JP2883555B2 - Transfer sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer sheet having excellent physical properties such as abrasion resistance and abrasion resistance.

[0002]

2. Description of the Related Art A transfer sheet for transferring a decorative transfer layer onto a transfer object such as a resin molded product has been used for various purposes. The transfer sheet generally comprises a support sheet on which a transfer layer is provided, and the transfer layer is a decoration comprising an adhesive layer for bonding the transfer layer to the surface of an object to be transferred and a pattern provided on the adhesive layer. And a hard coating layer for protecting the decorative layer transferred onto the transfer object.

As the main components of the hard coating layer which becomes the surface layer of the molded product after the transfer of the transfer sheet, the following are conventionally known as main components. 1. Those composed of non-crosslinked type resin (Jun 17-17404)
No.) 2. Made of ionizing radiation cross-linkable resin (Japanese Patent Publication No. 61-
No. 3272, No. 64-1114). Non-polygonal α-alumina particles dispersed in an ionizing radiation-crosslinkable resin as a lubricant (Japanese Patent Laid-Open No. 3-7 / 1990)
No. 6698)

[0004]

As a main component of the hard coating layer, the above-mentioned 1. Since the non-crosslinked resin is not crosslinked, its performance such as scratch resistance, abrasion resistance and chemical resistance is not sufficiently exhibited. In addition, 2. A resin made of the ionizing radiation cross-linkable resin is excellent in abrasion resistance and chemical resistance, but is still insufficient in abrasion resistance and three-dimensional moldability.
In addition, 3. Is to be filed by the applicant of the present invention, and the transfer sheet is made of an ionizing radiation-curable resin with the resin 100 in order to improve the abrasion resistance and scratch resistance of the surface of the transfer-receiving body after the transfer. A resin layer formed by adding 10 to 30 parts by weight per part by weight of an α-alumina powder having an irregular polygonal shape having a particle size of 1 to 5 μm, a surface protective layer located on the surface of an object to be transferred after transfer of a transfer sheet It is configured as

However, when a resin layer containing the above-mentioned α-alumina is used as a surface protective layer, or when a resin containing an inorganic material such as natural glass powder is used as a paint, the abrasion resistance of the transfer sheet is α. -Although improved compared to those without the addition of alumina, it is still insufficient. Further, for example, when forming a surface resin layer having abrasion resistance by applying to the surface of the support sheet using a coating material to which an inorganic material such as the amorphous polygonal α-alumina powder or natural glass powder is added. For example, when applying using a gravure roll coat, a gravure roll or a doctor blade is in direct contact with the coating material for forming the surface resin layer. At this time, since α-alumina is a rhombohedral crystal, α-alumina is used as an abrasive or abrasive in a paint.
-Since alumina or natural glass powder has an irregular or polygonal sharp point, there is a problem that a gravure roll or a doctor blade is worn or damaged. Incidentally, even when a transfer sheet using a melamine resin having high hardness as a surface resin is transferred to the surface and flexibility such as a decorative material does not matter, the problem of wear of the coating apparatus still remains.

Further, a coating film to which an inorganic material powder such as the above-mentioned irregular polygonal α-alumina powder or natural glass powder is added becomes cloudy and has reduced transparency, and the decorative layer of the transfer sheet has a sufficient design. Can not be used for Further, there is a problem that a coating film to which a hard and polygonal powder is added has a rough touch feeling by hand and also wears an object in contact with the coating film.

Accordingly, an object of the present invention is to provide a transfer sheet excellent in scratch resistance, abrasion resistance, chemical resistance, flexibility, moldability, transparency and the like. Another object of the present invention is to provide a transfer sheet that does not impair the coating apparatus when the surface protective layer of the transfer sheet is coated. Another object of the present invention is to provide a transfer sheet which is excellent in physical properties such as abrasion resistance and abrasion resistance and which does not wear other objects in contact with the transfer sheet.

[0008]

The above object of the present invention is achieved by the following constitution. (1) A transfer sheet having a transfer layer on a support sheet, wherein the transfer layer has an average molecular weight between crosslinks of at least 100 to
A crosslinked cured product comprising a curable resin comprising 1,000,
Transfer sheet than the cross-linked cured product dispersed in a crosslinked cured product having a hard coating layer consisting of spherical particles having a high hardness inorganic materials. (2) A transfer sheet having a transfer layer on a support sheet
The transfer layer has an average molecular weight of at least 50,000 to
600,000, glass transition temperature 50-130 ° C
Non-crosslinked thermoplastic acrylic resin and two or more per molecule
A prepro having an acryloyl group or a methacryloyl group
Cross-linking curing of ionizing radiation curable resin containing limmer
And the cross-linked cured product dispersed in the cross-linked cured product
Spherical particles of high hardness inorganic material with an average particle size of 0.1 to 3 μm
Coating film containing 1 to 20% by weight based on the crosslinked cured product
Transfer sheet having a layer.

The transfer sheet of the present invention is used for a printing method for transferring a transfer layer comprising a decorative layer such as a picture layer once formed on a support sheet (peelable substrate) to another transfer object. It is. A release layer may be provided on the support sheet as needed, and a hard coating layer is required. In addition, the transfer layer also includes a decorative layer such as a picture layer, a metal deposition layer, and an adhesive layer, and one or more of these layers are selected as necessary. Note that, here, the release layer is a layer that remains on the support sheet side even after transfer and facilitates peeling off from the transfer layer, and the hard coating layer is transferred to the transfer target side after transfer, A layer that becomes a surface protective layer of the transition layer. The peeling is performed between the release layer and the transfer layer.

The decorative layer such as a picture layer may be provided on the entire surface of the support sheet (peelable substrate) or partially in a pattern, and the pattern may be natural, such as wood grain, stone grain, cloth grain, etc. Any of design, characters, figures, symbols, and various abstract patterns may be used.

As the support sheet used for the transfer sheet, a 10-200 μm sheet having good releasability from the transfer layer is used. As the material, for example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate-isophthalate copolymer, polyethylene, polypropylene, polyolefin resins such as polymethylpentene, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene , Ethylene-fluorinated ethylene-based resins such as ethylene-tetrafluoroethylene copolymer, polyamides such as nylon 6, nylon 66,
Polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinyl polymers such as vinylon, cellulose triacetate, cellulose resins such as cellophane, Monolayer or multiple laminates of synthetic resin sheets such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, acrylic resin such as polybutyl acrylate, polystyrene, polycarbonate, polyarylate, polyimide, etc. Alternatively, paper such as high-quality paper, thin paper, glassine paper, or sulfuric acid paper is used.

As described above, if necessary, a release layer may be provided on the support sheet in order to promote the releasability between the transfer layer of the transfer sheet and the support sheet (peelable substrate). . As the release layer, a coating film of a paint obtained by adding a release agent composed of a fluorine-based resin, various waxes, silicone and the like to a known vehicle, for example, an acrylic resin, a cellulose-based resin, a vinyl-based resin, or the like, is formed. Or a release resin such as a silicone resin, a melamine resin, a polyolefin resin, an ionizing radiation cross-linkable polyfunctional acrylate, polyester, epoxy or other resin, or a film formed by extrusion coating or the like. Used.

In the present invention, the hard coating layer is formed from spherical particles dispersed in a binder made of a crosslinkable resin. The spherical particles may have a smooth curved surface such as a true sphere, a spheroid in which a sphere is flattened, and a shape close to the sphere or spheroid. The spherical particles preferably have no projections, corners, valleys, or depressions on the particle surface, and have no so-called cutting edge. Spherical particles greatly improve the abrasion resistance of the surface resin layer itself compared to amorphous particles of the same material, and do not wear the coating device, and other objects that come into contact with the coating film after curing. And the transparency of the coating film is also increased. When there is no cutting edge, the effect is particularly large.

The spherical particles preferably have an average particle size of 0.1 to 30 μm, and more preferably have an average particle size of 0.5 to 3 μm. When the average particle size is less than 0.1 μm, there is no effect on improving the wear resistance and scratch resistance of the hard coating layer, and when the average particle size exceeds 3 μm, the hard coating layer tends to become cloudy and the surface is protected. The transparency as a layer decreases. On the other hand, if the average particle size exceeds 30 μm, the flexibility of the coating film becomes insufficient, and cracks occur due to stress during transfer. In particular, this phenomenon is remarkable when the transfer target has an uneven shape.

The addition amount of the spherical particles is 1 to 20% by weight, more preferably 1 to 10% by weight, based on the crosslinkable resin. If the addition amount is less than 1% by weight, the hard coating layer has insufficient scratch resistance, abrasion resistance, etc., and the addition amount is 10% by weight.
If it exceeds 2,000, the transparency of the coating film will be poor, and if it exceeds 20% by weight, the flexibility of the coating film will be insufficient.

The spherical particles have an average particle size of 0.1 to 30 μm, and are appropriately selected within a range of 1 to 20% by weight based on the crosslinkable resin depending on the thickness of the hard coating layer. For example, when the thickness of the hard coating layer is formed to be 0.1 to 5 μm, the average particle diameter of the spherical particles is preferably in the range of 0.1 to 8 μm.

The material of the spherical particles is higher in hardness than the crosslinkable resin.
Particles of inorganic materials can be used. The difference in hardness between the spherical particles and the crosslinkable resin is measured by a method such as Mohs hardness or Vickers hardness, and is preferably 1 or more when expressed in Mohs hardness, for example.

Specific examples of the material of the spherical particles include inorganic particles such as α-alumina, silica, chromium oxide, iron oxide, diamond and graphite. Particularly preferred spherical particles include spherical α-alumina because they have very high hardness and a large effect on wear resistance, and spherical particles are relatively easily obtained. As described in JP-A-2-55269, spherical α-alumina is obtained by adding a mineralizing agent or a crystallizing agent such as alumina hydrate, a halogen compound or a boron compound to a fused alumina or a sintered alumina. Add a small amount to the pulverized product,
By performing the heat treatment at a temperature of 400 ° C. or more for 2 hours or more, a cutting edge in alumina is reduced and, at the same time, a spherical shape is obtained. Showa Denko Co., Ltd. has announced “spherical alumina” (Spheri alumina).
cAl Aluminum) AS-10, AS-20, A
S-30, AS-40 and AS-50 "having various average particle sizes are commercially available.

The spherical particles can be treated on the surface of the particles. For example, treatment with a fatty acid such as stearic acid improves dispersibility. In addition, by treating the surface with a silane coupling agent, the adhesion to a crosslinkable resin used as a binder and the dispersibility of particles in a coating composition are improved. Examples of the silane coupling agent include an alkoxysilane having a radical polymerizable unsaturated bond such as vinyl and methacryl in the molecule, and an alkoxysilane having a functional group such as epoxy, amino and mercapto in the molecule. Depending on the type of crosslinkable resin used with the spherical particles, the silane coupling agent may be, for example, (meth)
In the case of an ionizing radiation-curable resin such as acrylate, use an alkoxysilane having a radical polymerizable unsaturated bond, and in the case of a two-part curable urethane resin, use an alkoxysilane having an epoxy group or an amino group, It is preferable to select the type of radical polymerizable unsaturated bond or functional group.

The alkoxysilane having a radical polymerizable unsaturated bond is, specifically, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxy. Propyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldiethoxysilane , Γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, and other alkoxysilanes having a radically polymerizable unsaturated bond in the molecule, and epoxy, amino, and mercury in the molecule. And the like alkoxysilane having a functional group such as and.

The method of treating the surface of the spherical particles with a silane coupling agent is not particularly limited, and a known method can be used. For example, a method in which a predetermined amount of a silane coupling agent is sprayed while vigorously stirring spherical particles as a dry method, or a method in which a predetermined amount of a silane coupling agent is added after dispersing spherical particles in a solvent such as toluene as a wet method. A method for causing the reaction is mentioned. The treatment amount (predetermined amount) of the silane coupling agent for the spherical particles is preferably such that the minimum coverage area of the silane coupling agent is 10 or more with respect to the specific surface area of the spherical particles of 100. The minimum coverage area of the spherical particles is 10 per 100 of the specific surface area of the spherical particles.
Less than that is not very effective.

The crosslinkable resin used as the binder may be a hard coating layer of a conventionally known transfer sheet such as an ionizing radiation curable resin or a thermosetting resin (including a room temperature curable resin and a two-component reaction curable resin). Resins used as crosslinkable resins can be used. As the crosslinkable resin, an ionizing radiation curable resin is preferable because it has a high curing speed and good workability, and can easily adjust physical properties of the resin such as flexibility and hardness. The selection of the above-mentioned crosslinkable resin can be appropriately selected according to the use of the transfer sheet. After the crosslinkable resin is applied by dispersing spherical particles in an uncrosslinked state,
The coating is completed by crosslinking, polymerizing and curing.

The higher the crosslink density of the crosslinkable resin, the higher the abrasion resistance, but the lower the flexibility and flexibility. Therefore, it is preferable that the crosslink density of the crosslinkable resin is appropriately selected according to the wear resistance and flexibility depending on the use of the transfer sheet and the like in accordance with the type of the base material and the like. The crosslink density can be represented, for example, by the average molecular weight between crosslinks shown in the following formula (1).

Average molecular weight between crosslinks = total molecular weight / number of crosslink points (1) where the total molecular weight is Σ (the number of moles of each component × the molecular weight of each component), and the number of crosslink points is Σ [{(The number of functional groups of each component −1) × 2} × the number of moles of each component].

Table 1 below shows experimental examples in which the relationship between abrasion resistance and flexibility when the average molecular weight between crosslinks of the crosslinkable resin was changed was examined. Table 1 shows that a urethane acrylate oligomer and two types of acrylate monomers are used as the crosslinkable resin, the average molecular weight between crosslinks is adjusted by changing the mixing ratio of the components, and α-alumina having an average particle diameter of 3 μm is used as spherical particles. A composition obtained by adding 11 parts by weight to 100 parts by weight of the crosslinkable resin, applied on a support sheet at an application amount of 25 g / m ² , is cured, and transferred to a synthetic resin plate using a heat-sensitive adhesive. It is a comparison of the abrasion resistance and flexibility in the case of the above. The abrasion resistance test was performed according to JIS, K6902, and the number of times until the thickness of the hard coating layer became half was shown.

Regarding the flexibility, ◎ indicates that the cured crosslinkable resin is very flexible, 〇 indicates good, △ indicates that the flexibility is slightly low, and X indicates that the flexibility is considerably low. Note that the experiment No. In Experiment No. 6, a conventional α-alumina having an irregular shape with an average particle diameter of 3 μm without using spherical particles was used as an experimental No. 6.
The same amount as 1 to 5 was added. In the above resin system, the average molecular weight between crosslinks can be used in the range of 100 to 1,000, but is more preferably 150 to 700. Further, when a flexible substrate is used, it is more preferable to use one having an average molecular weight between crosslinks of 300 to 700, and a transfer sheet having good flexibility and abrasion resistance can be obtained within the above range. .

[0027]

[Table 1]

The experimental results in Table 1 show that, for the same type of cross-linkable resin, the smaller the average molecular weight between cross-links (ie, the higher the cross-link density), the more the cross-linkable resin as a binder holds the spherical particles more firmly. This shows that the wear resistance is further improved. Therefore, the abrasion resistance can be further improved by adjusting the average molecular weight between crosslinks of the crosslinkable resin to be small within a range that does not impair the flexibility.

The ionizing radiation-curable resin used as the crosslinkable resin is, for example, an ionized radiation-curable resin obtained by appropriately mixing a prepolymer, oligomer and / or monomer having a polymerizable unsaturated bond or a cationic polymerizable functional group in the molecule. A composition curable by radiation is used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum that can polymerize or crosslink a molecule, and usually an ultraviolet ray or an electron beam is used.

Examples of the ionizing radiation-curable resin forming the hard coating film include a radical polymerizable unsaturated group such as a (meth) acryloyl group and a (meth) acryloyloxy group, and a cationic polymerizable functional group such as an epoxy group in a molecule. Monomer, prepolymer or polymer having two or more thiol groups or thiol groups (hereinafter collectively referred to as compounds)
Consists of These monomers, prepolymers or polymers may be used alone or as a mixture of two or more. In this specification, (meth) acrylate is used to mean acrylate or methacrylate.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth)
Acrylate, melamine (meth) acrylate, triazine (meth) acrylate and the like can be used.

The molecular weight is usually about 100 to 100.
About 00 is used. Both acrylate and methacrylate can be used, but acrylate is faster in terms of crosslinking curing speed with ionizing radiation. Therefore, acrylate is more advantageous for the purpose of curing efficiently at high speed in a short time. As the polymer having a radical polymerizable unsaturated group, a polymer having a degree of polymerization of about 10,000 or more is used.

Examples of the prepolymer having a cationically polymerizable functional group include epoxy resins such as bisphenol type epoxy resin, novolak type epoxy resin, alicyclic type epoxy resin and aliphatic type epoxy resin, aliphatic type vinyl ether, aromatic vinyl ether and the like. There are prepolymers such as vinyl ether resins such as aromatic vinyl ethers, urethane vinyl ethers and ester vinyl ethers, cyclic ether compounds and spiro compounds.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers of (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate. A) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylamino Ethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) ) Ack relay , Ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate,
Phenoxy polyethylene glycol (meth) acrylate, tetrahydroxyfurfuryl (meth) acrylate, methoxytripropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2- (meth) acryloyloxypropyl Hydrogen phthalate and the like.

Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexyldiol di (meth) acrylate, 1,9 -Nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triprolylene glycol di (meth) acrylate, bisphenol A-di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Examples include hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, and tris (meth) acryloyloxyethyl phosphate.

As examples of the monomer having a cationically polymerizable functional group, the above-mentioned prepolymeric monomer having a cationically polymerizable functional group can be used. Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.

Among these compounds, a radically polymerizable urethane (meth) acrylate compound is preferred in view of surface physical properties after transfer, elongation, and flexibility. In addition, a cationically polymerizable epoxy compound is preferable because it has an adhesive property to a transfer object and hardly inhibits curing by oxygen in the air.

When curing with ultraviolet light or visible light, a photopolymerization initiator is added to the ionizing radiation-curable resin. In the case of a resin system having a radical polymerizable unsaturated group,
As photopolymerization initiators, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenyl biimidazole, isopropyl-N, N- Dimethylaminobenzoate or the like can be used alone or in combination.

In the case of a resin having a cationically polymerizable functional group, an aromatic diazonium salt as a photopolymerization initiator,
It can be used alone or as a mixture of an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoinsulfonic acid ester, a freeloxysulfoxonium salt, a diallyliodosyl salt and the like. In addition,
The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin. Further, n-butylamine, tri-n-butylphosphine, etc. may be further added as needed as a photopolymerization accelerator (sensitizer).

Usually, the above compounds are used alone or in combination of two or more, if necessary. In order to impart ordinary coating suitability to the ionizing radiation-curable resin, the prepolymer or polythiol is used in combination with the above-mentioned compound. It is preferable that the content of the monomer be not less than 95% by weight and not more than 95% by weight.

In selecting the monomer, if the flexibility of the cured product is required, the amount of the monomer may be reduced as long as the coatability is not impaired, or a monofunctional or bifunctional acrylate monomer may be used. The structure has a low crosslinking density. If the cured product requires abrasion resistance, heat resistance, solvent resistance, etc., use a larger amount of monomer within the range that does not affect coating suitability, or use a trifunctional or higher acrylate monomer. And a structure having a high crosslinking density can be obtained. In addition, a monofunctional monomer and a trifunctional or higher functional monomer may be mixed to adjust coating aptitude and physical properties of a cured product.

The above-mentioned monofunctional acrylate monomers include 2-hydroxyl acrylate, 2-hexyl acrylate and phenoxyethyl acrylate. Examples of the bifunctional acrylate include ethylene glycol diacrylate and 1,6-hexanediol diacrylate, and examples of the trifunctional or higher acrylate include trimethylolpropane triacrylate, pentaerythritol tri (tetra) acrylate, and dipentaerythritol hexaacrylate. Acrylate and the like.

Further, a non-ionizing radiation curable resin for adjusting physical properties such as flexibility and surface hardness of the cured product can be added to the ionizing radiation curable resin. As the non-cured ionizing radiation resin, thermoplastic resins such as urethane-based, cellulose-based, polyester-based, acrylic-based, butyral-based, polyvinyl chloride, and polyvinyl acetate are used. Particularly, cellulose-based and urethane-based resins are used. Butyral is preferred from the viewpoint of flexibility.

The flexibility of the hard coating layer (when preparing the transfer sheet,
Or deformation during transfer, prevention of cracking due to bending) and abrasion resistance, abrasion resistance, and when the coating film is dried with a solvent, it is dry to the touch even in the uncured state, and the decorative layer, adhesive From the point that layers can be overprinted, an ionizing radiation-curable resin hard coating film has an average molecular weight of 50,000 to 600,000,
It is preferable to use a resin containing a non-crosslinked thermoplastic acrylic resin having a glass transition temperature of 50 to 130 ° C and a prepolymer having two or more acryloyl groups or methacryloyl groups in one molecule.

The non-crosslinked thermoplastic acrylic resin includes (meth) acrylic acid, methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, Alkyl (meth) acrylates such as n-hexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, 2-chloroethyl (meth) acrylate, (meth) acryl Alkyl (meth) acrylates such as acid-3-chloropropyl, (meth)
2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, and the like, (meth) acrylates having an OH group, methyl α-chloro (meth) acrylate, ethyl α-chloro (meth) acrylate OH such as halogenated (meth) acrylates, such as 1-chloro-2-hydroxyethyl (meth) acrylate;
A homo- or copolymer of one or more of (meth) acrylic monomers such as α-alkyl (meth) acrylates having a group and glycidyl (meth) acrylate, and an average Molecular weight 50,000
Those having a glass transition temperature of 50 to 130 ° C, preferably a glass transition temperature of 80 to 110 ° C can be used.

When the average molecular weight is 50,000 or less, the scratch resistance after curing of the ionizing radiation-curable resin hard coating layer is extremely reduced. On the other hand, the average molecular weight is 600,0
When the ratio is more than 00, the elongation of the ionizing radiation-curable resin hard coating layer at the time of transfer is reduced, and thus the coating layer is cracked due to deformation at the time of transfer.

When the glass transition temperature is 50 ° C. or lower, the abrasion resistance after curing of the ionizing radiation-curable resin hard coating layer is extremely reduced. Properties (dryness to the touch) are insufficient. On the other hand, when the glass transition temperature is 130 ° C. or higher, the elongation of the ionizing radiation-curable resin hard coating layer during transfer decreases.

The prepolymer which is a component of the ionizing radiation-curable resin hard coating layer is a prepolymer which can be cross-linked by ionizing radiation.
An acryloyl group-containing molecular weight of 100 to 10,000,
More preferably, from 100 to 5,000 of the prepolymer can be used.

When the molecular weight is less than the lower limit, the cured hard coating layer has insufficient elongation and flexibility, and when the molecular weight exceeds the upper limit, the cured hard coating layer has abrasion resistance. Run out. Of these, urethane (meth) acrylate having both properties of elongation during transfer and scratch resistance of the surface after transfer is preferable.

The content of the prepolymer in the ionizing radiation-curable resin coating layer of the present invention is preferably 30 to 90 parts by weight based on 100 parts by weight of the acrylic resin. Here, if the prepolymer content is 30 parts by weight or less, the crosslinking density of the ionizing radiation-curable resin hard coating layer due to ionizing radiation becomes extremely coarse, the strength of the hard coating layer itself is insufficient, and the abrasion resistance is poor. Decrease.

On the other hand, if the amount of the prepolymer is 90 parts by weight or more, the non-adhesiveness of the coating film in an uncured state after drying the solvent becomes insufficient. In addition, since the crosslinking density of the ionizing radiation-curable resin hard coating layer due to ionizing radiation becomes too dense, the elongation of the hard coating layer itself decreases, and deformation, breakage, and cracks occur during transfer.

In the case of the transfer sheet described above, the hard coating layer has a non-crosslinked plastic acrylic resin having an average molecular weight of 50,000 to 600,000 and a glass transition temperature of 50 to 130.degree. It is formed from an ionizing radiation-curable resin composition in which a prepolymer having a (meth) acryloyl group is compatible, and is crosslinked and cured by irradiation with ionizing radiation before or after transfer.

The non-crosslinkable plastic acrylic resin is applied on a support sheet and, after the diluting solvent is dried and volatilized, is compatible with the prepolymer to form an uncured ionizing radiation-curable resin hard coating layer. Form. In this compatible state,
The part in which the acrylic resin molecule unit is intertwined with the prepolymer molecule unit, the part in which the acrylic resin molecule group is intertwined with the prepolymer molecule group, and the prepolymer molecule invades the acrylic resin molecule group. It is presumed that it is composed of a mixed portion and a portion where the single acrylic resin molecule has penetrated into the prepolymer molecule population.

The hard coating layer at this stage has a moderate elastic limit and sufficient plastic deformation (ie, flexibility) at room temperature,
It behaves as a flexible solid film. The hard coating layer has thermoplasticity.

This is because the acrylic resin molecules or the molecular group and the prepolymer molecules are close to each other and are entangled with each other and are fixed by the intermolecular force. This is because there is no mutual chemical bond. Therefore, when a stress is applied to the hard coating layer, the hard coating layer easily bends and deforms due to elastic deformation while the force within a range not exceeding the intermolecular force is applied between the molecules, and the stress is reduced. If it disappears, it will be restored to its original shape. Also, when a force exceeding the intermolecular force is applied between the molecules, it is considered that the molecules or the molecular groups slide, causing plastic deformation. Therefore, the hard coating layer has sufficient flexibility due to external stress in the uncured state.

Further, when the hard coating layer is heated to a high temperature, each molecule is gradually released from the binding of the potential energy of the intermolecular force due to the thermal kinetic energy of the molecule, and the elastic restoring force of the molecules decreases. Come. for that reason,
Plastic deformation becomes stronger, and it becomes even hotter,
When the thermal kinetic energy of the molecule completely overcomes the potential energy of the intermolecular force, the hard coating layer becomes fluid. Therefore, the hard coating layer has thermoplasticity. Because of this flexibility, plastic deformation, and thermoplasticity, the uncured hard coating layer has sufficient moldability.

After the application of the ionizing radiation-curable resin composition, even in an uncured state, if the solvent is volatilized and dried,
It becomes a non-sticky solid. The reason is that the acrylic resin molecules and the prepolymer molecules are entangled and bound by the intermolecular force.

The hard coating layer having the acrylic resin and the prepolymer has a greater flexibility and flexibility even after being cross-linked and cured by ionizing radiation as compared with a cured layer of a conventional ionizing radiation-curable resin. It has elasticity and plasticity. In addition, it has the same level of heat resistance, chemical resistance and abrasion resistance as compared with a conventional cured layer of ionizing radiation-curable resin.

This is because the hard coating layer after cross-linking and curing has a structure in which the non-cross-linked thermoplastic acrylic resin molecules and the three-dimensional cross-linked structure of the pre-polymer molecules enter each other and are entangled (so-called interpolymer network). This is considered to be because the prepolymer molecule is composed of a hybrid of a portion consisting only of the three-dimensional crosslinked structure and a portion consisting only of the non-crosslinked thermoplastic acrylic resin molecule population.

By cooperating with the mechanical strength of the three-dimensionally crosslinked structure of the prepolymer molecule and the deformability, slipperiness and shock absorption of the acrylic resin molecule group, it resists external stress during wear, In addition, it is considered that sufficient abrasion resistance is generated by absorbing and relaxing a part thereof.

The acrylic resin molecule group, the acrylic resin molecule and the three-dimensional crosslinked structure of the prepolymer molecule enter each other with respect to external stress during molding, and the entangled structure portion deforms and follows. It is considered that greater moldability can be exhibited as compared with a cured layer of a conventional ionizing radiation-curable resin.

Compared with a transfer sheet obtained by ionizing radiation curing of a liquid monomer and a prepolymer as described in JP-B No. 62-3272, the transfer sheet of the present invention has a protective layer applied after drying of a diluting solvent. Is characterized in that it becomes a non-adhesive solid coating even in an uncured state. Therefore, the transfer sheet of the present invention can be used in a state where the protective layer is transferred in a state where the protective layer is uncured and has flexibility and thermoplasticity, and then cured by ionizing radiation.

Therefore, the transfer sheet of the present invention has an uneven shape without causing cracks and the like with respect to a transfer object having the uneven shape, compared with a transfer sheet obtained by ionizing radiation curing of a liquid monomer and a prepolymer. It is possible to perform the transfer following.

In this case, since the uncured protective layer is a non-adhesive solid coating film, a pattern layer, an adhesive layer and the like can be overprinted on the protective layer by inline multicolor printing. In addition, the transfer sheet can be stored and transported by being wound up on a roll while the protective layer is in an uncured state. This is not possible with transfer sheets using liquid monomers and prepolymers.

Since the obtained transfer sheet has a hard coating layer having the above-mentioned composition, even if the hard coating layer is cured on the transfer sheet and then used for transfer, the transfer sheet is obtained by Compared with a transfer sheet obtained by curing a liquid monomer and prepolymer by ionizing radiation as described in JP-A-62-2272, the rigidity of the hard coating layer is higher (although the thermoplasticity has been lost) and it has an uneven shape. When transferred to an object to be transferred, cracks and damage are less likely to occur, and the ability to follow irregular shapes is good.

The hard coating layer described in Japanese Patent Publication No. 5-57120 is a crosslinkable polymer having a radical polymerizable unsaturated group which is solid at room temperature in an uncured state and is thermoplastic. Compared with the transfer sheet, the obtained transfer sheet is similar in that the hard coating layer has the above-described composition, so that it is printed and coated and then dried to the touch after the solvent is dried, but the cured hard coating layer is hardened. It is more excellent in that it can achieve both the abrasion resistance, heat resistance, chemical resistance, and abrasion resistance, and the moldability of the uneven shape.

The thermosetting resin used as the crosslinkable resin of the hard coating layer of the present invention is, specifically, a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin. Resins, polyurethane resins, epoxy resins, amino alkyd resins, melamine-urea co-condensation resins, silicon resins, polysiloxane resins, and the like. If necessary, a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, etc. may be added and used.

As the above-mentioned curing agent, isocyanate or organic sulfonate is usually used for unsaturated polyester resin or polyurethane resin, amine is used for epoxy resin, radical initiator such as peroxide such as methyl ethyl ketone peroxide or azoisobutyl nitrile is used. Agents are often used for unsaturated polyesters and the like.

As the above isocyanate, divalent or higher valent aliphatic or aromatic isocyanate can be used.
Aliphatic isocyanates are desirable from the viewpoint of preventing thermal discoloration and weather resistance. As specific isocyanates, tolylene diisocyanate, xylylene diisocyanate, 4,4′-
Examples thereof include diphenylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

In the coating composition comprising the crosslinkable resin as the hard coating layer and the spherical particles, in addition to the above components,
Colorants such as dyes and pigments, other CaCO ₃ , BaS
Fillers such as known matting regulators such as O ₄ and nylon resin beads and extenders, and other additives can be added.

The method of coating the hard coating layer is as follows: gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, wire bar coat , A flow coat, a comma coat, a pouring coat, a brush coat, a spray coat and the like can be used, and a gravure coat is preferable.

The timing of hardening of the hard coating layer is as follows: when the coating layer is uncured, but becomes dry to the touch (non-adhesive, non-flowable) after the solvent is dried, before the transfer and simultaneously with the transfer. Or after transfer. In the case where the hard coating layer does not dry to the touch even after solvent drying in an uncured state, it is transferred on a transfer sheet after being cured.

A coating film and another layer such as an adhesive layer, if necessary, are formed as a transfer layer on the release support sheet, and the coating film is cured by crosslinking. After bonding to the transfer object, only the support sheet is peeled off.

There are various transfer methods as follows. (A) JP-B-2-42080, JP-B-4-199
No. 24, etc., by simultaneous injection molding transfer method. (B) JP-A-4-288214, JP-A-5-57
No. 786, a vacuum forming simultaneous transfer method. (C) JP-B-59-51900, JP-B-61-5
No. 895, Japanese Patent Publication No. Hei 3-2666, and the like. (D) V-cut simultaneous transfer method as disclosed in JP-B-56-7866. (E) A so-called hot stamping method in which the transfer layer side of the transfer sheet is overlapped on the surface of the transfer object, and the transfer layer is adhered to the transfer object by pressing with a heating roller.

In the transfer sheet of the present invention, it is preferable that the decorative layer is provided on the hard coating layer (the back side after the transfer).
The decoration layer is decorated with a pattern or the like, and the pattern printing is performed by a method such as gravure printing, screen printing, or offset printing. For example, in gravure printing ink, a desired pattern is printed on the hard coating layer using an ink containing a vehicle alone or a mixture of polymethyl methacrylate, polyvinyl chloride-vinyl acetate copolymer, polyurethane, polymethacrylate, polyacrylate, etc. Just do it.
The decorative layer can also include a hiding layer and an antistatic layer made of conductive ink. In addition, a metal deposition layer (entire or patterned) may be formed.

In the constitution of the present invention, an adhesive layer can be provided on the ionizing radiation-curable resin hard coating layer or on the decorative layer. This adhesive layer is selected from heat-sensitive adhesives, pressure-sensitive adhesives, solvent-activated adhesives, ionizing radiation-curable adhesives, etc. according to the application as a layer for transferring and bonding the transfer layer to the transfer target. it can.

The transfer layer has a layer other than the adhesive layer such as a decorative layer, and these layers are on the side in contact with the transfer object when transferring the transfer sheet to the transfer object, and the layer itself is sufficient. The adhesive layer may be omitted when it has adhesiveness or when an adhesive layer is provided on the transfer-receiving body side.

The heat-sensitive adhesive develops adhesiveness by heating, and is usually made of a thermoplastic resin, an ionomer, or the like, which melts with heat to exhibit adhesive strength. Examples of the thermoplastic resin include cellulose derivatives such as cellulose nitrate and cellulose acetate; styrene resins or styrene copolymers such as polystyrene and poly α-methylstyrene; poly (methyl meth) acrylate; and poly (ethyl meth) acrylate. Acrylic resin, vinyl chloride vinyl acetate copolymer, vinyl polymer such as ethylene vinyl alcohol copolymer, rosin, rosin ester resin such as rosin-modified maleic resin, polyisoprene rubber, natural such as styrene butadiene rubber, or Synthetic rubbers and various ionomers are used.

In addition, a thermosetting resin which causes cross-linking polymerization, addition polymerization or the like by heat and is cured to exhibit an adhesive force is also used as the heat-sensitive adhesive. As the thermosetting resin, for example, an epoxy resin, a polyurethane resin, a phenol resin, or the like is used.

As the pressure-sensitive adhesive, any of conventionally known pressure-sensitive adhesive tapes and pressure-sensitive adhesives used for seals can be used.
For example, rubber resins such as polyisoprene rubber, polyisobutyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, (meth) acrylate resin, polyvinyl ether resin, polyvinyl acetate resin, polyvinyl chloride / vinyl acetate Polymeric resin, any resin based on one or a mixture of two or more kinds of polyvinyl butyral-based resin, a suitable tackifier, cumarone-indene-based resin and the like is added in an appropriate amount, Further, if necessary, a softener, a filler, an antioxidant, a crosslinking agent, and the like are added.

When the antistatic layer is provided as an independent layer, the hard coating layer may be formed between the hard coating layer and the adhesive layer, between the hard coating layer and the decorative layer, or between the decorative layer and the adhesive layer. Provided on other than the outermost surface of the film layer. This is the abrasion resistance of the hard coating layer,
This is because the surface properties such as chemical resistance are not impaired.

The antistatic layer provided as an independent layer is formed by adding an antistatic agent to the same vehicle as the decorative layer. Examples of the antistatic agent include a metal such as aluminum, gold, silver, copper, and nickel; a metal oxide such as tin oxide, indium oxide, and tin oxide-doped indium oxide (ITO); Pieces or surfactants.

The antistatic agent may be added to a hard coating layer, an adhesive layer, a decorative layer, etc., or a release layer. However, in order not to reduce the surface properties of the transfer layer,
It is preferable not to add it to the hard coating layer. The purpose of the antistatic layer is to prevent dust from being sucked and adhered, and to prevent electric shock and spark discharge when transferring a transfer sheet or using a product having a transfer layer after transfer.

An antistatic agent may be added to the release layer or the support sheet as long as it only prevents charging during transfer. However, it is necessary to add an antistatic agent to any one of the transfer layers in order to prevent the transfer target from being charged even after the transfer.

The transfer object of the present invention includes synthetic resins such as polyvinyl chloride resin, acrylic resin, ABS and phenol resin, metals such as iron, copper and aluminum, glass, and the like.
Ceramics such as earthenware, ceramics, cement, calcium silicate, etc., woody materials such as wood plywood, wood veneer, and particle board, paper, cloth, nonwoven fabric and the like can be targeted.
Sheets (or films) include
Examples include a flat plate, a curved plate, a columnar body, a sheet, and various three-dimensionally shaped three-dimensional objects.

[0086]

FIG. 2 is a view for explaining the action of the surface of the transfer-receiving body obtained by transferring the transfer layer including the hard coating layer using the transfer sheet of the present invention, and FIG. FIG. 2B shows an enlarged state near the surface when a stress is externally applied to the surface of the transfer sheet on which the spherical particles of the present invention have been transferred. FIG. This shows a state where the vicinity of the surface when the stress is applied to the surface of the transferred transfer sheet is enlarged. As shown in FIG. 2A, when a stress is applied to the surface of the transfer sheet of the present invention by another contact object 9, the contact object slides on the surface of the spherical particle 5 because the spherical particle 5 has a smooth surface. The stress is not easily transmitted to the particles. Therefore, there is no possibility that the spherical particles 5 fall off from the crosslinkable resin layer 4 as a binder. On the other hand, when the conventional amorphous particles 10 are used as shown in FIG. 2 (b), the contact material 9 is caught on the protruding portion of the surface of the particles 10 and stress is applied to the particles. The particles are easily transmitted, and the irregular shaped particles 10 easily fall off from the crosslinkable resin layer 4. Therefore, the crosslinkable resin layer 4 on the surface of the transfer sheet of the present invention has a good slip and abrasion resistance is remarkably improved. In addition, the spherical particles 5 on the surface are less likely to be caught during erosion and the like than the irregular-shaped particles 10 and do not damage or wear the surface of other contact objects.

In the case where extremely hard particles are added and dispersed in a soft resin which is a non-crosslinkable resin such as a thermoplastic resin, the resin is broken by the hard particles when an external force is applied. It has the effect of damaging the resin surface as if a hoe plows a field by falling off or being dragged by abrasion, and the wear resistance does not improve as expected. On the other hand, in the present invention, since the binder resin is the crosslinkable resin layer 4, the strength is high, and such hard particles (spherical particles 5) do not fall off or are damaged, so that the abrasion resistance of the coating film is remarkable. Can be improved.

Further, as shown in FIG. 2B, when the conventional irregular shaped particles 10 are used, the voids 11 and the like easily exist between the crosslinkable resin layer 4 and the irregular shaped particles 10. However, in the case of the present invention, since the particles are spherical particles 5, such voids are not easily generated. Therefore, it is difficult to form an air layer on the wear-resistant resin layer (crosslinkable resin layer 4), and the surface is not whitened, so that the design is not reduced. In addition, the absence of a gap increases the bonding strength between the spherical particles 5 and the crosslinkable resin layer 4 of the binder, which also contributes to the above-mentioned improvement in wear resistance.

[0089]

The present invention will be further described with reference to specific examples of the present invention. As shown in FIG. 1, a releaseable biaxially stretched polyethylene terephthalate film having a thickness of 25 μm (Reiko Co., Ltd.)
Co., Ltd.) as a support sheet 2 and a coating composed of the composition shown in Table 2 below (mixing ratio by weight) was applied to one surface of the support sheet 2 by gravure coating in an amount of 1 g / m ² . When the solvent was dried by blowing hot air at 40 ° C., the surface of the coating film was brought into a touch-dry state. At this point, the coating film is in an uncured state. However, the binder (crosslinkable resin layer 4) made of a crosslinkable resin and the spherical particles 5 (α-aluminum in Table 2 ) are referred to in the present invention.
, Silica ).

[0090]

[Table 2]

1) Thermoplastic acrylic resin manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dianal BR-88, average molecular weight 430,000, glass transition temperature 105 ° C. 2) Urethane acrylate prepolymer manufactured by Nippon Gosei Co., Ltd. , Trade name: UV-7210B, average molecular weight 2,000
0, average number of acryloyl groups in the molecule 2.5 3) Micro silica having a particle size of 0.1 μm or less manufactured by Nippon Silica Co., Ltd. 4) Mixed solvent consisting of methyl ethyl ketone + toluene

Then, an acrylic resin was applied on the above-mentioned dry-touched coating layer to improve the printability of the pattern by using a primer resin (manufactured by The Inktec Co., Ltd., trade name: MHO-3).
0) and gravure coated at 1 g / m ² (this primer layer is not shown). Thereafter, an abstract pattern is gravure-printed as a pattern using acrylic ink manufactured by Showa Ink Co., Ltd. as a decoration layer 6, and a vinyl chloride / vinyl acetate adhesive (Showa Ink Co., Ltd.) is applied on the decoration layer 6. Trade name FVH
1 g / m ² of S) is applied by gravure printing to form an adhesive layer 7
And

An electron beam (EB) was applied to the coating film thus obtained.
Was irradiated. The electron beam used at this time had an accelerating voltage of 175.
The hard coating layer 3 was crosslinked and cured at a KV of 8 Mrad. The obtained transfer sheet 1 is made of polymethyl methacrylate (trade name: Delpet 80N, manufactured by Asahi Kasei Corporation).
Is transferred to a transfer layer (hard coating layer 3 (= crosslinked) by simultaneous injection molding transfer using a molding machine (Matsuda Seisakusho (PM-150DM injection molding machine)) as a molding resin molded at a gate temperature of 240 ° C. and a mold temperature of 40 ° C. The transfer of the conductive resin layer 4 + the spherical particles 5) + the decorative layer 6 + the adhesive layer 7) was performed. Table 3 shows the results of the performance test of the coated film obtained after the transfer.

[0094]

[Table 3]

The evaluation methods of the above various tests are as follows. Pencil hardness: The method of JIS-K5400 6.14 was used (load: 500 g). Steel wool rubbing test: Using # 0000 steel wool, the surface was observed 10 times after reciprocating the surface under a load of 500 g to check for any scratches. Transparency: Measured with a direct-read haze meter manufactured by Toyo Seiki Seisaku-sho, Ltd. ΔHz = Hz ₁ −Hz ₀ ΔHz: Haze difference Hz ₁ : Haze value after transfer Hz ₀ : Haze value of only the substrate to be transferred Elongation (rupture): Tensilon tensile tester in the state of a transfer foil having a test piece length of 10 cm At a speed of 20 mm / min, and the elongation up to the point of occurrence of cracks was measured. Formability: 10mm
The presence or absence of cracks in the R portion when in-molded in the R shape was determined.

Examples 2 to 6 and Comparative Examples 4 to 6 A mixed resin of a melamine resin and an acrylic resin was baked on the surface of a biaxially stretched polyethylene terephthalate sheet having a thickness of 25 μm to form a release layer. Then, the urethane acrylate oligomer shown in Table 4
Spherical particles shown in Table 5 (Examples 2 to 6) were added to crosslinkable resins A to C composed of compositions in which the mixing ratios of the functional acrylate monomer a and the bifunctional acrylate monomer b were respectively changed.
Spherical α-alumina) or amorphous particles (Comparative Examples 4 to
The coating composition in which 6) is dispersed is applied at 30 g / m ² dry (film thickness 15 μm), and an electron beam is applied at 8 Mrad (175 kv).
Irradiation resulted in a transfer sheet having a wear-resistant resin layer formed on the surface of the transfer paper. Table 5 shows the results of the abrasion resistance test performed on each of the obtained transfer sheets.

The abrasion resistance test was performed in the same manner as in the experimental example. The evaluation of the flexibility test was performed in the same manner as in the experimental example. The wear resistance test method uses a taper wear tester,
The evaluation was carried out by a method of evaluating the number of rotations until the base material to be transferred was exposed under a load of 1 kg (wear wheels used CF-10F).

The flexibility test was conducted by a method of evaluating the surface by visual observation after bending at 0.5 mmR using a bending tester. When there was a crack at the time of bending, it was evaluated as ×, when there was a slight crack, Δ, and when there was no crack, ○.

[0099]

[Table 4]

[0100]

[Table 5]

As shown in Table 5, the wear resistance of Example 2 using spherical α-alumina was clearly higher than that of Comparative Example 4 when the same amount of amorphous α-alumina was added. When amorphous α-alumina was used, the same abrasion resistance as spherical α-alumina was not obtained even if the addition amount was doubled. Further, in the case of Comparative Example 5 using amorphous α-alumina, the abrasion of the roll of the coating apparatus was observed, but in the case of using silica of Comparative Example 6 and in any of Examples 2 to 6, No wear was observed on the rolls of the processing equipment.

Further, Examples 3 and 4 compare the difference in the average molecular weight between crosslinks of the crosslinkable resin. In this case, the smaller the average molecular weight between crosslinks, the better the abrasion resistance. When the average molecular weight between crosslinks increases, the abrasion resistance decreases. However, even in the case of Example 4 in which the molecular weight between crosslinks is 520, which is twice or more as large as that of Example 2, the abrasion resistance is better than that of Comparative Example 5 in which twice the amount of amorphous α-alumina is used. It is. Further, the results of Example 5 show that when the spherical particles having an average particle diameter of 3 μm (Example 2) were replaced with 1 μm spherical particles, the abrasion resistance was reduced. The abrasion resistance is better than when using irregular shaped particles. When the silica of Comparative Example 6 was used, the roll was not worn, but the wear resistance was significantly lower than those of Examples 2 to 6. As a reference example, the results of abrasion resistance tests of various general cosmetic materials currently on the market in the same manner as the examples of Table 5 are shown in Table 6 below. When comparing Table 6 with the transfer sheets of Examples 2 to 6,
Each of the transfer sheets of Examples 2 to 6 described above was a transfer of a thin film, but all exhibited better wear resistance than the conventional one.

[0103]

[Table 6]

[0104]

The present invention has the following effects. (Claims 1 and 2) A transfer sheet excellent in abrasion resistance, abrasion resistance, and chemical resistance, excellent in the flexibility of a hard coating film, and excellent in transparency can be obtained. Does not damage or wear the gravure roll or doctor blade when applying the hard coating layer of the transfer sheet. Although it has excellent abrasion resistance and abrasion resistance, which are incompatible with conventional transfer sheets, it has the property of not easily abrading other objects in contact with it. The abrasion resistance can be improved by the spherical particles without increasing the crosslink density of the crosslinkable resin as a binder, so that even a transfer sheet using a flexible base material has sufficient flexibility for the crosslinkable layer. Imparts wear resistance and improves wear resistance.

(Claim 3) In addition to the above-mentioned items, in addition to the above-mentioned items, even if uncured (uncrosslinked) by drying with a solvent after coating, it is dried by touch, so that a flexible and flexible uncured hard coating film The decoration layer and adhesive layer can be printed as they are. Therefore, since the transfer sheet can be transferred without being cured, it can be transferred to the uneven transfer object without causing cracks. In addition, by performing cross-linking and curing after transfer, sufficient surface properties such as scratch resistance are obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of one embodiment of a transfer sheet of the present invention.

FIG. 2 is a view for explaining the function of the surface of the transfer sheet of the present invention after being transferred to a transfer object.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Transfer sheet, 2 ... Support sheet, 3 ... Hard coating layer,
4: Crosslinkable resin layer, 5: spherical particles, 6: decorative layer, 7: adhesive layer

Claims (2)

(57) [Claims] 1. A transfer sheet having a transfer layer on a support sheet, wherein the transfer layer has at least an average molecular weight between crosslinks.
Cross-linking hardening composed of 100-1000 curable resin
Objects and the transfer sheet characterized by having a hard coating layer consisting of spherical particles having a high hardness inorganic material than the cross-linked cured product dispersed in the crosslinked cured product. 2. A transfer sheet having a transfer layer on a support sheet.
Wherein the transfer layer has an average molecular weight of at least 50,
000-600,000, glass transition temperature 50-130
Non-crosslinked thermoplastic acrylic resin with a temperature of
Has at least two acryloyl or methacryloyl groups
Radiation curable resin containing prepolymer
A cross-linked cured product, wherein the cross-linked cured dispersed in the crosslinked cured product
The average particle diameter of the inorganic substance having a hardness higher than that of the
Contains 1 to 20% by weight of spherical particles based on the crosslinked cured product
A transfer sheet having a hard coating layer.