阅读说明：本技术 低介电树脂组合物、成形品、薄膜、层叠薄膜、以及挠性印刷电路板 (Low dielectric resin composition, molded article, film, laminated film, and flexible printed wiring board ) 是由 今村雄一 大熊敬介 木户雅善 于 2020-04-23 设计创作，主要内容包括：提供熔融加工性良好、并且高频带下的低介电特性比液晶聚合物等低介电材料更优异的低介电树脂组合物、由该低介电树脂组合物形成的成形品及薄膜、在所述薄膜的至少一个主面层叠有金属箔的层叠薄膜、和包含所述薄膜的挠性印刷电路板。使用包含液晶聚合物(A)和具有极性基团的接枝改性聚烯烃(B)的树脂组合物作为低介电树脂组合物。低介电树脂组合物在频率10GHz下的介电常数优选为2.80以下。低介电树脂组合物在频率10GHz下的介电损耗角正切优选0.0025以下。(Provided are a low dielectric resin composition having good melt processability and having low dielectric characteristics at high frequency bands superior to those of low dielectric materials such as liquid crystal polymers, a molded article and a film formed from the low dielectric resin composition, a laminated film in which a metal foil is laminated on at least one main surface of the film, and a flexible printed wiring board including the film. A resin composition comprising a liquid crystalline polymer (A) and a graft-modified polyolefin (B) having a polar group is used as a low dielectric resin composition. The dielectric constant of the low dielectric resin composition at a frequency of 10GHz is preferably 2.80 or less. The dielectric loss tangent of the low dielectric resin composition at a frequency of 10GHz is preferably 0.0025 or less.)

1. A low dielectric resin composition comprising a liquid crystalline polymer (A) and a graft-modified polyolefin (B) having a polar group,

the relative dielectric constant of the low dielectric resin composition at a frequency of 10GHz is a value lower than the relative dielectric constant of the liquid crystal polymer (A) at a frequency of 10GHz, and the dielectric loss tangent at a frequency of 10GHz is a value lower than the dielectric loss tangent of the graft modified polyolefin (B) at a frequency of 10 GHz.

2. The low dielectric resin composition according to claim 1, having a dielectric constant of 2.80 or less at a frequency of 10 GHz.

3. The low dielectric resin composition according to claim 1 or 2, which has a dielectric loss tangent of 0.0025 or less at a frequency of 10 GHz.

4. The low dielectric resin composition according to any one of claims 1 to 3, wherein a sea-island structure comprising the liquid crystal polymer (A) and the graft-modified polyolefin (B) is formed in at least a part thereof.

5. The low dielectric resin composition according to claim 4, which comprises the sea-island structure in which the liquid crystal polymer (A) is a sea component, or a co-continuous structure comprising the sea-island structure and comprising the liquid crystal polymer (A) and the graft modified polyolefin (B) together forming a continuous phase.

6. The low dielectric resin composition according to any one of claims 1 to 5, wherein the liquid crystal polymer (A) has a melting point of 250 ℃ or higher.

7. The low dielectric resin composition of any of claims 1-6, wherein the polar group is an epoxy group.

8. The low dielectric resin composition according to any one of claims 1 to 7, wherein the graft-modified polyolefin (B) is a polyolefin graft-modified with glycidyl (meth) acrylate and styrene.

9. The low dielectric resin composition according to any one of claims 1 to 8, wherein the graft modified polyolefin (B) has a melting point of 200 ℃ or higher.

10. A molded article comprising the low dielectric resin composition according to any one of claims 1 to 9.

11. A film formed from the low dielectric resin composition according to any one of claims 1 to 9.

12. A laminated film comprising a metal foil laminated on at least one main surface of the film according to claim 11.

13. A flexible printed circuit board comprising the film of claim 11.

Technical Field

The present invention relates to a low dielectric resin composition, a molded article and a film formed from the low dielectric resin composition, a laminated film in which a metal foil is laminated on at least one main surface of the film, and a flexible printed wiring board including the film formed from the low dielectric resin composition.

Background

In recent years, communication devices such as smart phones and electronic devices such as new-generation televisions are required to transmit and receive large-capacity data at high speed. Along with this, the frequency of electric signals has been increased. Specifically, in the field of wireless communication, the introduction of the 5 th generation mobile communication system (5G) is expected in about 2020. It is considered that a high frequency band of 10GHz or more is used when the 5 th generation mobile communication system is introduced.

However, as the frequency of the signal used becomes higher, the quality of the output signal of erroneous recognition of information may be degraded, that is, the transmission loss may become larger. The transmission loss includes a conductor loss due to a conductor and a dielectric loss due to an insulating resin constituting an electric and electronic component such as a substrate in an electronic device or a communication device, and the conductor loss is proportional to the frequency to the power of 0.5 and the dielectric loss is proportional to the frequency to the power of 1.

Therefore, in order to reduce the transmission loss, a low dielectric material having a low relative dielectric constant and a low dielectric loss tangent, which are factors related to the dielectric loss, is required. In view of such circumstances, for example, the use of liquid crystal polymers as low dielectric materials for use in high frequency bands has been studied (see patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2012 and 077117

Disclosure of Invention

Problems to be solved by the invention

However, low dielectric resins such as liquid crystal polymers and compositions thereof are required to have further low dielectric characteristics in order to further reduce transmission loss.

In addition, the liquid crystal polymer has a problem of difficulty in melt processing due to its anisotropy. For example, when a liquid crystal polymer is made into a film by an extrusion method, which is a typical film production method, a molten liquid crystal polymer discharged from a die immediately sags due to a decrease in melt viscosity caused by a shear force in a discharge direction, and it is difficult to take up the film.

Even if the film can be taken up, the resulting film is very easily broken due to the orientation of the liquid crystal polymer in the film.

Further, the liquid crystal polymer has a problem that it is difficult to produce pellets by cutting strands due to its anisotropy. Specifically, for example, there is a problem that strands cannot be cut, or a clean cut surface cannot be formed even if cutting is possible, and burrs are likely to occur in pellets. The unevenness of the pellet shape and the burrs in the pellets are factors that cause instability in the metering of the liquid crystal polymer during the molding of the liquid crystal polymer.

The present invention has been made in view of the above problems, and an object thereof is to provide a low dielectric resin composition which has good melt processability and has low dielectric characteristics in a high frequency band more excellent than those of low dielectric materials such as liquid crystal polymers, a molded article and a film formed from the low dielectric resin composition, a laminated film in which a metal foil is laminated on at least one main surface of the film, and a flexible printed wiring board including the film.

Means for solving the problems

The present inventors have conducted extensive studies to solve the above problems, and as a result, the present invention has been completed.

That is, the present invention provides the following (1) to (12).

(1) A low dielectric resin composition comprising a liquid crystalline polymer (A) and a graft-modified polyolefin (B) having a polar group,

the relative dielectric constant of the low dielectric resin composition at a frequency of 10GHz is a value lower than the relative dielectric constant of the liquid crystal polymer (A) at a frequency of 10GHz, and the dielectric loss tangent at a frequency of 10GHz is a value lower than the dielectric loss tangent of the graft modified polyolefin (B) at a frequency of 10 GHz.

(2) The low dielectric resin composition according to (1), which has a relative dielectric constant of 2.80 or less at a frequency of 10 GHz.

(3) The low dielectric resin composition according to (1) or (2), which has a dielectric loss tangent of 0.0025 or less at a frequency of 10 GHz.

(4) The low dielectric resin composition according to any one of (1) to (3), wherein a sea-island structure comprising a liquid crystal polymer (A) and a graft-modified polyolefin (B) is formed in at least a part thereof.

(5) The low dielectric resin composition according to (4), which comprises a sea-island structure in which the liquid crystal polymer (A) is a sea component, or a co-continuous structure comprising a sea-island structure and a continuous phase formed by the liquid crystal polymer (A) and the graft modified polyolefin (B).

(6) The low dielectric resin composition according to any one of (1) to (5), wherein the melting point of the liquid crystal polymer (A) is 250 ℃ or higher.

(7) The low dielectric resin composition as described in any one of (1) to (6), wherein the polar group is an epoxy group.

(8) The low dielectric resin composition according to any one of (1) to (7), wherein the graft-modified polyolefin (B) is a polyolefin graft-modified with glycidyl (meth) acrylate and styrene.

(9) The low dielectric resin composition according to any one of (1) to (8), wherein the graft modified polyolefin (B) has a melting point of 200 ℃ or higher.

(10) A molded article comprising the low dielectric resin composition according to any one of (1) to (9).

(11) A film comprising the low dielectric resin composition according to any one of (1) to (9).

(12) A laminated film comprising a metal foil laminated on at least one main surface of the film of (11).

(13) A flexible printed circuit board comprising the film of (11).

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a low dielectric resin composition having good melt processability and having low dielectric characteristics at high frequency band superior to those of low dielectric materials such as liquid crystal polymers, a molded article and a film formed from the low dielectric resin composition, a laminated film in which a metal foil is laminated on at least one main surface of the film, and a flexible printed wiring board including the film.

Detailed Description

Low dielectric resin composition

The low dielectric resin composition is a resin composition comprising a liquid crystal polymer (a) and a graft-modified polyolefin (B) having a polar group.

The relative dielectric constant of the low dielectric resin composition at 10GHz is a value lower than the relative dielectric constant of the liquid crystal polymer (A) at a frequency of 10 GHz. Further, the dielectric loss tangent at 10GHz of the low dielectric resin composition is a value lower than the dielectric loss tangent at frequency 10GHz of the graft-modified polyolefin (B).

The dielectric loss tangent of the low dielectric resin composition at 10GHz is preferably 0.0025 or less. The lower limit of the dielectric loss tangent is not particularly limited. The lower limit of the dielectric loss tangent may be, for example, 0.0005 or more, or 0.0010 or more.

The relative dielectric constant of the low dielectric resin composition at a frequency of 10GHz is preferably 2.80 or less. The lower limit of the relative dielectric constant is not particularly limited. The lower limit of the relative permittivity may be, for example, 2.00 or more, or 2.50 or more.

The low dielectric resin composition can be suitably used for electric and electronic parts used in a high frequency band, information communication devices, parts of the information communication devices, and the like, taking advantage of low dielectric characteristics.

The low dielectric resin composition can be formed into various phases depending on various conditions such as a mixing ratio of the liquid crystal polymer (a) and the graft-modified polyolefin (B), a melting point of the liquid crystal polymer (a), a melting point of the graft-modified polyolefin (B), a difference between the melting point of the liquid crystal polymer (a) and the melting point of the graft-modified polyolefin (B), a temperature at the time of mixing the liquid crystal polymer (a) and the graft-modified polyolefin (B), and a modification ratio of the graft-modified polyolefin (B).

In the low dielectric resin composition, it is preferable that a sea-island structure comprising the liquid crystal polymer (a) and the graft-modified polyolefin (B) is formed in at least a part thereof. In the sea-island structure, either one of the liquid crystal polymer (a) and the graft-modified polyolefin (B) may be a sea component.

Here, the phrase "the sea-island structure is formed in at least a part of the low dielectric resin composition" means that the sea-island structure is observed in at least 1 region out of any 3 observation target regions having a size of 100 μm × 100 μm when a cross section of a sample of the low dielectric resin composition is observed with an electron microscope (SEM).

In the case of this phase, anisotropy derived from the properties of the liquid crystal polymer (a) is relaxed, and the melt processability of the low dielectric resin composition is good.

When the sea-island structure is formed in the low dielectric resin composition, the low dielectric resin composition preferably has a sea-island structure in which the liquid crystal polymer (a) is a sea component, or a co-continuous structure which has a sea-island structure and in which the liquid crystal polymer (a) and the graft-modified polyolefin (B) form a continuous phase.

Here, the term "the liquid crystal polymer (a) or the graft modified polyolefin (B) forms a continuous phase" means that when a cross section of a sample of the low dielectric resin composition is observed with an electron microscope (SEM), the liquid crystal polymer (a) or the graft modified polyolefin (B) forms a region whose outer periphery is not closed in a visual field.

The low dielectric resin composition including a sea-island structure and a co-continuous structure means that, when a cross section of a sample of the low dielectric resin composition is observed with an electron microscope (SEM), the co-continuous structure is observed in at least 1 region of arbitrary 3 observation target regions where the sea-island structure is observed and the size is 100 μm × 100 μm.

In this case, the liquid crystal polymer (a) forms a continuous phase in the sea component or the co-continuous structure, and thus the low dielectric resin composition easily exhibits excellent heat resistance derived from the liquid crystal polymer (a).

The low dielectric resin composition is produced by mixing a liquid crystal polymer (A) and a graft-modified polyolefin (B).

The method for mixing the liquid crystal polymer (a) and the graft-modified polyolefin (B) is not particularly limited. Preferred mixing methods include a method using a melt kneading apparatus such as a single-screw extruder or a twin-screw extruder.

The conditions for mixing the liquid crystal polymer (a) and the graft-modified polyolefin (B) are not particularly limited as long as the liquid crystal polymer (a) and the graft-modified polyolefin (B) can be uniformly mixed and each component contained in the low dielectric resin composition is not excessively thermally decomposed or sublimated. When a melt kneading apparatus is used, for example, melt kneading is carried out at a temperature which is preferably 5 ℃ or more and 100 ℃ or less, more preferably 10 ℃ or more and 50 ℃ or less higher than the melting point of the higher one of the melting point of the liquid crystal polymer (a) and the melting point of the graft modified polyolefin.

The low dielectric resin composition may contain other resins than the liquid crystal polymer (a) and the graft modified polyolefin (B) within a range not hindering the object of the present invention. The total ratio of the mass of the liquid crystal polymer (a) to the mass of the graft-modified polyolefin (B) is typically preferably 80 mass%, more preferably 90 mass% or more, further preferably 95 mass% or more, and particularly preferably 100 mass% with respect to the total mass of the resin components contained in the low dielectric resin composition.

Examples of the other resin include non-liquid crystal polyesters such as polyolefin, polyethylene terephthalate, and polybutylene terephthalate, polyamides, polyesteramides, polyimides, polyamideimides, polycarbonates, polyacetals, polyphenylene sulfides, polyphenylene oxides, polysulfones, polyether sulfones, polyether imides, silicone resins, and fluororesins, which are not graft-modified.

The low dielectric resin composition may contain an inorganic filler as needed. Examples of the inorganic filler include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, montmorillonite, gypsum, glass flake, glass fiber, milled glass fiber, carbon fiber, alumina fiber, silica alumina fiber, aluminum borate whisker, potassium titanate fiber, and the like. The inorganic filler may be used alone, or 2 or more kinds may be used in combination.

The amount of these inorganic fillers to be used may be determined as appropriate depending on the use of the low dielectric resin composition within a range not to impair the low dielectric characteristics of the low dielectric resin composition. For example, in the case of forming a film using a low dielectric resin composition, the upper limit of the amount of the inorganic filler is determined within a range not significantly impairing the mechanical strength of the film.

The low dielectric resin composition may further contain various additives such as an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, a colorant, a rust inhibitor, a crosslinking agent, a foaming agent, a fluorescent agent, a surface smoothing agent, a surface gloss improver, and a mold release improver, if necessary.

These additives may be used alone, or 2 or more of them may be used in combination.

Hereinafter, the liquid crystal polymer (a) and the graft-modified polyolefin (B) will be described.

< liquid Crystal Polymer >

The liquid crystal polymer is a polymer showing optical anisotropy when melted, and a polymer recognized as a thermotropic liquid crystal polymer by those skilled in the art may be used without particular limitation. The optical anisotropy at the time of melting can be confirmed by a conventional polarization inspection method using an orthogonal polarizer.

The liquid crystal polymer is typically produced by polycondensing a monomer mixture containing an acylate of a monomer having a phenolic hydroxyl group. The polycondensation is preferably carried out in the presence of a catalyst. Examples of the catalyst include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, and nitrogen-containing heterocyclic compounds such as 1-methylimidazole.

The amount of the catalyst used is preferably 0.1 part by mass or less, for example, relative to 100 parts by mass of the amount of the monomer mixture (a).

As described above, the monomer mixture is a mixture of monomers including an acylate of a monomer having a phenolic hydroxyl group. The monomer mixture may contain a monomer having no phenolic hydroxyl group such as an aromatic dicarboxylic acid typified by terephthalic acid and isophthalic acid.

As the method for producing the monomer mixture, a method of acylating a monomer mixture containing a monomer having a phenolic hydroxyl group to obtain a monomer mixture containing an acylate of the monomer having a phenolic hydroxyl group is preferable from the viewpoints of cost and production time.

Examples of the constituent unit constituting the liquid crystal polymer include an aromatic oxycarbonyl unit, an aromatic dicarbonyl unit, an aromatic dioxy unit, an aromatic aminooxy unit, an aromatic diamino unit, an aromatic aminocarbonyl unit, and an aliphatic dioxy unit.

The liquid crystal polymer may further contain an amide bond or a thioester bond as a bond other than an ester bond.

An aromatic oxycarbonyl unit is a unit derived from an aromatic hydroxycarboxylic acid.

Suitable specific examples of the aromatic hydroxycarboxylic acid include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4 ' -hydroxyphenyl-4-benzoic acid, 3 ' -hydroxyphenyl-4-benzoic acid, 4 ' -hydroxyphenyl-3-benzoic acid, and alkyl, alkoxy or halogen substituents thereof.

Ester-forming derivatives such as ester derivatives and acid halides of aromatic hydroxycarboxylic acids can also be suitably used in the same manner as the aromatic hydroxycarboxylic acids.

Among these aromatic hydroxycarboxylic acids, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable from the viewpoint of easy adjustment of the mechanical properties and melting point of the resulting liquid crystal polymer.

The aromatic dicarbonyl repeating unit is a unit derived from an aromatic dicarboxylic acid.

Suitable specific examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 1, 4-naphthalenedicarboxylic acid, and 4, 4' -dicarboxybiphenyl, and alkyl, alkoxy, and halogen substituents thereof.

Ester-forming derivatives such as ester derivatives and acid halides of aromatic dicarboxylic acids can also be suitably used in the same manner as the aromatic dicarboxylic acids.

Among these aromatic dicarboxylic acids, terephthalic acid and 2, 6-naphthalenedicarboxylic acid are preferable because the mechanical properties, heat resistance, melting point temperature and moldability of the resulting liquid crystal polymer can be easily adjusted to appropriate levels.

The aromatic dioxy repeating unit is a unit derived from an aromatic diol.

Suitable specific examples of the aromatic diol include hydroquinone, resorcinol, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4 '-dihydroxybiphenyl, 3' -dihydroxybiphenyl, 3,4 '-dihydroxybiphenyl, 4' -dihydroxybiphenyl ether, alkyl, alkoxy, and halogen substituents thereof.

Among these aromatic diols, hydroquinone, resorcinol, and 4, 4' -dihydroxybiphenyl are preferable, from the viewpoints of reactivity at the time of polycondensation, characteristics of the obtained liquid crystal polymer, and the like.

The aromatic amino oxy unit is a unit derived from an aromatic hydroxylamine.

Suitable specific examples of the aromatic hydroxylamine include aromatic hydroxylamines such as p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthol, 8-amino-2-naphthol, and 4-amino-4' -hydroxybiphenyl, and alkyl, alkoxy, and halogen substituents thereof.

An aromatic diamino unit is a unit derived from an aromatic diamine.

Suitable examples of the aromatic diamine include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1, 5-diaminonaphthalene and 1, 8-diaminonaphthalene, and alkyl, alkoxy and halogen substituents thereof.

An aromatic aminocarbonyl unit is a unit derived from an aromatic aminocarboxylic acid.

Suitable specific examples of the aromatic aminocarboxylic acid include aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, and 6-amino-2-naphthoic acid, and alkyl, alkoxy, and halogen substituents thereof.

Ester-forming derivatives such as ester derivatives and acid halides of aromatic aminocarboxylic acids can also be suitably used as monomers for producing liquid crystal polymers.

Specific examples of the monomer providing the aliphatic dioxy unit include aliphatic diols such as ethylene glycol, 1, 4-butanediol, and 1, 6-hexanediol, and acylates thereof.

Further, a liquid crystal polymer containing an aliphatic dioxy unit can also be obtained by reacting a polymer containing an aliphatic dioxy unit such as polyethylene terephthalate or polybutylene terephthalate with the above-mentioned aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, and an acylate, ester derivative, acid halide or the like thereof.

The liquid crystal polymer may also contain thioester linkages. Examples of the monomer providing such a bond include a mercapto aromatic carboxylic acid, an aromatic dithiol, and a hydroxy aromatic thiol.

The amount of these monomers to be used is preferably 10 mol% or less based on the total amount of monomers providing the aromatic oxycarbonyl repeating unit, the aromatic dicarbonyl repeating unit, the aromatic dioxy repeating unit, the aromatic aminoxy repeating unit, the aromatic diamino repeating unit, the aromatic aminocarbonyl repeating unit, the aromatic oxydicarbonyl repeating unit, and the aliphatic dioxy repeating unit.

Suitable examples of the liquid crystal polymer include the following 1) to 25).

1) 4-hydroxybenzoic acid/2-hydroxy-6-naphthoic acid copolymer

2) 4-hydroxybenzoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl copolymer

3) 4-hydroxybenzoic acid/terephthalic acid/isophthalic acid/4, 4' -dihydroxybiphenyl copolymer

4) 4-hydroxybenzoic acid/terephthalic acid/isophthalic acid/4, 4' -dihydroxybiphenyl/hydroquinone copolymer

5) 4-hydroxybenzoic acid/terephthalic acid/hydroquinone copolymer

6) 4-hydroxybenzoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl/hydroquinone copolymer

7) 2-hydroxy-6-naphthoic acid/terephthalic acid/hydroquinone copolymer

8) 4-hydroxybenzoic acid/2-hydroxy-6-naphthoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl copolymer

9) 2-hydroxy-6-naphthoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl copolymer

10) 4-hydroxybenzoic acid/2-hydroxy-6-naphthoic acid/terephthalic acid/hydroquinone copolymer

11) 4-hydroxybenzoic acid/2-hydroxy-6-naphthoic acid/terephthalic acid/hydroquinone/4, 4' -dihydroxybiphenyl copolymer

12) 4-hydroxybenzoic acid/2, 6-naphthalenedicarboxylic acid/4, 4' -dihydroxybiphenyl copolymer

13) 4-hydroxybenzoic acid/terephthalic acid/2, 6-naphthalenedicarboxylic acid/hydroquinone copolymer

14) 4-hydroxybenzoic acid/2, 6-naphthalenedicarboxylic acid/hydroquinone copolymer

15) 4-hydroxybenzoic acid/2-hydroxy-6-naphthoic acid/2, 6-naphthalenedicarboxylic acid/hydroquinone copolymer

16) 4-hydroxybenzoic acid/terephthalic acid/2, 6-naphthalenedicarboxylic acid/hydroquinone/4, 4' -dihydroxybiphenyl copolymer

17) 4-hydroxybenzoic acid/terephthalic acid/4-aminophenol copolymer

18) 2-hydroxy-6-naphthoic acid/terephthalic acid/4-aminophenol copolymer

19) 4-hydroxybenzoic acid/2-hydroxy-6-naphthoic acid/terephthalic acid/4-aminophenol copolymer

20) 4-hydroxybenzoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl/4-aminophenol copolymer

21) 4-hydroxybenzoic acid/terephthalic acid/ethylene glycol copolymer

22) 4-hydroxybenzoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl/ethylene glycol copolymer

23) 4-hydroxybenzoic acid/2-hydroxy-6-naphthoic acid/terephthalic acid/ethylene glycol copolymer

24) 4-hydroxybenzoic acid/2-hydroxy-6-naphthoic acid/terephthalic acid/4, 4' -dihydroxybiphenyl/ethylene glycol copolymer

25) 4-hydroxybenzoic acid/terephthalic acid/2, 6-naphthalenedicarboxylic acid/4, 4' -dihydroxybiphenyl copolymer.

As described above, the monomer mixture containing the monomer having a phenolic hydroxyl group is preferably acylated to obtain a monomer mixture containing an acylate of the monomer having a phenolic hydroxyl group. Acylation is preferably carried out by reacting a phenolic hydroxyl group with a fatty acid anhydride. As the fatty acid anhydride, for example, acetic anhydride and propionic anhydride can be used. Acetic anhydride is preferably used from the viewpoint of cost and handleability.

The amount of the fatty acid anhydride to be used is preferably 1.0 equivalent to 1.15 equivalent, more preferably 1.03 equivalent to 1.10 equivalent, relative to the amount of the phenolic hydroxyl group.

The acylation is carried out by mixing a monomer mixture containing a monomer having a phenolic hydroxyl group with the above-mentioned fatty acid anhydride and heating to obtain a monomer mixture containing an acylate of the monomer having a phenolic hydroxyl group.

The monomer mixture containing the acylate of the monomer having a phenolic hydroxyl group obtained as above is heated, and the fatty acid by-produced by polycondensation is distilled off, thereby obtaining a liquid crystal polymer.

When the liquid crystal polymer is produced by melt polycondensation alone, the temperature of melt polycondensation is preferably 150 ℃ or more and 400 ℃ or less, and preferably 250 ℃ or more and 370 ℃ or less.

When the liquid crystal polymer is produced by two stages of melt polycondensation and solid phase polymerization described later, the temperature of melt polycondensation is preferably 120 ℃ or higher and 350 ℃ or lower, and preferably 200 ℃ or higher and 300 ℃ or lower. The time for the polycondensation reaction is not particularly limited as long as a liquid crystal polymer having a desired melting point or a desired molecular weight can be obtained. For example, the reaction time of polycondensation is preferably 30 minutes to 5 hours.

The liquid crystal polymer produced by the above method can be subjected to polycondensation by heating in a cured state (solid phase) for further increasing the molecular weight, if necessary.

The liquid crystal polymer (a) was obtained by the above-described method. The melting point of the liquid crystal polymer (a) is not particularly limited within a range not to impair the object of the present invention. The melting point of the liquid crystal polymer (A) is preferably 250 ℃ or higher, more preferably 280 ℃ or higher. On the other hand, the melting point of the liquid crystal polymer (a) is preferably 400 ℃ or lower, more preferably 350 ℃ or lower, from the viewpoint of processability, from the viewpoint of suppressing decomposition of the graft-modified polyolefin (B) during production of the low dielectric resin composition, and the like.

The melting point of the liquid crystal polymer (a) is, for example, a temperature determined from a crystal melting peak measured with a Differential scanning calorimeter (hereinafter abbreviated as DSC) at a temperature increase rate of 20 ℃/min. More specifically, the endothermic peak temperature (Tm1) observed when a sample of a liquid crystal polymer was measured at a temperature rise condition of 20 ℃/min from room temperature was observed, then, the sample was held at a temperature higher than Tm1 by 20 ℃ to 50 ℃ for 10 minutes, then, the sample was cooled to room temperature at a temperature drop condition of 20 ℃/min, then, the endothermic peak when measured again at a temperature rise condition of 20 ℃/min was observed, and the temperature at the peak top was defined as the melting point of the liquid crystal polymer. For example, DSCQ1000 manufactured by TA Instruments, Inc. can be used as the measuring device.

< graft modified polyolefin (B) >

The graft-modified polyolefin is not particularly limited as long as it is a resin obtained by graft-modifying a polyolefin and has a polar group.

The polar group herein means a polar atomic group, and is a group which is polar when the group is present in an organic compound. Specific examples of the polar group which can be introduced into the polyolefin by grafting include carboxyl groups derived from unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid; acid anhydride groups, halocarbonyl groups, carboxylic acid amide groups, imide groups, and carboxylic acid ester groups derived from derivatives of the unsaturated carboxylic acids such as acid anhydrides, acid halides, amides, imides, and esters; epoxy groups derived from epoxy group-containing vinyl monomers such as glycidyl methacrylate, glycidyl acrylate, maleic acid monoglycidyl ester, maleic acid diglycidyl ester, itaconic acid monoglycidyl ester, itaconic acid diglycidyl ester, allyl succinic acid monoglycidyl ester, allyl succinic acid diglycidyl ester, p-styrenecarboxylate, allyl glycidyl ether, methacryloyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, 3, 4-epoxy-1-butene, 3, 4-epoxy-3-methyl-1-butene, and vinylcyclohexene monooxide. Among these polar groups, epoxy groups are preferably contained from the viewpoint of easy availability of a low dielectric resin composition in a preferred phase state, good adhesion between the low dielectric resin composition and another material when the low dielectric resin composition is used in contact with another material, and the like.

The epoxy group may react with a functional group of the liquid crystal polymer (a) such as a phenolic hydroxyl group or a carboxyl group. Therefore, the graft modified polyolefin (B) having an epoxy group as a polar group has a moderate affinity with the liquid crystal polymer (a) in the low dielectric resin composition, and can easily form a preferable phase structure such as a sea-island structure.

The island diameter in the sea-island structure is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 10 μm or less. The lower limit of the island diameter is not particularly limited, and may be, for example, 1 μm or more, 2 μm or more, or 3 μm or more.

With the miniaturization and thinning of various electric and electronic devices, a thin film to be applied to the devices is also required to have a thickness of, for example, 100 μm or less. Considering that the thickness of the thin film formed using the low dielectric resin composition is often 100 μm or less, the island diameter is preferably in the range of 1 μm or more and 100 μm or less in terms of being able to obtain the effect brought about by the layer structure being a sea-island structure and suppress the fluctuation of the film characteristics.

The phrase "the island diameter is X μm or less" means that 90% or more, usually 95% or more, and typically 99% or more of the island phase as a whole of the island phase in the discontinuous region has a size of X μm or less. The phrase "the island diameter is Y μm or more" means that 90% or more, usually 95% or more, and typically 99% or more of the island phases in the discontinuous region have a size of X μm or more.

Here, "diameter" generally refers to the diameter of the island. The shape of the island is significantly different from the circular shape, and the major axis (the length of the long side of the rectangle circumscribing the island) is defined as the "diameter". Here, the major axis means the length of the long side of a rectangle circumscribing the island or the length of one side of a square circumscribing the island.

Examples of the method for confirming the island diameter include the following methods: a film formed using a low dielectric resin composition as in the example described later was embedded in a thermosetting resin, the cross section in the thickness direction was polished with an ion beam to expose the cross section of the film, and the cross section of the film was observed with a scanning electron microscope.

The amount of modification by the vinyl monomer having an epoxy group in the graft-modified polyolefin (B) having an epoxy group is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less. The lower limit of the amount of modification by the epoxy group-containing vinyl monomer is not particularly limited within a range not to impair the object of the present invention. The lower limit may be, for example, 0.1 mass% or more, 0.3 mass% or more, or 0.5 mass% or more.

When the amount of modification by the vinyl monomer having an epoxy group of the graft-modified polyolefin (B) having an epoxy group is 0.1 mass% or more and 10 mass% or less, a low dielectric resin composition having excellent processability and low dielectric characteristics can be obtained particularly easily by using the graft-modified polyolefin (B).

The amount of modification by the vinyl monomer having an epoxy group can be measured in accordance with JIS K7236 using a potential difference automatic titrator (AT 700, manufactured by kyoto electronics industries co., ltd.). For the measurement of the amount of modification by the vinyl monomer having an epoxy group, the graft-modified polyolefin (B) recrystallized with xylene can be used.

Typically, the graft-modified polyolefin (B) is a resin in which polyolefin is graft-modified with a vinyl monomer having a polar group in the presence of a radical polymerization initiator.

The graft-modified polyolefin (B) is preferably a polyolefin graft-modified with a polar group-containing vinyl monomer and an aromatic vinyl monomer, and more preferably a polyolefin graft-modified with glycidyl (meth) acrylate and styrene.

Examples of the polyolefin include chain polyolefins such as polyethylene, polypropylene, poly-1-butene, polyisobutylene, polymethylpentene, propylene-ethylene copolymers, ethylene-propylene-diene copolymers, ethylene/1-butene copolymers, and ethylene/octene copolymers; cyclic polyolefins such as copolymers of cyclopentadiene and ethylene and/or propylene.

Among these polyolefins, polymethylpentene, polyethylene, polypropylene and propylene-ethylene copolymer are preferable from the viewpoint of easiness of modification reaction, and polymethylpentene is more preferable from the viewpoint of heat resistance and low dielectric characteristics.

Examples of the radical polymerization initiator that can be used for graft modification of polyolefin include ketone peroxides such as methyl ethyl ketone peroxide and methyl acetoacetate peroxide; peroxyketals such as 1, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, n-butyl 4, 4-bis (t-butylperoxy) valerate, and 2, 2-bis (t-butylperoxy) butane; hydroperoxides such as PERMENTA hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, dicumyl hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, α' -bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as bis (3-methyl-3-methoxybutyl) peroxydicarbonate and bis (2-methoxybutyl) peroxydicarbonate, t-butyl peroxyoctoate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy3, 5, 5-trimethylhexanoate, t-butyl peroxyisopropylcarbonate, 2, 5-dimethyl-2, 5-di (benzoyl peroxide) hexane, t-butyl peroxyacetate, t-butyl peroxybenzoate, and di-t-butyl peroxyisophthalate. The radical polymerization initiators may be used singly or in combination of 2 or more.

The amount of the radical polymerization initiator to be used is not particularly limited as long as the graft modification reaction proceeds well. The amount of the radical polymerization initiator to be used is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 0.2 part by mass or more and 5 parts by mass or less, per 100 parts by mass of the polyolefin.

Examples of the vinyl monomer having a polar group which can be used for graft modification include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid; derivatives of these unsaturated carboxylic acids such as acid anhydrides, acid halides, amides, imides, and esters; epoxy group-containing vinyl monomers such as glycidyl methacrylate, glycidyl acrylate, maleic acid monoglycidyl ester, maleic acid diglycidyl ester, itaconic acid monoglycidyl ester, itaconic acid diglycidyl ester, allyl succinic acid monoglycidyl ester, allyl succinic acid diglycidyl ester, p-vinylcarboxylic acid glycidyl ester, allyl glycidyl ether, methacryloyl glycidyl ether, styrene-p-glycidyl ether, p-glycidylstyrene, 3, 4-epoxy-1-butene, 3, 4-epoxy-3-methyl-1-butene, and vinylcyclohexene monooxide.

Among these, epoxy group-containing vinyl monomers are preferable, glycidyl methacrylate and glycidyl acrylate are more preferable, and glycidyl methacrylate is particularly preferable.

The polar group-containing vinyl monomers may be used singly or in combination of 2 or more.

The amount of the polar group-containing vinyl monomer to be used for graft modification of the polyolefin is preferably 0.1 part by mass or more and 12 parts by mass or less, more preferably 0.5 part by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the polyolefin.

By using the polyolefin modified with the polar group-containing vinyl monomer in an amount within the above range, a low dielectric resin composition exhibiting desired low dielectric characteristics in a preferred phase state can be easily obtained.

As described above, the graft-modified polyolefin (B) is preferably a polyolefin graft-modified with a vinyl monomer having a polar group and an aromatic vinyl monomer.

This is because: by using a vinyl monomer having a polar group and an aromatic vinyl monomer in combination, the graft reaction is stabilized, and thus, the vinyl monomer having a polar group can be easily grafted in a desired amount.

Specific examples of the aromatic vinyl monomer include styrene; alkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, α -methylstyrene, β -methylstyrene, dimethylstyrene, and trimethylstyrene; chlorostyrenes such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, α -chlorostyrene, β -chlorostyrene, dichlorostyrene, and trichlorostyrene; bromostyrenes such as o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, and tribromostyrene; fluorostyrenes such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, and trifluorostyrene; nitrostyrenes such as o-nitrostyrene, m-nitrostyrene, p-nitrostyrene, dinitrostyrene, and trinitrostyrene; hydroxystyrenes such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxy styrene, and trihydroxy styrene; and dienylbenzenes such as o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, o-diisopropenylbenzene, m-diisopropenylbenzene, and p-diisopropenylbenzene.

Among these aromatic vinyl monomers, styrene, α -methylstyrene, p-methylstyrene, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, or a divinylbenzene isomer mixture is preferable in terms of low cost, and styrene is particularly preferable.

The aromatic vinyl monomers may be used singly or in admixture of 2 or more.

The amount of the polar group-containing aromatic vinyl monomer used for graft modification of the polyolefin is preferably 0.1 part by mass or more and 12 parts by mass or less, more preferably 0.5 part by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 8 parts by mass or less, based on 100 parts by mass of the polyolefin.

The melting point of the graft-modified polyolefin (B) is preferably 80 ℃ or higher, more preferably 100 ℃ or higher, and still more preferably 200 ℃ or higher, from the viewpoint of ease of melt-kneading with the liquid crystal polymer (A). The upper limit of the melting point of the graft-modified polyolefin (B) is not particularly limited, but is preferably 350 ℃ or lower, more preferably 300 ℃ or lower.

The low dielectric resin composition described above is processed into various molded articles by known various production methods such as injection molding, extrusion molding, blow molding, and solution casting.

Since the low dielectric resin composition described above is excellent in low dielectric characteristics at high frequency bands, it is preferable to process the composition into a thin film and produce a flexible printed wiring board having low transmission loss using the thin film.

Examples of suitable methods for producing a thin film using the low dielectric resin composition include the following methods 1) and 2).

1) Melt extrusion using a T die.

2) Solution casting method.

In the solution casting method, specifically, an organic solvent solution of the low dielectric resin composition is cast on a support, and then the organic solvent is removed from the cast organic solvent solution by a method such as heating and/or pressure reduction to obtain a thin film.

The casting method is not particularly limited, and known methods such as a die Coater, a Comma Coater (registered trademark), a reverse Coater, and a knife Coater may be mentioned. As a method for removing the organic solvent, heating is preferable. As a heating method, a method using a known heating device such as a hot-air furnace or a far-infrared furnace can be cited.

The organic solvent solution of the low dielectric resin composition is obtained by, for example, mixing the low dielectric resin composition and xylene at a temperature of about 80 ℃. Note that, instead of mixing the low dielectric resin composition with xylene, 2 or more kinds of materials constituting the low dielectric resin composition may be mixed with xylene.

The thickness of the thin film formed from the low dielectric resin composition is not particularly limited, and is appropriately determined according to the application of the thin film. When a flexible printed wiring board is produced using a thin film, the thickness of the thin film is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less.

More specifically, a flexible printed wiring board is typically manufactured by etching a metal foil in a laminated film in which a film formed of the low dielectric resin composition and the metal foil are laminated to form a wiring.

The flexible printed wiring board has a high transmission speed and a low transmission loss, and thus can be suitably used as a circuit board for high-frequency applications.

Examples of the method for obtaining a laminated film in which a film formed of a low dielectric resin composition and a metal foil are laminated include the following methods I) and II).

I) A method for producing a laminated film by thermally pressing a film made of a low dielectric resin composition and a metal foil by heating and pressing.

II) a method of casting an organic solvent solution of the low dielectric resin composition on a metal foil, and removing the organic solvent from the cast organic solvent solution by heating and/or reducing pressure, etc. to obtain a laminated film.

I) In the method (3), the method and conditions for thermally and pressure-bonding the thin film formed of the low dielectric resin composition and the metal foil by heating and pressing may be appropriately selected from conventionally known methods and conditions. By including the graft modified polyolefin (B) having a somewhat low melting point in the low dielectric resin composition, the peel strength at the time of peeling the metal foil from the film can be maintained at a high strength of 5N/cm or more, and the thermocompression bonding temperature can be set low. The thermocompression bonding temperature is preferably 400 ℃ or lower, more preferably 200 ℃ or lower.

In the method of II), the method of laminating a thin film on a metal foil is the same as the method described above as the solution casting method, except that the metal foil is used as a support.

In the laminated film, the metal foil may be laminated on at least one main surface of the film, and the metal foil may be laminated only on one main surface of the film or may be laminated on both main surfaces of the film.

The metal foil to be attached to the film made of the low dielectric resin composition is not particularly limited. Examples of the material of the metal foil used for manufacturing a flexible printed wiring board for electric/electronic equipment include copper, a copper alloy, nickel, a nickel alloy (for example, 42 alloy), aluminum, an aluminum alloy, and stainless steel.

Copper foil is preferred as a metal foil used in the production of flexible printed wiring boards, from the viewpoints of excellent conductivity, workability, and high bonding strength with a film. As the copper foil, for example, a rolled copper foil, an electrolytic copper foil, or the like is preferably used.

If necessary, functional layers such as a rust-proof layer, a heat-resistant layer, and an adhesive layer may be provided on the surface of the metal foil described above.

The thickness of the metal foil is not particularly limited and is appropriately selected depending on the use of the flexible printed wiring board.

In the laminated film in which the film formed of the low dielectric resin composition and the metal foil are laminated, the peel strength as an index of difficulty in peeling the metal foil from the film is preferably 5N/cm or more.

The peel strength was measured in accordance with "6.5 peel strength" of JIS C6471. Specifically, a 1mm wide metal foil portion was peeled at a peeling angle of 90 ° and a speed of 100 mm/min, and the load at the time of peeling was measured as the peel strength.

Examples

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

[ production example 1]

(production of modified polyolefin 1)

100 parts by mass of (a1) polymethylpentene resin (TPX grade MX002, manufactured by Mitsui chemical Co., Ltd.), (b1) 1.5 parts by mass of 1, 3-bis (t-butylperoxyisopropyl) benzene (PERBUTYLP, manufactured by Nichikoku Co., Ltd.) (twin-screw extruder) supplied from a hopper port at a cylinder temperature of 230 ℃ and a screw rotation speed of 150rpmL/D63, manufactured by shenko steel products), 8 parts by mass of (c1) styrene and 8 parts by mass of (D1) glycidyl methacrylate were added from the middle of the cylinder. Thereafter, vacuum devolatilization was performed from the exhaust port, thereby obtaining pellets of a modified polyolefin resin.

The amount of glycidyl methacrylate modified was measured by a potential difference automatic titrator (AT 700, manufactured by Kyoto electronics) in accordance with JIS K7236 using a recrystallized resin precipitated when the obtained resin pellets were dissolved in xylene AT 130 ℃ and cooled again to room temperature. The modified polyolefin 1 had a glycidyl methacrylate modification amount of 2.64 mass%.

[ production example 2]

(production of modified polyolefin 2)

100 parts by mass of (a1) polymethylpentene resin (TPX grade MX002, manufactured by Mitsui chemical Co., Ltd.), (b1) 0.5 part by mass of 1, 3-bis (t-butylperoxyisopropyl) benzene (PERBUTYLP, manufactured by Nichikoku Co., Ltd.) (twin-screw extruder) supplied from a hopper port at a cylinder temperature of 230 ℃ and a screw rotation speed of 150rpmL/D63, manufactured by Kohyo Steel Co., Ltd.) was subjected to melt kneading2 parts by mass of (c1) styrene and 2 parts by mass of (d1) glycidyl methacrylate were charged into the cylinder. Thereafter, vacuum devolatilization was performed from the exhaust port, thereby obtaining pellets of a modified polyolefin resin.

The amount of glycidyl methacrylate modified was measured by a potential difference automatic titrator (AT 700, manufactured by Kyoto electronics) in accordance with JIS K7236 using a recrystallized resin precipitated when the obtained resin pellets were dissolved in xylene AT 130 ℃ and cooled again to room temperature. The modified polyolefin 2 had a glycidyl methacrylate modification amount of 0.74 mass%.

[ production example 3]

(production of modified polyolefin 3)

100 parts by mass of (a1) polymethylpentene resin (TPX grade MX002, manufactured by Mitsui chemical Co., Ltd.), (b1)1, 3-bis (t-butylperoxyisopropyl) benzene (PERBUTYLP, manufactured by Nichikoku Co., Ltd.) (2.6 parts by mass) was fed from a hopper port to a twin-screw extruder having a cylinder temperature of 230 ℃ and a screw rotation speed of 150rpm (twin-screw extruder)L/D63, manufactured by shenko steel products), 12.0 parts by mass of (c1) styrene and 12.0 parts by mass of (D1) glycidyl methacrylate were added from the middle of the cylinder. Thereafter, vacuum devolatilization was performed from the exhaust port, thereby obtaining pellets of a modified polyolefin resin.

The amount of glycidyl methacrylate modified was measured by a potential difference automatic titrator (AT 700, manufactured by Kyoto electronics) in accordance with JIS K7236 using a recrystallized resin precipitated when the obtained resin pellets were dissolved in xylene AT 130 ℃ and cooled again to room temperature. The modified polyolefin 2 had a glycidyl methacrylate modification amount of 4.29 mass%.

[ production example 4]

(production of modified polyolefin 4)

100 parts by mass of (a1) polymethylpentene resin (TPX grade MX002, manufactured by Mitsui chemical Co., Ltd.), (b1)1, 3-di (t-butylperoxyisopropyl) benzene (manufactured by Nichigan Co., Ltd.: PERBUTYLP)0.25 part by mass were fed from a hopper portTo a twin-screw extruder set at a cylinder temperature of 230 ℃ and a screw rotation speed of 150rpm (L/D63, manufactured by shenko steel products), 1 part by mass of (c1) styrene and 1 part by mass of (D1) glycidyl methacrylate were added from the middle of the cylinder. Thereafter, vacuum devolatilization was performed from the exhaust port, thereby obtaining pellets of a modified polyolefin resin.

The amount of glycidyl methacrylate modified was measured by a potential difference automatic titrator (AT 700, manufactured by Kyoto electronics) in accordance with JIS K7236 using a recrystallized resin precipitated when the obtained resin pellets were dissolved in xylene AT 130 ℃ and cooled again to room temperature. The modified polyolefin 2 had a glycidyl methacrylate modification amount of 0.35 mass%.

[ examples 1 to 12 and comparative examples 1 to 6 ]

In examples and comparative examples, a wholly aromatic liquid crystalline polyester resin having a melting point of 280 ℃ was used as the liquid crystalline polymer (A) (component (A)). In the examples, modified polyolefins 1 to 4 obtained in production examples 1 to 4 were used as the graft-modified polyolefin (B) (component (B)).

In comparative examples, unmodified polymethylpentene and an ethylene/glycidyl methacrylate/methyl acrylate/vinyl acetate copolymer (BONDFAST 7L (BF-7L) manufactured by Sumitomo chemical Co., Ltd.) were used as resins to be mixed with the liquid crystal polymer (A). BONDFAST 7L is a non-graft-modified resin having an epoxy group as a polar group.

(ii) feeding the respective materials in the amounts shown in tables 1 to 4 from a hopper port to a twin-screw extruder set at a cylinder temperature of 300 ℃ and a screw rotation speed of 150 rpm: (40, manufactured by TECHNOLOGICAL CORPORATION) and melt-kneaded to obtain resin compositions of examples and comparative examples. In comparative examples 1 to 4, the liquid crystal polymer (A), the modified polyolefin 1, the modified polyolefin 2, and,Or BONDFAST 7L alone. The resins or resin compositions of the examples and comparative examples were evaluated for relative permittivity, dielectric loss tangent, heat resistance, and processability by the following methods. The evaluation results are shown in tables 1 to 4.

[ relative dielectric constant, dielectric loss tangent ]

As a measuring apparatus, a cavity resonator perturbation complex dielectric constant evaluation apparatus was used to measure the dielectric constant and the dielectric loss tangent of the resin composition obtained at the following frequencies.

Measuring frequency: 10GHz

The measurement conditions were as follows: the temperature is 22-24 ℃ and the humidity is 45-55 percent

Measurement of the sample: the sample left standing under the aforementioned measurement conditions for 24 hours was used.

[ Heat resistance ]

As the measuring apparatus, a dynamic viscoelasticity measuring apparatus was used to measure a storage modulus of 10⁷Temperature (. degree. C.) under MPa.

The sample assay range; width 5mm, distance between clamps 20mm

The measurement temperature range; 25-260 deg.C

The rate of temperature rise; 5 ℃ per minute

Strain amplitude; 0.1 percent of

Measuring the frequency; 1Hz

Minimum tension/compression force; 0.1g

An initial value of force amplitude; 100g

[ processability ]

For using a twin-screw extruder (L/D40, manufactured by techinovel CORPORATION) was water-cooled, and the workability at the time of cutting with a pelletizer was evaluated as follows.

Very good: cylindrical pellets obtained without crack defects

O: some of the particles contained a crack defect and became a flat shape.

X: the strand could not be cut and the pellet could not be obtained. Or a majority of the pellets contain flash, crack defects.

[ phase Structure ]

The phase structure of each composition was confirmed by microscopic observation. Observations were classified according to the following criteria. The observation results are set forth in table 1.

A: sea-island structure ((A) component is sea)

B: island structure ((A) composition is island)

C: partial sea-island structure and co-continuous structure

D: phase separation

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

It is understood from the examples that a composition containing a liquid crystal polymer (A) and a graft-modified polyolefin (B) having a polar group can achieve both good low dielectric characteristics and excellent melt processability.

On the other hand, it is found from the comparative examples that at least one of the low dielectric characteristics and the melt processability is poor in a composition in which the liquid crystal polymer (a), the graft-modified polyolefin having a polar group, or the non-graft resin having a polar group is used alone or in which the non-graft resin having a polar group and the unmodified polyolefin are mixed with the liquid crystal polymer (a).

[ example 13 and comparative example 7 ]

In example 13, a double-sided copper-clad laminate film including a film formed of the resin composition and a copper foil was obtained using the resin composition obtained in example 9. In comparative example 7, a double-sided copper-clad laminate film was obtained in the same manner as in example 13, using the liquid crystal polymer (a) described in comparative example 1.

Specifically, a double-sided copper-clad laminate film was produced by the following method.

The copper foil used has a thickness of 12 μm and has a surface roughness Ra of 0.45 μm or less on the surface in contact with the film of the resin composition.

The width w of the wiring formed of the copper foil was calculated from the following equation.

Z＝(d/ε×w)^0.5

In the above formula, Z is a characteristic impedance of 50 Ω. D is the thickness of the film and is 100 μm. ε represents a dielectric constant of the resin composition.

The thermal compression bonding conditions were 360 ℃ temperature, 0.8 ton pressure and 1 m/min lamination speed.

A microstrip line having a line length of 10cm was produced using a double-sided copper-clad laminated film obtained from a film formed from a resin composition and a copper foil.

Specifically, after the drilling, through-hole plating and patterning steps, a cover film CISV1225 made of NIKKAN industires co., ltd. was heated and bonded at 160 ℃ for 90 minutes, and a portion of a pad (pad) for measurement was gold-plated to prepare a test piece in a microstrip line shape.

Using the obtained test piece, the peel strength and the transmission loss were measured.

The transmission loss was measured as a transmission loss (dB/100mm) at a frequency of 10GHz after drying at 150 ℃ for 30 minutes and conditioning the test piece for 24 hours or more in a laboratory adjusted to 23 ℃ and 55% RH, after which the transmission loss S21 parameter was measured using a network analyzer E5071C (Keysight Technologies) and a Probe Station (Probe Station) GSG 250.

The transmission loss of the test piece produced using the double-sided copper-clad laminate of example 13 was-1.9, and the transmission loss of the test piece produced using the double-sided copper-clad laminate of comparative example 7 was less than-2.1.