JP3029071B2 - Laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate mainly composed of a polyphenylene sulfide resin and a fiber sheet.
In particular, the present invention relates to a laminate optimally used for a circuit board or the like.

[0002]

2. Description of the Related Art In the field of electric and electronic components, various characteristics such as heat resistance, thermal dimensional stability, low moisture absorption, flame retardancy, high frequency characteristics, etc. have been taken to a high degree from the viewpoint of miniaturization and high performance of equipment. The demand for balanced insulating substrates is increasing. Above all, the required characteristics of the circuit board include flatness, smoothness (necessary for fine patterning), workability of through holes, and thinning.

[0003] As a substrate in this field, there are a substrate in which glass cloth is impregnated with an epoxy resin (hereinafter sometimes abbreviated as glass epoxy), a polyimide film, a fluorine-based film, and the like. Furthermore, unstretched sheets and biaxially oriented films of poly-p-phenylene sulfide (hereinafter sometimes abbreviated as PPS) have recently received particular attention. Also,
Examples of a laminated film or a laminate using a biaxially oriented poly-p-phenylene sulfide film (hereinafter, may be abbreviated as a PPS film) include (1) a laminated film with a polyester film (Japanese Patent Application Laid-Open No. 62-292431). JP-A-60-63158, (2) Laminated with aromatic polyamide fiber sheet via an adhesive, and (3) Infusible at a temperature of 300 ° C and at a temperature of 150 ° C A laminate with a fiber sheet having a coefficient of thermal expansion of 50 × 10 ⁻⁶ / ° C. or less (Japanese Patent Application Laid-Open No. 1-95585) is known. In addition, (4) a laminate of an unstretched sheet of PPS (hereinafter sometimes abbreviated as PPS sheet) and a PPS film is also known (Japanese Patent Application Laid-Open No. 2-45144).

[0004]

However, each of the above films and laminates has the following problems. The glass epoxy is inferior in low hygroscopicity and high frequency characteristics, and it is difficult to make it thinner. Polyimide films have high heat resistance, but are poor in low moisture absorption and high frequency characteristics. Further, the fluorine-based film has poor adhesiveness, and it is difficult for the conductive paste to be applied during processing of the through-hole.

On the other hand, a PPS sheet alone satisfies various properties such as thermal dimensional stability, low moisture absorption, flame retardancy, and high-frequency characteristics, but has a lower heat resistance temperature than a biaxially oriented film (glass When the temperature exceeds the transition point, thermal deformation tends to occur.), And as the number of heating steps increases, crystallization proceeds and the material becomes brittle. When used as a printed circuit board, the heat resistance and the brittleness are satisfied to some extent by controlling the crystal size and the like, but there is a problem that heat deformation easily occurs when heat is applied suddenly.

In addition, since the PPS film itself undergoes dimensional changes due to thermal shrinkage, for example, when heat is applied in the process of manufacturing a circuit board, circuit misalignment is likely to occur. Further, there is a problem that the laminated circuit board is easily torn at the time of processing a through hole.

[0007] In the laminated film with the polyester film of the above item (1), the tearability during the above-mentioned through-hole processing is improved, but the thermal dimensional stability and heat resistance are not improved. In the case of laminating the aromatic polyamide fiber sheet of item (2) with an adhesive, the heat resistance is improved.
PPS has an adverse effect on the heat resistance of the adhesive (that is, the heat resistance of the adhesive governs the heat resistance of the entire substrate).
Cannot take full advantage of its excellent characteristics. Further, the conductive paste permeates into the aromatic polyamide fiber sheet during the through-hole processing, and the through-hole processing cannot be performed.

The laminate of item (3), in which the PPS film and the fiber sheet are laminated by heat fusion, has poor adhesion and is easily peeled off when a force such as bending is applied. Further, the conductive paste permeates the fiber sheet during the through-hole processing, and the through-hole processing cannot be performed. Further, the laminate of the item (4) lacks thermal dimensional stability and heat resistance similarly to the PPS film alone.

Further, it is conceivable to impregnate the fiber sheet with the PPS resin, but in order to improve the impregnating property, it is necessary to set the impregnation temperature to be higher than the melting point of the PPS resin. As a result, the planarity of the resin-impregnated fiber sheet is deteriorated, and there is a problem particularly in the processability of forming a high-density circuit.

The present invention focuses on the excellent low moisture absorption, flame retardancy, and high frequency characteristics of PPS, and while maintaining these characteristics,
The object is to provide a heat-resistant base material which has improved heat resistance and thermal dimensional stability, and has excellent flatness, smoothness, and through-hole workability, and is particularly suitable for use in circuit boards (including multilayer circuit boards). And

[0011]

According to the present invention, there is provided a fibrous sheet (A) comprising at least a p-phenylene sulfide unit as a main repeating unit and a p-phenylene sulfide unit as a main repeating unit.
A resin-impregnated sheet impregnated with a resin composition (B) comprising a copolymerized polyphenylene sulfide obtained by copolymerizing at least one copolymer unit other than a phenylene sulfide unit, and a resin composition containing poly-p-phenylene sulfide as a main component It is a laminate composed of the product (C) layer.

The fiber sheet (A) in the present invention is a thin sheet composed of an aggregate of fibers, and is a generic term for cloth, cloth, felt, nonwoven fabric, paper, etc., and has a thickness of 10%.
５００500 μm (preferably 10-300 μm). The fiber sheet may be subjected to processing such as easy adhesion and coloring, or may be a mixture or a laminate of two or more materials. Among the fiber sheets, cloth is preferable, and glass fiber cloth is particularly preferable in terms of heat resistance, dimensional stability, and workability. Here, the impregnation means that the resin enters around the element fibers constituting the fiber sheet and is adhered and solidified to the element fibers.

It is preferable that the fiber sheet does not have a melting point up to a temperature of 400 ° C., ie, is infusible at a temperature of 400 ° C. Here, the term "infusible" means a state in which it is not melted or softened when exposed to a temperature of 400 ° C. If the fiber sheet used in the present invention does not have the above-described properties, the impregnated sheet of the present invention has insufficient thermal dimensional stability when exposed to a temperature around 300 ° C.

In the present invention, copolymerized polyphenylene sulfide (hereinafter sometimes abbreviated as copolymerized PPS).
The term “p-phenylene sulfide unit” refers to a unit formed by copolymerizing one or more other copolymerized units with a p-phenylene sulfide unit as a main repeating unit. The content of p-phenylene sulfide unit in the copolymerized polyphenylene sulfide is in the range of 50 to 95 mol% (preferably 70 to 92 mol%) based on all repeating units. If the content is less than 50 mol%, the heat resistance and thermal dimensional stability of the resin-impregnated sheet when the resin is impregnated into the fiber sheet are poor, and conversely, 95%.
If it exceeds mol%, the impregnating property of the fiber sheet deteriorates, and the flatness of the impregnated sheet significantly deteriorates.

As the copolymerized unit, m-phenylene sulfide unit, (Chem. 1), (Chem. 2), (Chem. 3), (Chem. 4)
And these composite units may be present. Preferred copolymerized units are m-phenylene sulfide units. The copolymerization amount of these units is such that the copolymer unit next to the p-phenylene sulfide unit, which is the main repeating unit of the copolymerized PPS, is 3 to the total repeating units.
~ 50 mol% (preferably 5-30 mol%). If the content is less than 3 mol%, the impregnating property of the fiber sheet deteriorates, and the flatness of the impregnated sheet significantly deteriorates. On the other hand, when the content exceeds 50 mol%, the heat resistance and the thermal dimensional stability of the resin-impregnated sheet when the fiber sheet is impregnated with the resin become poor.

The remaining part of the repeating unit of the copolymerized PPS may be constituted by other copolymerizable units, but the trifunctional phenylene sulfide unit represented by the formula (5) It is preferably at most 1 mol% of the whole.

[0017]

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[0018]

Embedded image (Where X represents an alkylene, CO, or SO2 unit)

[0019]

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[0020]

Embedded image (Here, R represents an alkyl, nitro, phenylene, or alkoxy group.)

[0021]

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The mode of copolymerization of the copolymerized PPS of the present invention may be random or block, but is preferably random. The copolymer composition can be determined by any means depending on the composition.

Further, a resin composition comprising a copolymerized PPS (hereinafter sometimes abbreviated as a copolymerized PPS composition).
(B) means that the copolymerized PPS accounts for 80% by weight or more (preferably 90% by weight or more) of the resin component. If the remaining amount is less than 20% by weight, organic and inorganic additives other than the copolymerized PPS, inert particles and the like may be contained.

The melting point of the copolymerized PPS composition of the present invention is 2
The range of 00-285 degreeC is preferable. Melt viscosity is 30
50-2000 at 0 ° C. and a shear rate of 200 / sec.
0 poise (more preferably, 100 to 10,000 poise) is preferable.

In the present invention, poly-p-phenylene sulfide refers to a polymer in which 80 mol% or more (preferably 90 mol% or more) of the repeating unit is constituted by a structural unit represented by the following structural formula (Formula 6). . When the content of such a component is less than 80 mol%, the crystallinity of the polymer, the heat transition temperature, and the like are low, and the PPS
The heat resistance, dimensional stability, mechanical properties, and the like, which are characteristics of the resin composition containing as a main component, are impaired.

[0026]

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In the above PPS, the repeating unit 20
If the amount is less than mol%, preferably less than 10 mol%, a unit containing a copolymerizable sulfide bond may be contained. The method of copolymerizing the polymer may be random or block type.

In the present invention, the resin composition containing poly-p-phenylene sulfide as a main component (hereinafter sometimes abbreviated as a PPS composition) (C) refers to poly-p-phenylene sulfide of 60% by weight. Refers to a composition containing the above.
When the content of PPS is less than 60% by weight, mechanical properties, heat resistance, heat-fusibility and the like of a laminate comprising the composition are impaired. The remaining less than 40% by weight of the composition may contain additives other than PPS, such as polymers, inorganic or organic fillers, lubricants, and coloring agents. Further, the melt viscosity of the PPS composition is 100 to 50,000 poise (more preferably 50 to 50,000 poise) at a temperature of 300 ° C. and a shear rate of 200 / sec.
The range of 0 to 20,000 poise) is preferable from the viewpoint of workability of lamination.

The laminate of the present invention comprises a resin-impregnated sheet obtained by impregnating a fiber sheet with the above-mentioned copolymerized PPS composition and a PP-impregnated sheet.
It consists of a layer of the S composition. As described above, impregnation refers to a state in which a resin enters around the element fibers constituting the fiber sheet and is adhered and solidified to the element fibers. The impregnation state can be measured, for example, by the degree of ink penetration.
In the laminate of the present invention, a fiber sheet (A) is basically impregnated with a copolymerized PPS composition (B), and a PPS composition (C) layer is formed on the copolymerized PPS composition layer of the sheet. Is thermally fused, but a part of the (C) layer may be impregnated in the fiber sheet (A) together with the copolymerized PPS composition (B). That is, the following three aspects can be considered as the basic configuration of the laminate of the present invention.

(1) A laminate in which a layer C is heat-sealed to at least one surface of a structure in which A is impregnated with B and the resin-impregnated fiber sheet has the same thickness as A and B. (2) A laminate in which a layer of C is heat-sealed on at least one surface of a structure in which B has a thickness greater than A of a resin-impregnated fiber sheet in which A is impregnated with B. (3) At least one surface of the resin-impregnated layer of the resin-impregnated fiber sheet has a part of the C layer penetrated (meaning that a part of the C layer is impregnated with A together with B). Do) laminate.

In order to achieve the object of the present invention, it is preferable that the fiber sheet (A) is impregnated with the copolymerized PPS composition (B), and the PPS composition (C) is laminated on both sides of the sheet. The body is preferred. Further, PP in the laminate of the present invention
The layer of the S composition (C) may be substantially non-oriented or uniaxially or biaxially oriented. Where the copolymerized PPS
Although there is no particular limitation on the ratio of the PPS composition layer and the fiber sheet layer, when the thickness of each layer is measured with a microscope or the like from the cross section of the impregnated sheet, the thickness (b +
The ratio ((b + c) / a) of c) to the thickness (a) of the fiber sheet layer impregnated with PPS is preferably in the range of 0.25 to 2.5 in view of impregnation and thermal dimensional stability. Further, the layer (A) of the laminate of the present invention does not necessarily need to be present at the center in the thickness direction of the laminate, and may be located at a shifted position.

The layer thickness (b) of the copolymerized PPS resin composition in the layer of the laminate of the present invention consisting of the PPS resin alone and PP
The ratio (b / c) of the thickness (c) of the S resin composition is 2.0 or less when both layers are not oriented, and 1.5 or less when the layer (C) is oriented with the fiber sheet. It is preferable in terms of impregnation, heat resistance, thermal dimensional stability, flatness, and smoothness. In the case where the layered structure of the layered product of the present invention is the embodiment of the above item (3), the layer thickness (b ′) of the copolymerized PPS resin composition in the layer of (A)
) And the thickness (c ′) of the PPS resin composition (b ′ /
c ′) is preferably 2.0 or more from the viewpoint of impregnation. In addition,
The thickness of the layer having the thickness of (b) or (b ') and the thickness of the layer having the thickness of (c) or the layer having the thickness of (c') can be determined by, for example, a deflection microscope due to the difference in crystallization behavior between the two. It can be measured from a cross-sectional photograph of the laminate.

In the present invention, the difference between the melting point of the resin composition of the layer (C) and the melting point of the resin composition of the layer (B) is 5 to 90 ° C.
Is preferable in terms of processability and easy achievement of the object of the present invention.

The laminate of the present invention preferably has a permeation degree of the ink described below of 2.0 or less (more preferably 1.5 or less). When the degree of permeation exceeds 2.0, the rate of thermal dimensional change becomes large, and through-hole processing becomes difficult, and it becomes difficult to achieve the object of the present invention. Here, the degree of penetration of the ink means that when magic ink is applied to the surface in the cross-sectional direction (thickness direction) of the laminate, the ink penetrates into the inside, but the length of the ink penetrated (from the position where the magic ink is applied) The maximum distance reached by the ink) is a value represented by the length (mm) measured from the surface of the sheet, and is a parameter representing the degree of impregnation of the laminate.

[Production Method] Next, a method for producing the PPS resin-impregnated fiber sheet of the present invention will be described. First, there are various methods for polymerization of the copolymerized PPS used in the present invention.
A method in which alkali sulfide, p-dihalobenzene (main monomer) and auxiliary monomer are blended in the ratio according to the present invention, and polymerization is carried out at a high temperature and a high pressure in a polar solvent in the presence of a polymerization aid, It is preferable because the degree increases easily.
In particular, it is preferable to use sodium sulfide as an alkali sulfide, p-dichlorobenzene as a main component monomer, and N-methylpyrrolidone as a solvent. Examples of the subcomponent monomer in which the subcomponent monomer coexists with p-dihalobenzene (main component monomer) include (Chemical Formula 7), (Chemical Formula 8), (Chemical Formula 9),
(Formula 10) and (Formula 11), and a plurality of these subcomponent monomers may be present. A preferred subcomponent monomer is (Chemical Formula 12).

[0036]

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[0037]

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[0038]

Embedded image (Where X represents an alkylene, CO, or SO ₂ unit)

[0039]

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[0040]

Embedded image (Where R represents an alkyl, nitro, phenylene, or alkoxy group)

[0041]

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On the other hand, the PPS of the present invention is polymerized in the same manner as the copolymerized PPS, but does not include or reduces the amount of the auxiliary component monomer as described in the present invention. Of course, for the purpose of adjusting the copolymerized PPS and the melt viscosity of the PPS, a trifunctional monomer such as shown in (Chemical Formula 13) may be blended during the polymerization.

[0043]

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The copolymerized PPS and PP thus obtained
If necessary, add an inorganic or organic additive to S,
A copolymerized PPS composition and a PPS composition are provided.

Various methods can be used to impregnate this polymer into the fiber sheet, and the following method can be exemplified as a typical method. (1) The above-mentioned copolymerized PPS composition (B) and PPS composition (C) are co-extruded into unstretched and unoriented laminated sheets of (B) and (C) (hereinafter abbreviated as PPS laminated sheets). Is manufactured, and the B side of the PPS laminated sheet is aligned with the fiber sheet and thermocompression-bonded to produce a laminate.

First, a method for producing the above-mentioned PPS laminated sheet (unstretched sheet) will be described. The composition of (B) and the composition of (C) are merged and laminated in a polymer flow path between a melt extruder represented by an extruder and a die (slit die), or merged and laminated in a die. Is done. That is, the composition of B and the composition of C supplied to separate extruders and melted at a temperature equal to or higher than the melting point of each composition are mixed between an extruder and a die or a merging device provided in the die. They are laminated in a molten state and extruded from a die. By rapidly cooling such a molten laminate to a temperature below the glass transition point of the sheet, a substantially non-oriented PPS laminated sheet is obtained. Here, the merging device is 2 in the molten state.
It has the function of laminating more than one kind of polymer composition. Further, after preparing only an unstretched sheet of the PPS composition (hereinafter sometimes abbreviated as PPS sheet) under the above conditions, an unstretched sheet of the copolymerized PPS composition (hereinafter referred to as copolymerized PPS) is formed on the sheet. The sheet may be abbreviated as a sheet.) May be extruded from a die and laminated.

The non-oriented PPS laminate sheet obtained in this manner is superposed on the fiber sheet at the side (B), and the temperature is preferably between the melting point of the copolymerized PPS composition and the melting point of the PPS composition (preferably 200 to 290). ℃), pressure 1-30kg
/ Cm ² under a condition of hot roll press or hot plate press. Further, the laminate is cooled through a cooling roll, a cooling plate, fresh air, water, or the like for the purpose of maintaining the flatness of the laminate. If the thermocompression bonding temperature is lower than the melting point of the copolymerized PPS composition, the impregnation is poor. The pressure is 1k
If it is less than g / cm ² , the impregnation is poor, and conversely, 30 kg / c
If it exceeds m ² , the planarity of the laminate tends to deteriorate.
Further, the laminated structure of the laminated body of the present invention may have two layers of a fiber sheet and a laminated PPS sheet, a laminated PPS sheet,
There are cases in which three layers of a fiber sheet and a laminated PPS sheet are superposed in this order, and the latter is preferred from the viewpoint of impregnation. Further, the fiber sheet (A) before thermocompression bonding and the laminated PP
The thickness ratio ((B + C) / A) of the S sheet (B + C) is 0.
The range of 3-3.0 is preferable, and the thickness ratio (B / C) of (B) and (C) before thermocompression bonding is preferably in the range of 0.05-3.0 in order to achieve the object of the present invention. .

(2) While melt extruding the resin composition,
A method of producing a laminate by thermocompression bonding to a fiber sheet. The following two methods can be considered for this method. That is, the PPS laminated sheet is extruded by co-extrusion and laminated on the lower fiber sheet and thermocompression-bonded by the method described in (1). In this case, the thermocompression bonding may be performed simultaneously with the lamination, or may be performed in another step after the lamination. The conditions for the thermocompression bonding are the same as in the item (1). Yet another method is to laminate the PPS sheet in a lower fiber sheet while extruding the copolymerized PPS composition, and then laminate the PPS sheet in a subsequent thermocompression bonding step. Also in this case, the thermocompression bonding may be performed simultaneously with the lamination, or may be performed in another step after the lamination. The conditions for the thermocompression bonding are the same as in the item (1).

(3) A method of producing a laminate by thermocompression bonding a copolymerized PPS sheet and a PPS sheet to a fiber sheet.
First, a copolymerized PPS sheet and a PPS sheet are prepared according to the method and conditions described in (1). The obtained sheet is used as a fiber sheet (A) / copolymerized PPS sheet / PPS sheet or PPS sheet / copolymerized PPS sheet / fiber sheet (A)
/ Copolymerized PPS sheet / PPS sheet in this order and thermocompression bonded under the condition of (1). The latter configuration is preferred from the viewpoint of impregnation. Also, when the fiber sheet (A) and the copolymerized PPS sheet are thermocompressed and impregnated first, and then the PPS sheet is thermocompressed, the copolymerized PPS sheet and the PPS sheet are thermocompressed beforehand, and then the copolymerized PPS sheet. The portion may be thermocompression-bonded to the fiber sheet (A) for impregnation.

(4) A method for producing the laminate of the present invention in which the PPS fiber sheet (A) composition of the layer (C) is oriented.
Uniaxially or biaxially stretched and oriented film of the PPS laminated sheet of item (1) (hereinafter, laminated PPS uniaxial (or biaxial))
It may be abbreviated as an oriented laminated film. ) Copolymerization P
The surface of PS is superimposed on the fiber sheet and thermocompression bonded. The method and conditions of the thermocompression bonding are the same as in the item (1). Here, a method for producing a uniaxially and biaxially oriented film of the laminated PPS will be described. The uniaxially oriented film uniaxially stretches and orients the laminated PPS sheet in the longitudinal direction or the width direction by a known method. The stretching conditions are such that the stretching temperature is 90 to 1 in both the longitudinal direction and the width direction.
It is usually carried out at 20 ° C. and a draw ratio of 2.0 to 4.5. The biaxially oriented film of the laminated PPS is obtained by biaxially stretching and orienting the PPS laminated sheet by a known method. For example, when the sequential biaxial stretching method is used, the stretching conditions can be the same as those for the above uniaxial stretching in both the longitudinal direction and the width direction. Subsequently, heat treatment is performed as necessary. As a heat treatment method, a tenter method is used. Heat treatment conditions are 200-2
It is usually carried out in a temperature range of 90 ° C. under a fixed length or limited shrinkage of 15% or less. In this case, the copolymerized PPS composition layer of the biaxially oriented film of the laminated PPS may or may not be oriented, but subsequent impregnation is easier if the layer is not oriented. Further, both directions may be relaxed to improve the thermal dimensional stability of the film. In order to make the present invention effective, it is preferable to use the latter biaxially stretched film. The method for producing a monoaxially oriented or biaxially oriented film of the laminated PPS is obtained by stretching an unstretched sheet obtained by laminating a copolymerized PPS composition layer and a PPS composition layer between an extruder and a die or in a die. Yes, PP
After uniaxially or biaxially stretching and orienting a single film of an S sheet (unstretched sheet) (hereinafter sometimes abbreviated as a uniaxially or biaxially oriented PPS film), the copolymer PP is fed from another die.
A method in which the S composition is extruded and laminated with the uniaxially or biaxially oriented film can also be used. In addition, the laminated structure of the laminate of the present invention includes two layers of a fiber sheet and a monoaxially or biaxially oriented film of laminated PPS, and a thermocompression bonding of a uniaxially or biaxially oriented film of laminated PPS on both surfaces of the fiber sheet. Although there may be three layers, the latter embodiment is preferred from the viewpoint of resin impregnation. In addition, the thickness ratio ((B + C) / A) of the fiber sheet (A) before thermocompression bonding and the uniaxial or biaxially oriented film (B + C) of the laminated PPS is in the range of 0.3 to 3.0. The thickness ratio (B / C) of (B) and (C) is 0.1.
The range of from 0.05 to 2.0 is preferable for achieving the object of the present invention.

(5) While melt extruding the resin composition,
A method for producing a laminate by thermocompression bonding to a fiber sheet, a uniaxial or biaxially oriented film. Copolymerized PPS as described in (1)
While extruding the composition and laminating on the lower fiber sheet,
Thermocompression bonding is carried out together with a single uniaxially stretched or biaxially stretched PPS film previously produced in the manner of (4). The thermocompression bonding may be performed simultaneously with the lamination, or may be performed after the lamination. The conditions of the thermocompression bonding are the same as in the item (5). Further, the step of impregnating the fiber sheet with the copolymerized PPS composition and the step of laminating (thermocompression bonding) the above films may be performed separately.

(6) A method of producing an impregnated sheet by thermocompression bonding a copolymerized PPS sheet and a uniaxially or biaxially oriented PPS film to a fiber sheet. Fiber sheet (A), copolymer P
The PS sheet (B) and the uniaxially or biaxially oriented PPS film (C) are superimposed in the order of A / B / C or C / B / A / B / C and thermocompression-bonded under the conditions of (4). The latter configuration is preferred from the viewpoint of impregnation. A / B (or B /
A / B) impregnation step and subsequent lamination (thermocompression bonding) of layer (C) or B / C lamination (thermocompression bonding) and thermocompression bonding to layer (A) may be performed separately.

Further, a powdery, granular or pelletized copolymerized PPS composition is brought into direct contact with a fiber sheet and impregnated under the above conditions (1) to (6).
There is also a method of laminating (thermocompression bonding) PPS films of uniaxial orientation or biaxial orientation.

Further, after the laminated structure of the present invention is formed by the above-mentioned method or other methods, the surface of the laminated body is polished or etched by a physical or chemical method to obtain a final product. Does not matter if the object of the present invention is achieved.

[Method of Evaluating Characteristics] Next, the method of evaluating characteristics and the evaluation criteria used in the description of the present invention will be described. (1) Heat resistance A 2 cm square sample was floated in a solder bath set at a temperature of 280 ° C. and evaluated according to the following criteria. : No change at all △: Softening, deformation, peeling, and wrinkles are observed in a part. ×: The entire surface is deformed or peeled, such as waving or bending, and the dimensional change rate of each layer is greatly different.

(2) Degree of Penetration of Ink When the magic ink (magic ink portion) is brought into contact with the surface in the cross-sectional direction (thickness direction) of the impregnated sheet for 3 seconds,
The ink permeates inside. The permeated length (the longest distance that the ink reached from the position where the magic ink came into contact) was represented by the length (mm) measured from the surface of the sheet. The magic used was that of Pentel Co., Ltd. (oil of penterpene middle character N50).

(3) Average Surface Roughness (Ra) Shows the value (μm) measured by a stylus type surface roughness meter specified in JIS-R-0601 (cutoff 0.08 m
m, value at a measurement length of 4 mm).

(4) Thermal Shrinkage Rate The direction in which the sample is located is set as a reference direction, and the sample is cut into 100 mm × 10 mm in 90 ° directions of the reference direction, and the length in the longitudinal direction is accurately read with a microscope (xmm). Then 24
After aging for 30 minutes in a furnace (hot air system) heated to a temperature of 0 ° C., the length is accurately measured (ymm).
The heat shrinkage rate (%) in each direction was determined by the following formula, and the value was shown in the direction in which the heat shrinkage rate was large. Heat shrinkage (%) = (xy) / xx100

(5) Adhesion The sample was bent five times at 180 degrees, and the bent portion was observed and evaluated according to the following criteria. ：: There is no peeling of the bent portion and no decrease in the peel strength of the bent portion. Δ: The bent portion was partially peeled, and the peel strength was slightly reduced. ×: The bent portion peels off.

(6) Dielectric Characteristics (Dielectric Loss) Changes in dielectric loss were examined by changing the frequency (JIS-C
It measured according to -6481. ).

(7) Circuit Displacement The circuit board was passed through a furnace (far-infrared ray system) set at a temperature of 240 ° C. for 5 seconds, and the circuit was deviated from that of a circuit not passing through the furnace.

(8) Printability of Circuit A circuit having a width of 200 μm (line width of 200 μm) was printed on the sample with a conductive paint by silk printing. After drying, the state of the circuit was observed with a microscope and evaluated according to the following criteria. did. : Almost no swelling of circuit width, no change in line width, and no distortion. Δ: The width of the circuit is swollen, the line width is changed, and a part of the distortion is observed. ×: There are many swelling of the circuit width, change of the line width, and distorted portions.

(9) Through-Hole Properties The through-hole portions of the through-hole processed samples were observed with a microscope, and the adhesion of the conductive paint was examined.

(10) Coefficient of thermal expansion Using a balance incorporating a differential transformer and a heating furnace,
After the temperature is raised to a temperature of 100 ° C., the temperature is lowered to 100 ° C., and the dimensional change of the sample with respect to the temperature change at the time of the temperature drop is plotted and determined from the gradient. Sample size is 50mm x 5
mm and a load having a width of 0.2 g / 5 mm was applied. The measurement was performed in the direction at the time of the measurement of the thermal shrinkage, and the value was shown in the direction in which the coefficient of thermal expansion was large.

(11) The thickness of the impregnated layer (a) of the laminate, the copolymerized PPS composition layer (b, b ') of the resin layer and the PPS composition layer (c, c') and the thickness ratio (b / c, b '/
c ′) Measurement A cross-sectional photograph of the laminate was taken with an electron microscope. The fiber sheet layer and the layer in which the resin was impregnated with the resin were defined as (a), the layer composed of only the resin was defined as (b + c), and the thickness of each layer was determined as It was determined from the photograph. Also, observe with a polarizing microscope as above,
The lamination interface of the (b, b ') layer and the (c, c') layer was read from the photograph, and the thickness ratio (b / c, b '/ c') was determined.

(12) Flatness The sample was placed on a glass plate and visually observed according to the following criteria. : The surface is almost flat and has no wavy lines or lines. Δ: Ripple, linear wrinkles, etc. are present in a part of the sample. ×: Wavy wrinkles, linear wrinkles, etc. are present throughout the sample, and the flatness is extremely poor.

(13) Melt viscosity Melt viscosity was measured by a Koka type flow tester method.

(14) Melting point Measured using a differential scanning calorimeter (DSC-2).

[0069]

Next, the present invention will be described in detail with reference to examples. Example 1, Comparative Example 1 (1) Preparation of copolymerized PPS composition In an autoclave, 100 mol of sodium sulfide nonahydrate, 45 mol of sodium hydroxide and 25 l of N were added.
-Methyl-pyrrolidone (hereinafter sometimes abbreviated as NMP) was charged, the temperature was gradually raised to 220 ° C. with stirring, and the contained water was removed by distillation. 91 mol% of p-dichlorobenzene as a main component monomer, 10 mol% of m-dichlorobenzene as a subcomponent monomer, and 0.2 mol% of 1,2,4 trichlorobenzene are introduced into the dehydrated system. Add with 5 liters of NMP and add 1
After pressurizing and filling nitrogen at 3 kg / cm ² at 70 ° C.,
Polymerization was performed at 60 ° C. for 4 hours. After the completion of the polymerization, the mixture was cooled, the polymer was precipitated in distilled water, and a small block polymer was collected by a wire mesh having a 150 mesh opening. The polymer was washed five times with distilled water at 90 ° C., and then dried under reduced pressure at 120 ° C.
At a melt viscosity of 1000 poise and a melting point of 25.
A 3 ° C. white particulate copolymerized PPS composition was obtained. Next, 50 g of spherical silica having a diameter of 0.5 μm was blended with 10 kg of the copolymerized PPS, and the mixture was extruded at 320 ° C. into a gut shape using a 30 mm φ twin screw extruder to form pellets.

(2) Preparation of PPS Composition PPS was prepared in the same manner as in the preparation of the copolymerized PPS composition (1) except that 101 mol of p-diclebenzene was used as the main component monomer and no subcomponent monomer was used. A composition was prepared. The melt viscosity of the PPS composition was 300
The melting point was 0 poise and the melting point was 283 ° C.

(3) Production of Laminated Sheet of Copolymerized PPS and PPS The copolymerized PPS composition and the PPS composition obtained in the above (1) and (2) were each treated at 180 ° C. for 3 hours.
After drying under reduced pressure of mmHg, the mixture is supplied to a separate extruder, and in a molten state, the above-mentioned polymers are guided to be laminated by a double-tube laminating apparatus at the upper part of the die. And then cooled and solidified by a cooling rotating drum, and a two-layer laminated sheet of copolymerized PPS / PPS (unoriented)
Were obtained. The thickness of the laminated sheet is 25 μm, the thickness (B) of the copolymerized PPS layer is 12 μm (PPS laminated sheet-1), the thickness of the B is 18 μm (PPS laminated sheet-2), and the B Thickness of 5 μm (P
PS laminated sheet-3) were three kinds of PPS laminated sheets.

(4) Preparation of Fiber Sheet Glass cloth (EPC030 manufactured by Arisawa Seisakusho)
4 μm was used (fiber sheet-1).

(5) Production of Laminate A PPS laminate sheet-1 was provided on both sides of the fiber sheet-1.
The PPS laminated sheet-2 and the PPS laminated sheet-3 were each subjected to thermocompression bonding to obtain three types of laminated bodies (laminated bodies-1, 2, and 3 in that order).
3). The thermocompression bonding method was such that three sheets were superimposed on the above structure and thermocompression bonded by a hot plate press method. The thermocompression bonding conditions were a temperature of 270 ° C., a pressure of 10 kg / cm ² , a pressing time of 1 hour, and then quenched to 50 ° C. Next, the above-mentioned copolymerized PPS composition and PPS composition were
The co-polymerized PPS sheet (unstretched sheet) having a thickness of 25 μm (m-PPS sheet-) is supplied to an extruder having an m-hole diameter, discharged from a T-die die, cooled and solidified by a cooling rotary drum.
1) and a PPS sheet (unstretched sheet) having a thickness of 25 μm (p-PPS sheet-1) were obtained. The two types of sheets are superimposed on both sides of the fiber sheet-1 and thermocompression bonded under the above conditions, and a resin-impregnated sheet (impregnated sheet-1) made of m-PPS sheet-1 and a p-PPS sheet-1
A resin impregnated sheet (impregnated sheet-2) consisting of Further, a thermocompression-bonding temperature of the resin-impregnated sheet using the p-PPS sheet-1 was set to 295 ° C., and the others were thermocompression-bonded under the above conditions (impregnated sheet-3).

Example 2, Comparative Example 2 A PPS laminated sheet obtained in the same manner as in Example 1 was biaxially stretched. Stretching conditions are such that a sequential stretching method is used and the longitudinal direction is low.
The stretching temperature was 90 ° C., the stretching ratio was 3.7 times, and the stretching direction was 10 ° in the width direction. The stretching temperature was 100 ° C., and the stretching ratio was 3.5 times. Subsequently, heat treatment was performed at 260 ° C. for 10 seconds in the same tenter. The thickness of the obtained PPS laminated biaxially oriented film was 25 μm, and the thickness of the copolymerized PPS layer was 17 μm.
The film was superimposed on both sides of the fiber sheet-1 such that the copolymerized PPS surface of the film was in contact with the fiber sheet-1, and was thermocompression-bonded with a heated press roll. Temperature 270 ° C, pressure 10k
g / cm ² and the line speed was 0.5 m / min (Laminate-4). Further, the p-PPS sheet of Comparative Example 1 was biaxially stretched under the above conditions to obtain a PPS biaxially oriented film of 25 μm. The film was subjected to a thermocompression bonding temperature of 270 ° C. and 295 ° C. by the method of Laminate-4 to obtain two types of laminates (Laminates-5 and 6 in order).

Example 3 The amount of the main component monomer, p-dichlorobenzene, added was 94.8.
The copolymerized PPS was polymerized under the same conditions as in Example 1 except that the addition amount of the auxiliary component monomer m-dichlorobenzene was 5 mol%. (Melting point: 264 ° C.) The same PPS as used in Example 1 was used. Further, a PPS laminated sheet was prepared under the conditions of the laminated sheet-2 of Example 1, and only the thermocompression bonding temperature was set to 280 ° C. under the conditions of Example 1 to prepare a laminated body (Laminate-7).

Example 4 Addition amount of the main component monomer p-dichlorobenzene 69.8
The copolymerized PPS was polymerized under the same conditions as in Example 1 (melting point: 201 ° C.) except that the amount of the auxiliary component monomer m-dichlorobenzene was 30 mol%. Further, the same PPS as in Example 1 was used. Further, the laminated sheet-2 of Example 1
A PPS laminated sheet was produced under the conditions of (1), and only the thermocompression bonding temperature was set to 260 ° C. under the conditions of Example 1 to produce a laminate (laminate-8).

Example 5 By the method of Comparative Example 1, a copolymerized PPS sheet having a thickness of 15 μm and an unstretched PPS sheet having a thickness of 10 μm (p-PPS sheet-2) were obtained. The sheet and the fiber sheet-1 were overlaid so as to have a C / B / A / B / C configuration, and thermocompression-bonded under the conditions of Example 1 (laminate-
9).

Comparative Example 3 An unstretched PPS sheet having a thickness of 100 μm was prepared by the method of Comparative Example 1 or Example 5, and heat-treated at a temperature of 250 ° C. for 5 minutes (p-PPS sheet-2).

Comparative Example 4 A biaxially stretched PPS film having a thickness of 100 μm was produced under the conditions of Comparative Example 2 (PPS film-1).

Comparative Example 5 One side of the biaxially stretched PPS film having a thickness of 25 μm used in Comparative Example 2 was subjected to a corona discharge treatment of 5000 J / m ² , and laminated on both sides of the fiber sheet-1 via an adhesive.
The adhesive used was an epoxy adhesive (“Chemit Epoxy” TE-5920 manufactured by Toray Industries, Inc.).
10 μm (dry condition) was applied to the corona discharge treated surface of the PS film by a gravure roll method, and laminated on both surfaces of the fiber sheet. The drying condition of the adhesive was a temperature of 100 ° C. for 3 minutes, and the laminating condition was a pressing pressure of 3 kg / cm ² at a temperature of 120 ° C. Further, it was thermally cured at a temperature of 150 ° C. for 2 hours (laminate-10).

(Evaluation of Examples and Comparative Examples)
Tables 1 and 2 show the evaluation results of the laminates, polymer sheets, and films of Comparative Examples 1 to 5. The laminates of the present invention of Examples 1 to 5 retain the low moisture absorption and flame retardancy of PPS in addition to the thermal dimensional stability, dielectric properties, heat resistance, adhesion, etc., and are suitable for circuit boards. It turns out that it is. Furthermore, it has excellent flatness, smoothness, and processability of through-holes required for processing high-density circuits. There is no distortion of the circuit. Further, the processability of the through holes was good, and no circuit deviation occurred even when the circuit board was heated (240 ° C.).

Further, as a result of observing the cross section of each of the laminates 1-3 of Example 1 with a microscope and using a microscope photograph, the laminate constitution was classified into three aspects of the present invention. That is, the laminate-1 has a layer in which the layer of the fiber sheet is impregnated with the copolymerized PPS composition and the layer of the copolymerized PPS composition have the same thickness, and the layer of the PPS composition is provided thereon. Was. Laminate-2 had a copolymerized PPS composition layer thicker than the resin-impregnated layer, and a PPS composition layer was provided thereon. Further, the laminate-3 was obtained by copolymerizing PPS from the resin impregnated layer.
The composition layer is thin and the PPS is provided thereon.
Part of the composition layer in the thickness direction enters the resin-impregnated layer. As can be seen from Tables 1 and 2, these three types of properties all achieved the object of the present invention.

Further, the objects of the present invention can be achieved regardless of whether the PPS composition layer of Example C is unstretched or oriented. Further, the copolymer PP of the B layer was obtained from Examples 1, 3, and 4.
The object of the present invention can be achieved even if the addition ratio of the main component monomer and the auxiliary component monomer (copolymer component) of S is changed. However, when the addition ratio of the copolymer component exceeds 30 mol%, heat resistance and heat dimensional stability become stable. It can be seen that the impregnating property with the fiber sheet and the flatness of the laminate deteriorate when the property is reduced, and when it is less than 5 mol%. It can be seen from Examples 1, 2, and 5 that the object of the present invention can be achieved even if the manufacturing method is changed.

As described above, the laminate of the present invention completely impregnates the fiber sheet with the copolymerized PPS composition having a relatively low melting point and has a PPS composition layer having high heat resistance laminated thereon. It was with.

On the other hand, the impregnated sheet-1 of Comparative Example 1 has poor heat resistance because the resin layer is only the copolymerized PPS composition, and has poor flatness because the impregnation temperature is higher than the melting point, which hinders circuit printing. The impregnated sheet-2 has a problem in through-hole processing because the impregnation degree of the resin is poor. Further, the impregnated sheet-3 has the same problem as the impregnated sheet-2 because the impregnation temperature is higher than the melting point.

The laminate 5 of Comparative Example 2 has a problem in through-hole processing due to poor impregnation degree, and hinders circuit printing due to large surface roughness. Laminate-6 has poor flatness. The unstretched PPS sheet of Comparative Example 3 has poor heat resistance, and the biaxially oriented PPS film of Comparative Example 4 has a large thermal dimensional change rate.

In the laminate 10 of Comparative Example 5, since the adhesive is interposed, the adhesive deteriorates heat resistance and dielectric properties. Further, since the laminate uses a biaxially oriented PPS film, the adhesive softens when heated, and the biaxially oriented PPS film is used.
The PS film layer thermally shrinks and the circuit is greatly shifted. Also, the workability of the through hole is poor.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

As described above, the laminate of the present invention is a material having a high-dimensional balance of heat resistance, dimensional stability (heat and humidity), flame retardancy, high-frequency characteristics, and the like. It has excellent workability, flatness, and smoothness, and is excellent in workability of precision circuits. It has become an optimal heat-resistant base material especially used for high-performance, high-density circuit boards (including multilayer circuit boards).

Since the laminate of the present invention has the above-mentioned excellent characteristics, it can be used for covering not only circuit boards and laminated circuit boards but also heat-resistant insulating materials such as transformers and motors, and cables used for high-temperature and high-pressure parts. Ideal for materials, heat-resistant adhesive tape, prepreg base material, heat-resistant label, speaker cone, electrical shield base material, etc.

The laminate of the present invention may have another material (metal, sheet, film, or the like) laminated on at least one side, or may have another resin or coating material coated thereon, depending on the application. Or molded. Further, the laminate of the present invention may be oxidatively cross-linked by heat or ultraviolet rays.

Continuation of the front page (56) References JP-A-4-319436 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 H05K 1/03

Claims (4)

(57) [Claims] 1. The fiber sheet (A) has at least p-
A resin-impregnated sheet impregnated with a resin composition (B) comprising a copolymerized polyphenylene sulfide obtained by copolymerizing at least one copolymer unit other than a p-phenylene sulfide unit with a phenylene sulfide unit as a main repeating unit; A laminate comprising a resin composition (C) layer containing p-phenylene sulfide as a main component. 2. The laminate according to claim 1, wherein the fiber sheet (A) has substantially no melting point up to 400 ° C. 3. The laminate according to claim 2, wherein the fiber sheet (A) is a glass cloth. 4. The resin composition according to any one of claims 1 to 3, wherein, in the resin composition comprising the copolymerized polyphenylene sulfide, the copolymer unit contained in the second largest amount after the p-phenylene sulfide unit is an m-phenylene sulfide unit. Laminate.