JPH01192547A - Polyphenylene sulfide resin laminate and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain a structural material having good mechanical characteristics, by laminating a polyphenylene sulfide injection molded plate having a specific thickness and a polyphenylene sulfide film having a specific thickness. CONSTITUTION:A polyphenylene sulfide resin laminate is formed by laminating a polyphenylene sulfide injection molded plate having a thickness of 0.5-5mm and a polyphenylene sulfide film having a thickness of 5-250mum. In this case, the polyphenylene sulfide injection molded plate and the polyphenylene sulfide film may be laminated through an adhesive layer having a thickness of 2-50mum. Further, the laminate may be formed by applying the polyphenylene sulfide film to the single surface of a mold and molding a polyphenylene sulfide resin in said mold by injection molding. By this method, a structural material improved in mechanical characteristics, especially, in impact resistance to a large extent while holding the excellent heat resistance, fire retardant property, chemical resistance and electric characteristics possessed by the polyphenylene sulfide resin molded body is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polyphenylene sulfide resin a-layer body that can be used as an electric circuit board or various structural materials.

[Conventional technology] Polyphenylene sulfide resin moldings have good heat resistance,
It exhibits flame retardancy and chemical resistance and is used in many electrical and electronic components. In particular, a thin molded plate made of polyphenylene sulfide resin is described, for example, in JP-A-61-256684.

゛Used as an electric circuit board.

[Problems to be Solved by the Invention] However, the thin-walled polyphenylene sulfide resin molded plate has problems in its mechanical properties, particularly in its impact resistance and bending strength.

An object of the present invention is to provide a structural material that has improved mechanical properties while retaining the excellent heat resistance, flame retardance, chemical resistance, electrical properties, etc. of polyphenylene sulfide resin molded articles.

[Means for Solving the Problems] As a result of intensive research, the inventors of the present application discovered that the above objectives can be achieved by laminating a polyphenylene sulfide film on a polyphenylene sulfide resin molded plate, and completed the present invention. did.

That is, the present invention provides a polyphenylene sulfide resin laminate comprising a polyphenylene sulfide injection molded plate having a thickness of 0.5 mm to 5 mm and a polyphenylene sulfide film having a thickness of 5 to 250 g.

Furthermore, in the present invention, a polyphenylene sulfide film having a thickness of 5 mm or more and 250 mm or less is pasted on one side of a mold, and a polyphenylene sulfide resin is injection molded into the mold to have a thickness of 0.5 +*. mM or more and 5 mm or less of polyphenylene sulfide injection molded plate and the above film
Provided is a method for producing a polyphenylene sulfide resin H1 layer body comprising forming a J-body.

[Effects of the Invention] This invention provides a structure that significantly improves mechanical properties, especially impact resistance, while retaining the excellent heat resistance, flame retardance, chemical resistance, electrical properties, etc. of polyphenylene sulfide resin molded products. Materials provided. When the laminate of the present invention is used as an electric circuit board, it exhibits excellent mechanical properties in addition to excellent electrical properties. Furthermore, by laminating it with a film, the smoothness of the surface of the polyphenylene sulfide molded product is improved, and printing, fine circuit patterns, etc. that cannot be applied to polyphenylene sulfide laminates can be applied to the polyphenylene sulfide film. Additionally, the film is pre-printed.

By performing processes such as core attachment and bonding, it is possible to provide a polyphenylene sulfide resin substrate whose surface has been efficiently processed.

The injection molded plate used in this invention is obtained by injection molding a resin composition containing polyphenylene sulfide resin as a main component or a polyphenylene sulfide sulfite compound obtained by kneading this with an inorganic substance by a conventional method. Here, the resin composition containing a 2-bottom phenylene sulfite resin as a main component refers to a composition containing polyphenylene sulfide in an amount of 70% by weight or more, preferably 90% by weight or more.

If the content of polyphenylene sulfide is less than 70% by weight, the resin composition will have low crystallinity, thermal transition degree, etc., and the characteristics of the composition such as heat resistance, dimensional stability, mechanical properties, etc. will be impaired.

The resin composition may contain a polymer other than polyphenylene sulfide in an amount of 30% by weight or less, as long as it does not have a significant adverse effect on the heat resistance, dimensional stability, mechanical properties, etc. It may contain inorganic or organic fillers such as glass fiber or talc, colorants, ultraviolet absorbers, etc.

In the present invention, polyphenylene sulfide (hereinafter referred to as PPS)
(sometimes abbreviated as ) means 70 mol% or more (preferably 85 mol% or more) of the repeating unit or the constituent formula -(--
5-) Refers to a polymer consisting of the structural units represented by -. If this component is less than 70 mol %, the crystallinity, thermal transition temperature, etc. of the polymer will be low, and molding made of a resin composition containing polyphenylene sulfide as the main component. It impairs the heat resistance, dimensional stability, mechanical properties, etc. that are the characteristics of the board.

Less than 30 mol% of repeating units, preferably 15 mol%
If the amount is less than 1, there is no problem even if a unit containing a copolymerizable bond is included.

Polyphenylene sulfite injection used in this invention °
The thickness of the molded plate is 0.51 to 51, preferably 0.5 to 314. If the thickness of the injection molded plate is less than 0.51 m, the strength will be low, and if it exceeds 5 x 1 m, it will not only be unnecessarily heavy as a board, but may also cause problems with through holes, etc.

The polyphenylene sulfide film used in the present invention is a film obtained by melt-molding a resin composition containing polyphenylene sulfide as a main component into a sheet, stretching it, and heat-treating it.

Here, the definitions of "resin composition containing polyphenylene sulfide as a main component" and "polyphenylene sulfide" are the same as above. The melt viscosity of the resin composition is 5 at a temperature of 300° C. and a shear rate of 20 1/sec.
00 to 12,000 voices (more preferably 700 to 10
000 voids) is preferable from the viewpoint of film formability.

The thickness of the polyphenylene sulfide film is 5JLm or more and 250g or less, preferably 5JLm to 125JLm.
It is L11. If the thickness of the polyphenylene sulfide film is less than 5 JL, the breaking strength is low and it is easy to tear.
In addition, the effect of improving mechanical properties such as impact resistance of the laminate is small, and if it exceeds 250 #Lll, problems such as thermal shrinkage of the film may adversely affect warpage of the injection molded plate.

The polyphenylene sulfide is preferably a biaxially stretched film, and its breaking strength is 15 in both the longitudinal direction and the width direction.
It is preferable that it be more than "kg/am".

A polyphenylene sulfide film is laminated to one or both sides of a polyphenylene sulfide injection molded plate. Lamination can be performed through a urethane-based, epoxy-based, acrylic-based, silicone-based, etc. adhesive layer, or can be performed without using an adhesive layer by the so-called in-mold method described later. When using an adhesive layer, the thickness of the adhesive layer is preferably 2 μL or more and 50 μL or less.

The polyphenylene sulfide resin laminate of the present invention can be produced, for example, as follows.

The polyphenylene sulfide used in the present invention is obtained by reacting an alkali sulfide and a baladihalobenzene in a polar solvent at high temperature and high pressure. In particular, it is preferable to react sodium sulfide and baladichlorobenzene in an amide-based high-boiling polar solvent such as N-methylpyrrolidone. The pressure and polymerization time in the polymerization system, which is most preferably carried out at 230° C. to 280° C., are appropriately determined depending on the type and amount of the auxiliary agent used, the desired degree of polymerization, etc. The obtained powdered or granular polymer is washed with water and/or a solvent, and the by-product salt 5 is a polymerization aid.
Separate unreacted sludge, etc.

In order to form this polymer into a film, the resin melted by an extruder is quantitatively cast from a die onto a metal drum, and rapidly cooled to form a non-oriented film.
A sheet in an amorphous state is obtained, and the sheet is stretched by a known method, preferably biaxially stretched, and heat treated. The stretching is carried out at 90 to 110° C. in both the longitudinal direction and the width direction in a range of 3.0 to 4.5 times. The heat treatment is carried out at a temperature ranging from 240° C. to the melting point for 1 to 60 seconds under constant length or limited shrinkage of 15% or less.

Furthermore, it may be relaxed in one or two directions to improve the thermal dimensional stability of the film;
It is preferable to subject the film to a surface treatment such as corona discharge treatment or plasma treatment in order to improve adhesiveness when adhering to a metal plate and/or metal foil in a later step.

When producing a laminate using an in-mold method without using an adhesive, the polyphenylene sulfide film thus obtained is pasted on one side of the injection mold, and the polyphenylene sulfide resin or The compound is injected into a mold and molded. Preferably resin temperature 30°C to 350°C 1 mold temperature room temperature to 25°C
Molded between 0°C.

After the resin is cooled, it is taken out from the mold to obtain the polyphenylene sulfide resin laminate of the present invention.

In the method of laminating using an adhesive, the above-mentioned polyphenylene sulfide film and a polyphenylene sulfide injection molded plate obtained by injection molding similar to 1- are prepared, and at least one of them is coated with a TU agent. death,
Paste.

The adhesive is not particularly limited, but from the viewpoint of heat resistance and workability, thermosetting solvent-based adhesives are preferred, such as urethane-based,
Epoxy adhesives, acrylic adhesives, silicone adhesives, etc. can be used, and lithographic adhesives can be used.

Further, as a method for applying the adhesive, well-known methods such as a gravure roll method, a reverse roll coater method, a die coater method, etc. can be employed.

When using the hatch method, the adhesive can be applied with a metering bar, applicator, glass rod, etc.

Further, drying of the solvent after coating varies depending on the type of solvent used, and usually a temperature near the boiling point of the solvent is selected to completely eliminate residual solvent.

Also, the bonding conditions are room temperature to ZOO''C, linear pressure 1 to
It is best to do this within a range of 50 kg/cm.

In addition, the adhesive is cured if necessary.

Curing conditions vary depending on the type, composition, and thickness of the adhesive, and are preferably in the range of 0.5 to 100 hours at room temperature to 170°C.

In addition, as mentioned above, is it preferable to apply the adhesive directly to the polyphenylene sulfide film or injection molded plate?
It may be applied to a film or paper having another template, and then transferred to a polyphenylene sulfide film or an injection molded plate.

In addition, whether in the case of in-mold molding or the case of using an adhesive, polyphenylene sulfide is subjected to various processes in advance, depending on the purpose of the laminate. It is possible to apply a core, print, or paste with another film.

However, these treatments can also be performed after forming the laminate.

In addition, when forming polyphenylene sulfide films on both sides of a polyphenylene sulfide injection molded plate,
One side can be laminated by in-mold molding and the other side can be laminated with an adhesive, or both sides can be laminated with an adhesive.

1 ton of polyphenylene sulfide tree of this invention! The a-calendar typeface can be used for various purposes such as:

(1) An electric circuit is formed on a polyphenylene sulfide film and used as a circuit board.

(2) Used as, for example, insulating thin plates, cases for calculators, IC cards, and any other structural materials that require heat resistance or chemical resistance.

(3) Polyphenylene sulfide film is printed and used for wallboards, airplane storage, etc.

[Example] Next, Examples and Comparative Examples of the present invention will be shown to specifically explain the effects of the present invention.

Example 1 50uL-thick PPS two-car stretched film "TORELINA"
(manufactured by Toshi Co., Ltd.) on one side of a test piece mold with a thickness of lam and dimensions of 1/Z inch x 15 cm, and PPS resin R-4 (manufactured by Phillips Oil Co., Ltd.) was applied to the mold. Injection molding was performed at a temperature of 130°C and a resin temperature of 320°C to obtain a laminate of the present invention.

The bending strength of this laminate was tested. Bending strength is ASTM
Lateral determination was made according to D790.

The results are shown in the table below.

Example 2 Except that the PPS film was not applied to the mold surface of the mold,
A PPS injection molded plate was produced in the same manner as in Example 1. The same PPS film as in Example 1 was laminated and adhered to this using an adhesive rkamit epoxy TE5920 J to obtain a laminate of the present invention. The thickness of the adhesive layer was 15 μm.

The impact resistance of this laminate was tested in the same manner as in Example 1. The results are shown in the table below.

Comparative Example 1 Except for not applying PPS film to the mold surface of the mold,
A PPS injection molded plate was produced in the same manner as in Example 1.

The impact resistance of this laminate was tested in the same manner as in Example 1. The results are shown in the table below.

Claims (4)

[Claims] (1) A polyphenylene sulfide resin laminate comprising a polyphenylene sulfide injection molded plate having a thickness of 0.5 mm to 5 mm and a polyphenylene sulfide film having a thickness of 5 μm to 250 μm. (2) The polyphenylene sulfide resin laminate according to claim 1, wherein the polyphenylene sulfide injection molded plate and the polyphenylene sulfide film are laminated without an adhesive layer interposed therebetween. (3) The polyphenylene sulfide injection molded plate and the polyphenylene sulfide film have a thickness of 2 μm to 5 μm.
The polyphenylene sulfide resin laminate according to claim 1, wherein the polyphenylene sulfide resin laminate is laminated with an adhesive layer having a thickness of 0 μm interposed therebetween. (4) A polyphenylene sulfide film with a thickness of 5 μm or more and 250 μm or less is pasted on one side of the mold, and the polyphenylene sulfide resin is injection molded into the mold to achieve a thickness of 0.
．． A method for producing a polyphenylene sulfide resin laminate, which comprises forming a laminate of a polyphenylene sulfide injection molded plate having a thickness of 5 mm or more and 5 mm or less and the above film.