EHPE-3150" (2,2-bis(hydroxymethyl)-1-butanol, 1,2-epoxy-4-(2-epoxyethyl), manufactured by Daicel Chemical Industry Co., Ltd. Alkyl) cyclohexene adduct) and the like.

((B) Aromatic diamine compound)

The reason why the (B) aromatic diamine compound is used is because it has a certain degree of flexibility.

The aromatic diamine compound means a compound having an aromatic group and two amine groups.

In a preferred embodiment, the cured product has a degree of flexibility by introducing the polymethylene structure into the epoxy resin backbone.

In this case, the number of methylene groups which the polymethylene group provided in the main chain has is preferably three or more, and more preferably 16 or less.

Specifically, the aromatic diamine compound may, for example, be trimethylene-bis(4-aminobenzoic acid ester) or poly(tetrakis/3-methyltetramethylene ether) glycol bis(4-amine). The benzoic acid ester), the polytetramethylene oxide-di-p-amino benzoate, the polytetramethylene oxide amino benzoate, and the like may be used alone or in combination of two or more.

((C) solvent-soluble polyimine and/or solvent-soluble polyamidoximine at a temperature above 250 °C)

The reason for using the component (C) is to have flexibility, and by making the Tg at 250 ° C or higher, the volume expansion can be reduced even at the temperature of the welding temperature or the rate of change of the dimensional change, and the warpage can be made. Good stability and dimensional stability.

Tg (glass transition temperature) is measured by the TMA method.

(C) Solvent-soluble polyimine is a polyimine resin which is soluble in an organic solvent used in the production of the composition. Further, (C) a solvent-soluble polyamidoximine which is a polyamidoximine resin which is soluble in an organic solvent used in the production of the composition.

The composition of the present invention may contain only one of polyamine and polyamidoximine, and may contain both. Further, when both the polyimine and the polyamidimide are contained, the mass ratio of the two is not particularly limited, and may be polyimine: polyamidoximine = 1:0 to 0: 1.

The molecular weight of the component (C) is preferably 50,000 or less by weight average molecular weight (Mw), and more preferably 35,000 or less. Further, the weight average molecular weight (Mw) is preferably 20,000 or more, and more preferably 25,000 or more.

The component (C) preferably has a phenyl decane structure. Further, a fully fluorinated soluble polyimine resin obtained by reacting a diaminotrialkylnonane with a tetracarboxylic dianhydride or a derivative thereof is preferred. Here, the diaminotrialkylnonane can be exemplified by, for example, diaminotrimethylnonane or diaminotriethyldecane; and the derivative of tetracarboxylic dianhydride can be exemplified by benzophenone. Tetracarboxylic dianhydride.

Diaminotrimethylphenylnonane and benzophenone tetracarboxylic acid The fully fluorinated soluble polyimine resin obtained by the reaction of an anhydride is shown in (Formula 1). Further, a fully fluorinated soluble polyimine resin obtained by reacting diaminotrimethylphenyl nonane with tetracarboxylic dianhydride is also preferred.

(1)

Specifically, the component (C) may, for example, be Q-VR-0163 manufactured by PI Technology Research Co., Ltd., SN-20 manufactured by Nippon Chemical Co., Ltd., HR-16NN manufactured by Toyobo Co., Ltd., HPC-9100 manufactured by Hitachi Chemical Co., Ltd., etc. These may be used alone or in combination of two or more.

(composition)

In the present invention, when the total amount of the (A) alicyclic epoxy resin and the (B) aromatic diamine compound is 100 parts by mass, (C) solvent-soluble polyimine, solvent-soluble polyfluorene The total amount of the amine imine is set to 30 to 100 parts by mass. By setting it to 30 parts by mass or more, the thermal expansion coefficient of the resin composition is lowered, and the warpage property and dimensional stability of the cured product are improved. From this point of view, it is more preferable to set the total amount of the component (C) to 50 parts by mass or more. In addition, by setting the total amount of the component (C) to 100 parts by mass or less, the melt viscosity at the time of mixing can be lowered, and the moldability can be improved. From this point of view, the total amount of the component (C) is set to 80 parts by mass. The following is better.

When the total amount of the (A) alicyclic epoxy resin and the (B) aromatic diamine compound is 100 parts by mass, the amount of the (B) aromatic diamine compound is preferably 20 parts by mass or more, and It is more preferably set to 30 parts by mass or more. According to this, by improving the signal conductivity by completing the reaction of the epoxy group, it is possible to form a substrate having moderate flexibility.

In addition, the amount of the (B) aromatic diamine compound is preferably 60 parts by mass or less, and more preferably 50 parts by mass or less. According to this, by reducing the modulus of elasticity at normal temperature, warpage can be reduced when a flexible printed circuit board is formed.

((D) filler)

(D) Filler does not have to be added. However, by adding a filler, it is very useful from the viewpoint of reducing the expansion coefficient of the cured product and improving warpage and dimensional stability.

When the total amount of the (A) alicyclic epoxy resin and the (B) aromatic diamine compound is 100 parts by mass, the filler is preferably added in an amount of 60 to 140 parts by mass, more preferably 80 to 120 parts by mass. .

Specific examples of the filler include alumina, aluminum nitride, boron nitride, tantalum nitride, cerium oxide, aluminum hydroxide, and the like, and they may be used alone or in combination of two or more.

(other additives)

Further, in the composition of the present invention, a curing accelerator may be used in combination as needed. As the hardening accelerator, various general materials such as imidazoles can be used. It is mainly selected from the viewpoints of reaction rate and pot life. For example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-undecylimidin trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6-[2'-methylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-three 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-three Trimeric isocyanate adduct, 2-phenylimidazolium trimeric isocyanate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 4,4'-methylenebis(2-ethyl-5-methylimidazole), TPP Wait.

Further, in order to impart flame retardancy, a flame retardant may be added to the composition of the present invention. Halogen-free flame retardants are condensed phosphates, phosphazenes, polyphosphates, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide The derivative, the phosphorus-containing phenoxy resin, and the like are not particularly limited.

(Use of thermosetting resin composition)

A resin film can be obtained by subjecting the thermosetting resin composition of the present invention to a B-stage. That is, the resin composition of the present invention described above can be produced by a general method in which a B-state thermosetting resin film is obtained by diluting the resin composition of the present invention into a suitable mixed organic solvent to form a varnish (varnish). And applying it to a polyethylene terephthalate film (PET film) which is subjected to release treatment as needed by a die coater or the like, and drying. The B stage refers to a state in which the resin composition is semi-hardened.

Further, by applying the thermosetting resin composition of the present invention to a copper foil, a copper foil with an insulating resin film can be produced.

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples.

(Example 1)

35 parts by mass of alicyclic epoxy resin CEL-2081 (manufactured by Daicel Industries, Ltd.), 21 parts by mass of an aromatic diamine compound ELASMER 250P (manufactured by Ihara Chemical Co., Ltd.), and 392 parts by mass of a polyamidoximine resin A varnish composed of HR-16NN (Tg = 304 ° C, a solid portion of 14% by weight, manufactured by Toyobo Co., Ltd.) and 1 part by mass of 2-ethyl-4-methylimidazole.

(Example 2)

37 parts by mass of CEL-2081, 14 parts by mass of the aromatic diamine compound CUA-4 (manufactured by Ihara Chemical Co., Ltd.), 125 parts by mass of HR-16NN, and 1 part by mass of 2-ethyl-4-methyl. A varnish composed of imidazole.

(Example 3)

18 parts by mass of alicyclic epoxy resin TTA21P (manufactured by Jiangsu TetraChem Co., Ltd.), 17 parts by mass of an aromatic diamine compound ELASMER 250P, and 122 parts by mass of a polyimine resin Q-VR-0163 (Tg = 308 ° C) A varnish composed of 20 parts by weight of a solid portion, manufactured by PI Institute of Technology, and 1 part by mass of 2-ethyl-4-methylimidazole.

(Example 4)

Made of 35 parts by mass of CEL-2081, 21 parts by mass of aroma Group diamine compound ELASMER 250P, 392 parts by mass of HR-16NN (solid portion 14% by weight, manufactured by Toyobo Co., Ltd.), 1 part by mass of 2-ethyl-4-methylimidazole, and 80 parts by mass of filler SC-2050NNE A varnish composed of 70% by weight of a solid portion, manufactured by ADMAFINE Co., Ltd.

(Comparative Example 1)

16 parts by mass of EPICLON 850-S (manufactured by DIC Corporation), 24 parts by mass of an aromatic diamine compound ELASMER 250P, 142 parts by mass of HR-16NN, and 1 part by mass of 2-ethyl-4-methylimidazole were produced. The varnish that is formed.

(Comparative Example 2)

25 parts by mass of CEL-2081, 22 parts by mass of melamine-modified phenol novolak resin (solid portion 60% by weight, manufactured by DIC Corporation), 202 parts by mass of HR-16NN, and 1 part by mass of 2-ethyl- A varnish consisting of 4-methylimidazole.

(Comparative Example 3)

A varnish composed of 37 parts by mass of CEL-2081, 14 parts by mass of CUA-4, 71 parts by mass of Q-VR-0163, and 1 part by mass of 2-ethyl-4-methylimidazole was prepared.

(Comparative Example 4)

A varnish composed of 37 parts by mass of CEL-2081, 14 parts by mass of the aromatic amine compound CUA-4, 260 parts by mass of Q-VR-0163, and 1 part by mass of 2-ethyl-4-methylimidazole was prepared. .

(characteristic evaluation)

Blending of Examples 1 to 4 and Comparative Examples 1 to 4 by a die coater The material was coated on a 38 μm polyethylene terephthalate (PET film) and dried at 110 ° C to prepare a 25 μm B-staged resin film. Further, the layers cooperate to form a polyethylene film of a protective film.

It was made to overlap with 18 μm of the untreated copper foil, fed to a vacuum heat extrusion, and formed at 180 ° C, 120 °, 1 MPa, and subjected to characteristic evaluation. The characteristic results are shown in Table 1.

However, each characteristic was evaluated as follows.

Elasticity: After etching copper foil, IPC-TM-650

The measurement is based on 2.4.18.3.

Expansion coefficient: after copper foil etching, IPC-TM-650

The measurement is based on 2.4.24.3.

Bending property: After the copper foil was etched, the number of times of bending until the resin film was broken was measured by an MIT test method having a radius of curvature of 0.38 mm and a load of 500 g.

Dimensional change rate: measured by IPC-TM-650 2.2.4 150 ° C for 30 min.

Warpage: After etching the copper foil on one side, the substrate was cut into 50 mm × 50 mm, the substrate was placed on a horizontal table, and the length from the table to the apex of the substrate was measured.

Formability: The B-staged resin film from which the protective film was peeled off was laminated on a substrate on which a comb pattern of L/S = 30/30 was formed at 110 ° C, and dried in an oven at 180 ° C for 120 minutes. . When the drying is not observed, no hole is formed between the patterns, and "○" is formed when the hole is generated.

The evaluation results in each case and the numerical values of the mass parts of each component are shown In Table 1, Table 2.

It was confirmed that Examples 1 to 4 have excellent formability and dimensional stability. Sex, warp, and bendability.

In Comparative Example 1, since an aromatic epoxy resin was used as the epoxy resin, the elastic modulus at normal temperature was high, and the warpage was large.

In Comparative Example 2, since the phenol resin was used as the curing agent, the flexibility was poor.

In Comparative Example 3, since the amount of the polyimine or the polyamidimide was small, the expansion coefficient was increased and the dimensional change rate was increased.

In Comparative Example 4, since the amount of the polyimine or the polyamidimide was too large, the melt viscosity was high and the formability was adversely affected.

Claims (8)

A thermosetting resin composition comprising: (A) an alicyclic epoxy resin; (B) an aromatic diamine compound; and (C) a solvent-soluble polyimine at a Tg of 250 ° C or higher and At least one of a solvent-soluble polyamidoximine having a Tg of 250 ° C or higher; wherein the total amount of the (A) alicyclic epoxy resin and (B) the aromatic diamine compound is 100 parts by mass In the case of (C), the total amount of the solvent-soluble polyimine and the solvent-soluble polyamidoximine is 30 parts by mass or more and 100 parts by mass or less. The composition of claim 1 further comprising (D) a filler. The composition of the first or second aspect of the patent application, wherein the number of times of bending of the cured product by the MIT test method having a radius of curvature of 0.38 mm and a load of 500 g is 100 or more. The composition according to any one of claims 1 to 3, wherein the cured product has an elastic modulus at room temperature of 1.5 GPa or less. The composition according to any one of claims 1 to 4, wherein the cured product has a coefficient of thermal expansion of from 25 ° C to 200 ° C of 50 ppm / ° C or less. A B-staged resin film produced by the thermosetting resin composition according to any one of claims 1 to 5. A copper clad plate comprising the resin film of item 6 of the patent application, and a copper foil bonded to at least one side of the resin film. A flexible printed circuit board comprising the interlayer insulating material comprising the thermosetting resin composition according to any one of claims 1 to 5.