JPS5945378A - Self-adhesive material - Google Patents

Abstract

PURPOSE:To provide a self-adhesive material having high strength and heat resistance, and suitable as electrical insulation tape, wire binding tape, packaging tape, surface-protection tape, etc., by using a film composed mainly of polyether imide as a substrate, and applying a self-adhesive layer thereto. CONSTITUTION:The objective self-adhesive material is prepared by applying a self-adhesive layer to a substrate composed of an undrawn film composed mainly of a polyether imide, and preferably having a yield strength and/or breaking strength of >=7kg/mm.<2> at 20 deg.C and a 2% strength (F2 value) of >=1.5kg/mm.<2> at 180 deg.C, or a drawn film having a 5% strength (F5 value) of >=8kg/cm<2> at 20 deg.C and a breaking strength of >=12kg/mm.<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a strong and highly heat-resistant adhesive material that uses a film containing polyetherimide as a main component as a support.

Traditionally, adhesive tape supports include Japanese paper, kraft paper,
Paper such as art paper, high-quality paper, tissue paper, cotton cloth, soft cloth,
Fabrics such as nonwoven fabrics, plastic films such as polyethylene/polyvinyl chloride, stretched polypropylene, and stretched polyethylene terephthalate, as well as special films such as C for tetrafluoroethylene and polyimide, and aluminum?
? i, 1fijil? '? There are a wide variety of materials, including lead foil, metal foil, and even plastic foam.

Except for special products, adhesive tapes made from paper or plastic film supports are easy to manufacture and easy to use.
There is also a lot of production. Paper supports are easy to cut, but have low strength, and are also weak when immersed in water. Polyethylene or vinyl chloride films are flexible and easy to roll, but have low strength and poor heat resistance. Stretched polypropylene and polyethylene terephthalate films are strong at room temperature (near
If the temperature is above ℃, it becomes quite soft. Also, these +4' r
l&yo unstretched film is weak, humidity 90℃~100℃
It cannot be used unless the temperature is below °C, and only after stretching can the strength and heat resistance be improved. Polypropylene and polyethylene terephthalate are stretched because the resin price is low and biaxial stretching has a great effect of improving physical properties, but biaxial stretching requires a complicated process.

Ordinary plastic films can be stretched uniaxially to produce a strong film, but when stretched to a high magnification, the film becomes fibrillated and easily cracks into small pieces.

When particularly strong strength is required, polyester film laminated with glass cloth or polyester cloth is used, but the process is complicated and the price is high.

The adhesive tape of the present invention, which uses a polyetherimide-based film as a support, overcomes these drawbacks, and is extremely strong even as an unstretched film alone without laminating other materials, and is highly effective as a single unstretched film. 1. In tape form. OOpm
It is 10 kg thick and has a strength of 10 kq. This film has a yield elongation of 1.1 qb and a yield sag of 10 kg, and is characterized by a high initial resistance when one tape is stretched. This property does not change even when the temperature is increased, up to a high temperature of 200°C, and even at high temperatures it is hard and difficult to stretch. By the way, the strength at a temperature of 160°C and an elongation of 2% is 1 kg/md even for biaxially oriented polyethylene terephthalate film and biaxially oriented nylon film.
In L-almost 12-axis oriented polypropylene, the melting point is just below the melting point, so it is almost close to Okg/-.Compared to this, the polyneedleimide film of the present invention f 3.8 kQ
/ mrl, and even with J-7 at a temperature of 180℃, it is about 3
kq/nrA continues to rise and maintain a high value. Although it is an unstretched film, its elongation at break is approximately 90% at room temperature.
Even when cutting with at least one tape cutter, it shows good cutting performance equivalent to Sellotape 2.

Also, stretched polyetherimide has more elasticity than an unstretched film.

The strength at elongation of 5 cm is 10 kq/mtJ or more, preferably 12 to 15 cm and the breaking strength is 18 kg/-
Above, preferably 22 to 28 kQ/- is the temperature O
℃~260℃, the magnification can be easily obtained by simply stretching to 62 times. Even in a film that has been uniaxially stretched with one free width until just before breakage, it does not become fibrillated and therefore does not crack even when the film is laterally bent. This is a very desirable property for an adhesive tape.

In comparison, polypropylene, polyethylene, and even polyethylene terephthalate, which are stretched to a high magnification by free rljl stretching, easily fibrillate when subjected to stress or bend, resulting in longitudinal cracks, and although they are strong, they are not practical. It cannot be offered.

As described above, the polyetherimide of the present invention is elastic even in an unstretched film, and has good heat resistance and dimensional stability, and has a dry heat shrinkage rate of 0.8% or less at 180°C, preferably only 0. It's as small as 5 inches.

Biaxial stretching is also possible, but is it possible to easily create a tape that has strong mechanical properties and heat resistance even if it is uniaxially stretched? iI will be beaten. Also, this polyetherimide is 38
It cuts out light of 0 nm or less and has excellent resistance to light, making it excellent for outdoor use. In addition, it is resistant to deterioration due to radiation and is also effective for nuclear power-related applications. Furthermore, it has excellent electrical properties fl.

As described above, a film containing polyetherimide as a main component is a particularly preferable material as a support for an adhesive tape.

The polyetherimide used in the present invention has the following formula: [wherein a represents an integer greater than 1, such as 10 to to, ooo or more, and -Q-Z-〇-
is at the 3- and I′i4-positions and the 3′-straddling 4′-positions, and Z is a group consisting of (1) a group represented by the following formula: and (2) a group consisting of the following formula: and -S- represents a divalent group or atom selected from the group consisting of divalent acid groups represented by (Sq is 0 to 1 and SV is an integer from 1 to 5), and -0-2-〇-〇 The divalent bond is due to the terminal group of phthalic anhydride, so for example, 3.3'-13,4/-
It is present at the 14,3/- or 4,41-position, and R is (a) an aromatic hydrocarbon group having 6 to jO carbon atoms and its halogenated derivative, (b) % z to 20 carbons. alkylene group and cycloalkylene group, carbon number 2~
Polydimerganosiloxane terminal-terminated with 8 alkylene groups and (c) a divalent atom selected from above the hole, represented by t, is di, (where X is an integer from 1 to 5) It is a polyetherimide with divalent acidic groups selected from the group consisting of the following groups.

The polyneedlelimide of formula 1 is an aromatic bis(
ether acid anhydride) and diaminated etherimide (hereinafter abbreviated as PET) of the formula II: H2N -R-N ) (2(m) (wherein R has the above-mentioned meaning)) and m- solid viscosity [η] greater than 0.2111/liter, preferably from 0.35 to 0.60, measured in cresol at 25°C;
or has an intrinsic viscosity of 0.7 dl/9 or greater.

Many of Uko's polyetherimides have a gas transition point of 19
The temperature is 0°C or higher, and the heat resistance is extremely poor.

This polyetherimide can be used as a homopolymer, or as a copolymer or a polymer alloy with other polymers as long as the strength and heat resistance are not reduced. Polymer alloys include polyester 1 polyamide, polyolefin, polyacetal, polyvinyl chloride, fluororesin, polystyrene 1 polyamideimide, polysulfate, polyphenylene sulfide, polyphenylene ether, polyether sulfone, polyarylate, polyallyl sulfone, polyphenylene oxide, polycarbonate. It is said to be based on resins such as and polyetherimide.

These homopolymers, co-organizers, and polymer alloys contain antistatic agents, ## agents, coloring agents, stabilizers, weathering agents,
There is no problem in adding a mold release agent, filler, etc. There is no problem even if the surface of the film is subjected to antistatic processing, vapor deposition processing, coating processing such as a back treatment agent, spray processing, etc.

The film may also be dyed. In addition, when used, it can be used as a composite material or an RL1 layer material by combining it with a tF film, other plus deck films, or other composite films.

= Adhesives include elastomers such as natural rubber, isoprene rubber, styrene-butadiene rubber, styrene-butadiene block copolymer, blue rubber, polyisobutylene, rosin, ester gum, polyterpene resin, petroleum resin, etc. agent, polybutene, lanolin, additive
<f, Softeners such as 1il and 4jlj plasticizers, fillers such as lead oxide, titanium oxide, clay, talc, silica, etc., aging such as 2.6 sheeter butyl-4-methylphenol, phenyl beta naphthylamine, etc. A rubber-based adhesive 2 consisting of an inhibitor, a stabilizer, and a coloring agent, or a comonomer composition consisting of a mixture of an acrylic acid alkyl ester, vinyl acetate, and a small amount of maleic anhydride, is added to a polymerization initiator under a nitrogen stream. Acrylic adhesives, styrene-isoprene block copolymers, styrene-butadiene floc copolymers, and solid acrylic adhesives obtained by polymerization in single or mixed solvents of -toluene or benzene-1-ethyl acetate in the presence of hot melt adhesives,
There are peracid FLR materials, liquid curing adhesives that are cured by electron beams, and ultraviolet rays, and you can choose the one that suits your application.

The adhesive tape made of a film containing polyetherimide as a main component of the present invention takes advantage of its excellent strength and heat resistance and can be used as insulation tape, wire binding tape, light packaging tape, etc.
For heavy packaging, surface preservation sheets, reflective sheets)
It can be effectively used as adhesive tapes such as painting tapes, anti-corrosion tapes, bi-lining tapes, vapor-deposited tapes, tapes for aerospace equipment and nuclear power equipment, and also as labels and stickers with adhesive layers.

Next, we will explain how to measure physical properties.

1) Strength at 2 inches elongation (F2 value) and strength at 5% elongation (F5 value): ASTM, 1) A82 (fcN
lsl: In an atmosphere with a temperature of 20° C. and a humidity of 65%, or with a heating oven. 1. Using a universal tensile tester UTM-3 model manufactured by Toyo Baldwin Co., Ltd. LI, attempt 4゜1
Measurement was carried out for 7 minutes at a tensile rate of 4 mW/min.

2) Breaking strength and elongation: Try 4 in the same way as F2 value and P”5 value.
0mm/min, 1 tension? lilθ20mm flff in 1 minute
I did f'N.

3) Dry heat shrinkage rate: Temperature 1 according to J Engineering Ft02318
The film was treated at 80° C. for 30 minutes and determined from the change in film dimensions before and after the treatment.

4) Accelerated weathering resistance: Measured using JT, S Z0237.

5) Glass transition point: ASTM D3418 K semi-Sitehagin Elmer, differential scanning calorimetry M gt DS a
-2 type, increase the wetting speed with sample 1omy】O'
It was determined from the endothermic peak quality of the glass transition measured in O/min.

Hereinafter, the present invention will be described in more detail based on Examples.

No special mention is made of the mechanical properties; the measurement direction is the longitudinal direction of the tape.

Example 1 A resin of polyetherimide (trademark: ULTIIiM No. 1000, the glass transition point of this polymer is 216°C, and the melting point is 343υ) manufactured by General Electric Co., USA, was heated at 150° C. under a vacuum of 0.5 tnm Hg.
℃ for 5 hours, then melt-extruded using a new Nippon Steel 4oφ extruder (minor modified to enable high-temperature extrusion) using a T die with a width of 6 ocl II at a temperature of 380℃ once a month to hard chrome plating. The film was cooled and solidified in a cooling drum to form RAJJ51t.

The obtained film had a thickness of about 6,077,121 mm, and was a transparent, stiff film. The composition of the adhesive, primer, and release agent used in the following Km will be described.

Adhesive: Natural rubber 100 parts polyterpene resin 50 parts 11 parts toluene
Homogeneous mixed solution Brimer consisting of 4 ao 1jli parts: Chlorobutadiene rubber 20 parts Phenol-formalin How many 11 tons? 15 Tf
C1i11tel! Toluene 150
A homogeneous mixed solution stripping agent consisting of: A toluene solution containing a reactant of N-octadecylisocyte and 11] soluble I powder.

Using a well-known adhesive tape manufacturing method using a coating device, the adhesive, primer, and release agent were coated to form a sticky X1 sheet (lq, i 0.5 rn).
), wrap it around a paper tube, and then cut it to a width of 50 mm.
The adhesive tape in between? Lt.

Using this tape, evenly pack the contents of #7f 30 kg into a cardboard box (dimensions 30 cm x 30
(t: m x 50 cm) was pasted with adhesive tape.

JIS-Z-0 using a correctly sealed cardboard box
A rotating hexagonal drum test and a drop impact test as specified in 209 were conducted. The rotating hexagonal drum test 'lA is based on the above JIS standard.
After repeated falls up to the expected number of falls N=29 using the calculation formula specified in , the damage state of the tape was observed. Drop Impact Test: The tape was dropped from a height of 1 m, and the bottom surface of the cardboard box was impacted once each, and the state of damage to the tape was observed.

The above two tests were conducted, and in neither case was the tape damaged.

For comparison, when commercially available gummed tape was used, the tape was damaged.

Example 2 For comparison with the adhesive tape support of Example 1, a commercially available biaxially oriented polypropylene adhesive tape support (thickness: approximately 60 mm) was used.
The strength and elongation of μ) was measured at temperatures of 20°C and 120°C. The polyetherimide of the present invention has a large resistance force at the initial stage of deformation,
It was also strong and resistant to deformation even at a temperature of 120°C. The comparative product was very flexible and easily deformed at 120°C.The results are shown in Table 1. Furthermore, the weather resistance was tested using a xenon arc light weathering tester for 400 hours.

The product of the present invention has less change in strength and elongation, and has the highest ivy
The comparative products in the table showed a large decrease in strength and elongation. The results are shown in Table 2.

Table 2 Furthermore, the dimensional stability at 180°C was investigated. The shrinkage rate of the product of the present invention was only 0.5%, but the comparative film did not melt and retain its original shape.

Example 3 Using the polyetherimide film made in Example 1,
Adhesives: 100 parts of natural rubber, 3 parts of tetramethylthium disulfite, 3 parts of stearic acid, 10 parts of diester, 10 parts of zinc white, 2oIJ titanium white, 80 parts of calcium carbonate, 100 parts of machine oil No. 3, Barcolin. After kneading 30 parts of the blend with a kneading roll, it was heated to 50% at 145°C.
Prepare a solid adhesive that has been vulcanized for 10 minutes and then kneaded for 10 minutes with a kneading roll, and apply it uniformly to the film with a hot curm roll so that 11 is approximately 50 ltm. A master roll was obtained by winding it up, and this was cut into a 50 mm width using a cutting machine, yielding 74% of the adhesive tape of the present invention.

Similarly, a commercially available biaxially stretched polyethylene terephthalate film was coated with an adhesive to prepare a comparative product. The strength and elongation of the support at the initial stage of deformation was measured at high temperatures, and the product of the present invention had stronger resistance at the initial stage of deformation than the comparative product, and was superior as a heat-resistant adhesive tape. The results are shown in Table 3.

Table 3 Example 4 Using the polyetherimide film prepared in Example 1, the film was stretched at a magnification of 2 in the longitudinal direction using a roll stretching machine at each temperature.
Stretched twice. An adhesive was applied to this stretched film in the same manner as in Example 1. A very strong adhesive tape was obtained in the longitudinal direction. Table 4 shows the strength and elongation of the supports measured at 20°C.

In addition, since the residual elongation was low, it exhibited good cuttability when cut with a tape cutter. Makani tape does not crack vertically even when bent.

Table 4 Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Scope of Claims] (1) An adhesive material comprising an adhesive layer provided on a support, wherein the support is a film containing polyl-telimine 2 as a main component. (2) The adhesive material according to claim 1, wherein the support is an unstretched film support whose yield strength and/or breaking strength at a temperature of 20° C. is 7 kq/- or more. (3) Elongation of the film when the support is at a temperature of 180°C2
The adhesive material according to claim 1, which is an unstretched film support having a strength (F2 value) in % of 1.5 kQ/- or more. (4) The adhesive material according to claim 3, wherein the support has a dry heat shrinkage rate of 0.8% or less at 180°C. (5) A patent in which the support is a support for a stretched film having a strength (IF5 value) at a film elongation of 5 inches at a temperature of 20°C of 8 kq/tn- or more and/or a breaking strength of 12&g/- or more. The adhesive material according to claim 1. (6) The temperature of the support in the longitudinal direction of the film is 0°C to 330°C.
The adhesive material according to claim 5, comprising a non-fibrillated support film stretched 1-11 at a magnification of 1.2 times or more in the range of .degree. (7) The magnification is 1.2 when the support is in the humidity range of 0°C to 330°C.
The adhesive material according to claim 5, which has been multiaxially stretched in two or more directions by a factor of at least 2 times. (8) Claim 1 in which the adhesive material is an adhesive tape
Adhesive material at the top. (9) Claim 1 in which the adhesive material is an adhesive label
Adhesive material at the top. 00) The adhesive material according to claim 1, wherein the adhesive material is an adhesive sticker. (11) The adhesive material according to claim 1, wherein the adhesive material is an adhesive sheet.