KR20120010134A - Solution composition and method for producing copper-clad laminate using the same - Google Patents

Abstract

PURPOSE: A manufacturing method of a cooper-clad laminate is provided to wire-patternize the copper layer of the cooper-clad laminate by etching, etc, thereby making a wiring hardly separate from a polyester layer, and obtaining a print wiring board useable as a flexible print wiring plate. CONSTITUTION: A liquid compound comprises liquid crystal polyester, solvent, and a surface-treated inorganic filler which is surface-treated by a silane compound having an alkyl group of six or more carbon number for an inorganic filler. The content of liquid crystal polyester is 10-50 weight% on the basis of the sum of the liquid crystal polyester and the solvent. A manufacturing method of the copper-clad laminate comprises: a step of softening the liquid compound on a cooper foil; and a step of removing the solvent from the outcome.

Description

The liquid composition and the manufacturing method of the copper clad laminated board using the same {SOLUTION COMPOSITION AND METHOD FOR PRODUCING COPPER-CLAD LAMINATE USING THE SAME}

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

As a method of manufacturing the copper clad laminated board for flexible printed wiring boards which make a liquid crystalline polyester layer an insulating layer, the method of removing a solvent after flexible the liquid composition containing liquid crystalline polyester and a solvent on copper foil is examined (example For example, Japanese Patent Laid-Open No. 2002-326312, Japanese Patent Laid-Open No. 2005-342980, Japanese Patent Laid-Open No. 2007-106107, Japanese Patent Laid-Open No. 2007-129208 and Japanese Patent Laid-Open No. 2009-241594 See the Gazette publication. Moreover, in order to provide predetermined | prescribed performance to a liquid-crystal polyester layer, including an inorganic filler in a liquid-crystal polyester layer is also examined by including an inorganic filler in the said liquid composition, For example, Unexamined-Japanese-Patent No. 2005-342980 The publication discloses that an inorganic filler is included in the liquid crystal polyester layer in order to lower the linear expansion coefficient of the liquid crystal polyester layer. In addition, Japanese Patent Application Laid-Open No. 2007-106107 and Japanese Patent Laid-Open No. 2009-241594 describe surface treatment of an inorganic filler in order to increase the affinity and adhesion between the inorganic filler and the liquid crystal polyester, and in particular, Japanese Unexamined Patent Application Publication No. 2007-106107 discloses using a silane compound having an epoxy group or the like as a surface treating agent for an inorganic filler.

The copper clad laminate obtained by using a conventional liquid crystal polyester and a liquid composition containing a solvent and an inorganic filler is excellent in the adhesion between the liquid crystal polyester layer and the copper foil, but when a force is applied to remove the two, It is because the affinity and adhesiveness of an inorganic filler and liquid crystalline polyester are not enough, or breakage of the liquid crystalline polyester layer by the interface peeling easily occurs, and the problem that a liquid crystalline polyester layer and copper foil easily peels as a result arises. have. Therefore, the objective of this invention is providing the liquid composition which contains a liquid-crystal polyester, a solvent, and an inorganic filler, and gives a copper clad laminated board which a liquid crystal polyester layer and a copper foil are hard 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 surface treatment with a silane compound having an inorganic group having an alkyl group having 6 or more carbon atoms. Moreover, according to this invention, the manufacturing method of the copper clad laminated board which removes the said solvent after softening the said liquid composition on metal foil is also provided.

By using the liquid composition of this invention, the copper clad laminated board which a liquid crystal polyester layer and copper foil are hard to peel off can be obtained.

Liquid crystalline polyester is liquid crystalline polyester which shows liquid crystallinity in a molten state, and it is preferable to melt at 450 degrees C or less temperature. Moreover, liquid crystalline polyester may be sufficient as liquid crystal polyester, liquid crystalline polyester ether may be sufficient, liquid crystalline polyester carbonate may be sufficient, and liquid crystalline polyester imide may be sufficient as it. It is preferable that liquid crystalline polyester is all aromatic liquid crystalline polyester which uses only an aromatic compound as a raw material monomer.

As a typical example of liquid crystalline polyester, what is obtained by superposing | polymerizing (polycondensing) the compound chosen from the group which consists of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, and aromatic diamine, and several types of aromatic hydroxide Polymerizing hydroxycarboxylic acid, polymerizing a compound selected from the group consisting of aromatic dicarboxylic acid and aromatic diol, aromatic hydroxyamine and aromatic diamine, and polyester such as polyethylene terephthalate and aromatic hydroxycarbo The thing formed by superposing | polymerizing an acid is mentioned. Here, instead of some or all of the aromatic hydroxycarboxylic acid, the aromatic dicarboxylic acid, the aromatic diol, the aromatic hydroxyamine and the aromatic diamine, a derivative capable of polycondensation may be used.

Examples of derivatives capable of polycondensation of a compound 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, converting a carboxyl group to a haloformyl group, The thing formed by converting a carboxyl group into an acyloxycarbonyl group is mentioned. As an example of the derivative which can be polycondensed of the compound which has hydroxyl groups, such as aromatic hydroxycarboxylic acid, aromatic diol, and aromatic hydroxyamine, what is formed by acylating a hydroxyl group and converting into an acyloxyl group is mentioned. Examples of derivatives capable of polycondensation of compounds having an amino group such as aromatic hydroxyamine and aromatic diamine include those obtained by acylating an amino group and converting it into an acylamino group.

The liquid crystal polyester may be a repeating unit represented by the following formula (1) (hereinafter 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 (hereinafter, referred to as "repeating unit (3)") represented by the following general formula (3).

(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), and X and Y Each independently represents an oxygen atom or an imino group (-NH-), and the hydrogen atoms in the group represented by Ar ¹ , Ar ² or Ar ³ may each be independently substituted with a halogen atom, an alkyl group or an aryl group)

(Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group, and 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 fluorine atom, chlorine atom and 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. 1 to 10. As an example of an aryl group, a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group, and 2-naphthyl group are mentioned, The carbon number is 6-20 normally. Examples of the alkylidene group include methylene group, ethylidene group, isopropylidene group, n-butylidene group and 2-ethylhexylidene group, and the carbon number is usually 1 to 10.

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

The repeating unit (2) is a repeating unit derived from an aromatic dicarboxylic acid, and as Ar ² , p-phenylene group (derived from terephthalic acid), m-phenylene group (derived from isophthalic acid), and 2,6-naphthylene group ( Preference is given to 6-hydroxy-2-naphthoic acid) and diphenylether-4,4'-diyl groups (derived from diphenylether-4,4'-dicarboxylic acid).

The repeating unit (3) is a repeating unit derived from an aromatic diol, an aromatic hydroxylamine or an aromatic diamine, and as Ar ³ , p-phenylene group (derived from hydroquinone, p-aminophenol or p-phenylenediamine) and 4,4 Preference is given to '-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 the repeating units constituting the liquid crystalline polyester (the amount of the substance equivalent of each repeating unit by dividing the mass of each repeating unit constituting the liquid crystal polyester by the food content of each repeating unit (mol) Value, and the sum thereof is preferably from 30 to 80 mol%, more preferably from 30 to 60 mol%, still more preferably from 30 to 40 mol%. The more content of the repeating unit (1), the liquid crystal polyester tends to be improved, and the less the content of the repeating unit (1) is, the more the solubility in the solvent of the liquid crystalline polyester tends to be improved.

The content of the repeating unit (2) is preferably 10 to 35 mol%, more preferably 20 to 35 mol%, further preferably 30 to 30 with respect to the total amount of all the repeating units constituting the liquid crystal polyester. 35 mol%. The more content of the repeating unit (2), the solubility in the solvent of the liquid crystalline polyester tends to be improved, and the less the content of the repeating unit (2) is, the more likely the liquid crystallinity of the liquid crystalline polyester is improved.

The content of the repeating unit (3) is preferably 10 to 35 mol%, more preferably 20 to 35 mol%, and still more preferably 30 to 30, based on the total amount of all the repeating units constituting the liquid crystal polyester. 35 mol%. The more content of the repeating unit (3), the solubility in the solvent of the liquid crystalline polyester tends to be improved, and the less the content of the repeating unit (3) is, the more the liquid crystallinity of the liquid crystalline polyester tends to be improved.

The content ratio of the repeating unit (2) and the repeating unit (3) is represented by [repeating unit (2)] / [repeating unit (3)] (mol / mol), and it is liquid crystal that it is 0.9 / 1 to 1 / 0.9 Since polyester expresses high liquid crystallinity, it is preferable.

The liquid crystalline polyester has a thing which X and / or Y is an imino group as a repeating unit (3), ie, what has a repeating unit derived from aromatic hydroxylamine, and / or a repeating unit derived from aromatic diamine, is a solvent. Since it is excellent in solubility with respect to, it is preferable, and it is more preferable that X and / or Y of substantially all the repeating units (3) are imino groups.

It is preferable to manufacture liquid crystalline polyester by solid-state-polymerizing the polymer (prepolymer) obtained by melt-polymerizing a raw material monomer. Thereby, the high molecular weight liquid crystal polyester with high heat resistance and strength can be manufactured highly operable. The melt polymerization may be performed in the presence of a catalyst. Examples of the catalyst include metal compounds such as magnesium acetate, first tin acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, and N, N. Nitrogen containing heterocyclic compounds, such as -dimethylamino pyridine and N-methylimidazole, are mentioned, A nitrogen containing heterocyclic compound is used preferably.

It is preferable that the fluid start temperature is 250 degreeC or more, as for liquid crystalline polyester, it is more preferable that it is 250 degreeC-350 degreeC, and it is still more preferable that it is 260 degreeC-330 degreeC. The higher the flow start temperature of the liquid crystalline polyester, the higher the heat resistance and strength of the liquid crystalline polyester tends to be improved, but too high the solubility of the liquid crystalline polyester in the solvent or the viscosity of the liquid composition is increased, making it difficult to handle. Lose.

In addition, the flow initiation temperature is also referred to as flow temperature or flow temperature, using a capillary rheometer having a nozzle having an internal diameter of 1 mm and a length of 10 mm, and a liquid crystal at a temperature rising rate of 4 ° C./min under a load of 9.8 MPa (100 kg / cm ² ). Melt viscosity is the temperature which shows 4800 Pa.s (48,000 poise) when extrude | heating a melt of polyester from a nozzle, and becomes a reference | standard of the molecular weight of liquid crystalline polyester. Plastic Molding, ”CMC, June 5, 1987, p. 95).

The liquid composition of this invention contains the above-mentioned liquid crystalline polyester, a solvent, and an inorganic filler, As a solvent, the liquid crystalline polyester to be used can melt | dissolve, specifically, the density | concentration ([ Liquid crystalline polyester] / [liquid crystal polyester + solvent]) is suitably selected and used.

Examples of the solvent include halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane and o-dichlorobenzene; halogenated phenols such as p-chlorophenol and pentachlorophenol; Ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane; Ketones such as acetone and cyclohexanone; Esters such as ethyl acetate and γ-butyrolactone; Carbonates such as ethylene carbonate and propylene carbonate; Amines such as triethylamine; Nitrogen-containing heterocyclic aromatic compounds such as pyridine; Nitriles such as acetonitrile and succinonitrile; Urea compounds such as amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and tetramethylurea; Nitro compounds such as nitromethane and nitrobenzene; Sulfur compounds such as dimethyl sulfoxide and sulfolane; And phosphorus compounds such as hexamethyl phosphate amide and trin-butyl phosphate. These two or more kinds may be mixed and used as necessary.

As a solvent, since the corrosion property is low and it is easy to handle, the solvent which mainly uses an aprotic compound, especially an aprotic compound which does not have a halogen atom, is preferable, and the ratio of the aprotic compound which occupies for the whole solvent, Preferably it is 50-100 mass%, More preferably, it is 70-100 mass%, More preferably, it is 90-100 mass%. Moreover, as said aprotic compound, since it is easy to melt | dissolve liquid crystalline polyester, amides, such as N, N- dimethylformamide, N, N- dimethylacetamide, N-methylpyrrolidone, are preferable.

Moreover, as a solvent, since the liquid crystal polyester is easy to melt | dissolve, the solvent whose dipole moment is 3-5 is preferable, and since it is easy to remove after casting | flow_spread of a liquid composition, the solvent whose boiling point in 1 atmosphere is 220 degrees C or less is preferable. desirable.

Content of liquid crystalline polyester in a liquid composition is 5-60 mass% normally with respect to the total amount of a liquid crystalline polyester and a solvent, Preferably it is 10-50 mass%, More preferably, it is 15-45 mass%, The liquid phase of a desired viscosity While a composition is obtained, it adjusts suitably so that the liquid-crystal polyester layer of a desired thickness can be obtained.

The liquid composition of the present invention contains, as an inorganic filler, a surface-treated inorganic filler obtained by treating the surface with a silane compound having an alkyl group having 6 or more carbon atoms. Thereby, the copper clad laminated board with which a liquid crystal polyester layer and copper foil are hard to peel can be obtained.

An inorganic filler is suitably selected so that the liquid-crystal polyester layer of desired performance, such as low linear expansion property, high thermal conductivity, high rigidity, high elasticity, is obtained. As an inorganic filler, For example, Oxides, such as a beryllium oxide, magnesium oxide, aluminum oxide, a silicon oxide, titanium oxide, zinc oxide; Nitrides such as boron nitride, aluminum nitride, and silicon nitride; Carbides such as silicon carbide; And oxo-acid salts such as aluminum borate, magnesium sulfate, potassium titanate, and the like, and two or more kinds thereof may be used as necessary. Especially, oxide and nitride are preferable. Also. The shape may be granular, fibrous or plate-shaped, or two or more types may be mixed.

The silane compound having an alkyl group having 6 or more carbon atoms used as the surface treating agent for the inorganic filler is preferably formed by the alkyl group being directly bonded to the silicon atom, and the groups other than the alkyl group bonded to the silicon atom are leaving groups such as alkoxyl groups. desirable.

It is preferable that the said silane compound is a compound represented by following formula (I).

[Formula I]

(R ¹ represents an alkyl group having 6 or more carbon atoms, R ² represents an alkyl group, n is 1 or 2, and when n is 1, three R ² may be the same as or different from each other, and when n is 2, , Two R ¹ may be the same as or different from each other, two R ² may be the same as or different from each other)

Here, as an example of the C6 or more alkyl group represented by R <^1> , n-hexyl group, n-octyl group, and n-decyl group are mentioned, The carbon number is 12 or less normally. As an example of the alkyl group represented by R <^2> , a methyl group, an ethyl group, n-propyl group, and isopropyl group are mentioned, The carbon number is 1-4 normally.

Examples of the silane compound include n-hexyltrimethoxysilane, n-hexyltriethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyl diethoxysilane, n-octyltrimethoxysilane and n- Octyltriethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-decyltrimethoxysilane, n-decyltriethoxysilane, di-n-decyldimethoxysilane And di-n-decyldiethoxysilane.

Surface treatment of an inorganic filler may be performed by immersing an inorganic filler in the said silane compound or its solution, and may be performed by spraying the said silane compound or its solution to an inorganic filler, and gasifying the said silane compound or its solution and an inorganic filler You may carry out by making it contact. In addition, when using the solution of the said silane compound, removal of a solvent is normally performed by evaporating a solvent, and may be performed by heating, may be performed by injecting hot air, and may be performed by irradiating electromagnetic waves.

It is preferable to perform surface treatment of an inorganic filler by spraying 0.01-2 mass% aqueous solution of the said silane compound to an inorganic filler, and then heat-processing at 80-120 degreeC for 10 minutes-10 hours. Moreover, it is preferable that pH of the aqueous solution of the said silane compound is adjusted to 3-5 by addition of acids, such as an 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 with respect to the total amount of the liquid crystal polyester and the surface-treated inorganic filler so that a liquid crystal polyester layer having a desired performance can be obtained. Adjusted accordingly.

In addition, in a liquid composition, resin other than liquid crystalline polyester, for example, polypropylene, polyamide, polyester other than liquid crystalline polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone as needed Thermoplastic resins other than liquid crystalline polyesters such as polyphenylene ether and modified substances thereof, and polyetherimide; Elastomers such as copolymers of glycidyl methacrylate and polyethylene; Although 1 type (s) or 2 or more types of thermosetting resins, such as a phenol resin, an epoxy resin, a polyimide resin, and a cyanate resin, may be contained, the content is up to 20 mass parts normally with respect to 100 mass parts of liquid crystalline polyester.

In addition, the liquid composition contains one type of additives such as organic fillers such as a cured epoxy resin, a crosslinked benzoguamine resin and a crosslinked acrylic resin, a leveling agent, an antifoaming agent, an antioxidant, an ultraviolet absorber, a flame retardant, a dye, and a pigment. Or two or more types may be contained.

Production of the liquid composition can be carried out by mixing the liquid crystal polyester, the solvent, the surface-treated inorganic filler, and other components used as necessary in a batch or in an appropriate order, but the liquid crystal polyester is dissolved in a solvent to form the liquid crystal polyester. It is preferable to carry out by obtaining a solution and disperse | distributing a surface treatment inorganic filler in this liquid crystal polyester solution. The other component used as needed at that time may melt | dissolve or disperse | distribute a liquid-crystal polyester in a solvent, before or after, or may disperse | distribute in a solvent, and when disperse | distributing a surface treatment inorganic filler to a liquid-crystal polyester solution, or the before Or you may melt | dissolve or disperse | distribute in liquid crystalline polyester solution later.

After the liquid composition obtained in this way is flexible on copper foil, a liquid crystal polyester layer is formed on copper foil by removing a solvent from a liquid composition, and the copper clad laminated board which a liquid crystal polyester layer and copper foil are hard to peel off can be manufactured. .

As a casting method of a liquid composition, the roller coating method, the dip coating method, the spray coating method, the spinner coating method, the curtain coating method, the slot coating method, and the screen printing method are mentioned, for example. In addition, although removal of a solvent is normally performed by evaporating a solvent by heating, pressure reduction, ventilation, etc., it is preferable to carry out by heating, and it is more preferable to carry out by heating, while ventilating. Heating temperature is 80-200 degreeC normally, and a heat time is 10-120 minutes normally.

The thickness of copper foil is 1-100 micrometers normally, Preferably it is 5-80 micrometers, The thickness of the liquid crystal polyester layer formed is 0.5-500 micrometers normally, Preferably it is 1-200 micrometers. The smaller the thickness of the copper foil or the liquid crystal polyester layer, the more the flexibility of the copper clad laminate is improved, but too small the strength is insufficient.

By patterning the copper foil of the copper clad laminated board obtained in this way by etching etc., wiring is hard to peel from a liquid crystal polyester layer, and the 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 at the time of manufacturing a multilayer printed wiring board.

<Examples>

[Measurement of Flow Start Temperature of Liquid Crystal Polyester]

Using a flow tester ("CFT-500" by Shimadzu Corporation), about 2 g of liquid crystal polyester was filled in a capillary rheometer with a die of 1 mm in inner diameter and 10 mm in length, and then 9.8 MPa (100 kg). / cm under a load of ^2), by extruding from a nozzle a heated melt of the liquid crystal polyester at a heating rate of 4 ℃ / min, the melt viscosity was measured in the temperature indicating the 4800Pa? s (48000 poises).

[Measurement of Surface Roughness of Liquid Crystal Polyester Layer]

Rz, Rmax, and Ra were measured about the surface with which the copper foil of the liquid crystal polyester layer of the copper clad laminated board was not affixed using the non-contact surface roughness meter ("Feltmeter" of Perthen).

[Measurement of Peel Strength of Liquid Crystal Polyester Layer and Copper Foil]

The copper foil of a copper clad laminated board is etched, and it is set as the strip shape of width 10mm, and peeling strength (N / cm) at the time of peeling this strip-shaped copper foil at 50 mm / min so that it may become perpendicular | vertical with respect to a liquid-crystal polyester layer is measured. did.

Example 1

(1) Preparation of Liquid Crystalline Polyester

1976 g (10.5 mol) of 6-hydroxy-2-naphthoic acid, 1474 g (9.75 mol) of 4-hydroxyacetoanilide in a reactor equipped with a stirring device, a torque meter, a nitrogen gas introduction tube, a thermometer and a reflux condenser 1620 g (9.75 mol) of phthalic acid and 2374 g (23.25 mol) of acetic anhydride were added. 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 kept at reflux for 3 hours. Then, while distilling off by-product acetic acid and unreacted acetic anhydride which distilled off, it heated up to 300 degreeC over 170 minutes, and when the torque rise was confirmed, the contents were taken out and cooled to room temperature. The obtained solid material was pulverized with a grinder to obtain a powdery liquid crystalline polyester. The flow start temperature of this liquid crystalline polyester was 235 degreeC. Subsequently, this liquid-crystalline polyester was heat-processed at 223 degreeC for 3 hours in nitrogen atmosphere, and solid-state polymerization was performed. The flow start temperature of the liquid crystalline polyester after this solid state polymerization was 270 degreeC.

(2) surface treatment of inorganic filler

0.5 g of acetic acid and 6 g of n-hexyltrimethoxysilane ("Z-6582" of Toray Dow Corning Co., Ltd.) were added to 594 g of pure water, and stirred at 200 rpm for 30 minutes at room temperature to obtain a silane compound solution of pH4. . After spraying this silane compound solution to aluminum oxide ("Sumiko Random AA-1.5" of Sumitomo Chemical Co., Ltd.), and stirring at high speed with a super mixer ("SMP-2" of Kawata Co., Ltd.) for 10 minutes, It heat-dried at 120 degreeC for 2 hours, and obtained surface-treated aluminum oxide. Here, the usage-amount of n-hexyl trimethoxysilane was 1 mass% with respect to aluminum oxide.

(3) Preparation of Liquid Composition

2200 g of liquid crystalline polyester obtained in said (1) was added to 7800 g of N, N- dimethylacetamide, and it heated at 100 degreeC for 2 hours, and obtained the liquid-crystal polyester solution. The surface-treated aluminum oxide obtained by said (2) was added to this liquid crystal polyester solution, and it stirred for 5 minutes by the centrifugal degassing | fever, and obtained the liquid composition. Here, the usage-amount of surface-treated aluminum oxide was 40 volume% with respect to the total amount of liquid crystalline polyester and surface-treated aluminum oxide.

(4) Production of copper clad laminate

The liquid composition obtained by said (3) was apply | coated so that it might become thickness of 350 micrometers on copper foil of 70 micrometers in thickness, and after drying a coating film at 100 degreeC for 20 minutes, it heat-processed at 320 degreeC for 3 hours, and obtained the copper clad laminated board. About the obtained copper clad laminated board, the surface roughness of the liquid crystal polyester layer was measured, and the peeling strength of the liquid crystal polyester layer and copper foil was measured. The results are shown in Table 1.

Comparative Example 1

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

Comparative Example 2

In Example (2), except having used 3-glycidoxy propyl trimethoxysilane ("Z-6040" of Toray Dow Corning Co., Ltd.) instead of n-hexyl trimethoxysilane, Operation similar to Example 1 was performed. The results are shown in Table 1.

Comparative Example 3

Operation similar to Example 1 in (2) of Example 1 except having used phenyl trimethoxysilane ("Z-6124" of Toray Dow Corning Co., Ltd.) instead of n-hexyl trimethoxysilane. Done. The results are shown in Table 1.

Claims (12)

The liquid composition containing liquid crystalline polyester, a solvent, and the surface-treated inorganic filler in which the inorganic filler is surface-treated with the silane compound which has a C6 or more alkyl group. The liquid composition according to claim 1, wherein the liquid crystal polyester is a liquid crystal 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).
[Formula 1]

(2)

(3)

(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), and X and Y Each independently represents an oxygen atom or an imino group, and the hydrogen atoms in the group represented by Ar ¹ , Ar ^2, or Ar ³ may each independently be substituted with a halogen atom, an alkyl group, or an aryl group)
[Chemical Formula 4]

(Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group, and Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylidene group) The method according to claim 2, wherein 30 to 80 mol% of the repeating unit represented by the formula (1) and 10 to 35 mol% of the repeating unit represented by the formula (2) with respect to the total amount of all the repeating units of which the liquid crystal polyester constitutes it , A liquid composition which is a liquid crystal polyester having a repeating unit represented by the formula (3) 10 to 35 mol%. The liquid composition according to claim 2 or 3, wherein X and / or Y are imino groups. 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 any one of claims 1 to 7, 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 represents an alkyl group having 6 or more carbon atoms, R ² represents an alkyl group, n is 1 or 2, and when n is 1, three R ² may be the same as or different from each other, and when n is 2, , Two R ¹ may be the same as or different from each other, two R ² may be the same as or different from each other) The liquid composition according to claim 1, wherein the content of the liquid crystal polyester is 10 to 50% by mass based on the total amount of the liquid crystal polyester and the solvent. The liquid composition according to claim 1, wherein the content of the surface-treated inorganic filler is 10 to 80% by volume with respect to the 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 softening the liquid composition of any one of Claims 1-3 on copper foil.