KR20170063508A - Composition and laminate - Google Patents

Abstract

A composition for providing a laminate which is excellent in adhesion properties when bonded to various adherends having different surface shapes and is hard to cause contamination on an adherend even when stored under extreme conditions of high temperature and high pressure, To a laminate. The composition satisfies the following condition (1).
Condition 1 The temperature dispersion of the loss tangent of the dynamic viscoelasticity measured at a frequency of 1 Hz and a strain of 0.01% has at least two maximum values in the range of -50 캜 to 50 캜.

Description

≪ Desc / Clms Page number 1 > COMPOSITION AND LAMINATE &

The present invention relates to a composition for providing a laminate which is excellent in adhesion properties when bonded to an adherend having various surface shapes and which is less prone to contamination on an adherend even when stored under extreme conditions of high temperature and high pressure, And the like.

Products made of various materials such as synthetic resin, metal, and glass are often handled with a material protecting the surface thereof in order to prevent scratches and contamination that occur during processing, transportation, and storage. Typically, a surface protective film is used, in which an adhesive layer is formed on a support substrate made of thermoplastic resin or paper in general, and the surface is protected by adhering the adhesive layer surface to an adherend and covering the surface with a support substrate.

Particularly in recent years, although liquid crystal displays and touch panel devices are being widely used, they are composed of a large number of optical sheets made of synthetic resin and optical members. Since such optical members are required to reduce defects such as optical deformation as much as possible, surface protective films are often used in order to prevent scratches or contamination which may cause defects.

Examples of the characteristics of the surface protective film include those that do not readily peel off from the adherend at a degree of environmental change such as temperature or humidity or under a small stress and that the adherend and the adhesive component remain on the adherend when peeled from the adherend .

Among members for optical members such as a diffusion plate and a prism sheet, in the case of a member having projections and depressions on the surface, the adhesion of the adhesive layer to the concave-convex portion is insufficient immediately after the surface protective film is bonded, have. In view of this, a method of softening the adhesive layer or a method of increasing the adhesive strength by using a tackifier is known (see, for example, Patent Documents 1 to 5).

Japanese Patent Application Laid-Open No. 2008-214437 Japanese Patent Application Laid-Open No. 2005-298630 Japanese Patent Application Laid-Open No. 2007-77244 Japanese Patent Laid-Open No. 05-194923 Japanese Patent Application Laid-Open No. 121-111793

However, in the above method, the adhesive strength increases with time, and the peelability may deteriorate. In addition, even when stored at a high temperature or under pressure, the peelability may be deteriorated in the same manner. Further, at the time of peeling, an adhesive layer component adheres to the surface of the adherend, which may cause contamination.

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a laminate which is suitable for various adherends having irregularities on its surface and which has appropriate adhesive properties and is difficult to cause contamination on the adherend even when stored under extreme conditions of high temperature and high pressure And a laminate constituted by using the composition.

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have completed the following inventions. That is, the present invention is as follows.

1) A composition according to the above item 1, which satisfies the following condition (1).

Condition 1 Loss of dynamic viscoelasticity measured at frequency 1 Hz, strain 0.01% The temperature dispersion of tangent has at least two maximum values in the range of -50 DEG C to 50 DEG C

2) The composition according to 1), wherein the composition satisfies Condition 2 below.

Condition 2 The maximum value on the high temperature side of the temperature dispersion of the loss tangent is 0.1 or more and 1.0 or less

3) The composition according to 1) or 2), wherein the composition satisfies Condition 3 below.

Condition 3: The maximum value at the high temperature side of the temperature dispersion of the loss tangent is 0.3 or more and 1.0 or less

(Effects of the Invention)

According to the present invention, in view of the above-described problems, it is possible to provide a laminate which has appropriate adhesion properties to various adherends having irregularities on the surface and is hard to cause contamination on the adherend even when stored under extreme conditions of high temperature and high pressure And a laminate composed of the composition.

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

<Composition>

The composition of the present invention satisfies Condition 1 below.

Condition 1: loss of dynamic viscoelasticity measured at frequency 1 Hz, strain 0.01% The temperature dispersion of tangent has at least two maximum values in the range of -50 캜 to 50 캜.

When the composition of the present invention is used in the adhesive layer of the laminate for protecting the adherend by having two maximum values in the above-mentioned range, good adherence is obtained even for an adherend having irregularities on the surface of a prism sheet or the like It is difficult to peel off even after a lapse of time, and when peeled from an adherend, good peelability is obtained.

Here, the maximum value means a value at which the temperature dispersion of the loss tangent of dynamic viscoelasticity, which continuously changes, changes from increasing to decreasing before and after the temperature, and the shape of the temperature dispersion curve of the loss tangent of dynamic viscoelasticity , Or from the differential coefficient thereof. That is, the point at which the differential coefficient becomes zero, and the point at which the differential coefficient changes from plus to minus before and after the point becomes the maximum value.

Here, the dynamic viscoelasticity measurement is a measurement for examining the mechanical properties of a sample by giving a strain or a stress that changes (vibrates) to the sample over time and measures a stress or deformation caused thereby, Compression, shearing, three-point bending, etc., but the measurement by shearing is targeted here.

The loss tangent refers to a value obtained by dividing the loss elastic modulus obtained by the dynamic viscoelasticity measurement by the storage modulus. Herein, the loss elastic modulus means a viscous component in which the energy imparted when the stress is applied is lost due to heat, and the storage elastic modulus means an elastic component that retains the accumulated stress therein.

The temperature dispersion is a method of determining the temperature dependency of the dynamic viscoelasticity while changing the temperature under the conditions of constant frequency and amount of deformation, that is, the frequency of 1 Hz according to the present invention and the strain of 0.01%. Details of the measurement method of viscoelastic behavior will be described later.

It is preferable that the above-mentioned at least two maximum values are in the range of -50 ° C to 10 ° C on the low temperature side and the maximum value in the high temperature side is in the range of -10 ° C to 50 ° C. The maximum value on the low temperature side is more preferably in the range of -50 DEG C to 0 DEG C, more preferably in the range of -50 DEG C to -10 DEG C, and the maximum value on the high temperature side is in the range of 0 DEG C to 40 DEG C More preferably in the range of &lt; RTI ID = 0.0 &gt; Here, when there are three or more of the maximum values in the range of -50 占 폚 to 50 占 폚, the maximum value on the low temperature side and the maximum value on the high temperature side of the maximum value and the second maximum value, . It is preferable to adjust the maximum value on the low temperature side within the above range because good releasability can be obtained when the laminate is peeled from the adherend. In addition, it is preferable to adjust the maximum value on the high-temperature side within the above-mentioned range because good adhesion to the adherend can be obtained.

The maximum value of the loss tangent at 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 when bonded to an adherend may be insufficient. When the maximum value on the high temperature side is larger than 1.0, the adhesiveness becomes excessive, and it may be difficult to peel off from the adherend or to cause contamination (paste residue) on the adherend.

The composition of the present invention is not particularly limited as long as it satisfies Condition 1, which is a constituent requirement, and it is possible to use any of the non-crosslinked or pseudo crosslinked (thermoplastic) materials such as acrylics and silicones, natural rubber, However, from the viewpoint of recyclability, it is preferable to use a thermoplastic resin as a main component. Here, the thermoplastic resin as the main component means that the proportion of the thermoplastic resin in the composition is 50 mass% or more, and more preferably 70 mass% or more.

The composition of the present invention may be composed of a mixture of a plurality of resins even if a single resin satisfies Condition 1 as a constituent requirement. However, it is also possible that the composition exhibiting a maximum value of the temperature dispersion of loss tangent , A method using a mixture of at least two kinds of resins is preferable. As the resin having the maximum value of the loss tangent to the low temperature side, a resin having a maximum value in the range of -50 DEG C to 10 DEG C, preferably -50 DEG C to 0 DEG C, more preferably -50 DEG C to 10 DEG C And a resin having a maximum value in the range of -10 占 폚 to 50 占 폚, preferably 0 占 폚 to 40 占 폚 is preferably used as the resin having the maximum loss tangent on the high temperature side.

As the resin having a maximum value of loss tangent on the low temperature side, those known in the field can be used, and examples thereof include styrene elastomers. Specific examples thereof include styrene / butadiene copolymer (SBR), styrene / isoprene / styrene Styrene / butadiene / styrene copolymer (SBS), and styrene / conjugated diene copolymers such as styrene / butadiene / styrene copolymer (SBS) and their hydrogenated products such as hydrogenated styrene / butadiene copolymer (HSBR) For example, a styrene / isoprene / styrene copolymer (SEBS) or a styrene / isobutylene copolymer such as a styrene / isobutylene / styrene triblock copolymer (SIBS), a styrene / isobutylene diblock copolymer And mixtures thereof. These styrene-based elastomers may be used alone or in combination of two or more.

The weight average molecular weight of the styrene-based 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 pressure-sensitive adhesive layer is lowered, resulting in a residue of the paste when peeled from the adherend. When the weight average molecular weight is more than 400,000, the viscosity is increased and the productivity is lowered.

The styrene content in the styrene-based elastomer is preferably in the range of 5 to 30 mass%, more preferably in the range of 8 to 20 mass%. When the content of styrene is less than 5 mass%, the cohesive force of the pressure-sensitive adhesive layer is lowered, resulting in a residue of the paste when peeled off from the adherend. When the content of styrene is more than 30 mass%, the adherence to the adherend is deteriorated. The adherend may be insufficiently adhered to the adherend.

The resin having the maximum value of loss tangent on the high temperature side is not particularly limited, but it is preferable that the maximum value of the temperature dispersion of the loss tangent measured in the same manner as in Condition 1, which is a constituent of the composition of the present invention, Is preferably in the range of 0 占 폚 to 40 占 폚, and the value thereof is preferably 0.3 or more. The maximum value is more preferably 0.5 or more, particularly preferably 0.8 or more. When the maximum value is less than 0.3, the composition of the present invention may not satisfy the condition 1. That is, the composition of the present invention may exhibit only a maximum value in the range of -50 캜 to 50 캜 in the temperature dispersion of the loss tangent.

Examples of the resin having a maximum value of loss tangent on the high temperature side include olefinic elastomers such as low crystalline polypropylene, amorphous polypropylene and alpha -olefin copolymer, styrene / vinyl isoprene / styrene copolymer, styrene / butadiene And styrene elastomers such as hydrogenated products thereof.

Examples of the? -Olefin copolymer include ethylene /? - olefin copolymer, propylene /? - olefin copolymer, 4-methyl-1-pentene /? -Olefin copolymer and the like. As the? -olefin, a straight-chain or branched? -olefin having 2 to 20 carbon atoms is preferable, and a carbon number of 2 to 10 is particularly preferable. For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and the like can be used.

Among the resins having the maximum value of the loss tangent on the high temperature side, the olefinic elastomer such as low crystalline polypropylene, amorphous polypropylene, and alpha -olefin copolymer is preferably used, and more preferably, A 4-methyl-1-pentene /? - olefin copolymer as disclosed in Patent Publication No. 2013-194132 is preferably used.

Generally, when a plurality of resins are mixed and used, resins having good compatibility are selected. In the case of poor compatibility, a compatibilizing agent may be used to improve compatibility. On the other hand, in the composition of the present invention, it is preferable to use a resin having a maximum value of the loss tangent at the low temperature side and a resin having the maximum value of the loss tangent at the high temperature side in combination with each other. When the resins having excellent compatibility are used, the composition of the present invention may not satisfy Condition 1. That is, the composition of the present invention shows only one maximum value in the temperature range of -50 DEG C to 50 DEG C in the temperature dispersion of loss tangent, and the object of the present invention may not be achieved.

The content of the resin having the maximum loss tangent on the low temperature side and the resin having the maximum loss tangent on the high temperature side are preferably adjusted in the range of 10 to 90 mass% , More preferably from 20 to 80 mass%, and particularly preferably from 30 to 70 mass%. The temperature dispersion of the loss tangent of the composition can be preferably adjusted by adjusting the content of the resin having the maximum loss tangent at the low temperature side and the resin having the maximum loss tangent at the high temperature side within the above range.

The composition of the present invention can be constituted by suitably combining the above materials. For example, a hydrogenated styrene-butadiene copolymer (HSBR) and / or styrene-ethylene-butyl (Styrene / isobutylene / styrene triblock copolymer (SIBS) and / or styrene / isobutylene diblock copolymer (SIB) and / or styrene / isobutylene copolymer ) And the low-crystalline polypropylene and / or the amorphous polypropylene and / or the -olefin copolymer as the resin having the maximum value of the loss tangent on the high-temperature side are preferably selected and combined. More preferably, a styrene / isobutylene copolymer such as styrene / isobutylene / styrene triblock copolymer (SIBS) and / or styrene / isobutylene diblock copolymer Copolymer (SIB), and a combination using a 4-methyl-1-pentene -olefin copolymer as a resin having a maximum loss tangent at high temperature.

When the styrene / isobutylene copolymer and the 4-methyl-1-pentene /? - olefin copolymer are contained, the composition of the present invention may further contain a styrene / conjugated diene copolymer or a hydrogenated product thereof When the composition of the present invention is used for the adhesive layer of the laminate for protecting the surface of the adherend, a laminate excellent in the appearance of the surface of the adhesive layer can be obtained.

The styrene / conjugated diene-based copolymer or the hydrogenated product thereof may be a known one, 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 of only the resin having the maximum value of the loss tangent to the low temperature side and the resin having the maximum value of the loss tangent to the high temperature side and may contain other components than the above. The total content of the resin having the maximum loss tangent value on the low temperature side and the resin having the maximum loss tangent value on the high temperature side in the composition is preferably 40% by mass or more, more preferably 50% More preferable. When the content of the composition is less than 30 mass%, sufficient adhesion may not be obtained when the laminate is bonded to an adherend.

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

For example, the composition of the present invention may contain at least one selected from the following (d), (e) and (f), whereby the adhesive strength of the adhesive layer surface Or the like can be controlled favorably.

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

(e) at least one resin selected from petroleum resins, terpene resins, terpene phenol resins, rosin resins, alkylphenol resins, xylene resins and hydrogenated products thereof

(f) at least one lubricant selected from fatty acids, fatty acid metal salts and fatty acid amides.

As the above-mentioned wax, known ones can be used, and paraffin wax, olefin wax and modified waxes thereof can be used. For example, in the case of olefin wax, polyethylene wax, polypropylene wax, polybutene wax and modified waxes thereof can be used. The wax used in the present invention preferably has a melting point of 70 to 170 캜, more preferably 90 to 160 캜, further preferably 110 to 160 캜. If the melting point is less than 70 deg., Stickiness may occur. If the melting point is higher than 160 deg. C, the moldability may be lowered, which may make handling difficult. The content of the wax in the composition is preferably 10% by mass or less based on 100% by mass of the entire composition. If it is more than 10% by mass, the tackiness may be deteriorated.

As the resin of (e), those generally used as a tackifier can be used. For example, in the case of a petroleum resin, an aliphatic copolymer, an aromatic copolymer, an aliphatic / aromatic copolymerization system or an alicyclic copolymer Coalescence, etc. may be used. The content of the resin (e) is preferably 10 mass% or less, more preferably 5 mass% or less, and particularly preferably 3 mass% or less, when 100 mass% When the content of the resin of (e) is more than 10% by mass, when the pressure-sensitive adhesive layer is molded by the melt extrusion method, a part of the resin of (e) sublimates and may contaminate the detachment and adhere to the product . In addition, when the laminate of the present invention is bonded to an adherend and then peeled from the laminate, a paste residue may be formed to contaminate the adherend.

The above-mentioned lubricants may be any of those known in the art, and include fatty acids, fatty acid amides, and fatty acid metal salts having at least one of an alkyl group or alkenyl group having 4 to 60 carbon atoms, particularly a linear or branched alkenyl group having 4 to 30 carbon atoms, And examples thereof include fatty acids such as lauric acid, palmitic acid, stearic acid, behenic acid, oleic acid and erucic acid, and metal salts and amide compounds of these fatty acids. The content of the lubricant is preferably 2% by mass or less, more preferably 1% by mass or less, based on 100% by mass of the entire composition. When the content of the lubricant is more than 2% by mass, there is a case where the adherend is contaminated by the bleeding-out on the surface or the adhesiveness is deteriorated in some cases.

Further, the composition of the present invention may be added with a resin such as polyolefin in addition to the above-mentioned resin having a maximum value of loss tangent to the high temperature side. By adjusting the adhesive force thereby, or when used as a laminate, The appearance can be controlled favorably.

Examples of the polyolefin include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, low crystalline or amorphous ethylene -olefin copolymer, polypropylene, propylene ethylene copolymer (random copolymer and / Propylene / ethylene /? - olefin copolymer, polybutene, ethylene / ethyl (meth) acrylate copolymer, ethylene · methyl (meth) acrylate copolymer, ethylene · n- Butyl (meth) acrylate copolymer, and ethylene-vinyl acetate copolymer. These may be used singly or in combination. The? -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 the like. Among the above-mentioned polyolefins, low density polyethylene, linear low density polyethylene, ethylene /? - olefin copolymer, polypropylene, propylene /? - olefin copolymer and polybutene are more preferable. When the total amount of the polyolefin is 100 mass%, the amount is preferably 50 mass% or less, more preferably 40 mass% or less.

The composition of the present invention may contain, in addition to the above components, additives such as an antioxidant, a lubricant, an antistatic agent, and an adhesion-inhibiting agent. These additives may be used singly or in combination, but the total content is preferably 3% by mass or less, more preferably 2% by mass or less, based on 100% by mass of the entire composition. If the total content of the additive is more than 3% by mass, the product may bleed out from the pressure-sensitive adhesive layer to cause defects in the product or contaminate 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 obtained by the following method. First, the composition molded to a thickness of 2 mm and acetone were mixed at a mass ratio of 1: 9 by the method shown in the later-described examples, and the mixture was stirred in a room at 25 캜 for 5 hours. Thereafter, the remaining solid content was taken out, After drying for 3 hours, the mass (W ₁ ) was measured. Thereafter, the acetone dissolution rate was calculated from the mass (W ₀ ) of the composition before acetone dissolution and the mass (W ₁ ) of the acetone insolubles obtained as described above, as shown in the following formula (a).

S = ((W ₀ -W ₁ ) / W ₀ ) × 100 (a)

S: Dissolution rate of acetone (%)

W ₀ : Mass (g) of the composition before acetone dissolution

W ₁ : mass of acetone insoluble matter (g).

<Laminate>

The laminate of the present invention is a laminate having a pressure-sensitive adhesive layer on one side of a substrate, and the pressure-sensitive adhesive layer includes the above-mentioned composition. Hereinafter, the laminate of the present invention will be described in detail.

<Description>

The substrate constituting the laminate of the present invention is not particularly limited, but for example, resins such as polyolefin and polyester can be used. Among them, polyolefin is preferably used as a main component from the viewpoints of productivity and processability. Here, the main component of the polyolefin means that the proportion of the polyolefin is 50% by mass or more, more preferably 70% by mass or more, when the entire substrate is 100% by mass.

Examples of the polyolefin include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, low crystalline or amorphous ethylene /? - olefin copolymer, polypropylene, propylene / ethylene copolymer Propylene / ethylene /? - olefin copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, ethylene n -Butyl (meth) acrylate copolymer, ethylene-vinyl acetate copolymer and the like. These may be used alone or in combination. The? -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 the like. Of the above-mentioned polyolefins, propylene-based materials such as polypropylene, propylene-ethylene copolymer (random copolymer and / or block copolymer), propylene-ethylene -olefin copolymer and propylene -olefin copolymer, Is more preferable.

The melt flow rate (MFR, measured at 230 DEG C under a condition of 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, more preferably in the range of 5 to 30 g / min . If the MFR is less than 2 g / min, the melt viscosity may be excessively high and the productivity may be lowered. If the MFR is larger than 30 g / min, the substrate may be withdrawn, which may be difficult to handle in the production of a laminate or in use.

The substrate in the present invention may have a two-layer structure or more.

Various additives such as a lubricant, an antioxidant, an anti-fogging agent, an antistatic agent, a nucleating agent and a pigment may be appropriately added to the composition constituting the base material of the present invention within a range that does not impair the properties of the laminate of the present invention.

The thickness of the base material can be suitably adjusted in accordance with the required characteristics of the laminate, but is preferably 5 to 200 占 퐉, more preferably 10 to 100 占 퐉, and particularly preferably 10 to 80 占 퐉. If it is thinner than 5 占 퐉, the strength is insufficient and it may be difficult to transport in the manufacturing process, or may be broken at the time of processing or use. If it is thicker than 200 탆, transparency of the film may be insufficient or the productivity may be 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 pressure-sensitive adhesive layer of the present invention can be appropriately adjusted depending on the material, thickness, surface shape and required level of the adherend, but is preferably 1 to 20 占 퐉, more preferably 2 to 10 占 퐉, Particularly preferred. If the thickness of the adhesive layer is less than 1 占 퐉, sufficient adhering force may not be exhibited to the adherend, and when it is more than 20 占 퐉, the adhering force may be excessive or the productivity may be deteriorated.

&Lt;

The laminate of the present invention is a laminate having at least a substrate and an adhesive layer, but it is a preferable form to form a three-layer laminate structure by forming a release layer on a surface of the substrate opposite to the adhesive layer. The material, thickness, and surface shape constituting the release layer can be selected and adjusted from the viewpoints of the adhesive strength of the pressure-sensitive adhesive layer, the processability at the time of producing the laminate, and the like, and known techniques can be used in the field. It is preferable that it is composed mainly of a propylene resin containing 0.5% by mass to 10% by mass of a fluorine compound having both a polyfluoro hydrocarbon group and a polyoxyethylene group from the viewpoint of favorably controlling the releasability.

The propylene-based resin may be the same as or different from the propylene-based resin constituting the above-described base, but it is preferable that the propylene-based resin contains at least 20 mass% or more of a copolymer of propylene and ethylene and / Is preferably roughened to have a surface roughness Rz of not less than 3.0 mu m. When the propylene-based polymer is copolymerized with ethylene and / or an -olefin, the higher the content of the monomer, the lower the melting point of the copolymer. From the viewpoint of easy co-extrusion and low-temperature extrusion, The range of mass% is more preferable. When it is desired to add heat resistance to the release layer, it is also possible to reduce the content of such a monomer and properly select it so as to obtain desired heat resistance.

The MFR of the propylene resin at 230 캜 is preferably in the range of 3 to 40 g / 10 min. In particular, an MFR in the range of 10 to 40 g / 10 min is more preferable because it can be extruded at a low temperature and is easily combined with low-density polyethylene to make the release layer rough.

Further, in order to roughen the release layer, it is preferable to contain at least 4 mass% of high-pressure processed low-density polyethylene which is incompatible with the propylene resin.

Furthermore, it is preferable that the release layer is composed of a propylene resin containing 0.5% by mass to 10% by mass of a fluorine compound simultaneously containing a polyfluoro hydrocarbon group and a polyoxyethylene group. Examples of the fluorinated compound having a polyfluoro hydrocarbon group and a polyoxyethylene group include (meth) acrylic acid esters having a perfluoroalkyl group having 1 to 18 carbon atoms as the monomer (a) (meth) acrylate having a polyoxyethylene group of the monomer (b) and the monomer (c).

The perfluoroalkyl group of the monomer (a) preferably has 1 to 18 carbon atoms, more preferably 1 to 6 carbon atoms. Such a perfluoroalkyl group may be either straight or branched. These may be used alone or in combination of two or more.

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

As the monomer (b) containing a polyoxyethylene group, it is preferable that it has a structure in which oxyethylene units (-CH ₂ -CH ₂ -O-) are connected in a chain of 1 to 30, more preferably 1 to 20 units . In addition, an oxypropylene unit (-CH ₂ -CH (CH ₃ ) -O-) may be contained in the chain. As a preferable example, eight polyethylene glycol monomethacrylates and the like having an oxyethylene unit can be exemplified. The monomers (b) may be used singly or in combination of two or more.

As another monomer (c) containing a polyoxyethylene group, di (meth) acrylate having a structure in which an oxyethylene unit is 1 to 30 contiguous units and having a double bond at both terminals, Polyethylene glycol dimethacrylate having a chain number of 8, and the like. These monomers (c) may be used singly or in combination of two or more.

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

The fluorine-containing compound having a polyfluoro hydrocarbon group and a polyoxyethylene group may be copolymerized with a monomer capable of copolymerizing with the above three monomers within a range of less than 50 mass%. Examples of such a monomer include methylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl halide, styrene, methylstyrene, (meth) acrylic acid and its ester, (meth) acrylamide monomer and (meth) allyl monomer.

The polymerization method for obtaining the fluorine compound having a polyfluoro hydrocarbon group and a polyoxyethylene group using the monomer may be any of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and in addition to thermal polymerization, Energy ray polymerization may also be employed.

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

The weight average molecular weight of the fluorine compound used in the present invention is preferably 1,000 to 100,000, particularly preferably 5,000 to 20,000. Adjustment of the weight average molecular weight can be adjusted by polymerization chain transfer agents such as thiol, mercaptan, and? -Methylstyrene.

The proportion of the fluorinated compound in the release layer of the present invention is preferably 0.5% by mass to 10% by mass. When the amount is less than 0.5% by mass, blocking with the pressure-sensitive adhesive layer tends to occur, so that it may be difficult to obtain a desired releasing force. In addition, when it is intended to contain more than 10% by mass, it is difficult to uniformly mix the resin because of low solubility in the resin. In addition, at the time of melt extrusion, the propylene resin for forming the release layer is affected by the fluorine compound, So that it may be difficult to uniformly discharge the ink.

In addition to the fluorine compound, the release layer of the present invention more preferably contains 0.1 to 10 mass% of inorganic or organic particles having an average particle diameter of 1 to 20 占 퐉 at the same time. The average particle diameter of such an inorganic or organic particle is 3 to 15 占 퐉 and a relatively large particle diameter is particularly preferable from the viewpoints of sliding property and blocking property.

Examples of such inorganic particles include silica, calcium carbonate, magnesium carbonate, titanium oxide, clay talc, magnesium hydroxide, aluminum hydroxide and zeolite, among which silica is more preferable.

Examples of the organic particles include polystyrene and polymethyl methacrylate.

Due to the synergistic effect of the above-mentioned fluorine compound, inorganic or organic particles, and the release layer to be described later, it is difficult to block and easy to obtain good releasability.

The surface roughness of the release layer of the present invention is preferably not less than 3 탆 in 10-point average roughness (Rz). When Rz is less than 3 mu m, wrinkles tend to occur when the laminate is wound into a roll shape in the production process of the laminate, thereby deteriorating the quality. Such surface roughness can be achieved by, for example, a method of adding a small amount of an ethylenic resin having insufficient compatibility as described above to a propylene resin as a main component.

&Lt; Method for producing laminate >

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

The method for producing the laminate of the present invention is not particularly limited. For example, in the case of a three-layer laminated structure of a substrate, a pressure-sensitive adhesive layer and a release layer, the resin composition constituting each of them is melt-extruded from an individual extruder, Extruding the substrate, the pressure-sensitive adhesive layer, and the release layer, respectively, and then laminating them by a laminate method. From the viewpoint of productivity, however, it is preferable to use a co- desirable. The material constituting each layer may be mixed with each other in a Henschel mixer or the like, or all or some of the materials of each layer may be kneaded in advance. Known methods such as the inflation method and the T-die method are used for the co-extrusion method, but the method of hot-melt co-extrusion by the T-die method is particularly preferable from the viewpoint of thickness precision and surface shape control.

<Usage example>

The laminate composed of the composition of the present invention can be used as a surface protective film for prevention of scratches and prevention of adhesion of stains during the manufacture, processing and transportation of a synthetic resin plate, a metal plate and a glass plate. Lt; / RTI &gt; For example, a diffusion plate or a prism sheet, which is a display member made of a synthetic resin, is used. Particularly, a laminate composed of the composition of the present invention is particularly preferably used for protecting the surface of a prism sheet.

The prism sheet protected by the laminate constituted by the composition of the present invention is arranged such that a triangular prism on one side of the sheet is parallel to the sheet surface such that the ridgeline thereof is an outer surface. The material constituting the prism is not particularly limited, but a resin having translucency is used, and examples thereof include acrylic resin and polycarbonate. The distance between adjacent ridges of the prism is preferably 10 to 1,000 mu m, more preferably 10 to 300 mu m. The height of the prism (the length of the water line from the base of the triangular column to the ridgeline) is preferably 5 to 200 占 퐉, more preferably 10 to 100 占 퐉. In addition, the prism sheet to be protected by the present invention may be composed of only prism having the same shape, or two or more types of prisms having different shapes. In the case of a prism having a different shape, for example, the prisms having different heights may be arranged alternately one by one, or a large prism and a plurality of small prisms may be alternately arranged. However, Is designed.

The prism sheet to be protected by the laminate of the present invention preferably has a prism portion having a compressive strength of 3,000 mN / mm or less, more preferably 2,000 mN / mm or less, particularly preferably 1,000 mN / mm or less, Or less. In the present invention, the compressive strength of a prism is calculated by the method described in the following embodiments. With respect to the prism, the laminate of the present invention exhibits good adhesion and can be particularly preferably used.

Example

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

(1) Viscoelasticity of the composition

The compositions shown in Examples 1 to 9 and Comparative Examples 1 to 3 were mixed at a predetermined mixing ratio and kneaded at 200 ° C and 20 rpm for 15 minutes using Labo Plastomill 100MR3 manufactured by Toyo Seiki Seisakusho Co., Subsequently, the obtained kneaded product was melted and molded into a thickness of 2 mm, and the composition was kneaded in a shear mode at a temperature of -80 to 120 占 폚, a heating rate of 3 占 폚 / min, a frequency of 1 Hz, and a strain of 0.01% using a rheometer AR2000ex Was evaluated. From the results obtained, the number of maximum values in the temperature dispersion of the loss tangent of -50 ° C to 50 ° C was confirmed. 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) and acetone were mixed in a mass ratio of 1: 9, and the mixture was stirred in a room at 25 캜 for 5 hours. The remaining solid was taken out and dried in an oven at 80 캜 for 3 hours Then, the mass (W ₁ ) was measured. Thereafter, the acetone dissolution rate was calculated from the mass (W ₀ ) of the composition before acetone dissolution and the mass (W ₁ ) of the acetone insolubles obtained as described above, as shown in the following formula (a).

S = ((W ₀ -W ₁ ) / W ₀ ) × 100 (a)

S: Dissolution rate of acetone (%)

W ₀ : Mass (g) of the composition before acetone dissolution

W ₁ : mass of acetone insoluble matter (g).

(3) Compressive strength of prism

The ridge portion of the prism tip was compressed by a diamond rosette flat indenter (φ = 50 μm) in a room at a load speed of 41 mN / s and a room temperature of 23 ° C. using a micro compression tester MCTW-500 manufactured by Shimadzu Seisakusho Co., . The load at the time of 3 占 퐉 deformation was divided by the length (contact length) of the ridge portion of the prism which was in contact with the planar indenter at the time of compression. The contact length refers to a length in which one prism is in contact with only one prism when the prism is in contact with the planar indenter. When two or more prisms are in contact with the planar indenter, Total value.

(4) Bonding to the prism

The laminate obtained in the following Examples 1 'to 9', 2 '' and Comparative Examples 1 'to 3' was laminated on a predetermined prism sheet shown in each of Examples or Comparative Examples in a roll press machine (manufactured by Yasuda Seiki Co., By Sakusho special pressing roller) at a pressure of 0.35 MPa.

(5) Adhesiveness

The samples obtained in (4) above were observed immediately after bonding and after being stored for 1 week in a room at 25 캜, and the adhesion was evaluated in the following five steps.

5: Immediately after attachment and after one week storage, all are attached.

4: It is attached to the front immediately after attaching, but slightly peeled off at the end after storing for one week.

3: The ends were slightly peeled off immediately after attachment and after 1 week

2: Immediately after the attachment, peeling occurs at half or more of the side face.

1: Immediately after the attachment, peeling occurs on the entire surface of the attachment surface.

(6) Contamination

The sample obtained in the above step (4) was stored for 3 days under a load of 10 g / cm &lt; 2 &gt; in a hot air drier at 50 DEG C and then the laminate was peeled off. Viscous stain on the surface of the prism sheet was visually observed, I appreciated.

5: No contamination at all

3: Very little contamination is confirmed.

1: Pollution is clearly identified.

(7) Surface roughness of the adhesive layer

(SURFCORDER ET4000A) manufactured by Kensaku Kosaka Co., Ltd. was used for the adhesive layer of the laminate obtained in Examples 1 'to 9', 2 '' and Comparative Examples 1 'to 3' The measurement was performed two times in the film transverse direction and 21 times in the longitudinal direction (machine direction) at intervals of 10 탆 in accordance with JIS B0601-1994, and the three-dimensional analysis was performed to obtain the arithmetic average roughness (Ra) Further, the appearance of the pressure-sensitive adhesive film was visually observed, and as a result, it was found that as the numerical value of the following evaluation was larger, that is, the arithmetic mean illuminance ( Ra was smaller, the roughness on the surface of the adhesive layer was less and the appearance was good.

5: Ra < 0.3 탆

3: 0.3 탆? Ra <0.7 탆

1: Ra? 0.7 탆.

(Composition)

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 viscoelasticity and acetone dissolution rate were evaluated by the methods (1) and (2). The results are shown in Table 1.

(Example 1)

Composition A: 80% by mass of SEBS (manufactured by Asahi KASEI CHEMICAL Co., Ltd., Torftec H1052) as a resin having a maximum loss tangent on the low temperature side, 4-methyl-1-pentene-propylene copolymer as a resin having a maximum loss tangent And 20 mass% of the coalescent were used. The 4-methyl-1-pentene-propylene copolymer had a copolymerization ratio of 73 mol% of 4-methyl-1-pentene and 27 mol% of propylene and had the same viscoelasticity as that of the pressure- The temperature dispersion of the loss tangent obtained by the measurement showed a maximum at 30 캜 and a value of 2.9 was used.

(Example 2)

Composition B: 40% by mass of SEBS (Turfec H1052 manufactured by Asahi Kasei Chemicals Co., Ltd.) and 40% by mass of a styrene / isobutylene block copolymer (Kaneka Seeshibita 062M) were added to a resin having a maximum loss tangent on the low temperature side, 20% by mass of the same 4-methyl-1-pentene-propylene copolymer as that used in the composition A was used as the resin having the maximum loss tangent.

(Example 3)

Composition C: 20% by mass of SEBS (Torftec H1052 manufactured by Asahi Kasei Chemicals Co., Ltd.), 50% by mass of styrene / isobutylene block copolymer (Kanekasebushite 062M), 4-methyl- Propylene copolymer was 30% by mass.

(Example 4)

Composition D: the ratio of SEBS (Torftec H1052 manufactured by Asahi Chemical Industry Co., Ltd.) was set at 0% by mass, the proportion of styrene / isobutylene block copolymer (Kanekasebushite 062M) was 50% Propylene copolymer was 50% by mass.

(Example 5)

Composition E: 10% by mass of SEBS (manufactured by Asahi Chemical Industry Co., Ltd.), 55% by mass of a styrene / isobutylene block copolymer (Kaneka Seabsitta 062M), and 50% by mass of a high- Methyl-1-pentene-propylene copolymer as used in Composition A as a resin having a maximum value of loss tangent, 5 mass% of a hydrogenated terpene phenol (YS Polyster TH130 made by Yasuhara Chemical Co., Ltd.) as a tackifier, .

(Example 6)

Composition F: As with the composition D, except that the ratio of the styrene / isobutylene block copolymer (Kaneka sieve 632M) was 70% by mass and the proportion of 4-methyl-1-pentene-propylene copolymer was 30% did.

(Example 7)

Composition G: A resin composition was prepared in the same manner as in Example 1 except that the ratio of the styrene / isobutylene block copolymer (Kaneka Corp.Substa 062M) was 67% by mass, the proportion of 4-methyl-1-pentene-propylene copolymer was 30% The composition was the same as the composition D except that the wax (Sanyo Chemical Industries, Ltd. bis-550P) was used in an amount of 3 mass%.

(Example 8)

Composition H: A resin composition was prepared in such a manner that the ratio of the styrene / isobutylene block copolymer (GK) was 65 mass%, the proportion of 4-methyl-1-pentene-propylene copolymer was 30 mass% And 5% by mass of hydrogenated terpene phenol (YS Polyster TH130 made by Yasuhara Chemical Co., Ltd.).

(Example 9)

Composition I: 69.8 mass% of a styrene / isobutylene block copolymer (Kaneka sieve 692M), 30 mass% of a 4-methyl-1-pentene / propylene copolymer, and a stearic acid The composition was the same as the composition D except that 0.2 mass% of calcium was used.

(Comparative Example 1)

Composition X: Styrene-isobutylene block copolymer (Kaneka Seibu Shita 062M) was used alone.

(Comparative Example 2)

Composition Y: 70% by mass of a styrene isobutylene block copolymer (Kaneka Seabsitta 062M) and 30% by mass of a hydrogenated terpene phenol (YS Polyster TH130, Yasuhara Chemical Co., Ltd.) was used as a tackifier.

(Comparative Example 3)

Composition Z: 95 mass% of 4-methyl-1-pentene-propylene copolymer and 5 mass% of hydrogenated terpene phenol (YS Polyster TH130 made by Yasuhara Chemical Co., Ltd.) was used as a tackifier.

(Laminate)

A laminate was prepared and evaluated as shown in the following examples and comparative examples. 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.

Commercially available homopolypropylene having MFR of 5 g / 10 min measured at 230 캜 was used.

Release layer: A homopolypropylene homopolymer having a homopolypropylene content of 45% by mass and a MFR of 35 g / 10 min as measured at 230 캜 was measured at 190 占 폚 in an amount of 24 mass% (ethylene content: 5 mass%) of a propylene- Density polyethylene having a density of 0.92 g / cm 3 with an MFR of 2 g / 10 min was added in an amount of 6 mass%, and 4 mass% of silica having an average particle diameter of 11 탆, a polyfluoro hydrocarbon group and a poly And 6% by mass of a fluorine-containing compound having an oxyethylene group was prepared as a master batch, and 25% by mass of the mixture was homogeneously mixed with a Henschel mixer.

Here, the fluorine-containing compound having a polyfluoro hydrocarbon group and a polyoxyethylene group is obtained by reacting perfluoroalkyl acrylate (CH ₂ = CHCOOC ₂ H ₄ C ₆ F ₁₃ ) of C ₆ F ₁₃ as the monomer (a) with 25 50% by mass of polyethylene glycol monoacrylate {CH ₂ = CHCOO (CH ₂ CH ₂ O) ₈ H} as the monomer (b) and 8 oxyethylene repeating units as the monomer (b) 25% by mass of polyethylene glycol dimethacrylate {CH ₂ ═C (CH ₃ ) COO (CH ₂ CH ₂ O) ₈ COC (CH ₃ ) = CH ₂ } was used as a solvent and trifluoro toluene was used as a solvent Azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and laurylmercaptan as a chain transfer agent were polymerized at 60 ° C for 5 hours while stirring in a nitrogen stream, And then precipitated in methanol, filtered, and dried under reduced pressure.

Subsequently, the constituent resin of each layer was laminated on a multi-manifold T-die composite material block having three extruders having a diameter of 115 mm (for substrate), 90 mm (for adhesive layer) and 65 mm (for release layer) And extruded from the composite T-die at an extrusion temperature of 200 占 폚, respectively, so that the extrusion rate of each extruder was adjusted so that the adhesive layer thickness ratio was 12.5%, the release layer thickness ratio was 8.5%, and the base thickness ratio was 79% To form a three-layer laminated film having a film thickness of 40 mu m. Thereafter, the adhesion of the laminate obtained by using the prism sheet having a prism compression strength of 380 mN / mm, the stain resistance, and the surface roughness of the adhesive layer were evaluated.

(Example 2 ')

A laminate was prepared and evaluated in the same manner as in Example 1 'except that the composition B shown in Example 2 was used in the adhesive layer.

(Example 2 ")

A laminate was prepared and evaluated in the same manner as in Example 2 'except that a prism sheet having a prism compression strength of 1,650 mN / mm was used.

(Example 3 ')

A laminate was prepared and evaluated in the same manner as in Example 1 'except that the composition C shown in Example 3 was used in the adhesive layer.

(Example 4 ')

A laminate was prepared and evaluated in the same manner as in Example 1 except that the composition D shown in Example 4 was used as the adhesive layer.

(Example 5 ')

A laminate was prepared and evaluated in the same manner as in Example 1 'except that the composition E shown in Example 5 was used in the adhesive layer.

(Example 6 ')

A laminate was prepared and evaluated in the same manner as in Example 1 'except that the composition F shown in Example 6 was used in the adhesive layer.

(Example 7 ')

A laminate was prepared and evaluated in the same manner as in Example 1 'except that the composition G shown in Example 7 was used in the adhesive layer.

(Example 8 ')

A laminate was prepared and evaluated in the same manner as in Example 1 except that the composition H shown in Example 8 was used as the adhesive layer.

(Example 9 ')

A laminate was prepared and evaluated in the same manner as in Example 1 'except that the composition I shown in Example 9 was used in the adhesive layer.

(Comparative Example 1 ')

A laminate was prepared and evaluated in the same manner as in Example 1 'except that the composition X shown in Comparative Example 1 was used as the adhesive layer.

(Comparative Example 2 ')

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

(Comparative Example 3 ')

A laminate was prepared and evaluated in the same manner as in Example 1 'except that the composition Z shown in Comparative Example 3 was used as the adhesive layer.

Examples 1 'to 9' and 2 'which satisfy the requirements of the present invention are excellent in adhesion property, stain resistance and appearance, while Comparative Examples 1' to 3 ', which do not satisfy the requirements of the present invention, .

(Industrial availability)

The composition and the laminate of the present invention are preferably used as surface protective films for various products made of various materials such as synthetic resin, metal, and glass, as well as surface protective films for preventing scratches and contamination of adherends having irregularities on the surface Can be used.

Claims (13)

Wherein the composition satisfies the following condition (1).
Condition 1 The temperature dispersion of the loss tangent of dynamic viscoelasticity measured at a frequency of 1 Hz and strain 0.01% has at least two maximum values in the range of -50 캜 to 50 캜 The method according to claim 1,
Wherein the composition meets the following Condition 2:
Condition 2 The maximum value on the high temperature side of the temperature dispersion of the loss tangent is 0.1 or more and 1.0 or less 3. The method according to claim 1 or 2,
Wherein the composition satisfies Condition 3 below.
Condition 3: The maximum value at the high temperature side of the temperature dispersion of the loss tangent is 0.3 or more and 1.0 or less 4. The method according to any one of claims 1 to 3,
Wherein the composition comprises (b).
(b) 4-methyl-1-pentene -olefin copolymer 5. The method according to any one of claims 1 to 4,
Wherein the composition contains (c)
(c) styrene-conjugated diene-based copolymer or hydrogenated product thereof 6. The method according to any one of claims 1 to 5,
Wherein the composition contains at least one selected from the following (a) or styrene-ethylene-butylene-styrene copolymer.
(a) a styrene / isobutylene copolymer 7. The method according to any one of claims 1 to 6,
Wherein the composition comprises (a) and (b).
(a) a styrene / isobutylene copolymer
(b) 4-methyl-1-pentene -olefin copolymer 8. The method according to any one of claims 1 to 7,
Wherein the composition contains at least one selected from the following (d), (e) and (f).
(d) at least one wax selected from paraffin wax, olefin wax and modified waxes thereof
(e) at least one resin selected from petroleum resins, terpene resins, terpene phenol resins, rosin resins, alkylphenol resins, xylene resins and hydrogenated products thereof
(f) at least one lubricant selected from fatty acids, fatty acid metal salts and fatty acid amides 9. The method according to any one of claims 1 to 8,
Wherein the composition has an acetone dissolution rate of 5% or less. A laminate having a pressure-sensitive adhesive layer on one side of a substrate, wherein the pressure-sensitive adhesive layer comprises the composition according to any one of claims 1 to 9. 11. The method of claim 10,
And the laminate is formed by a co-extrusion method. The method according to claim 10 or 11,
A laminate used for protecting the surface of a prism sheet. The method according to claim 10 or 11,
A laminate used for surface protection of a prism sheet having a compressive strength of 3,000 mN / mm or less.