TWI665276B - Composition and laminated body - Google Patents

Abstract

The present invention relates to a composition for providing a laminated body having excellent adhesion characteristics and processing characteristics when adhered to an adherend, and a laminated body composed of the foregoing composition.

A composition characterized in that it satisfies the following conditions 1 and 2.

Condition 1 The shear loss tangent (tanδ _{0 ° C} ) at a frequency of 1 Hz and a temperature of 0 ° _C is 0.20 or more and 0.60 or less.

Condition 2 The shear loss tangent (tan δ _{100 ° C} ) at a frequency of 1 Hz and a temperature of 100 ° _C is 0.40 or more and 0.80 or less.

Description

Composition and laminated body

The present invention relates to a composition and a laminated body composed of the aforementioned composition, and the composition is used to provide a laminated body having excellent adhesion characteristics and processing characteristics when adhered to an adherend.

In order to prevent the products containing synthetic resin, metal, glass and other materials from being damaged or stained during the processing steps, transportation steps, and storage, many materials are used to protect the surface. A typical example of this is a surface protection film, which is generally one in which an adhesive layer is formed on a supporting substrate containing a thermoplastic resin or paper, and the surface is protected by attaching an adhesive layer to an adherend and coating the substrate with the supporting substrate.

Especially in recent years, liquid crystal displays or touch panel devices have become widespread, and these are composed of a plurality of members such as optical sheets and optical films containing synthetic resin. In order to prevent defects such as optical distortion as much as possible for the optical member, a surface protective film is often used in order to prevent a flaw or a stain that may be a source of the defect.

In terms of the characteristics of the surface protective film, it is required that it is not easy to peel from the adherend when it is subjected to external force such as punching processing or due to environmental changes such as temperature and humidity; it can be easily peeled from the adherend. Peeling; In addition, no adhesive remains on the adherend during peeling And adhesive ingredients.

Among the above-mentioned optical members, particularly those having unevenness on the surface of the diffuser plate and the cymbal, for example, after bonding the surface protection film, the contact area between the unevenness portion and the adhesive layer is small. When the external force is fully absorbed and peeled off from the adherend. In this regard, a method of softening the adhesive layer, a method of improving the adhesive force using a thickener, and the like are known (for example, Patent Documents 1 to 4).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-214437

[Patent Document 2] Japanese Patent Laid-Open No. 2005-298630

[Patent Document 3] Japanese Unexamined Patent Publication No. 05-194923

[Patent Document 4] Japanese Patent Application Publication No. 2012-111793

However, in the above-mentioned method, there is a case where the adhesive force increases with time and the peelability deteriorates, and it is difficult to have both peelability and processing characteristics.

The problem of the present invention is to provide a composition and a laminated body composed of the aforementioned composition in view of the above-mentioned problems, and the composition is used to provide a laminated layer having excellent adhesion characteristics and processing characteristics when adhered to an adherend. body.

The inventors of this case have repeatedly worked to solve the above problems As a result of the studies, the following inventions were completed. That is, the present invention is as follows.

1) A composition characterized in that it satisfies the following conditions 1 and 2.

Condition 1 The shear loss tangent (tan δ _{0 ° C} ) at a frequency of 1 Hz and a temperature of 0 ° _C is 0.20 or more and 0.60 or less

Condition 2 The shear loss tangent (tan δ _{100 ° C} ) at a frequency of 1 Hz and a temperature of 100 ° _C is 0.40 or more and 0.80 or less

2) 1) the composition described in respect to the frequency 1Hz, temperature 60 ℃ shear loss tangent (tanδ _{60 ℃),} temperature 100 ℃ and shearing loss tangent (tanδ _{100 ℃),} the composition of the system to meet Condition 3 below.

Condition 3 0.20 ≦ tanδ _{100 ℃} -tanδ _{60 ℃} ≦ 0.60

3) The composition according to 1) or 2), wherein the composition has an endothermic peak in a range of 60 ° C. to 100 ° C. in differential scanning calorimetry.

4) The composition according to any one of 1) to 3), wherein the composition contains at least the following components (1) to (3).

(1) Styrenic elastomer

(2) Propylene · α-olefin copolymer

(3) Adhesive

5) A laminated body comprising a laminated body having an adhesive layer on one side of a substrate, wherein the adhesive layer contains the composition according to any one of 1) to 4).

6) The laminated body according to 5), which is used for surface protection of a sepal.

In view of the above-mentioned problems, according to the present invention, there can be provided a composition for providing a laminated body having excellent adhesion characteristics and processing characteristics when adhered to an adherend, and a laminated body composed of the aforementioned composition.

[Form of Implementing Invention]

Hereinafter, the constituent elements of the composition and the laminated body of the present invention will be described in detail.

<Composition>

The composition of the present invention is characterized by satisfying the following conditions 1 and 2.

Condition 1: The shear loss tangent (tan δ _{0 ° C} ) at a frequency of 1 Hz and a temperature of 0 ° _C is 0.20 or more and 0.60 or less.

Condition 2: The shear loss tangent (tan δ _{100 ° C} ) at a frequency of 1 Hz and a temperature of 100 ° _C is 0.40 or more and 0.80 or less.

By satisfying the above conditions 1 and 2, when the composition of the present invention is used for an adhesive layer for protecting a laminated body of an adherend, good adhesive properties and processing characteristics can be obtained. That is, it has excellent adhesion to the adherend, and it is difficult to peel off during press processing, and it can be easily peeled from the adherend. The tan δ _{0 ° C is} preferably 0.30 to 0.50, and the tan δ _{100 ° C is} preferably 0.50 to 0.80.

Here, the so-called loss tangent refers to a value obtained by dividing a loss modulus obtained by dynamic viscoelasticity measurement by a storage modulus. In addition, the loss modulus refers to the dissipation of energy in the form of heat when stress is applied. Viscous component; storage modulus refers to the elastic component that accumulates energy inside and maintains stress.

In addition, the so-called dynamic viscoelasticity measurement refers to the measurement of the mechanical properties of a sample by imparting a change (vibration) to the sample over time and measuring the resulting stress or deformation. The measurement mode is There are various types such as tensile / compression, shear, and 3-point bending. In the present invention, the loss tangent is at a frequency of 1 Hz and a distortion of 0.01%, and the value measured in the shear mode is an object. The measurement method will be described in detail later.

When the tan δ _{0 ° C is} less than 0.20, the processing characteristics may be reduced, and when it is greater than 0.60, the peelability may be reduced. When the tan δ _{100 ° C is lower} than 0.40, the processing characteristics may be reduced, and when the tan δ is higher than 0.80, the adhesive force may increase with time and the peelability may decrease.

In addition, the composition of the present invention has a difference between a tan delta shear tangent (tanδ _{60 ° C} ) at a frequency of 1 Hz and a temperature of 60 ° C and a tan delta shear tan (tanδ _{100 ° C} ) at a temperature of 100 ° C (tanδ _{100 ° C-} tanδ _{60 ° C} ) It is preferably 0.20 or more and 0.60 or less. It is more preferably 0.30 or more and 0.60 or less, and still more preferably 0.40 or more and 0.60 or less.

When the difference between tanδ _{100 ° C} and tanδ _{60 ° C} (tanδ _{100 ° C-} tanδ _{60 ° C} ) is less than 0.20, the processing characteristics may be reduced, and when it is greater than 0.60, the peelability may be reduced.

The composition of the present invention preferably has an endothermic peak in a range of 60 ° C to 100 ° C in differential scanning calorimetry. The temperature is more preferably in the range of 70 ° C to 100 ° C, and particularly preferably in the range of 70 ° C to 90 ° C. The composition preferably has an endothermic peak. By being above 60 ℃ A temperature range of 100 ° C or lower has an endothermic wave peak. When the composition of the present invention is used to protect an adhesion layer of a laminated body of an adherend, the adhesion characteristics and processing characteristics can be better controlled.

When the endothermic peak is less than 60 ° C, heat resistance may be reduced, and when it exceeds 100 ° C, processing characteristics may be reduced.

The composition of the present invention is not particularly limited as long as it satisfies the conditions 1 and 2 constituting the requirements. However, it is also possible to use a cross connection of acrylic, polysiloxane, or the like, or a non-cross connection of natural rubber, synthetic rubber, or Any material that is pseudo-connected (thermoplastic) is preferably a thermoplastic resin as a main component from the viewpoint of recyclability. Here, the term "using a thermoplastic resin as a main component" means that the proportion of the thermoplastic resin in the composition is 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

The composition of the present invention preferably contains at least a styrene-based elastomer, a propylene · α-olefin copolymer, and a tackifier.

The styrene-based elastic system in the present invention refers to a resin having a structural unit derived from styrene and exhibiting rubber-like elasticity at room temperature. A well-known one can be used, and examples thereof include a styrene-butadiene copolymer (SBR ), Styrene, isoprene, styrene copolymer (SIS), styrene, butadiene, styrene copolymer (SBS), styrene and diene copolymers and their hydrides, such as Styrene, ethylene, butene, styrene copolymer (SEBS), copolymers of styrene and isobutylene, such as styrene, isobutylene, styrene triblock copolymer (SIBS), styrene, isobutylene diblock copolymerization (SIB), or a mixture of these Ene · isobutylene block copolymer, etc. These styrene-based elastomers may be used alone or in combination of two or more. Among the above styrene-based elastomers, hydrogenated styrene · butadiene copolymer (HSBR), styrene · ethylene · butene · styrene copolymer (SEBS), and styrene · isobutylene · styrene triblock copolymer are particularly used. (SIBS), styrene-isobutylene diblock copolymer (SIB), or a mixture thereof is preferred.

The weight average molecular weight of the styrene-based elastomer is preferably in the range of 50,000 to 400,000, and more preferably in the range of 50,000 to 200,000. When the weight-average molecular weight is less than 50,000, the cohesive force of the adhesive layer is reduced, and adhesive residue may occur when it is peeled from the adherend. When it exceeds 400,000, the viscosity may increase and the productivity may decrease.

The styrene content in the styrene-based elastomer is preferably in the range of 5 to 30% by mass, and more preferably in the range of 8 to 20% by mass. When the styrene content is less than 5% by mass, the cohesive force of the adhesive layer is reduced, and adhesive residue may occur when it is peeled from the adherend. When it exceeds 30% by mass, the adhesion to the adherend is reduced. This is a case where the adhesion to the adherend having unevenness is insufficient.

The aforementioned propylene · α-olefin copolymer refers to a copolymer composed of a structural unit derived from propylene, ethylene, and a structural unit derived from an α-olefin. Examples include propylene‧ethylene copolymer, propylene‧1-butene copolymer, propylene‧1-pentene copolymer, propylene‧1-hexene copolymer, propylene‧1-octene copolymer, propylene‧ethylene‧1 -Butene copolymer and the like, but it is not limited thereto. In the present invention, only one kind of propylene · α-olefin copolymer may be used, or two or more kinds may be used in combination.

The aforementioned propylene · α-olefin copolymer preferably has a melting point In the range of 60 ° C to 100 ° C. The temperature is more preferably in the range of 70 ° C to 100 ° C, and particularly preferably in the range of 70 ° C to 90 ° C. The melting point of propylene · α-olefin copolymer can be controlled by changing the type of α-olefin and the copolymerization ratio.

The so-called tackifier is defined in JIS Z0109 (1992). It is a material blended to improve the adhesion of the adhesive layer, and a softening point of 80 to 150 ° C. can be used. For example, petroleum resins, terpene resins, terpene phenol resins, rosin resins, petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic and aromatic copolymers, and alicyclic copolymers can be used. Alkylphenol-based resins, xylene-based resins, or these hydrides are generally used. In the present invention, only one kind of the tackifier may be used, or two or more kinds may be used in combination.

In the composition of the present invention, when the entire composition is 100% by mass, the total content of the styrene-based elastomer, propylene · α-olefin copolymer, and tackifier is preferably 60% by mass or more, and more preferably It is 70% by mass or more, and more preferably 80% by mass or more. When the aforementioned total content is less than 60% by mass, there may be a case where the balance between the adhesion property and the processing property is reduced.

When the entire composition is 100% by mass, the content of the styrene-based elastomer is preferably 40% by mass or more, and more preferably 50% by mass or more. The content of the propylene · α-olefin copolymer is preferably 10% by mass or more, and more preferably 15% by mass or more. The content of the tackifier is preferably 5% by mass or more, and more preferably 10% by mass or more.

To the extent that the object of the present invention is not impaired, the composition of the present invention includes the above-mentioned styrene-based elastomer, propylene · α-olefin copolymer, and In addition to the adhesive, other resin components, additives, and the like may be appropriately added to adjust the adhesion.

As another resin component for adjusting the adhesive force, a resin such as polyolefin can be used, and examples thereof include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, low crystallinity, and non- Crystalline ethylene‧α-olefin copolymers, polypropylene, propylene‧ethylene copolymers (random copolymers and / or block copolymers), propylene‧α-olefins different from the above-mentioned propylene‧α-olefin copolymers Copolymers, propylene‧ethylene‧α-olefin copolymers, ethylene‧ (meth) acrylate copolymers, ethylene‧ (meth) acrylate copolymers, ethylene‧ (butyl) (meth) acrylate copolymers, Ethylene, vinyl acetate copolymers, etc. These resins can be used alone or in combination of two.

When the entire composition is 100% by mass, the total content of other resin components for adjusting the adhesion is preferably 20% by mass or less, and more preferably 10% by mass or less. When the total content of other resin components for adjusting adhesion exceeds 20% by mass, when the composition of the present invention is used to protect an adhesive layer of a laminated body of an adherend, it has both adhesive properties and processing properties. For difficult situations.

As the additive, for example, a slip agent, an antioxidant, a weathering agent, an antistatic agent, an anti-adhesive acceleration inhibitor, or the like can be added. These additives may be used alone or in combination of two or more. When the entire composition is 100% by mass, the total content of the additives is preferably 3% by mass or less, and more preferably 2% by mass or less. In the case where the total content of the additive is more than 3% by mass, there may be a case where the product oozes out from the adhesive layer, causing defects in the product, and a case where the adherend is contaminated.

<Layered body>

The laminated body of the present invention is characterized by a laminated body having an adhesive layer on one side of a substrate, and the adhesive layer includes the aforementioned composition. Hereinafter, the laminated body of this invention is demonstrated in detail.

<Substrate>

The base material constituting the laminated body of the present invention is not particularly limited, and resins such as polyolefin and polyester can be used. Among them, from the viewpoints of productivity and processing suitability, polyolefins are preferred as the main component. Here, the term "mainly containing polyolefin" means that when the entire substrate is 100% by mass, the proportion of polyolefin is 50% by mass or more, and more preferably 70% by mass or more.

Examples of the polyolefin include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, low crystalline or amorphous ethylene · α-olefin copolymer, polypropylene, Propylene‧ethylene copolymer (random copolymer and / or block copolymer), propylene‧α-olefin copolymer, propylene‧ethylene‧α-olefin copolymer, ethylene‧ethyl (meth) acrylate copolymer, ethylene ‧Methyl (meth) acrylate copolymer, ethylene ‧ (butyl) (meth) acrylate copolymer, ethylene ‧ vinyl acetate copolymer, etc. These can be used alone or in combination. The α-olefin is not particularly limited as long as it can be copolymerized with propylene and ethylene, and examples thereof include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1 -Pentene, 1-heptene and the like. Among the above-mentioned polyolefins, it is particularly possible to obtain high-rigidity polypropylene, propylene‧ethylene copolymers (random copolymers and / or block copolymers), propylene‧ethylene‧α-olefin copolymers, and propylene‧α-olefin copolymers. Equal acrylic materials are more preferred.

The melt flow rate (MFR; measured under the conditions of 230 ° C. and 2.16 kg) of the polyolefin mainly used in the substrate of the present invention is preferably in the range of 2 to 30 g / min, particularly preferably in the range of 5 to 30 g / min. When the MFR is less than 2 g / minute, productivity may be reduced due to excessively high melt viscosity. Moreover, when MFR is larger than 30 g / min, a base material may become brittle, and it may become difficult to handle at the time of manufacture of a laminated body, and use.

The substrate in the present invention may be composed of two or more layers.

In addition, to the composition constituting the substrate of the present invention, a lubricant, an antioxidant, a weathering agent, an antistatic agent, and a crystal nucleating agent (crystal nucleating agent) may be appropriately added within a range that does not impair the characteristics of the laminated body of the present invention. agents), pigments and other additives.

The thickness of the substrate can be appropriately adjusted in accordance with the required characteristics of the laminate, and is preferably 5 to 200 μm, more preferably 10 to 100 μm, and particularly preferably 10 to 80 μm. When it is thinner than 5 μm, it may have insufficient strength, may be difficult to transport in the manufacturing step, and may crack during processing and use. When the thickness is more than 200 μm, the transparency of the film may be insufficient or the productivity may be reduced.

<Adhesive layer>

The above-mentioned composition is preferably used as the adhesive layer constituting the laminated body of the present invention.

The thickness of the adhesive layer of the present invention can be appropriately adjusted according to the material, thickness, surface shape, and required degree of the adherend, preferably 1 to 20 μm, further preferably 2 to 10 μm, and particularly preferably 2 to 8 μm. When the thickness of the adhesive layer is less than 1 μm, it may not be possible to exhibit sufficient adhesion to the adherend; when it is larger than 20 μm, the adhesive force may be too large and the productivity may be reduced.

<Release layer>

The laminated system of the present invention has at least a laminated body of a base material and an adhesive layer, and a preferred aspect thereof is to form a three-layer laminated structure by providing a release layer on a surface of the base material opposite to the side of the adhesive layer. The material, thickness, and surface shape of the release layer may be selected and adjusted based on the viewpoints of the adhesive force of the adhesive layer, processing suitability of the laminated body during manufacture, and use, and techniques known in this field may be used. From the viewpoint of good mold release control, it is preferable to mainly use a propylene resin containing 0.5% to 10% by mass of a fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group. Make up.

The propylene-based resin may be the same as or different from the propylene-based resin constituting the substrate described above, and the surface roughness of the release layer described later is roughened to 3.0 μm or more in terms of Rz, A copolymer containing at least 20% by mass or more of propylene and ethylene and / or an α-olefin is preferred. When the propylene polymer is a copolymer with ethylene and / or α-olefin, the more the monomer content, the lower the melting point of the copolymer. From the viewpoint of easy co-extrusion and low-temperature extrusion, the more Preferably, the monomer content is in the range of 3 to 7 mass%. In addition, in the case where heat resistance is to be imparted to the release layer, it may be appropriately selected so that the monomer content can be reduced and desired heat resistance can be obtained.

The MFR of the propylene resin at 230 ° C is preferably in the range of 3 to 40 g / 10 minutes. In particular, those having an MFR in the range of 10 to 40 g / 10 minutes can be extruded at a low temperature. Furthermore, by combining with a low-density polyethylene, it is easy to roughen the release layer, so it is more preferable.

In addition, in order to roughen the release layer, it is preferably contained to A high-pressure process low-density polyethylene having 4 mass% less compatibility with the aforementioned propylene resin.

The mold release layer is preferably made of a propylene resin containing 0.5 to 10% by mass of a fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group. Examples of the fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group include, as the monomer (a), a (meth) acrylic acid ester having a perfluoroalkyl group having 1 to 18 carbon atoms, and a monomer described later may be used. (b) A copolymer obtained by copolymerizing a (meth) acrylate having a polyoxyethylene group with the monomer (c).

The perfluoroalkyl group as the monomer (a) is preferably 1 to 18 carbon atoms, and more preferably 1 to 6 carbon atoms. The perfluoroalkyl group may be linear or branched. These may be used alone or in combination of two or more.

This (meth) acrylic acid ester having a perfluoroalkyl group is sold by Kyoeisha Chemical Co., Ltd. or the like, or can be synthesized by a known method using a commercially available fluorine-containing compound as a raw material.

As the polyoxyethylene-containing monomer (b), it is preferable to have a structure in which 1 to 30 oxyethylene units (-CH ₂ -CH ₂ -O-) are connected in succession, and the unit has 1 to 30 in particular. Twenty is better. In addition, the chain may contain an oxypropylene unit (-CH ₂ -CH (CH ₃ ) -O-). As a preferred example, a polyethylene glycol monomethacrylate having eight oxyethylene units and the like can be exemplified. The monomer (b) may be used alone or in combination of two or more.

In addition, as another monomer (c) containing polyoxyethylene group, it is a di (meth) acrylate having a structure in which 1 to 30 oxyethylene units are connected successively and having double bonds at both ends. As better Specific examples include polyethylene glycol dimethacrylate having a chain number of 8, and the like. This monomer (c) may be used alone or in combination of two or more.

The ratio of each of the monomer (a), the monomer (b), and the monomer (c) is preferably 1 to 80% by mass and 1 to 80% by mass of the monomer (a). 80% by mass, and the monomer (c) is 1 to 50% by mass.

In addition, in addition to the above-mentioned three monomers, the above-mentioned fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group can be copolymerized in a range of less than 50% by mass of a monomer that can be copolymerized with these. Examples of the monomer include methylene, vinyl acetate, vinyl chloride, ethylene fluoride, vinyl halide, styrene, methylstyrene, (meth) acrylic acid and its ester, and (meth) acrylic acid. Amine monomer, (meth) allyl monomer, and the like.

The polymerization method used to obtain the above-mentioned fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group by using the above monomers may be any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the heat is removed. In addition to polymerization, photopolymerization and energy ray polymerization can also be used.

As the polymerization initiator, existing organic azo compounds, peroxides, persulfates, and the like can be used.

The weight average molecular weight of the fluorine-containing compound used in the present invention is preferably 1,000 to 100,000, and particularly preferably 5,000 to 20,000. The weight average molecular weight can be adjusted with a polymer chain transfer agent such as thiol, mercaptan, or α-methylstyrene.

The proportion of the fluorine-containing compound in the release layer of the present invention is preferably 0.5% by mass to 10% by mass. When it is less than 0.5% by mass, adhesion to the adhesive layer is likely to occur, and it is difficult to obtain a desired winding force. shape. When it is desired to contain more than 10% by mass, it is difficult to blend uniformly because the solubility in the resin is low. In addition, during melt extrusion, the propylene-based resin constituting the release layer is subjected to the fluorine-containing compound. In some cases, it may slide along the extrusion screw and may not be discharged uniformly.

In addition, in addition to the fluorine-containing compound, the release layer of the present invention preferably contains inorganic or organic particles having an average particle diameter of 1 to 20 μm in an amount of 0.1% to 10% by mass. From the viewpoint of smoothness and blocking properties, it is particularly preferable that the average particle diameter of the inorganic or organic particles is 3 to 15 μm and a larger particle diameter.

Examples of the inorganic particles include silica, calcium carbonate, magnesium carbonate, titanium oxide, clay, talc, magnesium hydroxide, aluminum hydroxide, and zeolite. Among them, silica is more preferred.

Examples of the organic particles include polystyrene and polymethyl methacrylate.

With the multiplier effect of the surface roughness of the fluorine-containing compound, inorganic or organic particles, and a release layer described later, it is easier to obtain blocking, and good rollability.

The surface roughness of the release layer of the present invention is preferably such that the ten-point average roughness (Rz) is 3 μm or more. When Rz is less than 3 μm, wrinkles are likely to occur when rolled into a roll shape in the manufacturing process of a laminated body, and quality may be deteriorated. This surface roughness can be achieved by a method of mixing and adding a small amount of a main propylene-based resin, such as the aforementioned ethylene-based resin lacking compatibility.

<Manufacturing method of laminated body>

Next, the manufacturing method of the laminated body of this invention is demonstrated.

The manufacturing method of the laminated body of this invention is not specifically limited, For example, when it consists of three laminated layers of a base material, an adhesive layer, and a mold release layer, the resin composition which comprises each can be mentioned in a separate extruder. A so-called co-extrusion method in which melt extrusion is performed to integrate layers in a nozzle; a method in which the above-mentioned base material, adhesive layer, and release layer are individually melt-extruded and then laminated by a lamination method, etc. From the viewpoint of productivity, it is preferably produced by a coextrusion method. As for the co-extrusion method, a well-known method such as an inflation method and a T-die method can be used, and from the viewpoint of excellent thickness accuracy or control of the surface shape, a hot melt co-extrusion method using a T-die method is particularly preferred.

Here, if the tackifier is uniformly mixed with a styrene-based elastomer and / or a propylene α-olefin copolymer beforehand, and is master pelletized, the resin constituting the adhesive layer may be melt-extruded. It is preferable to obtain a uniform adhesive layer easily. The content of the tackifier in the masterbatch can be appropriately adjusted according to the physical properties of the tackifier and the resin to be mixed. From the viewpoint of productivity, it is preferably 30% by mass or more, more preferably 40% by mass or more.

<Application example>

The laminated body composed of the composition of the present invention can be used as a surface protective film for preventing scratches during the manufacture, processing, and transportation of synthetic resin plates, metal plates, and glass plates, and for preventing the adhesion of dirt, and is particularly suitable for having Concavo-convex adherend. For example, a diffuser plate or a cymbal used for a display member made of a synthetic resin, and the laminated body composed of the composition of the present invention is particularly preferably used for surface protection of a cymbal.

The cymbals protected by the laminated body composed of the composition of the present invention are those in which triangular columnar cymbals are arranged parallel to the surface of the sheet on one side of the sheet, and the ridge line is the outer surface. The materials that make up 稜鏡 It is specifically limited to use a light-transmitting resin, and examples thereof include acrylic resins and polycarbonates. The distance between the adjacent edges of is preferably 10 to 1,000 μm, and more preferably 10 to 300 μm. The height of 长度 (the length of the perpendicular from the bottom of the triangular column to the ridgeline) is preferably 5 to 200 μm, and more preferably 10 to 100 μm. In addition, the cymbals protected by the present invention may be composed of only cymbals of the same shape, or of two or more different types of cymbals. In the case of 稜鏡 with different shapes, for example, 稜鏡 with different heights are arranged alternately one by one, or 1 large 稜鏡 is alternately arranged with a plurality of small 稜鏡, and it may be appropriately designed according to the purpose. .

[Example]

Hereinafter, the present invention will be further specifically described based on examples, but the present invention is not limited to these examples. The measurement and evaluation of various physical properties are performed according to the following methods.

(1) Determination of dynamic viscoelasticity

The resins constituting the compositions illustrated in the examples and comparative examples were blended at a specified mixing ratio, and kneaded for 15 minutes at a temperature of 200 ° C and a number of revolutions of 20 rpm using LABO PLASTOMILL 100MR3 manufactured by Toyo Seiki Seisakusho. Next, the obtained kneaded product was melt-molded to a thickness of 2 mm, and was evaluated in a shear mode using a rheometer AR2000ex manufactured by TA Instriments, at a temperature of -80 to 120 ° C, a heating rate of 3 ° C / min, a frequency of 1 Hz, and a deformation of 0.01%. Viscoelasticity of the composition. From the obtained results, the loss tangent at 100 ° C (tanδ _{100 ° C} ), the loss tangent at 0 ° C (tanδ _{0 ° C} ), the difference between the loss tangent at 60 ° C and the loss tangent at 100 ° C (tanδ _{100 ° C-} tanδ) _{60 ° C} ).

(2) Differential scanning calorimetry

After the compositions exemplified in the examples and comparative examples were kneaded in the same manner as in the above (1), the obtained kneaded materials were melt-molded to a thickness of 50 μm, and further weighed 5 mg as a measurement sample. Thereafter, the sample was taken and placed on an aluminum plate, and a differential scanning calorimeter (SEIKO Electronics Industry RDC220) was used to raise the temperature from room temperature to 40 ° C / minute to 230 ° C under a nitrogen atmosphere, and held at 230 ° C for 5 minutes. After that, the temperature was lowered to 20 ° C at 40 ° C / min, and the temperature was maintained at 40 ° C for 5 minutes. Thereafter, the temperature was further increased to 230 ° C at 40 ° C / minute, and the endothermic peak temperature (T _m ) obtained at this time was confirmed.

(3) Lamination of sepals

The laminated bodies obtained in the examples and comparative examples were bonded to a cymbal with a thickness of 160 μm and a surface roughness (Rz) of 27 μm using a roller press (special pressure bonding roller of Yasuda Seiki Seisakusho Co., Ltd.) under the condition of 0.35 MPa. .

(4) Peelability

After the sample obtained in the above (3) was stored at a temperature of 23 ° C and a relative humidity of 50% for one week, a tensile tester (ORIENTEC (Tensilon) universal tester) was used at a tensile speed of 300 mm / Min, peeling angle 180 °, peeling force (S) was measured, and peelability was evaluated according to the following criteria.

5: 0.02N / 25mm ≦ S ≦ 0.08N / 25mm

3: 0.08N / 25mm <S ≦ 0.12N / 25mm

1: S <0.02N / 25mm, or S> 0.12N / 25mm.

(5) Processing characteristics

Visually observe the bonding state of the cymbals and the laminated body after the following treatment: After the sample obtained in the above (3) is stored at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, it is processed with a Thomson type punching tool. Die-cut, stored for one week immediately after stamping and at a temperature of 40 ° C and a relative humidity of 50% ; And evaluated based on the following criteria.

5: Immediately after pressing and after storage at 40 ° C for 1 week, no peeling was observed at all.

4: No peeling was observed at all immediately after punching, but there was very slight peeling at the rear end after storage at 40 ° C for 1 week

3: Immediately after the stamping and after storage at 40 ° C for 1 week, the ends are very slightly peeled off.

2: After storage at 40 ° C for 1 week, 1/2 or more of the entire length around the end sample is peeled off

1: Immediately after punching, the entire length around the end sample is peeled off by more than 1/2.

(Composition)

Prepare the following materials A to E, X to Z, and S as shown in Examples 1 to 5 and Comparative Examples 1 to 4, and perform dynamic viscoelasticity measurement as shown in (1) and (2) above. Differential scanning calorimetry. The results are shown in Table 1.

(Example 1)

Composition A: 14% by mass of SEBS (Tuftec H1052, manufactured by Asahi Kasei Chemicals) and 30% by mass of HSBR (1321P, manufactured by JSR) were used as styrene-based elastomers; 20% by mass of propylene ‧ 1-butene copolymer (Tafmer, manufactured by Mitsui Chemicals) XM-7080 (melting point: 83 ° C.) was used as a propylene · α-olefin copolymer; 36% by mass of a hydrogenated terpene phenol (YS Polyster TH130 manufactured by Yasuhara Chemical) was used as a tackifier.

The 50% by mass master batch of the hydrogenated terpene phenol is obtained by granulating 50% by mass of the hydrogenated terpene phenol and 50% by mass of the SEBS with a biaxial extruder.

(Example 2)

Composition B: Except the use of 8% by mass of SEBS (Asahi Kasei Chemicals Tuftec H1052), 27% by mass HSBR (1321P made by JSR), 25% by mass propylene‧1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C), and 40% by mass of hydrogenated terpene phenol (Yasuhara Except for 50% by mass of master batches of YS Polyster TH130 (manufactured by Chemical Co., Ltd.), it was carried out in the same manner as in Composition A.

(Example 3)

Composition C: The same procedure as in Composition B was performed except that a propylene‧1-butene copolymer (Tafmer XM-7070 manufactured by Mitsui Chemicals, melting point: 75 ° C) was used as the propylene · α-olefin copolymer.

(Example 4)

Composition D: Except 14% by mass of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynaron 1321P manufactured by JSR), 10% by mass of propylene ‧ 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C), 36% by mass of hydrogenated terpene phenol (YS Polyster TH130 manufactured by Yasuhara Chemical), 50% by mass master batch, 10% by mass of 921 kg / m ³ , and a MFR at 190 ° C of 5 g / min. Except for the polymerization of polyethylene (LLDPE), it was carried out in the same manner as in Composition A.

(Example 5)

Composition E: Except using 25% by mass of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynaron 1321P manufactured by JSR), 10% by mass of propylene ‧ 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point) 83 ° C), 20% by mass of 50% by mass master batch of hydrogenated terpene phenol (YS Polyster TH130 manufactured by Yasuhara Chemical), 15% by mass of resin mainly composed of amorphous polypropylene (Tafthren T3712 manufactured by Sumitomo Chemical), and Composition A was performed in the same manner.

(Comparative example 1)

Composition X: Except 50% by mass of 15% by mass of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynaron 1321P manufactured by JSR), and 30% by mass of hydrogenated terpene phenol (YS Polyster TH130, manufactured by Yasuhara Chemical) Except for the pellets and 25% by mass of the same LLDPE as those used by the user in Example 4, the same procedure was performed as in Composition A.

(Comparative example 2)

Composition Y: It carried out similarly to composition A except using 50 mass% of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals) and 50 mass% of HSBR (Dynaron 1321P manufactured by JSR).

(Comparative example 3)

Composition Z: Except the use of 70% by mass propylene‧1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point: 83 ° C), and 30% by mass of resin mainly composed of amorphous polypropylene (Tafthren T3712 manufactured by Sumitomo Chemical) ) Was carried out in the same manner as in Composition A.

(Comparative Example 4)

Composition S: Except using 35% by mass of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals), 35% by mass of HSBR (Dynaron 1321P manufactured by JSR), and 30% by mass of a resin composed mainly of amorphous polypropylene (Tafthren T3712, manufactured by Sumitomo Chemical) It is carried out in the same manner as in Composition A.

(Laminated body)

As shown in the following Examples and Comparative Examples, a laminated body was prepared and evaluated. The evaluation results are shown in Table 2.

(Example 1 ')

The constituent resin of each layer was prepared as follows.

Adhesive layer: Composition A shown in Example 1 was used.

Substrate: A commercially available average polypropylene having an MFR of 5 g / 10 minutes measured at 230 ° C was used.

Mold release layer: Except for 45% by mass of the same polypropylene as the user of the substrate, 24% by mass of propylene-ethylene · random copolymer (Methylene content: 5 mass) measured at 230 ° C with an MFR of 5 g / 10 min. %), 6 mass% Low-density polyethylene having a MFR measured at 190 ° C of 2 g / 10 minutes and a density of 919 kg / m ³ , prepared in advance in 90 mass% of the above-mentioned homopolypropylene containing an average particle diameter of 4 mass% A mixed composition of 11 μm silica, 6% by mass of a fluoro compound having a polyfluorocarbon group and polyoxyethylene group was used as a master batch, and 25% by mass was uniformly mixed with a Henschel mixer.

Among them, a fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group is used; a C ₆ F ₁₃ acrylic perfluoroalkyl ester (CH ₂ = CHCOOC ₂ H ₄ C ₆ ) having 25% by mass as a monomer (a). F ₁₃ ), 50% by mass of the ethylene oxide repeating unit as the monomer (b), 8 polyethylene glycol monoacrylates {CH ₂ = CHCOO (CH ₂ CH ₂ O) ₈ H}, and 25% by mass as Polyethylene glycol dimethacrylate with 8 ethylene oxide repeating units in monomer (c) {CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₈ COC (CH ₃ ) = CH ₂ } Using trifluorotoluene as a solvent, 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and lauryl mercaptan as a chain transfer agent. Polymerization was carried out at 60 ° C for 5 hours while stirring under a nitrogen stream, followed by precipitation in methanol, filtration, and drying under reduced pressure.

Next, the constituent resin of each layer is charged Adjust the diameter of each extruder of the multi-manifold T-die composite film making machine with a nozzle width of 2,400 mm in three extruders of φ115 mm (for substrates), φ90 mm (for adhesive layers), and φ65 mm (for release layers) The discharge amount of each extruder was set to 12.5% of the thickness of the adhesive layer, 8.5% of the thickness of the release layer, and 79% of the thickness of the substrate, and then extruded from the compound T die at an extrusion temperature of 200 ° C. Then, a three-layer laminated film having a film thickness of 40 μm was molded. Then, after bonding to the cymbals, the peelability and processing characteristics were evaluated.

(Example 2 ')

A laminated body was produced in the same manner as in Example 1 'except that the composition B shown in Example 2 was used as the adhesive layer, and evaluated.

(Example 3 ')

A laminated body was produced in the same manner as in Example 1 'except that the composition C shown in Example 3 was used as the adhesive layer, and evaluation was performed.

(Example 4 ')

A laminated body was produced in the same manner as in Example 1 'except that the composition D shown in Example 4 was used as the adhesive layer, and evaluated.

(Example 5 ')

A laminated body was produced in the same manner as in Example 1 'except that the composition E shown in Example 5 was used as the adhesive layer, and evaluated.

(Comparative Example 1 ')

A laminated body was produced in the same manner as in Example 1 'except that the composition X shown in Comparative Example 1 was used as the adhesive layer, and evaluated.

(Comparative Example 2 ')

A laminated body was prepared in the same manner as in Example 1 'except that the composition Y shown in Comparative Example 2 was used as the adhesive layer, and evaluated.

(Comparative Example 3 ')

A laminated body was produced in the same manner as in Example 1 'except that the composition Z shown in Comparative Example 3 was used as the adhesive layer, and evaluated.

(Comparative Example 4 ')

A laminated body was produced in the same manner as in Example 1 'except that the composition S shown in Comparative Example 4 was used as the adhesive layer, and evaluated.

The laminates of Examples 1 'to 5' that satisfy the requirements of the present invention have excellent peelability and processing characteristics. On the other hand, Comparative Examples 1 'to 4' that do not satisfy the requirements of the present invention have peelability or processing characteristics as a result. Worse.

[Industrial availability]

The composition and the laminated body of the present invention can be used not only as a surface protection film for preventing scratches or stains on adherends having unevenness on the surface, but also as various materials such as synthetic resins, metals, and glass. The surface protection film used in various products.

Claims (4)

A composition characterized in that it contains at least the following components (1) to (3): (1) a styrene-based elastomer (2) a propylene · α-olefin copolymer (3) a tackifier; and An object has endothermic peaks in the range of 60 ° C to 100 ° C in differential scanning calorimetry, and the following conditions 1 and 2 are satisfied: Condition 1 The shear loss tangent (tanδ _{0 ° C} ) of frequency 1Hz and temperature 0 ° _C is 0.20 or more 0.60 or less; Condition 2 The shear loss tangent (tan δ _{100 ° C} ) at a frequency of 1 Hz and a temperature of 100 ° _C is 0.40 or more and 0.80 or less. For example, if the composition of claim 1 relates to a shear loss tangent (tanδ _{60 ° C} ) at a frequency of 1 Hz and a temperature of 60 ° _C , and a shear loss tangent (tanδ _{100 ° C} ) at a temperature of 100 ° _C , the composition satisfies the following Condition 3; Condition 3 0.20 ≦ tanδ _{100 ° C} -tanδ _{60 ° C} ≦ 0.60. A laminated body is a laminated body having an adhesive layer on one side of a substrate, and the adhesive layer contains the composition as claimed in claim 1 or 2. The laminated body of claim 3 is used for the surface protection of cymbals.