JP2010274496A - Transfer sheet and manufacturing method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer sheet which can easily be manufactured, is suppressed in an environmental hazard at disposal, has the capability of transferring a transfer layer excellent in adhesive properties, acid resistance, alkali resistance, water resistance, etc. <P>SOLUTION: The transfer sheet has a transfer layer laminated at one side of a support which is formed of an aliphatic polyester resin where the transfer layer contains an acid modified polyolefin resin and has no release layer between the transfer layer and the support. Furthermore, the transfer sheet can be manufactured by a manufacturing method including a process to apply a liquid-like material containing the acid modified polyolefin resin to the surface of the support formed of the aliphatic polyester resin without a release agent laid between, and dry the liquid-like material later. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a transfer sheet and a method for producing the same, and more particularly to a transfer sheet in which a transfer layer for constituting a protective layer and an adhesive layer is laminated on a support and a method for producing the same.

  As a protective layer or adhesive layer provided on an object, one formed by transferring a resin is known. When such transfer is performed, a transfer sheet having a structure in which a release layer is laminated on a support such as a film and the transfer layer is laminated on the release layer is generally used. However, providing a release layer not only increases the cost, but also when the transfer layer is an adhesive layer by transferring the components of the release layer laminated on the support to the surface of the transfer layer. There is a possibility of inhibiting adhesion after transfer. Furthermore, since the support is unnecessary after the transfer layer is transferred, it is discarded. Therefore, it is desired to reduce the environmental load at the time of disposal.

In recent years, the protective layer and the adhesive layer are increasingly required to have various functions such as acid resistance, alkali resistance, and water resistance.
As a means for forming such a protective layer or adhesive layer, polyurethane resin, polyamide resin, polyester resin, or polyolefin resin is used for the adhesive layer, and these resins are released from a support such as paper or polyester resin. A transfer sheet provided as an adhesive layer has been proposed (Patent Document 1).

Moreover, the example (patent document 2) which uses as a protective layer or an adhesive layer by laminating | stacking and adhere | attaching a heat-adhesive polyolefin layer on both surfaces of a base film is proposed.
As a method for reducing the environmental load associated with discarding a support, for example, in a transfer sheet intended to transfer a pattern layer, it has been proposed to use a polylactic acid resin for the support (Patent Literature). 3).

Japanese Patent No. 3359963 Japanese Patent Laid-Open No. 08-190902 JP-A-11-216996

  The thing of patent document 1 is a thing with a heavy environmental load by use, since the support body after transferring an adhesive layer is discarded. Furthermore, the polyester resin and the polyurethane resin still have a problem of poor acid resistance and alkali resistance. In addition, since the polyamide resin has high hygroscopicity and moisture permeability, there is a problem that the adhesiveness decreases with time due to moisture.

  Specifically, Patent Document 2 relates to a technique of using a film in which a heat-adhesive polyolefin resin is laminated as both outer layers of a polyolefin base layer containing a filler as a film for a sealing material of a thin battery. Thereby, the layer excellent in adhesiveness, acid resistance, alkali resistance, and water resistance can be obtained. However, since it is necessary to form an adhesive film having a three-layer structure including a base material layer, the cost is increased and there is a problem in thinning. Furthermore, depending on the type of resin to be laminated, there is a concern that when a film is transported in a roll shape, a sheet having releasability must be laminated to prevent blocking of the film surface.

  In Patent Document 3, only an evaluation of a case where a release layer is laminated on a polylactic acid resin substrate serving as a support has been performed, and since the components in the release layer are not biodegradable, they are discarded. Sometimes there is a potential for environmental impact. Also, when forming a transfer layer by applying a liquid material to the polylactic acid resin base material to be a support, the liquid material may be repelled unless the coating amount is increased. It is difficult to form on a layer.

  In view of these problems, the present invention provides a transfer sheet that is easy to manufacture, has a low environmental impact during disposal, and can transfer a transfer layer excellent in adhesiveness, acid resistance, alkali resistance, water resistance, and the like. It is something to be offered.

  As a result of diligent studies to solve the above problems, the present inventors have laminated a transfer layer containing an acid-modified polyolefin resin on one side of a support made of an aliphatic polyester resin that is not laminated with a release layer. The present inventors have found that the body is effective as a transfer sheet capable of constituting a transfer layer excellent in adhesiveness, water resistance, acid resistance, alkali resistance and the like, and have reached the present invention.

That is, the gist of the present invention is as follows.
(1) A transfer layer is laminated on one side of a support, the support is formed of an aliphatic polyester resin, the transfer layer contains an acid-modified polyolefin resin, and a mold release is performed between the transfer layer and the support. A transfer sheet characterized by not having a layer.

  (2) A step of applying a liquid material containing an acid-modified polyolefin resin on a support formed of an aliphatic polyester resin without interposing a mold release agent, followed by drying. A method for producing a transfer sheet.

  Since the transfer layer laminated on the support in the transfer sheet of the present invention contains an acid-modified polyolefin resin, the transfer layer is excellent in acid resistance, alkali resistance, water resistance, solvent resistance, and moisture resistance. In addition, a release layer composed of waxes, low molecular weight silicone compounds, surfactants and the like is not required between the transfer layer and the support formed of the aliphatic polyester resin. For this reason, there is no cost for forming the release layer, and there is no contamination of the transfer layer due to migration of the release layer components. In addition, since the support is an aliphatic polyester resin having biodegradability, the burden on the environment during disposal is small.

The transfer layer in the transfer sheet of the present invention is suitable for laminating as a protective layer or an adhesive layer on the surface of various substrates.
Moreover, according to the manufacturing method of the transfer sheet of this invention, the transfer sheet can be obtained industrially simply.

Hereinafter, the present invention will be described in detail.
The support used in the transfer sheet of the present invention needs to be an aliphatic polyester resin. Examples of the aliphatic polyester resin include L-lactic acid, D-lactic acid, DL-lactic acid, and mixtures thereof. Moreover, lactic acids, such as lactide of the cyclic dimer of lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, and 6-hydroxycarboxylic acid can be mentioned. Furthermore, cyclic ester intermediates of hydroxycarboxylic acid, for example, glycolide, which is a dimer of glycolic acid, and ε-caprolactone, which is a cyclic ester of 6-hydroxycaproic acid. Of these, polylactic acid, which is a homopolymer of lactic acids, and polyglycolic acid, which is a homopolymer of glycolic acid, are preferred because of their availability.

  The method for producing the aliphatic polyester resin is not particularly limited. For example, in the case of polylactic acid, a method of directly dehydrating polycondensation of L-lactic acid, D-lactic acid, and DL-lactic acid, and a method of ring-opening polymerization of lactide, which is a cyclic dimer of lactic acid, can be mentioned. You may use what is marketed.

  The aliphatic polyester resin used for the support may contain known additives and stabilizers, that is, for example, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, flameproofing agents and the like. However, additives generally used as mold release agents such as silicone compounds, fluorine compounds, long-chain alkyl compounds, waxes, surfactants, and the like have a total content of 100 parts by mass of the support. The amount is preferably 1 part by mass or less. The smaller the amount, not only the better the wettability to the support when forming the transfer layer by coating, but also the better the adhesion between the transfer layer and the support, and the transfer layer and transferred object. Contamination is suppressed. Therefore, this content is preferably 0.5 parts by mass or less, and more preferably 0.1 parts by mass or less. It is particularly preferred not to contain it.

  The wax means a plant wax, animal wax, mineral wax, petrochemical wax or the like having a number average molecular weight of 10,000 or less. Specifically, candelilla wax, carnauba wax, rice wax, wood wax, berry wax, jojoba wax, shea butter, beeswax, shellac wax, lanolin wax, whale wax, montan wax, ceresin, paraffin wax, microcrystalline wax, synthetic Examples thereof include polyethylene wax, synthetic polypropylene wax, and synthetic ethylene-vinyl acetate copolymer wax.

  Examples of the surfactant include a cationic surfactant, an anionic surfactant, a nonionic (nonionic) surfactant, an amphoteric surfactant, a fluorosurfactant, and a reactive surfactant. In addition to those generally used for emulsion polymerization, emulsifiers are also included. For example, anionic surfactants include sulfates of higher alcohols, higher alkyl sulfonic acids and salts thereof, alkyl benzene sulfonic acids and salts thereof, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfone salts. Examples include succinate. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide copolymer, etc. And a sorbitan derivative such as a polyoxyethylene sorbitan fatty acid ester. Examples of amphoteric surfactants include lauryl betaine and lauryl dimethylamine oxide. Examples of reactive surfactants include alkylpropenylphenol polyethylene oxide adducts and their sulfate esters, allyl alkylphenol polyethylene oxide adducts and their sulfate esters, allyl dialkylphenol polyethylene oxide adducts and their sulfate esters, etc. A compound having a reactive double bond may be mentioned.

  Although the shape of a support body is not specifically limited, A sheet-like thing is preferable. There is no limitation on the method of forming a sheet, and a stretching process may be performed when forming a sheet, or an annealing (heat) process may be performed. Furthermore, although the thickness is not particularly limited, it may be usually 1 to 1000 μm, preferably 1 to 500 μm, more preferably 1 to 100 μm, and particularly preferably 1 to 50 μm.

  The surface of the support may be subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as pretreatment. Further, in order to avoid a failure due to charging, an antistatic layer may be laminated on the surface of the support opposite to the surface on which the transfer layer is laminated.

The transfer layer used in the transfer sheet of the present invention contains an acid-modified polyolefin resin.
The acid-modified polyolefin resin used in the transfer layer is not particularly limited in its acid-modified component, but the ratio of the acid-modified component in the acid-modified polyolefin resin is preferably 0.01 to 5% by mass, -4 mass% is more preferable, and 1-3 mass% is further more preferable. When the ratio of the acid-modified component is less than 0.01% by mass, sufficient adhesion to the transfer destination substrate may not be obtained. Furthermore, when a transfer layer is provided by application of an acid-modified polyolefin resin, it tends to be difficult to form this resin. On the other hand, when it exceeds 5 mass%, acid resistance, alkali resistance, water resistance, etc. may fall.

  Examples of the acid-modifying component include an unsaturated carboxylic acid component. Examples of unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. It is done. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable from the viewpoint of stabilizing the dispersion of the resin, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferable.

  Although the olefin component which is the main component of the acid-modified polyolefin resin is not particularly limited, an alkene having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene and 1-hexene is preferable. . Mixtures of these may be used. Among these, alkene having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene is more preferable, ethylene and propylene are further preferable, and ethylene is most preferable.

  The acid-modified polyolefin resin preferably contains an ethylenically unsaturated compound having an oxygen atom in the side chain for the purpose of improving the adhesion to the transfer target. Examples of the ethylenically unsaturated compound containing an oxygen atom in the side chain include a (meth) acrylic acid ester component, a maleic acid ester component, a (meth) acrylic acid amide component, an alkyl vinyl ether component, and a vinyl ester component. Of these, a (meth) acrylic acid ester component is preferable. When a (meth) acrylic acid ester component is included, the content is preferably 0.5 to 40% by mass. This range is more preferably from 1 to 20% by mass, and even more preferably from 3 to 10% by mass, in order to provide good adhesion to various transferred materials.

  Examples of the (meth) acrylic acid ester component include an esterified product of (meth) acrylic acid and an alcohol having 1 to 30 carbon atoms, and (meth) acrylic acid and carbon number 1 from the viewpoint of easy availability. Esterified products with ˜20 alcohols are preferred. Specific examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid. Examples include octyl, decyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like. Mixtures of these may be used. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl acrylate, and octyl acrylate are more preferable from the viewpoint of adhesiveness to the transfer target, and ethyl acrylate. More preferred is butyl acrylate, and particularly preferred is ethyl acrylate. In addition, “(meth) acrylic acid˜” means “acrylic acid˜ or methacrylic acid˜”.

  Each component constituting the acid-modified polyolefin may be copolymerized in the acid-modified polyolefin resin, and its form is not limited. Examples of the state of copolymerization include random copolymerization, block copolymerization, and graft copolymerization (graft modification).

  The melt flow rate of the acid-modified polyolefin resin is preferably 1 to 1000 g / 10 min at 190 ° C. and 21.2 N (2160 g) load, more preferably 1 to 500 g / 10 min, and 2 to 300 g / 10 minutes is more preferable, and 2 to 200 g / 10 minutes is particularly preferable. If it is less than 1 g / 10 min, it is difficult to produce a resin, it is difficult to make a liquid, and transfer may be difficult. Moreover, adhesiveness falls in the thing of 1000 g / 10min or more.

  In the present invention, the absence of a release layer between the support and the transfer layer means that a release agent such as a silicone compound, fluorine compound, long chain alkyl compound, wax, polyethylene, polypropylene, poly This means that a release layer made of a general release material such as polyolefin resin such as methylpentene or an alkyd resin is not formed between the support and the transfer layer. A transfer layer containing an acid-modified polyolefin resin is directly laminated on the body. Since the release layer is not laminated on the support, it is possible to simplify the process, reduce the environmental load during disposal, and suppress contamination of the transfer layer with the release agent.

  The thickness of the transfer layer is not particularly defined, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, further preferably 1 μm or more, and 2 μm or more. Is particularly preferred. If it is less than 0.01 μm, the function of the transfer layer may not be exhibited, and the adhesiveness may be inferior.

  The transfer layer can contain various additives as long as the characteristics are not impaired. Examples of such additives include antioxidants, antistatic agents, ultraviolet absorbers, colorants, dyes, crosslinking agents, and resins other than the acid-modified polyolefin resins described above. Two or more kinds of such additives may be used in combination.

  The method for producing the transfer sheet of the present invention is not particularly limited. For example, a method of co-extrusion molding of an aliphatic polyester resin and an acid-modified polyolefin resin as a support, a method of extrusion-laminating an acid-modified polyolefin resin on an aliphatic polyester resin sheet, and the like can be applied. In particular, a transfer sheet can be easily obtained industrially by a production method in which a liquid containing an acid-modified polyolefin resin is coated on a support and then dried. Thus, it is possible to form a thin transfer layer by a method in which a liquid material is coated on a support and then dried.

  In the production method in which the liquid material is coated on the support and then dried, the solvent in the liquid material containing the acid-modified polyolefin resin is not particularly limited as long as it can be applied on the support. For example, water, an organic solvent, or an aqueous medium containing water and an amphiphilic organic solvent can be used. Among them, it is preferable to use water or an aqueous medium in view of the environment.

  Examples of organic solvents include diethyl ketone (3-pentanone), methyl propyl ketone (2-pentanone), methyl isobutyl ketone (4-methyl-2-pentanone), 2-hexanone, 5-methyl-2-hexanone, and 2-to. Ketones such as butanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone; aromatic hydrocarbons such as toluene, xylene, benzene, Solvesso 100, Solvesso 150; butane, pentane, hexane, cyclohexane, heptane Aliphatic hydrocarbons such as octane, nonane; methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, Halogen-containing compounds such as p-dichlorobenzene; acetic acid Esters such as til, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, γ-butyrolactone, isophorone; Amphiphilic organic solvents and the like can be mentioned.

  The aqueous medium means a solvent composed of water and an amphiphilic organic solvent and having a water content of 2% by mass or more. The amphiphilic organic solvent means one having a water solubility of 5% by mass or more in the organic solvent at 20 ° C. The solubility of water in an organic solvent at 20 ° C. is described in documents such as “Solvent Handbook” (Kodansha Scientific, 1990, 10th edition).

  Specific examples of aqueous media include alcohols such as methanol, ethanol, n-propanol, and isopropanol (hereinafter abbreviated as “IPA”); ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone and methyl ethyl ketone. Esters such as methyl acetate, acetic acid-n-propyl, isopropyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate; diethylamine, triethylamine (hereinafter abbreviated as “TEA”), diethanolamine, triethanol, including ammonia Organic amine compounds such as amine, N, N-dimethylethanolamine (hereinafter abbreviated as “DMEA”), N, N-diethylethanolamine, N-diethanolamine; lactams such as 2-pyrrolidone and N-methyl-2-pyrrolidone And the like can be given.

  A method for dispersing the acid-modified polyolefin resin in the aqueous medium as described above is not particularly limited, and examples thereof include those described in WO 02/055598.

  The dispersed particle size of the acid-modified polyolefin resin in the aqueous medium is preferably a number average particle size of 1 μm or less, preferably 0.8 μm or less, from the viewpoint of film forming property and storage stability (dispersion stability). Is more preferable. Such a particle size can be achieved by the production method described in the pamphlet. The particle diameter can be measured by a dynamic light scattering method.

  Since the aqueous dispersion obtained by dispersing the acid-modified polyolefin resin in an aqueous medium is used to form a transfer layer, it is preferable that it does not contain a non-volatile aqueous additive. By using the production method described in International Publication No. 02/055598 pamphlet, it is possible to obtain an aqueous dispersion not containing a non-volatile aqueous additive. Examples of the nonvolatile aqueous auxiliary agent include the aforementioned surfactants and compounds having a protective colloid effect. When a non-volatile aqueous additive is included, the non-volatile aqueous additive remains in the transfer layer after the aqueous dispersion is applied and dried, resulting in adhesion, water resistance, alkali resistance, and solvent resistance. May adversely affect acid resistance.

  The compounds having protective colloidal action include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl pyrrolidone, polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing Acid-modified polyolefin waxes having a weight average molecular weight of usually 5,000 or less such as polypropylene wax and carboxyl group-containing polyethylene-propylene wax and salts thereof, acrylic acid-maleic anhydride copolymers and salts thereof, styrene- (meth) Acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth) acrylic acid- (meth) a Carboxyl group-containing polymers having an unsaturated carboxylic acid content of 20% by mass or more, such as lauric acid ester copolymers, and salts thereof, polyitaconic acid and salts thereof, water-soluble acrylic copolymers having amino groups, gelatin, and gum arabic And compounds generally used as dispersion stabilizers for fine particles, such as casein.

  The solid content of the liquid can be appropriately selected depending on the lamination conditions of the transfer layer, the thickness and performance of the target transfer layer, and is not particularly limited. However, in order to keep the viscosity of the liquid material moderate and to form a good transfer layer, the content is preferably 1 to 60% by mass, and more preferably 5 to 30% by mass.

  As a method for applying the liquid material to the support, known methods may be mentioned. For example, a liquid is uniformly applied to the surface of the support by gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc. In accordance with the above, after setting near room temperature, it is subjected to drying treatment or heat treatment for drying. Thereby, a uniform transfer layer can be formed in close contact with the support.

  The material to be transferred as an object to which the transfer sheet of the present invention is applied is not limited in its material. For example, resin material, paper, synthetic paper, cloth, metal material, glass material, wood, ceramics, cements, etc. Etc. The shape is also arbitrary, such as a sheet (film), a flat plate, a curved plate, a rod-shaped body, a three-dimensional object, and the like.

  Examples of resin materials that can be used for the transfer target include thermoplastic resins such as polyethylene terephthalate (PET), polyester resins such as polyethylene naphthalate (PEN), polyolefin resins such as polyethylene and polypropylene (PP), and vinyl chloride resins. , Polystyrene resin, 6-nylon, polyamide resin such as poly-m-xylylene adipamide (MXD6 nylon), polycarbonate resin, acrylic resin such as polyacrylonitrile, polyimide resin, phenol resin, multilayer of these resins (For example, nylon 6 / MXD / nylon 6, nylon 6 / ethylene-vinyl alcohol copolymer / nylon 6) and mixtures. The resin material may be stretched. In addition, the resin material may contain known additives and stabilizers, such as antistatic agents, plasticizers, lubricants, antioxidants, etc., in order to improve adhesion when laminated with other materials, The surface may be subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment or the like as pretreatment. Moreover, silica, alumina, etc. may be vapor-deposited, and other layers, such as a barrier layer, an easily bonding layer, an antistatic layer, an ultraviolet absorption layer, and a release layer, may be laminated.

  Examples of paper that can be used for the transfer medium include Japanese paper, craft paper, liner paper, art paper, coated paper, carton paper, glassine paper, and semi-glassine paper.

  The structure of the synthetic paper that can be used for the transfer target is not particularly limited, and may be a single layer structure or a multilayer structure. As the multilayer structure, for example, a two-layer structure of a base material layer and a surface layer, a three-layer structure in which a surface layer exists on the front and back surfaces of the base material layer, and another resin film layer exists between the base material layer and the surface layer. A multilayer structure can be exemplified. Moreover, each layer may contain the inorganic or organic filler, and does not need to contain it. A microporous synthetic paper having a large number of fine voids can also be used.

  Examples of the cloth that can be used for the transfer target include non-woven fabrics, woven fabrics, and knitted fabrics made of the above-described synthetic resin and natural fibers such as cotton, silk, and hemp.

  Examples of the metal material that can be used for the transfer target include metal foil such as aluminum foil and copper foil, and metal plate such as aluminum plate and copper plate. In addition to metal materials, silicon wafers, carbon wafers, and the like can be given. Examples of the glass material include a glass plate and cloth made of glass fiber, and examples of the wood include wood plywood, wood veneer, medium density fiber board (MDF), etc. Ceramics, tiles and the like can be mentioned, and examples of the concrete include ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), slag cement and the like.

  As the material to be transferred, a laminate using the above materials, for example, a laminate obtained by laminating paper, synthetic paper, cloth, other resin materials, metal materials, etc. on the resin material can be used.

  In order to improve the adhesion to the transfer layer, the surface of the transfer material may be subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as pretreatment.

  The transfer method using the transfer sheet of the present invention is not particularly limited, and various conventionally known transfer methods can be used. For example, a method in which the transfer layer on the transfer sheet is pressed from the support side toward the transfer target and the transfer layer is pressure-bonded to the transfer target and the support is peeled off, or the transfer layer on the transfer sheet is directed to the transfer target. For example, a method of heat-pressing and peeling the support after the transfer layer is pressure-bonded to the transfer target.

  Another transfer body is further stacked on the transfer layer that is stacked on the transfer body, and a laminate composed of three layers can be formed by applying pressure and / or heating. Furthermore, it is also possible to form a laminate having five layers by laminating a laminate in which transfer layers are laminated via a transfer layer. Here, the laminate further laminated may be a laminate comprising a transfer layer and a transfer target, or the transfer sheet of the present invention. By repeating this, it is possible to make multiple layers.

  In addition, two laminates in which a transfer layer is laminated on a transfer object or a support are prepared, and the transfer layers of these laminates are laminated from both sides of another transfer object, and are pressed and / or heated. Thus, a laminate composed of five layers or a package in which the above-mentioned another transfer target is packed can also be used. The laminate used here may be a laminate in which a transfer layer is laminated on a transfer target as described above, or may be a transfer sheet of the present invention in which a transfer layer is laminated on a support. .

Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited by these.
In the following examples and comparative examples, the measuring methods for various physical properties were as follows.

(1) Configuration of acid-modified polyolefin resin The structure was determined by ¹ H-NMR analysis (300 MHz) using an apparatus manufactured by Varian. Orthodichlorobenzene (d ₄ ) was used as a solvent, and measurement was performed at 120 ° C.

(2) Melt flow rate (MFR) of acid-modified polyolefin resin
It was measured by the method described in JIS K6730 (190 ° C., 21.2 N (2160 g) load).

(3) Melting point of acid-modified polyolefin resin Using 10 mg of resin as a sample, a DSC (Differential Scanning Calorimetry) apparatus (Perkin Elmer product name: DSC7) is used for measurement at a temperature rising rate of 10 ° C./min. The melting point was determined from the obtained temperature rise curve.

(4) Vicat softening point of acid-modified polyolefin resin Measured by the method described in JIS K7206.

(5) Organic solvent content of aqueous dispersion Shimadzu Corporation gas chromatograph, product name: GC-8A [FID detector used, carrier gas: nitrogen, column packing material (manufactured by GL Sciences): PEG-HT (5 %)-Uniport HP (60/80 mesh), column size: diameter 3 mm × 3 m, sample charging temperature (injection temperature): 150 ° C., column temperature: 60 ° C., internal standard substance: n-butanol], aqueous dispersion A body or an aqueous dispersion diluted with water was directly put into the apparatus, and the content of the organic solvent was determined. The detection limit was 0.01% by mass.

(6) Solid Concentration of Liquid Material An appropriate amount of the liquid material was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight to determine the solid content concentration.

(7) Number average particle diameter of acid-modified polyolefin resin particles The number average particle diameter was determined using Nikkiso Co., Ltd., Microtrac particle size distribution meter, product name: UPA150 (MODEL No. 9340, dynamic light scattering method). The refractive index of the resin used for particle diameter calculation was 1.50.

(8) Transfer Layer Thickness Using a contact-type film thickness meter, the total thickness of a transfer sheet obtained by coating a liquid material on a support and drying, and laminating the transfer layer on the support, is obtained. It was measured by subtracting the thickness of the support from the thickness.

(9) Transferability The transfer sheet was bonded to the transfer target and pressed with a heat press to form a laminate composed of the support / transfer layer / transfer target. Thereafter, the state of the transfer layer when the support was peeled from the laminate was visually observed and evaluated as follows.

○: All of the transfer layer was transferred to the transfer medium.
X: The transfer layer could not be transferred to the transfer target, or a part of the transfer layer remained on the support.
In addition, the transferred material includes
PET film: manufactured by Unitika Ltd., product name: emblet PET38, thickness 38 μm
PP film: manufactured by Tosero Co., Ltd., product name: # 20u-1, thickness 20 μm
It was used.

(10) Adhesiveness Adhesiveness between the transfer layer and the transferred material was evaluated by tape peeling (cross cut test) by the cross-cut method described in JIS K5400. More specifically, the transfer layer was cut into 100 sections by cross-cutting, and evaluated according to the following criteria using the section function of the coating surface remaining after the tape was peeled.

○: 100 section remaining △: 90-99 section remaining ×: 0-89 section remaining

(11) Adhesive strength After producing a laminate comprising a transfer object / transfer layer in accordance with the above transferability test, another PET film (manufactured by Unitika, product name: emblet PET38, thickness 38 μm) is further formed on the transfer layer side. The laminate which consists of a to-be-transferred body / transfer layer / PET film was formed by bonding and pressing with a heat press machine. The laminate was cut out with a width of 15 mm, and the tensile strength was measured by T-type peeling at a tensile speed of 200 mm / min using a tensile tester (Intesco Corporation, Intesco Precision Universal Material Tester Model 2020).

(12) Water resistance test The laminate obtained by conducting the transferability test was visually observed for the state of the coating film after being immersed in pure water at 25 ° C for one day, and evaluated according to the following criteria.

○: No change Δ: The coating film becomes cloudy ×: The coating film peels off

(13) Alkali resistance test The laminate obtained by conducting a transferability test was visually observed for the state of the coating film after being immersed in a 40% aqueous potassium hydroxide solution at 25 ° C for 1 day. evaluated.

○: No change Δ: The coating film becomes cloudy ×: The coating film peels off

(14) Acid resistance test The laminate obtained by conducting the transferability test was visually observed for the state of the coating film after being immersed in a 35% hydrochloric acid aqueous solution at 25 ° C for one day, and evaluated according to the following criteria. .

○: No change Δ: The coating film becomes cloudy ×: The coating film peels off

(15) Solvent resistance test The laminate obtained by conducting the transferability test was visually observed for the state of the coating film after being immersed in toluene at 25 ° C for one day, and evaluated according to the following criteria.

○: No change Δ: The coating film becomes cloudy ×: The coating film peels off

(16) Biodegradability of substrate after transfer Biodegradability was evaluated by evaluating the biodegradability after 8 weeks of composting under the following conditions in accordance with the test procedure of JIS K6953.

○: Biodegradation degree is 60% or more ×: Biodegradation degree is less than 60%

[Production of Aqueous Dispersion E-1]
Using a stirrer equipped with a hermetically sealed 1 liter glass container equipped with a heater, 60.0 g bondine “LX-4110” (acid-modified polyolefin resin manufactured by Arkema), 90.0 g IPA (Wako Pure Chemical Industries, Ltd.) 3.0 g of TEA (manufactured by Wako Pure Chemical Industries, Ltd.) and 147.0 g of distilled water were charged into the glass container, and the rotation speed of the stirring blade was 300 rpm. Then, the system temperature was kept at 140 to 145 ° C. and further stirred for 30 minutes. Then, it put on the water bath and cooled to room temperature (about 25 degreeC), stirring with a rotational speed of 300 rpm. Furthermore, pressure filtration (air pressure 0.2 MPa) was performed with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform acid-modified polyolefin resin aqueous dispersion E-1.

[Production of aqueous dispersion E-2]
Using a stirrer equipped with a hermetic pressure-resistant 1 liter glass container with a heater, 60.0 g bondine “HX-8210” (acid-modified polyolefin resin made by Arkema), 90.0 g IPA (Wako Pure Chemical Industries, Ltd.) 2.6 g DMEA (manufactured by Wako Pure Chemical Industries, Ltd.) and 147.4 g distilled water were charged into the glass container. And the rotational speed of the stirring blade was 300 rpm, the system temperature was kept at 120 ° C., and stirring was performed for 40 minutes. Then, it cooled to room temperature (about 25 degreeC), stirring with air cooling with the rotational speed of 300 rpm. Furthermore, pressure filtration (air pressure 0.2 MPa) was performed with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white aqueous dispersion E-2. At this time, almost no resin remained on the filter.

[Production of aqueous dispersion E-3]
Bondin “HX-8290” (manufactured by Arkema) was used as the acid-modified polyolefin resin, and the same operation as in the production of the aqueous dispersion E-1 was performed to obtain an aqueous dispersion E-3 of an acid-modified polyolefin resin.

[Production of Aqueous Dispersion E-4]
Bondin “TX-8030” (manufactured by Arkema) was used as the acid-modified polyolefin resin, and the same operation as in the production of the aqueous dispersion E-1 was performed to obtain an aqueous dispersion E-4 of an acid-modified polyolefin resin.

[Production of Aqueous Dispersion E-5]
In order to remove a part of IPA from this aqueous dispersion E-2 using the aqueous dispersion E-2, the solvent was distilled off at a bath temperature of 80 ° C. while adding water using a rotary evaporator. Then, it is cooled to room temperature (about 25 ° C.) by air cooling, and further filtered under pressure (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform polyolefin resin aqueous solution Dispersion E-5 was obtained.

[Production of Solution E-6]
Using a stirrer equipped with a heat-resistant 1-liter glass container with a heater, 15.0 g of Bondine “HX-8210” and 285.0 g of toluene are charged into the glass container, and the rotation speed of the stirring blade is adjusted. Stir at 300 rpm. Then, the system temperature was kept at 120 ° C. and further stirred for 40 minutes. Then, it air-cooled and it cooled to about 50 degreeC, stirring with a rotational speed of 300 rpm. Furthermore, pressure filtration (air pressure 0.2 MPa) was performed with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain Solution E-6. At this time, almost no resin remained on the filter.

[Production of Aqueous Dispersion E-7]
Using a stirrer equipped with a heat-resistant 1-liter glass container equipped with a heater, 60.0 g of Primacol 5980I (acid-modified polyolefin resin manufactured by Dow Chemical Co.), 16.8 g of TEA and 223.2 g of distillation Water was charged into the glass container, and the stirring speed was 300 rpm and stirring was performed. The system temperature was maintained at 140 to 145 ° C. and stirred for 30 minutes. Then, it put on the water bath and cooled to room temperature (about 25 degreeC), stirring with a rotational speed of 300 rpm. Furthermore, pressure filtration (air pressure 0.2 MPa) was performed with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a slightly cloudy aqueous dispersion E-7. At this time, almost no resin remained on the filter.

  These aqueous dispersions E-1 to E-7 correspond to the liquid substances referred to in the present invention, but the composition of the acid-modified polyolefin resin used for the production is shown in Table 1, and the composition of the dispersion is shown. It shows in Table 2. In addition, the organic solvent content of E-6 was calculated by subtracting the solid content concentration.

Example 1
An aqueous dispersion E-1 of acid-modified polyolefin resin is applied to the corona-treated surface of a biaxially stretched polylactic acid film (Unitika Ltd., Terramac film TFE-15, biaxially stretched polylactic acid film having a thickness of 15 μm) as a support. After coating using a Mayer bar, it was dried at 120 ° C. for 30 seconds to form a transfer layer having a thickness of 3.0 μm, thereby obtaining a transfer sheet. The transfer sheet thus obtained was evaluated for transferability, adhesion, adhesive strength, water resistance, alkali resistance, acid resistance, and solvent resistance. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Example 2
Compared with Example 1, the coating amount was changed so that the thickness of the transfer layer was 2.0 μm. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Example 3
Compared with Example 1, the coating amount was changed so that the thickness of the transfer layer was 1.0 μm. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Example 4
Compared to Example 1, the coating amount was changed so that the thickness of the transfer layer was 9.0 μm. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Example 5
Instead of the acid-modified polyolefin resin aqueous dispersion E-1 in Example 1, an acid-modified polyolefin resin aqueous dispersion E-2 was used. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Example 6
Instead of the acid-modified polyolefin resin aqueous dispersion E-1 in Example 1, an acid-modified polyolefin resin aqueous dispersion E-3 was used. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 80 ° C.

Example 7
In place of the acid-modified polyolefin resin aqueous dispersion E-1 in Example 1, an acid-modified polyolefin resin aqueous dispersion E-4 was used. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Example 8
In place of the acid-modified polyolefin resin aqueous dispersion E-1 in Example 1, an acid-modified polyolefin resin aqueous dispersion E-5 was used. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Example 9
In place of the acid-modified polyolefin resin aqueous dispersion E-1 in Example 1, an acid-modified polyolefin resin aqueous dispersion E-6 was used. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Example 10
Instead of the acid-modified polyolefin resin aqueous dispersion E-1 of Example 1, an acid-modified polyolefin resin aqueous dispersion E-7 was used. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Example 11
In place of the acid-modified polyolefin resin aqueous dispersion E-1 in Example 1, an acid-modified polyolefin resin aqueous dispersion E-1 and an aqueous solution of an oxazoline group-containing polymer as a crosslinking agent (Nippon Shokubai Co., Ltd., "Epocross" WS- 500 ”, solid content concentration: 40% by mass) was used so that the solid content of the oxazoline group-containing polymer compound was 5 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 140 ° C.

Example 12
In place of the acid-modified polyolefin resin aqueous dispersion E-1 in Example 1, an acid-modified polyolefin resin aqueous dispersion E-3 and a tin oxide sol ultrafine particle dispersion as an antistatic agent (manufactured by Unitika, "AS11T", The solid content of 11.5% by mass) was mixed with 100 parts by mass of the acid-modified polyolefin resin so that the solid content of tin oxide was 100 parts by mass. Otherwise, a transfer sheet was prepared in the same manner as in Example 1, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 120 ° C.

  Table 3 shows the evaluation results of the coating thickness of the transfer sheet, that is, the transfer layer thickness, transferability, adhesion, adhesive strength, water resistance, alkali resistance, acid resistance, and solvent resistance for Examples 1 to 12.

Comparative Example 1
Instead of the acid-modified polyolefin resin aqueous dispersion E-1 in Example 1, an aqueous polyester resin dispersion (KA-3556, manufactured by Unitika Ltd., solid content concentration: 30% by mass) was used. Other than that was carried out similarly to Example 1, and produced the transfer sheet and tried to evaluate various performances. The press temperature when transferring the transfer layer onto the transfer target was 100 ° C.

  However, the transfer layer could not be transferred to the transfer target. For this reason, performance evaluation could not be performed.

Comparative Example 2
Instead of the acid-modified polyolefin resin aqueous dispersion E-1 in Example 1, an aqueous polyurethane resin dispersion (Adeka Bontiter HUX380, solid content concentration: 38% by mass, manufactured by Adeka Corporation) was used. Other than that was carried out similarly to Example 1, and produced the transfer sheet and tried to evaluate various performances. The press temperature when transferring the transfer layer onto the transfer target was 100 ° C.

  However, the transfer layer could not be transferred to the transfer target. For this reason, performance evaluation could not be performed.

Comparative Example 3
In place of the biaxially stretched polylactic acid film of Example 1, a biaxially stretched polyester film (Embret PET38 manufactured by Unitika Ltd., PET film having a thickness of 38 μm) was used as the support. Other than that was carried out similarly to Example 1, and produced the transfer sheet and tried to evaluate various performances. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

  However, the transfer layer could not be transferred to the transfer target. For this reason, performance evaluation could not be performed.

Comparative Example 4
As a support, in place of the biaxially stretched polylactic acid film of Example 1, a biaxially stretched polyester film (Embret PET38 manufactured by Unitika Ltd., PET film having a thickness of 38 μm) was added to a silicone release agent (TSM6341 manufactured by Toshiba Silicone Corp.). , Solid content concentration: 40% by mass) was used to form a release layer by coating to a thickness of 0.5 μm. Then, using the same acid-modified polyolefin resin aqueous dispersion E-1 as in Example 1, the same operation as in Example 1 was performed to try to produce a transfer sheet having a transfer layer having a thickness of 3.0 μm.

  However, when the acid-modified polyolefin resin aqueous dispersion E-1 was applied to the surface of the release agent, repelling occurred and the transfer layer could not be formed. For this reason, performance evaluation could not be performed.

Comparative Example 5
Compared to Comparative Example 4, the coating amount was changed so that the thickness of the transfer layer was 9.0 μm. Otherwise in the same manner as in Comparative Example 4, a transfer sheet could be produced. For this reason, various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Comparative Example 6
Instead of the biaxially stretched polyester film of Comparative Example 5, a biaxially stretched polylactic acid film (TFE-15) was used. Other than that was carried out similarly to the comparative example 5, produced the transfer sheet, and evaluated various performances. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Comparative Example 7
Instead of the silicone release agent in Comparative Example 5, a long-chain alkyl-modified polymer dispersion (K-256 manufactured by Chukyo Yushi Co., Ltd., solid content concentration: 19%) was used. Otherwise, a transfer sheet was prepared in the same manner as in Comparative Example 4, and various performances were evaluated. The press temperature when transferring the transfer layer to the transfer target was 90 ° C.

Comparative Example 8
As a support, an aqueous polylactic acid resin dispersion (LAE-013N manufactured by Unitika, solid content concentration: 50%) and polyethylene paraffin wax (MS-40 manufactured by San Nopco, solid) (Partial concentration: 40%) is mixed with 100 parts by mass of polylactic acid resin so that polyethylene paraffin wax is 10 parts by mass, and coated so as to have a thickness of 0.5 μm. What formed the layer was used. Otherwise, a transfer sheet was prepared in the same manner as in Comparative Example 4, and various performances were evaluated.

  Table 4 shows the evaluation results of the transfer layer thickness, transferability, adhesive strength, water resistance, alkali resistance and acid resistance of Comparative Sheets 1 to 8.

The transfer sheet of the present invention in which an acid-modified polyolefin resin is laminated on a support made of an aliphatic polyester resin in Examples 1 to 12 can be used even if it does not have a release layer between the support and the transfer layer. Good transferability to the transfer body was exhibited, and the transfer layer was excellent in adhesion, adhesive strength, water resistance, alkali resistance, acid resistance, and solvent resistance. The substrate after transfer was also biodegradable. Furthermore, when a crosslinking agent was added to cure the acid-modified polyolefin, better solvent resistance was exhibited (Example 11). When tin oxide ultrafine particles were added (Example 12), the surface resistivity of the transfer layer was 10 ¹⁰ Ω / □ and excellent antistatic performance could be imparted. On the other hand, the surface resistivity of the transfer layer in other examples was 10 ¹⁵ Ω / □.

  On the other hand, when a resin other than the present invention was used for the transfer layer on the support made of an aliphatic polyester resin, the transfer could not be sufficiently performed on the transfer target (Comparative Examples 1 and 2). Furthermore, even when the acid-modified polyolefin resin constituting the transfer layer was laminated on a support other than the aliphatic polyester resin, the transfer could not be sufficiently performed on the transfer target (Comparative Example 3). A support coated with a silicone release agent (Comparative Examples 4, 5, 6), a release agent added with a long-chain alkyl-modified polymer (Comparative Example 7), and a release agent added with a wax (Comparative Example 8) When used, not only is it difficult to form a thin transfer layer on the release layer, but the transfer layer is contaminated by the silicone, emulsifier, and wax components contained in the release agent, resulting in adhesion. In addition, deterioration of water resistance, alkali resistance, acid resistance, and solvent resistance was observed.

Claims (7)

  A transfer layer is laminated on one side of the support, the support is formed of an aliphatic polyester resin, the transfer layer contains an acid-modified polyolefin resin, and a release layer is provided between the transfer layer and the support. The transfer sheet characterized by not having.   The transfer sheet according to claim 1, wherein the aliphatic polyester resin is a polylactic acid resin.   The transfer sheet according to claim 1 or 2, wherein the acid-modified polyolefin resin contains 0.01 to 5% by mass of an acid-modified component.   The transfer sheet according to any one of claims 1 to 3, wherein the acid-modified polyolefin resin contains an ethylenically unsaturated component having an oxygen atom in a side chain.   A transfer comprising a step of coating a liquid containing an acid-modified polyolefin resin on a support formed of an aliphatic polyester resin without interposing a release agent, and then drying. Sheet manufacturing method.   6. The method for producing a transfer sheet according to claim 5, wherein a liquid material containing an acid-modified polyolefin resin containing 0.01 to 5% by mass of an acid-modified component is used.   7. The method for producing a transfer sheet according to claim 5, wherein the liquid medium is a liquid material that is an aqueous medium.