JPH05311104A - Ink or coating composition for forming transfer layer, production of transfer sheet and transfer sheet - Google Patents

Abstract

PURPOSE:To obtain an ink or coating composition, etc., capable of drying in a short time, causing no thermal deterioration in formed transfer layer or substrate sheet, etc., free from trouble such as blocking when transfer sheets are A stacked. CONSTITUTION:The ink or coating composition for forming transfer layer consists of mixture of three kinds of solvents of (A) a quickly drying solvent having evaporation rate >=4 times that of n-butyl acetate, (B) a volatile and slowly drying solvent having evaporation rate >=1 times and < 4 times that of n-butyl acetate and (C) a slowly drying solvent having residual property and having evaporation rate <=0.8 times that of n-butyl acetate and >=115 deg.C boiling point and contains the component (C) in an amount of 2-10wt.% based on total solvent. This composition is applied to a releasable substrate sheet 3 and then dried at <=115 deg.C. Thereby, a transfer layer 2 is formed to provide the transfer sheet 1.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ink or coating composition for forming a transfer layer of a transfer sheet, a method for producing a transfer sheet using the composition, and a transfer sheet.

[0002]

2. Description of the Related Art Conventionally, in the case of producing a transfer sheet, as an ink or a paint for forming a transfer layer, a coloring agent such as a pigment or a dye is added to a binder resin (binder) and the viscosity is adjusted to an appropriate value with a solvent. Is used to form a transfer layer by applying the composition and drying the composition to produce a transfer sheet.

The solvent used for the ink or coating composition for forming the transfer layer is a solvent (so-called low) which has a relatively low boiling point (less than 115 ° C.) and a relatively high evaporation rate (about 80% or more of n-butyl acetate). Boiling point, highly volatile solvent) was used. Further, when a transfer layer is formed using the ink or coating composition using the above low boiling point and high volatility solvent, it is formed by slowly drying the composition after coating at a relatively low temperature of less than 115 ° C. It is known that a good transfer layer can be formed without causing air bubbles to be mixed in the transferred layer due to foaming of a solvent or floating between the coated layer and the lower layer.

[0004]

However, the transfer layer dried at a relatively low temperature using the low boiling point and high volatility solvent as described above is not sufficiently dried, and the solvent easily remains in the layer.
There is a problem that blocking easily occurs when the transfer sheets are laminated. Further, if the drying time is lengthened, there is a problem that the workability of transfer sheet production is deteriorated.

Therefore, in order to solve the above problems, if a quick-drying solvent that does not cause blocking is used and drying is performed at a relatively high temperature, the problem of blocking is solved, but the bumping of the solvent causes a problem in the transfer layer or the transfer layer. Problems such as foaming and foil floating occur at the interface between the peelable base material sheet and the peelable base material sheet.
On the other hand, in order to improve the above-mentioned foaming, it has been attempted to form a transfer layer by using an ink or coating composition having a relatively high boiling point of 115 ° C. or more and a low volatility solvent and raising the drying temperature. However, after all, the solvent is likely to be insufficiently dried, and there is a possibility that blocking occurs. Also, if the drying temperature is raised too much, the binder resin and the base sheet for forming the transfer sheet are thermally deteriorated, and if heated above the boiling point of the residual solvent, problems such as foaming and foil floating may occur. It had the drawback of remaining.

When the surface on which the transfer layer is provided has large irregularities or when relatively large particles such as bead pigments and luster pigments are present, a peeling layer or a pattern layer having a certain thickness with a single coating is provided. Must be formed, and in that case, the above problems are particularly remarkable. In particular, since the transfer sheet does not have very high adhesion strength at the interface with the transfer layer (usually the release layer) in contact with the releasable base material, there is a problem that foil blowout easily occurs during drying.

The present invention has been made in order to solve the above-mentioned drawbacks of the prior art. The drying time is short and the formed transfer layer, substrate sheet, etc. do not undergo thermal deterioration and the like. It is an object of the present invention to provide a transfer layer-forming coating material or an ink composition, a method for producing a transfer sheet, and a transfer sheet, which are free from problems such as blocking when the layers are laminated.

[0008]

The transfer layer forming ink or coating composition of the present invention is a transfer layer forming ink or coating composition comprising at least a binder resin, a colorant and an organic solvent, wherein the organic solvent is A fast-drying solvent having an evaporation rate of 4 times or more that of n-butyl acetate, a volatile slow-drying solvent having an evaporation rate of 1 time or more and less than 4 times that of n-butyl acetate, and an evaporation rate of 0.8 times that of n-butyl acetate. It is composed of three kinds of mixed solvents with a residual slow-drying solvent having a boiling point of 115 ° C. or higher and a boiling point of 115 ° C. or more, and the residual slow-drying solvent is contained in an amount of 2 to 10% by weight in all solvents. ..

In the method for producing a transfer sheet of the present invention, the transfer layer-forming ink or coating composition is used to apply the composition to a releasable substrate, and the transfer layer is dried at a temperature of less than 115 ° C. Forming a transfer sheet.

The transfer sheet of the present invention is a transfer sheet in which a composition of ink or paint is applied on the surface of a releasable substrate and dried to form a transfer layer, wherein the composition of ink or paint is at least a binder. It consists of a resin, a colorant and an organic solvent, and the organic solvent has a vaporization rate of 4 times or more that of n-butyl acetate, and a vaporization rate of 1 time or more that of n-butyl acetate.
It is a mixed solvent of three kinds of volatile slow-drying solvent of less than twice and residual slow-drying solvent having an evaporation rate of 0.8 times or less of n-butyl acetate and a boiling point of 115 ° C. or more. The slow-drying solvent is 2 to 10% by weight in the total solvent, and the transfer layer is formed by applying the coating material to a releasable substrate and then drying it at a temperature of less than 115 ° C. Is.

The fast-drying solvent used in the ink or coating composition for forming a transfer layer of the present invention is the evaporation amount (weight part) of the solvent when the evaporation rate is 100 (parts by weight) of the evaporation amount of n-butyl acetate. (Parts), a solvent having an evaporation rate of 400 or more is used, and specific examples include the solvents shown in Table 1.

[0012]

[Table 1] [Fast-drying solvent] ─────────────────────────────────── Solvent name Boiling point (℃) Evaporation rate ─────────────────────────────────── Methyl acetate 59-60 1040 Acetone 56.1 720 Ethyl acetate 77.1 525 Methyl ethyl ketone 79.6 465 Isopropyl acetate 89.0 435 ──────────────────────────────────────

Further, examples of the volatile slow-dry solvent having an evaporation rate of 1 to 4 times that of n-butyl acetate include the solvents shown in Table 2.

[0014]

[Table 2] [Volatile slow-drying solvent] ─────────────────────────────────── Solvent name Boiling point ( ℃) Evaporation rate ─────────────────────────────────── Methanol 64.5 370 Isopropanol 82.5 205 Ethanol 78.5 203 Toluene 111 195 Isobutyl acetate 118.3 152 n-Butyl acetate 124-125 100 ────────────────────────────── ──────

Further, examples of the residual slow-drying solvent include the solvents shown in Table 3.

[0016]

[Table 3] [Residual slow-drying solvent] ──────────────────────────────────── Solvent name Boiling point ( ℃) evaporation rate ─────────────────────────────────── xylene 135-145 68 ethylene glycol monomethyl ether 124. 6 57 ethylene glycol monoethyl ether 124.5 55 diethylene glycol monoethyl ether 218 52 diethylene glycol monobutyl ether 119 30 diethylene glycol monobutyl ether acetate 246.8 0.1 isoamyl alcohol 132 36 ──────────────── ─────────────────────

The residual slow-drying solvent dries slower than the above-mentioned two kinds of solvents and has good compatibility with the resin used, and even if it remains in the transfer layer, it has a bad influence on the physical properties and blocking properties of the layer. Anything that doesn't exist. For example, when acrylic + vinyl chloride-vinyl acetate copolymer is used as the binder resin, ethyl acetate / methyl ethyl ketone is used as the fast-drying solvent, and toluene is used as the volatile slow-drying solvent, the residual slow-drying solvent is diethylene glycol monoether. It is preferable to use a class. In this case, diethylene glycol monobutyl ether is particularly preferable because it has good compatibility with the resin and good drying property. Further, in consideration of the water resistance of the transfer layer after transfer, an esterified product of a glycol ether obtained by esterifying the glycol ether with acetic acid is preferable.

The composition of the solvent is such that the residual slow-drying solvent is contained in an amount of 2 to 10% by weight of the total solvent. When the residual slow-drying solvent is less than 2% by weight, the coating film surface has a high drying rate. The skin-preventing effect is not sufficiently obtained, and foaming and foil floating easily occur. Further, when the residual slow-drying solvent exceeds 10% by weight, the drying speed becomes slow and the workability of the transfer sheet production is deteriorated, and when the residual solvent is further increased, bubbles and foil floating easily occur. Blocking property decreases. The more preferable amount of the residual slow-drying solvent added is 4 to 8% by weight.

The binder resin used in the transfer layer-forming ink or coating composition is appropriately selected according to the application of the transfer layer. The binder resin is, for example, a thermoplastic resin such as ethyl cellulose, cellulose nitrate, cellulose acetate, ethyl hydroxyethyl cellulose, cellulose derivative such as cellulose acetate propionate, polystyrene, styrene resin such as poly α-methylstyrene or styrene copolymer, poly Acrylic resins such as ethyl methacrylate, ethyl polyacrylate, polybutyl acrylate, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, vinyl polymers such as polyvinyl butyral, rosin, rosin modified maleic acid Examples thereof include resins, rosin-modified phenol resins, rosin ester resins such as polymerized rosins, coumarone resins, vinyltoluene resins, polyamide resins and other natural or synthetic resins. Further, as the thermosetting resin,
Phenol resin, urea resin, diallyl phthalate resin,
Examples include melamine resin, guanamine resin, unsaturated polyester resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicon resin and polysiloxane resin.

Further, other additives are appropriately used according to the transfer layer to be formed. For example, in the case of a composition for a picture layer, a coloring agent such as a coloring pigment or a dye is used, and in the case of a composition for a release layer, a matte pigment or a bead pigment for controlling the luster or surface texture. Gloss control agent,
A bright pigment or the like is added. These specific materials are shown below.

1) As the matte pigment, for example, fine powder of calcium carbonate, barium sulfate, silica, alumina, glass balloon, polyethylene or the like having a particle size of about 0.1 to 10 μm is used. 2) The bead pigment is a pigment composed of spherical resin fine particles, and if necessary, contains a coloring agent such as a pigment or a dye therein. In particular, as a form having excellent matting effect and scratch resistance, conventional pigment fine powders such as Fe ₂ O ₃ , TiO ₂ , CaCO ₃ , and quinacridone are used as polyurethane, epoxy, acrylic, polyester, nylon, fluororesin. ,
It may be dispersed in a composition containing an elastic resin such as vinyl chloride-vinyl acetate copolymer, and optionally a plasticizer, a stabilizer, a surfactant, or the like, or may be coated with the composition. Spheres or sphere-like particles. Regarding the particle size, the distribution range is 5 to 80 μm, and the maximum value of the distribution is 10 to 35.
Those in the μm range give particularly good matting.

3) As the bright pigment, metal powder such as aluminum powder, copper powder, brass powder or the like, metal powder pigment such as metal flakes or pigment having metal luster such as cut pieces of metal vapor deposition synthetic resin film, titanium dioxide. Pearlescent pigments (pearl pigments) with pearl luster and interference luster such as coated mica, fish scale foil, bismuth acid chloride, and two or more resin layers with different refractive index such as polyester resin layer and acrylic resin layer are several μm or less Examples include pigments made of foil powder obtained by cutting a film (for example, a Marl film manufactured by Marl Co., Ltd.), which is laminated in multiple layers with a certain thickness to produce a coloration due to light interference.

As the colorant used when forming the pattern layer, yellow pigments such as organic pigments such as isoindolinone, thren yellow G, and permanent yellow HR, inorganic pigments such as yellow iron oxide and nickel titanium yellow, and red pigments. Quinacridone Red, Permanent Red F
Organic pigments such as GR and Permanent Red F4RH, inorganic pigments such as red iron oxide, mercury cadmium sulfide, organic pigments such as phthalocyanine blue and indanthrene blue RS as blue pigments, inorganic pigments such as ultramarine blue and navy blue, carbon black as black pigments As the white pigment, titanium dioxide, diammonium trioxide, etc. can be used. The particle size of the pigment is appropriately selected depending on the intended use, physical properties, etc.
About 100 μm is used.

[0024]

Embodiments of the present invention will now be described in detail with reference to the drawings. FIG. 1 is a sectional view of an essential part showing an example of the transfer sheet of the present invention. As shown in FIG. 1, the transfer sheet of the present invention has a transfer layer 2 formed on the surface of a releasable base material sheet 3, and the transfer layer 2 is composed of a release layer 8, a pattern layer 7 and the like. Any layer may be provided as long as it is provided. Further, the transfer layer 2 may be provided with an adhesive layer 6 if necessary. In addition to the pattern layer 7, a decorative layer such as a metal vapor deposition layer can be provided.

The releasable base material 3 of the transfer sheet 1 of the present invention is a film having a releasability of 5 to 200 μm from the transfer layer, and is made of polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate-isophthalate copolymer or the like. Polyester resin, polyethylene, polypropylene, polyolefin resin such as polymethylpentene, polyvinyl fluoride, polytetrafluoroethylene, polyfluoroethylene resin such as ethylene-tetrafluoroethylene copolymer, nylon 6, nylon 66, etc. Polyamide, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinyl polymer such as vinylon, cellulose triacetate, cellophane such as cellophane resin Acrylic resin such as methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate, polybutyl acrylate, etc., single layer or plural laminates of synthetic resin film or sheet such as polystyrene, polycarbonate, polyarylate and polyimide Alternatively, high quality paper, thin paper, glassine paper, sulfuric acid paper and the like are used.

Although the releasable substrate 3 may be composed of only the above-mentioned substrate sheet 4, as shown in FIG. 1, if necessary, a releasability between the transfer layer 2 and the releasable substrate 3 is provided. You may provide the mold release layer 5 for promoting. As the release layer 5, a coating film of a paint to which a release agent such as a fluororesin, various waxes and silicones is added to a known vehicle, for example, an acrylic resin, a fibrin resin, a vinyl resin, or the like, Mold-releasing resin such as fluorine resin, silicone resin, melamine resin, polyolefin resin, ionizing radiation cross-linking polyfunctional acrylate, polyester, epoxy resin, or film formed by extrusion coating To use.

The peelable base material 3 is appropriately selected according to the purpose of the transfer sheet. For example, when transferring a pattern with high dimensional accuracy to a flat transfer target, polyethylene terephthalate, polycarbonate, polyimide, polyarylate,
It is preferable to use a resin such as a material coated with polymethylpentene such as polyetheretherketone, cellulose acetate, and high-quality paper, which is unlikely to change in dimension due to heat or stress. When the surface of the transferred material is generally a curved surface such as in-mold transfer (simultaneous injection molding transfer), polyamide such as nylon 6, nylon 6,6, polyolefin such as polyethylene or polypropylene, polyethylene terephthalate,
A crystalline thermoplastic polyester such as polybutylene terephthalate or a copolymer such as polyethylene terephthalate-isophthalate, a thermoplastic resin sheet or film having plasticity such as polyvinyl chloride or vinylon, or a laminate thereof is preferable. The thickness of the above various releasable base materials 3 is selected according to the application, but is usually about 12 to 100 μm.
Also, if the transfer layer side of the above various releasable base materials 3 has a desired glossiness, various glossinesses can be imparted to the surface of the transfer layer from complete gloss to complete matte.

The peeling layer 8 has a peeling property with respect to the peeling base material, and after transfer, a resin composition having a desired physical property is selected as a surface protective layer of the transfer layer. In particular, the above-mentioned additives are used in order to give the surface a matte appearance or luster. The film thickness of the release layer is not particularly limited, but in the present invention, it is most suitable when a layer having a film thickness of about 20 to 100 μm when dried is formed by one coating. Particularly, when a pigment (coarse-grained pigment) having a relatively large diameter such as a bead pigment or a bright pigment is added, the drying becomes easy.

The pattern layer 7 may be formed on the entire surface or partially, and the pattern may be a design of natural products such as wood grain, stone grain, cloth grain, letters, figures, symbols and various abstract patterns. Any of In the transfer sheet of the present invention, at least one of the transfer layers such as the above-mentioned pattern layer and release layer may be formed by using the transfer layer forming ink or the paint using the above-mentioned specific solvent.

In the transfer sheet of the present invention, the adhesive layer 6 is a layer for satisfactorily transferring and adhering the transfer layer to an object to be transferred, such as a heat sensitive adhesive, a solvent activated adhesive, an ionizing radiation curable adhesive and the like. Select from among the above according to the application. The adhesive layer may be omitted if the layers other than the adhesive layer such as the pattern layer and the release layer have sufficient adhesiveness.

The production method of the present invention is to coat the surface of the releasable substrate 2 with the above-mentioned transfer layer-forming ink or composition and then dry it at a drying temperature of less than 115 ° C. .. When the drying temperature is 115 ° C. or higher, the base material sheet or the transfer layer itself is thermally deteriorated and the solvent is apt to foam. Further, when heated above the boiling point of the residual solvent, foaming, foil floating, etc. will eventually occur. In addition to that,
The temperature of the environment where the transfer foil is stored and the transfer layer is exposed after transfer is usually sufficiently lower than 115 ° C, and almost all of the quick-drying solvents that completely volatilize have a boiling point of less than 115 ° C and allow residue. Most of the residual slow-drying solvent
Since the boiling point of the residual slow-drying solvent is more than 5 ° C, the upper limit of the boiling point of the residual slow-drying solvent is 115 ° C or higher, and the drying temperature is lower than 115 ° C to completely dry the fast-drying solvent and prevent the residual slow-drying solvent It is possible to achieve both prevention of foaming of the dry solvent, and also to prevent foaming, foil floating, etc. occurring during storage of the transfer foil and in the transfer product over time.

As the means for forming the transfer layer on the surface of the releasable substrate, various known coating means can be used. In particular, in the present invention, coating is carried out by a gravure method which requires dilution to a low viscosity with an organic solvent. It is effective when

The present invention will be described in more detail with reference to specific examples. Example 1 A shaped film made of polyethylene terephthalate having a thickness of 25 μm [manufactured by Kimoto Co., Ltd .: release mat 1017-
On the surface of [6], a suede resin containing a bead pigment having an average particle diameter of 25 μm [Suede Ink No. 2 manufactured by Showa Ink Kogyo Co., Ltd.] was applied in a fountain reverse system so that the coating amount was 28 μm in a dry state Coating to form a suede layer. Further, an adhesive having the following composition on the suede layer [manufactured by Showa Ink Industry Co., Ltd .:
HS-32 gray], an adhesive layer was provided by the fountain reverse method so that the coating amount including the suede layer would be 32 μm in a dry state, to obtain a transfer sheet.

[Adhesive composition] Unit: wt% Solid content (55) -Acrylic resin 22-Vinyl chloride-vinyl acetate copolymer 3-Pigment 30 Solvent content (45) -Toluene 22-Ethyl acetate 13-Methyl ethyl ketone 8- Acetic acid diethylene glycol monobutyl ether 2

Although the adhesive layer was formed into a thick film by one coat during the production of the transfer sheet, no foaming or foil floating occurred and no blocking was observed after the production. When the transfer sheet thus obtained was used to perform transfer to a polystyrene substrate, a transfer layer having good physical properties was obtained.

Example 2 A shaped film based on polyethylene terephthalate having a thickness of 38 μm [manufactured by Kimoto Co., Ltd .: release mat 101]
7-6] on the surface of suede ink [Showa Ink Mfg. Co., Ltd .: Suede ink No. 2
-2] was coated by a fountain reverse method so that the coating amount was 28 μm in a dry state to form a suede layer.

[Suede ink composition] Unit: wt% Solid content (49) -Resin 14-Bead pigment 35 Solvent content (51) -Toluene 24-Ethanol 24-Diethylene glycol monobutyl ether acetate 3

The formed suede layer did not show foaming or foil floating, and a smoother surface was obtained as compared with the suede layer formed in Example 1. Next, an adhesive layer having the same composition as in Example 1 was formed on the suede layer in Example 1.
An adhesive layer was provided by the same method as above to obtain a transfer sheet.

No blocking was observed in the obtained transfer sheets when the transfer sheets were laminated, and when the obtained transfer foil was injection-molded, a transfer layer having no problem in terms of physical properties was formed. A molded product was obtained.

[0040]

As described above, the ink or coating composition for forming a transfer layer of the present invention can be sufficiently dried at a normal drying temperature of 115 ° C. or less by a quick-drying solvent. In addition, the volatile slow-drying solvent prevents cell clogging inside the gravure plate during printing and the increase in ink viscosity.By adding the residual slow-drying solvent, the mechanism of action is unknown, but relative Evaporative drying of the volatile slow-drying solvent having a high drying rate is accelerated, and evaporation of the volatile slow-drying solvent is accelerated compared with the case where the residual slow-drying solvent is not added, and the drying property is improved.
Further, the boiling point of the residual slow-drying solvent is set higher than the printing drying temperature (of course higher than room temperature), and the addition amount is 1% of the total solvent.
Since the content is 0% by weight or less, residual residual slow-drying solvent is not vaporized to form bubbles or foil floating.

The method for producing the transfer sheet of the present invention employs a method of drying at a temperature of 115 ° C. or lower using the above-mentioned ink or coating composition. Since the drying temperature is low, the binder resin, the base sheet, etc. In addition, there is no possibility of deterioration due to heat, and since the drying property is improved, the workability of transfer sheet production is not reduced.

The transfer sheet of the present invention can be obtained as one having a good transfer layer without foaming or foil floating in the transfer layer.

[Brief description of drawings]

FIG. 1 is a sectional view of an essential part showing an example of a transfer sheet of the present invention.

[Explanation of symbols]

 1 Transfer Sheet 2 Transfer Layer 3 Releasable Base Material

Claims (3)

[Claims] 1. A transfer layer forming ink or coating composition comprising at least a binder resin, a colorant and an organic solvent, wherein the organic solvent is a fast-drying solvent having an evaporation rate four times or more that of n-butyl acetate. A volatile slow-drying solvent having an evaporation rate of 1 time or more and less than 4 times that of n-butyl acetate, and a residual slow-drying solvent having an evaporation rate of 0.8 times or less that of n-butyl acetate and a boiling point of 115 ° C. or more. 2. An ink or coating composition for forming a transfer layer, characterized in that the residual slow-drying solvent is contained in an amount of 2 to 10% by weight based on the total solvent. 2. A transfer layer-forming ink or coating composition according to claim 1 is used to coat the composition onto a releasable substrate.
A method for producing a transfer sheet, which comprises forming the transfer layer by drying at a temperature of less than ° C. 3. A transfer sheet in which a transfer layer is formed by applying a composition of ink or paint on the surface of a releasable substrate and drying the composition, wherein the composition of ink or paint is at least a binder resin and a colorant. And an organic solvent, wherein the organic solvent is a fast-drying solvent having an evaporation rate of 4 times or more that of n-butyl acetate, and a volatile slow-drying solvent having an evaporation rate of 1 time or more and less than 4 times that of n-butyl acetate. It is a mixed solvent of three kinds with a residual slow-drying solvent having a rate of 0.8 times or less that of n-butyl acetate and a boiling point of 115 ° C. or higher, and the residual slow-drying solvent is 2 to 3 in all the solvents.
10% by weight, which is 1 after applying the coating material to a peelable substrate.
A transfer sheet comprising a transfer layer formed by drying at a temperature lower than 15 ° C.