JP2007217598A - Adhesive laminate and its producing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive laminate which enables adhesion easily to be conformed to a surface of an adherend even if the surface is curved, is superior in scatter prevention of the adherend, and hardly tears when peeled and hardly leaves an adhesive on the adherend, and to provide its producing method. <P>SOLUTION: This adhesive laminate comprises a first substrate, a first adhesive layer sequentially laminated on one surface of the first substrate, a second substrate and a second adhesive layer. The first substrate is composed of one or more resins selected from the group consisting of a polyvinyl chloride material, a polyolefin material and a copolyester material. The second substrate has tensile strength of 80-300 MPa in a machine direction when produced. Adhesive force of the first adhesive layer is larger than that of the second adhesive layer when measured based on the 180 degree peeling method of JIS Z0237-1991. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an adhesive laminate that is attached to an adherend such as a window and a method for manufacturing the same.

The adherends such as glass windows of buildings are embossed on the surface in order to reduce the visibility from one side to the other side and to provide blindness, or to improve decoration In some cases, a sticky laminate having a print layer or a sticky laminate provided with a printing layer may be stuck.
Since the surface of the adherend may be a curved surface, a material that can easily follow the curved surface for pasting is used as the adhesive laminate. For example, Patent Document 1 proposes a sticky laminate in which a pressure-sensitive adhesive layer is provided on one surface of a soft polyvinyl chloride film and irregularities are formed on the other surface.
Japanese Patent Laid-Open No. 9-221641

In recent years, from the viewpoint of disaster prevention, an adherent laminate that is stuck to an adherend is also required to have an adherend scattering prevention function when the adherend is broken. However, in the sticky laminate described in Patent Document 1, as a result of using a soft polyvinyl chloride film that can be pasted easily following a curved surface, the adherend scattering prevention property may be lowered.
In addition, the sticky laminate may be peeled off again from the adherend for re-sticking, but the sticky laminate described in Patent Document 1 is torn during re-peeling and cannot be used. There was a case. Furthermore, as the adhesive laminate, there is a demand for an adhesive laminate that peels without leaving a part of the adhesive laminate on the adherend.

  The present invention has been made in view of the above circumstances, and can adhere easily even when the surface of the adherend is a curved surface, has excellent anti-adherent scattering prevention properties, and at the time of re-peeling An object of the present invention is to provide an adhesive laminate that is difficult to tear and remains on an adherend and a method for producing the same.

The present inventors have found that the adhesive laminate described in Patent Document 1 has a low overall glass tensile strength, and thus has a low glass scattering prevention property and is easily broken during re-peeling. Further, based on the knowledge, the following [1] to [7] having high tensile strength despite the fact that the adherend surface can be easily followed and pasted even when the surface of the adherend is a curved surface. Invented a method for producing an adhesive laminate of [8] and [9].
[1] Adhesive laminate having a first base material, and a first adhesive layer, a second base material, and a second adhesive layer sequentially laminated on one surface of the first base material. Body,
The first base material is composed of one or more resins selected from the group consisting of polyvinyl chloride materials, polyolefin materials, and copolyester materials,
The second substrate has a tensile strength in the flow direction during production of 80 to 300 MPa,
The first adhesive layer is an adhesive laminate characterized in that the adhesive force measured based on the 180-degree peeling method of JIS Z0237-1991 is higher than that of the second adhesive layer.
[2] The adhesive laminate according to [1], wherein the second adhesive layer has removability.
[3] The adhesive laminate according to [1] or [2], wherein the second substrate is a film made of polyethylene terephthalate or polypropylene.
[4] The adhesive laminate according to any one of [1] to [3], wherein the first base material has a tensile strength in the flow direction of 10 to 70 MPa.
[5] The adhesive laminate according to any one of [1] to [4], wherein a surface of the first base material opposite to the first adhesive layer is matted.
[6] The adhesive laminate according to any one of [1] to [5], wherein a release sheet is laminated on a surface opposite to the second base material in the second adhesive layer.
[7] The adhesive laminate according to any one of [1] to [6], wherein a printed layer is provided on the first substrate or the second substrate.
[8] A method for producing the adhesive laminate according to [6],
A first adhesive layer is provided on one surface of the second substrate, the first substrate is laminated on the first adhesive layer, and the second adhesive is applied to the other surface of the second substrate. A method for producing an adhesive laminate comprising providing a layer and laminating a release sheet on the second adhesive layer.
[9] A method for producing the adhesive laminate according to [6],
A second adhesive layer is provided on one surface of the second substrate, a release sheet is laminated on the second adhesive layer, and a first adhesive layer is provided on the other surface of the second substrate. The manufacturing method of the adhesive laminated body characterized by laminating | stacking a 1st base material on a 1st adhesive layer.

The sticky laminate of the present invention can be stuck and followed easily even when the surface of the adherend is a curved surface. In addition, since the tensile strength is high, the adherend scattering prevention property is excellent, and it is difficult to tear at the time of re-peeling, and it is difficult to remain on the adherend.
According to the method for producing an adhesive laminate of the present invention, it is possible to produce an adhesive laminate having a high tensile strength in addition to being able to easily follow and adhere even when the surface of the adherend is a curved surface. . Furthermore, the sticking laminated body excellent in sticking property can be manufactured.

(Adhesive laminate)
An embodiment of the sticky laminate of the present invention will be described.
In FIG. 1, sectional drawing of the sticking laminated body of this embodiment is shown. The adhesive laminate 10 includes a first base material 11, a first adhesive layer 12 sequentially laminated on one surface of the first base material 11, a second base material 13, and a first base material 11. 2 adhesive layers 14 and a release sheet 15.
In the present embodiment, all of the resin constituting the first base material 11, the second base material 13, the first adhesive layer 12, and the second adhesive layer 14 are transparent to visible light. . Therefore, the whole sticking laminated body 10 has visible-light transmittance, and is suitable for the use stuck to transparent adherends, such as glass. Here, being transparent to visible light means having a light transmittance of 50% or more (JIS K7361-1997) as an adhesive laminate.

[First base material]
The 1st base material 11 consists of 1 or more types of resin chosen from the group which consists of a polyvinyl chloride material, polyolefin material, and copolyester material. The adhesive laminate 10 in which the first substrate 11 is made of the resin can be easily followed and adhered even when the surface of the adherend is a curved surface.

Among the polyvinyl chloride materials, a soft polyvinyl chloride material is preferable because it becomes easier to adhere the sticking laminate 10 following the curved surface.
The soft polyvinyl chloride material contains polyvinyl chloride and a plasticizer. The content of the plasticizer is preferably 10 to 200 parts by mass, more preferably 30 to 100 parts by mass with respect to 100 parts by mass of polyvinyl chloride. If the plasticizer content of the soft polyvinyl chloride material is 10 parts by mass or more, it becomes easier to adhere the sticking laminate 10 following the curved surface, and if it is 200 parts by mass or less, plasticity is achieved. The stickiness due to the bleeding of the agent can be prevented.
Examples of plasticizers include phthalate ester plasticizers, trimellitic ester plasticizers, aliphatic dicarboxylic ester plasticizers, aliphatic monocarboxylic ester plasticizers, organophosphate ester plasticizers, and epoxy. System plasticizers and the like. These plasticizers can be used alone or in admixture of two or more.

The polyolefin materials, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, olefin-based elastomer obtained by copolymerizing C ₃ or more α-olefins to ethylene, metallocene polyethylene using metallocene catalyst as a polymerization process, the metallocene Add styrene thermoplastic elastomer (TPS) such as polypropylene, metallocene elastomer, hydrogenated styrene-butadiene copolymer rubber (hydrogenated SBR), hydrogenated styrene-isoprene-styrene block copolymer (hydrogenated SIS) Polypropylene, high rubber content polypropylene (reactor TPO) with propylene (crystalline polyolefin part) as a hard segment and a large amount of rubber component as a soft segment in the vapor phase polymerization process, CAP resin Blends of amorphous alpha polyolefin and polypropylene), ethylene - vinyl acetate resin (EVA), ethylene - methacrylic resin (EMMA), and the like.
Among these, low-density polyethylene, olefin elastomer, metallocene elastomer, high rubber content polypropylene (reactor TPO), and the like are preferable because the light transmittance of the adhesive laminate 10 can be increased.

The copolyester material is obtained by copolymerizing a diol component as a soft segment with a dicarboxylic acid that becomes a hard segment, and is particularly preferably an amorphous polyester copolymer or an amorphous polyester copolymer.
Specifically, the amorphous polyester copolymer uses, for example, terephthalic acid or a derivative thereof as the dicarboxylic acid component of the hard segment, and, for example, ethylene glycol, 1,4-butanediol, The thing using 1 or more types, such as 1, 4- cyclohexane dimethanol, is mentioned. Such a copolyester material is composed of multiple components, so that the crystallization sites in the molecular chain are reduced.
The copolyester material may be copolymerized in the presence of a hydroxycarboxylic acid component in order to reduce the crystallization sites in the molecular chain.
The difference between the crystallization temperature of the copolyester material and the glass transition temperature is preferably 60 ° C. or less. If the difference between the crystallization temperature of the copolyester material and the glass transition temperature is 60 ° C. or less, the first substrate 11 containing the copolyester material becomes flexible, and the sticking laminate 10 becomes curved. Can be made to follow and stick more easily.

In this embodiment, the embossing which is a kind of matting process is given to the surface of the 1st base material 11 on the opposite side to the 1st adhesion layer.
Embossed pattern is not particularly limited, for example, pear, silk, cloth, home span, wave pattern, lattice, checkered, arabesque, etc., circle, triangle, square, polygon, doll, dog , Cat shape, bird shape, fish shape, insect shape, flower shape, grass shape, fruit shape, tree shape, star shape and the like.
When the surface of the first substrate 11 is embossed as in the present embodiment, when the sticky laminate 10 is viewed from the side on which the emboss is formed, light is caused by the unevenness of the emboss. Diffusely reflected and appears translucent. Therefore, the adhesive laminate 10 has reduced visibility from the embossed surface side to the other surface side while ensuring visible light transparency, for example, providing blindness to a glass window, etc. It is suitable for the application.

The first base material 11 preferably has a tensile strength (JIS K7127-1999) in the flow direction during production of 10 to 70 MPa, and more preferably 20 to 50 MPa. If the tensile strength of the 1st base material 11 is 10 Mpa or more, the tensile strength of the sticking laminated body 10 whole will become higher, and if it is 70 Mpa or less, the sticking laminated body 10 is made to follow a curved surface and sticks. It will be easier to wear.
The flow direction at the time of production in the present invention is the film or sheet forming direction when the first base material 11 (or the second base material 13) is continuously formed, and is the longitudinal direction and the machine direction. , MD (Machine Direction).
In addition, the 1st base material 11 (or 2nd base material 13) in this invention is manufactured by the shaping | molding method of a general resin film or sheet. As a specific example of the molding method, after a molten resin is extruded into a sheet using a single layer or a multilayer T die or I die connected to a screw type extruder, a continuous resin sheet is cooled by a roll or the like. Examples thereof include a cast molding method and an inflation molding method using a circular die.
Moreover, in order to increase the tensile strength, the resin film or sheet obtained by the above molding method was further uniaxially stretched by longitudinal stretching utilizing the peripheral speed difference of the roll group, and a tenter oven was used after uniaxial stretching. The film may be stretched by a biaxial stretching method that combines transverse stretching, a simultaneous biaxial stretching method that combines a tenter oven and a linear motor, or the like.

The first substrate 11 preferably has a tensile modulus of 0.1 to 40 kg / mm ² . If the tensile modulus of the first substrate 11 is 0.1 kg / mm ² or more, it becomes easier to adhere the sticking laminate 10 following the curved surface, and the tensile modulus is 40 kg / mm. If it is mm < ² > or less, the tensile strength of the sticking laminated body 10 whole becomes higher.

In order to set the tensile strength or the tensile elastic modulus within the above range, for example, the mass average molecular weight of the resin constituting the first substrate 11 may be appropriately selected. The higher the mass average molecular weight, the higher the tensile strength and the lower the tensile modulus.
Also, the tensile strength or tensile elastic modulus can be set in the above range by appropriately selecting the thickness of the first base material 11. Specifically, if the first base material 11 is thickened, the tensile strength increases. , The tensile elastic modulus is lowered.

  The thickness of the first substrate 11 is preferably 20 to 1,000 μm, more preferably 25 to 500 μm, and particularly preferably 30 to 300 μm. If the thickness of the 1st base material 11 is 20 micrometers or more, tensile strength will become higher, and if it is 1,000 micrometers or less, it is easier to stick the stickable laminated body 10 following a curved surface. become.

[First adhesive layer]
The 1st sticking layer 12 is a layer comprised from sticking agents, such as an adhesive agent or an adhesive. Here, the adhesive loses its tackiness by being cured after sticking, and the pressure-sensitive adhesive maintains a certain degree of tackiness even after sticking.
Examples of the adhesive include natural rubber-based, synthetic rubber-based, acrylic-based, vinyl acetate-based, cyanoacrylate-based, silicone-based, and urethane-based adhesives. These may be various types such as solvent-based, solvent-free, one-component, two-component, and ultraviolet curable types. As the adhesive, various hot melt adhesives such as styrene block copolymers and ethylene-vinyl acetate copolymers can be used. These are preferably selected as appropriate according to the method applied when the first base material and the second base material are attached.
Examples of the pressure-sensitive adhesive include rubber-based, acrylic-based, urethane-based, and vinyl ether-based pressure-sensitive adhesives. As the acrylic pressure-sensitive adhesive, there are an emulsion type, a solvent type, a hot melt type, and the like, and any type can be used in the present invention. Among these, emulsion-type acrylic pressure-sensitive adhesives are preferable from the viewpoints of safety, quality, and cost.
When using an adhesive, a tackifier may be added. Examples of the tackifier include rosin resins, terpene resins, aliphatic petroleum resins, aromatic petroleum resins, hydrogenated petroleum resins, styrene resins, alkylphenol resins, and the like.

  The first adhesive layer 12 preferably has a thickness of 1 to 15 μm, and more preferably 2 to 8 μm. If the thickness of the 1st sticking layer 12 is 1 micrometer or more, the sticking force of the 1st sticking layer 12 will become higher, and a part of sticking laminated body 10 will peel when it peels from a to-be-adhered body. It can be further prevented from remaining on the adherend. If the thickness of the 1st sticking layer 12 is 15 micrometers or less, since it is not necessary to use a sticking agent more than necessary, it is economical.

The first adhesive layer 12 has an adhesive force measured based on the 180-degree peeling method of JIS Z0237-1991 higher than that of the second adhesive layer 14.
As a method for making the adhesive force of the first adhesive layer 12 stronger than the adhesive force of the second adhesive layer 14, the second adhesive layer 14 is composed of an adhesive, and the first adhesive layer. The method of comprising 12 with an adhesive, the method of comprising the second adhesive layer 14 with a releasable adhesive, and the first adhesive layer 12 with a strong adhesive, the second adhesive layer 14 and the 1st adhesion layer 12, the same adhesive is used, and the method of forming an unevenness | corrugation only in the surface of the 2nd adhesion layer 14 etc. are mentioned.

[Second base material]
The second base material 13 has a tensile strength (JIS K7127-1999) in the flow direction during production of 80 to 300 MPa, preferably 100 to 250 MPa. If the tensile strength is 80 MPa or more, the tensile strength of the entire adhesive laminate 10 can be increased. On the other hand, if the tensile strength of the 2nd base material 13 is 300 Mpa or less, it will become easier to stick the sticking laminated body 10 to a curved surface.
The tensile strength of the second substrate 13 can also be adjusted as appropriate depending on the mass average molecular weight and thickness of the resin constituting the second substrate 13, as with the first substrate 11.

  Examples of the material of the second base material 13 include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polystyrene, polycarbonate, polyamide, polyimide, polyvinyl alcohol, poly (ethylene vinyl alcohol), polyvinylidene chloride, Examples thereof include resins such as acrylic resin, polyacetate, polyacrylonitrile, polyethersulfone, polyetheretherketone, polyarylate, polyphenylene sulfide, polyetherimide, and polysulfone. Among these, polyethylene terephthalate or polypropylene film is preferable from the viewpoint of cost.

  The thickness of the second base material 13 is preferably 5 to 100 μm, more preferably 10 to 60 μm, and particularly preferably 15 to 40 μm. If the thickness of the second substrate 13 is 5 μm or more, the tensile strength of the adhesive laminate 10 can be increased, and if it is 100 μm or less, the adhesive laminate 10 becomes thin. Handleability is improved.

[Second adhesive layer]
As the adhesive that constitutes the second adhesive layer 14, the same adhesive as the first adhesive layer 12 can be used. However, it is preferable that the second adhesive layer 14 has removability because the workability at the time of peeling from the adherend becomes higher. As a method for giving the second adhesive layer 14 removability, for example, a method using a releasable pressure-sensitive adhesive as an adhesive for providing the second adhesive layer 14, in the second adhesive layer 14 Examples thereof include a method of forming irregularities on the surface of the release sheet 15 to reduce the contact area.

The adhesion force measured based on the 180 degree peeling method of JIS Z0237-1991 of the second adhesion layer 14 is preferably 100 to 2,000 g / 25 mm, and 200 to 1,000 g / 25 mm. It is more preferable, and it is especially preferable that it is 300-500 g / 25mm. If the adhesive force of the second adhesive layer 14 is 100 g / 25 mm or more, the adhesive laminate 10 can be reliably adhered to the adherend, and if it is 2,000 g / 25 mm or less, the adhesive laminate. The removability of the body 10 can be improved.
In order to adjust the adhesive force of the second adhesive layer 14, for example, the thickness may be adjusted. If the 2nd sticking layer 14 becomes thick, sticking power can be made high.

  The thickness of the second adhesive layer 14 is preferably 10 to 100 μm, more preferably 15 to 75 μm, and particularly preferably 20 to 50 μm. If the thickness of the 2nd sticking layer 14 is 10 micrometers or more, sufficient sticking force can be ensured, and if it is 100 micrometers or less, since it is not the thickness more than necessary, it is economical.

[Peeling sheet]
Examples of the release sheet 15 include those in which a release agent is applied to a release sheet substrate to form a release surface. Here, the release sheet substrate may be natural paper or a plastic film. Examples of natural paper include glassine paper, high-quality paper, coated paper, clay-coated paper, and kraft paper. Examples of plastic film include films of polyethylene, polypropylene, polyethylene terephthalate, polyamide, and the like. Further, as the release sheet substrate, a laminated paper obtained by laminating plastic on one or both sides of paper, a metal foil, or a bonded product of a metal foil and paper, a plastic film, or the like can be used.
Examples of the release agent that forms the release surface include a silicone resin, a fluororesin, an aminoalkyd resin, and a polyester. Among these, a silicone resin is preferable because of excellent peelability. These release agents are used as an emulsion, a solvent type or a solventless type.

  Moreover, as the peeling sheet 15, what has many through-holes can be used. If the release sheet 15 having a large number of through-holes is used, irregularities can be formed on the surface of the second adhesive layer 14, so that the second adhesive layer 14 can easily have removability.

  The release sheet 15 preferably has a thickness of 20 to 500 μm, preferably 30 to 300 μm, and particularly preferably 40 to 150 μm. If the thickness of the release sheet 15 is 20 μm or more, the second adhesive layer 14 can be peeled more easily, and if it is 500 μm or less, it is economical because it does not need to be thicker than necessary.

  The sticking laminate 10 is used by peeling the release sheet 15, exposing the second sticking layer 14, and sticking the second sticking layer 14 to the adherend. Examples of the adherend include transparent adherends such as automobiles and trains, resin or glass windows of buildings, and opaque adherends such as outer walls and inner walls.

Since the sticking laminate 10 described above has the second base material 13 having a specific tensile strength, as the first base material 11, a polyvinyl chloride material that easily follows a curved surface, Despite the use of one or more resins selected from the group consisting of polyolefin materials and copolyester materials, the tensile strength is high. Therefore, even if the adherend to which the adherent laminate 10 is stuck is broken, the adherent laminate 10 is prevented from being broken along with it, and the adherend scattering prevention property is enhanced. Moreover, even if it peels from a to-be-adhered body, when the once-adhesive laminated body 10 is once affixed on an to-be-adhered body and it reapplies, the adherent-laminated body 10 becomes difficult to tear.
In addition, in the adhesive laminate 10, the adhesive force of the first adhesive layer 12 is stronger than the adhesive force of the second adhesive layer 14, and therefore the adhesive laminate 10 is temporarily attached to the adherend. Then, when re-peeling, peeling between the first base material 11 and the second base material 13 can be prevented, and peeling between the adherend and the second adhesive layer 14 is ensured. it can. Therefore, at the time of re-peeling, a part of the sticking laminate 10 can be peeled without remaining on the adherend.

(Method for producing an adhesive laminate)
Next, an embodiment of the method for producing an adhesive laminate of the present invention will be described.
In the manufacturing method of the present embodiment, first, as shown in FIG. 2A, the first adhesive layer 12 is provided on one surface of the second base material 13, and the first adhesive layer 12 is provided on the first adhesive layer 12. The first substrate 11 is laminated. Thereby, the 1st substrate 11 and the 2nd substrate 13 are pasted up.

  Examples of the method for providing the first adhesive layer 12 include a method in which a coating liquid containing an adhesive is applied to one surface of the second substrate 13 and dried. Examples of the application method of the coating liquid include roll coating, knife coating, bar coating, die coating, comma coating, lip coating, reverse gravure coating, vario gravure coating, curtain coating, and screen printing.

Examples of the method for bonding the first base material 11 and the second base material 13 through the first adhesive layer 12 include a dry laminating method, a wet laminating method, a print laminating method, and a cold laminating method. A hot press laminating method, a hot melt laminating method, an extrusion laminating method and the like can be applied.
When bonding, the 1st base material 11 and the 2nd base material 13 may be flat form, and may be web form.

Next, as shown in FIG. 2 (b), the second adhesive layer 14 is provided on the other surface of the second base material 13, and the release sheet 15 is laminated on the second adhesive layer 14, A sheet with a smooth surface is obtained.
Examples of the method of providing the second adhesive layer 14 include the same method as the method of providing the first adhesive layer 12.

  And in order to give blindness, as shown in FIG. 3, the sheet | seat 10a with the smooth surface is formed in the embossing roll 20 in which the emboss was formed in the surrounding surface, and the surface of the 1st base material 11 is the embossing roll 20 The mat is processed by supplying it so as to be in contact with the peripheral surface of the sheet. Embossing is formed by bringing the surface of the first base material 11 into contact with the peripheral surface of the embossing roll 20, and the sticking laminate 10 shown in FIG. 1 is obtained.

In the manufacturing method of this embodiment, since the specific resin is used for the first substrate 11, the sticking laminate 10 that can be easily followed and pasted even when the surface of the adherend is a curved surface is provided. Can be manufactured.
Moreover, in the manufacturing method of this embodiment, since the 2nd base material 13 of specific tensile strength is bonded to the 1st base material 11 via the 1st bonding layer 12, the adhesive property obtained is obtained. The tensile strength of the laminate 10 can be increased. Therefore, according to the above production method, it is possible to obtain an adherent laminate that is excellent in adherence scattering prevention, is not easily torn during re-peeling, and is unlikely to remain on the adherend.
Furthermore, in the manufacturing method of this embodiment, since the 2nd bonding layer 14 is provided after bonding the 1st base material 11 and the 2nd base material 13, the heat concerning the 2nd bonding layer 14 is applied. The history can be reduced. Therefore, the deterioration of the second adhesive layer 14 can be suppressed, and the adhesiveness of the adhesive laminate 10 to the adherend can be improved.

In addition, this invention is not limited to embodiment mentioned above. In the embodiment described above, the surface of the first base material 11 is embossed so that the sticking laminate 10 is blinded, but other matting treatment may be applied. Other matting treatments include, for example, sand blasting, water blasting, wrinkled wrinkling, creping, pleating, flocking, chemical treatment, and electron beam irradiation. As the matting treatment, embossing and sandblasting treatment are preferable because they can be easily matted.
Furthermore, in the present invention, the surface of the first substrate 11 may be glossy without being matted.

Moreover, the sticking laminated body 10 may be one in which a printed layer is provided on the first base material 11 or the second base material 13. As a printing layer, the layer by which the pattern, the pattern, the character, the photograph, etc. were printed with printing ink is mentioned, for example. The printed layer can also be blindfolded or decorative.
Printing methods for providing the printing layer include inkjet methods, thermal transfer methods, thermal recording methods, laser recording methods, electrophotographic methods, letterpress printing methods, gravure printing methods, flexographic printing methods, solvent-based offset printing methods, and UV curable types. Examples include an offset printing method and a silk screen printing method.

  When providing the printing layer when the first substrate 11 is made of a soft polyvinyl chloride material, it is preferable to provide the printing layer 16 on the surface of the second substrate 13 as shown in FIG. Since the soft polyvinyl chloride material has low printability, if it is intended to provide the printing layer 16 on the surface of the first substrate 11, a special printing method must be applied, and productivity may be reduced. . However, if the printing layer 16 is provided on the surface of the second substrate 13, a special printing method need not be applied, and productivity is high.

  Moreover, the sticking laminated body 10 may be one in which an aluminum vapor deposition film is provided on the first base material 11 or the second base material 13. As an aluminum vapor deposition film, for example, a film obtained by heating and evaporating aluminum by an electron beam or high frequency induction in a high vacuum state and attaching the vapor to the film surface can be cited.

  In addition, the sticking laminate 10 includes at least one of the first base material 11, the second base material 13, the first sticking layer 12, and the second sticking layer 14 such as a pigment or a dye. It may be colored by.

  Furthermore, the sticking laminate 10 is embossed on the surface of the first base material 11 according to the purpose such as blindfolding or decoration, and the first base material 11 or the second base material 13. A printing layer is provided, an aluminum vapor deposition film is provided on the first base material 11 or the second base material 13, the first base material 11, the second base material 13, and the first adhesive layer. 12, Two or more may be used together among any one or more of the second adhesive layers 14 being colored.

  In the embodiment described above, the resin constituting the first base material 11, the second base material 13, the first adhesive layer 12, and the second adhesive layer 14 are all transparent to visible light. However, one or more of the resin constituting the first base material 11, the second base material 13, the first adhesive layer 12, and the second adhesive layer 14 may be opaque.

Moreover, in this invention, any one or more of the 1st base material 11, the 2nd base material 13, the 1st adhesion layer 12, and the 2nd adhesion layer 14 has an ultraviolet absorption function. Also good. If any one or more of the first base material 11, the second base material 13, the first adhesive layer 12, and the second adhesive layer 14 have an ultraviolet absorption function, for example, a window When the sticking laminate 10 is stuck on the indoor side, the amount of ultraviolet rays entering the indoor can be reduced.
If an ultraviolet absorber is added to the adhesive layer to impart an ultraviolet absorbing function, the adhesive force of the adhesive layer may be reduced. Therefore, when the ultraviolet absorbing function is imparted, the first substrate 11 and It is preferable that one or both of the second base materials 13 contain an ultraviolet absorber.

  The adhesive laminate of the present invention can be produced by a production method other than the production method of the above-described embodiment. For example, there is a method in which the first base material 11 and the second base material 13 are bonded via the first adhesive layer 12 after the second adhesive layer 14 is provided on the second base material 13. Applicable. In this method, the load on the first base material 11 and the first adhesive layer 12 can be reduced. Further, since heat and stress are not applied after the first base material 11 and the second base material 13 are attached, it is possible to prevent the adhesive laminate 10 from being bent or curled.

  Hereinafter, the present invention will be described with reference to examples. In addition, the tensile strength in the following examples is the tensile strength of the flow direction at the time of preparation.

(First base material)
The following first substrates (A-1) to (A-4) were prepared as the first substrate.
[First base material (A-1)]
A polyvinyl chloride resin film in which a film (thickness 100 μm, tensile strength 25 MPa) made of a soft polyvinyl chloride material containing polyvinyl chloride and a plasticizer component 24% by mass is subjected to sand blasting to give unevenness to one side of the film. Manufactured. This polyvinyl chloride resin film was used as the first substrate (A-1).
Two types were prepared, one in roll form and one cut into a lithographic form.

[First base material (A-2)]
An olefin-based thermoplastic elastomer containing polypropylene and ethylene-propylene rubber (trade name: Zelas # 7053, DSC melting peak temperature of 165 ° C., manufactured by Mitsubishi Chemical Corporation), and a film that is extruded using a T-die ( A thickness of 100 μm and a tensile strength of 32 MPa were prepared, and the film was embossed with an embossing roll to obtain an olefin-based resin film having unevenness on one side of the film. This olefin resin film was used as the first substrate (A-2).

[First base material (A-3)]
An amorphous PET copolymer film (trade name: Diafix CHI, thickness 100 μm, tensile strength 45 MPa, manufactured by Mitsubishi Plastics, Inc.) using an amorphous polyester PET-G is embossed using an embossing roll. To obtain a polyester-based resin film having irregularities on one side of the film. This polyester resin film was used as the first substrate (A-3).

[First base material (A-4)]
A polyethylene terephthalate film (trade name: Lumirror S10, thickness 75 μm, tensile strength 217 MPa, manufactured by Toray Industries, Inc.) was used as the first substrate (A-4).

(Second base material)
As the second base material, the following second base materials (B-1) to (B-4) were prepared.
[Second base material (B-1)]
A polyethylene terephthalate film (trade name: Lumirror S10, thickness 25 μm, tensile strength 229 MPa, manufactured by Toray Industries, Inc.) was used as the second substrate (B-1).

[Second base material (B-2)]
Biaxially stretched polypropylene film (trade name: Dazai FO (FOH), thickness 40 μm, tensile strength 140 MPa, Nimura Chemical Industries, Ltd.) having a heat seal layer made of an ethylene-vinyl acetate adhesive as a first adhesive layer on one side (Made by Co., Ltd.) was prepared, and a stained glass-like design by gravure printing was applied to the surface opposite to the heat seal surface. The printed film was used as the second substrate (B-2).

[Second base material (B-3)]
A para-aramid film (trade name: Miktron, thickness 12 μm, tensile strength 460 MPa, manufactured by Toray Industries, Inc.) was used as the second substrate (B-3).

[Second base material (B-4)]
An amorphous PET copolymer film (trade name: Diafix CHI, thickness 100 μm, tensile strength 45 MPa, manufactured by Mitsubishi Plastics Co., Ltd.) using PET-G which is an amorphous polyester is used as a second base material (B -4).

(Peeling sheet)
The following release sheets (C-1) to (C-2) were prepared as release sheets.
[Peeling sheet (C-1)]
A stretched polypropylene film (trade name: Treffan 2535 # 60, light transmittance (JIS K6714): 92%, manufactured by Toray Industries, Inc.) having a thickness of 60 μm was subjected to through-piercing processing by a hot needle punching method. This perforation forms a perforated portion, and the film near the perforated portion is rolled up on one side. And the silicone process was given to the surface where the film rolled up, and the peeling sheet (C-1) was obtained.
In this release sheet (C-1), the hole diameter of the perforated part was 400 μm, the number of holes was 60 / cm ² , and the depth of the perforated part was 120 μm. Further, in this release sheet (C-1), as a result of the silicone treatment being performed on the rolled-up portion near the perforated portion, a convex portion was formed, and the height of the convex portion was 60 μm.

[Peeling sheet (C-2)]
Glassine paper (trade name: G7B, manufactured by Oji Tac Co., Ltd.) subjected to silicone treatment was used as a release sheet (C-2).

(Method for producing an adhesive laminate)
[Example 1]
On one side of the polyethylene terephthalate film that is the second base material (B-1), a two-component solvent-based acrylic pressure-sensitive adhesive (trade name: Olivevine BPS1109, manufactured by Toyo Ink Manufacturing Co., Ltd.) The film was applied with a comma coater so as to have a thickness of 25 μm, and dried to form a second adhesive layer.
Next, the surface of the release sheet (C-1) on which the silicone treatment is applied is bonded to the second adhesive layer provided on one side of the second base material, wound up, and second A laminate with a release sheet consisting of: base material / second adhesive layer / release sheet was obtained.
Gravure so that the solid content is 4 g / m ² (thickness of about 4 μm) after drying adhesive (trade name: TM265, manufactured by Toyo Morton Co., Ltd.) on the surface of the second substrate side of this laminate. The first adhesive layer was laminated by applying and drying with a coater. Next, the polyvinyl chloride resin film as the first base material (A-1) is brought into contact with the first adhesive layer, and the first adhesive layer is in contact with the surface not subjected to the sandblasting treatment. (So that the treated mat surface becomes the outer surface). Then, it is pressure-bonded using a pressure-bonding roll (dried and laminated), and has an adhesive property comprising a first substrate / first adhesive layer / second substrate / second adhesive layer / release sheet. A laminate was obtained. The thickness of this sticky laminated body was 270 μm.

[Example 2]
On the surface opposite to the heat seal layer of the biaxially stretched polypropylene film as the second base material (B-2), a two-component solvent-based acrylic pressure-sensitive adhesive (trade name: Olivevine BPS1109, Toyo Ink Manufacturing Co., Ltd.) Manufactured) was applied with a comma coater so that the thickness after drying was 25 μm, and dried to form a second adhesive layer.
Next, the release sheet (C-1) is bonded to the second adhesive layer provided on one side of the second base material, and the surface on which the silicone treatment is applied, and the first side is wound. A laminate with a release sheet consisting of: adhesive layer (heat seal layer) / second substrate / second adhesive layer / release sheet was obtained.
The pressure-bonding roll heated so that the surface on the heat seal layer side of this laminate is in contact with the surface of the olefin-based resin film that is the first base material (A-2) that has not been embossed. Adhesive lamination consisting of first substrate / first adhesive layer / second substrate / second adhesive layer / release sheet by introducing between them and thermocompression bonding (thermal lamination) Got the body. The thickness of this sticky laminated body was 280 μm.

[Example 3]
On the polyethylene terephthalate film which is the second base material (B-1), a two-component solvent-based acrylic pressure-sensitive adhesive (trade name: Olivevine BPS1109, manufactured by Toyo Ink Manufacturing Co., Ltd.) has a thickness after drying of 25 μm. Then, coating was performed with a comma coater and dried to form a second adhesive layer.
Next, the release sheet (C-1) is bonded to the second adhesive layer provided on one side of the second base material, and the surface on which the silicone treatment is performed is bonded and wound, and the second sheet is wound. A laminate with a release sheet consisting of: base material / second adhesive layer / release sheet was obtained.
On the surface of the laminate on the second substrate side, an acrylic emulsion adhesive (trade name: TGW-3991-1, manufactured by Toyo Morton Co., Ltd.) was dried and the solid content was 4 g / m ² (thickness). The first adhesive layer was formed by applying and drying with a gravure coater so as to be about 4 μm). Next, a lithographic polyvinyl chloride resin film as the first base material (A-1) is applied to the first adhesive layer, and the first adhesive layer is applied to the surface on which the sandblast treatment is not performed. Were laminated so that And it sticks by the press lamination method using a crimping | compression-bonding roll, it cuts into a lithographic plate, and it is from 1st base material / 1st adhesive layer / 2nd base material / 2nd adhesive layer / release sheet. A sticky laminate was obtained. The thickness of this sticky laminated body was 270 μm.

[Example 4]
To the polyethylene terephthalate film as the second base material (B-1), an adhesive prepared by mixing polyurethane anchor coating agents “BLS-2080A” and “BLS-2080B” of Toyo Morton Co., Ltd. with 4 g / m ² ( The ratio of solid content) was applied with a comma coater and dried to form a first adhesive layer.
Next, the polyvinyl chloride resin film as the first base material (A-1) is brought into contact with the first adhesive layer, and the first adhesive layer is in contact with the surface not subjected to the sandblasting treatment. Laminated. And it crimped | bonded using the crimping | compression-bonding roll (dry lamination), and obtained the laminated body which consists of a 1st base material / 1st adhesion layer / 2nd base material.
On the surface of the laminate on the second substrate (PET) side, a two-component solvent-based acrylic pressure-sensitive adhesive (trade name: Olivevine BPS1109, manufactured by Toyo Ink Manufacturing Co., Ltd.) was dried to a thickness of 25 μm. Then, coating was performed with a comma coater and dried to form a second adhesive layer.
Next, the surface of the release sheet (C-1) on which the silicone treatment is applied is bonded to the second adhesive layer provided on one side of the second base material, wound up, and the first An adhesive laminate comprising substrate / first adhesive layer / second substrate / second adhesive layer / release sheet was obtained. The thickness of this sticky laminated body was 270 μm.

[Example 5]
On the polyethylene terephthalate film which is the second base material (B-1), a two-component solvent-based acrylic pressure-sensitive adhesive (trade name: Olivevine BPS1109, manufactured by Toyo Ink Manufacturing Co., Ltd.) has a thickness after drying of 25 μm. Then, coating was performed with a comma coater and dried to form a second adhesive layer.
Next, the surface of the release sheet on which the silicone treatment is applied is bonded to the second adhesive layer provided on one side of the second base material, wound up, and the second base material / second base material is wound. A laminate with a release sheet comprising an adhesive layer / release sheet was obtained.
Thickness after drying a two-component solvent acrylic strong adhesive (trade name: Olivevine BPS5513, manufactured by Toyo Ink Manufacturing Co., Ltd.) on the surface of the second substrate (PET) of the laminate with release sheet Was applied directly with a comma coater so as to be 25 μm, and dried to form a first adhesive layer.
After that, the glassine paper which is the release sheet (C-2) is laminated on the first adhesive layer of the laminate with release sheet on the surface on which the silicone treatment has been performed, wound up, and once from glassine paper A double-sided adhesive sheet consisting of a release sheet / first adhesive layer / second substrate / second adhesive layer / release sheet was obtained.
The double-sided adhesive sheet obtained above is attached to the unwinding side of the laminator, the release sheet made of glassine paper is peeled off, and the first base material (by the cold lamination method using a crimping roll) A-3) The polyester resin film which is not embossed is bonded to the first base material / first adhesive layer / second base material / second adhesive. An adhesive laminate comprising a layer / release sheet was obtained. The thickness of this sticky laminate was 300 μm.

[Comparative Example 1]
To the polyvinyl chloride resin film as the first base material (A-1), a two-component solvent-based acrylic pressure-sensitive adhesive (trade name: Olivevine BPS1109, manufactured by Toyo Ink Manufacturing Co., Ltd.) has a thickness after drying. The coating layer was directly coated with a comma coater so as to have a thickness of 25 μm and dried to form a second adhesive layer.
Next, the surface of the release sheet (C-1) on which the silicone treatment is applied is bonded to the second adhesive layer provided on one side of the first base material, wound up, and the first A film with a release sheet comprising: base material / second adhesive layer / release sheet was obtained.
This film with a release sheet is obtained by omitting the second base material and the first adhesive layer of the adhesive laminate of the present invention, and is the first base material depending on the solvent content contained in the adhesive. Since a certain polyvinyl chloride resin film swelled, it was crushed and the appearance was not good.

[Comparative Example 2]
An amorphous PET copolymer film as the first substrate (A-3) is used as the first substrate, and an amorphous PET copolymer as the second substrate (B-4) is used as the second substrate. A sticky laminate was obtained in the same manner as in Example 1 except that the film was used.
In this sticky laminate, when a solvent-based adhesive is applied to an amorphous PET copolymer film, the amorphous part of the resin swells due to the solvent contained in the adhesive, resulting in blurring and poor appearance. It was a thing.

[Comparative Example 3]
The sticking laminated body was obtained by the same method as Example 1 except having used the aramid film which is a 2nd base material (B-3) as a 2nd base material.

[Comparative Example 4]
A sticky laminate was obtained in the same manner as in Example 1 except that the polyethylene terephthalate film as the first substrate (A-4) was used as the first substrate.

[Comparative Example 5]
The polyethylene terephthalate film as the second substrate (A-1) is coated with a two-component solvent-based acrylic strong adhesive (trade name: Olivevine BPS5513, manufactured by Toyo Ink Manufacturing Co., Ltd.), and the thickness after drying is 25 μm. Then, it was coated with a comma coater and dried to form a second adhesive layer.
Next, the surface of the second adhesive layer provided on one side of the second base material is bonded to the surface of the release sheet (C-2) that is not subjected to silicone treatment of the glassine paper, and wound. Then, a laminate with a release sheet comprising a second substrate / second adhesive layer / release sheet was obtained.
A two-component solvent-based acrylic pressure-sensitive adhesive (trade name: Olivevine BPS1109, manufactured by Toyo Ink Manufacturing Co., Ltd.) is dried on the surface of the laminate on the second substrate side so that the thickness after drying becomes 25 μm. The first adhesive layer was formed by coating directly with a comma coater and drying.
Next, the first adhesive layer is in contact with the surface of the polyvinyl chloride resin film that is the first base material (A-1) that is not sandblasted (the treated mat surface is the outer surface). The first base material / the first adhesive layer / the second base material / the second adhesive layer / the release sheet are subjected to pressure bonding (dry lamination) using a pressure bonding roll. The sticking laminated body which consists of was obtained.

(Evaluation)
The following method evaluated the adhesive laminated body manufactured by said Example and comparative example, and the film with a peeling sheet. The results are shown in Tables 1 and 2.
(1) Evaluation of followability About the sticking laminated body of each Example and a comparative example, and the film with a peeling sheet, the followability at the time of sticking to curved glass by manual labor was evaluated by the following references | standards.
◯: Wrinkles and tarmi were not generated on the appearance, and it was possible to adhere evenly.
×: Hard to work due to rigidity, wrinkles and tarmi occurred in the periphery, and there was a defect in appearance.

(2) Evaluation of glass scattering prevention property After sticking uniformly on a flat glass plate about the sticking laminated body of each Example and a comparative example, and a film with a peeling sheet, this glass plate is split with a hammer, The glass scattering situation was evaluated according to the following criteria.
○: The laminate did not break and retained glass fragments.
Δ: A crack occurred in a part of the laminate, and there was a problem.
X: The laminated body or sheet was similarly broken by glass fragments and scattered finely.

(3) Evaluation of removability For each of the examples and comparative examples, the adhesive laminate and the film with a release sheet were uniformly attached to a flat glass plate, and then a part of the substrate was held by hand and peeled off. The state of the laminate or film was evaluated according to the following criteria.
○: The laminate or sheet could be easily peeled off manually, and re-sticking was possible.
(Triangle | delta): When peeling a laminated body by manual work, the base material extended or the material broke and it was difficult to re-stick.
X: The laminate was delaminated at the time of peeling (the first sticking layer was agglomerated and broken), and resticking was difficult.

(4) Evaluation of adhesive residue at the time of re-peeling For each example and comparative example of the adhesive laminate and the film with release sheet, after evenly sticking to a flat glass plate, hold a part of the substrate by hand The remaining condition of the glue (second adhesive layer) on the window glass when peeled off was visually evaluated according to the following criteria.
○: No adhesive residue was observed.
(Triangle | delta): Some glue residue was recognized and there was a malfunction.
X: The glue remained.

The sticky laminates of Examples 1 to 5 having the second base material having a tensile strength of 80 to 300 MPa have high followability to the adherend, excellent glass scattering prevention properties, and are not easily broken during re-peeling. It was hard to stay on the adherend.
In Comparative Example 1 having no second substrate, the glass scattering prevention property was low, the removability was insufficient, and a slight adhesive residue was observed at the time of removability.
The sticking laminate of Comparative Example 2 in which the tensile strength of the second base material was less than 80 MPa was insufficient in glass scattering prevention and removability.
The sticking laminate of Comparative Example 3 in which the tensile strength of the second base material exceeded 300 MPa had low followability.
The sticky laminate of Comparative Example 4 using a polyethylene terephthalate film as the first substrate had low followability.
The adhesive laminate of Comparative Example 5, in which the first adhesive layer was weaker than the adhesive strength of the second adhesive layer, had low removability, and there was considerable adhesive residue at the time of re-exfoliation.

It is sectional drawing which shows one Embodiment of the sticking laminated body of this invention. It is a figure explaining one Embodiment of the manufacturing method of the sticking laminated body of this invention. It is a figure explaining one Embodiment of the manufacturing method of the sticking laminated body of this invention. It is sectional drawing which shows other embodiment of the sticking laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Adhesive laminated body 11 1st base material 12 1st adhesive layer 13 2nd base material 14 2nd adhesive layer 15 Release sheet 16 Printing layer 20 Embossing roll

Claims (9)

An adhesive laminate having a first base material, a first adhesive layer, a second base material, and a second adhesive layer sequentially laminated on one surface of the first base material. And
The first base material is composed of one or more resins selected from the group consisting of polyvinyl chloride materials, polyolefin materials, and copolyester materials,
The second substrate has a tensile strength in the flow direction during production of 80 to 300 MPa,
The first adhesive layer is an adhesive laminate characterized in that the adhesive force measured based on the 180-degree peeling method of JIS Z0237-1991 is higher than that of the second adhesive layer.   The sticking laminated body according to claim 1, wherein the second sticking layer has removability.   The adhesive laminate according to claim 1 or 2, wherein the second substrate is a film made of polyethylene terephthalate or polypropylene.   The adhesive laminate according to any one of claims 1 to 3, wherein the first base material has a tensile strength in the flow direction at the time of production of 10 to 70 MPa.   The sticking laminated body in any one of Claims 1-4 by which the matting process is given to the surface on the opposite side to the 1st sticking layer in a 1st base material.   The adhesive laminate according to any one of claims 1 to 5, wherein a release sheet is laminated on a surface of the second adhesive layer opposite to the second substrate.   The adhesive laminate according to any one of claims 1 to 6, wherein a printed layer is provided on the first substrate or the second substrate. A method for producing the adhesive laminate according to claim 6,
A first adhesive layer is provided on one surface of the second substrate, the first substrate is laminated on the first adhesive layer, and the second adhesive is applied to the other surface of the second substrate. A method for producing an adhesive laminate comprising providing a layer and laminating a release sheet on the second adhesive layer. A method for producing the adhesive laminate according to claim 6,
A second adhesive layer is provided on one surface of the second substrate, a release sheet is laminated on the second adhesive layer, and a first adhesive layer is provided on the other surface of the second substrate. The manufacturing method of the adhesive laminated body characterized by laminating | stacking a 1st base material on a 1st adhesive layer.

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