WO2021024862A1 - 光架橋性粘着剤およびその利用 - Google Patents
光架橋性粘着剤およびその利用 Download PDFInfo
- Publication number
- WO2021024862A1 WO2021024862A1 PCT/JP2020/028917 JP2020028917W WO2021024862A1 WO 2021024862 A1 WO2021024862 A1 WO 2021024862A1 JP 2020028917 W JP2020028917 W JP 2020028917W WO 2021024862 A1 WO2021024862 A1 WO 2021024862A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- photocrosslinkable
- weight
- less
- Prior art date
- Legal status (The legal status 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 status listed.)
- Ceased
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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- 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
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- 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
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
- C09J157/10—Homopolymers or copolymers containing elements other than carbon and hydrogen containing oxygen atoms
-
- 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
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- 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
- C09J2301/30—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
- C09J2301/302—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 the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
-
- 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
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/14—Glass
- C09J2400/143—Glass in the substrate
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to a photocrosslinkable pressure-sensitive adhesive, the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing the photo-crosslinkable pressure-sensitive adhesive, a method for producing a laminate using the photo-crosslinkable pressure-sensitive adhesive, a method for producing a photo-crosslinkable pressure-sensitive adhesive, and photocrosslinkability.
- the present invention relates to a pressure-sensitive adhesive composition used in the production of a pressure-sensitive adhesive.
- an adhesive also referred to as a pressure-sensitive adhesive; the same applies hereinafter
- exhibits a soft solid state viscoelastic body
- a property of easily adhering to an adherend by pressure Taking advantage of these properties, adhesives are widely used in various fields.
- Patent Document 1 is mentioned as a technical document relating to the pressure-sensitive adhesive.
- Adhesives are required to have various properties depending on the application. Among these characteristics, there are some that are difficult to achieve at a high level, for example, when trying to improve one characteristic, the other characteristic tends to decrease. As an example of the characteristics that are difficult to achieve at the same time, the property of deforming according to the surface shape of the adherend (hereinafter, also referred to as “surface shape following property”) and the property of being difficult to be deformed by stress. (Hereinafter, also referred to as "deformation resistance").
- an object of the present invention is to provide a pressure-sensitive adhesive capable of forming a bond having good surface shape followability to an adherend and high deformation resistance, and a pressure-sensitive adhesive sheet using the pressure-sensitive adhesive.
- a photocrosslinkable pressure-sensitive adhesive containing a polymer having a benzophenone structure in a side chain is provided.
- the photocrosslinkable pressure-sensitive adhesive can be photocrosslinked by utilizing the benzophenone structure after being attached to an adherend, whereby the deformation resistance of the pressure-sensitive adhesive can be enhanced.
- the pressure-sensitive adhesive having good surface shape followability can be suitably adhered to the surface of the adherend by deforming (absorbing the step) along a step that may exist on the surface of the adherend.
- some adhesive adherends generate so-called outgas under conditions such as a high temperature environment.
- the outgas from the adherend is then the interface between the adhesive and the adherend. It is possible that new bubbles may be formed by accumulating in the air. The generation (foaming) of such bubbles can reduce the contact area of the pressure-sensitive adhesive with the adherend, and can lead to a decrease in the reliability of bonding by the pressure-sensitive adhesive.
- the pressure-sensitive adhesive which is expected to be bonded to an adherend that easily generates outgas, suppresses the formation of the bubbles even if it is held in a high temperature environment after being attached to the adherend. It is desirable that it is configured so that it can adhere to the surface with good durability. Since the above-mentioned bubbles are formed by deforming the pressure-sensitive adhesive, increasing the deformation resistance of the pressure-sensitive adhesive may help suppress the formation of bubbles. Since the photocrosslinkable pressure-sensitive adhesive disclosed herein can be photocrosslinked after being attached to an adherend to enhance the deformation resistance of the pressure-sensitive adhesive, the photocrosslinkable pressure-sensitive adhesive has a surface shape followability. Adhesion durability can be suitably compatible.
- the photocrosslinkable pressure-sensitive adhesive has an emission amount of a volatile organic compound of 500 ⁇ g / g or less.
- a photocrosslinkable pressure-sensitive adhesive having a small amount of volatile organic compounds (VOC) emitted (hereinafter, also referred to as "VOC emission amount”) has a low odor and is preferable from the viewpoint of environmental hygiene.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein can be a cured product of a pressure-sensitive adhesive composition containing an ethylenically unsaturated compound and a benzophenone structure-containing component.
- a benzophenone structure-containing component include a polymer having a benzophenone structure in a side chain (hereinafter, also referred to as “BP polymer”) and a compound having an ethylenically unsaturated group and a benzophenone structure in the molecule (hereinafter, also referred to as “BP polymer”).
- BP polymer polymer having a benzophenone structure in a side chain
- BP polymer a compound having an ethylenically unsaturated group and a benzophenone structure in the molecule
- the BP polymer can be preferably employed as the benzophenone structure-containing component.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein may preferably be a cured product of a pressure-sensitive adhesive composition containing an ethylenically unsaturated compound and a BP polymer.
- a photocrosslinkable pressure-sensitive adhesive containing two or more polymers having different monomer compositions, and at least one of the two or more polymers is a BP polymer.
- the characteristics of the photocrosslinkable pressure-sensitive adhesive and the photo-crosslinked product (that is, light) of the photocrosslinkable pressure-sensitive adhesive are determined by the selection and combination of the polymers. The characteristics of the above-mentioned photocrosslinkable adhesive after cross-linking) can be appropriately adjusted.
- the photocrosslinkable pressure-sensitive adhesive containing the above two or more kinds of polymers can be, for example, a cured product of a pressure-sensitive adhesive composition containing an ethylenically unsaturated compound and a BP polymer.
- the photocrosslinkable pressure-sensitive adhesive containing the above two or more kinds of polymers preferably has a VOC emission amount of 500 ⁇ g / g or less.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein has a shear storage elastic modulus of Gb'[kPa] at 80 ° C. and an illuminance of 300 mW / cm 2 using a high-pressure mercury lamp as the photocrosslinkable pressure-sensitive adhesive.
- the relationship between the shear storage elastic modulus Gc'[kPa] at 80 ° C. of the photocrosslinked product obtained by irradiating ultraviolet rays under the condition of an integrated light amount of 10000 mJ / cm 2 is as follows: Gc'[kPa] -Gb' [KPa] ⁇ 2 kPa; can be satisfied.
- the shear storage elastic modulus Gb' may be referred to as “modulus pre-photobridge elastic modulus Gb'” or simply “elastic modulus Gb'”, and the shear storage elastic modulus Gc'is referred to as “post-photobridge elastic modulus Gc'”. It may be simply called “modulus Gc'”.
- Gc'[kPa] -Gb'[kPa] that is, the amount of increase in the shear storage elastic modulus at 80 ° C. due to photocrosslinking may be referred to as " ⁇ G'” (unit: kPa).
- the photocrosslinkable pressure-sensitive adhesive having ⁇ G'of 2 kPa or more, the effect of improving the deformation resistance by photocrosslinking is likely to be suitably exhibited.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein irradiates the photocrosslinkable pressure-sensitive adhesive with ultraviolet rays under the conditions of an illuminance of 300 mW / cm 2 and an integrated light amount of 10,000 mJ / cm 2 using a high-pressure mercury lamp.
- the shear storage elasticity Gc'[kPa] at 80 ° C. of the obtained photocrosslinked product can be 40 kPa or more.
- a photocrosslinkable pressure-sensitive adhesive having an elastic modulus Gc'after photocrosslinking of 40 kPa or more tends to exhibit excellent adhesion durability to the adherend by photocrosslinking after being attached to the adherend. Therefore, it is preferable.
- an adhesive sheet having an adhesive layer made of any of the photocrosslinkable adhesives disclosed herein is provided.
- Such an adhesive sheet has good surface shape followability of the photocrosslinkable adhesive layer when attached to an adherend, and the photocrosslinkable adhesive is photocrosslinked after application to form a highly deformable bond. can do.
- the pressure-sensitive adhesive sheet may have a peel strength of 1.0 N / 10 mm or higher as measured by the procedure below. According to the pressure-sensitive adhesive sheet exhibiting such peel strength, highly reliable bonding can be preferably realized.
- Peel strength measurement procedure The surface of the pressure-sensitive adhesive layer is pressure-bonded to a glass plate by reciprocating a 2 kg rubber roller once, autoclaving (50 ° C., 0.5 MPa, 15 minutes), and then using a high-pressure mercury lamp on the glass plate side.
- the adhesive sheet After irradiating ultraviolet rays under the conditions of an illuminance of 300 mW / cm 2 and an integrated light intensity of 10000 mJ / cm 2 , the adhesive sheet is then applied from the glass plate under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 degrees in an atmosphere of 25 ° C. Measure the peeling strength at the time of peeling.
- the photocrosslinkable pressure-sensitive adhesive is obtained by laminating any of the photocrosslinkable pressure-sensitive adhesives disclosed herein and a member and reacting the benzophenone structure contained in the photocrosslinkable pressure-sensitive adhesive. Is provided, and a method for producing a laminate including the above is provided in this order. According to this method, when the photocrosslinkable adhesive is laminated on the member, the photocrosslinkable adhesive is made to follow the surface shape of the member well, and after the lamination, the photocrosslinkable adhesive is photocrosslinked. Since the deformation resistance can be improved, it is possible to obtain a laminated body in which the photocrosslinked product of the photocrosslinkable adhesive and the member are reliably bonded.
- a pressure-sensitive adhesive composition containing a BP polymer (A) and an ethylenically unsaturated compound (B) is prepared, and the pressure-sensitive adhesive composition is irradiated with active energy rays.
- a method for producing a photocrosslinkable pressure-sensitive adhesive is provided. The irradiation with the active energy rays is carried out so as to react the ethylenically unsaturated group of the ethylenically unsaturated compound (B) and leave the benzophenone structure of the BP polymer (A).
- a photocrosslinkable pressure-sensitive adhesive containing a BP polymer can be obtained as an active energy ray-cured product of the pressure-sensitive adhesive composition.
- the above-mentioned production method can be preferably adopted as a method for producing any of the photocrosslinkable pressure-sensitive adhesives disclosed herein.
- the pressure-sensitive adhesive composition may include, as the ethylenically unsaturated compound (B), a compound (B1) having one ethylenically unsaturated group.
- the properties of the photocrosslinkable pressure-sensitive adhesive formed from the composition can be appropriately adjusted by selecting the type and amount of the compound (B1).
- the pressure-sensitive adhesive composition may include, as the ethylenically unsaturated compound (B), a compound (B2) having two or more ethylenically unsaturated groups.
- the properties of the photocrosslinkable pressure-sensitive adhesive formed from the composition can be appropriately adjusted by selecting the type and amount of the compound (B2).
- the pressure-sensitive adhesive composition may further comprise a photoinitiator (C).
- a photoinitiator (C) By using the photoinitiator (C), the reaction of the ethylenically unsaturated group of the ethylenically unsaturated compound (B) can be promoted.
- the photoinitiator (C) As the photoinitiator (C), a compound that absorbs light having a wavelength of 300 nm to 500 nm to generate radicals can be preferably adopted. Since the excitation wavelength of the benzophenone structure is generally lower than 300 nm, the reaction of ethylenically unsaturated groups is effectively promoted while retaining the benzophenone structure by using a photoinitiator that absorbs light having a wavelength of 300 nm or more to generate radicals. can do.
- the active energy ray to irradiate the pressure-sensitive adhesive composition for example, ultraviolet rays containing substantially no component having a wavelength of less than 300 nm can be preferably adopted. With such ultraviolet rays, the ethylenically unsaturated group is reacted while leaving the benzophenone structure to cure the pressure-sensitive adhesive composition, and a photocrosslinkable pressure-sensitive adhesive containing a BP polymer can be suitably produced.
- a pressure-sensitive adhesive composition used for producing a photocrosslinkable pressure-sensitive adhesive containing a BP polymer contains a BP polymer (A) and an ethylenically unsaturated compound (B).
- the photocrosslinkability of the pressure-sensitive adhesive composition is obtained by reacting the ethylenically unsaturated group of the ethylenically unsaturated compound (B) and curing the benzophenone structure of the BP polymer (A) so as to remain.
- Adhesives can be manufactured.
- the curing of the pressure-sensitive adhesive composition can be performed, for example, by irradiating the pressure-sensitive adhesive composition with active energy rays.
- the pressure-sensitive adhesive composition may include a photoinitiator (C) that absorbs light having a wavelength of 300 nm to 500 nm to generate radicals.
- a photoinitiator (C) that absorbs light having a wavelength of 300 nm to 500 nm to generate radicals.
- the pressure-sensitive adhesive composition preferably has a weight fraction of less than 5% by weight of a compound having two or more ethylenically unsaturated groups in the total monomer components constituting the pressure-sensitive adhesive composition. .. According to the pressure-sensitive adhesive composition having such a composition, a photocrosslinkable pressure-sensitive adhesive exhibiting good surface shape followability tends to be formed before photocrosslinking.
- FIG. 1 is a cross-sectional view schematically showing the configuration of the pressure-sensitive adhesive sheet according to the embodiment.
- FIG. 2 is a cross-sectional view schematically showing the configuration of the pressure-sensitive adhesive sheet according to another embodiment.
- FIG. 3 is a cross-sectional view schematically showing an optical member with an adhesive sheet to which the adhesive sheet according to the embodiment is attached to the optical member.
- the "acrylic polymer” refers to a polymer derived from a monomer component containing an acrylic monomer in an amount of more than 50% by weight (preferably more than 70% by weight, for example, more than 90% by weight).
- the acrylic monomer refers to a monomer having at least one (meth) acryloyl group in one molecule.
- (meth) acryloyl means a comprehensively referring to acryloyl and methacryloyl.
- (meth) acrylate” means acrylate and methacrylate
- “(meth) acrylic” means acrylic and methacrylic, respectively.
- the "ethylenically unsaturated compound” means a compound having at least one ethylenically unsaturated group in the molecule.
- ethylenically unsaturated groups include (meth) acryloyl groups, vinyl groups, allyl groups and the like.
- a compound having one ethylenically unsaturated group may be referred to as a "monofunctional monomer”
- a compound having two or more ethylenically unsaturated groups may be referred to as a "polyfunctional monomer”.
- a compound having X ethylenically unsaturated groups may be described as "X-functional monomer”.
- the fact that the pressure-sensitive adhesive composition contains an ethylenically unsaturated compound means that the above-mentioned ethylenically unsaturated compound is contained in the form of a partial polymer, unless otherwise specified.
- a partial polymer usually contains the above ethylenically unsaturated compound (unreacted monomer) in which the ethylenically unsaturated group is unreacted and the above ethylenically unsaturated compound in which the ethylenically unsaturated group is polymerized. It is a mixture containing.
- the entire monomer component constituting the pressure-sensitive adhesive composition refers to the monomer component constituting the polymer contained in the pressure-sensitive adhesive composition and the monomer contained in the pressure-sensitive adhesive composition in the form of an unreacted monomer.
- the composition of the monomer component constituting the pressure-sensitive adhesive composition is generally substantially the same as the composition of the monomer component of the photocrosslinkable pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition and the composition of the monomer component constituting the photocrosslinked product. ..
- active energy ray is a concept including light such as ultraviolet rays, visible rays, and infrared rays, and radiation such as ⁇ rays, ⁇ rays, ⁇ rays, electron rays, neutron rays, and X-rays. is there.
- a photocrosslinkable pressure-sensitive adhesive containing a polymer having a benzophenone structure in a side chain is provided.
- the photocrosslinkable pressure-sensitive adhesive is a cured product of a pressure-sensitive adhesive composition containing an ethylenically unsaturated compound and a benzophenone structure-containing component; the VOC emission amount is 500 ⁇ g / g or less; and the monomer composition. It corresponds to at least one of the above two or more kinds of polymers, and at least one of the above two or more kinds of polymers is the above BP polymer.
- the BP polymer in the technique disclosed herein (the BP polymer contained in the photocrosslinkable pressure-sensitive adhesive disclosed herein and BP that can be used as a constituent component of the pressure-sensitive adhesive composition for producing the photocrosslinkable pressure-sensitive adhesive).
- a preferable example of the polymer including the polymer; the same applies hereinafter) includes an acrylic polymer having a benzophenone structure in a side chain.
- the BP polymer may or may not have an ethylenically unsaturated group.
- the BP polymer is preferably a polymer that is substantially free of ethylenically unsaturated groups.
- Ar 1 in the above general formula is selected from phenyl groups which may have a substituent.
- Ar 2 and Ar 3 in the above general formula are independently selected from phenylene groups which may have a substituent.
- Ar 2 and Ar 3 may be the same or different.
- the benzophenone structure-containing component refers to a compound having at least one such benzophenone structure in the molecule.
- the benzophenone structure can be excited by irradiation with ultraviolet rays, and in the excited state, hydrogen radicals can be extracted from other molecules or other parts of the molecules.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein contains a polymer (BP polymer) having a benzophenone structure in a side chain, thereby exciting the benzophenone structure to form a crosslinked structure by utilizing the above-mentioned hydrogen radical abstraction reaction. Can be formed.
- a polymer having a benzophenone structure, which is a phenylene group which may have a group, in a side chain is preferable.
- the substituents are independently alkoxy groups (for example, alkoxy groups having 1 to 3 carbon atoms, preferably methoxy groups). It can be selected from the group consisting of halogen atoms (eg, F, Cl, Br, etc., preferably Cl or Br), hydroxyl groups, amino groups and carboxy groups, but is not limited thereto.
- the BP polymer in the technique disclosed herein may have a benzophenone structure as described above having a side chain directly bonded to the main chain, and may be one or more types such as an ester bond and an oxyalkylene structure. It may have a side chain bonded to the main chain via an ester.
- Preferable examples of the BP polymer include polymers containing repeating units derived from ethylenically unsaturated BP.
- the repeating unit may be a polymerization residue reacted with an ethylenically unsaturated group of the corresponding ethylenically unsaturated BP.
- Examples of ethylenically unsaturated BP include 4-acryloyloxybenzophenone, 4-acryloyloxy-4'-methoxybenzophenone, 4-acryloyloxyethoxy-4'-methoxybenzophenone, 4-acryloyloxy-4'-bromobenzophenone, 2 -Acryloyloxybenzophenone which may have a substituent such as hydroxy-4-acryloyloxybenzophenone; 4-[(2-acryloyloxy) ethoxy] benzophenone, 4-[(2-acryloyloxy) ethoxy] -4 Acryloyloxyalkoxybenzophenone which may have a substituent such as'-bromobenzophenone; 4-methacryloyloxybenzophenone, 4-methacryloyloxy-4'-methoxybenzophenone, 4-methacryloyloxy-4'-bromobenzophenone, 4 Methoxyloyloxybenzophenone which may have
- Ethylene unsaturated BPs can be used alone or in combination of two or more to prepare BP polymers.
- a commercially available product can be used, and the ethylenically unsaturated BP can be synthesized by a known method.
- an ethylenically unsaturated BP having a (meth) acryloyl group that is, an ethylenically unsaturated BP which is an acrylic monomer can be preferably adopted.
- the BP polymer has a repeating unit derived from an ethylenically unsaturated BP and a repeating unit derived from an ethylenically unsaturated compound (hereinafter, also referred to as “another monomer”) that does not correspond to the ethylenically unsaturated BP. It may be a copolymer.
- Such a BP polymer can be a copolymer of a monomer component containing the ethylenically unsaturated BP and the other monomer.
- one or more acrylic monomers may be preferably employed as the other monomers.
- a preferable example of the BP polymer is an acrylic BP polymer in which more than 50% by weight (preferably more than 70% by weight, for example, more than 90% by weight) of the monomer components constituting the BP polymer is an acrylic monomer.
- the monomer component constituting the BP polymer may include, as the other monomer, one or more selected from (meth) acrylic acid alkyl esters having an alkyl group at the ester terminal.
- a (meth) acrylic acid alkyl ester having a linear or branched-chain alkyl group having an number of carbon atoms of X or more and Y or less at the ester terminal shall be referred to as "(meth) acrylic acid CXY alkyl ester".
- the monomer component constituting the BP polymer preferably contains at least (meth) acrylic acid C 1-20 alkyl ester as the other monomer, and more preferably contains (meth) acrylic acid C 4-20 alkyl ester.
- (Meta) acrylic acid C 4-18 alkyl ester eg, acrylic acid C 4-9 alkyl ester is more preferably included.
- Non-limiting specific examples of (meth) acrylic acid C 1-20 alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, ( N-butyl acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) ) Decyl acrylate, Isodecy
- Particularly preferable (meth) acrylic acid alkyl esters include n-butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), and isononyl acrylate.
- Other specific examples of (meth) acrylic acid alkyl esters that may be preferably used include n-butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2EHMA), isostearyl acrylate (iSTA) and the like.
- the (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.
- the monomer component constituting the BP polymer may contain one or more selected from the copolymerizable monomers described later as the other monomer.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein is a light in which more than 50% by weight (preferably more than 70% by weight, for example, more than 90% by weight) of the total monomer components constituting the photocrosslinkable pressure-sensitive adhesive is an acrylic monomer. It can be a crosslinkable acrylic pressure-sensitive adhesive.
- the photocrosslinkable acrylic pressure-sensitive adhesive forms an acrylic photocrosslinked product by photocrosslinking.
- the photocrosslinkable acrylic pressure-sensitive adhesive can be preferably used, for example, in optical applications because the photocrosslinked product can have good transparency.
- the weight average molecular weight (Mw) of the BP polymer is not particularly limited, and may be, for example, about 0.5 ⁇ 10 4 to 500 ⁇ 10 4 .
- Mw of the BP polymer is a normal, 1 ⁇ 10 4 or more It is appropriate, preferably 5 ⁇ 10 4 or more, 10 ⁇ 10 4 or more, 15 ⁇ 10 4 or more, and 20 ⁇ 10 4 or more.
- an adherend in terms of the surface shape followability of the photocrosslinkable adhesive against, Mw of BP polymer contained in the light-crosslinkable adhesive is a normal, 200 ⁇ 10 4 or less it is appropriate, preferably at 0.99 ⁇ 10 4 or less, may be a 100 ⁇ 10 4 or less, may be a 70 ⁇ 10 4 or less, may be 50 ⁇ 10 4 or less.
- the Mw of the BP polymer may be 40 ⁇ 10 4 or less, 30 ⁇ 10 4 or less, 25 ⁇ 10 4 or less, or 20 ⁇ 10 4 or less.
- the weight average molecular weight (Mw) of the polymer means a standard polystyrene-equivalent value obtained by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- a model name "HLC-8320GPC” (column: TSKgelGMH-H (S), manufactured by Tosoh Corporation) can be used.
- the glass transition temperature (Tg) of the BP polymer is not particularly limited.
- the Tg of the BP polymer may be, for example, ⁇ 80 ° C. or higher and 150 ° C. or lower, ⁇ 80 ° C. or higher and 50 ° C. or lower, or ⁇ 80 ° C. or higher and 10 ° C. or lower.
- the Tg of the BP polymer is preferably less than 0 ° C., preferably ⁇ 10 ° C. or lower, and preferably ⁇ 20 ° C. It may be less than or equal to ⁇ 30 ° C., may be ⁇ 35 ° C.
- the Tg of the BP polymer is usually ⁇ 75 ° C. or higher. Is advantageous, and may be ⁇ 70 ° C. or higher, or ⁇ 65 ° C. or higher. In some embodiments, the Tg of the BP polymer may be ⁇ 55 ° C. or higher, ⁇ 45 ° C. or higher, or ⁇ 40 ° C. or higher.
- the Tg of the BP polymer can be adjusted by the type and amount of the monomer components constituting the BP polymer.
- the glass transition temperature (Tg) of the polymer in the present specification means the glass transition temperature obtained by the Fox formula based on the composition of the monomer components constituting the polymer.
- Tg is the glass transition temperature (unit: K) of the copolymer
- Wi the weight fraction of the monomer i in the copolymer (copolymerization ratio based on the weight)
- Tgi is the monomer i.
- the glass transition temperature of the homopolymer used for calculating Tg the value described in the publicly known material shall be used.
- the monomers listed below the following values are used as the glass transition temperature of the homopolymer of the monomer.
- the values described in "Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989) shall be used. When multiple types of values are described in this document, the highest value is adopted.
- the value obtained by the measuring method described in Japanese Patent Application Publication No. 2007-51271 shall be used.
- the nominal value may be adopted.
- the BP polymer in the technique disclosed herein preferably contains a benzophenone structure in an amount of, for example, about 0.5 mg or more in terms of 4-benzoylphenyl acrylate, per 1 g of the polymer.
- the value obtained by converting the number of benzophenone structures contained in 1 g of the BP polymer into the amount converted to 4-benzoylphenyl acrylate may be referred to as the BP equivalent (unit: mg / g) of the BP polymer.
- the BP equivalent of the polymer is calculated to be 10 mg / g.
- the BP equivalent of the BP polymer is usually 1 mg / g or more. It is preferably 1.5 mg / g or more, for example, 2 mg / g or more, 5 mg / g or more, 8 mg / g or more, 10 mg / g or more, 15 mg / g or more, and so on. It may be 20 mg / g or more.
- the BP equivalent of the BP polymer is usually 100 mg / g or less, and 80 mg / g, from the viewpoint of enhancing the impact resistance and peel strength of the joint portion by the photocrosslinked product. It may be 60 mg / g or less, 40 mg / g or less, 25 mg / g or less, or 15 mg / g or less. In some embodiments, the BP equivalent of the BP polymer may be less than 10 mg / g and less than 5 mg / g. The BP equivalent of the BP polymer can be adjusted by the composition of the monomer components constituting the BP polymer.
- the weight ratio of the BP polymer to the entire photocrosslinkable adhesive is not particularly limited, and the surface shape followability of the photocrosslinkable adhesive and its photocrosslinking are not particularly limited. It can be set so as to have a suitable balance with the deformation resistance of the object.
- the weight fraction of the BP polymer may be, for example, 1% by weight or more, usually 5% by weight or more, 10% by weight or more, 15% by weight or more. It may be 25% by weight or more, 30% by weight or more, 35% by weight or more, 45% by weight or more, 50% by weight or more, or 55% by weight or more.
- the weight fraction of the BP polymer in the photocrosslinkable pressure-sensitive adhesive is substantially 100% by weight (for example, 99.5% by weight or more).
- the weight fraction of the BP polymer in the photocrosslinkable adhesive may be, for example, less than 99% by weight, 95% by weight. It may be less than 85% by weight, less than 70% by weight, less than 60% by weight, less than 50% by weight, less than 40% by weight, less than 35% by weight.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein preferably contains, for example, about 0.1 mg or more of a benzophenone structure in terms of 4-benzoylphenyl acrylate, per 1 g of the photocrosslinkable pressure-sensitive adhesive.
- a benzophenone structure in terms of 4-benzoylphenyl acrylate per 1 g of the photocrosslinkable pressure-sensitive adhesive.
- the weight of the benzophenone structure in terms of 4-benzoylphenyl acrylate contained in 1 g of the photocrosslinkable adhesive may be referred to as the BP equivalent (unit: mg / g) of the photocrosslinkable adhesive.
- the BP equivalent of the photocrosslinkable pressure-sensitive adhesive is usually 0.3 mg / g or more. Is appropriate, and may be 0.5 mg / g or more, 1 mg / g or more, 5 mg / g or more, 10 mg / g or more, or 20 mg / g or more. Further, in some embodiments, the BP equivalent of the photocrosslinkable adhesive is usually 100 mg / g or less from the viewpoint of impact resistance of the joint portion by the photocrosslinked product and suppression of strain in the photocrosslinked product. It is suitable, and may be 80 mg / g or less, 60 mg / g or less, 40 mg / g or less, 25 mg / g or less, or 15 mg / g or less.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein can be a cured product of a pressure-sensitive adhesive composition containing an ethylenically unsaturated compound and a benzophenone structure-containing component.
- the pressure-sensitive adhesive composition may contain one or more monomers selected from the ethylenically unsaturated BP as described above as the benzophenone structure-containing component, and may contain a pre-synthesized BP polymer. It may be included, or both of them may be included.
- the BP polymer contained in the photocrosslinkable pressure-sensitive adhesive may be, for example, the BP polymer contained in the pressure-sensitive adhesive composition or a modified product thereof, and may be an ethylenically non-ethyleney component contained in the pressure-sensitive adhesive composition. It may be formed by copolymerizing saturated BP and other monomers.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein may be a photocrosslinkable pressure-sensitive adhesive containing two or more polymers having different monomer compositions, and at least one of the two or more polymers is the BP polymer.
- the photocrosslinkable pressure-sensitive adhesive may contain only two or more types of BP polymers as the two or more types of polymers, and may contain only two or more types of BP polymers, and may contain a polymer having no benzophenone structure (hereinafter, also referred to as “non-BP polymer”) and a BP polymer. And may be included in combination.
- the non-BP polymer can be formed, for example, by polymerizing the ethylenically unsaturated compound using a pressure-sensitive adhesive composition containing an ethylenically unsaturated compound having no benzophenone structure.
- the BP polymer and the non-BP polymer are preferably acrylic polymers from the viewpoint of compatibility and the like.
- the above two or more kinds of polymers may or may not be chemically bonded.
- the photocrosslinkable pressure-sensitive adhesive may contain at least one BP polymer in a form that is not chemically bonded to a polymer other than the BP polymer.
- a photocrosslinkable pressure-sensitive adhesive can form a photocrosslinked product in which the BP polymer and a polymer other than the BP polymer are chemically bonded.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein can contain other components that can be used in the pressure-sensitive adhesive, if necessary. Photocrosslinkable pressure-sensitive adhesives containing such optional components can be formed using a pressure-sensitive adhesive composition having a corresponding composition.
- the VOC emission amount of the photocrosslinkable pressure-sensitive adhesive disclosed herein is not particularly limited.
- the VOC emission amount may be, for example, 5000 ⁇ g / g or less, 3000 ⁇ g / g or less, or 1000 ⁇ g / g or less.
- the VOC emission amount of the photocrosslinkable pressure-sensitive adhesive is preferably 500 ⁇ g / g or less, more preferably 300 ⁇ g / g or less, and even more preferably 100 ⁇ g / g or less.
- a photocrosslinkable adhesive having a small amount of VOC emissions has a low odor and is preferable from the viewpoint of environmental hygiene.
- VOC emission amount of the photocrosslinkable pressure-sensitive adhesive is measured by the following method using an appropriate amount of the photocrosslinkable pressure-sensitive adhesive (for example, about 1 mg to 2 mg) as a measurement sample.
- the thickness of the measurement sample is preferably 1 mm or less.
- VOC measurement test Place the measurement sample in a 20 mL vial and seal it tightly. Next, the vial is heated at 80 ° C. for 30 minutes, and 1.0 mL (sample gas) of the heated gas is injected into a gas chromatograph (GC) measuring device using a headspace autosampler (HSS). Based on the obtained gas chromatogram, the amount of gas generated from the measurement sample is determined as an n-decane equivalent amount. From the obtained value, the VOC emission amount ( ⁇ g / g) per 1 g of the measurement sample is determined.
- GC gas chromatograph
- HSS headspace autosampler
- the n-decane conversion amount is obtained by regarding the detection intensity of the generated gas obtained by GC Mass as the detection intensity of n-decane and applying a calibration curve of n-decane prepared in advance.
- the settings for HSS and GC are as follows.
- HSS Agilent Technologies model "7694" Heating time: 30 minutes Pressurization time: 0.12 minutes Loop filling time: 0.12 minutes Loop equilibrium time: 0.05 minutes
- volatile organic compounds that can increase the VOC emission amount of a pressure-sensitive adhesive include organic solvents (for example, residues of the organic solvent contained in the pressure-sensitive adhesive composition used for preparing a photocrosslinkable pressure-sensitive adhesive. ), An unreacted product of an ethylenically unsaturated compound contained in the pressure-sensitive adhesive composition (for example, an unpolymerized acrylic monomer; hereinafter, also referred to as “residual monomer”) and the like.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein may be one in which the content of such an organic solvent or residual monomer is suppressed to such an extent that it satisfies any of the above-mentioned VOC emission amounts.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein has a structure in which the amount of residual monomers is limited, and can form a new crosslink in the system by utilizing the benzophenone structure of the BP polymer. This makes it possible to form a photocrosslinked product having improved deformation resistance.
- the VOC emission amount is determined. For example, it may be 10 ⁇ g / g or more, 30 ⁇ g / g or more, 80 ⁇ g / g or more, 150 ⁇ g / g or more, or 200 ⁇ g / g or more.
- the shear storage elastic modulus Ga'[kPa] of the photocrosslinkable pressure-sensitive adhesive at 30 ° C. is not particularly limited.
- the shear storage elastic modulus Ga'[kPa] of the photocrosslinkable pressure-sensitive adhesive at 30 ° C. is usually preferably more than 1 kPa.
- the shear storage elastic modulus Ga' may be referred to as "room temperature elastic modulus Ga'before photocrossover” or simply "room temperature elastic modulus Ga'".
- the room temperature elastic modulus Ga' should be more than 5 kPa. It is preferably more than 10 kPa, more preferably more than 15 kPa, more than 25 kPa, and more than 30 kPa. In some embodiments, the room temperature elastic modulus Ga'may be greater than 50 kPa, greater than 65 kPa, or greater than 75 kPa.
- the room temperature elastic modulus Ga' is usually preferably 500 kPa or less, preferably 200 kPa or less, and may be 100 kPa or less. In some embodiments, the room temperature elastic modulus Ga'may be less than 80 kPa or less than 60 kPa.
- the room temperature elastic modulus Ga'of the photocrosslinkable pressure-sensitive adhesive can be determined by performing dynamic viscoelasticity measurement under the same conditions as the pre-photocrosslinking elastic modulus Gb' described in Examples described later.
- the room temperature elastic modulus Ga' can be adjusted by the composition of the photocrosslinkable pressure-sensitive adhesive (for example, the BP equivalent of the BP polymer, Mw, the composition of the monomer components constituting the BP polymer, the weight fraction of the BP polymer) and the like.
- the composition of the photocrosslinkable pressure-sensitive adhesive for example, the BP equivalent of the BP polymer, Mw, the composition of the monomer components constituting the BP polymer, the weight fraction of the BP polymer
- the shear storage elastic modulus of the photocrosslinkable adhesive at 80 ° C. (that is, the pre-photocrosslinking elastic modulus Gb') is not particularly limited.
- the elastic modulus Gb' is usually more than 3 kPa from the viewpoint of the cohesiveness of the photocrosslinkable adhesive and the handleability of the adhesive sheet having the photocrosslinkable adhesive (for example, the storage stability of the adhesive sheet). Is appropriate, preferably more than 5 kPa, more preferably more than 10 kPa, and more than 15 kPa.
- the elastic modulus Gb' may be greater than 30 kPa, greater than 40 kPa, greater than 50 kPa, or greater than 52 kPa from the viewpoint of processability of the pressure-sensitive adhesive sheet having the photocrosslinkable pressure-sensitive adhesive.
- the photocrosslinkable pressure-sensitive adhesive having such an elastic modulus Gb' is, for example, a pressure-sensitive adhesive layer having a thickness of more than 50 ⁇ m, more than 70 ⁇ m, or more than 90 ⁇ m made of the photocrosslinkable pressure-sensitive adhesive, or a component of a pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer.
- the elastic modulus Gb' can be measured by the method described in Examples described later.
- the elastic modulus Gb' can be adjusted by the composition of the photocrosslinkable pressure-sensitive adhesive (for example, the BP equivalent of the BP polymer, Mw, the composition of the monomer components constituting the BP polymer, the weight fraction of the BP polymer) and the like.
- the composition of the photocrosslinkable pressure-sensitive adhesive for example, the BP equivalent of the BP polymer, Mw, the composition of the monomer components constituting the BP polymer, the weight fraction of the BP polymer
- the shear storage elastic modulus Gc'[kPa] of the photocrosslinked product obtained by irradiating ultraviolet rays under the conditions of an illuminance of 300 mW / cm 2 and an integrated light amount of 10000 mJ / cm 2 using a high-pressure mercury lamp as a photocrosslinkable adhesive at 80 ° C. ] (That is, the elastic modulus after photocrosslinking Gc') is not particularly limited. From the viewpoint of suppressing cohesive fracture of the joint portion due to the photocrosslinked product, the elastic modulus Gc'is usually preferably 15 kPa or more, and preferably 25 kPa or more.
- the elastic modulus Gc' is advantageous to be 30 kPa or more, and 35 kPa or more. It is preferably 40 kPa or more, and more preferably 40 kPa or more. In some embodiments, the elastic modulus Gc'may be 45 kPa or higher, 50 kPa or higher, 55 kPa or higher, or 60 kPa or higher. Further, the elastic modulus Gc'may be, for example, 200 kPa or less, 150 kPa or less, or 120 kPa or less.
- the elastic modulus Gc' is advantageous to be 100 kPa or less, and 80 kPa or less, from the viewpoint of making it easy to achieve a good balance between adhesion durability to the adherend and other characteristics (for example, peel strength). Preferably, it may be 70 kPa or less, or 65 kPa or less.
- the elastic modulus Gc' is lowered, the peel strength of the photocrosslinked product formed by laminating the photocrosslinkable pressure-sensitive adhesive on the adherend and then photocrosslinking the adherend tends to be generally improved.
- the modulus of elasticity Gc' may be less than 60 kPa, less than 55 kPa, less than 50 kPa, or less than 45 kPa.
- the elastic modulus Gc'can be measured by the method described in Examples described later.
- the elastic modulus Gc'can be adjusted by the composition of the photocrosslinkable pressure-sensitive adhesive (for example, the BP equivalent of the BP polymer, Mw, the composition of the monomer components constituting the BP polymer, the weight fraction of the BP polymer) and the like.
- the relationship between the elastic modulus Gb'of the photocrosslinkable adhesive and the elastic modulus Gc'of the photocrosslinked product is not particularly limited, but is typically Gc'[kPa] -Gb'[kPa]> 0 [kPa].
- Meet. ⁇ G' may be, for example, 0.5 kPa or more, preferably 1 kPa or more, and more preferably 2 kPa or more. According to the photocrosslinkable pressure-sensitive adhesive having ⁇ G'of 2 kPa or more, the effect of improving the deformation resistance by photocrosslinking is likely to be suitably exhibited.
- ⁇ G' may be 3 kPa or more, 5 kPa or more, preferably 8 kPa or more, and 10 kPa or more. It may be 15 kPa or more, 20 kPa or more, 25 kPa or more, or 30 kPa or more.
- the upper limit of ⁇ G' is not particularly limited, but it is usually appropriate to be 150 kPa or less from the viewpoint of achieving a good balance between surface shape followability at the time of attachment to the adherend and deformation resistance after photocrosslinking. , 100 kPa or less, preferably 80 kPa or less, 65 kPa or less, 50 kPa or less, or 40 kPa or less.
- the gel fraction of the photocrosslinkable pressure-sensitive adhesive disclosed herein is not particularly limited, but the cohesiveness of the photocrosslinkable pressure-sensitive adhesive, the handleability of a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the photocrosslinkable pressure-sensitive adhesive, and the like. From the above viewpoint, it is usually appropriate that it is 5% or more, preferably 15% or more, 25% or more, or 35% or more. In principle, the gel fraction of the photocrosslinkable pressure-sensitive adhesive is 100% or less. Further, from the viewpoint of followability to the surface shape of the adherend, the gel fraction of the photocrosslinkable adhesive is preferably less than 85%, may be less than 70%, may be less than 55%, and may be less than 40%. It may be.
- the gel fraction is measured by the following method. That is, about 0.5 g of the measurement sample is precisely weighed, and the weight thereof is defined as W1.
- This measurement sample is wrapped in a porous PTFE (polytetrafluoroethylene) sheet, immersed in ethyl acetate at room temperature for 1 week, dried, and the weight W2 of the ethyl acetate insoluble matter is measured, and W1 and W2 are measured as follows.
- formula: Gel fraction (%) W2 / W1 ⁇ 100; Substitute in to calculate the gel fraction.
- the porous PTFE sheet the trade name "Nitoflon NTF1122" manufactured by Nitto Denko Corporation or an equivalent product thereof can be used.
- the photocrosslinkable pressure-sensitive adhesive is irradiated with ultraviolet rays using a high-pressure mercury lamp under the conditions of an illuminance of 300 mW / cm 2 and an integrated light amount of 10000 mJ / cm 2.
- the gel fraction of the obtained photocrosslinked product may be, for example, 70% or more, preferably 90% or more, 95% or more, or 98% or more. In principle, the gel fraction of the photocrosslinked product is 100% or less. The gel fraction is measured by the method described above.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein can be photocrosslinked, for example, by irradiating the benzophenone structure with ultraviolet rays containing an excitable wavelength component. It is preferable to use a light source capable of irradiating ultraviolet rays containing a component having a wavelength of less than 300 nm. Examples of such a light source include, but are not limited to, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, super UV lamps, and the like. The light emitted by the light source may contain a component having a wavelength of 300 nm or more.
- Examples of a light source that does not contain a wavelength component capable of exciting a benzophenone structure (for example, a component having a wavelength of less than 300 nm) or can irradiate ultraviolet rays having a small wavelength component include a black light and a UV-LED lamp. These light sources can be preferably adopted as a light source for advancing the reaction of ethylenically unsaturated groups (polymerization reaction or curing reaction) by light irradiation performed in the presence of a benzophenone structure. In ultraviolet irradiation for reacting an ethylenically unsaturated group, a photoinitiator described later can be used to promote the reaction.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein may have a composition substantially free of a photoinitiator that absorbs light having a wavelength of 300 nm or more and generates a radical, and is visible, for example, at 380 nm or more (particularly 400 nm or more).
- the composition may be substantially free of photoinitiators that absorb light and generate radicals. This can be advantageous in terms of the optical properties of the photocrosslinkable pressure-sensitive adhesive.
- the term "not including a photoinitiator that absorbs light having a wavelength of 300 nm or more and generates a radical” does not include the above-mentioned photoinitiator in a form capable of generating the above-mentioned radical (a form having a portion cleaved by the above-mentioned light). That is, it is acceptable to contain the cleavage residue of the photoinitiator.
- the photocrosslinkable pressure-sensitive adhesive does not substantially contain a photoinitiator containing a phosphorus element in the molecule.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein may be substantially free of either a photoinitiator containing a phosphorus element in the molecule or a cleavage residue of the photoinitiator.
- a pressure-sensitive adhesive composition containing a polymer (BP polymer) (A) having a benzophenone structure in a side chain and an ethylenically unsaturated compound (B) is provided.
- BP polymer polymer
- the pressure-sensitive adhesive composition is an acrylic in which more than 50% by weight (preferably more than 70% by weight, for example, more than 90% by weight) of the total monomer components constituting the pressure-sensitive adhesive composition is an acrylic monomer. It can be a based pressure-sensitive adhesive composition.
- the same BP polymer (A) contained in the photocrosslinkable pressure-sensitive adhesive can be used, so duplicate description will be omitted.
- (Ethylene unsaturated compound (B)) examples of the compound that can be used as the ethylenically unsaturated compound (B) include the above-mentioned (meth) acrylic acid alkyl ester and the above-mentioned ethylenically unsaturated BP. Of these, at least (meth) acrylic acid alkyl ester (eg, (meth) acrylic acid C 1-20 alkyl ester, more preferably (meth) acrylic acid C 4-18 alkyl ester, still more preferably acrylic acid C 4-9. Alkyl ester) is preferably used.
- Particularly preferred (meth) acrylic acid alkyl esters include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).
- Other specific examples of (meth) acrylic acid alkyl esters that may be preferably used include isononyl acrylate, n-butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2EHMA), isostearyl acrylate (iSTA) and the like.
- BMA n-butyl methacrylate
- EHMA 2-ethylhexyl methacrylate
- iSTA isostearyl acrylate
- the (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.
- the ethylenically unsaturated compound (B) preferably comprises one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA). In one aspect, it is more preferred to include at least 2 EHA. In another aspect, it is more preferred to include at least BA.
- the ethylenically unsaturated compound (B) may contain the acrylic acid C 4-9 alkyl ester in a proportion of 40% by weight or more.
- the ratio of the acrylic acid C 4-9 alkyl ester to the ethylenically unsaturated compound (B) may be, for example, 50% by weight or more, 60% by weight or more, or 65% by weight or more.
- the ratio of acrylic acid C 4-9 alkyl ester to the ethylenically unsaturated compound (B) is usually preferably 99.5% by weight or less. It may be 95% by weight or less, 85% by weight or less, 70% by weight or less, or 60% by weight or less.
- a compound that can be used as the ethylenically unsaturated compound (B) is an ethylenically unsaturated compound (copolymerizable monomer) that is copolymerizable with a (meth) acrylic acid alkyl ester.
- a monomer having a polar group for example, a carboxy group, a hydroxyl group, a nitrogen atom-containing ring, etc.
- a monomer having a polar group can be useful, for example, to introduce a cross-linking point into a polymer containing a repeating unit derived from the monomer, or to enhance the cohesive force of a photocrosslinkable pressure-sensitive adhesive.
- the copolymerizable monomer may be used alone or in combination of two or more.
- Non-limiting specific examples of the copolymerizable monomer include the following.
- Carboxylic group-containing monomer For example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.
- Acid anhydride group-containing monomer For example, maleic anhydride, itaconic anhydride.
- Hydroxyl group-containing monomers for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic.
- Monomer containing sulfonic acid group or phosphoric acid group For example, styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfo Propyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, 2-hydroxyethylacryloyl phosphate, etc.
- styrene sulfonic acid allyl sulfonic acid, sodium vinyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfo Propyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, 2-hydroxyethy
- Epoxide group-containing monomer For example, an epoxy group-containing acrylate such as glycidyl (meth) acrylate or -2-ethylglycidyl ether (meth) acrylate, allyl glycidyl ether, glycidyl ether (meth) acrylate and the like.
- Cyanide-containing monomer For example, acrylonitrile, methacrylonitrile, etc.
- Isocyanate group-containing monomer for example, 2- (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, m-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate and the like.
- Amide group-containing monomers (meth) acrylamide; for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) N, N-dialkyl (meth) acrylamide such as acrylamide, N, N-di (n-butyl) (meth) acrylamide, N, N-di (t-butyl) (meth) acrylamide; N-ethyl (meth) acrylamide , N-alkyl (meth) acrylamide such as N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, Nn-butyl (meth) acrylamide; N-vinylcarboxylic acid amides such as N-vinylacetamide; Monomers having a hydroxyl group and an amide group, for example
- N-alkoxyalkyl (meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide, N- (meth) acryloylmorpholine and the like.
- Amino group-containing monomer For example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate.
- Monomers having an epoxy group for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether.
- N-vinyl-2-pyrrolidone N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N- Vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N- (meth) acryloyl-2-pyrrolidone, N- (meth) acryloyl piperidine, N- (meth) acryloylpyrrolidin, N-vinylmorpholin, N- (meth) Acryloyl morpholine, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxadin-2-one, N-vinyl-3,5-morpholindione, N-vinylpyrazole, N -Viny
- Monomers having a succinimide skeleton for example, N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyhexamethylene succinimide and the like.
- Maleimides For example, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like.
- Itaconimides For example, N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-lauryl. Itaconimide, etc.
- Aminoalkyl (meth) acrylates For example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t (meth) acrylate. -Butylaminoethyl.
- Alkoxy group-containing monomers for example, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, (meth) acrylate.
- Alkoxyalkyl (alkoxyalkyl (meth) acrylates) such as butoxyethyl, ethoxypropyl (meth) acrylate; (meth) methoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, (meth) (Meta) Alkoxyalkylene glycol acrylate (for example, alkoxypolyalkylene glycol (meth) acrylate) such as methoxypolypropylene glycol acrylate.
- Alkoxysilyl group-containing monomers for example 3- (meth) acryloxipropyltrimethoxysilane, 3- (meth) acryloxipropyltriethoxysilane, 3- (meth) acryloxipropylmethyldimethoxysilane, 3- (meth) acryloxy Alkoxysilyl group-containing (meth) acrylates such as propylmethyldiethoxysilane, alkoxysilyl group-containing vinyl compounds such as vinyltrimethoxysilane and vinyltriethoxysilane, and the like.
- Vinyl esters For example, vinyl acetate, vinyl propionate and the like.
- Vinyl ethers For example, vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether.
- Aromatic vinyl compounds for example, styrene, ⁇ -methylstyrene, vinyltoluene and the like.
- Olefins For example, ethylene, butadiene, isoprene, isobutylene and the like.
- (Meta) acrylic acid ester having an alicyclic hydrocarbon group For example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate and the like. Alicyclic hydrocarbon group-containing (meth) acrylate.
- (Meta) acrylic acid ester having an aromatic hydrocarbon group For example, an aromatic hydrocarbon group-containing (meth) acrylate such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and benzyl (meth) acrylate.
- heterocyclic-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, halogen atom-containing (meth) acrylates such as vinyl chloride and fluorine atom-containing (meth) acrylates, and silicon atom-containing silicone (meth) acrylates.
- the amount used is not particularly limited, but it is usually appropriate to use 0.01% by weight or more of the total monomer components constituting the pressure-sensitive adhesive composition.
- the amount of the copolymerizable monomer used (that is, the weight fraction of the copolymerizable monomer in the entire monomer component) is 0.1% by weight of the total monomer component. It may be more than 0.5% by weight or more.
- the amount of the copolymerizable monomer used is usually preferably 50% by weight or less of the total monomer component, and preferably 40% by weight or less.
- the copolymerizable monomer may comprise a monomer having a nitrogen atom.
- a monomer having a nitrogen atom By using a monomer having a nitrogen atom, the cohesive force of the photocrosslinkable pressure-sensitive adhesive can be enhanced, and the peel strength after photocrosslinking can be preferably improved.
- a preferred example of a monomer having a nitrogen atom is a monomer having a nitrogen atom-containing ring.
- the monomer having a nitrogen atom-containing ring those exemplified above can be used, and for example, the general formula (1):
- the N-vinyl cyclic amide represented by is used.
- R 1 is a divalent organic group, specifically ⁇ (CH 2 ) n ⁇ .
- n is an integer of 2 to 7 (preferably 2, 3 or 4). Of these, N-vinyl-2-pyrrolidone can be preferably adopted.
- Other preferred examples of monomers having a nitrogen atom include (meth) acrylamide.
- the amount used is not particularly limited, and for example, a monomer component. It may be 1% by weight or more, 2% by weight or more, 3% by weight or more, and 5% by weight or more or 7% by weight or more of the whole. In one aspect, the amount of the monomer having a nitrogen atom used may be 10% by weight or more, 15% by weight or more, or 20% by weight or more of the total monomer component.
- the amount of the monomer having a nitrogen atom to be used is appropriately set to, for example, 40% by weight or less of the total monomer component, 35% by weight or less, 30% by weight or less, or 25% by weight or less. May be good.
- the amount of the monomer having a nitrogen atom used may be, for example, 20% by weight or less, 15% by weight or less, or less than 10% by weight or less than 6% by weight of the total monomer component.
- the copolymerizable monomer may include a hydroxyl group-containing monomer.
- the hydroxyl group-containing monomer By using the hydroxyl group-containing monomer, the cohesive force of the photocrosslinkable pressure-sensitive adhesive and the degree of cross-linking (for example, cross-linking with an isocyanate cross-linking agent) can be suitably adjusted.
- the amount used is not particularly limited, and may be, for example, 0.01% by weight or more, 0.1% by weight or more, or 0.5% by weight or more of the entire monomer component. It may be 1% by weight or more, 5% by weight or more, or 10% by weight or more.
- the amount of the hydroxyl group-containing monomer used is, for example, 40% by weight or less of the total monomer component in some embodiments. , 30% by weight or less, 25% by weight or less, or 20% by weight or less. In another aspect, the amount of the hydroxyl group-containing monomer used may be, for example, 15% by weight or less, 10% by weight or less, or 5% by weight or less of the total monomer component. Alternatively, the hydroxyl group-containing monomer may not be used as the copolymerizable monomer.
- the proportion of the carboxy group-containing monomer in the total monomer component may be, for example, 2% by weight or less, 1% by weight or less, and 0.5% by weight or less (for example, less than 0.1% by weight). ) May be.
- the pressure-sensitive adhesive composition does not have to substantially contain a carboxy group-containing monomer as a constituent monomer component thereof.
- the fact that the carboxy group-containing monomer is substantially not contained means that the carboxy group-containing monomer is not used at least intentionally. This can be advantageous from the viewpoint of the photocrosslinkable pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition and the metal corrosion prevention property of the photocrosslinked product.
- the copolymerizable monomer may comprise an alicyclic hydrocarbon group-containing (meth) acrylate.
- an alicyclic hydrocarbon group-containing (meth) acrylate those exemplified above can be used, and for example, cyclohexyl acrylate and isobornyl acrylate can be preferably adopted.
- the amount used is not particularly limited, and may be, for example, 1% by weight or more, 3% by weight or more, or 5% by weight or more of the total monomer component.
- the amount of the alicyclic hydrocarbon group-containing (meth) acrylate used may be 10% by weight or more, 15% by weight or more, or more than 20% by weight of the total monomer components. It may be more than 25% by weight.
- the upper limit of the amount of the alicyclic hydrocarbon group-containing (meth) acrylate used is appropriately about 40% by weight or less, for example, 30% by weight or less, and 25% by weight or less (for example, 15% by weight). % Or less, and even 10% by weight or less).
- the copolymerizable monomer may include an alkoxysilyl group-containing monomer.
- the alkoxysilyl group-containing monomer is typically an ethylenically unsaturated compound having at least one (preferably two or more, for example, two or three) alkoxysilyl groups in one molecule, and examples thereof. Is as described above.
- the above-mentioned alkoxysilyl group-containing monomer may be used alone or in combination of two or more.
- a crosslinked structure by a silanol group condensation reaction silanol group condensation
- the alkoxysilyl group-containing monomer can also help improve the peel strength against the adherend.
- the amount used when the alkoxysilyl group-containing monomer is used is not particularly limited.
- the amount of the alkoxysilyl group-containing monomer used can be, for example, 0.005% by weight or more, and usually 0.01% by weight or more, of the total monomer components constituting the pressure-sensitive adhesive composition. It may be 0.03% by weight or more, 0.05% by weight or more, 0.07% by weight or more, and more than 0.1% by weight from the viewpoint of obtaining a higher effect of use. It may be more than 0.2% by weight or more than 0.3% by weight.
- the amount of the alkoxysilyl group-containing monomer used is 1.0% by weight or less of the total monomer component, and 0.5% by weight. % Or less, 0.35% by weight or less, 0.25% by weight or less, 0.1% by weight or less, or less than 0.1% by weight.
- a compound that can be used as the ethylenically unsaturated compound (B) is a polyfunctional monomer.
- the composition was crosslinked by the polyfunctional monomer by reacting the polyfunctional monomer when the composition was cured to produce a photocrosslinkable pressure-sensitive adhesive.
- a photocrosslinkable pressure-sensitive adhesive can be obtained.
- the polyfunctional monomer include 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polyethylene.
- Glycoldi (meth) acrylate polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, etc.
- Functional Monomer Polyfunctional Monomer with Trifunctionality or higher, such as Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Tetramethylol Methantri (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, etc.
- epoxy acrylate polyester acrylate, urethane acrylate and the like; can be mentioned.
- preferred examples include 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
- the polyfunctional monomer may be used alone or in combination of two or more.
- the amount used when the polyfunctional monomer is used is not particularly limited, and can be set so as to form a photocrosslinkable pressure-sensitive adhesive exhibiting suitable properties in the photocrosslinkable pressure-sensitive adhesive.
- the amount of the polyfunctional monomer used can be less than 5.0% by weight of the total monomer components constituting the pressure-sensitive adhesive composition. This makes it possible to avoid the formation of an excessively crosslinked structure during the formation of the photocrosslinkable adhesive (that is, at the stage before photocrosslinking) and to improve the surface shape followability of the photocrosslinkable adhesive. ..
- the amount of the polyfunctional monomer used may be, for example, 4.0% by weight or less of the total monomer component, 3.0% by weight or less, 2.0% by weight or less, or 1.0% by weight.
- the amount of the polyfunctional monomer used with respect to the entire monomer component may be, for example, 0.001% by weight or more, and is 0, from the viewpoint of imparting appropriate cohesiveness to the photocrosslinkable pressure-sensitive adhesive. It may be .005% by weight or more, 0.01% by weight or more, or 0.03% by weight or more.
- a bifunctional monomer can be preferably adopted as the polyfunctional monomer in some embodiments.
- the proportion of the bifunctional monomer in the total polyfunctional monomer used may be, for example, 50% by weight or more, 70% by weight or more, 90% by weight or more, or 100% by weight.
- the weight ratio of the BP polymer (A) to the total amount of the BP polymer (A) and the ethylenically unsaturated compound (B) contained in the pressure-sensitive adhesive composition is not particularly limited, and is formed from the pressure-sensitive adhesive composition. It can be set so that the surface shape followability of the photocrosslinkable adhesive and the deformation resistance of the photocrosslinked product are suitably balanced.
- the weight fraction of the BP polymer may be, for example, 1% by weight or more, usually 5% by weight or more, and 10% by weight from the viewpoint of enhancing the effect of photocrosslinking. It may be 15% by weight or more, 25% by weight or more, 35% by weight or more, 45% by weight or more, 55% by weight or more.
- the weight ratio of the BP polymer to the total amount may be less than 99% by weight, for example, 95% by weight. It may be less than 85% by weight, less than 70% by weight, less than 50% by weight, less than 40% by weight.
- the ratio of the weight of the organic solvent to the total weight of the pressure-sensitive adhesive composition may be, for example, 30% by weight or less, and it is advantageous that it is 20% by weight or less. It is preferably 10% by weight or less, and more preferably 5% by weight or less. In some embodiments, the weight ratio of the organic solvent may be 3% by weight or less, 1% by weight or less, 0.5% by weight or less, 0.1% by weight or less, 0.05% by weight or less. % Or less, and substantially no organic solvent may be contained. It is preferable to suppress the weight ratio of the organic solvent in the pressure-sensitive adhesive composition from the viewpoint of reducing the VOC of the photocrosslinkable pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive composition disclosed herein contains an ethylenically unsaturated compound (B) in addition to the BP polymer (A), the ethylenically unsaturated compound (B) is used as a diluent for the BP polymer (A). Can be used.
- the pressure-sensitive adhesive composition is coated in a normal temperature range (for example, 20 ° C. to 40 ° C.). An organic solvent for enhancing the properties is not required, or the amount of the organic solvent used can be reduced.
- the pressure-sensitive adhesive composition has a viscosity (BH type viscometer, No. 5 rotor, 10 rpm, etc.) from the viewpoint of coatability in the normal temperature range. It is measured under the condition of a measurement temperature of 30 ° C. (the same applies hereinafter) is preferably 1000 Pa ⁇ s or less, preferably 100 Pa ⁇ s or less, and more preferably 50 Pa ⁇ s or less.
- the viscosity of the pressure-sensitive adhesive composition may be, for example, 30 Pa ⁇ s or less, 20 Pa ⁇ s or less, 10 Pa ⁇ s or less, or 5 Pa ⁇ s or less.
- the lower limit of the viscosity of the pressure-sensitive adhesive composition is not particularly limited, but from the viewpoint of suppressing the repelling of the pressure-sensitive adhesive composition within the coating range and the protrusion of the pressure-sensitive adhesive composition at the outer edge of the coating range, it is usually 0.1 Pa. It is appropriate that it is s or more, and it may be 0.5 Pa ⁇ s or more, or 1 Pa ⁇ s or more.
- the pressure-sensitive adhesive composition contains at least a compound having one ethylenically unsaturated group (that is, a monofunctional monomer) (B1) as the ethylenically unsaturated compound (B).
- a monofunctional monomer that is, a monofunctional monomer
- the corresponding compound can be selected and used from the above-mentioned examples of the ethylenically unsaturated compound (B).
- the monofunctional monomer (B1) can be used alone or in combination of two or more.
- the weight ratio of the monofunctional monomer (B1) to the total amount of the BP polymer (A) and the ethylenically unsaturated compound (B) may be, for example, 1% by weight or more, or 5% by weight or more. It may be 15% by weight or more. In some embodiments, the weight ratio of the monofunctional monomer (B1) may be 25% by weight or more, 35% by weight or more, from the viewpoint of ease of preparation and coatability of the pressure-sensitive adhesive composition. It may be 45% by weight or more.
- the weight ratio of the monofunctional monomer (B1) to the total amount is, for example, 99% by weight or less, usually 95% by weight or less, and 85% by weight or less. It may be 75% by weight or less, 65% by weight or less, 55% by weight or less, or 45% by weight or less.
- the glass transition temperature (Tg) determined by the Fox formula based on the composition of the monofunctional monomer (B1) is not particularly limited, for example. It can be -80 ° C or higher and 250 ° C or lower.
- the Tg based on the composition of the monofunctional monomer (B1) is usually preferably 150 ° C. or lower from the viewpoint of compatibility between the polymer derived from the monofunctional monomer (B1) and other components. It may be 100 ° C. or lower, 70 ° C. or lower, 50 ° C. or lower, or 30 ° C. or lower.
- the Tg based on the composition of the monofunctional monomer (B1) is preferably less than 0 ° C., preferably ⁇ 10 ° C. or lower, from the viewpoint of surface shape followability of the photocrosslinkable pressure-sensitive adhesive. More preferably, it may be ⁇ 20 ° C. or lower, ⁇ 30 ° C. or lower, or ⁇ 40 ° C. or lower. Further, from the viewpoint of the cohesiveness of the photocrosslinkable adhesive and the deformation resistance after photocrosslinking (for example, adhesion durability to the adherend), Tg based on the composition of the monofunctional monomer (B1) is usually used. It is advantageous that the temperature is ⁇ 60 ° C. or higher, and may be ⁇ 54 ° C.
- the Tg can be adjusted by the compound used as the monofunctional monomer (B1) and the usage ratio thereof.
- Tg of the BP polymer (A) (hereinafter referred to as , "Tg A ") and Tg based on the monomer composition of the monofunctional monomer (B1) (hereinafter, also referred to as "Tg B1 ”) is Tg calculated by Tg B1 [° C.]-Tg A [° C.].
- the difference [° C.] (hereinafter, also referred to as ⁇ Tg) can be set to be, for example, in the range of ⁇ 50 ° C.
- ⁇ Tg may be, for example, ⁇ 10 ° C. or higher, preferably 0 ° C. or higher, 7 ° C. or higher, 10 ° C. or higher, 20 ° C. or higher, or 30 ° C. or higher. Good. Further, in some embodiments, ⁇ Tg may be, for example, 50 ° C. or lower, 30 ° C. or lower, or 15 ° C. or lower.
- the pressure-sensitive adhesive composition contains at least a compound having two or more ethylenically unsaturated groups (that is, a polyfunctional monomer) (B2) as the ethylenically unsaturated compound (B).
- the polyfunctional monomer (B2) can be used alone or in combination of two or more from the above-mentioned examples of the polyfunctional monomer.
- the amount of the polyfunctional monomer (B2) used can be set in the same manner as the ratio of the polyfunctional monomer to the total monomer components constituting the pressure-sensitive adhesive composition.
- the weight of the monofunctional monomer (B1) in the ethylenically unsaturated compound (B) may be, for example, 1% by weight or more, usually 25% by weight or more, 50% by weight or more, 75% by weight or more, 95% by weight or more, 99% by weight. It may be% or more.
- the weight ratio of the monofunctional monomer (B1) to the ethylenically unsaturated compound (B) may be, for example, 99.9% by weight or less, or 99.8% by weight or less.
- the ethylenically unsaturated compound (B) may be contained in the form of a partial polymer, or the entire amount thereof may be contained in the form of an unreacted monomer.
- the pressure-sensitive adhesive composition according to a preferred embodiment contains the ethylenically unsaturated compound (B) in the form of a partial polymer.
- the polymerization method for partially polymerizing the ethylenically unsaturated compound (B) is not particularly limited, and for example: photopolymerization performed by irradiating light such as ultraviolet rays; radiation performed by irradiating radiation such as ⁇ -rays and ⁇ -rays.
- Polymerization Various conventionally known polymerization methods such as solution polymerization, emulsion polymerization, thermal polymerization such as bulk polymerization; etc. can be appropriately selected and used. From the viewpoint of efficiency and convenience, the photopolymerization method can be preferably adopted. According to photopolymerization, the polymerization conversion rate (monomer conversion) can be easily controlled by the polymerization conditions such as the irradiation amount of light (light amount).
- the polymerization conversion rate of the ethylenically unsaturated compound (B) in the above partial polymer is not particularly limited. From the viewpoint of ease of preparation and coatability of the pressure-sensitive adhesive composition, it is usually appropriate that the polymerization conversion rate is about 50% by weight or less, and about 40% by weight or less (for example, about 35% by weight or less). ) Is preferable.
- the lower limit of the polymerization conversion rate is not particularly limited, but is typically about 1% by weight or more, and usually about 5% by weight or more is appropriate.
- the pressure-sensitive adhesive composition containing a partial polymer of the ethylenically unsaturated compound (B) is, for example, an appropriate polymerization of a monomer mixture containing the entire amount of the ethylenically unsaturated compound (B) used in the preparation of the pressure-sensitive adhesive composition. It can be obtained by partial polymerization by a method (for example, a photopolymerization method).
- the pressure-sensitive adhesive composition containing a partial polymer of the ethylenically unsaturated compound (B) is a monomer mixture containing a part of the ethylenically unsaturated compound (B) used in the preparation of the pressure-sensitive adhesive composition.
- the partial polymer can be prepared, for example, by irradiating an ethylenically unsaturated compound with ultraviolet rays.
- the ethylenically unsaturated compound portion is formed by reacting the ethylenically unsaturated group and setting the irradiation conditions of ultraviolet rays so that the benzophenone structure is not photoexcited.
- a pressure-sensitive adhesive composition containing a polymer and a BP polymer can be obtained.
- a light source such as the above-mentioned black light or UV-LED lamp that does not contain a component having a wavelength of less than 300 nm or can irradiate ultraviolet rays having a small wavelength component can be preferably adopted.
- the partial polymer and the BP polymer may be mixed to prepare a pressure-sensitive adhesive composition.
- a partial polymer is prepared by irradiating an ethylenically unsaturated compound with ultraviolet rays in the absence of a benzophenone structure-containing component, either a light source that does not excite the benzophenone structure or a light source that excites the benzophenone structure is used as the ultraviolet source. It is possible.
- the reaction of the ethylenically unsaturated group can be promoted by using a photoinitiator.
- the photoinitiator include a ketal-based photoinitiator, an acetophenone-based photoinitiator, a benzoin ether-based photoinitiator, an acylphosphine oxide-based photoinitiator, an ⁇ -ketol-based photoinitiator, and an aromatic sulfonyl chloride-based photoinitiator.
- Photoactive oxime-based photoinitiators benzoin-based photoinitiators, benzyl-based photoinitiators, benzophenone-based photoinitiators, alkylphenone-based photoinitiators, thioxanthone-based photoinitiators, and the like can be used.
- a photoinitiator that absorbs light having a wavelength of 300 nm or more (for example, light having a wavelength of 300 nm or more and 500 nm or less) to generate radicals can be preferably adopted.
- the photoinitiator may be used alone or in combination of two or more.
- the pressure-sensitive adhesive composition may contain a photoinitiator, if necessary, for the purpose of improving or imparting photocurability.
- a photoinitiator include a ketal-based photoinitiator, an acetophenone-based photoinitiator, a benzoin ether-based photoinitiator, an acylphosphine oxide-based photoinitiator, an ⁇ -ketol-based photoinitiator, and an aromatic sulfonyl chloride-based photoinitiator.
- Photoactive oxime-based photoinitiators benzoin-based photoinitiators, benzyl-based photoinitiators, benzophenone-based photoinitiators, alkylphenone-based photoinitiators, thioxanthone-based photoinitiators, and the like can be used.
- the photoinitiator may be used alone or in combination of two or more.
- ketal-based photoinitiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one and the like.
- acetophenone-based photoinitiators include 1-hydroxycyclohexyl-phenyl-ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1- [4- (2-hydroxyethoxy) -phenyl]-. 2-Hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, methoxyacetophenone and the like are included.
- benzoin ether-based photoinitiator examples include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether and benzoin isobutyl ether, and substituted benzoin ethers such as anisole methyl ether.
- acylphosphine oxide-based photoinitiator examples include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -2,4-di-n-butoxyphenyl.
- Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like are included.
- Specific examples of the ⁇ -ketol-based photoinitiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one, and the like. ..
- Specific examples of the aromatic sulfonyl chloride-based photoinitiator include 2-naphthalene sulfonyl chloride and the like.
- the photoactive oxime-based photoinitiator examples include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like.
- Specific examples of the benzoin-based photoinitiator include benzoin and the like.
- Specific examples of the benzyl-based photoinitiator include benzyl and the like.
- Specific examples of the benzophenone-based photoinitiator include benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexylphenyl ketone and the like.
- thioxanthone-based photoinitiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, and the like. 2,4-Diisopropylthioxanthone, dodecylthioxanthone and the like are included.
- a photoinitiator that absorbs light having a wavelength of 300 nm or more for example, light having a wavelength of 300 nm or more and 500 nm or less
- the photoinitiator may be used alone or in combination of two or more.
- photoinitiators that do not contain a phosphorus element in the molecule may be preferably employed.
- the pressure-sensitive adhesive composition disclosed herein may be substantially free of a photoinitiator containing a phosphorus element in the molecule.
- the content of the photoinitiator in the pressure-sensitive adhesive composition is not particularly limited, and can be set so that the desired effect is appropriately exhibited.
- the content of the photoinitiator can be, for example, approximately 0.005 parts by weight or more, typically 0.01 parts by weight, based on 100 parts by weight of the monomer components constituting the pressure-sensitive adhesive composition. It is appropriate to have parts or more, preferably 0.05 parts by weight or more, 0.10 parts by weight or more, 0.15 parts by weight or more, or 0.20 parts by weight or more. Good. Increasing the content of the photoinitiator improves the photocurability of the pressure-sensitive adhesive composition.
- the content of the photoinitiator with respect to 100 parts by weight of the monomer component constituting the pressure-sensitive adhesive composition is usually preferably 5 parts by weight or less, preferably 2 parts by weight or less, and 1 part by weight. It may be less than or equal to 0.7 parts by weight or less than 0.5 parts by weight. It may be advantageous from the viewpoint of suppressing gelation of the pressure-sensitive adhesive composition that the content of the photoinitiator is not too large.
- the pressure-sensitive adhesive composition may contain, for example, an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, a carbodiimide-based cross-linking agent, a melamine-based cross-linking agent, a urea-based cross-linking agent, and a metal alkoxydo.
- Known cross-linking agents such as system cross-linking agents, metal chelate-based cross-linking agents, metal salt-based cross-linking agents, hydrazine-based cross-linking agents, and amine-based cross-linking agents can be blended.
- Peroxide may be used as a cross-linking agent. These cross-linking agents may be used alone or in combination of two or more.
- the photocrosslinkable pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition containing a cross-linking agent preferably contains the cross-linking agent mainly in the form after the cross-linking reaction. By using the cross-linking agent, the cohesive force of the photocrosslinkable adhesive can be appropriately adjusted.
- the amount used when a cross-linking agent is used is not particularly limited.
- the amount of the cross-linking agent used is usually 100 parts by weight with respect to 100 parts by weight of the monomer component constituting the pressure-sensitive adhesive composition. It is appropriate that it is about 5 parts by weight or less, and it may be 3 parts by weight or less, 1 part by weight or less, 0.50 parts by weight or less, 0.30 parts by weight or less, and 0. It may be 20 parts by weight or less.
- the lower limit of the amount of the cross-linking agent used is not particularly limited, and may be more than 0 parts by weight with respect to 100 parts by weight of the monomer component constituting the pressure-sensitive adhesive composition.
- the amount of the cross-linking agent used may be, for example, 0.001 part by weight or more, or 0.01 part by weight or more, based on 100 parts by weight of the monomer component constituting the pressure-sensitive adhesive composition. It may be 0.05 parts by weight or more, or 0.10 parts by weight or more.
- the techniques disclosed herein can also be preferably performed in aspects that do not use cross-linking agents.
- the pressure-sensitive adhesive composition may contain various conventionally known chain transfer agents.
- chain transfer agent mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, and ⁇ -thioglycerol can be used.
- a chain transfer agent containing no sulfur atom non-sulfur chain transfer agent may be used.
- non-sulfur chain transfer agent examples include anilins such as N, N-dimethylaniline and N, N-diethylaniline; terpenoids such as ⁇ -pinene and turpinolene; ⁇ -methylstyrene and ⁇ -methylstyrene dimer.
- the chain transfer agent may be used alone or in combination of two or more. When a chain transfer agent is used, the amount used can be, for example, about 0.01 to 1 part by weight with respect to 100 parts by weight of the monomer component.
- the techniques disclosed herein may also be preferably practiced in aspects that do not use chain transfer agents.
- the pressure-sensitive adhesive composition include silane coupling agents.
- silane coupling agents can improve the peel strength against an adherend (for example, a glass plate).
- the photocrosslinkable pressure-sensitive adhesive disclosed herein may contain a silane coupling agent.
- the photocrosslinkable pressure-sensitive adhesive containing a silane coupling agent can be suitably formed by using a pressure-sensitive adhesive composition containing a silane coupling agent.
- the silane coupling agent may be used alone or in combination of two or more.
- the pressure-sensitive adhesive composition disclosed herein includes, if necessary, a pressure-imparting resin (for example, a rosin-based, petroleum-based, terpene-based, phenol-based, ketone-based or other pressure-imparting resin), and a viscosity modifier (for example, thickening).
- a pressure-imparting resin for example, a rosin-based, petroleum-based, terpene-based, phenol-based, ketone-based or other pressure-imparting resin
- a viscosity modifier for example, thickening
- Agents leveling agents, antioxidants, plasticizers, fillers, colorants such as pigments and dyes, stabilizers, preservatives, anti-aging agents, and other additives that are common in the field of adhesives. It may be included as any other optional ingredient.
- additives conventionally known ones can be used by a conventional method and do not particularly characterize the present invention, and thus detailed description thereof will be omitted.
- the technique disclosed herein can exhibit good adhesive strength without using the above-mentioned tackifier resin. Therefore, in some embodiments, the content of the tackifier resin in the pressure-sensitive adhesive layer or the pressure-sensitive adhesive composition is, for example, less than 10 parts by weight, more than 5 parts by weight, based on 100 parts by weight of the monomer component. can do.
- the content of the tackifier resin may be less than 1 part by weight (for example, less than 0.5 parts by weight) or less than 0.1 parts by weight (0 parts by weight or more and less than 0.1 parts by weight). Good.
- the pressure-sensitive adhesive layer or pressure-sensitive adhesive composition may not contain a tackifier resin.
- the pressure-sensitive adhesive composition disclosed herein is configured so that a photocrosslinkable pressure-sensitive adhesive containing a BP polymer can be formed by curing the pressure-sensitive adhesive composition.
- the curing of the pressure-sensitive adhesive composition is preferably carried out so as to react the ethylenically unsaturated group contained in the pressure-sensitive adhesive composition and leave the benzophenone structure contained in the pressure-sensitive adhesive composition.
- the curing can be preferably performed by irradiation with active energy rays.
- active energy ray for forming the photocrosslinkable pressure-sensitive adhesive ultraviolet rays are preferable, and ultraviolet rays containing no component having a wavelength of 300 nm or less or having a small wavelength component are more preferable.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein may be manufactured using any of the pressure-sensitive adhesive compositions disclosed herein.
- a photocrosslinkable pressure-sensitive adhesive may include a BP polymer (A) and a polymer (E) derived from an ethylenically unsaturated compound (B).
- the pressure-sensitive adhesive composition may be such that the ethylenically unsaturated compound (B) does not contain an ethylenically unsaturated BP.
- the BP polymer (A) and the polymer (E) derived from the ethylenically unsaturated compound (B) are contained, and the polymer (E) is a non-BP polymer. Photocrosslinkable adhesives can be produced.
- a method for producing a photocrosslinkable pressure-sensitive adhesive which can be photocrosslinked by a benzophenone structure includes preparing a pressure-sensitive adhesive composition containing an ethylenically unsaturated group and a benzophenone structure, and irradiating the pressure-sensitive adhesive composition with active energy rays (preferably ultraviolet rays).
- the pressure-sensitive adhesive composition may contain a photoinitiator. Irradiation with active energy rays for curing the pressure-sensitive adhesive composition is preferably carried out so as to react the ethylenically unsaturated group and leave the benzophenone structure.
- a pressure-sensitive adhesive composition containing a BP polymer (A) and an ethylenically unsaturated compound (B) can be preferably used.
- the method for producing a photocrosslinkable pressure-sensitive adhesive can be preferably carried out using any of the pressure-sensitive adhesive compositions disclosed herein.
- a light source for curing the pressure-sensitive adhesive composition to form a photocrosslinkable pressure-sensitive adhesive ultraviolet rays containing no component having a wavelength of less than 300 nm or having a small wavelength component, such as the above-mentioned black light and UV-LED lamp, are used.
- An irradiable light source can be preferably adopted.
- a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of any of the photocrosslinkable pressure-sensitive adhesives disclosed herein is provided.
- An example of the configuration of the pressure-sensitive adhesive sheet disclosed herein is shown in FIG.
- the adhesive sheet 1 includes an adhesive layer 10 in which one surface 10A is a surface (adhesive surface) to be attached to an adherend, and a base material 20 laminated on the other surface 10B of the adhesive layer 10. It is configured as a single-sided adhesive adhesive sheet containing.
- the pressure-sensitive adhesive layer 10 is bonded to one surface 20A of the base material 20.
- a plastic film such as a polyester film can be used.
- the base material 20 may be an optical film such as a polarizing plate.
- the pressure-sensitive adhesive layer 10 has a single-layer structure.
- the adhesive sheet 1 before use (before being attached to the adherend) has a release liner 30 having an adhesive surface 10A having at least the adhesive layer side as a peelable surface (peeling surface). It may be in the form of an adhesive sheet 50 with a release liner protected by.
- the second surface 20B of the base material 20 (the surface opposite to the first surface 20A and also referred to as the back surface) is a peeling surface, and the adhesive surface 10A is on the second surface 20B of the base material 20.
- the adhesive surface 10A may be protected by being wound or laminated so as to be in contact with each other.
- the release liner is not particularly limited, and for example, a release liner in which the surface of a liner base material such as a resin film or paper is peeled off, a fluoropolymer (polytetrafluoroethylene, etc.), a polyolefin resin (polyethylene, polypropylene, etc.), etc. ), A release liner made of a low-adhesive material or the like can be used.
- a silicone-based or long-chain alkyl-based peeling agent can be used for the peeling treatment.
- the peeled resin film can be preferably used as the peel liner.
- the pressure-sensitive adhesive sheet disclosed here may be in the form of a base-less double-sided pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer.
- each side surface 10A and 10B of the pressure-sensitive adhesive layer 10 has at least a peelable surface (peeling surface) on the pressure-sensitive adhesive layer side. It may be in the form protected by the liners 31 and 32.
- the back surface of the release liner 31 (the surface opposite to the adhesive side) is the release surface, and the adhesive surface is wound or laminated so that the adhesive surface 10B abuts on the back surface of the release liner 31.
- 10A and 10B may be in a protected form.
- Such a base material-less double-sided pressure-sensitive adhesive sheet can be used, for example, by bonding a base material to the surface of either one of the pressure-sensitive adhesive layers.
- the pressure-sensitive adhesive sheet disclosed here may be a component of an optical member with a pressure-sensitive adhesive sheet in which an optical member is bonded to one surface of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet 1 shown in FIG. 1 can be a component of an optical member 100 with a pressure-sensitive adhesive sheet in which an optical member 70 is bonded to one surface 10A of the pressure-sensitive adhesive layer 10, as shown in FIG.
- the optical member may be, for example, a glass plate, a resin film, a metal plate, or the like.
- the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet disclosed herein can be a cured layer of the corresponding pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive layer may be one obtained by applying (for example, applying) the pressure-sensitive adhesive composition to an appropriate surface and then curing the pressure-sensitive adhesive composition. Curing of the pressure-sensitive adhesive composition can be preferably performed by irradiation with active energy rays.
- active energy ray for forming the pressure-sensitive adhesive layer ultraviolet rays are preferable, and ultraviolet rays containing no component having a wavelength of 300 nm or less or having a small wavelength component are more preferable.
- the pressure-sensitive adhesive composition can be applied using, for example, a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater.
- a conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater.
- a direct method of directly applying the pressure-sensitive adhesive composition to the base material to form the pressure-sensitive adhesive layer may be used, and peeling may be used.
- a transfer method may be used in which the pressure-sensitive adhesive layer formed on the surface is transferred to the base material.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, and may be, for example, about 3 ⁇ m to 2000 ⁇ m. From the viewpoint of adhesion to the adherend such as surface shape followability (for example, step followability), the thickness of the pressure-sensitive adhesive layer may be, for example, 5 ⁇ m or more, and 10 ⁇ m or more is appropriate in some embodiments. Yes, preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more. The thickness of the pressure-sensitive adhesive layer may be 50 ⁇ m or more, more than 50 ⁇ m, 70 ⁇ m or more, 100 ⁇ m or more, or 120 ⁇ m or more.
- the thickness of the pressure-sensitive adhesive layer may be, for example, 1000 ⁇ m or less, 700 ⁇ m or less, or 500 ⁇ m or less in some embodiments. , 300 ⁇ m or less, and further 200 ⁇ m or less or 170 ⁇ m or less.
- the technique disclosed herein can also be preferably carried out in the form of a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 130 ⁇ m or less, 90 ⁇ m or less, 60 ⁇ m or less, or 40 ⁇ m or less.
- the thickness of the pressure-sensitive adhesive layer is the thickness from the pressure-sensitive adhesive surface attached to the adherend to the surface opposite to the pressure-sensitive adhesive surface.
- the pressure-sensitive adhesive layer having a multi-layer structure is within the thickness of the pressure-sensitive adhesive layer (that is, between the pressure-sensitive adhesive surface attached to the adherend and the surface opposite to the pressure-sensitive adhesive surface).
- the pressure-sensitive adhesive sheet may be in the form of a base-based pressure-sensitive adhesive sheet containing a base material bonded to the pressure-sensitive adhesive layer.
- the material of the base material is not particularly limited, and can be appropriately selected depending on the purpose and mode of use of the adhesive sheet.
- Non-limiting examples of base materials that can be used include a polyolefin film containing a polyolefin such as polypropylene or an ethylene-propylene copolymer as a main component, a polyester film containing a polyester such as polyethylene terephthalate or polybutylene terephthalate as a main component, and the like.
- Plastic film such as polyvinyl chloride film containing polyvinyl chloride as the main component; foam sheet made of foam such as polyurethane foam, polyethylene foam, polychloroprene foam; various fibrous substances (linen, cotton, etc.) Natural fibers, synthetic fibers such as polyester and vinylon, semi-synthetic fibers such as acetate, etc.) Woven fabrics and non-woven fabrics made by single or blended spinning; papers such as Japanese paper, high-quality paper, kraft paper, crepe paper; Examples include metal foils such as aluminum foil and copper foil; and the like.
- a base material having a composite structure thereof may be used. Examples of a base material having such a composite structure include a base material having a structure in which a metal foil and the plastic film are laminated, a plastic sheet reinforced with an inorganic fiber such as glass cloth, and the like.
- the support film may be a porous film such as a foam film or a non-woven fabric sheet, or may be a non-porous film, and the porous layer and the non-porous layer are laminated. It may be a film having a structure.
- a film containing an independently shape-maintainable (self-supporting or independent) resin film as a base film can be preferably used as the support film.
- the term "resin film” means a resin film (of voidless) having a non-porous structure and typically containing substantially no bubbles. Therefore, the resin film is a concept that is distinguished from a foam film and a non-woven fabric.
- the resin film may have a single-layer structure or a multi-layer structure having two or more layers (for example, a three-layer structure).
- Examples of the resin material constituting the resin film include polycycloolefin derived from a monomer having an aliphatic ring structure such as polyester, polyolefin, and norbornene structure, nylon 6, nylon 66, and polyamide (PA) such as partially aromatic polyamide.
- polycycloolefin derived from a monomer having an aliphatic ring structure such as polyester, polyolefin, and norbornene structure
- nylon 6, nylon 66 such as polyamide (PA) such as partially aromatic polyamide.
- PA polyamide
- Polyimide such as transparent polyimide (CPI), polyamideimide (PAI), polyether ether ketone (PEEK), polyether sulfone (PES), polyphenylene sulfide (PPS), polycarbonate (PC), polyurethane (PU), Fluororesin such as ethylene-vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), polystyrene, ABS resin, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene (PTFE), acrylic resin such as polymethylmethacrylate, Resins such as cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose (TAC), vinyl butyral-based polymers, allylate-based polymers, polyimide-based polymers, and epoxy-based polymers can be used.
- PI such as transparent polyimide (CPI), polyamideimide (PAI), polyether ether ketone (PEEK), polyether
- the resin film may be formed by using a resin material containing one kind of such a resin alone, or may be formed by using a resin material in which two or more kinds are blended. May be good.
- the resin film may be unstretched or stretched (for example, uniaxially stretched or biaxially stretched).
- the resin material constituting the resin film include polyester resin, PPS resin, polyolefin resin, and polyimide resin.
- the polyester-based resin refers to a resin containing polyester in a proportion of more than 50% by weight.
- the PPS resin is a resin containing PPS in a proportion exceeding 50% by weight
- the polyolefin resin is a resin containing a polyolefin in a proportion exceeding 50% by weight
- the polyimide resin is a polyimide resin.
- polyester-based resin a polyester-based resin containing a polyester obtained by polycondensing a dicarboxylic acid and a diol as a main component is typically used.
- the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate and the like.
- polyolefin resin one kind of polyolefin can be used alone, or two or more kinds of polyolefins can be used in combination.
- the polyolefin can be, for example, a homopolymer of an ⁇ -olefin, a copolymer of two or more kinds of ⁇ -olefins, a copolymer of one kind or two or more kinds of ⁇ -olefins and another vinyl monomer, or the like.
- Specific examples include ethylene-propylene copolymers such as polyethylene (PE), polypropylene (PP), poly-1-butene, poly-4-methyl-1-pentene, and ethylene propylene rubber (EPR), and ethylene-propylene-.
- Examples thereof include butene copolymers, ethylene-butene copolymers, ethylene-vinyl alcohol copolymers and ethylene-ethyl acrylate copolymers. Both low density (LD) polyolefin and high density (HD) polyolefin can be used.
- polyolefin resin films include unstretched polypropylene (CPP) film, biaxially stretched polypropylene (OPP) film, low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, medium density polyethylene (MDPE).
- Examples thereof include a film, a high-density polyethylene (HDPE) film, a polyethylene (PE) film in which two or more types of polyethylene (PE) are blended, and a PP / PE blend film in which polypropylene (PP) and polyethylene (PE) are blended.
- HDPE high-density polyethylene
- PE polyethylene
- the resin film that can be preferably used as the base material include PET film, PEN film, PPS film, PEEK film, CPI film, CPP film and OPP film.
- Preferred examples from the viewpoint of strength include PET film, PEN film, PPS film, PEEK film, and CPI film.
- Preferred examples include PET film, CPI film, and TAC film from the viewpoint of availability, dimensional stability, optical characteristics, and the like.
- additives such as light stabilizers, antioxidants, antistatic agents, colorants (dye, pigment, etc.), fillers, slip agents, antiblocking agents, etc. shall be added to the resin film, if necessary. Can be done.
- the blending amount of the additive is not particularly limited, and can be appropriately set according to the use of the pressure-sensitive adhesive sheet and the like.
- the manufacturing method of the resin film is not particularly limited.
- conventionally known general resin film molding methods such as extrusion molding, inflation molding, T-die casting molding, and calender roll molding can be appropriately adopted.
- the base material may be substantially composed of such a resin film.
- the base material may include an auxiliary layer in addition to the resin film.
- the auxiliary layer include an optical property adjusting layer (for example, a colored layer, an antireflection layer), a printing layer or a laminating layer for imparting a desired appearance to a base material or an adhesive sheet, an antistatic layer, and an undercoat layer.
- a surface treatment layer such as a release layer.
- the base material may be an optical member (for example, an optical film) described later.
- the thickness of the base material is not particularly limited and can be selected according to the purpose of use and the mode of use of the adhesive sheet.
- the thickness of the base material may be, for example, 1000 ⁇ m or less, 500 ⁇ m or less, 100 ⁇ m or less, 70 ⁇ m or less, 50 ⁇ m or less, 25 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less.
- the thickness of the base material may be, for example, 2 ⁇ m or more, and may be 5 ⁇ m or more or 10 ⁇ m or more.
- the thickness of the substrate may be, for example, 20 ⁇ m or greater, 35 ⁇ m or greater, or 55 ⁇ m or greater.
- a conventionally known surface treatment such as the above may be applied.
- Such a surface treatment may be a treatment for improving the adhesion between the base material and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer on the base material.
- the composition of the primer is not particularly limited and can be appropriately selected from known ones.
- the thickness of the undercoat layer is not particularly limited, but is usually about 0.01 ⁇ m to 1 ⁇ m, preferably about 0.1 ⁇ m to 1 ⁇ m.
- the surface of the base material opposite to the side bonded to the pressure-sensitive adhesive layer (hereinafter, also referred to as the back surface) is subjected to peeling treatment, adhesiveness or adhesiveness improving treatment, antistatic treatment, etc., as necessary.
- Conventionally known surface treatment may be applied. For example, by surface-treating the back surface of the base material with a release treatment agent, the unwinding force of the adhesive sheet wound in a roll shape can be reduced.
- a silicone-based stripping agent a long-chain alkyl-based stripping agent, an olefin-based stripping agent, a fluorine-based stripping agent, a fatty acid amide-based stripping agent, molybdenum sulfide, silica powder, or the like can be used. ..
- the peel strength measured by the above-mentioned peel strength measuring procedure is, for example, about 0.5 N / 10 mm. It may be more than that, and usually it is suitable that it is about 1.0 N / 10 mm or more. From the viewpoint of improving the joining reliability, the peel strength is preferably, for example, about 1.5 N / 10 mm or more, and more preferably about 2.0 N / 10 mm or more.
- the peel strength may be, for example, about 3.0 N / 10 mm or more, about 4.5 N / 10 mm or more, or about 5.5 N / 10 mm or more.
- the adhesive sheet disclosed herein has a peel strength of about 5.7 N / 10 mm or more, about 6.5 N / 10 mm or more, about 7 N / 10 mm or more, about 8 N / 10 mm or more, about 9 N / 10 mm or more, about 10 N / 10 mm. As described above, it can also be carried out in an embodiment of about 11 N / 10 mm or more, about 12 N / 10 mm or more, or about 13 N / 10 mm or more.
- Such a strong adhesive force can be preferably realized by using, for example, a silane coupling agent.
- the upper limit of the peel strength is not particularly limited, and may be, for example, 25 N / 10 mm or less, 20 N / 10 mm or less in consideration of the balance with other physical properties, 15 N / 10 mm or less, or 10 N / 10 mm or less. It may be 8N / 10mm or less.
- the haze value of the pressure-sensitive adhesive sheet is preferably about 10% or less, and can be about 5% or less (for example, about 3% or less). In some embodiments, the haze value of the pressure-sensitive adhesive sheet is preferably 1.0% or less. Such a highly transparent pressure-sensitive adhesive sheet is suitable for optical applications that require high light transmission. The haze value of the pressure-sensitive adhesive sheet may be less than 1.0%, less than 0.7%, or 0.5% or less (for example, 0 to 0.5%). These haze values can also be preferably applied to the haze values of the pressure-sensitive adhesive layer made of a photocrosslinkable pressure-sensitive adhesive.
- the "haze value” refers to the ratio of diffuse transmitted light to total transmitted light when the measurement target is irradiated with visible light. Also called cloudy value.
- the haze value can be measured using a haze meter (for example, "MR-100" manufactured by Murakami Color Technology Laboratory). The haze value can be adjusted by selecting, for example, the composition and thickness of the pressure-sensitive adhesive layer.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein can be preferably used in an embodiment in which the photocrosslinkable pressure-sensitive adhesive is laminated on a member as an adherend and then the photocrosslinkable pressure-sensitive adhesive is photocrosslinked. As a result, it is possible to produce a laminate in which the photocrosslinked product is reliably bonded to the adherend.
- the photocrosslinking of the photocrosslinkable pressure-sensitive adhesive can be carried out by irradiating the photocrosslinkable pressure-sensitive adhesive with active energy rays.
- ultraviolet rays containing a wavelength component capable of exciting the benzophenone structure contained in the photocrosslinkable pressure-sensitive adhesive are preferable.
- the photocrosslinkable pressure-sensitive adhesive can be used in the production of the laminate in the form of a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the photocrosslinkable pressure-sensitive adhesive. Therefore, according to this specification, a pressure-sensitive adhesive sheet having an pressure-sensitive adhesive layer made of any of the photocrosslinkable pressure-sensitive adhesives disclosed herein is attached to an adherend, and the pressure-sensitive adhesive sheet is irradiated with active energy rays.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet used in the embodiment of photocrosslinking after being attached to an adherend has a multi-layer structure
- the pressure-sensitive adhesive layer to be photocrosslinked is a part of the layers included in the multi-layer structure (for example, It may be one layer) or all layers.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein can be used, for example, in the form of a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the photo-crosslinkable pressure-sensitive adhesive, in a manner of being laminated on a surface having a step.
- the photocrosslinkable pressure-sensitive adhesive can exhibit good surface shape followability (step followability) with respect to the surface of the adherend having such a step.
- step followability By laminating the photocrosslinkable pressure-sensitive adhesive and then photocrosslinking the photocrosslinkable pressure-sensitive adhesive, a highly reliable bond can be formed.
- the step may be, for example, a printing layer provided on the surface of the adherend.
- the height of the step may be, for example, 5 ⁇ m or more, 10 ⁇ m or more, 20 ⁇ m or more, or 30 ⁇ m or more.
- the height of the step may be, for example, 100 ⁇ m or less, preferably 70 ⁇ m or less.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein is not particularly limited, and can be used for various purposes.
- the photocrosslinkable pressure-sensitive adhesive disclosed herein is in the form of a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer made of the photo-crosslinkable pressure-sensitive adhesive, for fixing, joining, molding, decorating, and protecting members constituting various products. It can be used for applications such as support.
- the material constituting at least the surface of the member is, for example, glass such as alkaline glass or non-alkali glass; metal material such as stainless steel (SUS) and aluminum; ceramic material such as alumina and silica; acrylic resin, ABS resin and polycarbonate.
- Resin material such as resin, polystyrene resin, transparent polyimide resin; etc.
- the member may be, for example, a member constituting various portable devices (portable devices), automobiles, home appliances, and the like.
- the surface to which the adhesive sheet is attached is acrylic-based, polyester-based, alkyd-based, melamine-based, urethane-based, acid-epoxy cross-linked system, or a composite system thereof (for example, acrylic melamine-based or alkyd melamine-based). ) Or the like, or a surface coated with a zinc-plated steel plate or the like.
- the member may be any support film (for example, a resin film) exemplified as a material that can be used as a base material.
- the pressure-sensitive adhesive sheet disclosed herein can be, for example, a component of a member with a pressure-sensitive adhesive sheet in which such a member is bonded to at least one surface of the pressure-sensitive adhesive layer.
- An example of a preferable application is an optical application. More specifically, it is disclosed here as, for example, an optical adhesive sheet used for bonding optical members (for bonding optical members), manufacturing products using the above optical members (optical products), and the like.
- the adhesive sheet to be used can be preferably used.
- the optical member is a member having optical characteristics (for example, polarization, light refraction, light scattering, light reflectivity, light transmission, light absorption, light diffractivity, light turning property, visibility, etc.).
- the optical member is not particularly limited as long as it has optical characteristics, but is used, for example, as a member constituting a device (optical device) such as a display device (image display device) or an input device, or a member thereof.
- Members include, for example, polarizing plates, wavelength plates, retardation plates, optical compensation films, brightness improving films, light guide plates, reflective films, antireflection films, hard coat (HC) films, shock absorbing films, antifouling films, etc.
- Photochromic film dimming film, transparent conductive film (ITO film), design film, decorative film, surface protection plate, prism, lens, color filter, transparent substrate, and members in which these are laminated (collectively referred to as these). (Sometimes referred to as “functional film”) and the like.
- the above-mentioned “plate” and “film” shall include a plate-like, a film-like, a sheet-like form, respectively, and for example, the "polarizing film” shall include a “polarizing plate”, a “polarizing sheet” and the like. ..
- Examples of the display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), electronic paper, and the like, and in particular, such as a foldable display device and an in-vehicle display device. It can be preferably applied when an expensive member is included.
- Examples of the input device include a touch panel and the like.
- the optical member is not particularly limited, and examples thereof include members made of glass, acrylic resin, polycarbonate, polyethylene terephthalate, a metal thin film, and the like (for example, sheet-shaped, film-shaped, and plate-shaped members).
- the "optical member” in this specification also includes a member (design film, decorative film, surface protective film, etc.) that plays a role of decoration and protection while maintaining the visibility of the display device and the input device.
- the mode in which the optical members are bonded using the pressure-sensitive adhesive sheet disclosed herein is not particularly limited, but for example, (1) a mode in which the optical members are bonded to each other via the pressure-sensitive adhesive sheet disclosed here, or (2).
- the optical member may be attached to a member other than the optical member via the pressure-sensitive adhesive sheet disclosed herein, or (3) the pressure-sensitive adhesive sheet disclosed here includes the optical member.
- the adhesive sheet may be attached to an optical member or a member other than the optical member.
- the pressure-sensitive adhesive sheet including the optical member may be, for example, a pressure-sensitive adhesive sheet whose base material is an optical member (for example, an optical film).
- the pressure-sensitive adhesive sheet including the optical member as the base material can also be grasped as a pressure-sensitive optical member (for example, a pressure-sensitive optical film).
- a pressure-sensitive optical member for example, a pressure-sensitive optical film
- the pressure-sensitive adhesive sheet disclosed here is a type of pressure-sensitive adhesive sheet having a base material and the above-mentioned functional film is used as the above-mentioned base material
- the pressure-sensitive adhesive sheet disclosed here is a functional film. It can also be grasped as a "adhesive functional film" having an adhesive layer disclosed herein on at least one side.
- the peeling method disclosed here can be preferably applied to peeling an adhesive sheet attached to a non-water-absorbing smooth surface such as a glass plate, a metal plate, a resin plate, or the like. Further, the peeling method disclosed herein can be preferably used as a method for peeling the pressure-sensitive adhesive sheet from any of the above-mentioned optical members. Above all, it is suitable as a method for peeling off an adhesive sheet attached to a glass plate such as alkaline glass or non-alkali glass.
- the matters disclosed in this specification include the following.
- (1) Contains a polymer having a benzophenone structure in the side chain, A photocrosslinkable pressure-sensitive adhesive which is a cured product of a pressure-sensitive adhesive composition containing an ethylenically unsaturated compound and a benzophenone structure-containing component, and has an emission amount of a volatile organic compound of 500 ⁇ g / g or less.
- (2) The photocrosslinkable pressure-sensitive adhesive according to (1) above, wherein the benzophenone structure-containing component is a polymer having a benzophenone structure in a side chain.
- (3) The shear storage elastic modulus Gb'[kPa] of the photocrosslinkable adhesive at 80 ° C.
- the relationship between the shear storage elastic modulus Gc'[kPa] at 80 ° C. of the photocrosslinked product obtained by irradiating with ultraviolet rays under the conditions is as follows. Gc'[kPa] -Gb' [kPa] ⁇ 2 kPa; The photocrosslinkable pressure-sensitive adhesive according to (1) or (2) above. (4) Shear storage elasticity at 80 ° C.
- the surface of the pressure-sensitive adhesive layer is pressure-bonded to a glass plate by reciprocating a 2 kg rubber roller once, autoclaving (50 ° C., 0.5 MPa, 15 minutes), and then using a high-pressure mercury lamp on the glass plate side. After irradiating ultraviolet rays under the conditions of an illuminance of 300 mW / cm 2 and an integrated light intensity of 10000 mJ / cm 2 , the adhesive sheet is then applied from the glass plate under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 degrees in an atmosphere of 25 ° C. Measure the peeling strength at the time of peeling.
- a method for producing a crosslinkable adhesive is carried out so as to react the ethylenically unsaturated group of the ethylenically unsaturated compound (B) and leave the benzophenone structure of the polymer (A).
- the pressure-sensitive adhesive composition contains the compound (B1) having one ethylenically unsaturated group as the ethylenically unsaturated compound (B).
- the pressure-sensitive adhesive composition contains the compound (B2) having two or more ethylenically unsaturated groups as the ethylenically unsaturated compound (B). .. (11) The method according to any one of (8) to (10) above, wherein the pressure-sensitive adhesive composition further contains a photoinitiator (C).
- the photocrosslinkable adhesive according to any one of (1) to (4) above and (13) to (18) below, which contains a polymer having a benzophenone structure in a side chain.
- a pressure-sensitive adhesive composition in which the weight fraction of the compound (B2) having two or more ethylenically unsaturated groups in the entire monomer component constituting the pressure-sensitive adhesive composition is less than 5% by weight.
- a photocrosslinkable pressure-sensitive adhesive containing a polymer having a benzophenone structure in a side chain (14) The photocrosslinkable pressure-sensitive adhesive according to (13) above, which contains two or more polymers having different monomer compositions, and at least one of the two or more polymers has a benzophenone structure in a side chain. .. (15) The photocrosslinkable pressure-sensitive adhesive according to (12) or (13) above, wherein the emission amount of the volatile organic compound is 500 ⁇ g / g or less.
- the photocrosslinkable pressure-sensitive adhesive according to any one of (13) to (15) above, which is a cured product of a pressure-sensitive adhesive composition containing an ethylenically unsaturated compound and a benzophenone structure-containing component.
- the relationship between the shear storage elastic modulus Gc'[kPa] at 80 ° C. of the photocrosslinked product obtained by irradiating with ultraviolet rays under the conditions is as follows.
- a photoinitiator P1 manufactured by IGM Regins, trade name: Omnirad 651
- a pressure-sensitive adhesive composition C1 for producing a photocrosslinkable pressure-sensitive adhesive.
- the viscosity of this pressure-sensitive adhesive composition C1 (BH type viscometer, No. 5 rotor, 10 rpm, measurement temperature 30 ° C.) was 2.4 Pa ⁇ s, and the organic solvent content was less than 1% by weight.
- the pressure-sensitive adhesive composition C1 prepared above is applied to the peeling surface of a release film R1 (MRF # 38, manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 38 ⁇ m in which one side of the polyester film is a peeling surface, and one side of the polyester film is formed.
- the peeling film R2 (MRE # 38 manufactured by Mitsubishi Resin Co., Ltd.), which is the peeling surface, was covered to block the air.
- the photocrosslinkable pressure-sensitive adhesive A1 which is a cured product of the pressure-sensitive adhesive composition C1 is obtained in the form of a pressure-sensitive adhesive layer (base material-less pressure-sensitive adhesive sheet) having a thickness of 150 ⁇ m sandwiched between the release films R1 and R2. It was.
- the illuminance value of the black light is a value measured by an industrial UV checker (manufactured by Topcon Corporation, trade name: UVR-T1, light receiving unit model UD-T36) having a peak sensitivity wavelength of about 350 nm.
- an industrial UV checker manufactured by Topcon Corporation, trade name: UVR-T1, light receiving unit model UD-T36 having a peak sensitivity wavelength of about 350 nm.
- the release film R2 was peeled off from the photocrosslinkable pressure-sensitive adhesive A1 obtained above, and was attached to a corona-treated 75 ⁇ m-thick polyethylene terephthalate (PET) film.
- PET polyethylene terephthalate
- a single-sided pressure-sensitive adhesive sheet S1 with a base material having a structure in which one side of the pressure-sensitive adhesive layer made of the photocrosslinkable pressure-sensitive adhesive A1 was fixed to the PET film (base material) was obtained.
- the release film R1 was removed from the adhesive surface of the single-sided adhesive sheet, and the exposed adhesive surface was pressure-bonded to a glass plate (Gorilla Glass 3 manufactured by Corning Inc.) as a member by reciprocating a 2 kg rubber roller once.
- a glass plate Gorilla Glass 3 manufactured by Corning Inc.
- a high-pressure mercury lamp manufactured by Toshiba, trade name H3000L / 22N was used to illuminate 300 mW / cm 2 from the glass plate side and the integrated light intensity.
- the pressure-sensitive adhesive A1 was photocrosslinked by irradiating with ultraviolet rays under the condition of 10000 mJ / cm 2 . In this way, a laminate having a structure of PET film / adhesive layer / glass plate was produced.
- the illuminance value of the high-pressure mercury lamp is a value measured by an industrial UV checker (manufactured by Topcon, trade name: UVR-T1, light receiving unit model UD-T25) having a peak sensitivity wavelength of about 350 nm.
- an industrial UV checker manufactured by Topcon, trade name: UVR-T1, light receiving unit model UD-T25 having a peak sensitivity wavelength of about 350 nm.
- Example 2 30 parts of acrylic copolymer having a benzophenone structure in the side chain (manufactured by BASF, trade name: acResin UV3532), 38 parts of 2EHA, 4 parts of NVP, 28 parts of isobornyl acrylate (IBXA), 0.04 part of HDDA , 3-Acryloxipropyltrimethoxysilane (manufactured by Shinetsu Silicone Co., Ltd., trade name: KBM-5103) 0.08 part, and photoinitiator P2 (manufactured by IGM Regins) having an absorption peak in the wavelength range of 300 nm to 500 nm.
- Example 3 A monomer mixture consisting of 78 parts of 2EHA, 18 parts of NVP and 4 parts of 2-hydroxyethyl acrylate (HEA) was put into a four-necked flask together with 0.07 parts of a mixture of photoinitiators P1 and P2 having a weight ratio of 1: 1.
- a mixture of photoinitiators P1 and P2 having a weight ratio of 1: 1.
- the viscosity BH type viscometer, No. 5 rotor, 10 rpm, measurement temperature 30 ° C.
- Example 4 Acrylic copolymer having a benzophenone structure in a side chain (BASF Corp., trade name: acResin A260UV, Tg: -39 °C , Mw: 19 ⁇ 10 4, BP equivalent: 2 mg / g) and 50 parts, n- butyl 34 parts of acrylate (BA), 16 parts of NVP, and 0.2 part of photoinitiator P2 (Omnirad 184) were mixed to prepare a pressure-sensitive adhesive composition C4 for producing a photocrosslinkable pressure-sensitive adhesive.
- the viscosity of this pressure-sensitive adhesive composition C4 (BH type viscometer, No.
- the photocrosslinkable pressure-sensitive adhesive A4 which is a cured product of the pressure-sensitive adhesive composition C4, was sandwiched between the release films R1 and R2 in the same manner as in Example 1 except that the pressure-sensitive adhesive composition C4 was used instead of the pressure-sensitive adhesive composition C1. It was obtained in the form of a pressure-sensitive adhesive layer (base material-less pressure-sensitive adhesive sheet) having a thickness of 150 ⁇ m.
- a laminate having a PET film / pressure-sensitive adhesive layer / glass plate configuration was produced in the same manner as in Example 1.
- VOC emission amount of the pressure-sensitive adhesive (base material-less adhesive sheet) according to each example was measured according to the above-mentioned VOC measurement test. The results are shown in Table 1.
- the peeling film R2 was peeled off from the pressure-sensitive adhesive (base material-less pressure-sensitive adhesive sheet) according to each example, and bonded to a corona-treated 75 ⁇ m-thick PET film to prepare a single-sided pressure-sensitive adhesive sheet. This was cut into a size of 20 mm in width and 100 mm in length to prepare a test piece. In an environment of 23 ° C. and 50% RH, the release film R1 was peeled off from the test piece, and a 2 kg rubber roller was placed on a glass plate (Gorilla Glass 3 manufactured by Corning Inc.) with the exposed adhesive surface as an adherend. It was reciprocated and crimped.
- a glass plate Gorilla Glass 3 manufactured by Corning Inc.
- the photocrosslinkable pressure-sensitive adhesives of Examples 1, 2 and 4 showed clearly superior adhesion durability as compared with the pressure-sensitive adhesive of Example 3.
- the photocrosslinkable pressure-sensitive adhesives of Examples 1, 2 and 4 had a smaller VOC emission amount than the pressure-sensitive adhesive of Example 3, and had a clearly low odor.
- Adhesive sheet 10 Adhesive layer 10A One surface (adhesive surface) 10B Another surface 20 Base material 20A First surface 20B Second surface (back surface) 30, 31, 32 Peeling liner 50 Adhesive sheet with peeling liner 70 Optical member 100 Member with adhesive sheet
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
本出願は、2019年8月2日に出願された日本国特許出願2019-143392号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
上記光架橋性粘着剤は、被着体への貼付け後に上記ベンゾフェノン構造を利用して光架橋させることができ、これにより粘着剤の耐変形性を高めることができる。このことによって、被着体への貼付け時には表面形状追従性がよく、かつ貼付け後に光架橋させることで耐変形性の高い接合を形成することができる。表面形状追従性のよい粘着剤は、被着体の表面に存在し得る段差に沿って変形する(段差を吸収する)ことにより、該被着体の表面に好適に密着させることができる。
[剥離強度の測定手順]
粘着剤層の表面を、2kgのゴムローラーを一往復させてガラス板に圧着し、オートクレーブ処理(50℃、0.5MPa、15分)を行った後、高圧水銀ランプを用いて上記ガラス板側から照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射し、その後、25℃の雰囲気下、引張速度300mm/分、剥離角度180度の条件で上記粘着シートを上記ガラス板から引き剥がす際の剥離強度を測定する。
この明細書によると、ベンゾフェノン構造を側鎖に有するポリマー(BPポリマー)を含む光架橋性粘着剤が提供される。上記光架橋性粘着剤は、以下の条件:エチレン性不飽和化合物とベンゾフェノン構造含有成分とを含む粘着剤組成物の硬化物である;VOC放散量が500μg/g以下である;および、モノマー組成の異なる2種以上のポリマーを含み、上記2種以上のポリマーのうち少なくとも1種が上記BPポリマーである;の少なくとも一つに該当する。
ここに開示される技術におけるBPポリマー(ここに開示される光架橋性粘着剤に含まれるBPポリマーと、該光架橋性粘着剤を製造するための粘着剤組成物の構成成分として用いられ得るBPポリマーとを包含する。以下同じ。)の好適例として、ベンゾフェノン構造を側鎖に有するアクリル系ポリマーが挙げられる。上記BPポリマーは、エチレン性不飽和基を有していてもよく、有していなくてもよい。いくつかの態様において、上記BPポリマーは、エチレン性不飽和基を実質的に含有しないポリマーであることが好ましい。
なお、この明細書においてポリマーの重量平均分子量(Mw)とは、ゲルパーミエーションクロマトグラフィ(GPC)により得られた標準ポリスチレン換算の値をいう。GPC装置としては、例えば機種名「HLC-8320GPC」(カラム:TSKgelGMH-H(S)、東ソー社製)を使用することができる。
1/Tg=Σ(Wi/Tgi)
なお、上記Foxの式において、Tgは共重合体のガラス転移温度(単位:K)、Wiは該共重合体におけるモノマーiの重量分率(重量基準の共重合割合)、Tgiはモノマーiのホモポリマーのガラス転移温度(単位:K)を表す。
2-エチルヘキシルアクリレート -70℃
n-ブチルアクリレート -55℃
イソステアリルアクリレート -18℃
メチルメタクリレート 105℃
メチルアクリレート 8℃
シクロヘキシルアクリレート 15℃
N-ビニル-2-ピロリドン 54℃
2-ヒドロキシエチルアクリレート -15℃
4-ヒドロキシブチルアクリレート -40℃
イソボルニルアクリレート 94℃
アクリル酸 106℃
メタクリル酸 228℃
より高い光架橋効果(例えば、光架橋により耐変形性を高める効果)を得る観点から、いくつかの態様において、BPポリマーのBP当量は、通常、1mg/g以上であることが適当であり、1.5mg/g以上であることが好ましく、例えば2mg/g以上であってよく、5mg/g以上でもよく、8mg/g以上でもよく、10mg/g以上でもよく、15mg/g以上でもよく、20mg/g以上でもよい。また、いくつかの態様において、光架橋物による接合部の耐衝撃性や剥離強度を高める観点から、BPポリマーのBP当量は、通常、100mg/g以下であることが適当であり、80mg/g以下でもよく、60mg/g以下でもよく、40mg/g以下でもよく、25mg/g以下でもよく、15mg/g以下でもよい。いくつかの態様において、BPポリマーのBP当量は、10mg/g未満でもよく、5mg/g未満でもよい。BPポリマーのBP当量は、該BPポリマーを構成するモノマー成分の組成により調節することができる。
ここに開示される光架橋性粘着剤のVOC放散量は、特に限定されない。上記VOC放散量は、例えば5000μg/g以下であってよく、3000μg/g以下でもよく、1000μg/g以下でもよい。いくつかの態様において、光架橋性粘着剤のVOC放散量は、500μg/g以下であることが好ましく、300μg/g以下であることがより好ましく、100μg/g以下であることがさらに好ましい。VOC放散量が少ない光架橋性粘着剤は、低臭気であり、環境衛生の観点から好ましい。光架橋性粘着剤のVOC放散量が少ないことは、該光架橋性粘着剤中の揮発性有機物(VOC)に起因する発泡の抑制や、低汚染性の観点からも好ましい。光架橋性粘着剤のVOC放散量は、該光架橋性粘着剤の適当量(例えば、凡そ1mg~2mg程度)を測定試料として、以下の方法で測定される。なお、測定試料の厚さは1mm以下であることが好ましい。
測定試料を20mLのバイアル瓶に入れて密栓する。次いで、上記バイアル瓶を80℃で30分間加熱し、加熱状態のガス1.0mL(サンプルガス)をヘッドスペースオートサンプラー(HSS)を用いてガスクロマトグラフ(GC)測定装置に注入する。得られたガスクロマトグラムに基づいて、上記測定試料から発生したガス量をn-デカン換算量として求める。得られた値から、測定試料1g当たりのVOC放散量(μg/g)を求める。なお、このn-デカン換算量は、GC Massにより得られる発生ガスの検出強度をn-デカンの検出強度とみなして、あらかじめ作成したn-デカンの検量線を適用することにより求める。HSSおよびGCの設定は以下のとおりである。
HSS:Agilent Technologies社製 型式「7694」
加熱時間:30分間
加圧時間:0.12分
ループ充填時間:0.12分
ループ平衡時間:0.05分
注入時間:3分
サンプルループ温度:160℃
トランスファーライン温度:200℃
GC装置:Agilent Technologies社製 型式「6890」
カラム:ジーエルサイエンス社製 J&W キャピラリーカラム 商品名「DB-ffAP」(内径0.533mm×長さ30m、膜厚1.0μm)
カラム温度:250℃(40℃から90℃まで10℃/分で昇温し、引き続き250℃まで20℃/分で昇温して5分保持)
カラム圧力:24.3kPa(定流モード)
キャリアーガス:ヘリウム(5.0mL/分)
注入口:スプリット(スプリット比 12:1)
注入口温度:250℃
検出器:FID
検出器温度:250℃
なお、ここに開示される光架橋性粘着剤のVOC放散量は、原則としては低いほど好ましいが、生産性やコスト等の実用上の観点から、いくつかの態様において、上記VOC放散量は、例えば10μg/g以上であってよく、30μg/g以上でもよく、80μg/g以上でもよく、150μg/g以上でもよく、200μg/g以上でもよい。
ここに開示される技術において、光架橋性粘着剤の30℃におけるせん断貯蔵弾性率Ga’[kPa]は、特に限定されない。光架橋性粘着剤の30℃におけるせん断貯蔵弾性率Ga’[kPa]は、通常、1kPa超であることが好ましい。以下、上記せん断貯蔵弾性率Ga’を「光架橋前室温弾性率Ga’」または単に「室温弾性率Ga’」ということがある。光架橋性粘着剤の凝集性や該光架橋性粘着剤からなる粘着剤層を有する粘着シートの取扱い性(例えば加工性)等の観点から、室温弾性率Ga’は、5kPa超であることが好ましく、10kPa超であることがより好ましく、15kPa超でもよく、25kPa超でもよく、30kPa超でもよい。いくつかの態様において、室温弾性率Ga’は、50kPa超でもよく、65kPa超でもよく、75kPa超でもよい。また、被着体の表面形状に対する追従性の観点から、室温弾性率Ga’は、通常、500kPa以下であることが適当であり、200kPa以下であることが好ましく、100kPa以下でもよい。いくつかの態様において、室温弾性率Ga’は、80kPa未満でもよく、60kPa未満でもよい。
光架橋性粘着剤の室温弾性率Ga’は、後述の実施例に記載の光架橋前弾性率Gb’と同様の条件で動的粘弾性測定を行うことにより求めることができる。室温弾性率Ga’は、光架橋性粘着剤の組成(例えば、BPポリマーのBP当量、Mw、BPポリマーを構成するモノマー成分の組成、BPポリマーの重量分率)等により調節することができる。
弾性率Gb’は、後述の実施例に記載の方法で測定することができる。弾性率Gb’は、光架橋性粘着剤の組成(例えば、BPポリマーのBP当量、Mw、BPポリマーを構成するモノマー成分の組成、BPポリマーの重量分率)等により調節することができる。
弾性率Gc’は、より具体的には、後述の実施例に記載の方法で測定することができる。弾性率Gc’は、光架橋性粘着剤の組成(例えば、BPポリマーのBP当量、Mw、BPポリマーを構成するモノマー成分の組成、BPポリマーの重量分率)等により調節することができる。
ここに開示される光架橋性粘着剤のゲル分率は、特に限定されないが、該光架橋性粘着剤の凝集性や該光架橋性粘着剤からなる粘着剤層を有する粘着シートの取扱い性等の観点から、通常は5%以上であることが適当であり、15%以上であることが好ましく、25%以上でもよく、35%以上でもよい。光架橋性粘着剤のゲル分率は、原理上、100%以下である。また、被着体の表面形状に対する追従性の観点から、光架橋性粘着剤のゲル分率は、85%未満であることが好ましく、70%未満でもよく、55%未満でもよく、40%未満でもよい。
ゲル分率(%)=W2/W1×100;
に代入してゲル分率を算出する。多孔質PTFEシートとしては、日東電工社製の商品名「ニトフロンNTF1122」またはその相当品を使用することができる。
ここに開示される光架橋性粘着剤は、例えば、ベンゾフェノン構造を励起可能な波長成分を含む紫外線を照射することにより光架橋させることができる。波長300nm未満の成分を含む紫外線を照射可能な光源を用いることが好ましい。かかる光源の例としては、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、スーパーUVランプ等が挙げられるが、これらに限定されない。上記光源により照射される光は、波長300nm以上の成分を含んでいてもよい。
この明細書によると、ベンゾフェノン構造を側鎖に有するポリマー(BPポリマー)(A)と、エチレン性不飽和化合物(B)と、を含む粘着剤組成物が提供される。かかる粘着剤組成物は、ここに開示されるいずれかの光架橋性粘着剤の製造に用いられ得る。いくつかの態様において、上記粘着剤組成物は、該粘着剤組成物を構成するモノマー成分全体の50重量%超(好ましくは70重量%超、例えば90重量%超)がアクリル系モノマーであるアクリル系粘着剤組成物であり得る。
エチレン性不飽和化合物(B)として使用し得る化合物の例示には、上述した(メタ)アクリル酸アルキルエステルと、上述したエチレン性不飽和BPとが含まれる。これらのうち、少なくとも(メタ)アクリル酸アルキルエステル(例えば(メタ)アクリル酸C1-20アルキルエステル、より好ましくは(メタ)アクリル酸C4-18アルキルエステル、さらに好ましくはアクリル酸C4-9アルキルエステル)を用いることが好ましい。特に好ましい(メタ)アクリル酸アルキルエステルとして、アクリル酸n-ブチル(BA)およびアクリル酸2-エチルヘキシル(2EHA)が挙げられる。好ましく用いられ得る(メタ)アクリル酸アルキルエステルの他の具体例としては、アクリル酸イソノニル、メタクリル酸n-ブチル(BMA)、メタクリル酸2-エチルヘキシル(2EHMA)、アクリル酸イソステアリル(iSTA)等が挙げられる。(メタ)アクリル酸アルキルエステルは、1種を単独でまたは2種以上を組み合わせて用いることができる。いくつかの態様において、エチレン性不飽和化合物(B)は、アクリル酸n-ブチル(BA)およびアクリル酸2-エチルヘキシル(2EHA)のうちいずれか一方または両方を含むことが好ましい。一態様では、少なくとも2EHAを含むことがより好ましい。他の一態様では、少なくともBAを含むことがより好ましい。
カルボキシ基含有モノマー:例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等。
酸無水物基含有モノマー:例えば、無水マレイン酸、無水イタコン酸。
水酸基含有モノマー:例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル、(メタ)アクリル酸8-ヒドロキシオクチル、(メタ)アクリル酸10-ヒドロキシデシル、(メタ)アクリル酸12-ヒドロキシラウリル、(4-ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキル等。
スルホン酸基またはリン酸基を含有するモノマー:例えば、スチレンスルホン酸、アリルスルホン酸、ビニルスルホン酸ナトリウム、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシナフタレンスルホン酸、2-ヒドロキシエチルアクリロイルホスフェート等。
エポキシ基含有モノマー:例えば、(メタ)アクリル酸グリシジルや(メタ)アクリル酸-2-エチルグリシジルエーテル等のエポキシ基含有アクリレート、アリルグリシジルエーテル、(メタ)アクリル酸グリシジルエーテル等。
シアノ基含有モノマー:例えば、アクリロニトリル、メタクリロニトリル等。
イソシアネート基含有モノマー:例えば、2-(メタ)アクリロイルオキシエチルイソシアネート、(メタ)アクリロイルイソシアネート、m-イソプロペニル-α,α-ジメチルベンジルイソシアネート等。
アミド基含有モノマー:例えば、(メタ)アクリルアミド;N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N,N-ジプロピル(メタ)アクリルアミド、N,N-ジイソプロピル(メタ)アクリルアミド、N,N-ジ(n-ブチル)(メタ)アクリルアミド、N,N-ジ(t-ブチル)(メタ)アクリルアミド等のN,N-ジアルキル(メタ)アクリルアミド;N-エチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-n-ブチル(メタ)アクリルアミド等のN-アルキル(メタ)アクリルアミド;N-ビニルアセトアミド等のN-ビニルカルボン酸アミド類;水酸基とアミド基とを有するモノマー、例えば、N-(2-ヒドロキシエチル)(メタ)アクリルアミド、N-(2-ヒドロキシプロピル)(メタ)アクリルアミド、N-(1-ヒドロキシプロピル)(メタ)アクリルアミド、N-(3-ヒドロキシプロピル)(メタ)アクリルアミド、N-(2-ヒドロキシブチル)(メタ)アクリルアミド、N-(3-ヒドロキシブチル)(メタ)アクリルアミド、N-(4-ヒドロキシブチル)(メタ)アクリルアミド等のN-ヒドロキシアルキル(メタ)アクリルアミド;アルコキシ基とアミド基とを有するモノマー、例えば、N-メトキシメチル(メタ)アクリルアミド、N-メトキシエチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド等のN-アルコキシアルキル(メタ)アクリルアミド;その他、N,N-ジメチルアミノプロピル(メタ)アクリルアミド、N-(メタ)アクリロイルモルホリン等。
アミノ基含有モノマー:例えばアミノエチル(メタ)アクリレート、N,N-ジメチルアミノエチル(メタ)アクリレート、t-ブチルアミノエチル(メタ)アクリレート。
エポキシ基を有するモノマー:例えばグリシジル(メタ)アクリレート、メチルグリシジル(メタ)アクリレート、アリルグリシジルエーテル。
窒素原子含有環を有するモノマー:例えば、N-ビニル-2-ピロリドン、N-メチルビニルピロリドン、N-ビニルピリジン、N-ビニルピペリドン、N-ビニルピリミジン、N-ビニルピペラジン、N-ビニルピラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルオキサゾール、N-(メタ)アクリロイル-2-ピロリドン、N-(メタ)アクリロイルピペリジン、N-(メタ)アクリロイルピロリジン、N-ビニルモルホリン、N-(メタ)アクリロイルモルホリン、N-ビニル-3-モルホリノン、N-ビニル-2-カプロラクタム、N-ビニル-1,3-オキサジン-2-オン、N-ビニル-3,5-モルホリンジオン、N-ビニルピラゾール、N-ビニルイソオキサゾール、N-ビニルチアゾール、N-ビニルイソチアゾール、N-ビニルピリダジン等(例えば、N-ビニル-2-カプロラクタム等のラクタム類)。
スクシンイミド骨格を有するモノマー:例えば、N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、N-(メタ)アクリロイル-8-オキシヘキサメチレンスクシンイミド等。
マレイミド類:例えば、N-シクロヘキシルマレイミド、N-イソプロピルマレイミド、N-ラウリルマレイミド、N-フェニルマレイミド等。
イタコンイミド類:例えば、N-メチルイタコンイミド、N-エチルイタコンイミド、N-ブチルイタコンイミド、N-オクチルイタコンイミド、N-2-エチルへキシルイタコンイミド、N-シクロへキシルイタコンイミド、N-ラウリルイタコンイミド等。
(メタ)アクリル酸アミノアルキル類:例えば、(メタ)アクリル酸アミノエチル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸N,N-ジエチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチル。
アルコキシ基含有モノマー:例えば、(メタ)アクリル酸2-メトキシエチル、(メタ)アクリル酸3-メトキシプロピル、(メタ)アクリル酸2-エトキシエチル、(メタ)アクリル酸プロポキシエチル、(メタ)アクリル酸ブトキシエチル、(メタ)アクリル酸エトキシプロピル等の(メタ)アクリル酸アルコキシアルキル(アルコキシアルキル(メタ)アクリレート)類;(メタ)アクリル酸メトキシエチレングリコール、(メタ)アクリル酸メトキシポリエチレングリコール、(メタ)アクリル酸メトキシポリプロピレングリコール等の(メタ)アクリル酸アルコキシアルキレングリコール(例えばアルコキシポリアルキレングリコール(メタ)アクリレート)類。
アルコキシシリル基含有モノマー:例えば3-(メタ)アクリロキシプロピルトリメトキシシラン、3-(メタ)アクリロキシプロピルトリエトキシシラン、3-(メタ)アクリロキシプロピルメチルジメトキシシラン、3-(メタ)アクリロキシプロピルメチルジエトキシシラン等のアルコキシシリル基含有(メタ)アクリレートや、ビニルトリメトキシシラン、ビニルトリエトキシシラン等のアルコキシシリル基含有ビニル化合物等。
ビニルエステル類:例えば、酢酸ビニル、プロピオン酸ビニル等。
ビニルエーテル類:例えば、メチルビニルエーテルやエチルビニルエーテル等のビニルアルキルエーテル。
芳香族ビニル化合物:例えば、スチレン、α-メチルスチレン、ビニルトルエン等。
オレフィン類:例えば、エチレン、ブタジエン、イソプレン、イソブチレン等。
脂環式炭化水素基を有する(メタ)アクリル酸エステル:例えば、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、アダマンチル(メタ)アクリレート等の脂環式炭化水素基含有(メタ)アクリレート。
芳香族炭化水素基を有する(メタ)アクリル酸エステル:例えば、フェニル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート等の芳香族炭化水素基含有(メタ)アクリレート。
その他、(メタ)アクリル酸テトラヒドロフルフリル等の複素環含有(メタ)アクリレート、塩化ビニルやフッ素原子含有(メタ)アクリレート等のハロゲン原子含有(メタ)アクリレート、シリコーン(メタ)アクリレート等のケイ素原子含有(メタ)アクリレート、テルペン化合物誘導体アルコールから得られる(メタ)アクリル酸エステル等。
多官能性モノマーとしては、例えば、1,6-ヘキサンジオールジ(メタ)アクリレート、1,12-ドデカンジオールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、アリル(メタ)アクリレート、ビニル(メタ)アクリレート、ジビニルベンゼン等の、2官能性モノマー;トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、テトラメチロールメタントリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の、3官能性以上の多官能性モノマー;その他、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート等;が挙げられる。なかでも好ましい例として、1,6-ヘキサンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレートが挙げられる。多官能性モノマーは、1種を単独でまたは2種以上を組み合わせて使用することができる。
粘着剤組成物には、光硬化性の向上または付与等を目的として、必要に応じて光開始剤を含有させることができる。光開始剤としては、ケタール系光開始剤、アセトフェノン系光開始剤、ベンゾインエーテル系光開始剤、アシルホスフィンオキサイド系光開始剤、α-ケトール系光開始剤、芳香族スルホニルクロリド系光開始剤、光活性オキシム系光開始剤、ベンゾイン系光開始剤、ベンジル系光開始剤、ベンゾフェノン系光開始剤、アルキルフェノン系光開始剤、チオキサントン系光開始剤等を用いることができる。光開始剤は、1種を単独でまたは2種以上を適宜組み合わせて用いることができる。
アセトフェノン系光開始剤の具体例には、1-ヒドロキシシクロヘキシル-フェニル-ケトン、4-フェノキシジクロロアセトフェノン、4-t-ブチル-ジクロロアセトフェノン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、メトキシアセトフェノン等が含まれる。
ベンゾインエーテル系光開始剤の具体例には、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾインエーテルおよびアニソールメチルエーテル等の置換ベンゾインエーテルが含まれる。
アシルホスフィンオキサイド系光開始剤の具体例には、ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド、ビス(2,4,6-トリメチルベンゾイル)-2,4-ジ-n-ブトキシフェニルホスフィンオキシド、2,4,6-トリメチルベンゾイルジフェニルホスフィンオキシド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルホスフィンオキシド等が含まれる。
α-ケトール系光開始剤の具体例には、2-メチル-2-ヒドロキシプロピオフェノン、1-[4-(2-ヒドロキシエチル)フェニル]-2-メチルプロパン-1-オン等が含まれる。芳香族スルホニルクロリド系光開始剤の具体例には、2-ナフタレンスルホニルクロライド等が含まれる。光活性オキシム系光開始剤の具体例には、1-フェニル-1,1-プロパンジオン-2-(o-エトキシカルボニル)-オキシム等が含まれる。ベンゾイン系光開始剤の具体例にはベンゾイン等が含まれる。ベンジル系光開始剤の具体例にはベンジル等が含まれる。
ベンゾフェノン系光開始剤の具体例には、ベンゾイル安息香酸、3,3’-ジメチル-4-メトキシベンゾフェノン、ポリビニルベンゾフェノン、α-ヒドロキシシクロヘキシルフェニルケトン等が含まれる。
チオキサントン系光開始剤の具体例には、チオキサントン、2-クロロチオキサントン、2-メチルチオキサントン、2,4-ジメチルチオキサントン、イソプロピルチオキサントン、2,4-ジクロロチオキサントン、2,4-ジエチルチオキサントン、イソプロピルチオキサントン、2,4-ジイソプロピルチオキサントン、ドデシルチオキサントン等が含まれる。
粘着剤組成物には、必要に応じて、例えばイソシアネート系架橋剤、エポキシ系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、カルボジイミド系架橋剤、メラミン系架橋剤、尿素系架橋剤、金属アルコキシド系架橋剤、金属キレート系架橋剤、金属塩系架橋剤、ヒドラジン系架橋剤、アミン系架橋剤等の、公知の架橋剤を配合し得る。架橋剤として過酸化物を用いてもよい。これらの架橋剤は、1種を単独でまたは2種以上を組み合わせて用いることができる。架橋剤を含む粘着剤組成物から形成された光架橋性粘着剤は、該架橋剤を主に架橋反応後の形態で含むことが好ましい。架橋剤の使用により、光架橋性粘着剤の凝集力等を適切に調節することができる。
粘着剤組成物は、従来公知の各種の連鎖移動剤を含んでいてもよい。連鎖移動剤としては、n-ドデシルメルカプタン、t-ドデシルメルカプタン、チオグリコール酸、α-チオグリセロール等のメルカプタン類を用いることができる。あるいは、硫黄原子を含まない連鎖移動剤(非硫黄系連鎖移動剤)を用いてもよい。非硫黄系連鎖移動剤の具体例としては、N,N-ジメチルアニリン、N,N-ジエチルアニリン等のアニリン類;α-ピネン、ターピノーレン等のテルペノイド類;α-メチルスチレン、α―メチルスチレンダイマー等のスチレン類;ジベンジリデンアセトン、シンナミルアルコール、シンナミルアルデヒド等のベンジリデニル基を有する化合物;ヒドロキノン、ナフトヒドロキノン等のヒドロキノン類;ベンゾキノン、ナフトキノン等のキノン類;2,3-ジメチル-2-ブテン、1,5-シクロオクタジエン等のオレフィン類;フェノール、ベンジルアルコール、アリルアルコール等のアルコール類;ジフェニルベンゼン、トリフェニルベンゼン等のベンジル水素類;等が挙げられる。連鎖移動剤は、1種を単独でまたは2種以上を組み合わせて用いることができる。連鎖移動剤を使用する場合、その使用量は、モノマー成分100重量部に対して、例えば凡そ0.01~1重量部程度とすることができる。ここに開示される技術は、連鎖移動剤を使用しない態様でも好ましく実施され得る。
ここに開示される粘着剤組成物は、必要に応じて、粘着付与樹脂(例えば、ロジン系、石油系、テルペン系、フェノール系、ケトン系等の粘着付与樹脂)、粘度調整剤(例えば増粘剤)、レベリング剤、酸化防止剤、可塑剤、充填剤、顔料や染料等の着色剤、安定剤、防腐剤、老化防止剤等の、粘着剤の分野において一般的な各種の添加剤を、その他の任意成分として含み得る。このような各種添加剤については、従来公知のものを常法により使用することができ、特に本発明を特徴づけるものではないので、詳細な説明は省略する。
なお、ここに開示される技術は、上述の粘着付与樹脂を用いることなく、良好な接着力を発揮することができる。このため、いくつかの態様において、上記粘着剤層または粘着剤組成物における上記粘着付与樹脂の含有量は、モノマー成分100重量部に対して、例えば10重量部未満、さらには5重量部未満とすることができる。上記粘着付与樹脂の含有量は、1重量部未満(例えば0.5重量部未満)であってもよく、0.1重量部未満(0重量部以上0.1重量部未満)であってもよい。上記粘着剤層または粘着剤組成物は、粘着付与樹脂を含まないものであり得る。
ここに開示される粘着剤組成物は、該粘着剤組成物を硬化させることにより、BPポリマーを含有する光架橋性粘着剤を形成し得るように構成されている。粘着剤組成物の硬化は、該粘着剤組成物に含まれるエチレン性不飽和基を反応させ、かつ該粘着剤組成物に含まれるベンゾフェノン構造を残存させるように行われることが好ましい。上記硬化は、活性エネルギー線の照射により好ましく行われ得る。光架橋性粘着剤を形成するための活性エネルギー線としては、紫外線が好ましく、波長300nm以下の成分を含まないか該波長成分が少ない紫外線がより好ましい。
この明細書によると、ここに開示されるいずれかの光架橋性粘着剤からなる粘着剤層を有する粘着シートが提供される。
ここに開示される粘着シートの一構成例を図1に示す。この粘着シート1は、一方の表面10Aが被着体への貼付面(粘着面)となっている粘着剤層10と、粘着剤層10の他方の表面10Bに積層された基材20と、を含む片面接着性の粘着シートとして構成されている。粘着剤層10は基材20の一方の表面20Aに接合している。基材20としては、例えばポリエステルフィルム等のプラスチックフィルムが用いられ得る。基材20は、例えば偏光板等の光学フィルムであってもよい。図1に示す例では、粘着剤層10は単層構造である。使用前(被着体への貼付け前)の粘着シート1は、例えば図1に示すように、粘着面10Aが、少なくとも該粘着剤層側が剥離性表面(剥離面)となっている剥離ライナー30で保護された、剥離ライナー付き粘着シート50の形態であり得る。あるいは、基材20の第二面20B(第一面20Aとは反対側の表面であり、背面ともいう。)が剥離面となっており、基材20の第二面20Bに粘着面10Aが当接するように巻回または積層されることで粘着面10Aが保護された形態であってもよい。
いくつかの態様に係る粘着シートは、粘着剤層に接合した基材を含む基材付き粘着シートの形態であり得る。基材の材質は特に限定されず、粘着シートの使用目的や使用態様等に応じて適宜選択することができる。使用し得る基材の非限定的な例としては、ポリプロピレンやエチレン-プロピレン共重合体等のポリオレフィンを主成分とするポリオレフィンフィルム、ポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステルを主成分とするポリエステルフィルム、ポリ塩化ビニルを主成分とするポリ塩化ビニルフィルム等のプラスチックフィルム(樹脂フィルム);ポリウレタンフォーム、ポリエチレンフォーム、ポリクロロプレンフォーム等の発泡体からなる発泡体シート;各種の繊維状物質(麻、綿等の天然繊維、ポリエステル、ビニロン等の合成繊維、アセテート等の半合成繊維等であり得る。)の単独または混紡等による織布および不織布;和紙、上質紙、クラフト紙、クレープ紙等の紙類;アルミニウム箔、銅箔等の金属箔;等が挙げられる。これらを複合した構成の基材であってもよい。このような複合構造の基材の例として、例えば、金属箔と上記プラスチックフィルムとが積層した構造の基材、ガラスクロス等の無機繊維で強化されたプラスチックシート等が挙げられる。
(剥離強度)
ここに開示される粘着シートにおいて、上述した剥離強度測定手順により測定される剥離強度、より具体的には後述する実施例に記載の方法で測定される剥離強度は、例えば凡そ0.5N/10mm以上であってよく、通常は凡そ1.0N/10mm以上であることが適当である。接合信頼性向上の観点から、上記剥離強度は、例えば凡そ1.5N/10mm以上であることが好ましく、凡そ2.0N/10mm以上であることがより好ましい。一態様に係る粘着シートにおいて、上記剥離強度は、例えば凡そ3.0N/10mm以上であってよく、凡そ4.5N/10mm以上でもよく、凡そ5.5N/10mm以上でもよい。ここに開示される粘着シートは、剥離強度が凡そ5.7N/10mm以上、凡そ6.5N/10mm以上、凡そ7N/10mm以上、凡そ8N/10mm以上、凡そ9N/10mm以上、凡そ10N/10mm以上、凡そ11N/10mm以上、凡そ12N/10mm以上または凡そ13N/10mm以上である態様でも実施され得る。このような強接着力は、例えばシランカップリング剤を用いることによって好ましく実現され得る。剥離強度の上限は特に制限されず、例えば25N/10mm以下であってよく、他の物性とのバランス等を考慮して20N/10mm以下でもよく、15N/10mm以下でもよく、10N/10mm以下でもよく、8N/10mm以下でもよい。
ここに開示される技術において、粘着シートのヘイズ値は、凡そ10%以下であることが適当であり、凡そ5%以下(例えば凡そ3%以下)であり得る。いくつかの態様において、粘着シートのヘイズ値は1.0%以下であることが好ましい。このように透明性の高い粘着シートは、高い光透過性が求められる光学用途に好適である。粘着シートのヘイズ値は、1.0%未満であってよく、0.7%未満であってもよく、0.5%以下(例えば0~0.5%)であってもよい。これらのヘイズ値は、光架橋性粘着剤からなる粘着剤層のヘイズ値にも好ましく適用され得る。
Th[%]=Td/Tt×100
上記式において、Thはヘイズ値[%]であり、Tdは散乱光透過率、Ttは全光透過率である。
ヘイズ値は、ヘイズメーター(たとえば、村上色彩技術研究所製の「MR-100」)を用いて測定することができる。ヘイズ値は、例えば、粘着剤層の組成や厚さ等の選択によって調節することができる。
ここに開示される光架橋性粘着剤は、該光架橋性粘着剤を被着体としての部材に積層した後に、上記光架橋性粘着剤を光架橋させる態様で好ましく用いられ得る。これにより、上記光架橋物が上記被着体に信頼性よく接合した積層体を製造することができる。上記光架橋性粘着剤の光架橋は、該光架橋性粘着剤に活性エネルギー線を照射することにより行うことができる。活性エネルギー線としては、上記光架橋性粘着剤に含まれるベンゾフェノン構造を励起可能な波長成分を含む紫外線(例えば、波長300nm未満の成分を含む紫外線)が好ましい。上記光架橋性粘着剤は、該光架橋性粘着剤からなる粘着剤層を有する粘着シートの形態で、上記積層体の製造に用いられ得る。したがって、この明細書により、ここに開示されるいずれかの光架橋性粘着剤からなる粘着剤層を有する粘着シートを被着体に貼り合わせることと、上記粘着シートに活性エネルギー線を照射して上記光架橋性粘着剤を光架橋させることと、をこの順序で含む積層体製造方法が提供される。
被着体への貼合わせ後に光架橋させる態様で用いられる粘着シートの有する粘着剤層が多層構造である場合、上記光架橋させる粘着剤層は、上記多層構造に含まれる一部の層(例えば一つの層)であってもよく、全部の層であってもよい。
ここに開示される光架橋性粘着剤の用途は特に限定されず、各種の用途に用いることができる。例えば、ここに開示される光架橋性粘着剤は、該光架橋性粘着剤からなる粘着剤層を有する粘着シートの形態で、各種製品を構成する部材の固定、接合、成形、装飾、保護、支持等の用途に用いられ得る。上記部材の少なくとも表面を構成する材質は、例えば、アルカリガラスや無アルカリガラス等のガラス;ステンレス鋼(SUS)、アルミニウム等の金属材料;アルミナ、シリカ等のセラミック材料;アクリル樹脂、ABS樹脂、ポリカーボネート樹脂、ポリスチレン樹脂、透明ポリイミド樹脂等の樹脂材料;等であり得る。上記部材は、例えば各種の携帯機器(ポータブル機器)、自動車、家電製品等を構成する部材であり得る。また、上記部材は、該粘着シートが貼り付けられる面が、アクリル系、ポリエステル系、アルキド系、メラミン系、ウレタン系、酸エポキシ架橋系、あるいはこれらの複合系(例えばアクリルメラミン系、アルキドメラミン系)等の塗料による塗装面や、亜鉛メッキ鋼板等のメッキ面であってもよい。また、上記部材は、基材に用いられ得る材料として例示したいずれかの支持フィルム(例えば、樹脂フィルム)であってもよい。ここに開示される粘着シートは、例えば、このような部材が粘着剤層の少なくとも一方の表面に接合された粘着シート付き部材の構成要素であり得る。
(1) ベンゾフェノン構造を側鎖に有するポリマーを含み、
エチレン性不飽和化合物とベンゾフェノン構造含有成分とを含む粘着剤組成物の硬化物であり、かつ
揮発性有機化合物の放散量が500μg/g以下である、光架橋性粘着剤。
(2) 上記ベンゾフェノン構造含有成分は、ベンゾフェノン構造を側鎖に有するポリマーである、上記(1)に記載の光架橋性粘着剤。
(3) 上記光架橋性粘着剤の80℃におけるせん断貯蔵弾性率Gb’[kPa]と、上記光架橋性粘着剤に高圧水銀ランプを用いて照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射して得られた光架橋物の80℃におけるせん断貯蔵弾性率Gc’[kPa]との関係が、以下の式:
Gc’[kPa]-Gb’[kPa]≧2kPa;
を満たす、上記(1)または(2)に記載の光架橋性粘着剤。
(4) 上記光架橋性粘着剤に高圧水銀ランプを用いて照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射して得られた光架橋物の80℃におけるせん断貯蔵弾性率Gc’[kPa]が40kPa以上である、上記(1)~(3)のいずれかに記載の光架橋性粘着剤。
(5) 上記(1)~(4)および下記(13)~(18)のいずれかに記載の光架橋性粘着剤からなる粘着剤層を有する、粘着シート。
(6) 下記手順により測定される剥離強度が1.0N/10mm以上である、上記(5)に記載の粘着シート。
[剥離強度の測定手順]
粘着剤層の表面を、2kgのゴムローラーを一往復させてガラス板に圧着し、オートクレーブ処理(50℃、0.5MPa、15分)を行った後、高圧水銀ランプを用いて上記ガラス板側から照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射し、その後、25℃の雰囲気下、引張速度300mm/分、剥離角度180度の条件で上記粘着シートを上記ガラス板から引き剥がす際の剥離強度を測定する。
(7) 上記(1)~(4)および下記(13)~(18)のいずれか一項に記載の光架橋性粘着剤と部材とを積層することと、
上記光架橋性粘着剤に含まれる上記ベンゾフェノン構造を反応させて該光架橋性粘着剤を光架橋させることと、
をこの順序で含む、積層体製造方法。
(8) ベンゾフェノン構造を側鎖に有するポリマー(A)とエチレン性不飽和化合物(B)とを含む粘着剤組成物を用意すること;および、
上記粘着剤組成物に活性エネルギー線を照射すること;
を包含し、
ここで、上記活性エネルギー線の照射は、上記エチレン性不飽和化合物(B)の有するエチレン性不飽和基を反応させ、かつ上記ポリマー(A)の有するベンゾフェノン構造を残存させるように行われる、光架橋性粘着剤製造方法。
(9) 上記粘着剤組成物は、上記エチレン性不飽和化合物(B)として、エチレン性不飽和基を1つ有する化合物(B1)を含む、上記(8)に記載の方法。
(10) 上記粘着剤組成物は、上記エチレン性不飽和化合物(B)として、エチレン性不飽和基を2つ以上有する化合物(B2)を含む、上記(8)または(9)に記載の方法。
(11) 上記粘着剤組成物は、さらに光開始剤(C)を含む、上記(8)~(10)のいずれか一項に記載の方法。
(12) ベンゾフェノン構造を側鎖に有するポリマーを含む光架橋性粘着剤(例えば、上記(1)~(4)および下記(13)~(18)のいずれか一項に記載の光架橋性粘着剤)の製造に用いられる粘着剤組成物であって、
ベンゾフェノン構造を側鎖に有するポリマー(A)と、
エチレン性不飽和化合物(B)と、
波長300nm~500nmの光を吸収してラジカルを発生する光開始剤(C)と
を含み、
上記粘着剤組成物を構成するモノマー成分全体におけるエチレン性不飽和基を2つ以上有する化合物(B2)の重量分率が5重量%未満である、粘着剤組成物。
(14) モノマー組成の異なる2種以上のポリマーを含み、上記2種以上のポリマーのうち少なくとも1種がベンゾフェノン構造を側鎖に有するポリマーである、上記(13)に記載の光架橋性粘着剤。
(15) 揮発性有機化合物の放散量が500μg/g以下である、上記(12)または(13)に記載の光架橋性粘着剤。
(16) エチレン性不飽和化合物とベンゾフェノン構造含有成分とを含む粘着剤組成物の硬化物である、上記(13)~(15)のいずれかに記載の光架橋性粘着剤。
(17) 上記光架橋性粘着剤の80℃におけるせん断貯蔵弾性率Gb’[kPa]と、上記光架橋性粘着剤に高圧水銀ランプを用いて照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射して得られた光架橋物の80℃におけるせん断貯蔵弾性率Gc’[kPa]との関係が、以下の式:
Gc’[kPa]-Gb’[kPa]≧2kPa;
を満たす、上記(13)~(16)のいずれかに記載の光架橋性粘着剤。
(18) 上記光架橋性粘着剤に高圧水銀ランプを用いて照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射して得られた光架橋物の80℃におけるせん断貯蔵弾性率Gc’[kPa]が40kPa以上である、上記(13)~(17)のいずれかに記載の光架橋性粘着剤。
(粘着剤組成物の調製)
側鎖にベンゾフェノン構造を有するアクリル系共重合体(BASF社製、商品名:acResin UV3532、Tg:-60℃、Mw:25×104、BP当量:10mg/g)60部と、2-エチルヘキシルアクリレート(2EHA)30部と、N-ビニル-2-ピロリドン(NVP)10部と、1,6-ヘキサンジオールジアクリレート(HDDA)0.2部と、波長300nm~500nmの範囲に吸収ピークを有する光開始剤P1(IGM Regins社製、商品名:オムニラッド651)0.15部とを混合して、光架橋性粘着剤作製用の粘着剤組成物C1を調製した。この粘着剤組成物C1の粘度(BH型粘度計、No.5ローター、10rpm、測定温度30℃)は2.4Pa・sであり、有機溶媒含有量は1重量%未満であった。
ポリエステルフィルムの片面が剥離面となっている厚さ38μmの剥離フィルムR1(三菱樹脂社製、MRF#38)の剥離面に上記で調製した粘着剤組成物C1を塗布し、ポリエステルフィルムの片面が剥離面となっている剥離フィルムR2(三菱樹脂社製、MRE#38)を被せて空気を遮断した。この積層体の片側から、ブラックライト(東芝社製、商品名FL15BL)を用いて照度5mW/cm2、積算光量800mJ/cm2の条件で紫外線を照射した。これにより、上記粘着剤組成物C1の硬化物である光架橋性粘着剤A1を、上記剥離フィルムR1,R2に挟まれた厚さ150μmの粘着剤層(基材レス粘着シート)の形態で得た。
なお、上記ブラックライトの照度の値は、ピーク感度波長約350nmの工業用UVチェッカー(トプコン社製、商品名:UVR-T1、受光部型式UD-T36)による測定値である。
上記で得られた光架橋性粘着剤A1から剥離フィルムR2を剥がし、コロナ処理された厚さ75μmのポリエチレンテレフタレート(PET)フィルムに貼り合わせた。これにより、光架橋性粘着剤A1からなる粘着剤層の片面がPETフィルム(基材)に固着した構成の基材付き片面粘着シートS1を得た。
この片面粘着シートの粘着面から剥離フィルムR1を除去し、露出した粘着面を、部材としてのガラス板(コーニング社製、ゴリラガラス3)に、2kgのゴムローラーを一往復させて圧着した。これにオートクレーブ処理(50℃、0.5MPa、15分)を行った後、高圧水銀ランプ(東芝社製、商品名H3000L/22N)を用いて上記ガラス板側から照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射することにより、粘着剤A1を光架橋させた。このようにして、PETフィルム/粘着剤層/ガラス板の構成を有する積層体を作製した。
なお、上記高圧水銀ランプの照度の値は、ピーク感度波長約350nmの工業用UVチェッカー(トプコン社製、商品名:UVR-T1、受光部型式UD-T25)による測定値である。
側鎖にベンゾフェノン構造を有するアクリル系共重合体(BASF社製、商品名:acResin UV3532)30部と、2EHA38部と、NVP4部と、イソボルニルアクリレート(IBXA)28部と、HDDA0.04部と、3-アクリロキシプロピルトリメトキシシラン(信越シリコーン社製、商品名:KBM-5103)0.08部と、波長300nm~500nmの範囲に吸収ピークを有する光開始剤P2(IGM Regins社製、商品名:オムニラッド184)0.2部とを混合して、光架橋性粘着剤作製用の粘着剤組成物C2を調製した。この粘着剤組成物C2の粘度(BH型粘度計、No.5ローター、10rpm、測定温度30℃)は0.4Pa・sであり、有機溶媒含有量は1重量%未満であった。
粘着剤組成物C1に代えて粘着剤組成物C2を用いた他は例1と同様にして、粘着剤組成物C2の硬化物である光架橋性粘着剤A2を、剥離フィルムR1,R2に挟まれた厚さ150μmの粘着剤層(基材レス粘着シート)の形態で得た。
この光架橋性粘着剤A2を用いて、例1と同様にしてPETフィルム/粘着剤層/ガラス板の構成を有する積層体を作製した。
2EHA78部、NVP18部および2-ヒドロキシエチルアクリレート(HEA)4部からなるモノマー混合物を、光開始剤P1,P2の重量比1:1の混合物0.07部ととともに4つ口フラスコに投入し、窒素雰囲気下で上記高圧水銀ランプを用いて粘度(BH型粘度計、No.5ローター、10rpm、測定温度30℃)が約15Pa・sになるまで紫外線を照射して光重合させることにより、上記モノマー混合物の部分重合物を含むモノマーシロップを調製した。このモノマーシロップに、NVP10部、IBXA20部、HDDA0.15部、連鎖移動剤としてのα-メチルスチレン二量体(日油社製、商品名:ノフマー MSD)0.2部および光開始剤P1(オムニラッド651)0.5部を添加して混合することにより、粘着剤組成物C3を調製した。
剥離フィルムR1(三菱樹脂社製、MRF#38)の剥離面に上記で調製した粘着剤組成物C3を塗布し、剥離フィルムR2(三菱樹脂社製、MRE#38)を被せて空気を遮断した。この積層体の片側から、上記ブラックライトを使用して照度5mW/cm2の紫外線を照射した。このとき、粘着剤組成物C3の調製に用いられたエチレン性不飽和化合物全体の約5%が未反応のまま残るように(すなわち、重合転化率が約95%となるように)紫外線の照射時間を調節した。このようにして、上記粘着剤組成物C3の硬化物である粘着剤A3を、上記剥離フィルムR1,R2に挟まれた厚さ150μmの粘着剤層(基材レス粘着シート)の形態で得た。
この粘着剤A3を用いて、例1と同様にしてPETフィルム/粘着剤層/ガラス板の構成を有する積層体を作製した。
側鎖にベンゾフェノン構造を有するアクリル系共重合体(BASF社製、商品名:acResin A260UV、Tg:-39℃、Mw:19×104、BP当量:2mg/g)50部と、n-ブチルアクリレート(BA)34部と、NVP16部と、光開始剤P2(オムニラッド184)0.2部とを混合して、光架橋性粘着剤作製用の粘着剤組成物C4を調製した。この粘着剤組成物C4の粘度(BH型粘度計、No.5ローター、10rpm、測定温度30℃)は27Pa・sであり、有機溶媒含有量は1重量%未満であった。
粘着剤組成物C1に代えて粘着剤組成物C4を用いた他は例1と同様にして、粘着剤組成物C4の硬化物である光架橋性粘着剤A4を、剥離フィルムR1,R2に挟まれた厚さ150μmの粘着剤層(基材レス粘着シート)の形態で得た。
この光架橋性粘着剤A4を用いて、例1と同様にしてPETフィルム/粘着剤層/ガラス板の構成を有する積層体を作製した。
(1)光架橋前弾性率Gb’の測定
各例に係る粘着剤(基材レス粘着シート)を、厚さが約1.5mmになるように重ね合わせ、直径7.9mmの円盤状に打ち抜いて測定試料を作製した。この測定試料をパラレルプレートで挟み込み、粘弾性試験機(ARES、レオメトリックス社製)を用いて周波数1Hzのせん断歪みを与えながら、温度領域-70~150℃、5℃/分の昇温速度でせん断モードにより動的粘弾性測定を行い、80℃におけるせん断貯蔵弾性率Gb’を求めた。結果を表1に示した。
各例に係る粘着剤(基材レス粘着シート)を、剥離フィルムR1,R2に挟んだまま上記高圧水銀ランプを用いて片面側から照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射して光架橋させた後、剥離フィルムR1,R2を除いて約1.5mmになるように重ね合わせ、直径7.9mmの円盤状に打ち抜いて測定試料を作製した。この測定試料について、上記光架橋前弾性率Gb’の測定と同様にして動的粘弾性測定を行い、80℃におけるせん断貯蔵弾性率Gc’を求めた。結果を表1に示した。
上述したVOC測定試験に従って、各例に係る粘着剤(基材レス粘着シート)のVOC放散量を測定した。結果を表1に示した。
偏光板(日東電工製、商品名「REGQ-HC3」、厚さ92mm)の一方の表面に厚さ15μmの粘着剤を用いてアルミホイル(三菱アルミホイル製、商品名「ニッパクホイル」、厚さ12μm)を貼り合わせたものを、基材レス粘着シートの一方の表面に接合させる被着体として使用した。
各例に係る粘着剤(基材レス粘着シート)を、剥離フィルムR1,R2ごと60mm×120mmのサイズにカットした後、剥離フィルムR2を剥がし、露出した粘着面を上記被着体の偏光板側の表面にハンドローラーで貼り合わせた。次いで、上記粘着剤から剥離ライナーR2を剥がし、露出した粘着面をガラス板(松浪硝子工業社製、商品名「MICRO SLIDE GLASS」、品番「S」、厚さ1.3mm、ヘイズ0.1%、水縁磨)に貼り合わせた。このようにして、ガラス板/粘着剤/偏光板/アルミホイルの構成を有する積層体を得た。
この積層体に、オートクレーブ処理(50℃、0.5MPa、15分)を行った後、上記高圧水銀ランプを用いて上記ガラス板側から照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射したものを、耐久性評価用サンプルとした。
この評価用サンプルを85℃の環境下に24時間保存した後、23℃、50%RHの環境下で目視観察を行い、以下の2水準で耐久性を評価した。結果を表1の「密着耐久性」の欄に示した。なお、いずれの例に係る粘着シートを用いた場合も、上記耐久性評価用サンプルの作製直後には気泡は全く認められなかった。
E(Excellent):気泡の発生は認められなかった(密着耐久性に優れる)。
P(Poor):気泡の発生が明らかに認められた(密着耐久性に乏しい)。
各例に係る粘着剤(基材レス粘着シート)から剥離フィルムR2を剥がし、コロナ処理された厚さ75μmのPETフィルムに貼り合わせて片面粘着シートを作製した。これを幅20mm、長さ100mmのサイズにカットして試験片を作製した。
23℃、50%RHの環境下において、上記試験片から剥離フィルムR1を剥がし、露出した粘着面を被着体としてのガラス板(コーニング社製、ゴリラガラス3)に、2kgのゴムローラーを一往復させて圧着した。これにオートクレーブ処理(50℃、0.5MPa、15分)を行った後、上記高圧水銀ランプを用いて上記ガラス板側から照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射した。
その後、23℃、50%RHの環境下において、引張試験機(ミネベア社製、万能引張圧縮試験機、装置名「引張圧縮試験機、TCM-1kNB」)を用いて、引張速度300mm/分、剥離角度180度の条件で試験片のガラス板からの剥離強度を測定した。測定は3回行い、それらの平均値を幅10mm当たりの値(単位:N/10mm)に換算して表1に示した。
10 粘着剤層
10A 一方の表面(粘着面)
10B 他方の表面
20 基材
20A 第一面
20B 第二面(背面)
30,31,32 剥離ライナー
50 剥離ライナー付き粘着シート
70 光学部材
100 粘着シート付き部材
Claims (12)
- ベンゾフェノン構造を側鎖に有するポリマーを含み、
エチレン性不飽和化合物とベンゾフェノン構造含有成分とを含む粘着剤組成物の硬化物であり、かつ
揮発性有機化合物の放散量が500μg/g以下である、光架橋性粘着剤。 - 前記ベンゾフェノン構造含有成分は、ベンゾフェノン構造を側鎖に有するポリマーである、請求項1に記載の光架橋性粘着剤。
- 前記光架橋性粘着剤の80℃におけるせん断貯蔵弾性率Gb’[kPa]と、前記光架橋性粘着剤に高圧水銀ランプを用いて照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射して得られた光架橋物の80℃におけるせん断貯蔵弾性率Gc’[kPa]との関係が、以下の式:
Gc’[kPa]-Gb’[kPa]≧2kPa;
を満たす、請求項1または2に記載の光架橋性粘着剤。 - 前記光架橋性粘着剤に高圧水銀ランプを用いて照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射して得られた光架橋物の80℃におけるせん断貯蔵弾性率Gc’[kPa]が40kPa以上である、請求項1~3のいずれか一項に記載の光架橋性粘着剤。
- 請求項1~4のいずれか一項に記載の光架橋性粘着剤からなる粘着剤層を有する、粘着シート。
- 下記手順により測定される剥離強度が1.0N/10mm以上である、請求項5に記載の粘着シート。
[剥離強度の測定手順]
粘着剤層の表面を、2kgのゴムローラーを一往復させてガラス板に圧着し、オートクレーブ処理(50℃、0.5MPa、15分)を行った後、高圧水銀ランプを用いて前記ガラス板側から照度300mW/cm2、積算光量10000mJ/cm2の条件で紫外線を照射し、その後、25℃の雰囲気下、引張速度300mm/分、剥離角度180度の条件で前記粘着シートを前記ガラス板から引き剥がす際の剥離強度を測定する。 - 請求項1~4のいずれか一項に記載の光架橋性粘着剤と部材とを積層することと、
前記光架橋性粘着剤に含まれる前記ベンゾフェノン構造を反応させて該光架橋性粘着剤を光架橋させることと、
をこの順序で含む、積層体製造方法。 - ベンゾフェノン構造を側鎖に有するポリマー(A)とエチレン性不飽和化合物(B)とを含む粘着剤組成物を用意すること;および、
前記粘着剤組成物に活性エネルギー線を照射すること;
を包含し、
ここで、前記活性エネルギー線の照射は、前記エチレン性不飽和化合物(B)の有するエチレン性不飽和基を反応させ、かつ前記ポリマー(A)の有するベンゾフェノン構造を残存させるように行われる、光架橋性粘着剤製造方法。 - 前記粘着剤組成物は、前記エチレン性不飽和化合物(B)として、エチレン性不飽和基を1つ有する化合物(B1)を含む、請求項8に記載の方法。
- 前記粘着剤組成物は、前記エチレン性不飽和化合物(B)として、エチレン性不飽和基を2つ以上有する化合物(B2)を含む、請求項8または9に記載の方法。
- 前記粘着剤組成物は、さらに光開始剤(C)を含む、請求項8~10のいずれか一項に記載の方法。
- ベンゾフェノン構造を側鎖に有するポリマーを含む光架橋性粘着剤の製造に用いられる粘着剤組成物であって、
ベンゾフェノン構造を側鎖に有するポリマー(A)と、
エチレン性不飽和化合物(B)と、
波長300nm~500nmの光を吸収してラジカルを発生する光開始剤(C)と
を含み、
前記粘着剤組成物を構成するモノマー成分全体におけるエチレン性不飽和基を2つ以上有する化合物の重量分率が5重量%未満である、粘着剤組成物。
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17/632,261 US12492327B2 (en) | 2019-08-02 | 2020-07-28 | Photo-crosslinkable pressure-sensitive adhesive and use thereof |
| CN202080052401.5A CN114144488B (zh) | 2019-08-02 | 2020-07-28 | 光交联性粘合剂及其利用 |
| KR1020227006412A KR20220044299A (ko) | 2019-08-02 | 2020-07-28 | 광 가교성 점착제 및 그 이용 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-143392 | 2019-08-02 | ||
| JP2019143392 | 2019-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2021024862A1 true WO2021024862A1 (ja) | 2021-02-11 |
Family
ID=74502617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2020/028917 Ceased WO2021024862A1 (ja) | 2019-08-02 | 2020-07-28 | 光架橋性粘着剤およびその利用 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US12492327B2 (ja) |
| JP (1) | JP7720688B2 (ja) |
| KR (1) | KR20220044299A (ja) |
| CN (1) | CN114144488B (ja) |
| TW (1) | TWI908734B (ja) |
| WO (1) | WO2021024862A1 (ja) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022045130A1 (ja) * | 2020-08-28 | 2022-03-03 | 日東電工株式会社 | 光硬化性粘着シート |
| CN114635219A (zh) * | 2022-03-31 | 2022-06-17 | 业成科技(成都)有限公司 | 缓冲材料层、模压治具和压合工艺方法 |
| JP2023127040A (ja) * | 2022-03-01 | 2023-09-13 | 三菱ケミカル株式会社 | 活性エネルギー線硬化性粘着剤組成物、およびそれを用いてなる粘着剤、粘着テープ |
| EP4310117A1 (en) * | 2022-07-20 | 2024-01-24 | Arkema France | Curable compositions |
| CN118742855A (zh) * | 2022-02-22 | 2024-10-01 | 日产化学株式会社 | 包含自交联性聚合物的光固化性树脂组合物 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20240010881A1 (en) * | 2020-11-09 | 2024-01-11 | Denka Company Limited | Adhesive tape and processing method |
| JP7818978B2 (ja) * | 2022-02-14 | 2026-02-24 | 東京応化工業株式会社 | 接着剤組成物、積層体、積層体の製造方法、及び電子部品の製造方法 |
| WO2024176580A1 (ja) * | 2023-02-24 | 2024-08-29 | リンテック株式会社 | ワーク加工用シートおよびその使用方法 |
| CN119547198A (zh) * | 2023-02-24 | 2025-02-28 | 琳得科株式会社 | 工件加工用片及其使用方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62284651A (ja) * | 1986-05-19 | 1987-12-10 | ミネソタ マイニング アンド マニユフアクチユアリング カンパニ− | 皮膚用感圧接着剤組成物 |
| JP2010509439A (ja) * | 2006-11-07 | 2010-03-25 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | アクリルホットメルト接着剤 |
| JP2013040256A (ja) * | 2011-08-12 | 2013-02-28 | Three M Innovative Properties Co | 放射線硬化性粘着シート |
| JP2015214601A (ja) * | 2014-05-07 | 2015-12-03 | 積水フーラー株式会社 | 放射線硬化型ホットメルト粘着剤 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847137A (en) | 1986-05-19 | 1989-07-11 | Minnesota Mining And Manufacturing Company | Pressure-sensitive adhesive crosslinked by copolymerizable aromatic ketone monomers |
| CA2236555C (en) * | 1997-06-05 | 2002-07-16 | Joseph John Spanier | Low voc ultra high solids thermosetting coating composition and method of its preparation |
| JP2009051915A (ja) * | 2007-08-24 | 2009-03-12 | Nitto Denko Corp | 光重合型のアクリル系粘着剤および粘着シート |
| JP5477944B2 (ja) * | 2009-04-03 | 2014-04-23 | 日東電工株式会社 | 粘着製品 |
| JP2012140497A (ja) | 2010-12-28 | 2012-07-26 | Toagosei Co Ltd | 活性エネルギー線硬化型組成物及び粘着剤 |
| KR20120140497A (ko) | 2011-06-21 | 2012-12-31 | 대우조선해양 주식회사 | Dme fpso의 전기 생산 장치 및 방법 |
| JP6530410B2 (ja) * | 2013-09-10 | 2019-06-12 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | オキシムエステル光開始剤 |
| WO2019065375A1 (ja) * | 2017-09-28 | 2019-04-04 | 日東電工株式会社 | 補強フィルム |
| KR102144950B1 (ko) | 2017-09-29 | 2020-08-14 | 주식회사 엘지화학 | 점착 조성물 및 점착 필름 |
| CN113646393B (zh) * | 2019-06-28 | 2023-09-19 | 三菱瓦斯化学株式会社 | 树脂组合物、树脂片、多层印刷电路板和半导体装置 |
-
2020
- 2020-07-28 CN CN202080052401.5A patent/CN114144488B/zh active Active
- 2020-07-28 US US17/632,261 patent/US12492327B2/en active Active
- 2020-07-28 KR KR1020227006412A patent/KR20220044299A/ko not_active Ceased
- 2020-07-28 JP JP2020127561A patent/JP7720688B2/ja active Active
- 2020-07-28 WO PCT/JP2020/028917 patent/WO2021024862A1/ja not_active Ceased
- 2020-07-31 TW TW109125996A patent/TWI908734B/zh active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62284651A (ja) * | 1986-05-19 | 1987-12-10 | ミネソタ マイニング アンド マニユフアクチユアリング カンパニ− | 皮膚用感圧接着剤組成物 |
| JP2010509439A (ja) * | 2006-11-07 | 2010-03-25 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | アクリルホットメルト接着剤 |
| JP2013040256A (ja) * | 2011-08-12 | 2013-02-28 | Three M Innovative Properties Co | 放射線硬化性粘着シート |
| JP2015214601A (ja) * | 2014-05-07 | 2015-12-03 | 積水フーラー株式会社 | 放射線硬化型ホットメルト粘着剤 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022045130A1 (ja) * | 2020-08-28 | 2022-03-03 | 日東電工株式会社 | 光硬化性粘着シート |
| CN118742855A (zh) * | 2022-02-22 | 2024-10-01 | 日产化学株式会社 | 包含自交联性聚合物的光固化性树脂组合物 |
| US12339586B2 (en) | 2022-02-22 | 2025-06-24 | Nissan Chemical Corporation | Photocurable resin composition containing self-crosslinkable polymer |
| JP2023127040A (ja) * | 2022-03-01 | 2023-09-13 | 三菱ケミカル株式会社 | 活性エネルギー線硬化性粘着剤組成物、およびそれを用いてなる粘着剤、粘着テープ |
| CN114635219A (zh) * | 2022-03-31 | 2022-06-17 | 业成科技(成都)有限公司 | 缓冲材料层、模压治具和压合工艺方法 |
| CN114635219B (zh) * | 2022-03-31 | 2023-09-05 | 业成科技(成都)有限公司 | 缓冲材料层、模压治具和压合工艺方法 |
| EP4310117A1 (en) * | 2022-07-20 | 2024-01-24 | Arkema France | Curable compositions |
| WO2024018040A1 (en) * | 2022-07-20 | 2024-01-25 | Arkema France | Curable compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| US20220275250A1 (en) | 2022-09-01 |
| CN114144488A (zh) | 2022-03-04 |
| JP7720688B2 (ja) | 2025-08-08 |
| TWI908734B (zh) | 2025-12-21 |
| JP2021025043A (ja) | 2021-02-22 |
| KR20220044299A (ko) | 2022-04-07 |
| CN114144488B (zh) | 2025-04-04 |
| US12492327B2 (en) | 2025-12-09 |
| TW202113016A (zh) | 2021-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7720688B2 (ja) | 光架橋性粘着剤およびその利用 | |
| JP6632846B2 (ja) | 粘着シート | |
| US12215258B2 (en) | Pressure-sensitive adhesive sheet and use thereof | |
| WO2020196434A1 (ja) | 粘着剤組成物、粘着剤層、及び粘着シート | |
| JP2021161192A (ja) | 剥離フィルム付き粘着シート | |
| CN111978883A (zh) | 粘合片 | |
| JP7650716B2 (ja) | 粘着剤組成物、光硬化性粘着剤層、及び光硬化性粘着シート | |
| JP7696246B2 (ja) | 光硬化性粘着シート | |
| JP7733975B2 (ja) | 粘着シートおよびその利用 | |
| US20190106605A1 (en) | Pressure-sensitive adhesive sheet | |
| CN114051521B (zh) | 粘合片及其利用 | |
| CN115989143B (zh) | 粘合剂组合物、光固化性粘合剂层和光固化性粘合片 | |
| JP2025023630A (ja) | 光学粘着シート | |
| JP2025023631A (ja) | 光学粘着シート | |
| JP2025023632A (ja) | 光学粘着シート | |
| WO2024043165A1 (ja) | 硬化性組成物および複合材料 | |
| CN116806249A (zh) | 粘合剂组合物、粘合片材、粘合剂组合物的制造方法以及对水或水蒸气的存在进行检测的方法 |
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: 20849269 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 20227006412 Country of ref document: KR Kind code of ref document: A |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 20849269 Country of ref document: EP Kind code of ref document: A1 |
|
| WWR | Wipo information: refused in national office |
Ref document number: 1020227006412 Country of ref document: KR |
|
| WWG | Wipo information: grant in national office |
Ref document number: 202080052401.5 Country of ref document: CN |
|
| WWR | Wipo information: refused in national office |
Ref document number: 1020227006412 Country of ref document: KR |
|
| WWC | Wipo information: continuation of processing after refusal or withdrawal |
Ref document number: 1020227006412 Country of ref document: KR |

