TW201615786A - Composition and laminate - Google Patents

Abstract

The present invention relates to a composition for providing a laminate that has a surface shape exhibiting excellent adhesion properties when the laminate is adhered onto various adherends, and that hardly causes contamination on adherends even when the laminate is stored under severe conditions of high temperature and pressure, as well as a laminate formed from the composition. Provided is a composition characterized by satisfying the following condition 1. Condition 1: the temperature variance of the loss tangent of the dynamic viscoelasticity has at least two maxima within the range from -50 DEG C to 50 DEG C, where the temperature variance is measured at a frequency of 1 Hz and at a distortion of 0.01 %.

Description

Composition and laminate

The present invention relates to an adhesive property for providing a wide variety of adherends in a surface shape, and is not easily contaminated by adherends when stored under severe conditions of high temperature and high pressure. The composition of the laminate and the laminate composed of the above composition.

A product containing various materials such as synthetic resin, metal, glass, etc., is used to prevent the processing steps, the transporting steps, and the scars or dirt generated during storage, and is often applied to a material for protecting the surface. A representative example thereof is a surface protective film which is generally used to form an adhesive layer on a support substrate comprising a thermoplastic resin or paper, and the surface is protected by attaching the adhesive layer to the adherend and coating the support substrate.

In particular, in recent years, liquid crystal displays or touch panel devices have become popular, and these are composed of a plurality of optical sheets or optical films including synthetic resins. The optical member is required to minimize defects such as optical distortion, and a surface protective film is often used in order to prevent scratches or dirt which may be a source of defects.

The properties of the surface protective film are not easily peeled off by the adherend due to environmental changes or micro stresses such as temperature and humidity; and when the adherend is peeled off, the adhesive and the adhesive remain in the adherend. Ingredients, etc.

Among the optical members, such as a member having irregularities on the surface such as a diffusion plate or a cymbal sheet, the adhesion layer has insufficient followability to the uneven portion after bonding the surface protective film, and the desired adhesive force is not obtained, but occurs. The situation of stripping. In view of this, a method of softening the adhesive layer or a method of using a tackifier to improve the adhesion is known (for example, Patent Documents 1 to 5).

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2008-214437

Patent Document 2 Japanese Patent Laid-Open Publication No. 2005-298630

Patent Document 3 Japanese Patent Laid-Open Publication No. 2012-77244

Patent Document 4 Japanese Patent Publication No. 05-194923

Patent Document 5 Japanese Patent Laid-Open Publication No. 2012-111793

However, in the above method, there is a case where the adhesion is increased over time and the peeling property is deteriorated. Further, when it is stored in a state where high temperature or pressure is applied, the peeling property is also deteriorated. Furthermore, at the time of peeling, there is a case where the adhesive layer component adheres to the surface of the adherend and becomes a source of contamination.

The present invention has been made in view of the above problems, and provides an adhesive property for providing various types of adherends having irregularities on a surface, and is also difficult to adhere to when being stored under severe conditions of high temperature and high pressure. A composition of a contaminated laminate and a laminate comprising the above composition.

The inventors of the present invention have completed the following inventions in order to solve the above problems and strive to repeat the research. That is, the present invention is as follows.

1) A composition characterized by satisfying the following condition 1: Condition 1 The temperature dispersion of the dynamic viscoelasticity measured at a frequency of 1 Hz and a strain of 0.01%, and having a temperature range of -50 ° C or more and 50 ° C or less At least 2 maxima.

2) The composition according to 1), wherein the composition satisfies the following condition 2: Condition 2: The maximum value of the temperature at which the loss tangent is dispersed on the high temperature side is 0.1 or more and 1.0 or less.

3) The composition according to 1) or 2), wherein the composition satisfies the following condition 3: Condition 3: The maximum value of the temperature at which the loss tangent is dispersed on the high temperature side is 0.3 or more and 1.0 or less.

According to the present invention, in view of the above problems, it is possible to provide a proper adhesive property for providing various types of adherends having irregularities on the surface, and it is also difficult to be stored under severe conditions of high temperature and high pressure. A composition of a layered body in which a sticky substance is contaminated, and a layered body composed of the above-mentioned composition.

[Formation of the Invention]

Hereinafter, the constituent elements of the present invention and the constituent elements of the laminate will be described in detail.

<composition>

The composition of the present invention satisfies the following condition 1: Condition 1: Temperature dispersion of the dynamic viscoelasticity measured at a frequency of 1 Hz and a strain of 0.01%, and a temperature dispersion of at least 2 in the range of -50 ° C or more and 50 ° C or less. Maximum value.

When the composition of the present invention is used for the adhesive layer of the laminate for protecting the adherend by having two maximum values in the above range, a good adhesion can be obtained for the adherend having irregularities on the surface such as a crepe sheet. It is not easy to peel off over time, and good peelability is obtained when peeled off from the adherend.

Here, the maximum value refers to the temperature dispersion in which the dynamic viscoelasticity of the continuous change is tangential, the value of the point from the increase to the decrease before and after the temperature, the shape of the temperature dispersion curve which can be tangent to the loss of the dynamic viscoelasticity, or Its differential coefficient is judged. That is, the point at which the differential coefficient is zero, and the point at which the differential coefficient is changed from negative to positive is the maximum value.

Here, the term "dynamic viscoelasticity measurement" refers to the measurement of the mechanical properties of a sample by imparting strain (stress) to the sample over time (vibration), and measuring the resulting stress or strain. The measurement modes include stretching/compression, shearing, and 3-point bending. Here, the measured values obtained by shearing are used.

Further, the loss tangent is a value obtained by dividing the loss elastic modulus obtained by the dynamic viscoelasticity measurement by the storage elastic modulus. Here, the loss elastic modulus refers to the energy supplied to the heat when the stress is applied. Dispersive viscous component; storage elastic modulus refers to the elastic component that maintains the internal cumulative stress.

Further, the temperature dispersion means a method of determining the temperature dependence of the dynamic viscoelasticity while changing the temperature under the condition that the frequency is constant and the amount of strain is constant, that is, the frequency of the present invention is 1 Hz and the strain is 0.01%. The details of the measurement method of the viscoelastic behavior are as follows.

Further, among the at least two maximum values, it is preferable that the maximum value on the low temperature side is in the range of -50 ° C or more and 10 ° C or less, and the maximum value on the high temperature side exists in the range of -10 ° C or more and 50 ° C or less. The maximum value on the low temperature side is preferably present in a range of preferably from -50 ° C to 0 ° C, more preferably from -50 ° C to -10 ° C, and the maximum value on the high temperature side is preferably from 0 ° C to 40 ° C. The scope. Here, when there are three or more of the maximum values in the range of -50 ° C or more and 50 ° C or less, among the maximum maximum value and the second largest maximum value, the low temperature side is the maximum value on the low temperature side, The high temperature side is the maximum value on the high temperature side. By adjusting the maximum value on the low temperature side to the above range, it is preferable to obtain a good peeling property when the laminated body is peeled off from the adherend. Further, by adjusting the maximum value on the high temperature side to the above range, good adhesion to the adherend can be obtained, which is preferable.

Further, the maximum value of the loss tangent on the high temperature side is preferably 0.1 or more and 1.0 or less, more preferably 0.3 or more and 1.0 or less, and particularly preferably 0.5 or more and 0.8 or less. When the maximum value on the high temperature side is less than 0.1, the adhesion to the adherend is insufficient. When the maximum value on the high temperature side is more than 1.0, the adhesion is too large, and it is difficult to peel off when the adherend is peeled off, or it may cause contamination (residue) to the adherend.

The composition of the present invention is not particularly limited as long as it satisfies the condition 1 which is a constituent element, and it is possible to use a cross-linking such as an acrylic or polyoxygen system, a non-crosslinking or a cross-linking of a natural rubber system or a synthetic rubber system (heat). Any of the materials of the plastic system, and based on the recyclability, it is preferred to use a thermoplastic resin as a main component. Here, the term "the thermoplastic resin as a main component" means that the proportion of the thermoplastic resin in the composition is 50% by mass or more, and more preferably 70% by mass or more.

The composition of the present invention may be a single resin or a mixture containing a plurality of resins as long as it satisfies the condition 1 which is a constituent element, and is preferably used to display a temperature of loss tangent measured in the same manner as in Condition 1. A method of dispersing a mixture of at least two or more resins having different temperatures at different temperatures. The resin having the maximum value of the loss tangent on the low temperature side is preferably -50 ° C or more and 10 ° C or less, preferably -50 ° C or more and 0 ° C or less, more preferably -50 ° C or more and 10 ° C or less. The resin having a maximum value is preferably a resin having a maximum value in the range of -10 ° C to 50 ° C, preferably from 0 ° C to 40 ° C, as the resin having the maximum value of the loss tangent on the high temperature side.

As the resin having a maximum value of the loss tangent on the low temperature side, those known in the art can be used, and examples thereof include a styrene-based elastomer, and specific examples thereof include a styrene-butadiene copolymer (SBR) and benzene. Styrene ‧ conjugated diene copolymers such as ethylene ‧ isoprene ‧ styrene copolymer (SIS), styrene ‧ butadiene ‧ styrene copolymer (SBS) and their hydrides, such as hydrogenation Styrene ‧ butadiene copolymer (HSBR) or styrene ‧ ethylene ‧ butylene styrene copolymer (SEBS), styrene ‧ isobutylene copolymer, such as styrene ‧ isobutylene ‧ styrene triblock Copolymer (SIBS) or styrene ‧ isobutylene diblock copolymer (SIB), or mixtures of these, and the like. These styrene-based elastomers may be used alone or in combination of two or more.

The weight average molecular weight of the styrene elastomer is preferably in the range of 50,000 to 400,000, 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 lowered, and residual glue occurs when peeled off from the adherend; when the viscosity is more than 400,000, the viscosity becomes high, resulting in a decrease in productivity.

The styrene content in the styrene-based elastomer is preferably in the range of 5 to 30% by mass, 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 lowered, and residual glue occurs when peeled off from the adherend; when it is more than 30% by mass, the adhesion to the adherend is lowered, especially for the adherend having irregularities. Insufficient adhesion.

The resin having a maximum value of the loss tangent on the high temperature side is not particularly limited, and it is preferable that the maximum value of the temperature dispersion of the loss tangent measured in the same manner as the condition 1 of the constituent elements of the composition of the present invention exists in -10 ° C or more and 50 ° C or less, preferably 0 ° C or more and 40 ° C or less, and the value is 0.3 or more. The maximum value is more preferably 0.5 or more, and particularly preferably 0.8 or more. When the maximum value is less than 0.3, the composition of the present invention does not satisfy the condition 1. That is, the composition of the present invention exhibits only one maximum value in the range of -50 ° C to 50 ° C under the temperature dispersion of the loss tangent.

The resin having a maximum value of the loss tangent on the high temperature side may, for example, be an olefin-based elastomer such as a low-crystalline polypropylene, an amorphous polypropylene or an α-olefin copolymer, or a styrene-vinyl isoprene. A styrene-based elastomer such as an ene-styrene copolymer, a styrene-butadiene copolymer, or a hydride such as these.

Examples of the α-olefin copolymer include a vinyl ‧ α-olefin copolymer, a propylene ‧ α-olefin copolymer, and a 4-methyl-1-pentene ‧ α-olefin copolymer. The α-olefin is preferably a linear or branched α-olefin having 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms. For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or the like can be mentioned, but it can be used without being limited thereto.

The resin having a maximum value of the loss tangent on the high temperature side is preferably an olefin-based elastomer such as a low-crystalline polypropylene, an amorphous polypropylene or an α-olefin copolymer, and more preferably, for example, preferably used. The 4-methyl-1-pentene‧α-olefin copolymer disclosed in Japanese Laid-Open Patent Publication No. 2013-194132.

In general, when a plurality of resins are used in combination, resins having good compatibility are selected. Alternatively, when the compatibility is poor, a phase solvent may be used to improve compatibility. On the other hand, in the composition of the present invention, the resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side are preferably used in combination with a resin having low compatibility. When the resin having excellent compatibility is used, the composition of the present invention does not satisfy the condition 1. That is, the composition of the present invention exhibits only one maximum value in the range of -50 ° C to 50 ° C under the temperature dispersion of the loss tangent, and the object of the present invention cannot be achieved.

The resin having a maximum value of the loss tangent on the low temperature side and the resin having a maximum value of the loss tangent on the high temperature side are preferably adjusted to a ratio of 10 to 90% by mass when the total amount is 100% by mass. The circumference is preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass. By adjusting the content of the resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side in the above range, the temperature dispersion of the loss tangent of the composition can be desirably adjusted.

The composition of the present invention may be suitably combined with the above materials. For example, hydrogenated styrene ‧ butadiene copolymer (HSBR) and/or styrene ‧ ethylene ‧ butylene styrene copolymer (SEBS) and / or styrene ‧ isobutylene copolymer, such as styrene ‧ isobutylene ‧ styrene triblock copolymer (SIBS) and / or styrene ‧ isobutylene diblock copolymer (SIB) as a loss tangent on the low temperature side The resin of a value is selected from a low crystalline polypropylene and/or an amorphous polypropylene and/or an α-olefin copolymer as a resin having a maximum value of loss tangent on a high temperature side and combined. More preferably, a styrene ‧ isobutylene copolymer such as styrene ‧ isobutylene styrene triblock copolymer (SIBS) and/or styrene ‧ isobutylene diblock copolymer (SIB) is used as A resin having a maximum value of loss tangent on the low temperature side and a combination of a resin having a maximum value of loss tangent on the high temperature side using a 4-methyl-1pentene‧α-olefin copolymer.

Further, when the composition of the present invention contains the above-mentioned styrene ‧ isobutylene copolymer and 4-methyl-1-pentene ‧ α-olefin copolymer, it may further contain a styrene ‧ conjugated diene copolymer Further, when the composition of the present invention is used for the adhesive layer of the laminate which protects the surface of the adherend, a laminate having excellent appearance on the surface of the adhesive layer can be obtained.

The above styrene ‧ conjugated diene copolymer or a hydride thereof can be suitably used, and hydrogenated styrene ‧ butadiene copolymer (HSBR) or styrene ‧ ethylene ‧ butylene styrene copolymer (SEBS) is preferably used. ).

The composition of the present invention may be composed only of the resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side, and may contain other components than these. In the composition, the total amount of the resin having a maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side is preferably 40% by mass or more when the entire composition is 100% by mass. More preferably, it is 50% by mass or more. When the content of the composition is less than 30% by mass, sufficient adhesion cannot be obtained when the laminate is bonded to the adherend.

In the composition of the present invention, in addition to the resin having the maximum value of the loss tangent on the low temperature side and the resin having the maximum value of the loss tangent on the high temperature side, other components may be appropriately added insofar as the object of the present invention is not impaired.

For example, the composition of the present invention may contain at least one selected from the following (d), (e), and (f), whereby the adhesion can be adjusted, or the adhesion as a laminate can be favorably controlled. The appearance of the layer surface.

(d) at least one wax selected from paraffin wax, olefin wax and such modified wax

(e) at least one resin selected from the group consisting of petroleum resin, terpene resin, terpene phenol resin, rosin resin, alkylphenol resin, xylene resin, and the like

(f) at least one lubricant selected from the group consisting of a fatty acid, a fatty acid metal salt, and a fatty acid decylamine.

As the above-mentioned wax, a known one can be used, and paraffin wax, olefin wax, and the like modified wax can be used. For example, when it is an olefin wax, a polyethylene wax, a polypropylene wax, a polybutylene wax or the like modified wax can be used. Further, the wax used in the present invention has a melting point of preferably 70 to 170 ° C, more preferably 90 to 160 ° C, still more preferably 110 to 160 ° C. When the melting point is less than 70 degrees, the viscosity will occur; when it is higher than 160 ° C, the formability is poor, and it is difficult to take it. When the total amount of the composition is 100% by mass, the content of the wax in the composition is preferably 10% by mass or less. When it is more than 10% by mass, the adhesion is poor.

Further, as the resin of the above (e), those generally used as a tackifier can be used. For example, an aliphatic copolymer, an aromatic copolymer, an aliphatic ‧ aromatic copolymer or a fat can be used as the petroleum resin. A cycloolefin copolymer or the like. When the total amount of the composition of the above (e) is 100% by mass, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the content of the resin (e) is more than 10% by mass, when the adhesive layer is formed by a melt extrusion method, a part of the resin of the above (e) is sublimated to contaminate the nozzle and even adhere to the product. Further, when the laminate of the present invention is bonded to the adherend, when the laminate is peeled off, residual glue is generated to contaminate the adherend.

Further, as the lubricant, a known one may be used, and a fatty acid having at least one alkyl group or alkenyl group having 4 to 60 carbon atoms, particularly a linear alkyl group or a linear alkenyl group having 4 to 30 carbon atoms, may be used. The fatty acid guanamine and the fatty acid metal salt may, for example, be a fatty acid such as lauric acid, palmitic acid, stearic acid, behenic acid, oleic acid or erucic acid, or a metal salt of such a fatty acid or a guanamine compound. When the total amount of the composition is 100% by mass, the content of the lubricant is preferably 2% by mass or less, and more preferably 1% by mass or less. When the content of the lubricant is more than 2% by mass, it may bleed toward the surface to contaminate the adherend or have poor adhesion.

Further, the composition of the present invention may be added with a resin such as a polyolefin which is used as a resin having a maximum value of loss tangent on the high temperature side, whereby the adhesive force can be adjusted or controlled as a laminate. The appearance of the surface of the adhesive layer when the body is used.

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, and polypropylene. Propylene/ethylene copolymer (random copolymer and/or block copolymer), propylene ‧α-olefin copolymer, propylene ‧ ethylene ‧ α-olefin copolymer, polybutene, ethylene ‧ (meth) acrylate copolymer The product, the ethylene ‧ (meth) acrylate copolymer, the ethylene ‧ (meth) acrylate copolymer, the ethylene ‧ vinyl acetate copolymer, etc., may be used alone or in combination. In addition, the α-olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene, and examples thereof include 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. 1-pentene, 1-heptene, and the like. Among the above polyolefins, more preferred are low density polyethylene, linear low density polyethylene, ethylene ‧ α-olefin copolymer, polypropylene, propylene ‧ α-olefin copolymer, and polybutene. When the total amount of the composition is 100% by mass, the polyolefin is preferably 50% by mass or less, and more preferably 40% by mass or less.

The composition of the present invention may contain an additive such as an antioxidant, a weathering agent, an antistatic agent, or an adhesion preventing agent in addition to the above components. These additives can be used as a single substance, or can be used in combination; if the total content is 100% by mass, preferably 3% by mass. Hereinafter, it is more preferably 2% by mass or less. When the total content of the additive is more than 3% by mass, it may bleed out from the adhesive layer to cause enthalpy or contamination of the adherend.

The composition of the present invention preferably has an acetone dissolution rate of 5% or less. In the present invention, the acetone dissolution rate (S) of the composition is determined by the following method. First, the method shown in the examples described later was molded into a composition having a thickness of 2 mm and acetone was mixed at a mass ratio of 1:9, and after stirring in a room at 25 ° C for 5 hours, the residual solid content was taken out, and the oven was dried at 80 ° C. The mass (W ₁ ) was measured after drying for 3 hours. Thereafter, the mass (W ₀ ) of the composition before dissolution by acetone and the mass (W ₁ ) of the acetone-insoluble component obtained above were determined, and the acetone dissolution rate was calculated according to the following formula (a).

S=((W ₀ -W ₁ )/W ₀ )×100...(a)

S: acetone dissolution rate (%)

W ₀ : mass of the composition before acetone is dissolved (g)

W ₁ : mass (g) of the acetone insoluble component.

<Laminated body>

The laminated system of the present invention has a laminated body having an adhesive layer on one side of the substrate, and the adhesive layer contains the above-described composition. Hereinafter, the laminate of the present invention will be described in detail.

<Substrate>

The substrate constituting the laminate of the present invention is not particularly limited, and a resin such as polyolefin or polyester can be used. Among them, polyolefin is preferred as a component based on productivity or processing suitability. Here, the term "polyolefin as a main component" means that when the entire substrate is 100% by mass, the proportion of the 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, and polypropylene. , propylene/ethylene copolymer (random copolymer and/or block copolymer), propylene ‧ α-olefin copolymer, propylene ‧ ethylene ‧ α-olefin copolymer, ethylene ‧ (meth) acrylate copolymer, ethylene ‧ (Methyl) methacrylate copolymer, ethylene ‧ (butyl) methacrylate copolymer, ethylene ‧ vinyl acetate copolymer, etc. These can be used alone or in combination. In addition, the α-olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene, and examples thereof include 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. 1-pentene, 1-heptene, and the like. Among the above polyolefins, more preferred are polypropylene, propylene/ethylene copolymer (random copolymer and/or block copolymer), propylene ‧ ethylene ‧ α olefin copolymer, propylene ‧ α olefin A propylene-based material such as a copolymer.

The melt flow rate (MFR; measured at 230 ° C, 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/min, productivity is lowered due to excessively high melt viscosity. Further, when the MFR is more than 30 g/min, the substrate is brittle and is difficult to handle during the production of the laminate or during use.

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

Further, in the composition constituting the substrate of the present invention, a lubricant, an antioxidant, a weather resistance agent, an antistatic agent, a crystal nucleating agent, and a pigment may be appropriately added without impairing the characteristics of the layered body of the present invention. Various additives such as.

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 the thickness is less than 5 μm, the strength is insufficient, it is difficult to transport in the manufacturing step, or cracking occurs during processing or use. When the thickness is 200 μm, the transparency of the film is insufficient or the productivity is lowered.

<adhesive layer>

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

The thickness of the adhesive layer of the present invention can be appropriately adjusted in accordance with the material, thickness, surface shape or degree of the adherend, and is preferably 1 to 20 μm, more preferably 2 to 10 μm, and particularly preferably 2 to 8 μm. When the thickness of the adhesive layer is less than 1 μm, sufficient adhesion to the adherend cannot be exhibited; when it is larger than 20 μm, the adhesive force is excessively large or the productivity is lowered.

<release layer>

The laminated system of the present invention has at least a laminate of a substrate and an adhesive layer, and preferably has a release layer formed on one surface of the substrate opposite to the adhesive layer to form a three-layer laminate. The material, thickness, and surface shape constituting the release layer may be selected or adjusted depending on the adhesion of the adhesive layer, the manufacturing property of the laminate, or the processing suitability at the time of use, and a technique well known in the art may be employed. It is preferable to use a propylene-based resin containing a fluorine-containing compound having a polyfluorocarbon group and a polyoxyethylene group in an amount of 0.5% by mass to 10% by mass, based on the viewpoint of controlling the mold release property.

The propylene-based resin may be the same as or different from the propylene-based resin constituting the base material, and the release layer to be described later may be used. The surface roughness is roughened to a value of 3.0 μm or more in terms of Rz, and preferably at least 20% by mass or more of a copolymer of propylene and ethylene and/or an α-olefin. When the propylene-based polymer is a copolymer with ethylene and/or an α-olefin, the more the monomer content, the lower the melting point of the copolymer, the easier the co-extrusion, the low-temperature extrusion, and therefore, the monomer The content is more preferably in the range of 3 to 7 mass%. Further, when heat resistance is to be imparted to the release layer, it can be appropriately selected, and the content of the monomer can be reduced to obtain desired heat resistance.

Further, the MFR of the propylene resin at 230 ° C is preferably in the range of 3 to 40 g/10 minutes. In particular, when the MFR is in the range of 10 to 40 g/10 minutes, it can be extruded at a low temperature, and it is more preferable to use a combination with a low-density polyethylene to easily roughen the release layer.

Further, in order to roughen the release layer, it is preferred to contain at least 4% by mass of a high-pressure process low-density polyethylene which is incompatible with the above-mentioned propylene-based resin.

Further, the release layer is preferably composed of a propylene resin containing a fluorine-containing compound having a polyfluorocarbon group and a polyoxyethylene group in an amount of 0.5% by mass to 10% by mass. The fluorine-containing compound having a polyfluorocarbon group and a polyoxyethylene group, for example, as the monomer (a), a (meth) acrylate having a perfluoroalkyl group having 1 to 18 carbon atoms, etc., which will be described later. It is obtained by copolymerization of a monomer (b) or a (meth) acrylate having a polyoxyethylene group of the monomer (c).

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

The (meth) acrylate 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.

The polyoxyethylene group-containing monomer (b) preferably has an oxyethylene unit (-CH ₂ -CH ₂ -O-) in a structure of 1 to 30, in particular, the unit has 1 to 20 The one is better. Further, the chain may also contain an oxypropylene unit (-CH ₂ -CH(CH ₃ )-O-). As a preferable example, polyethylene glycol monomethacrylate or the like having eight oxyethylene units can be exemplified. The monomer (b) may be used alone or in combination of two or more.

Further, another monomer (c) containing a polyoxyethylene group is a di(meth)acrylate having a structure in which 1 to 30 oxyethylene units are successively connected and having a double bond at both terminals. Preferred examples of the compound include polyethylene glycol dimethacrylate having a chain number of 8, and the like. The monomer (c) may be used alone or in combination of two or more.

With respect to the ratio of each of the monomer (a), the monomer (b), and the monomer (c), it is preferred that the monomer (a) is 1 to 80% by mass and the monomer (b) is 1 ~80% by mass and monomer (c) is 1 to 50% by mass.

Further, in the above fluorine-containing compound having a polyfluorocarbon group and a polyoxyethylene group, in addition to the above three kinds of monomers, a monomer copolymerizable therewith can be copolymerized in a range of less than 50% by mass. Examples of the monomer include methylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl halide, styrene, methyl styrene, (meth)acrylic acid and esters thereof, and (meth) acrylamide. Monomer, (meth)allyl monomer, and the like.

A polymerization method for obtaining the above fluorine-containing compound having a polyfluorocarbon group and a polyoxyethylene group using the above monomer, which may be a bulk polymerization Any one of solution, solution polymerization, suspension polymerization, and emulsion polymerization, and in addition to thermal polymerization, photopolymerization and energy ray polymerization can also be employed.

As the polymerization initiator, an existing organic azo compound, a peroxide, a persulfate or the like can be used.

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

Further, the proportion of the fluorine-containing compound in the release layer of the present invention is preferably from 0.5% by mass to 10% by mass. When it is less than 0.5% by mass, adhesion to the adhesive layer is liable to occur, and the desired winding force is not easily obtained. In addition, when the content is more than 10% by mass, the solubility in the resin is low, and it is difficult to uniformly stir, and the propylene-based resin constituting the release layer is affected by the fluorine-containing compound during melt extrusion. , sliding along the extrusion screw portion, and not easily discharged uniformly.

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

Examples of the inorganic particles include calcium carbonate, magnesium carbonate, titanium oxide, clay, talc, magnesium hydroxide, aluminum hydroxide, and zeolite, and more preferably cerium oxide.

Examples of the organic particles include polystyrene or polymethyl methacrylate.

By the effect of multiplying the fluorine-containing compound, inorganic or organic particles, and the surface roughness of the release layer described later, adhesion is less likely to occur, and it is easier to obtain good roll-out properties.

The surface roughness of the release layer of the present invention is preferably 3 μm or more in terms of ten-point average roughness (Rz). When Rz is less than 3 μm, when it is wound into a roll shape in the production step of the laminated body, wrinkles are likely to occur, and the quality is deteriorated. The surface roughness can be achieved by a method of adding a small amount of a propylene-based resin as a main component to the above-described ethylene-based resin lacking compatibility.

<Method of Manufacturing Laminates>

Next, a method of producing the laminate of the present invention will be described.

The method for producing the layered product of the present invention is not particularly limited. For example, when the base material, the pressure-sensitive adhesive layer, and the release layer are three-layered, the resin composition constituting each of them is melt-extruded from an individual extruder. a so-called co-extrusion method in which a layer is integrated in a nozzle; or a method in which the substrate, the adhesive layer, and the release layer are individually melt-extruded, laminated by lamination, or the like, based on The productive point of view is preferably manufactured by coextrusion. The materials constituting each layer may be used after being mixed by a Henschel mixer or the like, or all or a part of the materials of each layer may be kneaded in advance and used. As the co-extrusion method, a well-known method such as an inflation method or a T-die method can be employed, and a hot melt co-extrusion method using a T-die method is particularly preferable from the viewpoint of excellent thickness accuracy or control of surface shape.

<Use example>

The laminate comprising the composition of the present invention can be used as a surface protection film for preventing scratches during construction, processing, and transportation of synthetic resin sheets, metal sheets, glass sheets, and the like, and for preventing contamination, and is particularly suitable for use in unevenness. Sticky. For example, it is used for a diffusion plate or a sheet which is a member for a display including a synthetic resin, and a laminate composed of the composition of the present invention is particularly preferably used for surface protection of a sheet.

The ruthenium sheet which is protected by the laminate of the composition of the present invention is arranged on one side of the sheet, and is arranged in parallel with the surface of the sheet so that the ridge line of the triangular column is the outer surface. The material constituting the crucible is not particularly limited, and a translucent resin is used, and examples thereof include an acrylic resin or a polycarbonate. The distance between the adjacent ridges of the crucible is preferably from 10 to 1,000 μm, more preferably from 10 to 300 μm. The height of the crucible (the length from the bottom edge of the triangular prism to the perpendicular of the ridge line) is preferably 5 to 200 μm, more preferably 10 to 100 μm. Further, the ruthenium sheet protected by the present invention may be composed only of ruthenium of the same shape, or may be composed of two or more different shapes of ruthenium. When it is composed of 形状 of different shapes, for example, a case in which the heights are different are arranged one by one, or a case where one large 稜鏡 is alternately arranged with a plurality of small cymbals, it is appropriately designed for the purpose.

Moreover, the compression strength of the enamel portion protected by the laminate of the present invention is preferably 3,000 mN/mm or less, more preferably 2,000 mN/mm or less, and particularly preferably 1,000 mN/mm or less, and most preferably Below 500mN/mm. Further, in the present invention, the compressive strength of ruthenium refers to a value calculated by the method described in the examples below. The laminate of the present invention exhibits good adhesion to the above-mentioned crucible, and can be particularly preferably used.

[Examples]

Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited by the examples. In addition, the measurement and evaluation of various physical properties were carried out according to the following methods.

(1) Viscoelasticity of the composition

The compositions shown in Examples 1 to 9 and Comparative Examples 1 to 3 were blended at a predetermined mixing ratio, and LABO PLASTOMILL 100MR3 manufactured by Toyo Seiki Seisakusho Co., Ltd. was mixed and kneaded at a temperature of 200 ° C and a number of revolutions of 20 rpm for 15 minutes. Next, the obtained kneaded product was melt-molded to a thickness of 2 mm, and a shearing mode was performed at a temperature of -80 to 120 ° C, a temperature increase rate of 3 ° C / min, a frequency of 1 Hz, and a strain of 0.01% using a rheometer AR2000ex manufactured by TA Instruments. The viscoelasticity of the composition was evaluated. From the results obtained, the number of maximum values of the temperature dispersion of the loss tangent of -50 ° C or more and 50 ° C or less was confirmed. Further, when the maximum value is two or more, the maximum value on the high temperature side is obtained.

(2) Acetone dissolution rate of the composition

The composition having a thickness of 2 mm obtained in the same manner as in the above (1) was mixed with acetone at a mass ratio of 1:9, and after stirring in a room at 25 ° C for 5 hours, the residual solid component was taken out and dried in an oven at 80 ° C. The mass (W ₁ ) was measured after 3 hours. Thereafter, the mass (W ₀ ) of the composition before dissolution by acetone and the mass (W ₁ ) of the acetone-insoluble component obtained above were determined, and the acetone dissolution rate was calculated according to the following formula (a).

S=((W ₀ -W ₁ )/W ₀ )×100...(a)

S: acetone dissolution rate (%)

W ₀ : mass of the composition before acetone is dissolved (g)

W ₁ : mass (g) of the acetone insoluble component.

(3) Compressive strength of 稜鏡

Using a micro compression tester MCTW-500 manufactured by Shimadzu Corporation, a diamond-made flat press is used in a room with a load speed of 41 mN/s and a room temperature of 23 °C. = 50 μm) The ridge portion of the front end of the 稜鏡 is compressed to obtain a load-displacement curve. Further, the load at the time of deformation of 3 μm was divided by the length (contact length) of the ridge line portion of the contact planar pressing member during compression, and the obtained value was used as the compressive strength of 稜鏡. In addition, in the case of the aforementioned contact length, if only one of the 稜鏡 contacts the planar pressing member, it means the length of the contact with the one; if there are more than two 稜鏡 contact with the planar pressing member, it means each 稜鏡The total value of the length of the contact.

(4) Fit for 稜鏡

The laminates obtained in the following Examples 1' to 9', 2" and Comparative Examples 1' to 3' were subjected to a roll press (Yaoda Seiki Co., Ltd. special pressure-bonding roll) at a condition of 0.35 MPa. It is attached to the predetermined enamel sheets shown in the respective examples or comparative examples.

(5) Fit

With respect to the sample obtained in the above (4), the bonded state immediately after the bonding at room temperature of 25 ° C for one week was observed, and the adhesion was evaluated in the following five stages.

5: After the fit, it will be fully fitted after 1 week of storage.

4: After the fitting, it was fully fitted, but it was slightly peeled off at the back end for one week.

3: Shortly after the fitting, one week later, the ends were slightly peeled off.

2: Shortly after the bonding, 1/2 or more of the bonding surface peeled off.

1: Shortly after the fitting, the entire surface of the fitting surface peeled off.

(6) Pollution

The sample obtained in the above (4) was stored in a hot air dryer at 50° C. under a load of 10 g/cm ² for 3 days, and then the laminate was peeled off, and the contamination on the surface of the ruthenium sheet was visually confirmed to be carried out in the following three stages. assessment.

5: No pollution is seen in the whole

3: Only a small part of the pollution is seen

1: The pollution can be clearly seen.

(7) Surface roughness of the adhesive layer

For the adhesive layers of the laminates obtained in the following Examples 1' to 9', 2" and Comparative Examples 1' to 3', a high-precision fine shape measuring device (SURFCORDER ET4000A) manufactured by Otaru Research Institute Co., Ltd. was used. According to JIS B0601-1994, the measurement was performed 21 times in the lateral direction of the film 2 mm and the longitudinal direction (mechanical direction) of 10 μm to perform three-dimensional analysis, and the arithmetic mean roughness (Ra) was determined and evaluated in the following three stages. A diamond needle having a needle tip radius of 2.0 μm was measured at a measuring force of 100 μN and a intercept of 0.8 mm. Further, as a result of visually observing the appearance of the adhesive film, the larger the value of the following evaluation, that is, the arithmetic mean roughness (Ra) Small, the less the surface of the adhesive layer is rough, which is the result of good appearance.

5: Ra<0.3μm

3: 0.3 μm ≦ Ra < 0.7 μm

1: Ra ≧ 0.7 μm.

(composition)

The materials of the following compositions A to I and X to Z were prepared as shown in Examples 1 to 9 and Comparative Examples 1 to 3, and the viscoelasticity and acetone dissolution rate were evaluated by the methods (1) and (2) above. The results are shown in Table 1.

(Example 1)

Composition A: 80% by mass of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals Co., Ltd.) is used as the resin having a maximum value of loss tangent on the low temperature side, and 20% by mass is used as the resin having a maximum value of loss tangent on the high temperature side. 4-methyl-1-pentene propylene copolymer. Further, the above 4-methyl-1-pentene propylene copolymer has a copolymerization ratio of 73 mol% for 4-methyl-1-pentene and 27 mol% for propylene; 1) Viscoelasticity of the adhesive layer described in the same manner. The temperature at which the loss tangent was measured in the same manner was dispersed at 30 ° C to show an extremely large value, and the value was 2.9.

(Example 2)

Composition B: a resin having a maximum value of loss tangent on the low temperature side, 40% by mass of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals) and 40% by mass of styrene/isobutylene block copolymer (SIBSTAR 062M by Kaneka) were used. As the resin having a maximum value of loss tangent on the high temperature side, 20% by mass of the same 4-methyl-1-pentene propylene copolymer as the user of the composition A was used.

(Example 3)

Composition C: The ratio of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals) was 20% by mass, and the ratio of styrene ‧ isobutylene block copolymer (SIBSTAR 062M by Kaneka) was 50% by mass, and 4- The ratio of the methyl-1-pentene/propylene copolymer was set to 30% by mass, and the same composition B was used.

(Example 4)

Composition D: The ratio of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals) was 0% by mass, and the ratio of styrene ‧ isobutylene block copolymer (SIBSTAR 062M by Kaneka) was 50% by mass, and 4- The ratio of the methyl-1-pentene/propylene copolymer is the same as that of the composition B except that the ratio is 50% by mass.

(Example 5)

Composition E: a resin having a loss tangent maximum value on the low temperature side, 10% by mass of SEBS (Tuftec H1052 manufactured by Asahi Kasei Chemicals) and 55 mass% of styrene/isobutylene block copolymer (SIBSTAR 062M by Kaneka) were used. As the resin having a maximum value of the loss tangent on the high temperature side, 30% by mass of the same 4-methyl-1-pentene propylene copolymer as the user of the composition A was used, and 5 mass was used as the tackifier. % hydrogenated terpene phenol (YS Polyster TH130, manufactured by YASUHARA CHEMICAL).

(Example 6)

Composition F: The ratio of the styrene ‧ isobutylene block copolymer (SIBSTAR 062M by Kaneka) was 70% by mass, and the ratio of the 4-methyl-1-pentene propylene copolymer was 30% by mass. The same as the composition D is used.

(Example 7)

Composition G: The ratio of the styrene ‧ isobutylene block copolymer (SIBSTAR 062M by Kaneka) was 67% by mass, and the ratio of the 4-methyl-1-pentene propylene copolymer was 30% by mass. Further, the same as the composition D was used except that 3% by mass of a polypropylene wax (wasan VISCOL 550P) was used.

(Example 8)

Composition H: The ratio of the styrene ‧ isobutylene block copolymer (SIBSTAR 062M manufactured by Kaneka) was 65 mass%, and the ratio of the 4-methyl-1-pentene propylene copolymer was 30 mass% Further, in the same manner as the composition D, a hydrogenated terpene phenol (YS Polyster TH130 manufactured by YASUHARA CHEMICAL) as a tackifier was further used in an amount of 5% by mass.

(Example 9)

Composition I: The ratio of the styrene ‧ isobutylene block copolymer (SIBSTAR 062M by Kaneka) was set to 69.8% by mass, and the ratio of the 4-methyl-1-pentene propylene copolymer was set to 30% by mass. Further, the same as the composition D was used except that 0.2% by mass of calcium stearate as a lubricant was used.

(Comparative Example 1)

Composition X: Only styrene ‧ isobutylene block copolymer (SIBSTAR 062M manufactured by Kaneka) was used.

(Comparative Example 2)

Composition Y: 70% by mass of a styrene/isobutylene-based block copolymer (SIBSTAR 062M manufactured by Kaneka) and 30% by mass of a hydrogenated terpene phenol (YS Polyster TH130 manufactured by YASUHARA CHEMICAL) as a tackifier.

(Comparative Example 3)

Composition Z: 95% by mass of a 4-methyl-1-pentene propylene copolymer and 5% by mass of a hydrogenated terpene phenol (YS Polyster TH130 manufactured by YASUHARA CHEMICAL) as a tackifier.

(layered body)

As shown in the following examples and comparative examples, a laminate was produced and evaluated. The evaluation results are shown in Table 2.

(Example 1')

The constituent resins of the respective layers were prepared as follows.

Adhesive layer: The composition A shown in Example 1 was used.

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

Release layer: 5% by mass of the same homopolypropylene as the user of the substrate, 24% by mass of a propylene-ethylene ‧ random copolymer having an MFR of 35 g/10 min measured at 230 ° C (ethylene content 5 mass) %), 6% by mass of a low-density polyethylene having a MFR of 2 g/10 min and a density of 0.92 g/cm ³ measured at 190 ° C, which is prepared in advance to contain an average of 4% by mass in 90% by mass of the above homopolypropylene. A mixed composition of cerium oxide having a particle diameter of 11 μm and a fluorine-containing compound having a polyfluorocarbon group and a polyoxyethylene group of 6 mass% was used as a masterbatch, and 25% by mass was uniformly mixed by a Henschel mixer.

Here, a fluorine-containing compound having a polyfluorocarbon group and a polyoxyethylene group is used: a perfluoroalkyl acrylate having a C ₆ F ₁₃ as a monomer (a) (CH ₂ =CHCOOC ₂ H ₄ C ₆ F ₁₃ 25% by mass of polyethylene glycol monoacrylate {CH ₂ =CHCOO(CH ₂ CH ₂ O) ₈ H} having _{8 parts} by mass of oxyethylene repeating unit as monomer (b), and 50% by mass The oxyethylene repeating unit of the monomer (c) is 8 polyethylene glycol dimethacrylate {CH ₂ =C(CH ₃ )COO(CH ₂ CH ₂ O) ₈ COC(CH ₃ )=CH ₂ } Taking a ratio of 25% by mass, the solvent is trifluorotoluene, 2,2'-azobis(2,4-dimethylvaleronitrile) is used as a polymerization initiator, and lauryl mercaptan is used as a chain transfer agent. Under a nitrogen gas stream, the mixture was stirred at 60 ° C for 5 hours while stirring, and then precipitated in methanol, filtered, and dried under reduced pressure.

Next, the constituent resin of each layer is put into the inclusion 115mm (for substrate), 90mm (for adhesive layer), In each extruder of a multi-manifold T-die compound laminator having a nozzle width of 2,400 mm of 3 extruders for a 65 mm (for a release layer), the discharge amount of each extruder is adjusted to form an adhesive layer. The thickness ratio of 12.5%, the release layer thickness ratio of 8.5%, and the substrate thickness ratio of 79% were further extruded from a composite T-die at an extrusion temperature of 200 ° C to form a three-layer laminated film having a film thickness of 40 μm. Thereafter, a crepe sheet having a 稜鏡 compression strength of 380 mN/mm was used to evaluate the adhesion, contamination, and surface roughness of the obtained laminate.

(Example 2')

A laminate 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 evaluation was carried out.

(Example 2))

A laminate was produced in the same manner as in Example 2' except that a crucible having a crucible compressive strength of 1,650 mN/mm was used, and evaluation was carried out.

(Example 3')

A laminate 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 carried out.

(Example 4')

A laminate 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 evaluation was carried out.

(Example 5')

A laminate 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 evaluation was carried out.

(Example 6')

A laminate was produced in the same manner as in Example 1 except that the composition F shown in Example 6 was used as the adhesive layer, and evaluation was carried out.

(Example 7')

A laminate was produced in the same manner as in Example 1 except that the composition G shown in Example 7 was used as the adhesive layer, and evaluation was carried out.

(Example 8')

A laminate was produced in the same manner as in Example 1 except that the composition H shown in Example 8 was used as the adhesive layer, and evaluation was carried out.

(Example 9')

A laminate was produced in the same manner as in Example 1 except that the composition I shown in Example 9 was used as the adhesive layer, and evaluation was carried out.

(Comparative Example 1')

A laminate 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 evaluation was carried out.

(Comparative Example 2')

A laminate was produced 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 evaluation was carried out.

(Comparative Example 3')

A laminate 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 evaluation was carried out.

Examples 1' to 9' and 2" satisfying the requirements of the present invention have excellent adhesion characteristics, contamination property, and appearance; on the other hand, Comparative Examples 1' to 3' which do not satisfy the requirements of the present invention have adhesive properties, The balance between pollution and appearance is poor.

[Industrial availability]

The composition and the laminate of the present invention can be used not only as a surface protective film for preventing scratches or stains of adherends having irregularities on the surface, but also preferably used as various materials including synthetic resin, metal, and glass. The use of surface protection films for a wide variety of products.

Claims (13)

A composition characterized by satisfying the following condition 1: Condition 1 The temperature dispersion of the dynamic viscoelasticity measured at a frequency of 1 Hz and a strain of 0.01% is at least 2 in the range of -50 ° C or more and 50 ° C or less. Maximum value. The composition of claim 1, wherein the composition satisfies the following condition 2: Condition 2: The maximum value of the temperature at which the loss tangent is dispersed on the high temperature side is 0.1 or more and 1.0 or less. The composition of claim 1 or 2, wherein the composition satisfies the following condition 3: Condition 3: The maximum value of the temperature at which the loss tangent is dispersed on the high temperature side is 0.3 or more and 1.0 or less. The composition of any one of claims 1 to 3, wherein the composition comprises (b): (b) a 4-methyl-1-pentene ‧ a-olefin copolymer. The composition according to any one of claims 1 to 4, wherein the composition comprises the following (c): (c) a styrene ‧ conjugated diene copolymer or a hydride thereof. The composition according to any one of claims 1 to 5, wherein the composition contains at least one selected from the group consisting of (a) or a styrene ‧ ethylene ‧ butylene styrene copolymer: (a) benzene Ethylene ‧ isobutylene copolymer. The composition of any one of claims 1 to 6, wherein the composition comprises the following (a) and (b): (a) Styrene ‧ isobutylene copolymer (b) 4-methyl-1-pentene ‧ α-olefin copolymer. The composition according to any one of claims 1 to 7, wherein the composition contains at least one selected from the group consisting of (d), (e) and (f): (d) from paraffin wax, olefin wax and At least one wax (e) selected from the modified waxes is a petroleum resin, a terpene resin, a terpene phenol resin, a rosin resin, an alkylphenol resin, a xylene resin, and the like. At least one resin (f) selected from the group consisting of at least one lubricant selected from the group consisting of a fatty acid, a fatty acid metal salt, and a fatty acid decylamine. The composition of any one of claims 1 to 8, wherein the composition has an acetone dissolution rate of 5% or less. A laminate comprising a laminate having an adhesive layer on one side of a substrate, wherein the adhesive layer comprises the composition of any one of claims 1 to 9. The laminate of claim 10, wherein the laminate system is formed by a co-extrusion process. The laminate of claim 10 or 11 is used for surface protection of the cymbal. The laminate of claim 10 or 11 is used for surface protection of a slab having a compressive strength of 3,000 mN/mm or less.