JP3350858B2 - Adhesive sheet for pattern transfer printing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive sheet capable of printing a pattern on an object to be transferred such as a T-shirt, a trainer, a handkerchief or the like. The present invention relates to an adhesive sheet for pattern transfer printing, which is excellent in soaking properties, washing resistance, a feeling of creating a sense of unity between a film and an object to be transferred, and a blocking property in which adhesive film surfaces do not adhere to each other in a normal temperature range.

[0002]

2. Description of the Related Art An adhesive sheet for pattern transfer printing is a method in which a mirror image of a pattern is printed on the surface of an adhesive film, the printing surface is opposed to a transfer object, hot-pressed, and then the release paper is peeled off to form an image on the transfer object. This enables printing of symbols. Conventionally, an olefin resin is used as a thermoplastic resin used for the adhesive film.

[0003]

However, in the case of an adhesive film made of an olefin-based resin, 1) the adhesive strength to the transferred object is weak, 2) the washing resistance is poor, and the transferred object such as cloth is washed several times. Just by doing so, the pattern is peeled off from the object to be transferred and the pattern is distorted. 3) Due to the high crystallinity, there is a problem that the texture is impaired when transferred to a flexible material such as cloth.

[0004] The present invention has a strong adhesive force to a flexible transfer object such as a cloth, a good penetration property of the adhesive film into the transfer object at the time of hot pressing, excellent washing resistance, good texture, An object of the present invention is to provide an adhesive sheet for pattern transfer printing having good blocking properties in a normal temperature range.

[0005]

Means for Solving the Problems The present inventor has set forth an adhesive sheet comprising an adhesive film and release paper, wherein the adhesive film comprises 50 to 90 % by weight of an amorphous polyurethane resin, and 10 to 50% by weight. Consisting of a crystalline polyurethane resin, the number average molecular weight of the amorphous polyurethane resin,
The present inventors have found that the above-mentioned problems can be solved by the adhesive sheet for pattern transfer printing of 10,000 to 50,000, and have accomplished the present invention.

[0006] The thermoplastic polyurethane resin used in the present invention is synthesized from a polyol compound and an isocyanate compound.

As the polyol compound used for the amorphous polyurethane resin, conventionally known polyol compounds usually used for producing polyurethane resins can be used. Examples include polyester polyols, polyether polyols, and the like.

More specifically, examples of the polyester polyol include polycarboxylic acids such as terephthalic acid, isophthalic acid, succinic acid, glutaric acid, dicarboxylic acids such as adipic acid, pimelic acid, and suberic acid; Polyester polyols obtained by reaction with polyols such as glycol, propylene glycol, propanediol, 1,2-butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol and the like. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

The isocyanate compound used for synthesizing the above amorphous polyurethane resin includes 4,4.
4'-diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, p
-Phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate and the like.

The method for producing the amorphous polyurethane resin used in the present invention is a method of using the above-mentioned polyol compound and isocyanate compound to perform bulk polymerization in the absence of a solvent or bulk polymerization in the presence of a solvent. The polymerization may be carried out by any of the following solution polymerization methods, and furthermore, it can be produced by any of the prepolymer method and the one-shot method, and is not particularly limited.

The amorphous nature of the amorphous polyurethane resin used in the present invention indicates whether or not it shows a sharp peak of heat of crystal fusion in thermal analysis such as DSC, or shows a crystal structure by X-ray analysis. It can be easily measured depending on whether or not. More simply, the film can be distinguished by whether or not a necking phenomenon is observed when the film is stretched. Since the amorphous polyurethane resin does not show the necking phenomenon, it is important to use such a urethane resin.

The number average molecular weight of the amorphous polyurethane resin used in the present invention is from 10,000 to 50,000. When the number average molecular weight is less than 10,000, the blocking property in a normal temperature range is reduced, and the adhesive film surfaces adhere to each other after press bonding, and the pattern is damaged when peeled off. If the number average molecular weight is more than 50,000, the adhesive film will not easily penetrate the transfer material during hot pressing, resulting in poor hand feeling and insufficient washing resistance.

[0013] The softening point of the amorphous polyurethane resin is not particularly limited, but is preferably 50 to 150 ° C.
If the temperature is 0 ° C. or higher, the ability to penetrate into the transferred body during hot pressing is reduced.

Further, the glass transition temperature of the amorphous polyurethane resin is not limited, but the lower the glass transition temperature, the better the soaking property into the transfer object during hot pressing.

[0015] Amorphous polyurethane resin, the rubber elasticity amorphous polyurethane resin has, but good texture can be obtained, however, molecular motion due to its amorphous
Degree of freedom is high, and 10,000 to 50,
In the number average molecular weight region of 000, when it is more than 90 % by weight , when used for the adhesive sheet in the present invention,
After being transferred to the photo object, the adhesive film surfaces
Poor blocking performance. Amorphous polyurethane resin
However, when the content is less than 50% by weight, the property of impregnating into a transferred body at the time of hot pressing is poor, and the amorphous polyurethane has
It cannot be used because it does not sufficiently exhibit good texture.

As the polyol compound used for the crystalline polyurethane resin, a conventionally known polyol compound usually used for producing a polyurethane resin can be used. Examples include polyester polyols, polycarbonate polyols, short chain polyols, and the like.

More specifically, the polyester polyols include, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, undecamethylene Dicarboxylic acids, polycarboxylic acids such as dicarboxylic acids such as dodecamethylene dicarboxylic acid,
For example, ethylene glycol, propylene glycol,
1,4-butanediol, 1,5-pentanediol,
Ring-opening polymerization of ε-caprolactam and polyester polyols obtained by reaction with polyols such as 1,6-hexanediol, 1,8-octanediol, 1,9-nandiol, 1,10-decanediol and cyclohexanediol And the like. Examples of the short-chain polyol include ethylene glycol, propylene glycol, and 1,4-butanediol.

The isocyanate compound used for the synthesis of the crystalline polyurethane resin includes 4,4
'-Diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, p-
Examples include phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and isophorone diisocyanate.

The method for producing the crystalline polyurethane resin used in the present invention is the same as the above-mentioned method for producing the amorphous polyurethane resin using the above-mentioned polyol compound and isocyanate compound. And there is no particular limitation.

The crystallinity of the crystalline polyurethane resin used in the present invention can be judged by the crystal melting peak in DSC and the necking phenomenon, similarly to the above-mentioned amorphous polyurethane resin. Since a crystalline polyurethane resin has a crystal melting peak in DSC and a necking phenomenon is observed, such a polyurethane resin must be used.

The crystalline polyurethane resin of the present invention
Is relative to the weight percent of the amorphous polyurethane resin,
0 to 50% by weight. Crystalline polyurethane resin
The molecular motion at room temperature is small due to the crystallinity of
Excellent kingness. When the content of the crystalline polyurethane resin is more than 50% by weight, the rubber elasticity of the amorphous polyurethane resin is impaired, the hand feeling is deteriorated, and the heat treatment is difficult.
Insufficiency in penetration into the transfer receiving body at the time of pressing is also poor . When the crystalline polyurethane resin is less than 10 wt%, the amorphous Po
As described for the urethane resin , the blocking property is poor.

The adhesive film according to the present invention contains the above-mentioned thermoplastic polyurethane resin as a main component, but may further contain a dye, a pigment, an anti-blocking agent, an anti-aging agent, a filler, an adhesion-imparting resin, and the like, if desired.

Examples of the method for producing the adhesive film according to the present invention include known film forming methods such as a film forming method using a T-die extruder and a casting method in which a resin is dissolved in a solvent, coated on release paper and dried. Processing techniques can be used.

Although the thickness of the adhesive film according to the present invention is set to a desired thickness, it is preferably set to 5 to 100 μm. When the thickness is less than 5 μm, the washing resistance is reduced, and when the thickness is more than 100 μm, the feel is deteriorated.

As the release paper used for the adhesive sheet of the present invention, conventionally known release papers can be used. Examples include high quality paper, kraft paper,
Examples include glassine paper and parchment paper, and examples of the release agent include silicon-based, non-silicone-based, and mixed systems thereof. If necessary, both the surface on which the release agent is applied and the back surface may be impregnated with a resin such as PVA, polyethylene laminate, clay coating, matte surface treatment, mirror surface treatment, or the like.

[0026]

DETAILED DESCRIPTION OF THE INVENTION By using a polyurethane resin having a higher polarity than an olefin resin according to the present invention,
The adhesive strength to the transfer receiving body is increased, and the washing resistance is improved. Further, the number average molecular weight is 10,000 to 50,000.
The adhesive film and the amorphous polyurethane resin 50-90% by weight 0 of 10 to 50 wt% crystalline polyurethane resin, penetration of the material to be transferred the adhesive film during good heat pressing, texture properties, Blocking properties at room temperature are obtained.

[0027]

The contents of the present invention will be described below with reference to specific examples.

(Examples 1 to 4, Comparative Examples 1 to 5) Example 1
In Comparative Examples 1 to 4 and Comparative Examples 1 to 5, the thermoplastic resin having the compounding ratio shown in Table 1 was charged into a hopper of a φ40 single-screw extruder, and T
Extruding a 50 μm thick adhesive film using a die method,
Release paper was laminated to obtain an adhesive sheet. Extrusion conditions are:
Screw: 40φ full flight screw (L / D =
22, compression ratio 3), screw rotation speed; 20 rpm, cylinder temperature; C ₁ / C ₂ / C ₃ / C ₄ = 170 ° C./1
80 ° C / 190 ° C / 200 ° C, adapter-temperature; AD =
200 ° C., T-die temperature; D ₁ = 210 ° C. The unit of the compounding amount in the table represents% by weight. The release paper is made of 70GS which is made of glassine paper and has a silicone release treatment.
(6) (Oji Paper Co., Ltd.) was used.

In the table, the amorphous polyurethane resin (A)
Estene 5703 (manufactured by GOODRICH), number average molecular weight 48,000, MI (180 ° C) 2.3 g / 1
0 min, and the amorphous polyurethane resin (B)
R3200 (manufactured by Toyobo) with a number average molecular weight of 40,00
0, MI (180 ° C.) 2.6 g / 10 min, and amorphous polyurethane (C) was Nipporan 2304 (manufactured by Nippon Polyurethane Co., Ltd.) with a number average molecular weight of 56,000 and M
I (180 ° C.) 1.3 g / 10 min. The crystalline polyurethane resin (D) is made of Ilostic S-8735.
(Morton) with a number average molecular weight of 55,000. MI
(180 ° C.) 1.2 g / 10 min, and the crystalline polyurethane resin (E) is Ilostik S-6148.
(Morton), number average molecular weight 64,000, MI
(180 ° C.) 1.0 g / 10 min. EVA is U
E635 (manufactured by Tosoh Corporation) with a vinyl acetate content of 25%
It is 2.4 g / 10min of Mr (180 degreeC). The number average molecular weight of the polyurethane resin is measured by GPC and is a polystyrene equivalent molecular weight.
The MI of the above resin was measured using a flow tester.

(Preparation method of test piece)
The sample was hot-pressed on a cotton cloth at 0 ° C. for 10 seconds at 0.5 kgf / cm ² , the release paper was peeled off, and the cotton cloth on which the adhesive film was transferred was used as a test piece.

(Evaluation Method of Penetration Property) A cellophane tape was stuck to the surface of the adhesive film of the test piece by hand pressure bonding, peeled off by high-speed hand peeling, and peeling of the adhesive film was observed.・ ・ ・: No peeling of the adhesive film was observed ×: Peeling of the adhesive film was observed

(Evaluation Method for Washing Resistance) The test pieces were washed for one hour and dried at room temperature for one day, and this was repeated three times to observe the state of the adhesive film falling off.・ ・ ・: No adhesive film was observed. ×: Significant adhesive film was observed.

(Evaluation Method of Feeling) The feeling of unity of the adhesive film with the object to be transferred was confirmed by pulling the test piece by hand.・ ・ ・: There is a sense of unity, and the presence of the film is not felt. ×: There is no sense of unity, and the strength of the film is felt.

(Evaluation Method of Blocking Property in Normal Temperature Range)
At normal temperature, the surfaces of the adhesive film face each other,
Whether or not the adhesive films adhered to each other was checked for blocking.・ ・ ・: No blocking was observed ×: blocking was observed

Table 1 shows the results evaluated by the above method.

[0036]

According to the present invention, the adhesive sheet composed of the adhesive film and the release paper according to the present invention allows the adhesive force to be applied to a flexible transfer object such as fabric, and the ability of the adhesive film to penetrate the transfer object during hot pressing. Thus, an adhesive sheet for pattern transfer printing having all the required properties in a well-balanced manner, such as washing resistance, feeling, and blocking properties in a normal temperature range can be obtained.

[0037]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an adhesive sheet for pattern transfer printing of the present invention.

[Explanation of symbols]

1. Adhesive film 2. Release paper

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C09J 1/00-201/10 C08L 1/00-101/16 C08G 18/00-18/87

Claims (1)

(57) [Claims] 1. An adhesive sheet comprising an adhesive film and release paper, wherein the adhesive film comprises 50 to 90 % by weight of an amorphous polyurethane resin and 10 to 50% by weight of a crystalline polyurethane resin, An adhesive sheet for pattern transfer printing, wherein the number average molecular weight of the reactive polyurethane resin is 10,000 to 50,000.