WO2015079903A1 - 表面保護用粘着シートおよび表面保護用粘着シートの使用方法 - Google Patents

表面保護用粘着シートおよび表面保護用粘着シートの使用方法 Download PDF

Info

Publication number
WO2015079903A1
WO2015079903A1 PCT/JP2014/079845 JP2014079845W WO2015079903A1 WO 2015079903 A1 WO2015079903 A1 WO 2015079903A1 JP 2014079845 W JP2014079845 W JP 2014079845W WO 2015079903 A1 WO2015079903 A1 WO 2015079903A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
component
adhesive sheet
silyl group
Prior art date
Application number
PCT/JP2014/079845
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
花子 池田
征太郎 山口
智史 川田
翔 大高
宮田　壮
Original Assignee
リンテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201480063119.1A priority Critical patent/CN105745294A/zh
Priority to KR1020167012382A priority patent/KR20160090802A/ko
Priority to JP2015545217A priority patent/JP5898389B2/ja
Publication of WO2015079903A1 publication Critical patent/WO2015079903A1/ja

Links

Images

Classifications

    • 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
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C09J193/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/02—Polyureas
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences
    • C09J183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2475/00—Presence of polyurethane

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet for surface protection and a method for using the pressure-sensitive adhesive sheet for surface protection.
  • an adhesive sheet for surface protection excellent in adhesiveness and reworkability when protecting an image display screen of an electronic device such as a liquid crystal display or decorating, and a method for using such an adhesive sheet for surface protection About.
  • adhesive sheets are used to decorate window displays, indoor displays, outdoor signage, etc., and to protect and decorate image display screens such as liquid crystal displays mounted on mobile phones and personal computers.
  • a pressure-sensitive adhesive layer for example, an acrylic pressure-sensitive adhesive composition, a vinyl acetate-based pressure-sensitive adhesive composition, a rubber-based pressure-sensitive adhesive composition, a urethane-based pressure-sensitive adhesive composition, and a silicone-based pressure-sensitive adhesive composition Etc.
  • acrylic adhesive compositions in particular, a cross-linked acrylic adhesive composition is often used.
  • the adhesive sheet that is attached to the surface of the image display screen can be attached naturally without the use of special pressure and without air bubbles, without using special tools such as squeegees. Easy pasting is required. In order to improve the easy pasting property, it is necessary to improve the wettability of the pressure-sensitive adhesive sheet.
  • the wettability of the pressure-sensitive adhesive sheet refers to a phenomenon in which the adhesion surface spreads without any external force from the point of contact with the adherend so that the liquid spreads on a flat surface.
  • the adhesive sheet attached to the surface of the image display screen is peeled off when it is not successfully attached to the adherend when it is attached to the image display screen such as a liquid crystal display as the adherend.
  • the adherend there is a demand for excellent removability that allows the adherend to be peeled off without causing adhesive residue and easily peeled off with a slight peeling force.
  • Patent Document 1 discloses a pressure-sensitive adhesive composition for an optical film containing a predetermined acrylic polymer and a polyether compound having a predetermined reactive silyl group.
  • Patent Document 2 discloses a releasable double-sided pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer contains a pressure-sensitive adhesive composition containing a silicone polyurea elastomer and silicone oil, and has a predetermined adhesive force.
  • Patent Document 3 discloses that 100 parts by mass of a terminal silyl group polymer having a urethane bond and / or a urea bond in the main chain or side chain and containing a hydrolyzable silyl group represented by the following general formula (A) at the terminal.
  • a pressure-sensitive adhesive precursor in which less than 10 parts by mass of a tackifying resin and 0.01 to 10 parts by mass of a curing catalyst for a terminal silyl group polymer are uniformly mixed are applied to the surface of a tape substrate or sheet substrate.
  • a pressure-sensitive adhesive sheet is disclosed in which the pressure-sensitive adhesive precursor is used as a pressure-sensitive adhesive layer by curing the terminal silyl group polymer.
  • X represents a hydroxy group or an alkoxy group
  • R represents an alkyl group having 1 to 20 carbon atoms
  • n represents 0, 1 or 2.
  • JP 2011-219765 A (Claims) JP 2010-180367 A (Claims) JP 2011-6630 A (Claims)
  • the pressure-sensitive adhesive composition for an optical film described in Patent Document 1 has suitable reworkability obtained by using a predetermined acrylic polymer and a polyether compound having a predetermined reactive silyl group in combination.
  • a predetermined acrylic polymer and a polyether compound having a predetermined reactive silyl group in combination.
  • it is an acrylic pressure-sensitive adhesive composition, there has been a problem that it is difficult to easily apply it on an adherend such as glass without air entrapment.
  • the releasable double-sided pressure-sensitive adhesive sheet described in Patent Document 2 is composed of a silicone-based pressure-sensitive adhesive composition in which a silicone polyurea elastomer and a silicone oil are used in combination, it has excellent adhesion and is economically disadvantageous.
  • the double-sided pressure-sensitive adhesive sheet is made into a roll form because it contains silicone oil, there has been a problem that the pressure-sensitive adhesive oozes out from the side surface over time.
  • the predetermined terminal silyl group polymer contains a predetermined silane coupling agent and a predetermined curing catalyst, and includes a tackifier resin.
  • the amount is set to 0 or a small amount, it is easy to attach without applying external force from the point of contact with the adherend when affixed to the adherend, and air entrainment phenomenon (air).
  • the present invention has been completed by finding that it is possible to effectively prevent (bite). That is, an object of the present invention is that the pressure-sensitive adhesive layer has a predetermined pressure-sensitive adhesive, and can be easily applied with little external force when being applied to an adherend, and can be reworked. Another object of the present invention is to provide a surface-protective pressure-sensitive adhesive sheet having excellent properties and a method for using such a surface-protective pressure-sensitive adhesive sheet.
  • a pressure-sensitive adhesive sheet for surface protection which is provided with a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition on one side of a substrate, and is attached to the surface of an electronic device via the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive composition contains at least a terminal silyl group polymer as the component (A), a silane coupling agent as the component (B), and a curing catalyst as the component (C).
  • Component terminal silyl group polymer has a polyoxyalkylene structure in the main chain, has a urethane bond and / or a urea bond in a part of the main chain or a side chain, and further has a main chain
  • the hydrolyzable silyl group represented by the following general formula (1) is included at both ends and the tackifier resin is included as the component (D)
  • the blending amount of the tackifier resin is ,
  • X 1 and X 2 are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer contains a predetermined terminal silyl group polymer as a main ingredient, and also includes a predetermined silane coupling agent and a predetermined curing catalyst. Therefore, by these interactions, even when a small amount or no tackifying resin is contained, it is possible to obtain easy adhesion to an adherend while exhibiting appropriate tackiness. Therefore, when affixing the adhesive sheet for surface protection to the surface of the electronic device, it can be easily affixed with little external force, and can be easily affixed.
  • the terminal silyl group polymer as the component (A) has a polyoxyalkylene structure in the main chain, it is possible to impart appropriate flexibility to the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer to be obtained. Moreover, since it has the hydrolyzable silyl group represented by General formula (1) in the both ends of a principal chain, the crosslinking density of (A) components is adjusted to the suitable range, and in the adhesive composition after hardening Adjustment of the balance between adhesive force and cohesive force can be made easier.
  • the electronic device is a liquid crystal display device provided with a glass substrate or an electroluminescence device provided with a glass substrate, and measured according to JIS Z 0237. It is preferable that the adhesive strength by 180 ° peeling with respect to the glass substrate is a value within the range of 0.5 to 5 N / 25 mm.
  • the weight average molecular weight of the terminal silyl group polymer as the component (A) is preferably set to a value within the range of 15,000 to 200,000.
  • the crosslinking density of (A) component is adjusted to the suitable range, and the balance between the adhesive force and cohesion force in an adhesive composition can be adjusted to a more suitable range. it can.
  • the blending amount of the silane coupling agent as the component (B) is 0.1 to 100 parts by weight of the terminal silyl group polymer as the component (A). A value within the range of ⁇ 10 parts by weight is preferred.
  • the amount of the curing catalyst as the component (C) is 0.001 to 10 with respect to 100 parts by weight of the terminal silyl group polymer as the component (A). A value within the range of parts by weight is preferred.
  • the tackifier resin when the tackifier resin is included as the component (D), the tackifier resin is at least one of a rosin resin, a terpene phenol resin, and a rosin phenol resin. It is preferable that Thus, by configuring, even when a small amount of tackifying resin is included, the external force is hardly applied when sticking the adhesive sheet for surface protection on the surface of the electronic device while maintaining an appropriate adhesive force. It can be easily applied without the need.
  • Another aspect of the present invention is for surface protection, comprising a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition on one side of a substrate, and being attached to the surface of an electronic device via the pressure-sensitive adhesive layer.
  • a method for using a pressure-sensitive adhesive sheet comprising the following steps (1) to (4): (1) The terminal silyl group polymer as the component (A), the silane coupling agent as the component (B), and the curing catalyst as the component (C), and the terminal as the component (A)
  • the silyl group polymer has a polyoxyalkylene structure in the main chain, a urethane bond and / or a urea bond in a part of the main chain or a side chain, or one of them, and at both ends of the main chain,
  • a hydrolyzable silyl group represented by the following general formula (1) and including a tackifier resin as the component (D) the blending amount of the tackifier resin is changed to the component (A).
  • X 1 and X 2 are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.
  • the adhesive sheet for surface protection of the present invention in the step (4), is preferably applied to the surface of the electronic device with a pressing force of 10 kgf / cm 2 or less.
  • FIGS. 1 (a) to 1 (b) are diagrams for explaining a predetermined terminal silyl group polymer.
  • FIG. 2 is a diagram provided for explaining the relationship between the compounding amount of the tackifier resin, the adhesive strength to glass, and the easy peelability.
  • 3 (a) to 3 (e) are diagrams provided for explaining the embodiment of the surface protecting pressure-sensitive adhesive sheet.
  • FIGS. 4 (a) to 4 (b) are diagrams for explaining the sticking property to glass and polycarbonate in Example 1 and Example 2, respectively.
  • FIGS. 5 (a) to 5 (b) are diagrams for explaining the sticking property to glass and polycarbonate in Comparative Example 1 and Comparative Example 2, respectively.
  • FIGS. 6 (a) to 6 (b) are diagrams for explaining the sticking property to glass and polycarbonate in Comparative Example 3 and Comparative Example 4, respectively.
  • An embodiment of the present invention is a pressure-sensitive adhesive sheet for surface protection that is provided with a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition on one side of a substrate, and is attached to the surface of an electronic device via the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive composition contains at least a terminal silyl group polymer as the component (A), a silane coupling agent as the component (B), and a curing catalyst as the component (C).
  • the terminal silyl group polymer as component A) has a polyoxyalkylene structure in the main chain, has a urethane bond and / or a urea bond in a part of the main chain or a side chain, and further has a main chain
  • a hydrolyzable silyl group represented by the following general formula (1) and a tackifying resin is included as the component (D) the blending amount of the tackifying resin (A) terminal silyl group poly (component) Against over 100 parts by weight, and a value of less than 10 parts by weight, or contains no tackifier resin, a surface protective pressure sensitive adhesive sheet according to claim.
  • X 1 and X 2 are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.
  • Adhesive layer The adhesive sheet for surface protection of the present invention comprises a predetermined terminal silyl group polymer as the component (A), a silane coupling agent as the component (B), and a curing catalyst as the component (C). It consists of the predetermined
  • Component (A) Terminal silyl group polymer (1) -1 type
  • the terminal silyl group polymer as component (A) has a urethane bond and / or a urea bond in the main chain or side chain, It has the hydrolyzable silyl group represented by the general formula (1) described above at both ends of the main chain.
  • the component (A) has a bifunctional hydrolyzable terminal silyl group represented by the general formula (1), and is therefore effective by hydrolytic dehydration condensation between the components (A). This is because a three-dimensional network structure can be formed. Moreover, if it is such (A) component, since it has the bifunctional hydrolyzable terminal silyl group represented by General formula (1), in the adhesive composition after hardening, it is with respect to a to-be-adhered body. This is because sufficient adhesion can be exhibited. Therefore, even if the compounding amount of the tackifier is small, or even when the tackifier is not included, the adhesive composition and the adherend such as glass can be sufficiently adhered to each other.
  • the number of carbon atoms of the alkyl group represented by R is more preferably 1 to 12 and even more preferably 1 to 3 from the viewpoint of hydrolytic dehydration condensation reactivity.
  • the number of carbon atoms in the alkoxy group is preferably 1 to 12 from the viewpoint of hydrolytic dehydration condensation reactivity. 3 is more preferable.
  • the terminal silyl group polymer is composed of a predetermined end portion and a predetermined skeleton portion.
  • the urethane prepolymer (diisocyanate compound) represented by the formula (1) and the halogenated silyl group represented by the formula (2) shown in FIG. A specific method for synthesizing the terminal silyl group polymer will be described in the second embodiment.
  • terminal part-A the specific structure of the terminal part in the terminal silyl group polymer represented by the formula (3) in FIG. 1A is represented by the following general formulas (2) to (8) (terminal part-A). To G).
  • R 2 and R 3 are alkyl groups having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and R, X 1 and X 2 are the same as those in the general formula (1) The same applies to the following general formulas (3) to (8).
  • X 3 represents an alkylene group
  • X 4 represents an organic group having 1 to 20 carbon atoms.
  • (Iii) Skeletal portion The skeleton of the main chain or side chain (not shown) of the terminal silyl group polymer represented by the formula (3) in FIG. 1A is polyoxyalkylene. To do. The reason for this is that if it is polyoxyalkylene, an appropriate flexibility can be imparted to the resulting pressure-sensitive adhesive composition, and adhesion to an adherend can be improved. Specific examples of such polyoxyalkylene include polyoxypropylene and polyoxyethylene.
  • the predetermined terminal silyl group polymer as component (A) is hydrolyzable represented by the general formula (1) in the side chain as shown in FIG. It is characterized by being a both-end silyl group polymer having no hydrolyzable silyl group represented by the general formula (1) only at both ends of the main chain, having no silyl group.
  • the reason for this is that with such a terminal silyl group polymer, the crosslink density between the components (A) is adjusted to a suitable range, and the balance between the adhesive force and the cohesive force in the adhesive composition after curing is adjusted. This is because it can be made easier.
  • the polymer further contains a one-terminal silyl group polymer having a hydrolyzable silyl group represented by the general formula (1) only at one end of the main chain,
  • the value is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer.
  • the reason for this is that the cross-linking density between the components (A) is adjusted to a more suitable range by mixing the one-end silyl group polymer within a predetermined range with respect to the both-end silyl group polymer, and the pressure-sensitive adhesive after curing This is because the adjustment between the balance between the cohesive force and the cohesive force in the composition can be further facilitated.
  • the blending amount of the one-terminal silyl group polymer is less than 0.1 part by weight, the effect of addition may not be sufficiently obtained.
  • the blending amount of the one-terminal silyl group polymer exceeds 30 parts by weight, the crosslinking density between the components (A) may be excessively decreased, and it may be difficult to obtain a predetermined gel fraction. Because there is. Therefore, the blending amount of the one-terminal silyl group polymer is more preferably within a range of 0.5 to 10 parts by weight with respect to 100 parts by weight of both terminal silyl group polymers. More preferably, the value is within the range.
  • a pressure-sensitive adhesive composition having excellent adhesive force can be obtained even when only the both-end silyl group polymer is used, if not particularly required, a one-end silyl group polymer is used. It is also preferable to use only the terminal silyl group polymer without mixing from the viewpoint of simplification of the production process.
  • the weight average molecular weight of the predetermined terminal silyl group polymer as the component (A) is preferably set to a value within the range of 15,000 to 200,000.
  • the reason for this is that when the weight average molecular weight is less than 15,000, the molecular structure becomes dense and sufficient adhesion cannot be obtained, the viscosity becomes too low, and the workability is poor when forming a sheet by solution coating. This is because there may be cases.
  • the weight average molecular weight exceeds 200,000, a decrease in processability due to an increase in viscosity or the like becomes remarkable, or a crosslinking density decreases excessively, and a balance between adhesive force and cohesive force.
  • the weight average molecular weight of the predetermined terminal silyl group polymer as the component (A) is a value within the range of 20,000 to 150,000, and a value within the range of 30,000 to 100,000. More preferably.
  • the weight average molecular weight of the terminal silyl group polymer which is (A) component can be measured using well-known molecular weight measuring apparatuses, such as a gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the blending amount of the predetermined terminal silyl group polymer as component (A) should be 70% by weight or more with respect to 100% by weight of the total amount of the pressure-sensitive adhesive composition before curing. Is preferred. The reason for this is that when the blending amount is less than 70% by weight, the absolute amount of the component (A) with respect to the entire pressure-sensitive adhesive composition becomes excessively small, and it may be difficult to obtain sufficient adhesive force. It is. Therefore, the blending amount of the predetermined terminal silyl group polymer as the component (A) is more preferably 90% by weight or more with respect to 100% by weight of the total amount of the pressure-sensitive adhesive composition before curing, and 95% by weight. More preferably, the above is used.
  • the pressure-sensitive adhesive composition is characterized by containing a silane coupling agent as component (B). And it is preferable that the said silane coupling agent is a silane coupling agent which has an amino group.
  • the silane coupling agent is a silane coupling agent which has an amino group. The reason for this is that by blending a silane coupling agent having an amino group in such a range, the effect of the predetermined terminal silyl group polymer as a crosslinking aid is exhibited, and the cohesive force of the pressure-sensitive adhesive composition is more suitable. This is because the range can be adjusted.
  • silane coupling agent having an amino group examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like are preferably used.
  • the blending amount of the silane coupling agent as the component (B) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). It is preferable to set the value within the range. The reason for this is that by blending the silane coupling agent in such a range, the effect of the predetermined terminal silyl group polymer as a crosslinking aid is exhibited, and the cohesive force of the pressure-sensitive adhesive composition is adjusted to a more suitable range. Because it can.
  • the blending amount of the silane coupling agent as the component (B) is set to a value within the range of 0.2 to 3 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). More preferred is a value in the range of 0.3 to 1 part by weight.
  • Component (C) Curing Catalyst (3) -1 Type
  • the pressure-sensitive adhesive composition, as component (C) cures for promoting the curing of the predetermined terminal silyl group polymer as component (A)
  • the curing catalyst is preferably at least one selected from the group consisting of an aluminum-based catalyst, a titanium-based catalyst, a zirconium-based catalyst, and a boron trifluoride-based catalyst. The reason for this is that if these catalysts are used, the crosslinking density between the components (A) can be easily controlled, and the balance between the adhesive force and the cohesive force in the adhesive composition after curing is further facilitated. Because it can.
  • aluminum-based catalyst aluminum alkoxide, aluminum chelate, and aluminum (III) chloride are preferable.
  • titanium-based catalyst titanium alkoxide, titanium chelate, and titanium (IV) chloride are preferable.
  • zirconium-based catalyst Zirconium alkoxides, zirconium chelates, and zirconium (IV) chloride are preferable.
  • boron trifluoride-based catalyst an amine complex or an alcohol complex of boron trifluoride is particularly preferably used.
  • the blending amount of the curing catalyst as the component (C) is in the range of 0.001 to 10 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). It is preferable to set the value within the range. The reason for this is that when the amount is less than 0.001 part by weight, the catalytic action becomes insufficient and the cohesive force of the pressure-sensitive adhesive composition may be excessively reduced. On the other hand, when the blending amount exceeds 10 parts by weight, the catalytic action becomes excessive, and the pressure-sensitive adhesive composition may be cured before being applied to the substrate.
  • the blending amount of the curing catalyst as the component (C) is set to a value within the range of 0.005 to 5 parts by weight with respect to 100 parts by weight of the predetermined terminal silyl group polymer as the component (A). More preferably, the value is in the range of 0.01 to 1 part by weight.
  • the blending amount of the tackifying resin is the component (A).
  • the value is less than 10 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer, or does not contain a tackifier resin.
  • the reason for this is that when the tackifier resin has a value of 10 parts by weight or more, the adhesive force of the adhesive composition to an adherend such as glass rapidly increases, and the adhesive sheet for surface protection containing the adhesive composition is used. This is because it may be difficult to attach easily to the display screen of an electronic device or the like while preventing air clogging.
  • the blending amount of the tackifier resin is a value within the range of 0 to 7 parts by weight with respect to 100 parts by weight of the terminal silyl group polymer as the component (A). (However, 0 is not included), more preferably 0 to 5 parts by weight (however, 0 is not included).
  • it has been confirmed that it can be easily applied while preventing air bite and can be easily applied again. This is a more preferable aspect in terms of usability.
  • the kind of the tackifier resin is preferably at least one of a rosin resin, a terpene phenol resin, and a rosin phenol resin.
  • a tackifier resin exhibits good adhesiveness and reattachability even when added in a small amount to the adhesive composition.
  • FIG. 2 the blending amount (parts by weight) of a terpene phenol-based tackifier resin (YShara Chemical Co., Ltd., YS Polyster, TH-130) with respect to 100 parts by weight of a predetermined terminal silyl group polymer is taken on the horizontal axis.
  • characteristic curves A and B are shown, in which the pressure-sensitive adhesive sheet for surface protection having the obtained pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer and the easy-peelability (relative evaluation) to glass are taken.
  • the characteristic curve A is a characteristic curve showing the adhesive force to glass in the surface protective pressure-sensitive adhesive sheet having the obtained pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer with respect to the blending amount of a predetermined terpene phenol-based tackifying resin.
  • Curve B is a characteristic curve showing the easy releasability to glass in the surface protective pressure-sensitive adhesive sheet having the obtained pressure-sensitive adhesive composition as a pressure-sensitive adhesive layer with respect to the blending amount of a predetermined terpene phenol-based tackifier resin.
  • the specific composition of an adhesive composition and the evaluation method of the adhesive force with respect to glass and easy peelability are described in an Example.
  • the characteristic curve A indicating the adhesion to glass in the surface-protective pressure-sensitive adhesive sheet of the present invention
  • the compounding amount of the tackifying resin is 0 or less than 10 parts by weight
  • the adhesion to glass is less than 5 N / 25 mm.
  • the characteristic curve B showing the easy peelability (relative evaluation) for the glass in the adhesive sheet for surface protection
  • the blending amount of the tackifier resin is 0 or less than 10 parts by weight, it is easily peeled off with a slight force.
  • the amount of the predetermined tackifying resin is less than 0 or less than 10 parts by weight. It is understood that it should be a value.
  • the pressure-sensitive adhesive composition used for the surface-protective pressure-sensitive adhesive sheet of the present invention includes, for example, an anti-aging agent, a dehydrating agent such as a vinylsilane compound or calcium oxide, a filler, Difficulties such as plasticizers, conductive materials, heat conductive materials, thixotropic agents such as anhydrous silica and amide wax, diluents such as isoparaffin, aluminum hydroxide, halogen flame retardants, phosphorus flame retardants, silicone flame retardants A functional oligomer such as a flame retardant, a silicone alkoxy oligomer, and an acrylic oligomer, a pigment, a titanate coupling agent, an aluminum coupling agent, a drying oil, and the like may be added and mixed.
  • an anti-aging agent such as a vinylsilane compound or calcium oxide
  • a filler such as a vinylsilane compound or calcium oxide
  • Difficulties such as plasticizers, conductive materials, heat conductive materials,
  • additives when these additives are added, although depending on the type of the additive, it is preferable to add the additives so as not to impair the effects of the present invention.
  • a value within the range of 0.01 to 100 parts by weight is preferable with respect to 100 parts by weight of the silyl group polymer, and a value within a range of 0.01 to 70 parts by weight is preferable.
  • a value within the range of 40 parts by weight is particularly preferred.
  • the gel fraction of the pressure-sensitive adhesive layer is preferably set to a value in the range of 30 to 100%.
  • the reason for this is that by setting the gel fraction of the pressure-sensitive adhesive layer to a value within such a range, an excellent cohesive force can be exhibited, while preventing air clogging when pasting on a display screen such as an electronic device. This is because it can be easily pasted. That is, when the gel fraction of the pressure-sensitive adhesive layer is less than 30%, the cohesive force becomes excessively small, and it may be difficult to attach or reapply easily to the display screen. Because there is.
  • the gel fraction of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive composition is more preferably set to a value within the range of 35 to 100%, and further preferably set to a value within the range of 40 to 99%.
  • the “gel fraction of the pressure-sensitive adhesive layer” means that after the pressure-sensitive adhesive composition is applied to the base material or the release material, seasoning is performed for 14 days in a 23 ° C., 50% RH environment, and then after the seasoning. This means the gel fraction measured by the dipping method using the pressure-sensitive adhesive composition (pressure-sensitive adhesive layer) as a measurement sample. Moreover, about the specific measuring method of a gel fraction, it describes in an Example.
  • the thickness of the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is usually preferably a value in the range of 1 to 100 ⁇ m, more preferably a value in the range of 5 to 50 ⁇ m. preferable. The reason for this is that when the thickness of the pressure-sensitive adhesive layer is less than 1 ⁇ m, sufficient pressure-sensitive adhesive properties may not be obtained, and conversely, when the thickness of the pressure-sensitive adhesive layer exceeds 100 ⁇ m, the residual solvent increases. This is because the adhesive properties and the like are likely to change.
  • the pressure-sensitive adhesive sheet for surface protection of the present invention is characterized in that a pressure-sensitive adhesive layer 40 is provided on one side of the base material 2 as shown in FIG.
  • a substrate include polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyimide, polyetherimide, polyetherketone, polyetheretherketone, polycarbonate, polymethylmethacrylate, triacetylcellulose, polynorbornene.
  • the transparent decoration layer 6 on the base-material surface.
  • the appearance and aesthetics of the surface protecting pressure-sensitive adhesive sheet 100 ′ can be obtained by coloring or decorating the base material located on the outer surface during use, or by printing characters or the like. This is because information is improved.
  • the thickness of the substrate is not particularly limited, but it is usually preferably a value in the range of 1 to 1,000 ⁇ m, more preferably a value in the range of 10 to 100 ⁇ m. .
  • the surface protection adhesive sheet of this invention has the peeling base material (peeling film) 8 bonded with respect to the surface which is not in contact with the base material of an adhesive layer. It is also preferable that this is an embodiment. Such an embodiment is required when only the pressure-sensitive adhesive layer has to be transported, for example, because the production of the pressure-sensitive adhesive layer and the use of the pressure-sensitive adhesive layer are performed in different places.
  • a release substrate for example, a release agent such as a silicone resin is applied to a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or a polyolefin film such as polypropylene or polyethylene, and a release layer.
  • a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or a polyolefin film such as polypropylene or polyethylene
  • a release layer for example, a release agent such as a silicone resin is applied to a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, or a polyolefin film such as polypropylene or polyethylene, and a release layer.
  • the thickness of the release substrate can usually be a value within the range of 20 to 150 ⁇ m.
  • the second embodiment includes a pressure-sensitive adhesive sheet for surface protection that is provided with a pressure-sensitive adhesive layer made of a cured product of a pressure-sensitive adhesive composition on one side of a base material, and is attached to the surface of an electronic device via the pressure-sensitive adhesive layer.
  • a method of using a pressure-sensitive adhesive sheet for surface protection comprising the following steps (1) to (4).
  • the silyl group polymer has a polyoxyalkylene structure in the main chain, a urethane bond and / or a urea bond in a part of the main chain or a side chain, or one of them, and at both ends of the main chain,
  • a hydrolyzable silyl group represented by the following general formula (1) and including a tackifier resin as the component (D) the blending amount of the tackifier resin is changed to the component (A).
  • X 1 and X 2 are independent and are a hydroxy group or an alkoxy group, and R is an alkyl group having 1 to 20 carbon atoms.
  • Step (1) is a step of preparing a predetermined pressure-sensitive adhesive composition containing the components (A) to (C).
  • Fig.1 (a) the synthesis example of the terminal silyl group polymer which is (A) component is shown.
  • FIG. 1A an isocyanate compound having an isocyanate group at the end of the main chain or side chain of the molecule, represented by the formula (1), is prepared.
  • FIG. 1 (a) an active hydrogen group capable of reacting with an isocyanate group is present at one end of the molecule represented by formula (2), and the other end of the molecule is represented by general formula (1).
  • a silylating agent having a hydrolyzable silyl group is prepared.
  • the reaction is performed by heating under a nitrogen atmosphere at 80 ° C. for 1 hour.
  • the terminal silyl group polymer represented by (3) can be obtained.
  • the terminal silyl group polymer represented by the formula (3) passes through hydrolysis of the hydrolyzable silyl group represented by the general formula (1), and is further crosslinked by dehydration condensation. As the reaction proceeds, a three-dimensional network structure can be formed.
  • the silylating agent has an isocyanate group and a predetermined polymer skeleton, contrary to the case of FIG.
  • the compound which has may have an active hydrogen group.
  • the active hydrogen in the urethane bond or urea bond introduced into the main chain or side chain of the predetermined terminal silyl group polymer may be substituted with an organic group as described in the first embodiment. Therefore, allophanate bonds are also included in the category of urethane bonds, and burette bonds are also included in the category of urea bonds.
  • Step (2) is a step of forming the coating layer 4 by applying the pressure-sensitive adhesive composition to the substrate 2 as shown in FIG. Moreover, as a method of apply
  • the drying conditions are usually 50 to 150 ° C. and preferably 10 seconds to 10 minutes.
  • the details of the base material are the same as described above, and will be omitted.
  • Step (3) is a step of curing the coating layer 4 of the pressure-sensitive adhesive composition to make the coating layer 4 a pressure-sensitive adhesive layer 40. That is, as shown in FIGS. 3B to 3C, the surface of the coating layer 4 dried on the base material 2 is cured in a state where the release base material 8 is laminated, and the pressure-sensitive adhesive The layer 40 is preferable. Alternatively, the pressure-sensitive adhesive composition coating layer 4 coated on the substrate 2 may be first cured to form the pressure-sensitive adhesive layer 40 and then laminated to the release substrate 8. Or it is not necessary to laminate
  • hardening in the application layer 4 of an adhesive composition is performed through the drying process mentioned above and a seasoning process.
  • Conditions for the seasoning step include a temperature of 20 to 50 from the viewpoint of uniformly curing the coating layer 4 of the pressure-sensitive adhesive composition without damaging the coating layer 4 or the base material 2 of the pressure-sensitive adhesive composition.
  • the temperature is 23 ° C to 30 ° C.
  • the humidity is preferably 30 to 75% RH, more preferably 45 to 65% RH.
  • Step (4) is a step of sticking the pressure-sensitive adhesive layer of the surface protective pressure-sensitive adhesive sheet to the screen display portion of the electronic device. That is, as shown in FIG. 3 (d), it is preferable that the release substrate 8 of the pressure-sensitive adhesive sheet for surface protection is peeled and then bonded to the adherend 200.
  • the surface-protective adhesive sheet is attached to the surface of the electronic device, it is preferably attached with a pressing force of 10 kgf / cm 2 or less.
  • Adherent The type of adherend to which the surface-protective pressure-sensitive adhesive sheet of the present invention is applied is not particularly limited, and examples thereof include a glass substrate, a polycarbonate substrate, and an acrylic plate.
  • Example 1 Preparation of pressure-sensitive adhesive composition
  • silylating agent In a reaction vessel equipped with a stirrer, 206 parts by weight of N-aminoethyl- ⁇ -aminopropylmethyldimethoxysilane and 172 parts by weight of methyl acrylate were charged. The mixture was heated and reacted at 80 ° C. for 10 hours with stirring in a nitrogen atmosphere to obtain a silane compound serving as a silylating agent.
  • the obtained terminal silyl group polymer is a both-end silyl group polymer having a terminal moiety represented by the following formula (9) at both ends of polyoxypropylene as a main chain and having a weight average molecular weight of 40,000. there were.
  • a bifunctional terminal silyl group was introduced into the terminal silyl group polymer obtained.
  • the thickness of the pressure-sensitive adhesive layer after drying the obtained pressure-sensitive adhesive composition on one side of a 50 ⁇ m-thick polyester film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4100) by the knife coater method was applied so as to be 20 ⁇ m, followed by heat treatment at 100 ° C. for 1 minute to obtain a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet composed of the obtained pre-curing pressure-sensitive adhesive composition and the base material (polyester film) was left for 14 days in an environment of 23 ° C. and 50% RH ( Then, the pressure-sensitive adhesive composition was sufficiently cured, and a pressure-sensitive adhesive sheet for surface protection having a pressure-sensitive adhesive layer thickness of 20 ⁇ m was obtained and subjected to various evaluations.
  • the pressure-sensitive adhesive sheet of the surface protecting adhesive sheet was observed by visually observing how it was stuck naturally without any bubbles due to the wettability of the adhesive layer of the surface protecting adhesive sheet.
  • the obtained results are shown in Table 1.
  • photographed the external appearance by the side of the base material in the adhesive sheet for surface protection stuck on the glass plate at this time is shown on the left side of FIG.
  • a photograph of the appearance is shown on the left side of FIG. ⁇ :
  • the surface-protective adhesive sheet is naturally applied to almost the entire surface of the glass plate just by placing it lightly without applying pressure with a finger, and within 5 seconds after the surface-protective adhesive sheet is placed on the glass plate. 70% or more of the pressure-sensitive adhesive sheet for surface protection was attached.
  • Adhesive strength The adhesive strength of the obtained adhesive sheet for surface protection was measured. That is, a test piece having a width of 25 mm and a length of 300 mm was cut out from the obtained adhesive sheet for surface protection, and the release film of the adhesive sheet for surface protection was peeled off in an environment of 23 ° C. and 50% RH (relative humidity), It was attached to a glass plate (manufactured by NS Precision Corporation, Corning Glass Eagle XG, 150 mm ⁇ 70 mm ⁇ 2 mm) and a polycarbonate plate (Mitsubishi Gas Chemical Co., Ltd., Iupilon sheet NF-2000VU) placed on the pedestal. .
  • a glass plate manufactured by NS Precision Corporation, Corning Glass Eagle XG, 150 mm ⁇ 70 mm ⁇ 2 mm
  • a polycarbonate plate Mitsubishi Gas Chemical Co., Ltd., Iupilon sheet NF-2000VU
  • Example 2 a pressure-sensitive adhesive sheet for surface protection was produced and evaluated in the same manner as in Example 1 except that 5 parts by weight of a terpene phenol resin (manufactured by Yashara Chemical Co., Ltd., TH130) was added to the pressure-sensitive adhesive composition before curing. .
  • the obtained results are shown in Table 1.
  • photographed the external appearance by the side of the base material in the adhesive sheet for surface protections affixed on the glass plate at this time is shown on the right side of FIG.
  • a photograph of the appearance is shown on the right side of FIG.
  • Comparative Example 1 In Comparative Example 1, evaluation was performed using an adhesive sheet made of an acrylic adhesive (Lintec Corporation, PET50 (A) P58KX, base material: 50 ⁇ m thick polyethylene terephthalate film). The obtained results are shown in Table 1. Moreover, the photograph which image
  • Comparative Example 2 In Comparative Example 2, 90 parts by weight of n-butyl acrylate, 10 parts by weight of acrylic acid, and 0.2 parts by weight of azobisisobutyronitrile (polymerization initiator) were added in ethyl acetate under a nitrogen atmosphere. The mixture was reacted at 24 ° C. for 24 hours to obtain an acrylate copolymer solution having a weight average molecular weight of 650,000 (solid content concentration: 33% by weight).
  • Comparative Example 3 In the comparative example 3, it evaluated using the adhesive sheet (The Lintec company make, PET50 (A) PA10 8LK, a base material: 50 micrometers in thickness polyethylene terephthalate film) which consists of an acrylic adhesive. The obtained results are shown in Table 1. Moreover, the photograph which image
  • Comparative Example 4 an adhesive sheet for surface protection was produced and evaluated in the same manner as in Example 1 except that 100 parts by weight of a terpene phenol resin (manufactured by Yashara Chemical Co., Ltd., TH130) was added to the adhesive composition before curing. .
  • the obtained results are shown in Table 1.
  • photographed the external appearance by the side of the base material in the adhesive sheet for surface protections affixed on the glass plate at this time is shown on the right side of Fig.6 (a), and the base material side in the adhesive sheet for surface protections affixed on the polycarbonate plate is shown.
  • a photograph of the appearance is shown on the right side of FIG.
  • Examples 1-2 using the predetermined terminal silyl group polymer of the present invention as a pressure-sensitive adhesive composition can be easily affixed with little external force when affixed to a glass plate and a polycarbonate plate, In addition, almost no air bite was observed at the time of application. Moreover, when peeling, it was able to peel off easily without leaving glue. On the other hand, even in the case of using a predetermined terminal silyl group polymer, in Comparative Example 4 in which a large amount of tackifying resin was blended, especially when bonded to a glass plate, a large amount of airbite was observed and peeled off. When force was required and peeled off vigorously, adhesive residue was generated.
  • Comparative Examples 1 and 2 using a predetermined acrylate copolymer as the pressure-sensitive adhesive composition all had high adhesive strength, and could not prevent air clogging at the time of sticking, and were easily peelable. Both were not easy.
  • Comparative Example 3 using another acrylic ester copolymer as the pressure-sensitive adhesive composition had good adhesiveness to glass and easy peelability, but for polycarbonate, to prevent air bite. It was difficult and the adhesive strength was also increased.
  • a surface protective pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer comprising a cured product of a pressure-sensitive adhesive composition containing a predetermined terminal silyl group polymer on one surface of a substrate.
PCT/JP2014/079845 2013-11-26 2014-11-11 表面保護用粘着シートおよび表面保護用粘着シートの使用方法 WO2015079903A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201480063119.1A CN105745294A (zh) 2013-11-26 2014-11-11 表面保护用粘着片及表面保护用粘着片的使用方法
KR1020167012382A KR20160090802A (ko) 2013-11-26 2014-11-11 표면 보호용 점착 시트 및 표면 보호용 점착 시트의 사용 방법
JP2015545217A JP5898389B2 (ja) 2013-11-26 2014-11-11 表面保護用粘着シートおよび表面保護用粘着シートの使用方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-243910 2013-11-26
JP2013243910 2013-11-26

Publications (1)

Publication Number Publication Date
WO2015079903A1 true WO2015079903A1 (ja) 2015-06-04

Family

ID=53198851

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/079845 WO2015079903A1 (ja) 2013-11-26 2014-11-11 表面保護用粘着シートおよび表面保護用粘着シートの使用方法

Country Status (5)

Country Link
JP (1) JP5898389B2 (zh)
KR (1) KR20160090802A (zh)
CN (1) CN105745294A (zh)
TW (1) TW201520304A (zh)
WO (1) WO2015079903A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6597727B2 (ja) * 2017-05-11 2019-10-30 東洋インキＳｃホールディングス株式会社 表面保護用粘着剤および粘着シート
KR102313741B1 (ko) 2017-09-01 2021-10-18 동우 화인켐 주식회사 점착 필름
KR20190043012A (ko) 2017-10-17 2019-04-25 동우 화인켐 주식회사 점착제 조성물 및 그를 이용한 점착 필름
JP6676706B2 (ja) * 2018-06-26 2020-04-08 リンテック株式会社 粘着シート

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000109676A (ja) * 1998-10-08 2000-04-18 Asahi Glass Co Ltd 硬化性組成物
WO2008123552A1 (ja) * 2007-04-03 2008-10-16 Asahi Glass Company, Limited 粘着体、粘着シートおよびその用途
WO2010026995A1 (ja) * 2008-09-05 2010-03-11 旭硝子株式会社 粘着体、粘着シートおよびその用途
JP2010111862A (ja) * 2008-10-08 2010-05-20 Asahi Glass Co Ltd 粘着積層体
JP2011006630A (ja) * 2009-06-29 2011-01-13 Konishi Co Ltd 粘着テープ又はシートの製造方法
JP2011006644A (ja) * 2009-06-29 2011-01-13 Konishi Co Ltd 床面等の構築物面貼着用再剥離再接着型粘着シート
JP2011219765A (ja) * 2009-04-30 2011-11-04 Nitto Denko Corp 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、粘着型光学フィルムおよび画像表示装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2925517B1 (fr) * 2007-12-21 2010-01-08 Bostik Sa Adhesifs sensibles a la pression a pouvoir adhesif stable en temperature.
JP5284362B2 (ja) * 2008-09-30 2013-09-11 コニシ株式会社 粘着テープ又はシートの製造方法
JP2010180367A (ja) 2009-02-06 2010-08-19 Three M Innovative Properties Co 再剥離性両面粘着シート

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000109676A (ja) * 1998-10-08 2000-04-18 Asahi Glass Co Ltd 硬化性組成物
WO2008123552A1 (ja) * 2007-04-03 2008-10-16 Asahi Glass Company, Limited 粘着体、粘着シートおよびその用途
WO2010026995A1 (ja) * 2008-09-05 2010-03-11 旭硝子株式会社 粘着体、粘着シートおよびその用途
JP2010111862A (ja) * 2008-10-08 2010-05-20 Asahi Glass Co Ltd 粘着積層体
JP2011219765A (ja) * 2009-04-30 2011-11-04 Nitto Denko Corp 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、粘着型光学フィルムおよび画像表示装置
JP2011006630A (ja) * 2009-06-29 2011-01-13 Konishi Co Ltd 粘着テープ又はシートの製造方法
JP2011006644A (ja) * 2009-06-29 2011-01-13 Konishi Co Ltd 床面等の構築物面貼着用再剥離再接着型粘着シート

Also Published As

Publication number Publication date
TW201520304A (zh) 2015-06-01
JP5898389B2 (ja) 2016-04-06
KR20160090802A (ko) 2016-08-01
JPWO2015079903A1 (ja) 2017-03-16
CN105745294A (zh) 2016-07-06

Similar Documents

Publication Publication Date Title
TWI642542B (zh) 抗靜電表面保護膜
KR101643169B1 (ko) 대전 방지 표면 보호 필름용 박리 필름 및 대전 방지 표면 보호 필름
CN106189942B (zh) 粘结剂组合物及粘结膜
JP5658711B2 (ja) 粘着フィルム用剥離フィルム、及びそれを用いた粘着フィルム
TW201805383A (zh) 抗靜電表面保護膜的製備方法以及抗靜電表面保護膜
KR20130123325A (ko) 표면 보호 필름 및 그것이 첩합된 광학 부품
JP5898389B2 (ja) 表面保護用粘着シートおよび表面保護用粘着シートの使用方法
WO2014002203A1 (ja) 粘着剤組成物及びそれを用いた粘着テープ
KR20130132278A (ko) 표면 보호 필름 및 그것이 첩합된 광학 부품
KR20180080707A (ko) 박리성이 우수한 이형 필름
JP6272109B2 (ja) 粘着剤組成物、粘着シート、および粘着シートの製造方法
KR20110137339A (ko) 감압 접착제 화합물
TWI741110B (zh) 黏合劑組合物、黏合片及光學構件
JP6591841B2 (ja) ウレタン系粘着シートおよびウレタン系粘着シートの製造方法、ならびにウレタン系粘着シートの粘着力制御方法
JP2013245303A (ja) 耐ブリスター用粘着シート
JP5901044B2 (ja) 両面粘着シートおよび両面粘着シートの製造方法
TW202012569A (zh) 表面保護膜、及光學膜
JP5901045B2 (ja) 粘着剤組成物および粘着シートの製造方法
WO2015079904A1 (ja) 電子部品の仮固定用粘着シートおよび電子部品の仮固定用粘着シートの使用方法
JP6272108B2 (ja) 粘着剤組成物、粘着シート、および粘着シートの製造方法
JPWO2018056167A1 (ja) 粘着剤組成物、粘着シート、及び、光学部材
KR102349680B1 (ko) 실리콘계 점착성 보호 필름 및 이를 포함하는 광학 부재
KR960014762B1 (ko) 점착필름의 제조방법
JP6219694B2 (ja) 圧電フィルム用両面粘着シート、圧電フィルム積層体および電子機器
JP2019155921A (ja) 表面保護フィルム用剥離フィルム、及びそれが貼合された光学フィルム用表面保護フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14865768

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015545217

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20167012382

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14865768

Country of ref document: EP

Kind code of ref document: A1