JP2000256629A - Re-sticking sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sheet which scarcely leaves an adhesive when peeled off and undergoes less increase in tackiness with time by providing a pressure, adhesive urethane layer on one side of a base sheet having an image and protecting the layer with a release sheet. SOLUTION: The pressure urethane adhesive used preferably comprises one formed by blending a polyfunctional isocyanate compound with a polyurethane polyol obtained through the reaction of a polyester polyol, a polyether polyol and an organic polyisocyanate in the presence of two catalysts comprising e.g. a tertiary amine/organometallic compound system, an organotin compound/ organic non-tin compound system, or an organotin compound/organotin compound system, or in the absence of a catalyst at 100 deg.C or higher. Examples of the polyfunctional isocyanate compound used include organic polyisocyanates trimethylolpropane adducts thereof, biuret reacted with water and trimers having isocyanurate rings. The sheet is used for re-sticking to a picture book and a plastic toy for children, having the printed surface coated with a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a re-pasting sheet having an image, and more particularly to a re-applying sheet which can be used repeatedly for office toys, picture books, educational use, or plastic toys for children. The present invention relates to a sheet, a label, and a sticker having an adhesive property. The sheet referred to here includes labels and seals.

[0002]

2. Description of the Related Art Heretofore, adhesive sheets such as acrylic resins, vinyl acetate resins, rubber resins and the like have been mainly used for re-attachable sheets for office toys, picture books and plastic toys for children. However, although these are excellent in tackiness,
When the re-adhesive property is not sufficient and the adhesive is adhered to the adherend and then peeled off from the adherend, there is a problem that adhesive remains on the adherend and the adhesive strength is easily changed by temperature.

[0003] On the other hand, although urethane-based pressure-sensitive adhesives can satisfy various physical properties, they have problems such as high viscosity of resin solution, reaction control, and raw material cost. In particular, it has been difficult to control the compatibility and crosslinkability of the resin solution with the progress of the reaction to obtain a resin having desired physical properties.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a re-sticking sheet which can be re-sticked and has little adhesive residue when peeled off. More specifically, conventional acrylic pressure-sensitive adhesives, glue residue at the time of peeling off a coated product using a rubber-based pressure-sensitive adhesive, an increase in adhesive strength over time, a drawback that stable adhesive strength is difficult to obtain, and a urethane-based adhesive An object of the present invention is to provide a re-pasting sheet having a polyurethane pressure-sensitive adhesive layer in which the above-mentioned various drawbacks of the agent have been improved and having good re-pasting properties.

[0005]

Conventionally, two or more kinds of polyols such as polyester polyol and polyether polyol having different compatibility and reactivity and an organic polyisocyanate compound have been reacted in the presence of a single catalyst. . In this system, there was a problem that the reaction solution often became turbid or gelled. In particular, it is remarkable when the reaction temperature is 100 ° C. or lower. Therefore, as a result of various studies of reaction conditions, it was found that a polyurethane resin can be obtained by using two types of catalysts without causing the reaction solution to become turbid or gelled.

[0006] The re-pasting label using the urethane resin as the pressure-sensitive adhesive layer maintains the desired tackiness, and has no adhesive residue.
It has been found that it can be used repeatedly.

That is, the first invention relates to a re-sticking sheet in which one surface of an adhesive sheet substrate having an image has a urethane adhesive layer and is further protected by a release sheet. The second invention relates to a polyurethane polyol (A) obtained by reacting a urethane adhesive with a polyester polyol, a polyether polyol, and an organic polyisocyanate using two types of catalysts, and a polyfunctional isocyanate compound (B).
The present invention relates to the re-sticking sheet according to the first invention, characterized by comprising: In the third invention, a polyfunctional isocyanate compound (B) is blended with a polyurethane polyol (A) in which a urethane pressure-sensitive adhesive is reacted with a polyester polyol, a polyether polyol, and an organic polyisocyanate at 100 ° C. or higher without a catalyst. The present invention relates to a re-sticking sheet according to the first invention, which is characterized in that:

[0008] A fourth invention relates to the re-sticking sheet according to the first to third inventions, wherein the sheet is re-sticked to a picture book whose printing surface is covered with a film. The fifth invention relates to the re-sticking sheet according to the first to third inventions, wherein the sheet is re-sticked to a plastic toy for children.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

The adhesive sheet substrate having an image used in the present invention includes synthetic resin films such as polyester film, polyethylene film, vinyl chloride film, nylon film, polypropylene film, acrylic foam film, urethane foam film, art paper, and coat. There are paper, synthetic paper, plain paper, and non-woven fabric. The image is printed on the pressure-sensitive adhesive sheet substrate in advance, or the pressure-sensitive adhesive layer is provided on one surface of the pressure-sensitive adhesive sheet substrate, and subsequently printed on the other surface of the substrate after protection with a release sheet.

The urethane pressure-sensitive adhesive layer used in the present invention comprises a known polyester polyol, polyether polyol,
It is manufactured using an organic isocyanate or the like as a raw material. Examples of the acid component of the polyester polyol include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid, and the glycol component includes ethylene glycol, propylene glycol,
Diethylene glycol, butylene glycol, 1,6-
Hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, polyol Glycerin, trimethylolpropane, pentaerythritol, etc. are mentioned as a component. Other examples include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone) and polyvalerolactone. The molecular weight of the polyester polyol can be used from a low molecular weight to a high molecular weight, but is preferably 1,000 to 5,000.
And a polyester polyol having two or more functional groups, more preferably a part or all of the polyester has a molecular weight of 2,000.
It is trifunctional or more of ４，4,000. Polyester polio
The amount of the polyester used is preferably 1 to 50 mol% in the polyol constituting the polyurethane polyol (A).

Known polyether polyols are used as the polyether polyol used in the present invention. For example, propylene glycol, ethylene glycol, glycerin, using a low molecular weight polyol such as trimethylolpropane as an initiator, ethylene oxide, propylene oxide, butylene oxide, polyether polyol obtained by polymerizing an oxirane compound such as tetrahydrofuran, specifically Specifically, those having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol, are used. The molecular weight of the polyether polyol can be used from a low molecular weight to a high molecular weight, but preferably the molecular weight is 1,
A polyether polyol having a molecular weight of 2,000 to 5,000, more preferably bifunctional or more, and more preferably a part or all of the polyether polyol is trifunctional or more having a molecular weight of 2,000 to 4,000. The amount of the polyether polyol used is 1 to 80 in the polyol constituting the polyurethane polyol (A).
Molar% is preferred.

When the molecular weight is 2,000 or less, the trifunctional or more functional polyol used in the present invention has high reactivity and is easily gelled. If the molecular weight is 4,000 or more, the reactivity of the polyol becomes poor, and the cohesive force of the urethane pressure-sensitive adhesive decreases.

In the present invention, if necessary, some glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol; ethylenediamine; Polyvalent amines such as aminoethylethanolamine, isophoronediamine and xylylenediamine can also be used in combination.

Examples of the organic polyisocyanate compound used in the present invention include known aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

As aromatic polyisocyanates, 1,3
-Phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,
Examples thereof include 3,5-triisocyanatebenzene, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, and 4,4 ', 4 "-triphenylmethane triisocyanate.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, Examples include 2,4,4-trimethylhexamethylene diisocyanate.

As the araliphatic polyisocyanates, ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene , 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethyl xylylene diisocyanate, and the like.

As the alicyclic polyisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2 , 4-cyclohexanediisocyanate, methyl-
2,6-cyclohexane diisocyanate, 4,4'-
Methylene bis (cyclohexyl isocyanate), 1,
4-bis (isocyanatomethyl) cyclohexane,
1,4-bis (isocyanatomethyl) cyclohexane and the like can be mentioned.

In addition, a trimethylolpropane adduct of the above polyisocyanate, a burette that has been reacted with water, a trimer having an isocyanurate ring, and the like can also be used in combination.

As the polyisocyanate used in the present invention, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) and the like are preferable.

As the catalyst used in the present invention, a known catalyst can be used. For example, tertiary amine compounds, organometallic compounds and the like can be mentioned.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU) and the like.

Examples of the organometallic compound include a tin compound and a non-tin compound.

As the tin compound, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide,
Dibutyltin dimaleate, dibutyltin dilaurate (D
BTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, 2-ethylhexanoic acid Tin etc. are mentioned.

Examples of the non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, and lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate. Iron, such as iron, 2-ethylhexanoate and iron acetylacetonate; cobalt, such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc, such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium naphthenate And the like.

When these catalysts are used, in a system in which two kinds of polyols, that is, a polyester polyol and a polyether polyol, are present, due to a difference in reactivity and compatibility, a system of a single catalyst gels or a reaction solution is formed. The problem of cloudiness is likely to occur. By using two types of catalysts, the reaction rate, reactivity, and the like can be controlled, and these problems can be solved. As the combination, a tertiary amine / organic metal type, tin type / non-tin type, tin type / tin type or the like is used, preferably tin type / tin type, more preferably dibutyltin dilaurate and 2-ethylhexane. It is a combination of tin acid. The compounding ratio is tin 2-ethylhexanoate / dibutyltin dilaurate <1 by weight. More preferably, it is 0.2 to 0.6. If the compounding ratio is 1 or more, gelation is likely to occur due to the balance of the catalytic activity. These catalysts are used in an amount of 0.01 to 1.0% by weight based on the total amount of the polyol and the organic polyisocyanate.

When a catalyst is used, the temperature is preferably 100 ° C. or less. More preferably, the temperature is from 85C to 95C. 1
When the temperature is higher than 00 ° C., it is difficult to control the reaction rate and the crosslinked structure, and it is difficult to obtain a polyurethane polyol (A) having a predetermined molecular weight.

The urethane resin can be synthesized without a catalyst. In that case, the reaction temperature is preferably set to 100 ° C. or higher. More preferably, the temperature is 110 ° C. or higher. In such a synthesis without using a catalyst, since no metal-based or amine-based catalyst is contained at all, when an infant or child accidentally licks or drinks a label, the urethane adhesive is used, Various problems that may be caused in the future can be avoided. The reaction is preferably performed for 3 hours or more in the absence of a catalyst.

The polyfunctional isocyanate compound (B) used in the present invention includes the above-mentioned organic polyisocyanate compounds and their trimethylolpropane adducts,
A buret body reacted with water, a trimer having an isocyanurate ring, or the like is used.

In order to obtain the polyurethane polyol (A), various methods are possible, for example, 1) charging the whole amount,
2) It is also possible to charge a polyester polyol, a polyether polyol, and a catalyst in a flask and add dropwise an organic polyisocyanate. In particular, the method 2) is preferable for controlling the reaction.

The mixing ratio of the polyurethane polyol (A) to the polyfunctional isocyanate (B) used in the present invention is 1 to 20 parts (B) per 100 parts (parts by weight) of (A). If it is 1 part or less, the cohesive strength decreases, and if it is 20 parts or more, the adhesive strength decreases. Preferably it is 2 to 10 parts.

As the solvent used in the present invention, known solvents can be used. Examples include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone and the like. Toluene is particularly preferred in view of the solubility of the polyurethane polyol (A) and the boiling point of the solvent.

In the urethane pressure-sensitive adhesive layer constituting the present invention, if necessary, fillers such as talc, calcium carbonate, and titanium oxide, tackifiers, coloring agents, ultraviolet absorbers, antioxidants, defoamers, light An additive such as a stabilizer may be blended.

In the present invention, the urethane pressure-sensitive adhesive layer is formed on the pressure-sensitive adhesive sheet substrate by a known method. For example, coating with a roll coater, blade coater, gravure coater, etc.
After drying, a coating film having a thickness of 5 to 100 μm, preferably 20 to 50 μm is formed.

Although it is possible to form the pressure-sensitive adhesive layer directly on the base material sheet, an adhesive layer or a strong adhesive layer can be formed between the base material sheet and the pressure-sensitive adhesive layer due to the balance of the adhesion between the base material surface and the adherend surface. It is preferable to provide an adhesive layer. Examples of adhesives and strong adhesives include acrylic resins, vinyl acetates, urethanes, ethylene / vinyl acetates, and synthetic rubbers.

The release sheet is composed of a release sheet base material such as a coated paper, art paper, cast coated paper, polyolefin film or the like having a release resin layer such as a silicone resin or a polyester resin.

The re-sticking sheet of the present invention is widely used for memos, office work, children's picture book seals, plastic toys, etc., which are used daily.

Suitable as a picture book seal or label is a picture book whose printed surface is covered with a vinyl chloride film, a polyethylene film, a polypropylene film, or the like. It is preferable because the substrate surface is smooth and the re-applying label or seal does not directly contact the printing surface.

There is no particular limitation on the material of the plastic toy for children, but it is preferable that the surface to be affixed is smooth. It is difficult to stick if there is an uneven surface.

The urethane pressure-sensitive adhesive which is one of the features of the present invention can be obtained by the following synthesis examples.

Synthesis Example 1 Polyester polyol P-1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
010 (bifunctional polyester polyol, OH value 11
2, 108 g of Kuraray Co., Ltd., polyether polyol G-2000 (trifunctional polyether polyol, O
H value 112, manufactured by Asahi Denka Co., Ltd.) 67 g, hexamethylene diisocyanate (Sumitomo Bayer Co., Ltd.) 25
g, 134 g of toluene, 0.03 g of iron 2-ethylhexanoate and 0.04 g of lead naphthenate as catalysts, and 9
The temperature was gradually raised to 0 ° C., and the reaction was performed for 4 hours. The residual isocyanate group is confirmed by an infrared spectrophotometer (IR). If the remaining isocyanate group disappears, the reaction is terminated and cooled. This reaction solution was colorless and transparent, had a solid content of 60%, viscosity of 3,000 cps, MN (number average molecular weight) of 15,000, and MW (weight average molecular weight) of 50,000.
00.

Synthesis Example 2 Polyester polyol F-2 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
010 (trifunctional polyester polyol, OH value 85,
31 g, Kuraray Co., Ltd., polyether polyol P
P-2000 (bifunctional polyether polyol, OH value 56, manufactured by Sanyo Chemical Industries, Ltd.) 152 g, isophorone diisocyanate (manufactured by Huls Japan KK) 17
g, 134 g of toluene, 0.03 g of iron 2-ethylhexanoate and 0.02 g of tin 2-ethylhexanoate as catalysts, the temperature was gradually raised to 90 ° C., and the mixture was reacted for 3 hours.
The residual isocyanate group is confirmed by IR, and if it has disappeared, the reaction is terminated and cooled. The reaction solution was colorless and transparent and had a solid content of 6.
0%, viscosity 3,000 cps, MN 16,000, MW
It was 55,000.

Synthesis Example 3 Polyester polyol P-1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
010 (bifunctional polyester polyol, OH value 11
2, Kuraray Co., Ltd.) 81 g, polyether polyol G-3000B (trifunctional polyether polyol, O
H value 56, Asahi Denka Co., Ltd.) 101 g, hexamethylene diisocyanate (Sumitomo Bayer Co., Ltd.) 19
g, ethyl acetate 134 g, iron 2-ethylhexanoate 0.03 g as a catalyst, tetrabutyl titanate 0.02 g
, And the temperature was gradually raised to 75 ° C. to react for 5 hours.
The residual isocyanate group is confirmed by IR, and if it has disappeared, the reaction is terminated and cooled. The reaction solution was colorless and transparent and had a solid content of 6.
0%, viscosity 3,500 cps, MN 18,000, MW
60,000.

Synthesis Example 4 Polyester polyol P-1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
010 (bifunctional polyester polyol, OH value 11
2, Kuraray Co., Ltd.) 81 g, polyether polyol G-3000B (trifunctional polyether polyol, O
H value 56, Asahi Denka Co., Ltd.) 101 g, hexamethylene diisocyanate (Sumitomo Bayer Co., Ltd.) 19
g, 134 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and 0.02 g of tin 2-ethylhexanoate were gradually heated to 90 ° C. and reacted for 2 hours.
The residual isocyanate group is confirmed by IR, and if it has disappeared, the reaction is terminated and cooled. The reaction solution was colorless and transparent and had a solid content of 6.
0%, viscosity 3,300 cps, MN 15,500, MW
46,000.

Synthesis Example 5 Polyester polyol P-1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
010 (bifunctional polyester polyol, OH value 11
2, 67 g of Kuraray Co., Ltd., polyether polyol PP-2000 (bifunctional polyether polyol, O
H value 56, manufactured by Sanyo Chemical Industries, Ltd.) 107 g, hexamethylene diisocyanate (manufactured by Sumitomo Bayer, Ltd.)
26 g, toluene 134 g, dibutyltin dilaurate 0.03 g as a catalyst, tin 2-ethylhexanoate 0.02 g
g, the temperature was gradually raised to 90 ° C., and the reaction was carried out for 2 hours. The residual isocyanate group is confirmed by IR, and if it has disappeared, the reaction is terminated and cooled. The reaction solution was colorless and transparent, solid content was 60%, viscosity was 3600 cps, MN was 16,500,
W50,000.

Synthesis Example 6 Polyester polyol P-1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
010 (bifunctional polyester polyol, OH value 11
2, Kuraray Co., Ltd.) 56 g, polyether polyol PP-2000 (bifunctional polyether polyol, O
H value 56, manufactured by Sanyo Chemical Industries, Ltd.) 91 g, isophorone diisocyanate (manufactured by Huls Japan KK) 2
1 g, Takenate D-140N (isophorone diisocyanate trimethylolpropane adduct, manufactured by Takeda Pharmaceutical Co., Ltd.) 31 g, and toluene 134 g were charged.
The temperature is gradually raised to 100 ° C., and the reaction is performed for 5 hours. The residual isocyanate group is confirmed by IR, and if it has disappeared, the reaction is terminated and cooled. The reaction solution was colorless and transparent, the solid content was 60%, the viscosity was 3300 cps, the MN was 15,000, and the MW was 550,000.
It was 0.

Synthesis Example 7 Polyester polyol P-2 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
010 (bifunctional polyester polyol, OH value 56,
90 g, Kuraray Co., Ltd., polyether polyol G
-2000 (trifunctional polyether polyol, OH value 8
5, 24 g of Asahi Denka Co., Ltd.), 17 g of hexamethylene diisocyanate (manufactured by Sumitomo Bayer Ltd.), 134 g of ethyl acetate, and 0.1 g of dibutyltin dilaurate as a catalyst.
05 g was charged, the temperature was gradually raised to 80 ° C., and the reaction was carried out for 3 hours. The residual isocyanate group is confirmed by IR, and if it has disappeared, the reaction is terminated and cooled. This reaction solution was slightly turbid, with a solid content of 50%, a viscosity of 3,700 cps, and MN16,
500, MW 54,000.

Synthesis Example 8 75 g of butyl acrylate, 20 g of 2-ethylhexyl acrylate, 5 g of 2-hydroxyethyl acrylate, 135 g of ethyl acetate, 15 g of toluene and 15 g of toluene were placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a dropping funnel. A solution containing 0.2 g of benzoyl oxide was placed in a reactor equipped with a reflux condenser, and heated at 80 to 85 ° C. under a nitrogen gas stream.
Perform a time reaction. This solution is colorless and transparent and has a solid content of 40%.
The viscosity was 5,200 cps.

[0050]

The present invention will be described in detail with reference to the following examples.

Table 1 shows the composition of the polyurethane pressure-sensitive adhesive.

Table 2 shows the results of the adhesive strength and adhesive residue tests.

The test items are as follows. Adhesive strength: 25 μm dry coating film of the above adhesive solution on release paper
And dried at 100 ° C. for 2 minutes to prepare a coated product. Aged at room temperature for one week. An adhesive sheet made of a PET film substrate is adhered to a stainless steel plate (SUS304) having a thickness of 2 mm at 23 ° C. and 65% RH.
20 minutes after roll-press bonding according to IS, peeling strength (180 degree peel, pulling speed 3) with a shopper type peeling tester
00 mm / min). Adhesive residue: 25% after sticking adhesive sheet to various adherends
C. and 40.degree. C. for one day, and the adhesive residue was visually evaluated. After peeling, ◎ indicates no adhesive transfer to the adherend, ○ indicates very slight transfer, △ indicates partial transfer, and × indicates complete transfer.

[0054]

[Table 1]

For the compounding, 4 g of the polyfunctional isocyanate compound (B) was added to 100 g of the solid content of the polyurethane polyol (A). Polyfunctional isocyanate compound (B) Takenate D-160N (hexamethylene diisocyanate trimethylolpropane adduct),
Takeda Pharmaceutical Co., Ltd.)

[0056]

[Table 2]

PC (Polycarbonate) PP (Polypropylene, film thickness 50 μm) Toy (America, riding toy "Melody Car")

From the above results, it can be seen that the re-sticking sheet according to the present invention has excellent adhesive strength and removability by using a urethane adhesive.

[0059]

According to the present invention, the use of two kinds of catalysts in the synthesis of the polyurethane pressure-sensitive adhesive constituting the re-sticking sheet does not cause gelation and poor compatibility, and a resin having a high cohesion can be obtained. In addition, those synthesized without a catalyst at 100 ° C. or more have good removability although the synthesis time is long,
Shows tackiness.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J004 AA14 DB02 FA10 4J040 EF111 EF131 EF281 JA09 JB09

Claims (5)

[Claims] 1. A re-sticking sheet wherein one surface of an adhesive sheet substrate having an image has a urethane adhesive layer and is further protected by a release sheet. 2. A polyurethane polyol (A) obtained by reacting a urethane adhesive with a polyester polyol, a polyether polyol, and an organic polyisocyanate using two types of catalysts, and a polyfunctional isocyanate compound (B).
The sheet for re-sticking according to claim 1, characterized by comprising: 3. A polyurethane polyol (A) obtained by reacting a polyester polyol, a polyether polyol, and an organic polyisocyanate with a urethane adhesive at 100 ° C. or higher in the absence of a catalyst, and blending a polyfunctional isocyanate compound (B). The sheet for re-applying according to claim 1, characterized in that: 4. The re-sticking sheet according to claim 1, wherein the sheet is re-sticked to a picture book whose printing surface is covered with a film. 5. The re-sticking sheet according to claim 1, which is re-sticked to a plastic toy for children.