JPH07120839B2 - Printed wiring board - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a printed wiring board having excellent heat resistance, low hygroscopicity, and excellent electrical insulation. More specifically, the present invention relates to a printed wiring board formed of polyamide that is excellent in these properties and molding workability.

[Prior Art] In addition to having excellent heat resistance such as solder heat resistance for a resin for forming a printed wiring board, having low hygroscopicity, and having a small temperature dependence of electrical characteristics such as electric insulation, It is required that the workability at the time of molding a printed wiring board is excellent. Conventionally, printed wiring boards are usually made of various epoxy resins, and printed wiring boards required to have heat resistance are usually made of polybismaleimide. Since all of these molding resins are thermosetting resins, the work of molding and curing is complicated,
There is a strong demand for a printed wiring board made of a molding resin that has the drawback of requiring a long time and has excellent workability during molding. In addition, a printed wiring board made of polybismaleimide has excellent heat resistance but has the drawback of being expensive, and a printed wiring board made of epoxy resin has heat resistance, hygroscopicity, and electrical insulation depending on the application. There may be a lack of sex.

In addition, many printed wiring boards molded from thermoplastic resin have been proposed to improve the molding workability of printed wiring boards formed from conventional thermosetting resins, but they have excellent heat resistance and hygroscopicity. There are few printed wiring boards that are small in size and have excellent electrical insulation. Therefore, in the field of printed wiring boards, it has excellent heat resistance, low hygroscopicity,
There is a strong demand for a printed wiring board molded from a thermoplastic resin that has low temperature dependence of electrical characteristics such as electrical insulation and has excellent workability during molding.

[Problems to be Solved by the Invention] In view of the conventional technology in the field of printed wiring boards described above, the present inventors have excellent heat resistance, low hygroscopicity, electrical insulation and the like. As a result of investigating a printed wiring board molded from a thermoplastic resin which has a small temperature dependence of electrical characteristics and is excellent in workability at the time of molding, a printed board formed from a polyamide having a specific isophthaloyldiamine component unit. Has reached the present invention by discovering that the above-mentioned object is satisfied.

[Means and Actions for Solving Problems] According to the present invention, [A] the acid component is (a) an isophthalic acid component unit of 50 to 100 mol%, and (b) a terephthalic acid component unit of 0 to 50 mol%. The diamine component comprises (c) 40 to 85 mol% of a diamine component unit having an aliphatic hydrocarbon group having 4 to 25 carbon atoms, and (d) at least one alicyclic ring having 6 to 25 carbon atoms. A polyamide comprising 15 to 60 mol% of a diamine component unit having a group hydrocarbon group, wherein the acid component and the diamine component are randomly arranged, and (i) is soluble in concentrated sulfuric acid at 30 ° C. And (ii) the melt flow rate (MFR) measured at 300 ° C. under a load of 2 kg is in the range of 0.01 to 100 g / 10 min, and (iii) the crystallinity measured by X-ray diffraction is 7% or less. Yes, (iv) glass transition temperature (Tg) is 150 To a temperature of 240 ° C., a printed wiring board formed of the polyamide represented by:

Furthermore, the printed wiring board of the present invention may be formed from a polyamide composition comprising the above polyamide [A] and a filler [B].

Polyamide [A] forming the printed wiring board of the present invention
Is the general formula [I] And an isophthaloyldiamine component unit (a) represented by the general formula [II] A terephthaloyldiamine component unit (b) represented by the following formula (wherein R ⁰ is a divalent aliphatic hydrocarbon group having 4 to 25 carbon atoms or 6 to 25 carbon atoms) And at least one hydrocarbon group having an alicyclic structure. ] Is a randomly arranged polyamide. The composition of each component of the polyamide is such that the component (a) is 50 to 100.
Mol%, preferably 60 to 90 mol%, particularly preferably 65 to 80 mol%, and the component (b) is 0 to 50 mol%, preferably 10 to 40 mol%, particularly preferably 20 to 35 mol%. It is in the range of mol%. The melt flow rate (MFR) of the polyamide measured at 300 ° C. and a load of 2 kg is 0.01 to 100 g / 10 min, preferably 0.5 to
It is in the range of 50g / 10min. The polyamide is dissolved in concentrated sulfuric acid at 30 ° C., and the intrinsic viscosity [η] of this polyamide measured in concentrated sulfuric acid at 30 ° C. is usually 0.4 to 2.0 dl /
g, preferably in the range of 0.5 to 1.3 dl / g. Also,
The crystallinity of the polyamide measured by X-ray diffractometry is 7% or less, preferably 5% or less, particularly preferably 3%.
It is the following. The glass transition temperature (T) measured by a differential scanning calorimeter (temperature rising rate: 10 ° C / min) of the polyamide
g) is in the range 110 to 240 ° C, preferably 120 to 220 ° C. When the polyamide has crystallinity, its melting point is usually 220 to 350 ° C., preferably 240 to 3
It is in the range of 20 ° C.

In the diamine component constituting the isophthaloyldiamine component unit (a) represented by the general formula [I] and the terephthaloyldiamine component unit (b) represented by the general formula [II] that compose the polyamide. The corresponding R ⁰ is
Specific examples include a divalent aliphatic hydrocarbon group having 4 to 25 carbon atoms, and a divalent alicyclic hydrocarbon group having 6 to 25 carbon atoms and containing at least one alicyclic hydrocarbon ring. In particular, a divalent aliphatic hydrocarbon group R ¹ having 4 to 25 carbon atoms and a divalent aliphatic hydrocarbon group having 6 to 25 carbon atoms and containing at least one alicyclic hydrocarbon ring. It is preferably composed of a cyclic hydrocarbon radical R ² , especially the composition of which the R ¹ component is 40 to 85 mol% and the R ² component is 15
It is preferable that the mixed components are in the range of 60 to 60 mol%.
Divalent aliphatic hydrocarbon groups having 4 to 25 carbon atoms
Specifically as the diamine component corresponding to R ¹ , 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, 9-diaminononane, 1,10-diaminodecane,
1,11-diaminoundecane, 1,12-diaminododecane,
1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminonona Examples thereof include decane and 1,2-diaminoeicosane. As these alkylenediamine components, only one kind may be contained alone, or two or more kinds may be contained as a mixture. Of these alkylenediamine components, those having 6 to 16 carbon atoms are preferable, and 1,6-diaminohexane component is particularly preferable. Further, as the diamine component unit having 6 to 25 carbon atoms and corresponding to the divalent alicyclic hydrocarbon group R ² containing at least one alicyclic hydrocarbon ring, specifically, 1,3 -Diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis (4-amino Cyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,
4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylpropane, 4,4'-diamino-3,3 ', 5,5'-tetramethyldicyclohexyl Methane, 4,4'-diamino-3,
3 ', 5,5'-tetramethyldicyclohexylpropane,
4,4'-diamino-3,3'-dimethyldicyclohexyl,
4,4'-diamino-3,3 ', 5,5'-tetramethyldicyclohexyl, α, α'-bis (4-aminocyclohexyl) -p-diisopropylbenzene, α, α'-bis (4-aminocyclohexyl ) -M-Diisopropylbenzene, α, α′-bis (4-aminocyclohexyl)
Examples thereof include 1,4-cyclohexane and α, α′-bis (4-aminocyclohexyl) -1,3-cyclohexane. Of these diamine components constituting R ² , an alicyclic diamine component is preferable, and among them, bis (4-aminocyclohexyl) methane and 4,4′-diamino-3,3 ′ are particularly preferable. -Dimethyldicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane.

The aromatic dicarboxylic acid component constituting the terephthaloyldiamine component unit (b) represented by the general formula [II] constituting the polyamide is a divalent aromatic hydrocarbon group,
Specifically, it is terephthalic acid.

The polyamide is one in which the component (a) and the component (b) are randomly arranged and combined to form a chain structure. Here, the chain structure is not limited to a straight chain structure, but may be a branched chain structure. The branched chain structure is formed through the amine component of both the component units (a) and (b). Among the polyamides, a polyamide having a linear or branched chain structure, that is, a substantially linear structure, has a temperature of 30 ° C.
Soluble in concentrated sulfuric acid.

The molecular terminal of the polyamide may be any of a diamine component, an isophthalic acid component or a terephthalic acid component which constitutes the component (a) or the component (b). When the molecular end is the alkylenediamine component, the terminal amino group may be acylated with a lower carboxylic acid,
It does not matter if it forms salt. When the terminal of the molecule is a terephthalic acid component, an isophthalic acid component or a phthalic acid component, the terminal carboxyl group may be esterified with a lower alcohol, may be amidated with an amine, or may be a salt. It may be formed or an acid anhydride may be formed.

The polyamide can be produced by polycondensing a halide and a diamine of an aromatic dicarboxylic acid corresponding to both the component unit (a) and the component unit (b) of the polyamide by a solution method or by an interfacial method. It can also be produced by condensation. Further, it is produced by polycondensing a low-order condensate such as a nylon salt or an oligomer with an aromatic dicarboxylic acid and a diamine corresponding to the constituent components of the polyamide in a heating and melting state under shearing conditions using a kneading means. be able to. In any of these methods, by adjusting the composition of the aromatic dicarboxylic acid (halide) as the raw material and the composition of the raw material diamine component, the isophthaloyldiamine component unit (a) is 50 to 100 mol% and the terephthaloyl It is possible to produce a polyamide in which the diamine component unit (b) is in the range of 0 to 50 mol%. Of these, the third method is suitable as an industrial manufacturing method.

The printed wiring board of the present invention can be formed from the above polyamide, or can be formed from a polyamide composition comprising the polyamide [A] and a filler [B].

The filler [B] blended with the polyamide composition forming the printed wiring board of the present invention is an organic or inorganic compound having various forms such as powder, plate, fiber or cloth. Yes, specifically, silica, alumina, silica-alumina, talc, diatomaceous earth, clay, kaolin, quartz, glass, mica, graphite, molybdenum disulfide, gypsum, red iron oxide, titanium dioxide, zinc oxide, etc., powder, plate Inorganic compounds, glass fibers, boron fibers, ceramic fibers, asbestos fibers, and other inorganic products or secondary processed products of these cloth-like products, polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, Polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, diaminodiphenyl Ether and terephthalic acid (isophthalic acid) condensates, wholly aromatic polyamides such as p (m) -aminobenzoic acid condensates, diaminodiphenyl ether and trimellitic anhydride or pyromellitic anhydride Heterocycle-containing compounds such as wholly aromatic polyamide-imide, wholly aromatic polyimide, polybenzimidazole, polyimidazophenanthroline, etc., such as polytetrafluoroethylene powder, plate, fiber or cloth. Examples of the secondary processed products are as follows, and two or more kinds of them can be mixed and used. Those fillers treated with a silane coupler or a titanium coupler can be used in the same manner.

Among the above-mentioned fillers, it is preferable to use silica, silica-alumina, alumina, titanium dioxide, graphite, molybdenum disulfide, polytetrafluoroethylene as the powdery filler, particularly graphite, molybdenum disulfide or polytetrafluoroethylene. The use of ethylene is preferable because the molded article obtained from the composition has improved abrasion resistance such as dynamic friction coefficient, Taber abrasion, and limit PV value. The average particle size of such fillers is usually 0.1 mμ or
A range of 200 μm, particularly a range of 1 mμ to 100 μm is preferable because the above-mentioned wear resistance is remarkably improved. The blending ratio of such filler is 100 parts by weight of the polyamide.
0.1 to 200 parts by weight, preferably 0.5 to 100 parts by weight,
It is particularly preferably in the range of 1.0 to 50 parts by weight.

Further, among the above-mentioned fillers, examples of the organic fibrous filler include polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, diaminodiphenyl ether and terephthalic acid. Alternatively, when a wholly aromatic polyamide fiber such as a fiber obtained from a condensation product with isophthalic acid is used, the molded product obtained from the composition has mechanical properties such as tensile strength and Izod impact strength, and heat resistance properties such as heat distortion temperature. And the like are improved, which is preferable. Furthermore, when glass fiber or boron fiber is used as the inorganic fibrous filler among the above-mentioned fillers, mechanical properties such as tensile strength, bending strength and bending elastic modulus of a molded product obtained from the composition, It is preferable because heat resistance such as heat distortion temperature and chemical and physical characteristics such as water resistance are improved. The average length of the organic or inorganic fibrous filler is usually 0.1 to 20 m.
When it is in the range of m, particularly in the range of 1 to 10 mm, the moldability of the composition is improved and the heat resistance of the molded product obtained from the composition such as heat deformation temperature, mechanical strength such as tensile strength and bending strength. It is preferable because the characteristics and the like are improved. The mixing ratio of the organic or inorganic fibrous filler is 3 to 200 parts by weight, preferably 5 to 180 parts by weight, and particularly preferably 5 to 150 parts by weight based on 100 parts by weight of the polyamide.
The range is parts by weight.

If necessary, the polyamide or the polyamide composition forming the printed wiring board of the present invention may be mixed with a conventionally known stabilizer, plasticizer, release agent, lubricant, and the like. The method for preparing the polyamide or the polyamide composition in which the polyamide composition and the polyamide composition are mixed with these additives is to mix and knead the filler and / or the additive while maintaining the polyamide in a molten state. A method etc. can be illustrated. Specific examples of the melt kneading and blending method include a method of kneading and blending using an extruder, a kneader or the like.

INDUSTRIAL APPLICABILITY The printed wiring board of the present invention can be used for a printed wiring board of the same type as that in which a thermosetting resin such as an epoxy resin or polybismaleimide is conventionally used. The printed wiring board of the present invention can be used in the form of a printed wiring board such as an aluminum-based printed wiring board, a metal-based printed wiring board such as a steel plate-based printed wiring board or a glass cloth base material, a glass mat base material,
The polyamide is used as an insulating layer of the printed wiring board. Further, in the case of the metal-based printed wiring board, a laminate having a three-layer structure of a metal substrate layer, the polyamide layer and a conductive printed metal foil layer can be exemplified.

Further, the printed wiring board of the present invention is a resin core printed wiring board having a two-layer laminated structure composed of the polyamide layer and a conductive printed metal foil layer, or a multilayer in which the printed wiring boards having the two-layer laminated structure are further laminated. It can also be used in the form of a laminated printed wiring board.

Molded products of the copper foil or metal of these printed wiring boards and the polyamide are usually molded by the molding method of the polyamide, that is, melt molding such as injection molding, compression molding, and extrusion molding.

Example Next, the printed wiring board of the present invention will be specifically described by way of examples. The synthetic method of the polyamide used in the examples is shown in the reference example. In addition, a method for making a printed wiring board and an evaluation method for each performance thereof are also shown below.

The following abbreviations used in the table below are
The following compounds are shown.

TA: terephthalic acid IA: isophthalic acid C ₆ DA: 1,6-diaminohexane ACM: bis (4-aminocyclohexyl) methane DMACM: 4,4′-diamino-3,3′-dimethyldicyclohexylmethane AMC: 1,3 -Bis (aminomethyl) cyclohexane (Measurement of Polyamide Composition) A polyamide sample was dissolved in trifluoroacetic acid and the ¹³ C-NMR spectrum was measured to determine the composition of the isophthalic acid component unit and the terephthalic acid component unit. Further, 4 g of the fine pieces of the pressed film of the polyamide were heated in 200 ml of 6N hydrochloric acid under reflux for 50 hours while stirring. After removing hydrochloric acid and water from the mixture after depolymerization to dryness, NaOH aqueous solution was added to adjust the pH to 11 to 12, then extracted with chloroform, and the ¹³ C-NMR spectrum of the extract was measured. , The composition of the diamine component was determined. Further, if necessary, the diamine component was fractionated by GPC and then determined by measuring ¹³ C-NMR.

[I] Polyamide Production Reference Example 1 89.22 g (0.537M) terephthalic acid, 208.17 g isophthalic acid
(1.253M), bis (4-aminocyclohexyl) methane
193.54g (0.92M) and 1,6-diaminohexane 106.91g
(0.92M) ion-exchanged water 70g, sodium diphosphite 0.38g
(0.00358M) was charged into a 1 liter autoclave, and after sufficiently replacing with N ₂ , 250 with stirring for 3 hours.
The temperature was raised to ° C. After keeping the reaction in a sealed state at 250 ° C for 1 hour, stirring is stopped and the pressure difference from the bottom of the autoclave is 10
The reaction mixture was withdrawn at kg / cm ² . 50 ℃ in N ₂ , 100mmHg
After drying overnight, a low-order condensate was obtained. The [η] (30 ° C. in conc. H ₂ SO ₄ ) of this low-order condensate was 0.15 dl / g. This low-order condensate is a twin-screw extruder (screw diameter 30 mm, L / D = 4
2, barrel temperature (℃) 80/180/340/340/280/280/260/26
0, 3rd, 4th and 6th zones are atmospheric release vents, 5 rpm
The polycondensation under melting was advanced by 0 rpm, the oligomer supply rate was 2 kg / hr, and the exhaust was N ₂ purge) to obtain a colorless transparent polymer. Mol% of isophthalic acid component unit and terephthalic acid component unit in polymer, mol% of bis (4-aminocyclohexyl) methane, 1,6-diaminohexane, MFR (g / 10mi
Table 1 shows n), [η] (in conc. H ₂ SO ₄ , 30 ° C.) and glass transition temperature.

Reference Examples 2 to 5 In Reference Example 1, the polymers shown in Table 1 were obtained according to the method described in Reference Example 1 except that the type or amount of the diamine component was changed.

[II] Fabrication of printed wiring board Polyamide synthesized by melt polymerization using a twin-screw extruder is obtained as a strand and cut into a length of 0.8-1 cm.
The resin was dried for 12 hours under conditions of 1 ° C and 1 mmHg to obtain a resin for a printed wiring board. Next, put a 5g resin for printed wiring board on a 2mm-thick aluminum plate cut into 13x13cm, and cut a 200cm-thick aluminum foil and a 35μ-thick electrolytic copper foil into a 10cmx10cm spacer. The placed product is pressed by a press molding machine in a nitrogen atmosphere under a pressure of 100 kg / cm ² to obtain 8 from Tg.
After hot pressing at a temperature higher by 0 to 150 ° C., cold pressing was performed at a temperature of 20 ° C. to produce an aluminum-based printed wiring board.

[III] Evaluation method for each performance of printed wiring board Copper foil peeling strength, volume resistance, dielectric constant, dielectric loss tangent (ta
The test method for the measurement of nδ) was in accordance with JIS C 6481. Also,
The evaluation of solder heat resistance was performed by a float method on a solder bath. The dielectric breakdown voltage was measured using a commercially available dielectric breakdown voltage measuring device.

Example 1 Using the polyamide described in Reference Example 1, an aluminum-based printed wiring board was produced by the above method. The thickness of the resin layer was 250μ. The performance is shown in Table 2.

Examples 2 to 5, except that the polyamide described in Table 1 was used instead of the polyamide described in Reference Example 1 in Example 1,
By the method described in Example 1, an aluminum-based printed wiring board having a resin layer thickness of 250 μ was manufactured. These performances are shown in Table 2.

Comparative Example 1 Using a polyamide (Trigamide T ^™ manufactured by Dynamit Nobel Co., Ltd.) composed of a 2,2,4-trimethylhexamethylenediamine component unit and a terephthalic acid component unit dried under conditions of 100 ° C. and 1 mmHg for 12 hours. An aluminum-based printed wiring board was prepared in the same manner as in 1. The results are shown in Table 2.

EFFECTS OF THE INVENTION The printed wiring board of the present invention has excellent heat resistance, low hygroscopicity, and excellent performance such as insulation, and in addition, since the polyamide used as the resin layer is thermoplastic, it is molded. It has the advantage of excellent workability.

Claims (2)

[Claims] 1. An acid component [A] is composed of (a) an isophthalic acid component unit of 50 to 100 mol%, (b) a terephthalic acid component unit of 0 to 50 mol%, and a diamine component of (c) a carbon number of 4 40 to 85 mol% of a diamine component unit having 1 to 25 aliphatic hydrocarbon groups, and (d) 15 to 60 mol of a diamine component unit having 6 to 25 carbon atoms and having at least one alicyclic hydrocarbon group %, And a polyamide composed of component units in which the above acid component and diamine component are randomly arranged, (i) dissolved in concentrated sulfuric acid at 30 ° C., (ii) measured at a load of 2 kg at 300 ° C. Melt flow rate (MFR) is in the range of 0.01 to 100 g / 10 min, (iii) the crystallinity measured by X-ray diffraction is 7% or less, and (iv) the glass transition temperature (Tg) is 150. To 240 ° C, the po Printed circuit board formed from amide. 2. An acid component [A] is composed of (a) an isophthalic acid component unit of 50 to 100 mol%, (b) a terephthalic acid component unit of 0 to 50 mol%, and a diamine component of (c) a carbon number of 4 40 to 85 mol% of a diamine component unit having 1 to 25 aliphatic hydrocarbon groups, and (d) 15 to 60 mol of a diamine component unit having 6 to 25 carbon atoms and having at least one alicyclic hydrocarbon group %, A polyamide in which these acid components and diamine components are randomly arranged, (i) capable of being dissolved in concentrated sulfuric acid at 30 ° C., and (ii) a melt flow rate measured at 300 ° C. under a load of 2 kg. (MFR) is in the range of 0.01 to 100 g / 10 min, (iii) the crystallinity measured by X-ray diffraction is 7% or less, and (iv) the glass transition temperature (Tg) is 150 to 240 ° C. The polyamide represented by And a printed circuit board formed from a polyamide composition comprising [B] a filler.