JPH11236485A - Resin composition and heat transfer sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transferred image having high crazing resistance, durability and resistance to washing by thermally transferring a recorded image formed by an ink jet recording method to a material to be transferred. SOLUTION: This resin composition containing a polymer containing a monomer unit represented by the following formula [R1 and R2 are mutually the same or different and each hydrogen atom or methyl group; (k) is an integer of 1-6; (k) is an integer of 1-10; (m) is an integer of 2-12; (n) is an integer of 1-20; R2 may vary with (k)] and a hot-melt bonding resin (a nylon-based resin, a polyester-based resin and a polyurethane-based resin, etc.), is obtained. The resultant resin composition is then applied to at least either one of surfaces of a substrate to form an ink absorbing layer. Thereby, the heat transfer sheet is obtained. The polymer may be composed of a copolymer of the monomer represented by the formula and at least one kind of a monomer selected from among a cationic functional group-containing monomer, a cross-linking monomer and a hydrophilic monomer. The resin composition may further contain a hydrophilic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition and a thermal transfer sheet using the same. More specifically, the present invention relates to a resin composition and a heat transfer sheet useful for a heat transfer sheet having excellent ink absorbency, ink fixability, printability, water resistance, crack resistance, durability and washing resistance of a recorded image in an ink jet recording system. .

[0002]

2. Description of the Related Art Ink-jet recording systems are easy to achieve full color, have low noise, and are excellent in printing quality. In addition, inkjet printers are widely used as printing / output devices such as recording devices for computers, word processors, and copiers because they are inexpensive and easy to operate at high speed. As an ink component for ink jet recording, a water-based ink is mainly used in terms of safety and recording suitability, and recording is performed by flying small ink droplets from nozzles toward a recording sheet. If the ink absorption of the recording sheet used is low, the ink may scatter around the ink droplets that have been ejected, or the ink may remain on the surface of the recording sheet for a long time after the end of recording, causing contact with parts of the device. ,
By contacting the handler and superimposing the recording sheets,
The recorded part becomes dirty. In the high-density image area, a large amount of supplied ink is mixed without absorption and flows out, resulting in an unclear image. For this reason, the recording sheet is required to quickly absorb the ink and to have high fixability. Further, when a transfer image is formed by thermally transferring a recording image to a transfer target such as clothing, the transfer image sheet is required to have not only thermal transferability and adhesiveness but also high water resistance and washing resistance.

[0003] JP-A-63-60784 discloses an ink-jet recording method in which an ink absorbing layer containing organic polymer fine particles that dissolves or swells in a solvent in an ink (particularly oil-based ink) is formed on the surface of a support. A sheet is disclosed. JP-A-7-25133 discloses that a spherical fine particle polymer having an average particle diameter of 5 to 15 μm is coated on at least one surface of a support formed of a polyolefin resin-coated paper or a polyester film with a dry weight of 5 to 30 mg / m 2. ^Two
And an ink jet recording sheet on which an ink receiving layer having a thickness smaller than the average particle diameter of the spherical fine particle polymer is formed.

Japanese Patent Application Laid-Open No. 63-115780 discloses 4
An inkjet recording sheet in which a polymer containing a quaternary ammonium salt is applied to a support is disclosed, and it is described that synthetic silica is used in combination and polyvinyl alcohol or the like is used in combination as a binder.

However, these recording sheets cannot improve the fixability and water resistance of the ink to a high level. In particular, it is difficult to thermally transfer a recorded image to a transfer target. Furthermore, even if a transfer image is formed on the transfer object, the washing resistance and durability are poor.

JP-A-8-324106 discloses an ink receiving layer having a porous structure made of a hot melt resin (ethylene-vinyl acetate, polyester, rubber, etc.) on one surface of a substrate. A formed inkjet recording sheet is disclosed. JP-A-8-207425 discloses that a hot melt resin (a water-soluble hot melt resin such as a saturated polyester resin in addition to a polyamide or polyester resin) and a hydrophilic resin (polyacrylamide, An ink jet recording sheet having an ink receiving layer containing polyvinyl alcohol, polyvinylpyrrolidone, etc.) is disclosed. This recording sheet can be bonded to a film or the like by heating.

[0007] However, these ink receiving layers have insufficient ink fixability and water resistance. In particular, since the washing resistance and durability (cracking resistance, etc.) are not sufficient, even if a recorded image is thermally transferred to clothing or the like, a clear transferred image cannot be maintained for a long period of time.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to form a sheet and form an image on the sheet in an ink jet recording system, whereby the recorded image has high durability, especially high crack resistance. For example, forming an ink image receiving layer composed of the resin composition on a stretchable base material,
An object of the present invention is to provide a resin composition and a thermal transfer sheet which do not cause cracking even when a recorded image is expanded and contracted. Another object of the present invention is to provide a resin composition and a thermal transfer sheet having excellent ink absorbency, ink fixability, and printability. It is still another object of the present invention to provide a resin composition and a thermal transfer sheet having a good balance between ink absorption and water resistance of a recorded image at a high level, and having excellent durability of the recorded image.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a resin composition comprising a lactone-modified polymerizable monomer and a hot melt adhesive resin, When an ink-absorbing layer that can be peeled off from the base material is formed on at least one surface of the base material, the durability of the transferred image, particularly the crack resistance, can be significantly improved, and the cationic functional group-containing monomer can be further improved. It has been found that copolymerization with such as can further improve the ink absorbency, ink fixability, and printability, as well as the image durability and washing resistance, and completed the present invention.

That is, the resin composition of the present invention contains a polymer containing a monomer unit represented by the following formula (1) and a hot melt adhesive resin.

[0011]

Embedded image

Wherein R ₁ and R ₂ are the same or different and each is a hydrogen atom or a methyl group, k is an integer of 1 to 6, l is an integer of 1 to 10, m is an integer of 2 to 12, n Is an integer of 1 to 20, and R ₂ may be different depending on k.) The polymer is a monomer of the formula (1), a monomer having a cationic functional group, and a crosslinkable monomer And a copolymer with at least one monomer selected from hydrophilic monomers.

[0013] The cationic functional group-containing monomer is
A monomer having a quaternary amino group or a base thereof, a monomer having a quaternary ammonium base, a monomer forming a quaternary ammonium base, or the like. Monomer, a hydroxyl group-containing monomer, and a monomer having a polyoxyalkylene unit, and the crosslinkable monomer is an epoxy group-containing monomer, a methylol group-containing monomer, and It can be selected from monomers containing a silyl group or an alkoxysilyl group. The resin composition may further include a hydrophilic polymer,
This hydrophilic polymer includes (a) a polyoxyalkylene unit, an acetoacetyl group, a carboxyl group, a functional group selected from an acid anhydride group and an amino group, and (b) a cellulose derivative, a vinyl alcohol-based polymer, And vinyl ester-based polymers. Hot melt adhesive resin is nylon resin, polyester resin,
It can be selected from polyurethane resins and the like. Hot melt adhesive resin is nylon resin, polyester resin,
And polyurethane resins. The resin composition may further include a hydrophilic polymer.

In the present invention, at least one surface of a substrate is provided with at least an ink receiving layer which can be peeled from the substrate, and the ink receiving layer is formed of at least a monomer represented by the formula (1): A thermal transfer sheet composed of an ink receiving layer containing a polymer containing units and a hot melt adhesive resin and a method for producing the same are also included. The ink receiving layer may be formed on the substrate via a protective layer that can be separated from the substrate.
The protective layer can be selected from a thermoplastic resin, a thermosetting resin, an elastomer, and the like.

[0015] In the present specification, the term "hydrophilic polymer" means various polymers having an affinity for water, and is used to include a water-absorbing polymer and a water-soluble polymer. "Elastomer" means a polymer having rubber-like elasticity, not limited to rubbers such as natural rubber and synthetic rubber.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention contains a polymer containing a monomer unit represented by the above formula (1) and a hot melt adhesive resin.

[Lactone-modified monomer and copolymer thereof] In the lactone-modified monomer of the formula (1), R ₁ and R
₂ is a hydrogen atom or a methyl group. k is an integer of 1 to 6, preferably 2 to 4, l is an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3, and m is 2
-12, preferably 3-10, more preferably 4-8
And n is an integer of 1 to 20, preferably 1 to 10, and more preferably 1 to 5. R ₂ may be different depending on k. That is, when k is 2 or more, each R ₂ bonded to each carbon atom of the methylene chain may be a hydrogen atom or a methyl group (that is, in the formula,-(CH ₂
(R ₂ )) k- may be, for example, ethylene, propylene, tetramethylene or the like). Preferred R ₂ ,
The combination of k, l, and m is R ₂ : hydrogen atom, k: 2 to 2
4, 1: 1 to 5 and m: 3 to 10, and such a monomer can be obtained from Daicel Chemical Industries, Ltd., for example, in a lactone-modified hydroxyethyl (meth) acrylate having a structure of placcel ( Placcel) F (k = 2, l =
1, m = 5).

The polymer containing the monomer unit of the formula (1) includes a monomer of the formula (1), a cationic functional group-containing monomer, a crosslinkable monomer, and a hydrophilic monomer. And a copolymer with a monomer selected from the following.

[Monomer Containing a Cationic Functional Group] The monomers containing a cationic functional group include various monomers having a tertiary amino group or a base thereof, and a monomer having a quaternary ammonium base. Various monomers capable of forming a quaternary ammonium base can be used.

Examples of the cationic functional group-containing monomer, for example, C _1-4 alkylamino -C _2-3 alkyl (meth)
Acrylamide or a salt thereof [dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide or a salt thereof, etc.], di C _1-4 alkylamino-
_C2-3 alkyl (meth) acrylate or a salt thereof [dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate or a salt thereof, etc.], C _1-4 alkylamino-C _2-3 alkyl group-substituted aromatic vinyl or a salt thereof [4- (2-dimethylaminoethyl) styrene,
-(2-dimethylaminopropyl) styrene and the like and salts thereof], a nitrogen-containing heterocyclic monomer or a salt thereof [vinylpyridine, vinylimidazole, vinylpyrrolidone or a salt thereof] and the like. Salts include hydrohalides (hydrochlorides, hydrobromides, etc.), sulfates, alkyl sulfates (methyl sulfate, ethyl sulfate, etc.), alkyl sulfonates, aryl sulfonates,
Examples thereof include carboxylate (acetate and the like). In addition,
A quaternary ammonium base may be generated by reacting an alkylating agent (epichlorohydrin, methyl chloride, benzyl chloride, etc.) with a tertiary amino group.
These cationic functional group-containing monomers can be used alone or in combination of two or more.

[Crosslinkable Monomer] The crosslinkable monomer includes various monomers having a self-crosslinkable or reactive functional group, for example, an epoxy group-containing monomer [glycidyl (meth) methacrylate, (Meth) allyl glycidyl ether, 1-allyloxy-3,4-epoxybutane, 1- (3-butenyloxy) -2,3-epoxypropane, 4-vinyl-
1-cyclohexene-1,2-epoxide, etc.], a methylol group-containing monomer or a derivative thereof [N-methylol (meth) acrylamide, N-methoxymethyl (meth)
N-C _1-4 alkoxymethyl (meth) acrylamide, such as acrylamide, N-butyrol (meth) acrylamide, etc.], and a monomer having a hydrolytic condensable group such as a silyl group [vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltributoxysilane, vinylmethoxydimethylsilane, vinylethoxydimethylsilane, vinylisobutoxydimethylsilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinyltris (β-methoxyethoxy) silane, vinyldiphenylethoxysilane, vinyltriphenoxysilane , Γ- (vinylphenylaminopropyl) trimethoxysilane, γ
-(Vinylbenzylaminopropyl) trimethoxysilane, γ- (vinylphenylaminopropyl) triethoxysilane, γ- (vinylbenzylaminopropyl) triethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldi (β-methoxyethoxy) ) Silane, vinyldiacetoxymethylsilane, vinyltriacetoxysilane, vinylbis (dimethylamino)
Methylsilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyltrichlorosilane, vinylmethylphenylchlorosilane, allyltriethoxysilane, 3-allylaminopropyltrimethoxysilane, allyldiacetoxymethylsilane, allyltriacetoxysilane, allylbis (dimethylamino) Methylsilane,
Allylmethyldichlorosilane, allyldimethylchlorosilane, allyltrichlorosilane, methallylphenyldichlorosilane, β- (meth) acryloxyethyltrimethoxysilane, β- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxy Propyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyltris (Β-methoxyethoxy) silane etc.), aziridinyl group-containing monomer [2- (1-aziridinyl) ethyl (meth) acrylate, 2- (1-aziridinyl) propyl (meth) acrylate, (meth) acrylic acid 3- (1-aziridinyl) Propyl and the like]. These crosslinkable monomers can be used alone or in combination of two or more. Preferred crosslinkable monomers have a hydrolytic condensable group, particularly an alkoxysilyl group (such as a C _1-4 alkoxysilyl group such as a methoxysilyl group or an ethoxysilyl group).

[Hydrophilic monomer] The hydrophilic monomer includes a hydrophilic group such as a carboxyl group, an acid anhydride group, a hydroxyl group, an amide group, a sulfonic acid group, an ether group, and a polyoxyalkylene group. And the like.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid and the like, and acid anhydrides thereof and salts thereof ( Alkali metal salts,
Alkaline earth metal salts, ammonium salts, amine salts, etc.), half esters of polyunsaturated carboxylic acids or their anhydrides and linear or branched alcohols having about 1 to 20 carbon atoms (monomethyl maleate, maleic acid) Monoethyl, mono-2-ethylhexyl maleate, etc.).

Examples of the hydroxyl group-containing monomer include hydroxyalkyl esters of unsaturated fatty acids [for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy (meth) acrylate].
Hydroxypropyl, (meth) acrylic acid hydroxy C _2-6 alkyl ester such as 4-hydroxybutyl (meth) acrylate, 2-hydroxyethylmethyl maleate, mono (maleic acid) such as di (2-hydroxypropyl) maleate or such as carboxylic acid hydroxy hydroxyalkyl C _2-6 alkyl esters, such as dihydroxy C _2-6 alkyl esters, aliphatic having a hydroxyl group, alicyclic, or aromatic vinyl compounds (e.g., alpha-hydroxy styrene and the like) and the .

Examples of the amide group-containing monomer include a C _2-8 carboxylic acid which may be substituted with a substituent such as a C _1-4 alkyl group, a C _1-4 alkoxy group, or a C _1-4 acyl group. Amides [eg, (meth) acrylamide such as (meth) acrylamide, α-ethyl (meth) acrylamide, N-methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide and the like] and the like. Can be

As the amino group-containing monomer, the aforementioned carboxyl group or acid anhydride group-containing monomer having an amino group such as aminomethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate is used. it can.

Examples of the sulfonic acid group-containing monomer include aliphatic, alicyclic or aromatic vinyl compounds having a sulfonic acid group such as styrenesulfonic acid and vinylsulfonic acid, and sodium salts thereof.

Examples of the ether group-containing monomer include vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether.

As the polyoxyalkylene group-containing monomer, diethylene glycol mono (meth) acrylate,
Examples thereof include triethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate. The hydrophilic monomers can be used alone or in combination of two or more.

Preferred hydrophilic monomers are carboxyl group-containing monomers, in particular, (meth) acrylic acid or a salt thereof (eg, sodium salt, potassium salt, etc.). Among these monomers, a monomer having the hydrophilic group is also preferable. For example, a hydroxyl group-containing monomer [2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc.], a monomer having a polyoxyalkylene unit [diethylene glycol mono (meth) acrylate, triethylene glycol mono) (Meth) acrylate, polyethylene glycol mono (meth) acrylate, etc.].

The cationic functional group-containing monomer, crosslinkable monomer and hydrophilic monomer can be used alone or in combination of two or more. Preferred combinations of the monomers are as follows. Monomer of formula (1): R ₂ is a hydrogen atom, k is 2 to 6, l is 1 to 5, m is 3 to 10 Cationic functional group-containing monomer: diC _1-4 alkylamino-C _2-3 alkyl (meth) acrylate or its quaternary ammonium salt Crosslinkable monomer: (meth) acryloxy-C _2-3 alkyltri C _1-2 alkoxysilane Hydrophilic monomer: unsaturated carboxylic acid The monomer is usually used in combination with a nonionic monomer in order to adjust film forming properties and film properties.

Nonionic monomers include, for example, alkyl esters [eg, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth)
T-butyl acrylate, hexyl (meth) acrylate,
Octyl (meth) acrylate, 2- (meth) acrylate
(Meth) acrylic acid C such as ethylhexyl, lauryl (meth) acrylate, and stearyl (meth) acrylate
_1-18 alkyl esters, etc.], cycloalkyl esters [cyclohexyl (meth) acrylate, etc.], aryl esters [phenyl (meth) acrylate, etc.], aralkyl esters [benzyl (meth) acrylate, etc.], aromatic vinyls [ Styrene, vinyltoluene, α-methylstyrene, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl versatate, etc.], allyl esters [allyl acetate, etc.], halogen-containing monomers [vinylidene chloride, vinyl chloride, etc.] ], Vinyl cyanide [such as (meth) acrylonitrile], and olefins [such as ethylene and propylene]. These nonionic monomers can be used alone or in combination of two or more.

As the nonionic monomer, usually, a C _1-18 alkyl (meth) acrylate [particularly, a C _2-10 alkyl acrylate or a C _1-6 alkyl methacrylate], aromatic vinyl [Especially styrene] and vinyl esters [especially vinyl acetate] are used.

The copolymer composed of the above-mentioned monomers is not particularly limited with respect to the polymerization mode, and may be, for example, a random copolymer, a graft copolymer, a block copolymer or the like.

The content of the monomer of the formula (1) in all the monomers is about 5 to 40% by weight, preferably about 1 to 30% by weight, and more preferably about 15 to 25% by weight. Further, in all the monomers, the content of the cationic functional group-containing monomer is 1 to
50% by weight, preferably 5 to 45% by weight, the content of the crosslinkable monomer is 0.1 to 20% by weight, preferably 0.1 to
10% by weight, more preferably about 1 to 5% by weight, and the content of the hydrophilic monomer is 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight. %, And the balance is composed of about 10 to 80% by weight, preferably about 20 to 70% by weight of the nonionic monomer.

The proportion of the monomers is 5 to 300 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the lactone-modified monomer of the formula (1). About 250 parts by weight, and the amount of the crosslinkable monomer is 1
About 30 parts by weight, preferably about 5 to 20 parts by weight,
5 to 80 parts by weight of the hydrophilic monomer, preferably 10 to 60 parts by weight
It is about parts by weight.

The glass transition temperature of the copolymer can be selected within a range that does not impair the film-forming properties and the like.
° C, preferably -10 to 40 ° C, more preferably 0 to
It is about 30 ° C. The polymer having such a glass transition temperature appropriately combines the cationic functional group-containing monomer and the crosslinkable monomer with a hydrophilic monomer or a nonionic monomer as necessary. Can be prepared. The monomer is
Usually, a hard monomer [for example, a monomer which forms a homopolymer having a glass transition temperature of about 80 to 120 ° C. (particularly 90 to 105 ° C.) such as methyl (meth) acrylate, styrene, etc.], a soft monomer [C ₂ acrylate] Glass transition temperature of _-10 alkyl ester, etc. -85 to _-10 ° C (particularly -8
5-20 ° C.) and a monomer which forms a homopolymer of about 5 ° C. to −20 ° C.).

[Hot Melt Adhesive Resin] As the hot melt adhesive resin, various resins, for example, olefin resins (polyethylene, ethylene-propylene copolymer, atactic polypropylene, etc.), ethylene copolymer resins (ethylene- Vinyl acetate copolymer, ethylene-
(Meth) acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ionomer, etc.), nylon resin,
Examples thereof include a polyester resin, a polyurethane resin, an acrylic resin, and rubber. These hot melt adhesive resins can be used alone or in combination of two or more.
Hot melt adhesive resins are usually water-insoluble. Hot melt adhesive resins have reactive groups (carboxyl group, hydroxyl group, amino group, isocyanate group,
A reactive hot melt adhesive resin having a silyl group or the like may be used.

Preferred resins for imparting heat transferability and durability (such as washing resistance) are nylon resins, polyester resins and polyurethane resins. In particular, a hot-melt adhesive resin composed of a nylon-based resin can impart excellent washing resistance and water resistance to a transferred image and a high texture when the object to be transferred is clothing or the like.

As the nylon-based hot melt adhesive resin, a polyamide resin having at least one unit selected from nylon 11 and nylon 12 (for example,
Homopolyamide such as nylon 11, nylon 12, nylon 6/11, nylon 6/12, nylon 66/1
2, copolyamides such as copolymers of dimer acid and diamine with raum lactam or aminoundecanoic acid), and polyamide resins formed by the reaction of dimer acid with diamine.

The polyester hot melt adhesive resin includes at least a homopolyester resin or a copolyester resin using an aliphatic diol. Examples of the homopolyester resin include aliphatic diols (eg, C _2-10 alkylene thiol such as ethylene glycol, propylene glycol, 1,4-butane diol, and 1,6-hexane diol) and polyoxy C such as diethylene glycol.
_2-4 alkylene glycols), aliphatic dicarboxylic acids (eg, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid) and, if necessary, a saturated aliphatic polyester resin formed by a reaction with a lactone. The copolyester resin, some other diol components of polyethylene terephthalate or polybutylene terephthalate (ethylene glycol, propylene glycol, 1,4-butanediol, etc. C _2-6 alkylene glycol, and the like) or dicarboxylic acid (the fatty Asymmetric aromatic dicarboxylic acids such as aromatic dicarboxylic acids, phthalic acids, and isophthalic acids) or saturated polyester resins substituted with the lactone.

The polyurethane-based hot-melt adhesive resin includes, as at least a part of a diol component, a polyester resin using a polyester diol corresponding to the polyester-based hot-melt adhesive resin. Aromatic, cycloaliphatic or aliphatic diisocyanates can be used.

If necessary, the hot melt adhesive resin may include, for example, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), antistatic agents, flame retardants, lubricants, antiblocking agents, fillers, Coloring agents, defoamers, coatability improvers,
It may contain a thickener, a tackifier (rosin or a derivative thereof, a hydrocarbon resin or the like), a wax, or the like.
The melting point of the hot melt adhesive resin is usually 70 to 250.
° C, preferably 80 to 200 ° C, more preferably 10 ° C.
It can be selected from the range of about 0 to 150 ° C.

The hot melt adhesive resin is used as a powder. The hot-melt adhesive resin is formed of a powdery resin having an average particle diameter larger than the thickness of the ink-receiving layer, so that the resin is projected from the surface of the ink-receiving layer to effectively exhibit hot-melt adhesiveness. The average particle size of the hot melt adhesive resin is, for example, about 1 to 100 μm, preferably about 3 to 80 μm, and more preferably about 5 to 50 μm. The powder of the hot melt adhesive resin may be a porous material in order to improve the ink absorbency and the washing resistance.

The ratio of the polymer containing the monomer unit of the formula (1) to the hot-melt adhesive resin is the former /
The latter = 1 / 99-60 / 40 (% by weight), preferably 5
/ 95 to 60/40 (% by weight). When the polymer is composed of a copolymer of the above-mentioned monomers, 10 to 1500 parts by weight (for example, 10 to 1000 parts by weight) relative to 100 parts by weight of the polymer (the copolymer) is used.
Parts by weight), preferably about 10 to 900 parts by weight (for example, 50 to 900 parts by weight, particularly 80 to 900 parts by weight) of a hot melt adhesive resin.

The resin composition of the present invention may contain a hydrophilic polymer in addition to the above-mentioned copolymer of monomers. The hydrophilic polymer includes a water-soluble polymer, a water-dispersible polymer, and a polymer that is water-insoluble but has water absorption.

[Hydrophilic polymer] As the hydrophilic polymer,
For example, a natural polymer having a hydrophilic group (an acidic group such as a carboxyl group or a sulfonic acid group or a salt thereof, a basic group or a salt thereof) or a derivative thereof, a cellulose derivative, an olefin polymer, an acrylic polymer, Styrene polymer, vinyl polymer (vinyl acetate copolymer, vinyl ether polymer, etc.), vinyl alcohol polymer, polyalkylene oxide, polyester, polyamide,
Examples include polymers derived from polycarbonate, polyurethane, polysulfone, and epoxide.

Examples of the hydrophilic polymer include a hydrophilic natural polymer or a derivative thereof (starch, corn starch,
Sodium alginate, gum arabic, gelatin, casein, dextrin, etc., cellulose derivatives (methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, cyanoethyl cellulose, etc.), vinyl alcohol polymers (polyvinyl alcohol, ethylene-vinyl alcohol Polymer), ethylene-based polymer (ethylene-maleic anhydride copolymer, etc.), vinyl acetate-based copolymer (vinyl acetate-methyl acrylate copolymer, etc.), polyalkylene oxide (polyethylene oxide, ethylene oxide- Propylene oxide block copolymer), a polymer having a carboxyl group or a sulfonic acid group or a salt thereof [acrylic polymer (poly (meth) acrylic acid or Its salts (ammonium, alkali metal salts such as sodium), methyl methacrylate -
(Meth) acrylic acid copolymers, acrylic acid-polyvinyl alcohol copolymers, etc.), vinyl ether polymers (polyvinyl alkyl ethers such as polyvinyl methyl ether and polyvinyl isobutyl ether, methyl vinyl ether-maleic anhydride copolymers), Styrene-based polymers (styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, sodium polystyrenesulfonate, etc.), sodium polyvinylsulfonate, etc.], nitrogen-containing polymers (or cationic polymers)
Or salts thereof (quaternary ammonium salts such as polyvinylbenzyltrimethylammonium chloride and polydiallyldimethylammonium chloride, polydimethylaminoethyl (meth) acrylate hydrochloride, polyvinylpyridine, polyvinylimidazole, polyethyleneimine, polyamidepolyamine, polyacrylamide, polyvinylpyrrolidone) Etc.). These hydrophilic polymers can be used alone or in combination of two kinds.

Among these hydrophilic polymers, cellulose derivatives (especially hydroxyethyl cellulose), vinyl alcohol polymers (especially polyvinyl alcohol, modified polyvinyl alcohol, etc.), vinyl ester polymers (especially vinyl acetate copolymer) Etc.), polyvinyl pyrrolidone, etc. are preferred, and a polyvinyl alcohol polymer is particularly preferred. The degree of saponification of polyvinyl alcohol is not particularly limited.
It can be selected from a range of about 0%, and is usually about 70 to 95%. As the modified polyvinyl alcohol, for example,
The copolymer includes a completely or partially saponified product of a copolymer of vinyl acetate and a copolymer monomer (vinyl acetate copolymer), and an epoxy-modified polyvinyl alcohol. When using acetoacetyl-modified polyvinyl alcohol, the degree of saponification is usually about 60 to 95%.

Examples of the copolymerizable monomer constituting the vinyl acetate copolymer include olefins or dienes (eg, ethylene, propylene, butadiene, etc.), dialkyl maleate, and (meth) acrylic monomer. (Eg, alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, hydroxy-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and glycidyl (Meth) acrylates, vinyl cyanides such as (meth) acrylonitrile, etc.), allyl monomers (eg, epoxy-containing monomers such as allyl alcohol, allyl isocyanate, allyl glycidyl ether, etc.), sulfonic acid groups or salts thereof. Monomers (such as styrene sulfonic acid and its sodium salt), monomers containing a carboxyl group or its salt (such as a carboxyl group such as (meth) acrylic acid, crotonic acid, and monoalkyl maleate or its salt), and acid anhydrides Group-containing monomers (such as maleic anhydride), vinyl monomers (aromatic vinyl monomers such as vinyl isocyanate and styrene, heterocyclic vinylamines such as vinyl pyrrolidone and vinyl imidazole, vinyl methyl ether, vinyl ethyl Vinyl ethers such as ether and vinyl isobutyl ether; hydrolyzable silyl group-containing monomers such as vinyl trisalkoxysilane; and halogen-containing vinyl monomers such as vinyl chloride and vinylidene chloride). These copolymerizable monomers can be used alone or in combination of two or more.

Further, (1) a polyoxyalkylene unit,
(2) acetoacetyl group, (3) carboxyl group,
Hydrophilic polymers having at least one functional group selected from (4) acid anhydride groups and (5) amino groups are also preferred. In particular, a cellulose derivative having the functional group, a vinyl alcohol-based polymer, a vinyl ester-based polymer, and the like are preferable.

(1) The hydrophilic polymer having a polyoxyalkylene unit includes a copolymer of a monomer constituting the hydrophilic polymer and a vinyl monomer having an ether group, particularly an oxyalkylene unit. . As the vinyl monomer, for example, the number of alkylene oxide units (addition moles) is 1 to 100, preferably 20 to 8
0 (for example, 5 to 80), more preferably 5 to 70
About (for example, 10 to 50) (meth) acrylate or allyl ether can be used.

The vinyl monomer having an oxyalkylene unit includes, for example, diethylene glycol mono (meth)
Acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polypropylene glycol mono ( (Meth) acrylate, diethylene glycol mono (meth) allyl ether, triethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) allyl ether, dipropylene glycol mono (meth) allyl ether, tripropylene glycol mono (meth) allyl ether , Polypropylene glycol mono (meth) allyl ether and the like. These vinyl monomers can be used alone or in combination of two or more. Preferred monomers include (meth) acrylates, which are vinyl monomers in which the oxyalkylene units are oxyethylene units, especially polyoxyalkylene (meth) allyl ethers (among others, polyoxyethylene allyl ethers).

The proportion of the copolymerizable monomer can be selected within a range that does not impair the sharpness of the image and the water resistance.
About 0.1 to 50 mol%, preferably 1
About 30 mol%, more preferably about 2.5 to 25 mol% (for example, about 3 to 20 mol%).

(2) The acetoacetyl group-modified hydrophilic polymer includes an acetoacetyl group-containing hydrophilic polymer formed by a reaction between a hydroxyl group-containing hydrophilic polymer and an acetoacetate ester, for example, an acetoacetyl group-modified hydrophilic polymer. Vinyl acetate copolymer (acetoacetyl group-containing polyvinyl alcohol, acetoacetyl group-containing cellulose derivative, etc.)
Is included. An acetoacetyl group-modified vinyl acetate copolymer, for example, available from Nippon Synthetic Chemical Industry Co., Ltd.

The (3) carboxyl group-modified hydrophilic polymer includes (3a) carboxyl group-modified polyvinyl alcohol,
For example, vinyl esters (vinyl acetate, vinyl propionate, vinyl formate, etc.) and carboxyl group-containing unsaturated monomers (monocarboxylic acids such as (meth) acrylic acid), dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; These acid anhydrides or monoalkyl esters, etc.)
And partially saponified copolymers, for example, styrene-
(Meth) acrylic acid copolymer, (meth) acrylic acid ester- (meth) acrylic acid copolymer (eg, methyl methacrylate- (meth) acrylic acid copolymer), vinyl acetate-
(3) saponified compounds such as (meth) acrylic acid copolymer
b) carboxyl group-containing polysaccharides such as carboxy C
_1-4 alkyl cellulose, carboxymethyl dextran, alginic acid and the like.

(4) The acid anhydride group-modified hydrophilic polymer includes:
Alkyl vinyl ether-maleic anhydride copolymer (such as methyl vinyl ether-maleic anhydride copolymer),
Ethylene-maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, styrene-maleic anhydride copolymer, (meth) acrylate-maleic anhydride copolymer (methyl methacrylate-maleic anhydride copolymer) And the like).

(5) The amino group-modified hydrophilic polymer includes polyamide-polyamine, polyvinylamine and poly (N-
Vinyl formamide), amino group-containing polysaccharides (aminodextran, chitosan, etc.). The hydrophilic polymers can be used alone or in combination of two or more.

The modified hydrophilic polymer is preferably polyvinyl alcohol or the like modified with the above-mentioned modifying group, and particularly, a saponified product of a copolymer of vinyl acetate and a vinyl monomer having a polyoxyalkylene unit. (For example, available from Nippon Synthetic Chemical Co., Ltd. under the trade name "OKS-7158G"), epoxy-modified polyvinyl alcohol, and the like are preferable.

The epoxy-modified polyvinyl alcohol includes (1) saponification of a copolymer of vinyl acetate and a monomer having an epoxy group (such as allyl glycidyl ether and glycidyl (meth) acrylate), and (2) epichlorohydrin. By epoxidation of polyvinyl alcohol with an epoxidizing agent. The used amount (content) of the monomer containing an epoxy group and the introduced amount of the epoxy group are about 0.01 to 5 mol%, preferably 0.1 to 3 mol% (for example, 0.2 to 2.0 mol%). 5 mol%), especially 0.2 to
It is about 2 mol%.

The ratio of the copolymer composed of the above-mentioned monomers to the hydrophilic polymer was calculated as solid / solid when the former / latter = 9
0/10 to 50/50 (parts by weight), preferably 15/8
About 5 to 50/50 (parts by weight), more preferably 20
/ 80 to 40/60 (parts by weight).

The resin composition may contain, if necessary, other components such as an aqueous emulsion containing a non-crosslinkable polymer or polymer particles (eg, an acrylic resin emulsion, an acryl-urethane copolymer emulsion, a urethane System emulsion, ethylene-vinyl acetate copolymer emulsion, vinyl acetate emulsion, etc.). If necessary, the resin composition may contain conventional additives such as stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), antistatic agents, flame retardants, lubricants, You may add a blocking agent, a filler, a coloring agent (a pigment, a dye, etc.), an antifoaming agent, a coating improver, a thickener, and the like.

When at least one ink receiving layer that can be peeled off from the base material is formed on at least one surface of the base material using the resin composition, the ink receiving layer is recorded by an ink jet recording method, and the recorded image is thermally transferred to an object to be transferred. It can be used as a thermal transfer sheet for ink jet for forming a transfer image, and even when transferred to an elastic transfer object, the recorded image follows the expansion and contraction of the transfer object satisfactorily, and the image does not crack.

In the thermal transfer sheet of the present invention, at least one surface of the base material is provided with at least an ink receiving layer peelable from the base material, and the ink receiving layer is formed of the resin composition. I have.

[Substrate] As the substrate, an opaque, translucent or transparent substrate can be used as long as it can be peeled off from the protective layer. As the substrate, a release substrate, for example, a release treated paper, a plastic film which may be subjected to a release treatment, and the like are usually mentioned. As the polymer constituting the plastic film, for example, polyolefins such as polypropylene, cellulose derivatives such as cellulose acetate,
Polyester (polyalkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalate such as polyethylene naphthalate and polybutylene naphthalate, and the like), polyamide (polyamide 6, polyamide 6/6 and the like), and the like can be given. Of these films, polypropylene, polyester, polyamide and the like are usually used, and polyester (particularly polyethylene terephthalate and the like) is particularly preferable in terms of mechanical strength, heat resistance, workability and the like.

The thickness of the substrate can be selected according to the application, and is usually about 10 to 250 μm, preferably about 15 to 200 μm. The releasability can be imparted by a conventional method, for example, by treating the substrate with a release agent (eg, wax, higher fatty acid salt, higher fatty acid ester, higher fatty acid amide, silicone oil, etc.). If necessary, conventional additives such as antioxidants, ultraviolet absorbers, heat stabilizers, lubricants, and pigments may be added to the plastic film.

[Ink receiving layer] The ink receiving layer in the thermal transfer sheet of the present invention is composed of the above resin composition. The ink receiving layer may contain a plasticizer to impart high flexibility to the transferred image. Examples of the plasticizer include phthalate plasticizers (ethyl phthalate, butyl phthalate, hexyl phthalate, octyl phthalate, 2-ethylhexyl phthalate, lauryl phthalate, etc.),
Aliphatic dicarboxylic acid plasticizers (eg, 2-ethylhexyl adipate, dibutyl sebacate, 2-ethylhexyl sebacate), glycol plasticizers (eg, ethylphthalyl
Ethyl glycolate, polyethylene glycol ester, etc.), phosphate ester plasticizer (triphenyl phosphate, tricresyl phosphate, tri-2-ethylhexyl phosphate, etc.), polyester plasticizer, epoxy plasticizer (epoxy fatty acid ester, etc.) And the like. These plasticizers can be used alone or in combination of two or more.

The amount of the plasticizer used is, for example, 100% of the total amount of the polymer and resin components (hydrophilic polymer, hot melt adhesive resin, cationic polymer, and urethane polymer resin) constituting the ink receiving layer. 0.1 to 3 parts by weight
It can be selected from the range of 0 parts by weight, preferably 1 to 25 parts by weight, more preferably about 1 to 20 parts by weight.

Further, the ink receiving layer may contain a dye fixing agent independently or together with the plasticizer in order to improve the fixability of the colorant (dye). The polymer dye fixing agent can also function as the hydrophilic polymer.

Examples of the dye fixing agent include dicyan fixing agents (dicyandiamide-formalin polycondensate, dicyandiamide-diethylenetriamine polycondensate, etc.),
Polyamine fixing agents [aliphatic polyamines such as diethylenetriamine, triethylenetetramine, dipropylenetriamine and polyallylamine, aromatic polyamines such as phenylenediamine, dicyandiamide and (poly) C
Condensates with _2-4 alkylene polyamines (such as dicyandiamide-diethylenetriamine polycondensates)] and polycationic fixing agents. Examples of the polycationic fixing agent include an epichlorohydrin-di C _1-4 alkylamine addition polymer (e.g., epichlorohydrin-dimethylamine addition polymer), a polymer of allylamine or a salt thereof (a polymer of polyallylamine or a hydrochloride thereof) For example, Nitto Boseki Co., Ltd., PAA-10C, PAA-HCl-3L, PAA-HCl-1
0L), a polymer of diallyl C _1-4 alkylamine or a salt thereof (a polymer of diallyl methylamine or a hydrochloride thereof, for example, Nitto Boseki Co., Ltd., PAS-M-1, etc.), diallyl di C _1-4 Polymers of alkylammonium salts (polymers of diallyldimethylammonium chloride, such as Nitto Boseki Co., Ltd., PAS-H-5L, PAS-H-10L, etc.), and copolymers of diallylamine or its salts with sulfur dioxide ( Diallylamine hydrochloride-sulfur dioxide copolymer, such as Nitto Boseki Co., Ltd., PAS-92, etc., diallyldi C _1-4 alkylammonium salt-sulfur dioxide copolymer (diallyldimethylammonium chloride-sulfur dioxide copolymer,
For example, Nitto Boseki Co., Ltd., PAS-A-1, PAS-A-5, PAS-A-12
0L, PAS-A-120A etc.), a copolymer of diallyldi C _1-4 alkylammonium salt and diallylamine or a salt or derivative thereof (copolymer of diallyldimethylammonium chloride-diallylamine hydrochloride derivative, for example,
Nitto Spinning Co., Ltd., PAS-880, etc.), diallyl di C _1-4 alkyl ammonium salt polymer, di C _1-4 alkylaminoethyl (meth) acrylate quaternary polymer, diallyl di C _1-4 alkyl ammonium salt Acrylamide copolymer (diallyldimethylammonium chloride-acrylamide copolymer, for example, Nitto Boseki Co., Ltd., PAS-J-81
And amine-carboxylic acid copolymers (eg, Nitto Boseki Co., Ltd., PAS-410). These dye fixing agents may be used alone or in combination of two or more.

The amount of the dye fixing agent used is within a range capable of improving the fixability, for example, 0.1 to 50 parts by weight, based on 100 parts by weight of the total of the polymer and the resin component constituting the ink receiving layer in terms of solid content. Parts, preferably from 1 to 30 parts by weight, more preferably from about 2 to 20 parts by weight.

The thickness of the ink receiving layer is, for example, 5 to 90.
μm, preferably about 10 to 70 μm, usually 5 μm.
〜60 μm (especially 5 to 50 μm). In addition, the thickness of the ink receiving layer means the minimum thickness of a coating film formed using a coating agent containing a hot-melt adhesive resin or a coating film containing a hot-melt adhesive resin. .

A porous layer, an anti-blocking layer, a lubricating layer, an antistatic layer, etc. may be formed on the ink receiving layer, if necessary. The ink receiving layer may be formed on the substrate via a protective layer that can be separated from the substrate.

[Protective Layer] As the protective layer, various thermoplastic resins and thermosetting resins, in particular, as long as they can be peeled off from the base material and protect the ink receiving layer and do not significantly impair the quality of the transferred image, A polymer having a film forming property can be used. Examples of the thermoplastic resin include polyamide resins (such as polyamide 11, polyamide 12, and polyamide 612), polyester resins (such as PET-based copolyester and PBT-based copolyester), and styrene-based resins (styrene- (meth) acrylate copolymer). Etc.), polyolefin resins (polyethylene, polypropylene, ethylene-
Propylene copolymer), polycarbonate resin, polyvinyl acetate resin (polyvinyl acetate, ethylene-vinyl acetate copolymer, etc.), acrylic resin (poly (meth))
Examples thereof include various resins such as an acrylate ester), a polyacetal resin, a vinyl chloride resin (such as a vinyl chloride-vinyl acetate copolymer), and a fluorine resin. The thermoplastic resins may be used alone or as a mixture of two or more. As the thermosetting resin, urethane resin,
Various resins such as an epoxy resin, a phenol resin, a kylylene resin, a melamine resin, a urea resin, and a silicone resin can be exemplified.

In order to effectively protect the ink receiving layer after transfer and improve the durability, it is advantageous to form the protective layer with a soft polymer, especially a non-tacky polymer. The soft polymer may be non-elastomeric, but is preferably an elastomer. The elastomer includes at least one polymer selected from a synthetic rubber, a natural rubber, and a thermoplastic elastomer.

Examples of the synthetic rubber include diene rubbers (eg, styrene-butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, etc.), olefin rubbers (eg, butyl rubber, ethylene-propylene rubber (EPM, EPDM
Etc.), fluorine rubber, acrylic rubber, ethylene-acryl rubber, chlorosulfonated polyethylene rubber, etc.), and other rubbers (eg, silicone rubber, urethane rubber, ethylene-vinyl acetate copolymer, polynorbornene rubber, etc.). Various rubbers can be exemplified.

As the thermoplastic elastomer, an elastomer composed of a hard segment (or block) and a soft segment (or block), for example, a block copolymer such as a polystyrene-based elastomer (polybutadiene / polystyrene elastomer, polyisoprene / polystyrene elastomer, etc.) Coalesce), polyurethane elastomers (eg, block copolymers such as polyester or polyether-based polyurethane elastomers), polyamide elastomers (eg, block copolymers such as polyester or polyether-based polyamide elastomers),
Various types of polyolefin elastomers (eg, EPR / polypropylene elastomers, EPDM / polypropylene elastomers, polyolefin block copolymers), polyester elastomers (eg, block copolymers such as polyethylene terephthalate-based elastomers and polybutylene terephthalate-based elastomers), and polyvinyl chloride elastomers Elastomers.

When the thermal transfer sheet of the present invention is thermally transferred to a stretchable transfer object such as clothing cloth, the protective layer and the ink receiving layer flexibly follow the transfer object even when the transfer object expands and contracts. In order to prevent the occurrence of cracks in the transferred image, it is particularly preferable that the protective layer is made of synthetic rubber, natural rubber, or thermoplastic elastomer. The elastomer may be vulcanized with sulfur, peroxide or the like.

Preferred protective layers have a Young's modulus of 0.1 to 1.
It can be composed of an elastomer of about 100 MPa (for example, 1 to 100 MPa), preferably about 0.1 to 50 MPa (for example, 1 to 50 MPa). Further, the polymer of the protective layer has an elongation of 300% or more (for example, 300 to 1).
000%), preferably 400% or more (for example, 4%
Elastomers selected from the range of about 100 to 1000%).
It is about 900%.

Further, the polymer constituting the protective layer has a glass transition temperature of -100 to 100 ° C., preferably -50.
To 50 ° C, more preferably -30 to 30 ° C. When the polymer is an elastomer, the glass transition temperature of the elastomer is −10 ° C. or less (for example, −100 to 100 ° C.).
-10 ° C), preferably -15 ° C or less (for example,-
The temperature is preferably about 100 to -15 ° C), more preferably -20 ° C or lower (for example, about -100 to -20 ° C), and the polymer is preferably non-adhesive at room temperature (about 10 to 30 ° C).

When such a protective layer is formed, the flexibility can be greatly improved, the water resistance, the durability and the washing resistance are remarkably improved, and the occurrence of cracks and cracks due to expansion and contraction in the transferred image can be prevented. It can be significantly suppressed.

The polymer constituting the protective layer may contain various additives as necessary, for example, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), antistatic agents, flame retardants,
It may contain a lubricant, an anti-blocking agent, a filler, a colorant, an antifoaming agent, a coating improver, a thickener, and the like.

The thickness of the protective layer is, for example, about 1 to 90 μm, preferably about 3 to 70 μm, and usually about 5 to 5 μm.
It is about 0 μm (particularly about 5 to 30 μm). The ratio of the thickness of the protective layer to the thickness of the ink receiving layer is the former / the latter = 1/1 to 1
/ 10, preferably about 1/2 to 1/8, more preferably about 1/2 to 1/7, and usually 1/3 to 1
About / 6.

[Production Method] The thermal transfer sheet of the present invention can be produced by forming the ink receiving layer which can be peeled off from the substrate on at least one surface of the release substrate. The ink receiving layer includes a polymer containing at least a monomer unit of the formula (1), a hot melt adhesive resin, and other components as necessary (for example, a hydrophilic polymer).
Can be formed by applying a coating agent composed of The polymer containing at least the monomer unit is usually
It can be used in the form of an aqueous solution or emulsion, and the hot melt adhesive resin can be used in the form of a powder. Therefore, the coating solution for the ink receiving layer can be prepared by mixing the aqueous solution or emulsion, the powdery granules of the hot melt adhesive resin, and other components as necessary. The solvent of the aqueous solution or the aqueous emulsion may be water alone, or may contain a hydrophilic organic solvent such as an alcohol if necessary. Further, when a hydrophilic polymer is mixed as another component, the ink receiving ability is improved. When the ink receiving layer is formed on the base material via the protective layer, a protective layer coating agent composed of an elastomer or the like is applied, and dried if necessary to form a protective layer, and the ink receiving layer is formed as described above. May be formed. The coating agent for the protective layer can be prepared using an organic solvent or an aqueous solvent depending on the type of the polymer, and may be in the form of a solution or an emulsion.

The coating agent can be prepared by a conventional method, for example, a conventional casting or coating method, for example, a roll coater, an air knife coater, a blade coater, a rod coater, a bar coater, a comma coater, a gravure coater, a silk screen coater, a dip coater. It can be coated by a method or the like. 50 to 150 ° C (preferably 80 to 120 ° C)
The ink receiving layer and the protective layer can be formed by drying the coating film at a temperature of the order.

The ink receiving layer thus formed is suitable for forming an image by an ink jet system in which a small droplet of an ink (particularly, a water-based ink) is ejected and recorded. The recorded image is formed at an appropriate temperature (for example, 140 to 250 ° C., while the ink receiving layer is in contact with the transfer object).
Preferably about 140 to 200 ° C) and pressure (5 to 50 ° C).
By pressing under pressure for about an appropriate time (for example, about 5 seconds to 1 minute) at a pressure of about 0 g / cm ² and peeling the ink receiving layer from the base material, the ink can be smoothly transferred or transferred to the transfer receiving body. The transfer body including the transfer image may be crosslinked by heating if necessary.

As the object to be transferred, a two-dimensional or three-dimensional structure formed of various materials such as fiber, paper, wood, plastic, ceramics, and metal can be used. Usually, a plastic film, a plastic sheet, paper, cloth, or the like is used as the transfer object.

The thermal transfer sheet of the present invention is useful as an ink image receiving sheet of the ink jet system for recording by flying small ink droplets, but is useful for thermal transfer sheets such as offset printing and flexographic printing (particularly, sheets for aqueous ink). Also available as

[0089]

Since the resin composition of the present invention is composed of a polymer containing the monomer unit of the formula (1) and a hot-melt adhesive resin, the resin composition is formed on a peelable substrate and thermally transferred. The sheet is transferred to a stretchable transfer member, so that the crack resistance, durability, water resistance, and washing resistance of the transferred image can be significantly improved, and the ink absorbency during image formation can be significantly improved.

[0090]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. Monomers used in Examples and Comparative Examples,
The hot melt adhesive resin, the hydrophilic polymer and the substrate are as follows. 1. 1. Hydroxyethyl (meth) acrylates (a-1): lactone-modified hydroxyethyl methacrylate (Placcel FM4, manufactured by Daicel Chemical Industries, Ltd.) (a-2): hydroxyethyl methacrylate 2. Cationic functional group-containing monomer (b-1): diethylaminoethyl methacrylate 3. hydrophilic monomer (c-1): acrylic acid 4. Crosslinkable monomer (d-1): trimethoxysilanepropyl methacrylate (A-174, manufactured by Nippon Unicar Co., Ltd.) 5. Nonionic monomer (e-1): methyl methacrylate (e-2): n-butyl methacrylate 6. Hot melt adhesive resin (f-1): Nylon hot melt adhesive resin (430-P1 manufactured by Daicel Huls Co., Ltd.) 7. Hydrophilic polymer (g-1): 15% by weight modified vinyl acetate copolymer (OKS-7158G, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) aqueous solution Base material (h-1): polyethylene terephthalate film

In the thermal transfer sheets obtained in Examples and Comparative Examples, ink absorbency, printing state, washing resistance,
The crack of the transferred image due to the elongation of the transfer object was evaluated as follows. Inkjet printer (Canon Inc.)
, BJC-420J), solid colors of cyan, magenta, yellow, and black were printed on the ink receiving sheets obtained in Examples and Comparative Examples to form recorded images.

[Ink Absorption] After printing, a PPC copy sheet is placed on the printing unit at regular intervals, and after applying a weight (250 g / cm ² ) for 10 seconds from above the copy sheet, the copy sheet is peeled off. The presence or absence of ink set-off was visually determined, and evaluated by the time until no set-off was observed. [Printing condition] The printing condition was visually evaluated based on the following criteria. ○ The printed area is evenly printed △ Some unevenness is observed in the printed area × Notable unevenness is observed in the printed area [Washing resistance] Apply the recorded image of the thermal transfer sheet to the T-shirt and use a Harilon press machine. Temperature 160 ° C, pressure 15
The recording image was thermally transferred to a T-shirt by pressing for 20 seconds at g / cm ² . 1 liter of water at a temperature of 40 ° C. and a commercially available detergent 1
g was added, a sample (5 × 10 cm) from the T-shirt to which the recorded image was transferred was added, and the mixture was stirred for 20 minutes at 600 rpm using a stirrer (three one motor).
Then, the sample after washing was taken out, water was thoroughly removed and dried, and then the transferred image area was observed, and the washing resistance was evaluated based on the following criteria. ○ Transfer image portion remains completely △ Transfer image portion becomes slightly thinner × Transfer image portion does not remain [Crack due to elongation of transfer object] Washing is performed as described above. It was pulled 1 cm in the direction, and the presence or absence of cracks in the transferred image area was visually evaluated. ○ No cracks observed × No cracks observed

(Preparation of Copolymer Resin) Preparation Example 1 Acrylic copolymer resin A 219 parts by weight in a 2000 ml reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen inlet tube, and a thermometer Of isopropyl alcohol and 1.23 parts by weight of azobisisobutyrotrile were dissolved by stirring and heated to 80 ° C. As copolymer components, 49 parts by weight of a hydroxyethyl methacrylate monomer, 94 parts by weight of a cationic functional group-containing monomer, 5 parts by weight of a crosslinkable monomer, 25 parts by weight of a hydrophilic monomer, And 37 as a nonionic monomer.
Parts by weight of (e-1) and 37 parts by weight of (e-2) were mixed, and the mixture was dropped into the reactor over about 4 hours. After the addition, a mixed solution of 0.25 parts by weight of azobisisobutyronitrile and 25 parts by weight of isopropanol was added dropwise as an additional catalyst, and the reaction was continued for another 2 hours to complete the polymerization. After completion of the polymerization, 16 parts by weight of acetic acid was added to the reactor while stirring was continued, and then 705 parts by weight of water was added dropwise over about 2 hours, and then isopropanol was distilled off with a rotary evaporator. A copolymer resin A was obtained. The solid concentration was 34.7% by weight.

Preparation Example 2 Acrylic urethane copolymer resin B In a 1000 ml reactor equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube, and thermometer, 303 parts by weight of urethane emulsion (Zeneca Corporation) ), NeoRez
R-960) and 15 parts by weight of ion-exchanged water were stirred and heated to 75 ° C. As a copolymer component, 30
Parts by weight of a lactone-modified hydroxyethyl methacrylate monomer, 10 parts by weight of a cationic functional group-containing monomer,
4 parts by weight of a crosslinkable monomer, 4 parts by weight of a hydrophilic monomer, and 45 parts by weight of (e-1) and 45 parts by weight of (e-2) as a nonionic monomer, and 5 parts by weight of A surfactant (Newcol 707SF, manufactured by Nippon Emulsifier Co., Ltd.) and 60 parts by weight of ion-exchanged water were mixed, and this mixture was mixed with a catalyst aqueous solution (0.5%).
Of potassium persulfate and 16.5 parts by weight of ion-exchanged water) was dropped into the reactor over about 2 hours. After continuing the reaction for another hour, it was cooled to room temperature,
Copolymer resin B was obtained. The solid concentration was 40% by weight.

Preparation Example 3 Acrylic copolymer resin C Preparation Example 1 except that hydroxyethyl methacrylate (a-2) was used instead of the lactone-modified monomer (a-1).
Was performed in the same manner as in the above to obtain a copolymer resin C. Solids concentration is 3
It was 4.7% by weight.

Preparation Example 4 Acrylic urethane copolymer resin D Preparation Example 2 except that hydroxyethyl methacrylate (a-2) was used instead of the lactone-modified monomer (a-1)
Was carried out in the same manner as described above to obtain a copolymer resin D. Solids concentration is 4
It was 0% by weight.

Examples and Comparative Examples Copolymer resin and hot melt adhesive resin (f-1)
And the hydrophilic polymer (g-1) were mixed so that the solid content was in the ratio shown in Table 1, to prepare an aqueous coating liquid. This coating solution was applied on a substrate and dried at 100 ° C. for 3 minutes to obtain a thermal transfer sheet. The resin coating amount is 40 g / m ^{2 in} solid content.
Met. Table 1 shows the results of the evaluation performed using these thermal transfer sheets.

[0098]

[Table 1]

As is clear from the table, the examples containing the lactone-modified monomer are excellent in ink absorbency, printability and washing resistance, and can well follow the elongation of the transfer-receiving body even after washing. The image did not crack.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C08F 20/28 C08F 20/28 290/06 290/06 299/02 299/02

Claims (18)

[Claims] [Claim 1] The following formula (1) (Wherein R ₁ and R ₂ are the same or different and are hydrogen atoms or methyl groups, k is an integer of 1 to 6, l is an integer of 1 to 10, m is an integer of 2 to 12, and n is 1 to An integer of 20;
R ₂ may be different depending on k. A) a resin composition comprising a polymer containing a monomer unit represented by formula (1) and a hot melt adhesive resin. 2. The resin composition according to claim 1, wherein in the monomer of the formula (1), R ₂ is a hydrogen atom, k is 2 to 4, l is 1 to 5, and m is 3 to 10. 3. A polymer comprising a monomer represented by the formula (1) and at least one monomer selected from a cationic functional group-containing monomer, a crosslinkable monomer and a hydrophilic monomer. The resin composition according to claim 1, comprising a copolymer of 4. A copolymer comprising a monomer of the formula (1), a monomer having a cationic functional group, and at least one selected from a crosslinkable monomer and a hydrophilic monomer. 4. The resin composition according to claim 3, which is composed of a polymer. 5. The resin composition according to claim 3, wherein the content of the monomer of the formula (1) is 5 to 40% by weight based on all the monomers. 6. The cationic functional group-containing monomer is a monomer having a tertiary amino group or a base thereof, a monomer having a quaternary ammonium base, and a monomer forming a quaternary ammonium base. At least one selected from monomers, the hydrophilic monomer is at least one selected from a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and a monomer having a polyoxyalkylene unit. ,
The resin composition according to claim 3, wherein the crosslinkable monomer is at least one selected from an epoxy group-containing monomer, a methylol group-containing monomer, and a silyl group or an alkoxysilyl group-containing monomer. 7. The method according to claim 1, wherein the cationic functional group-containing monomer is C_1-4
Alkylamino-C _2-3Alkyl (meth) acrylamide
Do, C_1-4Alkylamino-C_2-3Alkyl (meth)
Acrylates or their salts, crosslinkable monomers
Is a silyl group or alkoxysilyl group-containing monomer.
And the hydrophilic monomer is an unsaturated carboxylic acid or an acid anhydride thereof.
, Unsaturated polycarboxylic acid or its anhydride and C_1-20Al
Half ester with coal, hydrosaturated carboxylic acid
At least one selected from xyalkyl esters
The resin composition according to claim 3. 8. The resin composition according to claim 1, wherein the hot melt adhesive resin is at least one selected from a nylon resin, a polyester resin and a polyurethane resin. 9. The resin composition according to claim 1, wherein the proportion of the hot melt adhesive resin is 10 to 900 parts by weight based on 100 parts by weight of the polymer. 10. The resin composition according to claim 1, further comprising a hydrophilic polymer. 11. A cellulose derivative, wherein the hydrophilic polymer has (a) at least one functional group selected from a polyoxyalkylene unit, an acetoacetyl group, a carboxyl group, an acid anhydride group and an amino group; The resin composition according to claim 10, wherein the resin composition is at least one selected from a vinyl alcohol-based polymer and a vinyl ester-based polymer. 12. The ratio between the copolymer and the hydrophilic polymer is as follows:
The resin composition according to claim 10, wherein the former / the latter is 90/10 to 50/50 (parts by weight). 13. A sheet having at least one surface of a substrate on which at least an ink receiving layer peelable from the substrate is formed, wherein the ink receiving layer is made of the resin composition according to claim 1. Thermal transfer sheet. 14. The thermal transfer sheet according to claim 13, wherein the ink receiving layer is formed on the substrate via a protective layer that can be separated from the substrate. 15. The thermal transfer sheet according to claim 14, wherein the protective layer is made of at least one selected from a thermoplastic resin, a thermosetting resin, and an elastomer. 16. The thermal transfer sheet according to claim 13, wherein the ink receiving layer contains at least one of a dye fixing agent and a plasticizer. 17. The thermal transfer sheet according to claim 13, wherein the hot melt adhesive resin is composed of a powdery resin having an average particle diameter larger than the thickness of the ink receiving layer. 18. A method for producing a sheet wherein at least one surface of a substrate has at least an ink-receiving layer peelable from the substrate, wherein the ink-receiving layer is provided.
A method for producing a thermal transfer sheet comprising the resin composition as described above.