JP2005001390A - Laminate, manufacturing method of laminate and multi-layered substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which has excellent heat resistance, shows smallness in relative dielectric constant, dielectric loss tangent and water absorption and a good appearance, and is cheap, and to provide a laminate using it and its manufacturing method. <P>SOLUTION: The laminate has a layer made of a liquid crystal polyester resin composition composed of a liquid crystal polyester (A) as a continuous phase and a copolymer (B) having a functional group capable of reacting with the liquid crystal polyester as a dispersed phase, and a layer of a fibrous material containing an organic fibrous material and/or an inorganic fibrous material. The laminate comprises a metallic foil, a layer made of a liquid crystal polyester resin composition composed of a liquid crystal polyester (A) as a continuous phase and a copolymer (B) having a functional group capable of reacting with the liquid crystal polyester as a dispersed phase, and a layer of a fibrous material containing an organic fibrous material and/or an inorganic fibrous material. The laminate is obtained by stacking each layer on each other and heat-pressing them. The multi-layered substrate is made of the laminate. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminate comprising a layer comprising a liquid crystal polyester resin composition and a fiber material layer, and further to a laminate comprising a metal foil, a layer comprising a liquid crystal polyester resin composition and a fiber material layer. The present invention relates to a laminate used for electrical, electronic parts, circuits, multilayer substrates, and the like, and a method for producing the same, which is excellent in performance, has a low dielectric constant, dielectric loss tangent, water absorption, and is inexpensive.

  In the electrical and electronic industries, laminates of fiber materials and thermosetting resins such as epoxy resins and polyimide films, as well as laminates of metal foil, thermosetting resins, polyimide films and fiber materials are multilayer substrates, Widely used in TAB tapes.

However, a glass fiber fabric impregnated with an epoxy resin and a laminate comprising a polyimide resin layer and a metal foil are widely used in the industry as a multilayer substrate, but the substrate has a high dielectric constant of the epoxy resin and is a manufacturing process. Is complicated and very expensive.
For example, Japanese Patent Application Laid-Open No. 62-11289 discloses a technique using an aramid fiber instead of a glass fiber, but in this case, the problem is that the dielectric constant of the aramid fiber is high and there is water absorption. was there.
U.S. Pat.No. 4,975,312 discloses a multilayer substrate using a laminate composed of biaxially oriented liquid crystal polymer film, glass fiber, and epoxy reinforcing material, but the liquid crystal polymer film cannot be thinned, The physical properties were also insufficient.
JP-A-2-175731 discloses a method in which a glass fiber is impregnated with an epoxy resin having a low relative dielectric constant and applied to a multilayer substrate, but the effect is not sufficient.
JP-A-62-283694, JP-A-8-157621, etc. disclose a method of impregnating a Teflon porous sheet with a thermosetting resin and using it as a prepreg, but it is very expensive. Or there were insufficient physical properties.
There has been a strong demand from the market for a laminate that is excellent in heat resistance, has a low dielectric constant, dielectric loss tangent, water absorption, and is inexpensive.

  The present invention provides a laminate having excellent heat resistance, low dielectric constant, dielectric loss tangent, water absorption, good appearance, and low cost, a multilayer substrate using the same, and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention comprises (A) a liquid crystal polyester as a continuous phase and (B) a layer comprising a liquid crystal polyester resin composition having a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase; an organic fiber material; And / or a laminate having a fiber material layer containing an inorganic fiber material, and a metal foil, and (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester as a dispersed phase And a laminate composed of a layer composed of a liquid crystal polyester resin composition and a fiber material layer containing an organic fiber material and / or an inorganic fiber material. Furthermore, the present invention relates to a method for manufacturing the laminate in which the respective layers are overlapped and thermocompression bonded, and a multilayer substrate made of the laminate.

  The laminate obtained by the present invention has a low dielectric constant, a low dielectric loss tangent, a low water absorption, and is inexpensive, and can be suitably used as a multilayer substrate.

Next, the present invention will be described in detail.
The liquid crystal polyester (A) used for the layer which consists of a liquid crystal polyester resin composition in this invention is polyester called a thermotropic liquid crystal polymer.
In particular,

(1) A combination of an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid,
(2) A combination of different kinds of aromatic hydroxycarboxylic acids,
(3) A combination of an aromatic dicarboxylic acid and a nucleus-substituted aromatic diol,
(4) those obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate,

The anisotropic melt is formed at a temperature of 400 ° C. or lower. In addition, these ester-forming derivatives may be used in place of these aromatic dicarboxylic acids, aromatic diols and aromatic hydroxycarboxylic acids. Examples of the repeating structural unit of the liquid crystalline polyester include the following, but are not limited thereto.

Repeating structural units derived from aromatic dicarboxylic acids:

Repeating structural units derived from aromatic diols:

Repeating structural units derived from aromatic hydroxycarboxylic acids:

なる繰り返し構造単位を、好ましくは３０モル％以上、含むものであり、具体的には繰り返し構造単位の組み合わせが下記（Ｉ）〜（VI）のものである。 A particularly preferred liquid crystal polyester is a balance of heat resistance, mechanical properties and processability.

The repeating structural unit is preferably contained in an amount of 30 mol% or more. Specifically, the combination of the repeating structural units is the following (I) to (VI).

  As for the production methods of the liquid crystalline polyesters (I) to (VI), for example, Japanese Patent Publication No. 47-47870, Japanese Patent Publication No. 63-3888, Japanese Patent Publication No. 63-3891, Japanese Patent Publication No. 56-18016, Japanese Patent Publication No. No. 2-51523. Among these, a combination of (I), (II) and (IV) is preferable, and a combination of (I) and (II) is more preferable.

  In the liquid crystal polyester resin composition of the present invention, in the field where high heat resistance is required, the liquid crystal polyester of the component (A) is composed of 30 to 80 mol% of the following repeating unit (a ′) and the repeating unit (b ′). Is preferably a liquid crystal polyester comprising 0 to 10 mol%, 10 to 25 mol% of the repeating unit (c ′), and 10 to 35 mol% of the repeating unit (d ′).

（式中、Ａｒは２価の芳香族基である。）

(In the formula, Ar is a divalent aromatic group.)

The component (B) used for the layer consisting of the liquid crystal polyester resin composition of the present invention is a copolymer having a functional group having reactivity with the liquid crystal polyester. The functional group having reactivity with the liquid crystal polyester may be anything as long as it has reactivity with the liquid crystal polyester, and specific examples thereof include an oxazolyl group, an epoxy group, and an amino group. Preferably, it is an epoxy group.
Epoxy groups may be present as part of other functional groups, examples of which include glycidyl groups.

  As a monomer having an epoxy group, particularly a monomer having a glycidyl group, an unsaturated carboxylic acid glycidyl ester and / or an unsaturated glycidyl ether is preferably used.

（Ｒはエチレン系不飽和結合を有する炭素数２〜１３の炭化水素基である。） The unsaturated carboxylic acid glycidyl ester unit has the general formula

(R is a C2-C13 hydrocarbon group having an ethylenically unsaturated bond.)

（Ｒはエチレン系不飽和結合を有する炭素数２〜１８の炭化水素基であり、Ｘは−ＣＨ₂ −Ｏ−または

である。）
で表される。 A compound represented by the above formula and giving an unsaturated glycidyl ether unit has the general formula

(R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ -O- or

It is. )
It is represented by

Specifically, examples of the unsaturated carboxylic acid glycidyl ester include glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, and p-styrene carboxylic acid glycidyl ester.
Examples of the unsaturated glycidyl ether include vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, methacryl glycidyl ether, and styrene-p-glycidyl ether.

  The copolymer (B) having a functional group having reactivity with the liquid crystal polyester is preferably a copolymer containing 0.1 to 30% by weight of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. It is a polymer.

  Further, the copolymer (B) having a functional group having reactivity with the liquid crystal polyester may be a thermoplastic resin or rubber, or a mixture of a thermoplastic resin and rubber. . A rubber having low crystallinity is more preferable.

Preferably, the copolymer (B) having a functional group having reactivity with the liquid crystal polyester is a copolymer having a crystal heat of fusion of less than 3 J / g.
The copolymer (B) of the present invention preferably has a Mooney viscosity of 3 to 70, more preferably 3 to 30, and particularly preferably 4 to 25.
The Mooney viscosity here refers to a value measured using a 100 ° C. large rotor according to JIS K6300.

  The term “rubber” as used herein corresponds to a polymer material having rubber elasticity at room temperature according to the new edition of the Dictionary of Polymers (edited by the Society of Polymer Science, published in 1988, Asakura Shoten). Specific examples thereof include natural rubber. , Butadiene polymer, butadiene-styrene copolymer (including random copolymer, block copolymer (including SEBS rubber or SBS rubber), graft copolymer, etc.) or hydrogenated product thereof, isoprene polymer , Chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer rubber, isobutylene-isoprene copolymer, acrylate-ethylene copolymer rubber, ethylene-propylene copolymer rubber , Ethylene-butene copolymer rubber, ethylene-propylene-styrene copolymer Rubber, styrene-isoprene copolymer rubber, styrene-butylene copolymer, styrene-ethylene-propylene copolymer rubber, perfluoro rubber, fluorine rubber, chloroprene rubber, butyl rubber, silicone rubber, ethylene-propylene-nonconjugated diene copolymer Examples thereof include polymer rubber, thiol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (for example, polypropylene oxide), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, and the like. Among them, an acrylate-ethylene copolymer is preferably used, and a (meth) acrylate-ethylene copolymer rubber is more preferable.

  These rubber-like substances may be produced by any production method (for example, emulsion polymerization method, solution polymerization method, etc.) and any catalyst (for example, peroxide, trialkylaluminum, lithium halide, nickel-based catalyst, etc.). .

In the present invention, the rubber as the copolymer (B) is a rubber having a functional group reactive with the liquid crystal polyester in the rubber as described above.
In such a rubber, a method for introducing a functional group having reactivity with liquid crystal polyester into the rubber is not particularly limited, and can be performed by a known method. For example, at the rubber synthesis stage, the monomer having the functional group can be introduced by copolymerization, or the monomer having the functional group can be graft-copolymerized on the rubber.

  As a specific example of the copolymer (B) having a functional group having reactivity with the liquid crystal polyester, as a copolymer rubber having an epoxy group, (meth) acrylate ester-ethylene- (unsaturated carboxylic acid glycidyl ester) and And / or unsaturated glycidyl ether) copolymer rubber.

  Preferably, the (meth) acrylic acid ester unit exceeds 40% by weight and is less than 97% by weight, more preferably 45 to 70% by weight, and the ethylene unit is 3% by weight or more and less than 50% by weight, more preferably 10 to 49% by weight. The unsaturated carboxylic acid glycidyl ether unit and / or the unsaturated glycidyl ether unit is 0.1 to 30% by weight, more preferably 0.5 to 20% by weight.

When the (meth) acrylic acid ester of the copolymer rubber is 40% by weight or less, the rubber elasticity is lowered, the effect of improving the impact resistance of the composition is reduced, and the (meth) acrylic acid ester is 97% by weight. If it is at least%, the embrittlement point of the copolymerized rubber becomes high, and the mechanical properties at low temperatures of the composition may be lowered, which is not preferred.
Further, when the unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether is less than 0.1% by weight, the impact resistance of the liquid crystal polyester resin composition is lowered, and when it exceeds 30% by weight, the rigidity of the composition is decreased. May decrease, which is not preferable.

  Here, the (meth) acrylic acid ester is an ester obtained from acrylic acid or methacrylic acid and an alcohol. As the alcohol, an alcohol having 1 to 8 carbon atoms is preferable. Specific examples of (meth) acrylic acid esters include methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and the like. be able to. In addition, as (meth) acrylic acid ester, the 1 type may be used independently or 2 or more types may be used together.

The copolymer rubber can be produced by a usual method, for example, bulk polymerization using a free radical initiator, emulsion polymerization, solution polymerization or the like. Representative polymerization methods include those described in JP-B-46-45085, JP-B-61-127709, and the like, in the presence of a polymerization initiator that generates free radicals, a pressure of 500 kg / cm ² or more, It can be manufactured under conditions of a temperature of 40 to 300 ° C.

The rubber used as the copolymer (B) can be vulcanized as necessary and used as a vulcanized rubber.
Vulcanization of the above (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is a polyfunctional organic acid, polyfunctional amine compound, imidazole compound, etc. However, the present invention is not limited to these.

  As specific examples of the copolymer (B), the thermoplastic resin having an epoxy group includes (a) 50 to 99% by weight of an ethylene unit, (b) an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl. Mention may be made of an epoxy group-containing ethylene copolymer having an ether unit of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, and (c) an ethylenically unsaturated ester compound unit of 0 to 50% by weight. it can.

  Examples of the ethylenically unsaturated ester compound (c) include vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and other carboxylic acid vinyl esters, α , Β-unsaturated carboxylic acid alkyl esters and the like. In particular, vinyl acetate, methyl acrylate, and ethyl acrylate are preferable.

  Specific examples of the epoxy group-containing ethylene copolymer include, for example, a copolymer composed of ethylene units and glycidyl methacrylate units, a copolymer composed of ethylene units, glycidyl methacrylate units and methyl acrylate units, ethylene units and glycidyl methacrylate units. And a copolymer composed of ethyl acrylate units, a copolymer composed of ethylene units, glycidyl methacrylate units and vinyl acetate units.

  The melt index (hereinafter sometimes referred to as MFR. JIS K6760, 190 ° C., 2.16 kg load) of the epoxy group-containing ethylene copolymer is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 50 g. / 10 minutes. The melt index may be outside this range, but if the melt index exceeds 100 g / 10 min, it is not preferable in terms of mechanical properties when it is made into a composition, and if it is less than 0.5 g / 10 min, the component (A) The compatibility with the liquid crystal polyester is inferior.

Further, the epoxy group-containing ethylene copolymer is preferably in the range stiffness modulus of 10~1300kg / cm ^2, further preferably from 20~1100kg / cm ^2.
If the bending rigidity is outside this range, the molding processability and mechanical properties of the composition may be insufficient, which is not preferable.

  The epoxy group-containing ethylene copolymer is usually an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by a high pressure radical polymerization method for copolymerization. It can also be produced by a method in which an unsaturated epoxy compound and a radical generator are mixed with polyethylene and melt graft copolymerized in an extruder.

The liquid crystal polyester resin composition used for the layer consisting of the liquid crystal polyester resin composition of the present invention is a resin composition containing the above liquid crystal polyester, (A) the liquid crystal polyester as a continuous phase, and (B) the liquid crystal polyester A resin composition having a copolymer having a reactive functional group as a dispersed phase.
When the liquid crystal polyester is not a continuous phase, the heat resistance, strength, water absorption rate, relative dielectric constant, etc. of the laminate may be insufficient, which is not preferable.

  In the resin composition of such a copolymer having a functional group and a liquid crystal polyester, although the details of the mechanism are unknown, a reaction occurs between the component (A) and the component (B) of the composition. Therefore, it is considered that the moldability of the composition is improved.

One embodiment of the liquid crystal polyester resin composition used in the layer comprising the liquid crystal polyester resin composition of the present invention is (A) 56.0 to 99.9% by weight, preferably 65.0 to 99.9% by weight of the liquid crystal polyester. %, More preferably 70 to 98% by weight, and (B) a copolymer having a functional group reactive with the liquid crystal polyester 44.0 to 0.1% by weight, preferably 35.0 to 0.1% by weight More preferably, it is a resin composition containing 30 to 2% by weight.
When the component (A) is less than 56.0% by weight, the heat resistance of the composition is lowered, and the gas barrier properties when formed into a film are also not preferred. On the other hand, if the component (A) exceeds 99.9% by weight, the effect of improving the film forming property of the composition may not be sufficient, and it is not preferable because it is expensive in price.

There is no restriction | limiting in particular in the method of manufacturing the liquid crystalline polyester resin composition in this invention, A well-known method can be used. For example, a method of mixing each component in a solution state and evaporating the solvent or precipitating in the solvent can be mentioned. From an industrial point of view, a method of kneading each component in a molten state is preferable. For melt kneading, generally used kneading apparatuses such as a single or twin screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable.
In the melt-kneading, the cylinder setting temperature of the kneading apparatus is preferably in the range of 200 to 360 ° C, more preferably 230 to 350 ° C.

  At the time of kneading, each component may be uniformly mixed in advance with an apparatus such as a tumbler or a Henschel mixer, and if necessary, a method of omitting the mixing and separately supplying each of the components to the kneading apparatus is also used. be able to.

  In the liquid crystal polyester resin composition used in the present invention, an inorganic filler is used as desired. Examples of such inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass flakes, aluminum borate whiskers, and potassium titanate fibers.

  If necessary, the liquid crystalline polyester resin composition used in the present invention may further include an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic colorant. Add various additives such as rust preventives, crosslinking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss improvers, mold release improvers such as fluororesins during the manufacturing process or in subsequent processing steps. Can do.

  In order to produce a liquid crystal polyester resin composition film or sheet, the liquid crystal polyester resin composition obtained by the above method can be obtained by melt kneading with an extruder and taking out the molten resin extruded through a die. Alternatively, the components can be dry blended at the time of molding and kneaded during the melt processing operation to obtain a resin composition without directly going through the kneading process, and a directly molded product can be obtained. As the die (die), a T-die (hereinafter sometimes referred to as a T-die) or an annular slit die can be used.

  In the case of film (sheet) molding using a T-die, the liquid crystal polyester resin composition melt-kneaded by an extruder usually becomes a sheet-like melt through a downward T-die, and then taken in the longitudinal direction through a pressure roll. It is wound up by the device.

  The setting conditions of the extruder at the time of film formation are appropriately selected according to the composition of the composition, but the set temperature of the cylinder of the extruder is preferably in the range of 200 to 360 ° C, and in the range of 230 to 350 ° C. Is more preferable. If it is outside this range, the composition may be thermally decomposed or it may be difficult to form a film.

  The thickness of the liquid crystal polyester resin composition film (sheet) in the T-die method can be controlled in the range of 1 to 1000 μm, but a thickness of 5 to 100 μm is practically used and preferable. The draft ratio of the liquid crystalline polyester resin composition film of the present invention is in the range of 1.1 to 40.0.

Moreover, the biaxially stretched film of the outer resin composition extruded from the T die can also be obtained.
Although there is no restriction | limiting in particular in the method of biaxial stretching in manufacture of the liquid crystalline polyester resin composition film of this invention, Specifically, the melt of the composition of this invention extruded from T die of the extruder is MD direction (longitudinal direction). ) And then stretching in the TD direction (transverse direction), sequential stretching in which the sheet extruded from the T die is stretched simultaneously in the MD and TD directions, and biaxial stretching in the unstretched sheet extruded from the T die. Examples of the biaxial stretching method include sequential stretching or simultaneous stretching with a machine, a tenter, or the like.

  Regardless of the method, the film formation temperature is preferably in the temperature range of the flow start temperature minus 60 ° C. or more and the flow start temperature plus 60 ° C. or less of the liquid crystal polyester resin composition of the present invention. More preferably, the film formation is performed in a temperature range of 30 ° C. or lower.

  The slit interval of the T die is preferably 0.2 mm to 1.5 mm. An appropriate value is determined for the draw ratio depending on the molding method. For example, in the case of stretching with a biaxial stretching machine, if the stretch ratio is defined by (length after stretching / original length), MD stretching direction, TD The draw ratio in each direction is 1.2 to 20.0, preferably 1.5 to 5.0. If the draw ratio is less than 1.2, the tensile properties may be lowered, and if it is more than 20.0, the smoothness of the film may be insufficient.

  In the case of inflation molding (film formation) using an annular slit die, the obtained liquid crystal polyester resin composition is supplied to a melt-kneading extruder equipped with an annular slit die, and a cylinder set temperature of 200 to 360 ° C., preferably Is melt kneaded at 230 to 350 ° C., and the tubular resin is extruded upward or downward from the annular slit of the extruder. The interval between the annular slits is usually 0.1 to 5 mm, preferably 0.2 to 2 mm, and the diameter of the annular slit is usually 20 to 1000 mm, preferably 25 to 600 mm.

A draft in the longitudinal direction (MD) is applied to the melt-extruded tubular molten resin film, and a transverse direction perpendicular to the longitudinal direction by blowing air or an inert gas such as nitrogen gas from the inside of the tubular film. The film can be expanded and stretched to (TD).
In the inflation film formation of the liquid crystal polyester resin composition in the present invention, a preferable blow ratio is 1.5 to 10, and a preferable MD stretch ratio is 1.5 to 40.
If the setting conditions at the time of inflation film formation are outside the above range, it is difficult to obtain a high-strength liquid crystal polyester resin composition film having a uniform thickness and no wrinkles.
The expanded film is air-cooled or water-cooled around the circumference, and then taken through a nip roll.

  In the inflation film formation, conditions can be selected such that the cylindrical melt film expands to a smooth surface with a uniform thickness according to the composition of the liquid crystal polyester resin composition.

  The film thickness of the liquid crystal polyester resin composition film in the inflation film formation can be controlled in the range of 5 to 1000 μm, but a film having a thickness of 5 to 100 μm is practically used.

  The film obtained from the liquid crystal polyester resin composition of the present invention can be subjected to a surface treatment as necessary. Examples of such surface treatment methods include corona discharge treatment, flame treatment, sputtering treatment, and solvent treatment.

The fiber material in the present invention usually has a role of reinforcing the strength of the laminate, and an inorganic fiber material or an organic fiber material can be used.
The thickness of the fiber material layer in the present invention is usually 5 to 1000 μm, preferably 10 to 500 μm.

Specific examples of the inorganic fiber material include glass fiber, quartz fiber, carbon fiber, alumina fiber, stainless steel fiber, titanium fiber, boron fiber, etc., and a mixture of these can also be used. Certain glass fibers are preferred.
Specific examples of the organic fiber material include aramid fiber, polyamide fiber, and liquid crystal polyester fiber, and a mixture thereof can also be used.
In the present invention, in order to obtain a lightweight laminate, an organic fiber material having a high elastic modulus is preferably used.

Moreover, in order to improve the adhesiveness of this organic fiber material and the thermosetting resin mentioned later, this organic fiber material can be surface-treated.
Examples of such surface treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment or solvent treatment.

  From the viewpoint of handling, the fiber material is preferably used in the form of a woven fabric, a non-woven fabric or the like, and more preferably in the form of a woven fabric.

  In the present invention, such a fiber material can be used as a component as it is, but such a fiber material can be used as a thermosetting material such as an epoxy resin, a phenol resin, a polyester resin, an acrylic resin, a polyimide resin, or a bismaleimide triazine resin. The resin can be impregnated and used as a prepreg.

Among these, an epoxy resin is preferably used from the viewpoint of being excellent in mechanical properties, heat resistance, etc. and inexpensive.
Well-known epoxy resins can be used here, such as bifunctional epoxy resins and polyfunctional epoxy resins, such as glycidyl ether of bisphenol A, glycidyl ether of phenol novolac, glycidyl ether of cresol novolac, maleimide resin, cyanate. Examples thereof include resins.

  In the present invention, a method for producing a prepreg by impregnating a fiber material with a thermosetting resin may be a known method, a method in which a thermosetting resin is dissolved in a solvent and impregnating the fiber material and drying, or a method without heating in a solvent. Examples thereof include a method of impregnating a fiber material with heating and pressurizing a curable resin. The ratio of the thermosetting resin to the fiber material is preferably 10 to 90% by weight of the fiber material.

  The laminate of the present invention is a laminate having a layer composed of the above-mentioned liquid crystal polyester resin composition and a fiber material layer containing an organic fiber material and / or an inorganic fiber material.

  In the present invention, a film or sheet comprising a liquid crystal polyester resin composition can be produced in advance, and the laminate can be formed by heating and pressing the film or sheet and the fiber material.

  In the present invention, the conditions for heating and pressurizing the film comprising the liquid crystal polyester resin composition obtained by the above-described method and the fiber material layer are not particularly limited, and the properties of the film and the fiber material layer are not limited. Conditions can be selected as appropriate.

  In order to obtain a laminate of the layer made of the liquid crystal polyester resin composition and the fiber material layer in the present invention, the liquid crystal polyester resin composition is melt-extruded from the T-die onto the fiber material layer, and then they are rolled and the like. A method of crimping can also be used. The melt extrusion of the liquid crystal polyester resin composition from the T die can be performed under the same conditions as in the above T die method.

As the metal foil used in the present invention, a metal alloy such as gold, silver, copper, nickel, aluminum, molybdenum, stainless steel, nickel, magnesium, brass, zinc, geraphite or nickel / chlor, a metal mixture, etc. should be used. However, gold, silver, copper, nickel or aluminum is preferable, and copper is more preferable.
The thickness of the metal foil used is preferably in the range of 1 to 1000 μm, more preferably in the range of 5 to 100 μm. Moreover, you may surface-treat one side or both surfaces of metal foil.

  The laminate containing the metal foil of the present invention comprises a metal foil, a layer made of the above-mentioned liquid crystal polyester resin composition, and a fiber material layer containing an organic fiber material and / or an inorganic fiber material.

In order to obtain a laminate including the metal foil in the present invention, the metal foil is superposed on the laminate of the layer made of the liquid crystal polyester resin composition and the layer made of the fiber material obtained by the above method, and heated and heated. The laminate can be obtained by pressure (thermocompression bonding).
Furthermore, a laminated body can be formed by stacking a metal foil, a film made of a liquid crystal polyester resin composition produced in advance, and a fiber material, and heating and pressurizing (thermocompression bonding) at a time.
The thermocompression bonding is simple and preferable to be performed by a press machine or a pressure roll in the vicinity of the flow start temperature of the liquid crystal polyester resin composition.

The laminate of the present invention can also have a structure having an adhesive layer between the liquid crystal polyester film and the metal foil according to the needs in the market.
Specific examples of such an adhesive layer include hot melt adhesives and polyurethane adhesives. Among these, an epoxy group-containing ethylene copolymer is preferably used.

The laminate including the metal foil obtained by the present invention is suitable for a multilayer substrate or the like, and is a laminate of three or more layers of a fiber material layer, a liquid crystal polyester resin composition layer, and a metal foil. A layer of fiber material, a three-layer structure of a layer made of the composition and a metal foil, a five-layer structure in which a layer made of the composition and a layer of fiber material are laminated on both surfaces of the metal foil, or a layer of fiber material and the layer A structure of six layers or more in which layers of the composition and metal foils are alternately laminated is also possible.
Further, a laminate structure in which an adhesive layer is provided between each layer of a fiber material layer, a layer made of a liquid crystal polyester resin composition, each layer of metal foil, or a part of layers is also possible.
The adhesive layer may be an adhesive film manufactured in advance, or may be melt extruded or coated between each layer using a T-die or a coater.

The configuration of the laminate in the present invention is as follows. When the fiber material is abbreviated as i, the layer made of the liquid crystal polyester resin composition is abbreviated as ii, and the metal foil is abbreviated as iii,
i / ii, ii / i / ii
iii / ii / i / ii / iii
iii / ii / i / ii / iii / ii / i
Many combinations are possible.

EXAMPLES Hereinafter, although an Example demonstrates this invention, these are only illustrations and this invention is not limited to these.
(1) Liquid crystalline polyester of component (A) (i) 8.3 kg (60 mol) of p-acetoxybenzoic acid, 2.49 kg (15 mol) of terephthalic acid, 0.83 kg (5 mol) of isophthalic acid and 4,4 ′ -5.45 kg (20.2 mol) of diacetoxydiphenyl was charged into a polymerization tank equipped with a comb-shaped stirring blade, heated while stirring in a nitrogen gas atmosphere, and polymerized at 330 ° C for 1 hour. Polymerization was performed under strong stirring while removing acetic acid by-produced during this period. Thereafter, the system was gradually cooled, and the polymer obtained at 200 ° C. was taken out of the system. The obtained polymer was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less. This was further treated in a rotary kiln under a nitrogen gas atmosphere at 280 ° C. for 3 hours to obtain a wholly aromatic polyester composed of the following repeating structural units in the form of particles having a flow temperature of 324 ° C.
Here, the flow temperature refers to a resin heated at a rate of temperature increase of 4 ° C./min using an enhanced flow tester CFT-500 manufactured by Shimadzu Corporation under a load of 100 kgf / cm ^2. It refers to the temperature at which the melt viscosity shows 48000 poise when extruded from a nozzle with a length of 1 mm and a length of 10 mm.
Hereinafter, the liquid crystal polyester is abbreviated as A-1. This polymer exhibited optical anisotropy at 340 ° C. or higher under pressure. The repeating structural unit of the liquid crystal polyester A-1 is as follows.

(Ii) Comb-shaped 16.6 kg (12.1 mol) of p-hydroxybenzoic acid, 8.4 kg (4.5 mol) of 6-hydroxy-2-naphthoic acid and 18.6 kg (18.2 mol) of acetic anhydride The mixture was charged into a polymerization vessel equipped with a stirring blade, heated while stirring in a nitrogen gas atmosphere, and polymerized at 320 ° C. for 1 hour and further at 320 ° C. under a reduced pressure of 2.0 torr for 1 hour. During this time, acetic acid produced as a by-product continued to be distilled out of the system. Thereafter, the system was gradually cooled, and the polymer obtained at 180 ° C. was taken out of the system.
After the obtained polymer was pulverized in the same manner as in the above (i), the polymer was treated in a rotary kiln under a nitrogen gas atmosphere at 240 ° C. for 5 hours, whereby the following repeating units in the form of particles having a flow temperature of 270 ° C. A wholly aromatic polyester was obtained. Hereinafter, the liquid crystal polyester is abbreviated as A-2. This polymer exhibited optical anisotropy at 280 ° C. or higher under pressure.
The ratio of the repeating structural unit of the liquid crystal polyester A-2 is as follows.

(2) Component (B)
(I) (Meth) acrylic acid ester-ethylene-unsaturated carboxylic acid ester copolymer rubber

  According to the method described in Example 5 of JP-A-61-127709, methyl acrylate / ethylene / glycidyl methacrylate = 59.0 / 38.7 / 2.3 (weight ratio), Mooney viscosity = 15 Got rubber. Hereinafter, the rubber may be abbreviated as B-1.

  Here, the Mooney viscosity is a value measured using a large rotor at 100 ° C. according to JIS K6300.

(Ii) Epoxy group-containing ethylene copolymer manufactured by Sumitomo Chemical Co., Ltd., Bond First 7M
ET / MA / GMA copolymer ET / MA / GMA = 64/30/6 (weight ratio)
MI (190 ° C.) = 9
ET: ethylene, MA: methyl acrylate,
GMA: Glycidyl methacrylate

(3) Measurement of dielectric constant and dielectric loss tangent: Using an LCR meter 4275A apparatus manufactured by Yokogawa Hewlett-Packard Company, gold electrodes were vapor-deposited on both surfaces of the sample and measured at 1 MHz.

(4) Film Formation of Liquid Crystalline Polyester Resin Composition Each component was mixed with a Henschel mixer with the composition shown in Table 1, and melt kneaded under the conditions shown in Table 1 using a TEX-30 type twin screw extruder manufactured by Nippon Steel Co., Ltd. To obtain a composition.
The pellets of this composition were melt-extruded under the conditions shown in Table 1 using a 50 mmφ single-screw extruder equipped with a cylindrical die, and upward from the cylindrical die having a diameter of 50 mm and a lip interval of 1.5 mm under the conditions shown in Table 1. The molten resin was extruded, dry air was pressed into the hollow portion of the tubular film to expand the tubular film, and then cooled, and then passed through a nip roll to obtain a liquid crystal polyester resin composition film.
The drawing direction (MD direction) of the liquid crystal polyester resin composition film and the draw ratio in the direction perpendicular to the drawing direction (TD direction) were controlled by the amount of dry air to be press-fitted and the film drawing speed. At this time, the blow ratio in the TD direction and the draw ratio in the MD direction are as shown in Table 1. Sample numbers and thicknesses of the obtained liquid crystal polyester resin composition films are as shown in Table 1.

Example 1
As epoxy resin, 100 parts by weight of novolak type epoxy resin ESCN-195 manufactured by Sumitomo Chemical Co., Ltd., 5.4 parts by weight of curing agent dicyanamide, and 0.2 weight of 2-ethyl-4-methylimidazole as a catalyst The untreated glass fiber cloth of TYPE 181 is immersed in the added part so that the glass content becomes 62% by weight, heat-treated at 200 ° C. for 3 hours under reduced pressure, and the epoxy resin is cured, and the thickness is 40 μm. A glass fiber cloth was given.
On both surfaces of the glass fiber cloth, resin film F-1, PermaTac AW-060 (epoxy resin manufactured by Kyodo Yakuhin Co., Ltd.) and electrolytic copper foil having a thickness of 35 μm are sequentially stacked, dried and PermaTac AW-060. After removing the solvent, the laminate was pressed at 330 ° C., 90 kg / cm ² , and molding conditions for 20 minutes.
The obtained laminate had a dielectric loss tangent of 0.007 and a dielectric constant of 2.5.

Comparative Example 1
A laminate was obtained in the same manner as in Example 1 except that the resin film F-1 was not used. The obtained laminate had a dielectric loss tangent of 0.030 and a relative dielectric constant of 4.3.

Example 2
To Sumitomo Chemical Co., Ltd. general-purpose epoxy resin Sumiepoxy ELA-128 (trade name) 100 parts by weight, Sumitomo Chemical Co., Ltd. terminal functional imide oligomer SM-20 (trade name) 127 parts by weight Carbon fiber woven fabric W-3121 (trade name) manufactured by Toho Bethron Co., Ltd. was impregnated and heated at 200 ° C. for 45 minutes to cure the resin, thereby obtaining a sheet having a thickness of 90 μm. At this time, the amount of carbon fiber was 39% by weight.
While four resin films F-3 were stacked, a total of three sheets of the above obtained sheets were sandwiched one by one, and an electrolytic copper foil with a thickness of 18 μm was stacked on the outer F-3, 250 ° C., 120 kg / It was press-molded under the conditions of cm ² and 30 minutes to obtain a 9-layer laminate. The laminate had a dielectric loss tangent of 0.005 and a relative dielectric constant of 2.5.

Example 3
Sumitomo Chemical Co., Ltd. novolak resin ESCN-195 is added to 100 parts by weight of epoxy resin containing 5.4 parts by weight of curing agent dicyanamide and 0.2 parts by weight of 2-ethyl-4-methylimidazole catalyst. A woven fabric of 100 μm aramid fibers (trade name: Twaron, manufactured by Nippon Aramid Co., Ltd.) was impregnated and dried to obtain a prepreg having 41% by weight aramid fibers.
5 sheets of the prepregs are stacked, and resin films F-4 and 18 μm thick electrolytic copper foils are stacked on both sides of the prepreg, and then press molded at 235 ° C., 30 kg / cm ² for 1 hour. A laminate was obtained. The obtained laminate had a dielectric loss tangent of 0.005 and a relative dielectric constant of 2.2.

Claims (22)

  (A) a layer composed of a liquid crystal polyester resin composition having a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group having reactivity with the liquid crystal polyester as a dispersed phase, and an organic fiber material and / or an inorganic fiber material A laminate having a fiber material layer containing   Metal foil, (A) a layer comprising a liquid crystal polyester resin composition comprising a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group having reactivity with the liquid crystal polyester as a dispersed phase, and an organic fiber material and / or A laminate comprising a fiber material layer containing an inorganic fiber material.   The laminate according to claim 2, wherein the metal foil is a metal foil made of any one of gold, silver, copper, nickel, and aluminum.   The laminate according to claim 2, wherein the metal foil is a copper foil.   The laminated material according to any one of claims 1 to 4, wherein the inorganic fiber material contains at least one selected from glass fiber, quartz fiber, carbon fiber, alumina fiber, stainless steel fiber, titanium fiber, and boron fiber. body.   The laminate according to any one of claims 1 to 5, wherein the organic fiber material contains at least one selected from aramid fibers, polyamide fibers, and liquid crystal polyester fibers.   The layered product according to any one of claims 1 to 6, wherein the layer of the fiber material is a woven fabric or a nonwoven fabric made of the fiber material.   The liquid crystal polyester resin composition comprises (A) 56.0 to 99.9% by weight of liquid crystal polyester, and (B) 44.0 to 0.1% by weight of a copolymer having a functional group reactive with the liquid crystal polyester. The laminate according to any one of claims 1 to 7, which is contained.   The liquid crystal polyester resin composition comprises (A) 56.0 to 99.9% by weight of liquid crystal polyester, and (B) 44.0 to 0.1% by weight of a copolymer having a functional group reactive with the liquid crystal polyester. It is a composition obtained by melt-kneading, The laminated body in any one of Claims 1-7 characterized by the above-mentioned.   The laminate according to any one of claims 1 to 9, wherein the functional group having reactivity with the liquid crystal polyester is an oxazolyl group, an epoxy group, or an amino group.   The laminate according to any one of claims 1 to 9, wherein the functional group having reactivity with the liquid crystal polyester is an epoxy group.   The copolymer (B) having a functional group reactive with the liquid crystal polyester is a copolymer containing 0.1 to 30% by weight of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units. The laminate according to any one of claims 1 to 9.   The laminate (1) according to any one of claims 1 to 12, wherein the copolymer (B) having a functional group having reactivity with the liquid crystal polyester is a thermoplastic resin having an epoxy group.   The thermoplastic resin having an epoxy group is (a) 50 to 99% by weight of ethylene units, (b) 0.1 to 30% by weight of unsaturated carboxylic acid glycidyl ester units or unsaturated glycidyl ether units, (c) The laminate according to claim 13, which is an epoxy group-containing ethylene copolymer comprising 0 to 50% by weight of an ethylenically unsaturated ester compound unit. The laminate according to any one of claims 1 to 14, wherein the liquid crystal polyester (A) contains at least 30 mol% of the following repeating structural units.

  The laminate according to any one of claims 1 to 14, wherein the liquid crystal polyester (A) is obtained by reacting an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid.   The laminate according to any one of claims 1 to 14, wherein the liquid crystal polyester (A) is obtained by reacting a combination of different kinds of aromatic hydroxycarboxylic acids.   The layered product according to any one of claims 1 to 17, wherein the layer of the liquid crystal polyester resin composition is a liquid crystal polyester resin composition film or sheet obtained by melt extrusion from a T-die.   The layer of the liquid crystal polyester resin composition is a film obtained by uniaxially stretching or biaxially stretching the liquid crystal polyester resin composition melt-extruded from a T-die. The laminated body as described in.   The layered product according to any one of claims 1 to 17, wherein the layer of the liquid crystal polyester resin composition is a film obtained by inflation molding the liquid crystal polyester resin composition.   The method for producing a laminate according to any one of claims 1 to 20, wherein the layers are overlapped and thermocompression bonded. A multilayer substrate comprising the laminate according to any one of claims 2 to 20.