WO2014024678A1 - Resin composition, and adhesive film and coverlay film each of which is formed of same - Google Patents

Abstract

The purpose of the present invention is to provide: an adhesive film for electrical/electronic applications and a coverlay film, each of which enables the achievement of a lower dielectric constant and a lower dielectric loss in the frequency range of 1-10 GHz, while having a flame retardancy meeting V-0 or VTM-0 according to UL-94 standard; and a resin composition which is used for the purpose of producing the adhesive film and the coverlay film. The present invention provides a resin composition which is characterized by containing (A) a vinyl compound represented by general formula (1) and having a mass average molecular weight (Mw) of 500-4,000, (B) a thermoplastic elastomer, (C) a thermosetting resin other than the vinyl compound represented by general formula (1), (D) a curing agent and (E) an organic aluminum phosphinate. This resin composition is also characterized in that the component (E) is contained in an amount of 10-50 parts by mass per 100 parts by mass of the total of the component (A), the component (B), the component (C), the component (D) and the component (E).

Description

Resin composition, and adhesive film and coverlay film thereby

The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition suitable for an adhesive film for electric / electronic use or a coverlay film for a printed wiring board.
Moreover, this invention relates to the adhesive film produced using this resin composition, and a coverlay film.

In recent years, printed wiring boards used in electrical and electronic equipment have been reduced in size, weight, and performance, especially for multilayer printed wiring boards. Thinning, lightening, high reliability, moldability, etc. are required.
In addition, with the recent demand for higher speed transmission signals in printed wiring boards, the frequency of transmission signals has increased significantly. Accordingly, it is required that the electric signal loss in the high frequency region, specifically, the frequency region of 1 to 10 GHz can be reduced with respect to the material used for the printed wiring board.
For adhesive films used as interlayer adhesives and surface protective films (ie, coverlay films) for printed wiring boards, excellent electrical properties (low dielectric constant (ε), low dielectric loss tangent (tan δ)) in the high frequency region Is required.

The adhesive film materials used in the above applications are inherently flammable, so that they can be used as industrial materials in addition to satisfying general chemical and physical properties in a well-balanced manner. That is, there are many cases where flame retardancy is required. In many cases, particularly when used in home appliances, a high level of flame retardancy such as “flame retardancy based on UL94 satisfies V-0 or VTM-0” is required. In general, as a method for imparting flame retardancy to a resin material such as an adhesive film, a method of adding a halogen-based organic compound as a flame retardant and further adding an antimony compound as a flame retardant aid to the resin can be mentioned.

However, this method has a problem of generating corrosive halogen gas and highly toxic dioxin during combustion. Therefore, in recent years, in order to eliminate the adverse effects of these halogen-based flame retardants on the environment, it has been strongly desired to use a halogen-free flame retardant that does not contain halogen at all.

For halogen-free flame retardant formulations, for example, a phosphorous flame retardant formulation is employed. For example, in the paragraph [0040] of Patent Document 1 by the present applicants, it is said that phosphate esters such as trimethyl phosphate, triphenyl phosphate, tricresyl phosphate and the like can be used as a flame retardant, The range of the flame retardant content when the flame retardant is contained in the coverlay film described in the document is shown.

JP 2011-068713 A

The cover lay film described in Patent Document 1 is intended for application to a flexible printed wiring board, and has the above-described high flame retardancy, that is, “flame retardancy based on UL94 is V-0 or VTM-0. It is not described that "satisfying" is required.
Therefore, the flame retardant content described in paragraph [0040] of Patent Document 1 achieves a high level of flame retardancy such as “flameability based on UL94 satisfies V-0 or VTM-0”. It is not intended.
In order to achieve high flame retardancy such as “flame retardancy based on UL94 satisfies V-0 or VTM-0”, it is necessary to increase the content of the flame retardant.

However, when an amount of a phosphorus-based flame retardant capable of achieving a high level of flame retardancy such as “flame retardancy based on UL94 satisfies V-0 or VTM-0” is included, the frequency is 1 to 10 GHz. It has been clarified that the dielectric constant (ε) and dielectric loss tangent (tan δ) in the high frequency region are increased, and electric signal loss in the high frequency region becomes a problem.

In order to solve the above-described problems of the prior art, the present invention can achieve low dielectric constant and low dielectric loss in a high frequency region, specifically, a frequency range of 1 to 5 GHz, and UL94 It is an object of the present invention to provide an adhesive film and a coverlay film for electric / electronic applications that can satisfy V-0 or VTM-0, and a resin composition used for producing them.

In order to achieve the above object, the present invention provides:
(A) A vinyl compound having a mass average molecular weight (Mw) of 500 to 4000 represented by the following general formula (1):

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group. — (O—X—O) — is represented by the following structural formula (2).

R ₈ , R ₉ , R ₁₀ , R ₁₄ , and R ₁₅ may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R _11, R _12, R ₁₃ are the same or different, it is a hydrogen atom, a halogen atom or more than 6 alkyl group or a phenyl group having a carbon. -(YO)-is one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) arranged at random.

R ₁₆ and R ₁₇ may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b each represents an integer of 0 to 300, at least one of which is not 0. c and d represent an integer of 0 or 1. )
(B) a thermoplastic elastomer,
(C) a thermosetting resin other than the vinyl compound represented by the general formula (1),
(D) a curing agent, and
(E) containing an organic aluminum phosphinate,
10 to 50 parts by mass of the component (E) with respect to 100 parts by mass in total of the component (A), the component (B), the component (C), the component (D), and the component (E) The resin composition characterized by containing is provided.

In the resin composition of the present invention, — (O—X—O) — of the component (A) is represented by the following structural formula (4), and — (YO) — of the component (A) is Structural formula (5), or a structure represented by the following structural formula (6), or a structure represented by the following structural formula (5) and a structure represented by the following structural formula (6) are randomly arranged. It is preferable.

In the resin composition of the present invention, it is preferable that — (YO) — of the component (A) has a structure represented by the structural formula (6).

In the resin composition of the present invention, the thermoplastic elastomer of component (B) is a styrene-butadiene block copolymer, a styrene-ethylene / butylene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, or a polybutadiene. And at least one selected from the group consisting of styrene- (ethylene-ethylene / propylene) -styrene block copolymers.

In the resin composition of the present invention, the thermosetting resin of the component (C) is a biphenyl type epoxy resin, a naphthalene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a bismaleimide, And at least one selected from the group consisting of carbodiimide and the like.

In the resin composition of the present invention, the content of the thermoplastic elastomer of the component (B) includes the component (A), the component (B), the component (C), the component (D), and the component. The amount is preferably 10 to 60 parts by mass with respect to 100 parts by mass in total of (E).

In the resin composition of the present invention, the content of the thermosetting resin of the component (C) is such that the component (A), the component (B), the component (C), the component (D), and the The amount is preferably 0.5 to 40 parts by mass with respect to 100 parts by mass in total of the component (E).

The resin composition of the present invention may further contain (F) a filler. In this case, the component (A), the component (B), the component (C), the component (D), the component (E), and the component (F) with respect to a total of 100 parts by mass. 10 to 60 parts by mass of (F) is contained.

The resin composition of the present invention may further contain (G) an organic peroxide.

The resin composition of the present invention has a dielectric constant (ε) of 3.0 or less and a dielectric loss tangent (tan δ) of 0.006 or less in the frequency range of 1 to 10 GHz of the cured product of the resin composition. preferable.

The resin composition of the present invention preferably has flame retardancy based on UL94 satisfying V-0 or VTM-0.

The present invention also provides an adhesive film produced using the resin composition of the present invention.

The present invention also provides a coverlay film produced using the resin composition of the present invention.

The present invention also provides a varnish containing the resin composition of the present invention.

The adhesive film and coverlay film of the present invention have excellent electrical characteristics in a high frequency region after heating and curing, specifically, a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in a frequency range of 1 to 10 GHz. ), It is possible to achieve low dielectric constant and low dielectric loss in a high frequency region, and flame retardancy based on UL94 satisfies V-0 or VTM-0.
Moreover, the adhesive film and coverlay film of this invention show the adhesive strength outstanding with respect to the organic material or inorganic material used for printed wiring boards, such as a polyimide, a liquid crystal polymer, and a ceramic, after heat-hardening.
Moreover, since the adhesive film and coverlay film of this invention are excellent in flexibility after heat-curing, they are suitable as an adhesive film and coverlay film for flexible printed wiring boards. In addition, since the film of this invention is excellent in flexibility before heat-hardening, the workability | operativity in the processing process of a film is favorable.
The adhesive film and coverlay film of the present invention can be prepared using the resin composition of the present invention.
In the present invention, instead of using a film in advance, a varnish containing the resin composition of the present invention may be applied to the film forming surface and then dried to form a film.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention contains the following components (A) to (E) as essential components.

Component (A): Vinyl compound represented by the following general formula (1) and having a mass average molecular weight (Mw) of 500 to 4000

In the general formula _{(1), R 1, R} 2, R 3, R 4, R 5, R 6, R 7 are the same or different, a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, or It is a phenyl group. Among _{these, R 1, R 2, R} 3, R 4, R 5, is preferably R _6, R ₇ is a hydrogen atom.
In the formula, — (O—X—O) — is represented by the following structural formula (2).

In the structural formula (2), R ₈ , R ₉ , R ₁₀ , R ₁₄ , and R ₁₅ may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Among these, R ₈ , R ₉ , R ₁₀ , R ₁₄ , and R ₁₅ are preferably alkyl groups having 6 or less carbon atoms.
R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Among these, R ₁₁ , R ₁₂ and R ₁₃ are preferably a hydrogen atom, a halogen atom or an alkyl group having 6 or less carbon atoms.
In the general formula (1),-(YO)-is a random arrangement of one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) It is a thing. Among these, — (YO) — is preferably an arrangement of one type of structure defined by the following structural formula (3).

In the structural formula (3), R ₁₆ and R ₁₇ may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Among these, R ₁₆ and R ₁₇ are preferably alkyl groups having 6 or less carbon atoms.
R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Among these, R ₁₈ and R ₁₉ are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms.
In general formula (1), Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. Among these, it is preferable that Z is a methylene group.
a and b each represents an integer of 0 to 300, at least one of which is not 0.
c and d represent an integer of 0 or 1. Among these, c and d are preferably 1.
Preferably Among _{these, R 8, R 9, R} 10, R 14, R 15 is alkyl group having 3 or less carbon _{atoms, R 11, R 12, R} 13 is a hydrogen atom or alkyl group having 3 or less carbon atoms, R ₁₆ and R ₁₇ are alkyl groups having 3 or less carbon atoms, and R ₁₈ and R ₁₉ are hydrogen atoms.

In addition, — (O—X—O) — in the general formula (1) is preferably represented by the following structural formula (4).

In the general formula (1), — (Y—O) — represents the structure represented by the following structural formula (5), the following structural formula (6), the structure represented by the following structural formula (5), and It is preferable to have a structure in which the structure represented by the following structural formula (6) is randomly arranged. Among these,-(YO)-preferably has a structure in which structures defined by the following structural formula (6) are arranged.

In the resin composition of the present invention, the component (A) is the thermosetting property, heat resistance, and excellent electrical properties at high frequencies of the adhesive film and coverlay film prepared using the resin composition, that is, the frequency. This contributes to a low dielectric constant (ε) and a low dielectric loss tangent (tan δ) in the region of 1 to 10 GHz.
In addition, component (A) acts as a compatibilizer for components (B) to (E) described below.

In the resin composition of the present invention, as the component (A), among the vinyl compounds represented by the general formula (1), those having a mass average molecular weight (Mw) of 500 to 4000 are used as follows.
When the mass average molecular weight (Mw) is less than 500, the flexibility of the adhesive film and coverlay film prepared using the resin composition is lost, and the film becomes brittle and easily broken. In addition, since the melt viscosity is too low during thermocompression bonding or heat curing, the film thickness uniformity may be impaired.
On the other hand, when the mass average molecular weight (Mw) exceeds 4000, the solubility is lowered, which causes a problem when preparing the resin composition. Specifically, long-time mixing and dissolution in hot toluene is required when preparing a varnish obtained by diluting a resin composition with a solvent. Further, when the varnish is returned to room temperature to form a film, recrystallization starts and the storage stability of the varnish is deteriorated. Moreover, since it crystallizes after film formation, it becomes difficult to maintain the shape as a film. For this reason, the adhesive film and coverlay film created using this resin composition are easily broken. Moreover, it becomes impossible to produce a thin film. Furthermore, the smoothness of the film surface is deteriorated.
As the component (A), among the vinyl compounds represented by the general formula (1), those having a mass average molecular weight (Mw) of 800 to 3500 are preferably used, and those having 1000 to 3000 are more preferably used.

The method for producing the vinyl compound represented by the general formula (1) is not particularly limited, and may be produced by any method. For example, chloromethylstyrene is added to a compound represented by the following general formula (7) in the presence of an alkali catalyst such as sodium hydroxide, potassium carbonate, sodium ethoxide, and the like, if necessary, benzyltri n-butylammonium bromide, 18- It can be obtained by reacting with a phase transfer catalyst such as crown-6-ether.

In formula (7), — (O—X—O) and — (Y—O) — are as described above for formula (1).

Component (B): Thermoplastic Elastomer In the resin composition of the present invention, component (B) is an excellent electrical property (frequency 1 to frequency) of an adhesive film and a coverlay film prepared using the resin composition. This contributes to low dielectric constant (ε) and low dielectric loss tangent (tan δ), film properties, and heat resistance in the 10 GHz region.

In the resin composition of the present invention, as the elastomer of component (B), styrene-butadiene block copolymer, styrene-ethylene / butylene-styrene block copolymer, styrene-isoprene-styrene block copolymer, polybutadiene, and , At least one selected from the group consisting of styrene- (ethylene-ethylene / propylene) -styrene block copolymers can be used. Among these, only any 1 type may be used and 2 or more types may be used.
Which of these is used can be appropriately selected depending on the properties to be imparted to the adhesive film and the coverlay film produced using the resin composition.
For example, a styrene-ethylene / butylene-styrene block copolymer has high heat resistance due to high crystallinity of the portion of -ethylene / butylene-, and is used as an adhesive film and a coverlay film formed using the resin composition. It is preferable for imparting heat resistance.
On the other hand, the styrene- (ethylene-ethylene / propylene) -styrene block copolymer has a crystallinity of the-(ethylene-ethylene / propylene)-moiety corresponding to that of the styrene-ethylene / butylene-styrene block copolymer. Since it is lower than (the ethylene / butylene portion), the adhesive strength to the substrate is higher than that of the styrene-ethylene / butylene-styrene block copolymer.
In addition, the styrene-butadiene block copolymer has a low elastic modulus of an adhesive film and a coverlay film prepared using the resin composition, and unevenness present on the adherend surface during thermocompression bonding of the film. Therefore, the adhesive strength of the film is increased. Moreover, the flexibility after curing of the film is also excellent.

In the resin composition of the present invention, the content of the component (B) is preferably 10 to 60 parts by mass with respect to 100 parts by mass in total of the components (A) to (E).
When the content of the component (B) is less than 10 parts by mass, the film properties of the adhesive film and coverlay film prepared using the resin composition, specifically, the folding resistance of the film alone is inferior. In addition, the amount of seepage during thermocompression increases, and the film thickness tends to be uneven.
On the other hand, if the content of the component (B) exceeds 60 parts by mass, the content of other components of the resin composition, in particular, the component (A) is reduced, so that the resin composition is used. The heat resistance of the adhesive film and the coverlay film is lowered. In addition, since the compatibility with the other components of the resin composition is reduced, the composition of the adhesive film and cover lay film prepared using the resin composition becomes non-uniform, and the adhesive film and cover lay film are bonded. Property and mechanical strength are reduced.
In the resin composition of the present invention, the content of the component (B) is more preferably 12 to 55 parts by mass, and 13 to 45 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). More preferably, it is a part.

Component (C): Thermosetting resin other than the vinyl compound represented by the general formula (1) In the resin composition of the present invention, the component (C) is an adhesive film and a coverlay prepared using the resin composition. Contributes to the thermosetting and adhesive properties of the film.

The thermosetting resin used as the component (C) is not particularly limited as long as it is a thermosetting resin other than the vinyl compound represented by the general formula (1) as the component (A).
The thermosetting resin used as the component (C) includes biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, bismaleimide, and carbodiimide. At least one selected from the group can be used.
In addition, among said thermosetting resin, any 1 type may be used and 2 or more types may be used together.
Which of these is used can be appropriately selected depending on the properties to be imparted to the adhesive film and the coverlay film produced using the resin composition.
Epoxy resins such as biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolak type epoxy resin are excellent in compatibility with other components of the resin composition, and the resin composition An adhesive film and a cover lay film produced using a product are excellent in moisture resistance reliability. Among the above epoxy resins, a biphenyl type epoxy resin is more preferable because the dielectric property of the resin itself is relatively good.
Moreover, when bismaleimide is used, the linear expansion coefficient after hardening of the adhesive film and coverlay film which are created using this resin composition becomes low.

In the resin composition of the present invention, the content of the thermosetting resin of component (C) is 0.5 to 40 parts by mass with respect to 100 parts by mass in total of components (A) to (E). preferable.
When content of a component (C) is less than 0.5 mass part, there exists a problem that the adhesiveness of the adhesive film and coverlay film which are created using this resin composition becomes inadequate.
When the content of the component (C) is more than 40 parts by mass, the amount of oozing during thermocompression bonding of the adhesive film and coverlay film prepared using the resin composition becomes excessively large. Moreover, since the ratio of the component (C) in all the components increases, the properties of the component (C) inferior in heat resistance affect the entire adhesive film and coverlay film formed using the resin composition. . Therefore, there exists a possibility that the heat resistance and sclerosis | hardenability of the adhesive film and coverlay film which are created using this resin composition may fall.
In the resin composition of the present invention, the content of component (C) is more preferably 1.0 to 30 parts by mass with respect to 100 parts by mass in total of components (A) to (E). More preferably, it is 5 to 15 parts by mass.

When the thermosetting resin used as component (C) is biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, or carbodiimide, the number average molecular weight ( Mn) is preferably from 150 to 2500 for reasons of thermosetting, adhesiveness, and post-curing mechanical properties of the adhesive film and coverlay film prepared using the resin composition.
When the thermosetting resin used as the component (C) is bismaleimide, the number average molecular weight (Mn) is 150 to 3500. The heat of the adhesive film and coverlay film prepared using the resin composition It is preferable for reasons of curability, adhesiveness, and mechanical properties after curing.

Component (D): Curing Agent The resin composition of the present invention contains an effective amount of a curing agent as the component (D).
The curing agent used as component (D) is not particularly limited. As the component (D), it is preferable to use at least one curing agent selected from the group consisting of a phenolic curing agent, an amine curing agent, an imidazole curing agent, and an acid anhydride curing agent.

Specific examples of the phenol-based curing agent include monomers, oligomers, and polymers in general having a phenolic hydroxyl group. Examples thereof include triphenol methane resin and dicyclopentadiene type phenol resin.

Specific examples of the amine curing agent include triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4, 0] tertiary amine compounds such as undecene-7 (DBU), triethylenediamine, benzyldimethylamine, triethanolamine and the like. Of these, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s-triazine is preferred.

Examples of imidazole curing agents include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl. Examples thereof include imidazole compounds such as -4-imidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Of these, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-imidazole are preferable.

Specific examples of the acid anhydride-based curing agent include phthalic anhydride, maleic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, benzophenone tetracarbanoic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride. .

In addition, any 1 type may be used among said hardening | curing agents, and 2 or more types may be used together.
Among these, an imidazole-based curing agent is preferable because it exhibits an effect even if the addition amount is small. In particular, 2-phenyl-4,5 dihydroxymethylimidazole is a varnish obtained by diluting a resin composition with a solvent. It is preferable because the pot life and the shelf life of the adhesive film and coverlay film produced using the resin composition are improved.

The effective amount of the curing agent varies depending on the type of the curing agent. The effective amount for each type of curing agent is shown below.
In the case of a phenolic curing agent, the effective amount is more preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass in total of components (A) to (E). Further preferred.
In the case of an amine-based curing agent, the effective amount is more preferably 1 to 10 parts by mass, and more preferably 1 to 3 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). Further preferred.
In the case of an imidazole-based curing agent, the effective amount is more preferably 0.1 to 5 parts by mass, and 0.2 to 3 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). More preferably.
In the case of an acid anhydride type epoxy curing agent, the effective amount is more preferably 1 to 10 parts by mass with respect to 100 parts by mass in total of components (A) to (E), preferably 1 to 5 parts by mass. More preferably it is.
Moreover, when using together 2 or more types among phenol type hardening | curing agents, amine type hardening | curing agents, imidazole type hardening | curing agents, and acid anhydride type hardening | curing agents, it adds so that each epoxy hardening | curing agent may become said effective amount. .

Component (E): Aluminum organophosphinate In the resin composition of the present invention, component (E) contributes to the flame retardancy of an adhesive film and a coverlay film prepared using the resin composition.
The organic aluminum phosphinate used as the component (E) is represented by the following general formula.

In the above general formula, R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, a phenyl group or a naphthyl group. The alkyl group may be linear, branched or cyclic. An alkyl group having 1 to 3 carbon atoms is preferable, and an ethyl group is more preferable.
The organic aluminum phosphinate used as component (E) is preferably aluminum dialkylphosphinate, more preferably aluminum diethylphosphinate.

The resin composition of the present invention uses an organoaluminum phosphinate as the component (E), so that an adhesive film and a coverlay film prepared using the resin composition have a flame retardancy based on UL94 of V-0. Or, VTM-0 is satisfied.
It is also described in JP-A-2009-179774 and JP-A-2011-225883 that, when an organic phosphinate aluminum is used as a flame retardant, flame retardancy based on UL94 satisfies V-0 or VTM-0. Has been.
However, in the former case, the electric signal loss in the high frequency region is not regarded as a problem, and the electrical characteristics in the high frequency region have not been studied at all. On the other hand, in the latter case, since the relative dielectric constant at a frequency of 1 GHz or higher includes a resin having a relative dielectric constant of 2.9 or lower, the relative dielectric constant of the resin composition at a frequency of 1 GHz or higher can be 3.0 or lower. Since the mass average molecular weight (Mw) of the resin having a relative dielectric constant of 2.9 or less at a frequency of 1 GHz or higher is as high as 1,000 to 300,000, it was used as a resin composition for adhesive films and coverlay films. In this case, the solubility is lowered, which causes a problem when preparing the resin composition. Specifically, long-time mixing and dissolution in hot toluene is required when preparing a varnish obtained by diluting a resin composition with a solvent. Further, when the varnish is returned to room temperature to form a film, recrystallization starts and the storage stability of the varnish is deteriorated. Moreover, since it crystallizes after film formation, it becomes difficult to maintain the shape as a film. For this reason, the adhesive film and coverlay film created using this resin composition are easily broken. Moreover, it becomes impossible to produce a thin film. Furthermore, the smoothness of the film surface is deteriorated.

The resin composition of the present invention contains 10 to 50 parts by mass of the component (E) with respect to 100 parts by mass in total of the components (A) to (E).
When the content of the component (E) is less than 10 parts by mass, the flame retardancy of the adhesive film and coverlay film prepared using the resin composition is lowered, and the flame retardancy based on UL94 is V-0 or Not satisfied with VTM-0.
When the content of the component (E) exceeds 50 parts by mass, it becomes impossible to form a film when an adhesive film and a coverlay film are produced using the resin composition.
In the resin composition of the present invention, the component (E) is preferably contained in an amount of 15 to 48 parts by mass, more preferably 18 to 45 parts by mass with respect to 100 parts by mass in total of the components (A) to (E). More preferred.

The resin composition of the present invention may contain the following components (F) and (G) as necessary in addition to the components (A) to (E).

Component (F): Filler The resin composition of the present invention may contain a filler as the component (F) in addition to the components (A) to (E).
By including a filler as the component (F), the adhesive film and coverlay film prepared using the resin composition of the present invention can have desired rheological properties, electrical properties, or physical properties, or Both can be granted. The filler used as the component (F) is appropriately selected according to the use of the adhesive film and the coverlay film prepared using the resin composition of the present invention. For example, a thermally conductive substance, an unnecessary radiation absorbing substance And ceramic dielectric materials.

Examples of the thermally conductive substance include oxides such as aluminum oxide and silicon dioxide, and nitrides such as aluminum nitride and boron nitride.
Examples of the unnecessary radiation absorbing material include iron oxides such as ferrite.
Examples of the ceramic dielectric material include barium titanate and titanium oxide.

When the filler is contained as the component (F), the content of the resin composition of the present invention is an amount necessary for exhibiting desired characteristics and an amount capable of forming a film. Although it does not restrict | limit in particular, it is 10 with respect to a total of 100 mass parts of a component (A), a component (B), a component (C), a component (D), a component (E), and a component (F). It is preferably from 60 parts by mass from the viewpoint of dispersibility in the resin composition and processability of an adhesive film and a coverlay film prepared using the resin composition, and more preferably from 20 to 55 parts by mass. More preferably, it is 25 to 50 parts by mass.

Moreover, when a filler is contained as the component (F), the shape is not particularly limited, and may be, for example, granular, powdery, flake shaped, etc. The maximum diameter) is preferably 0.5 μm or less from the viewpoint of dispersibility with respect to the resin composition and workability of an adhesive film and a coverlay film prepared using the resin composition.

In addition, when a filler is included as the component (F), a filler that has been subjected to a surface treatment as necessary may be used. Specific examples of such a filler include those in which an oxide film is formed on the particle surface.

Component (G): Organic Peroxide The resin composition of the present invention comprises an organic peroxide as component (G) in addition to the above components (A) to (E) (may contain component (F)). You may contain a thing.
Reaction of the vinyl compound used as the component (A) at the time of heat curing of the adhesive film and coverlay film prepared using the resin composition of the present invention by containing an organic peroxide as the component (G) Is promoted.

The organic peroxide of component (G) includes benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di (3,5,5- Diacyl peroxides such as trimethylhexanoyl) peroxide; peroxyketals such as 2,2-di (4,4-di- (di-tert-butylperoxy) cyclohexyl) propane; isopropyl purge carbonate, di-sec Peroxydicarbonates such as butyl purge carbonate, di-2-ethylhexyl purge carbonate, di-1-methylheptyl purge carbonate, di-3-methoxybutyl purge carbonate, dicyclohexyl purge carbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diperadipate, cumyl perneodecano Peroxyesters such as acrylate, tert-butylperoxybenzoate, 2,5-dimethyl-2,5di (benzoylperoxy) hexane; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; di-tert- Butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, di-tert-hexyl Dialkyl peroxides such as oxyoxide and di (2-tert-butylperoxyisopropyl) benzene; hydroperoxides such as cumene hydroxy peroxide, tert-butyl hydroperoxide, p-menta hydroperoxide, etc. Can do. Among these, tert-butyl peroxybenzoate has an optimum activation temperature, that is, a temperature range of 60 to 120 ° C. in the drying process of film formation, and around 80 ° C. at the time of transfer of an adhesive film or a coverlay film. It is not activated in the above temperature range, but it is activated in the temperature range of 180 to 210 ° C. during the heat curing of the adhesive film or coverlay film, and the shelf life of the adhesive film or coverlay film is good. preferable.

When an organic peroxide is contained as the component (G), the content in the resin composition of the present invention is as follows: Component (A), Component (B), Component (C), Component (D), Component (E) , (If included, component (F)) and 100 parts by mass of component (G), preferably 5 parts by mass or less, more preferably 3 parts by mass or less, More preferably, it is ˜1 part by mass.

The resin composition of the present invention may contain components other than the above components (A) to (G) as necessary. Specific examples of such components include silane coupling agents, antifoaming agents, flow control agents, film forming aids, dispersants, and the like.

The resin composition of the present invention can be produced by a conventional method. For example, in the presence or absence of a solvent, the above components (A) to (E) (if the resin composition contains the above components (F), (G) and other optional components, these optional Ingredients) are mixed with a heating vacuum mixing kneader.
(If the resin composition contains the above components (F), (G) and other optional components, these optional components) so that the above components (A) to (E) have a desired content ratio , Dissolved in a predetermined solvent concentration, put them in a reaction kettle heated to 10 to 80 ° C., mixed at atmospheric pressure for 3 hours while rotating at a rotational speed of 100 to 1000 rpm, The mixture can be further stirred for 30 to 60 minutes at (maximum 1 Torr).

The adhesive film and coverlay film of the present invention can be obtained from the resin composition of the present invention by a known method. For example, the resin composition of the present invention is diluted with a solvent to obtain a varnish, which is applied to at least one side of a support and dried, and then provided as a film with a support or a film peeled from the support. be able to.

Examples of the solvent that can be used as the varnish include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; high-boiling solvents such as dioctyl phthalate and dibutyl phthalate. The amount of the solvent used is not particularly limited and may be a conventionally used amount, but is preferably 20 to 90% by mass with respect to the solid content.

The support is appropriately selected depending on the desired form in the film production method, and is not particularly limited. Examples thereof include metal foils such as copper and aluminum, and carrier films of resins such as polyester and polyethylene. When providing the adhesive film of this invention as a form of the film peeled from the support body, it is preferable that the support body is mold-release-processed with the silicone compound etc.

The method for applying the varnish is not particularly limited, and examples thereof include a slot die method, a gravure method, a doctor coater method, and the like, which are appropriately selected according to a desired film thickness and the like. This is preferable because it can be designed to be thin. Application | coating is performed so that the thickness of the film formed after drying may turn into desired thickness. Such a thickness can be derived from the solvent content by those skilled in the art.

The thickness of the adhesive film and cover lay film of the present invention is appropriately designed based on characteristics such as mechanical strength required according to the application, but is generally 1 to 100 μm, and when thinning is required, It is preferably 1 to 30 μm.

The drying conditions are appropriately designed according to the type and amount of the solvent used in the varnish, the amount of varnish used and the thickness of the coating, and are not particularly limited, but are, for example, 60 to 120 ° C., It can be performed under atmospheric pressure.

The adhesive film and coverlay film of the present invention before use are stored in a state of being sandwiched between protective films in order to prevent foreign matter from adhering. As a protective film, what was described as a base material can be used.

The procedure for using the adhesive film of the present invention is as follows.
Among objects to be bonded using the adhesive film of the present invention, after the adhesive film of the present invention is placed on the surface to be bonded of one object, the other surface is exposed to the adhesive film. Place it in contact with the surface. Here, when using an adhesive film with a support, the adhesive film is placed so that the exposed surface of the adhesive film is in contact with the adherend surface of one object, and the adhesive film is transferred onto the adherend surface. . Here, the temperature at the time of transfer can be set to 80 ° C., for example.
Next, the other object is placed on the surface of the adhesive film exposed by peeling the support during transfer so that the surface to be bonded is in contact with the exposed surface of the adhesive film. After performing these procedures, thermocompression bonding is performed for a predetermined temperature and for a predetermined time, and then heat-cured.
The temperature during thermocompression bonding is preferably 100 to 200 ° C. The time for thermocompression bonding is preferably 0.5 to 10 minutes.
The temperature for heat curing is preferably 180 to 210 ° C. The heat curing time is preferably 30 to 120 minutes.
The procedure for using the coverlay film of the present invention is basically the same. After the coverlay film of the present invention is placed at a predetermined position on the printed wiring board, that is, at a position covered with the coverlay film, a predetermined temperature is set. Then, it may be heat-pressed for a predetermined time, and then heat-cured.
Moreover, instead of using what was previously filmed, a varnish obtained by diluting the resin composition of the present invention with a solvent is applied to the surface to be bonded (position to be covered with a film in the case of a coverlay film). After applying and drying, the above-described procedure of placing one object (in the case of a coverlay film, thermocompression bonding) may be performed.

Hereinafter, the characteristics of the adhesive film and coverlay film of the present invention will be described.

The adhesive film and coverlay film of the present invention are excellent in high frequency electrical characteristics after heat curing. Specifically, the heat-cured coverlay film preferably has a dielectric constant (ε) of 3.0 or less, more preferably 2.5 or less, in a frequency range of 1 to 10 GHz. Further, the dielectric loss tangent (tan δ) in the frequency region of 1 to 10 GHz is more preferably 0.01 or less, and more preferably 0.0025 or less.
When the dielectric constant (ε) and dielectric loss tangent (tan δ) in the frequency range of 1 to 10 GHz are in the above ranges, the electric signal loss in the frequency range of 1 to 10 GHz can be reduced.

The adhesive film and coverlay film of the present invention have sufficient adhesive strength after heat curing. Specifically, the adhesive film and the coverlay film after heat curing preferably have a peel strength (180 degree peel) with respect to the roughened surface of the copper foil measured in accordance with JIS C6471 of 5 N / cm or more, more preferably. Is 8 N / cm or more, more preferably 10 N / cm or more.

The adhesive film and coverlay film of the present invention have sufficient flame retardancy after heat curing. Specifically, it is preferable that the adhesive film and the coverlay film after heat curing pass with a flame retardancy class V-0 in a flame retardancy test performed in accordance with the flame retardancy standard of UL94V. Moreover, it is preferable that the adhesive film and coverlay film after heat curing pass with the flame retardancy class VTM-0 in the flame retardancy test conducted in accordance with the flame retardancy standard of UL94VTM.

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

(Examples 1 to 12, Comparative Examples 1 to 6)
Mix each component so that the blending ratio (parts by mass) shown in the table below is met, add toluene, put into a reaction kettle heated to 80 ° C., and mix at normal pressure while rotating at 150 rpm. For 3 hours.
The varnish containing the resin composition thus obtained was applied to one side of a base material (PET film subjected to release treatment) and dried at 100 ° C. to obtain an adhesive film with a support. .
The abbreviations in the table represent the following.
Ingredient (A)
OPE2200: Oligophenylene ether (vinyl compound represented by the above general formula (1)) (Mn = 2200), manufactured by Mitsubishi Gas Chemical Co., Ltd.
Ingredient (A ')
S202A: Modified polyphenylene ether (Mn = 16000), manufactured by Asahi Kasei Chemicals Corporation
Ingredient (B)
SEPTON 8007: Styrene-ethylene / butylene block copolymer, Kuraray Co., Ltd. SEPTON 4044: Styrene- (ethylene-ethylene / propylene) -styrene block copolymer, Kuraray Co., Ltd. TR2003: Styrene-butadiene-styrene block copolymer, PSR810 manufactured by JSR Corporation: Polybutadiene, manufactured by JSR Corporation
Ingredient (C)
NC3000H: Biphenyl type epoxy resin, Nippon Kayaku Co., Ltd. 828: Bisphenol A type epoxy resin, Mitsubishi Chemical Corporation HP4032D: Naphthalene novolac type epoxy resin, DIC Corporation BMI-70: Bismaleimide, Kay Kasei Co., Ltd. Company V-03: Carbodiimide, Nisshinbo Industries, Ltd.
Ingredient (D)
2E4MZ: 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals Co., Ltd. 2PHZ-PW: 2-phenyl-4,5-dihydroxymethylimidazole, manufactured by Shikoku Chemicals Co., Ltd.
Ingredient (E)
OP935: Aluminum organophosphinate, manufactured by Clariant Japan
Ingredient (E ')
FP2200: Phosphate flame retardant, ADEKA Corporation PX-200: Phosphate ester flame retardant, manufactured by Daihachi Chemical Industry
Ingredient (F)
SE2050: Silica filler, Admatechs Co., Ltd.
Ingredient (G)
Perbutyl Z: tert-butyl peroxybenzoate, NOF Corporation
Other components KBM403: Silane coupling agent, Shin-Etsu Chemical Co., Ltd. DISPERBYK2009: Dispersant, manufactured by Big Chemie Japan

The following evaluation was performed on the created adhesive film.

Dielectric constant (ε), dielectric loss tangent (tan δ): After the adhesive film was cured by heating at 180 ° C. and peeled from the support, a test piece (40 ± 0.5 mm × 100 ± 2 mm) was cut out from the adhesive film, and the thickness Was measured. The test piece was rolled into a cylindrical shape having a length of 100 mm and a diameter of 2 mm or less, and a dielectric constant (ε) and a dielectric loss tangent (tan δ) were measured by a cavity resonator perturbation method (10 GHz).

Glass transition point Tg: measured by dynamic viscoelasticity measurement (DMA). After the adhesive film was heat-cured at 180 ° C. and peeled from the support, a test piece (10 ± 0.5 mm × 40 ± 1 mm) was cut out from the adhesive film, and the width and thickness of the test piece were measured. Thereafter, measurement was performed with DMS6100 (3 ° C./min 25-220 ° C.). The peak temperature of tanD was read and used as Tg.

Peel strength: A copper foil was bonded to both surfaces of the adhesive film with the roughened surface inside, and thermocompression bonded with a press machine (180 ° C. 60 min, 10 kgf). This test piece was cut into a width of 10 mm, peeled off by an autograph, and peel strength was measured. About the measurement result, the average value of each N = 5 was calculated.

Linear expansion coefficient: Measured with a thermal analyzer (TMA). After the adhesive film was heat-cured at 180 ° C. and peeled off from the support, a test piece (5 ± 0.5 mm × 20 ± 1 mm) was cut out from the adhesive film and measured with TMA4000S (5 ° C./min 25− 230 ° C.). 90-100 ° C. C.I. T.A. The average of E was α1, C.C. T.A. The average of E was α2.

Flame retardancy evaluation: After the adhesive film was heat-cured at 180 ° C. and peeled from the support, a test piece (50 ± 0.5 mm × 200 ± 0.5 mm) was cut out from the adhesive film, and the thickness was measured. The test piece was rolled into a cylindrical shape having a length of 200 mm and a diameter of about 15 mm and fixed to a stand. The flame of the gas burner was adjusted to a height of about 20 mm, and after burning for 3 seconds at the lower end of the film, the burning time was measured. The flame contact was repeated 3 times per sample.
Each combustion time was 10 sec or less, and those having a total combustion time of 3 times of 30 sec or less were judged to be acceptable. Tests were performed at each N = 3, and all passed were regarded as equivalent to VTM-0.

Varnish stability: The varnish containing the resin composition obtained by the above procedure was sealed in a glass bottle and allowed to stand at 25 ° C., and the stability of the solution was confirmed. The number of days until the generation of crystals, precipitates, separation of the solution, etc. were compared, and those that were stable for one week or more were marked with ◯ and those with about 3 days were marked with Δ.

Solubility: The varnish containing the resin composition obtained by the above procedure was allowed to stand at room temperature. The resin composition components were not recrystallized.

Embedding property: A film was heated and laminated on a substrate (L / S = 30/30 μm, wiring height 20 μm) patterned on the surface, and it was confirmed whether the unevenness between patterns could be embedded. Those that could be embedded without problems were marked with ◯, those that were partially insufficient were marked with △, and those that could not be embedded were marked with ×.

Filming: When an adhesive film with a support is created using the above procedure, a uniform film is obtained. ○ The mixture cannot be homogenized, causing mottled patterns or cracks during filming. Was generated and could not be formed into a film.

In Examples 1 to 12, a uniform adhesive film was obtained, and the embedding property at the time of thermocompression bonding was excellent. Further, the adhesive film was excellent in all of the high frequency electric characteristics (dielectric constant ε, dielectric loss tangent Tan δ), peel strength, and flame retardancy after heat curing. Moreover, the solubility and stability of the varnish were also excellent.
In Comparative Example 1 in which the content of the component (E) is less than 10 parts by mass, the flame resistance of the obtained adhesive film was inferior.
In Comparative Example 2 in which the content of the component (E) exceeds 50 parts by mass, a mottled pattern occurred during film formation. Moreover, the embedding property at the time of thermocompression bonding of the obtained adhesive film was inferior. Moreover, the stability of the varnish was also inferior.
In Comparative Example 3 using a phosphate-based flame retardant instead of the component (E), the obtained adhesive film had poor flame retardancy.
In Comparative Example 4 using a phosphate ester-based flame retardant instead of the component (E), the obtained adhesive film had poor flame retardancy.
In Comparative Example 5 in which a phosphate-based flame retardant was used in place of the component (E) and the blending amount of the flame retardant was increased, the flame resistance of the obtained adhesive film was excellent. Occasionally mottled patterns occurred. Moreover, the embedding property at the time of thermocompression bonding of the obtained adhesive film was inferior. Moreover, the stability of the varnish was also inferior.
In Comparative Example 6 using a polyphenylene ether having a mass average molecular weight (Mw) of more than 4000 as the component (A), when the varnish containing the resin composition obtained by the above procedure was left at room temperature, the resin composition This component was recrystallized and could not be formed into a film.

Claims (14)

1. (A) a vinyl compound having a mass average molecular weight (Mw) of 500 to 4000 represented by the following general formula (1):
   

   

   (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group. — (O—X—O) — is represented by the following structural formula (2).
   

   

   R ₈ , R ₉ , R ₁₀ , R ₁₄ , and R ₁₅ may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -(YO)-is one type of structure defined by the following structural formula (3) or two or more types of structures defined by the following structural formula (3) arranged at random.
   

   

   R ₁₆ and R ₁₇ may be the same or different and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ₁₈ and R ₁₉ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. a and b each represents an integer of 0 to 300, at least one of which is not 0. c and d represent an integer of 0 or 1. )
   (B) a thermoplastic elastomer,
   (C) a thermosetting resin other than the vinyl compound represented by the general formula (1),
   (D) a curing agent, and
   (E) containing an organic aluminum phosphinate,
   10 to 50 parts by mass of the component (E) with respect to 100 parts by mass in total of the component (A), the component (B), the component (C), the component (D), and the component (E) A resin composition characterized by containing.
2. In the component (A), — (O—X—O) — is represented by the following structural formula (4), and — (YO) — in the component (A) is represented by the following structural formula (5), or The resin composition according to claim 1, which has a structure represented by the following structural formula (6), or a structure in which the structure represented by the following structural formula (5) and the structure represented by the following structural formula (6) are randomly arranged. object.
   

   

   
3. 3. The resin composition according to claim 2, wherein — (YO) — of the component (A) has a structure represented by the structural formula (6).
4. The thermoplastic elastomer of component (B) is a styrene-butadiene block copolymer, a styrene-ethylene / butylene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, polybutadiene, and styrene- (ethylene- The resin composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of (ethylene / propylene) -styrene block copolymers.
5. The thermosetting resin of the component (C) is selected from the group consisting of biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, bismaleimide, and carbodiimide. The resin composition according to any one of claims 1 to 4, which is at least one selected.
6. The content of the thermoplastic elastomer of the component (B) is 100 parts by mass in total of the component (A), the component (B), the component (C), the component (D), and the component (E). The resin composition according to any one of claims 1 to 5, wherein the amount is 10 to 60 parts by mass.
7. The content of the thermosetting resin of the component (C) is a total of 100 masses of the component (A), the component (B), the component (C), the component (D), and the component (E). The resin composition according to any one of claims 1 to 6, which is 0.5 to 40 parts by mass with respect to parts.
8. Furthermore, (F) filler is 100 mass parts in total of the said component (A), the said component (B), the said component (C), the said component (D), the said component (E), and the said component (F). The resin composition according to any one of claims 1 to 7, wherein the resin composition is contained in an amount of 10 to 60 parts by mass.
9. The resin composition according to claim 1, further comprising (G) an organic peroxide.
10. The dielectric constant (ε) is 3.0 or less and the dielectric loss tangent (tan δ) is 0.006 or less in a frequency range of 1 to 10 GHz of the cured product of the resin composition. The resin composition as described.
11. 11. The resin composition according to claim 1, wherein the flame retardancy based on UL94 satisfies V-0 or VTM-0.
12. An adhesive film produced using the resin composition according to any one of claims 1 to 11.
13. A coverlay film produced using the resin composition according to any one of claims 1 to 11.
14. A varnish comprising the resin composition according to any one of claims 1 to 11.