JP2016107410A - Decorative adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative adhesive sheet capable of securing excellent adhesive strength with a body to be decorated even if the body to be decorated is composed of a polyolefin-based resin, especially capable of maintaining the adhesive strength even when various detergents are used for the resulting decorative molding.SOLUTION: There is provided a decorative adhesive sheet obtained by laminating a hot-melt adhesive layer via a primer layer on one surface of a substrate layer, wherein the hot-melt adhesive layer is composed of a thermoplastic resin composition comprising an olefin-based block polymer and an alicyclic saturated hydrocarbon resin and the primer layer is composed of a primer composition comprising an acrylic resin and an aziridine-based curing agent.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative adhesive sheet.

Plastic molded products are excellent in mechanical properties, heat resistance, chemical resistance, and water resistance, so they are widely used in household appliances, water-related products, building materials, industrial materials such as automobiles, etc. Yes. Resin such as vinyl chloride resin, nylon, PET, polycarbonate, ABS resin, polyolefin, etc. is used as the base resin for such plastic molded products, and the opportunity to use polyolefin is increased due to environmental considerations. It's getting on.
However, polyolefins such as polyethylene and polypropylene generally have a low polarity because they do not have a polar group in the molecule, and there is a problem that painting and adhesion are difficult among the above-described resins.

On the other hand, plastic molded products are often required to have various appearances such as wood grain, texture, and metallic tone in order to enhance their design properties. In order to give such appearance to plastic molded products. The pasting of the decorative sheet to the resin base material is performed.
However, as described above, polyolefin resin has poor adhesion, and when a decorative sheet is attached to a resin substrate made of polyolefin resin to form a plastic molded product, the adhesive force between the resin substrate and the decorative sheet May become insufficient.

  Therefore, as a decorative sheet excellent in adhesiveness to a polyolefin substrate, for example, Patent Document 1 includes a decorative film composed of a base film, a pattern layer, and an adhesive layer containing a modified polyolefin, There has been proposed a decorative sheet in which an adhesive layer is formed by applying an aqueous dispersion or non-aqueous dispersion of a modified polyolefin and drying it.

JP 2007-262337 A

However, even the decorative sheet described in Patent Document 1 does not have sufficient adhesion to a decorated main body made of a polyolefin-based resin, and in particular, a decorative molded product used around a water such as a kitchen, toilet or bath. When the above decorative sheet is used, the durability against the detergent is insufficient, and peeling or the like may occur between the decorated main body and the decorative sheet.
Moreover, the adhesiveness of the base film which comprises a decorating surface, and an adhesive agent is inadequate, and peeling may generate | occur | produce between both.
Therefore, there is a demand for a decorative adhesive sheet that is excellent in adhesiveness with a decorated main body to be decorated and can maintain the adhesiveness for a long period of time.

  The present inventors have intensively studied to solve the above problems, and if the specific hot melt adhesive layer is a decorative adhesive sheet laminated on the base material layer via the specific primer layer, the decoration As the target decorated main body is made of polyolefin resin, sufficient adhesion can be secured with the decorated main body, especially when various detergents are used. As a result, the present invention was completed.

The decorative adhesive sheet of the present invention is a decorative adhesive sheet in which a hot melt adhesive layer is laminated on one side of a base material layer via a primer layer,
The hot melt adhesive layer is composed of a thermoplastic resin composition containing an olefin block polymer and an alicyclic saturated hydrocarbon resin,
The primer layer is characterized by comprising a primer composition containing an acrylic resin and an aziridine-based curing agent.

In the decorative adhesive sheet of the present invention, the base material layer is preferably made of a vinyl chloride resin composition.
Moreover, the said adhesive sheet for decorating WHEREIN: The compounding quantity of the said alicyclic saturated hydrocarbon resin in the said thermoplastic resin composition is 15-50 weight part with respect to 100 weight part of the said olefin type block polymers. Is preferred.

  The decorative adhesive sheet of the present invention is preferably used for decorating a decorated main body made of a polyolefin-based resin.

  According to the decorative adhesive sheet of the present invention, it is possible to ensure an excellent adhesive force with the decorated main body, assuming that the decorated main body is made of a polyolefin resin. The adhesiveness can be maintained even when various detergents are used in the decorated molded article.

It is sectional drawing which shows typically an example of the adhesive sheet for decorating of this invention.

The decorative adhesive sheet of the present invention is a decorative adhesive sheet in which a hot melt adhesive layer is laminated on one side of a base material layer via a primer layer, and the hot melt adhesive layer is an olefin-based adhesive sheet. It consists of a thermoplastic resin composition containing a block polymer and an alicyclic saturated hydrocarbon resin, and the primer layer is made of a primer composition containing an acrylic resin and an aziridine curing agent.
Hereinafter, the decorative adhesive sheet of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view schematically showing an example of the decorative adhesive sheet of the present invention.

As shown in FIG. 1, the decorative adhesive sheet 10 according to the present invention is formed by laminating a hot melt adhesive layer 13 on one surface of a base material layer 11 with a primer layer 12 interposed therebetween.
The base material layer 11 is a layer that constitutes a decorative surface when the decorative adhesive sheet 10 is attached to a decorated main body (not shown).
Examples of the base material layer 11 include a resin film made of a resin composition such as a vinyl chloride resin composition, a polyolefin resin composition, an acrylic resin composition, an ABS resin composition, or a polycarbonate resin composition. .

Examples of the vinyl chloride resin composition include a composition containing a vinyl chloride resin and a plasticizer, and various additives as required.
Examples of the vinyl chloride resin include vinyl chloride homopolymers, copolymers of vinyl chloride and other monomers copolymerizable therewith.
Examples of other copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, olefins such as ethylene, propylene and styrene, methyl acrylate, ethyl acrylate and methyl methacrylate ( ) Acrylic acid esters, maleic acid diesters such as dibutyl maleate and diethyl maleate, fumaric acid diesters such as dibutyl fumarate and diethyl fumarate, vinyl cyanide such as acrylonitrile and methacrylonitrile, vinylidene chloride and vinyl bromide And vinyl ethers such as vinyl halide, methyl vinyl ether, and ethyl vinyl ether. These may be used alone or in combination of two or more.

The content of the other copolymerizable monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less.
Among the vinyl chloride resins, a vinyl chloride homopolymer is preferable from the viewpoint of excellent printability, visibility, and dimensional stability.

The average degree of polymerization of the vinyl chloride resin is not particularly limited, but is preferably 700 to 1400.
When the average degree of polymerization is less than 700, the surface of the molded product may become rough or the molded product may become brittle when the resin composition is melted and calendered. On the other hand, when it exceeds 1400, the heat resistance of the melted resin composition may be insufficient and may not be processed, or the heat resistance and weather resistance of the molded product may be deteriorated.
The average degree of polymerization of the vinyl chloride resin is measured according to JIS K-6721 “Testing method for vinyl chloride resin”.

  It does not specifically limit as said plasticizer, What is necessary is just what is conventionally used for the vinyl chloride-type resin composition, for example, octyl phthalate (di-2-ethylhexyl phthalate (DOP)), dibutyl phthalate, Phthalic acid diesters such as dinonyl phthalate, dibasic dibasic acid diesters such as dioctyl adipate, phosphate triesters such as tricresyl phosphate and trioctyl phosphate, epoxidized soybean oil and epoxy resin, etc. An epoxy plasticizer, a high molecular weight polyester plasticizer, etc. are mentioned. These may be used alone or in combination of two or more.

  Examples of the polymer polyester plasticizer include polyalkylene glycol diesters such as polyethylene glycol diester, polypropylene glycol diester, and polyethylene glycol polypropylene glycol diester of phthalic acid, and polyethylene glycols of aliphatic dibasic acids such as adipic acid and sebacic acid. Examples include polyalkylene glycol diesters such as diesters, polypropylene glycol diesters, and polyethylene glycol polypropylene glycol diesters. These may be used alone or in combination of two or more.

The content of the plasticizer is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
If the content of the plasticizer is less than 5 parts by weight, the flexibility is poor and the surface shape of the decorated main body may not follow when pasted on the decorated main body. On the other hand, 40 parts by weight Exceeding this may cause the plasticizer to bleed to the surface side and deteriorate the sharpness of the decorative surface, or to bleed to the primer layer side and reduce the adhesive strength of the primer layer or adhesive layer.
The content of the plasticizer is more preferably 15 to 30 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

As said polyolefin resin composition, the composition etc. which contain polyolefin resin and various additives as needed are mentioned, for example.
It does not specifically limit as said polyolefin resin, A conventionally well-known polyolefin resin can be used. Specific examples thereof include a polypropylene resin, a polyethylene resin, and an olefin thermoplastic elastomer. These may be used alone or in combination of two or more.

The polypropylene resin is not particularly limited, and examples thereof include homopolymerized polypropylene (h-PP), random copolymerized polypropylene (r-PP), and block copolymerized polypropylene (b-PP).
The polypropylene resin may be a copolymer obtained from a monomer composition containing other monomers.
These may be used alone or in combination of two or more.

The polyethylene resin is not particularly limited, and examples thereof include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE).
The polyethylene resin may be a copolymer obtained from a monomer composition containing other monomers.
These may be used alone or in combination of two or more.

It does not specifically limit as said olefin type thermoplastic elastomer, For example, the copolymer etc. which have an ethylene-propylene copolymer component and / or a polybutylene component, and a polypropylene component are mentioned. Such a copolymer is composed of a crystalline polypropylene resin as a hard segment and an ethylene-propylene rubber component or a butyl rubber component as a soft segment. By adjusting the ratio of the hard segment and the soft segment, Various physical properties can be obtained.
The olefinic thermoplastic elastomer may be a copolymer obtained from a monomer composition containing other monomers.
These may be used alone or in combination of two or more.

As an acrylic resin composition, the composition etc. which contain an acrylic resin and various additives as needed are mentioned, for example.
It does not specifically limit as said acrylic resin, For example, the homopolymer of methyl methacrylate, the copolymer with the monomer copolymerizable with methyl methacrylate, etc. are mentioned.
These may be used alone or in combination of two or more.

Examples of the monomer copolymerizable with methyl methacrylate include methacrylic acid esters having 2 to 4 carbon atoms such as butyl methacrylate, acrylate esters having 1 to 8 carbon atoms such as butyl acrylate, styrene, α -Methylstyrene, acrylonitrile, acrylic acid, other ethylenically unsaturated monomers and the like.
The acrylic resin may be a homopolymer or a mixture of copolymers of these monomers.
Moreover, acrylic rubber may be mixed with the acrylic resin in the acrylic resin composition.

An appropriate amount of various additives may be added to these resin compositions as necessary.
Examples of the additive include a lubricant, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a colorant, a modifier, a flame retardant, an antistatic agent, a reinforcing agent, an antifogging agent, a filler, Examples include diluents and fungicides.

The substrate layer 11 is preferably made of a vinyl chloride tree composition.
This is because by providing the primer layer 12 described later, the adhesiveness with the adhesive layer 13 described later is remarkably improved.

  Although the thickness of the base material layer 11 is not specifically limited, Although it can select suitably according to the intended purpose etc. of the adhesive sheet for decorating, Usually, the thickness is in the range of 0.05-0.20 mm. Preferably there is. When the thickness is less than 0.05 mm, the degree of expansion and contraction of the base material layer is large, and the thickness difference between the formed base material layers may become significant. On the other hand, if it exceeds 0.20 mm, the followability to the surface shape of the body to be decorated is reduced, or the weight of the body is excessively large, the sheet hangs down during heating, wrinkles are entered, and the decoration position is There is a risk of slipping.

The primer layer 12 is made of a primer composition containing an acrylic resin and an aziridine curing agent.
In the present invention, by forming the primer layer 12, the adhesiveness between the base material layer 11 and the adhesive layer 13 can be improved, and the base material layer 11 is made of a vinyl chloride resin composition. In this case, the effect is particularly remarkable.

Examples of the acrylic resin include acrylic acid, methyl methacrylate, butyl methacrylate and the like. These may be used alone or in combination of two or more.
Among these, methyl methacrylate is preferable from the viewpoint of adhesive strength.
A commercial item can also be used as said acrylic resin.
As said commercial item, Arakawa Chemical Industries make and AB-2-10 etc. are mentioned, for example.

Examples of the aziridine-based curing agent include tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxyamide), N, N′-diphenylethane-4. , 4′-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinylpropionate, N, N′-toluene-2,4-bis (aziridinecarboxyamide), bisisophthaloyl Examples include -1- (2-methylaziridine) phosphine, trimethylolpropane-tri-β- (2-methylaziridine) propionate. These may be used alone or in combination of two or more.
A commercial item can also be used as said aziridine type | system | group hardening | curing agent.
As said commercial item, Arakawa Chemical Industry Co., Ltd. product, Alacoat CL910, etc. are mentioned, for example.

In the primer composition, the blending amount of the aziridine-based curing agent is preferably 30 to 50 parts by weight with respect to 100 parts by weight of the acrylic resin.
If the amount of the aziridine-based curing agent is less than 30 parts by weight, curing may be insufficient. On the other hand, if it exceeds 50 parts by weight, the ability of the primer may be impaired due to an excessive effect.

  Although the thickness of the primer layer 12 is not specifically limited, Usually, 0.001-0.05 mm is preferable. If it is less than 0.001 mm, the adhesion between the base material layer and the adhesive layer may not be sufficiently improved. On the other hand, if it exceeds 0.05 mm, the primer layer may follow the base material layer during use (when stretched or the like), and the primer layer may be easily broken.

The hot melt adhesive layer 13 is made of a thermoplastic resin composition containing an olefin block polymer and an alicyclic saturated hydrocarbon resin.
Since the decorative adhesive sheet of the present invention includes a hot melt adhesive layer made of the thermoplastic resin composition, the adhesive sheet is excellent in adhesiveness with the decorated main body, and the decorated main body is made of a polyolefin resin. Even if it becomes, sufficient adhesiveness can be ensured between the to-be-decorated main bodies.
The hot melt adhesive layer made of the thermoplastic resin composition is excellent in chemical resistance, and the decorative molded product decorated with the decorative adhesive sheet of the present invention is an acidic detergent, alkaline detergent, or neutral detergent. Even if it is used, peeling at the interface between the decorative adhesive sheet and the decorated main body is not particularly likely to occur.

As said olefin type block polymer, the block polymer etc. which consist of a polybutadiene unit and a styrene unit are mentioned, for example.
A block polymer composed of a polybutadiene unit and a styrene unit is excellent in adhesion to a decorated body made of polyolefin, particularly a decorated body made of polypropylene.
A commercial item can also be used as said olefin type block polymer.
As said commercial item, the Sotec company make, step 66 etc. are mentioned, for example.

The alicyclic saturated hydrocarbon resin is a component that functions as a tackifier.
Examples of the alicyclic saturated hydrocarbon resin include hydrogenated terpene resins using natural terpin oil as a raw material, olefin-based and diolefin-based aromatic unsaturated hydrocarbons generated during petroleum decomposition. Examples include hydrogenated petroleum resins. These may be used alone or in combination of two or more.
Among these, hydrogenated petroleum resins are preferable from the viewpoint of improving the adhesion between the adhesive layer and the primer layer.
A commercial item can also be used as said alicyclic saturated hydrocarbon resin.
Examples of the commercially available products include Archon P-90, Archon P-100, Archon P-115, Archon P-125, Archon P-140 (all manufactured by Arakawa Chemical Industries).

In the thermoplastic resin composition, the blending amount of the alicyclic saturated hydrocarbon resin is preferably 15 to 50 parts by weight with respect to 100 parts by weight of the olefin block polymer.
When the blending amount of the alicyclic saturated hydrocarbon resin is less than 15 parts by weight, the adhesive force between the adhesive and the primer layer may be insufficient. On the other hand, when it exceeds 50 parts by weight, the ratio of the olefin block polymer to the thermoplastic resin composition becomes low, and sufficient adhesiveness may not be exhibited.

  Although the thickness of the adhesive bond layer 13 is not specifically limited, Usually, 0.1-0.5 mm is preferable. If it is less than 0.1 mm, sufficient adhesive force may not be ensured with respect to the to-be-decorated main body. On the other hand, if the thickness exceeds 0.5 mm, the trace of the adhesive layer may be lifted on the surface of the base material when used after being stretched at a high temperature.

In the decorative adhesive sheet of the present invention, the front surface of the base material layer (the surface opposite to the side on which the primer layer is formed) is embossed or a printing layer is formed. It may be. A desired design can be provided to the adhesive sheet for decoration by these.
The embossing may be performed by a conventionally known method, for example.
The printing layer can be formed by a conventionally known method, for example, a printing method such as offset printing, gravure printing, ink jet printing, clean printing, flexographic printing, electrostatic printing or the like.
In the decorative adhesive sheet of the present invention, a transparent surface protective layer may be further formed on the front surface of the base material layer.

In the decorative adhesive sheet of the present invention, a release paper (separator) may be laminated on the surface of the hot melt adhesive layer opposite to the primer layer.
The release paper is not particularly limited, and conventionally known ones can be used. Examples thereof include resin films such as PET films and polypropylene films surface-treated with silicone resins.

Next, a method for producing the decorative adhesive sheet will be described. Here, a decorative adhesive sheet using a resin film made of a vinyl chloride tree composition as a base material layer will be described as an example.
(1) First, a resin film made of a vinyl chloride tree composition is prepared.
Specifically, each predetermined amount of the constituents of the vinyl chloride resin composition (vinyl chloride resin, plasticizer, and additives blended as necessary), continuous kneader, Banbury mixer, kneader, extruder Etc. are used to melt and knead to obtain a vinyl chloride resin composition, and then the vinyl chloride resin composition is formed by calender molding, extrusion molding, injection molding or the like to produce a resin film.
As a film forming method, calender molding is preferable. It is easy to make the thickness of the resin film uniform, can be formed regardless of the composition of the vinyl chloride resin composition, and is also suitable for forming substrates of various sizes such as larger sizes. This is because it is easy to handle small lots.
Examples of the calendar format used for the calendar molding include an inverted L shape, a Z shape, an upright two shape, an L shape, and an inclined three shape.
Moreover, what is necessary is just to select the roll temperature at the time of calendar molding suitably according to the composition of a vinyl chloride resin composition, and is 140-190 degreeC normally, Preferably it is 160-180 degreeC.
In this step, the surface of the resin film may be embossed or a printing layer may be formed as necessary.

(2) Next, a primer layer is formed on one side of the resin film.
For example, the primer composition may be applied with a machiscoater or a comma coater, and then dried under conditions of 80 to 100 ° C. for 1 to 2 minutes.

(3) Next, a hot melt adhesive layer is formed on the primer layer formed on one side of the resin film.
The hot-melt adhesive layer may be formed by a conventionally known method, and may be formed by applying a hot-melt applicator or the like directly on one side of the resin film (on the primer layer). Alternatively, it may be formed by once applying to a separately prepared support and then transferring. If release paper is used as the support, the release paper can be laminated simultaneously with the formation of the hot melt adhesive layer.
By undergoing such steps, the decorative adhesive sheet of the present invention can be produced.

Next, a usage method and a use are demonstrated to the adhesive sheet for decorating of this invention.
The said adhesive sheet for decorating is affixed and used for a to-be-decorated main body, and a decorating molded product can be produced by affixing to a to-be-decorated main body.
The decorated main body is not particularly limited as long as it is generally used for a decorative molded product, and for example, a decorated main body (core material) made of resin, metal, or ceramic can be used.
Moreover, the shape of the decorated main body is not particularly limited.

  The material of the decorated main body made of the resin is not particularly limited. For example, polyolefin resin such as polyethylene resin, polypropylene resin, olefin thermoplastic elastomer, polystyrene resin, polyethylene terephthalate resin, polyvinyl alcohol Resins, vinyl chloride resins, polyamide resins, polyacetal resins, polycarbonate resins, acrylonitrile / butadiene / styrene (ABS) resins, ionomer resins, and resin compositions in which various additives such as inorganic fibers are added to these resins Thing etc. are mentioned.

Of these, polyolefin resins such as polyethylene resins, polypropylene resins, and olefin thermoplastic elastomers are preferred.
This is because the effect of using the decorative adhesive sheet of the present invention can be remarkably enjoyed.

The method for attaching the decorative adhesive sheet to the body to be decorated is not particularly limited, and methods such as lamination, vacuum forming, pressure forming, vacuum / pressure forming, in-mold forming, film insert forming, etc. can be used. .
Among these, vacuum / pressure forming is preferable.

Examples of decorative molded products decorated with the decorative adhesive sheet of the present invention include products such as washstands, kitchen shelves such as shelves, toilets, bathrooms, electrical appliances such as mobile phone covers, and vehicles. It can be used for various decorative molded products whose surfaces are decorated with designs such as patterns, designs, letters, etc., such as interior parts, motorcycle cowlings, building materials such as floor materials and wall materials.
Among these, the above water-based products are preferable. The decorative molded product obtained by pasting the decorative adhesive sheet of the present invention is decorated with the decorative adhesive sheet, even when any detergent of acidic detergent, neutral detergent and alkaline detergent is used. This is because an excellent adhesion to the main body can be maintained.

  EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only to these Examples.

(Preparation of base material layer (resin film))
20 parts by weight of a plasticizer (manufactured by ADEKA Corporation, PN7535) is blended with 100 parts by weight of a vinyl chloride resin (manufactured by Kaneka Corporation, S-1001N: average polymerization degree 1050), and then an inverted L-type calendar. A resin film having a thickness of 0.10 μm was formed through each roll of the apparatus (roll temperature, 170 to 190 ° C.).
In the following examples and comparative examples, this resin film was used as a base material layer.

Example 1
(1) After applying the primer composition prepared by the following method on one side of the resin film using a bar coater so that the thickness after curing is 5 μm, the condition is 80 ° C. × 2 minutes. A primer layer was formed by curing.
The primer composition is prepared by mixing 100 parts by weight of an acrylic resin (Arakawa Chemical Industries, Ltd., AB-2-10) and 40 parts by weight of an aziridine-based curing agent (Arakawa Chemical Industries, Ltd., Aracoat CL910) with a screw. It went by.

(2) Next, the hot melt adhesive composition prepared by the following method is coated on a release paper made of a PET film whose surface has been subjected to a release treatment so that the thickness after drying is 40 μm. Then, this was transferred to the surface of the resin film on which the primer layer was formed to produce a decorative adhesive sheet in which the resin film, primer layer, hot melt adhesive layer and separator layer were laminated in this order.
The hot melt adhesive composition was prepared by adding 100 parts by weight of an olefin-based block polymer (manufactured by Sotec, skip 66) and 40 parts by weight of an alicyclic saturated hydrocarbon resin (manufactured by Arakawa Chemical Industries, Ltd., Alcon P90). It was prepared by mixing with a screw.

(Example 2)
A decorative adhesive sheet was produced in the same manner as in Example 1 except that the blending amount of the alicyclic saturated hydrocarbon resin in the hot melt adhesive composition was changed to 20 parts by weight.

(Comparative Example 1)
(1) On one side of the resin film, a polyurethane primer composition (Arakawa Chemical Industries, Juliano W600) was applied using a bar coater so that the thickness after drying was 5 μm. A primer layer was formed by drying at 80 ° C. for 2 minutes.

(2) Next, the hot melt adhesive composition prepared by the following method is coated on a release paper made of a PET film whose surface has been subjected to a release treatment so that the thickness after drying is 40 μm. Then, this was transferred to the surface of the resin film on which the primer layer was formed to produce a decorative adhesive sheet in which the resin film, primer layer, hot melt adhesive layer and separator layer were laminated in this order.
The hot melt adhesive composition was prepared by 100 parts by weight of styrene rubber (manufactured by Hitachi Chemical Polymer Co., Ltd., Hibon YA211-2) and 40 parts by weight of an alicyclic saturated hydrocarbon resin (manufactured by Arakawa Chemical Industries, Ltd., Alcon P90). The part was prepared by dissolving Alcon P90 in MEK in an equal amount and then mixing with a screw.

(Comparative Example 2)
In the preparation of the hot-melt adhesive composition, decoration was performed in the same manner as in Comparative Example 1 except that rosin ester (Arakawa Chemical Industries, Super Ester A-75) was used instead of the alicyclic saturated hydrocarbon resin. An adhesive sheet was manufactured.

(Comparative Example 3)
A decorative adhesive sheet was produced in the same manner as in Comparative Example 2 except that the primer layer was not formed.

(Comparative Example 4)
A decorative adhesive sheet was prepared in the same manner as in Example 1 except that the primer layer was not formed and the hot melt adhesive composition prepared by the following method was used.
The hot melt adhesive composition was prepared by mixing 100 parts by weight of an olefin block polymer (manufactured by Sotec Co., Ltd., Skip 66) and 40 parts by weight of rosin ester (manufactured by Arakawa Chemical Industries, Ltd., Superester A-75) with a screw. It was done by doing.

(Evaluation)
About the adhesive sheet for decoration produced in the Example and the comparative example, after sticking the adhesive sheet for decoration to a to-be-decorated main body by the following method and producing a decorative molded product, the obtained decorative molded product was obtained. (1) adhesive strength, (2) heat resistance, (3) wet heat resistance, (4) water resistance and (5) chemical resistance. The results are shown in Table 1.

(Production of decorative molded products)
The above-mentioned decorative adhesive sheet heated to 120 ° C. was attached to a base material made of a polypropylene plate (size: 25 mm × 180 mm × 3 mm) in a vacuum / pneumatic system to produce a decorative molded product.

(1) Adhesive strength The decorative molded product was cut into a size of 25 mm × 180 mm × 3 mm to obtain a test piece.
About the obtained test piece, 180 degree peeling of the adhesive sheet for decorating was performed on conditions with a tensile speed of 300 mm / min, and the adhesive force (N / 25 mm) was evaluated, and the destruction phenomenon was observed.
In addition, about the observation result of a destruction phenomenon, AC in a table | surface shows the following destruction phenomenon, respectively.
A: Interfacial peeling at primer layer-adhesive layer B: Interfacial peeling at substrate-adhesive layer C: Cohesive failure at adhesive layer

(2) Heat resistance The decorative molded product was cut into a size of 5 mm x 5 mm x 3 mm to obtain a test piece.
After the obtained test piece was stored in an oven at 60 ° C. for 240 hours, the state of the test piece was observed and evaluated according to the following criteria.
A: No swelling, peeling, cracking or discoloration was observed on the decorative adhesive sheet.
X: Swelling, peeling, cracking or discoloration was observed on the decorative adhesive sheet.

(3) Moisture and heat resistance The decorative molded product was cut into a size of 5 mm × 5 mm × 3 mm to obtain a test piece.
The obtained test piece was stored in a constant temperature bath at a temperature of 60 ° C. and a humidity of 95% for 240 hours, and then the state of the test piece was observed and evaluated according to the following criteria.
A: No swelling, peeling, cracking or discoloration was observed on the decorative adhesive sheet.
X: Swelling, peeling, cracking or discoloration was observed on the decorative adhesive sheet.

(4) Water resistance The decorative molded product was cut into a size of 5 mm × 5 mm × 3 mm to obtain a test piece.
After immersing the obtained test piece in water having a water temperature of 40 ° C. for 240 hours, the state of the test piece was observed and evaluated according to the following criteria.
A: No swelling, peeling, cracking or discoloration was observed on the decorative adhesive sheet.
X: Swelling, peeling, cracking or discoloration was observed on the decorative adhesive sheet.

(5) Chemical resistance The decorative molded product was cut into a size of 5 mm × 5 mm × 3 mm to obtain a test piece.
(5-1) Acid-resistant detergent After the obtained test piece was immersed for 48 hours in an acid detergent (manufactured by Dainippon Shikiku Co., Ltd., Sunpol (registered trademark)) at a temperature of 23 ° C, it was 24 hours at room temperature and normal humidity. Then, the state of the test piece was observed.

(5-2) Alkali-resistant detergent The obtained test piece was immersed in an alkaline detergent at 23 ° C. (Unimesa Japan, Domest (registered trademark)) for 48 hours, and then allowed to stand at room temperature and normal humidity for 24 hours. Then, the state of the test piece was observed.

(5-3) Neutral Resistant Detergent After the obtained test piece was immersed in a neutral detergent (manufactured by Kao Corporation, Magiclin (registered trademark)) for 48 hours at a temperature of 23 ° C., it was 24 hours at room temperature and normal humidity. Then, the state of the test piece was observed.

(5-4) Alcohol resistance After applying isopropyl alcohol (IPA) at 23 ° C. to the decorative surface of the obtained test piece, the test piece was stored in a sealed state for 10 minutes and further allowed to stand at room temperature and normal humidity for 24 hours. The state of the test piece was observed.

In the chemical resistance evaluations (5-1) to (5-4) above, the test pieces were evaluated according to the following criteria.
A: No swelling, peeling, cracking or discoloration was observed on the decorative adhesive sheet.
X: Swelling, peeling, cracking or discoloration was observed on the decorative adhesive sheet.

  As shown in Table 1, by using the decorative adhesive sheet of the present invention, a decorative molded product having excellent adhesion to the decorated main body and excellent chemical resistance, particularly alkali resistance. It became clear that it could be provided.

DESCRIPTION OF SYMBOLS 10 Adhesive sheet for decorating 11 Base material layer 12 Primer layer 13 Adhesive layer

Claims (4)

A decorative adhesive sheet in which a hot melt adhesive layer is laminated on one side of a base material layer via a primer layer,
The hot melt adhesive layer is composed of a thermoplastic resin composition containing an olefin block polymer and an alicyclic saturated hydrocarbon resin,
The said adhesive layer consists of a primer composition containing an acrylic resin and an aziridine type hardening | curing agent, The adhesive sheet for decorating characterized by the above-mentioned.   The decorative adhesive sheet according to claim 1, wherein the base material layer is made of a vinyl chloride-based tree composition.   The amount of the said alicyclic saturated hydrocarbon resin in the said thermoplastic resin composition is 15-50 weight part with respect to 100 weight part of the said olefin type block polymers, For decorating of Claim 1 or 2 Adhesive sheet. The adhesive sheet for decorating according to any one of claims 1 to 3, which is used for decorating a decorated main body made of a polyolefin resin.