JPS6245630A - Production of laminated sheet - Google Patents

Abstract

PURPOSE:To make it possible to improve the high-frequency characteristics and heat resistance of the obtained laminated sheet, by laminate-molding, by heating, a sheet comprising a resin composition containing a polyphenylene oxide, a specified crosslinkable resin and a crosslinking aid with a base impregnated with said resin composition. CONSTITUTION:A sheet comprising a resin composition containing a poly phenylene oxide (hereinafter abbreviated as PPO), a resin which can crosslink the PPO and a crosslinking aid is laminate-molded by heating together with a base impregnated with said resin composition. Said resin composition is pre ferred to contain 20-95wt% PPO, 2-80wt% crosslinking resin and 1-20wt% crosslinking aid. Examples of said crosslinking resins include 1,2-polybutadiene, styrene and butadiene copolymers. As the crosslinking aids, triallyl cyanurate and/or triallyl isocyanurate are preferable. Examples of the bases include glass cloth, aramid cloth, mats or nonwoven fabrics made of these materials and kraft paper.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for manufacturing a laminate having excellent dielectric properties in the so-called ultra-high frequency region, such as the X-band (10GH2) region for satellite communications.

[Background technology]

Laminated plates used in the X-band (IOGH2) region, the so-called ultra-high frequency region, used in satellite communications etc. are required to have excellent high frequency properties, particularly excellent dielectric properties. That is, the dielectric constant and loss are both constant over a wide frequency range, temperature range, and humidity range, and
It should preferably be a low material. These characteristics are not due to the structure of the laminate but are unique to the material, so materials with excellent characteristics must be selected when manufacturing the laminate.

Conventionally, poly(4-fluoroethylene), alumina ceramic, cross-linked polyethylene, etc. have been used for such applications, but alumina ceramics have difficulties in forming single circuits (copper cladding method), etc. , poly(4-fluoroethylene), and crosslinked polyethylene both have low glass transition points, so they are of practical use! It has the disadvantage that the dielectric constant and dielectric loss change significantly near the imaginary state, and furthermore, because of its nonpolar nature,
It has the disadvantage that the adhesive strength with the metal foil forming the circuit is insufficient.

Low dielectric constant materials with relatively high glass transition points include polyether sulfone, polyetherimide, polyphenylene oxide, and polysulfone, but most of these are thermoplastic resins and cannot be used to bond metal foils under normal conditions. It is well known that cross-linking is the most effective and reliable means to improve the heat resistance of the resins mentioned above, which had the disadvantage of poor solder heat resistance and other properties even if they were made. It is. However, it cannot be crosslinked (cured) by a simple procedure as with ordinary thermosetting resins.

A method has been proposed in which polyolefin such as polyethylene is crosslinked by adding a special peroxide and heating, but low dielectric constant materials such as polyphenylene oxide cannot be crosslinked by this method. Therefore, a method of blending thermosetting resins has been proposed. However, blending thermosetting resins results in deterioration of dielectric properties. Alternatively, the blending process requires high temperatures for melting, but at high temperatures, the resin gels, which is a drawback in processability.

Furthermore, a method using prepreg is known as a method for manufacturing a laminate. That is, a solution of thermoplastic resin and crosslinking agent dissolved in a solvent is used to make paper and glass fiber.

It is applied and impregnated onto a base material such as synthetic fiber, and heated in a dryer to evaporate and remove the solvent in the solution, and the polymerization reaction of the resin proceeds to create a so-called 3-stage prepreg. .

By stacking a predetermined number of sheets and applying heat and pressure, the resin is cured. However, the laminates obtained by this method are
Due to the poor dielectric properties of the base material, it could not be used in ultra-high frequency bands.

Under these circumstances, conventionally it has not been possible to simply obtain a laminate with excellent high frequency characteristics and heat resistance.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing a laminated board that can easily produce a laminated board with excellent high frequency characteristics and heat resistance.

[Disclosure of the invention]

The inventors used polyphenylene oxide as a material, which does not crosslink with heat but has excellent high frequency properties, and attempted to achieve the above object by improving the heat resistance without impairing the properties of this material. I did a lot of research. As a result, polyphenylene oxide,
We have discovered that it is sufficient to heat and laminate a sheet made of a resin composition containing a resin with good crosslinkability to polyphenylene oxide and a crosslinking aid, and a base material impregnated with the resin composition, and hereby, we have developed the present invention. completed.

Therefore, this invention provides polyphenylene oxide,
A sheet made of a resin composition containing a resin with good crosslinking properties for polyphenylene oxide and a crosslinking aid, and a base material impregnated with the resin composition are heated and laminated (the gist is the method for manufacturing the front laminate).

The present invention will be explained in detail below.

Here, in the polyphenylene oxide (also referred to as polyphenylene ether, hereinafter not referred to as rPPOJ), for example, the following general formula I may be the same or may be different.

An example of this is poly(2・
6-dimethyl-1,4-phenylene oxide).

Such a ppo is, for example, tJ S P 405
It can be synthesized by the method disclosed in No. 9568. Although not particularly limited, for example, if the molecule I (MW) is 50,000, M w / M n
= 4.2 polymers are preferably used.

Examples of resins with good crosslinking properties for PPO include, but are not limited to, 1,2-polybutadiene, 1,4-polybutadiene, methane 1/butadiene cobolima, and i-1,2-polybutadiene. - Polybutadiene (mylene-modified, acrylic-modified, epoxy-modified), rubbers, etc.

Examples of crosslinking aids include (1) ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, and alkyd acrylates.

Silicone Acrylic 1. ,, -1=acrylic M' such as class
b1, ■ triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate.

Polyfunctional monomers such as divinylbenzene and diallyl phthalate, ■monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene, and polyparamethylstyrene, ■
Examples include, but are not limited to, polyfunctional epoxies.

As a crosslinking aid, 1-realyl cyanurate and/or
Or, using triallyl isocyanurate is PP
The blending ratio of raw materials that have good compatibility with O and are preferable in terms of film-forming properties, crosslinking properties, heat resistance, and dielectric properties is not particularly limited. 2-80% by weight of resin and 1-80% crosslinking aid
Preferably, the proportion is 20% by weight. Further, although not particularly limited, it is preferable to use a resin with good crosslinking properties in a ratio of 20 parts by weight or less per 1 part by weight of the crosslinking aid.

In addition, an initiator is usually used in the resin composition. As an initiator, dicumyl peroxide, ter
ter L-butyl peroxite, 2,5-';, methyl=2,5-
Tert-F'tilver quinhexine-3,2-
5-dimethyl-2,5-di-tert-butylperoxyhexane, α・α″-bis-tert-butylperoxy-m-isopropyl)benzene [1.4 (or 1.
3)-bis(tert-butylperoxyisopropyl)benzene].

In this invention, a sheet made of the resin Ut composition as described above and a base material impregnated with the resin composition are appropriately combined and stacked to form a laminate.

First of all, the sheet can be made, for example, by a casting method.

To explain in detail about the casting method, the resin composition is mixed with trichlorethylene and chloroform.

Completely dissolve chlorinated hydrocarbons such as carbon tetrachloride and methylene chloride; tosylene, toluene, benzene, and acetone at a ratio of 5 to 50% by weight in a single or mixed solvent. 8 liquids are applied onto a mirror-treated iron plate or casting film to a thickness of 5 to 500 μm and sufficiently dried to obtain a PPO sheet. The casting film is preferably one that is insoluble in the solvent, such as a polyester film or a polyimide film, and that has been subjected to a mold release treatment. If the sheet is produced in this way, it is not necessary to melt the resin, so it can be done more easily at a relatively low temperature.

Next, the base material impregnated with the resin composition (hereinafter referred to as "prepreg") may be produced by any method, but generally, it can be produced by the following method.

That is, the resin composition is trichlorethylene.

Completely dissolve the solution in a proportion of 5 to 50% by weight in a medium selected from chloroform, carbon tetrachloride, methylene chloride, or other chlorinated hydrocarbons, xylene, toluene, benzene, and acetone. Immerse the base material in the (
These resin compositions are impregnated and adhered to the base material by dipping or the like. The resin content of the prepreg thus produced is not particularly limited, but is preferably 30 to 50% by weight. The base material can be a resin-impregnated or loss-like material such as glass cloth, aramid cloth, polyester cloth, or nylon cloth, a mat-like material made of these materials and/or a fibrous material such as nonwoven fabric, kraft paper,
Paper such as linter paper is used, but is not limited to these. If prepreg is produced in this way,
Since the resin does not need to be melted, it can be carried out more easily at relatively low temperatures.

The sheets and prepregs produced in this way are combined in a predetermined manner so as to have a predetermined design thickness, and if necessary, metal foil is also combined and laminated, and the resin is melted by heating and pressing, etc., so that the sheets can be bonded together. A laminate is obtained by bonding sheets and prepregs, prepregs to each other, sheets and metal foil, and prepregs and metal foil to each other. Strong adhesion is obtained by this fusion, and since a crosslinking reaction is performed by heating at this time, even stronger adhesion can be obtained. The crosslinking reaction may be carried out by ultraviolet irradiation or the like. Therefore, adhesion with excellent heat resistance can be achieved between sheets, between prepregs, between sheets and prepreg, between sheets and metal foil, and between prepreg and metal foil.

Here, although the combination of sheet and prepreg is not particularly limited, a symmetrical combination as shown in Figures 1 to 5 is said to prevent warping after molding and secondary processing (etching, etc.). Preferable from this point of view. Further, as shown in FIGS. 1 to 3, it is preferable in terms of adhesive strength to combine the sheets so that they are placed at the adhesive interface with the metal foil. This is thought to be because the resin flows easily. In addition, the first
In Figures 5 to 5, ■ indicates copper foil, 2 indicates sheet, and 3 indicates prepreg.

As the metal foil, JL11 foil, aluminum foil, etc. are used.

Pressing is performed to bond sheets to each other, sheets to prepreg, prepregs to prepreg, metal foil to sheet, metal foil to prepreg, and to adjust the thickness of the laminate, so the pressing conditions are selected as necessary. Furthermore, when crosslinking is carried out by heating, the crosslinking reaction depends on the reaction temperature of the initiator used, so it is preferable to select the heating temperature depending on the type of initiator. The heating time may also be selected depending on the type of initiator, etc. For example, temperature 150-300°C, pressure 50kg/cff1. The time is about 10 to 60 minutes. A predetermined number of sheets or prepregs may be heat-laminated in advance, metal foil may be superimposed on one or both sides of the sheets, and the sheets or prepregs may be heat-pressed again.

The thus obtained laminate has excellent high frequency properties such as dielectric properties without impairing the properties of PPO,
Moreover, it has excellent heat resistance. The manufacturing operation is also simple as described above.

Next, Examples and Comparative Examples will be shown.

(Example 1) 100 parts by weight of PPO (with a molecular weight of about 10.000), 25 parts by weight of styrene-butadiene copolymer (Asahi Kasei Kogyo's Trublen T406) as a resin with good crosslinking properties,
15 parts by weight of triallylisocyanurate (Nippon Kasei TAIC) as a crosslinking aid, and 2 parts by weight as a reaction initiator.
・5-dimethyl-2,5-di(t-butylperoxy)
Contains 1 part by weight of Hexine-3 (NOF Corporation Verhexin 25Bl) and trichlorethylene (Toagosei Chemical Industry Co., Ltd.).
(triclene) in the solvent, stir well and mix 15% and 25%.
% of two resin composition solutions were prepared.

A 25% solution of this was uniformly applied onto a polyethylene terephthalate film to a thickness of about 400 μm, and
A sheet (film) having a thickness of 100 μm was prepared by drying for 10 minutes in a dry product at ℃. This sheet was heated at 130℃ for 20
Further drying was performed for 1 minute to reduce residual trichlorethylene to zero. On the other hand, a glass cloth (100μ thick) was placed in the 15% solution.
m), scrape off the solution with a bar coater,
After drying for 10 minutes in a dry product at 60°C, it was dried for 20 minutes in a dry product at 130°C to produce a prepreg with a resin content of 40%.

Five of these sheets and two prepreg sheets were combined as shown in Figure 1, and 35 μm copper foil was layered on top and bottom, and heated at 200°C for 50 minutes.
Pressing was carried out for 30 minutes at 0 kg/cot to obtain a laminate.

(Example 2) A laminate was produced in the same manner as in Example 1 by combining the same six sheets and three prepregs as those produced in Example 1 as shown in FIG. 2.

(Example 3) A laminate was produced in the same manner as in Example 1 by combining the same five sheets and four prepregs as those produced in Example 1 as shown in FIG. 3.

(Example 4) Styrene-butadiene copolymer (
Asahi Kasei Corporation ■Turublen T406) 20 parts by weight and l
- A sheet and a prepreg were made in the same manner as in Example 1 except that 10 parts by weight of 2-polybutadiene was used, and a laminate was obtained using these in the same manner as in Example 1.

(Example 5) A sheet and a prepreg were made in the same manner as in Example 1, except that 25 parts by weight of 1,2-polybutadiene was used as a resin with good crosslinking properties, and a laminate was made using these in the same manner as in Example 1. I got it.

(Example 6) The same five sheets and two prepregs as those produced in Example 1 were pressed together in the same manner as in Example 1, and irradiated with ultraviolet rays to obtain a laminate.

(Comparative Example) Eight sheets produced in Example 1 were laminated and pressed in the same manner as in Example 1 to obtain a laminate.

The physical properties of each laminate obtained in Examples 1 to 6 and Comparative Example were measured under the conditions shown in Table 1 and are also shown in the same table.

As can be seen from Table 1, the laminates obtained in Examples j to G are excellent in high frequency characteristics such as dielectric constant and dielectric loss, which are comparable to those of the comparative example, and have better soldering heat resistance than the comparative example. much better than that one. In addition, compared to the comparative example, the copper foil peel strength and alkali resistance are the same,
Low water absorption and excellent trichlorethylene resistance. The coefficient of linear expansion in the thickness direction (z) is the same as that of the comparative example, but in the vertical and lateral directions (X and y) it is smaller than that of the comparative example, and has excellent dimensional stability.

From these results, it was found that the seal made of the above resin composition
It can be seen that heat lamination molding of a combination of a base material impregnated with the resin composition and a sheet is better from the viewpoint of the properties of the laminate than heating lamination molding of only the resin composition.

〔Effect of the invention〕

The method for producing a laminate according to the present invention involves heating and laminating a sheet made of a resin composition containing a resin having good crosslinkability against PPO and a crosslinking aid, and a base material impregnated with the resin composition. Therefore, a laminate with excellent high frequency characteristics and heat resistance can be easily obtained.

[Brief explanation of the drawing]

FIGS. 1 to 5 are side views schematically showing examples of how sheets and prepregs are combined. 2... Sea 1-3... Prepreg agent Patent attorney Hikoichi Matsuki Takeshi 1 Kozai to Neiichi "Shosho Yamasan Published October 15, 1985 Patent Application No. 186.347 of 1985 3. Relationship with Hanyu, the person making the amendment Patent applicant Address: 1048 Oaza Kadoma, Kadoma City, Osaka Name (583) Representative of Matsushita Electric Works Co., Ltd. (JIM Emperor Masato Fujii 4, Agent 6, Details subject to amendment Document 7, Contents of the amendment (1) The entire text of the scope of claims column of the specification is corrected as shown in the attached sheet. (2) The phrase "polyparamethylstyrene" in the fourth line of page 9 of the specification is changed to [ (3) In the second line of page 11 of the specification, r500j is corrected to r700j. [Full text of amended scope of claims] 2. Scope of claims (1) ) A method for producing a laminate by heating and laminating a base material impregnated with a sheet 1-1 made of polyphenylene oxide, a resin composition containing a resin with good crosslinking properties for polyphenylene oxide, and a crosslinking aid, and the resin composition. ( 2) A method for manufacturing a laminate according to claim 1, wherein the sheet is made by a casting method. (3) The resin composition comprises 11 phenylene oxide and 2
0 to 95% by weight, 2 to 80% by weight of a resin with good crosslinking properties, and 1 to 20% by weight of a crosslinking aid. . (4) The resin with good crosslinking property is 1,2-polybutadiene,
Claim 1, which is at least one member selected from the group consisting of 1,4-polybutadiene, styrene-butadiene copolymer, modified 1,2-polybutadiene, and rubbers.
A method for producing a laminate according to any one of Items 1 to 3. (5) The crosslinking aid is ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicone acrylate-1-111f, ToIJ
At least one member selected from the group consisting of allyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, divinylhenzene, diallyl phthalate, vinyltoluene, ethylvinylbenzene, styrene, paramethylstyrene, and polyfunctional epoxies. A method for manufacturing a laminate according to any one of claims 1 to 4. (6) Claims in which the base material is at least one selected from the group consisting of glass cloth, aramid cloth, polyester cloth, nylon cloth, mats made of these materials, nonwoven fabrics, kraft paper, and linter paper. A method for producing a laminate according to any one of Items 1 to 5.

Claims (6)

[Claims] (1) A method for producing a laminate in which a sheet made of polyphenylene oxide, a resin composition containing a resin with good crosslinking properties for polyphenylene oxide, and a crosslinking aid, and a base material impregnated with the resin composition are heated and laminated. (2) The method for manufacturing a laminate according to claim 1, wherein the sheet is made by a casting method. (3) The resin composition contains 20% polyphenylene oxide.
3. The method for producing a laminate according to claim 1 or 2, which contains a resin with good crosslinking properties in a proportion of 2 to 80% by weight, and a crosslinking aid in a proportion of 1 to 20% by weight. (4) The resin with good crosslinking property is 1,2-polybutadiene,
Claim 1, which is at least one member selected from the group consisting of 1,4-polybutadiene, styrene-butadiene copolymer, modified 1,2-polybutadiene, and rubbers.
A method for producing a laminate according to any one of Items 1 to 3. (5) The crosslinking aid is ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicone acrylates, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate , divinylbenzene, diallyl phthalate, vinyltoluene, ethylvinylbenzene,
The method for producing a laminate according to any one of claims 1 to 4, wherein the laminate is at least one selected from the group consisting of styrene, polyparamethylstyrene, and polyfunctional epoxies. (6) A patent claim in which the base material is at least one selected from the group consisting of glass cloth, aramid cloth, polyester cloth, nylon cloth, mats made of these materials, nonwoven fabrics, kraft paper, and linter paper. A method for producing a laminate according to any one of items 1 to 5.