CN110099799B - Resin composition for transfer paper protective layer, its production method, laminate, and decorative transfer paper - Google Patents

Abstract

The resin composition for a protective layer of transfer paper of the present invention is a resin composition for a protective layer of transfer paper comprising an acrylic polymer (A), a solvent (B), a defoaming agent (C), and a plasticizer (D), wherein the acrylic polymer (A) contains at least 50 mass% of monomer units derived from alkyl (meth) acrylate having 3 to 12 carbon atoms and derived from alkyl groups, based on the total of all the monomer units; the solvent (B) contains 70% by mass or more of a component having a kinematic viscosity of 1.5mm as measured at 25 ℃ according to ASTM D445²At least 1 solvent (B1) selected from the naphthenic solvents and the isoparaffinic solvents with a concentration of 2 mass% or less.

Description

Resin composition for transfer paper protective layer, its production method, laminate, and decoration transfer paper

technical field

The present invention relates to a resin composition for a transfer paper protective layer, a method for producing the same, a laminate, and a decorative transfer paper.

This application claims priority based on Japanese Patent Application No. 2017-007245 for which it applied in Japan on January 19, 2017, and the content is incorporated herein by reference.

Background technique

For decoration on plastics, wood, metal, ceramics, glass, enamel, ceramic tiles, other ceramics, etc. (hereinafter also referred to as "ceramic ware, etc."), the use of laminated backing paper, water-soluble ceramics, etc., has been widely used for a long time. A single-paper transfer method of a decorative transfer paper for a paste layer, a printing ink layer printed in a desired pattern, and a protective layer. In this method, first, the transfer paper is immersed in water or warm water, the protective layer with the printing ink layer is peeled off from the base paper, the transfer paper is pasted on a predetermined position such as a ceramic, and the printing ink layer is removed. on the inside. Next, moisture, air bubbles, and the like between the ceramics or the like and the protective layer are removed and dried. Finally, the protective layer can be removed by firing or peeling, and the printing ink layer can be transferred to the surface of ceramics or the like, whereby decoration can be performed.

Examples of resins contained in the resin composition for protective layers used in the production of decorative transfer paper include resins such as acrylic resins, vinyl acetate resins, alkyd resins, polyester resins, and cellulose-based resins. . Among them, acrylic resins are particularly suitably used. Acrylic resins have a wide variety of raw material monomers and can be copolymerized in any combination, so resins having a wide range of glass transition temperatures and molecular weights can be freely obtained. Therefore, the resin composition for a protective layer containing an acrylic resin has desirable characteristics that the printability is good and the physical properties of the coating film of the formed protective layer are easily adjusted.

Patent Document 1 describes a resin composition for a protective layer in which solvent SWASOL (registered trademark) 1000, ie, solvent gasoline, is mixed. Since this resin composition has few bubbles and pits on the formed protective layer, it is also excellent in printing properties, but since the solvent contains an aromatic compound, there is a problem of strong odor.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2003-183559

SUMMARY OF THE INVENTION

The problem to be solved by the invention

An object of the present invention is to provide a resin composition for a transfer paper protective layer, a method for producing the same, a laminate, and a decorative transfer paper, the resin composition for a transfer paper protective layer being used in the production of decorative transfer paper The resin composition used to form the protective layer covering the printing ink layer has less bubbles and pits on the protective layer and less odor.

means to solve the problem

<1> A resin composition for a transfer paper protective layer, comprising an acrylic polymer (A), a solvent (B), and a plasticizer (D), the acrylic polymerized resin composition for a transfer paper protective layer The substance (A) contains 50 mass % or more of monomer units derived from alkyl (meth)acrylates having 3 to 12 carbon atoms; the solvent (B) contains 70 mass % or more of the solvent (B1) , the solvent (B1) is at least one selected from the group consisting of naphthenic solvents and isoparaffin solvents whose kinematic viscosity measured according to the method of ASTM D445 at 25°C is 1.5 mm ² /s or less, and the aromatic compound is 2 mass % or less.

<2> The resin composition for a transfer paper protective layer according to the above <1>, wherein the acrylic polymer (A) contains 50 to 90 mass % of a methyl group having 3 to 6 carbon atoms derived from an alkyl group A monomer unit of an alkyl acrylate, and 10 to 50 mass % of a monomer unit of an alkyl group-derived alkyl methacrylate having 7 to 12 carbon atoms.

<3> The resin composition for a transfer paper protective layer according to the above <1> or <2>, which further contains an antifoaming agent (C).

<4> The resin composition for a transfer paper protective layer according to the above <3>, wherein the composition contains 70 to 500 parts by mass of the solvent (B) with respect to 100 parts by mass of the acrylic polymer (A). , 0.1-15 mass parts of defoamer (C), 5-35 mass parts of plasticizer (D).

<5> The resin composition for a transfer paper protective layer according to the above-mentioned <3> or <4>, wherein the defoaming agent (C) is a polysiloxane or an acrylic compound.

<6> The resin composition for a transfer paper protective layer according to any one of the above <1> to <5>, wherein the acrylic polymer (A) has a weight average molecular weight of 50,000 to 200,000.

<7> The resin composition for a protective layer for transfer paper according to any one of the above <1> to <6>, wherein the glass transition temperature of the acrylic polymer (A) is 10° C. or higher.

<8> The resin composition for transfer paper according to any one of the above <1> to <7>, wherein the plasticizer (D) is polyester-based, benzoic-acid-based, or phthalate-based of plasticizers.

<9> A method for producing a resin composition for a transfer paper protective layer, comprising: mixing acrylic acid A polymer (A), at least one solvent (B1) selected from naphthenic solvents and isoparaffinic solvents having a kinematic viscosity of 1.5 mm ² /s or less measured in accordance with ASTM D445 at 25°C, and plasticizers agent (D).

<10> The method for producing a resin composition for a transfer paper protective layer according to the above <9>, further mixing a defoaming agent (C).

<11> A laminate comprising a base paper, a water-soluble paste layer, a printing ink layer, and the resin composition for a transfer paper protective layer according to any one of the above <1> to <8>, laminated in this order The protective layer composed of dry matter.

<12> A decorative transfer paper comprising the laminate according to the above-mentioned <11>.

Invention effect

According to the present invention, it is possible to provide a resin composition for a transfer paper protective layer with few air bubbles and pits on the protective layer and less odor, and a method for producing the same, and a decorative transfer paper having a protective layer with few air bubbles and pits. etc. stacks.

Description of drawings

1 is a schematic cross-sectional view showing one embodiment of the decorative transfer paper of the present invention.

Explanation of symbols

1 Decorative transfer paper

3 backing paper

5 Water-soluble paste layer

7 Printing ink layers

9 protective layer

Detailed ways

In the present specification and the claims, "(meth)acrylate" is a general term for acrylate and methacrylate. The so-called "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid.

(Resin composition for transfer paper protective layer)

The resin composition for transfer paper protective layers of the present invention (hereinafter also simply referred to as "resin composition") contains an acrylic polymer (A), a solvent (B), and a plasticizer (D). The solvent (B) contains 70 mass % or more of the solvent (B1) selected from naphthenic-based solvents and isomeric solvents having a kinematic viscosity of 1.5 mm ² /s or less measured in accordance with ASTM D445 at 25° C. At least one of alkane-based solvents. The solvent (B) may contain a solvent (B2) other than the solvent (B1). Moreover, the aromatic compound contained in a solvent (B) is 2 mass % or less.

A defoaming agent (C) may be contained in a resin composition.

The resin composition may also contain other additives.

<Acrylic polymer (A)>

The acrylic polymer (A) contains a monomer unit derived from a C3-C12 (meth)acrylic acid alkyl ester of an alkyl group.

Specific examples of the alkyl (meth)acrylate having 3 to 12 carbon atoms in the alkyl group include propyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid, for example. Isobutyl, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and dodecyl (meth)acrylate Alkyl esters, etc. These can be used alone or in combination. In addition, from the viewpoint of solubility in the solvent (B) described later, the alkyl (meth)acrylate is more preferably one having 4 to 8 carbon atoms in the alkyl group.

In the acrylic polymer (A), the content of the monomer unit derived from the alkyl (meth)acrylate having 3 to 12 carbon atoms in the alkyl group is 50% by mass based on the total of all the monomer units More than 90 mass % or more is preferable, and 95 mass % or more is more preferable. When content of the monomeric unit derived from the said alkyl (meth)acrylate is more than the said lower limit, the intensity|strength of a protective layer will be excellent. The upper limit of the content of the monomer unit derived from the alkyl (meth)acrylate is not particularly limited, and may be 100% by mass.

The acrylic polymer (A) preferably contains a monomer unit derived from an alkyl group-derived C3-C6 alkyl methacrylate and an alkyl group-derived C7-C12 alkyl methacrylate the monomer unit. The monomer unit of the C3-C6 alkyl methacrylate derived from an alkyl group can improve the solubility of a polymer (A) in a solvent (B1), and can make a protective layer soft. The monomer unit of the C7-C12 alkyl methacrylate derived from an alkyl group can further improve the solubility of the polymer (A) in the solvent (B1). The acrylic polymer (A) preferably contains 50 to 90 mass % of monomer units derived from alkyl methacrylates having 3 to 6 carbon atoms, and 10 to 50 mass % of alkyl-derived monomer units. A monomer unit of an alkyl methacrylate having 7 to 12 carbon atoms.

The acrylic polymer (A) may further contain monomer units derived from other monomers other than the alkyl (meth)acrylate having 3 to 12 carbon atoms in the alkyl group.

As another monomer, what is necessary is just what can be copolymerized with the C3-C12 alkyl (meth)acrylate of an alkyl group, for example, a monofunctional vinyl monomer is mentioned. Specific examples of such vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, and alkyl (meth)acrylates having 13 or more carbon atoms in the alkyl group. (meth)acrylic acid alkyl ester, (meth)acrylic acid, maleic acid, itaconic acid and crotonic acid, α,β-monoethylenically unsaturated carboxylic acid, (meth)acrylic acid-2-hydroxyethyl (meth)acrylate, hydroxyalkyl (meth)acrylate such as 2-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, diethylaminoethyl (meth)acrylate esters, amino group-containing alkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate, aromatic monovinyl monomers such as styrene and α-methylstyrene, vinyl acetate, Vinyl propionate and (meth)acrylonitrile, etc. These can be used individually by any 1 type, or can be used individually by combining several types.

As other monomers, from the viewpoint of expressing the tensile strength of the protective layer, α,β-monoethylenically unsaturated carboxylic acid and amino group-containing alkyl (meth)acrylate are preferable, and (meth)acrylic acid is more preferable. and diethylaminoethyl (meth)acrylate.

From the viewpoint of obtaining good adhesion resistance, the glass transition temperature adhesion of the acrylic polymer (A) is preferably 10°C or higher, and more preferably 20 to 70°C. The higher the glass transition temperature, the more difficult it is for the formed protective layer to exhibit adhesion, and the better the adhesion resistance becomes.

The glass transition temperature of the acrylic polymer (A) can be obtained by the Fox equation represented by the following formula (1), depending on the type and mass fraction of the monomer unit.

1/Tg=Σ(W _i /Tg _i )...(1)

In the above formula (1), Tg represents the glass transition temperature (unit is K) of the acrylic polymer (A), and Wi represents the mass of the monomer unit derived from the monomer _i constituting the acrylic polymer (A) Fraction, Tgi represents the glass transition temperature (in K) of the self-polymer of monomer _i . As the value of Tgi, the value described in POLYMERHANDBOOK Volume 1 (WILEY-INTERSCIENCE) can be used.

The weight average molecular weight of the acrylic polymer (A) is preferably 50,000 to 200,000, and more preferably 70,000 to 150,000, from the viewpoints of the film-forming properties of the resin composition and the tensile properties of the protective layer when peeled from the printing ink layer. The larger the weight average molecular weight of the acrylic polymer (A), the more excellent the tensile properties of the protective layer obtained from the resin composition. In addition, as the weight average molecular weight of the acrylic polymer (A) is smaller, the viscosity of the resin composition is sufficiently lowered, and the film-forming properties at the time of forming a protective layer by printing or the like are better. In addition, the weight average molecular weight of the acrylic polymer (A) demonstrated in this invention is a polystyrene conversion value measured by GPC-LS method (Gel Permeation Chromatography-Light Scattering Method: GPC-light scattering method).

The acrylic polymer (A) can be produced by a known polymerization method such as suspension polymerization, solution polymerization, bulk polymerization, or emulsion polymerization. Among these methods, it is preferable from the viewpoints that the molecular weight of the acrylic polymer (A) to be obtained can be easily increased, the degree of freedom in selecting a solvent for the resin composition is increased, and the resin composition can be made into a high solid fraction or solvent-free. Suspension polymerization of the acrylic polymer (A) can be obtained as solid-type particles.

<Solvent (B)>

^The solvent (B) contains 70 mass % or more of a solvent ( B1). The solvent (B1) can improve the film-forming properties of the resin composition compared to a naphthenic solvent and/or an isoparaffin-based solvent having a kinematic viscosity exceeding 1.5 mm ² /s.

Examples of the solvent (B1) include ethane, heptane, and naphthenic solvents such as EXXSOL (registered trademark) DSP80/100, EXXSOL DSP100/120, EXXSOL D30, and EXXSOL D40 manufactured by Exxon Mobil Corporation, Solvents with a low aromatic content such as paraffin-based solvents such as ISOPAR (registered trademark) E and ISOPAR G manufactured by ExxonMobil Corporation. Among them, as the solvent (B1), EXXSOL D30, EXXSOL D40, and ISOPAR G are preferable from the viewpoint of the film-forming properties of the resin composition. The solvent (B1) may be used alone or in combination of two or more. The solvent (B1) may be a solvent mixed with other components such as the acrylic polymer (A), the antifoaming agent (C), the plasticizer (D), and additives.

The solvent (B) may contain a solvent (B2) other than the solvent (B1). As the solvent (B2) other than the solvent (B1), from the viewpoint of improving resin compatibility, printability, and the like, those selected from the following list may be mixed as the solvent (B). That is, examples of the solvent (B2) include aromatic solvents such as toluene, xylene, and ethylbenzene; ethyl acetate, n-butyl acetate, isobutyl acetate, n-propyl acetate, isopropyl acetate, and Acetate-based solvents such as amyl acetate; ketone-based solvents such as methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, and acetone; methanol, ethanol, isopropanol, n-propanol, n-propanol, etc. Alcohol solvents such as butanol, isobutanol, tert-butanol, benzyl alcohol, diacetone alcohol, dipropylene glycol n-propyl ether, dipropylene glycol methyl ether and propylene glycol n-propyl ether; ethylene glycol, diethylene glycol, triethyl ether Glycol-based solvents such as glycol and propylene glycol; glycol-ether-based solvents such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; acetate-based solvents such as methyl cellosolve acetate and methoxypropyl acetate Solvents; hydrocarbon solvents such as n-hexane, cycloethane, methylcycloethane, and heptane; naphthenic solvents such as EXXSOL (registered trademark) D80, EXXSOL D110, and EXXSOL D130 manufactured by ExxonMobil; Paraffin-based solvents such as ISOPAR (registered trademark) H, ISOPAR L and ISOPAR M manufactured by Exxon Mobil Corporation; SOLVESSO (registered trademark) 100, SOLVESSO 150, SOLVESSO 200 manufactured by Exxon Mobil Corporation, SWASOL ( Naphtha-based solvents such as registered trademark) 1000, SWASOL 1500, SWASOL 1800, IPZOLE (registered trademark) 100 and IPZOLE 150 manufactured by Idemitsu Kosan Co., Ltd., and the like. These solvents may be used alone or in combination of two or more. The solvent (B2) may be a solvent in which the acrylic polymer (A), the defoaming agent (C), the plasticizer (D), and other components such as additives are mixed together.

In the resin composition of the present invention, the compounding amount of the solvent (B) is preferably 70 to 500 parts by mass, more preferably 100 to 400 parts by mass, based on 100 parts by mass of the acrylic polymer (A). From a viewpoint, 150-300 mass parts is more preferable. The larger the compounding amount of the solvent (B), the smaller the bubbles in the protective layer. Moreover, as the compounding amount of the solvent (B) is smaller, the thickness of the protective layer becomes thicker, and the peeling from the base paper becomes easier.

The content of the solvent (B1) in the solvent (B) is 70% by mass or more as described above. That is, from the viewpoint of reducing the bubbles in the protective layer, the content thereof is 70% by mass or more, preferably 80% by mass or more.

Further, the content of the solvent (B2) is the residue of the solvent (B1), and is 30% by mass or less, preferably 20% by mass or less. When the solvent (B2) contains an aromatic group, the content of the solvent (B2) is preferably as small as possible from the viewpoint of odor.

Moreover, in the resin composition of this invention, a solvent (B1) and a solvent (B2) are selected so that the aromatic content contained in a solvent (B) may be 2 mass % or less. From the viewpoint of odor, the less aromatic content is, the better, and preferably 1.5% by mass or less. The aromatic content is generally determined by gas chromatography.

<Defoamer (C)>

The antifoaming agent (C) is an additive which prevents the generation of bubbles or collapses the generated bubbles. As the defoaming agent (C), for example, polyalkyldimethylsiloxane, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyether-modified polydimethylsiloxane may be mentioned. Polymethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified siloxane, and polydimethylsiloxane containing polyester-modified hydroxyl groups, etc. Silicone-based antifoaming agents using oxane as an active ingredient, non-silicone/polymer-based antifoaming agents using polymers such as acrylic compounds as active ingredients, and mineral oil-based antifoaming agents in which hydrophobic particles are dispersed in carrier oil Wait. As the antifoaming agent (C), from the viewpoint of film-forming properties, silicone-based antifoaming agents and non-silicone/polymer-based antifoaming agents are preferable, and those containing polyalkyldimethylsiloxane as an active ingredient are more preferable. Silicone-based antifoaming agent and non-silicone-polymer-based antifoaming agent containing acrylic compound as active ingredient.

In the resin composition of the present invention, the blending amount of the defoaming agent (C) is preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the acrylic polymer (A), in order to further reduce the bubbles of the protective layer and the strength of the protective layer From the viewpoint of the balance of , it is more preferably 0.3 to 5.0 parts by mass. As the blending amount of the antifoaming agent (C) increases, the number of bubbles in the protective layer decreases, so that the strength of the protective layer increases.

<Plasticizer (D)>

The plasticizer (D) is an additive having the ability to plasticize the acrylic polymer (A). As a plasticizer (D), a phthalate, a phosphoric acid ester, an adipate, and an ether type compound are mentioned, for example. Examples of the phthalate include dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate, and diisophthalate. Dialkyl phthalates such as isodecyl; alkyl benzyl phthalates such as butyl benzyl phthalate; alkyl aryl phthalates; dibenzyl phthalate Esters; diaryl phthalates, etc. Examples of the phosphoric acid ester include phosphoric acid esters such as triaryl phosphoric acid esters such as tricresyl phosphate, trialkyl phosphoric acid esters, and alkylaryl phosphoric acid esters. Examples of the adipate include aliphatic dibasic acid esters such as dibutyl adipate and dioctyl adipate. As an ether type compound, polyethylene glycol, polypropylene glycol, and dibutyl diglyceryl adipate etc. are mentioned, for example. As the plasticizer (D), other plasticizers such as benzoic acid, trimellitic acid, polyester, and soybean oil such as epoxidized soybean oil can be used. These plasticizers may not only be used alone, but two or more plasticizers may be used in combination. In addition, as the plasticizer (D), from the viewpoint of the film-forming properties of the resin composition, phthalate, adipate, benzoate, and trimellitate are preferred, and phthalate is more preferred. Dibutyl formate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dibutyl adipate, dibutyl adipate Octyl ester, trioctyl trimellitate, tris(2-ethylhexyl) trimellitate, and benzoate, particularly preferably dioctyl phthalate, diisononyl phthalate, hexamethylene phthalate Dioctyl diacid, trioctyl trimellitate and benzoate.

In the resin composition of the present invention, the blending amount of the plasticizer (D) is preferably 5 to 35 parts by mass relative to 100 parts by mass of the acrylic polymer, based on the balance between workability at the time of pattern transfer and the strength of the protective layer. From a viewpoint, 7-20 mass parts is more preferable. As the amount of the plasticizer (D) to be mixed increases, the protective layer becomes softer, so that the workability at the time of transferring a pattern to a ceramic or the like is improved. On the other hand, the smaller the compounding amount of the plasticizer (D), the higher the strength of the protective layer.

＜Other ingredients＞

In the resin composition of the present invention, in addition to the above-mentioned components (A), (B), (C) and (D), other components such as additives may be added. Examples of such additives include auxiliaries such as thixotropic agents for improving viscosity stability, flexibility, and drying properties at the time of coating by methods such as printing. Examples of the thixotropic agent include amide-based waxes such as fatty acid amide-based waxes, castor oil, and hydrogenated castor oil.

In the resin composition of this invention, 15 mass parts or less are preferable with respect to 100 mass parts of acrylic polymers (A), and, as for the compounding quantity of other components, 10 mass parts or less are more preferable. The smaller the mixing amount of other components, the tendency for the coating suitability to improve when the resin composition is coated by screen printing or the like to form a protective layer.

<Resin composition>

The solid content concentration of the resin composition of the present invention is preferably 20 to 50% by mass, and more preferably 25 to 45% by mass. The lower the solid content concentration, the lower the viscosity of the resin composition. On the other hand, the higher the solid content concentration of the resin composition, the thicker the coating film and the easier it is to stick to ceramics or the like. Here, the solid matter described in this specification refers to all components other than the solvent.

The viscosity of the resin composition of the present invention is preferably 100 to 5000 mPa·s, and more preferably 500 to 3000 mPa·s. The viscosity of the resin composition described in this specification is a value measured at 25° C. and a rotational speed of 60 rpm using a Brookfield viscometer. The lower the viscosity of the resin composition, the higher the coating suitability when the resin composition is applied by screen printing or the like to form a protective layer. On the other hand, the higher the viscosity of the resin composition, the thicker the coating film becomes, and the easier it becomes to stick the protective layer on the ceramics or the like. The viscosity of the resin composition can be mainly adjusted by the compounding amount of the solvent (B).

<Manufacturing method of resin composition>

The resin composition of the present invention can be prepared by mixing the acrylic polymer (A), a kinematic viscosity at 25° C. selected from a naphthenic-based solvent and an isoparaffin-based solvent having a kinematic viscosity of 1.5 mm ² /s or less measured in accordance with the ASTMD445 method. It is produced by at least one solvent (B1) and plasticizer (D). At this time, other components, such as an antifoamer (C) and an additive, can also be mixed as needed.

As a method for producing the resin composition of the present invention, a method is preferable in which the solvent (B1) is charged into a mixing device provided with a stirrer, a cooling pipe, and a thermometer, and the acrylic polymer (A) is added gradually while stirring, After confirming that the acrylic polymer (A) is dissolved, an antifoaming agent (C), a plasticizer (D), and other additives as necessary are added. The acrylic polymer (A), the defoaming agent (C), the plasticizer (D) or other components may be mixed with the solvent.

<Use of resin composition>

The resin composition of the present invention can be used as a material for a protective layer provided on a laminate such as decorative transfer paper. As a transfer paper for decoration, the thing which laminated|stacked a base paper, a water-soluble paste layer, a printing ink layer, and a protective layer in this order is mentioned, for example.

<Action effect>

The resin composition of the present invention contains an acrylic polymer (A), a solvent (B), and a plasticizer (D), and therefore has low odor and good film-forming properties when forming a protective layer, wherein the solvent (B) contains 70% by mass or more of at least one solvent (B1) selected from the group consisting of naphthenic solvents and isoparaffin solvents whose kinematic viscosity measured in accordance with ASTM D445 at 25°C is 1.5 mm ² /s or less, and aromatic The compound is 2 mass % or less. For example, when the resin composition is applied by printing or the like to form a coating film, bubbles and pits are less likely to be generated on the coating film. Therefore, the protective layer formed by drying it also becomes a substance with few bubbles and pits.

(Decorative transfer paper: laminate)

The laminate of the present invention will be described with reference to the accompanying drawings by taking a decorative transfer paper as an example, showing an embodiment thereof.

FIG. 1 is a schematic cross-sectional view showing one embodiment of the decorative transfer paper of the present invention.

In the decorative transfer paper 1 of the present embodiment, a base paper 3 , a water-soluble paste layer 5 , a printing ink layer 7 and a protective layer 9 are laminated in this order.

The water-soluble paste layer 5 is formed to cover the entire single side of the base paper 3 . The printing ink layer 7 is partially formed on the water-soluble paste layer 5 . The protective layer 9 is formed to cover the printing ink layer 7 . A part of the protective layer 9 is in contact with the water-soluble paste layer 5 .

As the base paper 3, a base paper (Japanese paper) etc. with good water absorption can be mentioned. As a water-soluble paste which forms the water-soluble paste layer 5, starch, polyvinyl alcohol, carboxymethyl cellulose, etc. are mentioned, for example.

As the printing ink layer 7, a thermosetting ink, a thermoplastic ink, a UV curable ink, etc. are mentioned, for example. The printing ink layer 7 is formed of a pattern transferred to a ceramic or the like. The printing ink layer 7 may be a single layer or multiple layers.

The protective layer 9 is composed of the above-mentioned dried product of the resin composition of the present invention, and contains an acrylic polymer (A) and a plasticizer (D). The protective layer 9 may contain an antifoaming agent (C) and other additives.

The decorative transfer paper 1 can be produced by, for example, forming a printing ink layer 7 using ink on a base paper 3 having a water-soluble paste applied to the entire surface to form a water-soluble paste layer 5, and applying the present invention thereon. The resin composition obtained is dried to form the protective layer 9 .

Examples of the ink include thermosetting inks, thermoplastic inks, UV curable inks, and the like.

The printing ink layer 7 can be formed by a known method. For example, the printing ink layer 7 can be formed by applying ink on the water-soluble paste layer 5 by screen printing, gravure printing, flexographic printing, lithographic printing, or the like, and curing it if necessary.

As a coating method of a resin composition, a screen printing, a gravure printing, a flexographic printing, a lithographic printing etc. are mentioned, for example. The drying of the resin composition should just volatilize the solvent (B).

When using the transfer paper 1 for decoration, decoration can be performed as follows, for example.

First, the decorative transfer paper 1 is immersed in water or warm water, the water-soluble paste layer 5 is dissolved, and the protective layer 9 with the printing ink layer 7 is peeled off from the base paper 3 . The protective layer 9 with the printing ink layer 7 is attached to a predetermined position of a transfer object such as a ceramic, for example, so that the ceramic or the like is in contact with the printing ink layer 7 . Then, moisture, air bubbles, etc. are removed between the protective layer 9 with the printing ink layer 7 and the ceramics, etc., and then the protective layer 9 is fired to leave the printing ink layer 7 on the surface of the ceramics, etc. Decorate on utensils, etc.

As mentioned above, although embodiment was shown and the transfer paper for decoration of this invention was demonstrated, this invention is not limited to the said embodiment. The respective configurations, combinations, and the like in the above-described embodiments are merely examples, and additions, omissions, substitutions, and other modifications of configurations are possible without departing from the gist of the present invention.

For example, the water-soluble paste layer 5 may be provided at a position where at least the printing ink layer 7 and the protective layer 9 are formed, and may not cover the entire single side of the base paper 3 .

Example

Hereinafter, the present invention will be described in more detail by way of examples, but these examples do not limit the scope of the present invention. In addition, "part" in the following Examples means "mass part", and "%" means "mass %". The evaluation method in an Example was based on the following method.

(Evaluation method)

＜Film-forming properties＞

Using a commercially available roller printing machine, on a backing paper (SPA 215 x 290 mm, manufactured by MURAKAMI Co., Ltd.) uniformly coated with a water-soluble paste on one side, a 300-mesh nylon-made thermosetting ink (Imperial) was screen-printed. MEG manufactured by Ink Co., Ltd.), a printing ink layer as a decorative pattern was formed, and it was left to stand at room temperature for 12 hours. Then, the resin composition was further screen-printed on the 60-mesh nylon to form a coating film of the resin composition, and it was left to stand for 1 minute. After standing, the coating film was visually observed, and the evaluation was carried out as follows. The results are shown in Table 2 below.

Good: No bubbles or pits.

Defect: There are air bubbles or pits.

＜Smells＞

The odor of the resin composition obtained above was confirmed, and the evaluation was carried out as follows. The results are shown in Table 2 below.

Good: No irritating odor was felt.

Bad: A pungent odor is felt.

<Manufacturing method of dispersant>

900 parts of deionized water, 60 parts of methacrylate-2-ethanesulfonate sodium salt, 10 parts of potassium methacrylate, and 12 parts of methyl methacrylate were added to a polymerization apparatus equipped with a stirrer, a cooling pipe, and a thermometer. While stirring, the temperature was raised to 50° C. while nitrogen-substituting the inside of the polymerization apparatus. Thereto was added 0.08 part of 2,2'-azobis(2-methylpropionamidine)dihydrochloride as a polymerization initiator, and the temperature was further raised to 60°C. After the temperature was raised, methyl methacrylate was continuously added dropwise at a rate of 0.24 parts/min for 75 minutes using a dropping pump. After the dropwise addition was completed, the reaction solution was kept at 60° C. for 6 hours, and then cooled to room temperature to obtain a 10% solids dispersant in a transparent aqueous solution.

<Manufacture of acrylic polymer A1>

145 parts of deionized water, 0.3 parts of sodium sulfate, and 0.3 parts of a dispersant (solid content 10%) were added to a polymerization apparatus equipped with a stirrer, a cooling pipe, and a thermometer, and stirred to prepare a homogeneous aqueous solution.

Next, 81 parts of isobutyl methacrylate, 19 parts of 2-ethylhexyl methacrylate, 0.2 part of dodecyl mercaptan, 2,2'-azobis(2-methylbutyronitrile) were added 0.3 part, prepared as an aqueous suspension.

Then, the inside of the polymerization apparatus was substituted with nitrogen, and the temperature was raised to 80° C. for reaction for 1 hour. In order to further increase the polymerization rate, the temperature was raised to 90° C. and held for 60 minutes as a post-treatment temperature. The reaction solution was then cooled to 40°C to obtain an aqueous suspension containing the polymer.

The aqueous suspension was filtered through a nylon filter cloth with a mesh size of 45 μm, and the filtrate was washed with deionized water, dehydrated, and dried at 40° C. for 16 hours to obtain 90 parts of acrylic polymer A1 having a weight average molecular weight of 110,000.

Acrylic polymer A1 contains 100% by mass of alkyl (meth)acrylate monomer units derived from alkyl groups having 3 to 12 carbon atoms, based on the amount of the raw material to be charged, wherein methacrylic acid iso 81 mass % of butyl ester units and 19 mass % of 2-ethylhexyl methacrylate units. Further, the glass transition temperature of the acrylic polymer A1 was 50°C.

(Examples 1 to 10, Comparative Examples 1 to 5)

The raw materials were mixed according to the mixing amounts (parts) shown in Table 1 below, and mixed with a high-speed disperser to obtain a resin composition for a transfer paper protective layer. About the obtained resin composition, the evaluation of the above-mentioned odor and film-forming property was performed, and the result is shown in Table 2 below.

[Table 1]

[Table 2]

Each component in Table 1 is as follows.

A-S-A (registered trademark) T-380-20BS: trade name, fatty acid amide wax (active ingredient 20%; solvent: petroleum solvent 65%, benzyl alcohol 15%)

BYK (registered trademark)-077: trade name, silicone-based defoamer (active ingredient 52%; solvent: high-boiling aromatic solvent) manufactured by BYK Japan

BYK (registered trademark)-052: trade name, acrylic defoamer (active ingredient 20%; solvent: Mineral spirit) manufactured by BYK Japan

EXXSOL (registered trademark) D30: trade name, naphthenic solvent manufactured by Exxon Mobil Corporation (active ingredient 100%; kinematic viscosity: 0.99 mm ² /s; aromatic content: 0.01% or less)

EXXSOL (registered trademark) D40: trade name, naphthenic solvent manufactured by Exxon Mobil Corporation (active ingredient 100%; kinematic viscosity: 1.3 mm ² /s; aromatic content: 0.05%)

ISOPAR (registered trademark) G: trade name, isoparaffin-based solvent manufactured by ExxonMobil Corporation (active ingredient 100%; kinematic viscosity: 1.49 mm ² /s; aromatic content: 0.005% or less)

ISOPAR (registered trademark) L: trade name, isoparaffin-based solvent manufactured by Exxon Mobil Corporation (active ingredient 100%; kinematic viscosity: 1.6 mm ² /s; aromatic content: 0.01% or less)

ISOPAR (registered trademark) M: trade name, isoparaffin-based solvent manufactured by Exxon Mobil Corporation (active ingredient 100%; kinematic viscosity: 3.57 mm ² /s; aromatic content: 0.01%)

SWASOL (registered trademark) 1000: trade name, aromatic hydrocarbon solvent manufactured by Maruzen Oil Co., Ltd. (active ingredient 100%; kinematic viscosity: 0.9 mm ² /s; aromatic content: 100%)

The resin compositions of Examples 1 to 10 were all good in the evaluation results of odor and film-forming properties. On the other hand, in Comparative Examples 1 and 2 using the isoparaffin-based solvent having a kinematic viscosity of more than 1.5 mm ² /s as the substitute solvent (B1), bubbles and pits were generated during printing, and the film-forming properties were poor. In Comparative Example 3 using an aromatic hydrocarbon-based solvent in place of the solvent (B1) and Comparative Example 5 in which part of the solvent (B1) was replaced with an aromatic hydrocarbon-based solvent, the aromatic content of the solvent (B) exceeded 2 mass % , so the odor is strong and difficult to operate. In Comparative Example 4 in which the amount of the solvent (B1) was less than 70% by mass and 60% by mass, bubbles, pits, etc. were generated during printing, and the film-forming properties were poor.

Industrial Availability

According to the resin composition for a transfer paper protective layer of the present invention, a protective layer with few bubbles and pits and less odor can be formed in a laminate of transfer papers or the like for decorating an object to be transferred, which is very suitable For example, it is used as the resin composition for protective layer formation of the transfer paper which decorates the surface of ceramics etc.

Claims (12)

1. A resin composition for a protective layer of transfer paper, which comprises an acrylic polymer A, a solvent B and a plasticizer D, wherein the acrylic polymer A contains 50 mass% or more of a monomer unit derived from an alkyl (meth) acrylate having 3 to 12 carbon atoms and an alkyl group; solvent B contains 70% by mass or more of a component selected from the group consisting of a component having a kinematic viscosity at 25 ℃ of 1.5mm as measured by ASTM D445²At least 1 solvent B1 selected from the naphthenic solvent and the isoparaffinic solvent having a concentration of 2 mass% or less of aromatic compounds.

2. The resin composition for a transfer paper protective layer according to claim 1, wherein the acrylic polymer A contains 50 to 90 mass% of monomer units derived from an alkyl (meth) acrylate having an alkyl group with 3 to 6 carbon atoms and 10 to 50 mass% of monomer units derived from an alkyl (meth) acrylate having an alkyl group with 7 to 12 carbon atoms.

3. The resin composition for a protective layer of transfer paper according to claim 1 or 2, further comprising a defoaming agent C.

4. The resin composition for a protective layer of transfer paper according to claim 3, comprising 70 to 500 parts by mass of the solvent B, 0.1 to 15 parts by mass of the defoaming agent C, and 5 to 35 parts by mass of the plasticizer D, based on 100 parts by mass of the acrylic polymer A.

5. The resin composition for a protective layer of transfer paper according to claim 3, wherein the defoaming agent C is a polysiloxane or an acrylic compound.

6. The resin composition for a transfer paper protective layer according to claim 1 or 2, wherein the weight average molecular weight of the acrylic polymer A is 50,000 to 200,000.

7. The resin composition for a transfer paper protective layer according to claim 1 or 2, wherein the glass transition temperature of the acrylic polymer a is 10 ℃ or higher.

8. The resin composition for a transfer paper protective layer according to claim 1 or 2, wherein the plasticizer D is a polyester-based, benzoic-based or phthalate-based plasticizer.

9. A method for producing a resin composition for a protective layer of transfer paper, which is the method for producing the resin composition for a protective layer of transfer paper according to any one of claims 1 to 8,

mixed acrylic polymer A having a kinematic viscosity at 1.5mm, measured at 25 ℃ according to ASTM D445²At least 1 solvent B1 of naphthenic solvent and isoalkane solvent and plasticizer D below s.

10. The method for producing a resin composition for a protective layer of transfer paper according to claim 9, further comprising mixing a defoaming agent C.

11. A laminate comprising a base paper, a water-soluble paste layer, a printing ink layer, and a protective layer comprising a dried product of the resin composition for a protective layer of transfer paper according to any one of claims 1 to 8, which are laminated in this order.

12. A decorative transfer paper comprising the laminate according to claim 11.

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