JPH0334478B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition for manufacturing transfer paper, and in particular, a transfer paper that has good printability and peelability from a base film, and forms a resin layer with excellent scratch resistance as a protective film for a metal vapor deposited layer. This invention relates to a resin composition for paper manufacturing. The transfer paper used for transfer printing is, for example, first,
As shown in FIG. 2, a resin layer 2 is provided on a base film 1, a metal vapor deposited layer 3 is formed on the resin layer 2, and a base material 5 on which an adhesive layer 4 is formed is coated with the metal vapor deposited layer 3. It can be obtained by attaching the film to the surface and then peeling off the base film 1 as shown in FIG. When performing transfer printing, the resin layer 2, which is the outermost layer of the transfer paper, is
After printing on the surface by a method such as gravure printing, a printing material such as vinyl chloride film is superimposed on the printing surface, and then the printing layer is heated and transferred onto the printing material by passing it through a transfer machine. . By the way, the resin layer 2 provided on the transfer paper as described above
Conventionally, these were made from materials such as wax, rosin, silicone, maleic acid resin, and acrylic resin, and were rather strongly conscious of the idea of a release layer, so it was difficult to peel off the base film. In some cases, the resin layer 2 itself may be peeled off from the surface of the metal-deposited layer without peeling off the base film 1, and the metal-deposit layer will be exposed on the surface of the transfer paper, making it difficult to withstand. Not only was the scratch resistance poor, but the printing properties for gravure, flexography, offset, etc. were also poor. The present invention has been made with attention to these circumstances. That is, the present inventors have found that the resin layer has good releasability to the base film, etc., and that the resin layer is not peeled off from the metal vapor deposited film when the base film is peeled, and that the resin layer is left on the metal vapor deposited layer. We have carried out extensive research in order to provide a resin composition for manufacturing transfer paper that can serve as a protective layer for the metal vapor deposited layer, improve the scratch resistance of the metal vapor deposited film, and improve the printing characteristics. The resin composition of the present invention, which has achieved the above object, is characterized in that it contains each of the following components (a) to (d). (a) Has a softening point of 200°C or lower, and has a dibasic acid residue (however, 40 mol% of terephthalic acid as the dibasic acid)
or a mixed acid of terephthalic acid and isophthalic acid (containing 40 mol% or more) and glycol residues: 30 to 80 parts by weight (b) Nitrocellulose resin: 20 to 70 parts by weight (c) Isocyanate compound: 1 to 20 parts by weight (d) Chlorinated polyolefin: 0.3 to 5 parts by weight Below, the composition and effects of the composition of the present invention will be explained in order. (a) Linear copolymerized polyester: 30 to 80 parts by weight The linear copolymerized polyester ensures adhesion between the resin layer and metal vapor deposited layer, and also ensures mechanical strength to function as a protective layer. It is a basic component for the purpose of this, and its softening point must be below 200°C. The lower limit of the softening point may be approximately 100°C. Furthermore, the linear copolymerized polyester is composed of dibasic acid residues and glycol residues, and the dibasic acid residues include at least terephthalic acid itself, or a total of 40 mol% of terephthalic acid and isophthalic acid. If the composition of the dibasic acid residue does not satisfy this condition, in other words, the dibasic acid must contain 40
If it is less than mol%, the degree of polymerization will be relatively low and the softening temperature will also be too low, making it difficult to achieve the object of the present invention. More preferably, it is recommended to contain the above dibasic acid in an amount of 95 to 50 mol%. Other dibasic acids that can be used in combination with the above dibasic acids include aliphatic dibasic acids such as succinic acid, adipic acid, and sebacic acid, and aromatic dibasic acids such as orthophthalic acid and diphenyldicarboxylic acid.
Examples include basic acids. On the other hand, glycol components constituting glycol residues include ethylene glycol, 1,4-butanediol, 1,2-
Examples include aliphatic glycols such as propylene glycol, 1,6-hexanediol, diethylene glycol, and neopentyl glycol, among which ethylene glycol and/or 1,
4-Butanediol accounts for 20 to 20% of the total glycol component.
Optimal results were obtained when it was used at 70 mol%. That is, these glycol components are 20
If it is less than mol % or exceeds 70 mol %, the solubility of the produced linear copolymerized polyester in organic solvents may decrease, resulting in poor workability. If the proportion of the linear copolymerized polyester having the above structure in the total resin composition is less than 30 parts by weight, the adhesion with the deposited film will decrease, while if it exceeds 80 parts by weight, it will not adhere to the base film. The removability of the resin and the scratch resistance of the resin surface itself are reduced. In addition, when the above-mentioned blending ratio is set in the range of 40 to 60 parts by weight, good results can be obtained more stably. In addition, as a linear copolymer polyester, the intrinsic viscosity [measured at 80°C in phenol/tetrachloroethane = 60/40 (weight ratio)] is 0.15.
It is desirable to select a molecular weight within the range of ~1.2 dl/g. (b) Nitrocellulose resin: 20 to 70 parts by weight Nitrocellulose resin is a main component of the resin composition along with linear copolymerized polyester, and contributes to improving coating workability by imparting appropriate strength and viscosity to the resin layer. The nitrocellulose resin has a nitrogen content of 10 to 12.5% by weight, and the viscosity display method of Hercules Powder (Kyoritsu Shuppansha, 1962), which indicates the characteristics of nitrocellulose, is used.
(See Chemistry Encyclopedia Vol. 6, page 760, published July 15)
It is preferable to have a degree of polymerization such that the value determined by gave favorable results. If the proportion of the nitrocellulose resin in the total resin composition is less than 20 parts by weight, the abrasion resistance and printability of the resin layer itself will deteriorate, while if it exceeds 70 parts by weight, the resin layer will become brittle. , when the resin layer is bent, the resin layer peels off. (c) Isocyanate compound: 1 to 20 parts by weight The isocyanate compound is a component that improves the hardness, heat resistance, and adhesive strength of the resin layer to the deposited film. Examples of the isocyanate compound include hexamethylene diisocyanate, diphenylmethane diisocyanate, Examples include polyisocyanate compounds such as condensates of 3 moles of one or more diisocyanate compounds selected from hexamethylene diisocyanate and 1 mole of trimethylolpropane, and derivatives thereof. etc. can be selected. If the amount of the above-mentioned isocyanate compound is less than 1 part by weight, the addition effect will not be sufficiently exhibited, and as the amount increases, the adhesion effect with the deposited film will increase, but if it exceeds 20 parts by weight Since the adhesive effect begins to deteriorate when the amount is lower than 20 parts by weight, the amount should be controlled to 20 parts by weight or less. (d) Chlorinated polyolefin: 30 to 5 parts by weight Chlorinated polyolefin moderately adheres the base film and resin layer, and prevents the resin layer (already attached to the vapor deposited layer) from falling off from the base film during processing. The chlorinated polyolefin is exemplified by those obtained by chlorinating chain hydrocarbon polymers such as polypropylene and polyethylene by a conventional method, and the degree of chlorination is 15 to 55. It is desired that the amount is within the range of parts by weight. That is, if the degree of chlorination is less than 15 parts by weight, the solubility in organic solvents will decrease, while if it exceeds 55 parts by weight, the adhesive function will be lost, which is not preferable. If the proportion of the chlorinated polyolefin in the total resin composition is less than 0.3 parts by weight, the adhesive force enhancement effect will not be sufficiently exhibited, while if it exceeds 5 parts by weight, the adhesive force will become too strong and the Releasability from the material film deteriorates. Although the resin composition of the present invention contains each of the above-mentioned components as essential components, for example, a coloring dye may be added as other components, if necessary. In addition, examples of flexible films for the base film used to obtain transfer paper include polyolefin films, polyester films, and polyamide films, and those with smooth surfaces, matte processing, hairline processing, etc. You can arbitrarily select one that has been given. The amount of the resin composition applied to the base film is preferably 0.1 to 10 g/m ² in terms of solid content.
If the coating amount is less than 0.1 g/m ² , the abrasion resistance of the resin layer itself will be poor, and if it exceeds 10 g/m ² , burning will occur during vapor deposition and the gloss of the vapor-deposited surface will be impaired. After applying the resin composition to the base film,
Aluminum is preferred as the metal to be deposited, but various metals such as gold, silver, nickel chrome, etc. can be used. The vapor deposition method is generally vacuum vapor deposition, but methods such as ion plating and sputtering may also be used. Deposited layer thickness is 200~800Å
is generally used, but is not particularly limited. The substrate to be transferred in the present invention includes:
Various papers, cloth, non-woven fabrics, plastic sheets,
You can choose from a wide range of leather etc. Further, the substrate and the vapor deposited layer can be easily bonded together using a commonly used isocyanate-based dry laminating adhesive or the like. The present invention is constructed as described above, and the resin layer made of the resin composition of the present invention has excellent printability, good peelability from the base film, and excellent scratch resistance. It has become possible to obtain transfer paper for transfer printing that has excellent properties without damaging the vapor deposited layer covered with the resin layer. Next, examples of the present invention will be described. Examples 1 to 4 and Comparative Examples 5 to 10 Terephthalic acid residue 50 mol%, isophthalic acid residue
A linear copolymerized polyester (softening temperature 163°C) consisting of 50 mol% of ethylene glycol residues and 45 mol% of neopentyl glycol residues, nitrocellulose (RS1/2 manufactured by Daicel) and tolylene diisocyanate. Trimethylolpropane reactant (Coronate L manufactured by Nippon Polyurethane Co., Ltd.)
and chlorinated polypropylene (Hardren 13LP manufactured by Toyo Kasei Co., Ltd.) with a chlorination degree of 26% by weight were mixed in various proportions, and this was dissolved in a mixed solvent of toluene/ethyl acetate/methyl ethyl ketone (1/1/1 weight ratio). A 20% by weight resin composition solution was prepared. The solution was applied to a biaxially stretched polypropylene film (P1261 25μm
Toyobo Co., Ltd.) was coated on one side with a bar coating and dried at 110°C for 30 seconds, and the coating amount (solid content) was 1.9 g/m ² .
Aluminum was vacuum-deposited (deposited layer thickness: 500 Å) on top of this resin coating, and this was bonded to high-quality paper (basis weight: 75 g) via an adhesive.
The axially oriented polypropylene was peeled off to obtain vapor-deposited transfer papers No. 1 to 10. Example 11 Linear copolymerized polyester (same as Example 1), nitrocellulose (RS1 manufactured by Daicel)
Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.) and Hardren 13LP (manufactured by Toyo Kasei Co., Ltd.) at 50/44.5/
Mix at a ratio of 5/0.5 (weight ratio) and mix toluene/methyl acetate/methyl ethyl ketone (1/
Dissolved in a mixed solvent of 1/1/weight ratio) to 16% by weight
A resin composition solution was prepared. The solution was bar coated on one side of a biaxially stretched polyester film (E506, 12 μm, manufactured by Toyobo Co., Ltd.), and dried at 120° C. for 30 seconds. The coating amount (solid content) was 2.2 g/m ² .
Aluminum was vacuum-deposited on this resin coating layer (deposited film 500 Å), and high-quality paper (basis weight 75 g) was bonded to this material via adhesive, and then the biaxially stretched polyester was peeled off. A vapor-deposited transfer paper was obtained. Comparative Examples 12 and 13 As Comparative Example 12, an aluminum film was prepared, and as Comparative Example 13, an aluminum vapor-deposited polyester film whose vapor-deposited surface was not bar-coated with a resin layer or the like was prepared. The above Examples 1 to 4, 11 and Comparative Examples 5 to 10,
When samples 12 and 13 were examined for peelability, scratch resistance, etc., the results shown in Table 1 were obtained. The method for measuring each characteristic value is as follows. (1) Peelability Peeling condition when 25mm wide cellophane tape is applied to the surface of the resin layer applied to the transfer base material and rapidly peeled off. ○: Peeling off without feeling any resistance ×: Feeling of resistance (2) Dust Condition when the resin laminate applied to the transfer base material is slightly bent. ○: Resin layer does not fall off ×: Resin layer cracks finely and falls off (3) Adhesion between resin layer/deposited layer When 25mm wide sellotape is attached to the resin layer surface after transfer to the substrate and quickly peeled off. peeling condition. ○: The resin layer does not peel off by itself ×: Only the resin layer is removed by the tape (4) Scratch resistance After transfer to the substrate, dye fastness tester (manufactured by Toyo Seiki Seisakusho) is applied to the resin layer surface. to determine the state of scratches after rubbing with gauze 300 times. ○: Almost no scratches △: Some scratches, but not very noticeable ×: Many scratches (5) Printability After transfer to the substrate, two-color overprinting is performed on the resin layer surface using a gravure printing machine or an offset printing machine. A 25 mm wide cellophane tape was applied to the printed area and quickly peeled off to evaluate the state of the printing ink coming off. ○: The ink does not fall off from the resin layer ×: The adhesion of the ink is poor, and some or all of the ink adheres to the cellophane tape and falls off.

【table】

[Table] * Adhesion between resin layer and aluminum vapor deposited film As shown in Table 1, Nos. 1 to 4 and 11 satisfied all required performances. On the contrary
In No. 5, the amount of linear copolymerized polyester was as small as 15 parts by weight, resulting in poor adhesion between the resin layer and the aluminum vapor-deposited layer, and the excessive amount of nitrocellulose resin, 75 parts by weight, resulted in poor printability. Furthermore, dust was generated when the resin layer was slightly bent. In No. 6, the amount of isocyanate compound was excessive at 23 parts by weight, so the adhesion between the resin layer and the aluminum vapor deposited layer was reduced. In No. 7, the amount of chlorinated polypropylene was too large (6 parts by weight), so the adhesiveness became too strong and the peelability between the base film and the resin layer deteriorated. In No. 8, the amount of nitrocellulose resin was as low as 18 parts by weight, resulting in poor scratch resistance and printability, and the excessive amount of chlorinated polypropylene, 6 parts by weight, resulted in poor peelability. In No. 9, since the amount of nitrocellulose resin was as small as 15 parts by weight, the peelability, scratch resistance, and printability deteriorated. In No. 10, the amount of linear copolymerized polyester was excessive at 85 parts by weight, and the amount of nitrocellulose resin was small at 5 parts by weight, resulting in extremely poor peelability, scratch resistance, and printability.

[Brief explanation of drawings]

FIGS. 1 and 2 are cross-sectional explanatory diagrams showing the steps for manufacturing transfer paper. DESCRIPTION OF SYMBOLS 1... Base film, 2... Resin layer, 3... Vapor deposition layer, 4... Adhesive layer, 5... Substrate.

Claims (1)

[Claims] 1. A resin layer is provided on a base film, a metal vapor deposition layer is formed on the resin layer, and the base film is further bonded to a substrate via an adhesive, and then the base film is peeled off from the resin layer. A resin composition for manufacturing a transfer paper, which is a resin composition for the resin layer used in manufacturing a transfer paper, and is characterized in that it contains the following components (a) to (d). (a) Has a softening point of 200°C or lower, and has a dibasic acid residue (however, 40 mol% of terephthalic acid as the dibasic acid)
or a mixed acid of terephthalic acid and isophthalic acid (containing 40 mol% or more) and glycol residues: 30 to 80 parts by weight (b) Nitrocellulose resin: 20 to 70 parts by weight (c) Isocyanate compound: 1 to 20 parts by weight (d) Chlorinated polyolefin: 0.3 to 5 parts by weight