JP2012025848A - Liquid composition and method for production of copper-clad laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid composition which includes a liquid crystal polyester, solvent and inorganic filler and by which a copper-clad laminate having the hardly-peeling liquid crystal layer and copper foil is obtained.SOLUTION: The liquid composition is produced by blending a liquid crystal polyester, solvent and a surface-treated inorganic filler prepared by surface-treating an inorganic filler with a silane compound having ≥6C alkyl groups. The inorganic filler is preferably oxides or nitrides, and the silane compound is preferably a compound represented by formula (I): RSi(OR)(wherein Ris ≥6C alkyl; Ris alkyl; and n is 1 or 2).

Description

  The present invention relates to a liquid composition containing a liquid crystal polyester, a solvent, and an inorganic filler. Moreover, this invention relates to the method of manufacturing a copper clad laminated board using this liquid composition.

  As a method for producing a copper-clad laminate for a flexible printed wiring board having a liquid crystal polyester layer as an insulating layer, a method of removing a solvent after casting a liquid composition containing a liquid crystal polyester and a solvent on a copper foil It has been studied (see Patent Documents 1 to 5). In addition, in order to impart predetermined performance to the liquid crystal polyester layer, it has been studied to include an inorganic filler in the liquid crystal polyester layer by including an inorganic filler in the liquid composition (Patent Documents 1 to 3). 5), for example, Patent Document 2 describes that an inorganic filler is included in the liquid crystal polyester layer in order to reduce the linear expansion coefficient of the liquid crystal polyester layer. Patent Documents 3 and 5 describe that the inorganic filler is surface-treated in order to improve the affinity and adhesion between the inorganic filler and the liquid crystalline polyester. It describes that a silane compound having an epoxy group or the like is used as a surface treatment agent for the material.

JP 2002-326312 A JP 2005-342980 A JP 2007-106107 A JP 2007-129208 A JP 2009-241594 A

  The copper-clad laminate obtained by using a liquid composition containing a conventional liquid crystal polyester, a solvent, and an inorganic filler is excellent in the adhesion between the liquid crystal polyester layer and the copper foil, but has a force to peel off both. Is added, the liquid crystal polyester layer and the copper foil are likely to be broken due to the interfacial peeling because the affinity or adhesion between the inorganic filler in the liquid crystal polyester layer and the liquid crystal polyester is not sufficient. There is a problem that it is easy to peel off. Accordingly, an object of the present invention is to provide a liquid composition containing a liquid crystal polyester, a solvent, and an inorganic filler, and giving a copper clad laminate in which the liquid crystal polyester layer and the copper foil are difficult to peel off.

  In order to achieve the above object, the present invention provides a liquid composition comprising a liquid crystal polyester, a solvent, and a surface-treated inorganic filler obtained by subjecting the inorganic filler to a surface treatment with a silane compound having an alkyl group having 6 or more carbon atoms. I will provide a. Moreover, according to this invention, the manufacturing method of the copper clad laminated board which removes the said solvent after casting the said liquid composition on metal foil is also provided.

  By using the liquid composition of the present invention, a copper-clad laminate in which the liquid crystal polyester layer and the copper foil are difficult to peel can be obtained.

  The liquid crystalline polyester is a liquid crystalline polyester that exhibits liquid crystallinity in a molten state, and is preferably melted at a temperature of 450 ° C. or lower. The liquid crystal polyester may be a liquid crystal polyester amide, a liquid crystal polyester ether, a liquid crystal polyester carbonate, or a liquid crystal polyester imide. The liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer.

  A typical example of the liquid crystal polyester is obtained by polymerizing (polycondensing) an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and a compound selected from the group consisting of an aromatic diol, an aromatic hydroxyamine, and an aromatic diamine. One obtained by polymerizing a plurality of types of aromatic hydroxycarboxylic acids, one obtained by polymerizing an aromatic dicarboxylic acid and a compound selected from the group consisting of aromatic diols, aromatic hydroxyamines and aromatic diamines, and Examples include those obtained by polymerizing a polyester such as polyethylene terephthalate and an aromatic hydroxycarboxylic acid. Here, instead of part or all of the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine and aromatic diamine, a polycondensable derivative thereof may be used.

  Examples of polycondensable derivatives of compounds having a carboxyl group such as aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid include those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group, Those obtained by converting into a haloformyl group and those obtained by converting a carboxyl group into an acyloxycarbonyl group can be mentioned. Examples of polycondensable derivatives of compounds having a hydroxyl group such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines include those obtained by acylating a hydroxyl group and converting it to an acyloxyl group. It is done. Examples of the polycondensable derivative of a compound having an amino group such as aromatic hydroxyamine and aromatic diamine include those obtained by acylating an amino group and converting it to an acylamino group.

  The liquid crystalline polyester includes a repeating unit represented by the following formula (1) (hereinafter sometimes referred to as “repeating unit (1)”) and a repeating unit represented by the following formula (2) (hereinafter referred to as “repeating unit”). (2) ") and a repeating unit represented by the following formula (3) (hereinafter also referred to as" repeating unit (3) ").

(1) —O—Ar ¹ —CO—
(2) —CO—Ar ² —CO—
⁽³⁾ -X-Ar 3 -Y-

(Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylylene group. Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylylene group, or a group represented by the following formula (4). X And Y each independently represents an oxygen atom or an imino group (—NH—), and each hydrogen atom in the group represented by Ar ¹ , Ar ² or Ar ³ independently represents a halogen atom or an alkyl group. Alternatively, it may be substituted with an aryl group.)

(4) -Ar ⁴ -Z-Ar ^5-

(Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group.)

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and 2-ethylhexyl group. Is usually 1-10. Examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, and a 2-naphthyl group, and the number of carbon atoms is usually 6-20. Examples of the alkylidene group include a methylene group, an ethylidene group, an isopropylidene group, an n-butylidene group, and a 2-ethylhexylidene group, and the number of carbon atoms is usually 1-10.

The repeating unit (1) is a repeating unit derived from an aromatic hydroxycarboxylic acid, and Ar ¹ includes a p-phenylene group (derived from p-hydroxybenzoic acid) and a 2,6-naphthylene group (6-hydroxy- 2) derived from 2-naphthoic acid.

The repeating unit (2) is a repeating unit derived from an aromatic dicarboxylic acid, and Ar ² includes p-phenylene group (derived from terephthalic acid), m-phenylene group (derived from isophthalic acid), 2,6- A naphthylene group (derived from 6-hydroxy-2-naphthoic acid) and a diphenyl ether-4,4′-diyl group (derived from diphenyl ether-4,4′-dicarboxylic acid) are preferred.

The repeating unit (3) is a repeating unit derived from aromatic diol, aromatic hydroxylamine or aromatic diamine, and Ar ³ is derived from p-phenylene group (hydroquinone, p-aminophenol or p-phenylenediamine). And 4,4′-biphenylylene groups (derived from 4,4′-dihydroxybiphenyl, 4-amino-4′-hydroxybiphenyl or 4,4′-diaminobiphenyl).

  The content of the repeating unit (1) is the total amount of all repeating units constituting the liquid crystalline polyester (the amount of each repeating unit by dividing the mass of each repeating unit constituting the liquid crystalline polyester by the formula weight of each repeating unit). It is preferably 30 to 80 mol%, more preferably 30 to 60 mol%, still more preferably 30 to 40 mol% with respect to the equivalent amount (mol). As the content of the repeating unit (1) is larger, the liquid crystal polyester tends to improve the liquid crystallinity, and as the content of the repeating unit (1) is smaller, the solubility of the liquid crystalline polyester in the solvent tends to be improved. .

  The content of the repeating unit (2) is preferably 10 to 35 mol%, more preferably 20 to 35 mol%, still more preferably 30 with respect to the total amount of all repeating units constituting the liquid crystal polyester. -35 mol%. As the content of the repeating unit (2) is larger, the solubility of the liquid crystalline polyester in the solvent tends to be improved, and as the content of the repeating unit (2) is smaller, the liquid crystalline property of the liquid crystalline polyester tends to be improved. .

  The content of the repeating unit (3) is preferably 10 to 35 mol%, more preferably 20 to 35 mol%, still more preferably 30 with respect to the total amount of all repeating units constituting the liquid crystal polyester. -35 mol%. As the content of the repeating unit (3) increases, the solubility of the liquid crystalline polyester in the solvent tends to be improved, and as the content of the repeating unit (3) decreases, the liquid crystalline property of the liquid crystalline polyester tends to improve. .

  The content ratio of the repeating unit (2) and the repeating unit (3) is expressed as [Repeating unit (2)] / [Repeating unit (3)] (mol / mol), 0.9 / 1 to 1/0. .9 is preferable because the liquid crystalline polyester exhibits high liquid crystallinity.

  The liquid crystalline polyester has a repeating unit (3) in which X and / or Y is an imino group, that is, a repeating unit derived from an aromatic hydroxylamine and / or a repeating unit derived from an aromatic diamine. In view of excellent solubility in a solvent, X and / or Y of substantially all repeating units (3) is more preferably an imino group.

  The liquid crystal polyester is preferably produced by melt polymerization of raw material monomers and solid-phase polymerization of the obtained polymer (prepolymer). Thereby, high molecular weight liquid crystal polyester with high heat resistance and strength can be produced with good operability. The melt polymerization may be carried out in the presence of a catalyst. Examples of the catalyst include magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide. And nitrogen-containing heterocyclic compounds such as N, N-dimethylaminopyridine and N-methylimidazole, and nitrogen-containing heterocyclic compounds are preferably used.

  The liquid crystal polyester preferably has a flow start temperature of 250 ° C or higher, more preferably 250 ° C to 350 ° C, and further preferably 260 ° C to 330 ° C. The higher the flow start temperature of the liquid crystal polyester, the better the heat resistance and strength of the liquid crystal polyester. However, if the liquid polyester is too high, the solubility of the liquid crystal polyester in the solvent decreases and the viscosity of the liquid composition increases. And it becomes difficult to handle.

The flow start temperature is also called flow temperature or flow temperature, and is 4 ° C / min under a load of 9.8 MPa (100 kg / cm ² ) using a capillary rheometer having a nozzle having an inner diameter of 1 mm and a length of 10 mm. This is a temperature at which the melt viscosity shows 4800 Pa · s (48,000 poise) when the heated melt of liquid crystal polyester is extruded from the nozzle at a temperature rising rate, and is a measure of the molecular weight of the liquid crystal polyester (Naoyuki Koide) Ed., “Liquid Crystal Polymer—Synthesis / Molding / Application—”, CMC, June 5, 1987, p. 95).

  The liquid composition of the present invention contains the liquid crystal polyester as described above, a solvent, and an inorganic filler. As the solvent, the liquid crystal polyester to be used can be dissolved, specifically, 1 mass at 50 ° C. Those that can be dissolved at a concentration of at least% ([liquid crystal polyester] / [liquid crystal polyester + solvent]) are appropriately selected and used.

  Examples of solvents include: halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, o-dichlorobenzene; halogenated p-chlorophenol, pentachlorophenol, etc. Phenol; diethyl ether, tetrahydrofuran, ether such as 1,4-dioxane; ketone such as acetone and cyclohexanone; ester such as ethyl acetate and γ-butyrolactone; carbonate such as ethylene carbonate and propylene carbonate; amine such as triethylamine; Nitrogen-containing heterocyclic aromatic compounds; nitriles such as acetonitrile and succinonitrile; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, and ureation such as tetramethylurea Nitro compounds such as nitromethane and nitrobenzene; sulfur compounds such as dimethyl sulfoxide and sulfolane; and phosphorus compounds such as hexamethylphosphoric acid amide and tri-n-butyl phosphoric acid. May be used.

  As the solvent, since it is low in corrosivity and easy to handle, an aprotic compound, particularly a solvent mainly composed of an aprotic compound having no halogen atom is preferred, and the proportion of the aprotic compound in the whole solvent is preferably Is 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 90 to 100% by mass. The aprotic compound is preferably an amide such as N, N-dimethylformamide, N, N-dimethylacetamide, or N-methylpyrrolidone because it easily dissolves liquid crystal polyester.

  Further, the solvent is preferably a solvent having a dipole moment of 3 to 5 because it easily dissolves the liquid crystalline polyester, and is easily removed after casting the liquid composition. Some solvents are preferred.

  Content of the liquid crystal polyester in a liquid composition is 5-60 mass% normally with respect to the total amount of liquid crystal polyester and a solvent, Preferably it is 10-50 mass%, More preferably, it is 15-45 mass%, desired The liquid composition is appropriately adjusted so as to obtain a liquid composition having a viscosity of 5 and a liquid crystal polyester layer having a desired thickness.

  The liquid composition of the present invention includes a surface-treated inorganic filler whose surface is treated with a silane compound having an alkyl group having 6 or more carbon atoms as an inorganic filler. Thereby, the copper clad laminated board from which a liquid crystal polyester layer and copper foil cannot peel easily can be obtained.

  The inorganic filler is appropriately selected so as to obtain a liquid crystal polyester layer having desired performance such as low linear expansion, high thermal conductivity, high rigidity, and high elasticity. Examples of the inorganic filler include oxides such as beryllium oxide, magnesium oxide, aluminum oxide, silicon oxide, titanium oxide, and zinc oxide; nitrides such as boron nitride, aluminum nitride, and silicon nitride; carbides such as silicon carbide; and Examples include oxo acid salts such as aluminum borate, magnesium sulfate, and potassium titanate, and two or more of them may be used as necessary. Of these, oxides and nitrides are preferable. Further, the shape may be granular, fibrous, plate-shaped, or two or more shapes may be mixed.

  The silane compound having an alkyl group having 6 or more carbon atoms, which is used as a surface treatment agent for an inorganic filler, is preferably one in which the alkyl group is directly bonded to a silicon atom. The group other than the alkyl group is preferably a leaving group such as an alkoxyl group.

  The silane compound is preferably a compound represented by the following formula (I).

(I) R ¹ _n Si (OR ² ) _4-n

(R ¹ represents an alkyl group having 6 or more carbon atoms. R ² represents an alkyl group. N is 1 or 2. When n is 1, three R ^{2 s} are identical to each other. And when n is 2, two R ^{1 s} may be the same or different from each other, and two R ² may be the same or different from each other.)

Here, examples of the alkyl group having 6 or more carbon atoms represented by R ¹ include an n-hexyl group, an n-octyl group and an n-decyl group, and the carbon number thereof is usually 12 or less. Examples of the alkyl group represented by R ² include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and the carbon number is usually 1 to 4.

  Examples of the silane compound include n-hexyltrimethoxysilane, n-hexyltriethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, n-octyltrimethoxysilane, n-octyltri. Ethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-decyltrimethoxysilane, n-decyltriethoxysilane, di-n-decyldimethoxysilane and di-n-decyldi An ethoxysilane is mentioned.

  The surface treatment of the inorganic filler may be performed by immersing the inorganic filler in the silane compound or a solution thereof, or may be performed by spraying the silane compound or a solution thereof on the inorganic filler, You may carry out by gasifying the said silane compound or its solution, and making it contact with an inorganic filler. In the case of using the silane compound solution, the solvent is usually removed by evaporating the solvent, heating may be performed, hot air may be blown, or electromagnetic waves may be irradiated. May be performed.

  The surface treatment of the inorganic filler is preferably performed by spraying a 0.01 to 2% by mass aqueous solution of the silane compound onto the inorganic filler and then heat-treating at 80 to 120 ° C. for 10 minutes to 10 hours. Moreover, it is preferable that pH of the aqueous solution of the silane compound is adjusted to 3 to 5 by adding an acid such as acetic acid.

  The content of the surface-treated inorganic filler in the liquid composition is usually 5 to 85% by volume, preferably 10 to 80% by volume, based on the total amount of the liquid crystal polyester and the surface-treated inorganic filler, and the desired performance. It adjusts suitably so that the liquid crystal polyester layer of this may be obtained.

  In addition, liquid compositions include resins other than liquid crystal polyester, for example, polypropylene, polyamide, polyesters other than liquid crystal polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenylene ether, and modified products as necessary. Thermoplastic resins such as polyetherimide and other liquid crystal polyesters; elastomers such as copolymers of glycidyl methacrylate and polyethylene; and thermosetting resins such as phenol resins, epoxy resins, polyimide resins, and cyanate resins. Although the seed | species or more may be contained, the content is normally to 20 mass parts with respect to 100 mass parts of liquid crystalline polyester.

  In addition, liquid compositions include organic fillers such as cured epoxy resins, cross-linked benzoguanamine resins, and cross-linked acrylic resins, leveling agents, antifoaming agents, antioxidants, ultraviolet absorbers, flame retardants as necessary. In addition, one or more additives such as dyes and pigments may be contained.

  The liquid composition can be prepared by mixing the liquid crystal polyester, the solvent, the surface-treated inorganic filler, and other components used as necessary, all at once or in an appropriate order. It is preferable to carry out by dissolving it in a liquid crystal polyester solution and dispersing a surface-treated inorganic filler in the liquid crystal polyester solution. At that time, the other components used as necessary may be dissolved or dispersed in the solvent before or after the liquid crystal polyester is dissolved in the solvent, or the surface-treated inorganic filler is added to the liquid crystal polyester solution. You may make it melt | dissolve or disperse | distribute to a liquid-crystal polyester solution at the time of disperse | distributing or before or after that.

  After casting the liquid composition thus obtained on the copper foil, the liquid crystal polyester layer is formed on the copper foil by removing the solvent from the liquid composition, and the liquid crystal polyester layer and the copper foil are peeled off. It is possible to manufacture a copper-clad laminate that is difficult to perform.

  Examples of the casting method of the liquid composition include a roller coating method, a dip coating method, a spray coating method, a spinner coating method, a curtain coating method, a slot coating method, and a screen printing method. The removal of the solvent is usually performed by evaporating the solvent by heating, reduced pressure, ventilation, etc., but is preferably performed by heating, more preferably by heating while ventilating. The heating temperature is usually 80 to 200 ° C., and the heating time is usually 10 to 120 minutes.

  The thickness of the copper foil is usually 1 to 100 μm, preferably 5 to 80 μm, and the thickness of the formed liquid crystal polyester layer is usually 0.5 to 500 μm, preferably 1 to 200 μm. As the thickness of the copper foil or the liquid crystal polyester layer is smaller, the flexibility of the copper clad laminate tends to be improved, but if it is too small, the strength is insufficient.

  By forming the copper foil of the copper clad laminate thus obtained into a wiring pattern by etching or the like, the wiring is difficult to peel off from the liquid crystal polyester layer, and a printed wiring board suitable as a flexible printed wiring board can be obtained. Moreover, this printed wiring board can also be used as a printed wiring board for lamination when manufacturing a multilayer printed wiring board.

[Measurement of flow start temperature of liquid crystalline polyester]
Using a flow tester (“CFT-500 type” manufactured by Shimadzu Corporation), about 2 g of liquid crystal polyester was filled into a capillary rheometer with a die having an inner diameter of 1 mm and a length of 10 mm, and 9.8 MPa (100 kg / Under a load of cm ² ), a heated melt of the liquid crystalline polyester was extruded from the nozzle at a heating rate of 4 ° C./min, and the temperature at which the melt viscosity was 4800 Pa · s (48000 poise) was measured.

[Measurement of surface roughness of liquid crystal polyester layer]
Using a non-contact type surface roughness meter ("Pertometer" manufactured by Perthen), Rz, Rmax and Ra were measured on the surface of the copper-clad laminate without the copper foil of the liquid crystal polyester layer.

[Measurement of peel strength between liquid crystal polyester layer and copper foil]
The copper foil of the copper clad laminate is etched to form a strip having a width of 10 mm, and the peel strength when peeling the strip of copper at a rate of 50 mm / min so as to be perpendicular to the liquid crystal polyester layer ( N / cm).

Example 1
(1) Production of liquid crystalline polyester In a reactor equipped with a stirrer, a torque meter, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 1976 g (10.5 mol) of 6-hydroxy-2-naphthoic acid, 4-hydroxy Acetanilide 1474 g (9.75 mol), isophthalic acid 1620 g (9.75 mol) and acetic anhydride 2374 g (23.25 mol) were charged. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream, and the temperature was maintained and refluxed for 3 hours. Thereafter, while distilling off by-product acetic acid and unreacted acetic anhydride, the temperature was raised to 300 ° C. over 170 minutes, and when an increase in torque was observed, the contents were taken out and cooled to room temperature. . The obtained solid was pulverized with a pulverizer to obtain a liquid crystalline polyester. The flow start temperature of this liquid polyester was 235 ° C. Next, this liquid crystalline polyester was subjected to solid phase polymerization by heat treatment at 223 ° C. for 3 hours in a nitrogen atmosphere. The flow starting temperature of the liquid crystal polyester after this solid phase polymerization was 270 ° C.

(2) Surface treatment of inorganic filler 0.5 g of acetic acid and 6 g of n-hexyltrimethoxysilane (“Z-6582” from Toray Dow Corning Co., Ltd.) were added to 594 g of pure water, and 200 rpm for 30 minutes at room temperature. To obtain a pH 4 silane compound solution. After spraying this silane compound solution on aluminum oxide (“Sumicorundum AA-1.5” from Sumitomo Chemical Co., Ltd.) and stirring at high speed for 10 minutes with a super mixer (“SMP-2” from Kawata Corp.), It heat-dried at 120 degreeC for 2 hours, and obtained the surface treatment aluminum oxide. Here, the usage-amount of n-hexyl trimethoxysilane was 1 mass% with respect to the aluminum oxide.

(3) Production of Liquid Composition 2200 g of the liquid crystal polyester obtained in (1) above was added to 7800 g of N, N-dimethylacetamide and heated at 100 ° C. for 2 hours to obtain a liquid crystal polyester solution. To this liquid crystal polyester solution, the surface-treated aluminum oxide obtained in (2) above was added and stirred for 5 minutes with a centrifugal defoamer to obtain a liquid composition. Here, the usage-amount of surface treatment aluminum oxide was 40 volume% with respect to the total amount of liquid crystalline polyester and surface treatment aluminum oxide.

(4) Production of copper clad laminate The liquid composition obtained in (3) above was applied onto a copper foil having a thickness of 70 μm so as to have a thickness of 350 μm, and the coating film was dried at 100 ° C. for 20 minutes. Then, heat treatment was performed at 320 ° C. for 3 hours to obtain a copper clad laminate. About the obtained copper clad laminated board, the measurement of the surface roughness of a liquid crystal polyester layer and the peel strength of a liquid crystal polyester layer and copper foil were performed. The results are shown in Table 1.

Comparative Example 1
The same operation as in Example 1 was performed except that the step of Example 1 (2) was omitted and aluminum oxide was used without being surface-treated. The results are shown in Table 1.

Comparative Example 2
In Example 1 (2), Example 1 was used except that 3-glycidoxypropyltrimethoxysilane (“Z-6040” manufactured by Toray Dow Corning Co., Ltd.) was used instead of n-hexyltrimethoxysilane. The same operation was performed. The results are shown in Table 1.

Comparative Example 3
In Example 1 (2), in place of n-hexyltrimethoxysilane, phenyltrimethoxysilane (“Z-6124” from Toray Dow Corning Co., Ltd.) was used, and the same operation as in Example 1 was performed. went. The results are shown in Table 1.

Claims (12)

  A liquid composition comprising a liquid crystal polyester, a solvent, and a surface-treated inorganic filler obtained by subjecting the inorganic filler to a surface treatment with a silane compound having an alkyl group having 6 or more carbon atoms. The liquid crystalline polyester is a liquid crystalline polyester having a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3). The liquid composition according to 1.
(1) —O—Ar ¹ —CO—
(2) —CO—Ar ² —CO—
⁽³⁾ -X-Ar 3 -Y-
(Ar ¹ represents a phenylene group, a naphthylene group, or a biphenylylene group. Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylylene group, or a group represented by the following formula (4). X And Y each independently represents an oxygen atom or an imino group, and each hydrogen atom in the group represented by Ar ¹ , Ar ² or Ar ³ is independently substituted with a halogen atom, an alkyl group or an aryl group. May be.)
(4) -Ar ⁴ -Z-Ar ^5-
(Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group.)   The liquid crystal polyester has a repeating unit represented by the formula (1) of 30 to 80 mol% and a repeating unit represented by the formula (2) of 10 with respect to the total amount of all repeating units constituting the liquid crystalline polyester. The liquid composition according to claim 2, which is a liquid crystal polyester having about 35 mol% and 10 to 35 mol% of the repeating unit represented by the formula (3).   The liquid composition according to claim 2 or 3, wherein X and / or Y is an imino group.   The liquid composition according to claim 1, wherein the solvent is a solvent containing 50% by mass or more of an aprotic compound.   The liquid composition according to claim 5, wherein the aprotic compound is an aprotic compound having no halogen atom.   The liquid composition according to claim 5 or 6, wherein the aprotic compound is an amide.   The liquid composition according to claim 1, wherein the inorganic filler is an oxide and / or a nitride. The liquid composition according to claim 1, wherein the silane compound is a compound represented by the following formula (I).
(I) R ¹ _n Si (OR ² ) _4-n
(R ¹ represents an alkyl group having 6 or more carbon atoms. R ² represents an alkyl group. N is 1 or 2. When n is 1, three R ^{2 s} are identical to each other. And when n is 2, two R ^{1 s} may be the same or different from each other, and two R ² may be the same or different from each other.)   The liquid composition according to any one of claims 1 to 9, wherein a content of the liquid crystal polyester is 10 to 50% by mass with respect to a total amount of the liquid crystal polyester and the solvent.   The liquid composition according to any one of claims 1 to 10, wherein a content of the surface-treated inorganic filler is 10 to 80% by volume with respect to a total amount of the liquid crystal polyester and the surface-treated inorganic filler.   The manufacturing method of the copper clad laminated board which removes the said solvent, after casting the liquid composition in any one of Claims 1-11 on copper foil.