JPH06166080A - Easily adhesive reinforced sheet - Google Patents

Abstract

PURPOSE:To provide an easily adhesive sheet which is comprised of a composition containing crystalline thermoplastic polyester resin enabling coating of the sheet directly with ink or various paste or coating without having the undercoating. CONSTITUTION:This is an easily adhesive reinforced sheet comprised by performing extrusion molding of a composition comporised of (C) a 5-60 pts.wt. platelike reinforced material such as platelike glass and (D) a 5-60 pts.wt. fibrous reinforced material [provided that the sum total of the (C) and (D) is not exceeding 65 pts.wt.] on the basis of the sum total of 100 pts.wt. of (A) and (B) of the (A) 50-97 pts.wt. thermoplastic polyester like polyethylene terephthalate and the (B) 3-50 pts.wt. polycarbonate. The same is a heat-treated and easily adhesive reinforced sheet comprised by heat-treating further the sheet by a hot press.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is useful as a molding sheet material and has a small amount of heat deformation, high mechanical strength, excellent secondary workability, and an adhesive agent without impairing chemical resistance. The present invention relates to an easy-adhesion reinforced sheet that can obtain excellent adhesion even when directly adhered to paints, inks, metals, various pastes, and the like.

[0002]

2. Description of the Related Art Conventionally, most thermosetting resin sheets in the field of electronics are glass epoxy resin laminates, paper phenol resin laminates, paper epoxy resin laminates,
It is used as a polyimide board, fiber-composite base material, etc. These sheets are used as a flat electrical insulating board and a printed wiring board, and a technique such as silk printing is used on the surface to form a circuit with letters, symbols, conductor paste, and resistor paste. It is a thing.

As the thermoplastic resin sheet, a stampable sheet made of a crystalline resin such as polypropylene resin or polyester resin is used. Unlike the case of thermosetting resin, these sheets are used as a flat electrical insulating board and a printed wiring board by using technology such as silk printing on the surface and printing letters or symbols and conductor patterns with printing ink. When a circuit is formed by a paste or a resistor paste, the surface is under-coated or processed to have an uneven surface for the purpose of increasing the adhesion.

[0004]

In recent years, with the development of electronics, electronic parts have become lighter, thinner and smaller. There is also a strong demand for inexpensive and high-performance products. Under such a technical background, the present invention is a composite sheet based on a crystalline thermoplastic polyester resin having excellent secondary processability, and has a high resistance to the crystalline thermoplastic polyester resin. Adhesive, without impairing chemical properties,
It is an object of the present invention to provide a sheet which can be directly adhered to paints, inks, pastes, etc. and which is a substrate having excellent adhesion. Further, the present invention can further three-dimensionally design the shape of the plate by pressing or bending,
The purpose of the circuit board is to provide a composite sheet in which the protruding portion can be embedded by an embedding process and which can be manufactured inexpensively and easily.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventor has melt-kneaded a crystalline thermoplastic polyester resin and a polycarbonate resin in an incompatible system. The inventors have found that a specific extrusion molding sheet achieves the above-mentioned object and arrived at the present invention.

That is, in the present invention, the thermoplastic polyester resin (A) is 50 to 97 parts by weight, the polycarbonate resin (B) is 3 to 50 parts by weight, and the total amount of the above (A) and (B) is 10.
It is composed of 5 to 60 parts by weight of the plate-like reinforcing material (C) and 5 to 60 parts by weight of the fibrous reinforcing material (D) with respect to 0 parts by weight (however, the total of (C) and (D) is 65 parts by weight or less). Provided is an easy-adhesion reinforced sheet obtained by extrusion-molding a composition. Furthermore, the present invention provides a heat-treated easy-adhesion reinforced sheet obtained by heating the above-mentioned easy-adhesion reinforced sheet with a hot press.

The thermoplastic polyester resin (A) used in the present invention is a crystalline polyester resin obtained from a dicarboxylic acid compound and a diol compound. Examples of the dicarboxylic acid compound include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylsulfonedicarboxylic acid, 5-sodiumsulfoisophthalic acid, adipic acid, azelaic acid, sebacic acid, dodecane-1,12-dicarboxylic acid. acid,
Examples thereof include tetradecane-1,14-dicarboxylic acid, octadecane-1,18-dicarboxylic acid, 6-ethyl-hexadecane-1,16-dicarboxylic acid and the like. Of these, terephthalic acid is preferred. It goes without saying that one or more of these dicarboxylic acid compounds may be used as a copolymerization component.

As the diol compound component constituting the thermoplastic polyester resin used in the present invention, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, pentyl glycol, neopentyl glycol, polytetramethylene glycol,
1,4-cyclohexane dimethanol etc. can be mentioned. Of these, ethylene glycol and butylene glycol are preferable. It goes without saying that one or more of these diol compound components may be used as a copolymerization component.

Preferred combinations of these dicarboxylic acid compounds and diol compounds are terephthalic acid and ethylene glycol, terephthalic acid and butylene glycol,
2,6-naphthalenedicarboxylic acid and ethylene gluco-
1,4 with terephthalic acid and / or isophthalic acid
-Cyclohexanedimethanol. In addition to the dicarboxylic acid compound and the diol compound, p- is used as a component constituting the thermoplastic polyester resin of the present invention.
(2-Hydroxyethoxy) benzoic acid and the like may be contained.

Polycarbonate used in the present invention
The resin (B) has an average molecular weight of about 2 obtained by reacting a dioxy compound with phosgene or carbonic acid diester.
10,000 to 40,000 homo or copolymer polycarbonate resin.

The dioxy compound constituting the polycarbonate resin includes hydroquinone, resorcinol, 4,
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl)
Cycloalkane, bis (4-hydroxyphenyl)-
Examples thereof include ter, bis (4-hydroxyphenyl) sulfone, and compounds in which a hydrogen atom on these aromatic nuclei is substituted with a lower alkyl group or halogen. It goes without saying that one or more of these may be used as a copolymerization component. Of these, 2,2-bis (4-hydroxyphenyl) propane is preferable.

Examples of the plate-like reinforcing material (C) used in the present invention include mica and plate-like glass, and those having a diameter of 10 to 1000 microns are preferable, and the diameter / thickness ratio is 5 or more. Those are preferable.

When using these plate-like reinforcing materials, a surface treating agent can be used if necessary. Examples of the surface treatment agent include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds and titanate compounds. Although it is possible to use the plate-like reinforcing material such as plate-like glass as it is, it is preferable to use granules granulated with a binder for the purpose of improving extrusion processability. If the particle size is too small, the effect of improving extrusion processability will be small, and if it is too large, the uniform dispersibility in the matrix resin will be reduced. Therefore, when a granular plate-like reinforcing material such as plate glass is used in the present invention, the average particle size is usually 100 to 5000 μm, preferably 300.
It is preferable that the particle size is ˜2000 μm and the maximum particle size does not exceed 8000 μm. The binder is not particularly limited as long as it can bond the plate-shaped glasses to each other, and a binder that does not adversely affect the matrix resin may be selected. Specific examples of the binder that can be used include polyvinyl acetate exemplified in JP-A-63-225554, page 2, lower right column to page 3, upper left column,
Polyacrylate, polyvinylpyrrolidone, (acid modified)
Addition polymers of olefins such as polyethylene and (acid-modified) polypropylene and copolymers of these olefins, polyaddition reaction products such as polyurethane and polyurea, nylon 6
Etc. It is preferable to use a mixture of one or more of these.

Examples of the fibrous reinforcing material (D) used in the present invention include glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicon carbide fibers, various organic fibers and the like. It is selected and used according to the purpose of imparting electrical conductivity, improving frictional characteristics, improving flame retardancy, improving dimensional accuracy, etc. The fiber diameter, length, etc. of the fibrous reinforcing material are also arbitrary and may be appropriately selected depending on the required mechanical properties, performance such as deformability. Usually, diameter is 1 μm or more, length is 15
μm or more, preferably 3 to 20 μm in diameter, 50 μm in length
The above glass fibers are suitable. When using these fibrous reinforcing materials, it is desirable to use a sizing agent or a surface treatment agent if necessary. If this example is shown, an epoxy compound, a silane compound, an isocyanate compound,
It is a functional compound such as a titanate compound. The fibrous reinforcing material is used after being subjected to surface treatment or converging treatment with these compounds in advance, or these converging agents and surface treating agents may be added at the same time when the composition of the present invention is prepared.

The amount of the plate-shaped reinforcing material (C) such as plate glass used in the present invention is 5 to 60 parts by weight based on 100 parts by weight of the total amount of the thermoplastic polyester resin (A) and the polycarbonate resin (B). Parts, preferably 5 to 50
Parts by weight. Similarly, the compounding amount of the fibrous reinforcing material (D) is 5
To 60 parts by weight, preferably 5 to 50 parts by weight. However, the total amount of the plate-like reinforcing material (C) and the fibrous reinforcing material (D) does not exceed 65 parts by weight. If the total exceeds 65 parts by weight, it becomes difficult to form the composition into a sheet, which is not preferable.

The composition used in the present invention is a known substance generally added to a thermoplastic resin, a thermosetting resin or the like, that is, an antioxidant, in order to impart desired properties according to its purpose. It is also possible to blend a heat stabilizer, a stabilizer such as an ultraviolet absorber, a flame retardant, an antistatic agent, a lubricant, a plasticizer and a crystallization accelerator, a crystal nucleating agent and the like.

As a method for producing the easily-adhesive reinforced sheet of the present invention, a thermoplastic polyester resin (A) and a polycarbonate resin (B) are usually melt-kneaded by a twin-screw extruder to obtain a thermoplastic polyester resin ( A resin mixture is prepared by uniformly dispersing the polycarbonate resin (B) using A) as a matrix, and the resin composition obtained by melt-kneading each reinforcing material into the resin mixture is further extrusion-molded into a sheet-like shape. Cut to size.

Next, this extrusion sheet is further pressed by hot pressing if necessary. By heat treatment with a hot press, the crystallinity can be improved, and it has mechanical strength, dimensional stability, low warpage, and heat resistance, making it suitable for circuit boards that can be widely adopted in almost all industries. Also improves. The heat treatment condition is a temperature of 110 to 2
50 ° C., preferably 150 to 220 ° C., heating rate 3 to 1
5 ° C / min, preferably 5-10 ° C / min, surface pressure 15-90
Kg / cm ^2, preferably 30~70Kg / cm ^2, the holding time at the treatment temperature is 5 to 30 minutes, preferably 10 to 20 minutes.

The easy-adhesion-strengthening sheet or heat-treatment easy-adhesion-strengthening sheet obtained in the present invention has good adhesion to adhesives, paints, inks, etc., and is therefore used as a circuit board or the like by printing conductive ink or the like. be able to. The printing method applied to the easy-adhesion strengthening sheet of the present invention is as follows. As a method of displaying the symbols and characters, printing ink is used, and as a method of forming the electric resistor, silver paste,
A method of forming by a printing method such as silk screen printing using a conductive ink such as carbon paste, copper paste or nickel paste can be preferably used.

[0020]

EXAMPLES The present invention will be described more specifically by way of examples. (Examples 1 to 6) As shown in Table 1, the intrinsic viscosity was 0.78.
Polyethylene terephthalate (PET) or Polybutylene terephthalate (PBT) with an intrinsic viscosity of 0.78
And a mixed resin of a polycarbonate having an average molecular weight of 32,000, and a granular plate glass having an average particle diameter of 1000 μm as a filler (“FLECA” manufactured by Nippon Glass Co., Ltd., an average diameter of plate glass 600 μm). , Diameter 1 as fibrous reinforcement
Glass fibers each having a length of 5 μm and a length of 3 mm were prepared in the blending amounts shown in Table 1, and melt-kneaded at 290 ° C. using a twin-screw extruder to obtain pellets. The pellets were molded by a sheet molding device using a T die to obtain a sheet having a thickness of 1.0 mm. This sheet is sandwiched between aluminum plates and the surface pressure is 50 kg.
/ Cm < ² >, 180 [deg.] C., a heating rate of 3 [deg.] C./min. A silver conductive paste (LS-made by Asahi Chemical Laboratory) is attached to this sheet.
506J) and carbon conductive paste (TU-30SK manufactured by Asahi Chemical Research Institute) are silk screen printed,
It was dried in a dry hot air oven at 150 ° C. for 30 minutes to form an electric resistor. The adhesiveness of this printed wiring board substrate was measured and evaluated by the sero tape peeling property. Also, the bending measurement is performed according to ASTM D638, and the chemical resistance is 30.
After dipping in methylene chloride at 2 ° C for 2 hours and then removing the solvent, the bending strength was measured according to ASTM D638, and the bending strength retention rate (%) before and after dipping was evaluated.

(Comparative Examples 1 to 9) As shown in Tables 2 and 3, as in Examples, except that PET having an intrinsic viscosity of 0.78, PBT, glass fiber, and granular glass plate were blended. A press sheet was prepared and evaluated. The evaluation results are shown in Table-2,
It shows in Table-3.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3]

[0025]

EFFECT OF THE INVENTION The easy-adhesion-strengthening sheet provided by the present invention can be directly used without using an undercoat and an adhesive, which were necessary for the purpose of increasing the adhesive strength in the crystalline thermoplastics. It has become possible to apply ink, various pastes and paints. Moreover, the workability is improved, the economy is improved by shortening the process, and the mechanical strength is not impaired.
In addition, it has become possible to manufacture easy-adhesive composite sheets without impairing chemical resistance. In addition, bending, embedding, deep drawing, etc. have become possible, and the printed wiring board can be made extremely compact.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 67/02 LPE 8933-4J 69/00 LPR 9363-4J // C08J 5/12 CFD 9267-4F B29K 67: 00 105: 06 105: 16 B29L 7:00 4F (72) Inventor Mikio Kusunoki 31 31 Uji Hinojiri, Uji City, Kyoto Prefecture Unitika Uji Plastic Factory (72) Inventor Yasuki Nakayama Uji, Uji City, Kyoto Prefecture 31 Hinojiri 3 Unitika Uji Plastic Factory

Claims (3)

[Claims] 1. A thermoplastic polyester resin (A) 50-
97 parts by weight, 3 to 50 parts by weight of the polycarbonate resin (B), 5 to 60 parts by weight of the plate-like reinforcing material (C) per 100 parts by weight of the above (A) and (B), and the fibrous reinforcing material (D). ) 5 to 60 parts by weight (however, the total of (C) and (D) is 6)
5 parts by weight or less]. 2. The easily-adhesive strengthened sheet according to claim 1, wherein the plate-shaped reinforcing material is plate-shaped glass or mica. 3. A thermoplastic polyester resin (A) 50-
97 parts by weight, 3 to 50 parts by weight of the polycarbonate resin (B), 5 to 60 parts by weight of the plate-like reinforcing material (C) per 100 parts by weight of the above (A) and (B), and the fibrous reinforcing material (D). ) 5 to 60 parts by weight (however, the total of (C) and (D) is 6)
5 parts by weight or less] is a heat-treated easy-adhesion-strengthening sheet obtained by heat-treating an easy-adhesion-strengthening sheet obtained by extrusion-molding a composition comprising: