JP2002321497A - Antistatic transfer foil and method for manufacturing molded item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic transfer foil which can prevent easily and reliably the surface of a molded item from being charged with electricity, by a method wherein the base sheet of a transfer foil can be effectively prevented from being charged with electricity during the manufacturing process thereof, thereby surely preventing dust or the like from attaching to the base sheet, while the manufacturing process is simplified and costs are reduced, and to provide a manufacturing method of molded items using the antistatic transfer foil. SOLUTION: In the antistatic transfer foil, an antistatic layer composed of a polyurethane resin containing a silanol group, a melamine curing agent, a strong basic tertiary amine, an electroconductive inorganic filler, and a blocking inhibitor is formed on the rear side of a transfer material wherein a transfer layer is formed on a base sheet having release properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antistatic transfer foil.

[0002]

2. Description of the Related Art Conventionally, materials such as plastic, metal, glass, etc., which are difficult to apply a pattern or the like by directly printing on the surface, and scratch resistance, antistatic, hard coat, antireflection, etc. For materials that require each function,
A transfer foil is used to give a picture and various functions by printing. The transfer foil uses a type of printing method in which a transfer layer, in which a pattern layer, a hard coat layer, an antireflection layer, an antistatic layer, and the like are sequentially laminated, is transferred to an object to be transferred, and a release layer is formed. A transfer layer is formed on the base sheet thus formed, and an adhesive layer and the like are further formed thereon. When such a transfer foil is manufactured, generally, in a series of transfer foil manufacturing lines, the transfer foil is formed by sequentially applying layers such as a pattern layer and a hard coat layer to the surface of a base sheet conveyed by a roll. . At this time, since the base sheet is formed of a plastic film such as polyethylene or polyester, static electricity may be generated due to friction by a roll or the like, and as a result, dirt and dust adhere to the base sheet and transfer foil. There are problems such as the aesthetics being impaired.

On the other hand, a surface-active agent is coated on the side (back side) of the base sheet, particularly the side opposite to the side on which the transfer layer is laminated, or a layer in which a conductive filler is mixed with an ultraviolet curable resin is formed. To prevent charging of the base sheet. However, the surfactant applied to the back surface of the base sheet is easily detached due to friction by a roll, a washing step or a heat treatment step of the base sheet in a transfer foil manufacturing step, and an antistatic effect during a desired step. There was a problem that can not be maintained. on the other hand,
When a layer in which a conductive filler is mixed with a resin is formed, the base sheet becomes thicker due to the viscosity of the resin itself, the elongation of the coating film, and the like, which hinders the flexibility and flexibility of the transfer foil and causes the transfer to be performed. There have been problems such as difficulty in transferring to a three-dimensional curved surface of a body or a surface having fine irregularities. There is also a problem that the transparency of the transfer foil is impaired by the particle size and amount of the conductive filler, the thickness of the layer containing the conductive filler, and the like.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and effectively prevents static electricity during a manufacturing process of a transfer foil on a base sheet, thereby reliably preventing adhesion of dust and the like. At the same time, by transferring the transfer layer simultaneously with the molding of the product, it is possible to simply, reliably and powerfully prevent charging on the surface of the molded product while simplifying the manufacturing process and suppressing the manufacturing cost. An object of the present invention is to provide a method for manufacturing a transfer foil and a molded product using the transfer foil.

[0005]

According to the present invention, a silanol group-containing polyurethane resin, a melamine-based curing agent, and a strong base are provided on the back surface of a transfer material having a transfer layer formed on a release sheet. An antistatic transfer foil provided with an antistatic layer comprising a tertiary amine, a conductive inorganic filler and an antiblocking agent is provided. Further, according to the present invention, there is provided a transfer material in which a transfer layer is formed on a substrate sheet having releasability, wherein the transfer layer comprises a silanol group-containing polyurethane resin, a melamine-based curing agent, and a strongly basic third An antistatic transfer foil comprising an antistatic layer comprising a graded amine and a conductive inorganic filler is provided. Furthermore, according to the present invention, the antistatic transfer foil is sandwiched in an injection mold, and a molten resin is injected into the transfer layer to form a resin molded product, and at the same time, the surface of the resin molded product is formed. The transfer layer is adhered, or the transfer layer side of the antistatic transfer foil is overlaid on a resin molded product, and the transfer layer is adhered to the surface of the resin molded product by applying heat and pressure from the back of the base sheet, and then There is provided a method for producing a molded article, comprising peeling a substrate sheet having releasability.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The antistatic transfer foil of the present invention is mainly constituted by forming a transfer layer on the surface of a base sheet and forming an antistatic layer on the back surface, or forming a transfer layer on the surface of the base sheet. The transfer layer includes an antistatic layer. In such an antistatic transfer foil, the base sheet and the antistatic layer or the base sheet are peeled off from the transferred body after the transfer layer is transferred to the transferred body.

[0007] The substrate sheet used in the antistatic transfer foil of the present invention is not particularly limited as long as it has releasability, but a plastic film that can be deformed or bent is suitable. For example, polyester, cellulose acetate, polypropylene, polyethylene, polyamide, polyimide, polyether sulfone, polysulfone, polyvinyl acetal, polyether ketone,
Polyvinyl chloride, polyvinylidene chloride, polymethyl acrylate, polymethyl methacrylate, polycarbonate,
A stretched or unstretched transparent plastic film of polyurethane or the like may be used. The thickness of the base sheet is not particularly limited, and may be, for example, about 3 to 500 μm.

The above-mentioned base sheet itself has a releasing property such that no transfer layer remains on the base sheet side when a transfer layer described later is peeled from the base sheet, or the release property is imparted. (For example, waxes, salts or esters of higher fatty acids, fluorinated alkylated compounds, polyvinyl alcohol, release agents such as low molecular weight polyethylene, etc. are added). Further, if the base sheet does not have a sufficient release property with respect to the transfer layer, it is appropriate to form a release layer on the base sheet and between the transfer layer and the base sheet. is there.

The release layer is formed of, for example, a melamine resin, an epoxy resin, an epoxy melamine resin, an amino alkyd resin, a silicon resin, a fluorine resin, an olefin resin, or a composite resin thereof. Can be. The release layer includes, for example, a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a dip coating method, a spin coating method, a bar coating method, an extrusion coating method, a screen coating method, a reverse roll coating method, and microgravure. The above-mentioned material can be applied on a base sheet and dried by a known method such as a coating method or a flexo coating method. In this case, the thickness of the release layer is, for example, about 0.1 to 10 μm.

The antistatic layer in the antistatic transfer foil of the present invention mainly comprises a silanol group-containing polyurethane resin, a melamine-based curing agent, a strongly basic tertiary amine, and a conductive inorganic filler. In particular, when the antistatic layer is formed on the back surface of the base sheet (the surface opposite to the surface on which the transfer layer is formed), it is preferable that the antistatic layer further contains an antiblocking agent. The silanol group-containing polyurethane resin means a polyurethane resin having at least one silanol group in a molecule thereof, and a compound A having at least two isocyanate groups in a molecule.
Reacting a compound B having at least two active hydrogen groups in one molecule with a compound C having an active hydrogen group and a hydrolyzable silicon group which react with at least one isocyanate group in one molecule. Can be formed.

The compound A having at least two isocyanate groups in one molecule is not particularly restricted but includes, for example, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate and araliphatic diisocyanate. , Triisocyanate, tetraisocyanate and the like. Examples of the aliphatic diisocyanate include trimethylene diisocyanate,
Tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,
2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate,
Examples thereof include 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanatomethyl caproate.

As the alicyclic diisocyanate, 1,3
-Cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5
-Trimethylcyclohexyl isocyanate, 4,4 '
-Methylene bis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4
-Bis (isocyanatomethyl) cyclohexane, 1,
3-bis (isocyanatomethyl) cyclohexane and the like. As the aromatic diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate,
5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,
4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate and the like.

As the araliphatic diisocyanate,
1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω, ω′-diisocyanate
Examples thereof include 1,4-diethylbenzene, 1,3-bis (1-isocyanate-1-methylethyl) benzene, and 1,4-bis (1-isocyanate-1-methylethyl) benzene. Examples of the triisocyanate include triphenylmethane-4,4 ', 4 "-triisocyanate,
Examples thereof include 3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, and 1,3,5-triisocyanatehexane. As the tetraisocyanate, 4,4′-diphenyldimethylmethane-2,
2'-5,5'-tetraisocyanate and the like can be mentioned.

In addition, dimers and trimers derived from the above polyisocyanate monomers, biuret, allophanate, polyisocyanate having a 2,4,6-oxadiazinetrione ring, and addition of a polyol described later to the above polyisocyanate Body and the like. Of these, alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, and methylcyclohexyl-2,4-diisocyanate are preferred. In addition, these compounds can be used alone or in combination of two or more.

The compound B having at least two active hydrogen groups in one molecule includes, for example, a hydroxyl group, an amino group,
A compound having at least two mercapto groups and the like are mentioned, and a compound having a hydroxyl group, particularly a polyol, is preferable in consideration of a reaction rate with an isocyanate group. Further, the number of functional groups of the compound having a hydroxyl group is preferably 2 to 6 from the viewpoint of maintaining good mechanical properties of the coating film,
2 to 4 are particularly preferred. The molecular weight of the compound having a hydroxyl group is preferably from 200 to 10,000, particularly preferably from 300 to 5,000, from the viewpoint of the urethane bond concentration giving the final coating film performance and the workability in production. As the compound having a hydroxyl group, for example, polyester polyol,
Examples thereof include polyether polyol, polyether ester polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyalkane, castor oil, and polyurethane polyol.

Specific examples of the polyester polyol include, for example, dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid and sebacic acid or dialkyl esters thereof, and ethylene glycol, propylene glycol, diethylene glycol and butylene. Glycol, neopentyl glycol, 1,6-
Polyester obtained by reacting glycols such as hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, and polytetramethylene ether glycol Polyols, that is, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, and poly (β-methyl-γ-valerolactone) are exemplified.

Specific examples of polyether polyols include, for example, water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin and other low molecular weight polyols as initiators, for example, ethylene oxide, propylene oxide, butylene oxide,
Examples thereof include polyether polyols obtained by polymerizing an oxirane compound such as tetrahydrofuran. Specific examples of polyether ester polyols include, for example, terephthalic acid, isophthalic acid, adipic acid, azelaic acid, dibasic acids such as sebacic acid or dialkyl esters thereof, and poly (polyether polyol) obtained by reacting the above. And ether ester polyols.

As a specific example of the polyesteramide polyol, an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine or the like is used as a raw material in the above-mentioned polyesterification reaction and added to the raw material of the polyesterification reaction product. And those obtained by reacting the same. Specific examples of the acrylic polyol include polymerizable monomers having one or more hydroxyl groups in one molecule, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and the like, and their corresponding methacrylic acid derivatives. And, for example, those obtained by copolymerizing acrylic acid, methacrylic acid or esters thereof.

Specific examples of the polycarbonate polyol include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl -1,5-pentanediol, 1,
9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,
4-cyclohexanedimethanol, bisphenol-A
And 1 selected from the group consisting of hydrogenated bisphenol-A
One or more glycols and dimethyl carbonate,
Examples thereof include those obtained by reacting diphenyl carbonate, ethylene carbonate, phosgene, and the like. Specific examples of the polyhydroxyalkane include isoprene, butadiene, and a liquid rubber obtained by copolymerizing butadiene and acrylamide.

Specific examples of the polyurethane polyol include, for example, a polyol having a urethane bond in one molecule.
5,000 to 5,000 polyether polyols, polyester polyols, polyether ester polyols and the like and the above-mentioned isocyanate group-containing compound having at least two isocyanate groups per molecule with NCO groups / OH
Those obtained by reacting the group with less than 1 mole, preferably 0.9 or less, are exemplified. In addition, these compounds can be used alone or in combination of two or more.

Further, in addition to the compound having a hydroxyl group, a low molecular weight polyol having a molecular weight of 62 to 200 may be mixed for the purpose of adjusting the average molecular weight. Specific examples of these low molecular weight polyols include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,9-nonane Diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol,
Glycols used in the production of polyester polyols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, pentaerythritol and the like can be mentioned. Further, monools such as methanol, ethanol, propanols, butanols, 2-ethylhexanol, lauryl alcohol, and stearyl alcohol may be used in combination.

In the compound C having an active hydrogen group that reacts with at least one isocyanate group and a hydrolyzable silicon group in one molecule, the hydrolyzable silicon group is defined as a compound in the presence or absence of a silanol condensation catalyst. Means a group in which a hydrolyzable group which is hydrolyzed by moisture is bonded to a silicon atom, and specific examples of the hydrolyzable group include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, and an amino group. Examples include commonly used groups such as a group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among them, an alkoxy group is preferred because of its relatively low hydrolyzability and easy handling. The hydrolyzable group is usually bonded to one silicon atom in a range of 1 to 3, but in consideration of the reactivity of the hydrolyzable silicon group after coating, two to three are bonded. Are preferred. In the compound C having at least one active hydrogen group that reacts with at least one isocyanate group and a hydrolyzable silicon group in one molecule, examples of the active hydrogen group that can react with the isocyanate group include a mercapto group, a hydroxyl group, and an amino group. And the like.

Examples of the compound C having an active hydrogen group capable of reacting with at least one isocyanate group and a hydrolyzable silicon group in one molecule include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane Γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2 -Aminoethyl) aminopropyldimethoxysilane, γ- (2-aminoethyl)
Examples include aminopropyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyldiethoxysilane, and the like. In addition,
These compounds can be used alone or in combination of two or more.

The ratio of the isocyanate group-containing compound A to the active hydrogen group-containing compound B is such that the ratio of the isocyanate group in the isocyanate group-containing compound A to the active hydrogen group in the active hydrogen group-containing compound B is greater than 1.0. It is preferable that the ratio is not less than 1.2, more preferably 1.2 or more. Further, the amount of the hydrolyzable silicon group-containing compound C is such that the isocyanate group-containing compound A and the active hydrogen group-containing compound B are reacted with each other in order to allow the polyurethane resin to exhibit sufficient curability, and have an isocyanate group at the terminal. When a polyurethane prepolymer is synthesized and then reacted with the hydrolyzable silicon group-containing compound C, the ratio of the active hydrogen groups in the hydrolyzable silicon group-containing compound C to the isocyanate groups in the polyurethane prepolymer is set to 0.0.
An amount of about 5 to 1.0 is preferable, and an amount of about 0.1 to 0.8 is more preferable.

Examples of the melamine-based curing agent include iminomethylol group type methylated melamine, alkyl type methylated melamine and the like. The amount of the melamine-based curing agent used is, for example, about 50 to 100% by weight of a silanol group-containing polyurethane resin. The strongly basic tertiary amine is used as a curing catalyst, and the type thereof is not particularly limited, but preferably has a pKa of 11 or more. For example, 1,8-diazabicyclo [5,4,
0] undecene-7 (DBU) or 1,6-diazabicyclo [3,4,0] nonene-5. The amount of the strongly basic tertiary amine to be used is about 0.001 to 10% by weight of the silanol group-containing polyurethane resin, preferably 0.1 to 10% by weight.
01 to 5% by weight.

Examples of the conductive inorganic filler include antimony-doped tin dioxide, zinc oxide, tin oxide, titanium oxide, antimony-indium-tin composite oxide, indium-tin oxide.
Conductive ceramics such as tin composite oxide, conductive carbon black, copper, nickel, silver, iron or composite powders thereof;
Various metal particles are included. Above all, antimony-doped tin dioxide is preferable, and the antimony-doped tin dioxide preferably has an antimony / tin molar ratio of about 0.005 to about 3. The particle size of the conductive inorganic filler is
For example, about 0.01 to 5 μm is mentioned. The amount of the conductive inorganic filler used is about 30 to 400% by weight of the silanol group-containing polyurethane resin.

Examples of the antiblocking agent include silica, aluminosilicate, sodium calcium aluminosilicate, alumina, zeolite and Teflon (registered trademark).
And inorganic anti-blocking agents such as powder. Among them, silica, aluminosilicate and alumina are preferred. In addition, it is preferable to use a combination of these inorganic anti-blocking agents with an anti-blocking silicone additive such as polysiloxane, dimethyl polysiloxane, or hydroxyl-containing dimethyl polysiloxane. When used in combination, the weight ratio between the inorganic anti-blocking agent and the anti-blocking silicone additive is suitably about 40:60 to 80:20. The use amount of the antiblocking agent is about 2 to 10% by weight of the silanol group-containing polyurethane resin.

The antistatic layer in the present invention can be formed by the following method. For example, first, isocyanate group-containing compound A, active hydrogen group-containing compound B
And a melamine-based curing agent to produce a polyurethane prepolymer. The reaction temperature at this time is, for example, 30
-100 ° C. Further, when producing the polyurethane prepolymer, it is preferable to mix a hydrophilic group-containing compound. Examples of the hydrophilic group-containing compound that can be used here include, for example, a compound having at least one or more active hydrogen groups in a molecule and having a carboxyl group, a sulfonic group, a sulfonate group, an epoxy group, a polyoxyalkylene group, or the like. And a compound having a hydrophilic group.

Specifically, 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid,
1,3-phenylenediamine-4,6-disulfonic acid,
Sulfonic acid-containing compounds such as 2,4-diaminotoluene-5-sulfonic acid or derivatives thereof, or polyester polyols obtained by copolymerizing them, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid , 2,2-Dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4-diaminobenzoic acid and other carboxyl group-containing compounds or derivatives thereof, maleic anhydride, phthalic anhydride, succinic anhydride Acid, trimellitic anhydride, carboxy group-containing compound or a derivative thereof obtained by reacting an acid anhydride such as pyromellitic anhydride with a compound having an active hydrogen group, or a polyester polyol obtained by copolymerizing them.
Nonionic group-containing compounds such as polyoxyalkylene compounds having a molecular weight of 300 to 10,000 and containing at least 30% by weight or more of ethylene oxide repeating units and at least one active hydrogen group in the polymer, or copolymerizing these. And the like. These compounds can be used alone or in combination of two or more.

Next, the obtained polyurethane prepolymer is reacted with a strong base tertiary amine as a curing catalyst in the presence or absence of an organic solvent or water (preferably in the presence of an organic solvent or water). The compound C is mixed with a hydrolyzable silicon group-containing compound C and optionally an additive such as an elongating agent. As the organic solvent, those having relatively high solubility in water are preferable, for example, pyrrolidone solvents such as N-methyl-2-pyrrolidone, amide solvents such as dimethylformamide, lactone solvents such as α-butyl lactone, Examples thereof include ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as tertiary butanol, and ether solvents such as butyl cellosolve. The amount of the organic solvent based on the reaction raw material is, for example, about 10 to 50% by weight.

Examples of the extender include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3 Diamines such as 3'-dimethyl-4,4'-dicyclohexylmethanediamine and 1,4-cyclohexanediamine; polyamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine and tetraethylenepentamine; hydroxyethylhydrazine, hydroxyethyl Diethylenetriamine,
2-[(2-aminoethyl) amino] ethanol, 3-
Compounds having an amino group and a hydroxyl group such as aminopropanediol; hydrazines, acid hydrazides and the like.
These compounds can be used alone or in combination of two or more. Note that the conductive inorganic filler and the antiblocking agent can be added in any step. Further, in addition to the above, additives such as a chain extender, a neutralizing agent, a surfactant, a film forming aid, a plasticizer, a thickener, a preservative, an antifoaming agent, and an ultraviolet absorber may be blended. .

The molecular weight of the silanol group-containing polyurethane resin is not particularly limited, but is preferably about 3000 or more. In addition, the content of the silanol group-containing polyurethane resin in the obtained solution or dispersion is preferably about 60% by weight or less in order not to increase the viscosity so much and to maintain the storage stability. Then, the obtained solution or dispersion,
For example, coating on a base sheet by a method known per se such as a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a dip coating method, a spin coating method, a bar coating method, an extrusion coating method, and a screen coating method. And dry. In this case, the thickness of the antistatic layer is, for example, about 0.5 to 10 μm.

As the transfer layer in the antistatic transfer foil of the present invention, a layer which transfers from the transfer foil to the transfer object, for example, a release layer, an anchor layer, a picture layer, a vapor deposition layer, an antireflection layer, a protective layer, an adhesive layer Etc. are all included. The order of lamination of these layers is not particularly limited, but it is preferable that the release layer is formed adjacent to the base sheet or the release layer,
It is preferable that the adhesive layer is formed so as to be in direct contact with the outermost surface, that is, the transfer object. Each of these layers can be formed by a method known per se, and also has a thickness of
It can be adjusted appropriately according to the function of each layer. For example, the protective layer has a function of protecting the transfer layer from scratches, humidity, oxygen, light, and the like.
It can be formed in any thickness by using an active energy ray irradiation-curable resin such as an electron beam, a thermosetting resin, or the like.

The picture layer is a layer in which a so-called picture such as a character or a pattern is formed with various printing inks containing a coloring material such as a known pigment or dye, and has a thickness of, for example, about 0 to 50 μm. Can be formed. The anchor layer is
This is a kind of adhesive layer, and can be formed by, for example, an urethane-based, titanate-based, isocyanate-based, or polyethyleneimine-based adhesive. The thickness of the anchor layer is, for example, about 0.1 to 5 μm. The adhesive layer is, for example, acrylic resin, chlorinated olefin resin, vinyl chloride-vinyl acetate copolymer resin, maleic acid resin, chloride rubber resin, cyclized rubber resin, polyamide resin, cumarone indene resin It can be formed from a resin, an ethylene-vinyl acetate copolymer resin, a polyester resin, a urethane resin, a styrene resin, or the like. The thickness of the adhesive layer is, for example, about 0.1 to 10 μm.

In the present invention, when the antistatic layer is included not in the back surface of the base sheet but in the transfer layer, the antistatic layer may be formed at any position of the transfer layer. It is preferably formed adjacent to the surface (adjacent to the surface of the release layer when the release layer is formed on the base sheet). Thereby, even after the transfer layer is transferred to the transfer object, the antistatic effect can be most effectively imparted to the surface of the transfer object. Further, according to the method for manufacturing a molded product of the present invention, the transfer foil is sandwiched in an injection molding die, and a molten resin is injected toward the transfer layer to form a resin molded product. As a result, the transfer layer can be adhered to the surface of the molded product, and thereafter, the base sheet having releasability can be peeled off, so that various functions can be imparted to the surface of the molded product.

Here, the molded article is not particularly limited. For example, the surface of a polarizing plate used for various displays such as a word processor, a computer, a television, a display panel, a mobile phone, a liquid crystal display device, etc. Optical lenses such as sunglass lenses made of transparent plastics, prescription glasses lenses, camera viewfinder lenses, etc.
Examples include display units of various instruments, window glasses of automobiles, trains, and the like. It should be noted that these molded products can exhibit the same effects as the resin even when formed from a material other than the resin, for example, glass. As the molten resin, the material is not particularly limited as long as it can form the surface of the polarizing plate, an optical lens, a display section of various instruments, a window glass of an automobile, a train, and the like. Acrylic resin, styrene resin (ABS, AS,
Polyphenylene oxide styrene copolymer, etc.), polyolefin resin (polyethylene, polypropylene, etc.),
Those in a molten state such as a polycarbonate resin are exemplified. In addition, any injection molding die can be used as long as it is generally used when manufacturing a resin molded product.

According to another method of manufacturing a molded article of the present invention, the transfer layer side of the transfer foil is overlapped with the molded article, and hot pressure is applied from the back surface of the base sheet to the transfer layer on the surface of the molded article. Can be adhered, and thereafter, the base sheet having releasability is peeled off, whereby various functions can be imparted to the surface of the molded product. For example, a heat pressure can be applied from above the back surface of the base sheet by a silicon rubber roll or the like.
It is appropriate that the pressure is about 50 to 250 ° C. and the pressure is about 5 to ²⁰ kg / cm ² . Hereinafter, the antistatic transfer foil of the present invention and a method for producing a molded article using the same will be specifically described.

Example 1 An antistatic layer having the following composition was coated on one surface of a 38 μm-thick polyethylene terephthalate film by a gravure coating method.
It was applied to a thickness of 0.6 μm and dried. Strongly basic tertiary amine-containing silanol group-containing urethane resin (Takelac WS-4000, Takeda Pharmaceutical Co., Ltd.) Base dispersion (30%, water dispersion) 30 parts by weight Antimony-doped tin dioxide mixed polyolefin (HYTEC SN-20) 01, Toho Chemical Co., Ltd.) 20 parts by weight Methylol-imino group-containing methylated melamine (Cymel 701, Mitsui Cytec Co., Ltd.) 5 parts by weight Sodium calcium aluminosilicate (Silton AMT-08, Mizusawa Chemical ( Co., Ltd.) 1.5 parts by weight Hydroxyl group-containing dimethylpolysiloxane (BYK-375, BYK Chemie) 1.5 parts by weight 42 parts by weight ion-exchanged water Epoxy melamine resin release layer on the opposite side of the film on which the antistatic layer is formed Is applied to a thickness of 1 μm by gravure printing, and the substrate sheet having releasability is applied. It was obtained. An acrylic release protective layer, an acrylic colored ink layer, and an acrylic adhesive layer were sequentially formed on the release layer of the obtained base sheet by a gravure printing method to obtain an antistatic transfer foil.

Example 2 In the formulation of the antistatic layer, 10 parts by weight and 0.1 part by weight were added.
A transfer foil was formed in the same manner as in Example 1 except that 5 parts by weight, 0.5 parts by weight, and 39 parts by weight were used.

Example 3 In the formulation of the antistatic layer, 40 parts by weight and 10 parts by weight
A transfer foil was formed in the same manner as in Example 1 except that the weight part was changed to 17 parts by weight.

Example 4 In the formulation of the antistatic layer, 40 parts by weight and 10 parts by weight
Parts by weight, 0.5 parts by weight, 0.5 parts by weight, 1 part by weight
A transfer foil was formed in the same manner as in Example 1 except that the amount was 9 parts by weight.

Comparative Example 1 A transfer foil was formed in the same manner as in Example 1 except that the composition of the antistatic layer was as follows. Water-dispersed polyurethane (Superflex 410, Daiichi Kogyo Seiyaku Co., Ltd.) 10 parts by weight Cationic surfactant (Katiogen ES-L, Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts by weight ・ Ion exchange water 62.5 parts by weight ・ Isopropyl alcohol 27 parts by weight

Comparative Example 2 A transfer foil was formed in the same manner as in Example 1 except that the composition of the antistatic layer was as follows. -Water-dispersed polyurethane (Superflex 410, Daiichi Kogyo Seiyaku Co., Ltd.) 30 parts by weight-Antimony-doped tin dioxide mixed polyolefin (HYTEC SN-201, Toho Chemical Co., Ltd.) 40 parts by weight-Cationic surfactant ( Katiogen ES-L, Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight Methylol / imino group-containing methylated melamine (Symel 701, Mitsui Cytec Co., Ltd.) 10 parts by weight Sodium calcium aluminosilicate ( Shilton AMT-08, Mizusawa Chemical Co., Ltd. 1.5 parts by weight ・ Hydroxy group-containing dimethylpolysiloxane (BYK-375, BYK Chemie) 1.5 parts by weight ・ Ion-exchanged water 17 parts by weight

Test Examples The transfer foils obtained in Examples 1-4 and Comparative Examples 1-2 were evaluated as follows. Antistatic properties Under a low humidity atmosphere (about 30% humidity), use a surface resistance meter (TO
Company A, SUPERMEGOHMETER MODEL
SM-8215). ：: Surface resistance value of 10 ¹⁰ Ω or less. Δ: Surface resistance value of 10 ¹⁰ Ω to ^{10 11} Ω. ×: Surface resistance value of 10 ¹¹ Ω or more. Antistatic property The coated surface of the antistatic layer was rubbed several times with a dish paper, and the state of ash adhesion was observed when the ash of the antistatic layer was brought close to 5 cm to the ash of tobacco. ：: No ash adhesion was observed. ×: Adhesion of ash is observed. Surface curability ：: Sufficiently cured without scratches on nails and no sticky feeling. X: Insufficient curing due to insufficient curing. Anti-blocking property Transfer foil (2 cm x 2 cm) obtained in Examples and Comparative Examples
10 test pieces were stacked in the order of front / back / front / back, a 500 g load was applied thereon, and the test piece was held at 60 ° C. for 24 hours to measure the anti-blocking property. ：: When the film was peeled, it was peeled without resistance, and there was no transfer of ink. Δ: When the film was peeled, there was resistance, but there was no ink transfer. ×: When the film was peeled, the ink was transferred to the opposite surface.

Water resistance The appearance and resistance after washing with running water for 60 seconds are checked. ：: no change in appearance, surface resistance value of 10 ¹⁰ Ω or less. Δ: No change in appearance, surface resistance value of 10 ¹⁰ Ω to ^{10 11} Ω. ×: Flow of appearance was observed, and the surface resistance value was 10 ¹¹ Ω or more. Water resistance The appearance and resistance after immersion at 40 ° C. for 24 hours are checked. ：: no change in appearance, surface resistance value of 10 ¹⁰ Ω or less. Δ: No change in appearance, surface resistance value of 10 ¹⁰ Ω to ^{10 11} Ω. ×: Flow of appearance was observed, and the surface resistance value was 10 ¹¹ Ω or more. Heat resistance The appearance and the resistance value after being left in a constant temperature room at 170 ° C. for 30 seconds are checked. ：: no change in appearance, surface resistance value of 10 ¹⁰ Ω or less. Δ: No change in appearance, surface resistance value of 10 ¹⁰ Ω to ^{10 11} Ω. ×: Poor appearance, surface resistance value of 10 ¹¹ Ω or more. Table 1 shows the results of the transfer foils obtained in Examples 1 to 4 and Comparative Examples 1 and 2.

[0046]

[Table 1] Example 5 The transfer foil obtained in Example 1 is inserted into an injection mold.
The mold was heated to 55 ° C. Use the simultaneous molding transfer method
Acrylic resin melted at a temperature of about 240 ° C
(Mitsubishi Rayon, Acrypet VH) with resin pressure
300kg / cm ^TwoThen, the mixture was poured into a mold and allowed to cool. So
After that, the transfer layer is formed on the surface by peeling the base sheet.
A transcribed display cover for a mobile phone was obtained.

Example 6 An acrylic resin (Acrypet V, manufactured by Mitsubishi Rayon Co., Ltd.) was applied to the adhesive layer of the transfer foil obtained in Example 1 by injection molding.
The molded products formed in H) were overlapped, and heated and pressed with a roll of silicon rubber having a hardness of 80 degrees from the base sheet side to adhere the transfer layer to the molded products. The heating condition is that the surface temperature of the silicon rubber is 230 ° C., and the pressure is 10 k.
g / cm ² . Thereafter, by peeling off the base sheet, a display cover for a mobile phone having a transfer layer transferred to the surface was obtained.

Example 7 A resin-based release agent was applied to a 38 μm-thick polyethylene terephthalate film (F-39) by gravure printing at 1 μm.
To obtain a substrate sheet having releasability. A conductive release layer having the following composition was applied to the obtained base sheet to a thickness of 2 μm by a gravure coating method. The drying conditions at this time were 180 ° C. and 20 seconds. Strongly basic tertiary amine-containing silanol group-containing urethane resin (Takelac WS-4000, Takeda Pharmaceutical Co., Ltd.) 30 parts by weight Antimony-doped tin dioxide mixed polyolefin (HYTEC SN-2001, Toho Chemical Co., Ltd.) 40 parts by weight Part: methylol / imino group-containing methylated melamine resin (Cymel 701, Mitsui Seitec Co., Ltd.) 5 parts by weight ion-exchanged water 25 parts by weight On this release layer having an antistatic effect, a polyurethane resin (VH311 clear A / B = 1
0/10, Washin Chemical Industry Co., Ltd.) was applied and formed to a thickness of 1 μm by a gravure coating method. The drying conditions at this time were 150 ° C. and 30 seconds. On this anchor layer, a vinyl acetate salt resin (TS-58, Dainippon Ink Co., Ltd.) was used as an adhesive layer by a gravure coating method.
It was applied and formed to a thickness of μm. The drying condition at this time is 12
0 ° C., 20 seconds.

[0049]Example 8 The transfer foil obtained in Example 7 is sandwiched between injection molding dies.
The mold was heated to 55 ° C. Use the simultaneous molding transfer method
Acrylic resin melted at a temperature of about 240 ° C
(Mitsubishi Rayon, Acrypet VH) with resin pressure
300kg / cm ^TwoThen, the mixture was poured into a mold and allowed to cool. So
After that, the transfer layer is formed on the surface by peeling the base sheet.
A transcribed display cover for a mobile phone was obtained.

Example 9 An acrylic resin (Acrypet V, manufactured by Mitsubishi Rayon Co., Ltd.) was applied to the adhesive layer of the transfer foil obtained in Example 7 by injection molding.
The molded articles formed in H) were overlapped, and heated and pressed with a roll of silicon rubber having a hardness of 75 degrees from the base sheet side to adhere the transfer layer to the molded articles. The heating conditions are as follows: the surface temperature of the silicon rubber is 230 ° C., and the pressure is 8 kg.
/ Cm ² , 5 cm / sec. Thereafter, by peeling off the base sheet, a display cover for a mobile phone having a transfer layer transferred to the surface was obtained. The display covers obtained in Examples 8 and 9 had a surface resistance of 10 ⁹ Ω and had a sufficient antistatic effect. In addition, the abrasion was 10 times or more at a gakushin-type abrasion test load of 200 g, indicating good abrasion. For water resistance,
The appearance and surface resistance after washing with running water for 1 minute and immersion at 40 ° C. for 24 hours did not change before and after, and were good. Regarding the solvent resistance, even when the surface was rubbed 30 times or more in a rubbing test in which the surface was strongly rubbed with a gauze containing MEK (methyl ethyl ketone) and toluene, good solvent resistance was exhibited without any abnormality.

[0051]

According to the present invention, excellent antistatic properties are provided.
In addition, since the effect can be maintained for a long time, the static electricity during the manufacturing process of the transfer foil on the base sheet can be effectively prevented, so that the adhesion of dust and dust can be surely prevented. In addition, the present invention provides an excellent transfer foil that can provide a further added value to a transferred body because the abrasion resistance, anti-blocking property, water resistance, solvent resistance, heat resistance and the like are well-balanced. it can. Further, according to the molded article of the present invention, various functions, for example, high functions and multi-functionalization such as abrasion resistance, light resistance, antistatic property, etc. are easily and strongly imparted to the surface of the molded article. Thus, the manufacturing process can be simplified, the manufacturing cost can be reduced, and the added value of the molded product can be improved, and the price can be reduced.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3B005 EA01 EB01 EC30 FB00 FE09 GA02 GB01 4F206 AD10 JA07 JB19

Claims (10)

[Claims] 1. A transfer material having a transfer layer formed on a base sheet having releasability, a silanol group-containing polyurethane resin, a melamine-based curing agent, a strongly basic tertiary amine, and a conductive inorganic filler. And an antistatic transfer foil comprising an antistatic layer comprising an antiblocking agent. 2. A transfer material in which a transfer layer is formed on a substrate sheet having releasability, wherein the transfer layer comprises a silanol group-containing polyurethane resin, a melamine-based curing agent, a strongly basic tertiary amine, An antistatic transfer foil comprising an antistatic layer comprising a conductive inorganic filler. 3. The method of claim 1, wherein the silanol group-containing polyurethane resin is
The antistatic transfer foil according to claim 1 or 2, which is a reaction product of an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, or an araliphatic diisocyanate, a polycarbonate polyol, and a compound containing a hydrolyzable silicon group. 4. The method according to claim 1, wherein the strongly basic tertiary amine is 1,8-diazabicyclo [5,4,0] undecene-7 or 1,6-
The antistatic transfer foil according to any one of claims 1 to 3, wherein the foil is diazabicyclo [3,4,0] nonene-5. 5. The antistatic transfer foil according to claim 1, wherein the conductive inorganic filler is antimony-doped tin dioxide. 6. The anti-blocking agent is one or two selected from inorganic anti-blocking agents consisting of silica, aluminosilicate, sodium calcium aluminosilicate, alumina, zeolite and Teflon powder.
The antistatic transfer foil according to any one of claims 1 to 3, which is a compound of at least one kind. 7. An anti-blocking agent comprising one or more compounds selected from silica, aluminosilicate or alumina, and an anti-blocking silicon additive comprising polysiloxane, dimethylpolysiloxane and hydroxyl-containing dimethylpolysiloxane. The antistatic transfer foil according to any one of claims 1, 3 to 6, wherein 8. The method according to claim 1, wherein the melamine-based curing agent is an iminomethylol group-type methylated melamine.
The antistatic transfer foil according to any one of the above. 9. A resin molded product is formed by sandwiching the antistatic transfer foil according to any one of claims 1 to 8 in an injection molding die and injecting a molten resin into a transfer layer side. At the same time, a method for producing a molded article, comprising: adhering the transfer layer to the surface of the resin molded article; and thereafter, peeling off a base sheet having releasability. 10. The transfer layer side of the antistatic transfer foil according to any one of claims 1 to 8 is superimposed on a resin molded product, and the surface of the resin molded product is applied by applying heat and pressure from above the back surface of the base sheet. A method for producing a molded product, comprising: adhering the transfer layer, and thereafter peeling off a substrate sheet having releasability.