CN108707442B - Adhesive composition and adhesive sheet - Google Patents
Adhesive composition and adhesive sheet Download PDFInfo
- Publication number
- CN108707442B CN108707442B CN201810292799.4A CN201810292799A CN108707442B CN 108707442 B CN108707442 B CN 108707442B CN 201810292799 A CN201810292799 A CN 201810292799A CN 108707442 B CN108707442 B CN 108707442B
- Authority
- CN
- China
- Prior art keywords
- meth
- mass
- acrylate
- adhesive composition
- acrylic copolymer
- 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.)
- Active
Links
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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/005—Presence of polyester in the release coating
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Abstract
The invention provides a pressure-sensitive adhesive sheet which does not become a grapefruit peel shape, is excellent in weather resistance, foaming resistance and removability, and does not cause zipper sound, and also provides a pressure-sensitive adhesive composition from which the pressure-sensitive adhesive sheet can be obtained. The adhesive composition of the present invention is an adhesive composition comprising a (meth) acrylic copolymer (a) which is a copolymer of monomer components comprising an alkyl (meth) acrylate ester having a homopolymer Tg of 0 ℃ or higher, an alkyl (meth) acrylate ester having a homopolymer Tg of less than 0 ℃ and a carboxyl group-containing monomer; the (meth) acrylic copolymer (B) is a copolymer of monomer components comprising an alkyl methacrylate and an amino group-containing monomer; the amount of the polymerization initiator contained in 100 wt% solids of the adhesive composition is 800ppm or less.
Description
Technical Field
The invention relates to an adhesive composition and an adhesive sheet.
Background
Conventionally, an adhesive film has been attached to a transparent plastic material such as Polycarbonate (PC) or polymethyl methacrylate (PMMA) for the purpose of protecting the plastic material and preventing the plastic material from scattering. Further, the adhesive film is also attached to protect the glass and prevent the glass from scattering.
In a display of an image display device such as a liquid crystal display device, a front panel such as a plastic plate or a glass plate is generally provided on the outermost side in order to protect internal components. A pressure-sensitive adhesive sheet for preventing scattering may be attached to the front panel to prevent scattering of plastic or glass when the front panel is broken by an impact.
The scattering prevention pressure-sensitive adhesive sheet generally includes a polyethylene terephthalate (PET) film and a pressure-sensitive adhesive layer provided on the PET film.
As the adhesive used for such an adhesive layer, weather resistance, transparency, ease of controlling adhesive force, and the like are required. Further, the occurrence of foaming and bulging seriously impairs the appearance of the adhesive sheet, and therefore a property of preventing them from occurring, i.e., resistance to foaming, is also required.
An adhesive having weather resistance, transparency, ease of controlling adhesive force, foaming resistance, and the like, which satisfy these requirements, has been proposed (for example, see patent document 1).
Patent document 1 proposes an adhesive composition containing a resin composition (1) and a resin composition (2), wherein the resin composition (1) is obtained by copolymerizing an alkyl (meth) acrylate and a carboxyl group-containing copolymerizable unsaturated monomer, and has a weight average molecular weight of 80 ten thousand or more; the resin composition (2) is obtained by copolymerizing 1 or 2 or more kinds of monomers selected from alkyl methacrylate, cycloalkyl methacrylate, benzyl methacrylate and styrene, and an amino group-containing copolymerizable unsaturated monomer, and has a weight average molecular weight of 10 ten thousand or less. Patent document 1 discloses that by combining a main polymer having a carboxyl group and a low-molecular-weight polymer having an amino group, the foaming resistance is improved by the interaction between the carboxyl group and the amino group, and there is no problem in properties such as weather resistance, transparency, and easiness of controlling the adhesive force.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3516035
Disclosure of Invention
Technical problem to be solved by the invention
In recent years, a pressure-sensitive adhesive sheet for use in applications such as prevention of scattering is required to have further improved physical properties such as excellent removability (japanese: リワーク property) and no zipper sound phenomenon (japanese: ジッピング phenomenon) in addition to performances such as weather resistance, transparency, easiness in control of adhesive strength, and foaming resistance.
In addition, when a pressure-sensitive adhesive sheet is produced and used using a conventional pressure-sensitive adhesive composition, the pressure-sensitive adhesive layer may be formed into a so-called shaddock peel shape (Japanese: ゆず flesh shape). The appearance of the pressure-sensitive adhesive sheet that becomes a grapefruit peel shape is greatly deteriorated, and therefore improvement is required.
The purpose of the present invention is to provide a pressure-sensitive adhesive sheet that does not become grapefruit peel-like, has excellent weather resistance, foaming resistance, and removability, and does not cause zipper sound, and to provide a pressure-sensitive adhesive composition from which the pressure-sensitive adhesive sheet can be obtained.
Technical scheme for solving technical problem
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that a polymerization initiator remaining in an adhesive composition causes a reaction due to factors such as storage of the adhesive sheet in a high-temperature environment and UV irradiation, which causes a shaddock peel phenomenon in an adhesive layer. Therefore, when an adhesive composition having excellent weather resistance, i.e., UV resistance was used, it was found that the amount of the residual initiator in the adhesive composition was important in order to obtain an adhesive sheet in which the adhesive layer did not become a grapefruit peel and to prevent the adhesive layer from becoming a grapefruit peel, and the present invention was completed.
That is, the present invention relates to, for example, the following [1] to [3 ].
[1] An adhesive composition comprising a (meth) acrylic copolymer (A) which is a copolymer of monomer components comprising 13 to 35 mass% of a homopolymer of an alkyl (meth) acrylate having a glass transition temperature (Tg) of 0 ℃ or higher and having an alkyl group with 1 to 12 carbon atoms, 55 to 80 mass% of a homopolymer of an alkyl (meth) acrylate having a glass transition temperature (Tg) of less than 0 ℃ and having an alkyl group with 1 to 12 carbon atoms, and 3.5 to 10 mass% of a carboxyl group-containing monomer; the (meth) acrylic copolymer (B) is a copolymer of monomer components comprising an alkyl methacrylate having 1 to 20 carbon atoms in the alkyl group and an amino group-containing monomer; the adhesive composition comprises 1 to 40 parts by mass of a (meth) acrylic copolymer (B) and 0.01 to 5 parts by mass of a crosslinking agent (C) relative to 100 parts by mass of the (meth) acrylic copolymer (A); the amount of the polymerization initiator contained in 100 wt% of the solid content of the adhesive composition is 800ppm or less.
[2] The adhesive composition according to the above [1], wherein the (meth) acrylic copolymer (B) has a weight-average molecular weight of 1000 to 50000 and a glass transition temperature of 80 ℃ or higher.
[3] An adhesive sheet comprising the adhesive composition according to [1] or [2 ].
Effects of the invention
The present invention provides a pressure-sensitive adhesive sheet which does not become a grapefruit peel, has excellent weather resistance, foaming resistance and removability, and does not cause a zipper sound phenomenon, and a pressure-sensitive adhesive composition from which the pressure-sensitive adhesive sheet can be obtained.
Detailed Description
Next, the present invention will be specifically described.
In the present invention, "(meth) acrylic acid" is used as a general meaning of acrylic acid and methacrylic acid. That is, "(meth) acrylic acid alkyl ester" is used as a general meaning of acrylic acid alkyl ester and methacrylic acid alkyl ester. Furthermore, the method is simple. "(meth) acrylate" is used as the meaning of the generic term acrylate and methacrylate.
[ adhesive composition ]
The adhesive composition of the present invention is an adhesive composition comprising a (meth) acrylic copolymer (A) and a (meth) acrylic copolymer (B) and a crosslinking agent (C), wherein the (meth) acrylic copolymer (A) is a copolymer of monomer components comprising 13 to 35 mass% of a homopolymer of an alkyl (meth) acrylate having a glass transition temperature (Tg) of 0 ℃ or higher and 1 to 12 carbon atoms in the alkyl group, 55 to 80 mass% of a homopolymer of an alkyl (meth) acrylate having a glass transition temperature (Tg) of less than 0 ℃ and 1 to 12 carbon atoms in the alkyl group, and 3.5 to 10 mass% of a carboxyl group-containing monomer; the (meth) acrylic copolymer (B) is a copolymer of monomer components comprising an alkyl methacrylate having 1 to 20 carbon atoms in the alkyl group and an amino group-containing monomer; the adhesive composition comprises 1 to 40 parts by mass of a (meth) acrylic copolymer (B) and 0.01 to 5 parts by mass of a crosslinking agent (C) per 100 parts by mass of the (meth) acrylic copolymer (A); the amount of the polymerization initiator contained in 100 wt% of the solid content of the adhesive composition is 800ppm or less.
The pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention is preferably a pressure-sensitive adhesive sheet which does not take a grapefruit peel-like form, has excellent weather resistance, foaming resistance and removability, and does not cause a zipper sound phenomenon.
((meth) acrylic copolymer (A))
The adhesive composition of the present invention contains a (meth) acrylic copolymer (a). The (meth) acrylic copolymer (A) is a copolymer of monomer components comprising 13 to 35 mass% of a homopolymer of an alkyl (meth) acrylate (a-1) having a glass transition temperature (Tg) of 0 ℃ or higher and having an alkyl group with 1 to 12 carbon atoms, 55 to 80 mass% of a homopolymer of an alkyl (meth) acrylate (a-2) having a glass transition temperature (Tg) of less than 0 ℃ and having an alkyl group with 1 to 12 carbon atoms, and 3.5 to 10 mass% of a carboxyl group-containing monomer (a-3).
((meth) acrylic acid alkyl ester (a-1))
The alkyl (meth) acrylate (a-1) is an alkyl (meth) acrylate having a homopolymer glass transition temperature (Tg) of 0 ℃ or higher and an alkyl group having 1 to 12 carbon atoms.
The alkyl (meth) acrylate (a-1) is preferably a homopolymer having a glass transition temperature (Tg) of 0 to 120 ℃ and more preferably 0 to 100 ℃. When the Tg is within the above range, the durability of the resulting adhesive layer can be improved, which is preferable in this point.
The alkyl (meth) acrylate (a-1) preferably has 1 to 8 carbon atoms in the alkyl group, more preferably 1 to 4 carbon atoms in the alkyl group. The alkyl group may be a linear alkyl group or a branched alkyl group.
Specific examples of the alkyl (meth) acrylate (a-1) include methyl acrylate (Tg:8 ℃ C.), n-propyl acrylate (Tg:3 ℃ C.), t-butyl acrylate (Tg:43 ℃ C.), pentyl acrylate (Tg:22 ℃ C.), methyl methacrylate (Tg:105 ℃ C.), ethyl methacrylate (Tg:65 ℃ C.), n-propyl methacrylate (Tg:35 ℃ C.), isopropyl methacrylate (Tg:81 ℃ C.), n-butyl methacrylate (Tg:20 ℃ C.), isobutyl methacrylate (Tg:48 ℃ C.), and t-butyl methacrylate (Tg:118 ℃ C.).
The alkyl (meth) acrylate (a-1) may be used singly or in combination of 2 or more. The alkyl (meth) acrylate (a-1) is preferably at least 1 monomer selected from the group consisting of methyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and t-butyl methacrylate, more preferably methyl acrylate and t-butyl acrylate, and particularly preferably methyl acrylate.
In the present invention, the glass transition temperature (Tg) of the homopolymer of each monomer may be, for example, a value described in Polymer Handbook fourth Edition (Wiley-Interscience 2003).
((meth) acrylic acid alkyl ester (a-2))
The alkyl (meth) acrylate (a-2) is an alkyl (meth) acrylate having a homopolymer glass transition temperature (Tg) of less than 0 ℃ and an alkyl group having 1 to 12 carbon atoms.
The glass transition temperature (Tg) of the homopolymer as the alkyl (meth) acrylate (a-2) is preferably from-80 to-10 ℃ and more preferably from-65 to-10 ℃. When Tg is within the above range, the pressure-sensitive adhesive layer obtained has appropriate stress relaxation properties, which is preferable.
The alkyl (meth) acrylate (a-2) preferably has 2 to 12 carbon atoms in the alkyl group, more preferably 4 to 10 carbon atoms in the alkyl group. The alkyl group may be a linear alkyl group or a branched alkyl group.
Specific examples of the alkyl (meth) acrylate (a-2) include ethyl acrylate (Tg: -24 ℃ C.), isopropyl acrylate (Tg: -3 ℃ C.), n-butyl acrylate (Tg: -50 ℃ C.), isobutyl acrylate (Tg: -40 ℃ C.), n-hexyl acrylate (Tg: -57 ℃ C.), n-octyl acrylate (Tg: -65 ℃ C.), isooctyl acrylate (Tg: -58 ℃ C.), 2-ethylhexyl acrylate (Tg: -70 ℃ C.), nonyl acrylate (Tg: -58 ℃ C.), lauryl acrylate (Tg: -3 ℃ C.), n-pentyl methacrylate (Tg: -5 ℃ C.), n-hexyl methacrylate (Tg: -5 ℃ C.), n-octyl methacrylate (Tg: -20 ℃ C.), isooctyl methacrylate (Tg: -45 ℃ C.) 2-ethylhexyl methacrylate (Tg: -10 ℃ C.), isodecyl methacrylate (Tg: -41 ℃ C.), lauryl methacrylate (Tg: -65 ℃ C.).
The alkyl (meth) acrylate (a-2) may be used singly or in combination of 1 or more. As the alkyl (meth) acrylate (a-2), at least 1 monomer selected from the group consisting of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate is preferable, n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isodecyl methacrylate, lauryl methacrylate is more preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable.
(carboxyl group-containing monomer (a-3))
The carboxyl group-containing monomer (a-3) is a monomer having a carboxyl group in the molecule.
By using the carboxyl group-containing monomer (a-3) as a monomer component used for obtaining the (meth) acrylic copolymer (A), it is possible to interact with an amino group of the (meth) acrylic copolymer (B) described later, and a pressure-sensitive adhesive sheet having excellent aging properties (Japanese character: エージング properties) can be obtained.
Specific examples of the carboxyl group-containing monomer (a-3) include acrylic acid, methacrylic acid, β -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, succinic acid mono (meth) acryloyloxyethyl ester, ω -carboxypolycaprolactone mono (meth) acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like.
As the carboxyl group-containing monomer (a-3), 1 kind may be used alone, or 2 or more kinds may be used.
As the carboxyl group-containing monomer (a-3), at least 1 monomer selected from acrylic acid, methacrylic acid, and β -carboxyethyl (meth) acrylate is preferably used, and at least 1 monomer selected from acrylic acid and methacrylic acid is more preferably used. These monomers are industrially readily available and are therefore preferred.
(monomer component of (meth) acrylic copolymer (A))
As described above, the (meth) acrylic copolymer (A) is a copolymer of monomer components comprising 13 to 35 mass% of an alkyl (meth) acrylate (a-1), 55 to 80 mass% of an alkyl (meth) acrylate (a-2), and 3.5 to 10 mass% of a carboxyl group-containing monomer (a-3). However, the total monomer component was 100 mass%.
The monomer component may contain monomers other than (a-1) to (a-3) as long as they are contained within the above-mentioned ranges. Examples of the monomers other than (a-1) to (a-3) include alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate; cyclic alkyl group-containing (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; aromatic ring-containing (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. The monomer component preferably does not contain an amino group-containing monomer described later.
When monomers other than (a-1) to (a-3) are used, the monomers other than (a-1) to (a-3) are usually 20% by mass or less, preferably 10% by mass or less, assuming that the total monomer components are 100% by mass.
The monomer component preferably contains 13 to 35 mass% of an alkyl (meth) acrylate (a-1), 55 to 80 mass% of an alkyl (meth) acrylate (a-2), and 3.5 to 10 mass% of a carboxyl group-containing monomer (a-3), and preferably contains 15 to 30 mass% of an alkyl (meth) acrylate (a-1), 60 to 78 mass% of an alkyl (meth) acrylate (a-2), and 4 to 10 mass% of a carboxyl group-containing monomer (a-3).
(production conditions of (meth) acrylic copolymer (A))
The (meth) acrylic copolymer (a) used in the present invention can be obtained by copolymerizing the above monomer components.
The copolymerization method can be carried out by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or a suspension polymerization method, and among them, the solution polymerization method is preferable.
Specifically, the (meth) acrylic copolymer (A) can be obtained by charging a polymerization solvent and monomer components into a reaction vessel, adding a polymerization initiator under an inert gas atmosphere such as nitrogen, setting the reaction starting temperature to 40 to 100 ℃ in general, and 50 to 90 ℃ in preferred embodiments, and reacting the reaction system for 3 to 20 hours while maintaining the temperature of 50 to 90 ℃ in general, and 60 to 90 ℃ in preferred embodiments.
Examples of the polymerization initiator include azo initiators and peroxide polymerization initiators.
Examples of the azo compound include 2,2 ' -azobisisobutyronitrile, 2 ' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2 ' -azobis (2-cyclopropylpropionitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2-methylbutyronitrile), 1 ' -azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2, 4-dimethylvaleronitrile, 2 ' -azobis (2-amidinopropane) dihydrochloride, 2 ' -azobis (N, N ' -dimethyleneisobutyramidine), 2, azo compounds such as 2 '-azobis [ 2-methyl-N- (2-hydroxyethyl) -propionamide ], 2' -azobis (isobutyramide) dihydrate, 4 '-azobis (4-cyanovaleric acid), 2' -azobis (2-cyanopropanol), dimethyl-2, 2 '-azobis (2-methylpropionate), and 2, 2' -azobis (2-methyl-N- (2-hydroxyethyl) propionamide).
Examples of the peroxide-based polymerization initiator include t-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, hexanoyl peroxide and diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl peroxypivalate, 2-bis (4, 4-di-tert-butylcyclohexyl peroxy) propane, 2-bis (4, 4-di-tert-pentylcyclohexyl peroxy) propane, 2-bis (4, 4-di-tert-octylcyclohexyl peroxy) propane, 2-bis (4, 4-di-alpha-cumylcyclohexyl peroxy) propane, 2-bis (4, 4-di-tert-butylcyclohexyl peroxy) butane and 2, 2-bis (4, 4-di-tert-octylcyclohexyl peroxy) butane.
The polymerization initiator may be used alone in 1 kind, or may be used in 2 or more kinds. Further, it is not limited to add the polymerization initiator a plurality of times during the polymerization.
The polymerization initiator is used in an amount of usually 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass, based on 100 parts by mass of the monomer component forming the (meth) acrylic copolymer (a). In the polymerization reaction, a polymerization initiator, a chain transfer agent, a polymerizable monomer, and a polymerization solvent may be added as appropriate.
Examples of the polymerization solvent used in the solution polymerization include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; ethers such as diethyl ether, isopropyl ether, 1, 2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenetole, and diphenyl ether; halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1, 2-dichloroethane, chlorobenzene, and the like; esters such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethyl sulfoxide and sulfolane.
The polymerization solvent may be used alone in 1 kind, or 2 or more kinds.
Physical Properties of (meth) acrylic copolymer (A)
The weight average molecular weight (Mw) of the (meth) acrylic copolymer (a) measured by, for example, gel permeation chromatography (GPC method) is usually 40 ten thousand or more, preferably 50 to 150 ten thousand, more preferably 60 to 130 ten thousand, and further preferably 70 to 120 ten thousand in terms of polystyrene. When Mw is not less than the lower limit, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is excellent in durability and cohesive force, which is preferable. When Mw is not more than the above upper limit, the coatability of the adhesive composition is good, which is preferable.
The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the (meth) acrylic copolymer (A) as measured by GPC is usually 1.5 to 20, preferably 2 to 18, and more preferably 2 to 15. When Mw/Mn is not less than the lower limit, it is preferable in that adhesiveness between the pressure-sensitive adhesive layer and the substrate in the pressure-sensitive adhesive sheet and adhesiveness between the pressure-sensitive adhesive sheet and an adherend are exhibited. When the Mw/Mn is not more than the above upper limit, the heat resistance is excellent and the durability is maintained, which is preferable.
The glass transition temperature (Tg) of the (meth) acrylic copolymer (A) as calculated by the Fox equation is usually-70 to 0 ℃ and preferably-70 to-20 ℃. In such a form, an adhesive having excellent adhesive strength can be obtained.
The amount of the polymerization initiator (residual initiator amount) measured by a method described in examples (gas chromatograph-mass spectrometer (GCMS)) described later is usually 800ppm or less, preferably 750ppm or less, and more preferably 700ppm or less, with respect to 100% by weight of the (meth) acrylic copolymer (a). In the present invention, ppm means ppm based on weight, that is, ppmw (parts per million weight: parts per million by weight). The lower limit of the amount of the residual initiator is not particularly limited, but is, for example, 50ppm or more based on 100% by weight of the (meth) acrylic copolymer (A).
The amount of the polymerization initiator contained in the (meth) acrylic copolymer (a) can be increased or decreased by, for example, adjusting the production conditions of the (meth) acrylic copolymer (a). For example, the reaction time in the production of the (meth) acrylic copolymer (a) tends to be prolonged, the reaction temperature tends to be increased, and an appropriate amount of an initiator tends to be used. On the contrary, the reaction time is shortened, the reaction temperature is lowered, and the amount of the initiator used is increased.
By setting the amount of the residual initiator of the (meth) acrylic copolymer (a) to the above range, the amount of the residual initiator of the adhesive composition of the present invention can be set to 800ppm or less. According to the studies of the present inventors, it was found that by setting the residual initiator amount of the adhesive composition to 800ppm or less, side reactions of the conventional adhesive sheet due to factors such as storage in a high-temperature environment and UV irradiation can be suppressed, and the adhesive layer can be prevented from becoming a grapefruit peel. Therefore, by controlling the amount of the residual initiator in the adhesive composition, an adhesive sheet having excellent weather resistance, foaming resistance and removability and free from the zipper sound phenomenon can be obtained.
((meth) acrylic copolymer (B))
The adhesive composition of the present invention contains a (meth) acrylic copolymer (B). The (meth) acrylic copolymer (B) is a copolymer of monomer components comprising an alkyl methacrylate (B-1) having 1 to 20 carbon atoms in the alkyl group and an amino group-containing monomer (B-2).
(alkyl methacrylate (b-1))
The alkyl methacrylate (b-1) is an alkyl methacrylate having 1 to 20 carbon atoms in the alkyl group.
The alkyl methacrylate (b-1) preferably has 1 to 18 carbon atoms in the alkyl group, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms in the alkyl group.
Examples of the alkyl methacrylate (b-1) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, undecyl methacrylate, lauryl methacrylate, stearyl methacrylate and isostearyl methacrylate. These compounds may be used alone in 1 kind, or in 2 or more kinds.
As the alkyl methacrylate (b-1), at least 1 monomer selected from the group consisting of methyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate and isostearyl methacrylate is preferable, and at least 1 monomer selected from the group consisting of methyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and 2-ethylhexyl methacrylate is more preferable.
(amino group-containing monomer (b-2))
The amino group-containing monomer (b-2) is a monomer having an amino group in the molecule. The amino group-containing monomer (b-2) may have 1 amino group in one molecule, or may have 2 or more amino groups.
Examples of the amino group-containing monomer (b-2) include N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate.
As the amino group-containing monomer (b-2), 1 kind may be used alone, or 2 or more kinds may be used.
The (meth) acrylic copolymer (B) obtained by copolymerizing the amino group-containing monomer (B-2) is preferable because it has excellent compatibility with the (meth) acrylic copolymer (A).
(monomer component of (meth) acrylic copolymer (B))
As described above, the (meth) acrylic copolymer (B) is a copolymer of monomer components comprising an alkyl methacrylate (B-1) and an amino group-containing monomer (B-2).
The monomer component preferably contains 80 to 98 mass% of an alkyl methacrylate (b-1) and 2 to 20 mass% of an amino group-containing monomer (b-2), more preferably 85 to 96 mass% of an alkyl methacrylate (b-1) and 4 to 10 mass% of an amino group-containing monomer (b-2). However, the total monomer component was 100 mass%.
The monomer component may contain only (b-1) and (b-2), or may further contain monomers other than (b-1) and (b-2). Examples of the monomer other than (b-1) and (b-2) include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, undecyl acrylate, lauryl acrylate, stearyl acrylate, and isostearyl acrylate; alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate; cyclic alkyl group-containing (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; aromatic ring-containing (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. In addition, the monomer component preferably does not contain the above-mentioned carboxyl group-containing monomer.
When monomers other than (b-1) and (b-2) are used, the monomers other than (b-1) and (b-2) are usually 15% by mass or less, preferably 10% by mass or less, assuming that the total monomer components are 100% by mass.
(production conditions of (meth) acrylic acid-based copolymer (B))
The (meth) acrylic copolymer (B) used in the present invention can be obtained by copolymerizing the above monomer components.
The copolymerization method can be carried out by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, or a suspension polymerization method, and among them, the solution polymerization method is preferable.
Specifically, the (meth) acrylic copolymer (B) can be obtained by charging a polymerization solvent and monomer components into a reaction vessel, adding a polymerization initiator under an inert gas atmosphere such as nitrogen, setting the reaction starting temperature to be usually 40 to 100 ℃, preferably 50 to 90 ℃, and reacting the reaction system for 4 to 20 hours while maintaining the temperature of the reaction system to be usually 50 to 90 ℃, preferably 60 to 90 ℃.
As the polymerization initiator, the polymerization initiators described in the above item ((production conditions of the (meth) acrylic copolymer (a)) can be suitably used. The polymerization initiator used for producing the (meth) acrylic copolymer (a) and the polymerization initiator used for producing the (meth) acrylic copolymer (B) may be the same or different.
The polymerization initiator is used in an amount of usually 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass, based on 100 parts by mass of the monomer component forming the (meth) acrylic copolymer (B). In the polymerization reaction, a polymerization initiator, a chain transfer agent, a polymerizable monomer, and a polymerization solvent may be added as appropriate.
As the polymerization solvent used in the solution polymerization, the polymerization solvent described in the above item ((production conditions of the (meth) acrylic copolymer (a)) can be suitably used. The polymerization solvent used for the production of the (meth) acrylic copolymer (a) and the polymerization solvent used for the production of the (meth) acrylic copolymer (B) may be the same or different.
Physical Properties of (meth) acrylic copolymer (B)
The weight average molecular weight (Mw) of the (meth) acrylic copolymer (B) as measured by, for example, gel permeation chromatography (GPC method) is usually 1000 to 50000, preferably 2000 to 30000, more preferably 3000 to 10000 in terms of polystyrene. When the content is within the above range, the compatibility with the (meth) acrylic copolymer (A) is good, which is preferable.
The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the (meth) acrylic copolymer (B) as measured by GPC is usually 1.1 to 10, preferably 1.2 to 8, more preferably 1.2 to 7, and still more preferably 1.3 to 6.5.
The glass transition temperature (Tg) of the (meth) acrylic copolymer (B) as calculated by the Fox equation is usually 80 ℃ or higher, preferably 85 to 120 ℃, more preferably 90 to 110 ℃. In such a form, a pressure-sensitive adhesive having excellent durability can be obtained.
The amount of the polymerization initiator (residual initiator amount) measured by a method described in examples (gas chromatograph-mass spectrometer (GCMS)) described later is usually 200ppm or less, preferably 150ppm or less, and more preferably 100ppm or less, with respect to 100% by weight of the (meth) acrylic copolymer (B). The lower limit of the amount of the residual initiator is not particularly limited, but is preferably, for example, 10ppm or more based on 100% by weight of the (meth) acrylic copolymer (B).
The amount of the polymerization initiator contained in the (meth) acrylic copolymer (B) can be increased or decreased by, for example, adjusting the production conditions of the (meth) acrylic copolymer (B). For example, the reaction time in the production of the (meth) acrylic copolymer (B) is prolonged, the reaction temperature is increased, and an appropriate amount of an initiator is used, which tends to decrease. On the contrary, the reaction time is shortened, the reaction temperature is lowered, and the amount of the initiator used is increased.
By setting the amount of the residual initiator of the (meth) acrylic copolymer (B) within the above range, the amount of the residual initiator of the adhesive composition of the present invention can be set to 800ppm or less. According to the studies of the present inventors, it was found that when the amount of the residual initiator in the adhesive composition is 800ppm or less, side reactions of the adhesive sheet due to factors such as storage in a high-temperature environment and UV irradiation can be suppressed, and the adhesive layer can be prevented from becoming a grapefruit peel. Therefore, by controlling the amount of the residual initiator in the adhesive composition, an adhesive sheet having excellent weather resistance, foaming resistance and removability and free from the zipper sound phenomenon can be obtained.
(crosslinking agent (C))
The adhesive composition of the present invention contains a crosslinking agent (C).
The crosslinking agent (C) is not particularly limited, and an epoxy crosslinking agent, an isocyanate crosslinking agent, a metal chelate compound, or the like can be used. As the crosslinking agent, can use a single kind, can also use more than 2 kinds.
Examples of the epoxy-based crosslinking agent include (1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N' -tetraglycidylmethylm-tolyldimethylamine, N, N, N ', N' -tetraglycidylaminotoluene, triglycidyl isocyanate, m-N, N-diglycidylaminophenylglycidyl ether, N, N-diglycidyltoluidine, N, N-diglycidylaniline, pentaerythritol polyglycidyl ether, and 1, 6-hexanediol diglycidyl ether.
Examples of the isocyanate-based crosslinking agent include isocyanate monomers such as toluene diisocyanate, chlorobenzene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate, isocyanate compounds obtained by addition reaction of trimethylolpropane or the like to these isocyanate monomers, biuret-type isocyanate compounds, and urethane prepolymer-type isocyanates obtained by addition reaction of polyether polyol or polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, and the like to isocyanate monomers.
Examples of the metal chelate compound include compounds obtained by coordinating a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, or zirconium, such as alkoxide, acetylacetone, or ethyl acetoacetate. Specifically, the aluminum isopropoxide, aluminum sec-butoxide, aluminum diisopropylacetoacetate, aluminum ethylacetoacetate, and aluminum triacetylacetonate may, for example, be mentioned.
As the crosslinking agent, an epoxy crosslinking agent is preferable from the viewpoint of excellent heat resistance.
In the adhesive composition of the present invention, the crosslinking agent can form a three-dimensional crosslinked structure by reaction, and can exhibit high adhesive force and cohesive force.
(composition of adhesive composition)
The adhesive composition of the present invention contains 1 to 40 parts by mass of the (meth) acrylic copolymer (B) and 0.01 to 5 parts by mass of the crosslinking agent (C) per 100 parts by mass of the (meth) acrylic copolymer (a), preferably contains 3 to 35 parts by mass of the (meth) acrylic copolymer (B) and 0.03 to 3 parts by mass of the crosslinking agent (C), and more preferably contains 5 to 30 parts by mass of the (meth) acrylic copolymer (B) and 0.05 to 2.5 parts by mass of the crosslinking agent (C). When the blending amount of each component is within the above range, a psa sheet having excellent removability and no zipper noise phenomenon can be obtained by using the psa composition of the present invention, which is preferable.
The pressure-sensitive adhesive composition of the present invention may further contain various additives such as a tackifier resin, an antistatic agent, a silane coupling agent, an antioxidant, a UV absorber, a plasticizer, fine particles, and a coloring agent, as long as the physical properties of the pressure-sensitive adhesive composition of the present invention are not impaired. When the adhesive composition of the present invention contains the components other than (a) to (C), the content of the components other than (a) to (C) is usually 0.03 to 30% by mass, preferably 0.05 to 25% by mass, and more preferably 0.08 to 20% by mass, based on 100% by mass of the solid content of the adhesive composition.
The adhesive composition of the present invention may contain an organic solvent in addition to the above components within a range not impairing the effects of the present invention.
The organic solvent may, for example, be the polymerization solvent described in the description of the process for producing the (meth) acrylic copolymer (a). The adhesive composition of the present invention can be prepared, for example, by mixing a polymer solution containing the (meth) acrylic copolymer (a) and a polymerization solvent, a polymer solution containing the (meth) acrylic copolymer (B) and a polymerization solvent, and the crosslinking agent (C). In the adhesive composition of the present invention, the content of the organic solvent is usually 0 to 90% by mass, preferably 10 to 80% by mass.
(method for producing adhesive composition)
The pressure-sensitive adhesive composition of the present invention can be obtained by mixing the components (for example, (a) to (C) described above) contained in the pressure-sensitive adhesive composition by a known method using a stirring device or the like.
That is, the adhesive composition of the present invention can be obtained by mixing and stirring the components together or by mixing and stirring the components one by one. The stirring time is not particularly limited, but in view of workability and productivity, the stirring may be carried out at room temperature for about 10 to 120 minutes.
(physical Properties of adhesive composition)
In the adhesive composition of the present invention, the amount of the polymerization initiator (residual initiator amount) contained in 100 wt% solids of the adhesive composition is 800ppm or less. The amount of the residual initiator is the amount of the polymerization initiator contained in the adhesive composition, and is expressed by the amount when the solid content of the adhesive composition is 100% by weight. The polymerization initiator contained in the pressure-sensitive adhesive composition of the present invention is derived from a polymerization initiator used in polymerizing the (meth) acrylic copolymer (a) and the (meth) acrylic copolymer (B), and the polymerization initiator remaining unreacted in the polymerization is contained in the pressure-sensitive adhesive composition in an amount corresponding to the amount of the remaining initiator. In the case where the adhesive composition of the present invention contains a polymer other than the above-mentioned (meth) acrylic copolymer (a) and (meth) acrylic copolymer (B), the amount of the polymerization initiator remaining in the adhesive composition is also included in the amount of the remaining initiator in the adhesive composition in the case where the polymerization initiator used in the production of the polymer other than the (meth) acrylic copolymer (a) and (meth) acrylic copolymer (B) remains in the adhesive composition.
The amount of the residual initiator may be calculated by measuring the amount of the polymerization initiator contained in the binder composition by using a gas chromatograph-mass spectrometer (GCMS), or by measuring the amount of the polymerization initiator contained in the binder composition by using GCMS and simultaneously or separately determining the ratio of the solid components in the binder composition, or by measuring the amount of the residual initiator in each component constituting the binder composition and calculating the amount of the residual initiator from the amount of the residual initiator in each component and the amount (ratio) of the residual initiator in each component.
In the adhesive composition of the present invention, the amount of the polymerization initiator contained in 100 wt% solids of the adhesive composition is 800ppm or less, more preferably 700ppm or less, and particularly preferably 650ppm or less. In the case of being within the above range, the layer (adhesive layer) formed from the adhesive composition of the present invention is preferably inhibited from being changed into a grapefruit peel shape when irradiated with ultraviolet rays or the like. The lower limit of the amount of the residual initiator in the adhesive composition of the present invention is not particularly limited as it is lower, but it is usually 30ppm or more.
[ adhesive layer ]
The adhesive layer is prepared from the adhesive composition described above. For example, the pressure-sensitive adhesive layer is obtained by performing a crosslinking reaction in the above-mentioned pressure-sensitive adhesive composition, specifically, by crosslinking the (meth) acrylate-based copolymer (a) with the crosslinking agent (C).
The conditions for forming the adhesive layer are, for example, as follows. The pressure-sensitive adhesive composition of the present invention is applied to the release-treated surface of a substrate or a release sheet, and dried at a temperature of usually 50 to 150 ℃ and preferably 60 to 100 ℃ for usually 1 to 10 minutes and preferably 2 to 7 minutes depending on the kind of the solvent to remove the solvent, thereby forming a coating film. The thickness of the dried coating film is usually 5 to 125 μm, preferably 10 to 100 μm.
The adhesive layer is preferably formed under the following conditions. The adhesive composition of the present invention is applied to the release-treated surface of a substrate or a release sheet, and after the release sheet is adhered to the coating film formed under the above conditions, the coating film is cured in an environment of usually 5 to 60 ℃, preferably 15 to 40 ℃, usually 5 to 70% RH, preferably 5 to 50% RH for usually 3 days or longer, preferably 7 to 10 days. When crosslinking is carried out under the above-mentioned curing conditions, a crosslinked material (network polymer) can be efficiently formed.
As a method for applying the adhesive composition, a known method, for example, a method of applying and drying under a condition of forming a predetermined thickness by spin coating, knife coating, roll coating, bar coating, blade coating, die coating, or gravure coating, may be used.
[ adhesive sheet ]
The adhesive sheet of the present invention has an adhesive layer prepared from the adhesive composition of the present invention.
The pressure-sensitive adhesive sheet of the present invention is not likely to be in the form of a grapefruit peel, is excellent in weather resistance, foaming resistance and removability, and does not cause a zipper sound phenomenon, and therefore, can be suitably used for applications requiring these physical properties.
The pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive sheet composed only of a pressure-sensitive adhesive layer produced from the pressure-sensitive adhesive composition, or may be a pressure-sensitive adhesive sheet as a laminate having a base layer and a pressure-sensitive adhesive layer.
The thickness of the pressure-sensitive adhesive layer is not particularly limited as long as it is appropriately set according to the use of the pressure-sensitive adhesive sheet, and is usually 5 to 125 μm, preferably 10 to 100 μm.
In the case where the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet composed of only a pressure-sensitive adhesive layer produced using the pressure-sensitive adhesive composition, for example, the pressure-sensitive adhesive composition is applied to a release-treated substrate, and the release-treated substrate is further disposed on the applied surface as needed to form the pressure-sensitive adhesive layer, whereby the pressure-sensitive adhesive sheet of the present invention can be obtained. The pressure-sensitive adhesive sheet composed only of the pressure-sensitive adhesive layer is stored, moved, or the like together with the substrate subjected to the peeling treatment during storage, movement, or the like, but when used, the substrate subjected to the peeling treatment is peeled off and used as a pressure-sensitive adhesive sheet composed only of the pressure-sensitive adhesive layer.
In the case where the pressure-sensitive adhesive sheet of the present invention is a laminate having a base layer and a pressure-sensitive adhesive layer, for example, the pressure-sensitive adhesive composition is applied to a substrate, and if necessary, a release-treated substrate is further disposed on the applied surface to form the pressure-sensitive adhesive layer on the substrate, whereby the pressure-sensitive adhesive sheet of the present invention can be obtained. When the pressure-sensitive adhesive layer is used, the substrate subjected to the peeling treatment is peeled off and used as a pressure-sensitive adhesive sheet composed of a substrate layer and a pressure-sensitive adhesive layer.
In addition, as another example, a pressure-sensitive adhesive sheet may be obtained by providing pressure-sensitive adhesive layers on both sides of a base material layer, and further disposing a base material subjected to a peeling treatment on both sides thereof.
The substrate is not particularly limited, and examples thereof include plastic, glass, woven fabric, nonwoven fabric, and paper. The plastic is preferably transparent, and examples of the transparent plastic include Polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polypropylene (PP), acrylonitrile-butadiene-styrene copolymer (ABS), and polyamide (nylon).
The use of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and the pressure-sensitive adhesive sheet can be used as a pressure-sensitive adhesive sheet for protecting plastics and glass and preventing scattering.
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited thereto.
The physical properties of the copolymer obtained in the following production examples and the amount of the residual initiator in the adhesive composition were measured by the following methods.
(Mw、Mw/Mn)
The weight average molecular weight and the molecular weight distribution of the copolymer obtained in the following production example were measured by gel permeation chromatography (GPC method) under the following conditions. The measurement device: HLC-8320GPC (manufactured by Tosoh corporation of imperial sciences, China, Inc. (ソー))
GPC column composition: the following 4-column (all manufactured by Tosoh corporation) (1) TSKgel HxL-H (guard column) (2) TSKgel GMHxL (3) TSKgel GMHxL (4) TSKgel G2500HxL
Flow rate: 1.0 ml/min
Column temperature: 40 deg.C
Sample concentration: 1.5% (w/v) (diluted with tetrahydrofuran)
Mobile phase solvent: tetrahydrofuran (THF)
Conversion to Standard polystyrene
(residual initiator amounts of copolymer and adhesive composition)
The amounts of the residual initiator contained in the copolymers obtained in the following production examples and the adhesive compositions obtained in the respective examples and comparative examples were measured by a gas chromatograph-mass spectrometer (GCMS method) under the following conditions.
Pretreatment
A polymer solution or an adhesive composition is taken and dissolved with acetone. The acetone-dissolved sample was mixed while n-hexane was added dropwise, and the mixture was allowed to stand for 1 hour after thorough mixing. Then, the supernatant was collected and filtered, and the filtrate was used as a sample solution. The residual initiator amount of the obtained sample solution was measured by using a gas chromatograph-mass spectrometer (GCMS method). The measured values obtained are shown in tables 1 and 2 in terms of 100 mass% solid content.
The measurement device: agilent 6890N/5973 insert (made by Agilent technologies, Inc. (アジレント. テクノロジー))
Column: HP-5ms 30 m.times.0.25 mm, 0.25 μm (manufactured by Agilent technologies Co., Ltd.)
Furnace: 100 ℃ for 15 minutes, injection port: 110 deg.C
The detector: MS (ion source: 230 ℃, MS quadrupole: 150 ℃)
The detection method: SIM (subscriber identity Module)
Split ratio: 30:1
The temperature of the furnace and the temperature of the injection port can be set according to the kind of the polymerization initiator (half-life temperature of the polymerization initiator), and the above conditions are suitable for the temperature of 2, 2' -azobisisobutyronitrile used in the production example.
[ production example A-1 ]
In a four-necked flask having a capacity of 2 liters and equipped with a stirrer, a thermometer, a nitrogen inlet tube and a cooling tube, 75 parts by mass of n-Butyl Acrylate (BA), 18 parts by mass of Methyl Acrylate (MA) and 7 parts by mass of Acrylic Acid (AA) were charged as polymerizable monomers, and 150 parts by mass of ethyl acetate was charged as a solvent.
Then, while stirring under a nitrogen atmosphere, 0.1 part by mass of 2, 2' -Azobisisobutyronitrile (AIBN) was charged as a polymerization initiator, and the reaction was carried out at 70 ℃ for 7 hours. After the completion of the reaction, the reaction mixture was diluted with ethyl acetate to prepare a polymer solution containing the copolymer A-1 and having a solid content concentration of 20% by mass.
The Mw of the copolymer A-1 was 80 ten thousand, the Mw/Mn was 3.1, and the residual initiator amount was 660 ppm.
[ production example A-2 ]
A polymer solution having a solid content concentration of 20% by mass comprising the copolymer A-2 was prepared in the same manner as in production example A-1, except that the amount of n-Butyl Acrylate (BA) was changed from 75 parts by mass to 77.5 parts by mass and the amount of Acrylic Acid (AA) was changed from 7 parts by mass to 4.5 parts by mass.
The Mw of the copolymer A-2 was 80 ten thousand, the Mw/Mn was 3.3, and the residual initiator amount was 670 ppm.
[ production example A-3 ]
A polymer solution having a solid content concentration of 20% by mass, which contained the copolymer A-3, was prepared in the same manner as in production example A-1, except that the amount of n-Butyl Acrylate (BA) was changed from 75 parts by mass to 63 parts by mass and the amount of Methyl Acrylate (MA) was changed from 18 parts by mass to 30 parts by mass.
The Mw of copolymer A-3 was 75 ten thousand, the Mw/Mn was 3.4, and the residual initiator amount was 680 ppm.
[ production example A-4 ]
A polymer solution containing the copolymer A-4 and having a solid content concentration of 20% by mass was prepared in the same manner as in production example A-1, except that the amount of the polymerization initiator was changed from 0.1 part by mass to 0.2 part by mass and the reaction time was changed from 7 hours to 4 hours.
The Mw of copolymer A-4 was 75 ten thousand, the Mw/Mn was 3.5, and the residual initiator amount was 1200 ppm.
[ production example A-5 ]
A polymer solution having a solid content concentration of 20% by mass comprising the copolymer A-5 was prepared in the same manner as in production example A-1, except that the amount of n-Butyl Acrylate (BA) was changed from 75 parts by mass to 79 parts by mass and the amount of Acrylic Acid (AA) was changed from 7 parts by mass to 3 parts by mass.
The Mw of the copolymer A-5 was 80 ten thousand, the Mw/Mn was 3.4, and the residual initiator amount was 680 ppm.
[ production example A-6 ]
A polymer solution having a solid content concentration of 20% by mass comprising the copolymer A-6 was prepared in the same manner as in production example A-1, except that the amount of n-Butyl Acrylate (BA) was changed from 75 parts by mass to 70 parts by mass and the amount of Acrylic Acid (AA) was changed from 7 parts by mass to 12 parts by mass.
The Mw of the copolymer A-6 was 75 ten thousand, the Mw/Mn was 3.0, and the residual initiator amount was 630 ppm.
[ production example A-7 ]
A polymer solution having a solid content concentration of 20% by mass, which contained the copolymer A-7, was prepared in the same manner as in production example A-1, except that the amount of n-Butyl Acrylate (BA) was changed from 75 parts by mass to 83 parts by mass and the amount of Methyl Acrylate (MA) was changed from 18 parts by mass to 10 parts by mass.
The Mw of the copolymer A-7 was 80 ten thousand, the Mw/Mn was 3.1, and the residual initiator amount was 640 ppm.
[ production example A-8 ]
A polymer solution having a solid content concentration of 20% by mass, which contained the copolymer A-8, was prepared in the same manner as in production example A-1, except that the amount of n-Butyl Acrylate (BA) was changed from 75 parts by mass to 53 parts by mass and the amount of Methyl Acrylate (MA) was changed from 18 parts by mass to 40 parts by mass.
The Mw of the copolymer A-8 was 80 ten thousand, the Mw/Mn was 3.4, and the residual initiator amount was 730 ppm.
[ production example B-1 ]
In a four-necked flask having a capacity of 2 liters and equipped with a stirrer, a thermometer, a nitrogen introduction tube and a cooling tube, 95 parts by mass of Methyl Methacrylate (MMA) and 5 parts by mass of Dimethylaminoethyl Methacrylate (DM) were charged as polymerizable monomers, and 100 parts by mass of toluene was charged as a solvent.
Subsequently, 3 parts by mass of AIBN as a polymerization initiator was charged while stirring under a nitrogen atmosphere, and a reaction was carried out at 80 ℃ for 10 hours to prepare a solution containing the copolymer B-1 and having a solid content concentration of 50% by mass.
The Tg of the copolymer B-1 was 99 ℃, the Mw was 0.5 ten thousand, the Mw/Mn was 1.5, and the residual initiator amount was 50 ppm.
[ production example B-2 ]
A polymer solution having a solid content concentration of 50% by mass and containing the copolymer B-2 was prepared in the same manner as in production example B-1, except that 95 parts by mass of Methyl Methacrylate (MMA) was changed to 95 parts by mass of t-butyl methacrylate (t-BMA).
The Tg of the copolymer B-2 was 101 ℃, the Mw was 0.5 ten thousand, the Mw/Mn was 1.8 and the residual initiator amount was 60 ppm.
[ production example B-3 ]
A polymer solution having a solid content concentration of 50% by mass, which contained the copolymer B-3, was prepared in the same manner as in production example B-1, except that the amount of Methyl Methacrylate (MMA) was changed from 95 parts by mass to 100 parts by mass and the amount of Dimethylaminoethyl Methacrylate (DM) was changed from 5 parts by mass to 0 parts by mass.
The Tg of the copolymer B-3 was 105 ℃, the Mw was 0.5 ten thousand, the Mw/Mn was 1.5 and the residual initiator amount was 50 ppm.
The polymers obtained in the production examples are summarized in table 1.
[ Table 1]
[ example 1]
An adhesive composition was obtained by mixing the polymer solution (solid content concentration: 20% by mass) obtained in production example A-1, the solution (solid content concentration: 50% by mass) obtained in production example B-1, and an epoxy-based crosslinking agent E-5XM (manufactured by Hokko chemical Co., Ltd.: Kitsuki chemical) having a solid content concentration of 5% by mass) in such amounts that the solid content ratios of the polymer solution and the epoxy-based crosslinking agent were 100 parts by mass for copolymer A-1, 15 parts by mass for copolymer B-1, and 0.075 part by mass for E-5 XM.
[ examples 2 to 6, comparative examples 1 to 8 ]
A pressure-sensitive adhesive composition was prepared in the same manner as in example 1, except that the blending composition of the pressure-sensitive adhesive composition was changed to that shown in table 2.
The adhesive compositions obtained in examples and comparative examples were measured and evaluated by the following methods.
(preparation of adhesive sheet)
The adhesive composition was coated on a release-treated polyethylene terephthalate (PET) film to a thickness of 20 μm after drying, and dried at 80 ℃ for 2 minutes to form an adhesive layer.
A38 μm thick PET film was bonded to the surface of the pressure-sensitive adhesive layer opposite to the surface in contact with the PET film, and the resultant was cured at 23 ℃ and 50% RH for 7 days to obtain a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer (20 μm thick) on the PET film.
(evaluation of Re-peelability and zipper noise phenomenon)
The PET film having a thickness of 38 μm after the peeling treatment was peeled off from the above adhesive sheet, and after transferring the adhesive layer to a PET film having a thickness of 100 μm (DIAFOIL T680E 100; manufactured by Mitsubishi resin Co., Ltd.), a test piece was produced by cutting the adhesive layer to a width of 25 mm. The PET film subjected to the peeling treatment was peeled from the obtained test piece, and the exposed adhesive layer was adhered to a glass plate, and pressure-bonded by reciprocating 3 times with a 2kg roller. After the pressure-bonding, the pressure-sensitive adhesive sheet was left to stand at 23 ℃ and 50% RH for 24 hours, and then the end of the test piece was pulled at a speed of 300 mm/min at an angle of 90 ° with respect to the glass plate, and the removability and the zipper noise phenomenon were evaluated according to the following criteria.
Removability
Very good: no adhesive residue was left on the glass plate after the adhesive sheet was peeled off (Japanese: paste residue り)
O: the glass plate after the adhesive sheet was peeled off had no adhesive residue, but a sticking mark was visible
And (delta): residual glue exists on the glass plate after the adhesive sheet is stripped, and the area of the residual glue is less than 20 percent of the adhering area
X: residual glue exists on the glass plate after the adhesive sheet is stripped, and the area of the residual glue is more than 20 percent of the adhering area
Zipper sound
O: when the adhesive sheet is peeled from the glass plate, no sound is generated
X: when the adhesive sheet is peeled off from the glass plate, a sound is emitted
(evaluation of foaming resistance)
The PET film having a thickness of 38 μm after the peeling treatment was peeled off from the above adhesive sheet, and after transferring the adhesive layer to a PET film having a thickness of 100 μm (DIAFOIL T680E 100; manufactured by Mitsubishi resin Co., Ltd.), a test piece was produced by cutting the adhesive layer to a width of 50 mm. times.50 mm. The peeled PET film was peeled from the obtained test piece, and the exposed pressure-sensitive adhesive layer was adhered to a polycarbonate plate, which was left to stand at 80 ℃ for 150 hours, and then the presence or absence of air bubbles was visually judged.
Very good: absence of air bubbles
O: although a small amount of bubbles is present, there is no problem in practical use
X: the presence of bubbles in a wide range
(evaluation of UV resistance)
Manufactured by UV lamp (Shiga test K.) (スガ) (test), and high-energy xenon weather resistance tester (strong エネルギーキセノンウェザーメータ)ー), model number: SC750W) was irradiated with ultraviolet light (60W/m) for 168 hours to the pressure-sensitive adhesive sheet2)。
After the irradiation, the pressure-sensitive adhesive sheet was observed to determine whether or not the surface of the pressure-sensitive adhesive layer had irregularities, that is, whether or not the pressure-sensitive adhesive layer had a grapefruit peel shape.
O: does not turn into pomelo peel
X: become shaddock peel-like
The pressure-sensitive adhesive sheet that did not become grapefruit peel-like was also judged to be excellent in weather resistance.
The examples and comparative examples are shown in Table 2.
[ Table 2]
Claims (3)
1. An adhesive composition comprising a (meth) acrylic copolymer (A), a (meth) acrylic copolymer (B) and a crosslinking agent (C),
the (meth) acrylic copolymer (A) is a copolymer of monomer components comprising 13 to 35 mass% of a homopolymer of an alkyl (meth) acrylate having a glass transition temperature (Tg) of 0 ℃ or higher and having an alkyl group with 1 to 12 carbon atoms, 55 to 80 mass% of a homopolymer of an alkyl (meth) acrylate having a glass transition temperature (Tg) of less than 0 ℃ and having an alkyl group with 1 to 12 carbon atoms, and 3.5 to 10 mass% of a carboxyl group-containing monomer;
the (meth) acrylic copolymer (B) is a copolymer of monomer components comprising an alkyl methacrylate having 1 to 20 carbon atoms in the alkyl group and an amino group-containing monomer;
the adhesive composition comprises 1 to 30 parts by mass of a (meth) acrylic copolymer (B) per 100 parts by mass of a (meth) acrylic copolymer (A), and 0.01 to 5 parts by mass of a crosslinking agent (C);
the amount of the polymerization initiator contained in 100 wt% of the solid content of the adhesive composition is 800ppm or less.
2. The adhesive composition according to claim 1, wherein the weight average molecular weight of the (meth) acrylic copolymer (B) is 1000 to 50000 and the glass transition temperature is 80 ℃ or higher.
3. An adhesive sheet comprising an adhesive layer prepared from the adhesive composition according to claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017077566A JP7007100B2 (en) | 2017-04-10 | 2017-04-10 | Adhesive composition and adhesive sheet |
| JP2017-077566 | 2017-04-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108707442A CN108707442A (en) | 2018-10-26 |
| CN108707442B true CN108707442B (en) | 2021-06-01 |
Family
ID=63867109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810292799.4A Active CN108707442B (en) | 2017-04-10 | 2018-03-30 | Adhesive composition and adhesive sheet |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7007100B2 (en) |
| KR (1) | KR102306382B1 (en) |
| CN (1) | CN108707442B (en) |
| TW (1) | TWI801375B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101197530B1 (en) * | 2010-12-30 | 2012-11-09 | 한국원자력연구원 | Method of chemical decontamination of radwaste and the method of recycle for radwaste and decontamination solution |
| US11655056B2 (en) | 2018-09-21 | 2023-05-23 | Mitsubishi Electric Corporation | Orientation control device, satellite, orientation control method, and program |
| KR20210148084A (en) * | 2019-03-25 | 2021-12-07 | 니치유 가부시키가이샤 | Block copolymer, release agent composition, release layer, and release sheet |
| WO2020202762A1 (en) * | 2019-03-29 | 2020-10-08 | 綜研化学株式会社 | Pressure-sensitive adhesive composition for road surface or floor surface and marking sheet |
| JP7406908B2 (en) | 2019-09-06 | 2023-12-28 | 株式会社きもと | Glass shatter prevention sheet |
| CN114599756A (en) * | 2019-10-28 | 2022-06-07 | 综研化学株式会社 | Adhesive composition, adhesive sheet, and optical member |
| JP2021107474A (en) * | 2019-12-27 | 2021-07-29 | スリーエム イノベイティブ プロパティズ カンパニー | Heat shrinkage resistant adhesive film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101778915A (en) * | 2007-07-31 | 2010-07-14 | 3M创新有限公司 | Adhesive film, production method of shaped body |
| CN104024363A (en) * | 2011-12-28 | 2014-09-03 | 综研化学株式会社 | Optical member adhesive composition, adhesive sheet using same, optical member provided with adhesive layer, and flat panel display |
| CN106574160A (en) * | 2014-08-28 | 2017-04-19 | 德莎欧洲公司 | Water-resistant adhesive mass for bonding on wet surfaces, in particular for uses with automobiles |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5736150B2 (en) | 1974-07-03 | 1982-08-02 | ||
| JP3516035B2 (en) * | 1997-05-13 | 2004-04-05 | 綜研化学株式会社 | Adhesive composition |
| KR100555203B1 (en) * | 1997-05-13 | 2006-05-23 | 린텍 가부시키가이샤 | Adhesive composition |
| JP4682299B2 (en) | 2003-11-17 | 2011-05-11 | 綜研化学株式会社 | Pressure sensitive adhesive for protective sheet |
| JP5283221B2 (en) | 2006-07-20 | 2013-09-04 | 綜研化学株式会社 | PDP front filter adhesive composition and use |
| JP4942171B2 (en) * | 2006-09-14 | 2012-05-30 | 綜研化学株式会社 | Adhesive composition and adhesive sheet |
| JP6257128B2 (en) | 2011-06-27 | 2018-01-10 | 日本合成化学工業株式会社 | Adhesive composition for heat-resistant adhesive film, adhesive for heat-resistant adhesive film obtained by crosslinking this, and use of this adhesive |
| JP6093624B2 (en) | 2012-05-24 | 2017-03-08 | 日東電工株式会社 | Adhesive layer for optical film, optical film with adhesive layer, and image display device |
| TWI773060B (en) * | 2013-11-29 | 2022-08-01 | 日商三菱化學股份有限公司 | Adhesive composition and adhesive sheet |
| CN107148586A (en) * | 2014-11-04 | 2017-09-08 | 综研化学株式会社 | Polarizer adhesive composition and the polarizer with adhesive phase |
| JP6352196B2 (en) | 2015-01-23 | 2018-07-04 | 日本カーバイド工業株式会社 | Adhesive composition and adhesive film |
| KR20160100122A (en) * | 2015-02-13 | 2016-08-23 | 동우 화인켐 주식회사 | Heat-Sensitive Adhesive Composition and Heat-Sensitive Adhesive Tape Comprising the Same |
-
2017
- 2017-04-10 JP JP2017077566A patent/JP7007100B2/en active Active
-
2018
- 2018-03-30 CN CN201810292799.4A patent/CN108707442B/en active Active
- 2018-03-30 KR KR1020180037303A patent/KR102306382B1/en active IP Right Grant
- 2018-04-03 TW TW107111875A patent/TWI801375B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101778915A (en) * | 2007-07-31 | 2010-07-14 | 3M创新有限公司 | Adhesive film, production method of shaped body |
| CN104024363A (en) * | 2011-12-28 | 2014-09-03 | 综研化学株式会社 | Optical member adhesive composition, adhesive sheet using same, optical member provided with adhesive layer, and flat panel display |
| CN106574160A (en) * | 2014-08-28 | 2017-04-19 | 德莎欧洲公司 | Water-resistant adhesive mass for bonding on wet surfaces, in particular for uses with automobiles |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108707442A (en) | 2018-10-26 |
| KR102306382B1 (en) | 2021-09-29 |
| TWI801375B (en) | 2023-05-11 |
| JP7007100B2 (en) | 2022-02-10 |
| TW201842126A (en) | 2018-12-01 |
| JP2018177919A (en) | 2018-11-15 |
| KR20180114505A (en) | 2018-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108707442B (en) | Adhesive composition and adhesive sheet | |
| KR101495828B1 (en) | Pressure-sensitive adhesive composition for polarizing plates and polarizing plate having pressure-sensitive adhesive layer | |
| CN109021889B (en) | Image display device | |
| JP5424720B2 (en) | Photocurable adhesive composition, photocurable adhesive layer, and photocurable adhesive sheet | |
| EP2549303A1 (en) | Optical sheet with adhesive layer, method for producing optical sheet with adhesive layer, light source using optical sheet with adhesive layer, and image display device using optical sheet with adhesive layer | |
| JP5008870B2 (en) | Adhesive composition and adhesive sheet containing the same | |
| WO2010140442A1 (en) | Photocurable adhesive composition, photocurable adhesive layer, and photocurable adhesive sheet | |
| JP4968764B2 (en) | Adhesive composition, adhesive layer and method for producing the same, and adhesive sheets | |
| WO2012114921A1 (en) | Adhesive agent composition, adhesive agent layer, and adhesive sheet | |
| JP2020176202A (en) | Solvent type pressure sensitive adhesive composition and pressure sensitive adhesive sheet | |
| JP5498870B2 (en) | Adhesive composition excellent in heat resistance, adhesive layer, and adhesive sheet | |
| JP5379658B2 (en) | Photocurable adhesive composition, photocurable adhesive layer, and photocurable adhesive sheet | |
| CN112400002B (en) | Adhesive composition and adhesive tape | |
| EP4183849A1 (en) | Adhesive agent composition and adhesive sheet | |
| CN111742022B (en) | Double-sided adhesive sheet and use thereof | |
| JP7302159B2 (en) | Tackifier and adhesive composition | |
| JP7047851B2 (en) | Adhesive composition and its use | |
| JP6235346B2 (en) | Adhesive composition, adhesive tape and laminate | |
| JP2020176253A (en) | Solvent type pressure sensitive adhesive composition and pressure sensitive adhesive sheet | |
| JP6004788B2 (en) | RESIN COMPOSITION AND METHOD FOR PRODUCING POLYMER | |
| JP7322607B2 (en) | Solvent-based adhesives and adhesive sheets | |
| WO2021024863A1 (en) | Adhesive sheet and use thereof | |
| CN117120571A (en) | Adhesive composition and adhesive sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |