WO2013099833A1 - Activating agent composition for water pressure transfer printing, water pressure transfer printing method and article printed by water pressure transfer - Google Patents

Abstract

A solvent-based activating agent composition (60) which is to be applied to a printing pattern layer (40) on a transfer film (20) for water pressure transfer printing in order to activate the printing pattern layer (40) and which comprises a resin component, a solvent component and a plasticizer component, characterized in that the plasticizer component is at least one selected from among benzoic ester based plasticizers and phosphoric ester based plasticizers. This composition can avoid the use of dibutyl phthalate, which is a substance of very high concern for environment load, and ensures excellent plasticization of a resin component, good throwing power of a transfer film to a substrate article, excellent adhesion of a printing pattern layer to a substrate, and reduction in the bleeding of a plasticizer from the surface of an article printed by water pressure transfer, thus enabling good water pressure transfer printing.

Description

Hydraulic transfer activator composition, hydraulic transfer method and hydraulic transfer product

The present invention relates to an activator composition that is applied to a dry printed pattern layer on a transfer film for hydraulic transfer to activate the printed pattern layer and restore its adhesion. The present invention relates to a solvent-based activator composition for activating ink with a solvent component, a method for hydraulic transfer using this activator composition, and a hydraulic transfer product produced by this method.

In general, a solvent-based activator composition includes a resin component, a solvent component, and a plasticizer component. Some examples of prior art activator compositions are disclosed in Patent Documents 1 and 2 (Japanese Patent No. 3366149 and Japanese Patent No. 3385576). In these conventional technologies, the resin component is composed of a short oily alkyd resin and cellulose acetobutyrate (CAB), and ensures initial adhesion of the printed pattern layer to the base material (transfer article). Prevents ink diffusion, and the solvent component is made of butyl cellosolve and butyl carbitol acetate, which ensures the adhesiveness of the ink until the printing pattern transfer is completed by dissolving the ink in the printing pattern layer. Is made of dibutyl phthalate (DBP) and imparts plasticity to the resin component of the ink to ensure the extensibility of the printed pattern layer during transfer. Note that the activator composition of Patent Document 2 contains ultrafine silica, but this component is activated ink in the same manner as extender pigments added to other prior art activator compositions. In order to prevent dust from adhering to the ink, it is added for the purpose of maintaining the extensibility of the ink while increasing the viscosity of the ink to make the ink surface apparently dry and imparting thixotropy to the ink to prevent ink misalignment. ing.

As described above, the plasticizer of the activator composition disclosed in Patent Documents 1 and 2 is composed of dibutyl phthalate (dibutyl phthalate), and this component is composed of other prior art activator compositions. However, it is used similarly (see Patent Documents 3 to 5). However, dibutyl phthalate has been designated as a highly environmentally hazardous substance (SVHC) as stipulated in the EU Reach Act (REACH). There is a possibility that the use is restricted in the country, and it is desirable to avoid the use of dibutyl phthalate as a plasticizer.

On the other hand, the plasticizer for the activator composition is (1) excellent in plasticization of the resin, and (2) the transfer film in which the ink is activated during the hydraulic transfer is excellently attached to the substrate to be transferred. (3) The adhesion of the printed pattern layer to the substrate is excellent, and (4) The plasticizer is difficult to bleed from the surface of the hydraulic transfer product after transfer. , At least four requirements are required.

Patent Document 3 exemplifies several components other than dibutyl phthalate as a plasticizer, but none of these components can satisfy the above four conditions. The fact that these components do not satisfy the above conditions can be understood later by referring to the comparative examples described in contrast with the examples of the present invention.

Japanese Patent No. 3366149 Japanese Patent No. 3385576 Japanese Patent No. 3399700 JP 2008-247007 A JP 2010-83048 A

A first problem to be solved by the present invention is to provide an activator composition for hydraulic transfer containing a plasticizer that can satisfy the requirements of the plasticizer and can avoid the concern of environmental impact. It is in.

A second problem to be solved by the present invention is an article using a hydraulic transfer activator composition containing a plasticizer that can satisfy the requirements of the plasticizer and can avoid the concern of environmental impact. An object of the present invention is to provide a method for hydraulically transferring a printed pattern layer thereon.

A third problem to be solved by the present invention is to use a hydrostatic transfer activator composition containing a plasticizer that can satisfy the requirements of the plasticizer and avoid the concern of environmental impact. An object of the present invention is to provide a hydraulic transfer product having a decorative layer obtained by a transferred printed pattern layer.

Means for solving the first problem of the present invention is for activating the print pattern layer by applying it to a print pattern layer of a transfer film for hydraulic transfer, comprising a resin component, a solvent component, and a plasticizer component. The activator composition for water pressure transfer, wherein the plasticizer component is selected from at least one of a benzoate plasticizer and a phosphate ester plasticizer To provide things.

In the first problem-solving means of the present invention, the molecular weight of the plasticizer is preferably 300 or more. When the resin is based on a short oil alkyd resin, the SP value of the plasticizer is It is preferably 9.4 [(cal / cm ³ ) ^1/2 ] or more, and the addition amount of the plasticizer is preferably 0.9 to 4.0 in terms of the weight ratio to the resin.

In the first problem-solving means of the present invention, the solvent component is preferably a hydrophobic solvent, and the hydrophobic solvent preferably comprises at least an acetate ester solvent and a cyclic ketone solvent. . In this case, the blending ratio (weight ratio) of the cyclic ketone solvent to the acetate solvent is preferably 0.06 to 1. Specifically, the acetate solvent is preferably butyl carbitol acetate, and the cyclic ketone solvent is preferably cyclohexanone.

In the first problem solving means of the present invention, when the solvent component is a hydrophobic solvent, it is more desirable that the solvent component further contains hydrophobic silica.

The second problem solving means of the present invention is to provide a method of hydraulically transferring a print pattern layer of a transfer film for hydraulic transfer onto an article using the activator composition according to the first problem solving means.

The third problem solving means of the present invention is to provide a hydraulic transfer product having a decorative layer obtained by hydraulically transferring a print pattern layer of a transfer film for hydraulic transfer by the second problem solving means.

According to the present invention, the plasticizer of the activator composition is selected from at least one of a benzoate plasticizer and a phosphate ester plasticizer, so that the use is prohibited in the future. The use of dibutyl phthalate, a material of high environmental concern that may be avoided, can be avoided.

In addition, when the plasticizer is composed of a benzoate plasticizer or a phosphate ester plasticizer, (1) excellent plasticization of the resin, and (2) transfer in which the ink is activated during hydraulic transfer. The film adheres to the substrate to be transferred with good throwing power, (3) the adhesion of the printed pattern layer to the substrate is excellent, and (4) the plasticizer is a hydraulic transfer product after transfer. The four minimum requirements of being difficult to bleed from the surface can be satisfied, and an excellent activator composition can be provided.

It is the schematic of the method of carrying out the hydraulic transfer of the printing pattern layer of a transfer film on articles | goods using the activator composition of this invention. It is drawing which shows each process of the method of FIG. 1 typically. It is an expanded sectional view of the articles | goods which have a decoration layer obtained by the method of FIG.

An embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 schematically shows a hydraulic transfer method in which the activator composition for hydraulic transfer of the present invention is used. The transfer film 20 composed of the water-soluble film (carrier film) 30 provided with the pattern layer 40 should be supplied and floated on the water 50 in the transfer tank with the print pattern layer 40 on the upper surface, and should be hydraulically transferred. In this method, the article 10 is pressed into the water 50 through the transfer film 20 and is hydraulically transferred.

The water-soluble film 30 is made of a water-soluble material mainly composed of, for example, polyvinyl alcohol that absorbs water and gets wet and softens. The water-soluble film 30 touches the water 50 in the transfer tank at the time of water pressure transfer, and is attached to the article to be decorated so that water pressure transfer can be performed. In the case of general hydraulic transfer, the printing pattern layer 40 is previously applied on the water-soluble film 30 by appropriate printing means such as gravure printing or flexographic printing, and the transfer film is rolled up or the like. In order to store it, it is in a dry solidified state in which adhesion is completely lost before the hydraulic transfer. The printed pattern layer 40 includes a plain (non-patterned) printed layer in addition to a pattern in a strict sense.

The specific steps of this hydraulic transfer method are shown in FIG. 2, which is a solvent-based activator applied to the print pattern layer 40 of the transfer film 20 before hydraulic transfer to the article 10 (see FIG. 2A). The composition 60 is applied (see FIG. 2B), and the adhesiveness of the printed pattern layer 40 is recovered (reproduced) by the solvent content in the activator composition. The transfer film 20 having the printed pattern layer 40 whose adhesion has been restored by the activator composition 60 is hydraulically transferred to the article 10 (see FIGS. 2C and 2D). Thereafter, as shown in FIG. 2E, the article 10 is washed with water by a shower 70 or the like, and a water-soluble film (swelling dissolved film layer) covering the upper surface of the printed pattern layer 40 (decorative layer 42) transferred to the article 10. 2), and the surface is dried with hot air 80 to transfer the printed pattern layer 40 to the surface of the article 10 to form a decorative layer 42 (see FIG. 3). In order to protect the decorative layer 42, a clear top coat is further applied as necessary to complete the decorated article 12. As the top coat, for example, a transparent ultraviolet curable paint is used.

The activator composition 60 used in the present invention is a solvent-based composition containing a resin component, a solvent component, and a plasticizer component as essential components, and this composition may further contain fine-particle silica.

The resin component is for ensuring the initial adhesion of the printed pattern layer 40 to the base material of the ink (the article to be transferred) and preventing the ink from spreading. For example, (1) flaxseed oil, soybean oil, Various fats and oils such as synthetic drying oil, (2) natural resin such as rosin, hardened rosin, rosin ester, polymerized rosin, (3) phenol resin, rosin modified phenolic resin, maleic acid resin, alkyd resin, petroleum resin, vinyl Resin, acrylic resin, polyamide resin, epoxy resin, amino alkyd resin, synthetic resin such as fluororesin, (4) nitrocellulose, cellulose acetate butyrate resin, fiber derivative such as ethyl cellulose, (5) chlorinated rubber , Rubber derivatives such as cyclized rubber, (6) other resin components such as casein, dextrin and zein (Patent Documents) It can be any one or more combinations of reference). Of these, short oil alkyd resins are preferred, and it is more preferred to combine this with cellulose acetobutyrate (CAB), for the reason described in Patent Document 1 (see paragraph 0025).

The solvent content is to secure the adhesiveness of the ink until the ink of the print pattern layer 40 is dissolved and the transfer of the print pattern layer is completed, and is appropriate for the solvent-based activator composition used in the past. In order to supplement the improvement of the adhesion of the transfer film to the article and the adhesion of the article to the article during transfer, among the four requirements described later in relation to the plasticizer, A hydrophobic solvent is preferred. A hydrophobic solvent is a preferred solvent because it has an additional effect of reducing poor water marks in addition to improving the adhesion and adhesion of the transfer film to the article. Hydrophobic solvents include esters (eg, methyl acetate, ethyl acetate, n-butyl acetate), ethers (eg, diethyl ether, butyl ether), non-aromatic hydrocarbons (eg, n-hexane, cyclohexane), Known solvents such as aromatic hydrocarbons (for example, toluene) and cyclic ketones can be used. Specifically, at least an acetate solvent is preferable, but it is more preferable that the solvent is an acetate solvent and a cyclic ketone solvent. In this case, the desirable blending ratio (weight ratio) of the cyclic ketone solvent to the acetate solvent is 0.06 to 1. In addition, you may use the mixture of hydrophilic solvent and hydrophobic solvent like butyl cellosolve conventionally used.

A preferred hydrophobic solvent is an acetic ester solvent commonly used in conventional solvent activators, particularly butyl carbitol acetate (BCA), but has a solubility (SP) close to the SP value (solubility parameter) of the substrate of the article. More preferably, a hydrophobic solvent having a value) is further combined. Hydrophobic solvents preferably combined with butyl carbitol acetate (BCA) are generally cyclic ketones, but when the substrate of the article is ABS resin or polycarbonate (PC), cyclohexanone or cyclopenta Non is preferred. When cellulose acetobutyrate, which is relatively incompatible with butyl carbitol acetate, is contained in the resin component of the activator, the cyclic ketone is cyclohexanone or cyclopentanone, which easily dissolves cellulose acetobutyrate. Preferably there is.

As described above, when the hydrophobic solvent is composed of an acetate solvent and a cyclic ketone, the preferred weight ratio of the cyclic ketone to the acetate solvent (cyclic ketone / acetate solvent) is 0.06 to The reason for this is that when the weight ratio of the cyclic ketone to the acetate solvent exceeds 1, the solubility of the solvent in the ink resin component is lower than in the case of the weight ratio. When the ratio is less than 0.06, the solvent is more likely to volatilize after the activator is applied to the print pattern layer of the transfer film and re-dissolved, compared to the case within the above weight ratio range. Since the redissolved state cannot be maintained until the time of hydraulic transfer, it may be difficult to stably perform the hydraulic transfer, and the attack (solubility) of the printed pattern layer on the surface of the transferred substrate is large. It is in some cases cause a design failure of the transfer article too.

A preferable blending ratio of the resin component and the solvent component is 4 to 15% by weight of the resin component with respect to the total of the resin component and the solvent component (in other words, the weight ratio of the resin component and the solvent component is 1:24 to 1). The reason is that if the resin component is less than 4% by weight, the adhesiveness between the transfer layer (printed pattern layer) and the substrate is poor, or the ink retainability is deteriorated or the pattern is not deformed. Such problems are likely to occur, and if it exceeds 15% by weight, the coatability of the activator and the ink solubility are lowered, making it difficult to perform good ink activation.

The plasticizer component is for imparting plasticity to the resin component of the ink to ensure the extensibility of the printed pattern layer during transfer, but the plasticizer used in the present invention is high in environmental load in the reach method. In order to avoid the use of dibutyl phthalate (DBP), which is used in the prior art, which is regarded as a substance of concern, and to satisfy the following four requirements, benzoate plasticizers and phosphate ester plastics It consists of a component selected from at least one of the agents.
(1) Excellent plasticization of the resin content.
(2) At the time of hydraulic transfer, the transfer film on which the ink has been activated adheres to the substrate to be transferred with good throwing power.
(3) The adhesiveness of the printed pattern layer to the substrate is excellent.
(4) It is difficult for the plasticizer to bleed from the surface of the hydraulic transfer product after transfer.

The benzoate ester plasticizer that can be used in the present invention is a dibasic acid-glycol polyester or dialkylene glycol benzoate diester whose ends are sealed with benzoic acid. Examples thereof include dipropylene glycol. There are benzoate, N-butyl benzoate, 2,2,4-trimethyl-1,3-pentanediol isobutyrate benzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate.

Examples of the phosphate ester plasticizer that can be used in the present invention include tricresyl phosphate (TCP), trioctyl phosphate (TOP), trixylenyl phosphate (TXP), monooctyl diphenyl phosphate, monobutyl. -Dixylenyl phosphate (BZX), tributyl phosphate.

The plasticizer used in the present invention can easily satisfy the conditions (1) to (3) (plasticity, throwing power and adhesion) among the above four necessary conditions. When the resin component is based on a short oil alkyd resin, it preferably has an SP value of 9.4 [cal / cm ³ ) ^1/2 ] or more. If the SP value of the plasticizer is less than 9.4, it is not preferable because at least one of the conditions (1) to (3) is not satisfactory, but the basis for this is related to the description of the following examples. State.

The “SP value” of the plasticizer used in the present invention, the aforementioned base material, and the solvent is an abbreviation of a solubility parameter (Solubility parameter), which is defined as the square root of cohesive energy density. This is a parameter proposed by Hildebrand and Scott based on a regular solution in which entropy change due to mixing is almost zero and enthalpy change occurs. “Agglomeration energy density” means the ratio between the energy required to vaporize a molecule and the molecular volume of the molecule, and the SP value approaches the solvent and solute with similar chemical structures, and the heat of solution is It is easy to melt because it is small, and this is consistent with the rule of thumb that "similar things melt well with each other" and is used as the most familiar parameter for dissolution. In general, the SP value of the “solvent” is obtained from the heat of evaporation, and the SP value of the “polymer” is obtained by measuring the viscosity or the degree of swelling or by reverse gas chromatography, and when the SP value is unknown. As estimation methods, there are a method using the Hildebrand rule and an empirically derived relationship with the surface tension, and a Fedors method using the cohesive energy constant of the atomic group based on the structural formula.
That is, the basic formula of the SP value (δ) is δ = (ΔE / V) ^1/2 [cal / cm ³ ) ^1/2 ]
(In the above formula, ΔE: molecular cohesive energy (cal / mol), V: molecular volume (ml / mol))
However, the SP value used in the present invention is based on the small calculation method (J. Applied Chem. Vol. 3, page 71 (1953)).

In addition, the plasticizer used in the present invention has a molecular weight of 300 or more so that the condition (4) (low bleed property) among the above four necessary conditions can be easily satisfied. It is preferable to have. If the molecular weight of the plasticizer is less than 300, the bleed reduction effect is not sufficient and is not preferable. The reason for this will be described later in connection with the description of Examples. However, if the molecular weight is too large, the viscosity of the plasticizer becomes large and the viscosity of the entire active agent becomes high, or the plasticizing performance of the resin is lowered. However, the upper limit of the molecular weight of the plasticizer is preferably 700, more preferably 600 from the balance with the bleed reducing effect. In addition, the molecular weight in this invention is a number average molecular weight.

When a component having a hydroxyl group (OH group) such as benzoate-based dipropylene glycol benzoate is used as a plasticizer, reactivity such as isocyanate in the topcoat agent applied on the decorative layer formed by hydraulic transfer Since the bleed can be reduced by reacting with the component, a plasticizer component having a hydroxyl group is more preferable from the viewpoint of the condition (4). In this case, the preferred hydroxyl value in the plasticizer is 15 to 16 mg KOH / g.

The phosphoric ester plasticizer is a preferable component because it satisfies the requirements (1) to (4) and adds flame retardancy to the printed pattern layer 40 (decoration layer 42 after transfer).

A preferable blending amount of the plasticizer is in a range of 0.9 to 4.0, more preferably 1.4 to 3.0, most preferably in a weight ratio to the resin content (plasticizer weight / resin weight). Is 1.6 to 2.5. If this blending amount is less than 0.9, sufficient plasticity may not be imparted to the ink resin component necessary for good ink activation, and if the blending amount exceeds 4.0, the plasticizer Is not preferable because it tends to bleed or a sticky feeling (tackiness) tends to occur on the decorative surface of the transferred product.

The fine particle silica, which is further added to the essential component of the activator composition, increases the viscosity of the ink to prevent the dust from adhering to the activated ink to make the ink surface apparently dry and thixo the ink. It has the function of maintaining the extensibility of ink while preventing ink misalignment by imparting properties, but in the same manner as hydrophobic solvents, hydrophobic fine particles are used for the purpose of supplementing the adhesion and adhesion of transfer films to articles. Silica is preferred.

Examples of such hydrophobic fine particle silica include fumed silica represented by AEROSIL (registered trademark) of Nippon Aerosil Co., Ltd., REOLOSIL (registered trademark) of Tokuyama Corporation, and CAB-O-SIL (registered trademark) of CABOT. Of these, those having a primary particle size (particle size of a single particle) of 0.005 to 0.1 μm are preferably used. In addition, the numerical value of the primary particle diameter of the fine particle silica is the longest diameter of the contour of each of the primary particle images of 1000 fine particle silica randomly selected from an image having a magnification at which the primary particles can be visually recognized by SEM or TEM (transmission electron microscope). Is a numerical value obtained by measuring and arithmetically averaging.

In the activator composition of the present invention, known additives such as extender pigments, leveling agents and matting agents may be added as long as the effects of the present invention are not impaired.

(Examples 1 to 24 and Comparative Examples 1 to 12)
Hereinafter, specific Examples 1 to 24 (Tables 1 to 4) of the present invention will be described in comparison with Comparative Examples 1 to 12 (Tables 5 and 6). In each of the examples and comparative examples, hydraulic transfer was performed by the process of FIG. 2 except that the activator composition was different. In both Examples and Comparative Examples, a 25 ± 5 μm urethane-based UV curable transparent top coat (PG2455A-N7 clear manufactured by Fujikura Kasei Co., Ltd.) was applied to the surface of the hydraulic transfer surface (decorative layer) in a separate process. .

The transfer films, activators, and transferred materials used in Examples and Comparative Examples were as follows.
(1) Transfer film
A hydraulic transfer film called “G5100 Trust Walnut 4C” supplied by the applicant to the licensee was used. In addition, this transfer film has a print pattern layer with a wood grain pattern (solvent component is volatilized and removed) by gravure printing using a solvent-based ink composed of a mixture of a pigment and a synthetic resin on the transfer surface side of the PVA film. ) Is formed.
(2) Activators and coating conditions The activators used in the examples and comparative examples of the present invention are the plasticizers in Table 7, the resin components in Table 8, solvent components, and fine particle silica. Each was formulated with the composition shown in Tables 1-6. The activator was applied to the transfer film of (1) to a thickness of 10 μm by the Miyabar method.
(3) Transfer object As an article to be transferred, a 100 mm × 200 mm × 3 mm ABS resin flat plate (TM20 manufactured by UMG ABS Co., Ltd.) and a 100 mm × 200 mm × 3 mm PC / ABS resin flat plate ( The quality which changes with these flat plates was used for the evaluation result using both TECHNOPOLYMER CK50).

(Plasticizer list)

(Other ingredients list)

Each evaluation method in the results of “Evaluation” in Tables 1 to 6 is as follows.

(Adhesion)
About the water pressure transfer product obtained for each example and comparative example, using a cello tape (registered trademark) (manufactured by Nichiban Co., Ltd.), the test piece was peeled off by a cross cut test (according to the former JIS K5400-8.5). The adhesion was evaluated by observation. “A” indicates that there is no peeling of the printed pattern layer (surface decoration layer) on both the ABS flat plate and the PC / ABS flat plate, and “△” indicates that only the PC / ABS resin flat plate is peeled off. The case where the resin flat plate was peeled off was designated as “x”. Since the ABS flat plate has better adhesion than the PC / ABS flat plate, the ABS flat plate was peeled off and the PC / ABS flat plate was not peeled off.

(Catchability: cylindrical test)
The cylindrical test is a test in which the printed pattern layer of the transfer film is hydraulically transferred to the surface of a cylindrical test piece along its axial direction to perform curved surface printing, and the ink coverage on the surface of the test piece is confirmed. . In this test, since the transfer object is cylindrical, the pattern is deformed by a considerable deformation stress at the time of transfer, and the degree and scale of the deformation stress change according to the characteristics of the ink. The ink characteristics can be determined from the change in the number of inks (the ink coverage). The test piece is a cylindrical body made of thick paper (outer diameter) 30 mm × length 200 mm (“Tochiman First Kent Paper F160” Tochiman is a registered trademark) so that the central axis of the cylinder and the transfer liquid surface are substantially orthogonal to each other. A transfer film that has a printed pattern layer that has been coated with an activator and has recovered adhesion, and is floated on the surface of the water, and is immersed in water at a speed of 1.5 m / min from one end of the cylinder. When the pattern is transferred to the surface, the transfer start position is set to 0 mm, and the pattern is completely transferred over the entire length of 200 mm in the longitudinal direction of the cylinder, “◎”, the pattern collapses in the range of 150-200 mm “◯” when transferred, “Δ” when transferred with a pattern collapsed in the range of 100-200 mm, and “X” when transferred with a pattern already broken up to 100 mm after the start of transfer. In this case, since the cylindrical body is submerged in the water while wrapping the activated transfer film floating on the liquid surface, water pressure is applied to the transfer film (side surface of the cylindrical body) collected from the time of immersion. The pattern is transferred to the side surface of the cylindrical body.

(Poor water marks)
A hydraulic transfer product transferred using a transfer film of “J1502 Metallic Line Silver 2C”, which is easy to observe water mark defects, instead of “G5100 Trust Walnut 4C” (see paragraph 0047 (1)) used in other tests. Appearance “△” when traces of water adhering during film removal are visible, “◯” when visible but less visible than conventional active agents, “○”, no trace of moisture visible In this case, “◎” was used. The transfer film “J1502 Metallic Line Silver 2C” used in this test was used in other tests except that the printed pattern layer had a pattern in which silver thin lines were drawn in parallel with a very narrow interval. It had the same structure as the transfer film of “G5100 Trust Walnut 4C”.

(Bleedability: fogging test)
A test piece of 100 mm × 50 mm × 0.012 mm aluminum film (cooking foil manufactured by Toyo Aluminum Echo Products Co., Ltd.) was used instead of the ABS resin flat plate or the PC / ABS resin flat plate used in other tests. Use the above-mentioned glass fogging test equipment (equipment for fixing a bleed-out component to a dedicated glass plate by placing the test piece in a beaker, covering it with a special glass plate, and heating). A test piece formed by subjecting an aluminum film transfer body to water pressure transfer and top coat processing was set and treated at a heating temperature of 80 ° C. for a heating time of 20 hours. Measure the haze value (degree of haze) of an exclusive glass plate to which the bleed-out component has been fixed by this treatment using an integrating sphere light transmittance measuring device (direct reading haze computer manufactured by Suga Test Instruments Co., Ltd.) defined in JIS-K7105. did. The evaluation in this test is as follows. In each example and comparative example, the haze value is measured by the above method for each of the three test pieces, and when all three haze values are 10 or less, three haze values are obtained. The case where the average of the haze values was 10 or less but there were those having an individual haze value of 10 or more was marked as Δ, and the case where the average of the three haze values exceeded 10 was marked as x. The bleed test was performed when the adhesion was other than x.

(Evaluation results)
The evaluation of Examples and Comparative Examples is as described in the “Evaluation” column of Tables 1 to 6. The following can be understood from these evaluation results.
(1) In Examples 1 to 24 of the present invention in which the plasticizer is a benzoic acid (poly) ester or phosphoric acid (poly) ester, Comparative Example 6 in which the plasticizer is conventional DMP (dimethyl phthalate) , 12 close adhesion and throwing power can be realized. On the other hand, Comparative Examples 1 to 5 and Comparative Examples 7 to 11 using other plasticizers known in the art other than DMP show the adhesion and throwing power of Comparative Examples 6 and 12 using DMP as a plasticizer. Since it cannot be realized, it is understood that the benzoic acid (poly) ester type or phosphoric acid (poly) ester type, which is the plasticizer of the examples of the present invention, is extremely effective.
(2) Among Examples 1 to 24, Examples 4 and 8 in which the plasticizer has a molecular weight of less than 300 tend to have a lower bleed evaluation than other examples having a molecular weight of 300 or more. It can be seen that is preferably 300 or more.
(3) Among Examples 1 to 24, Examples 4 and 8 using an activator containing a plasticizer having an SP value of less than 9.4 [(cal / cm ³ ) ^1/2 ] have low adhesion. Therefore, when the short oil alkyd resin is used as the resin component, the SP value of the benzoic acid (poly) ester or phosphoric acid (poly) ester plasticizer is 9.4 [(cal / cm ³ ) ^{1 / 2} ] or more is preferable.
(4) When Examples 5 and 13 to 18 and Examples 19 and 20 having the same conditions other than the addition ratio of the plasticizer are compared with Examples 19 and 20, in order to achieve both good adhesion and bleed resistance. It can be seen that the weight ratio of the plasticizer to the resin component is preferably 0.9 to 4.0. The evaluations of the bleed tests of Examples 14 to 18 are all “◯”, but actually, even with the same “◯”, the amount of bleed increases as the amount of added plasticizer increases (haze value). (This is not listed in Table 3). From the viewpoint of the amount of bleed, the upper limit of the “more preferable” addition ratio of the plasticizer is 3.0, and as is clear from comparison between Examples 13 and 14, from the viewpoint of throwing power, The lower limit of the more preferable addition ratio of the plasticizer is 1.4. Therefore, from the viewpoint of both the freed and the throwing power, the addition ratio of the plasticizer is 1.4 to 3. A value of 0 was more preferred, and a range of 1.6 to 2.5 was most preferred.
(5) When comparing Examples 1 and 5, Examples 2 and 6, Examples 3 and 7, and Examples 4 and 8, when the other conditions were the same except for the solvent, Example 1-4 It can be seen that the use of cyclohexanone, which is the hydrophobic solvent of Example 5-8, in place of butyl cellosolve, which is the hydrophilic solvent, improves the throwing power and is effective in reducing water marks.
(6) Example 5 and Examples 21 to 24 are examples in which only the weight ratio of the cyclic ketone to the acetate solvent is changed in the blending of the hydrophobic solvent consisting of the acetate solvent and the cyclic ketone. The weight ratio of the cyclic ketone to the acetate solvent is 0.13 in Example 5, 0.03 in Example 21, 0.06 in Example 22, 1 in Example 23, and 1 in Example 24. .5. In these examples, when the weight ratio of the cyclic ketone to the acetic acid ester solvent is correlated with the evaluation results of the examples, Examples 21 and 24 are more tangled than Examples 5, 22, and 23. The weight ratio of the cyclic ketone to the acetate solvent is preferably 0.06 to 1 when the hydrophobic solvent is composed of the acetate solvent and the cyclic ketone. Recognize.
(7) When Examples 5 and 9 and Examples 7 and 10 are compared, and the other conditions are the same except for the type of fine particle silica, each of Examples 5 and 7 is more effective than the hydrophilic silica of Examples 9 and 10. It can be seen that the use of hydrophobic silica improves the throwing power and is more effective in reducing poor water marks.
(8) Although not described in “Evaluation” in Tables 1 to 3, when Examples 5 and 7 are compared with Examples 11 and 12 to which silica is not added, Examples in which fine particle silica is added are compared. In the case of 5 and 7, the design of the decorative layer of the transfer product compared to Examples 11 and 12 in which the fine particle silica is not added due to the function of the fine particle silica that maintains the extensibility of the ink while preventing ink misalignment. Was clearer than when the activator was used.

The activator composition for hydraulic transfer of the present invention contains a plasticizer selected from at least one of a benzoate plasticizer and a phosphate ester plasticizer, so that it is prohibited to use in the future. Can avoid the use of dibutyl phthalate, which is a highly concerned substance in the environmental load that may be regulated as well as excellent plasticization of the resin content and good circulation of the transfer film to the article substrate High pressure transfer, ensuring good adhesion to the substrate of the printed pattern layer and reducing the bleed of plasticizer from the surface of the hydraulic transfer product. Has the above utility.

10 Article 20 Transfer film 30 Water-soluble film (carrier film)
40 Print pattern layer 50 Water 60 Solvent-based activator composition 70 Shower 80 Hot air

Claims (11)

1. In the activator composition for water pressure transfer, which is for applying to the print pattern layer of the transfer film for water pressure transfer and activating the print pattern layer, comprising a resin component, a solvent component and a plasticizer component, The activator composition for hydraulic transfer, wherein the plasticizer component is selected from at least one of a benzoate plasticizer and a phosphate ester plasticizer.
2. 2. The hydraulic transfer activator composition according to claim 1, wherein the plasticizer has a molecular weight of 300 or more.
3. The activator composition for hydraulic transfer according to claim 1 or 2, wherein when the resin component is a short oil alkyd resin base, the SP value of the plasticizer component is 9.4 [(cal / cm ³ ) A hydraulic transfer activator composition, characterized in that it is ^1/2 ] or more.
4. The activator composition for hydraulic transfer according to any one of claims 1 to 3, wherein the plasticizer component is added in a weight ratio of 0.9 to 4.0 with respect to the resin component. An activator composition for hydraulic transfer.
5. 5. The hydraulic transfer activator composition according to claim 1, wherein the solvent component is a hydrophobic solvent.
6. 6. The hydraulic transfer activator composition according to claim 5, wherein the hydrophobic solvent comprises at least an acetate solvent and a cyclic ketone solvent. .
7. 7. The hydraulic transfer activator composition according to claim 6, wherein a mixing ratio (weight ratio) of the cyclic ketone solvent to the acetate solvent is 0.06 to 1. Activator composition.
8. The hydraulic transfer activator composition according to claim 6 or 7, wherein the acetate solvent is butyl carbitol acetate and the cyclic ketone solvent is cyclohexanone. Activator composition.
9. The hydraulic transfer activator composition according to any one of claims 5 to 8, further comprising hydrophobic silica.
10. A hydraulic pressure characterized in that the activator composition according to any one of claims 1 to 9 activates a print pattern layer of a transfer film for hydraulic transfer, and then hydraulically transfers the print pattern layer of the transfer film onto an article. Transcription method.
11. A hydraulic transfer product comprising a decorative layer obtained by hydraulic transfer of a printing pattern layer of a transfer film for hydraulic transfer by the method according to claim 10.

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