JP2000256547A - Resin composition for heat-resistant card - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition which causes no discoloration of the ink, etc., while suppressing decrease in character height brought after subjected to embossing finish, etc., by including a polycarbonate resin and two kinds of specific polybutylene terephthalates at a specific ratio. SOLUTION: This composition is obtained by including (A) 70-25 wt.% of a polycarbonate resin with a viscosity-average molecular weight of preferably 10,000-100,000, (B) 10-75 wt.% of a carboxylic acid-modified polybutylene terephthalate, and (C) 0-65 wt.% of polybutylene terephthalate with an intrinsic viscosity (JIS K-7233) of preferably 0.6-1.4. The component B is a polybutylene terephthalate copolymer containing, as a comonomer unit, isophthalic acid, an aromatic dicarboxylic acid such as naphthalenedicarboxylic acid, or an aliphatic dicarboxylic acid such as succinic acid or fumaric acid, and especially an isophthalic acid-modified polybutylene terephthalate is suitable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic card such as a medical card, a cash card, a credit card and the like which has excellent heat resistance and shape stability and can be used even when stored or left under relatively high temperature conditions. The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition for a heat-resistant plastic card which has excellent adhesion to the thermoplastic resin protective layer when a protective layer of a thermoplastic resin is provided on at least one surface layer of the plastic card.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resins have often been used for plastic cards. Further, in order to transfer necessary data such as characters, symbols, and numbers from a plastic card to a document or the like, it is widely practiced to emboss the data on the plastic card by embossing. However, in the case of a plastic card made of a vinyl chloride resin, when stored or left in harsh conditions exposed to relatively high temperatures in daily life, for example, under the scorching sun or in a car exposed to direct sunlight, the plastic card is embossed. There has been a problem that the height of the convex portion of the engraved character, symbol, numerical value, or the like is reduced, so that it is difficult to transfer data to a document or the like, and it is difficult to read even if it is transferred.

[0003] In order to solve the above problems, the use of a plastic material having higher heat resistance than a vinyl chloride resin has been studied. The heat distortion temperature of vinyl chloride resin is 80
It is proposed to substitute a plastic material having a heat distortion temperature of 90 ° C or higher assuming storage and leaving under high temperature conditions that can occur in daily life, such as about 130 ° C. Has been considered as a candidate and has been studied. However, when the polycarbonate resin is used for the plastic card, the problem that the height of the convex portion of the data stamped by embossing is reduced under high temperature conditions is solved, but the plastic card itself is embossed. A new problem of warping has arisen.

[0004] In order to solve the above-mentioned problem of warpage of the polycarbonate resin plastic card, the applicant has
The inventors of the present invention invented the use of a resin composition obtained by mixing polybutylene terephthalate with a polycarbonate resin, and filed a patent application (JP-A-11-60921).

[0005]

However, in the case of a plastic card, a polycarbonate resin, a polyester resin, or a vinyl chloride resin is used for printing on at least one surface layer or for protecting the surface layer even when printing is not performed. Such as a transparent thermoplastic resin film, sheet or the like (hereinafter referred to as oversheet) is bonded by means such as hot pressing. Further, there are cases where the base material constituting the card is composed of two or more layers. In such a case, depending on the temperature conditions of the hot press, the adhesiveness between the base material of the plastic card and the oversheet,
There is a new problem that the adhesion between the substrates is poor.

Specifically, the temperature condition of the hot press is 160
When the temperature is higher than ° C., the adhesion between the plastic card substrate and the oversheet is good, but the ink used for printing is discolored or bleeds, so that there is a problem that the value as a plastic card is significantly impaired. To avoid this, if the temperature is lowered, the problem of discoloration and bleeding of the ink is solved, but the adhesion between the plastic card substrate and the oversheet or the adhesion between the substrates is inferior and the ink is peeled off during use. There was a problem.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive efforts to prevent the discoloration and bleeding of the ink and to improve the adhesion between the plastic card substrate and the oversheet and the adhesion between the substrates. As a result of the research, by blending a specific carboxylic acid-modified polybutylene terephthalate with a polycarbonate resin, the ink height does not decrease or warp after embossing, ink discoloration and bleeding do not occur, and a plastic card base is used. The inventors have found that the adhesiveness between the material and the oversheet and the adhesiveness between the substrates are significantly improved, and have completed the present invention.

That is, the present invention provides a resin for a heat-resistant plastic card comprising 70 to 25% by weight of a polycarbonate resin, 10 to 75% by weight of a carboxylic acid-modified polybutylene terephthalate and 0 to 65% by weight of a polybutylene terephthalate. It provides a composition.

Hereinafter, the resin composition for heat-resistant plastic cards of the present invention will be described in detail.

The polycarbonate resin used in the present invention can be obtained by a phosgene method of reacting various dihydroxydiaryl compounds with phosgene, or a transesterification method of reacting a dihydroxydiaryl compound with a carbonate such as diphenyl carbonate. It is a polymer and a typical example is 2,2-bis (4
-Hydroxyphenyl) propane (bisphenol A)
And polycarbonate resins produced from the same.

The dihydroxydiaryl compounds include bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl).
Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4 -Hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether; dihydroxy diaryl sulfides such as 4,4'-dihydroxy diphenyl sulfide; 4,4'-dihydroxy diphenyl sulphoxide; 4,4'-dihydroxy-3,3 Dihydroxydiarylsulfoxides such as'-dimethyldiphenylsulfoxide; and dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

These may be used alone or as a mixture of two or more kinds. In addition, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like may be used in combination.

Further, the above-mentioned dihydroxyaryl compound and a phenol compound having three or more valences as shown below may be mixed and used.

The phenols having three or more valences include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, and 2,4,6-dimethyl-2,4,6-triphenol. -(4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4,4-
(4,4'-dihydroxydiphenyl) -cyclohexyl] -propane.

The viscosity average molecular weight of the polycarbonate resin is usually from 10,000 to 100,000, preferably 15,000.
~ 35000, more preferably 23000-32000
It is. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as required.

The carboxylic acid-modified polybutylene terephthalate used in the present invention is a polycarboxylic acid containing, as a comonomer unit, an aromatic dicarboxylic acid such as isophthalic acid and naphthalenedicarboxylic acid and an aliphatic dicarboxylic acid such as succinic acid and fumaric acid. Butylene terephthalate copolymer. Of these, isophthalic acid-modified polybutylene terephthalate can be suitably used.

The amount of isophthalic acid, a comonomer unit of isophthalic acid-modified polybutylene terephthalate, is
The isophthalic acid-modified polybutylene terephthalate is preferably in the range of 10 to 50 mol% based on the total amount of isophthalic acid and terephthalic acid as monomers constituting the polybutylene terephthalate. If the amount is less than 10 mol%, the effect of improving the adhesion may decrease, and if it exceeds 50 mol%, the heat resistance may decrease. More preferably, it is 20 to 40 mol%.

As the carboxylic acid-modified polybutylene terephthalate, those having a melting point of 150 to 205 ° C. can be suitably used.

The compounding amount of the carboxylic acid-modified polybutylene terephthalate is 10 to 75% by weight. If it is less than 10% by weight, the adhesiveness becomes insufficient, and if it exceeds 75% by weight, the heat resistance is low, and further, the shape change (shrinkage) due to heat is not preferable. A more preferred amount is 2
0 to 65% by weight.

The polybutylene terephthalate used in the present invention has an intrinsic viscosity of 0.6 to 1.4, preferably 0.7 to 1.1, measured according to JIS K-7233.
Those having a range of 4 can be suitably used.

The amount of polybutylene terephthalate is as follows:
0 to 65% by weight. If it exceeds 65% by weight, there is a problem that the plastic card itself is broken when embossing is performed, which is not preferable. A more preferred amount is in the range of 0 to 45% by weight.

The mixing method of the polycarbonate resin and the carboxylic acid-modified polybutylene terephthalate, and in some cases, the polybutylene terephthalate is not particularly limited, and is mixed by a known mixer, for example, a tumbler, a ribbon blender, a high-speed mixer, and melt-kneaded. Method.

Further, within a range that does not impair the effects of the present invention,
At the time of mixing, various additives such as an antioxidant, an antistatic agent, a release agent, a lubricant, a light stabilizer, an ultraviolet absorber, and a dye / pigment may be added as necessary.

[0024]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. In addition, "part" and "%" are based on weight.

(Examples 1 to 7 and Comparative Examples 1 to 3) A polycarbonate resin, isobutylic acid-modified polybutylene terephthalate and polybutylene terephthalate were preliminarily mixed by a tumbler based on the mixing ratio shown in Table 1. Then
A single screw extruder with a screw diameter of 40 mm (VS4 manufactured by Tanabe Plastics Machine Co., Ltd.) under the condition of a melting temperature of 240 ° C.
0-32) to obtain pellets of various resin compositions. The plastics used are as follows: Polycarbonate resin (hereinafter abbreviated as PC): PC: Caliber 200-3 manufactured by Sumitomo Dow Co., Ltd. Isophthalic acid-modified polybutylene terephthalate (hereinafter abbreviated as PBTI): PBTI- 1: Duranex 600JP, manufactured by Polyplastics Co., Ltd. Intrinsic viscosity: 1.0 Isophthalic acid amount: 12.5 mol% Melting point: 205 ° C. PBTI-2: Duranex 600KP, manufactured by Polyplastics Co., Ltd. Intrinsic viscosity: 1.0 Isophthalic acid content: 22 mol% Melting point: 185 ° C. PETI-3: Duranex 600LP manufactured by Polyplastics Co., Ltd. Intrinsic viscosity: 1.0 Isophthalic acid content: 30 mol% Melting point: 170 ° C. Polybutylene terephthalate ( (Hereinafter abbreviated as PBT): PBT: Polyplastics Co., Ltd. Lanex 400FP Intrinsic viscosity: 0.8 Melting point: 224 ° C

The pellets of the obtained various resin compositions were extruded at 240 ° C. using a T-die to obtain a sheet having a thickness of 0.35 mm. Various tests were performed using this resin plate.

Adhesion test between substrates: resin plate 14 cm
x 14cm size, put aluminum foil on one half of one side, put resin plate on the whole surface, hot press at 150 ° C and 160 ° C respectively, and paste resin plates together I combined. Thereafter, the test piece was cut into a test piece having a length of 14 cm and a width of 2 cm so as to include the aluminum foil part in half in the length direction, the aluminum foil was removed, and a test piece for measuring the adhesion between the substrates was obtained.

Using the obtained test pieces, a peeling test was performed in a constant temperature room at a temperature of 23 ° C. and a relative humidity of 50% under the following conditions. Tensile tester: Orientec universal tensile tester UCT
-1T Tensile speed: 50 mm per minute Table 1 shows the load at the peeling start point as the adhesive strength.
The adhesive strength was 4.0 Kgf or more or a resin sheet that was broken without peeling was judged to be acceptable.

Adhesion test with an oversheet: A resin plate was cut into a size of 14 cm x 14 cm, an aluminum foil was placed on one half of the surface, and an oversheet (*)
Was placed on the entire surface, and subjected to hot press working at 150 ° C. and 160 ° C., respectively, to bond the resin plate and the oversheet. Thereafter, the test piece was cut into a test piece having a length of 14 cm and a width of 2 cm so as to include the aluminum foil part in half in the length direction, the aluminum foil was removed, and a test piece for measuring the adhesion to the oversheet was obtained. (*) Polycarbonate resin oversheet: Sumitomo Dow Co., Ltd. Caliber 200-13 using T-die
Extrusion was performed at 60 ° C. to form a film having a thickness of 50 μm.
This was used as an overseat.

Using the obtained test piece, a peeling test was performed in a constant temperature room at a temperature of 23 ° C. and a relative humidity of 50% under the following conditions. Tensile tester: Orientec universal tensile tester UCT
-1T Tensile speed: 50 mm per minute Table 2 shows the load at the peeling start point as the adhesive strength.
In addition, the adhesive strength was 2.5 kgf or more, or the one in which the oversheet was broken without peeling was judged to be acceptable.

Warpage and embossed character height retention tests:
Two resin plates were stacked, and oversheets (*) were further stacked on both sides thereof and pressed at 160 ° C. to obtain a test resin plate. The resin plate was cut into a size (8.5 cm x 5.4 cm) specified in JIS X6301 to prepare a test plastic card. (*) Polycarbonate resin oversheet: Sumitomo Dow Co., Ltd. Caliber 200-13 using T-die
Extrusion was performed at 60 ° C. to form a film having a thickness of 50 μm.
This was used as an overseat.

The obtained test plastic card was used for 23
Perform embossing in a constant temperature room at 50 ° C and 50% relative humidity.
Engraved. The embosser used was a card embosser (TX-1050) manufactured by Tritronics Co., Ltd. In the first area, 19 characters, in the second area, 38 characters, and the character type were all engraved on the test plastic card with 8 of 7B number.
The height of the embossed characters was adjusted to 0.40 mm. The test methods and evaluation criteria for embossed plastic cards are as follows:

Warping: The embossed character convex portion of the plastic card is placed on a flat surface in a direction not in contact with the flat surface.
The maximum distance from the flat surface to the non-embossed character portion of the embossed character surface was measured with a video microscope, and was determined as warpage. If the warpage was 2.5 mm or less, it was judged as acceptable. Table 2 shows the results.

Maintaining the height of the embossed characters: After measuring the height of the embossed characters of the embossed plastic card with a micrometer, 90 ° C., 100 ° C., 11
It was left in a hot air circulating drier at 0 ° C. for 1 hour. After cooling to room temperature, the height of the embossed characters was measured again, and the amount of reduction was used as a criterion for evaluation. The decrease at 90 ° C is 0.05
mm, the amount of reduction at 100 ° C and 110 ° C is 0.1
mm or less was accepted. Table 2 shows the results.

Heat shrinkage test: Two resin plates were stacked, and oversheets (*) were further stacked on both sides thereof and pressed at 160 ° C. to obtain a test resin plate. The resin plate is JIS X630
Size specified in 1 (8.5cm x 5.4cm)
To make a test plastic card. (*) Polycarbonate resin oversheet: Sumitomo Dow Co., Ltd. Caliber 200-13 using T-die
Extrusion was performed at 60 ° C. to form a film having a thickness of 50 μm.
This was used as an overseat.

The obtained test plastic card was used for 23
After standing for 24 hours in a constant temperature room at 50 ° C. and a relative humidity of 50% to adjust the condition, the lengths in the long side direction and the short side direction were measured by digital calipers. The test piece after the measurement was left in a hot air circulating oven at 90 ° C. for one hour, and was taken out.
It was left in a constant temperature room of 0% relative humidity for 24 hours to adjust the condition, and the lengths in the long side direction and the short side direction were measured again with a digital caliper.

When the measured value before heating is X and the measured value after heating is Y, the shrinkage S (%) is expressed by the following equation: S (%) = ((X
-Y) / X) × 100 and the shrinkage ratio S (%) was determined to be 0.2% or less.

[0038]

[Table 1] Composition of resin composition and adhesiveness (substrates) ：: acceptable ×: unacceptable Shrinkage: 0.2% or less was accepted.

[0039]

[Table 2] ：: passed ×: failed Warpage: 2.5 mm or less was accepted. Decrease in embossed character height: 90 ° C .: 0.05 mm or less was accepted. 100 ° C: 0.1 mm or less was accepted. 110 ° C: 0.1 mm or less was accepted.

[0040]

By using the resin composition of the present invention in a plastic card, the adhesiveness between the substrates when the plastic card substrates are laminated and the thermoplastic resin on at least one surface layer of the plastic card can be obtained. Adhesion with the thermoplastic resin protective layer when the protective layer is provided is dramatically improved. In addition, even if it is left under relatively high temperature conditions in daily life, the reduction of the height of the convex portion of the data stamped by embossing is suppressed, and the warpage of the plastic card itself due to the embossing is also suppressed. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // G11B 5/73 G11B 5/704 F term (reference) 2C005 HA10 HB08 HB09 JA08 KA01 LA02 LA11 4F071 AA45 AA46 AA50 AH14 BC01 BC08 4J002 CF04X CF07X CF07Y CG00W GC00 GF00 GS00 5D006 CB01 CB07 DA01 FA00

Claims (5)

[Claims] (1) 70 to 25% by weight of a polycarbonate resin,
Carboxylic acid-modified polybutylene terephthalate 10 to 75
1. A resin composition for a heat-resistant plastic card, comprising: by weight, and 0 to 65% by weight of polybutylene terephthalate. 2. The compounding amount of a polycarbonate resin is 65 to 3
The resin composition for a heat-resistant plastic card according to claim 1, wherein 5% by weight, a compounding amount of the carboxylic acid-modified polybutylene terephthalate is 20 to 65% by weight, and a compounding amount of the polybutylene terephthalate is 0 to 45% by weight. 3. The carboxylic acid-modified polybutylene terephthalate comonomer unit is isophthalic acid.
Or the resin composition for a heat-resistant plastic card according to claim 2. 4. Isophthalic acid, which is a comonomer unit of carboxylic acid-modified polybutylene terephthalate, is used in an amount of 10 to 50 based on the total amount of isophthalic acid and terephthalic acid as monomers constituting said carboxylic acid-modified polybutylene terephthalate. The resin composition for a heat-resistant plastic card according to claim 3, which is mol%. 5. A carboxylic acid-modified polybutylene terephthalate comonomer unit having an isophthalic acid content of 20 to 40 based on the total amount of isophthalic acid and terephthalic acid as monomers constituting said carboxylic acid-modified polybutylene terephthalate. The resin composition for a heat-resistant plastic card according to claim 3, which is mol%.