JP3007326B2 - Transfer material and surface protection sheet excellent in abrasion resistance and chemical resistance, and method for producing molded articles excellent in abrasion resistance and chemical resistance using these - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer material, a surface protection sheet and a transfer material capable of obtaining a molded product excellent in abrasion resistance and chemical resistance without causing cracks in a protective printed layer at a curved surface of the molded product. Regarding the method of producing molded articles having excellent abrasion resistance and chemical resistance using these, it is necessary to prevent fluidity and adhesiveness from remaining in the protective printing layer before irradiation with active energy rays, especially in the in-line printing process. You can do it.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining a molded article having excellent abrasion resistance and chemical resistance, a protective printing layer made of an active energy ray-curable resin composition is provided on one surface of a base sheet having releasability. A method of adhering a transfer material provided with another print layer such as a pattern print layer and an adhesive print layer on a protective layer to the surface of a molded article and peeling the base sheet, and a base sheet having no release property A surface protection sheet provided with a protective print layer made of an active energy ray-curable resin composition on one side of the surface and another print layer such as a picture print layer and an adhesive print layer on the other side is adhered to the surface of the molded article. There are methods.

However, in order to obtain a molded article having excellent abrasion resistance and chemical resistance by the above-mentioned methods, active energy rays are irradiated during the production of a sheet material such as a transfer material or a surface protection sheet. If the reactive resin composition is cross-linked and cured (precured), cracks are likely to occur in the protective printing layer located on the curved surface of the molded product when the sheet material is adhered to the molded product.

On the other hand, if the active energy ray irradiation is performed after the sheet material is adhered to the molded article without performing the sheet material production (after-cure), cracks in the protective print layer can be eliminated. The protective printing layer before irradiation with energy rays has the following problems.

In general, in order to continuously form various printing layers on a sheet, a ready-made multicolor gravure rotary printing machine as shown in FIG. 9 is used. The main flow of printing by such a machine is that after the sheet to be printed is continuously fed out from the unwinding section 15, first, in the first printing unit of the multicolor gravure rotary printing section 16, the ink is applied from the ink pan 19 to the surface. The ink is transferred onto the sheet by passing the sheet between a rotating plate cylinder 18 supplied with the printing cylinder and an impression cylinder 20 for applying pressure to the plate cylinder 18 to form a printing layer;
Continue drying the sheet with steam drum, hot air, cold air, etc. 2
After the printing layer is dried by passing the sheet through the second printing unit, the sheet is sent to the next printing unit, and another printing layer is formed on the sheet in the same manner as in the previous printing unit. The sheet is wound around the winding section 17 after all the printed layers are formed while changing the forming surface or not. In this machine, a large number of guide rolls 2 are used for registration.
At 1 the tension is finely adjusted.

[0006] However, ordinary printing layers such as a pattern printing layer and an adhesive printing layer lose their fluidity and tackiness by passing through the drying section 22 of each printing unit. When the protective printing layer made of the resin composition is dried to such an extent, fluidity and tackiness remain. This is because the drying section 22 has a low heating temperature and a length of only about 2 m. Moreover, since the speed at which the sheet passes through the drying unit 22 is matched with the printing speed of the printing layer, the time required for heating the protective printing layer in the drying unit 22 is only about 3 seconds when the speed is 40 m / min. It doesn't.

As a result, in the case of a transfer material, the ink of the protective print layer once formed on the base sheet is transferred to the guide roll 21 of the printing press, or the pattern print layer,
The ink of the adhesive printing layer or the like is not transferred well onto the protective printing layer from the plate cylinder 18, and the ink of the protective printing layer once formed on the base sheet forms the pattern printing layer, the adhesive printing layer, etc. A so-called back trap which shifts toward 18 may occur. In the case of the surface protection sheet, the ink of the protection printing layer once formed on the base sheet is transferred to the guide roll 21 of the printing press or the like.
Since a protective printing layer is provided on one side of the base sheet having no release property and a picture printing layer, an adhesive printing layer, etc. are provided on the other side, protection is provided when the sheet is wound up by the winding section 17 after forming all the printing layers. The ink of the printing layer is transferred to the surface provided with the picture printing layer, the adhesive printing layer, and the like.

Therefore, when the transfer material or the surface protection sheet is adhered to the molded article, no crack is generated in the protective printed layer located on the curved surface of the molded article, and the protective printed layer before irradiation with the active energy ray has fluidity and adhesion. In order to prevent the property from remaining, special drying for exclusive use of the protective print layer is required after the protective print layer is formed in the manufacturing process of the sheet material. That is, FIG.
Designing and assembling a printing system dedicated to the protective printing layer as shown in FIG. 0, and continuously feeding out the sheet to be printed from the unwinding section 15, first printing the ink on the sheet in the gravure rotary printing section 23 for the protective printing layer. To form a protective print layer, and then pass the sheet through a protective print layer drying section 24 having a length of about 10 to 30 m and a temperature of about 200 ° C. to form the protective print layer with fluidity and adhesion. After drying until no properties remain, the sheet is once wound around the winding section 17. In this case, the printing speed can be set in accordance with the drying of the protective printing layer since the printing device is different from the other printing layers. Then, the wound sheet is set again on the unwinding section 15 of the ready-made multicolor gravure rotary printing press as shown in FIG. 9 to form another printing layer.

[0009]

However, when the transfer material or the surface protection sheet is manufactured by performing the special drying for the protective print layer as described above, the formation of the protective print layer 2 and the formation of the other print layers. In between, it must be removed from the line once, which takes time. In addition, a printing system dedicated to the protection printing layer must be newly designed and assembled only for the production of the transfer material and the surface protection sheet, which requires capital investment. In addition, since a plurality of devices are required, operating costs are extra than in the case where only a ready-made multicolor gravure rotary printing press is used.

Therefore, the present invention eliminates the above problems and eliminates the occurrence of cracks in the protective printing layer located on the curved surface of the molded article when the transfer material or the surface protective sheet is adhered to the molded article, and eliminates the in-line problem. A transfer material and a surface protective sheet having excellent abrasion resistance and chemical resistance capable of preventing fluidity and tackiness from remaining on the protective printing layer before irradiation with active energy rays even in the printing step, and using these materials. It is an object of the present invention to provide a method for producing a molded article having excellent wear resistance and chemical resistance.

[0011]

In order to achieve the above object, the transfer material of the present invention, which has excellent abrasion resistance and chemical resistance, comprises (meth) acrylic on the release surface of a substrate sheet having release properties. A polymer having an equivalent weight of 100 to 300 g / eq, a hydroxyl value of 20 to 500, a weight average molecular weight of 5,000 to 50,000 and a polyfunctional isocyanate, and having a urethane bond amount of 6000.
A protective printing layer comprising an active energy ray-curable resin composition containing a reaction product of 50,000 g / eq as an active ingredient is provided, and another printing layer is provided on the protective printing layer. did.

In the above transfer material, the polymer may be:
The glycidyl (meth) acrylate polymer was configured to be an addition product of an α, β-unsaturated monocarboxylic acid by an addition reaction.

In the above transfer material, the glycidyl (meth) acrylate-based polymer may be a glycidyl (meth) acrylate homopolymer or α, β not containing glycidyl (meth) acrylate and a carboxyl group.
-It was configured to be a copolymer of unsaturated monomers.

In the above transfer material, a base sheet having releasability may be formed on a surface of an epoxy resin, a melamine resin, or a copolymer resin or a mixture thereof as a main component and containing an acid catalyst. It was configured to have a matte layer.

The method for producing a molded article having excellent abrasion resistance and chemical resistance according to the present invention comprises the steps of: adhering the transfer material having excellent abrasion resistance and chemical resistance to the surface of the molded article; And a step of irradiating with active energy rays.

Further, according to the method of the present invention for producing a molded article having excellent wear resistance and chemical resistance, a transfer material excellent in wear resistance and chemical resistance is sandwiched in a molding die, and a resin is contained in a cavity. Was injected and filled to obtain a resin molded article, and at the same time, a transfer material was adhered to the surface of the resin molded article. Thereafter, a step of peeling the base sheet and a step of irradiating active energy rays were performed.

The surface protective sheet having excellent abrasion resistance and chemical resistance according to the present invention has a (meth) acrylic equivalent of 100 to 300 g / eq and a hydroxyl value of 20 to 20 on the release surface of a base sheet having release properties.
An active energy ray-curable composition containing a reaction product of a polymer having a weight average molecular weight of 5,000 to 50,000 and a polyfunctional isocyanate subjected to a polyaddition reaction and having a urethane bond amount of 6,000 to 50,000 g / eq as an active ingredient. A protective print layer made of a resin composition was provided, and another print layer was provided on the opposite surface of the base sheet.

In the construction of the surface protective sheet, the polymer is a reaction product obtained by an addition reaction of a glycidyl (meth) acrylate polymer and an α, β-unsaturated monocarboxylic acid.

In the surface protective sheet, the glycidyl (meth) acrylate-based polymer may be a glycidyl (meth) acrylate homopolymer or an α, β-non-glycidyl (meth) acrylate and carboxyl-free α, β-non-carboxy group. It was configured to be a copolymer of saturated monomers.

The method for producing a molded article having excellent wear resistance and chemical resistance according to the present invention comprises disposing the above-mentioned surface protective sheet having excellent wear resistance and chemical resistance on the surface of the molded article, and heating the base sheet. After the surface protection sheet was adhered to the surface of the molded product by applying vacuum suction from below, a process of irradiating active energy rays was performed.

Further, the method for producing a molded article excellent in abrasion resistance and chemical resistance according to the present invention is characterized in that the above-mentioned surface protection sheet excellent in abrasion resistance and chemical resistance is sandwiched in a molding die, and is placed in a cavity. The resin was injection-filled to obtain a resin molded product, and at the same time, a surface protective sheet was adhered to the surface of the resin molded product.

[0022]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings.

FIG. 1 is a schematic sectional view showing an embodiment of the transfer material according to the present invention, FIG. 2 is a schematic sectional view showing another embodiment of the transfer material according to the present invention, and FIG. FIG. 4 is a schematic view showing one embodiment of a manufacturing process of a molded article having excellent wear resistance and chemical resistance using a material, and FIG. 4 is excellent in wear resistance and chemical resistance using a transfer material according to the present invention. FIG. 5 is a schematic view showing another embodiment of the manufacturing process of the molded article, FIG. 5 is a schematic sectional view showing one embodiment of the surface protection sheet according to the present invention, and FIG. 6 is another embodiment of the surface protection sheet according to the present invention. FIG. 7 is a schematic sectional view showing
Is a schematic view showing one embodiment of a process for producing a molded article having excellent abrasion resistance and chemical resistance using the surface protection sheet according to the present invention, and FIG. 8 is abrasion resistance using the surface protection sheet according to the present invention. FIG. 7 is a schematic view showing another embodiment of the manufacturing process of a molded article having excellent properties and chemical resistance. In the figure, 1 is a base sheet, 2 is a protective printing layer, 3 is a picture printing layer, 4 is an adhesive printing layer, 5 is a transfer layer,
Reference numeral 6 denotes a transfer material, 7 denotes a molded product, 8 denotes a heat-resistant rubber-like elastic body, 9 denotes a movable type, 10 denotes a fixed type, 11 denotes a molten resin, 12 denotes a surface protection sheet, 13 denotes a heater, and 14 denotes vacuum suction. .

First, the transfer material 6 having excellent abrasion resistance and chemical resistance used in the present invention will be described.

The transfer material 6 shown in FIG. 1 has a polymer having a (meth) acrylic equivalent of 100 to 300 g / eq, a hydroxyl value of 20 to 500, a weight average molecular weight of 5,000 to 50,000 and a polyfunctional isocyanate before printing the protective printing layer. The protective printing layer 2 made of an active energy ray-curable resin composition containing a reaction product having a urethane bond amount of 6000 to 50,000 g / eq, which has been subjected to a polyaddition reaction and having an amount of 6000 to 50,000 g / eq, has releasability. The protective printing layer 2 provided on the release surface of the base sheet 1
Another printing layer such as a picture printing layer 3 and an adhesive printing layer 4 is provided thereon.

The base sheet 1 having releasability includes resin sheets such as polypropylene resin, polyethylene resin, polyamide resin, polyester resin, polyacrylic resin, polyvinyl chloride resin, aluminum foil, and copper foil. For example, a metal sheet such as a metal foil, a glassine paper, a coated paper, a cellulosic sheet such as cellophane, or a composite of the above sheets may be used.

When the transfer layer 5 composed of the protective print layer 2, the picture print layer 3, the adhesive print layer 4 and the like has good releasability from the base sheet 1, the transfer layer 5 can be provided directly on the base sheet 1. Good. In order to improve the releasability of the transfer layer 5 from the base sheet 1, a release layer may be formed on the entire base sheet body, and this may be used as a base sheet having releasability. The release layer is released together with the main body of the base sheet 1 when the base sheet 1 is peeled off after transfer or simultaneous transfer with molding. Materials for the release layer include epoxy resin release agents, epoxy melamine resin release agents, amino alkyd resin release agents, melamine resin release agents, silicone resin release agents, and fluororesin release agents. Agent, cellulose derivative release agent,
Urea resin-based release agents, polyolefin resin-based release agents, paraffin-based release agents, and composite release agents thereof can be used. Various printing methods, coating methods, and the like are used for forming the release layer.

The base sheet 1 having releasability may have a matte release surface. For example, embossing is performed, or fine particles such as calcium carbonate, silica, zinc oxide, magnesium carbonate, polyethylene wax, and glass beads are contained in the release layer. When the base sheet having releasability is peeled off after the transfer material 6 is adhered to the surface of the molded article 7 in this manner, fine irregularities on the release surface of the base sheet are transferred to the outermost surface of the transfer layer 5, and the matte surface is removed. A molded article having the same can be obtained.

A matting layer may be partially provided on the base sheet body or the release layer. By peeling the partially matte layer together with the base sheet from the transfer layer 5, a molded article having a partially matte surface can be obtained. As the material of the partial matte layer, a material in which the fine powder is contained in the same material as the material used for the release layer can be used. Various printing methods are used to form the partial matte layer. When an acid catalyst such as paratoluenesulfonic acid is contained in an ink containing an epoxy resin, a melamine resin or a copolymer resin or a mixture thereof as a main component, drying after printing becomes faster, and the protective printing layer and other In-line printing process becomes possible with the printed layer.

The protective print layer 2 is made of an active energy ray-curable resin composition, and is a layer for protecting the molded article 7 and the picture print layer 3 from chemicals and friction after irradiation with active energy rays. In the present invention, the amount of the polymer used for producing the active energy ray-curable resin composition is a specific amount in consideration of the physical and chemical requirements of the protective print layer 2 before and after irradiation with the active energy ray. That is, from the viewpoint of curability upon irradiation with active energy rays, (meth) acrylic equivalent 100
To 300 g / eq, preferably 150 to 300 g / eq. When the (meth) acrylic equivalent is greater than 300 g / eq, the abrasion resistance after irradiation with active energy rays is insufficient, and it is difficult to obtain one having less than 100 g / eq. Further, from the viewpoint of reactivity with the polyfunctional isocyanate to be subjected to the polyaddition reaction, the polymer has a hydroxyl value of 20 to 500, preferably 100 to 300. When the hydroxyl value is less than 20, the reaction with the polyfunctional isocyanate is insufficient, and the degree of crosslinking of the protective printing layer 2 before irradiation with active energy rays is low.
For this reason, tackiness remains or solvent resistance is insufficient. In addition, those having a hydroxyl value exceeding 500 are difficult to obtain. The weight average molecular weight of the polymer is 5,000 to 50,000, preferably 8,000 to 40,000. If the weight average molecular weight of the polymer is less than 5,000, the adhesiveness of the protective printing layer 2 before the irradiation with the active energy ray remains or the solvent resistance becomes insufficient. Also,
If it exceeds 50,000, the viscosity of the resin becomes too high, and the printing workability of the ink decreases.

The method for producing the polymer is not particularly limited, and a conventionally known method can be employed. For example, [1] a method of introducing a (meth) acryloyl group into a part of a side chain of a polymer containing a hydroxyl group, [2] α, β-unsaturation containing a hydroxyl group in a copolymer containing a carboxyl group A method of subjecting a monomer to a condensation reaction, [3] a method of adding an α, β-unsaturated monomer containing an epoxy group to a copolymer containing a carboxyl group, and [4] a method of adding an epoxy group-containing polymer. There is a method of reacting an α, β-unsaturated carboxylic acid.

Taking the method [4] as an example, the method for producing the polymer used in the present invention will be described more specifically. For example, α, β such as acrylic acid is added to a polymer having a glycidyl group.
-The polymer used in the present invention can be easily obtained by a method of reacting an unsaturated carboxylic acid. Preferred as the polymer having a glycidyl group are, for example, a copolymer of glycidyl (meth) acrylate and a copolymer of glycidyl (meth) acrylate and an α, β-unsaturated monomer containing no carboxyl group. No. Examples of the α, β-unsaturated monomer not containing a carboxyl group include various (meth) acrylates, styrene, vinyl acetate, acrylonitrile, and the like.
If an α, β-unsaturated monomer containing a carboxyl group is used, crosslinking occurs during a copolymerization reaction with glycidyl (meth) acrylate, resulting in high viscosity and gelation.

In any case, when each of the above methods [1] to [4] is adopted, the types of monomers and polymers to be used and the use of these are appropriately determined so as to satisfy the above numerical limitation range relating to the polymer. It is necessary to appropriately set conditions such as the amount. Such operations are well known to the parties.

In the present invention, the polyfunctional isocyanate used for preparing the active energy ray-curable resin composition is not particularly limited, and various known materials can be used.
For example, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, diphenyl methane diisocyanate, 1,6-hexane diisocyanate, the above trimer, a prepolymer obtained by reacting a polyhydric alcohol with the above diisocyanate, etc. Can be used. In the present invention,
The reason why the polyfunctional isocyanate is subjected to the polyaddition reaction with the polymer is that the tackiness of the protective print layer 2 before irradiation with active energy rays is kept low, and in the case of the transfer material 6, the pattern print layer 3 laminated on the protective print layer 2 And to satisfy a certain degree of solvent resistance to the solvent contained in the ink for forming the adhesive print layer 4. That is, a hydroxyl group contained in a polymer is reacted with an isocyanate group of a polyfunctional isocyanate to form a lightly crosslinked product, thereby imparting the above performance.

The ratio of the polyaddition reaction between the polymer and the polyfunctional isocyanate is such that the amount of urethane bonds in the reaction product obtained by the polyaddition reaction is 6,000 to 50,000 g / eq, more preferably 8,000 to 30,000 g / eq. Need to be decided. If the urethane bond amount is less than 6000 / eq, the crosslinking will proceed too much during the polyaddition reaction and a gel will be generated, so that a uniform varnish cannot be obtained. In addition, the urethane bond amount is 50,000g
If it exceeds / eq, the crosslinkability will be insufficient, the tackiness will remain, the solvent resistance will be insufficient, and it will be difficult to obtain the transfer material 6 by an in-line printing process such as a ready-made multicolor gravure rotary printing press. .

A feature of the present invention is that the protective printing layer 2 is an active ingredient containing, as an active ingredient, a reaction product obtained by previously performing a polyaddition reaction between a polymer and a polyfunctional isocyanate under the above-mentioned predetermined conditions before printing the protective printing layer. It has been provided by the thing which consists of an energy ray curable resin composition. That is, since the protective printing layer 2 made of the active energy ray-curable resin composition is in a tack-free state without performing special drying, another layer may be overprinted on the protective printing layer 2,
The transfer material can be wound up. Moreover, there is no need to perform printing and drying only on the protective printing layer with a special device. By performing printing and drying in the same manner as other printing layers in an in-line printing process such as an off-the-shelf multi-color gravure rotary printing press, the durability is improved. It is possible to manufacture a transfer material and a surface protection sheet excellent in abrasion and chemical resistance.

The active energy ray-curable resin composition used for the protective print layer 2 of the present invention contains an ethylenically unsaturated group. When the active energy ray-curable resin composition is exposed to active energy rays after the completion of the transfer, the ethylenically unsaturated groups are polymerized and the resin is crosslinked.

The active energy ray-curable resin composition used for the protective print layer 2 contains, as necessary, the following components in addition to a reaction product obtained by polyaddition reaction between a polymer and a polyfunctional isocyanate. be able to. For example, a reactive diluent monomer, a solvent, a colorant, and the like. When an electron beam is used for irradiation with active energy rays, crosslinking and curing can be sufficiently performed without using a photopolymerization initiator, but when ultraviolet rays are used, various known photopolymerization initiators are added. There is a need to.

The active energy ray-curable resin composition used for the protective print layer 2 may contain a lubricant, if necessary. Since the surface of the protective printing layer 2 is roughened,
This is because the sheet becomes easy to wind and blocking hardly occurs. In addition, resistance to rubbing and scratching can be increased. As the lubricant, for example, waxes such as polyethylene wax, paraffin wax, synthetic wax and montan wax, and synthetic resins such as silicone and fluorine can be used. The lubricant is contained in an amount of 0.5 to 15% by weight, preferably 1 to 6% by weight. The amount of lubricant is 0.
When the amount is less than 5% by weight, the effect of preventing blocking and frictional scratch resistance is reduced. When the amount is more than 15% by weight, the transparency of the protective printing layer 2 is extremely deteriorated.

The active energy ray-curable resin composition used for the protective print layer 2 may contain an ultraviolet absorber for the purpose of improving light resistance. Various UV absorbers can be used.

[0041]

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Hydroxyphenylbenzotriazole represented by the formula:

[0043]

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Hydroxyphenyl-S-triazine represented by the formula:

[0045]

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A compound represented by the formula (MBEP):

[0047]

Embedded image

It is preferable to use 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole or the like. When these compounds are used as an ultraviolet absorber, the protective printing layer 2 is superior in the ultraviolet absorption effect (light resistance) as compared with the case where another ultraviolet absorber is contained. In addition, since the ultraviolet absorber represented by the above formula has excellent compatibility with the active energy ray-curable resin composition, it can be contained in a large amount while maintaining the abrasion resistance and transparency of the protective printing layer 2. .

The pattern printing layer 3 is for decorating the surface of the molded article 7. Examples of the material of the picture printing layer 3 include resins such as polyvinyl resin, polyamide resin, polyester resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, and alkyd resin. Is used as a binder, and a colored ink containing an appropriate color pigment or dye as a colorant may be used.

The adhesive print layer 4 is for bonding the above-mentioned layers to the surface of the molded article 7. As the adhesive print layer 4, a heat-sensitive or pressure-sensitive resin suitable for the material of the molded article 7 is appropriately used. For example, when the material of the molded article 7 is a polyacrylic resin, a polyacrylic resin may be used. When the material of the molded article 7 is a polyphenylene oxide / polystyrene resin, a polycarbonate resin, a styrene copolymer resin, or a polystyrene blend resin, a polyacryl resin, a polystyrene resin having an affinity for these resins. , A polyamide resin or the like may be used. Further, when the material of the molded article 7 is a polypropylene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone indene resin can be used.

The configuration of the transfer layer 5 is not limited to the above-described embodiment. For example, a transfer material 6 for the purpose of only a surface protection treatment is used by utilizing the ground pattern and transparency of the molded product 7. In this case, the protective print layer 2 and the adhesive print layer 4 are sequentially formed on the base sheet 1 as described above, and the pattern print layer 3 can be omitted from the transfer layer 5 (see FIG. 2).

An anchor layer may be provided between each layer of the transfer layer 5. The anchor layer is a resin layer for increasing the adhesion between the layers of the transfer layer 5 and for protecting the molded product 7 and the pattern printing layer 3 from chemicals, and is, for example, a two-component curable urethane resin, a melamine-based resin. Thermosetting resins such as epoxy resins and thermoplastic resins such as vinyl chloride copolymer resins can be used.

Hereinafter, using the transfer material 6 having the above-described layer structure,
A method for producing a molded article having excellent wear resistance and chemical resistance according to the present invention will be described.

First, the transfer material 6 is placed on the molded product 7 with the adhesive print layer 4 side down (see FIG. 3). A roll transfer machine equipped with a heat-resistant rubber-like elastic body 8, for example, silicone rubber,
Using a transfer machine such as an up-down transfer machine, temperature of 80 to 260
Heat and / or pressure is applied from the side of the base sheet 1 of the transfer material 6 through the heat-resistant rubber-like elastic body 8 set at about 50 ° C. and a pressure of about 50 to 200 kg / m ² . By doing this,
The adhesive print layer 4 adheres to the surface of the molded article 7. Next, when the base sheet 1 is peeled off after cooling, peeling occurs at the interface between the base sheet 1 and the protective print layer 2. When a release layer is provided on the base sheet 1, when the base sheet 1 is peeled off,
Peeling occurs at the interface between the release layer and the protective printing layer 2. Finally, the molded article 7 is irradiated with active energy rays.
Is cross-linked and cured. The step of irradiating with the active energy ray may be performed before the step of peeling the base sheet 1.

Examples of the active energy rays include electron beams, ultraviolet rays, and γ rays. Irradiation conditions are determined according to the active energy ray-curable resin composition.

The material of the molded article 7 is not limited, but may be a resin molded article, a woodwork product or a composite product thereof. Examples of the resin include general-purpose resins such as a polystyrene resin, a polyolefin resin, an ABS resin, an AS resin, and an AN resin. In addition, polyphenylene oxide polystyrene resin, polycarbonate resin, polyacetal resin, acrylic resin, polycarbonate modified polyphenylene ether resin, polyethylene terephthalate resin,
General-purpose engineering resins such as polybutylene terephthalate resin and ultrahigh molecular weight polyethylene resin, polysulfone resin, polyphenylene sulfide resin, polyphenylene oxide resin, polyacrylate resin, polyetherimide resin, polyimide resin, liquid crystal polyester resin, polyallyl heat resistant resin, etc. Super engineering resin can also be used. Further, a composite resin to which a reinforcing material such as glass fiber or inorganic filler is added can be used.

Next, a method for imparting abrasion resistance and chemical resistance to the surface of the resin molded product 7 by using the above-described transfer material 6 and simultaneous injection molding by injection molding will be described (see FIG. 4). . First, the transfer material 6 is fed into the molding die including the movable die 9 and the fixed die 10 with the transfer layer 5 inside, that is, the base sheet 1 is in contact with the fixed die 10. After the molding die is closed, the molten resin 11 is injected and filled into the die from a gate provided in the movable die 9, and the transfer material 6 is adhered to the surface of the molded product 7 at the same time as the molded product 7 is formed. After cooling the resin molded product 7, the molding die is opened and the resin molded product 7 is taken out. Finally, after peeling off the base sheet 1, the protective printing layer 2 is cross-linked and cured by irradiating active energy rays. After irradiating with active energy rays,
The base sheet 1 may be peeled off.

As another embodiment of the present invention, there is another method for producing a molded article having excellent wear resistance and chemical resistance using the surface protective sheet 12. In this method, a protective print layer 2 is provided on one side of a base sheet 1 having no release property, and another print layer such as a picture print layer 3 or an adhesive print layer 4 is provided on the other side. A surface protection sheet 12 having excellent chemical resistance is used (see FIG. 5). Surface protection sheet 12
Uses a material having no releasability as the base sheet 1,
It is made of the same material and operation as the transfer material 6 except that the pattern print layer 3 and the adhesive print layer 4 are not formed on the protective print layer 2. As the base sheet 1 having no releasability, a resin sheet of an acrylic resin, a polycarbonate resin, a vinyl chloride resin, a urethane resin, a polyester resin, or the like can be used. When the surface protection sheet 12 for the purpose of surface protection only is used by making use of the ground pattern and transparency of the molded article 7, the picture printing layer 3 can be omitted (see FIG. 6). When the base sheet 1 and the pattern printing layer 3 have sufficient adhesiveness to the molded article 7, the adhesive printing layer 4 may not be provided.

Next, a method for imparting abrasion resistance and chemical resistance to the surface of the molded article 7 using the surface protective sheet 12 having excellent abrasion resistance and chemical resistance will be described (FIG. 7).
reference). First, the surface protection sheet 12 is arranged on the surface of the molded article 7 with the adhesive print layer 4 side down. Next, heater 1
After the base sheet 1 is heated and softened by 3 or the like, vacuum suction 14 is performed from below. By doing so, the adhesive print layer 4 is adhered to the surface of the molded article 7. Finally, the protective print layer 2 is cross-linked and cured by irradiating with an active energy ray. The vacuum suction 14 may be applied from below, and the pressure may be applied from above. The pressure applied to the surface protection sheet 12 is as follows.
This is performed directly by a fluid or the like or via a flexible sheet.

In addition, as in the case of a transfer material, a method of performing painting simultaneously with molding by injection molding (insert molding method) using the above-described surface protective sheet 12 having excellent wear resistance and chemical resistance is used. Thus, wear resistance and chemical resistance can be imparted to the surface of the resin molded product 7 (see FIG. 8). First, the surface protection sheet 12 is fed into a molding die including the movable die 9 and the fixed die 10 such that the protective print layer 2 is in contact with the fixed die 10. After closing the mold,
The molten resin 11 is injected and filled into the mold from the gate provided on the movable mold 9 to form the molded product 7 and, at the same time, the surface protective sheet 12 is bonded to the surface. After cooling the resin molded product 7, the molding die is opened and the resin molded product 7 is taken out. Finally, the protective print layer 2 is cross-linked and cured by irradiating with an active energy ray.

[0061]

The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, parts and% are based on weight.

Example 1 A polyester resin film having a thickness of 38 μm was used as a base sheet, and a release layer comprising a melamine-based release agent was applied to one side of the base sheet. A protective print layer containing 5 parts of an initiator (trade name: Irgacure 184, manufactured by Ciba Geigy), a picture print layer using an acrylic ink, and an adhesive print layer made of an acrylic resin are sequentially formed by gravure printing. A transfer material was obtained.

The varnish A was obtained as follows. First, 250 parts of glycidyl methacrylate (hereinafter referred to as GMA), lauryl mercaptan were placed in a reactor equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen inlet pipe.
After charging 1.3 parts, butyl acetate 1000 parts and 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) 7.5 parts, the temperature in the system becomes about 90 ° C. in about 1 hour under a nitrogen stream. And kept for 1 hour. Next, 750 parts of GMA, 225 parts of methyl methacrylate (hereinafter referred to as MMA), 3.7 parts of lauryl mercaptan and AIBN
From a dropping funnel charged with a mixture of 22.5 parts, the mixture was dropped into the system in about 2 hours under a nitrogen stream, and kept at the same temperature for 3 hours, 10 parts of AIBN was charged and kept for 1 hour. . Thereafter, the temperature was raised to 120 ° C. and kept for 2 hours. 60 ℃
After cooling to room temperature, replace the nitrogen inlet tube with an air inlet tube, charge and mix 507 parts of acrylic acid (hereinafter referred to as AA), 2.0 parts of methoquinone and 5.4 parts of triphenylphosphine to 110 ° C under air bubbling. The temperature rose. After keeping the temperature at the same temperature for 8 hours, 1.4 parts of methoquinone was charged, cooled, and methyl ethyl ketone was added so that the nonvolatile content became 50%. The polymer contained in the obtained varnish had an acrylic equivalent of 214 g / eq, a hydroxyl value of 262, and a weight average molecular weight of 20.
000 (based on styrene conversion by GPC). Further, 15.1 parts of hydrogenated xylylene diisocyanate (Takenate 600, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.) and 15.1 parts of methyl ethyl ketone were charged into this system, and the mixture was kept at 80 ° C. for 2 hours to carry out a polyaddition reaction to obtain Varnish A. . The amount of urethane bonds in the reaction product was calculated to be 9677 g /
eq.

The transfer material was adhered to the surface of a molded article by insert molding using an insert molding method, and then irradiated with ultraviolet rays. The molding conditions were a resin temperature of 220 ° C., a mold temperature of 55 ° C., and a resin pressure of about 300 kg / cm ² . The molded product is made of polycarbonate resin, 95 mm long, 65 mm wide, 4.5 m rise
m, formed into a tray shape of R2.5mm at the corner. The irradiation conditions were 120 w / cm, one lamp, lamp height 10 cm, and irradiation time was 6 seconds.

Example 2 The procedure of Example 1 was repeated, except that varnish B was used instead of varnish A of Example 1. Varnish B was obtained by changing 15.1 parts of hydrogenated xylylene diisocyanate of Example 1 to 15.1 parts of 1,6 hexane diisocyanate trimer (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.).

Example 3 The same procedure as in Example 1 was repeated except that a methyl ethyl ketone solution of epoxymelamine resin containing silica particles and 5% of paratoluenesulfonic acid as an acid catalyst was added between the release layer and the protective printing layer. Except that the matte layer was formed in the same in-line printing step as the protective print layer, the same operation as in Example 1 was performed.

Comparative Example 1 Example 1 was repeated except that a varnish before the polyaddition reaction of the hydrogenated xylylene diisocyanate was used.
Was performed in the same manner as described above.

Comparative Example 2 In Example 1, hydrogenated xylylene diisocyanate 1
5.1 parts was changed to 30.1 parts. In this case, the amount of urethane bonds in the reaction product is calculated to be 4902 g / eq.

Performance Evaluation The in-line suitability, chemical resistance, abrasion resistance, and the presence or absence of cracks of each of Examples 1 and 2 and Comparative Example using the above-described transfer material were evaluated.

The in-line suitability was evaluated as good or bad depending on whether the next layer was dry to the touch before printing, whether the next layer did not trap back, and the like.

The chemical resistance was evaluated by impregnating the gauze with methanol and rubbing 50 times back and forth and observing the surface condition.

The abrasion resistance was determined by applying a load (100 g, 300 g) to a 1 cm square # 000 steel wool and moving it at a distance of 2 c.
m, the number of reciprocations / second, the degree of damage to the surface after 200 reciprocations was observed, and evaluated by visual judgment, either good or bad.

The presence or absence of cracks was evaluated by observing the state of the curved surface of the molded product and visually determining whether any of ○ was not generated and X was generated.

[0074]

[Table 1]

From the evaluation results in Table 1, the following is clear. (Meth) acrylic equivalent 100-300g / e in outermost layer
q, a polymer having a hydroxyl value of 20 to 500 and a weight average molecular weight of 5,000 to 50,000 and a polyfunctional isocyanate previously subjected to a polyaddition reaction before printing the protective printing layer, and the urethane bond amount is 6,000 to 50,000 g / eq. Examples 1 and 2 having a protective printing layer made of an active energy ray-curable resin composition containing a reaction product as an active ingredient have excellent abrasion resistance and chemical resistance, and cracks occur on the curved surface of a molded product. In addition, it was excellent in in-line suitability.

On the other hand, in Comparative Example 1, the polymer and the polyfunctional isocyanate were not subjected to a polyaddition reaction before printing of the protective printing layer, even though they were excellent in abrasion resistance, chemical resistance, and cracks. He was inadequate.

In Comparative Example 2, the urethane bond amount in the polyaddition reaction between the polymer and the polyfunctional isocyanate was 6000.
Since the amount was less than g / eq, a gel-like substance was formed, and a uniform varnish was not obtained, so that evaluation could not be performed.

[0078]

According to the method of the present invention for producing a molded article excellent in abrasion resistance and chemical resistance, the transfer material to be used and the protective printing layer of the surface protective sheet are made of an active energy ray-curable resin composition. Since the protective print layer formed on the surface of the product is cross-linked and cured by irradiation with active energy rays, it is possible to obtain a molded product excellent in abrasion resistance and chemical resistance, and at the time of bonding a sheet material to the molded product. There is no crack in the protective printing layer located on the curved surface of the molded product.

The active energy ray-curable resin composition has a (meth) acrylic equivalent of 100 to 300 g / eq and a hydroxyl value of 20.
~ 500, a polymer having a weight average molecular weight of 5,000 to 50,000 and a polyfunctional isocyanate which has been subjected to a polyaddition reaction before printing of the protective printing layer and has a urethane bond amount of 6,000 to
Since the reaction product of 50,000 g / eq is contained as an active ingredient, fluidity and tackiness do not remain in the protective printing layer before irradiation with active energy rays. Moreover, no special drying is required for the protective printing layer. Therefore, even in an in-line printing process using a ready-made multicolor gravure rotary printing press or the like, a transfer material or a surface protection sheet having excellent wear resistance and chemical resistance can be manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing one embodiment of a transfer material according to the present invention.

FIG. 2 is a schematic sectional view showing another embodiment of the transfer material according to the present invention.

FIG. 3 is a schematic view showing one embodiment of a manufacturing process of a molded article having excellent wear resistance and chemical resistance using the transfer material according to the present invention.

FIG. 4 is a schematic view showing another embodiment of a process for producing a molded article having excellent wear resistance and chemical resistance using the transfer material according to the present invention.

FIG. 5 is a schematic sectional view showing one embodiment of the surface protection sheet according to the present invention.

FIG. 6 is a schematic sectional view showing another embodiment of the surface protection sheet according to the present invention.

FIG. 7 is a schematic view showing one embodiment of a manufacturing process of a molded article having excellent wear resistance and chemical resistance using the surface protective sheet according to the present invention.

FIG. 8 is a schematic view showing another embodiment of a process for producing a molded article having excellent wear resistance and chemical resistance using the surface protective sheet according to the present invention.

FIG. 9 is a schematic diagram showing a general multicolor gravure rotary printing press.

FIG. 10 is a schematic view showing a conventional printing system for forming a protective printing layer made of an active energy ray-curable resin composition so that fluidity and tackiness do not remain.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base sheet 2 Protective printing layer 3 Picture printing layer 4 Adhesive printing layer 5 Transfer layer 6 Transfer material 7 Molded product 8 Heat resistant rubber-like elastic body 9 Movable mold 10 Fixed mold 11 Molten resin 12 Surface protection sheet 13 Heater 14 Vacuum suction 15 winding Roll-out section 16 Multicolor rotogravure printing section 17 Rewind section 18 Plate cylinder 19 Ink pan 20 Impression cylinder 21 Guide roll 22 Drying section 23 Gravure rotoprinting section for protective printing layer 24 Drying section for protective printing layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FIB29L 9:00

Claims (11)

(57) [Claims] 1. A (meth) acrylic equivalent of 100 to 300 g / eq, a hydroxyl value of 20 to 20 on a release surface of a substrate sheet having release properties.
An active energy ray-curable composition containing a reaction product of a polymer having a weight average molecular weight of 5,000 to 50,000 and a polyfunctional isocyanate subjected to a polyaddition reaction and having a urethane bond amount of 6,000 to 50,000 g / eq as an active ingredient. A transfer material excellent in abrasion resistance and chemical resistance, wherein a protective print layer made of a resin composition is provided, and another print layer is provided on the protective print layer. 2. The abrasion resistance according to claim 1, wherein the polymer is a reaction product of an addition reaction of a glycidyl (meth) acrylate polymer and an α, β-unsaturated monocarboxylic acid.
Transfer material with excellent chemical resistance. 3. The glycidyl (meth) acrylate polymer is a glycidyl (meth) acrylate homopolymer,
3. The transfer material according to claim 2, which is a copolymer comprising glycidyl (meth) acrylate and an α, β-unsaturated monomer containing no carboxyl group. 4. The base sheet having releasability has a partial matting layer containing an epoxy resin, a melamine resin or a copolymer resin or a mixture thereof as a main component and containing an acid catalyst. 3. The transfer material according to any one of 3), which is excellent in abrasion resistance and chemical resistance. 5. A process for adhering the transfer material according to claim 1 to the surface of a molded article, followed by a step of peeling off a base sheet and a step of irradiating with an active energy ray. Manufacturing method for molded products with excellent chemical properties. 6. The transfer material according to claim 1 is sandwiched in a molding die, and a resin is injected and filled in the cavity to obtain a resin molded product and simultaneously adhere the transfer material to the surface thereof. A method for producing a molded article having excellent abrasion resistance and chemical resistance, which includes a step of peeling a base sheet and a step of irradiating with an active energy ray. 7. A (meth) acryl equivalent of 100 to 300 g / eq, a hydroxyl value of 20 to
An active energy ray-curable composition containing a reaction product of a polymer having a weight average molecular weight of 5,000 to 50,000 and a polyfunctional isocyanate subjected to a polyaddition reaction and having a urethane bond amount of 6,000 to 50,000 g / eq as an active ingredient. A surface protective sheet having excellent wear resistance and chemical resistance, wherein a protective print layer made of a resin composition is provided, and another print layer is provided on the opposite surface of the base sheet. 8. The abrasion resistance according to claim 7, wherein the polymer is a reaction product of an addition reaction of a glycidyl (meth) acrylate polymer and an α, β-unsaturated monocarboxylic acid.
Surface protection sheet with excellent chemical resistance. 9. The glycidyl (meth) acrylate polymer is a glycidyl (meth) acrylate homopolymer,
9. The surface protective sheet according to claim 8, which is a copolymer comprising glycidyl (meth) acrylate and an α, β-unsaturated monomer containing no carboxyl group. 10. The surface protective sheet according to claim 7, which is disposed on a surface of the molded article, and the base sheet is heated and softened.
A method for producing a molded article having excellent wear resistance and chemical resistance, which comprises a step of irradiating active energy rays after adhering a surface protective sheet to the surface of the molded article by vacuum suction from below. 11. A surface protection sheet according to claim 7 is sandwiched in a molding die, a resin is injected and filled in a cavity, and a resin molded product is obtained, and at the same time, the surface protection sheet is bonded to the surface. And then irradiating with active energy rays. A method for producing a molded article having excellent wear resistance and chemical resistance.