KR20130129210A - Pressure-sensitive adhesive resin composition and pressure-sensitive adhesive film - Google Patents

Abstract

When co-extrusion by an extruder is performed, this invention can laminate | stack an adhesive layer on a base material layer without causing lack of extending | stretching, and when it sticks with a protective film, it can be used for coating | covers, such as a prism sheet with a small contact area with a film. An adhesive resin composition and an adhesive film are provided. The adhesive resin composition of the present invention mainly comprises a block copolymer of a styrene polymer block and an olefin polymer block, a block copolymer of a styrene polymer block and a random copolymer block of styrene and an olefin, and / or a hydrogenated substance thereof. A resin composition comprising 2 parts by weight or more and less than 10 parts by weight of a tackifying resin and 2 parts by weight or more and less than 10 parts by weight of a polyolefin resin, based on 100 parts by weight of a styrene elastomer having a styrene component of 5 to 15% by weight. Characterized in that.

Description

Adhesive resin composition and adhesive film {PRESSURE-SENSITIVE ADHESIVE RESIN COMPOSITION AND PRESSURE-SENSITIVE ADHESIVE FILM}

The present invention relates to an adhesive resin composition (adhesive) and an adhesive film. The adhesive of this invention can be used suitably for the adhesive film for protecting the outer surface of the prism type lens part of the prism sheet especially used for optical use.

It also protects the surface of the automobile body during synthetic resin plates (for building materials), stainless steel plates (for building materials), aluminum plates, decorative plywood, steel sheets, glass plates, home appliances, precision machinery and manufacturing. To protect against scratches when overlapping, storing, transporting, or transporting the article, and to protect the scratches from secondary processing (e.g., bending or pressing). Even if it does, it can use preferably.

Conventionally, adhesive films for the purpose of protecting the surface of coatings have been used in the processing, storage, and transportation of building materials, electricity, electronic products, automobiles, etc. These adhesive films not only have good adhesiveness, but also after use Each surface should be easily peelable without contaminating the adhesive.

This kind of adhesive film is comprised by laminating | stacking an adhesion layer on the layer used as a base material. As a manufacturing method of an adhesive film, the method of coating a solution-form adhesive to the base material layer comprised from synthetic resin etc., a base material layer, and an adhesion layer are melt-extruded from several extruders, and coextrusion using a T die etc. The film forming method, etc. are mentioned. Among these, coextrusion film forming by the T-die method is superior in cost and quality.

As useful resin used for an adhesion layer at the time of co-extrusion film forming, the styrene-type elastomer which is one of thermoplastic elastomers is mentioned. The styrene-based elastomer is not only excellent in the anchoring force of the pressure-sensitive adhesive layer with respect to the base material layer containing the polyolefin resin when forming a film, but also easy to control the adhesive force by the addition of a tackifier. It has an advantage (patent document 1).

By the way, many of the above-mentioned coating bodies have not only smooth coating surfaces but also surface irregularities due to the diversification thereof. Examples of the coating having the surface irregularities include prism type lens portions of the prism sheet used for the optical member, and it is necessary to express sufficient adhesive force in use with respect to the coating having the surface irregularities such as the prism sheet. There is.

To this end, it is possible to increase the adhesive force of the adhesive layer so that the adhesive force is obtained even if the contact area is small, or to obtain the adhesive force by increasing the contact area by digging the surface irregularities of the coating into the adhesive layer by softening the adhesive layer. have.

In order to improve the self-adhesion of an adhesion layer, it is possible by adding tackifying resin to the styrene-type elastomer suitable as an adhesive (for example, refer patent document 1 etc.). However, when laminating the pressure-sensitive adhesive layer formed by excessively adding a tackifying resin to the styrene-based elastomer by coextrusion to the base material layer by an extruder, the melt viscosity of the pressure-sensitive adhesive layer is lowered, and it is difficult to stretch the base material layer, and the time is The problem arises. In the case of laminating by the feed block method, even after the adhesive layer is stretched to the substrate layer, since the melt viscosity of the adhesive layer is lower than that of the substrate layer, the adhesive layer gradually drips from the end portion in the film width direction and the end portion adheres. By using only a layer, it may become a cause of a problem, such as a film edge part sticking to a film forming machine.

In addition, by adding a tackifier to the styrene-based elastomer, it is possible to express the self-adhesive force necessary for use with respect to the prism sheet (see Patent Document 2, etc.), but only by adding the tackifier to the styrene-based elastomer Unwinding property is not necessarily favorable when removing a film after making a film into a roll state.

Japanese Patent Publication No. 10-151656 Japanese Patent Publication No. 2007-332329

The problem to be solved by the present invention is that when co-extrusion of the pressure-sensitive adhesive and the resin for the base layer with an extruder when producing the pressure-sensitive adhesive film, it is possible to laminate the pressure-sensitive adhesive on the base material layer without the lack of stretching, It is an object to provide the adhesive resin composition for adhesive films and such an adhesive film suitable for use with adherends, such as a prism sheet with few blocking on a roll and small contact area with an adhesive film, for example.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject can be eliminated by making the resin composition which comprises an adhesive into a predetermined range, and reached | attained this invention.

That is,

The styrene component whose main component is a block copolymer of a styrene polymer block and an olefinic polymer block, a block copolymer of a styrene polymer block, a random copolymer block of styrene and an olefin, and / or a hydrogenated substance thereof is 5 to 5, Adhesive resin characterized by including the resin composition containing 2 weight part or more and less than 10 weight part, and 2 weight part or more and less than 10 weight part of tackifying resin with respect to 100 weight part of styrene-type elastomers which are 15 weight%. It is a composition, and is characterized by content of polyolefin resin especially.

According to the present invention, when the pressure-sensitive adhesive film is produced, even when the pressure-sensitive adhesive and the resin for the base layer are coextruded with an extruder, the pressure-sensitive adhesive film obtained by laminating the pressure-sensitive adhesive on the base layer without causing shortage of stretching can be obtained.

A further invention is the pressure-sensitive adhesive film characterized in that the pressure-sensitive adhesive resin composition is laminated on one side of a base layer containing polypropylene-based resin as a main component.

The pressure-sensitive adhesive film of the present invention, as a protective film, has sufficient adhesive strength in practical use even if it is attached to a coating having surface irregularities such as a prism, for example, and furthermore, even if the pressure-sensitive adhesive films overlap, there is less advantage of blocking the pressure-sensitive adhesive films. Have

Moreover, in the base material layer which has the said polypropylene resin as a main component, it is preferable that a mold release layer is laminated | stacked on the opposite surface to the adhesive layer containing an adhesive resin composition.

Moreover, it is preferable that the base material layer which has the said polypropylene resin as a main component, the adhesion layer containing an adhesive resin composition, and a release layer are laminated | stacked by coextrusion.

In addition, it is preferable that the melt flow rate (MFR) of the styrenic elastomer at 230 ° C. 2.16 kgf in the adhesive layer is 0.5 to 10 g / 10 min.

Moreover, it is preferable that melt flow rate (MFR) in 230 degreeC * 2.16 kgf of polypropylene resin in the said base material layer is 1.0-15 g / 10min.

Moreover, it is preferable that the said adhesive film is for prism sheet coating.

Moreover, it is preferable that the said adhesive film is self-adhesive.

The adhesive resin composition (adhesive) of this invention can be laminated | stacked on the base material layer, without a lack of extending | stretching, when coextrusion with an extruder is carried out, Furthermore, even if it sticks together, there is little blocking of adhesive films. Has the advantage.

The adhesive film of this invention is useful because it has sufficient adhesive force, when affixing it as a protective film to a to-be-adhered body with a small contact area with films, such as a prism sheet, for example.

1 is a schematic diagram of a measurement sample.

Hereinafter, embodiment of the adhesive resin composition (adhesive) of this invention and an adhesive film is described. In addition, in this invention, when it makes it "main component", it means that 90 mass% or more is the component.

(Adhesive Resin Composition)

As the resin composition constituting the pressure-sensitive adhesive of the present invention, a mixture of styrene-based elastomers, tackifying resins, and polyolefin-based resins in a predetermined ratio may be softly laminated when co-extruded onto a base layer containing polypropylene-based resin as a main component. Elongation is satisfactory, and when laminating by a feed block method, it is hard to generate | occur | produce an adhesion layer at the edge part of a film width direction, and it is preferable at the time of expressing the self adhesive force to the coating body of the obtained adhesive film.

(Styrene-based elastomer)

Examples of the styrene-based elastomer include ABA type block polymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene copolymer-styrene, styrene-ethylene / propylene copolymer- styrene, and styrene-butadiene, styrene- , AB type block polymers such as styrene-ethylene / butylene copolymer and styrene-ethylene / propylene copolymer, styrene random copolymers such as styrene-butadiene rubber, and hydrogenated products thereof.

The hydrogenated substance of the styrene-based elastomer used in the present invention means that the double bond derived from the conjugated diene of the styrene-based elastomer is partially or completely saturated by hydrogenation. As saturation degree, Preferably it is 80 mol% or more, More preferably, it is 90 mol% or more, Especially preferably, it is 95-100 mol%. When the said saturation degree is less than 80 mol%, the weather resistance and heat resistance of an adhesive layer may become inadequate.

It is preferable that the styrene component in a styrene-type elastomer is 5 weight% or more and 15 weight% or less. If it is less than 5 weight%, granulation at the time of resin preparation becomes difficult, and when it exceeds 15 weight%, adhesive force will fall and it will become difficult to obtain the adhesive force required. Moreover, although adhesive force can be raised by increasing the addition amount of tackifying resin, the elongation of the adhesion layer at the time of co-extrusion deteriorates by that much. Moreover, when laminating | stacking by a feed block method, it will become easy to generate | occur | produce an adhesion layer in the edge part of a film width direction. In order to make the stretchability of the adhesion layer good at the time of co-extrusion, and to make it difficult to generate | occur | produce an adhesion layer at the edge part of a film width direction, expressing the required adhesive force, the styrene component of a styrene-type elastomer becomes like this. It is% or more and 13 weight% or less.

The melt flow rate (MFR) at 230 ° C. 2.16 kgf of the styrene-based elastomer to be used is preferably in the range of 0.5 to 10 g / 10 minutes, and more preferably in the range of 2.0 to 8.0 g / 10 minutes.

(Adhesion imparting resin)

Examples of the tackifying resin include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, terpene resins, coumarone indene resins, styrene resins, and rosin resins.

It is preferable that content of tackifying resin in a resin composition is 2 weight part or more and less than 10 weight part with respect to 100 weight part of styrene-type elastomers whose styrene components are 5 weight% or more and 15 weight% or less. When content of tackifying resin is less than 2 weight part, adhesive force improvement cannot be expected. When content of tackifying resin increases too much more than 10 weight part, melt viscosity will fall remarkably when melt extrusion is performed.

When laminating the adhesive layer having a low melt viscosity by coextrusion with a polypropylene resin having a melt flow rate (MFR) of less than 15 (g / 10 min) at 230 ° C and 2.16 kgf as a substrate layer, between the substrate layer and the adhesive layer Due to the difference in melt viscosities, the pressure-sensitive adhesive layer is less likely to be stretched with respect to the base material layer, and a problem that takes time occurs. In the case of laminating by the feed block method, even after the adhesive layer is stretched to the substrate layer, since the melt viscosity of the adhesive layer is lower than that of the substrate layer, the adhesive layer gradually drips from the end portion in the film width direction and the end portion adheres. By using only a layer, it may become a cause of a problem, such as a film edge part sticking to a film forming machine. Moreover, there is also a problem that blocking is likely to occur when the adhesive film is wound in a roll and then unwound again. In addition, there is a fear of contaminating the coating. Content of tackifying resin becomes like this. Preferably it is 4 weight% or more and 9 weight% or less.

(Polyolefin Resin)

The polyolefin resin is not particularly limited, and the crystalline polypropylene, a copolymer of propylene and a small amount of α-olefin, a low density polyethylene, a high density polyethylene, a copolymer of ethylene and a small amount of α-olefin, and an ethylene and vinyl acetate And copolymers. Especially, since a base material layer is comprised from polypropylene resin, polypropylene resin can be used suitably also in relationship with melt viscosity.

The melt flow rate (MFR) at 230 ° C. 2.16 kgf of the polyolefin resin to be used is preferably in the range of 0.5 to 10 g / 10 minutes, and more preferably in the range of 2.0 to 8.0 g / 10 minutes.

Content of polyolefin resin in a resin composition is a range of 2 weight part or more and less than 10 weight part with respect to 100 weight part of styrene-type elastomers whose styrene components are 5 weight% or more and 15 weight% or less. When it is 10 weight part or more, adhesive force falls and sufficient adhesive force with respect to the coating body which has surface unevenness | corrugation is not obtained, and elongation property is also inferior. If it is less than 2 parts by weight, the film is stored in a rolled state, and then, even when the film is unwound, blocking occurs to cause problems such as partially stretching or deforming the film. Content of polyolefin resin becomes like this. Preferably it is 4 weight% or more and 9 weight% or less.

In addition, the tackifying resin used for an adhesive may contain some powder depending on a kind, and may contaminate an extruder at the time of extrusion. Since such a problem is improved by using the tackifying resin master batch with polyolefin resin, it is preferable to use the tackifying resin and polyolefin resin master batch.

Among the pressure-sensitive adhesives used in the present invention, a crosslinking agent, a tackifier, an inorganic or organic filler, a softener, a plasticizer, a surfactant, a coupling agent, an antifoaming agent, an antistatic agent, a flame retardant, etc., as necessary, within a range that does not impair the achievement of the problems of the present invention. Although 1 type, or 2 or more types may be added among the various additives of, It is preferable to select and use the additive which does not inhibit the transparency of an adhesive layer or the adhesive film (surface protective film) obtained.

(Adhesive film)

As an adhesive layer, in the adhesive film laminated | stacked by coextrusion to the base material layer which has polypropylene resin as a main component using the said adhesive, an adhesive layer is fully extended | stretched to a base material layer. Moreover, it has sufficient adhesive force to to-be-adhered bodies, such as a prism, and also has the advantage that the blocking of adhesive films is few even if adhesive films overlap.

It is preferable from the viewpoint of the protective performance of a prism sheet that the adhesive force of the adhesive film of this invention is 23-50 degreeC with respect to a prism sheet in the range of 3-50 cN / 25cm. When adhesive force is less than 3 cN / 25cm, when a prism sheet is protected, overturning generate | occur | produces, and it cannot function as a protective film. On the other hand, when adhesive force exceeds 50 cN / 25cm, when peeling a film from a prism sheet, there exists a possibility that it may not peel smoothly. An adhesive force can be set suitably by changing resin composition, thickness, etc. of an adhesion layer.

The peeling force with respect to the mold release surface of the adhesive face of the adhesive film of this invention is a range of 100 cN / 25cm or less at 23 degreeC, It is preferable at the anneal property of a film when an adhesive film is made into a roll form. When the peeling force exceeds 100 cN / 25 cm, when the adhesive film is in the form of a roll, problems such as partial elongation of the film or deformation of the film unwinding occur. Peeling force can be suitably set by forming surface unevenness | corrugation in a mold release layer, and changing the contact area of an adhesive surface and a mold release surface, when winding up as a roll. Moreover, peeling force can also be reduced by adding resin which has an effect of lowering surface free energy, such as a fluororesin, silicone resin, and 4-methyl-1- pentene polymer, to a mold release layer.

The adhesive film of this invention can contain a well-known additive as needed. For example, a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistant agent, an impact improving agent, or the like may be contained.

However, it is preferable to make the low molecular weight substance of the adhesion layer surface into less than 1 mg / m <^2> . Here, the measurement of the low molecular weight substance on the adhesion layer surface was performed in the following procedure. The adhesive layer which wash | cleaned the surface of the adhesion layer using the organic solvent which does not erode the resin which comprises an adhesion layer, such as ethanol, removes the organic solvent from the washing | cleaning liquid with an evaporator, etc., and washes the numerical value calculated by weighing the residue. It was calculated by dividing the surface area of the surface.

When the residue is 1 mg / m ² or more, foreign matter is present between the adhesive layer surface and the adherend surface, which causes a decrease in the contact area and lowers the van der Waals force. When adding an additive, it is necessary to select an additive, such as a polymer type, or to examine the addition amount and the addition method, so that there may be no transition to an adhesion layer and transcription | transfer.

(Substrate layer)

The adhesive film of this invention requires the base material layer which has polypropylene resin as a main component. Examples of the polypropylene resin used herein include crystalline polypropylene, random copolymers of propylene and small amounts of α-olefins, block copolymers, and the like. More specifically, it is a crystalline polypropylene resin, which is an air of an n-heptane insoluble isotactic propylene homopolymer or propylene containing 60% by weight or more of polypropylene and other α-olefins used in ordinary extrusion molding. A copolymer is mentioned, This propylene homopolymer or the copolymer of propylene and another alpha-olefin can be used individually or in mixture.

Herein, n-heptane insolubility indicates the crystallinity of polypropylene and indicates safety, and in the present invention, n-heptane insolubility according to the Ministry of Health, Welfare, and Published Notice No. 20 (20 ° C, extracted for 60 minutes) It is a preferable aspect to use the thing suited to 150 ppm or less (it is 30 ppm or less for the use temperature to exceed 100 degreeC)).

As the α-olefin copolymer component of the copolymer of propylene with other α-olefins, α-olefins having 2 to 8 carbon atoms, for example, ethylene or 1-butene, 1-pentene, 1-hexene, 4-methyl- C4 or more alpha -olefins, such as 1-pentene, are preferable.

Here, the copolymer is preferably a random or block copolymer obtained by polymerizing propylene with one or more of the? -Olefins exemplified above.

For this reason, the melt flow rate (MFR) at 230 ° C and 2.16 kgf of the polypropylene resin to be used is preferably in the range of 1.0 to 15 g / 10 minutes, more preferably in the range of 2.0 to 10.0 g / 10 minutes. .

Moreover, you may use it in mixture of 2 or more types of copolymers of propylene and another alpha olefin.

Moreover, the waste film which came out at the time of product processing the film obtained by this invention can be reassembled as a recovery raw material, and can also be added to a base material layer. By using the recovered raw material, it is possible to suppress the production cost.

It is preferable that the stretchability with respect to the base material layer of the adhesion layer in the adhesive film of this invention is 90% or more. When the elongation property of an adhesion layer is low, operating time will deteriorate when a resin is substituted. Moreover, when laminating | stacking an adhesion layer by several micrometer order, there exists a problem that thickness nonuniformity becomes easy to arise in the width direction of a film. It is preferable that the stretchability of an adhesion layer is 90% or more, It is more preferable that it is 93% or more, It is especially preferable that it is 95% or more.

It is preferable that the fall rate with respect to the base material layer of the adhesion layer in the adhesive film of this invention is 3% or less. When the rate of falling of an adhesive layer is high, a film edge part will become an adhesive layer only, the problem of sticking to a film forming machine, etc. will arise and operability will deteriorate. The fall rate with respect to the base material layer of an adhesion layer is more preferable in it being 2.5% or less.

It is preferable that the thickness of the adhesion layer in the adhesive film of this invention is 1 micrometer or more and less than 30 micrometers. If the thickness of an adhesive film is less than 1 micrometer, the stable film forming by coextrusion will become difficult, and if it is 30 micrometers or more, it will become an unfavorable film from a cost viewpoint. At this time, when increasing adhesive force, it is preferable to consider that viscosity and to enlarge thickness. By increasing the thickness of the adhesive layer, the contact area with the adherend is likely to become large. It is preferable that the thickness of an adhesion layer is 2 micrometers or more and 20 micrometers or less, Furthermore, 3 micrometers or more and 15 micrometers or less are preferable, Especially 4 micrometers or more and 8 micrometers or less are preferable.

It is preferable that it is 5 micrometers or more and less than 100 micrometers, and, as for the thickness of the base material layer in the adhesive film of this invention, it is more preferable that they are 15 micrometers or more and less than 25 micrometers. If the thickness of the adhesive film is less than 5 µm, the elasticity is weakened, wrinkles are likely to occur when affixed to the coating as a protective film, and there is a problem that adhesive strength is not sufficiently obtained. In the disadvantageous film.

(Releasing layer)

It is preferable that the adhesive film of this invention forms a release layer in the surface opposite to the adhesion layer laminated | stacked on one side of the base material layer. By doing so, blocking can further be suppressed. In view of the resin composition of the pressure-sensitive adhesive layer of the present invention, it is preferable that the average surface roughness SRa of the surface of the release layer is 0.40 µm or more. The average surface roughness of the surface is preferably SR50, which is 0.850 µm or less, and more preferably 0.500 µm or more and 0.700 µm or less. It is preferable that the thickness of a mold release layer is 1 micrometer or more and less than 30 micrometers, and 3-10 micrometers is especially preferable.

In order to form surface irregularities as described above, by using a propylene-ethylene block copolymer, a rough surface layer can be formed in a mat shape. In addition, similar effects can be expected by mixing a polyethylene resin with homopolypropylene. In addition, by mixing the polyethylene-based resin with the propylene-ethylene block copolymer, it is possible to form a rougher surface layer. As a preferable resin for obtaining a mat surface, specifically, propylene ethylene block copolymers, such as Nippon Polypropylene Co., Ltd. product "BC4FC", can be illustrated.

It is preferable to handle the adhesive film of this invention in the form of a roll. Although the upper limit of the width | variety and the winding length of a film roll are not specifically limited, In terms of ease of handling, in general, when the width is 1.5 m or less and a winding length is 30 micrometers in film thickness, 6000 m or less is preferable. Moreover, as a winding core, the plastic core and metal cores, such as 3 inches, 6 inches, and 8 inches, can be used normally. Moreover, it is preferable that it is a film roll wound by the dimension of processing more than 200 m in length and 450 mm or more in width.

The adhesive film using the adhesive of this invention can be preferably used, especially in order to protect the outer surface of the prism-type lens part of the prism sheet used for optical use. In addition, synthetic resin plates (for building materials), stainless steel plates (for building materials), aluminum plates, decorative plywood, steel sheets, glass plates, home appliances, precision machines, and the surface of automobile bodies in manufacturing For protection, to protect against the occurrence of scratches when overlapping, storing, transporting or transporting the article in the manufacturing process, and when the article is secondary processed (e.g., bend or press). It can also be used to protect what is happening.

[Example]

Next, an Example is given and this invention is further demonstrated. However, unless the present invention deviates from the gist, the present invention is not limited to the following examples. In addition, the evaluation method of the physical property in a following example and a comparative example is as follows.

(1) Evaluation of stretchability with respect to the base material layer of the adhesion layer

Within three layers of T dies (feed block type, 850 mm in lip width, 1 mm in lip gap), the adhesive layer resin is discharged at 15 kg / hr by 40 mmφ single screw extruder, and the base layer resin is 15 kg / hr by 90 mmφ single screw extruder. In the discharge amount, the release layer resin is coextruded at a discharge amount of 5 kg / hour with a 65 mmφ single screw extruder, respectively. The unstretched film of 650 mm width is obtained by winding up the extruded film in the casting roll of temperature 30 degreeC at 20 m / min speed. The adhesive layer resin was put into a 40 mm diameter single screw extruder, and the elongation of the adhesive layer with respect to the base material layer was measured after 30 minutes passed from the beginning instead of the resin.

Elongation = lamination width of adhesive layer (mm) / 650 (mm) x 100 (%)

(2) Evaluation of the fallability with respect to the base material layer of an adhesion layer

Within three layers of T dies (feed block type, 850 mm in lip width, 1 mm in lip gap), the adhesive layer resin is discharged at 15 kg / hr by 40 mmφ single screw extruder, and the base layer resin is 15 kg / hr by 90 mmφ single screw extruder. In the discharge amount, the release layer resin is coextruded at a discharge amount of 5 kg / hour with a 65 mmφ single screw extruder, respectively. By taking out the extruded film to a casting roll with a temperature of 30 ° C. at a speed of 20 m / min, an unstretched film of 650 mm width is obtained. The adhesive layer resin was thrown into a 40 mm diameter single screw extruder, and the fall rate of the both ends of the film width direction of the adhesion layer with respect to a base material layer was measured after 120 minutes passed from the beginning instead of the resin.

Flow rate = width (mm) / 650 (mm) * 100 (%) that adhesion layer flowed down to both ends of film width direction

(3) Evaluation of adhesiveness

It measured by the following method based on JIS-Z-0237 (2000) adhesive tape and an adhesive sheet test method.

As a to-be-adhered body, an acryl plate (Mitsubishi Rayon Co., Ltd. make: 3mm thickness of acrylic light (trademark)) 50mm * 150mm, two types of prism sheets (lens part which consists of a triangular pillar with different surface treatment states, The height of the column is 25 μm, the width of the triangular pole is 50 μm) 50 mm × 150 mm, and as a test piece, a test piece of 25 mm is cut out in a winding direction at the time of film manufacture and in a direction orthogonal to it. Reciprocating once with a mass of 2000 g of rubber roll (with a spring hardness of 80 Hs on the surface of the roller, 45 mm in width and 95 mm in diameter (including rubber layer) covered with a rubber layer 6 mm thick) at a rate of 5 mm / sec The adherend and the test piece were pressed together. After pressing, the mixture was left for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 65%. The speed of 300 mm / min using "Autograph (trademark)" (AGS-J) manufactured by Shimadzu Corporation The resistance value at the time of 180 degree peeling was made into adhesive force [cN / 25mm]. 180 degree peeling means maintaining the peeling angle of an acryl plate and a film at the time of measuring the resistance value at the time of peeling at 180 degree | times.

At the time of measurement, a polyester sheet having a thickness of 190 µm and a size of 25 mm x 170 mm was prepared as a holding portion of the measurement sample, and the affixed portion was placed at the end of the adhesive film side of the measurement sample which crimped the adhesive film and the acrylic plate. It was affixed with the width | variety cellophane tape (trademark) and it was set as the holding part at the time of a measurement. The schematic diagram of the measurement sample is shown in FIG. The measurement was performed three times for one sample, and the average value was made into the adhesive force of the sample.

(4) Evaluation of blocking resistance

As evaluation of blocking resistance, the peeling force of the release layer of the adhesion film and the adhesion layer was measured as follows.

Adhesion plate (Mitsubishi Rayon Co., Ltd. make: 3mm thickness of acrylic light) 50 mm * 150 mm whole surface a double-sided adhesive tape (Nito Denko Co., Ltd. make: No.535A) is affixed on the other side of a double-sided adhesive tape The test piece of 150 mm (the winding direction at the time of film manufacture) x 50 mm (the direction orthogonal to the winding direction at the time of film manufacture) was stuck so that the adhesive surface of a test piece might come.

As a test piece, the test piece of 150 mm in the winding direction at the time of film manufacture and 25 mm in the direction orthogonal to it was cut out, and the release surface of the test piece stuck on the adhesive surface and the acrylic plate through the double-sided adhesive tape was superimposed. Afterwards, a mass of 2000 g of rubber roll (with a spring hardness of 80 Hs on the surface of the roller and a width of 45 mm covered with a rubber layer of 6 mm in thickness and 95 mm in diameter (including the rubber layer)) at a rate of 5 mm / sec. It reciprocated and crimped | bonded the mold release surface and the test piece. After being pressed for 30 minutes in an environment of a temperature of 23 ° C. and a relative humidity of 65%, the product was peeled 180 degrees at a speed of 300 mm / min using "Autograph" (AGS-J) manufactured by Shimadzu Corporation. The resistance value at the time was made into peeling force [cN / 25mm].

At the time of the measurement, a polyester sheet having a thickness of 190 μm and a size of 25 mm × 170 mm was prepared as a holding part of the measurement sample, and the end of the 150 mm × 25 mm test piece was affixed with a cellophane tape having a width of 15 mm. And the holding part at the time of a measurement. The measurement was performed three times for one sample, and the average value was taken as the peel force of the sample.

(5) Measurement of average surface roughness

Using a contact three-dimensional center surface roughness meter (model ET-30HK) manufactured by Kosaka Corporation, the center surface average roughness (SRa) of the surface of the release layer was measured by the styling method under the following conditions. The conditions were as follows and the average value of 3 measurements was made into the value.

Hand tip radius: 0.5 μm

Hand pressure: 20 mg

Cutoff value: 80 μm

Measuring length: 1000 ㎛

Measuring speed: 100 μm / sec

Measuring thickness: 2 ㎛

(6) handleability

The obtained film was made into rolls, and when the film was taken out of the rolls, the ones having small resistance of the film were ○ and the larger ones.

Example 1

(Preparation of base layer)

100 weight% of polypropylene resin (Sumitomo Chemical Co., Ltd. make: FS2011DG3, MFR: 2.5 g / 10min) was melt-extruded with the 90 mm diameter single screw extruder, and it was set as the base material layer.

(Production of adhesive layer)

Polypropylene resin (Sumitomo Chemical Co., Ltd. make) with respect to 100 weight part of styrene-type elastomers (Asahi Kasei Chemicals make: Taftec (trademark) H1221, styrene copolymerization ratio 12 weight%, MFR: 4.5 g / 10min): A mixture of 8.8 parts by weight of FS2011DG3 and MFR: 2.5 g / 10 min) and 8.8 parts by weight of a petroleum resin (Arakawa Chemical Industries, Ltd .: Alcon® P125) were melt-extruded with a 40 mmφ single screw extruder to form an adhesive layer. .

(Production of release layer)

100 weight% of the propylene ethylene block copolymer (made by Nippon Polypro: BC4FC) was melt-extruded with the 65 mm single screw extruder, and it was set as the release layer.

(Production of film)

The laminated extrusion was performed in 250 degreeC three-layer T die (feedblock type, 850 mm in width, 1 mm in lip gap) as the base material layer, the adhesion layer, and the release layer melted with each extruder. The extruded film was transferred to a casting roll at a temperature of 30 ° C. at a rate of 20 m / min, cooled and solidified, and the three kinds of three-layer unstretched films having a substrate layer thickness of 18 μm, an adhesive layer thickness of 6 μm, and a release layer thickness of 6 μm. Got.

[Example 2]

The adhesion layer and the release layer changed the base material layer into the following content as it was in Example 1, and obtained the unstretched film of three types and three layers by the manufacturing method similar to Example 1.

(Preparation of base layer)

100% by weight of the homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, MFR: 7.5 g / 10 min) was melt extruded with a 90 mmφ single screw extruder to obtain a base layer.

[Example 3]

The base material layer and the mold release layer changed the adhesion layer into the following content as it was in Example 1, and obtained the unstretched film of three types and three layers by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. make: Alcon P125) 3.2 with respect to 100 weight part of styrene-type elastomers (Asahi Kasei Chemicals make: Taftec H1221, styrene copolymerization ratio 12 weight%, MFR: 4.5 g / 10min) 3.2 A mixture of parts by weight and 3.2 parts by weight of polypropylene-based resin (manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min) was melt-extruded with a 40 mm single screw extruder to obtain an adhesive layer.

Example 4

As for the base material layer and the release layer, the adhesion layer was changed into the following content as it was in Example 1, and the three types and three unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. make: Alcon P125) 8.8 with respect to 100 parts by weight of styrene-based elastomer (Asahi Kasei Chemicals: Taftech H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) A mixture of parts by weight and 8.8 parts by weight of polypropylene-based resin (manufactured by Sumitomo Chemical Co., Ltd .: WF836DG3 :, MFR: 7.0 g / 10 min) was melt-extruded with a 40 mm single screw extruder to obtain an adhesive layer.

[Example 5]

As for the release layer, the base material layer and the adhesion layer were changed into the following content as it was in Example 1, and the three types and three layers of unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. product: Alcon P125) 5.7 with respect to 100 weight part of styrene-type elastomers (Asahi Kasei Chemicals make: Taftec H1221, styrene copolymerization ratio 12 weight%, MFR: 4.5 g / 10min) 5.7 A mixture of 8.0 parts by weight of a polypropylene-based resin (manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min) was melt-extruded with a 40 mmφ single screw extruder to obtain an adhesive layer.

(Preparation of base layer)

100% by weight of a homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, MFR: 7.5 g / 10 min) was melt-extruded with a 90 mmφ single screw extruder to obtain a base layer.

Comparative Example 1

As for the base material layer and the release layer, the adhesion layer was changed into the following content as it was in Example 1, and the three types and three unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. make: Alcon P125) 17.6 with respect to 100 parts by weight of styrene-based elastomer (Asahi Kasei Chemicals: Taphtec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) A mixture of parts by weight was melt extruded with a 40 mmφ single screw extruder to obtain an adhesive layer.

Comparative Example 2

As for the base material layer and the release layer, the adhesion layer was changed into the following content as it was in Example 1, and the three types and three unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. make: Alcon P125) 21.4 with respect to 100 weight part of styrene-type elastomers (Asahi Kasei Chemicals make: Taftec H1221, styrene copolymerization ratio 12 weight%, MFR: 4.5 g / 10min) 21.4 A mixture of parts by weight and 21.4 parts by weight of polypropylene-based resin (manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min) was melt-extruded with a 40 mm single screw extruder to obtain an adhesive layer.

[Comparative Example 3]

As for the base material layer and the release layer, the adhesion layer was changed into the following content as it was in Example 1, and the three types and three unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Polypropylene resin (Sumitomo Chemical Co., Ltd. make: FS2011DG3, MFR :) with respect to 100 weight part of styrene-type elastomers (made by Asahi Kasei Chemicals: Taftec H1221, styrene copolymerization ratio 12 weight%, MFR: 4.5 g / 10min) 2.5 g / 10 min) 17.6 parts by weight of the mixture was melt-extruded with a 40 mmφ single screw extruder to obtain an adhesive layer.

[Comparative Example 4]

As for the release layer, the adhesion layer and the base material layer were changed into the following content as it was in Example 1, and the three types and three unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. make: Alcon P125) 17.6 with respect to 100 parts by weight of styrene-based elastomer (Asahi Kasei Chemicals: Taphtec H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g / 10 min) A mixture of parts by weight was melt extruded with a 40 mmφ single screw extruder to obtain an adhesive layer.

(Preparation of base layer)

100% by weight of the homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, MFR: 7.5 g / 10 min) was melt extruded with a 90 mmφ single screw extruder to obtain a base layer.

[Comparative Example 5]

As for the base material layer and the release layer, the adhesion layer was changed into the following content as it was in Example 1, and the three types and three unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. make: Alcon P125) 6.4 with respect to 100 weight part of styrene-type elastomers (Asahi Kasei Chemicals make: Taftec H1221, styrene copolymerization ratio 12 weight%, MFR: 4.5 g / 10min) 6.4 A mixture of parts by weight was melt extruded with a 40 mmφ single screw extruder to obtain an adhesive layer.

[Comparative Example 6]

As for the base material layer and the release layer, the adhesion layer was changed into the following content as it was in Example 1, and the three types and three unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. make: Alcon P125) 6.3 with respect to 100 weight part of styrene-type elastomers (Asahi Kasei Chemicals make: Taftec H1221, styrene copolymerization ratio 12 weight%, MFR: 4.5 g / 10min) 6.3 A mixture of parts by weight and 18.8 parts by weight of polypropylene-based resin (manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min) was melt-extruded with a 40 mm single screw extruder to obtain an adhesive layer.

[Comparative Example 7]

As for the base material layer and the release layer, the adhesion layer was changed into the following content as it was in Example 1, and the three types and three unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. make: Alcon P125) 18.8 parts by weight of 100 parts by weight of a styrene-based elastomer (Asahi Kasei Chemicals: Taftec H1221, styrene copolymerization ratio 12% by weight, MFR: 4.5 g / 10 min) A mixture of parts by weight and 6.3 parts by weight of polypropylene-based resin (manufactured by Sumitomo Chemical Co., Ltd .: WF836DG3, MFR: 7.0 g / 10 min) was melt-extruded with a 40 mm diameter single screw extruder to obtain an adhesive layer.

[Comparative Example 8]

As for the base material layer and the release layer, the adhesion layer was changed into the following content as it was in Example 1, and the three types and three unstretched films were obtained by the manufacturing method similar to Example 1.

(Production of adhesive layer)

Petroleum resin (Arakawa Chemical Co., Ltd. make: Alcon P125) 8.8 with respect to 100 parts by weight of styrene-based elastomer (Asahi Kasei Chemicals: Taftec H1062, styrene copolymerization ratio 18 wt%, MFR: 4.5 g / 10 min) A mixture of parts by weight and 8.8 parts by weight of polypropylene-based resin (manufactured by Sumitomo Chemical Co., Ltd .: FS2011DG3, MFR: 2.5 g / 10 min) was melt-extruded with a 40 mm single screw extruder to obtain an adhesive layer.

The results are shown in Tables 1, 2, and 3 below.

As apparent from Table 1, the films obtained in Examples 1 to 5 had good stretchability at the time of film forming, had sufficient adhesive strength in practical use when used as a protective film, and had good handleability when the film was used as a roll.

On the other hand, the films obtained in Comparative Examples 1, 4, and 7 had insufficient stretchability at the time of film forming, and the adhesive layer dripping down, and the film forming property was not necessarily good. Moreover, also about the handleability at the time of using a film as a roll, it was not necessarily favorable. The films obtained in Comparative Examples 2 and 3 and 6 and 8 did not exhibit adhesive force to the prism sheet which is the coating body, and resulted in not having the adhesive force necessary in practical use. The film obtained in the comparative example 5 came to the result which cannot necessarily be said also favorable about the handleability at the time of using a film as a roll. Thus, all the films obtained by the comparative example were inferior in quality, and were low in practical use.

[Industrial Availability]

The adhesive of this invention can be used suitably for the adhesive film for protecting the outer surface of the prism type lens part of the prism sheet especially used for optical use.

It also protects the surface of the automobile body during synthetic resin plates (for building materials), stainless steel plates (for building materials), aluminum plates, decorative plywood, steel sheets, glass plates, home appliances, precision machinery and manufacturing. To protect from scratches when the articles are superimposed, stored, transported or conveyed in the manufacturing process, and when the articles are protected from scratches during secondary processing (eg bending or pressing). It can also be used suitably for E, and it contributes greatly to the industry.

Claims (8)

A styrene component comprising a block copolymer of a styrene polymer block and an olefin polymer block, a block copolymer of a styrene polymer block and a random copolymer block of styrene and an olefin, and / or a hydrogenated substance thereof A resin composition comprising 2 parts by weight or more and less than 10 parts by weight of tackifying resin and 2 parts by weight or more and less than 10 parts by weight of polyolefin resin, based on 100 parts by weight of a styrene-based elastomer having 5 to 15% by weight. Adhesive resin composition. The adhesive resin composition of Claim 1 is laminated | stacked on one side of the base material layer which has polypropylene resin as a main component, The adhesive film characterized by the above-mentioned. The release film is laminated | stacked on the opposite surface to the adhesive layer containing the adhesive resin composition of the base material layer which has polypropylene resin as a main component, The adhesive film of Claim 2 characterized by the above-mentioned. 4. The pressure-sensitive adhesive film according to claim 3, wherein the base layer mainly containing polypropylene-based resin, the pressure-sensitive adhesive layer containing the adhesive resin composition, and the release layer are laminated by co-extrusion. The pressure-sensitive adhesive film according to any one of claims 2 to 4, wherein a melt flow rate (MFR) at 230 ° C. 2.16 kgf of the styrenic elastomer in the pressure-sensitive adhesive layer is 0.5 to 10 g / 10 minutes. The pressure-sensitive adhesive film according to any one of claims 2 to 5, wherein a melt flow rate (MFR) at 230 ° C · 2.16 kgf of the polypropylene resin in the substrate layer is 1.0 to 15 g / 10 minutes. The adhesive film in any one of Claims 2-6 for coating a prism sheet. The adhesive film as described in any one of Claims 2-7 which is self-adhesive.

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