JPH0665482A - Extrusion-molded sheet-shaped material and insulating board - Google Patents

Abstract

PURPOSE:To enable efficient production of an extrusion-molded sheet low in anisotropy and excellent in flatness by using a small-scale facility and to provide an insulating board excellent in soldering resistance, dimensional stability and mechanical properties, exhibiting flame retardancy, free from plating bath pollution and applicable to wide-range industries. CONSTITUTION:With 100 pts.wt. polyester containing >=85mol% 1,4- cyclohexanedimethanol terephthalate-based repeating unit, (1) 5 to 50 pts.wt. fiber-shaped reinforcing material, (2) 5 to 50 pts.wt. granular inorganic compound, (3) 10 to 40 pts.wt. organic halide compound and (4) 5 to 20 pts.wt. sodium antimony are blended and the resultant mixture is extrusion-molded and hot-pressed.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an extruded sheet-like product obtained from a resin composition containing a polyester resin as a matrix resin and solder heat resistance obtained therefrom.
The present invention relates to an electrical insulating board which has excellent electrical insulation properties and dimensional stability, and also has flame retardancy and excellent punching workability at room temperature.

[0002]

2. Description of the Related Art At present, as an electrical insulating board, a laminated board in which a varnish of thermosetting resin typified by phenol resin or epoxy resin, which has excellent electrical insulation properties, is laminated on a substrate typified by paper or glass cloth. Widely used. However, in this method, the equipment is large-scale, the equipment cost is high, the productivity is poor, and the manufacturing cost is high.

Further, thermosetting resins have excellent chemical resistance and water resistance, but when paper is used as a substrate for laminated boards, not only the chemical resistance of the paper itself is poor, but also dimensional changes due to moisture absorption. As a result, the range of industrial use is considerably limited. Further, in the punching workability, cracks and delamination often occur, which increases the cost, but it is unavoidable that the heating is performed at 50 ° C. or higher.

On the other hand, in the case of a laminated plate using a glass cloth as a base material, the dimensional stability and chemical resistance are improved, but the cost of the glass cloth imposes economic restrictions, and the punching workability is poor. The problem remains.

Polyester resins have excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc. and are used in many industrial products. In addition, the one in which the polyester resin is reinforced with glass fiber or the like and further improved in mechanical properties and thermal properties is used as an injection molded product, but in the case of an injection molded product, the size and thickness are limited. However, productivity is poor.

[0006]

Generally, the demand for flame retardancy of molded products, which is mainly used for electrical insulation, has been increased in recent years, and by adding a large amount of flame retardant,
We are meeting that demand. And since the flame retardant is far more expensive than the matrix resin, it is known to blend antimony trioxide as a flame retardant aid in order to obtain an excellent flame retardant effect with a small amount of flame retardant. Antimony trioxide has a problem of electroless plating bath contamination because it has a Pd catalyst poison during plating. further,
Solder heat resistance is also required for use in a wide range of electrical insulation applications, but generally used polyethylene terephthalate or the like has poor thermal properties, and therefore satisfactory properties cannot be obtained.

According to the present invention, a polyester resin having heat resistance is used as a matrix resin, and a glass fiber reinforced resin is extruded to effectively utilize the advantages of the polyester resin, and at the same time, the size of the resin can be reduced at a low cost. The present invention is intended to provide an extruded sheet that can be produced, and a thermoplastic electrical insulating board that is excellent in solder heat resistance and is free from contamination by an electroless plating bath by hot rolling the extruded sheet.

[0008]

The present inventors have arrived at the present invention as a result of intensive research for such purpose. That is,
The present invention relates to (1) fibrous reinforcing material 5 to 50 with respect to 100 parts by weight of polyester having 85% by mole or more of 1,4-cyclohexanedimethylene terephthalate repeating unit.
Parts by weight, (2) 5 to 50 parts by weight of granular inorganic compound, (3)
An extruded sheet-like product characterized by being blended with 10 to 40 parts by weight of an organic halogen compound and 5 to 20 parts by weight of (4) sodium antimonate and produced by extrusion, and the sheet-like product was hot-rolled. It is an electrical insulation board characterized by the above.

It is well known that polyester resin has good electrical characteristics and also excellent characteristics in dimensional stability, water resistance and chemical resistance. When used as an electrical insulation board, 85 mol% is required to improve solder heat resistance.
It is necessary to have the above 1,4-cyclohexanedimethylene terephthalate-based repeating unit, and in order to improve mechanical properties, it is necessary to reinforce with a fibrous reinforcing material such as glass fiber which is the component (1). However, the molecules and the fibrous reinforcing material are oriented during the melt extrusion of the sheet forming, the sheet-like material exhibits remarkable anisotropy, and the sheet surface is deteriorated. Therefore, as a result of various investigations to alleviate these, it was found that the addition of the granular inorganic compound as the component (2) contributes to alleviation of anisotropy and improvement of the sheet surface condition.

Further, imparting flame retardancy is also indispensable. Use of flame retardants and antimony trioxide type, which are general techniques for imparting flame retardancy, is changed to use of flame retardant and sodium antimonate type. It was also found that this can suppress electroless plating bath contamination.

The present invention will be described in detail below. The polyester resin used in the present invention is a low polymer obtained by a normal esterification reaction or a transesterification reaction from a lower alkyl ester of terephthalic acid and 1,4-cyclohexanedimethanol, which is melt-polymerized by a normal method. Or a solid-state polymerized product thereof. And the polyester having 85 mol% or more of 1,4-cyclohexylene dimethylene terephthalate repeating units means 85 mol% or more of 1,4-cyclohexylene dimethylene terephthalate repeating units and other repeating units, that is, other And a glycol component can be used as the above-mentioned other copolymerization component.

For example, as the acid component, isophthalic acid, naphthalene dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl sulfone dicarboxylic acid, p- (2-hydroxyethoxy) benzoic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic azelate Examples thereof include acids, dodecane-1,12-dicarboxylic acid, tetradecane-1,14-dicarboxylic acid, octadecane-1,18-dicarboxylic acid, 6-ethyl-hexadecane-1,16 dicarboxylic acid and the like.

Examples of the glycol component include propylene glycol, diethylene glycol, butylene glycol, pentyl glycol, neopentyl glycol and the like, and polyalkylene glycol such as polytetramethylene glycol and the like.

When the 1,4-cyclohexanedimethylene terephthalate-based repeating unit of the polyester of the present invention does not satisfy 85 mol%, the melting point becomes as low as 250 ° C. or lower and it becomes impossible to have a solder heat resistance of 250 ° C. Therefore, the repeating unit of the component needs to be 85 mol% or more, and particularly preferably 88 mol% or more.

Specific examples of the fibrous reinforcing material used as the component (1) of the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, titanic acid fibers and the like. Usually, glass fiber is often used. Further, the diameter and length of various fibers are not particularly limited, but if the fiber length is too long, it is difficult to uniformly mix and disperse it with polyester and other compounding agents, and conversely the fiber length is short. If it is too much, the effect as a reinforcing material becomes insufficient, so that a fiber having a fiber length of 0.1 to 10 mm is usually used, and particularly when the fibrous reinforcing material is glass fiber, the fiber length is 0. It is preferably 1 to 7 mm, more preferably 0.3 to 4 mm.

The fibrous reinforcing material may be treated with various compounds as necessary for the purpose of improving the interfacial adhesion with polyester and enhancing the reinforcing effect. When glass fiber is used as the fibrous reinforcement, various surface treatment agents such as vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane are used. , Γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropylmethoxysilane, γ-mercaptopropyltrimethoxysilane, and other silane-based treatment agents, and methacrylic acid-chromic chloride and other chrome-based treatments. The one treated with the agent is used.

The blending ratio in the resin composition of the present invention can be widely selected according to the purpose of use, but it is necessary to be 5 to 50 parts by weight, particularly 8 to 8 parts by weight based on the whole sheet-like material.
It is preferably 40 parts by weight. If the amount of the fibrous reinforcing material is less than 5 parts by weight, the effect as the reinforcing material is insufficient, and if the amount of the fibrous reinforcing material exceeds 50 parts by weight, the anisotropy becomes strong. The surface smoothness of the sheet material is significantly deteriorated.

The granular inorganic compound used as the component (2) of the present invention is used as a smoothing agent for the surface of the sheet, a reinforcing material, an anisotropy reducing agent for mechanical properties, and a crystal nucleating agent depending on the particle size and shape. The effect is different. If the average particle size exceeds 1000 μm, the effect becomes small, so that the average particle size is usually 10
Granular inorganic compounds having a size of 00 μm or less are useful.

Specific examples include silica, calcium carbonate, synthetic silicic acid and silicate, zinc, halosite clay, kaolin, basic magnesium carbonate, mica, talc, quartz powder, wollastonite, dolomica powder, titanium oxide. , Barium sulfate, calcium sulfate, alumina,
Examples thereof include glass flakes, and one or more of these inorganic compounds can be used.
Among them, mica, glass flakes, and wollastonite are most effective in the present invention.

The blending ratio of the finely divided inorganic compound in the present invention can be widely selected according to the purpose of use, but in consideration of the balance of mechanical properties and surface smoothness, it is 5 to the whole sheet-like material. It should be 50 parts by weight, and particularly preferably 10 to 30 parts by weight. When the amount of the finely divided inorganic compound is less than 5 parts by weight, the effect of improving the anisotropy of the sheet-like material and improving the surface smoothness becomes insufficient, and the amount of the finely divided inorganic compound added is 5 or less.
If it exceeds 0 parts by weight, the mechanical properties of the sheet-like product will be significantly deteriorated.

The organic halogen compound used as the component (3) in the present invention is used as a flame retardant and is a bromide or chlorinated compound containing at least one aromatic ring, preferably bromine. It is a compound. When the organohalogen compound contains bromine, the bromine content is preferably at least 40% by weight of the organohalogen compound.

Specific examples include poly (dibromophenylene oxide), brominated polystyrene, decabromodiphenyl ether, 1,2,3,4-tetrabromobenzene, hexabromobenzene, chlorinated diphenyl, brominated diphenyl, tetrabromobisphenol. A, a reaction product of tetrabromobisphenol A and epichlorohydrin, tetrabromobisphenol A and an ethylene oxide adduct, and the like can be given.

The mixing ratio of the organic halogen compound in the present invention can be widely selected according to the purpose of use, but it is necessary to be 10 to 40 parts by weight, and particularly 15 to 25 parts by weight, based on the whole sheet material. It is desirable to use parts by weight. If the content is less than 10 parts by weight, the flame retardant effect is small, and if it exceeds 40 parts by weight, the mechanical properties are significantly adversely affected.

The sodium antimonate used as the component (4) in the present invention is used as a flame retardant aid and contains Na ₂ O in its chemical structure and has an antimony structure. The average particle size thereof is preferably 0.5 to 8 μm.

The compounding ratio of sodium antimonate in the present invention can be widely selected according to the purpose of use like the organic halogen compound, but is 5 to the whole sheet-like material.
It is necessary to make it 20 parts by weight, and it is particularly desirable to make it 8 to 15 parts by weight. If the amount is less than 5 parts by weight, the effect of the flame retardant as an auxiliary agent is small, and if it exceeds 20 parts by weight, the mechanical properties are significantly adversely affected.

In the present invention, as additives other than the above-mentioned compounds, additives such as heat stabilizers, antioxidants, light stabilizers, lubricants, pigments, plasticizers, cross-linking agents and impact-resistant agents may be added if necessary. You may mix.

Further, as an electrical insulating board which can be widely adopted in all industrial fields, dimensional stability, low warpage, heat resistance and the like are indispensable, and hot rolling is necessary as a countermeasure. The hot rolling conditions are usually a heating temperature of 110 to 250 ° C. and a heating rate of 3 to 15 ° C./min. However, it is preferably 150 to 220 ° C. and the temperature rising rate is 5 to 10
° C / min. Is. Moreover, the pressure is 15 to 90 kg / c.
m ² , preferably 30 to 70 kg / cm ² .

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[0029]

【Example】

Examples 1 to 3 Polycyclohexanedimethylene terephthalate / isophthalate having an intrinsic viscosity of 1.0 (95 mol% terephthalate, 5 mol% isophthalate) (hereinafter abbreviated as PCTA)
In addition, glass fiber having a diameter of 13 μm and length of 3 mm as a fibrous reinforcing material, mica having an average particle diameter of 100 μm as a granular inorganic compound, granular glass flakes manufactured by Nippon Sheet Glass Co., Ltd., and Pyrocheck 68Pb manufactured by Fellows as an organic halogen compound. ], And Nissan Chemical Industries Ltd. sodium antimonate at a compounding ratio shown in the columns of Examples 1 to 3 of Table 1, respectively, and melt-kneaded at 285 ° C. using a twin-screw extruder to obtain pellets. It was When each of these was molded into a sheet having a thickness of 1.0 mm by an extrusion sheet molding apparatus using a T-die, it was possible to obtain an extrusion molded sheet having a smooth surface and good appearance.

These extruded sheets were pressed at a pressure of 40
kg / cm ^{2 up} to 180 ° C., heating rate 5 ° C./min.
After heating for 15 minutes, the board was cooled promptly to obtain a board. When the bending strength, solder heat resistance and flame retardancy of these boards were measured, good results were obtained.

The measuring method and evaluation table were as follows. Surface smoothness: ○ Good, △ Fair, bad × Three levels of bending strength; Measured according to ASTM D790 Deformation rate; Measured according to ASTM D790 Flexural modulus; Measured according to ASTM D790 Flammability; Measured according to UL94 Solder resistance; Width 2 cm × 260 ° C for 5 cm long test piece
× Change for 60 seconds when immersed in solder bath ○ Good, △ Fair, Bad × 3 stages

[0032]

[Table 1]

Comparative Examples 1 to 6 Similar to Examples 1 to 3, the compounds were blended at the compounding ratios shown in the columns of Comparative Examples 1 to 6 in Table 1, melt-kneaded with a twin-screw extruder to prepare pellets. In Examples 2, 3, and 4, since the compounding ratio of mica, glass fiber, or an organic halogen compound (flame retardant) was excessive, strand breakage occurred frequently during compounding, resulting in poor compound operability. Further, when each of the obtained pellets was molded into a sheet having a thickness of 1.0 mm by an extrusion sheet molding device using a T-die, those shown in Comparative Examples 1 and 3 had a large amount of glass fiber mixed with mica. As a result, the surface roughness of the sheet was poor, and the board obtained by hot rolling had a large anisotropy in mechanical properties. And what was shown in the comparative example 5 was inferior in flame retardancy, and the comparative example 6 which used PET instead of PCTA as a matrix resin did not have a satisfactory result in solder resistance.

[0034]

As is apparent from the above description, according to the present invention, it is possible to produce a sheet-like material having a small anisotropy and excellent flatness with a small-scale facility and a high efficiency. Further, it is possible to obtain an electric insulating board which is excellent in solder resistance, dimensional stability, mechanical properties, and has flame retardancy and which is free from contamination of the plating bath and can be used in a wide range of industries.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mikio Kusunoki 31-3 Uji Hinojiri, Uji City, Kyoto Prefecture Unitika Ltd. Uji Plastic Factory (72) Inventor Yasuki Nakayama 31-3 Uji Hinojiri, Uji City, Kyoto Prefecture Unitika Corporation Uji Plastic Factory

Claims (2)

[Claims] 1. A fibrous reinforcing material 5 to (1) with respect to 100 parts by weight of a polyester having 85 mol% or more of 1,4-cyclohexanedimethylene terephthalate-based repeating units.
50 parts by weight, (2) 5 to 50 parts by weight of a granular inorganic compound,
An extruded sheet-like product, characterized in that 10 to 40 parts by weight of an organic halogen compound and (4) 5 to 20 parts by weight of sodium antimonate are mixed and produced by extrusion molding. 2. An electrical insulating board, which is obtained by hot rolling the extruded sheet according to claim 1.