JP3388643B2 - Self-adhesive elastomer sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to glass, ceramics,
A self-adhesive elastomer that can be easily attached to smooth surfaces such as metals (including alloys), plastics, and wood without using adhesives or adhesives and can be easily peeled off. Regarding the seat.

[0002]

2. Description of the Related Art Road signs and address displays, various signs such as bus stops and station yard, various signs and displays such as department stores and office buildings, and various other signs and displays are used throughout the living environment. There is. Conventionally, such signs and indications (hereinafter referred to as stickers) use paper, metal plates (sheets), plastic plates (sheets), etc. as media, and print, write, engrave, etc. letters on the media,
Numerical values, symbols, etc. are written, and chemical means such as adhesive or adhesive, nails, etc.
It is generally attached by mechanical means such as a screw or a wire.

[0003]

By the way, some of the above-mentioned various seals often require a change in notation. In this case, remove the old seal and replace it with a new one.However, if the old seal is attached by chemical means, it will be difficult to remove the adhesive or adhesive remaining after the seal is removed. If forced and attached by mechanical means, the difficult task of removing this attachment means is forced.

Further, as a conventional seal, paper, metal foil, or plastic sheet is used, and one side is adhered by using an adhesive, but peeling occurs due to deterioration of the adhesive, or a seal is formed. It is hard to peel off when removing,
The seal broke and remained on the way, and the adhesive remained after removing it. Further, when the same sticker is used again for sticking, there is a problem in that the sticky surface of the adhesive is often dusted and cannot be stuck. Further, JP-A-6-136186 reports on a self-adhesive elastomer composed of a hydrogenated diene block copolymer and an olefin polymer, but the adhesiveness remains unsatisfactory.

The present invention has been made in order to overcome the problems of these conventional pressure-sensitive adhesive seals. It is easy to attach, and there is no problem of the adhesive remaining after peeling, so that it can be reused. The present invention also provides a self-adhesive elastomer sheet that can be easily attached.

[0006]

That is, according to the present invention, hydrogenated diene block copolymers 10 to 100 are added to 100 parts by weight of the epoxidized diene block copolymer.
There is provided a self-adhesive elastomer sheet comprising a polymer composition mixed with parts by weight. Further, according to the present invention, there is provided a self-adhesive elastomer sheet comprising a polymer composition in which 10 to 100 parts by weight of an olefin polymer is blended with 100 parts by weight of an epoxidized diene block copolymer. Further, according to the present invention, 100 parts by weight of an epoxidized diene block copolymer is used, and at least one of a styrene polymer, a polyester polymer, a polycaprolactone polymer, a vinyl chloride polymer, a polycarbonate, and a polyamide is used. There is provided a self-adhesive elastomer sheet comprising a polymer composition containing 5 to 30 parts by weight of a seed. Hereinafter, the present invention will be described in detail.

The epoxidized diene block copolymer used in the present invention includes styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene. Copolymer, Styrene-SB
It is a copolymer obtained by epoxidizing a diene-based block copolymer such as an R block copolymer or a styrene-SBR-styrene block copolymer, and is derived from a conjugated diene in the diene-based block copolymer with an epoxidizing agent. 5% of heavy bonds
Above, 50% or less is preferably epoxidized,
Particularly preferred are those in which 10% or more and 40% or less of the double bond derived from the conjugated diene of the diene block copolymer is epoxidized. The epoxidized diene-based block copolymer may be a partially hydrogenated diene-based block copolymer epoxidized. The hydrogenation rate of the partially hydrogenated diene block copolymer is preferably 0 to 80%, particularly preferably 0 to 60%.

As the epoxidizing agent, peracetic acid, formic acid, perbenzoic acid, trifluoroperacetic acid and the like can be used.

The hydrogenated diene block copolymer used in the present invention includes styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene. Copolymer, Styrene-SBR-
A block copolymer and a styrene-SBR-styrene block copolymer are hydrogenated copolymers, respectively, and the double bond of the conjugated diene moiety in the block copolymer is 60 by hydrogenation.
% Or more and 100% or less is preferable, and especially 80% of the double bonds of the conjugated diene moiety in the block copolymer.
It is more preferable that the content is saturated in the range of 100% to 100%.

Examples of the olefin polymer used in the present invention include high density polyethylene, medium density polyethylene, low density polyethylene, copolymers of ethylene and other α-olefins; polypropylene, propylene and other α.
-Copolymers with olefins; polyolefins such as polybutene and poly-4-methylpentene-1, or oligomers; ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer,
Examples thereof include butyl rubber, butadiene rubber, propylene-butene copolymer, ethylene-acrylic acid ester copolymer and ethylene-methacrylic acid ester copolymer.
These polymers may be contained alone,
Alternatively, two or more kinds may be contained.

The styrene-based polymer used in the present invention includes polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-α-methylstyrene copolymer, acrylonitrile-methylmethacrylate-
Styrene-α-methylstyrene copolymer, ABS resin,
AS resin, MABS resin, MBS resin, AAS resin, A
ES resin, acrylonitrile-butadiene-styrene-
Examples thereof include α-methylstyrene copolymer, acrylonitrile-methylmethacrylate-butadiene-styrene-α-methylstyrene copolymer, and styrene-maleimide copolymer. These may be contained alone or in combination of two or more.

The polyester polymer used in the present invention is generally a thermoplastic resin obtained by polycondensation of a saturated dicarboxylic acid and a saturated dihydric alcohol, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexahexene. Examples thereof include methylene terephthalate, polycyclohexane-1,4-dimethylol terephthalate, and polyneopentyl terephthalate.

The polycaprolactone polymer used in the present invention is a ring-opening polymer of caprolactone.

The vinyl chloride polymers used in the present invention include homopolymers of vinyl chloride, copolymers of vinyl chloride with other monomers, and blends of vinyl chloride resins with other resins. Can also be used. Examples of the monomer to be copolymerized with vinyl chloride include vinyl acetate, ethylene, propylene, maleic acid ester, methacrylic acid ester such as methyl methacrylate and ethyl methacrylate, and acrylic acid ester such as methyl acrylate, ethyl acrylate and propyl acrylate. , Higher vinyl ether and the like.

The polycarbonate in the present invention is
(1) reaction of a dihydric phenol with a carbonate precursor such as phosgene in the presence of an acid acceptor and a molecular weight modifier,
Alternatively, (2) it can be produced by a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate. The dihydric phenol that can be used here is preferably bisphenol, and particularly preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Further, a part or all of bisphenol A may be replaced with another dihydric phenol. Examples of divalent phenols other than bisphenol A include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) sulfide, bis. (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, etc., and bis (3,5-dibromo-4-hydroxyphenyl) Mention may be made of halogenated bisphenols such as propane. It may be a homopolymer of these dihydric phenols, a copolymer using two or more kinds thereof, or a mixture thereof.

The polyamide used in the present invention includes aliphatic polyamides such as 6 nylon, 46 nylon, 66 nylon, 610 nylon, 11 nylon and 12 nylon, and aromatic polyamides containing aromatic components such as terephthalic acid and isophthalic acid. For example, hexamethylene terephthalamide, tetramethylene isophthalamide, hexamethylene isophthalamide, etc., and copolymer polyamides and mixed polyamides containing these as the main constituents are shown.

The self-adhesive elastomer sheet of the present invention contains 100 parts by weight of an epoxidized diene-based block copolymer, and in the case of a hydrogenated diene-based block copolymer or an olefin-based polymer, their blending. Quantity is 10-1
The amount is 00 parts by weight, preferably 10 to 60 parts by weight. If the blending amount is less than 10 parts by weight, the self-adhesive elastomer sheet obtained will have too strong tackiness and is unsuitable as a sheet material.

Further, the compounding amount of at least one of a styrene polymer, a polyester polymer, a polycaprolactone polymer, a vinyl chloride polymer, a polycarbonate and a polyamide is 100 parts by weight of an epoxidized diene block copolymer. 5 to 30 parts by weight, preferably 5 to
20 parts by weight. If the blending amount is less than 5 parts by weight, the self-adhesive elastomer sheet obtained will have too strong tackiness, and if the blending amount exceeds 30 parts by weight, the self-adhesiveness will be poor, such being undesirable.

The term "self-adhesiveness" as used in the present invention means that it can be easily attached to an adherend without using an adhesive or an adhesive.
Moreover, what is once adhered is firmly adhered to the adherend and is not easily peeled off even if it is rubbed by the wind or another object, but if it is peeled off from the end with a finger or the like. It means the property of easy peeling. At the time of sticking, particularly better wettability can be obtained by wetting with water or the like to eliminate air present between the sticky surface of the adherend.

At least one side of the self-adhesive elastomer sheet of the present invention may be subjected to corona discharge treatment. When corona discharge treatment is applied to the printing surface of the self-adhesive elastomer sheet, not only the printing ink rides well and printing is excellent, but also the adhesion between the printing ink and the self-adhesive elastomer sheet improves, and Problems such as peeling are extremely reduced. On the other hand, when the surface of the self-adhesive elastomer sheet that is to be adhered to the adherend is subjected to corona discharge treatment, the self-adhesiveness to the adherend is improved, and the adherence to the adherend becomes more difficult to peel off due to external force. It is a thing.

In the polymer composition for forming the self-adhesive elastomer sheet of the present invention, if necessary, a lubricant, an antioxidant, an antistatic agent, a light stabilizer, a colorant, a filler, a tackifier. Etc. can be added. However, it is preferable to add the lubricant as little as possible from the viewpoint of imparting tackiness, and most preferable is to add no lubricant.

Specific examples of the tackifier include rosin such as glycerin ester rosin and pentaerythritol ester rosin, and derivatives of modified rosin and phenol resin such as terpene phenol. The above tackifiers can be used alone or in combination of two or more.

As the antioxidant, one or more antioxidants such as phenol, thiodipropionate, and aliphatic sulfite can be used.

As the light stabilizer, hydroquinone,
Examples include hindered phenolic stabilizers such as 2,6-di-t-butyl-4-methylphenol, and 1,1-bis (4-hydroxyphenyl) cyclohexane.

The self-adhesive elastomer sheet of the present invention comprises a composition of an epoxidized diene block copolymer and a hydrogenated diene block copolymer, a composition of an olefin polymer, a styrene polymer, a polyester. Polymer,
Polycaprolactone polymer, vinyl chloride polymer, a polymer composition containing at least one of a polycarbonate and a polyamide, if necessary, a mixture containing an appropriate amount of the above various additives, extrusion molding, inflation It can be manufactured into a sheet by a molding means such as molding or calendar molding. The thickness of the self-adhesive elastomer sheet is 0.05 to 1.0 mm, preferably 0.1 to 0.5 mm
Is.

As the self-adhesive elastomer sheet made of the polymer composition of the present invention, it is sufficient that the composition layer is present at least on the side to be adhered to the adherend, and the other plastic sheet (film) and the composition are used. Those laminated with a physical layer are not excluded from the self-adhesive elastomer sheet of the present invention.

The self-adhesive elastomer sheet formed as described above is printed on one side and a release sheet having releasability is attached to the non-printed side to attach a label, an advertisement sheet, and various other types. Used in the field of.

For printing on the self-adhesive elastomer sheet, general printing inks such as oil-based inks, water-based inks, alcohol-based inks, and UV-curable inks can be used.
As a printing method, a commonly used printing method can be used, including flexographic printing, offset printing, letterpress printing,
A screen printing method, a gravure printing method, or the like can be used, and the printing ink used and the printing method are not limited.

As the release sheet attached to the non-printing surface of the self-adhesive elastomer sheet, any release sheet can be used so long as the self-adhesive elastomer sheet attached to the release sheet can be easily peeled off. However, polyethylene film, polypropylene film, polyester film, release paper treated with silicon or Teflon can be used.

[0030]

EXAMPLES The present invention will be described in more detail with reference to the following examples. In addition, various polymers as raw materials of the self-adhesive elastomer sheet of the present invention are shown in Reference Examples.

(Reference Example 1: Epoxidized diene-based block polymer A) Styrene-butadiene-styrene block polymer (trade name: TR2000, manufactured by Nippon Synthetic Rubber Co., Ltd.)
Was epoxidized with peracetic acid (epoxy equivalent 52
0).

Reference Example 2: Epoxidized diene block polymer B Partially hydrogenated styrene-butadiene block polymer (trade name: Tuftec TP094, manufactured by Asahi Kasei Co., Ltd.)
Was epoxidized with peracetic acid (epoxy equivalent 35
0).

(Reference Example 3: Epoxidized diene block polymer C) A styrene-isoprene-styrene block polymer (trade name: Hybler VS-3, manufactured by Kuraray Co., Ltd.) was epoxidized with peracetic acid ( Epoxy equivalent 53
5).

Reference Example 4: Hydrogenated diene block polymer "SEBS" Hydrogenated styrene-butadiene block polymer (trade name: Tuftec H1041, Asahi Kasei Corp.)
Made).

(Reference Example 5: Polyethylene "PE") VL
DPE Z522 (manufactured by Ube Industries, Ltd.)

[0036] (Reference Example 6: polypropylene "PP") Bruno <br/> over blanking Len D501 (manufactured by Sumitomo Chemical Co., Ltd.)

(Reference Example 7: Polyester "PBT") Duranex 400FP (Polyplastics Co., Ltd.)
Made)

Reference Example 8: Polycaprolactone "PC
L ”) Placcel H7 (manufactured by Daicel Chemical Industries, Ltd.)

(Reference Example 9: Styrenic resin "PS") Styron 683 (manufactured by Asahi Kasei Corp.)

Reference Example 10: Polycarbonate "P
C ") Panlite L1225 (manufactured by Teijin Chemicals Ltd.)

Reference Example 11: Vinyl chloride resin "PV
C ”) Geon 103EP (Mitsubishi Kasei Vinyl Co., Ltd.)
Made)

(Reference Example 12: Polyamide "PA") Ube Nylon 6 (manufactured by Ube Industries, Ltd.)

(Example 1-12, Comparative Example 1-6) Table 1 was used with respect to 100 parts by weight of the epoxidized diene block polymer.
The various polymers shown in Table 1 were blended in the blending amounts shown in Table-1. Then, the compound was melt-kneaded by an extruder and extruded from a T-die with a thickness of 0.3 mm to receive the sheet-shaped resin on a release paper to prepare a sealing material. A self-adhesive elastomer sheet was attached to this sealing material while the release paper was removed on the surface of the glass plate having a smooth surface, and the self-adhesiveness, the workability of sticking the seal, and the release test were performed. Table 1 shows the results. The self-adhesiveness, sticking workability, printability, and peeling test were evaluated as follows.

[Self-adhesiveness] The self-adhesive elastomeric sheet was attached to a glass plate having a smooth surface, and the peeling condition when the surface side was rubbed by hand was judged according to the following criteria. ◯: No peeling or floating, and the sheet was in close contact with the glass plate. X: Peeled off easily, and the sheet fell off the glass plate.

[Sealing workability] The following criteria are the smoothness of work, wrinkling of a sheet (wrinkling due to entrainment of air), and its easiness of correction when affixing to a glass plate while peeling off a release paper. It was judged by. ◯: No wrinkles, can be pasted smoothly, and the finish is good. In addition, it can be easily corrected. ×: Wrinkles are severe and difficult to correct. Or can not be pasted.

[Peeling test] The obtained sheet was press-bonded at room temperature for 10 seconds at 2 kg / cm ² to obtain 200 mm / m 2.
A 180 ° peel test and a shear peel test were carried out at an in tension rate.

[Printability] A self-adhesive elastomer sheet was prepared, and an aqueous ink was used as the printing ink to evaluate the printability. ○: Ink is good to ride. X: Ink is not well applied.

[0048]

[Table 1]

(Examples 13 to 15 and Comparative Example 7) Example 1
A self-adhesive elastomer sealant was prepared in the same manner as above, and various substrates were evaluated instead of glass. Table-2
The results are shown in. As is clear from Tables 1 and 2, it is only the examples of the present invention that the adhesiveness to the adherend (self-adhesiveness) is excellent and the workability of sticking to the adherend is excellent. is there.

[0050]

[Table 2]

[0051]

The self-adhesive elastomer sheet of the present invention is excellent in the adhesiveness (self-adhesiveness) with the adherend. In addition, the work of sticking to the adherend is easy, and the sticking can be performed without causing wrinkles. In addition, it has excellent printability and is suitable for repeated use as a sealant for advertising and other signs and displays, slip prevention for desk mats, bookends and table cloths, glass cosmetic sheets, It can be effectively used as a backing for a carpet to be laid, a mark on a helmet, etc., and a sheet for a peelable decorative material.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-136186 (JP, A) JP-A-7-300553 (JP, A) JP-A-6-340796 (JP, A) JP-A-6- 220124 (JP, A) JP 4-227930 (JP, A) JP 3-43446 (JP, A) JP 51-28850 (JP, A) JP 61-281 (JP, A) JP-A-6-136205 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 63/00-63/10 C08L 53/02 C09J 7/00 C09J 163/00-163 / Ten

Claims (3)

(57) [Claims] 1. An epoxidized diene block copolymer 1
Hydrogenated diene-based block copolymer 1 per 100 parts by weight
A self-adhesive elastomer sheet comprising a polymer composition containing 0 to 100 parts by weight. 2. An epoxidized diene block copolymer 1
Olefin polymer 10 to 100 parts by weight
A self-adhesive elastomer sheet comprising a polymer composition containing parts by weight. 3. An epoxidized diene block copolymer 1
A polymer composition in which 5 to 30 parts by weight of at least one of a styrene-based polymer, a polyester-based polymer, a polycaprolactone polymer, a vinyl chloride-based polymer, a polycarbonate, and a polyamide is mixed with 00 parts by weight. Self-adhesive elastomer sheet.