JPH0565352A - Production of thermosetting film of cyanate-modified polyphenylene ether resin - Google Patents

Abstract

(57) [Abstract] [Purpose] A method for producing a semi-cured thermosetting film obtained by modifying a thermoplastic polyphenylene ether resin with a cyanate compound, without using a solvent. [Constitution] (A) Number average molecular weight of 7,000 to 50,000, maximum particle size of 80 μm or less, particle size of 50 μm or less is 30% by weight of all powders.
90 to 60% by weight of the above polyphenylene ether resin fine powder
And (B) a cyanate resin monomer or a mixture of the cyanate resin monomer and a cyanate compound, which is a pre-reactant having a melt viscosity of 10 poise or less, of 10 to 40% by weight, was melt-kneaded at a temperature of 130 to 180 ° C. After, temperature 130 ~
A method for producing a thermosetting cyanate compound-modified polyphenylene ether resin film in a semi-cured state, which comprises forming a film having a thickness of 10 μm or more at 200 ° C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a method for producing a thermosetting resin film which is a semi-cured state obtained by modifying a highly heat-resistant thermoplastic polyphenylene ether resin with a cyanate compound, without using a solvent. .. The film of the present invention has a property of being heat-cured when heated, and is a film in a semi-cured state having excellent adhesiveness, heat resistance, dielectric properties, and flexibility, a printed wiring board material, an adhesive film, a heat resistant film, There are a wide range of industrial applications such as flexible circuits, flat cables, and insulation films.

[0002]

2. Description of the Related Art Polyphenylene ether resin (hereinafter referred to as "PP
E)) and a film of a cyanate compound mixture, a solution of a solvent such as toluene is applied thinly, and then the solvent is removed by drying to form a film (JP-A-58-57921,
Japanese Patent Publication 1-53700) is known. However, in order to dissolve high molecular weight PPE, a large amount of solvent is required, and a low solid content solution must be used, making it difficult to form a film.
There are drawbacks such as a complicated manufacturing process and a method for completely removing the solvent, which requires industrially enormous equipment.

Further, in Japanese Patent Laid-Open No. 2-194053, 5 to 30% by weight of heat-resistant engineering plastics and 95 to 70
There is known a method of modifying by melting and kneading a large amount by weight of a cyanate compound. When mixing a large amount of low melting point cyanate compound around 80 ℃ with a small amount of high melting point engineering plastics, the particle size
A heat-resistant engineering plastic having a size of 100 μm or less is melt-kneaded with a cyanate compound at a temperature of 200 ° C. or less to form a moldable mixed resin. It was impossible to make a flexible film.

When PPE exceeds 300 ° C., gelation or decomposition occurs, and a method of melt kneading alone to form a film or sheet cannot be carried out. Usually, polystyrene or the like is mixed and melt-mixed before use. Further, the most common cyanate compound derived from bisphenol A is
It becomes a liquid at about 70 ° C, and becomes a low-viscosity liquid of about several hundred centipoise at a temperature higher than 200 ° C. At such a high temperature, it self-polymerizes and crosslinks and hardens, and at about 300 ° C an extremely rapid reaction occurs. Was caused, and heat was generated, causing decomposition accompanied by smoke generation.

Therefore, a large amount of PPE having a high melting point and
It has been considered impossible to produce a film by directly melt-kneading a small amount of a cyanate compound that crosslinks at this melting point and easily generates heat and causes decomposition accompanied by smoke generation.

[0006]

DISCLOSURE OF THE INVENTION The present invention has made extensive studies to solve the above-mentioned drawbacks and to find a method that is industrially easy and economically advantageous. As a result, a large amount of specific fine powder PPE and a small amount of PPE are obtained. The present invention has been completed by finding out a method of melt-mixing with a cyanate compound in a specific range of.

[0007]

That is, the present invention is
(A) Number average molecular weight of 7,000 to 50,000, maximum particle size of 80 μm
Below, 90 to 60% by weight of polyphenylene ether resin fine powder having a particle size of 50 μm or less of 30% by weight or more of the total powder, and (B) a cyanate resin monomer or a cyanate resin monomer is a preliminary reaction product having a melt viscosity of 10 poise or less. A semi-cured state characterized by forming a film having a thickness of 10 μm or more at a temperature of 130 to 200 ° C. after melt-kneading a mixture containing 10 to 40% by weight of a cyanate compound as a main component at a temperature of 130 to 180 ° C. It is a method for producing a thermosetting cyanate compound-modified polyphenylene ether resin film.

The polyphenylene ether resin (PPE) as the component (A) of the present invention has at least the ortho position (2-position) of the hydroxyl group.
One of them is a lower alkyl group, and is suitably obtained by polycondensing one or more phenols having a lower alkyl group at the 3-, 5-, 6-positions. Specifically, poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-
1,4-phenylene ether), poly (2-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-dimethyl-6-
Propyl-1,4-phenylene ether), 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-
Examples thereof include a diethylphenol / 2,3,6-trimethylphenol copolymer and a 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer.

Further, a styrene graft copolymer obtained by graft-polymerizing styrene to PPE, a modified polymer obtained by adding maleic anhydride, maleimide or the like to PPE, and the like can be mentioned.
Especially poly (2,6-dimethyl-1,4-phenylene ether),
Preferred are 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymers and modified polymers obtained by adding maleic anhydride, maleimide or the like to these. Further, the number average molecular weight is in the range of 7,000 to 50,000, preferably 10,000 to 40,000.
The range is.

According to the present invention, the PPE has a maximum particle size of 80 μm.
Hereinafter, a fine powder having a particle diameter of 50 μm or less and 30% by weight or more of the total powder is used. The reason why a uniform mixture can be obtained by kneading PPE and the cyanate compound is presumed to be that the low molecular weight cyanate compound penetrates from the surface of the PPE powder to the inside, resulting in PPE having a low melting point and being melt-kneaded. From this point, if there is a powder with a maximum particle size of more than 80 μm, the penetration will be insufficient and it will remain as high melting point particles even after kneading, making it difficult to make a uniform mixture. When 50 μm or less does not account for 30% by weight or more of the total powder, it is difficult to produce a uniform kneaded product of the particles of 50 to 80 μm in the powder and the cyanate compound, which is not preferable. Further, the larger the specific surface area of the PPE powder, the easier the mixing operation is, which is preferable.

The cyanate compound as the component (B) of the present invention is a polyfunctional cyanate ester or a prepolymer thereof in which 2 to 5 cyanato groups (-OCN) are usually bonded to the aromatic ring. Specifically, 1,3- or 1,4-dicyanatophenylbenzene, 1,3,5-tricyanatobenzene, 1,3-, 1,4-, 1,6-,
1,8- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4
-Cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) propane, 2,2-bis (3,5 -Dibromo-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, terminal OH polycarbonate oligomer and cyanogen halide Examples include cyanate ester (USP-4026913) by reaction of cyanide, cyanate ester (USP-4022755, USP-3448079) obtained by reacting a compound having three or more phenolic hydroxyl groups such as phenol novolac with cyanogen halide. Examples thereof include those obtained by subjecting them to a preliminary reaction for forming a sym-triazine ring by heating or using a catalyst, and when mixing, they are usually used as a powder.

The mixing ratio of the above component (A) and component (B) is
(A) 90 to 60% by weight, (B) 10 to 40% by weight.
If the content of the cyanate compound as the component (B) exceeds 40% by weight, the film becomes brittle, which is not preferable, and if it is less than 10% by weight, the temperature at which the film is processed into a homogeneous mixture becomes high, and the reaction of the cyanate compound easily occurs, which is not practical. Absent.

The above (A) and (B) are mixed, kneaded, and appropriately preformed to obtain a film. Kneading is performed at a temperature of 130-18
The temperature is appropriately selected from the range of 1 to 10 minutes at 0 ° C. Kneading temperature
If it exceeds 180 ℃, gelation of cyanate will be promoted, making uniform kneading difficult, and if it is below 130 ℃, modified PPE
Since the melting point is less than the above, uniform kneading cannot be performed. If the time is too short, uniform kneading becomes difficult, and if it is too long, gelation of the cyanate compound is promoted, which is not preferable. As the kneading device, a single-screw or multi-screw extruder, a roll, or the like can be used.

It is also preferable to carry out preforming after kneading or at the end of kneading. For example, a T-die or the like may be set at the tip of a uniaxial or multiaxial extruder to preform into a sheet. It is suitable.

The kneaded product obtained above is processed into a film.
As a method for forming a film, a sheet is once formed and then rolled or stretched by a roll or the like as it is; for rolling or stretching by a roll or the like, for example, polyethylene terephthalate, polypropylene, polyethylene, polyvinylidene fluoride, or other mold release Of the above-mentioned sheet using a flexible plastic film and rolling or stretching as it is; it is carried out by a T-die extruder or the like, extruded into a sheet, and rolled or stretched at a temperature of 130 to 180 ° C using a roll or the like. A method to be performed subsequently is exemplified.

Although the present invention is as described above, it can be used as a composition containing a thermosetting monomer or prepolymer or a resin component, if necessary, within a range not impairing the above method. Further, it can be used as a mixture with other known various additives such as other fibrous reinforcing materials, fillers, dyes, pigments, thickeners, lubricants, coupling agents, flame retardants and the like. In addition, the composition prepared above may be applied to a reinforcing substrate or the like for use.

As the thermosetting monomer or prepolymer, acrylates such as polyfunctional (meth) acrylate, polyfunctional alkyl (meth) acrylate, tri (meth) acryloxyisocyanurate, and epoxy (meth) acrylate; Allyl compounds such as diallyl phthalate, divinylbenzene, diallylbenzene, trialkenyl isocyanurate, and triallyl isocyanurate; dicyclopentadiene and its prepolymers; xylene resins; polyfunctional epoxy compounds; known resins such as polyfunctional maleimide compounds. The kind is illustrated.

As the resin component, polyvinyl formal and other polyvinyl acetal resins; phenoxy resin; acrylic resin having OH group or COOH group; silicone resin; polybutadiene, butadiene-acrylonitrile copolymer large, polychloroprene, butadiene-styrene. Non-crosslinked (non-vulcanized) rubbers such as copolymers, polyisoprene, butyl rubber and natural rubber; polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl Toluene, polyvinylphenol, AS resin, A
Vinyl compound polymers such as BS resin, MBS resin, polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene, and polyvinylidene fluoride; polycarbonate, polyphenylene ether, polyester, polyamide, polyamideimide, polyesterimide, polyphenylene sulfide, and the like. Low polymerized products (prepolymers) of these thermoplastic resins can be mentioned.

Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, brominated epoxy compounds, brominated diphenyl ether, and brominated compounds such as hexabromobenzene.

Further, in the present invention, a known catalyst of a cyanate compound can be used in combination if necessary. Examples of thermosetting catalysts include zinc octylate, alkyltin oxides, carboxylate salts of alkyltin oxides, organic metal salts such as acetylacetone iron, organometallic chelates, metal compounds such as alkyltin oxides; benzoyl peroxide, lauroyl. Organic peroxides such as peroxide, di-tert-butyl peroxide, dicumyl peroxide, di-tert-butyl perphthalate; imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; triethylamine, Examples include tertiary amines such as N-methylpyridine; phenols such as phenol and cresol; trimellitic anhydride and phthalic anhydride.

[0021]

EXAMPLES The present invention will be described below with reference to examples.
The parts in Examples and Comparative Examples are based on weight unless otherwise specified. Example 1 Maximum particle size of 80 μm, 35% by weight of powder having a particle size of 50 μm or less
66 parts of poly (2,6-dimethyl-1,4-phenylene ether) with an intrinsic viscosity of 0.46 deciliters / g measured with chloroform at 25 ° C., 2,2-bis (4-cyanatophenyl) propane powder 34 The parts were premixed in a Henschel mixer for 3 minutes.

The premix was heated to temperature using a twin-screw extruder.
The mixture was kneaded at 155 ° C for an average residence time of 4 minutes, pressed to a thickness of 1 mm with a T-die, and cooled to room temperature with a water-cooled roll. This sheet was made into a film having a thickness of 0.1 mm by using a roll at 160 ° C. An electrolytic copper foil having a thickness of 18 μm was superposed on both sides of the film obtained above, and molded at 200 ° C. and 20 kg / cm ² for 1 hour to obtain a copper clad film. The results of measuring the characteristics of this film are as follows. Copper foil peeling strength 1.8 kg / cm Dielectric constant (at 1MHz) 2.8 Glass transition temperature 208 ℃ Solder heat resistance 260 ℃, no abnormality for 2 minutes or more

Comparative Example 1 Polyphenylene ether resin powder having a particle size of 150 μm
Premixes were prepared with powders of m or less. The temperature of this pre-mixture was increased by a twin-screw extruder from 130 ℃ to 10 ℃.
The temperature was changed to 180 ° C, and the mixture was kneaded at an average residence time of 4 minutes, pressed to a thickness of 1 mm with a T-die, and cooled to room temperature with a water cooling roll. The obtained sheet was made into a film having a thickness of 0.1 mm by using a roll at 200 ° C. In all cases, the spots of PPE remained in the obtained films.

Example 2 50% by weight of powder having a maximum particle size of 80 μm and 50 μm or less
Random copolymer with an intrinsic viscosity of 0.80 deciliter / g measured with chloroform at 25 ° C (95 mol% 2,6-dimethylphenol, 5 mol% 2,3,6-trimethylphenol)
75 parts, powder of 2,2-bis (4-cyanatophenyl) propane
25 parts, 11 parts of hexabromobenzene and 3 parts of antimony trioxide were premixed for 3 minutes with a Henschel mixer.

Using the premix obtained above, a thickness of 50
A copper clad film was obtained in the same manner as in Example 1 except that a film having a thickness of μm was produced and the molding pressure was 30 kg / cm ² . The results of measuring the characteristics of this film are as follows. Copper foil peeling strength 1.7 kg / cm Dielectric constant (at 1MHz) 2.7 Solder heat resistance 260 ℃, no abnormality for 2 minutes or more Flame resistance UL94V-0

Example 3 70 parts of the same PPE powder as used in Example 1, 15 parts of a cyanate compound and 15 parts of a bisphenol A type epoxy resin (epoxy equivalent 190, molecular weight 380) were mixed by hand and this was twin screw extruder. The mixture was kneaded at a temperature of 145 ° C. for an average residence time of 4 minutes, pressed to a thickness of 1 mm with a T-die, and cooled to room temperature with a water-cooling roll. This sheet was made into a film having a thickness of 30 μm by using a roll at 160 ° C.

Seven sheets of the above-obtained films were superposed on each other, and an electrolytic copper foil having a thickness of 18 μm was superposed on both sides, and molded at 190 ° C. and 20 kg / cm ² for 1 hour to obtain a copper-clad film. The results of measuring the characteristics of this film are as follows. Copper foil peeling strength 1.8 kg / cm Dielectric constant (at 1MHz) 2.9 Glass transition temperature 180 ℃ Solder heat resistance 260 ℃, no abnormality for 20 seconds or more

Example 4 Using the films prepared in Examples 1 to 3 and Comparative Example 1 at a temperature of 160 ° C., a surface of a patterned copper foil having a thickness of 35 μm was black-oxidized to obtain a 0.2 mm thick printed wiring board for an inner layer. Stack on both sides as shown in Table 1, and further stack 18μm copper foil, 200 ℃, 40kg
Laminate molding was performed at / cm ² for 2 hours. The results of evaluation of the obtained four-layer board are shown in Table 1.

[0029]

[Table 1] Table 1 Examples and Comparative Examples of Films Used Actual 1 Actual 2 Actual 3 Number of Single-sided Laminations of Film Used 1 Ratio 1 2 3 1 18 μm Bonding strength of outer layer copper foil (kg / cm ² ) 2.0 1.8 1.7 0.5 Pattern embedding property (* 1) ○ ○ ○ × * 1: Judged by visually observing the periphery of the 35 μm intermediate layer pattern of the inner layer. ◯: No whitening, ×: Whitening around the pattern.

[0030]

As described above in detail, since the resin film of the present invention is a uniform film produced without using a solvent, it is easy to industrially produce various thicknesses. It is manufacturable and has excellent economical efficiency. Moreover,
It has a desirable property of B-stage and can be suitably used in a wide range of industries such as printed wiring board materials, adhesive films, heat resistant films, flexible circuits, flat cables, and insulation films, and its industrial significance. Is serious.

Claims (1)

[Claims] 1. (A) The number average molecular weight is 7,000 to 50,000,
90 to 60 polyphenylene ether resin fine powder with a maximum particle size of 80 μm or less and a particle size of 50 μm or less of 30% by weight or more of the total powder
A mixture containing 10% by weight of the cyanate compound (B) as a pre-reactant having a melt viscosity of the cyanate resin monomer or the cyanate resin monomer of 10 poise or less at 10 to 40% by weight is melted at a temperature of 130 to 180 ° C. After kneading, the temperature
A method for producing a thermosetting cyanate compound-modified polyphenylene ether resin film in a semi-cured state characterized by forming a film having a thickness of 10 μm or more at 130 to 200 ° C.