WO2016063673A1 - Composition and laminate - Google Patents
Composition and laminate Download PDFInfo
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- WO2016063673A1 WO2016063673A1 PCT/JP2015/076910 JP2015076910W WO2016063673A1 WO 2016063673 A1 WO2016063673 A1 WO 2016063673A1 JP 2015076910 W JP2015076910 W JP 2015076910W WO 2016063673 A1 WO2016063673 A1 WO 2016063673A1
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- Prior art keywords
- composition
- mass
- laminate
- propylene
- copolymer
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Definitions
- the present invention relates to a composition for providing a laminate having excellent adhesion characteristics and processing characteristics when bonded to an adherend, and a laminate comprising the composition.
- a typical example is a surface protective film, which generally uses a support substrate made of thermoplastic resin or paper, with an adhesive layer formed on it, and attaches the adhesive layer surface to the adherend. Then, the surface is protected by coating with a supporting substrate.
- liquid crystal displays and touch panel devices have been widely used, and these are composed of a number of members such as optical sheets and optical films made of synthetic resin. Since such optical members need to reduce defects such as optical distortion as much as possible, surface protection films are frequently used to prevent scratches and dirt that may cause defects.
- the surface protection film As the characteristics of the surface protection film, it is not easily peeled off from the adherend when subjected to external force such as punching processing, environmental change such as temperature, humidity, etc., that it can be easily peeled off when peeled off from the adherend, Furthermore, it is required that the pressure-sensitive adhesive and the pressure-sensitive adhesive component do not remain on the adherend when peeled.
- the adhesive force increases with the passage of time, and the peelability may deteriorate, and it is difficult to achieve both the peelability and the processing characteristics.
- an object of the present invention is to provide a composition for providing a laminate having excellent adhesion characteristics and processing characteristics when bonded to an adherend, and a laminate composed of the composition. There is to do.
- the present invention is as follows. 1) A composition satisfying the following conditions 1 and 2.
- Condition 1 Shear loss tangent (tan ⁇ 0 ° C. ) at a frequency of 1 Hz and a temperature of 0 ° C. is 0.20 or more and 0.60 or less
- Condition 2 Shear loss tangent (tan ⁇ 100 ° C. ) at a frequency of 1 Hz and a temperature of 100 ° C. is 0.
- compositions above 40 frequency 1 Hz, for a shearing loss tangent at a temperature 60 °C (tan ⁇ 60 °C), and shear loss tangent at a temperature 100 °C (tan ⁇ 100 °C), the following condition 3.
- the composition according to 1) satisfying 3.
- Condition 3 0.20 ⁇ tan ⁇ 100 ° C. ⁇ tan ⁇ 60 ° C. ⁇ 0.60 3)
- the adhesive layer is 1) to 4) The laminated body containing the composition in any one. 6) The laminate according to 5), which is used for protecting the surface of the prism sheet.
- a composition for providing a laminate having excellent adhesion characteristics and processing characteristics when bonded to an adherend and a laminate composed of the composition are provided. be able to.
- composition of the present invention is characterized by satisfying the following conditions 1 and 2.
- Condition 1 Shear loss tangent (tan ⁇ 0 ° C. ) at a frequency of 1 Hz and a temperature of 0 ° C. is 0.20 or more and 0.60 or less.
- Condition 2 Shear loss tangent (tan ⁇ 100 ° C. ) at a frequency of 1 Hz and a temperature of 100 ° C. is 0.40 or more and 0.80 or less.
- the composition of this invention when used for the adhesion layer of the laminated body for protecting a to-be-adhered body, a favorable adhesion characteristic and processing characteristic can be obtained. That is, it is excellent in sticking to an adherend, hardly peels off during punching, and can be easily peeled off from the adherend.
- the tan ⁇ 0 ° C. is more preferably 0.30 or more and 0.50 or less, and the tan ⁇ 100 ° C. is more preferably 0.50 or more and 0.80 or less.
- the loss tangent means a value obtained by dividing the loss elastic modulus obtained by dynamic viscoelasticity measurement by the storage elastic modulus.
- the loss elastic modulus refers to a viscous component that releases its energy as heat when stress is applied
- the storage elastic modulus refers to an elastic component that stores energy therein and holds the stress.
- Dynamic viscoelasticity measurement is a measurement that examines the mechanical properties of a sample by applying a strain or stress that changes (vibrates) over time to the sample and measuring the stress or strain generated thereby.
- There are a plurality of measurement modes such as tension / compression, shear, and three-point bending.
- the loss tangent is a value measured in the shear mode at a frequency of 1 Hz and a strain of 0.01%. Details of the measurement method will be described later.
- the processing characteristics When the tan ⁇ 0 ° C. is less than 0.20, the processing characteristics may be deteriorated, and when it is greater than 0.60, the peelability may be deteriorated. Further, when the above tan ⁇ 100 ° C. is less than 0.40, the processing characteristics may be deteriorated, and when it is greater than 0.80, the adhesive strength may increase with time and the peelability may be deteriorated.
- compositions of the present invention frequency 1 Hz, and shear loss tangent at a temperature 60 °C (tan ⁇ 60 °C), the difference between the shear loss tangent at a temperature 100 °C (tan ⁇ 100 °C) ( tan ⁇ 100 °C -tan ⁇ 60 °C ) Is preferably 0.20 or more and 0.60 or less. More preferably, it is 0.30 or more and 0.60 or less, and further preferably 0.40 or more and 0.60 or less.
- the composition of the present invention preferably has an endothermic peak in the range of 60 ° C. to 100 ° C. in differential scanning calorimetry. More preferably, the composition has an endothermic peak in the range of 70 ° C. or higher and 100 ° C. or lower, particularly preferably in the range of 70 ° C. or higher and 90 ° C. or lower.
- the adhesion characteristics and processing characteristics are preferably controlled. can do.
- the heat resistance When the endothermic peak is less than 60 ° C., the heat resistance may be deteriorated, and when it exceeds 100 ° C., the processing characteristics may be deteriorated.
- the composition of the present invention is not particularly limited as long as the conditions 1 and 2 which are constituent requirements are satisfied.
- a crosslinking system such as an acrylic or silicone system, a non-crosslinking system such as a natural rubber system or a synthetic rubber system or a pseudo-crosslinking system
- Any material of (thermoplastic) may be used, but it is preferable that a thermoplastic resin is the main component from the viewpoint of recyclability.
- the main component of the thermoplastic resin means that the ratio of the thermoplastic resin in the composition is 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. .
- composition of the present invention preferably contains at least a styrene elastomer, a propylene / ⁇ -olefin copolymer and a tackifier.
- the styrene-based elastomer means a resin having a structural unit derived from styrene and exhibiting rubber-like elasticity at room temperature, and a known one can be used.
- a styrene / butadiene copolymer is used.
- Copolymers of styrene and diene such as (SBR), styrene / isoprene / styrene copolymer (SIS), styrene / butadiene / styrene copolymer (SBS), and hydrogenated products thereof, such as styrene / ethylene / butylene -Styrene copolymer (SEBS), styrene and isobutylene copolymer, for example, styrene-isobutylene-styrene triblock copolymer (SIBS), styrene-isobutylene diblock copolymer (SIB), or a mixture thereof And styrene / isobutylene block copolymers.
- SBR styrene / isoprene / styrene copolymer
- SIS styrene / but
- styrenic elastomers may be used alone or in combination of two or more.
- HSBR hydrogenated styrene / butadiene copolymer
- SEBS styrene / ethylene / butylene / styrene copolymer
- SIBS isobutylene / styrene triblock copolymer
- SIB isobutylene diblock copolymer
- 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.
- the weight average molecular weight is less than 50,000, the cohesive force of the pressure-sensitive adhesive layer may be reduced, and adhesive residue may be generated when peeled from the adherend.
- the weight average molecular weight exceeds 400,000, the viscosity increases and the productivity decreases. There is.
- the styrene content in the styrene-based elastomer is preferably in the range of 5 to 30% by mass, and more preferably in the range of 8 to 20% by mass.
- the styrene content is less than 5% by mass, the cohesive force of the adhesive layer is reduced, and adhesive residue may be generated when it is peeled off from the adherend.
- it exceeds 30% by mass the adherence to the adherend is likely. In particular, the adhesiveness may be insufficient for an adherend having unevenness.
- the propylene / ⁇ -olefin copolymer refers to a copolymer composed of a structural unit derived from propylene and a structural unit derived from ethylene or ⁇ -olefin.
- propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / 1-pentene copolymer, propylene / 1-hexene copolymer, propylene / 1-octene copolymer, propylene / ethylene / 1 -Butene copolymer and the like can be mentioned, but not limited thereto.
- only one type of propylene / ⁇ -olefin copolymer may be used, or two or more types may be used in combination.
- the propylene / ⁇ -olefin copolymer preferably has a melting point in the range of 60 ° C. to 100 ° C. More preferably, it is the range of 70 degreeC or more and 100 degrees C or less, Most preferably, it is the range of 70 degreeC or more and 90 degrees C or less.
- the melting point of the propylene / ⁇ -olefin copolymer can be controlled by changing the type of ⁇ -olefin and the copolymerization ratio.
- the tackifier is a material blended to enhance the adhesiveness of the adhesive layer as defined in JIS Z0109 (1992), and those having a softening point of 80 to 150 ° C. can be used.
- petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic / aromatic copolymers and alicyclic copolymers, terpene resins, terpene phenol resins, rosin resins
- Commonly used materials such as alkylphenol resins, xylene resins or hydrogenated products thereof can be used. In the present invention, only one type of tackifier may be used, or two or more types may be used in combination.
- the total content of the above-described styrene elastomer, propylene / ⁇ -olefin copolymer, and tackifier is preferably 60% by mass or more when the total composition is 100% by mass, 70 More preferably, it is more preferably 80% by weight or more. When the total content is less than 60% by mass, the balance between the adhesive property and the processing property may be lowered.
- the content of the styrene elastomer is preferably 40% by mass or more, and more preferably 50% by mass or more.
- the content of the propylene / ⁇ -olefin copolymer is preferably 10% by mass or more, and more preferably 15% by mass or more.
- 5 mass% or more is preferable and, as for content of a tackifier, 10 mass% is more preferable.
- composition of the present invention is not limited to the above-described styrene elastomer, propylene / ⁇ -olefin copolymer, and tackifier, as long as the object of the present invention is not impaired. Additives and the like may be added as appropriate.
- resins such as polyolefin can be used.
- low density polyethylene 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 / or block copolymer), and propylene / ⁇ other than the above-mentioned propylene / ⁇ -olefin copolymer -Olefin copolymer, propylene / ethylene / ⁇ -olefin copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, ethylene / n-butyl (meth) acrylate copolymer
- ethylene and vinyl acetate copolymer These resins may be used alone or
- the total content of other resin components for adjusting the adhesive strength is preferably 20% by mass or less, and more preferably 10% by mass or less, based on 100% by mass of the entire composition.
- the total content of other resin components for adjusting the adhesive strength exceeds 20% by mass, when the composition of the present invention is used for the adhesive layer of the laminate for protecting the adherend, It may be difficult to achieve both processing characteristics.
- a lubricant for example, a lubricant, an antioxidant, a weathering agent, an antistatic agent, an antiadhesive agent and the like can be added. These additives may be used alone or in combination of two or more.
- the total content of additives is preferably 3% by mass or less, and more preferably 2% by mass or less, based on 100% by mass of the entire composition. When the total content of the additives is more than 3% by mass, the product may bleed out from the adhesive layer to cause defects in the product, or the adherend may be contaminated.
- the laminate of the present invention is a laminate having an adhesive layer on one surface of a substrate, and the adhesive layer contains the above-described composition.
- the laminate of the present invention will be described in detail.
- the base material which comprises the laminated body of this invention is not specifically limited,
- resin such as polyolefin and polyester
- polyolefin is a main component from viewpoints of productivity, processing appropriateness, etc.
- having polyolefin as a main component means that the ratio of polyolefin is 50% by mass or more, more preferably 70% by mass or more, when the whole substrate is 100% by mass.
- polystyrene resin examples include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, low crystalline or amorphous ethylene / ⁇ -olefin copolymer, polypropylene, propylene / ethylene copolymer.
- Polymer (random copolymer and / or block copolymer), propylene / ⁇ -olefin copolymer, propylene / ethylene / ⁇ -olefin copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / methyl ( And a (meth) acrylate copolymer, an ethylene / n-butyl (meth) acrylate copolymer, and an ethylene / vinyl acetate copolymer. 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.
- 1-heptene examples include 1-heptene.
- polypropylene, propylene / ethylene copolymer (random copolymer and / or block copolymer), propylene / ethylene / ⁇ -olefin copolymer, and propylene / ⁇ -olefin can be obtained with high rigidity.
- a propylene-based material such as a copolymer is more preferable.
- the melt flow rate (measured under the conditions of MFR, 230 ° C. and 2.16 kg) of the polyolefin mainly used for 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. If the MFR is less than 2 g / min, the melt viscosity is too high, and the productivity may decrease. On the other hand, if the MFR is larger than 30 g / min, the base material becomes brittle and it may be difficult to handle at the time of manufacturing or using the laminate.
- the base material in the present invention may have a two-layer structure or more.
- composition constituting the substrate of the present invention a lubricant, an antioxidant, a weathering agent, an antistatic agent, a crystal nucleating agent, a pigment, etc., as long as the properties as the laminate of the present invention are not impaired.
- Various additives may be added as appropriate.
- the thickness of the substrate can be appropriately adjusted in accordance with the required characteristics of the laminate, but is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and particularly preferably 10 to 80 ⁇ m. If it is thinner than 5 ⁇ m, the strength may be insufficient, and it may be difficult to convey in the manufacturing process, or may be torn during processing or use. If it is thicker than 200 ⁇ m, the transparency of the film may be insufficient or the productivity may be reduced.
- composition is preferably used for the pressure-sensitive 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 according to the material, thickness, surface shape and required level of the adherend, but is preferably 1 to 20 ⁇ m, more preferably 2 to 10 ⁇ m, and particularly preferably 2 to 8 ⁇ m. If the thickness of the adhesive layer is smaller than 1 ⁇ m, sufficient adhesive strength may not be exhibited on the adherend, and if it is larger than 20 ⁇ m, the adhesive strength may be excessive or the productivity may be reduced. .
- the laminated body of the present invention is a laminated body having at least a base material and an adhesive layer. However, it is a preferable aspect to provide a release layer on the surface opposite to the adhesive layer of the base material to form a three-layer laminated structure. is there.
- the material, thickness, and surface shape constituting the release layer may be selected and adjusted from the viewpoint of the adhesive strength of the adhesive layer and the processing suitability during the production and use of the laminate, and use techniques known in the art. be able to.
- a propylene resin containing 0.5 to 10% by mass of a fluorine-containing compound having both a polyfluorohydrocarbon group and a polyoxyethylene group is mainly constituted. It is preferable.
- the propylene-based resin may be the same as or different from the propylene-based resin constituting the base material, but at least a copolymer of propylene and ethylene and / or ⁇ -olefin is used. It is preferable to contain 20% by mass or more in order to roughen the surface roughness of the release layer described later to 3.0 ⁇ m or more in terms of Rz.
- the propylene-based polymer is a copolymer with ethylene and / or ⁇ -olefin, the higher the monomer content, the lower the melting point of the copolymer. Since it is possible, the monomer content is more preferably in the range of 3 to 7% by mass.
- it can also select suitably so that such monomer content may be decreased and desired heat resistance may be acquired.
- the MFR of the propylene resin at 230 ° C. is preferably in the range of 3 to 40 g / 10 minutes.
- those having an MFR in the range of 10 to 40 g / 10 min are more preferred because they can be extruded at low temperature and are easy to roughen the release layer when combined with low density polyethylene.
- the release layer In order to roughen the release layer, it is preferable to contain at least 4% by mass of high-pressure low-density polyethylene having poor compatibility with the propylene resin.
- the release layer is composed of a propylene-based resin containing 0.5% by mass to 10% by mass of a fluorine-containing compound containing a polyfluorohydrocarbon group and a polyoxyethylene group at the same time.
- a fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group include a (meth) acrylic acid ester having a C 1-18 perfluoroalkyl group as the monomer (a).
- the monomer (b) described later and the (meth) acrylic acid ester having a polyoxyethylene group of the monomer (c) can be copolymerized.
- 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 linear or branched. These may be used alone or in combination of two or more.
- Such (meth) acrylic acid ester having a perfluoroalkyl group is commercially available from Kyoeisha Chemical Co., Ltd., or can be synthesized by a known method using a commercially available fluorine-containing compound as a raw material.
- the monomer (b) containing a polyoxyethylene group those having a structure in which oxyethylene units (—CH 2 —CH 2 —O—) are linked in an amount of 1 to 30 are preferable. Are more preferred.
- An oxypropylene unit (—CH 2 —CH (CH 3 ) —O—) may be contained in the chain.
- Preferable examples include polyethylene glycol monomethacrylate having 8 oxyethylene units.
- the monomer (b) may be used alone or in combination of two or more.
- Another monomer (c) containing a polyoxyethylene group is a di (meta) having a structure in which 1 to 30 oxyethylene units are linked and having double bonds at both ends.
- acrylate, a polyethylene glycol dimethacrylate having a chain number of 8 can be exemplified.
- Such monomer (c) can also be used alone or in combination of two or more.
- the proportions of the monomer (a), the monomer (b) and the monomer (c) are as follows: the monomer (a) is 1 to 80% by mass, and the monomer (b) is 1 to 80% by mass.
- the mass% and the monomer (c) are preferably 1 to 50 mass%.
- the fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group is copolymerized with a monomer that can be copolymerized with these three monomers in a range of less than 50% by mass. May be.
- monomers include methylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl halide, styrene, methylstyrene, (meth) acrylic acid and its esters, (meth) acrylamide monomers, (meth) allyl monomers. Examples include a polymer.
- the polymerization method for obtaining the fluorine-containing compound having the polyfluorohydrocarbon group and the polyoxyethylene group using the monomer may be any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In addition to thermal polymerization, photopolymerization and energy ray polymerization can also be employed.
- polymerization initiator existing organic azo compounds, peroxides, persulfates and the like can be used.
- the weight average molecular weight of the fluorine-containing compound used in the present invention is preferably from 1,000 to 100,000, particularly preferably from 5,000 to 20,000.
- the weight average molecular weight can be adjusted with a polymerization chain transfer agent such as thiol, mercaptan, or ⁇ -methylstyrene.
- the ratio of the fluorine-containing compound in the release layer of the present invention is preferably 0.5% by mass to 10% by mass. If it is less than 0.5% by mass, blocking with the adhesive layer is likely to occur, and it may be difficult to obtain a desired unwinding force. In addition, if the content exceeds 10% by mass, the solubility in the resin is low, so that it is difficult to mix uniformly, and at the time of melt extrusion, the propylene resin for forming the release layer is affected by the fluorine-containing compound. In some cases, it may be difficult to slide and uniformly discharge at the extrusion screw portion.
- the release layer of the present invention preferably contains 0.1 to 10% by mass of inorganic or organic particles having an average particle size of 1 to 20 ⁇ m at the same time in addition to the fluorine-containing compound.
- inorganic or organic particles having an average particle size of 3 to 15 ⁇ m are particularly preferred from the viewpoint of slipperiness and blocking properties.
- inorganic particles examples include calcium carbonate, magnesium carbonate, titanium oxide, clay, talc, magnesium hydroxide, aluminum hydroxide, zeolite, etc., other than silica, among which silica is more preferable.
- organic particles examples include polystyrene and polymethyl methacrylate.
- the synergistic effect of the fluorine-containing compound, the inorganic or organic particles, and the surface roughness of the release layer described later makes it difficult to block and makes it easy to obtain good unwinding properties.
- the surface roughness of the release layer of the present invention is preferably 3 ⁇ m or more in terms of 10-point average roughness (Rz). If Rz is less than 3 ⁇ m, wrinkles are likely to occur when the laminate is wound into a roll, and the quality may be lowered.
- Such surface roughness can be achieved by, for example, a method in which a small amount of an ethylene resin having poor compatibility is added to the main propylene resin as described above.
- the production method of the laminate of the present invention is not particularly limited.
- the resin composition constituting each is melt-extruded from an individual extruder, and a die is formed.
- the so-called coextrusion method for laminating and integrating the above, and the method of laminating by laminating after individually melting and extruding the base material, the adhesive layer, and the release layer are mentioned.
- it is manufactured by the method.
- the co-extrusion method known methods such as an inflation method and a T-die method are used. From the viewpoint of excellent thickness accuracy and surface shape control, a hot-melt co-extrusion method by the T-die method is particularly preferable.
- the tackifier when the tackifier is premixed uniformly with a styrene elastomer and / or propylene / ⁇ -olefin copolymer and used as a master pellet, when the resin constituting the adhesive layer is melt-extruded, It is preferable because a uniform adhesive layer is easily obtained.
- the content of the tackifier in the master pellet may be appropriately adjusted according to the physical properties of the tackifier and the resin to be mixed, but is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of productivity. .
- the laminate composed of the composition of the present invention can be used as a surface protection film for the prevention of scratches during the production, processing and transportation of synthetic resin plates, metal plates, glass plates, etc.
- it is suitably used for adherends having irregularities on the surface.
- it is used for a diffusion plate, a prism sheet or the like, which is a display member made of a synthetic resin, and a laminate composed of the composition of the present invention is particularly preferably used for protecting the surface of the prism sheet.
- the prism sheet protected by the laminate composed of the composition of the present invention is one in which a triangular prism is arranged on one side of the sheet in parallel on the sheet surface so that the ridge line is the outer surface.
- the material which comprises a prism is not specifically limited, Resin which has translucency is used, for example, acrylic resin, a polycarbonate, etc. are mentioned.
- the distance between adjacent ridge lines of the prism is preferably 10 to 1,000 ⁇ m, and more preferably 10 to 300 ⁇ m.
- the height of the prism (the length of the perpendicular from the base of the triangular prism to the ridge line) is preferably 5 to 200 ⁇ m, and more preferably 10 to 100 ⁇ m.
- the prism sheet protected by the present invention may be composed only of prisms having the same shape, or may be composed of two or more types of prisms having different shapes.
- the prism sheet protected by the present invention may be composed only of prisms having the same shape, or may be composed of two or more types of prisms having different shapes.
- the prism sheet protected by the present invention may be composed only of prisms having the same shape, or may be composed of two or more types of prisms having different shapes.
- prisms of different shapes for example, there are cases where large and small prisms having different heights are alternately arranged one by one, or one large prism and a plurality of small prisms are alternately disposed.
- it is designed appropriately according to the purpose.
- Dynamic viscoelasticity measurement Resins constituting the compositions shown in Examples and Comparative Examples are blended at a predetermined mixing ratio, and the temperature is 200 ° C. and the rotation speed is 20 rpm using a lab plast mill 100MR3 manufactured by Toyo Seiki Seisakusho. Kneaded for 15 minutes. Subsequently, the obtained kneaded material was melt-molded to a thickness of 2 mm, and the temperature was ⁇ 80 to 120 ° C., the temperature rising rate was 3 ° C./min, the frequency was 1 Hz, using a rheometer AR2000ex manufactured by TA Instruments. The viscoelasticity of the composition was evaluated in shear mode at a strain of 0.01%.
- composition Materials of the following compositions A to E, X to Z, and S were prepared as shown in Examples 1 to 5 and Comparative Examples 1 to 4, and dynamic viscoelasticity measurement was performed as shown in the above (1) and (2). And differential scanning calorimetry was performed. The results are shown in Table 1.
- Example 1 Composition A: 14% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals Co., Ltd.) and 30% by mass of HSBR (1321P manufactured by JSR) as styrene elastomer, and propylene / 1-butene copolymer as propylene / ⁇ -olefin copolymer 20% by mass of coalescence (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) and 36% by mass of 50% by mass master pellets of hydrogenated terpene phenol (YS Polystar TH130 manufactured by Yasuhara Chemical) as a tackifier were used.
- SEBS Teftec H1052 manufactured by Asahi Kasei Chemicals Co., Ltd.
- HSBR 1321P manufactured by JSR
- propylene / 1-butene copolymer as propylene / ⁇ -olefin copolymer 20% by mass
- the hydrogenated terpenephenol 50% by mass master pellets were obtained by preliminarily mastering 50% by mass of the hydrogenated terpenephenol and 50% by mass of the SEBS by using a twin screw extruder.
- Composition B 8% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 27% by mass of HSBR (1321P manufactured by JSR), propylene / 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.)
- Composition A was the same as composition A except that 40% by mass of 25% by mass, 50% by mass master pellets of hydrogenated terpene phenol (YS Polystar TH130 manufactured by Yasuhara Chemical) was used.
- Composition C The same as Composition B, except that a propylene / 1-butene copolymer (Tafmer XM-7070, Mitsui Chemicals, melting point 75 ° C.) was used as the propylene / ⁇ -olefin copolymer.
- a propylene / 1-butene copolymer Tefmer XM-7070, Mitsui Chemicals, melting point 75 ° C.
- Example 4 Composition D 14% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynalon 1321P manufactured by JSR), propylene / 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) 10% by mass, hydrogenated terpenephenol (YShara Chemical YS Polystar TH130) 50% by mass master pellets 36% by mass, density 921 kg / m 3 , hexene copolymer polyethylene (LLDPE) at 190 ° C. and MFR 5 g / min The same as composition A except that 10% by mass was used.
- SEBS Teftec H1052 manufactured by Asahi Kasei Chemicals
- HSBR Dynamicon 1321P manufactured by JSR
- propylene / 1-butene copolymer Tefmer XM-7080 manufactured by Mitsui Chemical
- Composition E 25% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynalon 1321P manufactured by JSR), propylene / 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) 10 mass%, hydrogenated terpenephenol (YShara Chemical YS Polystar TH130) 50 mass% master pellet 20 mass%, except that 15 mass% resin mainly made of amorphous polypropylene (Sumitomo Chemical Tough Selenium T3712) was used. The same as composition A.
- Composition X 15% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynalon 1321P manufactured by JSR), and 30% by mass of 50% by mass master pellet of hydrogenated terpene phenol (YS Polystar TH130 manufactured by Yasuhara Chemical) The same as composition A except that 25% by mass of LLDPE similar to that used in Example 4 was used.
- Composition Y Same as Composition A except that 50% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals) and 50% by mass of HSBR (Dynalon 1321P manufactured by JSR) were used.
- Composition Z 70% by mass of propylene / 1-butene copolymer (Tafmer XM-7080, Mitsui Chemicals, melting point 83 ° C.) and 30% by mass of a resin mainly composed of amorphous polypropylene (Tuff Selenium T3712 manufactured by Sumitomo Chemical) Except for the above, it was the same as Composition A.
- Composition S 35% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 35% by mass of HSBR (Dynalon 1321P manufactured by JSR), and 30% by mass of a resin mainly composed of amorphous polypropylene (Tuff Selenium T3712 manufactured by Sumitomo Chemical) Except for the above, it was the same as the composition A.
- Example 1 The constituent resin of each layer was prepared as follows.
- Adhesive layer Composition A shown in Example 1 was used.
- Substrate Commercially available homopolypropylene having an MFR measured at 230 ° C. of 5 g / 10 min was used.
- Release layer 45% by mass of the same homopolypropylene used for the base material, 24% by mass of propylene-ethylene random copolymer measured at 230 ° C. with an MFR of 5 g / 10 min (ethylene content 5% by mass) ), A low density polyethylene having an MFR measured at 190 ° C. of 2 g / 10 min and a density of 919 kg / m 3 is added to 6% by mass, and 90% by mass of the homopolypropylene is 4% by mass of silica having an average particle diameter of 11 ⁇ m.
- a mixed composition comprising 6% by mass of a fluorine-containing compound having a fluorohydrocarbon group and a polyoxyethylene group was prepared as a master batch, and 25% by mass was uniformly mixed with a Henschel mixer.
- the fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group is a C 6 F 13 perfluoroalkyl acrylate (CH 2 ⁇ CHCOOC 2 H 4 C 6 F 13 ) as the monomer (a).
- monomer (b) 50% by mass of polyethylene glycol monoacrylate ⁇ CH 2 ⁇ CHCOO (CH 2 CH 2 O) 8 H ⁇ having 8 oxyethylene repeating units, and monomer (c)
- fluorotoluene, 2,2'-azobis (2,4-dimethylvaleronitrile) as the polymerization initiator
- lauryl mercaptan as a chain transfer agent, under nitrogen stream, stirring was polymerized for 5 hours at 60 ° C., after which was precipitated, filtered with methanol used was dried under reduced pressure.
- the multi-manifold T-die having a die width of 2,400 mm having three extruders each consisting of ⁇ 115 mm (for base material), ⁇ 90 mm (for adhesive layer), and ⁇ 65 mm (for release layer) is used as the constituent resin of each layer.
- the amount of each extruder is adjusted so that the adhesive layer thickness ratio is 12.5%, the release layer thickness ratio is 8.5%, and the base material thickness ratio is 79%.
- the composite T die was extruded at an extrusion temperature of 200 ° C. to form a three-layer laminated film having a film thickness of 40 ⁇ m. Then, after bonding to a prism sheet, peelability and processing characteristics 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 for the adhesive layer.
- 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 for 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 for 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 for 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 for 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 for the adhesive layer.
- Comparative Example 4 ′ A laminate was prepared and evaluated in the same manner as in Example 1 ′ except that the composition S shown in Comparative Example 4 was used for the adhesive layer.
- composition and laminate of the present invention are not only a surface protective film for preventing scratches and stains on adherends having irregularities on the surface, but also surface protection for various products made of various materials such as synthetic resin, metal, and glass. It can be preferably used as a film application.
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Abstract
The present invention relates to: a composition for providing a laminate that exhibits excellent adhesion characteristics and excellent processing characteristics if bonded to an object to be bonded; and a laminate which is configured from the composition.
A composition which is characterized by satisfying the following conditions 1 and 2.
Condition 1: The shear loss tangent (tanδ0°C) at a frequency of 1 Hz at a temperature of 0°C is from 0.20 to 0.60 (inclusive).
Condition 2: The shear loss tangent (tanδ100°C) at a frequency of 1 Hz at a temperature of 100°C is from 0.40 to 0.80 (inclusive).
Description
本発明は、被着体に貼り合せた際の粘着特性および加工特性に優れる積層体を提供するための組成物、および前記組成物から構成される積層体に関する。
The present invention relates to a composition for providing a laminate having excellent adhesion characteristics and processing characteristics when bonded to an adherend, and a laminate comprising the composition.
合成樹脂、金属、ガラス等の各種素材からなる製品には、加工工程、輸送工程、保管中に生じるキズや汚れを防止するため、表面を保護する材料を貼って取り扱うことが多々ある。その代表的なものが表面保護フィルムであり、一般に、熱可塑性樹脂や紙からなる支持基材の上に、粘着層が形成されたものを用いており、粘着層面を被着体に貼着させて支持基材で被覆することにより表面を保護するものである。
Products made of various materials such as synthetic resin, metal, and glass are often handled with a material that protects the surface in order to prevent scratches and dirt during processing, transportation, and storage. A typical example is a surface protective film, which generally uses a support substrate made of thermoplastic resin or paper, with an adhesive layer formed on it, and attaches the adhesive layer surface to the adherend. Then, the surface is protected by coating with a supporting substrate.
特に近年、液晶ディスプレイやタッチパネルデバイスの普及が進んでいるが、これらは合成樹脂からなる多数の光学シートや光学フィルム等の部材から構成されている。かかる光学用部材は、光学的な歪み等の欠点を極力低減させる必要があることから、欠点の原因となり得るキズや汚れを防止するため、表面保護フィルムが多用されている。
Particularly in recent years, liquid crystal displays and touch panel devices have been widely used, and these are composed of a number of members such as optical sheets and optical films made of synthetic resin. Since such optical members need to reduce defects such as optical distortion as much as possible, surface protection films are frequently used to prevent scratches and dirt that may cause defects.
表面保護フィルムの特性としては、打ち抜き加工等で外力を受けた際や、温度、湿度などの環境変化で被着体から容易に剥離しないこと、被着体から剥離する際に容易に剥離できること、さらに、剥離した際に被着体に粘着剤および粘着剤成分が残らないことなどが求められる。
As the characteristics of the surface protection film, it is not easily peeled off from the adherend when subjected to external force such as punching processing, environmental change such as temperature, humidity, etc., that it can be easily peeled off when peeled off from the adherend, Furthermore, it is required that the pressure-sensitive adhesive and the pressure-sensitive adhesive component do not remain on the adherend when peeled.
上記光学用部材のなかでも、拡散板やプリズムシートのように表面に凹凸を有する部材では、表面保護フィルムを貼り合わせた直後は、凹凸部と粘着層との接触面積が少ないため、打ち抜き加工などで外力を受けた際に、十分に外力を吸収しきれずに被着体から剥離してしまう場合がある。このような点に対して、粘着層をやわらかくする方法や粘着付与剤を用いて粘着力を高くする方法等が知られている(例えば、特許文献1~4)。
Among the above optical members, in the case of a member having an uneven surface such as a diffusion plate or a prism sheet, the contact area between the uneven portion and the adhesive layer is small immediately after the surface protective film is bonded, and therefore, punching processing, etc. When an external force is applied, the external force may not be sufficiently absorbed and may be peeled off from the adherend. For such a point, methods for softening the pressure-sensitive adhesive layer and methods for increasing the adhesive strength using a tackifier are known (for example, Patent Documents 1 to 4).
しかしながら、上記の方法では時間の経過とともに粘着力が増大し、剥離性が悪化する場合があり、剥離性と加工特性との両立が困難であった。
However, in the above method, the adhesive force increases with the passage of time, and the peelability may deteriorate, and it is difficult to achieve both the peelability and the processing characteristics.
本発明の課題は、上述の課題に鑑み、被着体に貼り合せた際の粘着特性および加工特性に優れる積層体を提供するための組成物、および前記組成物から構成される積層体を提供することにある。
In view of the above-described problems, an object of the present invention is to provide a composition for providing a laminate having excellent adhesion characteristics and processing characteristics when bonded to an adherend, and a laminate composed of the composition. There is to do.
上記課題を解決するために本発明者らは、鋭意検討を重ねた結果、以下の発明を完成させた。すなわち、本発明は以下の通りである。
1)以下の条件1および2を満たすことを特徴とする組成物。
条件1 周波数1Hz、温度0℃でのせん断損失正接(tanδ0℃)が、0.20以上0.60以下
条件2 周波数1Hz、温度100℃でのせん断損失正接(tanδ100℃)が、0.40以上0.80以下
2)前記組成物が、周波数1Hz、温度60℃でのせん断損失正接(tanδ60℃)と、温度100℃でのせん断損失正接(tanδ100℃)とについて、以下の条件3を満たす1)に記載の組成物。
条件3 0.20≦tanδ100℃-tanδ60℃≦0.60
3)前記組成物が、示差走査熱量測定において60℃以上100℃以下の範囲に吸熱ピークを有する1)または2)に記載の組成物。
4)前記組成物が少なくとも以下の(1)~(3)の成分を含有する1)~3)のいずれかに記載の組成物。
(1)スチレン系エラストマー
(2)プロピレン・α-オレフィン共重合体
(3)粘着付与剤
5)基材の一方の面に粘着層を有する積層体において、前記粘着層が1)~4)のいずれかに記載の組成物を含む積層体。
6)プリズムシートの表面保護に用いられる5)に記載の積層体。 In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows.
1) A composition satisfying the following conditions 1 and 2.
Condition 1 Shear loss tangent (tan δ 0 ° C. ) at a frequency of 1 Hz and a temperature of 0 ° C. is 0.20 or more and 0.60 or less Condition 2 Shear loss tangent (tan δ 100 ° C. ) at a frequency of 1 Hz and a temperature of 100 ° C. is 0. 0.80 2) the composition above 40, frequency 1 Hz, for a shearing loss tangent at a temperature 60 ℃ (tanδ 60 ℃), and shear loss tangent at a temperature 100 ℃ (tanδ 100 ℃), the following condition 3. The composition according to 1) satisfying 3.
Condition 3 0.20 ≦ tan δ 100 ° C.− tan δ 60 ° C. ≦ 0.60
3) The composition according to 1) or 2), wherein the composition has an endothermic peak in a range of 60 ° C. or more and 100 ° C. or less in differential scanning calorimetry.
4) The composition according to any one of 1) to 3), wherein the composition contains at least the following components (1) to (3):
(1) Styrenic elastomer (2) Propylene / α-olefin copolymer (3) Tackifier 5) In a laminate having an adhesive layer on one side of the substrate, the adhesive layer is 1) to 4) The laminated body containing the composition in any one.
6) The laminate according to 5), which is used for protecting the surface of the prism sheet.
1)以下の条件1および2を満たすことを特徴とする組成物。
条件1 周波数1Hz、温度0℃でのせん断損失正接(tanδ0℃)が、0.20以上0.60以下
条件2 周波数1Hz、温度100℃でのせん断損失正接(tanδ100℃)が、0.40以上0.80以下
2)前記組成物が、周波数1Hz、温度60℃でのせん断損失正接(tanδ60℃)と、温度100℃でのせん断損失正接(tanδ100℃)とについて、以下の条件3を満たす1)に記載の組成物。
条件3 0.20≦tanδ100℃-tanδ60℃≦0.60
3)前記組成物が、示差走査熱量測定において60℃以上100℃以下の範囲に吸熱ピークを有する1)または2)に記載の組成物。
4)前記組成物が少なくとも以下の(1)~(3)の成分を含有する1)~3)のいずれかに記載の組成物。
(1)スチレン系エラストマー
(2)プロピレン・α-オレフィン共重合体
(3)粘着付与剤
5)基材の一方の面に粘着層を有する積層体において、前記粘着層が1)~4)のいずれかに記載の組成物を含む積層体。
6)プリズムシートの表面保護に用いられる5)に記載の積層体。 In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows.
1) A composition satisfying the following conditions 1 and 2.
Condition 1 Shear loss tangent (tan δ 0 ° C. ) at a frequency of 1 Hz and a temperature of 0 ° C. is 0.20 or more and 0.60 or less Condition 2 Shear loss tangent (tan δ 100 ° C. ) at a frequency of 1 Hz and a temperature of 100 ° C. is 0. 0.80 2) the composition above 40, frequency 1 Hz, for a shearing loss tangent at a temperature 60 ℃ (tanδ 60 ℃), and shear loss tangent at a temperature 100 ℃ (tanδ 100 ℃), the following condition 3. The composition according to 1) satisfying 3.
Condition 3 0.20 ≦ tan δ 100 ° C.− tan δ 60 ° C. ≦ 0.60
3) The composition according to 1) or 2), wherein the composition has an endothermic peak in a range of 60 ° C. or more and 100 ° C. or less in differential scanning calorimetry.
4) The composition according to any one of 1) to 3), wherein the composition contains at least the following components (1) to (3):
(1) Styrenic elastomer (2) Propylene / α-olefin copolymer (3) Tackifier 5) In a laminate having an adhesive layer on one side of the substrate, the adhesive layer is 1) to 4) The laminated body containing the composition in any one.
6) The laminate according to 5), which is used for protecting the surface of the prism sheet.
本発明によれば、上述の課題に鑑み、被着体に貼り合せた際の粘着特性および加工特性に優れる積層体を提供するための組成物および前記組成物から構成される積層体を提供することができる。
According to the present invention, in view of the above-described problems, a composition for providing a laminate having excellent adhesion characteristics and processing characteristics when bonded to an adherend and a laminate composed of the composition are provided. be able to.
以下、本発明の組成物および積層体の構成要件について詳細に説明する。
Hereinafter, the constituent requirements of the composition and laminate of the present invention will be described in detail.
<組成物>
本発明の組成物は、以下の条件1および2を満たすことを特徴とする。
条件1:周波数1Hz、温度0℃でのせん断損失正接(tanδ0℃)が、0.20以上0.60以下。
条件2:周波数1Hz、温度100℃でのせん断損失正接(tanδ100℃)が、0.40以上0.80以下。 <Composition>
The composition of the present invention is characterized by satisfying the following conditions 1 and 2.
Condition 1: Shear loss tangent (tan δ 0 ° C. ) at a frequency of 1 Hz and a temperature of 0 ° C. is 0.20 or more and 0.60 or less.
Condition 2: Shear loss tangent (tan δ 100 ° C. ) at a frequency of 1 Hz and a temperature of 100 ° C. is 0.40 or more and 0.80 or less.
本発明の組成物は、以下の条件1および2を満たすことを特徴とする。
条件1:周波数1Hz、温度0℃でのせん断損失正接(tanδ0℃)が、0.20以上0.60以下。
条件2:周波数1Hz、温度100℃でのせん断損失正接(tanδ100℃)が、0.40以上0.80以下。 <Composition>
The composition of the present invention is characterized by satisfying the following conditions 1 and 2.
Condition 1: Shear loss tangent (tan δ 0 ° C. ) at a frequency of 1 Hz and a temperature of 0 ° C. is 0.20 or more and 0.60 or less.
Condition 2: Shear loss tangent (tan δ 100 ° C. ) at a frequency of 1 Hz and a temperature of 100 ° C. is 0.40 or more and 0.80 or less.
上記の条件1および2を満たすことで、本発明の組成物を、被着体を保護するための積層体の粘着層に用いた際に、良好な粘着特性および加工特性を得ることができる。すなわち、被着体への貼り付き性に優れ、打ち抜き加工時に剥がれが生じにくく、さらには被着体から容易に剥離することができる。上記tanδ0℃は、0.30以上0.50以下がより好ましく、また、tanδ100℃は0.50以上0.80以下がより好ましい。
By satisfy | filling said conditions 1 and 2, when the composition of this invention is used for the adhesion layer of the laminated body for protecting a to-be-adhered body, a favorable adhesion characteristic and processing characteristic can be obtained. That is, it is excellent in sticking to an adherend, hardly peels off during punching, and can be easily peeled off from the adherend. The tan δ 0 ° C. is more preferably 0.30 or more and 0.50 or less, and the tan δ 100 ° C. is more preferably 0.50 or more and 0.80 or less.
ここで、損失正接とは、動的粘弾性測定により得られる損失弾性率を貯蔵弾性率で除した値のことをいう。なお、損失弾性率は、応力を加えた際に、そのエネルギーを熱として逃がす粘性成分のことをいい、貯蔵弾性率は、エネルギーを内部に蓄え応力を保持する弾性成分のことをいう。
Here, the loss tangent means a value obtained by dividing the loss elastic modulus obtained by dynamic viscoelasticity measurement by the storage elastic modulus. The loss elastic modulus refers to a viscous component that releases its energy as heat when stress is applied, and the storage elastic modulus refers to an elastic component that stores energy therein and holds the stress.
また、動的粘弾性測定とは、試料に時間によって変化(振動)する歪みまたは応力を与えて、それによって発生する応力または歪みを測定することにより、試料の力学的な性質を調べる測定で、その測定モードには引張/圧縮、せん断、3点曲げなど複数あるが、本発明において、損失正接は、周波数1Hz、ひずみ0.01%で、せん断モードにて測定された値を対象とする。測定方法詳細については後述する。
Dynamic viscoelasticity measurement is a measurement that examines the mechanical properties of a sample by applying a strain or stress that changes (vibrates) over time to the sample and measuring the stress or strain generated thereby. There are a plurality of measurement modes such as tension / compression, shear, and three-point bending. In the present invention, the loss tangent is a value measured in the shear mode at a frequency of 1 Hz and a strain of 0.01%. Details of the measurement method will be described later.
上記tanδ0℃が0.20未満の場合は加工特性が低下する場合があり、0.60より大きい場合は剥離性が低下する場合がある。また、上述のtanδ100℃が0.40未満の場合は加工特性が低下する場合があり、0.80より大きい場合は経時で粘着力が大きくなり剥離性が低下する場合がある。
When the tan δ 0 ° C. is less than 0.20, the processing characteristics may be deteriorated, and when it is greater than 0.60, the peelability may be deteriorated. Further, when the above tan δ 100 ° C. is less than 0.40, the processing characteristics may be deteriorated, and when it is greater than 0.80, the adhesive strength may increase with time and the peelability may be deteriorated.
さらに、本発明の組成物は、周波数1Hz、温度60℃でのせん断損失正接(tanδ60℃)と、温度100℃でのせん断損失正接(tanδ100℃)の差(tanδ100℃-tanδ60℃)が、0.20以上0.60以下であることが好ましい。より好ましくは0.30以上0.60以下、さらに好ましくは0.40以上0.60以下である。
Furthermore, the compositions of the present invention, frequency 1 Hz, and shear loss tangent at a temperature 60 ℃ (tanδ 60 ℃), the difference between the shear loss tangent at a temperature 100 ℃ (tanδ 100 ℃) ( tanδ 100 ℃ -tanδ 60 ℃ ) Is preferably 0.20 or more and 0.60 or less. More preferably, it is 0.30 or more and 0.60 or less, and further preferably 0.40 or more and 0.60 or less.
tanδ100℃とtanδ60℃の差(tanδ100℃-tanδ60℃)が、0.20未満の場合は加工特性が低下する場合があり、0.60より大きい場合は剥離性が低下する場合がある。
If the difference between tan δ 100 ° C. and tan δ 60 ° C. (tan δ 100 ° C.− tan δ 60 ° C. ) is less than 0.20, the processing characteristics may deteriorate, and if it exceeds 0.60, the peelability may decrease. is there.
本発明の組成物は、示差走査熱量測定において60℃以上100℃以下の範囲に吸熱ピークを有することが好ましい。より好ましくは70℃以上100℃以下の範囲、特に好ましくは、70℃以上90℃以下の範囲に組成物が吸熱ピークを有することが好ましい。60℃以上100℃以下の範囲に吸熱ピークを有することで、本発明の組成物を被着体を保護するための積層体の粘着層に用いた場合に、粘着特性と加工特性とを好ましく制御することができる。
The composition of the present invention preferably has an endothermic peak in the range of 60 ° C. to 100 ° C. in differential scanning calorimetry. More preferably, the composition has an endothermic peak in the range of 70 ° C. or higher and 100 ° C. or lower, particularly preferably in the range of 70 ° C. or higher and 90 ° C. or lower. By having an endothermic peak in the range of 60 ° C. or more and 100 ° C. or less, when the composition of the present invention is used for an adhesive layer of a laminate for protecting an adherend, the adhesion characteristics and processing characteristics are preferably controlled. can do.
前記吸熱ピークが60℃未満の場合は耐熱性が低下する場合があり、100℃を超える場合は、加工特性が低下する場合がある。
When the endothermic peak is less than 60 ° C., the heat resistance may be deteriorated, and when it exceeds 100 ° C., the processing characteristics may be deteriorated.
本発明の組成物は、構成要件である条件1および2を満たせば特に限定されないが、アクリル系、シリコーン系などの架橋系、天然ゴム系、合成ゴム系等の非架橋系もしくは擬似架橋系(熱可塑系)のいずれの材料を用いてもよいが、リサイクル性の観点から熱可塑性樹脂を主成分とすることが好ましい。ここで、熱可塑性樹脂を主成分とするとは、組成物中の熱可塑性樹脂の割合が50質量%以上であること意味し、より好ましくは70質量%以上、さらに好ましくは90質量%以上である。
The composition of the present invention is not particularly limited as long as the conditions 1 and 2 which are constituent requirements are satisfied. However, a crosslinking system such as an acrylic or silicone system, a non-crosslinking system such as a natural rubber system or a synthetic rubber system or a pseudo-crosslinking system Any material of (thermoplastic) may be used, but it is preferable that a thermoplastic resin is the main component from the viewpoint of recyclability. Here, the main component of the thermoplastic resin means that the ratio of the thermoplastic resin in the composition is 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. .
また、本発明の組成物は、少なくとも、スチレン系エラストマー、プロピレン・α-オレフィン共重合体および粘着付与剤を含有することが好ましい。
The composition of the present invention preferably contains at least a styrene elastomer, a propylene / α-olefin copolymer and a tackifier.
本発明において、スチレン系エラストマーとは、スチレン由来の構造単位を有し、室温でゴム状弾性を示す樹脂のことをいい、公知のものを用いることができるが、例えば、スチレン・ブタジエン共重合体(SBR)、スチレン・イソプレン・スチレン共重合体(SIS)、スチレン・ブタジエン・スチレン共重合体(SBS)等のスチレンとジエンとの共重合体およびそれらの水添物、例えばスチレン・エチレン・ブチレン・スチレン共重合体(SEBS)等やスチレンとイソブチレンの共重合体、例えば、スチレン・イソブチレン・スチレントリブロック共重合体(SIBS)、スチレン・イソブチレンジブロック共重合体(SIB)、またはこれらの混合物等のスチレン・イソブチレンブロック共重合体等が挙げられる。これらのスチレン系エラストマーは1種類のみを用いてもよいし、2種類以上を併用することもできる。上記したスチレン系エラストマーのなかでも、水添スチレン・ブタジエン共重合体(HSBR)、スチレン・エチレン・ブチレン・スチレン共重合体(SEBS)、スチレン・イソブチレン・スチレントリブロック共重合体(SIBS)、スチレン・イソブチレンジブロック共重合体(SIB)、またはこれらの混合物が好ましく用いられる。
In the present invention, the styrene-based elastomer means a resin having a structural unit derived from styrene and exhibiting rubber-like elasticity at room temperature, and a known one can be used. For example, a styrene / butadiene copolymer is used. Copolymers of styrene and diene such as (SBR), styrene / isoprene / styrene copolymer (SIS), styrene / butadiene / styrene copolymer (SBS), and hydrogenated products thereof, such as styrene / ethylene / butylene -Styrene copolymer (SEBS), styrene and isobutylene copolymer, for example, styrene-isobutylene-styrene triblock copolymer (SIBS), styrene-isobutylene diblock copolymer (SIB), or a mixture thereof And styrene / isobutylene block copolymers. These styrenic elastomers may be used alone or in combination of two or more. Among the styrene elastomers mentioned above, hydrogenated styrene / butadiene copolymer (HSBR), styrene / ethylene / butylene / styrene copolymer (SEBS), styrene / isobutylene / styrene triblock copolymer (SIBS), styrene An isobutylene diblock copolymer (SIB) or a mixture thereof is preferably used.
スチレン系エラストマーの重量平均分子量は、好ましくは50,000~400,000の範囲、より好ましくは50,000~200,000の範囲である。重量平均分子量が50,000未満では粘着層の凝集力が低下して被着体から剥離した際に糊残りが生じる場合があり、400,000を超えると粘度が高くなり生産性が低下する場合がある。
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 pressure-sensitive adhesive layer may be reduced, and adhesive residue may be generated when peeled from the adherend. When the weight average molecular weight exceeds 400,000, the viscosity increases and the productivity decreases. There is.
スチレン系エラストマー中のスチレン含有量は、5~30質量%の範囲が好ましく、8~20質量%の範囲がより好ましい。スチレン含有量が5質量%未満では粘着層の凝集力が低下して、被着体から剥離した際に糊残りが生じる場合があり、30質量%を超えると被着体への貼り付き性が低下することになり、特に凹凸を有する被着体に対して粘着性が不足する場合がある。
The styrene content in the styrene-based elastomer is preferably in the range of 5 to 30% by mass, and more preferably in the range of 8 to 20% by mass. When the styrene content is less than 5% by mass, the cohesive force of the adhesive layer is reduced, and adhesive residue may be generated when it is peeled off from the adherend. When it exceeds 30% by mass, the adherence to the adherend is likely. In particular, the adhesiveness may be insufficient for an adherend having unevenness.
また、前記プロピレン・α-オレフィン共重合体とは、プロピレン由来の構造単位およびエチレンやα-オレフィン由来の構造単位から構成される共重合体のことをいう。例えば、プロピレン・エチレン共重合体、プロピレン・1-ブテン共重合体、プロピレン・1-ペンテン共重合体、プロピレン・1-ヘキセン共重合体、プロピレン・1-オクテン共重合体、プロピレン・エチレン・1-ブテン共重合体、等が挙げられるが、これに限らず使用することができる。本発明において、プロピレン・α-オレフィン共重合体は、1種類のみを用いてもよいし、2種類以上を併用することもできる。
The propylene / α-olefin copolymer refers to a copolymer composed of a structural unit derived from propylene and a structural unit derived from ethylene or α-olefin. For example, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / 1-pentene copolymer, propylene / 1-hexene copolymer, propylene / 1-octene copolymer, propylene / ethylene / 1 -Butene copolymer and the like can be mentioned, but not limited thereto. In the present invention, only one type of propylene / α-olefin copolymer may be used, or two or more types may be used in combination.
前記プロピレン・α-オレフィン共重合体は、60℃以上100℃以下の範囲に融点を有することが好ましい。より好ましくは70℃以上100℃以下の範囲、特に好ましくは、70℃以上90℃以下の範囲である。プロピレン・α-オレフィン共重合体の融点は、α-オレフィンの種類や共重合比率を変化させることにより制御することができる。
The propylene / α-olefin copolymer preferably has a melting point in the range of 60 ° C. to 100 ° C. More preferably, it is the range of 70 degreeC or more and 100 degrees C or less, Most preferably, it is the range of 70 degreeC or more and 90 degrees C or less. The melting point of the propylene / α-olefin copolymer can be controlled by changing the type of α-olefin and the copolymerization ratio.
また、前記粘着付与剤とは、JIS Z0109(1992)に定義されている通り、粘着層の粘着性を高めるために配合する材料であり、軟化点が80~150℃のものを用いることができる。例えば、脂肪族系共重合体、芳香族系共重合体、脂肪族・芳香族系共重合体や脂環式系共重合体等の石油樹脂、テルペン系樹脂、テルペンフェノール系樹脂、ロジン系樹脂、アルキルフェノール系樹脂、キシレン系樹脂又はこれらの水添物等、一般的に用いられるものを使用することができる。本発明において、粘着付与剤は、1種類のみを用いてもよいし、2種類以上を併用することもできる。
The tackifier is a material blended to enhance the adhesiveness of the adhesive layer as defined in JIS Z0109 (1992), and those having a softening point of 80 to 150 ° C. can be used. . For example, petroleum resins such as aliphatic copolymers, aromatic copolymers, aliphatic / aromatic copolymers and alicyclic copolymers, terpene resins, terpene phenol resins, rosin resins Commonly used materials such as alkylphenol resins, xylene resins or hydrogenated products thereof can be used. In the present invention, only one type of tackifier may be used, or two or more types may be used in combination.
本発明の組成物において、上記したスチレン系エラストマー、プロピレン・α-オレフィン共重合体、粘着付与剤の合計含有量は、組成物全体を100質量%としたとき、60質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上がさらに好ましい。前記合計含有量が60質量%未満の場合は、粘着特性と加工特性のバランスが低下する場合がある。
In the composition of the present invention, the total content of the above-described styrene elastomer, propylene / α-olefin copolymer, and tackifier is preferably 60% by mass or more when the total composition is 100% by mass, 70 More preferably, it is more preferably 80% by weight or more. When the total content is less than 60% by mass, the balance between the adhesive property and the processing property may be lowered.
また、組成物全体を100質量%としたとき、スチレン系エラストマーの含有量は、40質量%以上が好ましく、50質量%以上がより好ましい。さらに、プロピレン・α-オレフィン共重合体の含有量は、10質量%以上が好ましく、15質量%以上がより好ましい。また、粘着付与剤の含有量は、5質量%以上が好ましく、10質量%がより好ましい。
Further, when the total composition is 100% by mass, the content of the styrene elastomer is preferably 40% by mass or more, and more preferably 50% by mass or more. Further, the content of the propylene / α-olefin copolymer is preferably 10% by mass or more, and more preferably 15% by mass or more. Moreover, 5 mass% or more is preferable and, as for content of a tackifier, 10 mass% is more preferable.
本発明の組成物は、本発明の目的を損なわない範囲で、上記したスチレン系エラストマー、プロピレン・α-オレフィン共重合体、粘着付与剤以外にも、粘着力調整のための他の樹脂成分や添加剤等を適宜添加してもよい。
The composition of the present invention is not limited to the above-described styrene elastomer, propylene / α-olefin copolymer, and tackifier, as long as the object of the present invention is not impaired. Additives and the like may be added as appropriate.
粘着力調整のための他の樹脂成分としては、ポリオレフィン等の樹脂を用いることができ、例えば、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン、低結晶性あるいは非晶性のエチレン・α-オレフィン共重合体、ポリプロピレン、プロピレン・エチレン共重合体(ランダム共重合体および/またはブロック共重合体)、上記したプロピレン・α-オレフィン共重合体とは別のプロピレン・α-オレフィン共重合体、プロピレン・エチレン・α-オレフィン共重合体、エチレン・エチル(メタ)アクリレート共重合体、エチレン・メチル(メタ)アクリレート共重合体、エチレン・n-ブチル(メタ)アクリレート共重合体、エチレン・酢酸ビニル共重合体等が挙げられる。これらの樹脂は、単独で用いてもよく、2種類以上を併用してもよい。
As other resin components for adjusting the adhesive strength, resins such as polyolefin can be used. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, low crystalline or amorphous Ethylene / α-olefin copolymer, polypropylene, propylene / ethylene copolymer (random copolymer and / or block copolymer), and propylene / α other than the above-mentioned propylene / α-olefin copolymer -Olefin copolymer, propylene / ethylene / α-olefin copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, ethylene / n-butyl (meth) acrylate copolymer For example, ethylene and vinyl acetate copolymer. These resins may be used alone or in combination of two or more.
粘着力調整のための他の樹脂成分の総含有量は、組成物全体を100質量%としたとき、20質量%以下が好ましく、10質量%以下がより好ましい。粘着力調整のための他の樹脂成分の総含有量が20質量%を超えると、本発明の組成物を被着体を保護するための積層体の粘着層に用いた場合に、粘着特性と加工特性の両立が困難な場合がある。
The total content of other resin components for adjusting the adhesive strength is preferably 20% by mass or less, and more preferably 10% by mass or less, based on 100% by mass of the entire composition. When the total content of other resin components for adjusting the adhesive strength exceeds 20% by mass, when the composition of the present invention is used for the adhesive layer of the laminate for protecting the adherend, It may be difficult to achieve both processing characteristics.
添加剤としては、例えば、滑剤、酸化防止剤、耐候剤、帯電防止剤、粘着昂進防止剤等を添加することができる。これらの添加剤は単体で用いてもよく、2種類以上を併用してもよい。添加剤の総含有量は、組成物全体を100質量%としたときに、3質量%以下が好ましく、2質量%以下がより好ましい。添加剤の総含有量が3質量%より多い場合は、粘着層からブリードアウトして、製品に欠点を生じる場合や、被着体を汚染する場合がある。
As the additive, for example, a lubricant, an antioxidant, a weathering agent, an antistatic agent, an antiadhesive agent and the like can be added. These additives may be used alone or in combination of two or more. The total content of additives is preferably 3% by mass or less, and more preferably 2% by mass or less, based on 100% by mass of the entire composition. When the total content of the additives is more than 3% by mass, the product may bleed out from the adhesive layer to cause defects in the product, or the adherend may be contaminated.
<積層体>
本発明の積層体は、基材の一方の面に粘着層を有する積層体であり、前記粘着層が前述の組成物を含むことを特徴とする。以下、本発明の積層体について詳細に説明する。 <Laminated body>
The laminate of the present invention is a laminate having an adhesive layer on one surface of a substrate, and the adhesive layer contains the above-described composition. Hereinafter, the laminate of the present invention will be described in detail.
本発明の積層体は、基材の一方の面に粘着層を有する積層体であり、前記粘着層が前述の組成物を含むことを特徴とする。以下、本発明の積層体について詳細に説明する。 <Laminated body>
The laminate of the present invention is a laminate having an adhesive layer on one surface of a substrate, and the adhesive layer contains the above-described composition. Hereinafter, the laminate of the present invention will be described in detail.
<基材>
本発明の積層体を構成する基材は、特に限定されないが、例えばポリオレフィンやポリエステル等の樹脂を用いることができる。なかでも、生産性や加工適正等の観点から、ポリオレフィンを主成分とすることが好ましい。ここで、ポリオレフィンを主成分とするとは、基材全体を100質量%としたとき、ポリオレフィンの割合が50質量%以上であることを意味し、より好ましくは70質量%以上である。 <Base material>
Although the base material which comprises the laminated body of this invention is not specifically limited, For example, resin, such as polyolefin and polyester, can be used. Especially, it is preferable that polyolefin is a main component from viewpoints of productivity, processing appropriateness, etc. Here, having polyolefin as a main component means that the ratio of polyolefin is 50% by mass or more, more preferably 70% by mass or more, when the whole substrate is 100% by mass.
本発明の積層体を構成する基材は、特に限定されないが、例えばポリオレフィンやポリエステル等の樹脂を用いることができる。なかでも、生産性や加工適正等の観点から、ポリオレフィンを主成分とすることが好ましい。ここで、ポリオレフィンを主成分とするとは、基材全体を100質量%としたとき、ポリオレフィンの割合が50質量%以上であることを意味し、より好ましくは70質量%以上である。 <Base material>
Although the base material which comprises the laminated body of this invention is not specifically limited, For example, resin, such as polyolefin and polyester, can be used. Especially, it is preferable that polyolefin is a main component from viewpoints of productivity, processing appropriateness, etc. Here, having polyolefin as a main component means that the ratio of polyolefin is 50% by mass or more, more preferably 70% by mass or more, when the whole substrate is 100% by mass.
前記ポリオレフィンとしては、例えば、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン、低結晶性あるいは非晶性のエチレン・α-オレフィン共重合体、ポリプロピレン、プロピレン・エチレン共重合体(ランダム共重合体および/またはブロック共重合体)、プロピレン・α-オレフィン共重合体、プロピレン・エチレン・α-オレフィン共重合体、エチレン・エチル(メタ)アクリレート共重合体、エチレン・メチル(メタ)アクリレート共重合体、エチレン・n-ブチル(メタ)アクリレート共重合体、エチレン・酢酸ビニル共重合体等が挙げられる。これらは単独で用いても併用してもよい。なお、前記α-オレフィンとしては、プロピレンやエチレンと共重合可能であれば特に限定されず、例えば、1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、1-オクテン、1-ペンテン、1-ヘプテン等を挙げることができる。上記したポリオレフィンのなかでも、高剛性が得られるポリプロピレン、プロピレン・エチレン共重合体(ランダム共重合体および/またはブロック共重合体)、プロピレン・エチレン・α-オレフィン共重合体、プロピレン・α-オレフィン共重合体等のプロピレン系材料がより好ましい。
Examples of the polyolefin include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, low crystalline or amorphous ethylene / α-olefin copolymer, polypropylene, propylene / ethylene copolymer. Polymer (random copolymer and / or block copolymer), propylene / α-olefin copolymer, propylene / ethylene / α-olefin copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / methyl ( And a (meth) acrylate copolymer, an ethylene / n-butyl (meth) acrylate copolymer, and an ethylene / vinyl acetate copolymer. These may be used alone or in combination. The α-olefin is not particularly limited as long as it can be copolymerized with propylene or ethylene. For example, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-pentene, Examples include 1-heptene. Among the above-mentioned polyolefins, polypropylene, propylene / ethylene copolymer (random copolymer and / or block copolymer), propylene / ethylene / α-olefin copolymer, and propylene / α-olefin can be obtained with high rigidity. A propylene-based material such as a copolymer is more preferable.
本発明の基材に主として用いるポリオレフィンのメルトフローレート(MFR、230℃、2.16kgの条件で測定)は、2~30g/分の範囲が好ましく、特に5~30g/分の範囲が好ましい。MFRが2g/分未満では、溶融粘度が高すぎるため生産性が低下する場合がある。また、MFRが30g/分より大きいと、基材が脆くなり積層体製造時や使用時に取り扱いにくい場合がある。
The melt flow rate (measured under the conditions of MFR, 230 ° C. and 2.16 kg) of the polyolefin mainly used for 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. If the MFR is less than 2 g / min, the melt viscosity is too high, and the productivity may decrease. On the other hand, if the MFR is larger than 30 g / min, the base material becomes brittle and it may be difficult to handle at the time of manufacturing or using the laminate.
本発明における基材は、2層構成以上とすることもできる。
The base material in the present invention may have a two-layer structure or more.
また、本発明の基材を構成する組成物中には、本発明の積層体としての特性を損なわない範囲で、滑剤、酸化防止剤、耐候剤、帯電防止剤、結晶核剤、顔料等の各種添加剤を適宜添加してもよい。
Further, in the composition constituting the substrate of the present invention, a lubricant, an antioxidant, a weathering agent, an antistatic agent, a crystal nucleating agent, a pigment, etc., as long as the properties as the laminate of the present invention are not impaired. Various additives may be added as appropriate.
基材の厚みは、積層体の要求特性にあわせて適宜調整することができるが、5~200μmが好ましく、さらに好ましくは10~100μm、特に好ましくは10~80μmである。5μmより薄いと強度が不足し、製造工程での搬送が困難な場合や、加工時や使用時に破れてしまう場合がある。200μmより厚い場合は、フィルムの透明性が不足したり、生産性が低下したりする場合がある。
The thickness of the substrate can be appropriately adjusted in accordance with the required characteristics of the laminate, but is preferably 5 to 200 μm, more preferably 10 to 100 μm, and particularly preferably 10 to 80 μm. If it is thinner than 5 μm, the strength may be insufficient, and it may be difficult to convey in the manufacturing process, or may be torn during processing or use. If it is thicker than 200 μm, the transparency of the film may be insufficient or the productivity may be reduced.
<粘着層>
本発明の積層体を構成する粘着層は前述の組成物が好ましく用いられる。 <Adhesive layer>
The above-mentioned composition is preferably used for the pressure-sensitive adhesive layer constituting the laminate of the present invention.
本発明の積層体を構成する粘着層は前述の組成物が好ましく用いられる。 <Adhesive layer>
The above-mentioned composition is preferably used for the pressure-sensitive adhesive layer constituting the laminate of the present invention.
本発明の粘着層の厚みは、被着体の材質、厚み、表面形状や要求レベルに応じて適宜調整できるが、1~20μmが好ましく、2~10μmがさらに好ましく、2~8μmが特に好ましい。粘着層の厚みが1μmより小さいと、被着体に対して十分な粘着力を発現できない場合があり、20μmより大きい場合は粘着力が過剰となったり、生産性が低下したりする場合がある。
The thickness of the pressure-sensitive adhesive layer of the present invention can be appropriately adjusted according to the material, thickness, surface shape and required level of the adherend, but is preferably 1 to 20 μm, more preferably 2 to 10 μm, and particularly preferably 2 to 8 μm. If the thickness of the adhesive layer is smaller than 1 μm, sufficient adhesive strength may not be exhibited on the adherend, and if it is larger than 20 μm, the adhesive strength may be excessive or the productivity may be reduced. .
<離型層>
本発明の積層体は、少なくとも基材と粘着層とを有する積層体であるが、基材の粘着層と反対側の面に離型層を設けて3層積層構成とすることは好ましい態様である。離型層を構成する材料や厚み、表面形状は、粘着層の粘着力や、積層体製造時や使用時の加工適性等の観点から選択、調整すればよく、当該分野で公知の技術を用いることができる。好ましくは、離型性を良好に制御するという観点から、ポリフルオロ炭化水素基及びポリオキシエチレン基を同時に有する含フッ素化合物を0.5質量%~10質量%含有したプロピレン系樹脂を主として構成されることが好ましい。 <Release layer>
The laminated body of the present invention is a laminated body having at least a base material and an adhesive layer. However, it is a preferable aspect to provide a release layer on the surface opposite to the adhesive layer of the base material to form a three-layer laminated structure. is there. The material, thickness, and surface shape constituting the release layer may be selected and adjusted from the viewpoint of the adhesive strength of the adhesive layer and the processing suitability during the production and use of the laminate, and use techniques known in the art. be able to. Preferably, from the viewpoint of favorably controlling releasability, a propylene resin containing 0.5 to 10% by mass of a fluorine-containing compound having both a polyfluorohydrocarbon group and a polyoxyethylene group is mainly constituted. It is preferable.
本発明の積層体は、少なくとも基材と粘着層とを有する積層体であるが、基材の粘着層と反対側の面に離型層を設けて3層積層構成とすることは好ましい態様である。離型層を構成する材料や厚み、表面形状は、粘着層の粘着力や、積層体製造時や使用時の加工適性等の観点から選択、調整すればよく、当該分野で公知の技術を用いることができる。好ましくは、離型性を良好に制御するという観点から、ポリフルオロ炭化水素基及びポリオキシエチレン基を同時に有する含フッ素化合物を0.5質量%~10質量%含有したプロピレン系樹脂を主として構成されることが好ましい。 <Release layer>
The laminated body of the present invention is a laminated body having at least a base material and an adhesive layer. However, it is a preferable aspect to provide a release layer on the surface opposite to the adhesive layer of the base material to form a three-layer laminated structure. is there. The material, thickness, and surface shape constituting the release layer may be selected and adjusted from the viewpoint of the adhesive strength of the adhesive layer and the processing suitability during the production and use of the laminate, and use techniques known in the art. be able to. Preferably, from the viewpoint of favorably controlling releasability, a propylene resin containing 0.5 to 10% by mass of a fluorine-containing compound having both a polyfluorohydrocarbon group and a polyoxyethylene group is mainly constituted. It is preferable.
かかるプロピレン系樹脂としては、上記基材を構成するプロピレン系樹脂と同一のものであっても、異なるものであってもよいが、プロピレンとエチレンおよび/またはα-オレフィンとの共重合体を少なくとも20質量%以上含有することが、後述の該離型層の表面粗さをRzで3.0μm以上と粗面化する上で好ましい。プロピレン系重合体がエチレンおよび/またはα-オレフィンとの共重合体の場合、単量体含有量が多くなるほど、該共重合体の融点を低下せしめることができ、共押出の容易さ、低温押出可能なことから、単量体含有量としては3~7質量%の範囲がより好ましい。なお、離型層に耐熱性を付加したい場合は、かかる単量体含有量を少なくし、所望の耐熱性を得られるよう適宜選定することもできる。
The propylene-based resin may be the same as or different from the propylene-based resin constituting the base material, but at least a copolymer of propylene and ethylene and / or α-olefin is used. It is preferable to contain 20% by mass or more in order to roughen the surface roughness of the release layer described later to 3.0 μm or more in terms of Rz. When the propylene-based polymer is a copolymer with ethylene and / or α-olefin, the higher the monomer content, the lower the melting point of the copolymer. Since it is possible, the monomer content is more preferably in the range of 3 to 7% by mass. In addition, when adding heat resistance to a mold release layer, it can also select suitably so that such monomer content may be decreased and desired heat resistance may be acquired.
また、前記プロピレン系樹脂の230℃でのMFRは3~40g/10分の範囲が好ましい。特に、MFRが10~40g/10分の範囲のものは、低温押出でき、かつ、低密度ポリエチレンと組み合わせることで離型層を粗面化し易いことから、より好ましい。
The MFR of the propylene resin at 230 ° C. is preferably in the range of 3 to 40 g / 10 minutes. In particular, those having an MFR in the range of 10 to 40 g / 10 min are more preferred because they can be extruded at low temperature and are easy to roughen the release layer when combined with low density polyethylene.
なお、離型層を粗面化するため、前記プロピレン系樹脂と相溶性の乏しい高圧法低密度ポリエチレンを少なくとも4質量%含有するのが好ましい。
In order to roughen the release layer, it is preferable to contain at least 4% by mass of high-pressure low-density polyethylene having poor compatibility with the propylene resin.
更にまた、上記離型層は、ポリフルオロ炭化水素基及びポリオキシエチレン基を同時に含有する含フッ素化合物を0.5質量%~10質量%含有したプロピレン系樹脂から構成されてなるのが好ましい。かかるポリフルオロ炭化水素基及びポリオキシエチレン基を有する含フッ素化合物は、例えば単量体(a)として炭素数1~18のパーフルオロアルキル基を有する(メタ)アクリル酸エステル等を挙げることができ、後述の単量体(b)、単量体(c)のポリオキシエチレン基を有する(メタ)アクリル酸エステル等とを共重合して得ることができる。
Furthermore, it is preferable that the release layer is composed of a propylene-based resin containing 0.5% by mass to 10% by mass of a fluorine-containing compound containing a polyfluorohydrocarbon group and a polyoxyethylene group at the same time. Examples of the fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group include a (meth) acrylic acid ester having a C 1-18 perfluoroalkyl group as the monomer (a). The monomer (b) described later and the (meth) acrylic acid ester having a polyoxyethylene group of the monomer (c) can be copolymerized.
上記単量体(a)のパーフルオロアルキル基としては炭素数1~18が好ましく、特に1~6のものがより好ましい。かかるパーフルオロアルキル基は直鎖状及び分岐状のどちらでも構わない。これらは1種のみ単独で用いてもよいし、2種以上を組み合わせて用いることができる。
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 linear or branched. These may be used alone or in combination of two or more.
かかるパーフルオロアルキル基を有する(メタ)アクリル酸エステルは共栄社化学(株)等から市販されているが、あるいは市販されているフッ素含有化合物を原料として既知の方法で合成することもできる。
Such (meth) acrylic acid ester having a perfluoroalkyl group is commercially available from Kyoeisha Chemical Co., Ltd., or can be synthesized by a known method using a commercially available fluorine-containing compound as a raw material.
ポリオキシエチレン基を含有する単量体(b)としては、オキシエチレン単位(-CH2-CH2-O-)が1~30連鎖した構造を有するものが好ましく、特に該単位が1~20のものがより好ましい。なお、該連鎖中にオキシプロピレン単位(-CH2-CH(CH3)-O-)を含有してもよい。好ましい例として、オキシエチレン単位が8つのポリエチレングリコールモノメタクリレート等を例示することができる。単量体(b)は、1種のみを単独で、または2種以上組み合わせてもよい。
As the monomer (b) containing a polyoxyethylene group, those having a structure in which oxyethylene units (—CH 2 —CH 2 —O—) are linked in an amount of 1 to 30 are preferable. Are more preferred. An oxypropylene unit (—CH 2 —CH (CH 3 ) —O—) may be contained in the chain. Preferable examples include polyethylene glycol monomethacrylate having 8 oxyethylene units. The monomer (b) may be used alone or in combination of two or more.
また、ポリオキシエチレン基を含有するもう1つ別の単量体(c)としては、オキシエチレン単位が1~30連鎖した構造を有し、かつ、両末端に2重結合を有するジ(メタ)クリレート、好ましい具体例としては、連鎖数8のポリエチレングリコールジメタクリレート等を例示することができる。かかる単量体(c)も1種のみを単独で、または2種以上組み合わせて用いることができる。
Another monomer (c) containing a polyoxyethylene group is a di (meta) having a structure in which 1 to 30 oxyethylene units are linked and having double bonds at both ends. ) As a preferred specific example, acrylate, a polyethylene glycol dimethacrylate having a chain number of 8 can be exemplified. Such monomer (c) can also be used alone or in combination of two or more.
かかる単量体(a)、単量体(b)、単量体(c)それぞれの割合としては、単量体(a)が1~80質量%、単量体(b)が1~80質量%、単量体(c)が1~50質量%であるのが好ましい。
The proportions of the monomer (a), the monomer (b) and the monomer (c) are as follows: the monomer (a) is 1 to 80% by mass, and the monomer (b) is 1 to 80% by mass. The mass% and the monomer (c) are preferably 1 to 50 mass%.
なお、上記ポリフルオロ炭化水素基及びポリオキシエチレン基を有する含フッ素化合物には、上記3つの単量体の他に、これらと共重合し得る単量体を50質量%未満の範囲で共重合してもよい。かかる単量体としては、メチレン、酢酸ビニル、塩化ビニル、フッ化ビニル、ハロゲン化ビニル、スチレン、メチルスチレン、(メタ)アクリル酸とそのエステル、(メタ)アクリルアミド単量体、(メタ)アリル単量体などを挙げることができる。
The fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group is copolymerized with a monomer that can be copolymerized with these three monomers in a range of less than 50% by mass. May be. Such monomers include methylene, vinyl acetate, vinyl chloride, vinyl fluoride, vinyl halide, styrene, methylstyrene, (meth) acrylic acid and its esters, (meth) acrylamide monomers, (meth) allyl monomers. Examples include a polymer.
上記単量体を用いて、上記ポリフルオロ炭化水素基及びポリオキシエチレン基を有する含フッ素化合物を得るための重合方式は、塊状重合、溶液重合、懸濁重合、乳化重合のいずれでもよく、また熱重合以外に光重合、エネルギー線重合も採用できる。
The polymerization method for obtaining the fluorine-containing compound having the polyfluorohydrocarbon group and the polyoxyethylene group using the monomer may be any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In addition to thermal polymerization, photopolymerization and energy ray polymerization can also be employed.
重合開始剤としては、既存の有機アゾ化合物、過酸化物、過硫酸塩等を用いることができる。
As the polymerization initiator, existing organic azo compounds, peroxides, persulfates and the like can be used.
本発明で用いる該含フッ素化合物の重量平均分子量は1,000~100,000が好ましく、特に5,000~20,000が好ましい。重量平均分子量の調整はチオール、メルカプタン、α-メチルスチレンなどの重合連鎖移動剤により調整できる。
The weight average molecular weight of the fluorine-containing compound used in the present invention is preferably from 1,000 to 100,000, particularly preferably from 5,000 to 20,000. The weight average molecular weight can be adjusted with a polymerization chain transfer agent such as thiol, mercaptan, or α-methylstyrene.
また、本発明の離型層中の該含フッ素化合物の割合は0.5質量%~10質量%が好ましい。0.5質量%未満では粘着層とのブロッキングが生じ易く、所望する巻戻力を得るのが困難な場合がある。また、10質量%を超えて含有させようとすると、樹脂への溶解度が低いため、均一に混ざり難い他、溶融押出時、離型層構成用のプロピレン系樹脂が該含フッ素化合物の影響を受け、押出スクリュー部で滑り、均一に吐出するのが困難となる場合がある。
Further, the ratio of the fluorine-containing compound in the release layer of the present invention is preferably 0.5% by mass to 10% by mass. If it is less than 0.5% by mass, blocking with the adhesive layer is likely to occur, and it may be difficult to obtain a desired unwinding force. In addition, if the content exceeds 10% by mass, the solubility in the resin is low, so that it is difficult to mix uniformly, and at the time of melt extrusion, the propylene resin for forming the release layer is affected by the fluorine-containing compound. In some cases, it may be difficult to slide and uniformly discharge at the extrusion screw portion.
なお、本発明の離型層は、かかる含フッ素化合物に加え、平均粒子径1~20μmの無機ないしは有機粒子を同時に0.1質量%~10質量%含有するのがより好ましい。かかる無機ないしは有機粒子の平均粒子径は3~15μmと比較的大きな粒径のものが滑り性及びブロッキング性の観点から、特に好ましい。
The release layer of the present invention preferably contains 0.1 to 10% by mass of inorganic or organic particles having an average particle size of 1 to 20 μm at the same time in addition to the fluorine-containing compound. Such inorganic or organic particles having an average particle size of 3 to 15 μm are particularly preferred from the viewpoint of slipperiness and blocking properties.
かかる無機粒子としては、シリカ以外、炭酸カルシウム、炭酸マグネシウム、酸化チタン、クレー、タルク、水酸化マグネシウム、水酸化アルミニウム、ゼオライト等を挙げることができるが、なかでもシリカがより好ましい。
Examples of such inorganic particles include calcium carbonate, magnesium carbonate, titanium oxide, clay, talc, magnesium hydroxide, aluminum hydroxide, zeolite, etc., other than silica, among which silica is more preferable.
有機粒子としては、ポリスチレンやポリメチルメタクリレート等を挙げることができる。
Examples of organic particles include polystyrene and polymethyl methacrylate.
上記含フッ素化合物と無機ないし有機粒子と後述する離型層の表面粗さの相乗効果によって、ブロッキングし難く、良好な巻出性を得られやすくなる。
The synergistic effect of the fluorine-containing compound, the inorganic or organic particles, and the surface roughness of the release layer described later makes it difficult to block and makes it easy to obtain good unwinding properties.
本発明の離型層の表面粗さは十点平均粗さ(Rz)で3μm以上が好ましい。Rzが3μm未満では、積層体の製造工程でロール状に巻き取るときに、シワが発生しやすくなり、品質を低下させる場合がある。かかる表面粗さは主体とするプロピレン系樹脂に前述の如く相溶性の乏しいエチレン系樹脂を少量混合添加する方法などで達成することができる。
The surface roughness of the release layer of the present invention is preferably 3 μm or more in terms of 10-point average roughness (Rz). If Rz is less than 3 μm, wrinkles are likely to occur when the laminate is wound into a roll, and the quality may be lowered. Such surface roughness can be achieved by, for example, a method in which a small amount of an ethylene resin having poor compatibility is added to the main propylene resin as described above.
<積層体の製造方法>
次に本発明の積層体の製造方法について説明する。 <Method for producing laminate>
Next, the manufacturing method of the laminated body of this invention is demonstrated.
次に本発明の積層体の製造方法について説明する。 <Method for producing laminate>
Next, the manufacturing method of the laminated body of this invention is demonstrated.
本発明の積層体の製造方法は特に限定されず、例えば、基材、粘着層、離型層の3層積層構成の場合、各々を構成する樹脂組成物を個別の押出機から溶融押出し、口金内で積層一体化させるいわゆる共押出法や、上記基材、粘着層、離型層をそれぞれ個別に溶融押出した後に、ラミネート法により積層する方法等が挙げられるが、生産性の観点から共押出法で製造されることが好ましい。共押出法については、インフレーション法、Tダイ法等の公知の方法が用いられるが、厚み精度に優れることや表面形状制御の観点から、Tダイ法による熱溶融共押出法が特に好ましい。
The production method of the laminate of the present invention is not particularly limited. For example, in the case of a three-layer laminated structure of a base material, an adhesive layer, and a release layer, the resin composition constituting each is melt-extruded from an individual extruder, and a die is formed. The so-called coextrusion method for laminating and integrating the above, and the method of laminating by laminating after individually melting and extruding the base material, the adhesive layer, and the release layer are mentioned. Preferably, it is manufactured by the method. As the co-extrusion method, known methods such as an inflation method and a T-die method are used. From the viewpoint of excellent thickness accuracy and surface shape control, a hot-melt co-extrusion method by the T-die method is particularly preferable.
ここで、粘着付与剤は、予めスチレン系エラストマーおよび/またはプロピレン・α-オレフィン共重合体と均一混合させ、マスターペレット化したものを用いると、粘着層を構成する樹脂を溶融押出する際に、均一な粘着層が得られやすく好ましい。マスターペレット中の粘着付与剤の含有量は、粘着付与剤や混合する樹脂の物性にあわせて適宜調整すればよいが、生産性の観点から30質量%以上が好ましく、40質量%以上がより好ましい。
Here, when the tackifier is premixed uniformly with a styrene elastomer and / or propylene / α-olefin copolymer and used as a master pellet, when the resin constituting the adhesive layer is melt-extruded, It is preferable because a uniform adhesive layer is easily obtained. The content of the tackifier in the master pellet may be appropriately adjusted according to the physical properties of the tackifier and the resin to be mixed, but is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of productivity. .
<用途例>
本発明の組成物から構成される積層体は、合成樹脂板、金属板、ガラス板等の製造、加工、運搬時の傷付き防止、汚れ付着防止用の表面保護フィルムとして用いることができるが、特に表面に凹凸を有する被着体に好適に用いられる。例えば、合成樹脂からなるディスプレイ用部材である拡散板やプリズムシート等に用いられ、なかでも本発明の組成物から構成される積層体はプリズムシートの表面保護に特に好ましく用いられる。 <Application example>
The laminate composed of the composition of the present invention can be used as a surface protection film for the prevention of scratches during the production, processing and transportation of synthetic resin plates, metal plates, glass plates, etc. In particular, it is suitably used for adherends having irregularities on the surface. For example, it is used for a diffusion plate, a prism sheet or the like, which is a display member made of a synthetic resin, and a laminate composed of the composition of the present invention is particularly preferably used for protecting the surface of the prism sheet.
本発明の組成物から構成される積層体は、合成樹脂板、金属板、ガラス板等の製造、加工、運搬時の傷付き防止、汚れ付着防止用の表面保護フィルムとして用いることができるが、特に表面に凹凸を有する被着体に好適に用いられる。例えば、合成樹脂からなるディスプレイ用部材である拡散板やプリズムシート等に用いられ、なかでも本発明の組成物から構成される積層体はプリズムシートの表面保護に特に好ましく用いられる。 <Application example>
The laminate composed of the composition of the present invention can be used as a surface protection film for the prevention of scratches during the production, processing and transportation of synthetic resin plates, metal plates, glass plates, etc. In particular, it is suitably used for adherends having irregularities on the surface. For example, it is used for a diffusion plate, a prism sheet or the like, which is a display member made of a synthetic resin, and a laminate composed of the composition of the present invention is particularly preferably used for protecting the surface of the prism sheet.
本発明の組成物から構成される積層体が保護するプリズムシートは、シートの片面に、三角柱状のプリズムがその稜線が外面になるようにシート表面に並行に配置されたものである。プリズムを構成する材料は特に限定されないが、透光性を有する樹脂が用いられ、例えばアクリル系樹脂やポリカーボネートなどが挙げられる。プリズムの隣接する稜線間の距離は、10~1,000μmが好ましく、10~300μmがより好ましい。プリズムの高さ(三角柱の底辺から稜線までの垂線の長さ)は、5~200μmが好ましく、10~100μmがさらに好ましい。また、本発明が保護するプリズムシートは、同じ形状のプリズムのみから構成されていてもよいし、2種類以上の異なる形状のプリズムから構成されていてもよい。異なる形状のプリズムから構成される場合、例えば、高さの異なる大小のプリズムが1つずつ交互に配置されていたり、大きいプリズム1個と小さいプリズム複数個が交互に配置されていたりする場合があるが、目的に応じて適宜設計される。
The prism sheet protected by the laminate composed of the composition of the present invention is one in which a triangular prism is arranged on one side of the sheet in parallel on the sheet surface so that the ridge line is the outer surface. Although the material which comprises a prism is not specifically limited, Resin which has translucency is used, for example, acrylic resin, a polycarbonate, etc. are mentioned. The distance between adjacent ridge lines of the prism is preferably 10 to 1,000 μm, and more preferably 10 to 300 μm. The height of the prism (the length of the perpendicular from the base of the triangular prism to the ridge line) is preferably 5 to 200 μm, and more preferably 10 to 100 μm. Moreover, the prism sheet protected by the present invention may be composed only of prisms having the same shape, or may be composed of two or more types of prisms having different shapes. When composed of prisms of different shapes, for example, there are cases where large and small prisms having different heights are alternately arranged one by one, or one large prism and a plurality of small prisms are alternately disposed. However, it is designed appropriately according to the purpose.
以下、本発明を実施例に基づいてさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、各種物性の測定および評価は、以下の方法により実施した。
Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. Various physical properties were measured and evaluated by the following methods.
(1)動的粘弾性測定
実施例および比較例に示す組成物を構成する樹脂を所定の混合比で配合し、東洋精機製作所製ラボプラストミル100MR3を用いて、温度200℃、回転数20rpmで15分間混練した。続いて、得られた混練物を厚み2mmに溶融成型し、ティー・エイ・インスツルメント社製レオメーターAR2000exを用いて、温度-80~120℃、昇温速度3℃/分、周波数1Hz、ひずみ0.01%で、せん断モードで組成物の粘弾性を評価した。得られた結果より、100℃での損失正接(tanδ100℃)、0℃での損失正接(tanδ0℃)、60℃での損失正接と100℃での損失正接の差(tanδ100℃-tanδ60℃)を求めた。 (1) Dynamic viscoelasticity measurement Resins constituting the compositions shown in Examples and Comparative Examples are blended at a predetermined mixing ratio, and the temperature is 200 ° C. and the rotation speed is 20 rpm using a lab plast mill 100MR3 manufactured by Toyo Seiki Seisakusho. Kneaded for 15 minutes. Subsequently, the obtained kneaded material was melt-molded to a thickness of 2 mm, and the temperature was −80 to 120 ° C., the temperature rising rate was 3 ° C./min, the frequency was 1 Hz, using a rheometer AR2000ex manufactured by TA Instruments. The viscoelasticity of the composition was evaluated in shear mode at a strain of 0.01%. From the obtained results, the loss tangent at 100 ° C. (tan δ 100 ° C. ), the loss tangent at 0 ° C. (tan δ 0 ° C. ), the difference between the loss tangent at 60 ° C. and the loss tangent at 100 ° C. (tan δ 100 ° C. − tan δ 60 ° C. ).
実施例および比較例に示す組成物を構成する樹脂を所定の混合比で配合し、東洋精機製作所製ラボプラストミル100MR3を用いて、温度200℃、回転数20rpmで15分間混練した。続いて、得られた混練物を厚み2mmに溶融成型し、ティー・エイ・インスツルメント社製レオメーターAR2000exを用いて、温度-80~120℃、昇温速度3℃/分、周波数1Hz、ひずみ0.01%で、せん断モードで組成物の粘弾性を評価した。得られた結果より、100℃での損失正接(tanδ100℃)、0℃での損失正接(tanδ0℃)、60℃での損失正接と100℃での損失正接の差(tanδ100℃-tanδ60℃)を求めた。 (1) Dynamic viscoelasticity measurement Resins constituting the compositions shown in Examples and Comparative Examples are blended at a predetermined mixing ratio, and the temperature is 200 ° C. and the rotation speed is 20 rpm using a lab plast mill 100MR3 manufactured by Toyo Seiki Seisakusho. Kneaded for 15 minutes. Subsequently, the obtained kneaded material was melt-molded to a thickness of 2 mm, and the temperature was −80 to 120 ° C., the temperature rising rate was 3 ° C./min, the frequency was 1 Hz, using a rheometer AR2000ex manufactured by TA Instruments. The viscoelasticity of the composition was evaluated in shear mode at a strain of 0.01%. From the obtained results, the loss tangent at 100 ° C. (tan δ 100 ° C. ), the loss tangent at 0 ° C. (tan δ 0 ° C. ), the difference between the loss tangent at 60 ° C. and the loss tangent at 100 ° C. (tan δ 100 ° C. − tan δ 60 ° C. ).
(2)示差走査熱量測定
上記(1)と同様の方法で実施例および比較例に示す組成物を混練した後、得られた混練物を厚み50μmに溶融成型し、さらに5mg秤量して、測定用試料とした。その後、試料をアルミニウム製パンに採取し、示差走査熱量計(セイコー電子工業製RDC220)を用いて、窒素雰囲気下で、室温から230℃まで40℃/分で昇温し、230℃で5分間保持した後、20℃まで40℃/分で降温し、40℃で5分保持した。さらに、その後、再度230℃まで40℃/分で昇温し、この際に得られた吸熱ピークの温度(Tm)を確認した。 (2) Differential scanning calorimetry After kneading the compositions shown in Examples and Comparative Examples in the same manner as in (1) above, the obtained kneaded material was melt-molded to a thickness of 50 μm, and further 5 mg was weighed and measured. A sample was prepared. Thereafter, the sample was collected in an aluminum pan, and heated at a rate of 40 ° C./min from room temperature to 230 ° C. in a nitrogen atmosphere using a differential scanning calorimeter (Seiko Denshi Kogyo RDC220), and at 230 ° C. for 5 minutes. After holding, the temperature was lowered to 20 ° C. at 40 ° C./min, and held at 40 ° C. for 5 minutes. Further, after that, the temperature was raised again to 230 ° C. at 40 ° C./min, and the temperature (T m ) of the endothermic peak obtained at this time was confirmed.
上記(1)と同様の方法で実施例および比較例に示す組成物を混練した後、得られた混練物を厚み50μmに溶融成型し、さらに5mg秤量して、測定用試料とした。その後、試料をアルミニウム製パンに採取し、示差走査熱量計(セイコー電子工業製RDC220)を用いて、窒素雰囲気下で、室温から230℃まで40℃/分で昇温し、230℃で5分間保持した後、20℃まで40℃/分で降温し、40℃で5分保持した。さらに、その後、再度230℃まで40℃/分で昇温し、この際に得られた吸熱ピークの温度(Tm)を確認した。 (2) Differential scanning calorimetry After kneading the compositions shown in Examples and Comparative Examples in the same manner as in (1) above, the obtained kneaded material was melt-molded to a thickness of 50 μm, and further 5 mg was weighed and measured. A sample was prepared. Thereafter, the sample was collected in an aluminum pan, and heated at a rate of 40 ° C./min from room temperature to 230 ° C. in a nitrogen atmosphere using a differential scanning calorimeter (Seiko Denshi Kogyo RDC220), and at 230 ° C. for 5 minutes. After holding, the temperature was lowered to 20 ° C. at 40 ° C./min, and held at 40 ° C. for 5 minutes. Further, after that, the temperature was raised again to 230 ° C. at 40 ° C./min, and the temperature (T m ) of the endothermic peak obtained at this time was confirmed.
(3)プリズムシートへの貼り合わせ
実施例および比較例で得られた積層体を、厚み160μm、表面粗さ(Rz)27μmのプリズムシートに、ロールプレス機((株)安田精機製作所特殊圧着ローラ)を用いて、0.35MPaの条件で貼り合わせた。 (3) Bonding to prism sheet The laminates obtained in the examples and comparative examples were applied to a prism sheet having a thickness of 160 μm and a surface roughness (Rz) of 27 μm on a roll press machine (Special Yasuda Seisakusho Co., Ltd. roller). ) Was used under the condition of 0.35 MPa.
実施例および比較例で得られた積層体を、厚み160μm、表面粗さ(Rz)27μmのプリズムシートに、ロールプレス機((株)安田精機製作所特殊圧着ローラ)を用いて、0.35MPaの条件で貼り合わせた。 (3) Bonding to prism sheet The laminates obtained in the examples and comparative examples were applied to a prism sheet having a thickness of 160 μm and a surface roughness (Rz) of 27 μm on a roll press machine (Special Yasuda Seisakusho Co., Ltd. roller). ) Was used under the condition of 0.35 MPa.
(4)剥離性
上記(3)で得られたサンプルを、温度23℃、相対湿度50%の条件下で1週間保管した後、引張試験機((株)オリエンテック“テンシロン”万能試験機)を用いて、引張速度300mm/分、剥離角度180°にて、剥離力(S)を測定し、下記の基準に従って剥離性を評価した。
5:0.02N/25mm≦S≦0.08N/25mm
3:0.08N/25mm<S≦0.12N/25mm
1:S<0.02N/25mm、またはS>0.12N/25mm。 (4) Peelability After the sample obtained in (3) above was stored for 1 week under conditions of a temperature of 23 ° C. and a relative humidity of 50%, a tensile tester (Orientec “Tensilon” universal tester) Was used to measure the peel force (S) at a tensile speed of 300 mm / min and a peel angle of 180 °, and the peelability was evaluated according to the following criteria.
5: 0.02 N / 25 mm ≦ S ≦ 0.08 N / 25 mm
3: 0.08 N / 25 mm <S ≦ 0.12 N / 25 mm
1: S <0.02N / 25mm, or S> 0.12N / 25mm.
上記(3)で得られたサンプルを、温度23℃、相対湿度50%の条件下で1週間保管した後、引張試験機((株)オリエンテック“テンシロン”万能試験機)を用いて、引張速度300mm/分、剥離角度180°にて、剥離力(S)を測定し、下記の基準に従って剥離性を評価した。
5:0.02N/25mm≦S≦0.08N/25mm
3:0.08N/25mm<S≦0.12N/25mm
1:S<0.02N/25mm、またはS>0.12N/25mm。 (4) Peelability After the sample obtained in (3) above was stored for 1 week under conditions of a temperature of 23 ° C. and a relative humidity of 50%, a tensile tester (Orientec “Tensilon” universal tester) Was used to measure the peel force (S) at a tensile speed of 300 mm / min and a peel angle of 180 °, and the peelability was evaluated according to the following criteria.
5: 0.02 N / 25 mm ≦ S ≦ 0.08 N / 25 mm
3: 0.08 N / 25 mm <S ≦ 0.12 N / 25 mm
1: S <0.02N / 25mm, or S> 0.12N / 25mm.
(5)加工特性
上記(3)で得られたサンプルを、温度23℃、相対湿度50%の条件下で24時間保管した後、トムソン型打ち抜きカッターにて型抜きをし、打ち抜き直後および温度40℃、相対湿度50%の条件下で1週間保管した後の、プリズムシートと積層体の貼り付き状態を目視観察し、以下の基準に従って評価した。
5:打ち抜き直後および40℃1週間保管後ともに、剥がれは全くみられない
4:打ち抜き直後は剥がれは全くみられないが、40℃1週間保管後は端部がごくわずかに剥がれている
3:打ち抜き直後および40℃1週間保管後ともに、端部がごくわずかにはがれている
2:40℃1週間保管後に、端部が、サンプル周囲の全長の1/2以上剥がれている
1:打ち抜き直後に、端部が、サンプル周囲の全長の1/2以上剥がれている。 (5) Processing characteristics The sample obtained in the above (3) was stored for 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then punched with a Thomson die-cutting cutter. The state of sticking of the prism sheet and the laminated body after storage for 1 week under the conditions of ° C and 50% relative humidity was visually observed and evaluated according to the following criteria.
5: No peeling at all immediately after punching and after storage for 1 week at 40 ° C. 4: No peeling at all immediately after punching, but very slightly peeled off after storage for 1 week at 40 ° C. 3: The edge is slightly peeled off both immediately after punching and after storage for 1 week at 40 ° C. 2: After storage for 1 week at 40 ° C., the edge is peeled off more than 1/2 of the total length around the sample 1: immediately after punching The end is peeled off by more than half of the total length around the sample.
上記(3)で得られたサンプルを、温度23℃、相対湿度50%の条件下で24時間保管した後、トムソン型打ち抜きカッターにて型抜きをし、打ち抜き直後および温度40℃、相対湿度50%の条件下で1週間保管した後の、プリズムシートと積層体の貼り付き状態を目視観察し、以下の基準に従って評価した。
5:打ち抜き直後および40℃1週間保管後ともに、剥がれは全くみられない
4:打ち抜き直後は剥がれは全くみられないが、40℃1週間保管後は端部がごくわずかに剥がれている
3:打ち抜き直後および40℃1週間保管後ともに、端部がごくわずかにはがれている
2:40℃1週間保管後に、端部が、サンプル周囲の全長の1/2以上剥がれている
1:打ち抜き直後に、端部が、サンプル周囲の全長の1/2以上剥がれている。 (5) Processing characteristics The sample obtained in the above (3) was stored for 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then punched with a Thomson die-cutting cutter. The state of sticking of the prism sheet and the laminated body after storage for 1 week under the conditions of ° C and 50% relative humidity was visually observed and evaluated according to the following criteria.
5: No peeling at all immediately after punching and after storage for 1 week at 40 ° C. 4: No peeling at all immediately after punching, but very slightly peeled off after storage for 1 week at 40 ° C. 3: The edge is slightly peeled off both immediately after punching and after storage for 1 week at 40 ° C. 2: After storage for 1 week at 40 ° C., the edge is peeled off more than 1/2 of the total length around the sample 1: immediately after punching The end is peeled off by more than half of the total length around the sample.
(組成物)
以下の組成物A~E、X~Z、Sの材料を実施例1~5、比較例1~4に示す通り準備し、上記(1)、(2)に示す通り、動的粘弾性測定および示差走査熱量測定を実施した。結果を表1に示す。 (Composition)
Materials of the following compositions A to E, X to Z, and S were prepared as shown in Examples 1 to 5 and Comparative Examples 1 to 4, and dynamic viscoelasticity measurement was performed as shown in the above (1) and (2). And differential scanning calorimetry was performed. The results are shown in Table 1.
以下の組成物A~E、X~Z、Sの材料を実施例1~5、比較例1~4に示す通り準備し、上記(1)、(2)に示す通り、動的粘弾性測定および示差走査熱量測定を実施した。結果を表1に示す。 (Composition)
Materials of the following compositions A to E, X to Z, and S were prepared as shown in Examples 1 to 5 and Comparative Examples 1 to 4, and dynamic viscoelasticity measurement was performed as shown in the above (1) and (2). And differential scanning calorimetry was performed. The results are shown in Table 1.
(実施例1)
組成物A:スチレン系エラストマーとして、SEBS(旭化成ケミカルズ製タフテックH1052)を14質量%、HSBR(JSR製1321P)を30質量%、プロピレン・α-オレフィン共重合体として、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を20質量%、粘着付与剤として水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレット36質量%を用いた。 (Example 1)
Composition A: 14% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals Co., Ltd.) and 30% by mass of HSBR (1321P manufactured by JSR) as styrene elastomer, and propylene / 1-butene copolymer as propylene / α-olefin copolymer 20% by mass of coalescence (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) and 36% by mass of 50% by mass master pellets of hydrogenated terpene phenol (YS Polystar TH130 manufactured by Yasuhara Chemical) as a tackifier were used.
組成物A:スチレン系エラストマーとして、SEBS(旭化成ケミカルズ製タフテックH1052)を14質量%、HSBR(JSR製1321P)を30質量%、プロピレン・α-オレフィン共重合体として、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を20質量%、粘着付与剤として水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレット36質量%を用いた。 (Example 1)
Composition A: 14% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals Co., Ltd.) and 30% by mass of HSBR (1321P manufactured by JSR) as styrene elastomer, and propylene / 1-butene copolymer as propylene / α-olefin copolymer 20% by mass of coalescence (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) and 36% by mass of 50% by mass master pellets of hydrogenated terpene phenol (YS Polystar TH130 manufactured by Yasuhara Chemical) as a tackifier were used.
ここで、前記該水添テルペンフェノール50質量%マスターペレットは、前記水添テルペンフェノール50質量%と前記SEBS50質量%とを予め二軸押出機を用いてマスターペレット化したものを用いた。
Here, the hydrogenated terpenephenol 50% by mass master pellets were obtained by preliminarily mastering 50% by mass of the hydrogenated terpenephenol and 50% by mass of the SEBS by using a twin screw extruder.
(実施例2)
組成物B:SEBS(旭化成ケミカルズ製タフテックH1052)を8質量%、HSBR(JSR製1321P)を27質量%、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を25質量%、水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレット40質量%を用いた以外は、組成物Aと同様にした。 (Example 2)
Composition B: 8% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 27% by mass of HSBR (1321P manufactured by JSR), propylene / 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) Composition A was the same as composition A except that 40% by mass of 25% by mass, 50% by mass master pellets of hydrogenated terpene phenol (YS Polystar TH130 manufactured by Yasuhara Chemical) was used.
組成物B:SEBS(旭化成ケミカルズ製タフテックH1052)を8質量%、HSBR(JSR製1321P)を27質量%、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を25質量%、水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレット40質量%を用いた以外は、組成物Aと同様にした。 (Example 2)
Composition B: 8% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 27% by mass of HSBR (1321P manufactured by JSR), propylene / 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) Composition A was the same as composition A except that 40% by mass of 25% by mass, 50% by mass master pellets of hydrogenated terpene phenol (YS Polystar TH130 manufactured by Yasuhara Chemical) was used.
(実施例3)
組成物C:プロピレン・α-オレフィン共重合体として、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7070、融点75℃)を用いた以外は、組成物Bと同様にした。 (Example 3)
Composition C: The same as Composition B, except that a propylene / 1-butene copolymer (Tafmer XM-7070, Mitsui Chemicals, melting point 75 ° C.) was used as the propylene / α-olefin copolymer.
組成物C:プロピレン・α-オレフィン共重合体として、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7070、融点75℃)を用いた以外は、組成物Bと同様にした。 (Example 3)
Composition C: The same as Composition B, except that a propylene / 1-butene copolymer (Tafmer XM-7070, Mitsui Chemicals, melting point 75 ° C.) was used as the propylene / α-olefin copolymer.
(実施例4)
組成物D:SEBS(旭化成ケミカルズ製タフテックH1052)を14質量%、HSBR(JSR製ダイナロン1321P)を30質量%、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を10質量%、水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレットを36質量%、密度921kg/m3、190℃でのMFRが5g/分のヘキセン共重合ポリエチレン(LLDPE)10質量%を用いた以外は、組成物Aと同様にした。 Example 4
Composition D: 14% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynalon 1321P manufactured by JSR), propylene / 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) 10% by mass, hydrogenated terpenephenol (YShara Chemical YS Polystar TH130) 50% by mass master pellets 36% by mass, density 921 kg / m 3 , hexene copolymer polyethylene (LLDPE) at 190 ° C. and MFR 5 g / min The same as composition A except that 10% by mass was used.
組成物D:SEBS(旭化成ケミカルズ製タフテックH1052)を14質量%、HSBR(JSR製ダイナロン1321P)を30質量%、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を10質量%、水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレットを36質量%、密度921kg/m3、190℃でのMFRが5g/分のヘキセン共重合ポリエチレン(LLDPE)10質量%を用いた以外は、組成物Aと同様にした。 Example 4
Composition D: 14% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynalon 1321P manufactured by JSR), propylene / 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) 10% by mass, hydrogenated terpenephenol (YShara Chemical YS Polystar TH130) 50% by mass master pellets 36% by mass, density 921 kg / m 3 , hexene copolymer polyethylene (LLDPE) at 190 ° C. and MFR 5 g / min The same as composition A except that 10% by mass was used.
(実施例5)
組成物E:SEBS(旭化成ケミカルズ製タフテックH1052)を25質量%、HSBR(JSR製ダイナロン1321P)を30質量%、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を10質量%、水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレットを20質量%、主として非晶性ポリプロピレンからなる樹脂(住友化学製タフセレンT3712)15質量%を用いた以外は、組成物Aと同様にした。 (Example 5)
Composition E: 25% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynalon 1321P manufactured by JSR), propylene / 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) 10 mass%, hydrogenated terpenephenol (YShara Chemical YS Polystar TH130) 50 mass% master pellet 20 mass%, except that 15 mass% resin mainly made of amorphous polypropylene (Sumitomo Chemical Tough Selenium T3712) was used. The same as composition A.
組成物E:SEBS(旭化成ケミカルズ製タフテックH1052)を25質量%、HSBR(JSR製ダイナロン1321P)を30質量%、プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を10質量%、水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレットを20質量%、主として非晶性ポリプロピレンからなる樹脂(住友化学製タフセレンT3712)15質量%を用いた以外は、組成物Aと同様にした。 (Example 5)
Composition E: 25% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynalon 1321P manufactured by JSR), propylene / 1-butene copolymer (Tafmer XM-7080 manufactured by Mitsui Chemicals, melting point 83 ° C.) 10 mass%, hydrogenated terpenephenol (YShara Chemical YS Polystar TH130) 50 mass% master pellet 20 mass%, except that 15 mass% resin mainly made of amorphous polypropylene (Sumitomo Chemical Tough Selenium T3712) was used. The same as composition A.
(比較例1)
組成物X:SEBS(旭化成ケミカルズ製タフテックH1052)を15質量%、HSBR(JSR製ダイナロン1321P)を30質量%、水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレットを30質量%、実施例4で用いたものと同様のLLDPE25質量%を用いた以外は、組成物Aと同様にした。 (Comparative Example 1)
Composition X: 15% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynalon 1321P manufactured by JSR), and 30% by mass of 50% by mass master pellet of hydrogenated terpene phenol (YS Polystar TH130 manufactured by Yasuhara Chemical) The same as composition A except that 25% by mass of LLDPE similar to that used in Example 4 was used.
組成物X:SEBS(旭化成ケミカルズ製タフテックH1052)を15質量%、HSBR(JSR製ダイナロン1321P)を30質量%、水添テルペンフェノール(ヤスハラケミカル製YSポリスターTH130)の50質量%マスターペレットを30質量%、実施例4で用いたものと同様のLLDPE25質量%を用いた以外は、組成物Aと同様にした。 (Comparative Example 1)
Composition X: 15% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 30% by mass of HSBR (Dynalon 1321P manufactured by JSR), and 30% by mass of 50% by mass master pellet of hydrogenated terpene phenol (YS Polystar TH130 manufactured by Yasuhara Chemical) The same as composition A except that 25% by mass of LLDPE similar to that used in Example 4 was used.
(比較例2)
組成物Y:SEBS(旭化成ケミカルズ製タフテックH1052)を50質量%、HSBR(JSR製ダイナロン1321P)を50質量%用いた以外は、組成物Aと同様にした。 (Comparative Example 2)
Composition Y: Same as Composition A except that 50% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals) and 50% by mass of HSBR (Dynalon 1321P manufactured by JSR) were used.
組成物Y:SEBS(旭化成ケミカルズ製タフテックH1052)を50質量%、HSBR(JSR製ダイナロン1321P)を50質量%用いた以外は、組成物Aと同様にした。 (Comparative Example 2)
Composition Y: Same as Composition A except that 50% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals) and 50% by mass of HSBR (Dynalon 1321P manufactured by JSR) were used.
(比較例3)
組成物Z:プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を70質量%、主として非晶性ポリプロピレンからなる樹脂(住友化学製タフセレンT3712)を30質量%用いた以外は、組成物Aと同様にした。 (Comparative Example 3)
Composition Z: 70% by mass of propylene / 1-butene copolymer (Tafmer XM-7080, Mitsui Chemicals, melting point 83 ° C.) and 30% by mass of a resin mainly composed of amorphous polypropylene (Tuff Selenium T3712 manufactured by Sumitomo Chemical) Except for the above, it was the same as Composition A.
組成物Z:プロピレン・1-ブテン共重合体(三井化学製タフマーXM-7080、融点83℃)を70質量%、主として非晶性ポリプロピレンからなる樹脂(住友化学製タフセレンT3712)を30質量%用いた以外は、組成物Aと同様にした。 (Comparative Example 3)
Composition Z: 70% by mass of propylene / 1-butene copolymer (Tafmer XM-7080, Mitsui Chemicals, melting point 83 ° C.) and 30% by mass of a resin mainly composed of amorphous polypropylene (Tuff Selenium T3712 manufactured by Sumitomo Chemical) Except for the above, it was the same as Composition A.
(比較例4)
組成物S:SEBS(旭化成ケミカルズ製タフテックH1052)を35質量%、HSBR(JSR製ダイナロン1321P)を35質量%、主として非晶性ポリプロピレンからなる樹脂(住友化学製タフセレンT3712)30質量%を用いた以外は、組成物Aと同様にした。 (Comparative Example 4)
Composition S: 35% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 35% by mass of HSBR (Dynalon 1321P manufactured by JSR), and 30% by mass of a resin mainly composed of amorphous polypropylene (Tuff Selenium T3712 manufactured by Sumitomo Chemical) Except for the above, it was the same as the composition A.
組成物S:SEBS(旭化成ケミカルズ製タフテックH1052)を35質量%、HSBR(JSR製ダイナロン1321P)を35質量%、主として非晶性ポリプロピレンからなる樹脂(住友化学製タフセレンT3712)30質量%を用いた以外は、組成物Aと同様にした。 (Comparative Example 4)
Composition S: 35% by mass of SEBS (Taftec H1052 manufactured by Asahi Kasei Chemicals), 35% by mass of HSBR (Dynalon 1321P manufactured by JSR), and 30% by mass of a resin mainly composed of amorphous polypropylene (Tuff Selenium T3712 manufactured by Sumitomo Chemical) Except for the above, it was the same as the composition A.
(積層体)
下記の実施例および比較例に示す通り、積層体を作成し、評価を実施した。評価結果を表2に示す。 (Laminate)
As shown in the following examples and comparative examples, laminates were prepared and evaluated. The evaluation results are shown in Table 2.
下記の実施例および比較例に示す通り、積層体を作成し、評価を実施した。評価結果を表2に示す。 (Laminate)
As shown in the following examples and comparative examples, laminates were prepared and evaluated. The evaluation results are shown in Table 2.
(実施例1’)
各層の構成樹脂を次のように準備した。 (Example 1 ')
The constituent resin of each layer was prepared as follows.
各層の構成樹脂を次のように準備した。 (Example 1 ')
The constituent resin of each layer was prepared as follows.
粘着層:実施例1に示す組成物Aを用いた。
Adhesive layer: Composition A shown in Example 1 was used.
基材:230℃で測定されたMFRが5g/10分の市販のホモポリプロピレンを用いた。
Substrate: Commercially available homopolypropylene having an MFR measured at 230 ° C. of 5 g / 10 min was used.
離型層:基材に用いたものと同一のホモポリプロピレンを45質量%、230℃で測定されたMFRが5g/10分のプロピレン-エチレン・ランダムコポリマを24質量%(エチレン含有量5質量%)、190℃で測定されたMFRが2g/10分の密度919kg/m3の低密度ポリエチレンを6質量%に加え、あらかじめ上記ホモポリプロピレン90質量%に平均粒子径11μmのシリカ4質量%、ポリフルオロ炭化水素基及びポリオキシエチレン基を有する含フッ素化合物6質量%からなる混合組成物をマスターバッチとして準備し、25質量%をヘンシェルミキサにて均一に混合した。
Release layer: 45% by mass of the same homopolypropylene used for the base material, 24% by mass of propylene-ethylene random copolymer measured at 230 ° C. with an MFR of 5 g / 10 min (ethylene content 5% by mass) ), A low density polyethylene having an MFR measured at 190 ° C. of 2 g / 10 min and a density of 919 kg / m 3 is added to 6% by mass, and 90% by mass of the homopolypropylene is 4% by mass of silica having an average particle diameter of 11 μm. A mixed composition comprising 6% by mass of a fluorine-containing compound having a fluorohydrocarbon group and a polyoxyethylene group was prepared as a master batch, and 25% by mass was uniformly mixed with a Henschel mixer.
ここで、ポリフルオロ炭化水素基及びポリオキシエチレン基を有する含フッ素化合物は、単量体(a)として、C6F13のパーフルオロアルキルアクリレート(CH2=CHCOOC2H4C6F13)を25質量%、単量体(b)として、オキシエチレン繰り返し単位8つのポリエチレングリコールモノアクリレート{CH2=CHCOO(CH2CH2O)8H}を50質量%、及び単量体(c)として、オキシエチレン繰り返し単位8つのポリエチレングリコールジメタクリレート{CH2=C(CH3)COO(CH2CH2O)8COC(CH3)=CH2}を25質量%の割合で、溶媒にトリフルオロトルエンを用い、重合開始剤として2,2‘-アゾビス(2,4-ジメチルバレロニトリル)を、また連鎖移動剤としてラウリルメルカプタンを用いて、窒素気流下、撹拌しながら60℃で5時間重合させ、しかる後、メタノール中で沈殿・濾過した後、減圧乾燥したものを用いた。
Here, the fluorine-containing compound having a polyfluorohydrocarbon group and a polyoxyethylene group is a C 6 F 13 perfluoroalkyl acrylate (CH 2 ═CHCOOC 2 H 4 C 6 F 13 ) as the monomer (a). 25% by mass, monomer (b), 50% by mass of polyethylene glycol monoacrylate {CH 2 ═CHCOO (CH 2 CH 2 O) 8 H} having 8 oxyethylene repeating units, and monomer (c) As an example, a polyethylene glycol dimethacrylate having eight oxyethylene repeating units {CH 2 ═C (CH 3 ) COO (CH 2 CH 2 O) 8 COC (CH 3 ) ═CH 2 } in a proportion of 25% by mass in a solvent Using fluorotoluene, 2,2'-azobis (2,4-dimethylvaleronitrile) as the polymerization initiator, Using lauryl mercaptan as a chain transfer agent, under nitrogen stream, stirring was polymerized for 5 hours at 60 ° C., after which was precipitated, filtered with methanol used was dried under reduced pressure.
次に、各層の構成樹脂を、φ115mm(基材用)、φ90mm(粘着層用)、φ65mm(離型層用)からなる3台の押出機を有する口金幅2,400mmのマルチマニホールドのTダイ複合製膜機のそれぞれの押出機に投入し、粘着層厚み比率12.5%、離型層厚み比率8.5%、基材厚み比率79%となるよう各押出機の吐出量を調整し、複合Tダイから押出温度それぞれ200℃にて押出し、フィルム厚み40μmの3層積層フィルムを成型した。その後、プリズムシートへ貼り合せた後、剥離性および加工特性を評価した。
Next, the multi-manifold T-die having a die width of 2,400 mm having three extruders each consisting of φ115 mm (for base material), φ90 mm (for adhesive layer), and φ65 mm (for release layer) is used as the constituent resin of each layer. The amount of each extruder is adjusted so that the adhesive layer thickness ratio is 12.5%, the release layer thickness ratio is 8.5%, and the base material thickness ratio is 79%. The composite T die was extruded at an extrusion temperature of 200 ° C. to form a three-layer laminated film having a film thickness of 40 μm. Then, after bonding to a prism sheet, peelability and processing characteristics were evaluated.
(実施例2’)
粘着層に実施例2に示す組成物Bを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
粘着層に実施例2に示す組成物Bを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
(実施例3’)
粘着層に実施例3に示す組成物Cを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
粘着層に実施例3に示す組成物Cを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
(実施例4’)
粘着層に実施例4に示す組成物Dを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
粘着層に実施例4に示す組成物Dを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
(実施例5’)
粘着層に実施例5に示す組成物Eを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
粘着層に実施例5に示す組成物Eを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
(比較例1’)
粘着層に比較例1に示す組成物Xを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
粘着層に比較例1に示す組成物Xを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
(比較例2’)
粘着層に比較例2に示す組成物Yを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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.
粘着層に比較例2に示す組成物Yを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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.
(比較例3’)
粘着層に比較例3に示す組成物Zを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
粘着層に比較例3に示す組成物Zを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (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 for the adhesive layer.
(比較例4’)
粘着層に比較例4に示す組成物Sを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (Comparative Example 4 ′)
A laminate was prepared and evaluated in the same manner as in Example 1 ′ except that the composition S shown in Comparative Example 4 was used for the adhesive layer.
粘着層に比較例4に示す組成物Sを用いたこと以外は、実施例1’と同様にして、積層体を作成し、評価を実施した。 (Comparative Example 4 ′)
A laminate was prepared and evaluated in the same manner as in Example 1 ′ except that the composition S shown in Comparative Example 4 was used for the adhesive layer.
本発明の要件を満足する実施例1’~5’の積層体は、剥離性および加工特性に優れる一方、本発明の要件を満たさない比較例1’~4’は、剥離性または加工特性に劣る結果となった。
While the laminates of Examples 1 ′ to 5 ′ that satisfy the requirements of the present invention are excellent in peelability and processing characteristics, Comparative Examples 1 ′ to 4 ′ that do not satisfy the requirements of the present invention are excellent in peelability or processing characteristics. The result was inferior.
本発明の組成物および積層体は、表面に凹凸を有する被着体のキズや汚れを防止する表面保護フィルムのみならず、合成樹脂、金属、ガラス等の各種素材からなる種々の製品の表面保護フィルム用途として好ましく用いることができる。
The composition and laminate of the present invention are not only a surface protective film for preventing scratches and stains on adherends having irregularities on the surface, but also surface protection for various products made of various materials such as synthetic resin, metal, and glass. It can be preferably used as a film application.
Claims (6)
- 以下の条件1および2を満たすことを特徴とする組成物。
条件1 周波数1Hz、温度0℃でのせん断損失正接(tanδ0℃)が、0.20以上0.60以下
条件2 周波数1Hz、温度100℃でのせん断損失正接(tanδ100℃)が、0.40以上0.80以下 A composition satisfying the following conditions 1 and 2.
Condition 1 Shear loss tangent (tan δ 0 ° C. ) at a frequency of 1 Hz and a temperature of 0 ° C. is 0.20 or more and 0.60 or less Condition 2 Shear loss tangent (tan δ 100 ° C. ) at a frequency of 1 Hz and a temperature of 100 ° C. is 0. 40 to 0.80 - 前記組成物が、周波数1Hz、温度60℃でのせん断損失正接(tanδ60℃)と、温度100℃でのせん断損失正接(tanδ100℃)とについて、以下の条件3を満たす請求項1に記載の組成物。
条件3 0.20≦tanδ100℃-tanδ60℃≦0.60 2. The composition according to claim 1, wherein the composition satisfies the following condition 3 with respect to a shear loss tangent (tan δ 60 ° C. ) at a frequency of 1 Hz and a temperature of 60 ° C. and a shear loss tangent at a temperature of 100 ° C. (tan δ 100 ° C. ). Composition.
Condition 3 0.20 ≦ tan δ 100 ° C.− tan δ 60 ° C. ≦ 0.60 - 前記組成物が、示差走査熱量測定において60℃以上100℃以下の範囲に吸熱ピークを有する請求項1または2に記載の組成物。 The composition according to claim 1 or 2, wherein the composition has an endothermic peak in a range of 60 ° C to 100 ° C in differential scanning calorimetry.
- 前記組成物が少なくとも以下の(1)~(3)の成分を含有する請求項1~3のいずれかに記載の組成物。
(1)スチレン系エラストマー
(2)プロピレン・α-オレフィン共重合体
(3)粘着付与剤 The composition according to any one of claims 1 to 3, wherein the composition contains at least the following components (1) to (3).
(1) Styrene elastomer (2) Propylene / α-olefin copolymer (3) Tackifier - 基材の一方の面に粘着層を有する積層体において、前記粘着層が請求項1~4のいずれかに記載の組成物を含む積層体。 A laminate comprising an adhesive layer on one surface of a substrate, wherein the adhesive layer comprises the composition according to any one of claims 1 to 4.
- プリズムシートの表面保護に用いられる請求項5に記載の積層体。 The laminate according to claim 5, which is used for protecting the surface of the prism sheet.
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WO2020122229A1 (en) * | 2018-12-14 | 2020-06-18 | 三菱ケミカル株式会社 | Adhesive agent resin composition, adhesive agent resin cured article, adhesive sheet, and image display device stack |
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- 2015-09-24 JP JP2015547597A patent/JPWO2016063673A1/en active Pending
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JP7562946B2 (en) | 2018-12-14 | 2024-10-08 | 三菱ケミカル株式会社 | Adhesive resin composition, cured adhesive resin, adhesive sheet, and image display device laminate |
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TWI665276B (en) | 2019-07-11 |
JPWO2016063673A1 (en) | 2017-08-03 |
JP2020186394A (en) | 2020-11-19 |
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