JPH03147892A - Resin composition easily dyed with sublimable dispersion dye - Google Patents

Abstract

PURPOSE:To improve resistance to light, dyeing sensitivity, resistance to blocking, stability, compatibility with a color sheet, and the like by a method wherein a composition obtained by compounding specific releasant, ultraviolet light absorber, and light stabilizer in specific polyester resin and crosslinker is applied on a base material and cured by an active energy beam. CONSTITUTION:At least one selected out of silicone releasants and fluorocarbon- containing releasants, at least one selected out of benzotriazole ultraviolet light absorbers, and at least one of hindered amine light stabilizers are incorporated in a mixture composed of 40-95wt.% polyester resin having a glass transition temperature in the range of 11-90 deg.C and 60-5wt.% crosslinker capable of curing by an active energy beam, respectively by the amount of 0.001-0.1 pts.wt., 0.1-10 pts.wt., and 0.1-10 pts.wt. per 100 pts.wt. of said mixture. If the composition ratio of the polyester resin is less than 40wt.%, a high dyeing density by a sublimable dispersion dye cannot be obtained under low energy conditions. On the contrary, if the composition ratio of the polyester resin is more than 95wt.%, the crosslinker is reduced in amount, and resistance to blocking with a color sheet (transfer paper) coated with the sublimable dispersion dye is getting worse.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present FiA relates to resin compositions for transfer to be subjected to a sublimation type heat-sensitive transfer method, and to thermal transfer printing of textiles for image-receiving paper and image-receiving films in a sublimation-type heat-sensitive transfer recording method. The present invention relates to a resin assembly that can be used for heat-sensitive transfer of plastic molded products (films, lenses, etc.).

[Conventional technology]

Conventionally, transfer compositions for the sublimation type heat-sensitive transfer method include sheet-like materials obtained by treating acrylic short fibers with alkylene carbonate and ammonium salts as described in JP-A-60-81559, and JP-A-60-81559. 112494, which is made of short polyester fibers having acidic groups converted to ammonium salt type, but these are dyed only with sublimable cationic dyes, and therefore have poor light resistance due to cationic dyes. However, the light resistance was poor.

On the other hand, resin compositions for transfer that can be dyed with sublimable disperse dyes, which generally have better Fi light resistance than cationic dyes, include:
There are compositions containing an acrylic polymer crosslinking agent, a phosphate ester compound, and an amine compound described in Japanese Patent Application No. 60-188644, but these compositions dye well with low energy! Dyeing Sensitivity - 251 is not enough, and it is dangerous to use transfer paper (color sheet) coated with a composition containing a sublimable disperse dye on a transferred object coated with these resin compositions and cured. When the dye-coated surfaces are overlapped and the dye is transferred by heating, depending on the heating conditions, the object to be transferred and the transfer paper may stick together, or a phenomenon called blocking may occur. If the amounts of the phosphoric acid ester compound and amine compound used as mold release agents are increased, the blocking will be reduced, but if the amount of 50 to 6
During a heat resistance test at about 0°C, a phenomenon occurred in which the dye was smudged. In addition, when a transfer material produced using this composition is used as image-receiving paper or image-receiving film for a color printer using a sublimation heat-sensitive transfer recording method, such as the 8CT-OF100 model manufactured by Mitsubishi Electric ■, The image receiving paper or image receiving film keeps slipping! (In some cases, the problem of not being able to record occurred.

[Problem to be solved by the invention]

The present invention has been made to improve the light resistance, dyeing sensitivity, blocking resistance, stability, compatibility with color sheets, etc. as described above, and uses a specific polyester resin and a crosslinking agent. When a composition containing a specific mold release agent, ultraviolet absorber, and light stabilizer is applied to a substrate and cured with active energy rays, the above-mentioned problems are solved by sublimable disperse dye dyeing. The present invention was completed by discovering that it could be used as a sex product.

[Means to solve the problem]

That is, the present invention provides 100 parts by weight of a mixture consisting of 40 to 95 parts by weight of a polyester resin having a glass transition temperature in the range of 11°C to 90°C and 60 to 5 parts by weight of a crosslinking agent that can be cured by active energy rays. , a silicone-based mold release agent, and a fluorine-containing mold release agent.
001 to 111 parts by weight, at least 1 to 10 parts by weight of a benzotriazole ultraviolet absorber, and at least 11 to 10 parts by weight of a hindered amine light stabilizer. It is a resin composition.

The present invention will be explained in detail below.

According to the invention, a composition is constituted. The 41J ester resin is one of the essential components of the present invention because it dyes well with sublimable disperse dyes and functions as a binder for the composition. Materials other than polyester resin, such as acrylic resin and acetate resin, cannot be dyed.

The polyester resin is a linear thermoplastic polyester resin obtained by the condensation polymerization of a dicarboxylic acid and a diol, or/and a linear thermoplastic polyester resin obtained by the condensation polymerization of an unsaturated polybasic acid having a reactive double bond and a polyhydric alcohol. Among them, linear thermoplastic polyester resins having a molecular weight of 2,000 to 40,000 obtained by polycondensation of at least 1 g of dicarboxylic acid and at least one diol, and having a molecular weight of 11 to 90 °C The polyester resin has a glass transition temperature (Tg) in the range of This is preferable in this respect. Tg of polyester is 1
If the temperature is less than 1°C, the blocking resistance with the color sheet will be poor, and the color sheet and the sublimable disperse dye easily dyeable article of the present invention may become separated or stick together during dyeing or recording. I'll get one. If a dyed or recorded item is stored in a high temperature and high humidity condition, the color of the dyed item may become lighter or the color may bleed.

On the other hand, if the Tg exceeds 90° C., the staining sensitivity during staining or recording becomes insufficient, high staining density cannot be obtained, and staining or recording takes a long time. The preferred and false range of Tg is 10H2O°C.

The blending amount of the polyester resin is 40 to 40% of the total amount of the crosslinking agent.
It is preferable that the amount of polyester resin is greater than 95% by weight, and if the weight is less than 40%, the dyeing density with the sublimable disperse dye will not become deep under low energy conditions.On the other hand, if the amount of polyester resin blended exceeds 95% by weight, the crosslinking agent will be As a result, the blocking resistance with the color sheet (transfer paper) coated with sublimable disperse dyes was poor. will cause blocking (sticking) during thermal transfer.

A more preferable range is 55 to 94 weight.

Specific examples of linear thermoplastic polynisder resins obtained by condensation polymerization of at least one dicarboxylic acid and at least one diol include those obtained from terephthalic acid/isophthalic acid/ethylene glycol/neopentyl glycol. Polyester resin, other terephthalic acid/inphthalic acid! ! ! / ethylene glycol / hisphenol penta-ethylene oxide adduct, terephthalic acid / inphthalic acid / ethylene glycol / also 6-hexanediol,
From terephthalic acid/isophthalic acid/sepacic acid/ethylene glycol/neopentyl glycol, terephthalic acid/sepacin rll/ethylene glycol/neopentyl glycol, terephthalic acid/inphthalic acid/adipic acid/ethyl glycol/neopentyl glycol, etc. The polyester resins obtained can be listed, and two or more types can also be used in combination. In particular, from the viewpoint of stability against light, heat, water, etc., it is preferable to use at least two of these polyesters in combination to improve stability. For example, when two types of polymers, Mu and B, are used together, the preferred range of use of the polymer is that Mu is 1.
0-90 weight 4, B is 90-10 weight. Even when three or more types of polymers are used, it is preferable to use the lowest mixing amount on a 10-weight board, and the largest mixing amount on a 90-weight board.However, even when one or more types of polymers are used together, the mixed polymer For the reasons mentioned above, 1g of
It needs to be in the range of 0°C.

Of course, it is also possible to use dimethyl terephthalate, dimethyl inphthalate, etc. esterified with (1) such as terephthalic acid and isophthalic acid as raw materials for condensation polymerization.

Examples of unsaturated polyester resins obtained by condensation polymerization of unsaturated polybasic acids with reactive double bonds and polyhydric alcohols include maleic anhydride/phthalic anhydride/propylene glycol, maleic anhydride/isophthalic acid/ Propylene glycol, maleic #/fumaric #/isophthalic acid/1. Examples include resins obtained from s-butanediol, maleic acid/hyphthalic acid/neopentyl glycol, maleic anhydride fa/tetrahydrophthalic anhydride/dipropylene glycol, and the like.

The crosslinking agent is necessary in order to cure the resin composition of the invention with active energy rays and to obtain blocking resistance of the cured resin composition, and is preferred! The desired blending amount is in the range of 5 to 60 weight, more preferably 6 to 45 weight of the total amount including the polyester resin. If the amount of crosslinking agent is less than 5% by weight, blocking tends to occur.On the other hand, if the amount exceeds 60% by weight, the blocking resistance will be good, but the proportion of polyester resin will decrease, and sufficient dyeing density will not be obtained. It becomes difficult to get caught.

Considering the curing of the composition by the crosslinking agent and the blocking resistance of the composition, it is preferable that the crosslinking agent has at least one type of polyfunctional heptamer, which can be easily handled as an active energy ray. When ultraviolet rays are used, the polymerizable group of these crosslinking agents is preferably a hexamer having an acryloyloxy group or a methacryloyloxy V group.

As an example of a monomer having a (meth)acryloyloxy group, polyether acrylate or polyether methacrylate type (hereinafter, "acrylate or methacrylate v-)" is simply abbreviated as "(meth)acrylate". ), polyester (meth)acrylate series, polyol (meth)acrylate series, epoxy (meth)acrylate series, amide urethane (meth)acrylate series,
Urethane (meth)acrylate type, spiroacetal (
It is recommended to mention polymers and oligomers such as meth)acrylate type and polybutadiene (meth)acrylate type.

Specific examples of such monomers or oligomers include 1, 2. <S-hexanetriol/propylene oxide/acrylic acid, trimethylolpropane/propylene oxide/acrylic acid Polyethers synthesized in this way (
meth)acrylate; polyester (meth) synthesized from adipic acid/1,6-hexanediol/acrylic acid, succinic acid/trimethylolethane/acrylic acid, etc.
Acrylates: triethylene glycol diacrylate, hexapropylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, 2-ethyl hequinol acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl methacrylate, ethyl carpitol Acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2.2-bis(4-acryloyloxyjetoxyphenyl)propane, 2.2-bis( (meth)acrylate or polyol (meth)acrylate such as 4-acryloyloxyglopoquinphenyl)propane; diglycidyl etherified bisphenol A
/ Acrylic acid, diglycidyl etherified boribisphenol / Acrylic acid, triglycidyl etherified glycerin / Epoxy (meth)acrylate such as acrylic acid;
γ-Butyσ lactone/N-methylethanolamine/bis(4-isocyanatocyclohexyl)methane/2-hydroxyethyl acrylate, γ-butyrolactone/N
-Methylethanolamine/2.6-)Lylene diisocyanate/tetraethylene glycol/amide urethane (meth)acrylates such as 2-hydroxyethyl acrylate;2,6-)Lylene diisocyanate diacrylate, inphorone diisocyanate diacrylate, hexamethylene diyne Urethane acrylates such as cyanate diacrylate: diarylidene pentaerythritol/2-hydroxyethyl acrylate Kara synthesized spiroacetal acrylate: epoxidized butadiene/
Examples include acrylated polybutadiene synthesized from 2-hydroxyethyl acrylate, and these monomers and oligomers may be used alone or in a mixture of two or more types.

Among the above monomer oligomers, the following general formula (T') is used! ! 1 X Also represents a polyoxyalkylene group having an alkylene group having 1 to B carbon atoms.
R*)mHc In the formula, R4 represents an alkylene group having 1 to 8 carbon atoms, and m is a positive integer Group or formula represented by a): -(on,)m-OH (in the formula, and m have the same meanings as above. ], such as dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol pentaacrylate, tripentaerythritol hexaacrylate, tripentaerythritol pentaacrylate, etc., or the following general compounds: Formula (It) I Okarasu-aH, cacHs-○co-ca=ca.

(■) (where n is a positive integer of 1 to 10; diacrylate of bisphenol A, diacrylate of Epicote+1oo1 (n=3, manufactured by Shell), etc.), the following general formula (■) OOR3 -o+xno-x, o -x, 0-)-0-c B
=c H, -(m)1 (wherein, XI+
FiO is an integer from 5 to 5), such as 2.2-bis(4-acryloyloxyjetoxyphenyl)furopane, 2.2-bis(4-acryloyloxynetriethoxyphenyl)propane, 2.2- Bis(4-acryloyloxydipropoxyphenyl)propane and the like have very good quick-drying properties in the air when ultraviolet rays are used as active energy rays, making them particularly desirable! It is a new crosslinking agent.

For the purpose of the present invention, a composition consisting of the above-described specific polyester resin 40 to 95 weight 4 and a specific crosslinking agent 60 to 5 weight 4 that can be cured by active energy rays is not sufficient, and Furthermore, at least one mold release agent selected from a silicone mold release agent and a fluorine-containing mold release agent is added to CLO.
1 part by weight of O1 to α, at least one benzotriazole ultraviolet absorber (part of L1 to 10iii), and at least one hindered amine light stabilizer [11 to 10
It is necessary to mix parts by weight.

At least one mold release agent selected from a silicone mold release agent and a fluorine-containing mold release agent has good mold releasability (blocking resistance) from the transfer paper (color sheet) coated with sublimable dye. It is essential to improve the polyester resin and crosslinking agent, and its blending amount is a001 per 100 parts by weight of the total amount of polyester resin and crosslinking agent.
~ (11 parts by weight. If the amount added is less than 1 part by weight, the releasability from the color sheet during dyeing or recording will be poor, and the color sheet and the sublimable disperse dye easily dyeable article of the present invention will be On the other hand, as the amount of mold release agent added increases, the mold releasability improves, but if the amount exceeds α1 part by weight,
The cured composition may become opalescent, or the color of the dyed article may bleed if the dyed article is stored for a long period of time. In particular, when the present invention is applied to image-receiving paper or image-receiving film for a printer using a sublimation type thermal transfer recording method, the recording dots appear to spread out, and the dye density increases when measured by physical optical density. - It appears that the storage stability has been improved, but when you look closely, the problem arises that the images become blurred. It has also been found that as the amount of release agent increases, the surface friction coefficient of the image-receiving paper or image-receiving film decreases, causing misalignment with the color sheet during dyeing or recording, resulting in image misalignment.

Silicone mold release agents include silicone oil; amino-modified silicone oil, polyether-modified F recon oil, and alkyl-modified! / Modified silicone oil such as IJ con oil, epoxy modified silicone oil, fluorine modified silicone oil, α-methylstyrene modified silicone oil, alcohol modified SY recon oil, carboxyl modified silicone oil; Silicone surfactant; γ-glycidoxy Silane coupling agents such as probyltrimethoxysilane and N-β(aminoethyl)r-aminopropyltrimethoxysilane; graft polymers with polyorganosiloxane as the trunk or branches can be used, but the mold release effect is From this point of view, silicone oil, modified silicone oil, and silicone-based surfactants are preferred, and when considering the appropriate surface friction coefficient of 1, silicone-based surfactants are most preferred.

Silicone oil is dimethylsiloxane type,
There are methylhydrodiene polysiloxane types, methylphenylsiloxane types, etc.A specific example is SH
200 (East silicone), BY16-873 (East silicone), 5x16-aos (East silicone), 8
H510 (Toshi Silicone), -KF-96 (Shin-Etsu Silicone), KF-69 (Shin-Etsu Silicone), KF-99
(Shin-Etsu Silicone), KF-56 (Shin-Etsu Silicone), and the like.

Modified V-licon oils include amino-modified silicone oils KIF-593 (Shin-Etsu Silicone) and KF-857.
(Shin-Etsu Silicone), 8F-8417 (Toshi Silicone); Ky-3s1 of Po'J ether modified silicone oil
(Shin-Etsu Silicone), 5H374q (Toy Silicone), 5H8400 (Toyoshi Silicone); Alkyl modified silicone oil KF412 (Shin-Etsu Silicone), BF3
416 ('J [Resilicone; epoxy modified silicone oil xy-1oo (Shin-Etsu Silicone), 8F8411
(East V Recon); Fluorine silicone oil x-2
2-a2o (fFiM silicone), XP81265 (
Shin-Etsu Silicone); α-methylstyrene-modified silicone oil KF-410CM Etsu V') Corn): Alcohol-modified silicone oil xp-asl (Shin-Etsu Silicone)
, EF-8427 (Toshi Silicone), carboxyl-modified silicone oil BF8418 (Toshi Silicone);
Specific examples include higher fatty acid-modified silicone oil KIF-910 (Shin-Etsu Silicone).

As silicone surfactants, KP-323 (Shin-Etsu Silicone), KP-3a o (Shin-Etsu Silicone), Kp
-s<1 (Shin-Etsu Silicone), Kp-ssa (Shin-Etsu Silicone), KP-566 (Shin-Etsu Silicone), BT94
Pmu (East Silicone), DCl 1 p * (East Silicone), Japan H28P Mu (East Silicone), BFi2
Specific examples include 9P (Toshi Silicone), but among these silicone surfactants, there are compounds with blocks of polydimethylsiloxane and polyoxyalkylene (slightly modified with other functional groups). ) is effective, especially the ass-(BiO') l/x- group and the 10R- group (R:
alkylene residue) is OHM (flio)t
/*/ 0R = 1/10 to 1/(11, more preferably 115 to 1/2) has improved blocking properties and leveling properties when the composition is used as a coating agent. These silicone surfactants have excellent reproducibility.
H.

Oh.

(P+0111.OH,O in the formula)! +○H! 0HO)
, - and OH.

m and n are 1, 2, 5. ..., and X and y represent the numbers Ot 1t 2t 3t.... R1 represents an -H5 alkyl group, an acyl group, a haaryl group, an acetoxy group, or the like. )OH3OH.

and m and nFil, l 3. −... positive integer,! X and y are 0. 1. 2. 3. ...represents the number z FiO or an integer from 1 to 5, ca.

R snow is -81-OHIJ, -H, alkyl group, acyl O
H3 represents a group or an aryl group, R3 is -H, an alkyl group,
Represents an acyl group, an aryl group, an acetoxy group, etc.

) There are compounds shown by these? i2[[It is also possible to use the above in combination.

Examples of fluorine-containing mold release agents include fluorine oligomer compounds, fluorine surfactants, and fluorine inert liquids.
Fluorine-based surfactants are good in terms of solubility in compositions and leveling effects! Shi-.

As the fluorine-based surfactant, any nonionic, anionic, cationic, or amphoteric fluorine-based surfactant may be used as long as it is soluble in the mixture of polyester resin and crosslinking agent and exhibits blocking resistance. Anionic surfactants such as fluoroalkoxypolyfluoroalkyl sulfate, fluorocarbon sulfonate, and fluorocarbon carboxylate; for example, N-fluoroalkylsulfonamidoalkylamine quaternary ammonium l; IJ-fluoroalkylsulfonamide alkylamine salt, N-fluoroalkylamidoalkylamine quaternary ammonium salt, N-
Cationic surfactants such as fluoroalkylamidoalkylamine salts, N-fluoroalkylsulfonamide alkyl halomethyl ether quaternary ammonium salts; for example, fluorocarbon sulfonamides, fluorocarbon aminosulfonamides, fluorocarbon carboquine sulfonamides, fluorocarbon hydroxysulfonamides, Fluorocarbon sulfonamide ethylene oxide adduct, fluorocarbon hydroxysulfonamide sulfate ester, fluorocarbon amino acid amide, fluorocarbon acid amide, fluorocarbon hydroxy acid amide, ethylene oxide addition condensate of fluorocarbon acid amide, fluorocarbon hydroxy acid amide sulfate ester, fluorocarbon hydroxy acid amide sulfate Nonionic compounds such as esters, fluorocarbon sulfonic acids, fluorohydrocarbon carboxylic acids, fluorohydrocarbon alkyl esters, fluorohydrocarbon alkyl ethers, fluorohydrocarbon carboquine alkyl esters, fluorocarbon hydroxyamides, fluorohydrocarbon alkyl ester sulfates, and fluoroalkyl diamines Surfactants: Examples include amphoteric surfactants such as alkylamines having a betaine type fluorocarbon sulfonamide bond and alkylamines having a betaine type fluorocarbon acid amide bond. Among the above-mentioned surfactants, nonionic surfactants are preferable, especially considering the improvement of leveling and elimination of blocking of the recording medium of the present invention.

Benzotriazole-based UV absorbers and hindered amine-based light stabilizers are blended to improve the light stability of articles dyed with sublimable disperse dyes. When stabilizers are used together in a specific ratio in a resin composition, the stability against light is significantly improved compared to when each stabilizer is used alone, and articles that are easily dyed with sublimable disperse dyes can be dyed. We have found that it is possible to stain at a higher concentration.

However, UV absorbers other than benzotriazole-based UV absorbers, such as benzophenone-based UV absorbers such as 2,4-dihydroxy-benzophenone and 2-hydroxy-n-octoxybenzophenone, and salicylic acid ester-based UV absorbers such as phenyl salicylate, P-tert, and butyl Phenyl salicylate etc. may be used, or light stabilizers other than hindered amine type, such as nickel complex salt type RGA8TAB■2002 (nickel complex-55-di-tart-butyl-4-manufactured by Chipa Geigy)
When using hydroxybenzyl phosphate monoethylate), it is not possible to obtain sufficient dyeing density, photostability, and dark fading resistance.

As the benzotriazole ultraviolet absorber, 2-(5
-Methyl-2-hydroxyphenyl)benzotriazole (T Engineering NUV Engineering N[F]P1 Ciba Geigy), 2-[
2-Hydroquine-5-bis(α,α-dimethyl-benzyl)phenyl)-2H-benzotriazole (NUVIN[F]234, Chipa Geigy), 2-(mu5
-di-t-butyl-2-hydroxyphenyl)benzotriazole (rxyryvxN@32a, Ciba Geigy), 2-(s-t-butyl-5-methyl-2-hydroxyphenyl)-S-chlorobenzotriazole, (Tnie NUVIN■ 326, Ciba Geigy), 2-(3,5
-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole (T Engineering NUVIN@527, Chipa Geigy), 2-(5,5-di-t-amyl 2-2-
Hydroxyphenyl) benzotriazole (T NUv
These include 1.
It is necessary to use at least 0.1 to 10 parts by weight based on the total of 100 parts by weight of the polyester resin and crosslinking agent. When the blending amount is less than (L1 parts by weight), the dyeing density, photostability, and improving effect are not sufficient; on the other hand, when it exceeds 10 parts by weight, the curability by active energy becomes poor. Preferably 'V-hfX The range is a2 to 8 parts by weight.

As a hindered amine light stabilizer, bis(2,2,
46-tetramethyl-4-piperidyl)separate (s
ANor, @Ls7yo, Sankyo), His (L2.2. 6-bentamethyl-4-piperidine) sebacate (SA
NOII[F]LB765, Sankyo), dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2 succinate
,2,46-titramethylbiveridine polycondensate (saM
ob[F]T, B6222D, Sankyo).

Poly((6-(1,1,5-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl)((
2,2,6,6-tetramethyl-4-biveridyl)imino]hexamethylene((2,2,46-tetramethyl-
4-piperidyl)imino) ) (Elanol [F]
L8944LD, Sankyo), 1-[2-[S-(5-di-t-butyl-4-hydroquinphenyl)propionyloxy]ethyl)-4-1j-(A5-!/-t-butyl-4-hydroxyV phenyl)propionyloxy)
-2,2,6,6-titramethylbiveridine (5Aao
r, ■LB2626. (Sankyo) etc. (Yes, one or more of these must be used in an amount of 1 to 10 parts by weight per 100 parts of the total of the polyester resin and crosslinking agent.

When the blending amount is less than 0.1 part by weight, dyeing density, photostability,
If the improvement effect is not sufficient and the amount exceeds 10 parts by weight, curability with active energy rays will deteriorate.

When using a composition composed of the above components as a component of a crosslinking agent such as ethylcarpitol acrylate, phenoxyethyl acrylate, or tetrahydrofurfuryl acrylate, which has a strong polymer solubility and a low viscosity, the 110-rucoat Coatings such as , barcode, and blade coating are possible, but in order to improve coating workability, these compositions should be blended with a solvent such as ethyl alcohol, methyl ethyl ketone, toluene, ethyl acetate, dimethyl formamide, etc. However, it is better to adjust the coating viscosity to an appropriate value.This makes it easier to perform spray coating, curtain coating, flow coating, dip coating, etc.

Depending on the purpose for which the above composition is used, it may be necessary to
Microscopic inorganic particles of less than m, such as V-rica, alumina,
Talc, titanium oxide, etc. may be added.

The composition of the present invention is cured with active energy rays such as electron beams and ultraviolet rays, but in consideration of radiation source control, it is preferable to use ultraviolet rays. When ultraviolet rays are used as active energy rays, it is preferable to add a photopolymerization initiator (L1 to 10 parts by weight) per 100 parts by weight of the polyester resin and crosslinking agent.Specific examples of the photopolymerization initiator include benzoin. , benzoin isobutyl ether, benzyl dimethyl ketal, ethylphenyl glyoxylate, Shedkin acetophenone, 1,1-dichloroacetophenone, 4'-isopropyl-2-hydroxy-
2-Methylpropiophenone, 1-hydroxychlorohexylphenylketone, benzophenone, benzophenone/jetanolamine, 4,4'-bisdimethylaminobenzophenone, 2-methylthioxanthone, ter
Carbonyl compounds such as t-butylanthraquinone and benzyl; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; Azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile; benzoyl peroxide ,
Examples include peroxide compounds such as di-tsrt-butyl peroxide, and these compounds may be used alone or in a mixed system of two or more.

Examples of articles to which the composition of the present invention can be applied include image-receiving paper or image-receiving film substrates used in sublimation heat-sensitive transfer recording systems, cotton fabrics, PKT films, PVC films,
Examples include PMMA sheets, PC sheets, acrylic lenses, polyester buttons, nylon buckles, paper, PP paper, etc. After the composition is applied by the above-mentioned coating method, it is cured with active energy rays.

These items may be used as such, or may be pretreated with cleaning, etching, corona discharge, active energy ray irradiation, color washing, printing, etc. as necessary. A sublimable disperse dye dyeable composition is uniformly coated on these articles by the coating method described above so that the film thickness after curing is CL5 to 100 μm, preferably 1 to 50 μm. Do this.

If the film thickness is less than 15 μm, the diffusion of the dye will reach saturation midway through, making it impossible to dye the dye in a deep color. On the other hand, if the film thickness exceeds 100 μm, blocking will likely occur during heating.

In the case of medium-dyed articles in the form of film or paper, it is better to apply the composition to only one side of the substrate in order to prevent migration of the disperse dye when stacking them. In order to prevent dye migration, it is more preferable to provide a non-migration layer on the surface opposite to the coated surface of the sublimable disperse dye dyeable composition.

The composition for forming the non-migration layer includes 100 parts by weight of a monomer/oligomer mixture consisting of the above-mentioned polyfunctional monomer or monomer and, if necessary, the above-mentioned photopolymerization initiator (L1 to 100 fii). However, in order to sufficiently prevent dye migration due to disperse dyes, it is necessary that the number of polymerizable groups in the 7-mer oligomer mixture be t5 or more per molecule on average. Similar to the sublimable disperse dye dyeable composition, these coating agents can also be used to adjust the viscosity with a solvent, apply to a substrate, and cure.

〔Example〕

Examples of the present invention will be described below in more detail. In the Examples and Comparative Examples, all "parts" represent parts by weight.

Reference example 1 Dyeing test method color sheet is dye sublimation color printer 5OT-cpl
oo (manufactured by Mitsubishi Electric @) Use the installed OHP cyan color sheet - 1 After aligning the dyed side of the article to be dyed with the dyed layer A side of the color sheet, mini-fax (NTT)
III) was used to record and stain in fine mode.

Reference Example 2 Evaluation of Blocking Resistance After the test in Reference Example 1, when the dyed article and the color sheet were peeled off, those that could be easily peeled off were evaluated as having "good" blocking resistance, and were evaluated as having good adhesive properties. Items that required special effort were described as ``defects.''

Reference example 3 Staining density measurement method Staining density was measured using a color analyzer (newly manufactured by Hitachi, 307).
The light transmittance T was measured using a mold (type) and was calculated as -1ogT. If the base material is opaque, measure the reflectance R and -
It was calculated as 1ogR.

Reference example 4 Light resistance evaluation method xenon fade meter (Suga test [1!111, FA
L-25AX type) @Color difference ΔK before and after dew (:r-8Z-
8730, using Hunter's color difference formula).

The larger ΔK is, the worse the light resistance is.

Reference Example 5 Dark fading evaluation method Under an atmosphere of temperature 60° C. and humidity 604, color density change after dew was evaluated as a percentage. A negative display indicates that the color density has become lighter than the initial value.

Reference Example 6 Color fringing evaluation method Samples that had undergone the dark fading test were visually observed, particularly for the degree of spread of dots recorded with a thermal head.

○ → Almost no bleeding Δ → Slight bleeding × → Large bleeding reference example 71t! Friction Coefficient Measuring Method An image-receiving film or image-receiving paper that is easily dyed with a sublimable disperse dye is fixed on a horizontal flat plate with the image-receiving surface facing upward. Next, a piece of plastic with a slightly roughened flat surface was placed on the image receiving surface with this side facing down, and a load of 1097 cm was applied, and the plastic was stretched using a tensile tester to determine the coefficient of static friction. I asked for it.

Reference Example 8 Slip evaluation method with color sheet Image receiving film or image receiving paper was used in sublimation type color printer EIOT-OP1
00 was used for recording, and the color shift of the image was observed. Image-receiving film or paper that was slippery with the color sheet caused color shift. Naka color sheet is Nichi CT-OP100
I used the one I already had.

Examples 1-4. Comparative Examples 1 to 13 After mixing and adjusting the compositions shown in Table 1, these were
Thick transparent polyester film (manufactured by Diafoil,
A sublimable disperse dye dyeable product having a film thickness of 5 to 6 μm, which is coated uniformly on one side of the product (product number 0-100K, 100 μm) by a flow coating method, and then irradiated with ultraviolet rays using a 2 ff high-pressure mercury lamp in the air. Therefore, evaluation was performed according to Reference Examples 1 to 8. The results are shown in Table 1. In addition, when a peel test was conducted on the adhesion of the cured material to the polynisder film using cellophane tape, the article of the present invention was found to be good and did not peel off.

In Example 4 #i, since it did not cure sufficiently in air, it was cured by irradiating ultraviolet rays in nitrogen.

(112P6A Nidipentaerythritol hexaacrylate (212P 5m: dipentaerythritol pentaacrylate (3) 2 I' 4 A Nidipentaerythritol tetraacryl/) (4) A-DIP: 2,2-bis(4-acryloyloxy) jetoxyphenyl)propane (51TMPTA nitrimethylolpropane triacrylate (6) Polyester resin A: resin condensed from terephthalic acid/inphthal a/ethylene glycol/neopentyl glycol (molecule-1: 15,000 to 20,000, T
(7) Polyester resin B: resin obtained by condensation polymerization of terephthalic acid/isophthalic acid/sepacic acid/ethylene glycol/neopentyl glycol (molecular weight: 20,000 to 25,000, TE10) (8
) Acrylic resin: Butyl methacrylate/methyl methacrylate = 60/40 copolymer 7g50
°C (9) Silicone surfactant A: =1,3 I Examples 5, 6, Comparative Examples 14 to 17 After mixing and adjusting the compositions shown in Table ■,
Thick transparent polyester film (manufactured by Dia Oil Co., Ltd.)
Coat it uniformly on one side of the product (product number o -1o 0110017) using the 70-coat method, and then apply 2ycwFiE in nitrogen.
Reference Examples 1 to 8 were obtained by irradiating ultraviolet rays with a pE mercury lamp to obtain sublimable disperse dye dyeable articles having a film thickness of 5 to 6 μm.
Evaluation was conducted according to the following. The results are shown in Table ■. Further, when the adhesiveness of the cured composition to the polyester film was tested for peeling using cellophane tape, the article of the present invention was found to be good and did not peel off.

(IIM-8060: manufactured by Toagosei ■, polyester acrylate (2) Polyester resin C: Terephthalic acid/isophthalic acid/sepacic acid/ethylene glycol/neopentyl glycol/1,4-butanediol was polymerized by i-polymerization. Resin (Molecular 11: 15000-20000.Tg 45°C) (3) Polyester resin D = resin consisting of terephthalic acid/isophthalic acid/ethylene glycol/neopentyl glycol (molecular weight: 20000-25000°Tg 40°C) Examples 7-9 After mixing and adjusting the compositions shown in Table ■,
It was coated uniformly on one side of a thick milky-white polyester film (manufactured by Diafoil Co., Ltd., !-300) by the dipping method, and further heated for 2K! in air. UV rays were irradiated with a high-pressure mercury lamp to obtain dyeable articles with dyeable disperse dyes having a film thickness of 5 to 6 μm, and evaluations were conducted according to Reference Examples 1 to 8. The results are shown in Table ■. Since the button base material was opaque, the dye density was determined by measuring the reflectance.

(11828DA: Epikote 828 diacrylate (2) A resin polymerized by condensation polymerization of near phthalate #/isophthalic acid/ethylene glycol/neobentyl glycol to polyester resin (molecular weight: 18,000 to 25,000.Tg 55°C) (Polyester resin F = Prephthalic acid/Isophthalic acid/Ethylene glycol/Neopentyl glycol/1. Resin polymerized by condensation polymerization of a-s/chlorhexanedimethanol (molecular weight: 20000-25000.Tg60°C) (4) Polyester I![i: Resin polymerized by condensation polymerization of terephthalic acid/sepacic acid/ethylene glycol/neopentyl glycol (molecule i: 15,000 to 20,000
．． Tg 20°C) (5) Silicone surfactant B: (2m+n+1)/(nx+ny)=2.3 (6) Silicone surfactant C: DH.

(2!II + n + 1)/(n x + n y
[Effects of the Invention] The composition easily dyeable with sublimable disperse dyes of the present invention can be easily dyed with sublimable disperse dyes at high concentration, and has significantly better color development and vividness than conventional compositions. In addition to being excellent in
It has excellent blocking resistance and high heat resistance, and the dyed articles obtained also have excellent light resistance and dark fading resistance. Therefore, the composition of the present invention can be used, for example, as a composition for dry transfer printing of textiles, or as a composition for plastic molded products (films, sheets, lenses, etc.).
It is extremely useful not only as a composition for dry thermal transfer of buttons, etc.), but also as an image-receiving layer of image-receiving paper or film for sublimation-type thermal transfer recording.

Claims (1)

[Claims] (1) Mixture 1 consisting of 40 to 95% by weight of a polyester resin having a glass transition temperature in the range of 11°C to 90°C and 60 to 5% by weight of a crosslinking agent that can be cured by active energy rays.
0.001 to 0.1 part by weight of at least one selected from silicone mold release agents and fluorine-containing mold release agents.
parts by weight, 0.1 to 10 parts by weight of at least one benzotriazole ultraviolet absorber, and 0.1 to 10 parts by weight of at least one hindered amine light stabilizer. Resin composition.