JP3289201B2 - Transfer foil for vinyl chloride resin base material - 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 foil for a vinyl chloride resin base material for coating the surface of a vinyl chloride resin base material. The present invention relates to a transfer foil capable of providing a cosmetic material suitable for applications requiring weather resistance, abrasion resistance, and hot water resistance, such as applications and water applications.

[0002]

2. Description of the Related Art Conventionally, in exterior or interior materials using a molded article of a vinyl chloride resin, since the molded article of the resin is poor in design, the surface of the molded article is patterned by various methods. The interior and exterior materials have a design feeling. For example, in the case of an extruded body of a vinyl chloride resin, there is a method in which a picture is directly formed on the surface by gravure offset printing or another printing method, and a transparent clear protective layer is further formed thereon to finish. Alternatively, there has been a method of forming a resin molded article formed by using a resin raw material in which a colored pigment, a pearl pigment, and the like are mixed in the resin itself forming the resin molded article, and then using the resin molded article as a final interior / exterior material. Further, a method of indirectly forming a pattern on the surface of a resin molded body, that is, a method of forming a pattern using a transfer foil has also been attempted.

[0003]

However, in the production of a decorative interior / exterior material made of a conventional vinyl chloride-based resin molded product, the above-described pattern is directly printed on the surface of the resin molded product by gravure printing, offset printing, or the like. In the case of a method of forming by another printing method, the surface of the resin molded body to be a printing surface has poor smoothness, or it is usually rare that the surface is a plane, and the resin molding formed by a combination of these planes is used. For the body, it was necessary to repeat printing for each plane. For this reason, when printing a picture for each of a plurality of surfaces, it is difficult to register the picture, and in multicolor printing, the picture becomes unclear, and it is difficult to provide an exterior material having an excellent design feeling. . In addition, since a drying step is required for each printing of one color, production efficiency is extremely low in the case of multicolor printing. In addition, in order to protect the pattern formed by printing, a post-process for separately forming a transparent clear protective layer after printing was necessary, and the cost was high for the design feeling obtained. .

[0004] In addition, as a resin raw material for forming a resin molded body,
When manufacturing interior and exterior materials using a mixture of color pigments and pearl pigments, it is essentially impossible to express the design of the pattern, and a step of mixing the pigment with the raw material resin is required On the other hand, only interior and exterior materials having a very monotonous design feeling were obtained.

[0005] Further, although attempts have been made to make the surface of the molded article indirectly on the resin molded article, that is, by a transfer method, it has been attempted to apply this method to a substrate having an uneven surface such as an extruded molded article. It is difficult to transfer evenly, and it is not used for cosmetics for indoor use, and it is used for exterior applications exposed to severe conditions such as rain breeze and direct sunlight, or for interior applications used around water such as bathrooms and kitchens However, a practical transfer foil having basic transfer performance and sufficiently satisfactory characteristics in terms of weather resistance, abrasion resistance, hot water and the like has not been obtained.

In particular, for exterior use and bathroom use, it is required that no discoloration or delamination occur even when a test of immersion in boiling water and heating is performed. Currently, the industry's most stringent standard is to withstand boiling for up to 10 hours. For exterior use, weather resistance is required to be free from discoloration and exfoliation of the transfer layer even when irradiated with a carbon arc lamp sunshine weatherometer (a weather resistance acceleration tester) for at least 1000 hours. You. Therefore, an object of the present invention is to provide a transfer foil for a vinyl chloride-based resin base material having excellent weather resistance, abrasion resistance, and hot water resistance, particularly in a transfer foil for a vinyl chloride-based resin base material.

[0007]

In the present invention, in order to solve the above-mentioned problems, in order to solve the above-mentioned problems, a hard coat layer made of an ionizing radiation-curable resin and having an abrasion resistance is provided on one surface of a transfer foil substrate. A decorative layer composed of a printed layer mainly composed of a base resin as a vehicle, and a secondary transition temperature (Tg) of 100 to 11
0 ° C (excluding 100 ° C) and average molecular weight of 6
A transfer foil for a vinyl chloride-based resin base material, characterized in that an adhesive layer made of a vinyl chloride-vinyl acetate copolymer resin of 0000 to 80000 is sequentially laminated.

Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a longitudinal sectional view of a transfer foil for a vinyl chloride-based resin substrate showing one embodiment according to the present invention. The transfer foil 1 for a vinyl chloride resin base material according to the present invention has a configuration in which a release layer 3, a primer layer 7, a decorative layer 4, and an adhesive layer 5 are sequentially provided on one surface of a base material 2 for a transfer foil. At the time of transfer, a layer that is peeled off at the interface between the transfer foil base material 2 and the release layer 3 and is transferred to the transfer-receiving substrate side, that is, the transfer layer 6 is, in the state after the transfer, the release layer 3, The primer layer 7, the decoration layer 4, and the adhesive layer 5 are formed.

As the transfer foil substrate 2, one having good releasability from the release layer 3 is used. For example, polyester films such as polyethylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polybutylene terephthalate, and polyolefin films such as polypropylene. And the like, and a biaxially stretched polyethylene terephthalate film having a thickness of 10 to 100 μm is particularly preferable. Although not shown, a release layer may be provided on the surface of the transfer foil substrate 2 on which the release layer 3 is formed, in order to control the releasability from the release layer 3. The release layer forms a coating film of a paint obtained by adding a release agent such as a fluororesin, various waxes, and silicone to a known vehicle, for example, an acrylic resin, a cellulose resin, a vinyl resin, or the like. A moldable resin such as a fluororesin, a silicone, a melamine-based resin, a polyolefin-based resin, an ionizing radiation-curable acrylic resin, or the like, or a film formed by extrusion coating may be used.

The release layer 3 is the outermost layer of the transfer layer 6 after the decorative layer is transferred from the transfer foil to the transfer-receiving substrate, and is decorated via the primer layer 7 (sometimes omitted). It serves as an upper layer of the layer 4 to protect the decorative layer 4 and is a particularly important component when realizing excellent abrasion resistance, which is one of the objects of the present application. As the release layer 3 having a remarkable effect on excellent wear resistance, an ionizing radiation-curable resin is preferable. Such ionizing radiation-curable resins include:
For example, a composition in which a prepolymer, an oligomer, and / or a monomer having a plurality of polymerizable unsaturated bonds such as acryloyl groups and methacryloyl groups or an epoxy group in a molecule as appropriate may be used.

The prepolymer and oligomer include:
For example, unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, epoxy resins, polyester methacrylate, polyether methacrylate, polyol methacrylate, methacrylates such as melamine methacrylate, polyester acrylate, epoxy acrylate, urethane acrylate, poly Examples include acrylates such as ether acrylate, polyol acrylate, and melamine acrylate.

Examples of the monomer include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, acrylic Acrylates such as butyl acrylate, methoxy butyl acrylate and phenyl acrylate, methacryl such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate Acid esters, acrylic acid-2- (N, N-
Diethylamino) ethyl, methacrylic acid-2- (N, N
-Dimethylamino) ethyl, acrylic acid-2- (N, N
-Dibenzylamino) ethyl, methacrylic acid-2-
(N, N-dimethylamino) methyl, acrylic acid-2-
Substituted amino alcohol esters of unsaturated acids such as (N, N-diethylamino) propyl, unsaturated carboxylic amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol dimethacrylate, neopentyl glycol diacrylate;
Polyfunctional compounds such as 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, or 2 Polythiol compound having at least two thiol groups, for example, trimethylolpropane trithioglycolate,
Trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and the like.

Here, the term "ionizing radiation" means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, and usually ultraviolet rays and electron beams are used. When ultraviolet rays are used, a photopolymerization initiator, a sensitizer, and the like are further added to the resin compositions listed above, but in order to provide weather resistance as a physical property of the transfer foil of the present invention. Are not preferable for photopolymerization initiators and sensitizers. The reason for this is that the release layer containing these deteriorates, such as yellowing, when they react with light and are exposed to sunlight for a long time. Therefore, the above-mentioned ionizing radiation-curable resin is cured without adding a photopolymerization initiator or a sensitizer,
It is preferable to cure with an electron beam. By the electron beam curing, a transfer foil having excellent weather resistance can be obtained.

The object of the present invention is to form a release layer having physical properties such as weather resistance and surface hardness, and also having flexibility for realizing transferability to a corner or a curved surface of a substrate to be transferred. In the above, among the compounds which become the ionizing radiation-curable resin, acrylate-based or methacrylate-based prepolymers, oligomers, and / or monomers having an acryloyl group or a methacryloyl group in the molecule are used. Is preferred.

In order to form a release layer, a resin composition in which one or more of the above compounds are used as required is used. However, in order to impart ordinary coating suitability to the resin composition,
In order to prevent cracks and exfoliation due to repeated expansion and contraction due to changes in temperature during outdoor exposure, the prepolymer or oligomer weight / monomer weight = 10/90 to 90
/ 10, more preferably 40/60 to 60/40. In this case, the viscosity and fluidity of the uncured resin composition are suitable for gravure coating, roll coating, and the like. Further, since the crosslinking density and the crosslinking unit (the molecular length between the crosslinking points) are appropriate, flexibility and flexibility are generated in the cured crosslinked product, and the repeated stress is reduced.

In selecting a monomer, in order to impart flexibility, the amount of the monomer may be reduced, or may be monofunctional or bifunctional.
The structure is adjusted to a relatively low crosslink density by using a functional acrylate or methacrylate monomer. On the other hand, in order to achieve the surface hardness of the release layer, the amount of the monomer is increased as long as the coating suitability is not hindered, or the crosslink density is adjusted to a higher level by using an acrylate monomer having three or more functional groups. I do. By mixing these monofunctional and difunctional monomers and trifunctional or higher functional monomers, the coating aptitude and the surface hardness and flexibility of the release layer can be adjusted. In order to balance surface hardness and flexibility, to prevent cracking and exfoliation due to repeated stress of temperature change, and to have sufficient scratch resistance, monofunctional or monofunctional as a monomer, prepolymer or oligomer Weight of bifunctional ones / weight of trifunctional or more = 10 / 90-30 / 70
It is preferred that

Examples of the above-mentioned monofunctional acrylate or methacrylate-based monomer include 2-hydroxy (meth) acrylate ((meth) acrylate means methacrylate or acrylate; the same applies hereinafter); 2-hexyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like can be mentioned. Also, 2
Examples of the functional (meth) acrylate-based monomer include ethylene glycol di (meth) acrylate,
6-hexanediol di (meth) acrylate, propylene glycol di (meth) acrylate and the like can be mentioned. Examples of the trifunctional or higher functional (meth) acrylate-based monomer include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The primer layer 7 is interposed between the release layer 3 and the decoration layer 4 and realizes adhesion between the release layer 3 and the decoration layer 4. If the peeling layer 3 and the decorative layer 4 have sufficient adhesion, this can be omitted. As the primer layer 7, methyl (meth) acrylate, ethyl (meth)
Acrylic resins composed of homo- or copolymers of alkyl (meth) acrylates such as acrylate and butyl (meth) acrylate; polyisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate; and ethylene glycol;
For example, a polyurethane resin comprising a polyol such as an acrylic polyol, a vinyl chloride / vinyl acetate copolymer, a polyester resin, or the like is used.

The decorative layer 4 is a printed layer mainly composed of a vehicle made of an acrylic resin exhibiting excellent characteristics in weather resistance. The coloring agent in the printing ink used for forming the decorative layer 4 may be a coloring agent used in a usual gravure ink, but, for example, bengara, titanium dioxide, vermilion, ultramarine, patina (basic copper carbonate) In addition, inorganic pigments such as carbon black, and organic pigments such as azo pigments, phthalocyanine pigments, and condensed polycyclic pigments such as quinacridone-based pigments and isoindolinone-based pigments exhibit excellent characteristics in terms of weather resistance. The main components of the vehicle include alkyl (meth) acrylates such as polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyethylhexyl (meth) acrylate, and polybutyl (meth) acrylate; alkyl (meth) acrylate and styrene. And an acrylic resin such as a copolymer with vinyl acetate. To this, another resin such as polyvinyl acetate is mixed if necessary. Acrylic resin is most suitable for the decorative layer 4 having a remarkable effect on excellent weather resistance. However, if the acrylic resin alone is used, the coating film is too hard, and the temperature changes during or after transfer and deformation processing. There is a disadvantage that a crack is formed due to external force at the time. In order to improve this, a vinyl chloride / vinyl acetate copolymer resin is mixed with an acrylic resin. The mixing ratio is in the range of acrylic resin / vinyl chloride / vinyl acetate copolymer resin = 9/1 to 7/3, and particularly preferably about 8/2. When the amount of the acrylic resin is small, the weather resistance is reduced, and yellowing or the like is easily caused by exposure to sunlight. Examples of the pattern to be printed include a natural product pattern such as a wood grain pattern and a marble pattern, a solid surface, a geometric pattern, characters, and symbols.

The adhesive layer 5 is made of a vinyl chloride / vinyl acetate copolymer resin in terms of heat resistance and water resistance. Particularly, the secondary transition temperature (Tg) of vinyl chloride / vinyl acetate copolymer resin is excellent in that it exhibits excellent hot water resistance and wet heat resistance.
Is 100-110 ° C, and the average molecular weight is 60,000-
Preferably, the resin is in the range of 80,000. T
g is less than 100 ° C. or the average molecular weight is 6
If it is less than 0000, the transfer layer has hot water resistance and
The wet heat properties tend to be insufficient, and conversely, Tg is 110
When the temperature exceeds ℃ or the average molecular weight exceeds 80,000, the initial adhesion to the substrate to be transferred may not be sufficiently obtained. Ri by the use of such a specific vinyl acetate copolymer resins chloride, even by boiling in hot water at 100 ° C. 10 hours, exfoliation of the transfer layer, blistering, no abnormality such as discoloration makeup Material. Further, by using such a resin, a transfer foil that can obtain uniform transfer even when the surface of the substrate to be transferred has poor smoothness is obtained. The thickness of the adhesive layer 5 is usually 1 to 50 μm (1 to
It is about 36 g / m ² ).

The vinyl chloride resin constituting the transfer substrate of the transfer foil for a vinyl chloride resin substrate according to the present invention includes:
Vinyl chloride resin which is a homopolymer of vinyl chloride, vinyl chloride, ethylene, propylene, acrylate,
A copolymer resin with another polymerizable vinyl monomer such as a methacrylic acid ester, a vinyl chloride resin such as a chlorinated vinyl chloride resin or a modified resin obtained by modifying the copolymer resin, or a vinyl chloride resin; And a blended resin obtained by blending another resin such as an acrylic resin, a chlorinated polyethylene, or an ethylene / vinyl acetate copolymer resin with the modified resin. The average degree of polymerization of these resins is selected to be approximately 700 to 2000. If necessary, a plasticizer, a heat stabilizer, a filler, a flame retardant, and the like are added to these vinyl chloride resins. Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate and dibutyl phthalate, phosphoric acid esters such as tricresyl phosphite, and compounds such as paraffin chloride, trimellitic acid, or epoxidized soybean oil. As for the surroundings, the addition amount is usually up to about 30 parts by weight. Examples of the heat stabilizer include carboxylate salts such as lead, tin, cadmium, barium, magnesium and calcium, metal soaps, chelators and the like. Further, as the substrate to be transferred, a molded or base material of various shapes such as a flat plate or a curved plate, a rod-shaped body, or molded by extrusion molding, injection molding, press molding or the like from the vinyl chloride resin. The present invention can be applied to a molded body or a base material whose body surface is made of a vinyl chloride resin.

FIG. 2 is a longitudinal sectional view showing another embodiment of the transfer foil for a vinyl chloride resin substrate according to the present invention. In FIG. 2, as the transfer foil substrate 2, for example, by using a substrate having an uneven pattern such as a matte surface or a hairline with a polyethylene terephthalate film or the like, the release layer 3 serving as a surface layer of the transfer layer 6 after transfer is used. The surface is made to have an uneven pattern such as a mat or a hairline. Although not specifically shown in FIG. 1, an example in which a solid layer is provided on the decorative layer 4 is clearly shown.

[0023]

According to the transfer foil for a vinyl chloride-based resin base material of the present invention, the release layer, which is the uppermost layer of the transfer layer after the transfer to the base material to be transferred, is made of an ionizing radiation curable resin. The transfer layer exhibits excellent physical properties especially in terms of weather resistance and abrasion resistance. In particular, by using an ionizing radiation-curable type which does not contain a photopolymerization initiator or a photosensitizer for the release layer, the weather resistance is particularly good. Further, in the vinyl chloride / vinyl acetate copolymer resin used for the adhesive layer, the secondary transition temperature (T
g) is 100 to 110 ° C and the average molecular weight is 6000
As a result of using a specific resin of 0 to 80,000, the physical properties of the transfer layer are particularly excellent in hot water resistance and wet heat resistance.

Example 1 Hereinafter, a specific structure of a transfer foil for a vinyl chloride resin substrate according to the present invention will be described with reference to examples. As a transfer foil substrate, biaxially stretched polyethylene terephthalate film (manufactured by Toray Industries, Inc. x-4)
5 having a thickness of 25 μm), and on one surface thereof, an ionizing radiation-curable resin liquid (60% by weight of a trifunctional urethane acrylate prepolymer, 20% by weight of a monofunctional acrylate monomer, 20% by weight of a bifunctional acrylate monomer) % Of trifunctional acrylate) by a gravure coater to form a release layer having a dry weight of 5 g / m ² .

Next, as a primer layer, a two-part curable polyurethane resin using isocyanate as a crosslinking agent was applied by a gravure coater at a dry weight of 3 g / m ² .

Next, the decorative layer is a picture printing layer made of a gravure ink using a mixture of acrylic resin / vinyl chloride / vinyl acetate copolymer resin = 8/2 (weight ratio) as a vehicle. Gravure ink (X ink manufactured by Showa Ink Industries Co., Ltd.).

Thereafter, an adhesive layer having a vinyl chloride / vinyl acetate copolymer resin (Tg = 105 ° C., average molecular weight: 80,000) was coated with a mechanically engraved gravure solid plate (Hell's heliocrisograph; cm, an angle setting of 0 °) to provide an adhesive layer having a dry weight of 6 g / m ^{2. Thus} , the transfer foil for a vinyl chloride resin substrate according to the present invention was prepared.

Next, the above-mentioned transfer foil for a vinyl chloride resin base material is brought into contact with the surface of an exterior material base material formed of an extruded body of a hard vinyl chloride resin as a base material to be transferred, and heated and pressurized. The transfer layer of the transfer foil for the base resin base material was transferred to the surface of the base material to be transferred to obtain an exterior decorative material. When the abrasion resistance of the obtained exterior decorative material was tested up to a Taber abrasion test CS-17, a wear wheel load of 500 g, and 200 rotations, the decorative layer exhibited sufficient performance without removing the pattern. The surface hardness is so hard that it is not damaged even if it is rubbed five times with steel wool # 0000, and the hot water resistance is 100 ° C.
After boiling in hot water for 10 hours, no abnormalities such as peeling, blistering and discoloration were observed in the transfer layer, and a cellophane tape adhesion test (Nichiban Industrial Cellophane tape 25 mm width was adhered to the transfer layer. ), And the release layer adhered to the cellophane tape and did not peel off, exhibiting sufficient hot water resistance.

Comparative Example 1 A transfer foil was prepared in the same manner as in Example except that the vinyl chloride / vinyl acetate copolymer used as the adhesive layer was changed to Tg = 60 ° C. and average molecular weight 24,800. As a result, immediately after the transfer, even in the cellophane tape adhesion test before hot water immersion,
There was no peeling and it was good. However, when the transfer layer was immersed in boiling water for 10 hours, blistering and peeling occurred in the transfer layer.

Comparative Example 2 A transfer foil was prepared in the same manner as in Example except that the vinyl chloride / vinyl acetate copolymer used as the adhesive layer was changed to Tg = 115 ° C. and the average molecular weight was 95,000. As a result, immediately after the transfer, in a cellophane tape adhesion test before immersion in hot water, the transfer layer adhered to the cellophane tape and peeled off.

[0031]

Since the present invention is configured as described above, it has the following effects. The transfer foil for a vinyl chloride-based resin base material of the present invention can make up the surface of the vinyl chloride-based resin base material by a normal transfer foil transfer step, and the obtained decorative material has Even in the case of an extruded molded article of vinyl chloride resin with poor smoothness, a clear pattern can be accurately expressed, and since the ionizing radiation curable resin is used for the release layer, sufficient performance of abrasion resistance, Surface hardness is obtained. In addition, since the photopolymerization initiator and the like are formed of a release layer made of a resin that is cured by an electron beam having no remaining amount and a decorative layer made of an acrylic resin, they have a remarkable effect of being excellent in weather resistance.

In addition, by using a vinyl chloride / vinyl acetate copolymer resin which forms an adhesive layer and having a specified secondary transition point (Tg) and average molecular weight, the transfer layer can be transferred to a vinyl chloride resin base material. The heat-resistant water and moisture-heat resistance of the cosmetic material transferred and adhered is good, and it is required for vinyl chloride resin members for interior and exterior use for water use, even after boiling for 10 hours in hot water at 100 ° C. It has a remarkable effect of sufficiently satisfying "heat-resistant water and hot-water resistance that does not cause abnormalities such as exfoliation, blistering, and discoloration of the layer".

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing one embodiment of a transfer foil for a vinyl chloride resin base material of the present invention.

FIG. 2 is a longitudinal sectional view showing another embodiment of the transfer foil for a vinyl chloride resin base material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transfer foil for vinyl chloride resin base materials 2 Transfer foil base material 3 Release layer 4 Decorative layer 4a Picture 4b Solid 5 Adhesive layer 6 Transfer layer 7 Primer layer

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 B44C 1/16-1/175 B41M 3/00-3/18

Claims (1)

(57) [Claims] 1. A transfer layer comprising a hard coat layer composed of an ionizing radiation curable resin, a decorative layer composed of a print layer mainly composed of an acrylic resin as a vehicle, and a second transition temperature (Tg). ) Is 100-110 ° C (However, 100 ° C is
) , And an adhesive layer made of a vinyl chloride / vinyl acetate copolymer resin having an average molecular weight of 60,000 to 80,000 is sequentially laminated.